Composi es o Sphe ical Polyelec oly e
B ushes and Nanopa icles
–
Syn hesis, Cha ac e iza ion and Thei
Use in Ca alysis
DISSERTATION
Zu E langung des akademischen G ades eines
Dok o s de Na u wissenscha en (D . e . na .)
im Fach Chemie de Fakul ä ü Biologie, Chemie und
Geowissenscha en de
Uni e si ä Bay eu h
Vo geleg on
F ank Polze
Gebo en in E langen, Deu schland
Bay eu h 2011
I
Table o Con en s
1.In oduc ion ................................................................................................ 1
1.1.Manganese Oxide Nanopa icles ............................................................................. 2
1.2.Nanopa icles in Ca alysis ........................................................................................ 4
1.3.S abiliza ion o Nanopa icles in Solu ion ............................................................... 7
1.4.Sphe ical Polyelec oly e B ushes o he S abiliza ion o Nanopa icles in
Solu ion .................................................................................................................... 8
1.5.X-Ray Abso p ion Fine S uc u e Spec oscopy on Nanosized Ma e ials ............. 10
1.6.C yogenic T ansmission Elec on Mic oscopy on Nanosized Ma e ials ............... 13
1.7.Objec i e o his Thesis ......................................................................................... 14
1.8.Re e ences .............................................................................................................. 15
2.O e iew ................................................................................................... 23
2.1.Fo ma ion o Ul a hin Bi nessi e-Type Nanopa icles Immobilized on Sphe ical
Polyelec oly e B ushes.......................................................................................... 25
2.2.S uc u al Analysis o Colloidal MnOx Composi es .............................................. 27
2.3.Ca aly ic Oxida ion o an O ganic Dye by MnOx Nanopa icles Immobilized on
Sphe ical Polyelec oly e B ushes ......................................................................... 29
2.4.Kine ic Analysis o he Ca aly ic Reduc ion o 4-Ni ophenol by Me allic
Nanopa icles Immobilized in Sphe ical Polyelec oly e B ushes ......................... 31
2.5.Syn hesis and Analysis o Zwi e ionic Sphe ical Polyelec oly e B ushes in
Aqueous Solu ion ................................................................................................... 33
2.6.Indi idual Con ibu ions o Join Publica ions ...................................................... 35
3.Fo ma ion o Ul a hin Bi nessi e-Type Nanopa icles Immobilized on
Sphe ical Polyelec oly e B ushes .......................................................... 39
3.1.Abs ac .................................................................................................................. 40
3.2.In oduc ion ............................................................................................................ 41
3.3.Expe imen al Sec ion ............................................................................................. 42
3.4.Resul s and Discussion .......................................................................................... 43
3.5.Conclusions ............................................................................................................ 50
3.6.Acknowledgemen s ................................................................................................ 50
II
3.7.Suppo ing In o ma ion .......................................................................................... 51
3.8.Re e ences .............................................................................................................. 52
4.S uc u al Analysis o Colloidal MnOx Composi es ............................. 57
4.1.Abs ac .................................................................................................................. 58
4.2.In oduc ion ............................................................................................................ 59
4.3.Expe imen al Sec ion ............................................................................................. 60
4.4.Resul s and Discussion .......................................................................................... 62
4.5.Conclusion ............................................................................................................. 75
4.6.Acknowledgemen s ................................................................................................ 76
4.7.Suppo ing In o ma ion .......................................................................................... 76
4.8.Re e ences .............................................................................................................. 77
5.Oxida ion o an O ganic Dye Ca alyzed by MnOx Nanopa icles ...... 83
5.1.Abs ac .................................................................................................................. 84
5.2.In oduc ion ............................................................................................................ 85
5.3.Expe imen al Sec ion ............................................................................................. 87
5.4.Resul s and Discussion .......................................................................................... 88
5.5.Conclusions ............................................................................................................ 98
5.6.Acknowledgemen s ................................................................................................ 98
5.7.Suppo ing in o ma ion .......................................................................................... 99
5.8.Re e ences ............................................................................................................ 100
6.Kine ic Analysis o Ca aly ic Reduc ion o 4-Ni ophenol by Me allic
Nanopa icles Immobilized in Sphe ical Polyelec oly e B ushes .... 103
6.1.Abs ac ................................................................................................................ 104
6.2.In oduc ion .......................................................................................................... 105
6.3.Expe imen al Sec ion ........................................................................................... 107
6.4.Resul s and Discussion ........................................................................................ 108
6.5.Conclusion ........................................................................................................... 117
6.6.Acknowledgmen ................................................................................................. 117
6.7.Re e ences ............................................................................................................ 117
7.Syn hesis and Analysis o Zwi e ionic Sphe ical Polyelec oly e
B ushes in Aqueous Solu ion ................................................................ 121
III
7.1.Abs ac ................................................................................................................ 122
7.2.In oduc ion .......................................................................................................... 123
7.3.Expe imen al Sec ion ........................................................................................... 124
7.4.Resul s and Discussion ........................................................................................ 126
7.5.Conclusion ........................................................................................................... 134
7.6.Acknowledgemen s .............................................................................................. 135
7.7.Suppo ing In o ma ion ........................................................................................ 135
7.8.Re e ences ............................................................................................................ 137
8.Summa y/Zusammen assung ............................................................... 141
Summa y ............................................................................................................................. 141
Zusammen assung .............................................................................................................. 142
ALis o Publica ions ................................................................................ 145
A1.Publica ions o his Thesis ................................................................................... 145
A2.Publica ions as a co-Au ho ................................................................................. 145
A3.Pa en s submi ed du ing he Cou se o he Thesis .............................................. 146
BP esen a ions a In e na ional Con e ences and Mee ings ................ 147
CAbb e ia ions ......................................................................................... 149
DDanksagung ............................................................................................ 151
ESchlusse klä ung .................................................................................... 153

IV
V
Die o liegende A bei wu de in de Zei on Augus 2007 bis Feb ua 2011 in Bay eu h am
Leh s uhl Physikalische Chemie I und am Helmhol z Zen um Be lin ü Ma e ialien und
Ene gie un e Be euung on He n P o . D . Ma hias Ballauff ange e ig .
Volls ändige Abd uck de on de Fakul ä Biologie, Chemie und Geowissenscha en de
Uni e si ä Bay eu h genehmig en Disse a ion zu E langung des akademischen G ades eines
Dok o s de Na u wissenscha en (D . e . na .)
Disse a ion einge eich am: 16. Feb ua 2011
Tag de Zulassung du ch die P ü ungskommission: 25. Juni 2011
Tag des wissenscha lichen Kolloquiums: 05. Juli 2011
Am ie ende Dekan:
P o . D . S ephan Clemens
P ü ungsausschuss:
P o . D . Ma hias Ballauff (E s gu ach e )
P o . D . Jose B eu (Zwei gu ach e )
P o . D . Axel H. E. Mülle (Vo si z)
P o . D . Geo ge Papas a ou
VI
VII
Well he e’s hose ha do
And hose ha jus do alking
We’ e all going h ough hell
I ’s bu n o keep on walking
Randy Bly he
Manganese Oxide Nanopa icles
2
shape.19,20,21 This ac has di ec ly led o a huge numbe o s udies in es iga ing he con ol o
he dimensions as well as o he mo phology o nanopa icles.22,23,24 In p inciple,
nanopa icles and hei assemblies can be subdi ided acco ding o hei dimensionali y in o
1D, 2D and 3D pa icles.25
Due o he huge a ie y o di e en nanopa icula ma e ials a ailable, he cha ac e is ics o
hese pa icles di e s ongly. In gene al, he p ope ies can be di ided in o h ee g oups.
Su ace-dependen p ope ies a e p ope ies he bulk ma e ial also possess bu ha become
dominan a high su ace- o- olume a ios, e.g. o ca aly ic applica ions o nanopa icles (see
Figu e 1.0.2a). Second, size-dependen p ope ies ha a e di ec ly ela ed o he small size,
e.g. in B agg s acks o in pho onic c ys als.26,27 Las ly, he e exis size-dependen quan um
e ec s. This means a di ec in luence o he size o nanopa icles on hei elec onic s uc u e,
e.g. he size-dependen su ace plasmon shi in me al nanopa icles (Figu e 1.0.2b).28,29,30
(a) (b)
Figu e 1.0.2. (a) Dependence o he size o gold nanopa icles on o he a io o inne a oms o
a oms a he su ace.31 (b) Illus a ion o he in luence o he size o me allic nanopa icles
on o he densi y o s a es. Pa icles wi h sizes be ween he size o small molecules and ha o
bulk me al display elec onic s uc u es, e lec ing he elec onic band s uc u e o he
nanopa icles, owing o quan um-mechanical ules.32
Applica ions o nanopa icles a e wide- anging and include medical applica ions like d ug
deli e y33 and sensing34, coa ings35, was e wa e ea men 36, ene gy con e sion37 and
s o age38 and many o he s mo e.39 Besides all o hese in e es ing applica ions, he use o
nanopa icles in ca alysis seems o be one o he mos p omising.40,41,42 This will be discussed
u he in sec ion 1.2.
1.1. Manganese Oxide Nanopa icles
Manganese oxide nanopa icles include all common oxida ion s a es o manganese, such as
MnO, Mn2O3, Mn3O4, MnO2 and also mixed alen compounds (MnOxNP).43,44,45,46,47,48 The e
exis nume ous epo s abou he syn hesis o all di e en kinds o MnOxNP including 1D, 2D

In oduc ion
3
and 3D s uc u es.49 Applica ions o manganese oxide nanos uc u ed ma e ials mos ly ocus
on he use as elec ode ma e ials o ene gy s o age, o magne ic da a s o age, as ion
exchange ma e ials, and o ca alysis.50,51,52,53
Wi h i s wide ange o polymo phs, MnO2 has ecei ed he mos a en ion among he
di e en manganese oxides. All di e en polymo phs a e buil om he same basic uni , ha
is he MnO6 oc ahed a (see Figu e 1.1.1a). Due o he di e en linkage o he MnO6
oc ahed a, α-, β-, γ- and δ-MnO2 also possess dis inc p ope ies.54 δ-MnO2 consis s
p edominan ly o edge-sha ing MnO6 uni s ha o m a laye ed opology simila o ha o clay
mine als like silica es o aluminosilica es.55
One o he mos in ensely s udied compounds in he amily o laye ed manganese oxides is
bi nessi e.56,57,58,59,60 This phyllomangana e is composed o hexagonal shee s o p edominan ly
edge-sha ed MnO6 oc ahed a.61,62 Typically, he in e laye s be ween single shee s bea
hyd olyzable ca ions.63 The ca ions balance he nega i e cha ges o he shee s.64 These
nega i e su ace cha ges a e due o he p esence o acancies wi hin he ab-plane o he
shee s.65,66 Fu he mo e, a ne cha ge can a ise by he inco po a ion o a ce ain amoun o
co ne -sha ed Mn3+ oc ahed a.67,68 The in e cala ion can be used o he so p ion o o he
posi i ely cha ge compounds which di ec ly leads o applica ions in was e wa e
ea men .69,70 In addi ion, he ca ion exchange o alkali me al ions by mo e bulky ca ions, e.g.
o ganic ca ions, su ac an s, polyelec oly es, e c., leads o a swelling o he in e laye dis ance
in aqueous solu ion.71,72,73 This e ec can be used o adjacen delamina ion o he hexagonal
shee s.74,75 Ex olia ion e e s o he gene a ion o single laye s o shee s which is mos ly
achie ed by mul i-s ep p ocesses.76,77,78,79 The e exis only a ew epo s on he syn hesis o
single lamellae o laye ed manganese oxides, e.g. bi nessi e.80,81 The gene a ion o single
laye ed nanoshee s is desi able because o hei la ge speci ic su ace a ea.80 The su ace can
di ec ly se e as a highly ac i e ca alys o i can be u he unc ionalized by o ganic ligands.
Fu he mo e, oc ahed al laye ed (OL) manganese oxides can be used as building blocks o
laye -by-laye sel -assemblies and pilla ed MnOx s uc u es.82,83 OL manganese oxides can
also be con e ed in o 1D unnel s uc u es ha a e e med oc ahed al molecula sie es
(OMS).84,85,86 Some common c ys allog aphic s uc u es o hese ma e ials a e shown in
Figu e 1.1.1.
OMS and OL ma e ials o e a b oad ange o di e en p ope ies depending on hei
a chi ec u e, he a e age oxida ion s a e and he in e laye ca ions.87 These pa ame e s a e
e y sensi i e o he syn he ic ou e and p o ed o ha e majo impac on he ca aly ic
p ope ies.88,89,90
Nanopa icles in Ca alysis
4
(a) (b)
(c) (d)
(e) ( )
Figu e 1.1.1. C ys allog aphic s uc u es o di e en OL and OMS s uc u es. (a) S uc u e o
MnO6 oc ahed a (Mn blue sphe e, O ed sphe e) which is he building block o all OL and
OMS ma e ials. (b) Na-Bi nessi e (Na ed sphe e); (c) Py olusi e; (d) K-C yp omelane (K
g ey sphe e); (e) Mg-Todo oki e (Mg b own sphe e) and ( ) Ba-Romanechi e (Ba g een
sphe e).
1.2. Nanopa icles in Ca alysis
Nanopa icles made hei b eak h ough as ca alys ma e ials a e Ha u a e al.91,92 epo ed
on he high pe o mance o gold nanopa icles on he CO oxida ion in he la e 1980s. A he
same ime Hu chings e al. disco e ed he ac i i y o gold nanopa icles o he
hyd ochlo ina ion o ace ylene.93 Since hen, a as amoun o s udies ha e been conduc ed on
he ca aly ic ac i i y o nanopa icles.9,94 Those include mos kinds o nanopa icles and
di e en ca aly ic eac ions, e.g. oxida ion eac ions, hyd ogena ion eac ions, educ ions,
coupling eac ions, pho oca aly ic eac ions, e c.11,33,42
In oduc ion
5
Besides he nume ous wo ks on applied ca alysis wi h nanopa icles many s udies ha e been
conduc ed o elucida e he ac i i y o nanosized ma e . Hence, di e en kinds o model
eac ions o de ailed in es iga ions ha e been es ablished. These include educ ion o
oxida ion eac ions o a a ie y o di e en dye molecules which enables in si u in es iga ions
by UV/ isible spec oscopy (UV/ is).95,96,97 One aspec o hese s udies was o elucida e he
size-dependence o he ca aly ic ac i i y o nanopa icles, e.g. gold nanopa icles.98,99,100
Ano he ocus has been laid on he in luence o he shape o nanopa icles on hei ca aly ic
ac i i y.101,102 Though he e exis s a high numbe o di e en in es iga ions, he e is s ill a
lack o comp ehension o he mechanism o eac ions ca alyzed by nanopa icles.
In p inciple, su ace ca alyzed eac ions can be di ided in o wo dis inc mechanisms: he
Eley-Rideal mechanism (ER) and he Langmui -Hinshelwood mechanism (LH).103 The basic
ca alys cycle o a LH mechanism is depic ed in Figu e 1.2.1.
Figu e 1.2.1. Illus a ion o a ca aly ic cycle o a bimolecula su ace eac ion ia a
Langmui -Hinshelwood mechanism. Reac an A and B concomi an ly adso b on o he ca alys
su ace in a e e sible s ep (a & b) which is ollowed by an i e e sible bimolecula su ace
eac ion o A and B (c). The eac ion p oduc P deso bs om he ca alys su ace (d) and
lea es ee ac i e si es on he ca alys (e). In he end, he ca aly ic cycle can s a again by he
adso p ion o u he eac an s ( & a).
Nanopa icles in Ca alysis
6
The main cha ac e is ic o LH eac ions is ha bo h eac an s ha e o be adso bed on o he
ca alys su ace.104 The adso p ion p ocess is desc ibed by a Langmui iso he m
=
1+ (1.2.1)
whe e θi is he su ace co e age o he eac an i, Ki ep esen s he adso p ion cons an o i
and ci i s concen a ion espec i ely.105
The adso bed eac an s unde go a su ace eac ion, which is he a e de e mining s ep o he
cycle. Subsequen ly he eac ion p oduc deso bs om he ca alys su ace, lea ing ee si es
on he ca alys o he s a o a new cycle. This is schema ically depic ed in Figu e 1.2.1. In
con as , in an ER mechanism, only one o he eac an s is adso bed on o he ca alys su ace.
This species eac s ia a collision wi h a molecule om he bulk phase.
The e exis ma ked di e ences be ween he wo mechanisms conce ning he dependency o
concen a ion o he eac an s on he a e o eac ion ( ). Fo a LH mechanism, he scheme in
Figu e 1.2.2 shows he cou se o wi h inc easing concen a ion o eac an A. A a low
su ace co e age θ o A, he su ace is p edominan ly occupied by B and he eac ion be ween
A and B is hinde ed. The cu e goes h ough a maximum, since he adso p ion o A becomes
mo e likely wi h an inc easing concen a ion. A highe concen a ions o A, is dec easing
again since he su ace is blocked by his species and su ace eac ion be ween A and B is
hinde ed again (see Figu e 1.2.2).103
Figu e 1.2.2. Illus a ion o he dependence o he concen a ion o eac an A on he a e o
he eac ion acco ding o a LH mechanism assuming one ype o ac i e si e. I he su ace is
p edominan ly occupied by one o he species, he su ace eac ion is hinde ed and he e o e
dec eases. Since he su ace co e age θ is de e mined by Langmui iso he ms i depends on
he concen a ion o he eac an s and hei adso p ion cons an s, espec i ely.
An i e e sible, bimolecula su ace eac ion whe e bo h eac an s a e adso bed on o he
su ace (see Figu e 1.2.2) can be desc ibed by he ollowing equa ion:103
In oduc ion
7
= ()()
(1++) (1.2.2)
He e, S ep esen s he o al su ace a ea o he ca alys , KA and KB a e he adso p ion
cons an s o A and B. The concen a ions o A and B a e exp essed by c
A and cB,
espec i ely. The kine ic cons an o he su ace eac ion o A and B is exp essed by k.
Fo an ER mechanism he e is no such dependence desc ibed by Eq. 1.2.2. In ac , he
cou se ollows ha o a Langmui iso he m since a some poin an inc ease o B does no lead
a u he inc ease o . This is because B has o eac wi h abso bed A and i he concen a ion
o B exceeds he concen a ion o adso bed A, nei he an inc ease no a dec ease o
ollows.103
The numbe o s udies in es iga ing he mechanism o ca alyzed benchma k eac ions wi h
nanopa icles is sca ce so a .106,107 The main easons o ha a e he limi ed s abili y and he
de ailed cha ac e iza ion o small nanopa icles.41 The e o e, new ways o he s abiliza ion o
e y small nanopa icles in solu ion a e equi ed. I would be an asse i he s abilizing agen
did no block he ac i e su ace o he nanopa icles since his would signi ican ly a ec he
ca aly ic s udies.108 I hese equi emen s a e ul illed, mo e de ailed insigh s o he ca aly ic
mechanisms will be possible in combina ion wi h s a e o he a cha ac e iza ion echniques.
1.3. S abiliza ion o Nanopa icles in Solu ion
Since mos o he me hods o he gene a ion o nanopa icles a e conduc ed in aqueous
medium o in an o ganic sol en , he s abiliza ion o hese pa icles agains coagula ion is o
g ea impo ance.19,109 I no s abiliza ion is p o ided, uncon olled g ow h wi h subsequen
Os wald ipening will occu . This leads o agglome a ion and p ecipi a ion. The
agglome a ion is caused by an de Waals o ces ha lead o an a ac ion o pa icles a sho
pa icle dis ances. I no epulsi e o ces a e p esen nanopa icles end o agg ega e.110 The
s abiliza ion mechanism o su ace cha ged colloidal pa icles is desc ibed by he heo y o
De jaguin, Landau, Ve wey and O e beek (DLVO heo y).111,112,113
Fo mos applica ions, agglome a ion leads o a loss o he unc ionali y o nanopa icles due
o he s ong ela ion be ween he p ope ies o he nanopa icles o hei size and shape, e.g.
in ca alysis.19 In gene al, nanopa icles can be s abilized in wo di e en ways. Ei he he
nanopa icles a e modi ied a hei su ace o hey a e immobilized on o suppo pa icles ha
p o ide su icien s abiliza ion agains coagula ion.40 Fo bo h p inciples wo di e en kinds
o s abiliza ion mechanisms and a combina ion o bo h can be dis inguished. A schema ic
ep esen a ion o elec os a ic, s e ic and elec os e ic s abiliza ion is gi en in Figu e
1.3.1.40,114

Sphe ical Polyelec oly e B ushes o he S abiliza ion o Nanopa icles in Solu ion
8
Figu e 1.3.1. Illus a ion o he di e en p inciples o s abilizing colloidal pa icles. (a)
Elec os a ic s abiliza ion by cha ges ha a e ei he chemically bound on he su ace (su ace
unc ionaliza ion) o a ixed by selec i e adso p ion. (b) S e ic s abiliza ion can ei he be
achie ed by adso p ion o by g a ing o polyme chains on o he colloidal pa icles. (c)
Elec os e ic s abiliza ion o colloidal pa icles by cha ged polyme chains ep esen s a
combina ion o bo h s abiliza ion mechanisms.
As al eady men ioned, nanosized ma e ials can also be s abilized by he immobiliza ion on o
suppo pa icles. This can be achie ed ei he by adso p ion o he nanopa icles o by in si u
gene a ion o he nanopa icles on/inside o he suppo . The p inciples o he s abiliza ion
mechanisms o he suppo pa icles emain iden ical o hose discussed in he sec ion abo e.
I nanopa icles a e immobilized on o suppo pa icles, so-called syne gis ic e ec s (also
suppo e ec s) ha e o be aken in o accoun .115 This e m is ela ed o an enhancemen o
any dis inc p ope y o he nanopa icles due o he in e ac ions wi h he suppo
ma e ial.116,117
1.4. Sphe ical Polyelec oly e B ushes o he S abiliza ion o
Nanopa icles in Solu ion
A sphe ical polyelec oly e b ush (SPB) is a sphe ical, solid pa icle on o which long
polyelec oly e chains a e densely g a ed (see Figu e 1.4.1).118 He eby, he dis ance be ween
wo neighbo ing g a ed chains has o be lowe han he chains adius o gy a ion Rg in a good
sol en .119,120 Figu e 1.4.1 shows a schema ic illus a ion o a SPB wi h i s main cha ac e is ic
pa ame e s.
In oduc ion
9
Figu e 1.4.1. Illus a ion o a sphe ical polyelec oly e b ush. The co e consis s o a
hyd ophobic polyme , e.g. poly(s y ene), on o which polyelec oly e chains a e densely
g a ed. Rco e ep esen s he adius o he co e pa icle, Rh is he hyd odynamic adius o he
SPB, L is he hyd odynamic hickness o he shell laye (= Rh - Rco e) and D is he dis ance
be ween he g a ed chain ends. The polyelec oly e chains a e s ongly s e ched in aqueous
solu ion due o he osmo ic p essu e inside o he shell laye . This can be seen in he c yoTEM
mic og aph o anionic SPBs wi h a pSS shell.121
In p incipal, SPBs can be classi ied by he ype o polyelec oly e p esen in he shell. An
annealed SPB is a b ush pa icle wi h a weak polyelec oly e o ming he shell, e.g.
poly(ac ylic acid). In con as , he shell o a quenched SPB consis s o a s ong
polyelec oly e, e.g. poly(sodium s y ene sul ona e). The di e ence o he wo classes o SPB
is ha he cha ge densi y o an annealed SPB can be in luenced by changing he pH, whe eas
o a quenched SPB no pH dependence is p esen .118
The high elec os a ic in e ac ion o he densely g a ed polyelec oly e chains leads o a
numbe o new p ope ies in compa ison o uncha ged g a ed mac omolecules. An essen ial
cha ac e is ic is gi en by he con inemen o he coun e ions o he polyelec oly e chains
wi hin he shell laye .118,122,123 This leads o a swelling o he polyelec oly e shell due o he
high osmo ic p essu e o he con ined coun e ions in sal ee solu ion. The e ec o he
con inemen o he coun e ions has success ully been used o he gene a ion o nanopa icles
wi hin he shell o he SPB.124 Cha ged molecula p ecu so s can be in oduced in o he shell
by a con olled exchange o he coun e ions. In a second s ep, he p ecu so s can be educed
o nanopa icles.125,126 The ion exchange can ei he be enhanced by he in oduc ion o
mul i alen coun e ions o by ions ha possess speci ic in e ac ions wi h he cha ged g oups
o he shell. A e educ ion o he cha ged p ecu so s, nanopa icles a e di ec ly gene a ed
and immobilized wi hin he shell o he SPB. Using his app oach, a numbe o di e en noble
me al nanopa icles and hei alloys ha e been success ully syn hesized.127,128,129,130
X-Ray Abso p ion Fine S uc u e Spec oscopy on Nanosized Ma e ials
10
This me hod p o ed o ha e a numbe o ad an ages. In gene al, he nanopa icles gene a ed
in SPBs a e s ongly bound o he he ca ie pa icle and a e o small size. The small size
e iden ly leads o a high su ace o olume a io whe eas he immobiliza ion helps o p e en
he uncon olled elease o nanopa icles in o he su ounding media.124 The e o e, he
immobiliza ion o nanopa icles on o colloidal s able pa icles simpli ies he handling o
nanopa icles, which is one o he main pu poses o so-called mesos uc u ed ma e ials. In
pa icula , his becomes impo an because nanosized ma e ials a e suspec ed o cause ha m o
li ing issue. Fu he mo e, he immobiliza ion o nanopa icles on colloidal pa icles is
ad an ageous o applica ions in ca alysis because i helps o sepa a e he ca alys om he
eac ion solu ion, e.g. by il a ion.40,124 This imp o es he ecyclabili y o he ca aly ic ac i e
composi e pa icles and also i p e en s he leaching o nanopa icles in he eac ion
p oduc s.40 The ca aly ic ac i i y o composi e ma e ials o nanopa icles a SPBs has been
shown in a ious s udies.124,126 These include hyd ogena ion eac ions, oxida ion and
epoxida ion eac ions as well as coupling eac ions like he Heck-Suzuki eac ion.131,132,133,134
1.5. X-Ray Abso p ion Fine S uc u e Spec oscopy on Nanosized
Ma e ials
The cha ac e iza ion o nanopa icles is some imes challenging, especially i hey a e
immobilized on o suppo pa icles. This is due o he ac ha nanopa icles syn hesized a
mild condi ions a e o en highly diso de ed ma e ials exhibi ing poo di ac ion pa e ns
ob ained by PXRD.135 In addi ion, he small pa icle size leads o a b oadening o he
e lec ions o he la ice planes. Fu he mo e, he p esence o suppo pa icles is o en
accompanied by a high amo phous backg ound o he composi e ma e ial which complica es
in es iga ions by me hods like PXRD o high esolu ion TEM (HRTEM).
Due o hese di icul ies, addi ional me hods should be conside ed o he analysis o
nanos uc u ed composi e ma e ials. Since X- ay ine s uc u e (XAFS) measu emen s can be
made on elemen s o mino i y and e en ace abundance i p o ides a unique and di ec
measu emen o he chemical and physical s a e o dilu e species in a a ie y o sys ems.
XAFS spec a can be measu ed o essen ially e e y elemen on he pe iodic able.
Impo an ly, no long ange o de wi hin he compounds is equi ed o XAFS measu emen s.
This makes XAFS one o he ew s uc u al p obes a ailable o non-c ys alline and highly
diso de ed ma e ials, e en including solu ions.
XAFS e e s o he de ails o how X- ays a e abso bed by an a om a ene gies nea and
abo e he co e-le el binding ene gies o ha a om. These spec a a e especially sensi i e o
he coo dina ion chemis y, o mal oxida ion s a e, and he dis ances, coo dina ion numbe
and species o he a oms immedia ely su ounding he selec ed elemen . Because o his
dependence, XAFS p o ides a p ac ical way o de e mine he chemical s a e and local a omic
s uc u e o a selec ed a omic species.136
The X- ay abso p ion spec um is ypically di ided in o wo egimes: The X- ay abso p ion
nea -edge spec oscopy (XANES) wi h i s ypical ange o up o 100 eV om he abso p ion
In oduc ion
11
edge. Secondly, he ex ended X- ay abso p ion ine s uc u e spec oscopy (EXAFS) spanning
a ange om he XANES egion up o 1000 eV abo e he abso p ion edge. The wo egions
ha e he same physical o igin, bu a dis inc ion is con enien o he in e p e a ion. Whe eas
XANES is s ongly sensi i e o he o mal oxida ion s a e and he coo dina ion chemis y o
he abso bing a om, he EXAFS is used o in es iga e he dis ances, coo dina ion numbe , and
species o he neighbo s o he abso bing a om.137,138
In simple e ms, o XAFS he dependence o he ene gy on he abso p ion coe icien µ a
and abo e he binding ene gy o a known co e le el o a known a omic species is measu ed.
Acco ding o Lambe -Bee s’ law, µ is ela ed o he X- ay in ensi y as ollows:
=
µ
 (1.5.1)
He e, I0 ep esen s he inciden X- ay in ensi y, I is he ansmi ed X- ay in ensi y and is
he hickness o he sample.
The abso p ion coe icien is ela ed o he ene gy o he X- ay beam E by
µ≈

 (1.5.2)
whe e ρ and Z a e he sample densi y and he a omic numbe o he abso bing elemen . A
ep esen s he a omic mass o he abso be . Due o he Z4 dependence, µ is e y sensi i e o
he chemical na u e o he abso be .136
Fo EXAFS, he oscilla ion abo e he abso p ion edge is o majo in e es and he EXAFS
unc ion can be w i en as:

()=µ()−µ()
Δµ(E) (1.5.3)
µ(E) is he measu ed abso p ion coe icien , µ0(E) is a smoo h backg ound unc ion
ep esen ing he abso p ion o an isola ed a om, and Δµ0 is he measu ed jump in he
abso p ion µ(E) a he h eshold ene gy E0.
χ(E) is con e ed in o χ(k) because he abso p ion p ocess o EXAFS is ea ed bes by he
wa e beha io o he pho oelec on. Fo his con e sion he ollowing ela ion is used:
=

2(−)
ℏ (1.5.4)
The wa eleng h o he pho oelec on is exp essed by k, whe eas m ep esen s he elec on
mass, ћ is Planck’s cons an and E0 is he ene gy a he abso p ion edge.
The EXAFS equa ion ha is used o i ing measu ed XAFS spec a can inally be w i en
as:
Re e ences
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Re e ences
22
O e iew
23
2. O e iew
The main objec i e o his hesis was he syn hesis o MnOxNP and o immobilize hese
nanopa icles on o a colloidal s able ca ie pa icle. The suppo pa icles consis o a PS co e
pa icle wi h a ypical diame e o abou 100 nm on o which long polyelec oly e chains a e
chemically g a ed. These sys ems a e deno ed as SPBs and possess a high colloidal s abili y
in aqueous solu ion.
 In Chap e 3, a de ailed desc ip ion o he syn hesis o he composi e ma e ial is
p esen ed. In addi ion, he composi e ma e ial was cha ac e ized ex ensi ely by TEM
and c yoTEM o elucida e i s s uc u e. A compa ison o PXRD pa e ns o di e en
e e ence compounds o he di ac ion pa e n o he composi e ma e ial ga e i s
insigh s in o he c ys allog aphic s uc u e o he MnOxNP immobilized on SPBs which
led o he de elopmen o a model o he composi e sys em.
 Chap e 4 is dedica ed o a de ailed analysis o he c ys allog aphic s uc u e o he
MnOxNP by XAFS measu emen s o o e come he p oblems o he missing long- ange
o de o he nanopa icles which hampe ed he cha ac e iza ion by PXRD. Special
emphasis has been laid on he local s uc u e o he MnOxNP a ound he Mn abso be
wi h ega ds o di e ences o he s uc u e o he composi e ma e ial in he d ied and in
he dispe sed s a e. Addi ionally, a new kind o composi e ma e ial composed o s a -
shaped pTMAEMC homopolyme and MnOxNP was syn hesized and cha ac e ized.
 The composi e ma e ial o MnOxNP immobilized on SPBs was es ed o i s ca aly ic
ac i i y on he oxida ion o mo in by hyd ogen pe oxide which is p esen ed in Chap e
5. The e o e, he kine ic model o a Langmui -Hinshelwood mechanism o
he e ogeneous ca alyzed eac ions has been applied o he oxida ion eac ion.
 In analogy o ha , Chap e 6 deals wi h he analysis o he educ ion o 4-ni ophenol by
sodium bo ohyd ide in he p esence o composi e pa icles o SPB and gold and
pla inum nanopa icles. A Langmui -Hinshelwood model was applied o his ca aly ic
eac ion. Fu he mo e, he induc ion pe iod obse ed du ing he in es iga ions was
analyzed in de ail and could be subsc ibed o a su ace econs uc ion o he
nanopa icles.
 Chap e 7 p esen s he syn hesis and cha ac e iza ion o no el SPB pa icles wi h a
zwi e ionic shell. The syn hesis o he shell was conduc ed by aqueous ATRP. A
combina ion o DLS, TEM and c yoTEM measu emen s lead o he conclusion ha he
zwi e ionic shell o pMEDSAH is p edominan ly in a collapsed s a e wi h a mino pa
o he chains eaching ou o he collapsed laye . This has been assigned o an in e nal
phase sepa a ion o he zwi e ionic shell. Tempe a u e- and sal -dependen DLS

O e iew
24
measu emen s p o ed he esponsi e beha io o ex e nal s imuli o he zwi e ionic
shell ha leads o a swelling o he la e .
This doc o al hesis comp ises i e publica ions gi en in he Chap e s 3, 4, 5, 6 and 7.
O e iew
25
2.1. Fo ma ion o Ul a hin Bi nessi e-Type Nanopa icles Immobilized
on Sphe ical Polyelec oly e B ushes
We s udied he in-si u gene a ion o MnOxNP on ca ionic SPBs wi h a shell o poly(2-
ime hyl ammoniume hyl me hac yla e chlo ide) (pTMAEMC). Fi s , we in es iga ed he
syn hesis o he MnOxNP by a ying he pa ame e s like he amoun o added KMnO4, he
speed o he addi ion and he empe a u e. This s udy showed ha no educing agen is needed
o gene a e he MnOxNP. In addi ion, he educ ion by he monome uni s o he
polyelec oly e shell could be uled ou . Based on hese indings we de eloped he mechanism
o a basic ca alyzed educ ion o he MnO4- ions wi hin he b ush laye .
Fu he mo e, DLS measu emen s showed ha he b ush hickness dec eases upon he
immobiliza ion o he MnOxNP indica ing he in e ac ion o he nega i ely cha ged
nanopa icles wi h he posi i ely cha ged polyelec oly e chains o he shell. This was
con i med by ze a po en ial measu emen s and p o es he excellen s abiliza ion o he
MnOxNP by he pTMAEMC shell.
A compa ison o he composi e pa icles by TEM and c yoTEM e ealed ha he e is a
signi ican di e ence in he mo phology o he MnOxNP immobilized on o SPBs be ween he
d ied s a e and he aqueous dispe sed s a e (see Figu e 2.1.1). This was assigned o a collapse
o he ul a hin pla ele -like nanopa icles on o he PS co e o he SPB upon d ying (see Figu e
2.1.1a). In con as o ha , he MnOxNP a e also p esen in he polyelec oly e shell o he
SPB which is con i med by he c yoTEM mic og aph in Figu e 2.1.1b.
(a) (b)
Figu e 2.1.1. (a) TEM mic og aph and (b) c yoTEM mic og aph o he composi e ma e ial
TMAEMC-MnOx-5 comp ised o ca ionic SPB pa icles and MnOxNP. Ma ked di e ences o
he composi e ma e ials exis be ween he d ied s a e and he aqueous dispe sed s a e as can be
seen by compa ing he wo mic og aphs.
O e iew
26
A compa ison o he PXRD pa e ns o he composi e ma e ial o e e ence compounds, e.g.
H
+
-bi nessi e and K
+
-bi nessi e, lead o he conclusion ha he MnO
x
NP a e composed o
hexagonal lamellae o bi nessi e (see Figu e 2.1.2). This mixed alen manganese oxide
possesses a laye ed opology and is composed o p edominan ly edge-sha ed MnO
6
oc ahed a.
The missing 00l e lec ions o he composi e ma e ial in combina ion wi h he elec on
mic og aphs p o e ha he MnO
x
NP a e composed o single o only a ew s acks o lamellae
o bi nessi e. Addi ionally, he hk bands a 36.5° and 65° in 2θ p o e a diso de along he
s acking axis o he lamellae.
(a) (b)
Figu e 2.1.2. (a) PXRD pa e ns o he composi e ma e ial TMAEMC-MnO
x
-5, H
+
-bi nessi e
and K
+
-bi nessi e. The missing 00l e lec ions and he hk bands a 36.5° and 65° in 2θ in
combina ion wi h he elec on mic og aphs p o e he gene a ion o ul a hin pla ele -like
MnO
x
NP exhibi ing a diso de along he c-axis. (b) Schema ic model o he composi e
ma e ial TMAEMC-MnO
x
-5. The nega i ely cha ged MnO
x
NP a e s abilized by he ca ionic
pTMAEMC chains. The MnO
x
NP a e composed o edge-sha ed MnO
6
oc ahed a (Mn whi e
sphe es, O ed sphe es) ha o m in o laye s wi h in e cala ed K
+
-ions and wa e molecules
(blue sphe es) be ween he laye s.
The ull publica ion can be ound in Chap e 3.
O e iew
27
2.2. S uc u al Analysis o Colloidal MnOx Composi es
This wo k epo s he i s syn hesis o MnOxNP wi h a laye ed opology s abilized by s a -
shaped pTMAEMC homopolyme . The educ ion o KMnO4 was s a ed by he addi ion o 2-
bu anol since no in-si u gene a ion o MnOxNP was obse ed, as ound o he syn hesis o
MnOxNP@SPB pa icles. The disk-like nanopa icles exhibi an a e age diame e o abou 5
nm as shown in he HRTEM mic og aph in Figu e 2.2.1. PXRD measu emen s e eal a
simila s uc u e o he MnOxNP s abilized by s a -shaped pTMAEMC compa ed o ha o
he composi e pa icles desc ibed in Chap e 2.1.
Figu e 2.2.1. HRTEM mic og aph o he composi e ma e ial composed o s a -shaped
pTMAEMC homopolyme and MnOxNP. The image shows he MnOxNP isible as da k,
disk-like pa icles embedded in he polyme . A some spo s, la ice planes o he MnOxNP a e
isible.
The lack o long- ange o de in he MnOxNP complica ed he de ailed analysis o he
ino ganic ma e ial by con en ional PXRD measu emen s. The e o e, XAFS measu emen s
we e conduc ed o p obe he local s uc u e a ound he Mn a om wi hin he MnOxNP
s abilized ei he by ca ionic SPBs o by s a -shaped pTMAEMC homopolyme . Fi s ly, he
XANES spec a we e used o de e mine he a e age oxida ion s a es o he Mn o he
MnOxNP by compa ing he posi ion o he abso p ion edge o ha o di e en manganese
oxide e e ence compounds. This showed ha he a e age oxida ion s a e o Mn o he
composi e ma e ial is be ween 3.5 - 3.7 indica ing he mixed alency o Mn wi hin he
c ys allog aphic s uc u e. A quali a i e compa ison o he EXAFS spec a o he di e en
composi e ma e ials o hose o H+-bi nessi e and K+-bi nessi e p o e simila i ies in he
c ys allog aphic s uc u e as al eady expec ed by PXRD analysis. The χ(k)k3 spec a as well as
he Fou ie ans o med spec a o all composi e ma e ials and o bi nessi e e e ence
compounds a e shown in Figu e 2.2.2.
O e iew
34
The p esence o an uppe c i ical solu ion empe a u e was in es iga ed by empe a u e-
dependen DLS measu emen s. The esul s shown in Figu e 2.5.2b p o e ha he e is a
dis inc swelling o he zwi e ionic co ona in he ange be ween 20 °C and 75 °C which could
be u he enhanced by he addi ion o KCl. The swelling is comple ely e e sible.
(a) (b)
Figu e 2.5.2. (a) In luence o he concen a ion o NaCl on he hyd odynamic b ush hickness
L o he zwi e ionic SPB. The addi ion o sal leads o a p onounced swelling o he
zwi e ionic co ona a sal concen a ion abo e 0.5 M. (b) In luence o he empe a u e on he
hyd odynamic b ush hickness L wi hou he addi ion o KCl ( hea ing,  cooling), 1 M
KCl ( hea ing,  cooling) and 2 M KCl ( hea ing,  cooling). The zwi e ionic co ona is
swelling upon hea ing o he sample whe eas adjacen cooling leads o a e-sh inking. The
e ec can be signi ican ly enhanced by he addi ion o sal .
Addi ional ze a po en ial measu emen s could show ha he nega i e su ace po en ial o he
zwi e ionic SPB is due o he p esence o nega i e cha ges o he PS-co-DVB co e pa icles.
These cha ges could be aced back o he p esence o emaining su ac an and o
inco po a ed agmen s o ini ia o molecules due o he co e syn hesis.
The ull publica ion can be ound in Chap e 7.

O e iew
35
2.6. Indi idual Con ibu ions o Join Publica ions
The esul s p esen ed in his hesis we e ob ained in close collabo a ion wi h di e en co-
wo ke s and published o submi ed as indica ed below. The indi idual con ibu ion o each
co-au ho o he publica ions is lis ed. The as e isk deno es he co esponding au ho .
Chap e 3
This wo k has been published in Chemis y o Ma e ials unde he i le “Fo ma ion o
Ul a hin Bi nessi e-Type Nanopa icles Immobilized on Sphe ical Polyelec oly e B ushes”
by F ank Polze , Daniel A. Kunz, Jose B eu and Ma hias Ballau *.
 I conduc ed he syn hesis and cha ac e iza ion o he ca ionic SPBs. Fu he mo e, I did
all he syn he ic wo k o he in-si u gene a ion o he bi nessi e- ype nanopa icles and
all TEM and c yoTEM measu emen s. Fu he mo e, I w o e he pape .
 Daniel A. Kunz assis ed du ing he syn hesis o he manganese oxide e e ence
compounds. He conduc ed he PXRD measu emen s and con ibu ed o hei
discussion.
 P o . Jose B eu w o e he discussion o he PXRD esul s. He also con ibu ed o he
scien i ic discussion.
 P o . Ma hias Ballau con ibu ed o he scien i ic discussion.
Chap e 4
This wo k has been submi ed o he Jou nal o Colloids and Polyme Science unde he i le
“S uc u al Analysis o Composi es o MnOx and a Polyme Colloid” by F ank Polze ,
Elisabe a Holub-K appe, He mann Rossne , Alexei E ko, Holm Ki mse, Felix Plampe ,
Alexande Schmalz, Axel H. E. Mülle and Ma hias Ballau *.
 I conduc ed he syn hesis o he composi e ma e ials and he e e ence compounds and
hei cha ac e iza ion including c yoTEM imaging. Fu he mo e, I w o e he
publica ion.
 Felix Plampe and Alexande Schmalz syn hesized and cha ac e ized he s a -shaped
p(TMAEMC) homopolyme .
O e iew
36
 He mann Rossne assis ed wi h he EXAFS e alua ion and con ibu ed o he
discussion o he XANES and EXAFS sec ion o he publica ion. Fu he mo e, he
w o e he desc ip ion o he Bayes-Tu chin app oach o he EXAFS e alua ion.
 Elisabe a Holub-K appe con ibu ed o he scien i ic discussion on XANES and
EXAFS.
 P o . Alexei E ko con ibu ed o he discussion o he XAFS measu emen s and
in oduced me in o he KMC2 beamline a BESSY II.
 Holm Ki mse in oduced me in o he echnique o HRTEM and con ibu ed o he
discussion o his me hod.
 P o . Ma hias Ballau and P o . Axel H. E. Mülle con ibu ed o he scien i ic
discussion.
Chap e 5
This wo k is accep ed by he Jou nal o Ca alysis unde he i le “Ca aly ic Oxida ion o an
O ganic Dye by MnOx Nanopa icles” by F ank Polze , S e anie Wunde and Ma hias
Ballau *.
 I conduc ed he syn hesis o he composi e pa icles and i s cha ac e iza ion. The
UV/ is measu emen s and hei e alua ion conside ing he ac i a ion ene gy, he LH
kine ics a oom empe a u e we e done by me. Fu he mo e, I w o e he pape .
 S e anie Wunde p o ed he ep oducibili y o he syn hesis and he UV/ is
measu emen s. Fu he mo e, she con ibu ed he s udy o he in luence o he bu e
concen a ion, he empe a u e dependence o he LH kine ics as well as he e ec o
oxygen on he eac ion kine ics. She also ook pa in he scien i ic discussion.
 P o . Ma hias Ballau con ibu ed o he scien i ic discussion.
Chap e 6
This wo k has been published in he Jou nal o Physical Chemis y C unde he i le
“Kine ic Analysis o Ca aly ic Reduc ion o 4-Ni ophenol by Me allic Nanopa icles
Immobilized in Sphe ical Polyelec oly e B ushes” by S e anie Wunde , F ank Polze , Yan
Lu, Yu Mei and Ma hias Ballau *.
O e iew
37
 I conduc ed he syn hesis and cha ac e iza ion o he gold nanopa icles immobilized
on o SPBs. Fu he mo e, I did all TEM measu emen s o he composi e ma e ials. All
UV/ is measu emen s conce ning kine ic educ ion o 4-ni ophenol using composi e
pa icles wi h gold nanopa icles we e conduc ed and e alua ed by mysel . I
es ablished he Langmui -Hinshelwood model o he desc ip ion o he eac ion
mechanism.
 S e anie Wunde and Yan Lu syn hesized he pla inum nanopa icle immobilized on
SPBs. Fu he mo e he Langmui -Hinshelwood model was modi ied by S e anie
Wunde aking in o accoun he F eundlich exponen s o he adso ben s. S e anie
Wunde conduc ed all he measu emen s o he P nanopa icle composi e ma e ials
conce ning he kine ic educ ion o 4-ni ophenol. The da a o P and Au
nanopa icles we e e alua ed using he Langmui -F eundlich model by S e anie
Wunde .
 P o . Ma hias Ballau con ibu ed o he scien i ic discussion.
Chap e 7
This wo k has been published in Mac omolecules unde he i le “Syn hesis and Analysis o
Zwi e ionic Sphe ical Polyelec oly e B ushes in Aqueous Solu ion” by F ank Polze ,
Johannes Heigl, Ch is ian Schneide , Oleg Bo iso and Ma hias Ballau *.
 I conduc ed he syn hesis o he zwi e ionic SPB and all measu emen s o his wo k
including TEM, c yoTEM, DLS and ze a po en ial measu emen s.
 Johannes Heigl assis ed he wo k du ing he cou se o his bachelo wo k unde my
supe ision.
 Ch is ian Schneide p o ided he i s o he ze a po en ial measu emen s and helped
wi h hei discussion.
 P o . Ma hias Ballau and Oleg Bo iso con ibu ed o he scien i ic discussion.
O e iew
38
Fo ma ion o Ul a hin Bi nessi e-Type Nanopa icles Immobilized on Sphe ical Polyelec oly e
B ushes
39
3. Fo ma ion o Ul a hin Bi nessi e-Type
Nanopa icles Immobilized on Sphe ical
Polyelec oly e B ushes
F ank Polze , § Daniel A. Kunz, ‡Jose B eu, ‡ Ma hias Ballau §*
§Helmhol z-Zen um Be lin ü Ma e ialien und Ene gie GmbH, Hahn-Mei ne -Pla z 1,
14109 Be lin, Ge many, and Depa men o Physics, Humbold Uni e si y Be lin, New ons .
15, 12489 Be lin, Ge many
‡ Depa men o Ino ganic Chemis y I, Uni e si y o Bay eu h, 95440 Bay eu h, Ge many
Email: Ma hias.Ballau[email p o ec ed]
Published in Chemis y o Ma e ials
Rep oduced wi h pe mission om
Chemis y o Ma e ials, 2010, 22, 2916.
© 2010 Ame ican Chemical Socie y.
DOI: 10.1021/cm100226h

Abs ac
40
3.1. Abs ac
A new ou e o in si u o ma ion and s abiliza ion o ul a hin, needle-like manganese
dioxide nanopa icles (MnO
2
NP) in aqueous solu ion by using sphe ical polyelec oly e b ush
(SPB) pa icles is p esen ed. The SPBs ha ac as ca ie pa icles consis o a solid
polys y ene co e o abou 50 nm adius on o which long chains o he posi i ely cha ged
polyelec oly e poly(2- ime hyl ammonium e hyl me hacyla e chlo ide) (pTMAEMC) a e
g a ed o yield a o e all adius o abou 85 nm. Po assium pe mangana e (KMnO
4
) is di ec ly
educed wi hin he b ush laye o hese pa icles due o he basic en i onmen wi hin his
laye . This mechanism seems o limi he size o he MnO
2
NP o he dimensions o he b ush
laye . Powde X- ay di ac ion, (PXRD), ansmission elec on mic oscopy (TEM) and
c yogenic ansmission elec on mic oscopy (c yoTEM) p o e ha bi nessi e- ype MnO
2
NP
wi h a c*-diso de a e gene a ed on he SPB wi hou adding any educing agen . The
bi nessi e nanopa icles ha e an a e age leng h o 20 nm and a b ead h o ca. 1.6 nm. They
a e composed o single lamellae o o ul a hin s acks o e y ew lamellae. Ene gy-dispe si e
X- ay spec oscopy (EDX) demons a es ha mos o he cha ges o he hin bi nessi e
pla ele s a e balance by po assium ions. The excellen s abiliza ion by he SPB ca ie
pa icles in aqueous solu ion can be aced back o a s ong in e ac ion o he bi nessi e
pa icles wi h he posi i ely cha ged pTMAEMC chains o he SPB.
Fo ma ion o Ul a hin Bi nessi e-Type Nanopa icles Immobilized on Sphe ical Polyelec oly e
B ushes
41
3.2. In oduc ion
Manganese oxide ma e ials and especially manganese dioxide (MnO2) ha appea s in a
wide a ie y o polymo phs such as α-, β-, γ-, and δ-MnO2 ha e a ac ed g ea in e es
ecen ly. This is due o he possible applica ions as e.g. elec ode ma e ials,1,2 ca alys s,3,4 ion
exchange,5 and magne ic ma e ials.6,7 All di e en polymo phs a e based on he MnO6
oc ahed on and di e in he linkage o hese basic uni s.8 In p inciple, he syn hesis can be
achie ed by he oxida ion o Mn2+, by he educ ion o pe mangana e (MnO4-) o by di ec
con e sion o manganese oxides (Mn2O3, MnOOH, e c.).9,8,10,11 The physical and chemical
p ope ies o hese ma e ials change when downsized o he nanoscopic scale and g ea e o s
ha e been made o design MnO2 nanome e -sized s uc u es o di e en size and
shape.12,13,14,15,16 Hence, a numbe o di e en mo phologies ha e been ealized, as e.g. one-
dimensional (1D) s uc u es (nano ods, nanowi es, nano ibe s, e c.), wo-dimensional (2D)
s uc u es (nanoshee s, e c.) and h ee-dimensional (3D) s uc u es (ball-like co e-co ona
pa icles, nanodisks, e c.).8,17,18,19,20
Among hese manganese oxides, bi nessi e has a ac ed pa icula a en ion because o i s
unique p ope ies and i s use as an in e media e o he p epa a ion o o he MnO2 based
ma e ials such as oc ahed al molecula sie es.21,22 Bi nessi e is a phyllomangana e meaning a
laye ed s uc u e o hyd ous manganese oxide comp ised o edge-sha ing oc ahed a
con aining p edominan ly Mn4+ ca ions as cen al ions. Due o he p esence o Mn3+ ca ions
and/o acan oc ahed al si es a ne laye cha ge a ises ha is compensa ed by he
inco po a ion o di e en ca ions in o he in e lamella space. Typically, hese in e laye
ca ions a e hyd a ed.23,24,25,26 The in e laye ca ions can be exchanged agains a ious o he
ions such as e aalkylammonium ions o posi i ely cha ged aluminium based oligo-ca ions
such as Keggin ions.27,28,29,30 The in e cala ion o bulky coun e ions can u he mo e be used
o expand he in e laye space and inally delamina e he hexagonal shee s o gain single
lamellae o bi nessi e.31 This delamina ion p ocess is well known om laye ed silica es o
simila ly s uc u ed ma e ials, e.g. laye ed double hyd oxides. Mo eo e , i is impo an o
he gene a ion o ul a hin ilms and o he building o laye -by-laye s uc u es.32 The
gene a ion o delamina ed o ex olia ed (s acks o only a ew lamellae) bi nessi es is usually a
edious mul is ep p ocess which in ol es he in e cala ion o bulky ions and subsequen
delamina ion.28,33,34 To ou bes knowledge he e is only one epo in li e a u e o single s ep
ou es o c ea ed ul a hin bi nessi e ma e ials.35 Aqueous suspensions o hese pa icles do no
exhibi a high colloidal s abili y and a e di icul o handle because o hei high su ace a ea
and he la ge la e al dimensions o he pla ele s o up o 0.5 µm. Applica ions in e.g. ca alysis,
howe e , equi e s able colloidal sys ems ha can be easily syn hesized in a kg scale.
In his pape we p esen he syn hesis and comp ehensi e cha ac e iza ion o ul a hin
bi nessi e nano-needles ha a e a ixed o sphe ical polyelec oly e b ushes (SPBs).36 The
SPBs used he ein consis o a solid polys y ene (PS) co e on o which long polyelec oly e
chains (PE chains) a e densely g a ed (see Figu e 3.2.1). He e we use he s ong
polyelec oly e poly(2- ime hylammonium e hyl me hac yla e chlo ide) (pTMAEMC) which
ca ies posi i e cha ges. Recen wo k has shown ha he immobiliza ion o me allic o oxidic
Expe imen al Sec ion
42
nanopa icles on SPB is a p omising way o colloidal s able composi e pa icles wi h a high
ca aly ic ac i i y.37,38,39,41 Mo eo e , ca ionic polyelec oly es ha e ecen ly been used
success ully o c ea e and s abilize hin ilms o bi nessi e.42,43
Figu e 3.2.1. Scheme o a ca ionic sphe ical polyelec oly e b ush wi h b ush monome 2-
ime hylammonium e hyl me hac yla e chlo ide (TMAEMC). He e R ep esen s he
hyd odynamic adius o he polys y ene co e, L s ands o he con ou leng h o he
polyelec oly e chains and D is he a e age dis ance o junc ions o polyelec oly e chains on
he su ace o he co e pa icle.
He e we demons a e ha ca ionic sphe ical polyelec oly e b ushes can be used o p epa e
and immobilize ul a hin bi nessi e needles by adding KMnO4 solu ion o he aqueous
suspension o he SPB. The esul ing composi e pa icles exhibi an excellen colloidal
s abili y and open new enues o he use o bi nessi e as ca alys in aqueous sys ems.
3.3. Expe imen al Sec ion
Ma e ials. All chemicals we e o analy ical g ade and used wi hou u he pu i ica ion. 2-
ime hylammonium e hyl me hac yla e chlo ide (TMAEMC) was ecei ed om
Polysciences. KMnO4 was pu chased om Fluka and used as ecei ed. Wa e used in all o
ou wo k desc ibed he e was 18 MΩ Millipo e wa e .
Syn hesis o he Ca ionic SPB. Ca ionic SPB TMAEMC-40 was syn hesized and
cha ac e ized as desc ibed ecen ly.44 In a ypical un, 62.5 g o 2-[p-(2-hyd oxy-2-
me hylp opiophe-none)]-e hylene glycol-me hac yla e (HMEM) unc ionalized polys y ene
la ex we e dispe sed in wa e o gi e a solid con en o 3.5 w %. A e addi ion o 56.0 g o
TMAEMC o he dispe sion and he mix u e was degassed and cooled down o 8 °C. The
polyme iza ion was s a ed by i adia ion o he dispe sion by UV ligh .45 The eac ion was
i adia ed and cooled o 30 minu es. The dispe sion was pu i ied by ul a il a ion (UF) un il
he conduc i i y o he se um eached alues lowe han 3 µScm-1.
Fo ma ion o Ul a hin Bi nessi e-Type Nanopa icles Immobilized on Sphe ical Polyelec oly e
B ushes
43
Syn hesis o he MnO2NP immobilized on SPB. The dispe sion o SPB was dilu ed wi h
wa e o a solid con en o abou 1.0 w %. The mix u e was bubbled wi h ni ogen unde
s i ing o hal an hou o emo e oxygen. A e wa ds, 20 mL o a 0.04 M solu ion o
KMnO4 we e injec ed and he solu ion was s i ed o 12 h. The composi e pa icles we e
cleaned wi h wa e by UF un il he conduc i i y o he se um eached a alue o lowe han 3
µScm-1.
Syn hesis o he H+-bi nessi e. This compound was syn hesized acco ding o McKenzie e
al.46 In a ypical eac ion, 1.58 g KMnO4 we e dissol ed in 100 mL wa e and 1.64 mL o
concen a ed hyd ochlo ic acid (HCl) we e added d opwise o he solu ion. The p ecipi a e
was il e ed and cleaned by dialysis agains wa e .
Syn hesis o he K+-bi nessi e. K
+-bi nessi e was syn hesized by he he mal
decomposi ion o KMnO4 a 800 °C o 16 h. In a ypical un, 5.0 g o KMnO4 we e hea ed a
2 °Cmin-1 o 800 °C and kep o 16 h a his empe a u e, be o e cooling down wi h 1
°Cmin-1. The p oduc was washed wi h wa e un il he il a e became clea .47
Me hods. T ansmission elec on mic oscopy (TEM) and c yogenic ansmission elec on
mic oscopy (c yoTEM) measu emen s we e conduc ed wi h a Zeiss EM922 EFTEM (Zeiss
NTS GmbH, Obe kochen, Ge many) as desc ibed ecen ly.48 Dynamic ligh sca e ing (DLS)
was pe o med wi h an ALV 4000 (Pe e s) ligh sca e ing goniome e . Samples o powde
X- ay di ac ion (PXRD) we e p epa ed on o a silicon ze o-backg ound pla e ia a back-
loading echnique o minimize ex u al e ec s. PXRD pa e ns we e ob ained using nickel
il e ed Cu-Kα adia ion (1.54187 Å) on a B agg-B en ano- ype di ac ome e (Panaly ical
XPERT-PRO) equipped wi h an X’Cele a o Scien i ic RTMS de ec o . Ene gy dispe si e X-
ay spec oscopy (EDX) was conduc ed wi h a Zeiss 1530 FESEM. The numbe o amino
g oups o he SPB, and he e o e he co e o shell a io, was de e mined by po en iome ic
i a ion o TMAEMC-40 wi h 0.01 M sil e ni a e (AgNO3) s anda d solu ion (Me ck) using
a WTW cond 197i conduc ome e . The amoun o MnO2 immobilized on he SPB was
de e mined by he mal g a ime ic analysis (TGA) using a Me le Toledo STARe sys em.
Ze a po en ial measu emen s we e pe o med wi h a Mal e n Ze asize Nano ZS.
3.4. Resul s and Discussion
Syn hesis. The syn hesis o he ca ionic sphe ical polyelec oly e b ushes was conduc ed as
desc ibed in p e ious wo k.44 The hyd odynamic adius Rh o he polys y ene-co-HMEM co e
due o DLS measu emen s is 42.7 nm ± 0.3 nm. A e he pho oemulsion polyme iza ion, Rh
o he ca ionic SPB inc eased o 84.7 nm ± 0.5 nm due o he g a ing- om p ocess o
polyelec oly e chains consis ing o pTMAEMC on o he co e pa icles. The pTMAEMC shell
hus g a ed om he su ace o he co e pa icles has a Rh o 42.0 nm ± 0.8 nm.
Po en iome ic Ti a ion wi h 0.01 M AgNO3 s anda d solu ion gi es he o al numbe o
cha ges on one pa icle. This analysis showed ha he SPB used in his s udy had a co e- o-
shell mass weigh ed a io o 6.6 o 1. Thus, he weigh ac ion o he shell is app oxima ely
Conclusions
50
Bi nessi e- ype single lamellae and ul a- hin, u bos a ically diso de ed s acks o only e y
ew lamellae a e sandwiched be ween ca ionic pTMAEMC chains and hus a e igh ly
immobilized by elec os a ic in e ac ions be ween he SPB ca ie and he nega i e su ace
cha ge o MnO2NP. Ne e heless, he high con en s o K+ ions ound by EDX analysis p o e
ha mos o he nega i e cha ges o he in e nal and ex e nal su aces o he bi nessi e- ype
nanopa icles a e no balanced by pTMAEMC chains bound o he ex e nal su ace bu ins ead
by in e cala ed and su ace-adso bed K+ ions, espec i ely. A pene a ion/in e cala ion o he
pTMAEMC chains be ween bi nessi e lamellae seems no o occu , since s e ic hind ance o
la ge ions leads o a dec easing p obabili y o in e cala ion wi h inc easing ion adius.28
Ins ead he pTMAEMC chains in e ac wi h he ex e nal su ace cha ge only. This is in good
ag eemen wi h he inding ha he leng h o he nanopa icles does no exceed he size o he
polyelec oly e chains.
3.5. Conclusions
A acile ou e has been de eloped o he p epa a ion o ul a hin bi nessi e- ype nano-
needles wi hin SPBs by in si u educ ion o KMnO4 p ecu so molecules. We conclude ha
he KMnO4 eac s wi h he qua e nized ammonium g oups o he b ush polyme o o m a
p(TMAEM MnO4) p ecu so which ge s di ec ly educed by he basic en i onmen wi hin he
b ush laye . This leads o a polyelec oly e-di ec ed g ow h and s abiliza ion o he
nanopa icles which causes a size limi a ion o he MnO2NP by he b ush ex en ion. TEM
mi c og aphs e eal a collapsed s uc u e o he bi nessi e nanopa icles immobilized on SPB
due o d ying e ec s and he loss o in e acial bound wa e be ween he single lamellae. In
con as o ha , c yoTEM images con i m he needle-like nanopa icles wi h an a e age
leng h o 20 nm and a b ead h o 1.6 nm a e well dis ibu ed among he ca ie pa icle and
ha no MnO2NP a e in ee solu ion. C yoTEM and he PXRD analysis poin ou ha he
needles exhibi a c*-diso de ed bi nessi e ype s uc u e o he MnO2. The excess cha ge o
hese nano-needles is mos ly balanced by K+ ions which could be in e ed om he EDX
analysis. Hence, we ob ained ul a hin bi nessi e- ype nanos uc u es wi hou u he
delamina ion p ocesses. Mo eo e , he composi es o he SPB and he nanopa icles exhibi an
excellen colloidal s abili y. These p ope ies make he composi e pa icles a p omising
ma e ial o applica ions in ca alysis. Wo k along his di ec ion is unde way.
3.6. Acknowledgemen s
We hank he Deu sche Fo schungsgemeinscha , Sonde o schungsbe eich 840 Bay eu h
and he Henkel AG & Co. KGaA o he inancial suppo . The au ho s a e indeb ed o
Benjamin Goßle o EDX measu emen s.

Fo ma ion o Ul a hin Bi nessi e-Type Nanopa icles Immobilized on Sphe ical Polyelec oly e
B ushes
51
3.7. Suppo ing In o ma ion
Figu e S3.1. P oposed mechanism o he MnO2NP gene a ion a SPB. By adding KMnO4
solu ion o he SPB dispe sion, a TAA MnO4 p ecu so is o med which ge s ins an ly
educed inside he b ush laye . As a consequence, bi nessi e- ype MnO2NP ( ed hexagon) a e
gene a ed which a e s abilized by he PE chains o he SPBs.
Figu e S3.2. PXRD pa e ns o he ba e SPB TMAEMC-40 and he composi e sys ems SPB-
MnO2-5, SPB-MnO2-8 and SPB-MnO2-9 om unde mos o uppe mos cu e. The hk-
e lec ions o he composi e sys ems e e o he bi nessi e nano-needles ha exhibi only a 2D
o de wi hin he ab-laye plane.
Re e ences
52
(a) (b)
Figu e S3.3. (a) SEM image o he sample SPB-MnO2-8 and (b) he co esponding EDX
pa e n ha indica es he o ma ion o he MnO2NP wi h K+-ions inside he in e laye s o
bi nessi e.
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2 Fische , A. E.; Pe ig ew, K. A.; Rolison, D. R.; S oud, R. M.; Long, J. W. Nano Le e s
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6 Zhu, H. T.; Luo, J.; Yang, H. X.; Laing, J. K.; Rao, G. H.; Li, J. B.; Du, Z. M. J. Phys.
Chem. C 2008, 112, 17089-17094.
7 Ge. J.; Zhou, L.; Yang, F.; Tang, B.; Wu, L.; Tung, C. J. Phys. Chem. B 2006, 110, 17854-
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Chem. C 2008, 112, 365-369.
9 Liu, Z.-H.; Ooi, K.; Kanoh, H.; Tang, W.; Yang, X.; Tomida, T. Chem. Ma e . 2001, 13,
473-478.
10 Chen, R.; Za alji, P.; Whi ingham, M. S. Chem. Ma e . 1996, 8, 1275-1280.
11 Ma, R.; Bando, Y.; Zhang, L.; Sasaki, T. Ad . Ma e . 2004, 16, 918-922.
12 Bu da, C.; Chen, X.; Na ayanan, R.; El-Sayed, M. A. Chem. Re . 2005, 105, 1025-1102.
13 Ali isa os, A. P. Science 1996, 271, 933-937.
14 Liang, S.; Teng, F.; Bulgan, G.; Zong, R.; Zhu, Y. J. Phys. Chem. C 2008, 112, 5307-5315.
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B ushes
53
15 Luo, J.; Zhu. H. T.; Fan, H. M.; Liang, J. K.; Shi, H. L.; Rao, G. H.; Li, J. B.; Du, Z. M.;
Shen, Z. X. J. Phys. Chem. C 2008, 112, 12594-12598.
16 Po e aul , D.; Cassaignon, S.; Nassi , N.; Baud in, E.; Joli e , J.-P. Angew. Chem. In . Ed.
2008, 47, 6441-6444.
17 Wang, X.; Li, Y. J. Am. Chem. Soc. 2002, 124, 2880-2881.
18 Oaki, Y.; Imai, H. Angew. Chem. In . Ed. 2007, 46, 4951-4955.
19 Fukuda, K.; Nakai, I.; Ebina, Y.; Tananka, M.; Mo i, T.; Sasaki, T. J. Phys. Chem. B 2006,
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20 Po e aul , D.; Cassaignon, S.; Baud in, E.; Joli e , J.-P. Chem. Ma e . 2008, 20, 6140-
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21 Cai, J.; Liu, J.; Suib, S. L. Chem. Ma e . 2002, 14, 2071-2077.
22 Yang., D. S.; Wang, M. K. Chem. Ma e . 2001, 13, 2589-2594.
23 Pos , J. E.; Veblen, D. R. Am. Mine . 1990, 75, 477-489.
24 Ching, S.; Pe o ay, D. J.; Jo gensen, M. L.; Suib, S. L. Ino g. Chem. 1997, 36, 883-890.
25 Gaillo , A.-C.; D i s, V. A.; Plancon, A.; Lanson, B. Chem.Ma e . 2004, 16, 1890-1905.
26 Gaillo , A.-C.; Flo , D.; D i s, V. A.; Manceau, A.; Bu ghamme , M.; Lanson, B. Chem.
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27 Tang, W. P.; Kanoh, H.; Yang, X. J.; Ooi, K. Chem. Ma e . 2000, 12, 3271-3279.
28 Liu, Z. H.; Ooi, K.; Kanoh, H.; Tang, W.-P.; Tomida, T. Langmui 2000, 16, 4154-4164.
29 B ock, S. L.; Sanab ia, M.; U ban, V.; Thiyaga ajan, P.; Po e , D. I.; Suib, S. L. J. Phys.
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30 Wong, S. T.; Cheng, S. Ino g. Chem. 1992, 31, 1164-1172.
31 Liu, Z.; Ma, R.; Ebina, Y.; Takada, K.; Sasaki, T. Chem. Ma e . 2007, 19, 6504-6512.
32 Mölle , M. W.; Handge, U. A.; Kunz, D. A.; Lunkenbein, T.; Al s äd , V.; B eu, J. ASC
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33 Gao Q.; Gi aldo, O.; Tong, W.; Suib, S. L. Chem. Ma e . 2001, 13, 778-786.
34 Omomo, Y.; Sasaki, T.; Wang, L. Z.; Wa anabe, M. J. Am. Chem. Soc. 2003, 125, 3568-
3575.
35 Kai, K.; Yoshida, Y.; Kageyama, H.; Sai o, G.; Ishigaki, T.; Fu ukawa, Y.; Kawama a, J. J.
Am. Chem. Soc. 2008, 130, 15938-15943.
36 Ballau , M. P og. Polym. Sci., 2007, 32, 1135-1151.
37 Lu, Y.; Wi emann, A.; Ballau , M. Mac omol. Rapid Commun. 2009, 30, 806-815.
38 Sch inne , M.; Polze , F.; Mei, Y.; Lu, Y.; Haup , B.; Göldel, A.; D echsle , M.; P eussne ,
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39 Sch inne , M.; P och, S.; Mei, Y.; Kempe, R.; Miyajima, N.; Ballau , M. Ad . Ma e .,
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40 Mei, Y.; Sha ma, G.; Lu, Y.; D echsle , M.; I gang, T.; Kempe, R.; Ballau , M. Langmui
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Re e ences
54
41 Sch inne , M.; Mölle , M.; Thun, J.; Kau mann, Y.; B eu, J.; Talmon, Y.; Ballau , M.
Science 2009, 323, 617-620.
42 Nakayama, M.; Tagashi a, H. Langmui 2006, 22, 3864-3869.
43 L o , Y.; Munge, B.; Gi aldo, O.; Ichinose, I.; Suib, S. L.; Rusling, J. F. Langmui 2000,
16, 8850-8857.
44 Sha ma, G.; Ballau , M. Mac omol. Rapid Commun. 2004, 25, 547-557.
45 Sch inne , M.; Haup , B.; Wi emann, A. Chem. Eng. J. 2008, 144, 138-145.
46 McKenzie, R. M. Mine al. Mag. 1978, 38, 493-502.
47 Kim, S. H.; Kim, S. J.; Oh, S. M. Chem. Ma e . 1999, 11, 557-563.
48 Wi emann, A.; D echsle , M.; Talmon, Y.; Ballau , M. J. Am. Chem. Soc., 2005, 127,
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49 Lu, Y; Spy a, P.; Mei, Y; Pich, A.; Ballau , M. Mac omol. Chem. Phys. 2007, 208, 254-
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Fo ma ion o Ul a hin Bi nessi e-Type Nanopa icles Immobilized on Sphe ical Polyelec oly e
B ushes
55

Re e ences
56
S uc u al Analysis o Colloidal MnOx Composi es
57
4. S uc u al Analysis o Colloidal MnOx
Composi es
F ank Polze ,1 Elizabe a Holub-K appe,1 He mann Rossne ,1 Alexei E ko,1 Holm Ki mse,2
Felix Plampe ,3 Alexande Schmalz,4 Axel H. E. Mülle ,4 Ma hias Ballau 1*
1Helmhol z-Zen um Be lin ü Ma e ialien und Ene gie GmbH, Hahn-Mei ne -Pla z 1,
14109 Be lin, Ge many and Depa men o Physics, Humbold Uni e si y Be lin, New ons .
15, 12489 Be lin, Ge many
2Depa men o Physics, Humbold Uni e si y Be lin, New ons . 15, 12489 Be lin
3Physical Chemis y II, RWTH Aachen, Landol weg 2, 52056 Aachen
4Mac omolecula Chemis y II, Uni e si y o Bay eu h, Uni e si ä ss . 30, 95447 Bay eu h
Email: Ma hias.Ballau[email p o ec ed]
Submi ed o he Jou nal o Colloid and Polyme Science
Abs ac
58
4.1. Abs ac
We epo on he de ailed s uc u e o MnO
x
nanopa icles (MnO
x
NP) which a e ei he
s abilized by ca ionic sphe ical polyelec oly e b ushes o by s a -shaped ca ionic
polyelec oly e chains. In bo h cases, he polyca ion is composed o 2-
( ime hylammonium)e hyl me hac yla e chlo ide (TMAEMC). The analysis by ansmission
elec on mic oscopy (TEM), c yogenic ansmission elec on mic oscopy (c yoTEM) and
powde X- ay di ac ion (PXRD) leads o he conclusion ha he MnO
x
nanopa icles in
aqueous dispe sed s a e a e composed o only a ew o e en single lamellae o c-diso de ed
po assium bi nessi e (K
+
-bi nessi e). Using s a -shaped pTMAEMC homopolyme o he
syn hesis o composi e pa icles we ob ain MnO
x
NP wi h an a e age diame e o abou 5 nm.
MnO
x
NP immobilized on ca ionic sphe ical polyelec oly e b ush (SPB) ha e a leng h o
abou 20 nm and a wid h o 1.6 nm. Compa ison o he ex ended X- ay abso p ion ine
s uc u e (EXAFS) spec a o he MnO
x
composi es wi h e e ence spec a leads o he
conclusion ha all ma e ials include c-diso de ed bi nessi e- ype nanopa icles. A compa ison
o he ene gy shi o Mn K-edge abso p ion peak o he X- ay abso p ion nea edge s uc u e
(XANES) spec a o di e en manganese oxide e e ence ma e ials wi h he di e en
MnO
x
NP e ealed an a e age oxida ion s a e o abou 3.5 - 3.7 o syn hesized compounds.
No dis inc s uc u al di e ence is ound when compa ing he d ied samples o samples
dispe sed in wa e . A compa ison o he EXAFS da a o he bi nessi e nanopa icles wi h he
c ys al s uc u e o mac oscopic sys ems showed a comp ession in he c-di ec ion
accompanied by a sligh elonga ion wi hin he ab-plane o he laye ed ma e ial.
S uc u al Analysis o Colloidal MnOx Composi es
59
4.2. In oduc ion
Mixed alen manganese oxides (MnOx) wi h laye ed opologies ha e been s udied in
li e a u e ex ensi ely in ecen yea s.1,2 These s uc u es can be syn hesized in a wide-sp ead
a ie y by changing he key pa ame e s such as he po osi y, he na u e o in e laye ed
ca ions, he deg ee o in e laye hyd a ion, he a e age oxida ion s a e o manganese and he
numbe o ca ion acancies wi hin he laye .3,4,5 The con ol o e hese pa ame e s has led o a
numbe o applica ions o laye ed MnOx, mos no ably as ca alys s and as new ypes o
elec ode ma e ials o li hium ion seconda y ba e ies.6,7,8,9,10 One ex ensi ely s udied
ma e ial is bi nessi e, a phyllomangana e composed o p edominan ly edge-sha ing MnO6
oc ahed a.11,12 The mixed alence o such ma e ials due o ca ion acancies and/o he
p esence o Mn3+ ca ions wi hin he MnOx laye s leads o a nega i e cha ge in he
laye s.13,14,15,16 This excess cha ge is balanced by he inco po a ion o di e en ca ions wi hin
he in e laye s which makes hese oxides sui able o hea y me al so p ion om was e wa e
o simila sys ems.17
The e a e se e al epo s in li e a u e abou he syn hesis o nanome e -sized laye ed MnOx
ma e ials.18 Mos o he me hods ha c ea e highly delamina ed o e en ex olia ed laye s o
MnOx a e low empe a u e solu ion-based me hods because o he s ong endency o hese
s uc u es o coagula ion and p ecipi a ion.19,20,21,22 These mild eac ion condi ions lead
mos ly o highly diso de ed ma e ials. Diso de may be a a ou able side e ec in some cases,
e.g. o applica ions as ca hode ma e ials.23 Howe e , he lack o a long- ange o de ed
c ys alline phase and he nano-scale size complica es he analysis o such oxides by
con en ional me hods such as PXRD.24,25 The e o e in es iga ions ha e been conduc ed using
X- ay abso p ion ine s uc u e (XAFS) measu emen s in o de o iden i y and analyze highly
diso de ed nanome e sized MnOx ma e ials.26,27,28,29 Thus, Fukuda and co-wo ke s s udied
he local s uc u e o Mn by XANES and EXAFS o ex olia ed unilamella c ys alli es o
manganese oxide nanoshee s.30 MnOxNP in di e en bac e ia ha e been cha ac e ized by
XAFS success ully by Sa a o sky e al. and G angeon e al.31,32 Ressle and co-wo ke s
p esen ed a de ailed analysis o MnOx colloids wi h in e cala ed e aalkylammonium ions.33
The ein i was shown ha EXAFS can be used o in es iga e s uc u al changes o MnOx
colloids due o sol-gel ansi ion p ocesses. All s udies p o ed ha EXAFS is well sui ed o
he analysis o dispe sed MnOx colloids.
We ha e ecen ly shown ha by adding po assium pe mangana e (KMnO4) o a dispe sion o
ca ionic SPB, ul a hin pla ele -like MnOxNP a e gene a ed in-si u.34
Figu e 4.2.1 displays he syn hesis o hese composi e pa icles in a schema ic ashion: The
SPB consis s o a solid polys y ene (PS) co e on o which long ca ionic chains o TMAEMC
a e chemically g a ed. The addi ion o KMnO4 leads o an ion exchange o MnO4- agains he
chlo ide coun e ions o he b ush laye . The educ ion o he MnO4- p ecu so in he basic
en i onmen o he b ush laye leads o he gene a ion o MnOxNP o laye ed opology which
was p o en by TEM and c yoTEM s udies ecen ly.34 The ul a- hin pla ele s a e s abilized
Resul s and Discussion
66
KMnO
4
. This is in good ag eemen wi h ecen indings ha he gene a ion o MnO
x
NP inside
a pTMAEMC b ush laye is ca alyzed by OH
-
ions inside he ca ionic b ush laye o SPBs.
34
Due o he highe cha ge densi y, and he e o e he highe exchange capaci y o a SPB in
compa ison o a s a -shaped homopolyme , he OH
-
concen a ion is signi ican ly highe
wi hin he b ush laye o a SPB. Hence, in case o he pTMAEMC
s a
he pH is no su icien ly
high enough o educe he MnO
4-
-ions. Thus, he gene a ion o he nanopa icles s abilized by
pTMAEMC
s a
has been induced by he addi ion o 2-bu anol. The edox p ocess can be
ollowed by a ading o he pu plish colo o KMnO
4
o b own, indica ing he gene a ion o
MnO
x
NP.
(a)
(b) (c)
(d)
Figu e 4.4.3. (a) HRTEM mic og aph o MnO
x
NP@pTMAEMC
s a
on a lacey ca bon g id
in he d ied s a e. The MnO
x
NP a e isible as da k objec s embedded in he TMAEMC
s a
ma ix. The la ice planes o he MnO
x
NP a e clea ly isible. The whi e squa e in Figu e
4.4.3a shows he selec ed a ea o he mic og aph in Figu e 4.4.3b and i s co esponding
di ac og am in Figu e 4.4.3c. Schema ic ep esen a ion o he composi e ma e ial composed
o pTMAEMC
s a
and MnO
x
NP. The nega i ely cha ged, pla ele -like MnO
x
NP wi h a ypical
diame e o 2-5 nm a e s abilized by he ca ionic pTMAEMC
s a
polyme due o elec os e ic
s abiliza ion. The c ys allog aphic s uc u e o a bi nessi e composed o Mn cen al a oms
(whi e sphe es) su ounded by 6 oxygen a oms ( ed sphe es) is displayed nex o he
composi e ma e ial. The p edominan ly edge-sha ed MnO
6
oc ahed a o he bi nessi e o m
in o laye s wi h in e cala ed K
+
-ions and wa e molecules (blue sphe es) be ween hese laye s.
HRTEM mic og aphs in Figu e 4.4.3 show he MnO
x
NP oge he wi h he pTMAEMCs a
in he d ied s a e. The nanopa icles a e displayed as da k objec s wi h a disk-like shape.

S uc u al Analysis o Colloidal MnOx Composi es
67
La ice planes a e clea ly isible. As al eady discussed, he e a e a la ge numbe o simila d-
spacings wi hin he c ys allog aphic s uc u e o he bi nessi e. The la ice planes in Figu e
4.4.3b show a d-spacing o 2.24 Å, mos p obably e e ing o (112) o (202) la ice planes o
a [111] o ien a ion acco ding o he discussion o he HRTEM mic og aphs o MnOx@SPB.
A second la ice plane is indica ed by he di ac og am in Figu e 4.4.3c bu could no be
esol ed by he HRTEM imaging. The weak con as o he MnOxNP in he TEM
mic og aphs poin s o he ac ha he pa icles a e composed o a low numbe o s acks o
lamellae only.
Based on he in es iga ions by TEM and he high colloidal s abili y o he composi e
ma e ial in wa e , he nega i ely cha ged, disk-like MnOxNP ( ypical diame e ca. 2-5 nm) a e
s abilized by he ca ionic pTMAEMCs a ha adso bs on o he MnOxNP due o Coulomb
in e ac ions (Figu e 4.4.3d). The adso bed pTMAEMCs a s abilizes he small nanopa icles
agains coagula ion in aqueous solu ion due o s e ic and elec os a ic in e ac ions. Due o he
s abiliza ion by pTMAEMCs a he MnOxNP exhibi a high colloidal s abili y o e se e al
mon hs. The size is in he same magni ude obse ed o MnOxNP syn hesized in he p esence
e aalkyl ammonium ions as epo ed p e iously by B ock e al.27 The MnOxNP gene a ed in
he p esence o pTMAEMCs a a e signi ican ly smalle han hose syn hesized wi hin he
ca ionic SPB. This could be e idence o a polyme di ec ed g ow h o he MnOxNP since he
pTMAEMC chains o he s a shaped polyme a e sho e compa ed o he pTMAEMC chains
o he SPB.
Since he HRTEM s udies only ep esen a small local a ea o he sample and due o he ac
ha a la ge numbe o di e en la ice planes wi h simila d-spacing a e p esen in bi nessi e
s uc u es, u he in es iga ions by PXRD and by XAFS a e necessa y o ge comple e
in o ma ion abou he c ys allog aphic s uc u e o he MnOxNP.
The esul s a e shown in Figu e 4.4.4. In p incipal, he di ac ion pa e n o he
MnOxNP@pTMAEMCs a ma e ial p o es ha he nanopa icles can be cha ac e ized as c-
diso de ed bi nessi e wi h a small c ys al size. He e, we would like o add ha ex emely
small bi nessi e c ys alli es composed o only a ew, andomly s acked lamellae a e
some imes e med as -MnO2 in li e a u e.42,53,54,55 Due o he absence o 00l e lec ions,
which co espond o he in e laye dis ance o s acked lamellae in he c-axis, he MnOxNP a e
composed only o a ew o e en o single lamellae (see Figu e S4.1). This ag ees wi h he low
elec on con as o he MnOxNP in he TEM mic og aphs in Figu e 4.4.1.
As al eady discussed in a p e ious wo k, he maximum o he hk bands a abou 36° and 65°
in 2

o MnOxNP@SPB ma ches wi h he co esponding e lec ions o a bi nessi e whe eas
he maximum o he hk bands o he c-diso de ed H+-bi nessi e is sligh ly shi ed o 36.3° and
65.4° in 2

. This sligh shi can ei he be aced back o small di e ences o d- alues o he
co esponding la ice planes o migh be an e ec o he small c ys alli e size. I is well known
o u bos a ically diso de ed smec i es, which also possess a 2D laye ed opology ha he
maxima o he s ongly asymme ic bands do no supe impose wi h he d- alue o a speci ic
e lec ion anymo e.56 The eason o his ac is ha he s uc u e ac o in luences he shape
o he hk bands when he c ys alli es come o nanoscopic dimensions so ha he maxima o
he hk bands do no ma ch he e lec ions o he co esponding la ice planes. Ne e heless,
Resul s and Discussion
68
he maxima o he hk bands i well wi h he e lec ions o he co esponding c-o de ed
bi nessi e as shown in Figu e 4.4.4. The pa e n o he MnOxNP@pTMAEMCs a composi e
ma ches wi h ha o he MnOxNP@SPB and he e o e can also be assigned o a c-diso de ed
bi nessi e s uc u e. Since bo h composi es show s uc u al simila i ies acco ding o he PXRD
pa e ns we conclude ha he pTMAEMC chains play an impo an ole in he pa icle
gene a ion mechanism.
Figu e 4.4.4. PXRD pa e n o MnO
xNP@pTMAEMCs a , MnOxNP@SPB, -MnO2, H+-
bi nessi e and bi nessi e. The e lec ion a a ound 36.5° and 65° in 2θ e e o he hk bands
due o a diso de in c-di ec ion o he composi e ma e ials and he H+-bi nessi e o he
hexagonal shee s composed o MnO6 oc ahed a. Figu e S4.1 shows he PXRD pa e ns o he
compounds om 15° o 70° in 2θ.
Howe e , no de ailed s uc u al analysis as e.g. in e a omic dis ances is possible by
analyzing he e y weak and b oad hk bands in PXRD. Fo his pu pose, XAFS measu emen s
we e conduc ed o elucida e he local s uc u e a ound he manganese a oms.
X- ay Abso p ion Nea Edge S uc u e (XANES)
The backg ound co ec ed and no malized XANES spec a measu ed a he Mn K-edge o
he MnOxNP@SPB and o K+- and H+-bi nessi e a e p esen ed in Figu e 4.4.5. The spec a
con ain se e al cha ac e is ics like a p e-edge peak, he whi e line, he high ene gy shoulde
and a second peak a 6580 eV. The p e-edge peak a ises om dipole o bidden quad upole
allowed Mn 1s  3d inne a omic ansi ion in an oc ahed al en i onmen .57,58 The in ensi y
o he p e-edge peak is enhanced i Mn(III)O6 oc ahed a wi h educed in e sion symme y
due o Jahn-Telle dis o ion a e p esen .33
S uc u al Analysis o Colloidal MnOx Composi es
69
Figu e 4.4.5. XANES spec a o composi e samples and e e ence compounds H+-
bi nessi e, bi nessi e and -MnO2. MnOxNP@SPB and MnOxNP@pTMAEMCs a . All
samples show he cha ac e is ic p e-edge ea u e below he Mn K-edge due o he oc ahed al
c ys al ield spli ing be ween eg and 2g o bi als.39
The XANES egion can be also used o a i s di e en ia ion o he samples om he huge
amoun o di e en laye ed MnOx s uc u es known so a . The e o e he XANES spec a o
MnOxNP@SPB and MnOxNP@pTMAEMCs a we e compa ed o he mos p obable
candida es o c ys allog aphic simila i y based on he PXRD s udy. Figu e 4.4.5 shows a
compa ison o he XANES and o K+- and H+-bi nessi e and -MnO2, and p o es he
excellen ag eemen o he MnOxNP o he composi e ma e ials wi h he e e ence
compounds. This implies ha hese s uc u es a e closely ela ed and ha MnOxNP@SPB and
MnOxNP@pTMAEMCs a a e mainly composed o edge-sha ing MnO6 oc ahed a ha o m a
laye ed opology. As i can be seen om Figu e 4.4.5, he shape and he posi ion o he main
peak and he high ene gy shoulde o he XANES o MnOx@SPB shows be e ag eemen
wi h he one o -MnO2. MnOxNP@pTMAEMCs a composi e ma ches be e o he spec um
o a iclinic K+-bi nessi e. This is in compliance wi h he esul s o Ressle e al. which
showed ha MnOx nanopa icles, gene a ed by he educ ion o KMnO4 wi h alcohols in he
p esence o e aalkylammonium ions, possess simila s uc u e han iclinic K+-bi nessi e.33
The XANES spec um is e y sensi i e o he oxida ion s a e o he sample and i s
coo dina ion chemis y.49 Due o he di e si y o di e en laye ed mine als composed o
MnO6 oc ahed a and hei di e ences in he a e age oxida ion s a e, he analysis o he
XANES egion can gi e impo an a p io i in o ma ion on he sample. The e o e a
compa ison o he K-edge posi ions o he samples and o he e e ence compounds wi h well-
de ined a e age oxida ion s a e has been done. The ene gy o he X- ay abso p ion edge is
inc easing wi h inc easing oxida ion s a e. This is due o he ac ha he successi e emo al
o elec ons om he abso bing a om is aising he elec on binding ene gy.59 The linea
ela ionship o he edge posi ion de e mined by he maximum o he i s de i a i e and he
Mn oxida ion s a e is shown in Figu e S4.2.33 This plo p o es he excellen linea dependency
o he a e age oxida ion s a e o Mn on he Mn K-edge posi ions o a ious manganese
oxides as expec ed. The a e age oxida ion s a es o he MnOxNP samples we e de e mined
Resul s and Discussion
70
based on his calib a ion and he esul s a e summa ized in Table 4.1. Though he p e-edge
ea u e is also sensi i e o he a e age oxida ion s a e, an analysis o he edge posi ion is mo e
s aigh o wa d and less ambiguous.33
The a e age oxida ion s a e o MnOx@SPB and o MnOxNP@pTMAEMCs a is abou 3.7
and 3.5, espec i ely. This indica es ha he samples a e p edominan ly o Mn4+ ca ions
including a ac ion o manganese ca ions in a lowe oxida ion s a e.39,60 This inding poin s
owa ds a bi nessi e s uc u e ha includes also Mn3+ si es and no only Mn4+ si es as ound
o sys ems wi h hexagonal shee symme y, e.g. -MnO2.42 The accu acy o he a e age
oxida ion s a e de e mina ion ia he X- ay abso p ion edge has an e o o abou 10%.31,61
The e o is highe han o me hods like i a ion educ ion/oxida ion echniques.62,63,64,65
Howe e , he analysis o composi e ma e ials by i a ion echniques may be p oblema ic
since i is no assu ed ha only he ino ganic pa , namely MnOx, is exclusi ely oxidized o
educed by he i an .31
Table 4.1. Edge Posi ions and A e age Mn Oxida ion S a es o Manganese Oxide
Compounds
sample abso p ion edge
posi ion [eV]
a e age oxida ion s a e o
Mn
H+-bi nessi e 6550.5 3.7 ± 0.3
bi nessi e 6549.1 3.3 ± 0.3
MnOxNP@SPB (powde ) 6550.7 3.7 ± 0.3
MnOxNP@pTMAEMCs a 6549.9 3.5 ± 0.3
Ex ended X- ay Abso p ion Fine S uc u e (EXAFS)
Since laye ed s uc u ed MnOx ma e ials exis in a g ea a ie y, a quali a i e compa ison
wi h e e ence compounds is necessa y o choosing a p ope c ys allog aphic model o he
polyme suppo ed MnOxNP samples. In ou p e ious wo k we could al eady show ha he
MnOxNP ha e simila PXRD pa e ns han ha o phyllomangana es like H+- and K+-
bi nessi e.34 The expe imen al χ(k) spec a o hose e e ence compounds and o he
composi e ma e ials a e displayed in Figu e 4.4.6 in a ange o 0 Å-1 ≤ k ≤ 11 Å-1. I should
be no ed a his poin ha in ou case EXAFS only p obes he local en i onmen a ound he
Mn cen al a om wi hin a dis ance o abou 6 Å. The e o e, neighbo ing a oms in adjacen
laye s along he c ys allog aphic c-axis a e no conside ed in his analysis. In gene al, he all
spec a show a good ag eemen in his ange indica ing simila i y in he c ys allog aphic
s uc u e, making a di e en ia ion a he di icul . I p o es ha he bi nessi e ma e ials a e
closely ela ed o each o he . Fo MnOxNP@pTMAEMCs a , K+-bi nessi e shows sligh ly
S uc u al Analysis o Colloidal MnOx Composi es
71
mo e spec al simila i ies acco ding o Figu e 4.4.6. The MnOxNP@SPB ma ches bes o -
MnO2 in be ween 2 Å-1 and 5 Å-1 compa ed o he o he wo e e ence compounds.
Figu e 4.4.6. Expe imen al Mn K-edge EXAFS signal, χ(k)k3, o composi e pa icles
MnOxNP@SPB and MnOxNP@pTMAEMCs a and o e e ence compounds K+- and H+-
bi nessi e and -MnO2. The composi e ma e ials show a good ag eemen wi h he e e ence
samples in he ange o 2 Å-1 ≤ k ≤ 11 Å-1.
Figu e 4.4.7 shows he Fou ie ans o med (FT) k2-weigh ed χ(k) unc ions o H+-bi nessi e,
K+-bi nessi e, -MnO2, MnOxNP@SPB and MnOxNP@pTMAEMCs a . The spec a a e no
phase co ec ed o he phase shi associa ed wi h he sca e ing p ocess o he pho oelec on
so ha he peak dis ances in his plo shi ed o lowe R alues o abou 0.4 Å. The e o e he
i s peak co esponding o he six oxygen a oms o he i s shell loca ed a a dis ance o ~1.9
Å appea s a ~1.5 Å in Figu e 4.4.7. The peak a a ound 2.5 Å ep esen s he dis ance be ween
o edge-sha ed MnO6 oc ahed a. The spec a in R-space a e domina ed by he i s wo shells
a ound he sca e ing cen e which is common o phyllomangana s. Ano he impo an
ea u e o laye ed manganese oxide wi h a mixed alency is an addi ional peak a abou 3.1 Å
which is due o he p esence o Mn-Mn co ne sha ing. The e is no signi ican signal a ound
his peak dis ance o he composi e ma e ials displayed in Figu e 4.4.7 leading o he
conclusion ha he amoun o co ne -sha ed MnO6 uni s is negligible in hese samples. The
a e age oxida ion s a es o he wo composi e ma e ials o abou 3.5 - 3.7 o he composi e
ma e ials (see Table 4.1) hen migh be aced back o he p esence o Mn3+ ions ac ing as
in e laye , cha ge compensa ing ca ions. This is common o poo ly c ys alline hexagonal
bi nessi e s uc u es which mos ly a e gene a ed a mild eac ion condi ions like i is he case
o bo h composi e ma e ials and he H+-bi nessi e. The peak a a ound 5.2 Å is due o he
ocusing e ec and e e s o a Mn-Mn dis ance o h ee edge-sha ed MnO6 uni s loca ed along
a cen e line.66,67 The o wa d sca e ing h ough he cen e a om inc eases he backsca e ing
powe and he e o e he ampli ude con ibu ion o χ(k) o he hi d a om in he ow.68 The
ampli ude o he backsca e ing signal o he hi d a om is s ongly dependen on he dihed al
angle be ween he h ee a oms in he ow. The peak is dec easing wi h inc easing de ia ion
om he dihed al angle om 180° and hence he in ensi y o he ocusing peak can be used as

Resul s and Discussion
72
a measu e o he dihed al angle.69,70 This was shown by Ressle e al. based on heo e ical
calcula ions o Fou ie ans o med XAFS o ou edge-sha ed MnO6 oc ahed a.33 The e is no
p onounced ocusing peak o he composi e ma e ials p esen ed in Figu e 4.4.7 which
indica es a de ia ion o a collinea a angemen o neighbo ing MnO6 oc ahed a. This inding
ma ches well wi h he diso de ed s uc u e ound by PXRD and HRTEM measu emen s
which do no sugges a long- ange o de ed ma e ial.
A e a quali a i e discussion o he XAFS da a we now u n o he quan i a i e analysis o
he EXAFS o MnOxNP@SPB. The compa ison o TEM and c yoTEM mic og aphs e ealed
signi ican di e ences in he mo phology o he MnOxNP in he d ied and he dispe sed s a e
as al eady shown. The e o e he local s uc u e o he MnOxNP was in es iga ed in bo h s a es
by EXAFS measu emen s o analyze i di e ences exis .
The compa ison o XANES and quali a i e EXAFS spec a e ealed a good ag eemen o
he composi e ma e ial MnOxNP@SPB wi h he bi nessi e e e ence compounds. We chose
he c ys allog aphic s uc u e o a monoclinic bi nessi e acco ding o Pos e al. o he
heo e ical EXAFS calcula ions.13 Please no e ha we also ied i ing he da a wi h a
hexagonal P63/mmc bu wi hin he limi s o e o a di e en ia ion be ween bo h s uc u es
could no be achie ed. A lis o he pa ame e s o he i s wo nea es neighbo ing shells o
he c ys allog aphic s uc u e is gi en in Table 4.2.
Figu e 4.4.7. Fou ie ans o med expe imen al Mn K-edge χ(k)k2 unc ions o MnOxNP
composi es and o H+- and K+-bi nessi e and -MnO2 (non-phase co ec ed). The i s peak
co esponds o he Mn-O dis ance whe eas he second peak a abou 2.5 Å co esponds o he
Mn-Mn dis ance be ween wo edge-sha ed MnO6 oc ahed a.
Fo he quan i a i e EXAFS analysis he Bayes-Tu chin me hod was used,71 based on he
s anda d EXAFS equa ion.72 This app oach compa es he measu ed abso p ion coe icien

exp
wi h he co esponding model da a compu ed by he FEFF code.51 The Bayes-Tu chin me hod
uses co ec ion pa ame e s o he a omic-like backg ound abso p ion besides he usual
s uc u e pa ame e s and yields i pa ame e s wi h unce ain ies consis en ly calcula ed om
he expe imen al and model unce ain ies. These we e assigned as ollows: 

exp/

exp = 0.5 %
o k < 10 Å-1 and 0.75 % o k ≥ 10 Å-1,  j/ j = 7 % and 

j = 0.07 ad o sca e ing
S uc u al Analysis o Colloidal MnOx Composi es
73
ampli udes and phases o each pa h j, espec i ely, and he unce ain y o he mean ee
elec on pa h was se o 



= 10 %. A o al numbe o 86 sca e ing pa hs we e used and he
expe imen al and model EXAFS oscilla ions we e Fou ie il e ed wi h R-window be ween 0
Å and 6 Å. The unca ion e o , which desc ibes he unce ain y o he i wi h espec o he
unca ion o he mul iple-sca e ing se ies, was calcula ed o ela i e sca e ing ampli ude o
4 %.
In an EXAFS analysis usually he Debye-Walle ac o


j is i ed o each sca e ing pa h
o es ima ed om Debye models. He e we use he app oach ha


j has a he mal diso de
componen


j, he m and a s uc u al diso de componen


j,s uc. Fo a pe ec c ys al s uc u e
he la e componen should be small and independen o empe a u e and usually is neglec ed
a ele a ed empe a u es. In ou case we ha e o conside signi ican diso de and he e o e
bo h componen s we e ea ed as i ing pa ame e s, whe e


j, s uc jus depends on he numbe
o a oms Nj in pa h j,


j, s uc =


s uc Nj /2. A he beginning


s uc was se o 0.001 [Å2] and


j, he m was calcula ed acco ding o he Debye model wi h Debye empe a u e o ΘDebye = 400
K. Du ing he i ing p ocedu e j, he m o he wo oxygen bonds a R1 ≈ R2 ≈ 1.9 Å and he
wo manganese bonds a R3 ≈ R4 ≈ 2.8 Å we e adjus ed wi h es ic ions


1, he m =


2, he m
and


3, he m =


4, he m.
Table 4.2. C ys allog aphic S uc u e o Monoclinic Bi nessi e o De i e Theo e ical
EXAFS Phases and Ampli udes (C2/m, a = 5.0 Å, b= 2.850 Å, c = 7.336 Å, , β = 103.18°)13
shellsa pai sb CNc Rd [Å]
i s shell Mn-O 4 1.908
Mn-O 2 1.910
second shell Mn-Mn 2 2.850
Mn-Mn 4 2.878
a nea es neighbo shells a ound he Mn abso be ; b co esponding a om pai o he shell; c
coo dina ion numbe o he a om pai s; d adial dis ance o he abso be and he sca e ing
a oms
The da a educ ion o he µ(E) spec a o bo h samples was conduc ed in he same way o
minimize an in luence on he ex ac ed χ(k). The numbe o i ing pa ame e s was minimized
by he in oduc ion o wo independen cell expansion ac o s: αab ep esen s he expansion o
he a om coo dina es wi hin he ab-plane whe eas αc is he expansion ac o along he c-axis
o he a om coo dina es ha is, he s acking axis o MnOx shee s. The coo dina ion numbe s
we e ixed o he alues om he c ys allog aphic in o ma ion ile.13 The ampli ude educ ion
ac o S02 was se o a alue o 0.9. The EXAFS analysis was conduc ed in k-space and
es ic ed o a dis ance in R-space o 6 Å. As a consequence, adjacen laye s o hyd ous
MnOxNP a e no included in he EXAFS i s since hey a e ypically mo e han 7 Å apa .
Resul s and Discussion
74
Hence, he in es iga ions by EXAFS p esen ed he ein a e limi ed o he ab-plane wi hin
indi idual hexagonal shee s. This es ic ion plays no ole he e inasmuch he long- ange o de
o he MnOxNP has al eady been deduced om PXRD measu emen s.
The esul s o he leas squa e i s o he MnOxNP@SPB in he d ied and in he dispe sed
s a e a e summa ized in Table 4.3, and he i s o he expe imen al da a a e p esen ed in
Figu e 4.4.8. The expansion ac o s indica e ha he MnOx nanoshee s a e comp essed along
he c-axis o abou 4 % whe eas hey a e sligh ly elonga ed wi hin he ab-plane, ha is, he
wo dimensional expansion o he hexagonal shee s composed o he MnO6 oc ahed a. The
e o co ela ions be ween he pa ame e s shown in Table 4.3 s ayed below 0.5 e en o σ2s uc
and j, he m R- ac o s a e below 0.006 and summa ized in Table 4.3.
(a) powde (b) liquid
Figu e 4.4.8. Expe imen al EXAFS unc ions (k) weigh ed by wa e numbe k a e shown by
open g een ci cles oge he wi h he unce ain ies. The solid cu es a e he mos p obable
cu es esul ing om he i s.
To e i y he new geome ical pa ame e s he i ing p ocedu e was epea ed using he new
c ys al pa ame e s a = 5.023 Å, b = 2.86289 Å, c = 7.044 Å o he solid sample o
MnOxNP@SPB, and a = 5.015 Å, b = 2.858 Å, c = 7.052 Å o he liquid sample o
MnOxNP@SPB. All o he s a ing alues we e no changed. The esul s shown in Table 4.3
we e ep oduced wi hin s anda d de ia ions.
Fukuda e al. obse ed an elonga ion wi hin he ab-plane o laye ed MnOx nanoshee s a e
delamina ion.30 They claimed ha his is due o a dec ease in he a e age oxida ion s a e o
he MnOxNP du ing he delamina ion p ocess. The au ho s also ind an expansion in he
hickness o he pla ele s in c-di ec ion, ha is, an o e all expansion o he c ys allog aphic
olume. As al eady men ioned, we ha e he ein obse ed a sligh elonga ion along he ab-
plane which is accompanied by a comp ession wi h ega ds o he c-di ec ion o a single
pla ele , ha is, along he s acking di ec ion o he laye ed MnOxNP. This is a new inding o
MnOxNP wi h laye ed opology which migh be an e ec o he small c ys alli e size oge he
wi h he high deg ee o delamina ion o he pla ele s.
-0.8
-0.4
0.0
0.4
 (k) * k
141210864 k [Å-1]
exp
i
powde
-0.8
-0.4
0.0
0.4
 (k) * k
141210864 k [Å-1]
exp
i
liquid
S uc u al Analysis o Colloidal MnOx Composi es
75
Table 4.3. EXAFS Bes Fi Resul s o MnOxNP@SPB in D ied and in Aqueous
Dispe sed S a e o he Fi s Two Shells.
pa ame e MnOx@SPB (powde ) MnOx@SPB (liquid)
E0 [eV] 6543.0 ± 0.3 6543.1 ± 0.3
αaba 1.004 ± 0.005 1.009 ± 0.005
αcb 0.960 ± 0.005 0.961 ± 0.006
σ2(Mn-O)c [Å 2] 0.00124 ± 0.00075 0.00263 ± 0.00088
σ2(Mn-Mn)d [Å 2] 0.00414 ± 0.00078 0.00572 ± 0.00090
σ2s uce [Å 2]0.00083 ± 0.00036 0.00153 ± 0.00040
R- ac o 0.0059 0.0034
a cell expansion ac o o he ab-plane, b cell expansion ac o o he c-axis, c Debye-
Walle ac o o he i s shell, d Debye-Walle ac o o he second shell, e s uc u al
diso de componen . s anda d goodness-o - i pa ame e
Despi e he signi ican di e ences obse ed by a compa ison o he mo phology o he
composi e pa icles in TEM and c yoTEM, he EXAFS analysis could p o e ha no
signi ican di e ence in he local en i onmen o he Mn o he MnOxNP in he d ied and in
he aqueous dispe sed s a e is p esen . The Debye-Walle ac o s σ2 a e highe o he liquid
sample indica ing a highe diso de in compa ison o he powde sample. The σ2 includes he
s uc u al diso de σs uc2 as well as he he mal diso de . Since no empe a u e dependen
measu emen s o σ2 a e a ailable and co ela ions o he he mal and s uc u al diso de a e
p esen , no de ailed in e p e a ion o he σ2 can be made a his poin .
4.5. Conclusion
We p esen ed he analysis o bi nessi e nanopa icles suppo ed by ca ionic s a -shaped
pTMAEMC homopolyme . The MnOxNP s abilized by pTMAEMCs a a e o disk-like shape
wi h a diame e be ween 2 - 5 nm. A combina ion o HRTEM, PXRD and XAFS analysis
e ealed ha he MnOxNP@pTMAEMCs a shows a s uc u e closely ela ed o he
MnOxNP@SPB which has been iden i ied as andomly s acked bi nessi e- ype nanopa icles
o small c ys alli e size. In addi ion, a XANES analysis p o ed he indings o he PXRD
measu emen s and e ealed oxida ion s a es be ween 3.5 - 3.7 o he composi e ma e ials.
The analysis o he EXAFS da a o MnOxNP@SPB in he d ied and in he dispe sed s a e
showed ha no signi ican e ec on he c ys allog aphic pa ame e s is obse ed, despi e he
signi ican s uc u al di e ence be ween he TEM and c yoTEM mic og aphs o he
Re e ences
82

Oxida ion o an O ganic Dye Ca alyzed by MnOx Nanopa icles
83
5. Oxida ion o an O ganic Dye Ca alyzed
by MnOx Nanopa icles
F ank Polze , † S e anie Wunde , † Yan Lu, † Ma hias Ballau † *
†Helmhol z-Zen um Be lin ü Ma e ialien und Ene gie GmbH, Hahn-Mei ne -Pla z 1,
14109 Be lin, Ge many, and Depa men o Physics, Humbold Uni e si y Be lin, New ons .
15, 12489 Be lin, Ge many
Email: Ma hias.Ballau[email p o ec ed]
Accep ed by he Jou nal o Ca alysis
Rep oduced wi h pe mission om
Jou nal o Ca alysis, 2012
© 2012 Else ie .
DOI: h p://dx.doi.o g/10.1016/j.jca .2012.01.016
Abs ac
84
5.1. Abs ac
We p esen a s udy on he ca aly ic oxida ion o he o ganic dye mo in by hyd ogen
pe oxide in he p esence o manganese oxide nanopa icles in aqueous solu ion. The ul a hin
manganese oxide nanopa icles consis o c*-diso de ed po assium bi nessi e and a e
immobilized on sphe ical polyelec oly e b ushes. The ca aly ic ac i i y o hese composi e
pa icles was in es iga ed using he oxida ion o mo in by hyd ogen pe oxide as a model
eac ion. The oxida i e deg ada ion o mo in was ollowed by UV/ is spec oscopy leading o
an appa en a e cons an kapp. We p opose a modeling o he esul s in e ms o a Langmui -
Hinshelwood model. kapp can be ela ed o he kine ic cons an k and o he appa en
adso p ion cons an s o H2O2 and mo in. Based on his model, he dependence o kapp on
empe a u e can be aced back o he ac i a ion ene gy o he a e cons an k and he
adso p ion en halpies o bo h educ s on he su ace o he nanopa icles.
Oxida ion o an O ganic Dye Ca alyzed by MnOx Nanopa icles
85
5.2. In oduc ion
In he las decade, manganese oxide nanos uc u es ha e become sys ems o pa icula
in e es as ca alys s o oxida ion eac ions.1,2,3,4,5 The e is a wide a ie y o polymo phs o
Mn(IV) oxides such as α-, β-, γ- and δ- ype MnO2 ha di e in hei espec i e linkage o he
basic s uc u e, he [MnO6] oc ahed on.6 In gene al, manganese oxide nanopa icles
(MnOxNP) a e good ca alys s o he ca aly ic decomposi ion o hyd ogen pe oxide (H2O2).
7,8,9 Fo laye ed manganese oxides, he o al su ace can be inc eased by ex olia ion which
leads o an enhanced ca aly ic ac i i y.10,11 Howe e , only a ew syn he ic ou es a e known
by now which c ea e delamina ed o highly ex olia ed bi nessi e nanopa icles, mos o hem
being mul i-s ep app oaches.12,13,14 Since nanopa icles a e mos ly gene a ed by solu ion-
based me hods, agg ega ion may occu unde he condi ions o ca aly ic eac ions. This
p ocess may lead o a ma ked dec ease o he ca aly ic ac i i y wi h ime.
Recen ly, we p esen ed a new and acile oom empe a u e me hod o gene a e and s abilize
nanome e scale laye ed MnOxNP on o ca ionic sphe ical polyelec oly e b ushes (SPB). 15
Figu e 1 displays he schema ic ep esen a ion o he composi e pa icles MnOxNP@SPB wi h
a co esponding c yogenic ansmission elec on mic oscopy (c yoTEM) mic og aph. The
SPB consis o a solid polys y ene (PS) co e on o which ca ionic polyelec oly e chains a e
densely g a ed.16 By adding po assium pe mangana e o an ca ionic SPB a oom empe a u e
MnOxNP a e o med di ec ly on he ca ie pa icles. The educ ion o KMnO4 leads o
pla ele s o bi nessi e ha a e a ixed o he co e pa icles by in e ac ion wi h he ca ionic
chains. This ixa ion p e en s he coagula ion o coa sening o he nanopa icles in an
e ec i e way.16 The composi e pa icles ha consis o he SPB oge he wi h he
immobilized MnOxNP exhibi an excellen colloidal s abili y.15
In oduc ion
86
(a)
(b)
Figu e 5.2.1. (a) Scheme o he composi e ma e ial consis ing o ca ionic sphe ical
polyelec oly e b ushes wi h b ush monome 2- ime hylammonium e hyl me hac yla e
chlo ide and bi nessi e nanopa icles (MnO
x
NP@SPB) used in he ca aly ic s udies. The
nega i ely cha ged bi nessi e nanopa icles a e bound o SPB ca ie pa icles by he ca ionic
polyelec oly e chains. (b) C yoTEM image o he composi e ma e ial MnO
x
NP@SPB. Thin
pla e like bi nessi e pa icles a e bound o he co e pa icles. The polyelec oly e chains a e
no isible because o hei low con as (see Re . 15).
He e we p esen a s udy o he ca aly ic ac i i y o MnO
x
NP@SPB.
15
The oxida ion o
mo in wi h H
2
O
2
was chosen as a model eac ion o analyze he mechanism o he ca alysis in
p esence o MnO
x
NP@SPB. Mo in belongs o a g oup o la onoid plan dyes (see Figu e
5.2.2).
17
Figu e 5.2.2. S uc u e o 2’,3,4’,5,7-pen ahyd oxy la one (mo in) which belongs o he
g oup o la onoid plan dyes. The oxida ion o his polyphenolic dye is a benchma k eac ion
o he ca aly ic ac i i y o bleach ca alys s.
These polyphenolic dyes a e p esen in ea, ui s and ege ables and can be used as model
compounds o s udying bleaching p ocesses in laund y de e gen s.
18
P e ious wo k has
demons a ed ha he oxida ion o dyes by hyd ogen pe oxide is ca alyzed by manganese
oxide. Mo eo e , clea e idence was ound ha his oxida ion is ela ed o he su ace o he
Oxida ion o an O ganic Dye Ca alyzed by MnOx Nanopa icles
87
pa icles. Fo example, Segal e al. demons a ed ha cyanine dyes can be decomposed using
well-de ined manganese oxide ca alys s and concluded ha he eac ion akes place on he
su ace o he pa icles.19 Gemeay e al. s udied he oxida i e decolo iza ion o o ganic dyes
on polyaniline/MnO2 composi es.20 Du ing his s udy, e idence o he compe ing adso p ion
o bo h he dye and H2O2 on he su ace o he ca alys was gi en. This was a gued om he
ac he a e cons an goes h ough a dis inc maximum as he unc ion o he concen a ion o
H2O2 while i dec eases wi h inc easing concen a ion o he dye. Zhang e al. analyzed he
oxida ion o me hylene blue wi h H2O2 on β-MnO2 nano ods 21 and concluded ha me hylene
blue and H2O2 adso b on o he manganese oxide su ace, whe e he eac ion akes place. I is
also in e es ing o no e ha he he e ogeneous epoxida ion o a ious alkenes wi h H2O2 in
p esence o manganese oxides s udied by Qi e al. is su ace-con olled as well.22 He e a
eac ion mechanism which in ol es a su ace bound Mn2+ was p oposed. Up o now,
howe e , a ull kine ic s udy o he oxida ion o a dye on manganese oxide is s ill missing.
The p esen in es iga ion gi es a ull kine ic s udy o he decomposi ion o a dye in
p esence o MnOx-nanopa icles. Since he composi e pa icle MnOxNP@SPB exhibi an
excellen colloidal s abili y, a p ecise analysis o hei ca aly ic ac i i y in solu ion can be
done. No p oblems as e.g. coagula ion o coa sening which would lead o a much smalle
ac i e su ace a e hampe ing he analysis. Hence, he in luence o he su ace on he kine ics
can be s udied quan i a i ely. Mo eo e , all esul s will be compa ed o ecen s udies on he
ca aly ic ac i i y o manganese ions in aqueous solu ion.Fehle ! Tex ma ke nich de inie .,23,24,25 The
kine ic s udy p esen ed he e will also p o ide a i m basis o u u e echnical applica ion o
hese sys ems in de e gen o mula ions.
5.3. Expe imen al Sec ion
Ma e ials: All chemicals we e o analy ical g ade and used wi hou u he pu i ica ion. 2-
ime hylammonium e hyl me hac yla e chlo ide (TMAEMC) was ecei ed om
Polysciences. KMnO4, Na2CO3 and NaHCO3 we e pu chased by Fluka and H2O2 and mo in
hyd a e we e ecei ed om Sigma-Ald ich. The bo ic acid bu e solu ion was pu chased
om Ca l Ro h.The wa e used he e was 18 MΩ Millipo e wa e .
Syn hesis o MnOxNP immobilized on SPB. The ca ionic SPB TMAEMC-40 was
syn hesized and cha ac e ized as desc ibed ecen ly.26 The syn hesis o he composi e pa icles
was conduc ed as desc ibed in p e ious wo k.15 The dispe sion o SPB was dilu ed wi h wa e
o gi e a solid con en o abou 1 w %. A e wa ds, 20 mL o a 0.04 mola solu ion o
KMnO4 we e injec ed and he solu ion was s i ed o 12 hou s. The composi e pa icles we e
cleaned wi h wa e by ul a il a ion agains pu e wa e un il he conduc i i y o he se um
eached a alue o lowe han 3 µS·cm-1. The o e all amoun o qua e nized ammonium
g oups in he polyelec oly e shell and he co e- o-shell mass a io we e de e mined as 6.6 o 1
by conduc i i y i a ion. The composi e pa icles we e analyzed by induc i ely-coupled
plasma op ical emission spec oscopy (ICP-OES; Va ian Vis a-P o Radial) o hei

Resul s and Discussion
88
manganese con en . Addi ionally, ansmission elec on mic oscopy (TEM) and c yogenic
TEM ( Zeiss LEO 922, Zeiss NTS GmbH, Obe kochen, Ge many) and powde X- ay
di ac ion (PXRD; Panaly ical XPERT-PRO) we e used o cha ac e iza ion. C yoTEM
samples we e p epa ed as desc ibed ecen ly.27
Ca alysis. All ca aly ic uns we e pe o med in 3 mL op ical qua z cells (Hellma). The
eac ions we e ca ied ou in a ca bona e bu e sys em o sodium bica bona e (NaHCO3) and
sodium ca bona e (Na2CO3) which was adjus ed by he addi ion o hyd ochlo ic acid o pH
10. In o de o in es iga e a possible in luence o his bu e on o he eac ion, a se o
expe imen s was done using a bo a e bu e . A eshly p epa ed 0.4 mM mo in solu ion was
dilu ed wi h bu e o esul in mo in solu ions wi h concen a ions be ween 0.01 o 0.15 mM
o all expe imen s. Then he desi ed amoun o ca alys solu ion wi h a solid con en o 0.1 w
% was added. In he ollowing, he ca alys concen a ion is always ela ed o he Mn con en
since he manganese oxide is he ac i e species. The solu ion in he e e ence cell con ained
he same concen a ion o ca alys o sub ac i s weak bu no iceable UV/ is-abso p ion. A
las he equi ed amoun o H2O2 solu ion was added o s a he ca aly ic oxida ion o mo in.
The mix u e was ins an aneously illed in o he op ical cell and he measu emen was s a ed.
All solu ions we e kep a a gi en empe a u e be o e mixing. The measu emen s we e ca ied
ou wi h a Lambda 650 (Pe kinElme ) UV/ is spec ome e a a ixed wa eleng h o 410 nm,
which is he abso p ion maximum o mo in a pH 10.
5.4. Resul s and Discussion
Syn hesis o MnOxNP@SPB
The syn hesis and cha ac e iza ion o he colloidal ca ie pa icles has been desc ibed in
de ail in ea lie wo k.15 TEM and dynamic ligh sca e ing analysis ga e a PS co e adius o
42.7 ± 0.3 nm and an a e age hickness o he polyelec oly e shell o 42.0 ± 0.8 nm. A e he
addi ion o KMnO4 solu ion o he aqueous dispe sion o he ca ionic SPB, he onse o
nanopa icle o ma ion could di ec ly be ollowed by a change in he colo om pu ple o
b own due o OH– ca alyzed educ ion o he MnO4- ions con ined in he b ush laye . No
u he educing agen needs o be added o his eac ion. The o al amoun o manganese in
he composi e pa icles de e mined by ICP-OES ga e a alue o 3.85 w % o he sample
used he e. C yoTEM mic og aphs e ealed an a e age leng h o 20 nm and a wid h o abou
1.6 nm o he MnOxNP pla ele s immobilized on SPB. PXRD measu emen s show a c*-
diso de ed K+-bi nessi e modi ica ion o he nanopa icles.15
Ca alysis.
P e ious wo k has demons a ed ha he SPBs p esen an ideal ca ie sys em inasmuch as
hey p esen no di usion ba ie o eac an s ha need o di use o he nanopa icles loca ed
inside he b ush laye .28 Mo eo e , he suspensions o hese hyb id pa icles can be pu i ied
om soluble species in he aqueous phase by p olonged ul a il a ion.28 As in p e ious
Oxida ion o an O ganic Dye Ca alyzed by MnOx Nanopa icles
89
s udies, only ini ial eac ion a es we e used o he kine ic analysis.28 Gi en hese
p e equisi es, he appa en a e cons an kapp is:

][][][ 221 Mo inkOHMo ink
d
Mo ind
app  (5.4.1)
The pH was kep cons an a pH 10 du ing he eac ions using a ca bona e bu e because
he abso bance o mo in depends on he pH. The pKa alues o mo in a e 3.5 and 8.1.29 The
oxida ion o mo in is inc easing wi h he pH due o he highe dep o ona ion o mo in.17, 30
Mo eo e , he pH will in luence he decomposi ion a e o H2O2. 31 The use o a basic bu e
sys em was necessa y because MnOxNP may dissol e unde acidic condi ions. The leaching
o MnO2 a pH alues highe han 9 we e ound o be a ound 1 ppb only which means ha any
in e e ence o he ca aly ic s udy wi h manganese ions in solu ion can be neglec ed 9 and any
in e e ence o he ca aly ic s udy wi h manganese ions in solu ion can be neglec ed.
The oxida ion o mo in can be moni o ed by measu ing he ime esol ed abso bance a 410
nm by UV/ is spec oscopy. Wi hou any ca alys , he oxida i e deg ada ion o mo in wi h
H2O2 in he ca bona e bu e does no p oceed in he ime ame o he expe imen s. The
co esponding spec a can be ound in Figu e S5.1 in he suppo ing in o ma ion. Figu e 5.4.1
shows he cha ac e is ic dec ease o he abso p ion maximum o mo in a 410 nm. In he
cou se o he oxida ion eac ion a new peak a 321 nm appea s which is inc easing wi h ime.
The isosbes ic poin s in Figu e 5.4.1 a 361 nm and 286 nm clea ly show ha only a single
eac ion p oduc is o med and ha o a a he sho ime ( < 12min) mo in is oxidized
wi hou any side p oduc s. A e a longe ime, he isosbes ic poin s anish and he peak a
321 nm is dec easing again. This inding poin s o a seconda y eac ion, mos p obably a
u he oxida ion o he p oduc s. Howe e , since we use only he ini ial a es o he kine ic
analysis, his la e s age o he eac ion is o no conce n and we only look in o he ea ly s age
whe e mo in is oxidized o a single species. The peak a 321 nm has been assigned o an
in e media e p oduc , a subs i u ed benzo u anone which decomposes u he o 2,4 dihyd oxy
benzoic acid and 2,4,6 ihyd oxy benzoic acid.32,33 This eac ion pa hway is qui e simila o
he one o que ce in which di e s wi h ega d o only he posi ion o one OH g oup.
Oxida ion o que ce in leads o he o ma ion o 2,3 dihyd oxy benzoic acid and 2,4,6
ihyd oxy benzoic acid.34 Simila indings we e epo ed ecen ly by Ro hba e al. who
s udied he ca aly ic ac i i y o manganese complexes in solu ion.25 He e i was shown ha
he oxida ion o mo in wi h H2O2 in ca bona e bu e solu ion leads o an inc ease o he peak
a 321 nm in he beginning. A e a ew minu es he peak dec eases again. In his case
isosbes ic poin s we e isible o he i s 5 spec a o he oxida ion. Wi hou any ca alys , he
oxida i e deg ada ion o mo in wi h H2O2 in he ca bona e bu e does no p oceed in he ime
ame o he expe imen s. The co esponding spec a can be ound in Figu e S5.1 in he
suppo ing in o ma ion.
Resul s and Discussion
90
(a)
(b)
Figu e 5.4.1. UV/ is spec a o a 0.1 mM mo in solu ion in 50 mM ca bona e bu e solu ion
a pH 10 wi h a concen a ion o 10 mM H2O2. The spec um shows a dec ease o he
cha ac e is ic abso p ion maximum a 410 nm o mo in wi h ime due o he decomposi ion o
he polyphenolic dye by ca aly ic oxida ion. The spec um on he le hand side shows he
eac ion in he ini ial s age (spec a e e y wo minu es). The isosbes ic poin s a e ma ked wi h
dashed lines. On he igh hand side he eac ion is shown o e a pe iod o one hou wi h
spec a aken e e y 6 minu es.
Topalo ic and co-wo ke s ha e also measu ed he inc easing peak a 321 nm in hei
mechanis ic s udy on mo in oxida ion wi h manganese 1,4,7- ime hyl-1,4,7-
iazacyclononane complexes by ai oxygen om ai .23 We also ound ha mo in unde goes
slow decomposi ion in aqueous solu ions a pH 10 in p esence o MnOx@SPB i oxygen is
p esen (see Figu e S5.2). Unde his condi ion, he peak a 321 nm is s eadily inc easing. To
exclude he ole o ai oxygen expe imen s we e conduc ed a e all solu ions we e pu ged
wi h ni ogen o exclude oxygen. No di e ence in he eac ion a e was ound by using he
pu ged solu ions. This sugges ed ha he oxida ion by ai is no ele an in p esence o H2O2.
The ela i e dec ease o he adso p ion A o mo in a 410 nm could be used bes o
de e mine he kine ics o he eac ion since i gi es a di ec measu e o he dec ease o he
mo in concen a ion. Typical kine ic uns showing he ela i e adso p ion A/A0 as he unc ion
o eac ion ime a e gi en in Figu e 5.4.2a. The eac ion immedia ely s a s a e addi ion o
he MnOxNP and he no malized abso p ion ollows a linea dec ease which can be well
desc ibed wi h a i s o de a e law as shown in Eq. (5.4.1). The ini ial a e was aken om
he slopes o hese cu es a =0.
Oxida ion o an O ganic Dye Ca alyzed by MnOx Nanopa icles
91
(a)
(b)
Figu e 5.4.2. Kine ics o he oxida ion o mo in. (a). Rela i e abso p ion A/A0 eco ded a 410
nm as he unc ion o he eac ion ime. The pa ame e s o he uns a e: 0.1 mM mo in
solu ion in 10 mM ca bona e bu e solu ion a pH 10; concen a ion o H2O2: 10 mM. The
concen a ions o he ca alys a e: □ 0.019 mg·L-1, ○ 0.039 mg·L-1,  0.077 mg·L-1,  0.116
mg·L-1 and  0.154 mg·L-1. (b) In luence o he concen a ion o ca alys on he appa en a e
cons an kapp o he oxida ion o mo in wi h H2O2 aken om 5.4.2a in 12.5 mM ca bona e
bu e .
The appa en a e cons an is p opo ional o he amoun o MnOxNP in he sys em as
shown in Figu e 5.4.2b. He e he appa en eac ion a e kapp ob ained om Figu e 5.4.2a is
plo ed agains he amoun o ca alys p esen in he sys em. A s ic ly linea ela ion is ound.
Since leaching o Mn-species can be uled ou wi h he p esen expe imen al p o ocol, his
inding is a clea indica ion o he in ol emen o he su ace o he MnOx-nanopa icles in
he a e-de e mining s ep.
Figu e 5.4.3. Dependence o he bu e concen a ion on he a e cons an a 20°C o wo
ca bona e bu e concen a ions (black squa es) and bo ic acid bu e (blue do s). The
concen a ion o mo in is 0.1 mM a pH 10 wi h a concen a ion o H2O2 = 10 mM and a
concen a ion o Mn in he MnOxNP = 0.39 mg·L-1. The a ows ma k he ca bona e
concen a ions used in he mechanis ic s udy.
Conclusions
98
Table 5.2: Summa y o he Tempe a u e Dependence o he Ra e Cons an s and
Adso p ion Cons an s.
EAa [kJ

mol-1] ΔHb [kJ

mol-1] ΔSc [Jmol-1K-1]
k*S [molm2L-2s-1] 45.8 ± 7.0 - -
KMo ind [Lmol-1] - -19.8 ± 8.7 0.2± 29.6
KH2O2e [Lmol-1] - -20.8 ± 7.1 -26.1 ± 10.7
a Ea: ac i a ion ene gy. b ΔH: en halpy. c ΔS: en h opy. d Kmo in: adso p ion cons an o mo in. e
KH2O2: adso p ion cons an o H2O2.
5.5. Conclusions
We p esen ed a kine ic s udy o he ca aly ic oxida ion o mo in by H2O2 in aqueous
solu ion using c*-diso de ed bi nessi e nanopa icles immobilized on ca ionic SPB as ca alys .
The analysis o he kine ic da a sugges ed ha he a e de e mining s ep akes place on he
su ace o he nanopa icles. Bo h eac an s need o be adso bed on o he su ace o he
ca alys in o de o eac . The adso p ion p ocess and he su ace eac ion a e desc ibed by he
he modynamic adso p ion cons an s K o bo h eac an s and he kine ic cons an k,
espec i ely. The mechanism ound o colloidal MnOx-pa icles is hence de e mined by he
su ace o he pa icles. Applica ions he e o e mus ensu e a su icien colloidal s abiliza ion
in o de o keep he ca alys in an ac i e o m.
5.6. Acknowledgemen s
We hank he Deu sche Fo schungsgemeinscha , and he Henkel AG & Co. KGaA o he
inancial suppo . The au ho s a e indeb ed o W. on Rybinski and A. Hä zel o help ul
discussion.

Oxida ion o an O ganic Dye Ca alyzed by MnOx Nanopa icles
99
5.7. Suppo ing in o ma ion
Figu e S5.1. Oxida ion o mo in wi h H2O2 wi hou MnOx-NP in 50 mM ca bona e bu e .
The spec a we e eco ded e e y 2 minu es.
Figu e S5.2. Oxida ion o mo in in p esence o MnOx@SPB wi hou H2O2 in 50 mM
ca bona e bu e . Le hand side: solu ions we e pu ged wi h ni ogen be o e he mixing o he
eac an s. Righ hand side: solu ions we e no pu ged wi h ni ogen be o e he mixing o he
eac an s. The spec a we e eco ded e e y 2 minu es.
Re e ences
100
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31 Ki ajima, N.; Fukuzumi, S.-I.; Ono, Y. J. Phys. Chem. 1978, 82, 1505-1509.
32 Topalo ic, T.; Ca aly ic Bleaching o Co on: Molecula and Mac oscopic Aspec s,
Uni e si y o Twen e, Ne he lands, 2007.
33 Colombini, M.P.; And eo i, A.; Ba aldi, C.; Degano, I.; Łucejko, J.J. Mic ochem. J. 2007,
85, 174.
34 Zhou, A. L.; Sadik, O. A. J. Ag ic. Food. Chem. 2008, 56, 12081.
35 Vannice, M. A. Reac ions; Sp inge Science + Business Media: Philadelphia, PA, 2005.
36 Wunde , S.; Polze , F.; Lu, Y.; Mei, Y.; Ballau , M. J. Phys. Chem. C 2010, 114, 8814-
8820.
37 Zhou, H.; Shen, Y. F.; Wang, J. Y.; O’Young, C.-L.; Suib, S. L. J. Ca alysis 1998, 176,
321-328.
38 Rill, C.; Kola , Z. I.; Kickelbick, G.;. Wol e beek, H. T; Pe e s, J.A. Langmui 2009, 25,
2294-2301.
39 László, K.; Podkościelny, P.; Dabo wski, A. Langmui 2003, 19, 5287-5294.
40 Zhou, X. W.; Xu, G.; Liu, D.; Panda, P. Chen, J. Am. Chem. Soc. 2010, 132, 138-146.
41 Ressle , T.; B ock, S.L.; Wong, J.; Suib, S. L. J. Phys. Chem. B 1999, 103, 6407-6420.
42 Sa a o sky, I.; Wigh man, P.G.; Pas én, P.A.; Gailla d, J.-F.; Poeppelmeie , K. R. J. Am.
Chem. Soc. 2006, 128, 11188-11198.
Re e ences
102
Kine ic Analysis o Ca aly ic Reduc ion o 4-Ni ophenol by Me allic Nanopa icles
Immobilized in Sphe ical Polyelec oly e B ushes
103
6. Kine ic Analysis o Ca aly ic Reduc ion
o 4-Ni ophenol by Me allic
Nanopa icles Immobilized in Sphe ical
Polyelec oly e B ushes
S e anie Wunde , F ank Polze , Yan Lu, Yu Mei, Ma hias Ballau 1
1Helmhol z-Zen um Be lin ü Ma e ialien und Ene gie GmbH, Hahn-Mei ne -Pla z 1,
14109 Be lin, Ge many, and Depa men o Physics, Humbold Uni e si y Be lin, New ons .
15, 12489 Be lin, Ge many
E-mail add ess: Ma hias.Ballau @helmhol z-be lin.de
Published in he Jou nal o Physical Chemis y C
Rep oduced wi h pe mission om
Jou nal o Physical Chemis y C, 2010, 114, 8814.
© 2010 Ame ican Chemical Socie y.
DOI: 10.1021/jp101125j

Abs ac
104
6.1. Abs ac
We p esen a s udy on he ca aly ic educ ion o 4-ni ophenol by sodium bo ohyd ide in he
p esence o me al nanopa icles. The nanopa icles a e embedded in sphe ical polyelec oly e
b ushes (SPBs), which consis o a polys y ene (PS) co e on o which a dense laye o ca ionic
polyelec oly e b ushes a e g a ed. The a e age size o he nanopa icles is app oxima ely 2
nm. The kine ic da a ob ained by moni o ing he educ ion o 4-ni ophenol by UV/ is-
spec oscopy could be explained in e ms o he Langmui -Hinshelwood model: The
bo ohyd ide ions ans e a su ace-hyd ogen species in a e e sible manne o he su ace.
Concomi an ly 4-ni ophenol is adso bed and he a e-de e mining s ep consis s o he
educ ion o ni ophenol by he su ace-hyd ogen species. The appa en eac ion a e can
he e o e be ela ed o he o al su ace S o he nanopa icles, o he kine ic cons an k ela ed
o he a e-de e mining s ep and o he adso p ion cons an s KNip and KBH4 o ni ophenol and
o bo ohyd ide, espec i ely. In all cases, an induc ion ime 0 was obse ed o he o de o
minu es. The ecip ocal induc ion ime can be ea ed as a eac ion a e ha is di ec ly ela ed
o he kine ics o he su ace eac ion because he e is a linea ela ion be ween 1/(k 0) and he
concen a ion o ni ophenol in he solu ion. All da a ob ained o 0 so a and a compa ison
wi h da a om li e a u e indica es ha he induc ion ime is ela ed o a slow su ace
econs uc ion o he nanopa icles, he a e o which is di ec ly ela ed o he su ace eac ion.
BH
BH
4
4¯
¯
Nip
Nip
Amp
Amp
300 350 400 450 500
0.0
0.5
1.0
1.5
2.0
abso p ion
wa eleng h [nm]
ime
Kine ic Analysis o Ca aly ic Reduc ion o 4-Ni ophenol by Me allic Nanopa icles
Immobilized in Sphe ical Polyelec oly e B ushes
105
6.2. In oduc ion
Me allic nanopa icles (NP) ha e been he subjec o in ense esea ch du ing he ecen yea s
because o hei po en ial use in ca alysis.1,2,3,4 In pa icula , edox eac ions ca alyzed by
nanopa icles ha e been ex ensi ely s udied.5,6,7,8,9 A cen al p oblem in his ield is he
quan i ica ion o he ca aly ic ac i i y o he nanopa icles a ixed o a ious ca ie sys ems.
A model eac ion sui able o his pu pose should be well-de ined, ha is, no by-p oduc s
should be o med. Mo eo e , he deg ee o con e sion should be easily moni o ed by a simple
and as echnique. Pal and cowo ke s we e he i s o iden i y he educ ion o 4-ni ophenol
(Nip) o 4-aminophenol (Amp) by sodium bo ohyd ide (BH4¯) as such a model eac ion.10
This eac ion is ca alyzed by ee o immobilized nanopa icles and p oceeds in aqueous
solu ion a ambien empe a u e. Mo eo e , i can be easily moni o ed ia UV/Vis-
spec oscopy by he dec ease o he s ong adso p ion o 4-ni ophenola e anion a 400nm,
leading di ec ly o he a e cons an .11 Se e al isosbes ic poin s in he spec a o he eac ing
mix u es demons a e ha no side eac ion occu s.12
This eac ion has been used equen ly o check he ca aly ic ac i i y o he
nanopa icles.13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34 The numbe o s udies di ec ly
ela ed o he mechanism o his eac ion, howe e , is much smalle . Esumi e al. in es iga ed
he ca aly ic ac i i y o dend ime -s abilized nanopa icles.25 These au ho s concluded ha he
eac ion is di usion-con olled. A sys ema ic s udy o he kine ics o he eac ion has been
p esen ed ecen ly by Saha e al. by a ying he ini ial concen a ions o bo ohyd ide, o Nip,
and o he me al nanopa icles.32 F om hei da a hese au ho s could demons a e ha he
educ ion o Nip mus ake place on he su ace o he nanopa icles. Zeng e al. in es iga ed
he ca aly ic p ope ies o Au-based nanocages, nanoboxes and pa icles using his model
eac ion in o de o elucida e he ole o pa icle mo phology o he ac i i y o he ca alys .31
Special a en ion was paid o he induc ion ime 0 a e which he eac ion s a s. This
induc ion ime has been obse ed by a numbe o au ho s wi h di e en ca ie sys ems
10,11,16,31,36 and was in e p e ed in e ms o he ime needed o he eac an s o di use o he
su ace o he pa icles.16
A mechanis ic explana ion o he su ace eac ion was p o ided by Zhang e al. by
in es iga ing he ca aly ic ac i i y o Ag nanoclus e s suppo ed on TiO2.30 These au ho s
assume ha a su ace hyd ogen species is i s ans e ed o he Ag-nanopa icles by
bo ohyd ide. This species eac s hen wi h he Nip o yield he p oduc Amp. This model
would imply ha he kine ics o he eac ion mus be modeled in e ms o a Langmui -
Hinshelwood mechanism, ha is, bo h eac an s need o be adso bed on he su ace p io o
eac ion. Howe e , Khala ka e al. ecen ly came o he conclusion ha only hyd ogen needs
o be adso bed on o he su ace (Eley-Rideal-mechanism).35 A numbe o au ho s ha e also
s udied he ac i a ion ene gy EA o his eac ion by ca ying ou kine ic uns a di e en
empe a u es.12,17,22,24,28,31,32,33,35,36,39,43 Zheng e al. ela ed EA o di usion ba ie s in he
sys em.31 Thus, al hough he educ ion o Nip by bo ohyd ide has become one o he mos
used benchma ks o he ca aly ic ac i i y o me al nanopa icles, a comp ehensi e kine ic
analysis o his eac ion is s ill lacking.
In oduc ion
106
Recen ly, we showed ha SPBs a e excellen sys ems o he gene a ion and immobiliza ion
o me al nanopa icles.
12,36,37,38
Figu e 6.2.1 demons a es he SPBs as ca ie s o
nanopa icles in a schema ic ashion:
Figu e 6.2.1. Scheme o he sphe ical polyelec oly e b ushes used in his s udy. Two
di e en polyelec oly es ha e been used o he syn hesis o he me al nanpa icles: Fo he
syn hesis o pla inum NP we used poly[2-(me hylac yloyloxy)e hyl- ime hylammonium
chlo ide] a ixed o he polys y ene co es whe eas Au-NP we e syn hesized using poly[(2-
aminoe hyl)-me hac yla e hyd ochlo ide].
36,39
The igh -hand side displays he TEM
mic og aphs o he composi e pa icles.
The SPBs consis o a solid PS co e on o which long chains o polyelec oly e chains ha e
been chemically g a ed. This b ush laye can be used o immobilize ions o noble me als as
e.g. gold o pla inum. Subsequen educ ion hen leads o me al nanopa icles o 1 - 3 nm in
diame e ha a e i mly embedded in a dense mesh o he polyelec oly e chains.
39
The
composi es o he nanopa icles and he SPBs exhibi a high colloidal s abili y and can be
used epea edly e en unde ha sh condi ions as e.g. in he phase- ans e hyd ogena ion o he
Heck- and Suzuki- eac ion.
40,41
The educ ion o Nip in he p esence o hese composi es has been used p e iously in o de
o compa e he ca aly ic ac i i y o di e en me al nanopa icles immobilized in he same
sys em.
42
In addi ion, his eac ion has been used o es he ca aly ic ac i i y o me al
nanopa icles immobilized in o he ca ie sys ems like co e-shell mic ogels o ee-like
b ushes.
12,43
P e ious wo k demons a ed ha Nip is educed o Amp only in he p esence o
he composi e pa icles; no eac ion akes place in absence o he nanopa icles.
36
I an excess
o bo ohyd ide is used, he eac ion is i s o de in he concen a ion o 4-ni ophenol c
Nip
.
Mo eo e , he appa en kine ic a e cons an k
app
is s ic ly p opo ional o he o al su ace S
o all me al nanopa icles.
12,29,36
Hence, he kine ic cons an s k
app
and k
1
can be de ined
h ough:
NipNipapp
Nip
cSkck
d
dc 
1
(6.2.1)
Kine ic Analysis o Ca aly ic Reduc ion o 4-Ni ophenol by Me allic Nanopa icles
Immobilized in Sphe ical Polyelec oly e B ushes
107
He e we aim a a ull analysis o he he e ogeneous educ ion o Nip in he p esence o
me allic nanopa icles. We shall demons a e ha he eac ion is su ace-con olled and can be
analyzed in e ms o he Langmui -Hinshelwood mechanism.44,45,46 In his mechanism i is
assumed ha bo h eac an s need o be adso bed on he su ace o he ca alys . The a e-
de e mining s ep is gi en by he eac ion o he adso bed species. The adso p ion/deso p ion
equilib ium is assumed o be much as e and is modelled in e ms o a Langmui iso he m.
The in luence o SPB ca ie pa icles on he educ ion o 4-ni ophenol will be excluded o
he s udy due o he open s uc u e o he b ush sys em.12 In addi ion o he analysis o he
eac ion a e, he dependence o he induc ion ime
0 on he a ious pa ame e s will be
analyzed quan i a i ely and ela ed o pa ame e s de i ed om he Langmui -Hinshelwood
analysis.
6.3. Expe imen al Sec ion
The sphe ical polyelec oly e b ushes and he me al nanopa icles we e syn hesized as
desc ibed p e iously.37,36,39 To 0.1 g o la ex pa icles, 10 mL o an aqueous solu ion o 2.55
mM me al sal was added d opwise. A e wa ds he mix u e was s i ed o 30 minu es unde
N2 o emo e he oxygen om he liquid and hen he me al ions we e educed by a h ee old
excess o BH4¯. The ea e he la ex was pu i ied ia ul a il a ion. T ansmission elec on
mic oscopy was done using a Zeiss EM922 Omega ansmission elec on mic oscope. The
TEM-mic og aphs o bo h sys ems a e shown in Figu e 6.2.1. The adius o he PS-co e is 45
nm and he polyelec oly e laye has a hickness o 86 nm in case o he P -NP. The ca ie
pa icles o he Au-NP ha e a PS-co e wi h a adius o 43 nm. The hickness o he
polyelec oly e laye is 76 nm.
The amoun o me al immobilized on he SPBs was de e mined by TGA using a Me le
Toledo STARe sys em. The samples we e i s d ied unde acuum a 50 °C. Then ca. 8 mg o
he solid composi e pa icles was hea ed o 800 °C unde a 60 mLmin-1 ni ogen low wi h a
hea ing a e o 10 °Cmin-1 and holding empe a u e a 800 °C o abou 30 minu es. The size
o he me al nanopa icles was calcula ed om he TEM-mic og aphs. App oxima ely 400
nanopa icles we e measu ed in o de o ob ain he a e age size. The speci ic su ace a ea o
he nanopa icles was calcula ed om he a e age adius hus ob ained and o hei o al mass
pe pa icle. The densi y o he pla inum nanopa icle was aken om li e a u e (P : 21.45
gcm-3; Re .36; Au: 19.32 gcm-3 Re .47).
The ca aly ic uns we e pe o med in 3 mL op ical cells made om qua z. The solu ions
had been pu ged p io o he un wi h N2 in o de o emo e O2. A e mixing esh solu ions
o BH4¯ and Nip, a gi en amoun o solu ions o he composi e pa icles was added. The
solu ion was ca e ully mixed by shaking sho ly be o e he measu emen . The ex inc ion o
Nip was subsequen ly de ec ed ia UV/ is spec oscopy using a Lambda 650 spec ome e
(Pe kin Elme ) a a cons an pH alue o 10.
Resul s and Discussion
114
(a) (b)
Figu e 6.4.5. Langmui -Hinshelwood kine ics o he educ ion o ni ophenol. The p oduc o
he appa en a e kapp and he concen a ion o Nip is plo ed agains he p oduc o θBH4 θNip
acco ding o eq.(6.4.2). The lines a e he p oduc o he a e cons an k and he su ace S o he
di e en me allic nanopa icles. The squa es a e ela ed o he P -NP ( illed squa es o he
su ace a ea o 0.00687 m2 L-1 and open squa es o a su ace a ea o 0.00481 m2 L-1), whe eas
he illed ci cles ep esen he da a deduced o he Au-NP (su ace a ea o 0.0107 m2 L-1).
The le hand side o he diag am displays he da a e e ing o he a ia ion o ni ophenol,
while he igh hand side displays he diag am e e ing o he a ia ion o sodium
bo ohyd ide.
As men ioned abo e, he ac i a ion ene gy o his eac ion has been measu ed by se e al
g oups.12,17,22,24,28,31,32,35,36,39,43 Figu e 6.4.6 displays he A henius plo o k1 and o he
ecip ocal induc ion ime 1/ 0 o he P -NP used in he p esen wo k. The concen a ion o Nip
and BH4¯ was 0.1 and 10 mM, espec i ely. These condi ions we e chosen o ensu e a
meaning ul compa ison wi h p e ious wo k.12,36,39
Figu e 6.4.6. A henius plo o he su ace no malized a e cons an k1 (eq. (6.2.1)) and he
in e se induc ion ime ob ained o P nanopa icles. The concen a ion o Nip and BH4¯ was
0.1 and 10 mM, espec i ely. The black squa es belong o he su ace no malized a e
cons an k1 whe eas he ed ci cles e e o he in e s induc ion pe iod 0.

Kine ic Analysis o Ca aly ic Reduc ion o 4-Ni ophenol by Me allic Nanopa icles
Immobilized in Sphe ical Polyelec oly e B ushes
115
The ac i a ion ene gy EA o he no malized a e cons an was 40 kJmol-1. This is in good
ag eemen wi h ou p e ious wo k o me al nanopa icles whe e EA was ound o be 44
kJ.12,36,39 Howe e , he da a ob ained o EA o di e en sys ems di e app eciably. Fo
example, Khala ka e al. ound he ac i a ion ene gy o he CTAB-s abilized gold- ods o be
38 kJmol-1.35 Chang e al. epo ed EA o 52 kJmol-1 o he magne ically eco e able Au-
NP.22 Mahmoud e al. compa ed P -nanocubes wi h nanocubes immobilized on PS-
mic osphe es and ob ained an EA o 14 kJmol-1 and 12 kJmol-1, espec i ely.24 Mo eo e , Pal
and cowo ke s poin ed ou ha he ac i a ion ene gy is dependen on he su ace o he
ca alys . Thus, smalle pa icles exhibi a highe ac i i y due o an inc ease in he oughness o
he a ailable su ace.29
An ac i a ion ene gy o 31 kJmol-1 was ound o ci a e-s abilized Au-NP and 21 kJmol-1
o calcium algina e s abilized Au-NP.29,32 Zeng e al. came o compa able conclusions in he
cou se o measu emen s o he ac i a ion ene gy o di e en ly shaped Au-NP. The ac i a ion
ene gy a ied om pa ially hollow Au-nanoboxes (55 kJmol-1), hollow Au-nanoboxes (44
kJmol-1) o Au-nanocages (28 kJmol-1).31 The p esen analysis demons a ed clea ly ha EA
e lec s he empe a u e dependence o he kine ic cons an s k and o he wo he modynamic
adso p ion cons an s KNip and KBH4. E iden ly, he la e cons an s may depend qui e s ongly
on he me hod o immobilizing o s abilizing he nanopa icles. The ac i a ion ene gy is
he e o e di icul o in e p e and addi ional measu emen s o he eac ion kine ics a di e en
empe a u es a e necessa y.
Induc ion ime 0
I es s o explain he induc ion ime 0 and i s ela ion o he a ious pa ame e s. Xia e al.
ha e also obse ed his induc ion ime and hey assumed ha he a e o adso p ion o Nip is a
dominan ac o o 0.31 Howe e , as al eady discussed di usion con ol can be de ini i ely
uled ou o he p esen sys em. In he ollowing, 0 is ela ed o he a e cons an s k de i ed
om he abo e analysis by. Thus, 1/ 0 is ea ed as a eac ion a e. This assump ion is alid
because he dependence o 1/ 0 on empe a u e can be ea ed by an A henius law. Mo eo e ,
he ac i a ion ene gy o 1/ 0 is p ac ically he same as EA o he appa en a e cons an .12,36,39,43
This was also obse ed he e and he A henius diag am o he P -NP used in p esen s udy is
shown in Figu e 6.4.6. I is in e es ing o no e ha Zhang e al. ha e obse ed a simila
induc ion pe iod in he ca aly ic hyd olysis o bo ohyd ide wi h Ru-NP.55 They also ound
ha he in e se induc ion pe iod ollows an A henius beha iou which is in acco d wi h he
p esen esul s.
In Figu e 6.4.7a we plo 0 o all expe imen s as he unc ion o he concen a ion o
bo ohyd ide. Wi hin he p esen limi s o e o , he induc ion pe iod is independen o he
concen a ion o sodium bo ohyd ide. This inding clea ly ules ou ha he ini ial s ep ela ed
o 0 is a ibu ed o any eac ion in ol ing bo ohyd ide such as he ans e o a su ace-
hyd ogen species o he me al nanopa icles. Howe e , Figu e 6.4.7b demons a es ha he
a e 1/ 0 no malized o he a e cons an k (see Table 6.1) is linea ly dependen on he
concen a ion o Nip, gi ing a mas e cu e o bo h Au- and P -NP wi hin he expe imen al
Resul s and Discussion
116
e o . This inding sugges s ha 0 is ela ed o a slow su ace econs uc ion ha is ela ed o
he kine ic cons an k ound p e iously o he s a iona y su ace eac ion (see Table 6.1).
(a) (b)
Figu e 6.4.7. Induc ion ime e sus he concen a ion o BH4¯ (a) and o Nip (b). The squa es
show he da a ob ained o he P -NP. Filled squa es e e o he su ace a ea o 0.00687 m2 L-
1 while open squa es e e o a su ace a ea o 0.00481 m2 L-1. The illed ci cles ep esen da a
ob ained o he Au-NP (su ace a ea: 0.0107 m2 L-1). Figu e 6.4.7a shows ha he induc ion
pe iod is independen o he concen a ion o BH4¯ (a). The black and da k blue colo
ep esen s a concen a ion o 0.1 mM Nip while he ed and ligh blue colo e e o he
concen a ion o 0.05 mM Nip. Figu e 6.4.7b demons a es ha he in e se induc ion ime
no malized by he kine ic cons an k (see Table 6.1) scales linea ly wi h he concen a ion o
Nip., He e he black and da k blue colo ep esen s he BH4¯ concen a ion o 10 mM and he
ed and ligh blue colo a concen a ion o 5 mM. The dashed line in Figu e 6.4.7b p esen s a
leas -squa e i o all da a indica ing a small bu ini e in e cep .
This inding can be explained as ollows: Recen wo k by Zhou e al. demons a ed ha a
ime scale in he o de o minu es may be caused by p ocesses ela ed o a dynamic
es uc u ing o he su ace o he nanopa icles.59 These au ho s ound a ime scale o
spon aneous su ace es uc u ing o ~ 60 – 250 s which is in he ange o he ime scale o 0
ound o he p esen eac ion in ou s udy and by o he s. Mo eo e , Zhou e al. could clea ly
demons a e ha he su ace es uc u ing is ela ed o he a e o eac ion, ha is, he a e o
es uc u ing is di ec ly coupled o he ca alysis.59 In absence o ca aly ic ac i i y, he e is a
ini e a e o spon aneous su ace es uc u ing which is mo e no able o small pa icles.
These indings can be di ec ly compa ed o Figu e 6.4.7b whe e a ini e in e cep sugges s a
spon aneous e ec on 0 in absence o Nip as well. Thus, a su ace es uc u ing o he
nanopa icles ela ed o he p esence o Nip and o he kine ic cons an k seems o be a
plausible explana ion o he long induc ion pe iods o his eac ion. Howe e , he na u e o
he su ace es uc u ing is no known. I may be ela ed o a shi o single a oms o o a
conce ed ea angemen o su ace a oms.59 The p esen da a only indica e ha he
es uc u ing is alle ia ed by he p esence o Nip. Mo eo e , i is he necessa y s ep ha
ac i a es he nanopa icles.
Kine ic Analysis o Ca aly ic Reduc ion o 4-Ni ophenol by Me allic Nanopa icles
Immobilized in Sphe ical Polyelec oly e B ushes
117
6.5. Conclusion
In conclusion, we ha e demons a ed ha he ca aly ic educ ion o Nip by bo ohyd ide in
he p esence o me allic nanopa icles (P , Au) can be modeled in e ms o he Langmui -
Hinshelwood model ha assumes he adso p ion o bo h eac an s on he su ace o he
ca alys . The kine ics o he eac ion can he e o e be desc ibed in e ms o h ee cons an s, a
kine ic cons an k desc ibing he su ace eac i i y o he adso bed species and he
he modynamic adso p ion cons an s o bo h componen s, namely KNip o ni ophenol and
KBH4 o bo ohyd ide. The induc ion pe iods 0, ha may be o he o de o minu es, could be
di ec ly ela ed o he a e cons an k ound o he a e de e mining s ep o he s a iona y
eac ion. Mos p obably, 0 is ela ed o a slow su ace es uc u ing o he nanopa icles ha is
di ec ly ela ed o hei ca aly ic ac i i y.
6.6. Acknowledgmen
Financial suppo by he Deu sche Fo schungsgemeinscha is g a e ully acknowledged.
6.7. Re e ences
1 As uc, D.; Nanopa icles and Ca alysis, Wiley-VCH, 2008.
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2, 18-45.
10 P adhan, N.; Pal, A.; Pal, T. Colloids Su . A 2002, 196, 247-257.
11 Gosh, S. K.; Mandal, M.; Kundu, S.; Na h, S.; Pal, T. Appl. Ca al. A 2004, 268, 61- 66.
12 Mei, Y.; Lu, Y.; Polze , F.; Ballau , M. Chem. Ma e . 2007, 19, 1062-1069.
13 Kuma , S. S.; Kuma , C. S.; Ma hiya asu, J.; Phani, K. L. Langmui 2007, 23, 3401-3408.
14 Liu, J.; Qin, G.; Ra eend an, P.; Ikushima, Y. Chem. Eu op. J. 2006, 12, 2131-2138.
15 Zhang, M.; Liu, L.; Wu, C.; Fu, G.; Zhao, H.; He, B. Polyme 2007, 48, 1989-1997.
16 Gao, Y.; Ding, X.; Zheng, Z.; Cheng, X.; Peng, Y. Chem. Commun. 2007, 3720-3722.
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17 Chen, X.; Zhao, D.; An, Y.; Zhang, Y.; Cheng, J.; Wang, B.; Shi, L. J. Colloid In e ace
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18 Rashid, M. H.; Mandal, T. K. Ad . Func . Ma e . 2008, 18, 2261-2271.
19 Lee, J.; Pa k, J. C.; Song, H. Ad . Ma e . 2008, 20, 1523-1528.
20 Dandapa , A.; Jana, D.; De, G. Appl. Ma e . In e aces 2009, 1, 833-840.
21 Ha ish, S.; Ma hiya asu, J.; Phani, K. L. N.; Yegna aman, V. Ca al. Le . 2009, 128, 197-
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22 Chang, Y.-C.; Chen, D.-H. J. Haza d. Ma e . 2009, 165, 664-669.
23 Beh ens, S.; Heyman, A.; Maul, R.; Essig, S.; S eige wald, S.; Quin illa, A.; Wenzel, W.;
Bü ck, J.; Dgany, O.; Shoseyo , O. Ad . Ma e . 2009, 21, 3515-3519.
24 Mahmoud, M. A.; Snyde , B.; El-Sayed, M. A. J. Phys. Chem. Le . 2010, 1, 28-31.
25 Esumi, K.; Isono, R.; Yoshimu a, T. Langmui 2004, 20, 237-243.
26 Wu, H.; Liu, Z.; Wang, X.; Zhao, B.; Zhang, J.; Li, C. J. Colloid In e ace Sci. 2006, 302,
142-148.
27 Wang, Y.; Wei, G.; Zhang, W.; Jiang, X.; Zheng, P.; Shi, L.; Dong, A. J. Mol. Ca al. A
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28 Ku oda, K.; Ishida, T.; Ha u a, M. J. Mol. Ca al. A 2009, 298, 7-11.
29 Panig ahi, S.; Basu, S.; P aha aj, S.; Pande, S.; Jana, S.; Pal, A.; Gosh, S. K.; Pal, T. J.
Phys. Chem. C 2007, 111, 4596-4605.
30 Zhang, H.; Li, X.; Chen, G. J. Ma e . Chem. 2009, 19, 8223-8231.
31 Zeng, J.; Zhang, Q.; Chen, J.; Xia, Y. Nano. Le . 2010, 10, 30-35.
32 Saha, S.; Pal, A.; Kundu, S.; Basu, S.; Pal, T. Langmui 2010, 26, 2885-2893.
33 Chin, K. S.; Choi, J.-Y.; Pa k, C. S.; Jang, H. J.; Kim, K. Ca al. Le . 2009, 133, 1-7.
34 Yang, H.; Nagai, K.; Abe, T.; Homma, H.; No ima su, T.; Rama aj, R. ACS Appl. Ma e .
In e aces 2009, 1, 1860-1864.
35 Khala ka, Y.; Becke , J.; Sönnichsen, C. J. Am. Chem. Soc. 2009, 131, 1871-1875.
36 Mei, Y.; Sha ma, G.; Lu, Y.; Ballau , M. Langmui 2005, 21, 12229-12234.
37 Lu, Y.; Wi emann, A.; Ballau , M. Mac omol. Rapid Coummun. 2009, 30, 806-815.
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39 Sch inne , S.; Polze , F.; Mei, Y.; Lu, Y.; Haup , B.; Ballau , M.; Göldel, A.; D echsle ,
M.; P eussne , J.; Gla zel, U. Mac omol. Chem. Phys. 2007, 208, 1542-1547.
40 Sha ma, G.; Mei, Y.; Lu, Y.; Ballau , M.; I gang, T.; P och, S.; Kempe, R. J. Ca al. 2007,
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Syn h. Ca al. 2008, 350, 493-500.
Kine ic Analysis o Ca aly ic Reduc ion o 4-Ni ophenol by Me allic Nanopa icles
Immobilized in Sphe ical Polyelec oly e B ushes
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42 Lu, Y.; Mei, Y.; Sch inne , M.; Ballau , M.; Mölle , M. W.; B eu, J. J. Phys. Chem. C
2007, 111, 7676-7681.
43 Lu, Y.; Mei, Y.; Walke , R.; Ballau , M.; D echsle , M. Polyme 2006, 47, 4985-4995.
44 Vannice, M. A. Reac ions, Sp inge Science + Business Media 2005.
45 Xu, W.; Kong, J. S.; Yeh, Y.-T. E.; Chen, P. Na u e Ma e . 2008, 7, 992-996.
46 Xu, W.; Kong, J. S.; Chen, P. J. Phys. Chem. C 2009, 113, 2393-2404.
47 Cu nell, J. D.; Johnson, K. W. Physics 4 h Edi ion New Yo k: Wiley, 1998, 308.
48 Ca egal-Rome o, S.; Pè ez-Jus e, J.; He ès, P.; Liz-Ma zàn, L.; Mul aney, P. Langmui
2010, 26, 1271-1277.
49 Liu, B. H.; Li, Z. B. J. Powe Sou ces 2009, 187, 527-534.
50 Henglein, A.; Lilie, J. J. Am. Chem. Soc. 1981, 103, 1059-1066.
51 Ung, T.; Liz-Ma zàn, L.; Mul aney, P. J. Phys. Chem. B 1999, 103, 6770-6773.
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Re e ences
120
Syn hesis and Analysis o Zwi e ionic Sphe ical Polyelec oly e B ushes in Aqueous Solu ion
121
7. Syn hesis and Analysis o Zwi e ionic
Sphe ical Polyelec oly e B ushes in
Aqueous Solu ion
F ank Polze , Johannes Heigl, Ch is ian Schneide , Ma hias Ballau *
*Helmhol z-Zen um Be lin ü Ma e ialien und Ene gie GmbH, Hahn-Mei ne -Pla z 1,
14109 Be lin, Ge many, and Depa men o Physics, Humbold Uni e si y Be lin, New ons .
15, 12489 Be lin, Ge many
Oleg V. Bo iso
Ins i u Plu idisciplinai e de Reche che su l'En i onnemen e les Ma é iaux, UMR 5254
CNRS/UPPA, Pau, F ance, and Ins i u e o Mac omolecula Compounds o he Russian
Academy o Sciences, 199004 S . Pe e sbu g, Russia
Email: Ma hias.Ballau[email p o ec ed]
Published in Mac omolecules
Rep oduced wi h pe mission om
Mac omolecules, 2011, 44, 1654.
© 2011 Ame ican Chemical Socie y.
DOI: 10.1021/ma102927c
Abs ac
122
7.1. Abs ac
We p esen he syn hesis and cha ac e iza ion o sphe ical polyelec oly e b ush (SPB)
pa icles ca ying zwi e ionic polyelec oly e chains. The colloidal pa icles consis o a
di inyl benzene c osslinked poly(s y ene) co e (PS-co-DVB co e) o abou 100 nm in
diame e on o which linea zwi e ionic poly(2-(me hac yloyloxy)e hyl dime hyl-(3-
sul op opyl)ammonium hyd oxide) (pMEDSAH) chains a e chemically g a ed ia ATRP.
Ze a po en ial measu emen s demons a ed ha he SPB has an elec opho e ic mobili y due o
he ne cha ge o he PS-co-DVB co e pa icles. The e is an inc ease o he b ush hickness L
o he zwi e ionic b ush a high concen a ions o sodium chlo ide a oom empe a u e.
Tempe a u e-dependen measu emen s by dynamic ligh sca e ing (DLS) showed ha he
zwi e ionic SPBs swell e e sibly wi h inc easing empe a u e because o he uppe c i ical
solu ion empe a u e (UCST) o he pMEDSAH chains in wa e . This e ec could be
enhanced by he addi ion o sal . C yogenic ansmission elec on mic oscopy (c yoTEM)
showed ha he shell o he pa icles is qui e compac a oom empe a u e. Howe e , he
hyd odynamic adius as measu ed by DLS was signi ican ly la ge han he pa icles adius
in e ed om mic oscopy. This esul is explained in e ms o a model in which he shell o
he zwi e ionic SPB unde goes a phase sepa a ion in o a dense phase and a ew chains
s icking ou in o he aqueous phase.
Syn hesis and Analysis o Zwi e ionic Sphe ical Polyelec oly e B ushes in Aqueous Solu ion
123
7.2. In oduc ion
Polyampholy es in gene al and speci ically zwi e ionic polyme s ha e become o g ea
impo ance in he las decades due o hei possible applica ions.1,2,3 This includes ul a-low
ouling coa ings and high- ech applica ions as biocompa ible componen s o d ug
deli e y.4,5,6 Colloidal polyme b ushes in which he adius o gy a ion o he g a ed polyme
chains exceeds he a e age dis ance be ween he join s o he polyme chains can be p epa ed
by su ace polyme iza ion o a ached ini ia o s (g a ing- om).7,8 Up o now, he e is a la ge
numbe o s udies de o ed o non-cha ged and cha ged polyme b ushes.7,8 Howe e , he e
exis s much less wo k on zwi e ionic polyelec oly e b ushes so a . To he au ho s’ bes
knowledge, he e a e only a ew s udies o plana zwi e ionic b ushes: Azza oni and co-
wo ke s success ully syn hesized zwi e ionic polyme b ushes consis ing o poly(2-
(Me hac yloyloxy)e hyl dime hyl-(3-sul op opyl)ammonium hyd oxide) (pMEDSAH) by
g a ing- om b omide unc ionalized gold and silicon dioxide su aces.9 They obse ed
hyd ophilic and hyd ophobic b ush egimes depending on he heigh o he syn hesized b ush.
In a u he in es iga ion hey showed ha one can une he b ush beha io by changing he
empe a u e, which was explained by he uppe c i ical solu ion empe a u e (UCST) o
polysul obe ains.10 Using a omic o ce mic oscopy and neu on e lec ome y Te ayama e al.
showed ha plana b ushes made om poly(3-dime hyl(me hac yloyloxye hyl)ammonium
p opane (pMPDSAH) swell by he addi ion o sal in aqueous solu ion.11 The in e ac ion o
p o eins wi h plana pMEDSAH and poly(1-ca boxy-N,N-dime hyl-N-(2’-
me hac yloyloxye hyl) me hanaminium inne sal ) (pCBMA) b ushes was ho oughly s udied
by Zhang and co-wo ke s.12 They obse ed ha hese sys ems possess a high esis ance
agains nonspeci ic p o ein adso p ion.13 Mo eo e , plana b ushes o poly(2-
me hac yloyloxye hyl phospho ylcholine) (pMPC) p o ide excellen lub ica ion in aqueous
media which makes hem p omising candida es o applica ions as bounda y lub ican s in
a i icial join s o simila sys ems.14, 15
All sys ems men ioned so a a e plana sys ems. Since one o he mos in e es ing
p ope ies o zwi e ionic polyme b ushes is hei esis ance agains nonspeci ic p o ein
adso p ion and hei biocompa ibili y, a p omising ield o applica ion is d ug deli e y.16,17,18
The e o e hese polyzwi e ions we e used as coa ings o ino ganic o o ganic nanopa icles
and colloids such as gold, magne i e o silica nanopa icles, quan um do s, ca bon nano ubes
o e en DNA.19,20,21,22,23,24 Howe e , he numbe o sys ema ical s udies in es iga ing he
solu ion beha io o zwi e ionic SPB in aqueous medium is sca ce. Ma suda e al.
in es iga ed he in e ac ions o a zwi e ionic SPB wi h a silica nanopa icle co e and pMPC
chains.25 They obse ed no sal induced changes o he b ush laye o he zwi e ionic SPB
in es iga ed by DLS. Since pMEDSAH possesses a UCST, empe a u e dependen
measu emen s we e conduc ed in p e ious in es iga ions on plana ca boxybe aine and
sul obe aine b ushes.26
Resul s and Discussion
130
(a)
(b)
(c)
Figu e 7.4.3. TEM mic og aphs o he zwi e ionic SPB p epa ed on a ca bon suppo . A 0.1
M CsI solu ion has been used o enhance he con as o he shell. The lowe pa displays he
s uc u e o he pa icles on he su ace in a schema ic ashion.
To ob ain de ailed mic oscopic in o ma ion o he zwi e ionic SPB in aqueous solu ion,
c yoTEM measu emen s ha e been conduc ed.40,41 Figu e 7.4.4 shows c yoTEM mic og aphs
o he zwi e ionic sys em dispe sed in sal - ee solu ion and in 0.1 M CsI solu ions.
Figu e 7.4.4a shows he dispe sed zwi e ionic SPB in non-saline en i onmen . The adius
o he pa icles inc eased compa ed o he adius o he ba e co e pa icles. Addi ionally, he
su ace o he SPB is co uga ed because o he pMEDSAH shell on he co e pa icles.
Vi i ying he pa icles in 0.1 M CsI solu ion leads o a signi ican inc ease in he elec on
densi y o he shell as i can be seen in he c yoTEM mic og aphs in Figu e 7.4.4b. In his way
he shell can be isualized in a much be e way. Howe e , subsequen DLS da a (see he
discussion o Figu e 7.4.4 below) demons a es ha he addi ion o sal in his concen a ion
egime does no al e he con o ma ion o he shell.
In Figu e 7.4.4b he pMEDSAH chains o he shell a e clea ly isible due o he p esence o
CsI. The adius o he pa icles is abou 80 nm. Figu e 7.4.4b demons a es ha a closed shell
o pMEDSAH is g a ed on o he PS-co-DVB/BIEM co e-shell la ex pa icles. Tha di ec ly
p o es ha a closed shell o BIEM has been gene a ed by he emulsion polyme iza ion unde
s a ed condi ions which is in ag eemen wi h pas s udies.7 The de ia ion be ween he esul s
o L and he shell hickness obse ed by c yoTEM gi es impo an in o ma ion abou he
con o ma ion o he pMEDSAH shell o he zwi e ionic SPB. The c yoTEM images show a
shell hickness o pMEDSAH chains o abou 32 nm, whe eas L ob ained by DLS is abou 48

Syn hesis and Analysis o Zwi e ionic Sphe ical Polyelec oly e B ushes in Aqueous Solu ion
131
nm. The ac ha he shell hickness acco ding o c yoTEM and DLS di e s can be explained
by he ac ha in ligh sca e ing he pa icle size is de e mined by he longes chains o he
SPB.
42
The longes o mos s e ched pMEDSAH chains a e no isible in he c yoTEM
images because o he poo con as o single polyme chains e en a e in oducing CsI o he
solu ion.
(a)
(b)
Figu e 7.4.4. C yoTEM mic og aphs o he zwi e ionic SPB in aqueous solu ion wi hou any
sal (a), and in 0.1 M CsI solu ion (b). Figu e 7.4.4b includes hyd odynamic adii o he ba e
co e pa icles R
co e
and o he co e-shell pa icles R
h
as de e mined by DLS.
This leads us o he conclusion ha he zwi e ionic shell o he SPB is no ully s e ched in
he dispe sed s a e. Mos o he chains a e collapsed so ha a laye o abou 40 nm hickness
esul s. Only a ew chains s e ch u he away om he co e and hus cause he measu ed L in
he DLS expe imen . This beha io is schema ically depic ed in Figu e 7.4.5 and is in
quali a i e ag eemen wi h he model de i ed om Wagne e al.
43
These au ho s conside ed a
collapse ansi ion in a polyme b ush caused by o ma ion o clus e s comp ising
3n
monome g oups.
43
In ou case, we can expec associa ion o
3n
dipole g oups inside he
b ush in o s able clus e s. Fu he mo e, he o ma ion o s able clus e s can also be induced by
hyd ophobic in e ac ions o he polyme backbone o he pMEDSAH chains. Bo h e ec s lead
o a collapse ansi ion accompanied by he mic ophase seg ega ion inside he b ush: A dense
phase is o med close o he g a ing su ace whe eas he spa se pe iphe y o he b ush is
o med by mo e ex ended chains. Thus, his phase sepa a ion causes a bimodal dis ibu ion o
he polyme chains wi h espec o hei ex ension. A simila end has also been p edic ed o
he complexa ion o polyme b ushes wi h su ac an s.
44
In he p esen case, wa e ep esen s
he poo sol en o he pMEDSAH chains, which leads o a collapse o he shell polyme .
45
A
pa o he pMEDSAH chains is no included in he su ace-nea laye leading o an in e nal
phase sepa a ion which causes a la e al inhomogenei y. The chains in he dilu e swollen laye
Resul s and Discussion
132
o he shell ex end u he ou in o he solu ion and cause a signi ican con ibu ion o L in he
DLS expe imen s.
Figu e 7.4.5. Model o he zwi e ionic SPB in aqueous solu ion. In a poo sol en , e.g. in
wa e , mos o he chains a e in a collapsed s a e. Only a small po ion o he chains is
s e ched u he away in o solu ion. This ac is e ealed by compa ing he shell hickness
obse ed in c yoTEM mic og aphs wi h he esul s o L de e mined by DLS. Thus, he shell
o he zwi e ionic SPB unde goes a phase sepa a ion in o a condensed phase nea he su ace
o he co e pa icles and a dilu e swollen laye o he shell which ex ends a in o he solu ion.
Since in he model shown in Figu e 7.4.5 he majo i y o he pMEDSAH chains a e in a
collapsed s a e, in es iga ions ha e been conduc ed o elucida e i his s uc u e can be
in luenced by ex e nal s imuli. The e o e DLS measu emen s o he co e-shell pa icles a
di e en concen a ions o NaCl ha e been done. Figu e 7.4.6 shows he esul s o he sal -
dependen measu emen s. The e is no no able inc ease in L o he zwi e ionic SPB wi hin he
limi s o e o upon sal addi ion up o concen a ions o 0.5 mol·L-1. These esul s a e in good
ag eemen wi h hose o Ma suda and co-wo ke s who also did no obse e a swelling o he
zwi e ionic pMPC shell upon he addi ion o up o 0.5 mol·L-1 sal .25 They conclude ha he
chains a e al eady ully ex ended e en in non-saline solu ion due o he excluded olume
e ec o densely packed polyme chains in polyme b ushes. Howe e , Figu e 7.4.6 indica es
an inc ease o L s a ing a sal concen a ions highe han 0.5 mol·L-1, which esul s in a 40 %
highe L a 2 mol·L-1 as compa ed o he non-saline s a e. The inc ease in L shows ha he
SPB shell is no ully ex ended in he non-saline s a e, which is in ull acco dance wi h he
model p oposed in Figu e 7.4.5.
Figu e 7.4.6 demons a es ha he solu ion beha io o he pMEDSAH chains is changed, i
he sal concen a ion is su icien ly high. The obse a ion ha he onse o he swelling o he
shell akes place a concen a ions highe han 0.5 mol·L-1 indica es ha he swelling canno be
Syn hesis and Analysis o Zwi e ionic Sphe ical Polyelec oly e B ushes in Aqueous Solu ion
133
ela ed o he con en ional an i-polyelec oly e e ec . The an i-polyelec oly e e ec is
gene ally unde s ood as a Coulomb sc eening e ec which is ypically obse ed o sal
concen a ion up o 0.01 mol·L-1.46 The esponse o he pMEDSAH shell a sal concen a ions
highe han 0.5 mol·L-1 sugges s ha ion-speci ic and hyd ophobic in e ac ions may play a
ole in hese sys ems.47 An al e na i e explana ion may be sough in he b eaking o sal
b idges in he zwi e ionic laye ha occu s only a high sal concen a ions.48
Figu e 7.4.6. Sal dependen measu emen s o L o he zwi e ionic SPB ia DLS a a
empe a u e o 25 °C. The pMEDSAH shell shows a swelling o L a concen a ions o NaCl
highe han 0.5 mol·L-1.
We now u n o he in es iga ions o he empe a u e-dependen beha io o he zwi e ionic
SPB. Figu e 7.4.7 demons a es ha he e is an inc ease in L o abou 7 nm upon hea ing. The
esul s o he cooling and ehea ing ully ag ee and show a good ep oducibili y. The
s e ching o he shell a high empe a u es is due o he UCST beha io o he pMEDSAH
chains. A highe empe a u es, he sol en quali y will inc ease o pMEDSAH chains due o
hei UCST empe a u e. This has been ound by di e en g oups in ea lie wo ks on plana
b ushes.9,10
In he sys em unde conside a ion he e, he expansion o he shell is no e y p onounced as
compa ed o he sal -dependen measu emen s p esen ed in Figu e 7.4.6. Since he esul s o
he p e ious pa ag aph showed ha he addi ion o high amoun s o sal signi ican ly
inc eased L a oom empe a u e, empe a u e-dependen DLS measu emen s a di e en sal
concen a ions ha e been conduc ed.
The esul s o hese measu emen s a e also p esen ed in Figu e 7.4.7 and show wo
impo an e ec s: On he one hand, L signi ican ly inc eases a oom empe a u e a sal
concen a ions highe han 1 mol·L-1. This inding has been shown ea lie in Figu e 7.4.6.
Addi ionally, empe a u e cycles a di e en sal concen a ions e eal a d as ic swelling o
he zwi e ionic shell upon hea ing. This is due o he inc ease o he sol en quali y o he
zwi e ionic polyme chains. The UCST beha io ge s mo e p onounced a e he addi ion o
sal which was expec ed since bo h, he sal concen a ions and he empe a u e, a e inc easing
he solubili y o he pMEDSAH chains. The in luence o he amoun o added sal on o he
UCST o pMEDSAH homopolyme was also obse ed by Ma y e al.26
Conclusion
134
Figu e 7.4.7. Tempe a u e dependen measu emen s o L o he zwi e ionic SPB wi h
pMEDSAH chains by DLS. Inc easing he empe a u e om 20 °C o 75 °C leads o a
swelling o he b ush laye o he zwi e ionic SPB. The beha io is comple ely e e sible,
which was shown by subsequen cooling o he sys em. The e o e i can be assigned o he
UCST o he pMEDSAH chains. The e ec o swelling can be signi ican ly enhanced by he
addi ion o high amoun s o sal . The lowes da ase ep esen s a hea ing cycle o he
zwi e ionic SPB in sal - ee solu ion (■ hea ing and □ cooling), he second cu e shows he
swelling o he zwi e ionic SPB in 1 mol·L-1 NaCl solu ion ( hea ing and  cooling) and 2
mol·L-1 NaCl solu ion o he uppe mos cu e ( hea ing and ○ cooling).
7.5. Conclusion
We p esen ed a me hod o he syn hesis o colloidal s able sphe ical polyme b ushes wi h
a zwi e ionic b ush laye o pMEDSAH chains. The ex ension o he shell can be in luenced
upon he addi ion o sal which may be due o ion-speci ic in e ac ions. Fu he mo e, he
zwi e ionic shell showed a ully e e sible swelling upon hea ing due o he UCST beha io
o he pMEDSAH chains. This e ec could be enhanced upon he addi ion o sal . By a
combina ion o DLS, TEM and c yoTEM measu emen s we p opose a model o he
zwi e ionic SPB including an in e nal phase sepa a ion o he pMEDSAH shell acco ding o
Wagne e al.43 In his model he shell is mos ly collapsed in a condensed s a e nea he
su ace o he co e pa icles whe eas only a small po ion o he shell is in a dilu e swollen
s a e wi h he pMEDSAH chains ex ending a ou in o solu ion.
Syn hesis and Analysis o Zwi e ionic Sphe ical Polyelec oly e B ushes in Aqueous Solu ion
135
7.6. Acknowledgemen s
We hank he Deu sche Fo schungsgemeinscha , Sonde o schungsbe eich 840 Bay eu h.
C.S. hanks he Eli e S udy P og am Mac omolecula Science in he Eli e Ne wo k Ba a ia
and he Ba a ian G adua e Suppo P og am o inancial suppo . We hank R. Hill o he
ex ensi e suppo p o ided o using he MPEK so wa e and J. Dzubiella o help ul
discussions.
7.7. Suppo ing In o ma ion
Figu e S7.1. H1-NMR o BIEM (250 MHz, CDCl3). δ (ppm) = 6.07 (1H, s), 5.53 (1H, s),
4.35 (4H, ), 1.87 (3H, dd), 1.86 (6H, s). 13C-NMR (62.5 MHz, CDCl3) d (ppm) = 170.2,
135.7, 126.2, 63.4, 61.7, 54.9, 30.4, 18.3.

Suppo ing In o ma ion
136
(a) (b)
Figu e S7.2. TEM mic og aphs o PS/BIEM1 (a) and PS-co-DVB/BIEM2 (b) co e pa icles.
The pa icles show a na ow size dis ibu ion wi h an a e age Rco e o 48.1 ± 0.2 nm o he
co e pa icles PS-co-DVB/BIEM1 and 59.9 ± 0.2 nm o PS-co-DVB/BIEM2 acco ding o
DLS.
Figu e S7.3. GPC cu e o he clea ed chains o he b ush polyme wi h a PDI o 1.16. The
GPC was calib a ed wi h pMAA s anda d.
Syn hesis and Analysis o Zwi e ionic Sphe ical Polyelec oly e B ushes in Aqueous Solu ion
137
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