Melt Synthesis, Structural, Characterization and Scaling of Swelling 2:1-Layer Silicate Materials

Mel Syn hesis,S uc u al,Cha ac e iza ionand Scalingo Swelling2:1Laye Silica eMa e ials  Disse a ion zu E langung des akademischen G ades eines Dok o s de Na u wissenscha en (D . e . na ) an de Fakul ä ü Biologie, Chemie und Geowissenscha en de Uni e si ä Bay eu h o geleg on Hussein Kalo aus Aleppo (Sy ia) Bay eu h 2012 Mel Syn hesis,S uc u al,Cha ac e iza ionand Scalingo Swelling2:1Laye Silica eMa e ials Disse a ion zu E langung des akademischen G ades eines Dok o s de Na u wissenscha en (D . e . na ) an de Fakul ä ü Biologie, Chemie und Geowissenscha en de Uni e si ä Bay eu h o geleg on Hussein Kalo aus Aleppo (Sy ia) Bay eu h 2012 Die o liegende A bei wu de in de Zei on Mä z 2007 bis Mai 2012 in Bay eu h am Leh s uhl Ano ganische Chemie I un e Be euung on He n P o . D . Jose B eu ange e ig . Volls ändige Abd uck de on de Fakul ä ü 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 . a . na .). Disse a ion einge eich am: 08.06.2012 Zulassung du ch die P ü ungskommission: 09.08.2012 Wissenscha liches Kolloquium: Am ie ende Dekanin: P o . D . Bea e Lohne P ü ungsausschuss: P o . D . J. B eu (E s gu ach e ) P o . D . J. Senke (Zwei gu ach e ) P o . D . H. Kepple P o . D . G. Papas a ou This hesis is dedica ed o my pa en s o hei lo e and endless suppo My since e acknowledgemen o my supe iso P o esso D . Jose B eu o his guidance, encou agemen and en husias ic suppo du ing he cou se o his esea ch p og am. Acknowledgemen This hesis is a cumula i e esul a e yea s o esea ch since joining P o . B eu’s g oup in 2007. I ha e wo ked wi h a la ge numbe o people who con ibu ed in a ious ways o my esea ch. I would like o ake he chance o exp ess my g a i ude o all o hem in my unassuming acknowledgmen . My g a e ul g a i ude o he ou s anding suppo and guidance goes o my supe iso P o . D . Jose B eu. He was always a g ea sou ce o mo i a ion and guidance du ing my esea ch. I would also like o deeply hank D . Wol gang Milius o his ad ice, scien i ic discussions, and supe ision in single c ys al e inemen . My hanks goes o my p e ious cowo ke s; Michael Mölle o s udying he hyd a ion beha io in he humidi y chambe and o SEM images, and o Daniel Kunz o AFM imaging. Du ing my academic s udy pe iod I was lucky o mee many people who helped me in di e en ways, in pa icula D . Micheal Schü z and D . Dunja Hi semann. I would like o hank my colleagues in he labo a o y; Ma hias S ö e and Jose Hausne , and he en i e ACI g oup. Many hanks goes o he echnical s a ; M . Be nha d Pu z who augh me how o ope a e he equency u nace echnology and o all o he help ul people who p o ided di e en measu emen s and help, especially o Bea e Boje , Die e Will, Sonja Lu schinge , and Lena Geiling. My g ea app ecia ion goes o my p o esso s back home a Uni e si y o Aleppo; Nawza Nabgaly. Abdalah Wi e, Mohammad Abd AL-ma iy. I wan o exp ess my g a i ude o my amily o he suppo and encou agemen . I am g a e ul o he unending lo e and suppo I ecei e om my pa en s, my wi e, my sis e s and my b o he s. Finally, I would like o hank he minis y o highe educa ion in Sy ia, Uni e si y o Aleppo, o sponso ing my g adua e s udies. Con en 1. Summa y – Zusammen assung . . . . . . . . . . . . . . . . . . . . . . 1 2. In oduc ion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 2.1. S uc u e o clay mine als . . . . . . . . . . . . . . . . . . . . . . 6 2.2. P ope ies and cha ac e iza ion o swelling 2:1-laye silica e . . . . . . . . 8 2.3. Syn hesis o swelling 2:1-laye silica e . . . . . . . . . . . . . . . . 9 2.4. Applica ion o laye silica e . . . . . . . . . . . . . . . . . . . . . 11 3. Synopsis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 3.1. Mo i a ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 3.2. Single c ys al s uc u e o hyd a e sodium luo ohec o i e . . . . . . . . . 13 3.3. La ge scale mel -syn hesis o sodium- luo ohec o i e . . . . . . . . . . 16 3.4. Syn hesis o li hium- luo ohec o i e . . . . . . . . . . . . . . . . . . 19 3.5. Syn hesis and s uc u e o hyd a e sodium b i le mica . . . . . . . . . . 22 4. Bibliog aphy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 5. Indi idual con ibu ions o join publica ions . . . . . . . . . . . . . . . . . 28 5.1. Appendix 1. C ys al s uc u e o hyd a e syn he ic sodium- luo ohec o i e . . 30 5.2. Appendix 2. La ge scale mel -syn hesis o sodium- luo ohec o i e. . . . . . 55 5.3. Appendix 3. Syn hesis o li hium luo ohec o i e . . . . . . . . . . . . 63 5.4. Appendix 4. C ys al s uc u e o hyd a e sodium b i le mica . . . . . . . 83 6. Cu iculum i ae . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104 7. Lis o publica ion . . . . . . . . . . . . . . . . . . . . . . . . . . . 105 8. Decla a ion/E klä ung . . . . . . . . . . . . . . . . . . . . . . . . . . 107 Summa y - Zusammen assung 1 Summa y – Zusammen assung Summa y Mel syn hesis, cha ac e iza ion, and e inemen o single c ys al s uc u es o swelling 2:1- laye silica es we e he main undamen al opics o he p esen ed hesis. In pa icula , la ge scale syn heses o bo h li hium and sodium luo ohec o i e we e success ully achie ed. Fu he mo e, he c ys al s uc u e o one-, and wo-laye hyd a e o sodium luo ohec o i e and he one-laye hyd a e o sodium b i le mica we e ho oughly in es iga ed and cha ac e ized in de ail. Swelling sodium luo ohec o i e wi h good c ys allini y in an ideal composi ion o Na0.85[Mg2.15Li0.85]Si4O10F2 was syn hesized o in es iga ing he hyd a ed s uc u e. Mel syn hesis was done in closed molybdenum c ucibles using pu e eagen s (glass wi h composi ion Na2O-2SiO2, Li2SiO3 MgF2, MgO, SiO2). The c ys al s uc u es o one- and wo- laye hyd a e o sodium luo ohec o i e we e s udied. The one-laye hyd a e o sodium luo ohec o i e (a ela i e humidi y 45 %) showed wo planes o in e laye sodium along [100]. The wo-laye hyd a e o sodium luo ohec o i e showed sodium in e laye ca ions being loca ed in he middle o he in e laye . In addi ion, sodium b i le mica wi h a a ge composi ion Na4[Mg6]Si4Al4O20F4 was success ully syn hesized ia mel syn hesis in a gas igh molybdenum c ucible and he e inemen o he one-laye hyd a e o sodium b i le mica was done. The syn he ic sodium b i le mica swells only o he one-laye hyd a e and could no be u he hyd a ed o he wo- laye hyd a e. Gene ally, na u al swelling laye silica es (smec i es) usually con ain impu i ies such as i on oxide (pigmen a ion ma e ial), qua z, and ca bona e. Howe e , hese impu i ies hinde he employmen o swelling laye silica es in indus y o cu ing edge and ad anced applica ions. In addi ion, hey su e om small pa icle size unde 5 µm limi ing hei aspec a io. Fo indus ial applica ions, pu e syn he ic swelling laye silica es wi h supe io p ope ies a e highly desi able. The e o e, a la ge scale syn hesis o sodium luo ohec o i e Na0.6[Mg2.4Li0.6]Si4O10F2 was ca ied ou in h ee s eps. (i) Syn hesis o glass, glass was used as p ecu so and low mel ing agen , he amo phous glass wi h composi ion Na2O-Li2O-6SiO2 was syn hesized om sodium ca bona e Na2CO3, li hium ca bona e Li2CO3, and silicic acid SiO2·nH2O ia mel syn hesis in an open glassy ca bon c ucible a 1075 °C unde lowing a gon in a high equency induc ion u nace, whe e he empe a u e was inc eased wi h a cons an a e o 300°C/h . (ii) In oduc ion 8 laye silica e ype is close o ze o and a ies in 2:1-laye silica es ype om 0.2 in mon mo illoni e and hec o i e o 2.0 in b i le mica pe o mula uni [1,4]. In Table 1 he laye cha ges and he ideal o mulae o some ypes o laye silica es a e p esen ed [1]. Table 1. Laye cha ge and he ideal o mula o selec ed ypes o phyllosilica es [1]. g oup name cha ge (pe o mula uni ). dioc ahed al ype ioc ahed al ype kaolini e – se pen ine g oup ~ 0 kaolini e (Si2)IV(Al2)VIO5(OH)4 se pen ine (Si2)IV(Mg3)VIO5(OH)4 alc-py ophylli e g oup ~ 0 p y ophylli e (Si4)IV(Al2)VIO10(OH)2 alc (Si4)IV(Mg3)VIO10(OH)2 smec i e g oup ~ 0.2-0.6 mon mo illoni e (Si4)IV(Al2- yMgy)VIO10(OH)2,yM+·nH2O beidelli e (Si4-xAlx)IV(Al2)VIO10(OH)2, xM+·nH2O hec oi e (Si4)IV(Mg3-yLiy)VIO10(OH)2, yM+·nH2O saponi e (Si4-xAlx)IV(Mg3)VIO10(OH)2, xM+·nH2O e miculi e g oup~ 0.6-0.9 e miculi e (Si4-xAlx)IV(Al2- yMgy)VIO10(OH)2, (x+y)M+· e miculi e (Si4-xAlx)IV(Mg3-yM3+y)VIO10 (OH)2, (x-y)/2Mg2+· ue mica g oup ~ 0.9-1.0 musco i e (Si3Al)IV(Al2)VIO10(OH)2, K+ p hlogopi e (Si3Al)IV(Mg3)VIO10(OH)2 K+ 2.2 Swelling p ope ies o 2:1-laye silica es Swelling laye silica es o he 2:1 amily a e igid 2-dimensional polyanions wi h a ich in ac ys alline eac i i y esul ing om sol a ion and exchange o he in e laye ca ions. Depending on he wa e apou p essu e, he laye cha ge and he ype o in e laye ca ion he 2:1-laye silica e amily o ms di e en hyd a ion s a es wi h one-, wo-, and h ee- o e en ou pseudo-laye o wa e molecules be ween silica e laye s [5-8]. Whe eas, he s epwise inc ease o he in e laye space is a cha ac e is ic o he swelling 2:1-laye silica es wi h in e laye ca ions such as sodium o li hium as shown in Figu e 3. The e ec o he in e laye ca ion on he hyd a ion beha io o smec i es was s udied by Cases e al. o alkaline-ea h me als (e.g. Mg2+, Ca2+, S 2+, and Ba2+) [9]. They obse ed a g adual a ia ion o wa e adso p ion and swelling depending on he hyd a ion en halpy o he ca ion [9]. Be end e al. ha e s udied di e en alkaline me als (e.g. Li+, Na+, Rb+, and Cs+) In oduc ion 9 [10-12] as in e laye ca ion, whe e he a e o in e laye space illing inc eased in ela ion o apou p essu e. E ic Fe age e al. in es iga ed he in luence o laye cha ge and cha ge loca ion on he hyd a ion p ope ies o smec i es and hey ound ha as he laye cha ge was inc eased, he basal spacing shi ed om he wo-laye hyd a e o he one-laye hyd a e a he same ela i e humidi y o bo h mon mo illoni e (cha ge loca ion in oc ahed al shee ) and beidelli e (cha ge loca ion in e ahed al shee ) [13,14]. Figu e 3. S epwise inc ease o he in e laye space o 2:1-laye silica es, d001~ 10 Å e e s o ze o-hyd a ion, d001~12.3 Å o one-laye hyd a e, d001~15.5 Å o wo-laye hyd a e, and d001~18.5 Å o h ee-laye hyd a e. 2.3. Syn hesis o swelling 2:1-laye silica es The mo i a ion o clay syn hesis is o p oduce highly pu e ma e ial a he lowes possible empe a u e wi h ema kable p ope ies such as homogenei y in laye cha ge densi y and high c ys allini y. Fo p epa a ion o syn he ic clay wo main pa hs can be used, ei he wi h a mel syn hesis o by hyd o he mal me hods. 2.3.1. Mel syn hesis The ad an ages o mel syn hesis o laye silica es a e:  Due o subs i u ion o F- anions wi h OH- in mel syn hesis, he ob ained luo o- silica es a e mo e s able a high empe a u e han hyd oxi-silica es. In oduc ion 10  Highly c ys alline laye silica es can be achie ed by using high empe a u e and slow cooling.  The me hod is easie o une o he syn hesis o di e en laye silica es such as Mg2+, Fe2+, Ni2+, and Co2+ ich oc ahed al shee s [15].  Homogenei y in laye cha ge densi y. Di e en me hods a e applied o he syn hesis o laye silica es ia he mel whe e he syn hesis depends on he s a e and ype o s a ing ma e ial such as mine als o ocks, glasses and gels. Fio e e al. has used mine als as p ecu so bu impu i ies we e obse ed in he inal p oduc . In addi ion, glass was used as a s a ing ma e ial as a sou ce o me al and as a low lux agen [15-19]. The mos used s a ing ma e ials a e gels, which can be p epa ed by one o hese h ee me hods: (i) using only o ganic sal s like e ae hoxysilane (TEOS), i-isop opyl alumina es, i on ace ylace ona e, e c [20], (ii) using TEOS and ni a es o Mg2+, Al3+, o Fe3+ ca ions and hea ing he gels a 800 °C o a comple e dehyd a ion [21-23], and inally (iii) using sodium me a-silica e and chlo ide o as sul a e anions [24]. Ne e heless, gels ake longe imes o d y and he d ied gel show he e ogenei y o he elemen dis ibu ion which migh a ec he homogenei y o he laye cha ge o he syn he ic laye silica e. 2.3.2. Hyd o he mal Syn hesis The e a e di e en d awbacks o using hyd o he mal me hods o he syn hesis o laye silica es;  Due o he hyd oxyl con en in syn he ic laye silica es he he mal s abili y o is low (no mo e han 350 °C).  He e ogenei y in he elemen dis ibu ion o he syn he ic ma e ial.  Using low empe a u e gene a es small pa icles  P oduc su e ing a high deg ee o s acking aul . Commonly, he hyd o he mal p ocess equi es long pe iods and p oduces a p oduc wi h a small pa icle size [25]. Fo example hec o i e was syn hesized by Ca ado e al. [26] in hyd o he mal ea men using silica sol, magnesium hyd oxide sol, and li hium luo ide. The mix u e was ea ed unde e lux o 2 days and he p oduc had a maximum pa icle size o 1-2 μm. In oduc ion 11 2.4. Applica ion o laye silica es Laye silica e ma e ials a e ex ensi ely used in di e en indus ial applica ions such as: polyme ille s [27], ca alysis, ce amics, e ac o y b icks, pape , pain , in ag icul u e, and senso s [28]. Table 2 shows some applica ions o di e en laye silica es. Table. 2 Selec ed applica ions o laye silica es in indus y Laye silica es ype Indus y Use mica elec ical indus y pain insula ion UV-, hea -s able, and unde -wa e pain e miculi e building indus y packaging indus y hea insula ion, sound dissipa ion shock p oo ma e ials, he mal p o ec ion smec i e ag icul u e building indus y soil imp o emen an i ic ion agen s o pipe jacking and sha sinking addi ions o conc e e and mo a kaolini e pape , plas ics, ubbe ille alc pape , plas ics, ubbe ille Synopsis 12 3. Synopsis 3.1 Mo i a ion The hyd a es o 2:1-laye silica es a e widely employed and s udied. When he s uc u e o his ype o ma e ials was in es iga ed ypically na u al clay mine als such as e miculi e we e used. S udies on he one-laye hyd a e demons a ed ha he loca ion o he in e laye ca ion is close o a one-side o he e ahed al shee . O he eco ds claimed o show ha he in e laye sodium ca ions a e loca ed in he middle o he in e laye in case o one-laye hyd a e. Ne e heless, he c ys al s uc u e o one-, and wo-laye o hyd a e sodium luo ohec o i e is s ill no well de e mined using comple e single c ys al X- ay di ac ion da a. Figu ing ou he hyd a e s uc u e can, howe e , help inding mo e ad anced applica ions o swelling sodium luo ohec o i e. Addi ionally, sodium b i le mica wi h he ideal composi ion Na4[Mg6]Si4Al4O20(OH,F)4 shows a swelling beha io al hough i has high laye cha ge (4 nega i e cha ge pe o mula uni ). Recen ly sodium b i le mica has d awn a en ion o scien is s due o i s high ca ion exchange capaci y (CEC). Mos o p e ious publica ions conce ning he syn hesis o sodium b i le mica epo ed a syn hesis p ocedu e which p oduces di e en ypes o sodium b i le mica (di e en laye cha ge) and small pa icle size. Howe e , he c ys al s uc u e o he one-laye hyd a e o sodium b i le mica is s ill no well de ined and an e icien syn hesis p ocedu e needs o be es ablished. The p epa a ion o syn he ic 2:1-laye silica es in a mel p ocedu e p oduces well de ined clay wi h much enhanced p ope ies such as:(i) homogenei y o chemical composi ion and laye cha ge densi y (ii) colo less (iii) high aspec a io (i ) la ge pa icles sizes ( ) highly pu e ma e ial ( i) uni o m in ac ys alline eac i i y. The a ia ion o in e laye chemis y gi es a b oad ange o possible unc ionaliza ions and ex olia ion ia osmo ic swelling. The ex olia ion o laye silica es by osmo ic swelling o ex e nal mechanical shea s ess p oduces nano-pla ele s wi h ex emely la ge aspec a ios which may be used in di e en applica ions[29,30]. Fo indus ial applica ions an economically and scalable me hod is highly desi able wi hou ha ing o accep any comp omises in he inal ma e ials p ope ies ega ding aspec a ios and homogenei y o cha ge densi y. Designing a mel syn hesis p ocess o swelling 2:1-laye silica es o Na0.6[Mg2.4Li0.6]Si4O10F2, and li hium luo ohec o i e wi h a pe ec ly uni o m dis ibu ion o isomo phous subs i u ion in an unsealed con aine was no p e iously epo ed. Synopsis 13 3.2. Single c ys al s uc u e o hyd a e o sodium luo ohec o i e Swelling p obably is he mos impo an ea u e o expandable 2:1-laye silica es. The dominan d i ing o ce o wa e up ake is he hyd a ion en halpy o in e laye ca ions ha o cou se a ies wi h cha ge densi y and ype o in e laye ca ion. Fo ue solid solu ion ype clays whe e he cha ge densi y is homogenous he in e cala ion occu s in well de ined s eps as a unc ion o wa e ac i i y [31-34]. The hyd a e s uc u es o 2:1-laye silica es we e s udied applying di e en me hods such as NMR spec oscopy, neu on sca e ing, X- ay di ac ion, and compu e simula ion[35-38]. The compu e simula ion was applied o unde s and he hyd a ion geome y and loca ion o he in e laye ca ion in espec o he lowe and uppe e ahed al shee [10,39,39-42]. Howe e , he e is a limi ed numbe o “single c ys al” e inemen s o hyd a ed phases a ailable in he li e a u e applying some a e occasions o semi-o de ed e miculi es (San a Olalla, Spain and Ca l Moss Ranch, Llano Coun y, Texas) [36,43]. In o de o s udy he s uc u e o hyd a e luo ohec o i e, Na0.85[Mg2.15Li0.85]Si4O10F2 was syn hesized. The syn hesis was done as desc ibed elsewhe e by B eu e al. [44], only he s a ing ma e ials was changed, ins ead o LiF and NaF he li hium me asilica e (Li2SiO3) and sodium o hosilica e (Na2O-2SiO2) (glass) we e used. The syn he ic sodium luo ohec o i e was cha ac e ized ia powde X- ay di ac ion PXRD, wa eleng h dispe si e X- ay WDX and induc i ely coupled plasma a omic emission spec oscopy ICP-AES. The syn he ic sodium luo ohec o i e showed a pu e phase and high c ys allin y, uni o m in ac ys alline eac i i y whe eas he 001 peak o he one-laye hyd a e o sodium luo ohec o i e a 12.5 Å was obse ed as shown in Figu e 4. Synopsis 14 Figu e 4. Powde X- ay di ac ion pa e n o one-laye hyd a e o syn he ic sodium luo ohec o i e Su p isingly, he PXRD o wo-laye hyd a e o syn he ic sodium luo ohec o i e showed ea u es indica ing o de ed s acking, he 02l and 11l peaks obse ed we e ela i ely sha p (Figu e 5). Figu e 5. Powde X- ay di ac ion pa e n o he wo-laye hyd a e o syn he ic sodium luo ohec o i e The single c ys al s uc u e e inemen o he one-laye hyd a e o syn he ic sodium luo ohec o i e showed wo planes o in e laye ca ions (sodium) along he [100] (Figu e 6A). The sodium in e laye ca ions a e loca ed app oxima ely abo e he cen e o hexagonal ca i y Synopsis 15 a he m3 si e. In he case o wo-laye hyd a e he sodium is loca ed in he middle o in e laye (Figu e 6B). The obse ed dis ance be ween he oxygen o wa e and he basal oxygen a oms o he e ahed al shee was 2.90 -3.03Å Figu e 7. Figu e 6. S uc u e o one-, and wo-laye hyd a e o sodium luo ohec o i e p ojec ed along [100] indica ing in pa icula he loca ion o in e laye ca ions Figu e 7. The s uc u e o wo-laye hyd a e o syn he ic sodium luo ohec o i e p esen he hyd ogen bonding be ween in e laye sodium wa e complex and he e ahed al shee s ixing he s acking o de . De ails and u he discussion: Appendix 1: C ys al s uc u e o he hyd a e o syn he ic sodium- luo ohec o i e. Synopsis 16 3.3. La ge scale mel -syn hesis o sodium luo ohec oi e Fo he pu pose o syn hesizing a 2:1-laye silica e wi h an ideal o mula Na0.6[Mg2.4Li0.6]Si4O10F2 in a scalable comme cially in e es ing way, mel syn hesis was ca ied ou in an open glassy ca bon c ucible. The syn hesis p ocedu e a o ded h ee s eps; (i) syn hesis o glass wi h composi ion Na2O-Li2O-6SiO2 a 1075 °C (ii) deca boxyla ion and dehyd a ion o MgCO3 ·Mg(OH)2 x H2O and silicic acid hyd a e, SiO2 ·x H2O wi h a mola a io o MgO/SiO2 = 1.4/2.2 (iii) mixing, g inding, and mel ing o 0.3 mole o he syn he ic glass wi h MgO/SiO2 = 1.4/2.2 and 1 mole o magnesium luo ide in an open glassy ca bon c ucible a 1265 °C o 15 min. The syn hesis equipmen (Figu e 8), including he c ucible, he cooling sys em o he u nace, and he coil o he high equency u nace, was de eloped o ep oduce he ma e ials a low cos . Figu e 8. The u nace used o scaling he syn hesis o he sodium luo ohec o i e. Synopsis 17 The powde X- ay di ac ion o syn he ic sodium luo ohec o i e (Figu e 9) showed uni o m in ac ys alline eac i i y, he basal spacing a ela i e humidi y 30 % was d001=12.3 Å. Figu e 9. PXRD pa e n o syn he ic Na0.6[Mg2.4Li0.6]Si4O10F2 (one laye hyd a e, d001 =12.3 Å). The sodium luo ohec o i e wi h laye cha ge o 0.6 (pe hal o mula uni ) ob ained, s ands ou o (i) phase pu i y as checked by X- ay powde di ac ion (PXRD), (ii) a supe b homogenei y o he cha ge densi y as demons a ed by he s epwise hyd a ion beha io ollowed by in-si u PXRD in a humidi y chambe and he Lagaly me hod wi h alkylammonium exchange [45], (iii) a high ca ion exchange capaci y (CEC) o 136 meq/100g as de e mined by he coppe complex ([Cu( ien)]2+) me hod, and inally (i ) ex emely la ge la e al ex ensions wi h a median alue o he pa icle size o 45 μm as measu ed by s a ic ligh sca e ing (SLS) which was con i med by scanning elec on mic oscopy (SEM) Figu e 10. Bibliog aphy 24 4. Bibliog aphy [1] F.Be gaya, G.Lagaly, Gene al In oduc ion: Clays, Clay Mine als, and Clay science, in Handbook o Clay Sceince, Vol. 1 (Eds.: F.Be gaya, B.K.G.Theng, G.Lagaly), Else ie , Ams e dam 2006. [2] J. B eu, W. Seidl, A. S oll, Diso de in smec i es in dependence o he in e laye ca ion, Zei sch i Fu Ano ganische Und Allgemeine Chemie 2003, 629, 503-515. [3] D. M. Moo e, R. C. Reynolds, X-Ray Di ac ion and he Iden i ica ion and Analysis o Clay Mine als, Ox o d Uni e si y P ess, Ox o d 1997. [4] M. F. B iga i, S. Guggenheim, Mica C ys al Chemis y and he In luence o P essu e, Tempe a u e, and Solid Solu ion on A omis ic Models, Re iews in Mine alogy and Geochemis y 2002, 46, 1-97. [5] L. J. Micho , I. Bihannic, M. Pelle ie , E. Rinne , J. L. Robe , Hyd a ion and swelling o syn he ic Na-saponi es: In luence o laye cha ge, Ame ican Mine alogis 2005, 90, 166-172. [6] P. Komadel, J. H oba iko a, L. Sm cok, B. Koppelhube -Bi schnau, Hyd a ion o educed-cha ge mon mo illoni e, Clay Mine als 2002, 37, 543-550. [7] D. Di aka , D. Manikandan, G. Kalidoss, T. Si akuma , Hyd ogena ion o benzaldehyde o e palladium in e cala ed ben oni e ca alys s: Kine ic s udies, Ca alysis Le e s 2008, 125, 277-282. [8] R. P. Teno io, M. Engelsbe g, J. O. Fossum, G. J. da Sil a, In e cala ed Wa e in Syn he ic Fluo hec o i e Clay, Langmui 2010, 26, 9703-9709. [9] J. M. Cases, I. Be end, M. F ancois, J. P. U io , L. J. Micho , F. Thomas, Mechanism o adso p ion and deso p ion o wa e apo by homoionic mon mo illoni e .3. The Mg2+, Ca2+, S 2+ and Ba2+ exchanged o ms, Clays and Clay Mine als 1997, 45, 8-22. [10] E. S. Boek, P. V. Co eney, N. T. Skippe , Mon e Ca lo molecula modeling s udies o hyd a ed Li-, Na-, and K-smec i es: Unde s anding he ole o po assium as a clay swelling inhibi o , Jou nal o he Ame ican Chemical Socie y 1995, 117, 12608- 12617. [11] J. F ipia , J. Cases, M. F ancois, M. Le ellie , The modynamic and Mic odynamic Beha io o Wa e in Clay Suspensions and Gels, Jou nal o Colloid And In e ace Science 1982, 89, 378-400. [12] I. Be end, J. M. Cases, M. F ancois, J. P. U io , L. Micho , A. Masion, F. Thomas, Mechanism o Adso p ion and Deso p ion o Wa e -Vapo by Homoionic Mon mo illoni es 2. he Li+, Na+, K+, Rb+ and Cs+-Exchanged Fo ms, Clays and Clay Mine als 1995, 43, 324-336. [13] E. Fe age, C. A. Ki k, G. C essey, J. Cuad os, Dehyd a ion o Ca-mon mo illoni e a he c ys al scale. Pa I: S uc u e e olu ion, Ame ican Mine alogis 2007, 92, 994- 1006. [14] E. Fe age, B. Lanson, B. A. Sakha o , N. Geo oy, E. Jacquo , V. A. D i s, In es iga ion o dioc ahed al smec i e hyd a ion p ope ies by modeling o X- ay di ac ion p o iles: In luence o laye cha ge and cha ge loca ion, Ame ican Mine alogis 2007, 92, 1731-1743. [15] Alexande , Baumga ne , Syn hese, Cha ak e isie ung und Modi izie ung on übe gangsme allhal igen Schich silica en, PhD hesis, Uni e si y o Bay eu h, 2008. Bibliog aphy 25 [16] K. Ki ajima, N. Daimon, Syn hesis and Swelling Cha ac e is ics o Li-Taenioli e, Nippon Kagaku Kaishi 1975, 1168-1174. [17] K. Ki ajima, Y. Shinomiya, N. Takusagawa, Syn hesis and Swelling o S -Fluo ine Micas, Chemis y Le e s 1984, 1473-1476. [18] K. Ki ajima, F. Koyama, N. Takusagawa, Syn hesis and Swelling P ope ies o Fluo ine Micas wi h Va iable Laye Cha ges, The Chemical Socie y o Japan, Bulle in 1985, 58, 1325-1326. [19] S. Fio e, F. J. Hue as, F. Hue as, J. Lina es, Smec i e o ma ion in hyoli ic obsidian as in e ed by mic oscopic (SEM-TEM-AEM) in es iga ion, Clay Mine als 2001, 36, 489-500. [20] C. R. Dekimpe, H. Kodama, R. Ri a d, Hyd o he mal Fo ma ion o A Kaolini e-Like P oduc om Nonc ys alline Aluminosilica e Gels, Clays and Clay Mine als 1981, 29, 446-450. [21] A. Deca eau, D. Bonnin, D. Badau au h, R. Cou y, P. Kaise , Syn hesis and C ys allogenesis o Fe ic Smec i e by E olu ion o Si-Fe Cop ecipi a es in Oxidizing Condi ions, Clay Mine als 1987, 22, 207-223. [22] J. T. Klop ogge, L. V. Duong, R. L. F os , A e iew o he syn hesis and cha ac e isa ion o pilla ed clays and ela ed po ous ma e ials o c acking o ege able oils o p oduce bio uels, En i onmen al Geology 2005, 47, 967-981. [23] J. T. Klop ogge, R. Vogels, Hyd o he mal Syn hesis o Ammonium-Beidelli e, Clays and Clay Mine als 1995, 43, 135-137. [24] A. Deca eau, O. G auby, S. Pe i , The ac ual dis ibu ion o oc ahed al ca ions in 2:1 clay mine als: Resul s om clay syn hesis, Applied Clay Science 1992, 7, 147-167. [25] F. Be gaya, K. G. T. Benny, G. Lagaly, Handbook o Clay Science, De elopmen s in Clay Science, Else ie , Ams e dam 2006. [26] K. A. Ca ado, L. Xu, D. M. G ego y, K. Song, S. Sei e , R. E. Bo o, C ys alliza ion o a laye silica e clay as moni o ed by small-angle X- ay sca e ing and NMR, Chemis y o Ma e ials 2000, 12, 3052-3059. [27] L. A. U acki, M. Sepeh , E. Boccale i, Syn he ic, laye nanopa icles o polyme ic nanocomposi es WNCO, Polyme s o Ad anced Technologies 2007, 18, 1-37. [28] C.C.Ha ey, G.Lagaly, Cone ional Applica ion , in Handbook o Clay Sceince, Vol. 1 (Eds.: F.Be gaya, B.K.G.Theng, G.Lagaly), Else ie , Ams e dam 2006. [29] A. Baumga ne , K. Sa le , J. Thun, J. B eu, A ou e o mic opo ous ma e ials h ough oxida i e pilla ing o micas, Angewand e Chemie-In e na ional Edi ion In English 2008, 47, 1640-1644. [30] I. Dekany, L. Tu i, Z. Ki aly, CdS, TiO2 and Pd-ci cle nanopa icles g owing in he in e lamella space o mon mo illoni e in bina y liquids, Applied Clay Science 1999, 15, 221-239. [31] N. Maliko a, E. Dubois, V. Ma y, B. Ro enbe g, P. Tu q, Dynamics in Clays - Combining Neu on Sca e ing and Mic oscopic Simula ion, Zei sch i u Physikalische Chemie-In e na ional Jou nal o Resea ch in Physical Chemis y & Chemical Physics 2010, 224, 153-181. Bibliog aphy 26 [32] M. W. Mölle , U. A. Handge, D. A. Kunz, T. Lunkenbein, V. Al s ad , J. B eu, Tailo ing Shea -S i , Mica-like Nanopla ele s, Acs Nano 2010, 4, 717-724. [33] T. J. Tambach, P. G. Bolhuis, E. J. M. Hensen, B. Smi , Hys e esis in clay swelling induced by hyd ogen bonding: Accu a e p edic ion o swelling s a es, Langmui 2006, 22, 1223-1234. [34] E. Fe age, B. Lanson, N. Maliko a, A. Plancon, B. A. Sakha o , V. A. D i s, New insigh s on he dis ibu ion o in e laye wa e in bi-hyd a ed smec i e om X- ay di ac ion p o ile modeling o 00l e lec ions, Chemis y O Ma e ials 2005, 17, 3499-3512. [35] P. G. Slade, P. A. S one, E. W. Radoslo ich, In e laye s uc u es o he wo-laye hyd a es o Na- and Ca- e miculi es, Clays and Clay Mine als 1985, 33, 51-61. [36] H. Shi ozu, S. W. Bailey, C ys al S uc u e o A 2-Laye Mg-Ve miculi e, Ame ican Mine alogis 1966, 51, 1124-1143. [37] N. T. Skippe , A. K. Sope , J. D. C. Mcconnell, The S uc u e o In e laye Wa e in Ve miculi e, Jou nal o Chemical Physics 1991, 94, 5751-5760. [38] N. T. Skippe , A. K. Sope , M. V. Smalley, Neu on-Di ac ion S udy o Calcium Ve miculi e - Hyd a ion o Calcium-Ions in A Con ined En i onmen , Jou nal o Physical Chemis y 1994, 98, 942-945. [39] N. T. Skippe , K. Re son, J. D. C. Mcconnell, Compu e -Simula ion o In e laye Wa e in 2-1 Clays, Jou nal o Chemical Physics 1991, 94, 7434-7445. [40] N. T. Skippe , F. R. C. Chang, G. Sposi o, Mon e-Ca lo Simula ion o In e laye Molecula -S uc u e in Swelling Clay-Mine als .1. Me hodology, Clays Clay Mine . 1995, 43, 285-293. [41] F. R. C. Chang, N. T. Skippe , G. Sposi o, Compu e -Simula ion o In e laye Molecula -S uc u e in Sodium Mon mo illoni e Hyd a es, Langmui 1995, 11, 2734- 2741. [42] N. T. Skippe , Compu e simula ion o aqueous po e luids in 2 : 1 clay mine als, Mine alogical Magazine 1998, 62, 657-667. [43] A. A guelles, M. Leoni, J. A. Blanco, C. Ma cos, Semi-o de ed c ys alline s uc u e o he San a Olalla e miculi e in e ed om X- ay powde di ac ion, Ame ican Mine alogis 2010, 95, 126-134. [44] J. B eu, W. Seidl, A. J. S oll, K. G. Lange, T. U. P obs , Cha ge homogenei y in syn he ic luo ohec o i e, Chemis y O Ma e ials 2001, 13, 4213-4220. [45] A. R. Me mu , G. Lagaly, Baseline s udies o The Clay Mine als Socie y Sou ce Clays: Laye -cha ge de e mina ion and cha ac e is ics o hose mine als con aining 2 : 1 laye s, Clays and Clay Mine als 2001, 49, 393-397. [46] M. K. Mu hy, F. A. Hummel, Phase Equilib ia in he Sys em Li hium Me asilica e - Fo s e i e-Silica, Jou nal o he Ame ican Ce amic Socie y 1955, 38, 55-63. [47] S. Ta u a, T. Ichinose, T. Yamaguchi, K. Ki ajima, P epa a ion o anspa en li hium- mica glass-ce amics, Jou nal O Non-C ys alline Solids 2006, 352, 5556-5563. [48] T. Kodama, Y. Ha ada, M. Ueda, K. Shimizu, K. Shu o, S. Koma neni, W. Ho baue , H. Schneide , C ys al-size con ol and cha ac e iza ion o Na-4-mica p epa ed om kaolini e, Jou nal o Ma e ials Chemis y 2001, 11, 1222-1227. Bibliog aphy 27 [49] M. D. Alba, M. A. Cas o, M. Na anjo, E. Pa on, Hyd o he mal eac i i y o Na-n- micas (n=2, 3, 4), Chemis y O Ma e ials 2006, 18, 2867-2872. [50] M. Pa k, D. H. Lee, C. L. Choi, S. S. Kim, K. S. Kim, J. Choi, Pu e Na-4-mica: Syn hesis and cha ac e iza ion, Chemis y O Ma e ials 2002, 14, 2582-2589. [51] M. G ego kiewi z, J. A. Rausellcolom, Cha ac e iza ion and P ope ies o A New Syn he ic Silica e wi h Highly Cha ged Mica-Type Laye s, Ame ican Mine alogis 1987, 72, 515-527. [52] T. Kodama, S. Koma neni, Na-4-mica: Cd2+, Ni2+, Co2+, Mn2+ and Zn2+ ion exchange, Jou nal o Ma e ials Chemis y 1999, 9, 533-539. [53] T. Kodama, S. Koma neni, W. Ho baue , H. Schneide , Na-4-mica: simpli ied syn hesis om kaolini e, cha ac e iza ion and Zn, Cd, Pb, Cu and Ba up ake kine ics, Jou nal o Ma e ials Chemis y 2000, 10, 1649-1653. [54] W. J. Paulus, S. Koma neni, R. Roy, Bulk Syn hesis and Selec i e Exchange o S on ium Ions in Na4Mg6Al4Si4O20F4 Mica, Na u e 1992, 357, 571-573. [55] W. H. Bau , Compu e -Simula ed C ys al-S uc u es o Obse ed and Hypo he ical Mg2SiO4 Polymo phs o Low and High-Densi y, Ame ican Mine alogis 1972, 57, 709-&. [56] W. Bo che , K. Jü gen, Bei äge zu Reak ions ähigkei de Silika e bei nied igen Tempe a u en, Con ibu ions o Mine alogy and Pe ology 1947, 1, 17-30. Indi idual con ibu ions o Join Publica ions 28 5. Indi idual con ibu ions o Join Publica ions: The publica ions/manusc ip s, which a e p esen ed in he appendix, we e ob ained in coope a ion wi h o he co-wo ke s a di e en depa men s. My con ibu ions o each publica ion a e speci ied below and he as e isk deno es he co esponding au ho (s). 5.1- Appendix 1. This wo k was submi ed o RSC Ad ance unde he i le “Single C ys al S uc u e Re inemen o One- and Two-laye Hyd a e o Sodium-Fluo ohec o i e”. By Hussein Kalo, Wol gang Milius, Jose B eu*. ¾ I ha e pe o med he syn hesis, cha ac e iza ion, and single c ys al measu emen in addi ion o w i ing he manusc ip . ¾ D . Wol gang Milius pe o med he e inemen o one-laye hyd a e o sodium luo ohec o i e and also con ibu ed o he scien i ic discussion. ¾ P o . Jose B eu con ibu ed o he scien i ic discussion. 5.2- Appendix 2: This wo k was published in Applied Clay Science unde he i le “La ge scale mel - syn hesis in an open c ucible o Na- luo ohec o i e wi h supe b cha ge homogenei y and pa icle size”. By Hussein Kalo, Michael W. Mölle , Mazen Ziadeh, Da id Dolejš, Jose B eu*. ¾ I ha e pe o med he syn hesis, cha ac e iza ion o sodium luo ohec o i e, and he scaling p ocedu e in addi ion o w i ing he manusc ip . ¾ Michael W. Mölle pe o med he swelling e alua ion p ocedu e in he humidi y chambe . ¾ Da id Dolejš pe o med he he modynamics calcula ion and e alua ion o he phase diag am. ¾ Mazen Ziadeh p o ided language help. ¾ P o . Jose B eu con ibu ed o he scien i ic discussion. 5.3- Appendix 3: This wo k submi ed o Nanoscale unde he i le “How o Maximize he Aspec Ra io o Clay Nanopla ele s”. By Hussein Kalo, Michael W. Mölle , Daniel A. Kunz, and Jose B eu*. Indi idual con ibu ions o Join Publica ions 29 ¾ I ha e pe o med he syn hesis, cha ac e iza ion o sodium luo ohec o i e and subsequen ly he scaling p ocedu e and he scien i ic w i ing. ¾ Michael W. Mölle conduc ed he swelling e alua ion in he humidi y chambe . ¾ Daniel A. Kunz made he a omic o ce mic oscope AFM measu emen . ¾ P o . Jose B eu con ibu ed o he scien i ic discussion. 5.4- Appendix 4: This wo k submi ed o Jou nal o Solid S a e Chemis y unde he i le “Syn hesis and Single C ys al S uc u e o he One-laye hyd a e o Sodium B i le Mica“. By Hussein Kalo, Wol gang Milius, Michael B äu and Jose B eu*. ¾ I ha e pe o med he syn hesis, cha ac e iza ion, single c ys al measu emen s and e inemen s, in addi ion o he scien i ic w i ing. ¾ D . Wol gang Milius con ibu ed o he e inemen discussion. ¾ D . Michael B äu con ibu ed o he winning discussion. ¾ P o . Jose B eu con ibu ed o he scien i ic discussion. Appendix 30 Appendix 1 Single C ys al S uc u e Re inemen o One- and Two-laye Hyd a e o Sodium-Fluo ohec o i e Hussein Kalo, Wol gang Milius, Jose B eu* Depa men o Ino ganic chemis y I, Uni e si y o Bay eu h, D-95440 Bay eu h, Ge many Run i le: c ys al s uc u e o hyd a e Sodium-Fluo ohec o i e Co esponding au ho : P o . D . Jose B eu Uni e si ä ss . 30 95440 Bay eu h Ge many * E-mail add ess: [email p o ec ed] RSC Ad ance, DOI: 10.1039/C2RA20457F C ys al s uc u e o hyd a e Sodium- luo ohec o i e 31 Single C ys al S uc u e Re inemen o One- and Two-laye Hyd a e o Sodium- Fluo ohec o i e Hussein Kalo, Wol gang Milius and Jose B eu* Leh s uhl ü Ano ganische Chemie I, Uni e si ä Bay eu h, D-95440 Bay eu h, Ge many * [email p o ec ed] Running i le: s uc u e e inemen o one- and wo-laye hyd a e * Co esponding au ho : P o . D . Jose B eu, Phone: 0049921552531 Fax: 0049921552788 E-mail: [email p o ec ed] Abs ac C ys al s uc u es o bo h, one- and wo-laye hyd a e o sodium luo ohec o i e could be e ined agains single c ys al da a o he i s ime because mel syn hesis yielded a sodium luo ohec o i e showing li le s acking diso de as compa ed o na u al clays. In bo h hyd a e phases, he ela i e shi o adjacen 2:1-laye is ixed by hyd ogen-bonding be ween wa e molecules coo dina ed o in e laye ca ions and basal oxygen a oms o e ahed al shee s encompassing he in e laye space. Despi e some eminiscen di use sca e ing, a decen single c ys al e inemen o he semi-o de ed s uc u e o he one-laye hyd a e could be achie ed e ealing s uc u al de ails o he in e laye space o he i s ime. Fo he wo- laye hyd a e he s uc u al model p oposed o e miculi es could be con i med bu a di e en o de ing pa e n o in e laye [Na(H2O)6]+ is sugges ed. While in he wo-laye hyd a e sodium ca ions eside a he cen e o he in e laye space, in he one-laye hyd a e sodium is displaced om he cen e o he in e laye space ei he owa ds he uppe o owa ds he lowe e ahed al shee . This displacemen allows o coo dina ion o he hexagonal ca i y on one side while he coo dina ion sphe e o sodium is comple ed by h ee coo dina ing wa e molecules on he o he side. These h ee wa e molecules in u n a e in ol ed in hyd ogen bonding o he opposi e e ahed al shee . In oduc ion Hyd a ed (swollen) clays o he 2:1 s uc u e amily (e.g. mon mo illoni e, hec o i e, o e miculi e; o nomencla u e o clay mine als see Ma in e al.1) a e among he mos impo an indus ial mine als. Wo ld p oduc ion o ben oni es ( ocks ich in mon mo illoni e) C ys al s uc u e o hyd a e Sodium- luo ohec o i e 32 in 2006 amoun ed o 13,700,000 me ic ons which we e mos ly used as heological addi i es o d illing luids and ci il enginee ing, as ound y sand binde , and as adso p i e o ins ance in pe li e .2 Mo e ecen ly, mo e ad anced applica ions such as mic opo ous hyb id ma e ials,3,4 unc ional ilms o op oelec onic packaging,5 halogen- ee lame e a dan s,6 and nano ille s in composi es 7 had been es ablished. All hese applica ions depend c ucially on he hyd a ion s a e o he clays and swelling p obably is he mos impo an ea u e o expandable 2:1 laye ed silica es. Despi e he indus ial impo ance o hyd a ed clay phases and despi e in ensi e esea ch o e decades, 8-17 de ails o he one-laye hyd a e s uc u e a e unde deba e. This is due o wo handicaps in insic o na u al clays: Hyd a ion is c i ically dependen on wo ac o s, he hyd a ion en halpy o in e laye ca ions and he cha ge densi y. Fo na u al 2:1-clays like mon mo illoni e isomo phic subs i u ion esponsible o he laye cha ge clus e s in o domains and he cha ge densi y is inhomogenous. As a consequence o cha ge he e ogenei y, indi idual in e laye s in any singula clay c ys al will ealize di e en s a es o hyd a ion. I is common ha a a gi en ela i e humidi y ( .h.) ze o-, one-, and wo-laye hyd a es a e ound concomi an ly in he same c ys al. The andom in e s a i ica ion o di e en basal spacings ende s e en a 1-dimensional Fou ie analysis o he elec on densi y dis ibu ion in he in e laye space di icul . Besides in e s a i ica ion, s uc u e solu ion is e en mo e se e ely hampe ed by plana de ec s. In e cala ed wa e ac s as a kind o lub ican and his is why mos hyd a ed clay phases a e u bos a ically diso de ed. Adjacen laye s acked in o a c ys al a e andomly o a ed o shi ed, he phase is no ixed, a uni cell canno be de ined, and sca e ing is comple ely di use. A comp ehensi e desc ip ion o he s uc u e o hese hyd a ed phases would ha e o deli e in o ma ion abou he coo dina ion o in e laye ca ions, he ela i e posi ion/phase ela ionship o adjacen 2:1-laye (in e laye displacemen ),18 and he “in e ac ion” pa e n be ween he in e laye species (ca ions and wa e ) and he basal oxygen a oms comp ising he in e laye . Al hough an amazingly de ailed pic u e o he s uc u e o he in e laye could be de i ed employing 1-dimensional Fou ie syn hesis o X- ay and neu on di ac ion da a, possibly in combina ion wi h NMR da a and di e en compu e simula ion me hods,19-22 expe imen al e idence o in e laye displacemen and speci ic in e ac ions be ween in e laye species and he silica e laye equi e 3-dimensionally o a leas semi-o de ed “c ys als” ha a e only li le a ec ed by plana de ec s (s acking diso de ). The e is, howe e , C ys al s uc u e o hyd a e Sodium- luo ohec o i e 33 only a limi ed numbe o “single c ys al” e inemen s o hyd a ed phases a ailable in he li e a u e applying some a e occasions o semi-o de ed e miculi es (San a Olalla, Spain and Ca l Moss Ranch, Llano Coun y, Texas) showing signi ican ly less s acking aul s and consequen ly much educed di use sca e ing.23,24 In addi ion o emaining s acking diso de , he elec on densi y o hese na u al e miculi es is, howe e , a ec ed by mixed occupa ion o all ca ionic posi ions (oc ahed al, e ahed al, and in e laye ). Consequen ly, c ys al s uc u e e inemen in all cases had o be es ic ed o ce ain classes o e lec ions ha a e leas a ec ed by he s acking diso de pa e ns (k=3n). Diso de pa e ns and s uc u es o wo-laye hyd a es o Na- and Mg- e miculi es was comp ehensi ely discussed by Suque and Pe ze a , and de la Calle e al. applying PXRD and Weissenbe g-came a single c ys al da a.10,11 In hese s udies, he one-laye hyd a e was ound o be comple ely diso de ed and de ails o he in e laye s uc u e could consequen ly no be esol ed. The wo-laye hyd a e was ound o be semi-o de ed and a s uc u al model o he in e laye space was deduced.Please no e, ha all hese “single c ys al” e inemen s used s anda d p og ams ha a e incapable o ake di use sca e ing in o accoun . Consequen ly, he in o ma ion abou diso de pa e ns hidden in he di use sca e ing is igno ed and only he main s uc u e o he 3-dimensionally o de ed olume o he c ys als is e ined. Mo e ecen ly, he Rie eld e inemen o a X- ay powde di ac ion (PXRD) ace o semi-o de ed San a Olalla e miculi e was e ined wi h DIFFaX+, a p og am ha indeed also akes s acking diso de and di use sca e ing in o accoun .25 To educe he complexi y we sough o syn hesize a well o de ed luo o e miculi e ( e miculi e whe e he hyd oxyl g oup is eplaced by luo ine) o nominal composi ion, [Na0.85]in e [Mg2.15Li0.85]oc [Si4] e O10F2, which we p e e o e e o as highly cha ged luo ohec o i e (Na-hec ) (hec o i e whe e he hyd oxyl g oup is eplaced by luo ine) because he ma e ial lacks he Tsche mak subs i u ion ypical o e miculi es. Fo una ely, o his syn he ic Na-hec s acking diso de and hus di use sca e ing a e indeed educed o a le el ha allows a ull c ys al s uc u e e inemen applying all hkl e lec ions deli e ing ull s uc u al de ails o bo h, he one-laye and he wo-laye hyd a es. Expe imen al Sec ion The luo ohec o i e used, was syn hesized ia mel syn hesis.16,26,27 The high pu i y eagen s (in o al ~4 g) o SiO2 (Me ck, ine g anula , calcined), MgF2 (chempu , 99.99%), MgO (al a aesa 99.95 %), Li2SiO3 (al a aesa 99.95 %), and Na2O-2SiO2-glass we e weighed in o a molybdenum c ucible in an A a mosphe e in acco dance wi h a s oichiome ic composi ion C ys al s uc u e o hyd a e Sodium- luo ohec o i e 40 hese di e ences a e due o he di e en ype o clay and cha ge pa e n o whe he i indeed would sugges ha he o ce ield pa ame e s applied would ha e o be u he e ined. Pa o he di e ence can ce ainly also be a ibu ed o he di e en empe a u es ha he da a we e collec ed a . Table 1 C ys allog aphic da a and de ails o he single c ys al s uc u e e inemen s o 1WL and 2WL o syn he ic Na-hec C ys al da a Fo mula uni [Na0.7·xH2O] i n e [Mg2.3Li0.7]oc [Si4] e O10F2 Fo mula weigh = 387.22 (g/mole) (wi hou in e laye wa e ) MoKα adia ion (λ = 0.71073 Å) g aphi e monoch oma o T = 173 K 1WL 2WL a = 5.2434(10) Å a = 5.2432(10) Å b = 9.0891(18) Å b = 9.0870(18) Å c = 12.165(2) Å c = 15.064(3) Å β = 93.92(3)° β = 96.42(3) ° V = 578.4(2) Å3 V = 713.2(2) Å3 Monoclinic. C2/m (No. 12) Monoclinic. C2/m (No. 12) Z = 2 Z = 2 Pla e colo less Pla e colo less 0.25mm x 0.20mm x 0.02mm 0.25mm x 0.20mm x 0.02mm Da a collec ion STOE IPDS I di ac ome e Comple eness o 2θ= 0.98 Comple eness o 2θ = 0.98 2006 measu ed e lec ions 2477 measu ed e lec ions 597 independen e lec ions 734 independen e lec ions 384 e lec ions wi h I>2σ(I) 426 e lec ions wi h I>2σ(I) R in = 0.181 Rin = 0.226 θmax = 25.90° θmax = 25.93° θmin = 3.36° θmin = 2.72 h = -5 → 6 h = -5 → 6 k = -11 → 10 k = -10 → 10 l = -14 → 14 l = -18 → 18 Re inemen applying SHELXTL 5.1 (B uke AXS). Re inemen on F2 Re inemen on F2 R[F2 > 2σ(F2)] = 0.109 R[F2 > 2σ(F2)] = 0.1150 wR(F2) = 0.2881 wR(F2) = 0.2787 S = 1.110 S = 1.042 w = 1/[σ2(Fο2) + (0.20000P)2+0.000P] whe e P = (Fο2 + 2 Fc2)/3 w = 1/[σ2(Fο2) + (0.20000P)2+0.000P] whe e P = (Fο2 + 2 Fc2)/3 Δ ρmax = 1.58 eÅ3 Δ ρmax = 1.12 eÅ3 Δ ρmin = -0.71 eÅ3 Δ ρmin = -0.76 eÅ3 61 pa ame e s 73 pa ame e s C ys al s uc u e o hyd a e Sodium- luo ohec o i e 41 Con a y o he 1WL, o he 2WL he in e laye ca ions eside a he cen al plane o he in e laye space as has been sugges ed by o he s23,31 be o e and also suppo ed by he Fo-map o he in e laye space (see Fig. S4). The ela i e posi ion o lowe and uppe e ahed al shee encompassing he in e laye egion (s acking o de ) as iewed along c* is p esen ed in (Fig. 3A) and (Fig. 3B) o 2WL and 1WL, espec i ely. The obse ed loca ion o sodium ca ions o 1WL and 2WL ela i e o he lowe e ahed al shee is depic ed in (Fig. 4). Fo 2WL uppe and lowe hexagonal ca i y a e s acked ace o ace. Con a y o mica s uc u es whe e his a angemen is assu ed by in e laye ca ions in he cen e in uding in o he hexagonal ca i ies on bo h sides, he ca i ies a e no occupied by in e laye ca ions in he 2WL s uc u e. Ins ead, he Na+ esides abo e he e ahed ons (see also (Fig. S4)). Fig. 3 Compa ison o he ela i e posi ion o lowe (black) and uppe (g ey) e ahed al shee encompassing he in e laye egion (s acking o de ) as iewed a long c*: 2WL (A) and 1WL (B). As poin ed ou by Beye and on Reichenbach31 wo se s o Na+ si es depic ed as m1 and m2 in (Fig. 4A) exis . Wi h a cha ge densi y o x = 1.0 p. .u. only hal o hese possible Na+ si es a e occupied, wi h x = 0.7 p. .u., as we ound o Na-hec , e en less han hal a e occupied. No su p isingly, s uc u e e inemen esul s in an equal s a is ical occupa ion o bo h si es, m1 and m2 as is also ob ious om he Fo-map (see Fig. S5). Beye and on Reichenbach31 ha e p oposed ha m1 and m2 si es a e concomi an ly occupied in he same in e laye space esul ing in zig-zag-chains o edge-sha ing oc ahed al unning along a. Beye and on Reichenbach31 had o p opose his o de ing pa e n in o de o ma ch oc ahed al coo dina ion o Na+ in e laye ca ions wi h a H2O/Na mola a io o only 4. While his mo i is wide- sp ead o µ-hyd oxy-b idges we a e no awa e o o he examples o µ-aquo-b idges o Na+ C ys al s uc u e o hyd a e Sodium- luo ohec o i e 42 in he li e a u e. Mo eo e , we de e mined a H2O/Na mola a io o close o six allowing o p opose isola ed [Na(H2O)6]+. We he e o e sugges ha he elec on densi y seen in he X- ay expe imen is in e p e ed in an al e na i e way: Fo any indi idual in e laye space, ei he pu ely m1 o pu ely m2 si es a e occupied and m1 and m2 in e laye s a e s acked andomly wi h equal p obabili y. Fig. 4 Posi ion o hyd a ed Na+ in e laye ca ions ela i e o lowe hexagonal ca i y; A: 2WL hyd a e he posi ion m1 and m2, B: 1WL hyd a e posi ion m3 along c* p ojec ion. Please no e ha non-occupied m3 si es hos wa e molecules coo dina ed o Na+ in con ac wi h he uppe e ahed al shee . This packing pa e n o [Na(H2O)6]+ complex ca ions is shown in (Fig. 4A). Each Na+ in he in e laye is coo dina ed by six oxygen o wa e (Ow) ( he a e age o Na-Ow bond leng h 2.45 Å). The coo dina ing oxygen a oms a e loca ed in wo sligh ly co uga ed planes abo e and below he plane o Na+ (Fig. 2). As poin ed ou by Beye and on Reichenbach,31 wi h x = 1.0 p .u. wo densely packed planes o in e laye wa e esul (Fig. S6). Howe e , wi h x = 0.7 p. .u., some Na+ si es a e no occupied and he hen non-coo dina ed wa e molecules a e expec ed o elax. This migh explain why Fe age e al.15 had o apply a Gaussian-shaped dis ibu ion in hei 1-dimensional Fou ie syn hesis. Simila ly, A gülles e al.25 in oduced in e s i ial, non-coo dina ed wa e si es. The s acking o de o adjacen 2:1 laye is assu ed by well de ined hyd ogen bonding mo i s be ween in e laye [Na(H2O)6]+ and he silica e laye s. Each coo dina ed wa e molecule is able o connec o one basal oxygen a om o he e ahed al shee ia hyd ogen bonding (Fig. 5). The dis ance be ween he wo oxygen a oms connec ed by hyd ogen bonding was 2.90 - 3.03Å. C ys al s uc u e o hyd a e Sodium- luo ohec o i e 43 Fig. 5 Hyd ogen bonding be ween in e laye [Na(H2O)6]+ and e ahed al shee s ixing he s acking o de in 2WL Na-hec . The s acking o de pu s he basal oxygen a oms o he wo e ahed al shee s encompassing he in e laye space on op o each o he . In o de o allow o concomi an connec ion o he oc ahed al in e laye species o bo h sides o he in e laye space, he wo iangles o oxygen a oms o ming [Na(H2O)6]+ need o be o a ed ela i e o he iangle o he basal oxygens o he e ahed al shee s. As was al eady ob ious om he PXRD ace, he 1WL su e s mo e se e ely om s acking aul s as compa ed o he 2WL. This is in line wi h obse a ions o e miculi e whe e he 1WL ma e ial has been labeled diso de ed.39 Consequen ly, he knowledge o in e laye s uc u es is much mo e limi ed as compa ed o he 2WL. Howe e , as shown in he inse o (Fig. 1), some compa a i ely sha p symme ic e lec ions a e supe imposed on he asymme ic λ-shaped 11/02-band indica ing ha he bulk ma e ial also con ained a iew much be e o de ed c ys als. Applying hese maxima a uni cell could be indexed and e ined e en o he 1WL (a= 5.2430 Å, b= 9.0851 Å, c=12.2150 Å, β=94.24°). By sc eening a la ge numbe o c ys als, we we e able o iden i y ela i ely well o de ed indi iduals ha allowed a single c ys al s uc u e e inemen . The uni cell ound o his single c ys al is in close ag eemen wi h he one e ined om PXRD. As became al eady ob ious om he me ic o he uni cell he s acking o de ound o Na-hec di e ed signi ican ly om wha has been C ys al s uc u e o hyd a e Sodium- luo ohec o i e 44 epo ed o he 1WL o e miculi e.39 While hese au ho s epo a monoclinic angle o 90°, we ge β = 93.92(3)° clea ly indica ing ha he ela i e posi ion o e ahed al shee s encompassing he in e laye space was di e en (Fig. 3B). The hexagonal ca i ies a e no a anged opposi e o each o he bu a e shi ed by 2.62 Å ela i e o each o he co esponding o an in e laye displacemen o a/2. Na+ occupies m3 posi ions (Fig. 4B). As will be explained nex , his shi ing is equi ed o he coo dina ion o he in e laye ca ion by basal oxygen a oms o he wo e ahed al shee s encompassing he in e laye space. In o al 4 Na+ si es, all pa ially occupied (≈ 0.35) a e loca ed in he uni cell. Clea ly, some o he dis ances o wa e si es a e oo sho o be occupied concomi an ly in he same in e laye space. I would no be expec ed ha o de ing o in e laye species in a pa icula in e laye space in luences he o de ing in adjacen in e laye spaces. Howe e , he X- ay beam a e ages wi hin he cohe ence leng h o e all possible posi ions and he elec on densi y is a i icially supe imposed in o an a e age in e laye space. A en a i e assignmen o supe imposed elec on densi ies in o an o de ing pa e n ha makes sense chemically is a emp ed in he ollowing (Fig. 6): The coo dina ion obse ed o Na+ is unusual. I in ol es bo h basal oxygen a oms o he e ahed al shee and in e laye wa e . In he di ec ion o he displacemen o he in e laye ca ion owa ds he e ahed al shee , Na+ esides abo e he hexagonal ca i y and is coo dina ed by 6 basal oxygens wi h dis ances anging be ween 3.22 Å and 3.24 Å. On he opposi e side o he in e laye egion a single siloxan b idge is loca ed a a a he long dis ance o 3.52 Å which was he e o e no ega ded o be pa o he coo dina ion sphe e. The coo dina ion o Na+ is a he comple ed by wa e molecules esiding a he cen al plane esul ing in 9- old coo dina ion ([Na(Ob)6(H2O)3]+). In (Fig. 6) we choose he h ee closes wa e (2.45-2.55 Å) posi ions o be coo dina ed. These h ee oxygen a oms a e in ol ed in hyd ogen bonding o basal oxygens (2.72-3.60 Å). While his in e ac ion pa e n explains why he in e laye space is b idged in a well de ined mode esul ing in he in e laye displacemen o a/2, some a bi a iness emains in he assignmen due o he many al e na i e oxygen posi ions gene a ed by he ou al e na i e Na+ si es clea ly isible in he Fo-map o 1WL (Fig. S3). Also, i was no clea whe he indeed adjacen uppe and lowe Na+ si es a e occupied concomi an ly in he same in e laye o whe he hese al e na e si es a e a he seg ega ed in o di e en in e laye spaces. C ys al s uc u e o hyd a e Sodium- luo ohec o i e 45 Fig. 6 Ten a i e coo dina ion o in e laye Na+ and connec ing mode o adjacen silica e laye s o 1WL o Na-hec . Diso de mode o 1WL Na-hec As has been poin ed ou in he li e a u e, s acking aul s may signi ican ly al e p ope ies and in consequence applica ions o clays.40,41 The e o e, we b ie ly ocus on he di use sca e ing con aining he in o ma ion on such diso de modes. As poin ed be o e, he 2WL s uc u e is only li le e ec ed by diso de and only li le di use sca e ing is appa en in he ecip ocal la ice (Fig. S1, S2). In ag eemen wi h he shape o he PXRD aces (Fig. 1), in he ecip ocal la ice o 1WL di use sca e ing is much mo e p ominen as compa ed o he 2WL. Mo eo e , only some hk- ods a e a ec ed by he diso de while o he s only show sha p B agg e lec ions, sugges ing ha he diso de pa e ns a e commensu a e wi h he la ice ( o compa ison see (Fig.1) in Slade and S one42). Clea ly, 1WL ep esen s a semi-o de ed s uc u e. The mos p ominen semi-o de ed s acking is obse ed o micas whe e ±b/3 shi s occu equen ly and e lec ions wi h k=3n emain sha p. Please no e ha e ahed al o a ion o he syn he ic Na-hec is close o ze o gene a ing an ideal hexagonal pseudo-symme y o in e laye species. The e o e, diso de modes will be a ailable ha a e no easible o e miculi es.24,25 In 1WL a di e en diso de mode was ealized as clea ly indica ed by he dis ibu ion o di use sca e ing in he ecip ocal la ice space: 02l, 42l, 24l, 06l, and 46l a e di use, while 22l, 62l, 04l, 44l, and 26l a e sha p. As shown in (Fig. 7), ansla ions o he uppe laye by combina ions o ±a/4 and ±b/4 c ea e he same en i onmen o he in e laye ca ions sugges ing ha andom shi s o ha ype will gene a e ene ge ically degene a e modes o s acking. This degene acy in u n is esponsible o he s acking diso de obse ed. C ys al s uc u e o hyd a e Sodium- luo ohec o i e 46 Fig. 7 Illus a ion o ene ge ically degene a e s acking modes o semi-o de ed 1WL explaining he obse ed di use sca e ing. T ansla ion o uppe e ahed al shee (g ey) ela i e o lowe e ahed al shee (black) wi h [(+a/4) + (+b/4)] o [(-a/4) + (+b/4)] p o ide a simila en i onmen o in e laye species. Conclusion By mel syn hesis swelling Na-hec could be syn hesized ha upon hyd a ion con e s o semi-o de ed (1WL) and o de ed (2WL) hyd a es. The signi ican educ ion o s acking aul s in hese syn he ic hyd a es allowed o he i s ime o sol e he s uc u e o he one-laye hyd a e. The in e laye ca ions eside o he cen al plane in a 9- old coo dina ion o 6 basal oxygen a oms and h ee wa e molecules. The s acking o de is de e mined by hyd ogen bonding o he la e o he second e ahed al shee . Fo he wo-laye hyd a e s uc u es p oposed o e miculi es in he li e a u e we e in la ge con i med. Howe e , modi ica ions in de ails like o de ing o al e na i e si es o [Na(H2O)6]+ we e sugges ed. Acknowledgemen s The au ho s hank he Baye isches Geoins i u , Bay eu h, Ge many, o he WDX measu emen . This wo k was suppo ed inancially by he g adua e school ‘S uc u e, Reac i i y and P ope ies o Oxide Ma e ials’ wi hin he Eli ene zwe k Baye n, he Deu sche Fo schungsgemeinscha (SFB 840), and he Uni e si y o Aleppo. C ys al s uc u e o hyd a e Sodium- luo ohec o i e 47 1 R. T. Ma in, S. W. Bailey, D. D. Ebe l, D. S. Fanning, S. Guggenheim, H. Kodama, D. R. Pe ea , J. S odon and F. J. Wicks, Clays Clay Mine ., 1991, 39, 333-335. 2 D. D. Eisenhou and R. K. B own, Elemen s, 2009, 5, 83-88. 3 A. Baumga ne , K. Sa le , J. Thun and J. B eu, Angew. Chem. In . Ed., 2008, 47, 1640- 1644. 4 M. S öcke , W. Seidl, L. Sey a h, J. Senke and J. B eu, Chem. Commun., 2008, 629- 631. 5 M. W. Mölle , T. Lunkenbein, H. Kalo, M. Schiede , D. A. Kunz and J. B eu, Ad . Ma e ., 2010, 22, 5245-5249. 6 M. R. Schu z, H. Kalo, T. Lunkenbein, A. H. G oschel, A. H. E. Mulle , C. A. Wilkie and J. B eu, J. Ma e . Chem., 2011, 21, 12110-12116. 7 M. W. Mölle , D. Hi semann, F. Haa mann, J. Senke and J. B eu, Chem. 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Lange and T. U. P obs , Chem. Ma e ., 2001, 13, 4213-4220. 29 S. W. Bailey, Ame . Mine al., 1982, 67, 394-398. 30 J. B eu, W. Seidl and A. S oll, Z. Ano g. Allg. Chem., 2003, 629, 503-515. 31 J. Beye and H. G. on Reichenbach, Clay Mine ., 2002, 37, 157-168. 32 G. M. Sheld ick, Ac a C ys allog . A, 2008, 64, 112-122. 33 C. Delacalle and H. Suque , Re . Mine al., 1988, 19, 455-496. 34 C. Delacalle, A. Plancon, C. H. Pons, J. Dube na , H. Suque and H. Peze a , Clay Mine ., 1984, 19, 563-578. 35 A. Be ghou , D. Tunega and A. Zaoui, Clays Clay Mine ., 2010, 58, 174-187. 36 N. T. Skippe , A. K. Sope and J. D. C. Mcconnell, J. Chem. Phys., 1991, 94, 5751-5760. 37 R. P. Teno io, M. Engelsbe g, J. O. Fossum and G. J. da Sil a, Langmui , 2010, 26, 9703- 9709. 38 E. Fe age, B. A. Sakha o , L. J. Micho , A. Del ille, A. Baue , B. Lanson, S. G angeon, G. F appe , M. Jimenez-Ruiz and G. J. Cuello, J. Phys. Chem. C, 2011, 115, 1867-1881. C ys al s uc u e o hyd a e Sodium- luo ohec o i e 49 39 C. Delacalle, H. Suque and H. Peze a , Clay Mine ., 1985, 20, 221-230. 40 A. Plancon, Clay Mine ., 2001, 36, 1-14. 41 T. Kogu e, J. Elzea-Kogel, C. T. Johns on and D. L. Bish, Clays Clay Mine ., 2010, 58, 62-71. 42 P. G. Slade and P. A. S one, Clays Clay Mine ., 1984, 32, 223-226. La ge scale mel -syn hesis o Sodium- luo ohec o i e 56 La ge scale mel -syn hesis o Sodium- luo ohec o i e 57 La ge scale mel -syn hesis o Sodium- luo ohec o i e 58 La ge scale mel -syn hesis o Sodium- luo ohec o i e 59 La ge scale mel -syn hesis o Sodium- luo ohec o i e 60 La ge scale mel -syn hesis o Sodium- luo ohec o i e 61 La ge scale mel -syn hesis o Sodium- luo ohec o i e 62 Appendix 63 Appendix 3 How o Maximize he Aspec Ra io o Clay Nanopla ele s Hussein Kalo†, Michael W. Mölle †, Daniel A. Kunz† and Jose B eu†* †Leh s uhl ü Ano ganische Chemie I, Uni e si y o Bay eu h, D-95440 Bay eu h, Ge many * Co esponding au ho : P o . D . Jose B eu, Phone: 0049921552531 Fax: 0049921552788 E-mail: [email p o ec ed] Nanoscale, DOI: 10.1039/C2NR31322G Syn hesis o Li hium- luo ohec o i e 64 How o Maximize he Aspec Ra io o Clay Nanopla ele s Hussein Kalo, Michael W. Mölle , Daniel A. Kunz, and Jose B eu* Leh s uhl ü Ano ganische Chemie I, Uni e si y o Bay eu h, D-95440 Bay eu h, Ge many * Co esponding au ho : P o . D . Jose B eu, Phone: 0049921552531 Fax: 0049921552788 E-mail: [email p o ec ed] Abs ac Mel -syn hesis yielded Li hium- luo ohec o i e (Li-hec x) wi h a iable laye cha ge (x = 0.4, 0.6, 0.8, 1.0). Coun e in ui i ely, bo h ac oid diame e and in ac ys alline eac i i y inc eased concomi an ly wi h inc easing laye cha ge. This way hec o i es wi h e y la ge diame e s we e ob ained (d50% = 48 μm) ha ne e heless s ill spon aneously delamina e when imme sed in o wa e and nano-pla ele s wi h huge aspec a ios (> 10000) a e o med. Mel -syn hesis o Li-hec x has been pe o med in an open glassy ca bon c ucible allowing o easy scaling o ba ches o 500g. These unp eceden ed huge aspec a io ille s p omise g ea po en ial o lame e a dan s and ba ie applica ions. Keywo ds: Li- luo ohec o i e, high aspec a io, spon aneous delamina ion, ba ie ille , osmo ic swelling. Syn hesis o Li hium- luo ohec o i e 65 1. In oduc ion Aspec a io o ille s is he key ac o in imp o ing p ope ies o polyme nanocomposi es.1-3 Fo una ely, o clays he in ac ys alline eac i i y allows o ex ensi e a ia ion o p ope ies and unc ions pos syn hesis.4-7 Fo ins ance he ionic conduc i i y may be op imized o ba e y applica ions,8 he mechanical p ope ies o clay pla ele s may be uned by con olled ex olia ion,9 o aspec a ios may be maximized ia osmo ic swelling.10 Ex olia ion in o hinne ac oids o delamina ion in o singula 2:1-lamellae ep esen s an aniso opic op-down p ocess (Figu e 1a) ha deli e s nano-pla ele s wi h la ge aspec a ios α, which o ins ance may be used in gas ba ie applica ions.11,12 Ex olia ion may be igge ed by applying mechanical o ce (pla ele s a e shea ed apa ), which, howe e , concomi an ly always will induce some b eakage o ac oids.3 Aspec a ios will hus only inc ease du ing mechanical agi a ion i shea ing wins o e b eakage (Figu e 1b). Due o compa a i ely high hyd a ion en halpies o selec ed in e laye ca ions, o 2:1 clay mine als spon aneous delamina ion ia osmo ic swelling ep esen s an a ac i e al e na i e o mechanical o ce o maximizing he aspec a io. Nume ous publica ions ocused on he in luence o in e laye ca ions such as Li+, Na+, K+, Mg2+, Ca2+, S 2+, and Ba2+ on he hyd a ion beha iou o swelling laye ed silica es,13,14 and usually he highes deg ee o hyd a ion was obse ed wi h Li+. In ha line, comme cially a ailable syn he ic Li-hec o i es (laponi e- ype clays) a e well known o spon aneous delamina ion. Un o una ely, hyd o he mal syn hesis o hese laponi es yields e y small ac oids (< 30 nm in diame e ) and he e o e e en comple e delamina ion deli e s only medioc e aspec a ios. The e o e, hese ma e ials a e e y good heological addi i es because he numbe o independen pa icles pe mass is high and edge- ace in e ac ions a e dominan in e pa icle in e ac ions in suspension igge ing gelling. Thei pe o mance as ille s is howe e d ead ul because o he low maximum aspec a ios (< 30). Fo high aspec a io nano-pla ele s, he diame e o ac oids ha e i s o be signi ican ly inc eased (Figu e 1c) ollowed by a maximiza ion o α by delamina ion (Figu e 1d). We ha e p e iously shown ha mel syn hesis yields Na-hec o i es wi h la ge ac oid sizes.15,16 While hese Na-hec o i es easily desagglome a ed and ex olia ed in pla ele s o some 10 nm hickness, his ma e ial did no spon aneously delamina e. Na-hec o i es can o coa se easily be con e ed o Li-hec by epea ed exchange wi h Li+ and his way he swelling in wa e can be imp o ed. This ion exchange is, howe e , ime consuming and we he e o e sough a e a di ec access o Li-hec . Syn hesis o Li hium- luo ohec o i e 72 desi ed o mulae (ci ed in pa en hesis) while in he ex he di e en samples a e e e ed o by hei nominal s oichiome y. Table 1. Chemical composi ions o washed syn he ic Li-hec x as de e mined ia AAS and ICP-AES (a e ca ion exchange wi h Co(en)3Cl3·3H2O). sample Mg w % Li w % Si w % Co w % Li-hec 0.4 15.45 (15.48) 1.63 (0.68) 25.00 (27.52) 1.30 (1.93) Li-hec 0.6 14.55 (13.86) 1.72 (0.99) 25.60 (26.70) 1.45 (2.80) Li-hec 0.8 13.35 (12.35) 1.01 (1.28) 24.35 (25.93) 2.26 (3.54) Li-hec 1.0 12.15 (10.91) 1.04 (1.56) 25.95 (25.21) 2.41 (4.41) 3.3. Ca ion exchange capaci y (CEC) De ia ions om he nominal o mula as seen in he chemical analysis will o cou se also g ea ly in luence he CEC. Table 2 lis s he expe imen ally obse ed CECs oge he wi h expec ed alues as calcula ed applying he desi ed o mulae. The p onounced disc epancies be ween expe imen al and calcula ed CECs again we e a ibu ed o bo h, c ys alline and possible amo phous impu i ies. Mo eo e , addi ionally a mino con ibu ion migh o igina e om he in luence o laye edges ha ep esen s oichiome ic de ec s. The e a e nume ous me hods a ailable o he de e mina ion o he CEC,32-34 he mos con enien being colo ime ic me hods applying ca ionic dyes wi h high ex inc ion coe icien s. Please no e ha we could no use he s anda d complex ca ion, [Cu( ien)]2+, since acco ding o Ammann e . al.34 [Cu( ien)]2+ is limi ed o medium and low laye cha ge o s e ic easons. We he e o e a he used [Co(en)3]3+ as dye ha due o i s highe cha ge is capable o also ma ching highe laye cha ge densi ies in a monolaye a angemen . Al hough CECs de ia ed signi ican ly om nominal alues (Table 2) he absolu e alues ne e heless consis en ly inc eased wi h nominal laye cha ge. The CEC o Li-hec 0.6 is close o he alue epo ed o he Co ning hec o i e (122 meq/100g ) o which a o mula o [Li0.56]in e [Mg2.44Li0.56]oc [Si4] e O10F2, has been gi en. As desc ibed in he pa en US 4339540, he Co ning ma e ial was made in a simila app oach: A e g inding he aw ma e ial in a ball mill, he mix u e was mel ed a 1450 °C o 5 h wi hou s i ing. Then he mel was allowed o c ys allize a 700 °C wi hin 4 h. The p oduc was pu i ied by imme sing he c ys allized ma e ial in wa e while s i ing, o emo e soluble impu i ies by washing. Un o una ely, he pa en gi es no in o ma ion wha means had been aken o limi and o coun e balance he loss o Li by ola iliza ion. Gi en he a he long eac ion imes, he e ec mus ha e been p onounced. Syn hesis o Li hium- luo ohec o i e 73 The maximum CEC o 185 meq/100 g obse ed o Li-hec 1.0 is among he highes epo ed CEC in he li e a u e o swelling 2:1 laye ed silica es. Fo compa ison, a comme cial Na- luo o e asilicic mica (nominal laye cha ge x = 1.0 p. .u) wi h an ideal o mula o NaMg2.5Si4O10F2 (COOP Chemicals Co. L d., Somasi ME-100) was epo ed o ha e a CEC o a ound 120 meq/100g.35 Table 2. CECs o syn he ic Li-hec x. Samples Li-hec 0.4 Li-hec 0.6 Li-hec 0.8 Li-hec 1.0 CECexp. (meq/100g) 70 118 130 185 CECcalc. (meq/100g) 106 159 213 268 3.4. Hyd a ion beha iou Since ou ul ima e goal was o ob ain high aspec a io nano- pla ele s by spon aneous delamina ion o Li-hec x in wa e ; hei in ac ys alline eac i i y was in es iga ed in some de ail by s udying hyd a ion in si u in a humidi y chambe . Figu e 3 illus a es he e olu ion o he basal spacings (d- alues o he 001- e lec ion) o Li-hec x as a unc ion o .h. eco ded a 25°C. I is commonly accep ed ha in ac ys alline eac i i y is diminished wi h inc easing laye cha ge. Besides he coulomb a ac ion be ween in e laye species and silica e lamellae, he s a e o hyd a ion is, howe e , de e mined by a second as impo an ac o , he hyd a ion en halpy o he in e laye ca ion. Bo h ac o s will inc ease wi h laye cha ge, because he hyd a ion en halpy will scale wi h he numbe o in e laye ca ions. Wi h in e laye ca ions ha ing high hyd a ion en halpies like Li+ i is he e o e a p io i no clea which o he wo ac o s is going o win and whe he hyd a ion will dec ease as commonly assumed o a he inc ease wi h inc easing laye cha ge. Syn hesis o Li hium- luo ohec o i e 74 Figu e 3. Wa e deso p ion expe imen s o eeze-d ied Li-hec x a) x=0.4, b) x=0.6, c) x=0.8 and d) x=1.0) a 25 °C as moni o ed in a humidi y chambe ia in-si u PXRD. The 2θ- ange, whe e he 001- e lec ion o he di e en hyd a es is expec ed, is eco ded as unc ion o he ela i e humidi y while di ac ion in ensi ies a e gi en as colou code. A ows ma k he d- alues o one-, wo-, and h ee-laye hyd a es. Gene ally, he ansi ion be ween he di e en s a es o hyd a ion o all syn he ic ma e ials was a he sha p and occu ed in s eps a well de ined .h. (Figu e 3). The absence o andomly in e s a i ied in e media es, as equen ly obse ed o na u al mon mo illoni es,36 indica ed a uni o m in ac ys alline eac i i y which in u n suppo ed a homogenous cha ge densi y. In e es ingly, only he ma e ial wi h he highes laye cha ge Li-hec 1.0 adop ed he 3 WL s a e o hyd a ion abo e 80 % .h. (d =18.6 Å) (Figu e 3d). E en wi h p olonged equilib a ion imes a 100 % . h., he 3WL-hyd a e could no be achie ed o he h ee ma e ials wi h lowe cha ge densi ies (Fo comple eness, we no e ha o Li-hec 0.8 ba ely isible aces o 3WL-hyd a e we e obse ed (Figu e 3c)). The maximum hyd a ion s a e achie ed o Li- hec 0.4-0.8 was he 2WL-hyd a e (d= 15.5 Å) (Figu e 3a-c). A ambien condi ions ( .h. < 40 %) all ma e ials adop ed he 1WL-hyd a e (d≈12 Å). Mo eo e , compa ing Li-hec 0.6 wi h Li- hec 0.8 , he la e showed he highe swelling powe as indica ed by he ac ha he ansi ion om he 1WL- o he 2WL-hyd a e was obse ed a lowe .h. These esul s p o e ha o Li- Syn hesis o Li hium- luo ohec o i e 75 hec he swelling powe indeed inc eases wi h he numbe o in e laye ca ions due o he high hyd a ion en halpy o he small li hium ca ion. Figu e 4. Swelling o Li-hec 1.0 a highe wa e ac i i ies. PXRD pa e ns o a ying H2O:Li- hec 1.0 a ios a e shown. To ex end he swelling s udies o he mos eac i e hec o i e o highe wa e ac i i ies, eeze-d ied Li-hec 1.0 was mixed wi h a ying amoun s o wa e . Figu e 4 shows PXRD pa e ns o hese H2O:Li-hec 1.0-mix u es. Wi h inc easing amoun o wa e a ailable in he mix u es, he 00l peaks we e shi ed o lowe di ac ion angle (highe d- alues). This g adual shi o d- alues wi h inc easing wa e ac i i y a ailable, indica ed, ha Li-hec 1.0 migh show osmo ic swelling when suspended in an excess o wa e . Simila o wha has been epo ed by Tamu a e al., 37 e en he highly hyd a ed s a es showed an in eg al se ies o 00l e lec ions. The d00l se ies o he mix u e wi h a a io o wa e o Li- hec x (H2O:Li-hec 1.0) o 3:1 was qui e a ional (d001= 70.1 Å, d002= 35.2 Å, and d003 = 23.8 Å). Wi h a ios o H2O:Li-hec 1.0 o 5:1 and highe he 001 peak is ou o he 2θ- ange ha can be measu ed, bu he 002 peak con inued o be shi ed o highe d- alues wi h inc easing amoun s o wa e a ailable ( o 5:1: d002=44 Å). Syn hesis o Li hium- luo ohec o i e 76 Figu e 5. AFM image (20 µm × 20 µm scan) o a ypical sample o syn he ic Li-hec 1.0. Fo H2O:Li-hec 1.0– a ios > 10 basal e lec ions could no longe be obse ed, indica ing ha he ac oids migh ha e delamina ed. AFM images we e in line wi h his in e p e a ion o he PXRD pa e n as mos ly delamina ed pla ele s could be seen a e suspending Li-hec 1.0 in deionized wa e (Figu e 5) (please see also Fig S1 in suppo ing in o ma ion). Beginning ex olia ion/delamina ion migh ha e al eady been indica ed wi h a ios o H2O:Li-hec 1.0 < 10 by he much b oadened basal e lec ions as compa ed o he 1WL-hyd a e (Figu e 2) ha has no been in con ac wi h liquid wa e . Fo comple ely delamina ed luo ohec o i e a speci ic su ace a ea o 800 m2.g-1 would be expec ed. I is, howe e , well known ha high acuum condi ions equi ed in N2-physiso p ion expe imen s induce massi e e-agg ega ion in o band-like s uc u es and only a mino pa o he po en ial su ace is accessible o he p obe gas. In line wi h his, we measu ed a BET-su ace a ea as low as 12.3 m2.g-1 o a eeze d ied sample o Li-hec 10.38 Syn hesis o Li hium- luo ohec o i e 77 3.5. Pa icle size dis ibu ion. Aspec a ios a e no only de e mined by he hickness o ac oids bu o cou se also by hei diame e (Figu e 1c). Usually he diame e o ac oids o laye ed silica es inc eases wi h inc easing laye cha ge p. .u.38,39 The syn he ic Li-hec x clea ly ollowed his end. As indica ed by SLS measu emen s (Table 3 and Figu e 6), a co ela ion was obse ed be ween median pa icle size and laye cha ge. SEM images o he ma e ials con i med his end (Figu e 7). The SLS measu emen s we e pe o med in aqueous dispe sions; he PSDs he e o e a e ep esen a i e o he bulk ma e ial. Mo eo e , i has been shown by Goossens40 ha he la e al ex ensions o ac oids co ela e well wi h he hyd odynamical adius ob ained om SLS. Conside ing he obse ed median alues o 20 o 40 µm and assuming comple e delamina ion by osmo ic swelling, a e age aspec a ios o hese hec o i es a e ce ainly signi ican ly abo e 1000 and may ange up o mo e han 10000 as con i med by he AFM-images o a ypical sample shown in Figu e 5. Table 3. Median pa icle sizes o syn he ic Li-hec x as measu ed by SLS. Sample Li-hec 0.4 Li-hec 0.6 Li-hec 0.8 Li-hec 1.0 d50% Pa icle size μm (SLS) 19 27 30 48 Figu e 6. Pa icle size dis ibu ions o he Li-hec x as analyzed by SLS. Syn hesis o Li hium- luo ohec o i e 78 Figu e 7. SEM images o p is ine Li-hec x as ob ained by syn hesis (a: x = 0.4; b: x = 0.6; c: x = 0.8; d: x =1.0). 4. Conclusion Mel -syn hesis yielded Li-hec x o a iable laye cha ge. Luckily and somewha coun e in ui i ely, bo h ac oid diame e and in ac ys alline eac i i y inc eased concomi an ly wi h inc easing laye cha ge. This way hec o i es wi h huge ac oid diame e s we e ob ained (d 50% = 48 μm) ha spon aneously delamina ed by osmo ic swelling when imme sed in o deionized wa e . Nano-pla ele s consis ing o a singula 2:1 lamella o app oxima ely 1 nm hickness and a diame e o mo e han 40 μm could hus easily be ob ained. These unp eceden ed huge aspec a io ille s p omise g ea po en ial o lame e a dan s and ba ie applica ion. P oo o concep pape s on ba ie p ope ies and lame e a dancy ha e al eady been published. 2,42,43 Acknowledgemen s This wo k was inancially suppo ed by he Deu sche Fo schungsgemeinscha (SFB 840) and he Uni e si y o Aleppo (Sy ia). Re e ences 1 K. Tamu a, S. Yokoyama, C. S. 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Sepeh and E. Boccale i, Polym. Ad . Technol., 2007, 18, 1-37. 36 K. De ineau, I. Bihannic, L. Micho , F. Villie as, F. Mas ou i, O. Cuisinie , G. F agne o and N. Michau, Appl. Clay Sci., 2006, 31, 76-84. 37 K. Tamu a, T. Sasaki, H. Yamada and H. Nakazawa, Langmui , 1999, 15, 5509-5512. 38 F.Be gaya, B.K.G.Theng and G.Lagaly, Handbook o Clay Science, Else ie , Ams e dam, 2006, ol 1. 39 S. Ta u a, R. Oba a, N. Takusagawa and K. Ki ajima, J. Ma e . Sci., 2005, 40, 5597-5602. 40 A. Meunie , Clay Mine ., 2006, 41, 551-566. 41 D. Goossens, Sedimen ology, 2008, 55, 65-96. 42 M. R. Schü z, H. Kalo, T. Lunkenbein, J. B eu and C. A. Wilkie, Polyme , 2011, 52, 3288-3294. 43 M. W. Mölle , D. A. Kunz, T. Lunkenbein, S. Somme , A. Nennemann and J. B eu, Ad . Ma e ., 2012, 24, 2142-2147. Syn hesis o Li hium- luo ohec o i e 81 TOC: By a no el mel syn hesis hec o i es wi h e y la ge diame e s we e ob ained ha spon aneously delamina e when imme sed in o wa e . These nano-pla ele s wi h unp eceden ed huge aspec a io (> 10000) p omise g ea po en ial as ille s o lame e a dan s and ba ie applica ions. C ys al s uc u e o hyd a e Sodium B i le Mica 88 Fig. 1 A; Cu ’s h ough he econs uc ed ecip ocal space. (A) hk0 showing he h ee domains 1 (blue), 3 ( ed), and 5 (black) ha a e ela ed by he 3- old o a ion axis || [001]. (B) h0l exempla ily showing how each o hese h ee domains is ela ed o a co esponding domain by a 2- old o a ion axis || [001], whe e he 2- old win domains is comple ely o e lap wi h h=3n. The composi ion o he syn he ic Na4-F-mica was de e mined by (WDX) wi h accele a ion ol age 15 kV, and a beam spo diame e o 1 μm on a Joel JXA 8200 spec ome e , which was calib a ed agains ce i ied mine al s anda ds (Si - and adi e Ca3Fe2Si3O12, O - SiO2, F - luo i e CaF2, Na - albi e NaAlSi3O8,Al- Spinel MgAl2O4, Mg- syn he ic Ens a i Mg2[Si2O6]). The coun ing ime was 20 s a he peak posi ion and 10 s on each side o he peak posi ion. The e y same c ys al ha has been used o s uc u e e inemen (Table 1) was ixed in esin on a glass slide and coa ed wi h ca bon. The composi ion o he syn he ic laye ed silica e was no malized o Mg6 pe o mula uni . Addi ionally, he Na+, Mg2+, and Al3+ con en o he bulk ma e ial was con i med independen ly by induc i ely coupled plasma a omic emission spec oscopy (ICP-AES). Two samples o abou 20 mg o d y syn he ic Na4- F-mica we e weighed in o a clean Te lon lask o 150 mL olume. A e addi ion o 1.5 mL 30 w . % HCl (Me ck), 0.5 mL o 85 w . % H3PO4 (Me ck), 0.5 mL 65 w . % HNO3 (Me ck) and 1 mL o 48 w . % HBF4 (Me ck) he sample was diges ed in a MLS 1200 Mega mic owa e diges ion appa a us o 6.5 min and hea ed a 600W (MLS GmbH, Mik owellen- Labo -Sys eme, Leu ki ch, Ge many). The closed sample con aine was cooled o oom empe a u e and he clea solu ion was dilu ed o 100 mL in a olume ic lask and analyzed. The wa e con en o one-laye hyd a ed o Na4-F-mica was de e mined g a ime ically. App oxima ely 100 mg o equilib a ed one-laye hyd a ed samples we e d ied a 250 °C a educed p essu e (2.0*10-2 mba ) o 24 h. The weigh loss du ing d ying was a ibu ed o C ys al s uc u e o hyd a e Sodium B i le Mica 89 in e laye wa e . The ca ion exchange capaci y (CEC) o syn he ic Na4-F-mica was de e mined by he po assium chlo ide me hod. A 0.2 g o syn he ic Na4-F-mica was suspended in 25 mL o dis illed wa e and 1 M po assium chlo ide solu ion was added. The mix u e was shaken o 48h and hen cen i uged, and he supe na an solu ion was collec ed. To ensu e comple e exchange o sodium, he ca ion exchange was epea ed ou mo e imes. The Na+ con en o he collec ed solu ions was de e mined by A omic Abso p ion Spec oscopy (AAS). SEM pic u es a e aken on a LEO 1530 FE-SEM a an ope a ion ol age o 2 kV using in-lens de ec ion modes. 3. Resul s and Discussions 3.1. Syn hesis o Na4-F-mica Fig. 2 shows he PXRD pa e n o ze o-, and one-laye hyd a e o syn he ic Na4-F-mica. Two c ys alline impu i ies could be iden i ied: magnesium o hosilica e (Mg2SiO4) [25] and sodium aluminum silica e Na6Al4Si4O17 [26]. Indexing o bo h di ac og ams was s aigh o wa d and ga e he ollowing uni cell pa ame e s: a= 5.3322 Å, b=9.2477 Å, c=10.0621 Å, β=99.717° and a= 5.3248 Å, b=9.2688 Å, c=12.1597 Å, β=99.054° o ze o-, and one-laye hyd a e, espec i ely. The pa ame e s a e in close ag eemen wi h wha had been published by G ego kiewi z and Rausellcolom [18]: a= 5.34 Å, b=9.24 Å, c=9.97 Å, β=100.3° and a= 5.35 Å, b=9.24 Å, c=12.32 Å, β=98.5 o ze o-, and one-laye hyd a e, espec i ely. Good quali y c ys als wi h li le di use sca e ing could qui e easily be ound o he one- laye hyd a e allowing o s uc u e e inemen s. Sc eening se e al “single c ys als” o he ze o-laye hyd a e, howe e , showed massi e di use sca e ing sugges ing ha ex ended plana diso de migh ha e p e en ed success ul s uc u e e inemen s, much simila o wha has been epo ed by G ego kiewi z and Rausellcolom [18]. Ob iously he s acking o de could be imp o ed signi ican ly wi h hyd a ion sugges ing ha he in e laye wa e helped o b idge he in e laye space in a mo e de ined way and hus ixing he phase o adjacen 2:1- silica e laye s. Despi e he plana de ec s, he ze o-laye hyd a e o Na4-F-mica ne e heless showed uni o m in ac ys alline eac i i y. A a ela i e humidi y o 43 % a a ional 00l se ies wi h a basal spacing o d001= 12.1 Å was obse ed. Nei he was esidual in ensi y a he posi ions o he ze o-laye hyd a e no was any signs o andom in e s a i ica ions ound indica ing a uni o m one-laye hyd a e o syn he ic Na4-F-mica. Fu he hyd a ion s eps o syn he ic Na4-F-mica we e no accessible (see discussion in c ys al s uc u e pa ). C ys al s uc u e o hyd a e Sodium B i le Mica 90 Fig. 2 PXRD o ze o- and one- laye hyd a e p Na4-F-mica. The one-laye wa e hyd a e was measu ed a a ela i e humidi y o 43%. Ticks indica e he impu i y phases: AS: Sodium aluminum silica e Na6Al4Si4O17, MS: Magnesium silica e Mg2SiO4. The a e age chemical composi ion o syn he ic Na4-F-mica as de e mined by WDX o h ee di e en c ys al [Na3.3]in e [Mg6]oc [Si4.7Al3.3] e O20F4. Using ICP-AES he a io o Na+ : Al3+ : Mg2+ was ound o be 3.3 : 6: 3.3. The CEC o syn he ic Na4-F-mica as de e mined ia Na+ in he supe na an a e K+ exchange was 2.40 meq.g-1. SEM mic og aphs showed ha mel syn hesis o Na4-F-mica no only yielded highly c ys alline bu also coa se g ained ma e ial (Fig. 3), con a y o es ablished syn hesis ou es ha epo ed pa icle sizes oo small o pick single c ys als (~5 µm) [5,6]. The wa e con en as de e mined g a ime ically was H2O:Na= 1.6, a a io in close ag eemen wi h wha has been epo ed by Kodama e . al. (1.5) [27]. Fu he mo e, his a io was con i med by he occupa ion ac o s ob ained in he s uc u e e inemen (see discussion below). Fig. 3 SEM images o syn he ic Na4-F-mica. 3.2. Single c ys al s uc u e e inemen C ys allog aphic da a, expe imen al de ails o he s uc u e e inemen , and de ails o he single c ys al s uc u e e inemen o one-laye wa e hyd a e o syn he ic Na4-F-mica a e included in Table 1. Al hough some di use in ensi y was isible in ecip ocal space, a C ys al s uc u e o hyd a e Sodium B i le Mica 91 s anda d single c ys al e inemen p og am was applied ha is no capable o handling di use (non-B agg) sca e ing. Di use sca e ing had o be igno ed bu e inemen was pe o med agains he comple e da a se . A comp ehensi e desc ip ion o he s uc u e o hyd a ed phases o laye ed silica es has o deli e in o ma ion abou he coo dina ion o in e laye ca ions, he ela i e posi ion/phase ela ionship o adjacen 2:1-laye (in e laye displacemen ) [28], and he “in e ac ion” pa e n be ween he in e laye species (ca ions and wa e ) and he basal oxygen a oms comp ising he in e laye . Fo Na4-F-mica ini ial s uc u al models canno be deduced om known mica s uc u e because i is no ob ious whe e he addi ional in e laye ca ions would i in. Ce ainly, he ex a in e laye ca ions will ha e a c ucial in luence he dis o ion o e ahed al shee o sodium b i le mica and ela i e posi ion o uppe and lowe e ahed al shee . To educe he complexi y o s uc u e solu ion and o inc ease he p ecision o he s uc u e e inemen , we sough o syn hesize a well o de ed Na4-F-mica. Fu he mo e, he syn hesis was op imized in o de o yield la ge c ys als Fig. 3 by applying high mel ing p ocedu es and dec easing he cooling a e (as desc ibed in expe imen al sec ion). Fo una ely, o his syn he ic Na4-F-mica s acking diso de and hus di use sca e ing a e indeed educed o a le el ha allows a ull c ys al s uc u e e inemen applying all hkl e lec ions deli e ing ull s uc u al de ails o he one-laye hyd a e. Al hough he s uc u e could be sol ed using he di ac ion o he da a o he main a s able and eliable e inemen was possible only a e ha ing iden i ied all wins igge ed by he high pseudo symme y o he in e laye . G ego kiewi z and Rausellcolom [18] had al eady no iced ha absences a e consis en wi h he assump ion o a win o wo indi iduals wi h a 1M cell and o a ion o 120° be ween hem. They, howe e , missed he second ype o winning ope a ions based on he 2- old o a ion axis. Mo eo e , hey no iced ha Laue symme y 2/m is iola ed which hey in e p e ed educed symme y (1Tc) ins ead o he monoclinic poly ype (1M). As Löwens ein´s ule would equi e an a leas locally o de ed dis ibu ion o an app oxima ely 1:1 a io o Al : Si, we educed he symme y o C 2 applying such an o de ed model. Taking in o accoun Löwens ein´s p inciple o a oidance o Al-O-Al geome ies, he Si4+ and Al3+ subs i u ion in he e ahed al shee was he e o e assumed o be a anged in an o de ed manne allowing each Al3+- e ahed al o be su ounded by h ee Si4+– e ahed al and ice e sa when he Si : Al a io is 1:1 [29,30]. An o de ed a angemen would be expec ed o be co obo a ed by Si-O being signi ican ly sho e han Al-O dis ances (1.63 and 1.78 Å, espec i ely). We see smalle di e ences in hese dis ances in ou e inemen which we C ys al s uc u e o hyd a e Sodium B i le Mica 92 a ibu ed o be ela ed o winning because win ope a ions in e ela e Al3+ and Si4+ si es. Addi ionally, he eal composi ion showed a Al3+ : Si4+- a io < 1 : 1 end hence some Si4+ mus eside on Al3+ -si es. Al e na i ely, he o de ing migh be long ange and he X- ay beam migh be a e aging o e he o de ed domains. The a e age obse ed Si-O and Al-O dis ance we e 1.67 and 1.72 Å, espec i ely and clea ly suppo an o de ed e ahed al shee . Taking in o accoun all six win domains he e inemen o he one-laye hyd a e o Na4-F- mica was s aigh o wa d. A omic displacemen pa ame e s (ADP) o all hea y a oms including he in e laye ca ions and he oxygen a oms o in e laye wa e could e en be e ined aniso opically. This unde lines he good quali y o he da a se s. Occupancies o in e laye ca ions and wa e we e eely e ined. The wa e con en as ob ained by he e inemen is in good ag eed wi h alues de e mined by g a ime ic analysis. F om he occupa ion ac o s ob ained in he e inemen he ollowing composi ions could be calcula ed: [Na3.4·6H2O]in e [Mg6]oc [Si4.6Al3.4] e O20F4. C ys al s uc u e o hyd a e Sodium B i le Mica 93 Table 1. C ys allog aphic da a and expe imen al de ails o he s uc u e e inemen o one- laye wa e hyd a e o syn he ic Na4-F-mica. C ys al da a Fo mula uni [Na3.4]in e [Mg6]oc [Si4.6Al3.4] e O20F4·6H2O Fo mula weigh (anhyd ous) = 822.54 g/mol MoKα adia ion (λ = 0.71073 Å) g aphi e monoch oma o T = 173 K a = 5.3520(11) Å b = 9.2700(19) Å c = 12.145(2) Å β = 98.35(3) ° V = 596.1(2) Å3 Monoclinic. C2 (No. 5) Z = 2 Pla e colo less 0.2 mm x 0.2 mm x 0.05 mm Da a collec ion STOE IPDS I di ac ome e Comple eness o 2 he a= 0.89 1825 measu ed e lec ions 720 me ged e lec ions 307 e lec ions wi h I>2σ(I) R in = 0.087 θmax = 25.33° θmin = 3.39° h = -6 → 6 k = -11 → 10 l = -14 → 14 Re inemen SHELXTL Re inemen on F2 R[F2 > 2σ(F2)] = 0.083 wR(F2) = 0.219 S = 1.31 w = 1/[σ2(Fο2) + (0.10000P)2+10.000P] whe e P = (Fο2 + 2 Fc2)/3 Δ ρmax = 1.691 eÅ3 Δ ρmin = -1.140 eÅ3 117 e ined pa ame e s C ys al s uc u e o hyd a e Sodium B i le Mica 94 3.3. S uc u e o one-laye hyd a e o Na4-F-mica The s uc u e o one-laye hyd a e Na4-F-mica p ojec ed along [100] is shown in Fig. 4. As sugges ed by G ego kiewi z and Rausellcolom [18], he in e laye wa e was ound o loca ed in he middle o he in e laye space. Sodium in e laye ca ions we e displaced om he cen e o he in e laye space owa ds he lowe and uppe e ahed al shee and on each side we e loca ed abo e he cen e o he dis o ed hexagonal ca i y (Fig. 6). Fig. 4 Re ined s uc u e o one-laye hyd a e o Na4-F-mica iewed along [100]. The ela i e posi ion o he lowe and he uppe e ahed al shee was, howe e , c ucially di e en om he s uc u e pu posed by G ego kiewi z and Rausellcolom (compa e Fig. 5 wi h Fig. 7 in e . [18]). This is o cou se no su p ising because he in e laye displacemen canno be de e mined eliably i massi e diso de is p esen . Because o he limi ed quali y o he c ys als a ailable o G ego kiewi z and Rausellcolom he sugges ed in e laye displacemen is e oneous. Un o una ely, his also a ec s de ails o he coo dina ion o in e laye ca ions, and he “in e ac ion” pa e n be ween he in e laye species (ca ions and wa e ) and he basal oxygen a oms comp ising he in e laye . While G ego kiewi z and Rausellcolom p oposed he displacemen o be +b/3, we ound he lowe e ahed al shee in ela ion o he uppe e ahed al shee being shi ed along [100] by app oxima ely +a/2. As poin ed ou by G ego kiewi z and Rausellcolom, ha ing o accommoda e 4 in e laye ca ions pe uni cell excludes a ace- o- ace s acking o he hexagonal ca i ies o he e ahed al shee s. Ra he , adjacen laye s mus be displaced and consequen ly each hexagonal ca i y becomes an independen si e la ge enough o hos a ela i ely small Na+. While bo h, shi s o +b/3 and +a/2 c ea e ou Na+ si es pe uni cell, he coo dina ion en i onmen c ea ed o he in e laye ca ion will be di e en . C ys al s uc u e o hyd a e Sodium B i le Mica 95 Fig. 5 Rela i e posi ion o uppe and lowe e ahed al shee comp ising he in e laye space as iewed along c* (please compa e Fig. 4 o assignmen o T1 and T2). Fig. 6 S uc u e o he hexagonal ca i y o six connec ed e ahed a showing he loca ion o he Na+ in e laye ca ion (m3). The e ahed on o a ion angle (α) was calcula ed applying he equa ion:  ∑120°Φ   , α= 24°. As p e iously obse ed o non-swollen b i le mica, he hexagonal ca i y o Na4-F-mica was ound o be se e ely dis o ed (Fig. 6). This dis o ion o he hexagonal ca i y is ela ed o he p onounced mis i be ween he oc ahed al and he e ahed al shee and also e lec s he ield s eng h o he in e laye ca ion [31]. The α angle o e ahed on o a ion was calcula ed o be α ~24°, while he model sugges ed by G ego kiewi z and Rausellcolom gi es only α =14° [18]. The sodium ca ions a e loca ed in he m3 posi ion abo e he cen e o he dis o ed hexagonal ca i y. The sodium in e laye ca ions a e coo dina ed o h ee basal oxygen a oms o he e ahed al shee (Ob) on one side and on he o he side hey a e coo dina ed o h ee oxygen a oms (Ow) o in e cala ed wa e . The dis ance be ween Na+ and he h ee coo dina ed inne basal oxygen a oms o he e ahed al shee is ~ 2.50 Å, while due o he dis o ion he emaining h ee C ys al s uc u e o hyd a e Sodium B i le Mica 96 oxygen a oms o he same hexagonal ca i y a e signi ican ly u he away (~3.2 Å). The dis ance be ween Na+ and he h ee oxygen a oms o wa e is ~ 2.57 Å, whe e he dis ance o Ow-Ow is 3.1 Å (Fig. 7A). The in e laye Na+ a e hus coo dina ed by h ee planes o oxygen a oms, basal oxygens o lowe and uppe e ahed al shee and he in e laye wa e . Two shee s o isola ed [Na(Ob)3(Ow)3] oc ahed a (blue and yellow in Fig. 7B) a di e en z- alues a e c ea ed, which a e connec ed by sha ed wa e molecules. Blue and yellow each sha e one edge and one co ne which gi es a a io o sodium : wa e o 1:1.5 which in u n co esponds o 5.1 wa e molecules pe uni cell o Na4-F-mica ( he sodium con en is 3.4 mole pe uni cell). This is in good ag eemen wi h he wa e con en as de e mined g a ime ically (5.28 mole wa e pe uni cell). Al hough he in e laye displacemen is di e en he mixed Ow/ Ob coo dina ion o he in e laye ca ion in some espec s esembles mo i s ound o he one- laye hyd a e o a highly cha ged Na-hec o i e [32]. While hese highly cha ged hec o i es like e miculi es eadily hyd a e o he wo-laye hyd a e s a e a highe .h., his was no obse ed o syn he ic Na4-F-mica. This can ce ainly be ela ed o he much highe Coulomb a ac ion. Bu i migh also be ela ed o c ys al chemically easons. In he wo-laye hyd a e o hec o i es and e miculi es, he sodium ca ions in he cen al plane o he in e laye space. I one would ha e o pack ou sodium ca ions pe uni cell in o one plane, he Na+ – Na+ dis ance would be much oo sho (3 Å). Fig. 7 Posi ion o in e laye sodium ca ions, oxygens o he in e laye wa e and oxygens o he e ahed al shee along p ojec ion [001]. A) he lowe oc ahed al shee o [Na(Ob)3(Ow)3] (cyan colo )and B) he lowe and he uppe oc ahed al shee o [Na(Ob)3(Ow)3] (yellow colo ). C ys al s uc u e o hyd a e Sodium B i le Mica 97 3.4. S acking aul s in one-laye hyd a e Na4-F-mica As has been poin ed ou in he li e a u e, s acking aul s may signi ican ly a y p ope ies and in consequence applica ions o clays [33,34]. Clea ly, scanning he ecip ocal la ice space o he one-laye hyd a e o Na4-F-mica e ealed ha he s uc u e has some s acking aul s on op o winning. As obse ed by G ego kiewi z and Rausellcolom [18] e lec ions wi h k=3n a e sha p whe eas all o he hk-bands showed some di use in ensi y pa allel o c* (Fig. 8). This pa e n in ecip ocal space is well known wi h micas and indica es a ce ain deg ee o ±b/3 s acking diso de in he one-laye hyd a e o Na4-F-mica. As shown in Fig. 8, shi s o he uppe laye by ±b/3 c ea e he same en i onmen o he in e laye ca ions sugges ing ha andom shi s o ha ype will gene a e ene ge ically degene a e modes o s acking. This degene acy in u n is esponsible o he s acking diso de obse ed. Mo eo e , since only some hk- ods a e a ec ed by he diso de while o he s only show sha p B agg e lec ions, sugges ing ha he diso de pa e ns a e commensu a e wi h he la ice, e en he domains o one-laye -hyd a e o Na4-F-mica ha su e o diso de a e no u bos a ically diso de ed bu s ill ha e a semi-o de ed s uc u e. The unusual high pseudo-symme y e lec ed in se e al degene a e al e na i e s ackings gene a ing simila coo dina ion o in e laye species ha gi e ise o winning and diso de is “p obing he limi s o he concep “c ys al” as i was ecen ly s a ed in a pape by Ge isch and Ruck [35]. Cu iculum Vi ae 104 Hussein Kalo Kölls . 5 95447 Bay eu h Phone: 00499211612301 Mobile:004917664131900 [email protected] Pe sonal Da a Da a o bi h 04.06.1975 Place o bi h Aleppo Sy ia Family S a us Ma ied N a ionali y Sy ian S udy 03/ 2007 – p esen PhD s uden a depa men o ino ganic chemis y I – uni e si y o Bay eu h. Ti le: „ M el Syn hesis, S uc u al, Cha ac e iza ion and Scaling o Swelling 2:1- L aye Silica e Ma e ials” 05/2004 - 05/2006 Lec u e in Chemis y Depa men a he Facul y o Science and Ci il Enginee ing – uni e si y o Aleppo 11/2001 - 12/2003 M.Sc. Applied chemis y – acul y o science – uni e si y o Aleppo Ti le o p ojec : “manu ac u ing o Silica e ac o y om Sy ian sand” 09/2001 - 06/2000 diploma in applied Chemis y – acul y o science – Uni e si y o Aleppo 09/1996 - 06/2000 Bachelo in applied Chemis y – acul y o science – Uni e si y o Aleppo 09/1995 - 06/1996 Sy ian Baccalau ea e , scien i ic sec ion -Aleppo - Sy ia Publica ion Lis 105 7. Publica ion Lis : The ollowing publica ions a e enclosed in his PhD hesis: 1- Hussein Kalo, Wol gang Milius and Jose B eu, Single C ys al S uc u e Re inemen o One- and Two-laye Hyd a e o Sodium-Fluo ohec o i e. Jou nal o RSC Ad ance, DOI: 10.1039/C2RA20457F. 2- Hussein Kalo, Michael W. Mölle , Mazen Ziadeh, Da id Dolejš and Jose B eu, La ge scale mel -syn hesis in an open c ucible o Na- luo ohec o i e wi h supe b cha ge homogenei y and pa icle size. Applied Clay Science, 2010, 48, 1-2, 1-290. 3- Hussein Kalo, Michael W. Mölle , Daniel A. Kunz and Jose B eu, How o Maximize he Aspec Ra io o Clay Nanopla ele s. Nanoscale, DOI: 10.1039/C2NR31322G. 4- Hussein Kalo, Wol gang Milius, Michael B äu and Jose B eu, Syn hesis and single c ys al s uc u e o hyd a e sodium b i le mica, Hussein kalo, Manusc ip submi ed o Jou nal o Solid S a e Chemis y. 5- Mölle , M.W., Lunkenbein, T., Kalo, H., Schiede , M., Kunz, D.A. and B eu, J. (2010) Ba ie P ope ies o Syn he ic Clay wi h a Kilo-Aspec Ra io. Ad anced Ma e ials, 22, 5245-5249. 6- Mölle , M.W., Lunkenbein, T., Kalo, H., Schiede , M., Kunz, D.A. and B eu, J. (2010) Kilo Aspec Ra io clay pla ele s. Zei sch i ü ano ganische und allgemeine Chemie. 2010, 636, 2113. 7- Schü z, M.R., Kalo, H., Lunkenbein, T., B eu, J. and Wilkie, C.A. (2011a) In umescen - like beha io o polys y ene syn he ic clay nanocomposi es. Polyme , 52, 3288-3294. 8- Schü z, M.R., Kalo, H., Lunkenbein, T., G oschel, A.H., Mulle , A.H.E., Wilkie, C.A. and B eu, J. (2011b) Shea s i , su ace modi ied, mica-like nanopla ele s: a no el ille o polyme nanocomposi es. Jou nal o Ma e ials Chemis y, 21, 12110-12116. 9- Mazen Ziadeh, Be ina Chwalka, Hussein Kalo, Michael R. Schü z, Jose B eu, A Facile App oach o P oducing High Aspec Ra io Fluo ohec o i e Nanopla ele s by U ilizing a S i ed Media Mill. Submi o Clay Mine als. 10- Ma kus M. He ling, Hussein Kalo, Sebas ian Seib , Raine Schobe , Jose B eu, Tailo ing he Po e Sizes o mic opo ous pilla ed in e laye ed clays. Manusc ip will submi o mic opo ous and mesopo ous ma e ials. Publica ion Lis 106 Pa en : 1- WO/2010/034408A1, syn he ic Phyllosilica es No Capable o swelling o Polyme Phyllosilica e Nanocomposi e. Nennemann A no, Bahnmuelle S e an, B eu Jose , Mölle Michael, Kalo Hussein. 2- WO/2011/089089A1, Me hod o p oducing Phyllosilica e Pla ele ha ing a High Aspec Ra io B eu Jose , Mölle Michael, Kalo Hussein, Nennemann A no. E klä ung 107 8. E klä ung Hie mi e siche e ich, die o liegende A bei selbs s ändig e ass und keine ande en als die on mi angegebenen Quellen und Hil smi el benu z zu haben. Fe ne e klä e ich, dass ich wede an de Uni e si ä Bay eu h, noch an eine ande en Hochschule e such habe, eine Disse a ion einzu eichen, ode mich eine P omo ionsp ü ung zu un e ziehen. Bay eu h den, 8/10/2012 Hussein kalo