Proceedings from the Ninth International Zeolite

Conference

Montreal 1992

Volume II

Edited by R. von Ballmoos, J.B. Higgins and M.M.J. Treacy

Ι/ε %oo -h

Butterworth-Heinemann Boston L o n d o n Oxford S i n g a p o r e S y d n e y To ron to W e l l i n g t o n

CONTENTS

VOLUME I

Preface:

Edi tors Hi C h a i r m a n Execut ive C o m m i t t e e of the 9 th IZC /V

Executive Committee of the 9th IZC ν

Program Committee of the 9th IZC w

International Advisory Board to the 9th IZC vii

Financial Support via

Keynote Lecture

O b s e r v a t i o n s a n d D e s c r i p t i o n s : O n a n U n k n o w n M i n e r a l - S p e c i e s C a l l e d Z e o l i t e s , b y A x e l F r e d r i c k C r o n s t e d t J o h n L. S c h l e n k e r a n d G ü n t e r Η. Küh l 3

Plenary Lectures

H o s t / G u e s t C h e m i s t r y a n d C a t a l y s i s i n Z e o l i t e s J e n s W e i t k a m p 13

C e r a m i c M e m b r a n e s f o r S e p a r a t i o n s a n d R e a c t i o n s A . J . Burggraaf , K. Keizer , R.S.A. de Lange , Z .A .E .P . V r o o n a n d V .T . Zaspa l i s . 4 7

R e c e n t A d v a n c e s a n d P e r s p e c t i v e s i n M o l e c u l a r S i e v e S y n t h e s i s H . K e s s l e r 73

S o d a l i t e S u p r a l a t t i c e s : F r o m M o l e c u l e s t o C l u s t e r s t o E x p a n d e d I n s u l a t o r s , S e m i c o n d u c t o r s a n d M e t a l s Andreas S te in a n d Geof f rey A. Oz in 9 3

Z e o l i t e S t r u c t u r a l P r o b l e m s F r o m a C o m p u t a t i o n a l P e r s p e c t i v e J . M . N e w s a m 127

D I S C U S S I O N - P l e n a r y L e c t u r e s 143

iii

iv Contents

Synthesis

T h e R o l e o f A l k a l i C a t i o n s in t h e S y n t h e s e s o f S i l i c a l i t e - 1 in F l u o r i d e M e d i u m F. C r e a , R. M o s t o w i c z , F. T e s t a , R. A ie l lo , A. N a s t r o a n d J .B. N a g y . . . . 147

S y n t h e s i s o f Ν Η 4 - F o r m H e t e r o a t o m - S u b s t i t u t e d M F I Z e o l i t e s in t h e

P r e s e n c e o f F l u o r i d e A n i o n s J o h n Dwyer , J i n g p i n g Z h a o a n d David R a w l e n c e 155

A n U n e x p e c t e d a n d H i g h l y V e r s a t i l e N e w Z e o l i t e S y n t h e s i s R o u t e L e a d i n g t o L a r g e P o r e A l u m i n o a n d B o r o s i l i c a t e S i e v e s S.I . Z o n e s , L.T. Y u e n , Y. N a k a g a w a , R.A. V a n N o r d s t r a n d and S.D. To to 163

O r g a n i c G u e s t S t a b i l i z a t i o n D u r i n g S y n t h e s i s o f H i g h S i l i c a Z e o l i t e s W i t h M u l t i d i m e n s i o n a l C h a n n e l s a n d L a r g e P o r e s : S S Z - 2 6 F r o m a P r o p e l l a n e -B a s e d O r g a n o c a t i o n S.I . Z o n e s a n d D.S. Sant i l l i 171

R a m a n S p e c t r o s c o p i c S t u d i e s i n Z e o l i t e S y n t h e s i s P.K. Dut ta 181

S y n t h e s i s a n d C h a r a c t e r i z a t i o n o f a N e w H i g h - S i l i c a , L a r g e - P o r e A l u m i n o s i l i c a t e Z e o l i t e , N C L - 1 R. K u m a r , K. R a m e s h Reddy , Anu j Raj a n d P. R a t n a s a m y 189

Z e o l i t e S y n t h e s i s i n A m m o n i a a n d A q u e o u s A m m o n i a S o l v e n t s : R e a c t i v i t y o f G r o u p IA C a t i o n s w i t h P r e - M a d e S i l i c a - A l u m i n a G e l s D.E.W. V a u g h a n a n d K.G. S t r o h m a i e r 197

S t u d y o n t h e I n s e r t i o n o f V a n a d i u m i n t h e S i l i c a l i t e F r a m e w o r k G. Bel luss i , G . Madd ine l l i , A. Cara t i , A. Gervas in i a n d R. Mülini 207

F~: A M u l t i f u n c t i o n a l T o o l f o r M i c r o p o r o u s S o l i d s a) M i n e r a l i z i n g , S t r u c t u r e D i r e c t i n g a n d T e m p l a t i n g E f f e c t s i n t h e S y n t h e s i s J.L. G u t h , H. Kess le r , P. Caul le t , J . H a z m , A . M e r r o u c h e a n d J . Patar in . . . 215

T h e S y n t h e s i s a n d C h a r a c t e r i z a t i o n o f G a - M F I a n d G a - M T W Z e o l i t e s S.L. Lamber t 223

S y n t h e s i s o f G a l l o - a n d G a l l o - A l u m i n o Z S M - 5 Z e o l i t e s w i t h V a r i a b l e a n d Q u a s i - H o m o g e n e o u s A l - G a D i s t r i b u t i o n , F r o m A l k a l i - F r e e M e d i a Z. G a b e l i c a , G . G ianne t to , F. D o s San tos , R. M o n q u e a n d R. Ga l iasso . . . 231

P r e p a r a t i o n o f Z e o l i t e F i l m U s i n g C e l l u l o s e M o u l d i n g T. S a n o , Y . K i y o z u m i , K. M a e d a , M. T o b a , S. N i w a a n d F. M izukami . . . . 239

ontents ν

C o n t r o l l e d G r o w t h o f T h i n F i l m s o f M o l e c u l a r S i e v e s o n V a r i o u s S u p p o r t s J . C . J a n s e n , W. N u g r o h o a n d H. v a n B e k k u m 2 4 7

M o l e c u l a r D e s i g n o f L a y e r e d Z i r c o n i u m P h o s p h o n a t e C a t a l y s t s K. S e g a w a , N. K i h a r a , H. Y a m a m o t o a n d S. N a k a t a 2 5 5

S y n t h e s i s a n d C h a r a c t e r i z a t i o n o f t h e N o v e l G a l l o p h o s p h a t e C l o v e r i t e w i t h 2 0 - M e m b e r e d R i n g C h a n n e l s J . Pa ta r in , C . S c h o t t , A. M e r r o u c h e , H. Kessler , Μ. Sou la rd , L. De lmot te , J .L . G u t h a n d J .F . Jo ly 2 6 3

T h e C r y s t a l l i z a t i o n o f A l u m i n o p h o s p h a t e M i c r o p o r o u s C o m p o u n d s i n A l c o h o l i c S y s t e m R u r e n X u , Q i s h e n g H u o a n d W e n q i n P a n g 271

S y n t h e s i s , C h a r a c t e r i z a t i o n a n d P h a s e T r a n s i t i o n o f t h e 2 0 - M e m b e r e d R i n g A I P 0 4 : J D F - 2 0

Q i s h e n g H u o , R u r e n X u , S h o u g u i Li , Y i h u a X u , Z h a n g u o M a , Y o n g Y u e , L iyun Li 2 7 9

H y d r o t h e r m a l T r a n s f o r m a t i o n o f Z e o l i t e Z S M - 3 9 i n t o Z S M - 2 3

S. Ernst , R. K u m a r a n d J . W e i t k a m p 2 8 7

S y n t h e s i s o f U l t r a f i n e Z e o l i t e L Xianp ing M e n g , Y a n Z h a n g , C h a n g g o n g M e n g a n d W e n q i n P a n g 2 9 7

N e w S i l i c a - A l u m i n a w i t h N a n o - S c a l e P o r e s P r e p a r e d f r o m K a n e m i t e S. Inagak i , Y. F u k u s h i m a , A . O k a d a , T. Ku rauch i , K. K u r o d a a n d C. Kato . . 3 0 5

A M i c r o p o r o u s T e t r a e t h y l a m m o n i u m P e r m u t i t e a s S y n t h e s i s I n t e r m e d i a t e o f t h e Z e o l i t e B e t a

M.A. Nicol le, F. d i R e n z o , F. Fa ju la , P. Espiau a n d T. d e s Cour ie res . . . . 3 1 3

M o d e l i n g a n d S i m u l a t i o n o f Z e o l i t e C r y s t a l l i z a t i o n

B. Subot ic and J . B ron ic 3 2 1

P r o b i n g t h e S y n t h e s i s o f C o A P O - n M o l e c u l a r S i e v e s b y A n a l y s i s o f W e t P r e c u r s o r G e l s M.G. Uy t te rhoeven a n d R.A. S c h o o n h e y d t 3 2 9

Z e o l i t e s S y n t h e s i z e d f r o m N o n a l k a l i n e M e d i a Daqing Z h a o , Sh i l un Q i u a n d W e n q i n P a n g 3 3 7

A N e w F a m i l y o f M i c r o p o r o u s G e r m a n i u m D i o x i d e C r y s t a l s Shougu i L i , R u r e n X u , Y u q i n Lu a n d Y i h u a Xu 3 4 5

vi Contents

S y n t h e s i s , D e a i u m i n a t i o n a n d P h y s i c o - C h e m i c a l C h a r a c t e r i z a t i o n o f Z e o l i t e E M T J . W e i t k a m p a n d R. S c h u m a c h e r 3 5 3

D I S C U S S I O N - S y n t h e s i s 3 6 1

Structure

C a t i o n D i s t r i b u t i o n a s a S t r u c t u r a l - C h e m i c a l P r o b e J.L. L i e v e n s a n d W . J . Mor t i e r 3 7 3

A C o m b i n a t o r i a l M e t h o d f o r G e n e r a t i n g N e w Z e o l i t e F r a m e w o r k s M.M.J . T r e a c y , S . R a o a n d I. R iv in 3 8 1

M e t h o d o f S o l u t i o n a n d S t r u c t u r e o f 3 N o v e l H i g h - S i l i c a M e d i u m - P o r e Z e o l i t e s w i t h M u l t i - D i m e n s i o n a l C h a n n e l S y s t e m s M.D. S h a n n o n 3 8 9

G r o u p 2 ( B e ) / 1 2 ( Z n ) - 1 5 ( P , A s ) 0 4 M o l e c u l a r S i e v e s Wi l l iam T.A. H a r r i s o n , T h u r m a n E. Gier , T i n a M. Nenof f a n d G a l e n D. S tucky 3 9 9

H y d r o g e n B o n d s D i s t o r t t h e A l u m i n o s i l i c a t e F r a m e w o r k o f A m m o n i u m - N a t r o l i t e E. S t u c k e n s c h m i d t , D. K a s s n e r , W . J o s w i g a n d W . H . B a u r 4 0 7

S y n t h e s i s a n d C h a r a c t e r i z a t i o n o f B r e c k S t r u c t u r e S i x , F a u j a s i t e , Z S M - 3 , a n d Z S M - 2 0 a n d t h e i r S t r u c t u r a l R e l a t i o n s h i p s G.W. S k e e l s , C S . B l a c k w e l l , K.B. Reu te r , N.K. M c G u i r e a n d C A . B a t e m a n 4 1 5

S i n g l e C r y s t a l S t r u c t u r e A n a l y s i s o f Z e o l i t e B e t a : T h e S u p e r p o s i t i o n S t r u c t u r e B. Mar ler , R. B ö h m e a n d H. G i e s 4 2 5

R i e t v e l d R e f i n e m e n t o f F - - C o n t a i n i n g G a P 0 4 - L T A

A. S i m m e n , J . Pa ta r in a n d C h . B a e r l o c h e r 4 3 3

D I S C U S S I O N - S t r u c t u r e 4 4 1

Characterization

T i t a n i u m S i l i c a l i t e - 1 P e r o x i d e s M.G. C le r ic i , P. Inga l l ina a n d R. Mi l l in i 4 4 5

ontents v i i

L o c a l E n v i r o n m e n t o f T i t a n i u m i n T i t a n i u m S i l i c a l i t e ( T S - 2 ) A. B'rttar, D. T r o n g O n , L. B o n n e v i o t , S . Ka l i agu ine a n d A . S a y a r i 4 5 3

P r o p e r t i e s o f I n d i u m C o n t a i n i n g Z e o l i t e s P r e p a r e d b y a S o l i d S t a t e R e a c t i o n V. Kanaz i rev , Y . N e i n s k a , T . T s o n c h e v a a n d L. K o s o v a 461

S p e c t r o s c o p y , E n e r g e t i c s a n d S i t i n g o f N H 4 + i n Z e o l i t e s :

T h e o r y a n d E x p e r i m e n t E.H. T e u n i s s e n , W . P . J . H . J a c o b s , A . P . J . J a n s e n a n d R.A. v a n S a n t e n . . . 4 6 9

S t u d i e s o n T e m p l a t e M o l e c u l e s : L o c a t i o n , O r i e n t a t i o n , P r o t o n a t i o n a n d I n t e r a c t i o n w i t h F r a m e w o r k i n H i g h S i l i c a Z e o l i t e s Y a o j u n S u n , Ta i l iu W u , L ip ing W a n g , L u n Fei a n d Y i n g c a i L o n g 479

E l e c t r o n S p i n E c h o S t u d i e s o f M n ( l i ) F r a m e w o r k S u b s t i t u t i o n i n M n A P O - 1 1 G u i l l a u m e B r o u e t , X i n h u a C h e n a n d Lar ry K e v a n 4 8 9

E l u c i d a t i n g t h e M o r p h o l o g y o f C l a y s : H R E M a n d E S E M S t u d i e s K.B. Reuter , J . J . A l c a r a z , J .A. T r i p h a h n , J . S . H o l m g r e n 4 9 7

C h a r a c t e r i s a t i o n a n d C a t a l y t i c P r o p e r t i e s o f T i t a n i u m I n c o r p o r a t e d i n t o Z e o l i t e s a n d S i l i c a s F r o m T i t a n i u m T r i f l u o r i d e P.J. K o o y m a n , J . C . J a n s e n a n d H. v a n B e k k u m 5 0 5

T h e P r e p a r a t i o n , C h a r a c t e r i s a t i o n a n d P r o p e r t i e s o f Z e o l i t e N U - 8 6 J .L . C a s c i , P.A. C o x a n d M . D . S h a n n o n 5 1 3

A p p l i c a t i o n o f D i f f u s e R e f l e c t a n c e F T I R S p e c t r o s c o p y i n M o l e c u l a r S i e v e R e s e a r c h

E. Loeff ler , C h . P e u k e r , B. Z i b r o w i u s , U. Z s c h e r p e l , K . -H . S c h n a b e l . . . . 5 2 1

A n I n f r a r e d S t u d y o f S t r u c t u r e R e l a x a t i o n i n M o l e c u l a r S i e v e s

W . P . J . H . J a c o b s , A . J . M . d e M a n , J . H . M . C . v a n W o l p u t a n d R.A. v a n S a n t e n 5 2 9

Q u a n t u m C h e m i c a l I n t e r p r e t a t i o n o f IR D a t a o f M e t h a n o l A d s o r p t i o n o n Z e o l i t e s a n d S i l i c a A . G . P e l m e n s c h i k o v , G . M o r o s i a n d A. G a m b a 5 3 7

T h e I n f l u e n c e o f Q u a d r u p o l a r E f f e c t o n H i g h - R e s o l u t i o n 2 7 A I D o u b l e R o t a t i o n ( D O R ) N M R o f A l u m i n o p h o s p h a t e M o l e c u l a r S i e v e s P.J. Grobet , H. G e e r t s , J .A. M a r t e n s a n d P.A. J a c o b s 5 4 5

N M R S t u d i e s o f t h e W a t e r M o t i o n i n A I P 0 4 - 5 , C o A I P 0 4 - 5 a n d V P I - 5

D. Go ld farb , I. K u s t a n o v i c h a n d J .O . P e r e z 5 5 3

vi i i

S o l i d S t a t e M A S N M R C h a r a c t e r i z a t i o n o f t h e T r a n s f o r m a t i o n o f VPI -5 t o AIPO4-8: P r e s e r v a t i o n o f t h e O c t a h e d r a l A l u m i n u m S i t e s ? D.E. Akpor iaye a n d M. S t ö c k e r

1 2 9 X e N M R a s a P r o b e o f S t r u c t u r e a n d D y n a m i c s i n M i c r o p o r o u s S o l i d s J.A. R i p m e e s t e r and C. I . Ratc l i f fe

Z e o l i t e I n t r i n s i c F r a m e w o r k R e a c t i v i t y a n d S e n s i t i v i t y A n a l y s i s o f F r a m e w o r k P e r t u r b a t i o n s B.G. Baeke land t , J.L. L ievens , W . J . Mor t ie r a n d R.A. S c h o o n h e y d t

D e p e n d e n c e o f C h a r g e D e n s i t y a n d E l e c t r i c F i e l d W i t h i n t h e C a g e s o f X a n d Y Z e o l i t e s o n t h e C a t i o n : P h o t o p h y s i c a l P r o b e s V. R a m a m u r t h y a n d D.F. E a t o n

L o c a t i o n o f I r o n i n F r a m e w o r k - S u b s t i t u t e d Z e o l i t e L U s i n g A n o m a l o u s P o w d e r X - R a y D i f f r a c t i o n a n d X - R a y A b s o r p t i o n F i n e S t r u c t u r e I.J. P icker ing , D.E.W. V a u g h a n , K .G . S t rohma ie r , G . N . G e o r g e a n d G . H . V i a

E l e c t r o n - A c c e p t i n g S t r e n g t h o f A l u m i n u m S p e c i e s i n H - Z e o l i t e s F.R. C h e n a n d J .J . Fripiat

F-: A M u l t i f u n c t i o n a l T o o l f o r M i c r o p o r o u s S o l i d s b ) 1 9 F N M R o f A s -S y n t h e s i z e d a n d P o s t - S y n t h e s i s T r e a t e d M a t e r i a l s E. K lock , L. De lmot te , M. S o u l a r d a n d J .L . G u t h

S y n c h r o t r o n B a s e d D i f f r a c t i o n S t u d i e s o f S o r p t i o n i n Z e o l i t e Y a t R o o m T e m p e r a t u r e Z.A. Kaszkur , J .W. C o u v e s , R .H . J o n e s , D. Wa l le r , C .R .A . C a t l o w a n d J . M . T h o m a s

C o m b i n e d In-Situ X - R a y P o w d e r D i f f r a c t i o n a n d X - R a y A b s o r p t i o n S p e c t r o s c o p i c S t u d i e s o f T r a n s i t i o n - M e t a l - I n c o r p o r a t e d A L P O a n d S A P O C a t a l y s t s J .W. C o u v e s , G . Sankar , J . M . T h o m a s , J . C h e n , C .R .A . C a t l o w , R. X u a n d G . N . G r e a v e s

C o r r e l a t i o n s B e t w e e n A c i d S t r e n g t h a n d S i E n v i r o n m e n t i n F a u j a s i t e T y p e M o l e c u l a r S i e v e s M. B r iend a n d D. Ba r thomeu f

T e m p l a t e - F r e e a n d A l k a l i - F r e e S y n t h e s i z e d S i l i c a t e s W i t h M F I - S t r u c t u r e -A C o m p a r a t i v e S t u d y M. W a l l a u , F. S c h ü t h , A. B renner , S . M e l s o n , R. Sp ich t i nge r , K. U n g e r , A. T iss le r a n d B. Z ib row ius

Contents

563

571

579

5 8 7

595

603

611

619

627

635

643

ontents ix

S p e c t r o s c o p i c I n v e s t i g a t i o n o f t h e R e d o x P r o p e r t i e s o f C o A P O M o l e c u l a r S i e v e s M . P . J . Pee te rs , J . H . C . v a n Hoof f , R.A. S h e l d o n , V . L . Z h o l o b e n k o , L . M . Kus tov a n d V . B . K a z a n s k y 651

E f f e c t o f D e h y d r a t i o n a n d C a t i o n i c E x c h a n g e o n t h e 2 3 N a a n d 7 L i M A S N M R S p e c t r a o f X a n d Y Z e o l i t e s J . M . C h e z e a u , A. S a a d a , L. D e l m o t t e a n d J .L . G u t h 6 5 9

D I S C U S S I O N - S t r u c t u r e 6 6 7

Modelling

P r o t o n T r a n s f e r f r o m A c i d i c S i t e s t o W a t e r , M e t h a n o l a n d A m m o n i a . A C o m p a r a t i v e a b i n i t i o S t u d y J o a c h i m Sauer , C h r i s t o p h K o l m e l , F r a n k H a a s e a n d Re inhard t Ah l r ichs . . . 6 7 9

S i t i n g o f A I a n d B r i d g i n g H y d r o x y l G r o u p s in Z e o l i t e C a t a l y s t s . C o m p u t e r S i m u l a t i o n s o f T h e i r S t r u c t u r e , V i b r a t i o n a l S p e c t r a a n d A c i d i t y K.-P. S c h r ö d e r a n d J . S a u e r 6 8 7

S t r u c t u r a l a n d D y n a m i c a l P r o p e r t i e s o f H y d r o c a r b o n s i n S i l i c a l i t e E. H e r n a n d e z , M. K a w a n o , A .A . S h u b i n , C M . F r e e m a n , C .R.A . Cat low, J . M . T h o m a s a n d K.I . Z a m a r a e v 695

C o m p u t e r M o d e l l i n g o f M i c r o p o r o u s S o l i d s R.G. Be l l , R.A. J a c k s o n a n d C .R.A . C a t l o w 703

D I S C U S S I O N - M o d e l l i n g 709

Author Index (Volumes I and II) 711

Subject Index (Volumes I and II) 7 1 7

VOLUME II

Adsorption

L i q u i d - P h a s e - A d s o r p t i o n o f B i n a r y M o n o s a c c h a r i d e - W a t e r a n d P o l y o l - W a t e r M i x t u r e s o n X a n d Y Z e o l i t e s R. Schö l lner , S . Unver r i ch t a n d W . - D . E in icke 3

x Contents

Z e o l i t e s a s M e d i a f o r H y d r o g e n S t o r a g e J . W e i t k a m p , Μ. Fritz a n d S. Ernst 11

A d s o r p t i o n o f P o l a r M o l e c u l e s o n t h e L a r g e P o r e M o l e c u l a r S i e v e V P I - 5 J . J ä n c h e n , Η. S t a c h , P.J. Grabet , J.A. M a r t e n s a n d P.A. J a c o b s 21

A d s o r b e n t F i l l e d M e m b r a n e s f o r G a s S e p a r a t i o n J . - M . D u v a l , B. Folkers, M.H.V. Mulder , G. D e s g r a n d c h a m p s a n d C A . S m o l d e r s 29

T r a n s p o r t i n Z e o l i t e s : A p p l i c a t i o n o f N M R t o P r o b e S o r p t i o n P h e n o m e n a R.L. P o r t s m o u t h , M.J. D u e r a n d L.F. G l a d d e n 3 7

D i f f u s i o n o f B e n z e n e , p - X y l e n e a n d t h e i r M i x t u r e i n S i l i c a l i t e - 1 U s i n g a F r e q u e n c y R e s p o n s e T e c h n i q u e D o n g m i n S h e n a n d Lovat V C . Rees 4 5

A d s o r p t i o n , C o a d s o r p t i o n a n d D i f f u s i o n o f I s o t o p i c H y d r o g e n M o l e c u l e s in N a A Z e o l i t e . E v i d e n c e f o r Q u a n t u m E f f e c t s at 8 0 Κ Ε. C o h e n d e La ra , R. K a h n , J .P . B o u c h a u d a n d H. I b n a s s 5 5

A S t u d y o f t h e D y n a m i c s o f A r o m a t i c A d s o r b a t e s i n F a u j a s i t e - T y p e Z e o l i t e s L M . Bul l , S .J . H e y e s a n d A .K . C h e e t h a m 63

M o l e c u l a r S i m u l a t i o n s o f L o w O c c u p a n c y A d s o r p t i o n o f A r o m a t i c s i n S i l i c a l i t e R.Q. Snur r , A T . Bel l a n d D.N. T h e o d o r o u 71

T h e H y d r o p h o b i c i t y I n d e x - A V a l u a b l e T e s t f o r P r o b i n g t h e S u r f a c e P r o p e r t i e s o f Z e o l i t i c A d s o r b e n t s o r C a t a l y s t s J . W e i t k a m p , P. K le inschmi t , A. Kiss a n d C H . Berke 7 9

S e p a r a t i o n o f G a s e o u s T e t r a c h l o r o e t h e n e / W a t e r M i x t u r e s b y A d s o r p t i o n o n Z e o l i t e s R. S c h u m a c h e r , S. Ernst a n d J . W e i t k a m p 8 9

A p p l i c a t i o n o f t h e Z L C M e t h o d t o t h e M e a s u r e m e n t o f I n t r a c r y s t a l l i n e C o u n t e r - D i f f u s i o n in L i q u i d - Z e o l i t e S y s t e m s D.M. R u t h v e n , P. S tap le ton a n d K. Dah lke 9 7

A M o n t e - C a r l o S i m u l a t i o n o f Z e o l i t i c A d s o r b e n t s D u r i n g a K i n e t i c a l l y C o n t r o l l e d P r e s s u r e S w i n g A d s o r p t i o n P r o c e s s R.L. P o r t s m o u t h a n d L.F. G l a d d e n 105

S o r p t i o n a n d D i f f u s i o n o f B e n z e n e i n B a X - T y p e Z e o l i t e M. Bü low, W . Mie tk a n d M. Nywl t 113

Ό η tents xi

T r a n s l a t i o n a l M o b i l i t y o f n - B u t a n e a n d n - H e x a n e in Z S M - 5 M e a s u r e d b y Q u a s i - E l a s t i c N e u t r o n S c a t t e r i n g

Η J o b i c , M . Bee a n d J . C a r o 121

D i f f u s i o n A n i s o t r o p y a n d S i n g l e - F i l e D i f f u s i o n in Z e o l i t e s

J . K ä r g e r a n d H. Pfe i fer 129

M o l e c u l a r D y n a m i c s S i m u l a t i o n s o f D i f f u s i o n in Z e o l i t e s P. D e m o n t i s a n d G . B . Suff r i t t i 137

D i f f u s i o n o f M o n a t o m i c , D i a t o m i c a n d S i m p l e P o l y a t o m i c S o r b a t e s i n 5 A a n d 1 3 X Z e o l i t e C r y s t a l s A s S t u d i e d b y t h e Z L C M e t h o d Z h i g e X u , M l a d e n Eic a n d D o u g l a s R u t h v e n 147

D I S C U S S I O N - A d s o r p t i o n 157

Solid State

i n t r a z e o l i t e C h e m i s t r y o f O r g a n o m e t a l l i c s w i t h M e t h y l L i g a n d s : C y c l o p e n t a d i e n y l M e t h y l I r o n d i c a r b o n y l A t i c h a B o r v o r n w a t t a n a n o n t a n d T h o m a s Bein 169

S y n t h e s i s o f O l i g o - a n d P o l y t h i o p h e n e s in Z e o l i t e H o s t s Pat r i c ia Enze l a n d T h o m a s B e i n 177

S t e p w i s e S y n t h e s i s o f l l -VI N a n o c l u s t e r s I n s i d e Z e o l i t e Y Sup«ercages U s i n g M O C V D T y p e P r e c u r s o r s M a r k R. S tee le , A n d r e w J . H o l m e s a n d Geof f rey A. Ozin 185

Z e o l i t e E n c a p s u l a t e d G a d o l i n i u m ( l l l ) C h e l a t e C o m p l e x e s K.J . Ba lkus , Jr., I. B r e s i n s k a a n d S .W. Y o u n g 193

D I S C U S S I O N - S o l i d S a t e 203

Natural Zeolites

R e c o n s t r u c t i o n o f a N a t u r a l Z e o l i t i z a t i o n P r o c e s s T h r o u g h L a b o r a t o r y S i m u l a t i o n s M. d e ' G e n n a r o , C. Co le l l a , M . Pans in i a n d A. Langel la 2 0 7

N a t u r a l Z e o l i t e s i n E n v i r o n m e n t P r e s e r v a t i o n : A n I n n o v a t i v e S t r a t e g y f o r C h r o m i u m R e m o v a l M. Pans in i , C . Co le l la , M . d e ' G e n n a r o a n d A. Langel la 215

xii Contents

C h a r a c t e r i z a t i o n o f t h e C l i n o p t i l o l i t e - R i c h T u f f s o f B i g a d i c : V a r i a t i o n o f t h e I o n - E x c h a n g e C a p a c i t y w i t h P r e t r e a t m e n t s a n d Z e o l i t e C o n t e n t A. E r d e m Senata la r , A . S i rkec iog lu , I. G u r a y , F. Esenl i a n d I. K u m b a s a r . . . 223

D I S C U S S I O N - N a t u r a l Z e o l i t e s 231

Acid Site Characterization

A c i d i c P r o p e r t i e s o f A I , S i - M F I Z e o l i t e s : I n f l u e n c e o f t h e S y n t h e s i s

C o n d i t i o n s ( F ~ o r OH*" ) . A n I n f r a r e d a n d M i c r o c a l o r i m e t r y S t u d y J.F. Joly, A. Au roux , J . C . Laval ley, A. Jan in a n d J .L . G u t h 2 3 5

T h e F o r m a t i o n o f S t o i c h i o m e t r i c A d s o r p t i o n C o m p l e x e s f o r S i m p l e T h i o l s i n H-ZSM-5 a n d H - Z S M - 1 2 C. Pere i ra , R.J. G o r t e a n d G.T. Kokota i lo 243

T h e R o l e o f t h e H a r d n e s s o f t h e Z e o l i t e L a t t i c e f o r t h e L o c a l A d s o r p t i o n S t r u c t u r e o f P o l a r M o l e c u l e s G. Mir th, A. K o g e l b a u e r a n d J.A. Le rcher 251

T h e Q u a n t i t a t i v e S t u d y o f B r ö n s t e d A c i d i t y in S A P O - 3 7 M.A. M a k a r o v a , A . F . O jo , K .M. Al -Ghefai l i a n d J . D w y e r 259

A s s e s s m e n t o f B r o e n s t e d A c i d i t y i n Z e o l i t e s b y C O A d s o r p t i o n : A n IR S t u d y E. Gar rone , R. C h i a p p e t t a , G. Spoto , P. Ug l iengo, A. Z e c c h i n a a n d F. Fa ju la 267

IR I n v e s t i g a t i o n o f C O P h y s i s o r p t i o n at L o w T e m p e r a t u r e a s a P r o b e f o r B r o n s t e d A c i d i t y i n Z e o l i t e s N. Echouf i and P. G e l i n 275

E S R M e a s u r e m e n t s f o r t h e C h a r a c t e r i z a t i o n o f A c i d i c L e w i s S i t e s i n Z e o l i t e s F. Wi tze l , H.G. K a r g e a n d A. Gutsze 283

D I S C U S S I O N - A c i d S i t e C h a r a c t e r i z a t i o n 293

Catalysis

T h e R o l e o f L e w i s A c i d S i t e s in A d s o r p t i o n a n d A c t i v a t i o n o f O x y g e n i n R e d o x T y p e R e a c t i o n s o n Z e o l i t e s V.L . Zho lobenko , L .M. Kus tov a n d V .B . Kazansky 299

Z e o l i t e C a t a l y z e d R e a r r a n g e m e n t s o f E p o x i d e s a n d G l y c i d i c E s t e r s W . F . Hoelder ich a n d N. Goe tz 309

ontents xi i i

In S i t u FT- IR S t u d y o f A c i d S i t e s R e s p o n s i b l e f o r C y c l o h e x e n e C o n v e r s i o n o n H Y Z e o l i t e s

S. Jo l ly , J . S a u s s e y , J . C . Lava l ley , N. Zan ie r , E. Benazz i a n d J .F. J o l y . . . 3 1 9

C u m e n e P r o d u c t i o n B a s e d o n M o d i f i e d M o r d e n i t e C a t a l y s t s

G. R. M e i m a , M . J . M . v a n d e r Aals t , Μ . S . U . S a m s o n , J . M . Garces a n d J .G. L e e . 3 2 7

T r a n s f o r m a t i o n o f P r o p a n e o v e r G a / H Z S M - 5 C a t a l y s t s : O n t h e A c t i v a t i o n P r o c e d u r e a n d t h e N a t u r e o f t h e A c t i v e S i te P. M o r i a u d e a u , G . S a p p a l y , M. Du faux a n d C. Naccache 3 3 5

M o d e l i z a t i o n o f S A P O - 3 7 a n d I t s V e r i f i c a t i o n T h r o u g h P h y s i c o c h e m i c a l C h a r a c t e r i z a t i o n a n d C h e m i c a l R e a c t i v i t y A. C o r m a , V. F o r n e s , M.J . F r a n c o , F. M e l o , J . Perez-Par iente and E. Sast re 3 4 3

C h a r a c t e r i z a t i o n o f L a r g e a n d E x t r a - L a r g e Z e o l i t e P o r e s w i t h t h e H e p t a d e c a n e T e s t J .A . M a r t e n s , G . M . V a n b u t s e l e a n d P.A. J a c o b s 3 5 5

P e r f o r m a n c e o f Z e o l i t e B e t a i n F r i e d e l - C r a f t s R e a c t i o n s o f F u n c t i o n a l i z e d A r o m a t i c s G . H a r v e y , A. Vog t , H.W. K o u w e n h o v e n a n d R. Prins 3 6 3

P e r m e a t i o n M e a s u r e m e n t s o n In S i t u G r o w n C e r a m i c MFI T y p e F i l m s E.R. G e u s , W . J . W . B a k k e r , P.J.T. V e r h e i j e n , M.J. d e n Exter, J.A. Mou l i jn a n d H. v a n B e k k u m 371

S o f t a n d H a r d A c i d i t y i n Z e o l i t e s a n d Z e o t y p e s : E v a l u a t i o n a n d C a t a l y t i c I m p l i c a t i o n s A. C o r m a , E. Sas t re , G . S a s t r e , P. V i rue la and C. Z icov ich 3 7 9

I s o m e r i z a t i o n o f L i g h t P a r a f f i n s o n M o r d e n i t e , M a z z i t e a n d Bet a. R e l a t i o n s h i p B e t w e e n A c i d i t y a n d C a t a l y t i c A c t i v i t y M . Boule t , E. B o u r g e a t - L a m i , F. Fa ju la , T. Des Cour ie res a n d E. G-arrone . . 3 8 9

S e l e c t i v e R e d u c t i o n o f N O b y H y d r o c a r b o n in 0 2 o n Meta l Ion- E x c h a n g e d Z e o l i t e C a t a l y s t s M a s a k a z u I w a m o t o , H i d e n o r i Yah i ro a n d Nor i taka Mizuno 3 9 7

D e c o m p o s i t i o n o f N O o n M e t a l i o s i l i c a t e s U n d e r a n E x c e s s of ( O x y g e n a n d a L o w C o n c e n t r a t i o n o f H y d r o c a r b o n s T. Inui, S . I w a m o t o a n d S . S h i m i z u 4 0 5

I n f l u e n c e o f H y d r o g e n S u l f i d e a n d o f A m m o n i a o n t h e H y d r o c ; r a c k i n g o f η - H e p t a n e o v e r a N i M o / Y Z e o l i t e C a t a l y s t M. Guisnet , J .L . L e m b e r t o n , C . T h o m a z e a u and S. Mignard 4 1 3

xiv Contents

I n h i b i t e d D e a c t i v a t i o n o f Pt S i t e s a n d S e l e c t i v e D e h y d r o c y c l i z a t i o n o f n-H e p t a n e w i t h i n L - Z e o l i t e C h a n n e l s Enr ique Ig les ia a n d J o s e p h E. B a u m g a r t n e r 4 2 1

T h e i n f l u e n c e o f H y d r o g e n P r e t r e a t m e n t o n t h e S t r u c t u r a l a n d C a t a l y t i c P r o p e r t i e s o f a P t / K - L T L C a t a l y s t M. V a a r k a m p , J . v a n Gronde l le , R.A. v a n S a n t e n , J .T . Mi l ler , B.L. M e y e r s , F.S. M o d i c a , G .S . Lane a n d D.C. K o n i n g s b e r g e r 4 3 3

C h a r a c t e r i z a t i o n o f P t - N i / K L - Z e o l i t e B i m e t a l l i c C a t a l y s t s b y C h e m i s o r p t i o n , C a t a l y s i s a n d X - R a y A b s o r p t i o n G u s t a v o L a r s e n a n d G a r y L. Hal ler 4 4 1

A l k y l a t i o n o f B e n z e n e w i t h P r o p y l e n e o v e r S A P O - 5 , S A P O - 1 1 a n d S A P O - 3 7 I.I. I vanova , Ν. D u m o n t , Ζ . Gabe l i ca , J .B . N a g y , E.G. D e r o u a n e , F. G h i g n y , O . E . I vashk ina , E.V. Dmi t ruk , A. S m i r n o v a n d B.V. R o m a n o v s k y 449

T h e I n f l u e n c e o f D i f f u s i o n L i m i t a t i o n s o n X y l e n e I s o m e r i z a t i o n J.A. A m e i s e 4 5 7

T h e E f f e c t o f O x y g e n a t e s o n t h e P r o p e n e O l i g o m e r i z a t i o n A c t i v i t y o f Z S M - 5 C.T. O 'Connor , S T . Lang fo rd a n d J .C.Q. F le tcher 4 6 7

S t u d y b y 1 2 9 X e a n d 2 7 A I N.M.R. S p e c t r o s c o p y o f t h e I n t e r a c t i o n s o f C o k e w i t h A l u m i n u m S p e c i e s in Z e o l i t e s J .L . Bonarde t , M . C Bar rage a n d J .P . F ra issard 475

I n v e s t i g a t i o n s o f L i q u i d - P h a s e Z e o l i t e - C a t a l y z e d D i e l s - A l d e r R e a c t i o n s Di tha H o c h g r a e b e r - P a e t o w and H a n s Lecher t 483

A c t i v i t y E n h a n c e m e n t o f M e N a A Z e o l i t e s b y S u l f i d i n g w i t h H y d r o g e n S u l f i d e f o r A c i d - C a t a l y z e d R e a c t i o n s M. S u g i o k a , N. Sato and D. Uch ida 493

E v o l u t i o n o f t h e G a l l i u m P h a s e o f G a - H - M F I A r o m a t i z a t i o n C a t a l y s t s : I n f l u e n c e o f H y d r o g e n J .F . Jo ly , H. Ajot, F. A lar io , D. Ait Ta leb , N.A. G n e p a n d M . G u i s n e t . . . . 501

B e c k m a n n R e a r r a n g e m e n t o f C y c l o h e x a n o n e O x i m e o v e r H i g h S i l i c a H Z S M - 5 Z e o l i t e s M o d i f i e d w i t h B o r i a T. T a k a h a s h i , T . Ka i a n d M. Nishi 509

A C o m p a r i s o n o f t h e P r o p e r t i e s o f M F I , M o r d e n i t e a n d Y Z e o l i t e s i n A r o m a t i c T r a n s f o r m a t i o n s K. E j - Jennane , C h . Marc i l ly , C. T rave rs , J .F . Jo l y a n d E. B e n a z z i 5 1 7

onteents xv

! L a t e r a l - C h a i n M e t h y l a t i o n o f T o l u e n e o v e r B o r o n a n d / o r Z i n c M o d i f i e d C e s i u m - X Z e o l i t e D. Arch ie r , G. C o u d u r i e r a n d C. N a c c a c h e 5 2 5

C a t a l y t i c O x i d a t i v e D e h y d r o g e n a t i o n o f E t h y l b e n z e n e t o S t y r e n e o n C a r b o n M o l e c u l a r S i e v e s P. C iambe l l i , R.P. Dar io a n d M. T u r c o 5 3 5

A c y l a t i o n o f P h e n o l a n d T r a n s f o r m a t i o n o f P h e n y l a c e t a t e o v e r Z e o l i t e s I. N e v e s , F.R. R ibe i ro , J .P . Bod ibo , Y . Poui l loux, M. Gube lmann , P. M a g n o u x , M. G u i s n e t a n d G . Perot 5 4 3

C a t a l y t i c P r o p e r t i e s o f [ A I ] - , [ G a ] - a n d [Fe ] -S i l i ca te A n a l o g s o f Z S M - 1 1 i n C 7 a n d C 8 A r o m a t i c H y d r o c a r b o n R e a c t i o n s : I n f l u e n c e o f I s o m o r p h o u s S u b s t i t u t i o n A n u j Raj , J . S u d h a k a r R e d d y a n d Raj iv K u m a r 551

C h a r a c t e r i z a t i o n o f D e a l u m i n a t e d M o r d e n i t e b y / > D e c a n e H y d r o c o n v e r s i o n M . M . O l k e n a n d J . M . G a r c e s 5 5 9

C o m p a r i s o n o f S h a p e S e l e c t i v i t y o f C o k e F o r m a t i o n in D i f f e r e n t Z e o l i t e s H. Schu lz , W. Böhr inger , a n d S. Z h a o 5 6 7

C a t a l y s i s o f A l k a l i A d d e d C u ( l l ) - N a Z Z e o l i t e s in B e n z y l A l c o h o l O x i d a t i o n H. H a y a s h i b a r a , T . N a n b u , S. N i s h i y a m a , S. Tsuruya a n d M. Masa i . . . . 5 7 5

T . E . M . a n d C a t a l y t i c P r o p e r t y S t u d y o f P t - G a o n H Z S M - 5 P. M e r i a u d e a u , G . S a p p a l y a n d C. N a c c a c h e 5 8 3

A l k e n e O l i g o m e r i z a t i o n A c t i v i t y o f S t e a m D e a l u m i n a t e d ZSM - 5 B. A n d e r s e n , J .C .Q . F le tcher a n d C.T. O 'Connor 591

P h y s i c o - C h e m i c a l C h a r a c t e r i z a t i o n a n d Catalytic Behavior Of Z n O - N a Z S M - 5 C a t a l y s t Bo -Q ing Xu , M i n g Y a n g , J u a n L iang a n d Sh i -Shan Sheng 5 9 9

E f fec t o f t h e C r y s t a l l i t e S i z e o f T i t a n i u m Si l i ca l i te -1 o n t h e A c t i v i t y i n t h e H y d r o x y l a t i o n o f P h e n o l A .J .H.P . v a n de r Pol , A . J . V e r d u y n a n d J .H.C. v a n Hooff 6 0 7

S e l e c t i v e H y d r o g e n a t i o n w i t h P d ( l l ) S a l e n C o m p l e x e s E n c a g e d in Y T y p e Z e o l i t e s D.E. de V o s a n d P.A. J a c o b s 6 1 5

xvi Contents

1 - P e n t e n e I s o m e r i z a t i o n o v e r S A P O - 1 1 a n d M e A P O - 1 1

S . M . Y a n g a n d S.Y. Liu 623

T h e S y n t h e s i s o f P i l l a r e d N i c k e l - S u b s t i t u t e d S a p o n i t e a n d i t s H y d r o i s o m e r i z a t i o n A c t i v i t y D a z h e n J iang , T i e S u n , Z i y a n g L iu , E n z e M in a n d M i n g y u a n H e 631

B e t a Z e o l i t e a s C a t a l y s t o r C a t a l y s t A d d i t i v e f o r t h e P r o d u c t i o n o f O l e f i n s D u r i n g C r a c k i n g o f G a s o i l L. Bone t to , A. C o r m a a n d E. Her re ro 639

B a s i c C a t a l y s i s o n B e t a Z e o t y p e s

M.A. Camblo r , A . C o r m a , R.M. M a r t i n - A r a n d a a n d J . P e r e z - P a r i e n t e . . . . 647

D I S C U S S I O N - C a t a l y s i s 655

Applications

Z e o l i t e s a s C e r a m i c s : E n g i n e e r i n g N e w a n d N o v e l C e r a m i c C o m p o s i t i o n s a n d M i c r o s t r u c t u r e s F r o m M o l e c u l a r S i e v e s R.L. B e d a r d a n d E.M. F lan igen 667

D y n a m i c s o f R e g e n e r a t i v e Z e o l i t e H e a t E x c h a n g e r s Dimi ter T c h e r n e v 675

O n t h e I n n o v a t i o n P o t e n t i a l o f A l i g n e d M o l e c u l a r S i e v e C r y s t a l s J . C a r o , G . F inger , E. J a h n , J . K o r n a t o w s k i , F. M a r l o w , Μ. N o a c k , L. W e r n e r and B. Z i b r o w i u s 683

P r e p a r a t i o n a n d P r o p e r t i e s o f a M e t a l H y d r i d e / Z e o l i t e I n c l u s i o n J inp ing Li , J i nx iang D o n g , W e n y a n g X u a n d F e n g W u 693

E l e c t r o c h e m i c a l a n d E l e c t r i c - F i e l d E f f e c t s a t D i s p e r s i o n s o f Z e o l i t e s Debra R. Ro l ison, J o s e p h Z . S t e m p l e a n d D a v i d J . C u r r a n 699

D I S C U S S I O N - A p p l i c a t i o n s 7 0 7

Author Index (Volumes I and II) 709

Subject Index (Volumes I and II) 715

S Y N T H E S I S O F O L I G O - A N D P O L Y T H I O P H E N E S IN Z E O L I T E H O S T S

Patr ic ia E N Z E L # and T h o m a s B E I N

D e p a r t m e n t of Chemis t ry , P u r d u e Univers i ty , W e s t La faye t te , IN 4 7 9 0 7 , U S A # P r e s e n t A d d r e s s : L a s h Mi l le r C h e m i c a l L a b o r a t o r i e s , Un ivers i t y of T o r o n t o , 8 0 St . G e o r g e S t ree t , T o r o n t o , Ontar io , M 5 S 1 A 1 , C a n a d a

A B S T R A C T

O l i g o m e r s a n d p o l y m e r s of t h i o p h e n e de r i va t i ves w e r e s y n t h e s i z e d in t h e c h a n n e l s of z e o l i t e Y a n d m o r d e n i t e . I n t r a z e o l i t e o x i d a t i o n of m o n o m e r s s u c h a s t h i o p h e n e , 3 -m e t h y l t h i o p h e n e , a n d b i t h i o p h e n e b y Fe ( l l l ) o r C u ( l l ) i ons resu l t s in f o r m a t i o n of i nso lub le p o l y m e r s tha t have s p e c t r o s c o p i c p rope r t i es s im i la r to t h e c o r r e s p o n d i n g bulk p o l y m e r s . T h e z e o l i t e s c o n t a i n i n g the p o l y m e r s a re n o n c o n d u c t i n g , but w h e n e x t r a c t e d f r o m t h e hos t , t h e p o l y m e r s s h o w d.c. conduct iv i t ies typ ica l for t h e bu lk mater ia ls . O l i go th iophene spec ies w i th we l l -d e f i n e d e lec t ron ic t rans i t ions c o u l d be p r o d u c e d in ac id ic zeol i te Y .

I N T R O D U C T I O N

T h e synthes is of m o l e c u l e - b a s e d c o n d u c t i n g mater ia ls h a s a t t rac ted g r o w i n g interest d u e

to the i r po tent ia l for app l ica t ions in mic roe lec t ron ics a n d electr ical c o m p o n e n t s s u c h as ba t te r i es . 1

W o r k in th is laboratory has recent ly d e m o n s t r a t e d the encapsu la t i on of c o n j u g a t e d p o l y m e r s s u c h

a s p o l y p y r r o l e , po lyan i l ine a n d p o l y t h i o p h e n e in t h e c rys ta l l ine c h a n n e l s y s t e m s of l a rge -pore

z e o l i t e s . 2 P r e c u r s o r m o n o m e r s a re i n t r o d u c e d into t h e zeo l i t e hos t a n d a r e s u b s e q u e n t l y

p o l y m e r i z e d by appropr ia te ox idan ts in the pore s y s t e m .

O t h e r i n c l u s i o n t e c h n i q u e s , e . g . , g r o w t h o f p o l y m e r f i b e r s in m e m b r a n e s , 3 a n d

i n t e r c a l a t i o n of p y r r o l e in l a y e r e d v a n a d i u m o x i d e 4 h a v e r e c e n t l y b e e n e x p l o r e d .

M e t h y l a c e t y l e n e gas w a s f o u n d to react w i t h the ac id s i tes in zeo l i tes L, Y , b e t a , Z S M - 5 , o m e g a ,

m o r d e n i t e , a n d S A P O - 5 to f o r m reac t i ve , c o n j u g a t e d o l i g o m e r s ^ . S h o r t - c h a i n o l i g o m e r s of

p o l y t h i o p h e n e w e r e p r e p a r e d in N a - p e n t a s i l z e o l i t e s 6 . In the lat ter s tudy it w a s f o u n d tha t the

p r e s e n c e of a l u m i n u m in the zeo l i te f r a m e w o r k is essen t ia l fo r o x i d a t i o n , but the c a u s e for the

f o r m a t i o n of the cat ion ic spec ies r e m a i n e d u n r e s o l v e d .

T h e p r e s e n t ar t ic le a d d r e s s e s t h e p o l y m e r i z a t i o n of d i f f e r e n t t h i o p h e n e s a n d t h e

q u e s t i o n of t he act ive si te in t h e f o r m a t i o n of o l i g o t h i o p h e n e s p e c i e s in l a r g e - p o r e zeo l i t es .

S p e c t r o s c o p i c m e a s u r e m e n t s s h o w tha t t h e p r e s e n c e of B r o n s t e d s i tes is essen t i a l f o r the

f o r m a t i o n of the s a m e o l igo th iophene spec ies as o b s e r v e d by C a s p a r et a l . in Z S M - 5 . 6

In t h e c h e m i c a l s y n t h e s i s of p o l y t h i o p h e n e ( P T h ) 7 - 8 , t h e d i rec t o x i d a t i o n of t h e

m o n o m e r s w i t h Fe(CI04>3 or C u ( C I 0 4 ) 2 , p r o d u c e s t h e c o r r e s p o n d i n g d o p e d p o l y m e r s . T h e

p o l y m e r i z a t i o n reac t ion i nvo lves r e m o v a l of 2 .25 to 2 .50 e lec t rons pe r m o l e c u l e of t h i o p h e n e .

T h e resu l t i ng p o l y m e r is p r o d u c e d in t h e o x i d i z e d s ta te w i t h 0 .25 to 0 .50 pos i t i ve c h a r g e s per

t h i o p h e n e uni t , d e p e n d i n g o n the syn thes is c o n d i t i o n s .

From the Proceedings of the 9th Internat ional Zeol i te Conference, Montreal 1992, Eds. R. von Bal lmoos et al., © 1993 by Bu t te rwor th -He inemann , a d iv is ion of Reed Publ ishing (USA) Inc. Al l r ights reserved.

177

78 Solid State

E X P E R I M E N T A L

N a Y ( L Z Y - 5 2 ) , N H 4 Y ( L Z Y - 6 2 ) , a n d N a - m o r d e n i t e (LZ -M5) w e r e g e n e r o u s l y d o n a t e d b y

t h e U n i o n C a r b i d e C o r p o r a t i o n . Z e o l i t e A (5A) w a s o b t a i n e d f r o m A l f a . T h e z e o l i t e s w e r e

d e h y d r a t e d in a f l ow of o x y g e n (1 ° C / m i n t o 100 ° C , 10 h at 100 ° C , a n d 8 h at 4 0 0 ° C (4 h u n d e r

v a c u u m ) . F e 1 1 1 a n d C u , ! zeo l i t es w e r e p r e p a r e d a c c o r d i n g to c o n v e n t i o n a l i o n - e x c h a n g e a n d

o x i d a t i o n t e c h n i q u e s 9 . T h e r e s u l t i n g z e o l i t e u n i t c e l l c o m p o s i t i o n s a r e : C u ^ Y :

C u i 5 N a 2 6 ( A I 0 2 ) 5 6 ( S i 0 2 ) i 3 6 , F e m Y : F e i 2 N a 3 2 ( A I 0 2 ) 5 6 ( S i 0 2 ) i 3 6 , C u M M :

CU2.5Na3(AIO2)8(SiO2)40. C u n A : C u 8 N a e o ( A I 0 2 ) 9 6 ( S i 0 2 ) l 9 2 -

2 ,2 ' -B i th iophene (BTh) a n d t e r t h i o p h e n e (TTh) w e r e i n t r o d u c e d into t h e zeo l i tes f r o m a

h e x a n e so lu t ion . T h e zeol i tes u s e d w e r e N a Y , H2Y, ΗβΥ (2 a n d 6 p ro tons pe r s u p e r c a g e / ß - c a g e ) ,

a n d F e m Y . Typ ica l l y , 0.5 g of zeo l i te w a s m i x e d w i th 2 0 ml of h e x a n e c o n t a i n i n g 0.01 g of t h e

o l i g o m e r (0 .06 m m o l 2 ,2 ' -b i th iophene , o r 0 .04 m m o l t e r t h i o p h e n e ) , s t i r red f o r 12 h o u r s , w a s h e d

w i t h an e x c e s s of h e x a n e , a n d d r i ed u n d e r n i t rogen . T h e o t h e r m o n o m e r s w e r e i n t r o d u c e d into

t h e zeo l i tes f r o m so lu t ions in w a t e r , c h l o r o f o r m , aceton i t r i le , h e x a n e , t o l u e n e , o r f r o m t h e v a p o r -

p h a s e . Bulk- l ike p o l y m e r s c o u l d be r e c o v e r e d f r o m the zeo l i tes af ter d i sso lu t ion of t h e f r a m e w o r k

w i t h a 2 5 % a q u e o u s s o l u t i o n of H F . P o l y t h i o p h e n e a n d p o l y ( 3 - m e t h y l t h i o p h e n e ) a r e no t

a t t a c k e d in ac id ic m e d i a 1 4 . Add i t i ona l l y , a b lank e x p e r i m e n t s h o w s tha t t h e m o n o m e r s d o not

p o l y m e r i z e a f te r e x p o s u r e to ac ids fo r 2 4 h o u r s . Bu lk p o l y m e r s w e r e p r e p a r e d c h e m i c a l l y b y

ox idat ive po lymer iza t ion w i th F e ( C I 0 4 ) 3 in M e C N .

R E S U L T S A N D D I S C U S S I O N

I n t r a z e o l i t e p o l y m e r i z a t i o n . If t h i o p h e n e m o n o m e r s are a d m i t t e d into t h e F e m o r C u " f o r m s

of zeo l i tes Y o r m o r d e n i t e f r o m the v a p o r p h a s e o r f r o m h e x a n e a n d t o l u e n e so lu t ions (Tab le 1) ,

t h e co lo rs of t h e resu l tan t a d d u c t s c h a n g e s low ly (w i th in 3 0 - 1 2 0 m in ) f r o m w h i t e to d i f fe ren t

s h a d e s of b lue o r d a r k g r e e n . T h e s e c o l o r c h a n g e s c o r r e s p o n d to t h o s e o b s e r v e d in bu lk

po lymer i za t ion . T h i o p h e n e m o n o m e r s in zeo l i te con ta in ing on ly s o d i u m ions d o not react to f o r m

p o l y m e r s , d u e to t h e a b s e n c e of ox ida t ion cen te rs .

No p o l y m e r f o rma t ion is o b s e r v e d w i th C u M A , w i t h a pore s ize of 4 .1 Ä , w h i c h is t o o sma l l

fo r the t h i o p h e n e m o n o m e r s . T h e m o n o m e r s have a k inet ic d i a m e t e r of a p p r o x i m a t e l y 6 Ä a n d

c a n not d i f fuse in to the zeo l i te cav i t i es , w h e r e t h e major i t y of t h e o x i d a n t ions a re l o c a t e d . In

con t ras t to t r e n d s o b s e r v e d in t h e bu lk p o l y m e r i z a t i o n reac t ions , po la r s o l v e n t s s u c h a s wa te r ,

ace ton i t r i l e , a n d c h l o r o f o r m d o not f a v o r t h e in t razeo l i te p o l y m e r i z a t i o n of t h i o p h e n e a n d 3-

m e t h y l t h i o p h e n e . T h e in t razeo l i t e m e t a l i ons a re p r o b a b l y s c r e e n e d b y t h e p o l a r s o l v e n t

mo lecu les . F r o m the es t ima ted sur face capac i t y of the zeol i te c rys ta ls , 0.2 m o l e c u l e s pe r unit ce l l

of zeol i te Y ( b a s e d o n 1 μητι c rys ta ls ) , a n d the o b s e r v e d m o n o m e r l oad ings (Tab le 1) , it c a n b e

c o n c l u d e d that m o s t of the m o n o m e r mo lecu les are in t roduced into the po re s y s t e m of t h e zeol i te

Synthesis of Oligo- and Polythiophenes in Zeolite Hosts 179

hos t . S c a n n i n g e lec t ron m i c r o g r a p h s ind icate no ev idence of p o l y m e r c o v e r i n g t h e s u r f a c e s of

z e o l i t e / p o l y m e r c r y s t a l s . P y r o l y s i s m a s s s p e c t r o m e t r y d e t e c t s c o n s i d e r a b l y l e s s m o n o m e r

evo lu t i on f r o m t h e z e o l i t e / p o l y m e r s a m p l e s t h a n f r o m t h o s e c o n t a i n i n g u n r e a c t e d m o n o m e r s in

t h e N a - f o r m s , a s e x p e c t e d if p o l y m e r i z a t i o n h a s t a k e n p l a c e . T h e a b o v e o b s e r v a t i o n s

d e m o n s t r a t e tha t t h e po ly th iophene c h a i n s f o r m wi th in the zeol i te p o r e s y s t e m s .

Af ter d isso lu t ion of the f r a m e w o r k ( C u " Y - 3 M T h - V ) w i th a n a q u e o u s so lu t ion of H F , a b lack

p o w d e r is o b t a i n e d w i th a 16 % y ie ld , b a s e d o n the amoun t of m o n o m e r l oaded into the zeo l i te . In

the c a s e of C u ^ Y - S M T h - V , th is va lue c o r r e s p o n d s to 5 m o l e c u l e s of 3 - m e t h y l t h i o p h e n e r e a c t e d

p e r un i t ce l l o f zeo l i t e , w h i c h c o r r e s p o n d s w e l l to the 2.3 to 1 ra t io of o x i d a n t to m o n o m e r

n e c e s s a r y fo r ox ida t i ve po lymer iza t ion .

T a b l e 1 : Z e o l i t e / t h i o p h e n e a n d 3 - m e t h y l t h i o p h e n e s a m p l e s

Sample Monomer b a d e d per unit cell P r o d u c t co lo r

T h a 3 M T h a

3 7 3 0 . 5 w h i t e 5.6 (6 .5) * 5.6 (6.5)* w h i t e

3 5 3 2 da rk b lue 5.6 (6 .5 ) * 5.6 (6 .5)* w h i t e 5.4 (6 .5)* 5.7 (6.5)* d a r k b lue

2 9 2 5 da rk g r e e n 2 2 w h i t e 1 ( 1 ) * 1 ( 1 ) * w h i t e

1.5 1 b l u e - g r e y 1 ( 1 ) * 1 ( 1 ) * w h i t e 1 ( 1 ) * 1 ( 1 ) * b l u e 1 1 g r e y - g r e e n

0 .2 l ight b l u e

N a Y - V N a Y - H C u H Y - V C u n Y - - W C u u Y - H F e m Y » V N a M « V N a M ~ H CUNm-V C U I ! M ~ W C u " M ~ H F e n M - - V C u n A - - V

a A b b r e v i a t i o n s : Y , zeo l i te Υ ; M, m o r d e n i t e ; T h , t h i o p h e n e ; 3 M T h , 3 - m e t h y l t h i o p h e n e ; V , v a p o r ; H, h e x a n e (similar w i th to luene) ; a n d W, w a t e r (similar w i th acetonitr i le, ch lo ro fo rm) . * T h e n u m b e r s in p a r e n t h e s e s c o r r e s p o n d to t h e a m o u n t of m o n o m e r s d o s e d f r o m s o l u t i o n t o a c h i e v e 2.3:1 ox idan t to m o n o m e r s to ich iomet ry .

S p e c t r o s c o p i c c h a r a c t e r i z a t i o n . T h e IR s p e c t r a of F e m Y - 3 M T h - V a n d of C u n Y - 3 M T h - V 2 b

s h o w typ ica l v ib ra t ions of p o l y ( 3 - m e t h y l t h i o p h e n e ) 1 0 « 1 1 . T h e w e a k b a n d at 1506 c m " 1 is a s s i g n e d

to a r o m a t i c C = C s t re t ch ing v ib ra t ions , a n d t w o s t rong b a n d s a r o u n d 1 4 0 0 , a n d 1331 c m " 1 a r e

re la ted to the he te rocyc le C-N s t re tch ing v ibra t ions (Figure 1). T h e p r e s e n c e of the in tense , fa i r ly

b r o a d b a n d s at 1400 a n d 1331 c m " 1 ind icates that the po lymer cha ins a re in the ox id ized f o r m . At

h ighe r e n e r g y (not s h o w n ) , the spec t ra a lso exhibi t a character is t ic ta i l of t he e lec t ron ic t rans i t i on

c o r r e l a t e d w i t h t h e p r e s e n c e of f r e e ca r r ie rs in h igh ly c o n d u c t i n g p o l y t h i o p h e n e s 1 2 . T h e IR

s p e c t r a of t h e b l a c k a g g l o m e r a t e d p r o d u c t s e x t r a c t e d f r o m t h e z e o l i t e s a n d t h o s e o f t h e

180 Solid State

zeo l i t e /po l y th iophene s a m p l e s a re c o m p a r a b l e to the IR spec t ra of c h e m i c a l l y s y n t h e s i z e d bu lk

mater ia ls .

N e u t r a l p o l y ( 3 - m e t h y l t h i o p h e n e ) ( a n d p o l y t h i o p h e n e ) f i l m s f o r m e d e l e c t r o c h e m i c a l l y

s h o w abso rp t i on in the v is ib le reg ion at about 2.5 eV , assoc ia ted w i th t h e π -> π* t rans i t ion of long

c o n j u g a t e d p o l y m e r c h a i n s 1 3 - 1 4 . W h e n t h e bulk p o l y m e r is o x i d i z e d , t w o in t ra -gap a b s o r p t i o n s

a s s o c i a t e d w i t h b ipo la rons d e v e l o p at abou t 0.65 a n d 1.6 eV. Wi th p rog ress ive ox ida t ion , t he 2.5

e V a b s o r p t i o n d e c r e a s e s in in tens i ty . A r e p r e s e n t a t i v e zeo l i te s a m p l e , C u ^ Y - T h - V , s h o w s

c o r r e s p o n d i n g f e a t u r e s at abou t 4 4 0 n m (ca . 2.8 e V ) , 6 7 0 n m (1 .9 e V ) , a n d a b r o a d a b s o r p t i o n

b e t w e e n c a . 1.4 a n d 0 .25 e V (see a lso F igure 2 C ) . S imi la r f ea tu res a re o b s e r v e d w i t h t h e F e 1 1 1 -

c o n t a i n i n g h o s t s a n d w i t h 3 M P T h - l o a d e d zeo l i tes . If t h e N I R a b s o r p t i o n of t h e s e s a m p l e s is

c o m p a r e d w i t h d a t a f o r t h i o p h e n e n o n a m e r s ( 9 2 + ) 6 , it c a n b e c o n c l u d e d tha t t h e in t razeo l i te

p o l y m e r c h a i n s s h o u l d be m u c h longer t h a n 10 uni ts .

Wove1ongth(um)

J I I I I I I I I I I I I

1800 1600 1400 1200 1000 800 600 Wavonumbore

F i g u r e 1 . FT IR spec t ra of po ly (3 -methy l th iophene) s a m p l e s . (A) N a Y , (B) F e m Y - 3 M T h - V , (C)

Ο υ ' Ύ ^ Μ Τ η - ν , a n d (D) bu lk po ly (3 -methy l th iophene) .

Synthesis of Oligo- and Polythiophenes in Zeolite Hosts 181

T h e E S R s p e c t r a of t he C u ^ - P T h s a m p l e s p resen t s igna ls at g = 2 . 0 0 2 7 . Th is v a l u e is

t yp i ca l o f a d e l o c a l i z e d c a r b o n - b a s e d r a d i c a l 1 5 . T h e s ignals are ra ther b r o a d , w i t h b a n d w i d t h s

g rea te r t h a n 6 G a u s s , character is t ic of local ized radical sp ins a n d a n ind icat ion of in teract ion of t he

e n c a p s u l a t e d p o l y m e r w i t h the zeo l i te hos ts . T h e p r e s e n c e of on ly a b o u t 2 .0 χ 1 0 " 3 sp ins p e r

m o n o m e r is c o n s i s t e n t w i t h t h e e x i s t e n c e of b i p o l a r o n s a s c h a r g e c a r r i e r s . P r e s s e d

z e o l i t e / p o l y m e r pe l le ts s h o w no s ign i f icant 'bulk ' conduc t iv i t y , w i t h σ < 1 0 " 8 S e m " 1 . T h e r e f o r e ,

t h e r e is n o s ign i f i can t d e p o s i t i o n of p o l y m e r o n the ex te rna l c rys ta l s u r f a c e s . A g g l o m e r a t e d

P 3 M T h r e c o v e r e d f r o m C u ^ Y - S M T h - V af ter d isso lu t ion of the host s h o w s a conduc t i v i t y of abou t

0.01 S e r n " 1 . T h i s v a l u e is c l o s e to tha t o b t a i n e d fo r p o l y ( 3 - m e t h y l t h i o p h e n e ) s y n t h e s i z e d by

c h e m i c a l m e t h o d s .

S t a b i l i z a t i o n o f t h i o p h e n e o l i g o m e r s w i t h i n z e o l i t e s . In a r e c e n t s t u d y , t h i o p h e n e

o l i g o m e r s w e r e f o r m e d w i th in the c h a n n e l s of zeol i te be ta a n d N a - Z S M - 5 6 . C h a r g e d shor t - cha in

o l i g o m e r s a re inheren t ly reac t ive s p e c i e s , a n d in t h e par t icu lar c a s e of p o l y t h i o p h e n e , o x i d i z e d

o l i g o m e r s are uns tab le w i t h respect to fu r ther o l igomer iza t ion in so lu t ion . T h u s , t h e zeol i te is a n

exce l l en t mat r ix to s tab i l i ze t h e m . O n e of t h e ques t i ons that the a b o v e s t u d y d i d not a d d r e s s

re la tes to t h e n a t u r e of t h e reac t ive s i tes a n d the react ion m e c h a n i s m in t h e zeo l i te , s i nce t h e

o l i g o m e r s w e r e f o r m e d wi thout any t radi t ional ox idant , such as ferr ic o r cupr ic ions .

A r e l a t e d p o l y h e t e r o c y c l e , p o l y p y r r o l e , is k n o w n to f o r m in t h e p r e s e n c e of p r o t o n i c

a c i d s 1 6 . A c c o r d i n g l y , o n e m igh t a s s u m e tha t the f o r m a t i o n of p o l y t h i o p h e n e c o u l d p r o c e e d

t h r o u g h t h e s a m e m e c h a n i s m as in po lypyr ro le . W e p ropose that t h e p r e s e n c e of ac id g r o u p s in

t h e zeo l i t e is respons ib le for the f o r m a t i o n of the t h iophene o l i g o m e r s . T o tes t th is a s s u m p t i o n ,

shor t o l i g o m e r s of t h i o p h e n e (Th ) , b i th iophene (BTh) a n d te r th iophene ( T T h ) , w e r e l o a d e d f r o m

h e x a n e into t h e ac id a n d F e m f o r m s of zeol i te Y. Dif ferent concen t ra t i ons o f p r o t o n s pe r uni t cel l

of z e o l i t e Y , H - | 6 N a 4 o Y (H2Y) a n d F U s N a e Y (ΗβΥ) w e r e u s e d t o s t u d y t h e e f fec t of p r o t o n

s to i ch iomet ry o n the p roduc ts f o r m e d . Af ter a f e w minutes a c h a n g e in co lo r w a s not iceab le in the

z e o l i t e s , but to d r i ve the reac t ion to c o m p l e t i o n , it w a s c o n t i n u e d f o r 12 h o u r s . N a Y - m o n o m e r

a d d u c t s p r o d u c e d on ly minor but de tec tab le spect ra l c h a n g e s .

H 2 Y a n d H e Y zeol i tes l oaded w i t h b i th iophene y ie ld a y e l l o w - g r e e n c o m p l e x . T h e s a m e

z e o l i t e s l o a d e d w i t h t e r t h i o p h e n e p r o d u c e a n in tense purp le c o m p l e x . T h e s e c o l o r s a re ve ry

d i f f e r e n t f r o m t h e g r e e n - b l a c k c o l o r o b t a i n e d w h e n t h i o p h e n e , b i t h i o p h e n e , o r t e r t h i o p h e n e

w e r e l o a d e d in F e ' ^ Y , w h e r e po lymer i za t ion to po ly th iophene takes p l a c e . T h e m a i n f e a t u r e s of

t h e U V / V I S / N I R re f lec tance spec t ra (F igure 2) a n d their a s s i g n m e n t s to d i f fe rent o l i gomer ca t ions

a c c o r d i n g to ref. [6] are s u m m a r i z e d in T a b l e 3. It is not qui te c l ea r if t he s p e c i e s o b s e r v e d here

a re rad ica l ca t ions , d ica t ions , o r rather p r o t o n a t e d heterocyc les . R e l a t e d s t u d i e s 1 7 o n t h e s e a n d

o t h e r m o n o m e r s sugges t the fo rmat ion of p ro tona ted spec ies .

182 Solid State

C

π 1 1 1 1 1 — 400 600 800 1000 1200 1400 nm

F i g u r e 2. UV/VIS/NIR ref lectance spect ra of th iophene ol igomers in acid zeoli tes. (A) H6Y-TTh-H, (B) H6Y-BTh-H, and (C) Fe( l l l )Y-BTh-H. T h e feature at 850 nm is an artifact due to change of detectors.

Synthesis of Oligo- and Polythiophenes in Zeolite Hosts 183

T a b l e 3: U V / V I S / N I R b a n d s for t h i o p h e n e o l i gomers in zeol i te Y a

S a m p l e B a n d P o s i t i o n s ( n m ) a n d A s s i g n m e n t s (a f te r r e f e r e n c e 6, in p a r e n t h e s e s )

F e m Y - T h - H 4 7 0 s h b road N IR b a n d π - π * i n n e u t r a l P T h o x i d i z e d P T h

N a Y - B T h - H 3 0 8 s 4 0 2 s h 6 7 8 w

2 ( 3 0 0 ) 2 o + ( 4 0 7 ) 8 2 + ( 6 6 1 ) H 2 Y - B T h - H 3 0 8 s 4 0 8 s 668S 1 2 7 4 b r o a d

2 2°+ 8 2 + 8 2 + . . . ( 1 3 8 3 ) H 6 Y - B T h - H 3 0 8 s 4 0 8 s 6 6 8 s 1 3 0 0 b r o a d

2 2°+ 82 + 8 2 + . . .

F e m Y - B T h - H b road N IR b a n d o x i d i z e d P T h

NaY-TTh-H 3 7 0 s 3 (354)

5 2 8 s h 3 ° + ( 5 2 2 )

H 2 Y - T T h - H 3 6 0 s 5 3 2 s 7 8 8 s b road NIR b a n d

3 30+ 6 ° + ( 7 7 5 ) o x i d i z e d P T h H 6 Y - T T h - H 3 6 0 s 528S 8 0 4 s 1024 + b r o a d NIR

3 3°+ 6 °+ o r 3 2 + ( 8 3 3 ) 6 2 + + o x . P T h

F e ^ Y - T T h - H b road NIR b a n d o x i d i z e d P T h

a 2, neu t ra l b i t h i o p h e n e ; 2 + , b i t h iophene radica l c a t i o n ; 3, neut ra l t e r t h i o p h e n e ; 3 + , t e r t h i o p h e n e rad ica l c a t i o n ; 6 + , h e x a t h i o p h e n e rad ica l ca t ion ; 6 2 + , h e x a t h i o p h e n e d i ca t i on ; 8 2 + , o c t a t h i o p h e n e d ica t ion . H, h e x a n e ; s h , shou lder ; s, s t rong ; a n d w , w e a k .

T h e s t rong b a n d s at abou t 3 0 8 n m for t h e b i th iophene l o a d e d zeo l i tes a n d at 3 6 0 n m fo r

the t e r t h i o p h e n e l o a d e d zeo l i tes c o r r e s p o n d to the b a n d g a p t rans i t i on in the neut ra l o l i g o m e r 6 .

In t h e s p e c t r a of N a Y zeo l i t es l o a d e d w i t h t h e s e m o n o m e r s , t h e a b o v e b a n d s a re d o m i n a n t .

D is t inc t ive b a n d s at l ower e n e r g i e s , on ly p resent in the ac id zeo l i tes , a re tenta t ive ly a s s i g n e d to

rad ica l c a t i o n s a n d d ica t ions t yp ica l of the t h i o p h e n e o l i g o m e r s . B i th iophene c a n f o r m a s t a b l e

radical ca t i on , 2 , + , in ac id zeol i tes as s h o w n by the b a n d at 4 0 8 n m . Addi t ional ly , t w o bands at 6 6 8

n m a n d at about 1300 n m , a s s i g n e d to the o c t a m e r d icat ion 8 2 + , are present in the spec t ra (F igure

2, B ) . For t e r t h i o p h e n e , a b a n d at 5 2 8 n m ass igned to the rad ica l c a t i o n 3 * + , a n d a b a n d a r o u n d

8 0 0 n m re la ted to the h e x a m e r 6 * + a re o b s e r v e d (F igure 2 , A ) . T h e s p e c t r a of F e m Y - B T h a n d

F e ^ Y - T T h are ve ry s imi lar to the s p e c t r u m of F e ^ Y - T h , in w h i c h the ma in spect ra l character is t ic is

a b r o a d a b s o r p t i o n b a n d e x t e n d i n g into t h e n e a r - I R , a s s i g n e d to t h e o x i d i z e d f o r m of

p o l y t h i o p h e n e (F igure 2 , C ) . It is impor tant to no te that the s p e c t r a of t he a d d u c t s in ac id zeo l i te

s h o w a lso the b r o a d near IR abso rp t i on typ ica l fo r the po l yme r , w h i c h ind ica tes t h e c o n c o m i t a n t

f o r m a t i o n of o l i gomers a n d p o l y m e r s in the zeo l i tes .

T h e d is t inc t i ve b a n d s re la ted to rad ica l c a t i o n s a n d d i c a t i o n s of sho r t o l i g o m e r s of

t h i o p h e n e in zeo l i t es are o n l y o b s e r v e d in t h e p r e s e n c e of p r o t o n s . T h e s e resu l ts c a n a l s o

exp la in t h e f o r m a t i o n of t he s a m e s p e c i e s in N a - Z S M - 5 s ince th is zeo l i te c a n c o n t a i n a s m a l l

184 Solid State

a m o u n t of p ro tons as w e l l . H o w e v e r , t h e react iv i ty of t h e t h i o p h e n e s p e c i e s in p r o t o n vs . F e m

zeol i te f o r m s is sti l l not c o m p l e t e l y u n d e r s t o o d . If a s t rong ox idan t ion is p resen t in the zeo l i t e ,

s u c h as F e 1 " , t h e o x i d a t i o n is d r i v e n to c o m p l e t i o n f o r m i n g o x i d i z e d p o l y m e r s . T h e r e a c t i o n

p a t h w a y is apparent ly a f u n c t i o n of the ox idat ion potent ia l of t he ox idant .

C O N C L U S I O N S

In s u m m a r y , th is s t u d y d e m o n s t r a t e s that it is poss ib le to p o l y m e r i z e t h i o p h e n e , 3 -

me thy l th iophene , a n d s m a l l o l i g o m e r s w i th in the c h a n n e l s y s t e m s of zeo l i tes , a n a l o g o u s to t h e

ox ida t i ve c o u p l i n g of t h i o p h e n e a n d 3 - m e t h y l t h i o p h e n e in so lu t ion in the p r e s e n c e of C u " a n d

F e ' " o x i d a n t s . O l i g o m e r i z a t i o n a n d po l ymer i za t i on reac t i ons p r o c e e d to d i f fe ren t d e g r e e s in

acidic and ox idan t -con ta in ing zeo l i tes .

A C K N O W L E D G E M E N T S

T h e au tho rs thank Dr. F ranco is B e u n e u (Ecole Po ly techn ique , Par is) fo r tak ing the E S R

spect ra . Partial fund ing for th is w o r k f r o m Sprague Electr ic C o m p a n y is apprec ia ted .

R E F E R E N C E S

1 Proceed ings of t he In ternat iona l Con fe rence o n Sc ience a n d T e c h n o l o g y of Synthet ic Meta ls , I C S M '88 a n d '90 ; S y n t h . Meta ls , 28 (1-3) a n d 29 (1) (1988) , a n d S y n t h . Meta ls , 4 1 - 4 3 ( 1 9 9 1 ) .

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1 1 1 , 4 1 3 9 ( 1 9 8 9 ) . 5 S. D. C o x , a n d G . D. S tucky , J . Phys . C h e m . , 9 5 , 710 (1991) . 6 J . V . Caspar , V. R a m a m u r t h y , a n d D. R. Corb in , J . A m . C h e m . S o c , 113, 600 (1991) . 7 N. Mermi l l i od -Theven in , a n d G . B idan , Mol . Cryst . L iq . Cryst . , 118 , 2 2 7 (1985) . 8 Μ. B. Inoue , E. F. V e l a z q u e z , a n d M. Inoue, S y n t h . Meta ls , 2 4 , 2 2 3 (1988) . 9 J . R. Pearce , W. J . Mort ier , J . B. Uy t te rhoeven, a n d J . H. Luns fo rd , J . C h e m . S o c ,

Faraday T rans . 1 , 7 7 , 9 3 7 (1981) . 1 0 H. Neugebauer , G. Nauer , A. Necke l , G. Tour i l lon, F. Gamie r , a n d P. Lang , J . Phys.

C h e m . , 8 8 , 6 5 2 ( 1 9 8 4 ) . 1 1 J . E. O s t e r h o l m , P. Sun i la , a n d T . Hjer tberg, S y n t h . Meta ls , 1 8 , 1 6 9 (1987) . 1 2 S. Ho t ta , W . S h i m o t s u m a , a n d M. Take tan i , S y n t h . Meta ls , 10, 8 5 (1984 /5 ) . 1 3 G. D ian , G . Barbey , a n d B. Decro ix , Syn th . Meta ls , 24 , 223 (1988) . 1 4 N. Co laner i , Μ. N o w a k , D. Sp iege l , S . Hot ta , A. J . Heeger , Phys . Rev. B, 3 6 , 7 9 6 4

( 1 9 8 7 ) . 1 5 D. P. Mur ray , L. D. K isper t , a n d S.Petrovic, S y n t h . Meta ls , 28 , C 2 6 9 (1989) . 1 6 M. S a l m o n , Κ. K. K a n a z a w a , A. F. Diaz, and M. Krounb i , J . Po lym. Sei. , Po lym. Lett. Ed . ,

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