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Ci e his: Ene gy En i on. Sci.,
2019, 12,2733
Rede ining he Robeson uppe bounds o CO
2
/
CH
4
and CO
2
/N
2
sepa a ions using a se ies o
ul ape meable benzo ip ycene-based polyme s
o in insic mic opo osi y†
Bibiana Comesan
˜a-Ga
´nda a, ‡
a
Jie Chen,‡
a
C. G azia Bezzu,
a
Ma iolino Ca a,
b
Ian Rose,
a
Ma ia-Chia a Fe a i,
c
Elisa Esposi o,
d
Alessio Fuoco,
d
Johannes C. Jansen *
d
and Neil B. McKeown *
a
Memb anes composed o Polyme s o In insic Mic opo osi y (PIMs) ha e he po en ial o ene gy efficien
indus ial gas sepa a ions. He e we epo he syn hesis and gas pe meabili y da a o a se ies o ul ape meable
PIMs, o wo-dimensional chain con o ma ion and based on benzo ip ycene s uc u al uni s, ha demons a e
ema kable ideal selec i i y o mos gas pai s o impo ance. In pa icula , he CO
2
ul ape meabili y and high
selec i i y o CO
2
o e CH
4
, o key impo ance o he upg ading o na u al gas and biogas, and o CO
2
o e
N
2
, o impo ance o cos -effec i e ca bon cap u e om powe plan s, exceed he pe o mance o he cu en
s a e-o - he-a polyme s. All o he gas pe meabili y da a om his se ies o benzo ip ycene-based PIMs
a e placed well abo e he cu en 2008 Robeson uppe bounds o CO
2
/CH
4
and CO
2
/N
2
. Indeed, he da a o
some o hese polyme s all in o a linea co ela ion on he benchma k Robeson plo s [i.e. log(P
CO2
/P
CH4
) e sus
log P
CO2
and log(P
CO2
/P
N2
) e sus log P
CO2
], which a e pa allel o, bu signi ican ly abo e, ha o he 2008
CO
2
/CH
4
and CO
2
/N
2
uppe bounds, allowing hei e ision. The ede ini ion o hese uppe bounds se s new
aspi a ional a ge s o polyme chemis s o aim o and will esul in mo e a ac i e pa ame ic es ima es o
ene gy and cos efficiencies o ca bon cap u e and na u al/bio gas upg ading using s a e-o - he-a CO
2
sepa a ion memb anes.
B oade con ex
The low-cos and ene gy-effec i e emo al o ca bon dioxide (CO
2
) om na u al gas and biogas would help he supply o me hane as he cleanes bu ning and lowes
ca bon-emi ing hyd oca bon uel. In addi ion, ca bon cap u e and s o age (CCS) om powe plan emissions will be equi ed o achie e he goals o he 2015 Pa is
Ag eemen , which aspi es o main ain global wa ming o less han 1.5 1C abo e ha o he p e-indus ial age by he end o he 21s Cen u y. Indeed, he combined use
o bio uels, such as biogas, and CCS echnology is ega ded as he key nega i e emissions echnology equi ed in o de o each he Ag eemen ’s ambi ious a ge s o
educed emissions. Despi e he u gen need o CCS, he bes echnology pla o m o i s deli e y is s ill unclea due o he difficul ies in he es ima ion o cos s and
he complex e alua ion o he ad an ages and disad an ages associa ed wi h each echnology. Highly pe meable memb anes ha a e selec i e o CO
2
o e me hane
(CO
2
/CH
4
)andCO
2
o e ni ogen (CO
2
/N
2
) a e o inc easing in e es o na u al gas/biogas upg ading and ca bon cap u e, espec i ely, due o he inhe en efficiency
o memb ane sepa a ions. He e we epo he syn hesis o a se ies o ul ape meable polyme s ha de ine he s a e-o - he-a in he ade-off be ween pe meabili y
and selec i i y o all impo an gas sepa a ions and, in pa icula , o CO
2
/CH
4
and CO
2
/N
2
. The da a om hese polyme s we e used o ede ine he benchma k
Robeson uppe bounds o hese wo gas sepa a ions a much highe alues o selec i i y. This enhancemen will imp o e he c edibili y o polyme memb anes o
CO
2
sepa a ions when e alua ed agains compe ing p ocesses. Hope ully, his will help o s imula e he undamen al polyme science and applied enginee ing
equi ed o de elop memb ane sys ems o hese CO
2
sepa a ions o key impo ance o ene gy and he en i onmen .
In oduc ion
Memb anes based on polyme s as he selec i e laye a e used o
he ene gy efficien sepa a ion o gas mix u es including hose o
key ele ance o ene gy and he en i onmen .
1–4
The de elop-
men o new polyme s wi h g ea e gas pe meabili y and selec-
i i y would u he enhance he e iciency o memb ane gas
sepa a ions o cu en indus ial in e es ,
5
including hyd ogen
eco e y du ing ammonia p epa a ion (H
2
om N
2
), oxygen o
a
EaS CHEM, School o Chemis y, Uni e si y o Edinbu gh, Da id B ews e Road,
Edinbu gh, EH9 3FJ, UK. E-mail: [email p o ec ed]
b
Depa men o Chemis y, Swansea Uni e si y, College o Science, G o e Building,
Single on Pa k, Swansea, SA2 8PP, UK
c
Ins i u e o Ma e ials and P ocesses, School o Enginee ing, The Uni e si y o
Edinbu gh, May ield Road, Edinbu gh EH9 3JL, UK
d
Ins i u e on Memb ane Technology, ITM-CNR, Via P. Bucci 17/C,
87036 Rende (CS), I aly
†Elec onic supplemen a y in o ma ion (ESI) a ailable. See DOI: 10.1039/c9ee01384a
‡The i s wo au ho s con ibu ed equally.
Recei ed 29 h Ap il 2019,
Accep ed 11 h July 2019
DOI: 10.1039/c9ee01384a
sc.li/ees
Ene gy &
En i onmen al
Science
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ni ogen en ichmen o ai (O
2
om N
2
)
6
and na u al gas o
biogas upg ading (p edominan ly CO
2
om CH
4
).
7–10
Inc easingly,
polyme memb anes a e also being conside ed as a p ac ical
al e na i e o sol en abso p ion o la ge-scale cap u e o CO
2
om
powe plan lue gas (p edominan ly CO
2
om N
2
).
7,9,11–14
Fo gas
sepa a ions on such a massi e scale, memb anes wi h e y high
pe meance (i.e. lux) a e desi able o minimise ene gy cos s o
gas comp ession and o educe he ac i e su ace a ea o he
memb ane, he eby, op imising he o e all size and manu ac u e
cos o he memb ane sys em.
5,15
Howe e , polyme memb ane
ma e ials su e om he well-es ablished ade-o be ween
gas pe meabili y (P
x
) and selec i i y o one gas o e ano he
(P
x
/P
y
),
16,17
so ha es ablished ul ape meable polyme s, such
as he polyace ylene poly( ime hylsilylp opyne) (PTMSP),
18,19
and ecen ly epo ed examples
20
a e insu icien ly selec i e o
use in gas sepa a ions.
The gene al ade-off be ween polyme pe meabili y and
selec i i y was i s quan i ied by Robeson in 1991 when he
iden i ied uppe bounds in plo s o log(P
x
/P
y
), e sus log P
x
o
O
2
/N
2
,H
2
/N
2
, He/N
2
,H
2
/CH
4
, He/CH
4
,CO
2
/CH
4
, and He/H
2
gas
pai s based on he gas pe meabili y o he bes pe o ming
polyme s a ha ime.
21
Subsequen ly, o a newly p epa ed
polyme (o a mixed ma ix memb ane)
22,23
he posi ion o i s
gas pe meabili y da a ela i e o he uppe bounds on Robeson
plo s allows o i s po en ial o gas sepa a ions o be es ima ed.
Robeson upda ed all o he uppe bounds in 2008 using ini ial
da a o wo spi obisindane-based Polyme s o In insic Mic o-
po osi y (PIM-1 and PIM-7; Table S1, ESI†),
24
whose igid and
con o ed mac omolecula s uc u es p o ided excep ionally
high pe meabili y wi h mode a e selec i i y.
25
In addi ion, da a
o hese woPIMswe ealsoused ode ineanuppe bound o he
CO
2
/N
2
gas pai , which is o key impo ance o pos -combus ion
ca bon cap u e bu had been conside ed o no p ac ical in e es in
1991.
24
Since 2008, many PIMs wi h enhanced igidi y ha e demon-
s a ed gas pe meabili y da a ha lie well abo e some o he 2008
uppe bounds.
26
These highly shape-pe sis en PIMs we e ob ained
by eplacing he ela i ely lexible spi obisindane s uc u al uni
wi h spi obi luo ene
27,28
uni s o highly igid b idged bicyclic
componen s such as e hanoan h acene,
29–32
ip ycene,
33–36
me hanopen acene
37
and T o
¨ge s base.
29,35
Indeed, in 2015
Pinnau e al.
38
p oposed ha he O
2
/N
2
,H
2
/N
2
and H
2
/CH
4
uppe bounds should be upda ed using pe meabili y da a
om aged ilms o highly selec i e ip ycene-based PIMs (e.g.
PIM-T ip-TB
35
and TPIM-1
33
). Howe e , e isions o he uppe
bound o CO
2
/N
2
and CO
2
/CH
4
we e no p oposed a ha ime
due o he da a o hese polyme s and o he high-pe o ming
PIMs being close o he exis ing 2008 CO
2
/N
2
and CO
2
/CH
4
uppe
bounds (Table S1, ESI†).
Recen ly, we in oduced a new PIM de i ed om a benzo-
ip ycene monome , PIM-TMN-T ip, which p o ed o be as
ul ape meable o gases as PTMSP due o enhanced in insic
mic opo osi y a ising om i s 2D chain s uc u e.
39
PIM-TMN-
T ip demons a es highe selec i i y han PTMSP due o i s
g ea e chain igidi y p o iding enhanced molecula sie ing
(i.e. diffusi i y selec i i y). Fu he mo e, i was ound ha he
unsubs i u ed benzo ip ycene-based PIM (PIM-BT ip) demon-
s a es e en g ea e selec i i y placing i s da a abo e he
p oposed 2015 O
2
/N
2
,H
2
/N
2
and H
2
/CH
4
uppe bounds and
e en abo e Robeson’s 2008 uppe bounds o CO
2
/N
2
and CO
2
/
CH
4
.
40,41
He e we epo on he syn hesis and p ope ies
o some new membe s o he benzo ip ycene-based PIM
se ies (Fig. 1), all o which demons a e high pe meabili y and
selec i i y. In pa icula , his polyme se ies demons a es pe me-
abili y da a o CO
2
/N
2
and CO
2
/CH
4
ha sugges new posi ions o
he Robeson uppe bound o hese impo an gas pai s ha a e o
key in e es o sepa a ions o ele ance o ene gy and he
en i onmen .
Resul s and discussion
Polyme design and syn hesis
A u he ou benzo ip ycene PIMs we e syn hesised along
wi h new ba ches o PIM-TMN-T ip and PIM-BT ip o allow o
di ec compa ison o hei gas pe meabili ies. The no el poly-
me s include PIM-HMI-T ip, o which he s e ically c owded
hexame hylindane (HMI)-solubilising g oup
42
would be expec ed
o be mo e igid han he e ame hylnaph halene (TMN) g oup
o PIM-TMN-T ip. P e iously o spi obi luo ene-based PIMs,
43
he in oduc ion o adjacen me hyl subs i uen s had been
Fig. 1 S uc u e and syn hesis o he benzo ip ycene PIMs. Reagen s and condi ions: i. B
2
,Fe,DCM, ,3h;ii.n-BuLi, u an, THF, 78 1C, 1.5 h; iii. 9,10-Dime hyl-
2,3,6,7- e ame hoxyan h acene, DMF, 250 1C, 7 ba , 2 h, mic owa e i adia ion, i . TFA o MeSO
4
H, , 24 h.; . BB
3
, DCM. (See ESI† o de ails).
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shown o be bene icial o pe o mance, he e o e, a PIM based
on dime hylbenzo ip ycene was p epa ed (PIM-DM-BT ip).
In addi ion, he po en ial bene i o in oducing one o wo
i luo ome hyl (TFM) solubilising g oups on o he benzo-
ip ycene uni was e alua ed by he syn hesis o PIM-TFM-
BT ip and PIM-DTFM-BT ip, espec i ely.
Each polyme was p epa ed om i s e ahyd oxy benzo-
ip ycene monome (1a– ) using he well-es ablished benzodioxin-
o ming polyme isa ion eac ion de ised o PIM syn hesis
(Fig. 1).
44
Monome s we e p epa ed by adap a ion o he classic
benzo ip ycene syn hesis, in ol ing he Diels–Alde eac ion
be ween 2,3,6,7- e ame hoxy-9,10-dime hylan h acene and
he app op ia e 1,4-dihyd o-1,4-epoxynaph halene
39
– wi h he
la e p epa ed om he Diels–Alde eac ion be ween he
app op ia e benzyne in e media e and u an.
45–47
PIM-TMN-T ip and PIM-HMI-T ip a e bo h soluble in chlo o-
o m, acili a ing analysis using Gel Pe mea ion Ch oma og aphy
(GPC) ha con i med ha high molecula mass polyme was
achie ed o bo h polyme s (Table 1). In con as , PIM-DM-B ip,
PIM-TFM-BT ip and PIM-DTFM-BT ip p o ed soluble only in
quinoline. The success o his high-boiling a oma ic sol en
o dissol ing hese o he wise in ac able polyme s p omp ed a
e-in es iga ion o he solubili y o unsubs i u ed PIM-BT ip,
which we had p e iously desc ibed as insoluble.
39
Pleasingly,
his polyme also p o ed soluble in quinoline. Al hough quino-
line is no an app op ia e sol en o GPC analysis, solu ions
o PIM-DM-BT ip, PIM-TFM-BT ip, PIM-DTFM-BT ip and PIM-
BT ip could be used o cas mechanically lexible and obus
ilms, implying ha a easonably high molecula mass had
been achie ed du ing he syn hesis. Syn he ic and s uc u al
cha ac e isa ion de ails, including solid s a e NMR (Fig. S1) a e
gi en in he ESI.†
Gas adso p ion and gas anspo p ope ies.
In hei powde o m, all benzo ip ycene-based PIMs adso b a
la ge amoun o ni ogen (N
2
, 77 K) a low ela i e p essu e.
Analysis o he N
2
adso p ion iso he ms (Fig. S1, ESI†) gi es
appa en B unaue –Emme –Telle (BET) su ace a eas (SA
BET
)
wi hin he ange o 848–1034 m
2
g
1
(Table 1), which a e
amongs he highes ob ained om solu ion p ocessable
polyme s.
29,39
The shapes o he N
2
iso he ms a e simila o all
polyme s excep o PIM-TMN-T ip and PIM-DTFM-BT ip, o
which he e is la ge up ake a highe p essu es associa ed wi h a
la ge hys e esis be ween he adso p ion and deso p ion iso he ms.
This migh be ela ed o he TMN and CF
3
subs i uen s
p o uding ou o he 2D plane o he polyme chain and hus
in e e ing wi h he elec os a ic ni ile–ni ile in e ac ions
which a e likely o domina e polyme cohesion. Adso p ion
o CO
2
a 273 K (Fig. S2, ESI†) shows simila up akes o
he benzo ip ycene-PIMs (2.5–3.3 mmol g
1
). The up ake o
PIM-BT ip is sligh ly highe a lowe p essu es, which may
be asc ibed o a g ea e concen a ion o ul amic opo es
(diame e o0.7 nm in i s po e size dis ibu ion (Fig. S3, ESI†)).
Sol en cas ilms (Fig. S4, ESI†) o he benzo ip ycene-
based PIMs all demons a e excep ionally high gas pe meabili y
(Table 2). Howe e , he e alua ion o gas pe meabili y da a o
a new polyme equi es ca e ul conside a ion o i s ilm
his o y and hickness as hese ac o s in luence g ea ly he
obse ed alues.
32
Gene ally, he highes epo ed alues o
gas pe meabili y o high ee olume polyme s such as he
PTMSP and PIMs we e ob ained om ilms eshly ea ed
wi h me hanol (o e hanol), which emo es any esidual cas ing
sol en bu also induces addi ional ee olume.
31,48
The alues
o gas pe meabili y om eshly me hanol ea ed hick ilms
(135–176 mm) o he benzo ip ycene PIMs a e some o highes
epo ed o a pu e polyme ilm (e.g.,P
CO
2
=21–5310
3
Ba e )
and a e compa able o hose om e hanol ea ed ul ape me-
able polyace ylenes (e.g.,P
CO
2
= 28–47 10
3
Ba e ).
19,42
Fo each
o he me hanol ea ed ilms he o de o dec easing gas
pe meabili y is CO
2
4H
2
4O
2
4He 4CH
4
4N
2
wi h he
excep ion o hose om he less pe meable and mo e size-
selec i e PIM-BT ip o which He pe mea es as e han O
2
.
The ideal selec i i ies o all o he me hanol ea ed ilms a e
signi ican ly highe han hose ob ained o he ul ape meable
polyace ylenes and all in he ange o hose epo ed o
me hanol ea ed ilms o less pe meable PIMs such as PIM-1
(e.g.,P
O
2
/P
N
2
= 2.6–3.6).
48
As no ed o all PIMs and highly pe meable polyme s,
31,32,49–51
he ex emely high alues o gas pe meabili y measu ed ini ially
om he eshly me hanol ea ed ilms a e no main ained on
ageing.
52
Howe e , he educ ion in pe meabili y is accompa-
nied by an inc ease in ideal selec i i y o all gas pai s.
In addi ion, on ageing, He pe meabili y su passes he alue
o O
2
o all he polyme s, indica ing enhanced size selec i i y.
Compa ing da a om app oxima ely like- o -like samples
(i.e. B120 day aged and 110–180 mm hick ilms) he o de
Table 1 Yield, molecula mass and gas adso p ion p ope ies o he benzo ip ycene-based PIMs
Polyme
Yield
(%) Solubili y
M
n
(g mol
1
)M
w
/M
n
Z
a
(cm
3
g
1
)
SA
BETb
(m
2
g
1
)
V
To alc
(ml g
1
)
V
Md
(ml g
1
)
CO
2
up ake
e
(mmol g
1
)
PIM-TMN-T ip 67 CHCl
3
52 300
3.8 74 1034 0.87 0.38 3.3
PIM-HMI-T ip 58 CHCl
3
61 300
2.4 58 1033 0.71 0.38 3.0
PIM-BT ip 78 Quinoline —
g
—
g
66 911 0.63 0.33 3.2
PIM-DM-BT ip 82 Quinoline —
g
—
g
72 920 0.72 0.33 3.0
PIM-TFM-BT ip 79 Quinoline —
g
—
g
37 848 0.66 0.31 2.5
PIM-DTFM-BT ip 84 Quinoline —
g
—
g
65 964 1.02 0.33 2.5
a
Inhe en iscosi y in quinoline a 25 1C.
b
BET su ace a ea calcula ed om N
2
adso p ion iso he m ob ained a 77 K.
c
To al po e olume
es ima ed om N
2
up ake a P/P
o
= 0.98.
d
Mic opo e olume es ima ed om N
2
up ake a P/P
o
= 0.05.
e
CO
2
adso p ion a 1 ba and 273 K.
Rela i e o polys y ene s anda ds.
g
No measu ed due o insolubili y in sol en s compa ible wi h GPC analysis.
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o dec easing pe meabili y and inc easing selec i i y o he
benzo ip ycene PIMs is PIM-TMN-T ip 4PIM-DTFM-BT ip 4
PIM-HMI-T ip 4PIM-TFM-T ip 4PIM-BT ip EPIM-DM-
BT ip. I can be deduced ha he bulky TMN and HMI
subs i uen s bo h enhance pe meabili y g ea ly, wi h he mo e
igid HMI subs i uen p o iding sligh ly highe selec i i y o e
TMN. The ela i ely small –CF
3
subs i uen s o PIM-TFM-BT ip
and PIM-DTFM-BT ip also enhance pe meabili y ela i e o
unsubs i u ed PIM-BT ip. In e es ingly, he –CF
3
subs i uen s
appea o slow ageing, wi h 54% o he alue o P
O
2
o he
me hanol ea ed ilm o PIM-DTFM-BT ip e ained a e one yea ,
and 56% o PIM-TFM-BT ip, as compa ed o only 30–36% o
ilms wi hou –CF
3
subs i uen s.
Depending on he gas, he s anda d de ia ion o he pe me-
abili y is in he ange 4–18% o he eshly MeOH ea ed
PIM-HMI-T ip and PIM-DM-BT ip ilms, and 3–6% o he aged
PIM-BT ip ilm. These a e small compa ed o he e ec o he
ageing in his wo k, and almos negligible when ep esen ed on
he double-loga i hmic Robeson diag ams (Fig. S6, ESI†).
A hinne ilm o PIM-BT ip (64 mm) demons a es lowe
ini ial pe meabili y a e me hanol ea men , consis en wi h
he well-es ablished end ha hinne ilms age mo e apidly
han hicke ilms.
32,52,53
I is also mo e size selec i e han he
hicke ilm o he same polyme wi h H
2
4CO
2
4He 4O
2
4
CH
4
4N
2
he o de o dec easing gas pe meabili y. Due o he
commonly encoun e ed a iabili y o gas pe meabili y om
diffe ing ilm hicknesses and his o y, da a o a new polyme
a e bes compa ed o hose o exis ing polyme s by using
Robeson plo s (Fig. 2). As no ed, he posi ion o he da a om
a new polyme ela i e o he Robeson uppe bounds p o ides a
use ul indica o o i s po en ial pe o mance as gas sepa a ion
memb anes. All da a poin s o he benzo ip ycene polyme s
lie a abo e he 2008 uppe bounds o O
2
/N
2
(Fig. 2a), H
2
/N
2
(Fig. 2b), H
2
/CH
4
,CO
2
/N
2
(Fig. 2c) and CO
2
/CH
4
(Fig. 2d). Da a
o he B1 yea aged ilms o all o he polyme s lie close o
he p oposed 2015 uppe bound o O
2
/N
2
. In pa icula , aged
PIM-BT ip demons a es excep ional selec i i y o a highly
pe meable polyme so ha i s da a lie well abo e he p oposed
Table 2 Thickness (l, mm), ideal gas pe meabili ies (Px, Ba e ) and selec i i ies o eshly me hanol ea ed and aged ilms measu ed a 25 1C and 1 ba o
eed p essu e
PIM-
a
l
b
P
N2
P
O2
P
CO2
P
CH4
P
H2
P
He
P
O2
/P
N2
P
H2
/P
N2
P
CO2
/P
N2
P
CO2
/P
CH4
BT ip 160 1190 4330 21 500 1690 12 100 4540 3.64 10.2 18.1 12.7
(130)
c,d
160 522 2570 13 200 570 8440 3110 4.92 16.2 25.3 23.2
(253)
c,d
160 401 2170 10 700 411 8930 3400 5.41 22.3 26.7 26.0
(365)
c,d
160 280 1580 8020 282 7160 2810 5.65 25.6 28.6 28.4
(490)
c,d
160 195 1240 6060 203 6380 2650 6.34 32.6 31.0 29.9
(633)
c,d
160 127 935 4350 130 5100 2180 7.36 40.1 34.2 33.5
(718)
e,g
160 112
(4)
838
(48)
3770
(166)
113
(4)
4820
(186)
2150
(64)
7.51
(0.19)
43.2
(0.53)
33.8
(0.53)
33.5
(0.33)
BT ip
d
64 339 1800 9200 412 9430 3960 5.31 27.8 27.1 22.3
(120) 64 200 1160 6040 237 7180 3020 5.79 35.8 30.2 25.5
(253)
d
64 190 1143 5990 225 8080 3490 6.01 42.5 31.5 26.6
(371)
c,d
64 154 997 5150 163 7730 3620 6.47 50.2 33.4 31.6
TMN-T ip 166 3540 10 400 52 800 7250 18 800 6490 2.94 5.31 14.9 7.28
(120) 166 1970 6620 33 300 3130 15 300 5600 3.36 7.77 16.9 10.6
(253) 166 1470 5440 25 900 2030 14 100 5190 3.71 9.59 17.6 12.8
(358) 166 1289 5082 23 648 1751 14 118 5290 3.94 11.0 18.4 13.5
(426) 166 1100 4620 20 400 1440 14 100 5420 4.20 12.8 18.5 14.2
HMI-T ip
d
135 2560 8540 44 200 4870 16 600 5700 3.34 6.48 17.3 9.08
(1)
,g
135 2120
(330)
7380
(989)
39 000
(3680)
3990
(708)
18 400
(1765)
6500
(762)
3.49
(0.14)
8.95
(2.16)
18.6
(1.7)
9.94
(1.44)
(120) 135 1440 5180 26 900 2150 11 800 4240 3.60 8.19 18.7 12.5
(253) 135 972 3930 18 900 1220 10 700 3960 4.04 11.0 19.5 15.6
(358) 135 907 3760 17 404 1083 11 141 4245 4.15 12.3 19.2 16.1
(426) 135 804 3580 16 400 967 11 000 4150 4.45 13.7 20.4 16.9
TFM-BT ip
c,d
176 1830 6210 33 700 2280 13 600 5150 3.39 7.43 18.4 14.8
(123)
c
176 1090 4230 22 100 1250 10 700 4120 3.88 9.82 20.3 17.7
(255)
c
176 875 3640 18 400 953 9870 4050 4.15 11.3 21.0 19.3
(367)
c
176 791 3450 17 000 873 10 100 4170 4.36 12.7 21.5 19.5
(496) 176 722 3260 15 600 792 9760 3920 4.51 13.5 21.6 19.7
DTFM-BT ip 112 3000 7770 42 600 4340 14 700 5860 2.59 4.90 14.2 9.82
(119) 112 1800 5410 29 000 2150 11 300 4690 3.01 6.28 16.1 13.5
(366) 112 1300 4460 22 900 1390 10 700 4590 3.41 8.23 17.5 16.4
(490) 112 864 3490 16 900 890 10 400 4770 4.04 12.1 19.6 19.0
(636) 112 741 3170 14 800 728 10 200 4730 4.27 13.8 20.0 20.3
DM-BT ip
d,
114 1020
(133)
3950
(374)
22 000
(1071)
1570
(85)
11 400
(482)
4000
(354)
3.90
(0.16)
11.3
(1.07)
21.8
(2.5)
14.0
(1.5)
(128)
d
114 521 2640 12 200 599 9870 3650 5.07 18.9 23.4 20.4
a
Numbe in pa en heses is he ageing ime in days a e me hanol ea men .
b
Thickness did no exhibi signi ican changes upon ageing.
c
Da a
de ining he p oposed CO
2
/CH
4
uppe bound.
d
Da a de ining he p oposed CO
2
/N
2
uppe bound.
e
A e age and s anda d de ia ion (in pa en heses)
o ou independen measu emen s o he same aged sample.
A e age and s anda d de ia ion (in pa en heses) o ou independen samples.
g
Da a
no included on Robeson plo s (Fig. 2).
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2015 uppe bounds o O
2
/N
2
(Fig. 2a), H
2
/N
2
(Fig. 2b), and
H
2
/CH
4
. A no able ea u e o he pe meabili y da a om aged
samples o he benzo ip ycene-PIMs on he O
2
/N
2
and H
2
/N
2
Robeson plo s is he nea linea co ela ion a a s eepe slope
han ha o he uppe bounds (Fig. S5, ESI†). This e lec s he a
la ge educ ion o pe meabili ies on ageing o gases composed
o la ge molecules such as N
2
and CH
4
as compa ed o hose
composed o he smalle O
2
and H
2
molecules.
Gas anspo h ough a polyme is desc ibed by he solu ion-
diffusion model
54
wi h P
x
=D
x
S
x
,whe eD
x
is he diffusi i y
coefficien (Table S2, ESI†) and S
x
is he solubili y coefficien
o gas x (Table S3, ESI†). The e o e, he ideal selec i i y (P
x
/P
y
)
o a polyme comes om a combina ion o diffusi i y selec i i y
(D
x
/D
y
) and solubili y selec i i y (S
x
/S
y
). The ema kable posi ions
o he da a o he benzo ip ycene-PIMs on he H
2
/N
2
,andO
2
/N
2
Robeson plo s a e due o e y high diffusi i y selec i i y
o igina ing om he size-sie ing beha iou o he polyme s,
which diffe en ia es be ween gas molecules o diffe ing effec-
i e diame e s (d
x
).
40
This is bes illus a ed by he co ela ion
be ween d
x2
and he diffusi i y coefficien (D
x
),
55
which is
s eepes o PIM-BT ip and less s eep o benzo ip ycene PIMs
ha possess a subs i uen , al hough he absolu e alue o
he diffusion coefficien is la ge (Fig. 3). Ageing dec eases he
diffusion coefficien o all polyme s bu s eepens he co ela ion
be ween d
x2
and D
x
, especially o PIM-BT ip, which is e idence
o i s u he enhanced size selec i i y (Fig. S7, ESI†).
40
The
ex ao dina y pe o mance o PIM-BT ip can be a ibu ed o
i s ul amic opo osi y, which acili a es he diffusi i y o small
Fig. 2 Robeson plo s o he (a) O
2
/N
2
,(b)H
2
/N
2
, (c) CO
2
/N
2
and (d) CO
2
/CH
4
gas pai s showing he posi ion o he gas pe meabili y da a o ilms o
PIM-BT ip ( ), PIM-TMN-T ip ( ), PIM-HMI-T ip ( ), PIM-DM-BT ip ( ), PIM-TFM-BT ip (K) and PIM-DTFM-BT ip ( ). P e iously epo ed da a a e
also shown o non-PIM polyme s (&) and PIMs ( ). Uppe bounds a e ep esen ed by black lines (1991), blue lines (2008), and ed lines o he p e iously
p oposed (2015) uppe bounds o O
2
/N
2
and H
2
/N
2
. The p oposed e ised uppe bounds o CO
2
/N
2
and CO
2
/CH
4
a e shown as do ed ed lines.
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gas molecules, oge he wi h e y high chain igidi y,
16,54
which
hinde s he ac i a ed anspo o la ge gas molecules by
educing he mal mo ions ha allow gaps o o m be ween
oids. The ex eme igidi y o PIM-BT ip accoun s o he e y
high ac i a ion ene gy o he diffusion o la ge gases such as N
2
and CH
4
.
40
The gas anspo p ope ies o PIM-BT ip appea s
simila o hose epo ed o he wo ip ycene-de i ed polyme s,
PIM-T ip-TB
35
and TPIM-1,
33
which we e used o de ine he
p oposed 2015 uppe bounds o O
2
/N
2
,H
2
/N
2
and H
2
/CH
4
.
38
I should be no ed ha he da a om PIM-T ip-TB used o de ine
he 2015 uppe bounds we e aken om a ilm ha was aged o
only 100 days a e me hanol ea men .
35
Recen emeasu e-
men o he gas pe meabili y o his ilm a e 1900 days gi es
da a ha a e also well o e he p oposed 2015 uppe bounds
o O
2
/N
2
(i.e. P
O
2
= 532 Ba e ; P
O
2
/P
N
2
=8.2)andH
2
/N
2
(i.e. P
H
2
=
4430 Ba e ; P
H
2
/P
N
2
= 65). The e o e, he design concep s used
o ob ain he ex ao dina y size selec i i y demons a ed by
PIM-BT ip and PIM-T ip-TB a e likely o p o ide PIMs ha
will p o oke u u e signi ican e isions o he O
2
/N
2
,H
2
/N
2
and H
2
/CH
4
Robeson uppe bounds.
Rede ining he CO
2
/N
2
and CO
2
/CH
4
uppe bounds
Sepa a ions in ol ing CO
2
a e mechanis ically mo e complex
han hose go e ned p edomina ely by diffusi i y selec i i y (e.g.
O
2
/N
2
o H
2
/N
2
)becauseS
CO
2
domina es anspo , especially o
CO
2
/N
2
due o he simila effec i e diame e s o he wo gas
molecules. Typically o PIMs, alues o S
CO
2
/S
N
2
lie in he ange
15–20 whe eas hose o D
CO
2
/D
N
2
lie be ween 0.9–1.5 and hese
alues a e simila o PIMs wi h bo h highe and lowe P
CO
2
pe meabili y. In gene al, solubili y selec i i y ends o emain
ai ly cons an du ing ageing, in con as o he inc eases
obse ed o ideal selec i i y alues o anspo domina ed by
di usi i y selec i i y.
52
Thus, plo ing da a o p e iously
epo ed PIMs on he Robeson plo o CO
2
/N
2
shows many
da a poin s sligh ly abo e he 2008 uppe bound a highe
pe meabili y (P
CO
2
43000 Ba e ) bu ew a lowe alues o
pe meabili y. Indeed, e y ew highly pe meable polyme s
possess a CO
2
/N
2
selec i i y 430,
56–59
which is he lowe limi
o in e es o a i s -pass polyme memb ane o pos -combus ion
ca bon cap u e (Table S1, ESI†).
12
Al hough all o he da a o he benzo ip ycene PIMs a e abo e
he 2008 uppe bound o CO
2
/N
2
, he da a om PIM-BT ip a e
pa icula ly p omising wi h bo h hick and hinne aged ilms
p o iding P
CO
2
44000 Ba e and P
CO
2
/P
N
2
430. The imp essi e
pe o mance o PIM-BT ip appea s o be due o an unusually high
D
CO
2
/D
N
2
o 2.0, whe eas ha o he subs i u ed membe s o he
se ies elies on g ea e S
CO
2
/S
N
2
esul ing om he g ea e numbe
o CO
2
adso p ion si es p o ided by he la ge amoun o in insic
mic opo osi y (Table S3, ESI†).Theele enda apoin son he
Robesonplo om ou diffe en polyme s ha allin oalinea
co ela ion pa allel o ha o he 2008 uppe bound allows us o
p opose a subs an ially imp o ed new uppe bound o CO
2
/N
2
(Fig. 2c and Tables 2 and 3). These da a poin s a e dis ibu ed o e
ala geP
CO
2
ange o 4400–52 000 Ba e .
In addi ion, he da a o all o he benzo ip ycene PIMs lie
well abo e he 2008 uppe bound o CO
2
/CH
4
a a highe
selec i i y han hose o p e iously epo ed polyme s. Indeed,
only da a o he highly igid ‘‘in e molecula ly-locked’’ de i a-
i e o PIM-1 (PIM-C1)
60
and PIM-SBF-2
43
come close o hose o
he benzo ip ycene PIMs (Table S1, ESI†). This excep ional
pe o mance appea s due o a combina ion o bo h high
diffusi i y selec i i y, wi h D
CO
2
/D
CH
4
in he ange 5.7–9.5 o
aged ilms, and good solubili y selec i i y (S
CO
2
/S
CH
4
43).
Ten da a poin s om wo di e en polyme s allows us o
p opose a new uppe bound o CO
2
/CH
4
pa allel o ha o
2008 (Fig. 2d and Tables 2 and 3). The benzo ip ycene PIMs ha
ei he de ine o p o ide da a ha a e e y close o his e ised
uppe bound a e ei he unsubs i u ed (PIM-BT ip) o possess
only small subs i uen s (i.e. PIM-DM-BT ip; PIM-TFM-BT ip and
PIM-DTFM-BT ip). In con as , hose possessing la ge cyclic
solubilising g oups (i.e. PIM-TMN-T ip and PIM-HMI-T ip) a e
sligh ly less selec i e.
When de ining his 2008 CO
2
/CH
4
uppe bound, Robeson
no ed ha da a o a se ies o The mally Rea anged (TR)
Fig. 3 Plo o diffusi i y coefficien (D
x
) e sus d
x2
(whe e d
x
= effec i e
diame e o gas molecule x: He = 1.78; H
2
= 2.14; O
2
= 2.89; CO
2
= 3.02;
N
2
=3.04;CH
4
= 3.18 Å)
55
o eshly me hanol ea ed ilms o PIM-BT ip
(), PIM-TMN-T ip ( ), PIM-HMI-T ip ( ), PIM-DM-BT ip ( ). Da a o
PIM-TFM-BT ip and PIM-DTFM-BT ip a e no shown o cla i y bu a e e y
simila o hose o PIM-TMN-T ip and PIM-HMI-T ip, espec i ely.
Table 3 Fi ing pa ame e s o he 2008 and p oposed CO
2
/N
2
and CO
2
/
CH
4
uppe bounds using he o mula P
x
=ka
xy
n
(whe e P
x
is pe meabili y
(Ba e ) o he mos pe meable x-gas, kis he on ac o (Ba e ), a
xy
is he
selec i i y o x/y gas pai , and nis he slope)
k(Ba e ) n
Robeson 2008 uppe bounds
24
CO
2
/CH
4
5.369 10
6
2.636
CO
2
/N
2
30.967 10
6
2.888
P oposed uppe bounds
CO
2
/CH
4
22.584 10
6
2.401
CO
2
/N
2
755.58 10
6
3.409
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polyme s, epo ed by Pa k e al.,
15,61
‘‘wi h excep ional CO
2
/CH
4
sepa a ion capabili ies’’,
24
appea ed o o m an uppe bound
abo e ha p oposed o solu ion p ocessable polyme s. Such
insoluble ne wo k polyme s as he TR polyme s o en pe o m
abo e he 2008 uppe bounds de ined o solu ion p ocessable
polyme s due o hei igidi y app oaching ha o ca bon mole-
cula sie es (i.e. polyme s ca bonised a high empe a u es).
Rema kably, he CO
2
/CH
4
uppe bound de ined by he solu ion
p ocessable benzo ip ycene-based PIMs lies a he same posi-
ion as ha o Robeson’s en a i ely p oposed TR polyme
uppe bound wi h a selec i i y 2.5 imes highe han ha o
he 2008 uppe bound.
Conclusions
The benzo ip ycene-based PIMs p o ide excep ional gas
pe meabili y da a o mos impo an gas pai s and allow o
he ede ini ion o he CO
2
/CH
4
and CO
2
/N
2
Robeson uppe
bounds. This is impo an in o de o se aspi a ional a ge s
o chemis s in he design and syn hesis o no el polyme s. In
addi ion, i will help pa ame ic s udies o ene gy and cos
efficiency o ca bon cap u e and na u al/bio gas upg ading by
p o iding enhanced bu ealis ic s a e-o - he-a alues o
memb ane pe meabili y and selec i i y. The esul ing es ima es
o ene gy efficiencies and cos s will be mo e a ac i e ela i e
o bo h p e ious calcula ions o memb ane sys ems and o
compe i i e CO
2
sepa a ion p ocesses. The esul ing imp o ed
c edibili y o polyme memb anes o hese c ucial sepa a ions
will s imula e esea ch ac i i y in his echnological a ea o
p ime impo ance o ene gy and he en i onmen .
Con lic s o in e es
The e a e no con lic s o in e es o decla e.
Acknowledgemen s
The esea ch leading o hese esul s has ecei ed unding om
he EU FP7 F amewo k P og am unde g an ag eemen no.
608490, p ojec M
4
CO
2
and om he EPSRC (UK) g an numbe s
EP/M01486X/1, EP/R000468/1 and EP/K008102/2.
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