Characterization of void spaces and
location of cations in zeolite Rho by means
of 129Xe-n,m,r,
T. Ito* a n d J. F r a i s s a r d
Laboratoh:e de Chimie des SIt~faces. associ: a, CNRS UA 870. U,ive~:vit: Pierre e/Marie
Curie Tour 55.3i'me Etage 4 Place J,.s:~'ieu. 75252 Paris Cedex 05. Fra.ce
(Received 11 Februa O' 1987; revised21 May 1987)
By observing the n.m.r, spectrum of 129Xe adsorbed on zeolite Rho, it is possible to determine the
xenon distribution over cages and octogonal prisms. In the case of H-Rho, the relative concentration in
prisms increases with pressure and temperature reduction. On the contrary, in the case of Cs-Rho, at
adsorption equilibrium, the xenon is not located in the prisms because of the presence of the Cs ÷
cations.
Keywords: Zeolite Rho; ~Z°Xe-n.m.r.; void space dimensions
INTRODUCTION
i':gXe is a n o n r e a c t i v e molecule, particularly sensitive
to its e n v i r o n m e n t and to collisions with o t h e r
chemical species, d e t e c t a b l e hy ii.m.r, anad can I)e used
as a probe for d e t e r m i n i n g certain p r o p e r t i e s o f
zeolites aiad metal-zeolitcs. T h e chemical shift o f
x e n o n situated in any zeolite without I-i° o r with
supported metal in-t5 is always the s u m o f t e r m s
c o r r e s p o n d i n g to the d i f f e r e n t perturbatio,as to
which it is subjected. M o r e precisely, in the case o f
zeolites:
6 -- 8,, + 6s + 6l.: + 6{x<.-x,.i.px<. (1)
w h e r e 6s is d u e to collisiorls I}etweeri xentoli and the
cage o r channel walls. It d e p e n d s on the m e a n free
path o f the aclsorbed Xe a t o m s 14 a n d , t h e r e f o r e , on
the zeolite structttre or, to be exact, the dintensions o f
t h e cages a n d ch;tnnels and their rehttive positions. 6t.:
is d u e to the electric field. It is g e n e r a l l y negligible in
the case o f H, Na a n d Li catiotls, but it is very
i m p o r t a n t t b r t?+ cations, s-lt~ T h e hlsl lerm t}l
E q u a t i o n (1) is the excess o f shift d u e to X e - X e
collisions.
EXPERIMENTAL
W e have s t u d i e d the adsorl}tion {}f Xe {}l] ze{}lites
H - R h o a n d Cs-Rho. T h e p r e p a r a t i o n and char;.iclei-is-
tics o f these sami}les were given previousl),. I{;'17 All
samples were p r e t r e a t e d as follows. A known a n l o u n t
of zeolite was taken in an n.m.r, tube and desorl}ed
under 10 -'s T o r t at r o o m temt}erattu'e, Ihen at a
t e m p e r a t u r e raised slowly to 400°C a n d n l a i n t a i n e d ;it
this value for 8 h.
T h e a d s o r p t i o n isotherms {if x e n o n gas w e , e
m e a s u r e d at 26°C on a classical volunaetric a p p a r a t u s .
*Present address: Research Institute for Catalysis, Hokkaido
University, Sapporo 060, Japan
0144-2449/87/060554-05 $03.00
(~) 1987 Butterworth Publishers
554 ZEOLITES, 7987, Vo/ 7, November
N.m.r. ahsorptitm o f P-'~Xe adsorbed {)l~ Ihese sam-
pies was ol)served with a B r u k e r C X P 100 speclro-
m e t e r at a freqttency (>f 24.9 MHz, witli<}ul ttsi,lg Ihe
m.a.s, technique. T h e latter leads to i~ti apl}ret:ial}le
n a r r o w i n g o f the lines but involves the p r e p a r a l i o l l o f
a large n t n n h e r o f sealed sat-nl}les. W e have c h e c k e d
that when the lines a r e nornlall)' sttfficielatly well
resoh'ed, no t u n d a n l e n t a l l y new inl'oFnlaliou is pro-
vided.
RESULTS
Figmes 1 ancl 2 show that the s p e c t r a ( m e a s u r e d at the
experimenltal teml}erature. T = 2(3°(:) t}i" xentm
a d s o r b e d on the zeolite H - R h o {:{lilsisl Df two dislincl
lines, c (for cavity) and r, (tor exchitnge); whose
chemical shifts vary from 108 t{} 138 pl)in and fron~
17(5 to 190 ppm, resl}ectively, whel~ the xent}ll
p r e s s u r e , P, incl'eases t'l'Olll (1 it) {1()0 "Iol'rs, 01", by
using the adsorptiola isothernl (Fig, re 3), when the
total launaber o f a t o m s a d s o r b e d p e r gl-am o f solid. ,t,
increases f r o m () Io 7 x I() 7n.
W e have also s t u d i e d the effect o f t e i u p e i a t u r e , T,
on the s p e c t r u m when ut is held at 1.8 x 10 "-'°
a t o n l s ' g - n (Figurt:s- 4 a n d 5). W h e n 7" d e c r e a s e s fnonn
70 ° to - 5 5 ° C , 8, is coilsiant :it 114 + 2 p p , n , whereas
Q. increases from 145 to 225 p p n l a n d woithl reach a
value close to 93(1 i}pm i f we were ahle to pcrliirn] the
e x p e r i m e n t s {it lower t e m l ) e r a t u r e without excessive
line-hroadelfing. At the s a m e lime, the intensity I,.,
which is very small at 70°C, increases c o n s i d e r a b l y
and becomes of the S;tlne order o f tmigniiude its I,
when T ( - 4 0 ° C .
T h e i s o t h e r m {Fig.re 3) shows thal for eiich
equilibriunl p r e s s u r e , thc a m o u n t o f x e n o n adst}rl}c{I
on Cs-Rho is m u c h less than t}n H-Rh{}. T h e
c o r r e s p o n d i n g u.m.r, s p e c t r u m consists o f a single
line whose chemical shift wu'ies in parallel with that oF
6,, from 130 to 168 I}pnl, when P increases [rout 1)
to 900 T{}ITS (Figtlre 2). This spectrtllll is itlni{iSl
tenlperature-indepeildeill.
 Characterization of void spaces and location of cations in zeolite Rho: 7". Ito and J. Fraissard
. . . . . . . . i . . . . . . . . I . . . . . . . .

o"

lit

,o=

lC~
/
....... tO ....... i(50 Torr " " iO00
Figure 3 Isotherms of xenon adsorption O, H-rho; A, Cs-Rho

Figure 1 Pressure dependence of the ~2exe n.m.r, spectrum of
adsorbed xenon (T = 26°C)
DISCUSSION
H-Rho
T h e existence o f two lines, e and c, in the spectra at
26°C (Figures 1 and 2) proves that the xenon is
adsorbed in two geometrically different zones. We
know also that:
• T h e zeolite Rho htttice contains two identical but
n o n c o n n e c t e d t,'idimensio,3al channel systems
6
that f o r m topologically d i f f e r e n t a d s o r p t i o n
volumes (Figure 7). O n e c a n distinguish cages close
to 12 ,a, di~tmeter, each linked by 3.9 x 5.1
openings to six 3.2 ~ high octogonal prisms. T h e
ntlml)ers ofcages and prisms are 3.55 x 102" and
1.07 x 10 '-'l g - t , respectively.
1,1 theory, tile internal space of" these w>lunles is the
most accessible when tile zeolite is decationized. In
['aCt, s o n l e atithol'S 18-21) h a v e SilOWI1 that tile
framework o f zeolite H - R h o u n d e r g o e s appreciable
distortion and loss of symmetry upon dehydration.
T h e lattice constant decreases from 15.0 ~, fin.
Iiydrated zeolite, where full lm3m s y m m e t r y is
observed, to 14.7 ,~ (143m) as the water molecules are
removed. Tiffs is due to a tetrahedral d e f o r m a t i o n o f
the co-cages and a concomitant shrinkage o f the
c

150 +
iT

100

i i ' ,~0 i i ,
~ , I , I ,
O'C

-4o°c

0 1O0 Torr
Figure 4 Influence of the experiment temperature, T, on the
Figure Z Chemical shift of ~ZgXe vs. xenon pressure (T = 26°C) spectrum, nz = 1.8 x 10 z° atom-g -1. The intensities of the
O, line e of H-Rho; r-I, line c of H-Rho; A, Cs-Rho spectra are not directly comparable
Characterization of void spaces and location of cations in zeolite Rho: 1". /to and J. Fraissard
. . . . . . . .
E For each value o f ,/. lhe nnmber. ,.. and ,.. o f
8:
200
T , . i . . . .
-50
Figure 5 Chemical shift of lines e and c (H-Rho) against 7". n, =
1.8 x 1 020 atom-g -
d o u b l e 8 - r i n g p o r e o p e n i n g s . A c c o r d i n g t() Fischer et
al., 2~ the shortest a p e r t u r e size o f D - S R for d e h y -
d r a t e d H - R h o is 2.73 A,, c o m p a r e d to 3.76 A. liw full)'
hydrated Rho.
H o w e v e r , these results would a p p e a r to be d e b a t -
able. M c C u s k e r 2~ foulld an u n d i s t o r t e d conformation
for H - R h o d e h y d r a t e d at 400°C, a n d Fisher el a/., '-'l a
3 . 7 6 / ~ o p e n i n g for D-8R when the solid is h e a t e d to
650°C in d e e p - b e d .
T h e value 6s o f 6 at zero x e n o n concentrati()n in
greatest when the mean free path 1- <d the Xe
atoms is smallest :s''-'~ and, t h e r e f o r e , when the
d i m e n s i o n s o f the v o l u m e in wlaich the x e n o n is
adsorbed are tlaemseh'es small.
It can be c o n c l u d e d from the above resuhs that the
x e n o n is adsorbe¢l in the cages a n d i~ris,ns. H o w e v e r ,
the x e n o n canl-tot cross a 2.73 ~ d i a m e t e r opelaing. I f
it is a s s u m e d that d u r i n g d e h y d r a t i o n this s a m p l e has
suffered a distortion as d e s c r i b e d above, in the light
o f otu" results we have to c o n c l u d e that it recovers ils
5-1(Y
ni
0 ~0~o
Figure 6 Partial number n~ of xenon atoms against the total
n u m b e r n r of adsorbed xenon atoms (T = 26°C). n= and n~: nos.
corresponding to lines c and e; n¢,~ and np: total sos. atoms
adsorbed in cages and prisms
556 ZEOLITES, 1987, Vol 7, N o v e m b e r
. . . .
initial Sylllniell'y d u r i l ) g xenml a(Isorpti<m. ;is il does
after rehydration.
x e n o n att)rns c(wresl~(m(ling t() Ihe intensities I, ; u l d / ,
o f the tw() lines can I)e d e t e r m i n e d [)'()m 1he ads(wl)-
tiol-i isotherm (Fig, re 6), At the I)eginnitlg o f atls()rl)-
lion, ,, is much greater than ,,,, I)t,! the laller
increases with , , much me)re r'l, I)i(ll ') that) wilh , , ,
especially when "z exceeds '2 x 0'-".
HoweveI-, I1,, illl(I I1, i l l e II111 I h e Ilnllll)ClS ()l" xell()li
a t o m s located in the prisms mad ('ages, resl)eclively.
e
l ' h e variatiml o f the spectra with lelnl)er:lttwe, T (at
constant ,/) shows Ih;ll at 26°(: line r' is (Ittc t() Ihe
coalescence' o f two lilies: one. r'. has ~he s;anlt' shil't as c
(6,, = 6, = 114 p p n 0 ; Ihe ()lher. p (ti>v prisms) is al
about 23() p p m . hi, :rod 6, a r e the chemical shifts (>F
x e n o n a t o m s a d s o r b e d in the i)visms a n d (ages. 6 I, is
tile limit <d" 6,. al low t e m p e r a t u r e . T h i s coalescence is
d u e to the r a p i d (on the n.m.r, time scale) e x c h , m g e
o f Xe atcm)s a d s o r b e d in the two) zones. "l'his
e x c h a n g e stops ill ;Ib()ut:--4{1°(:.
i . . . . i . . ,"r More~wer, fin" ;I given value (>t ,~, the dislribnti<m
0 50 *C o f Xe ;tt()ms in Ihe i)risms a n d cavilies d e p e n d s <+tl 7,
which explains the v a r i a t i o n <)f 6,. between 26 ° ;rod
- q 0 ° C . F o r e x a m p l e , al 70°C a n d t'~)r ,r = 1.8 × 111'-'".
the atmns are mainly in Ihe c;tges (,, ~ "D- A very
small n u m b e r o f them, ,,., e x c h a n g e between the
cages a,ad Ihe prisms, bul this nutnl)er increases ;tl the
e x p e n s e t)t" lhe t~wmer when 7" decreases. At -.55°(:,
the x e n o n atoms a r e situated in both volt|hieS. More
precisely, their e x c h a n g e [requencv is less Ihal) c'.3/,-
&l e x p r e s s e d m Hz, that ts, ,i )oul 1 0 . Ill , t h c r words,
for a given value ()1' ,/, Ilie n u m l ) e r "/' (d" I)risnls
o c c u p i e d by a xetl()RI H[()Ill, ()l lhe r e s i d e n c e lime o f
these atoms in the prisms, ila(reases as T htlls (,11 leasl,
in the t e n ] p e r a l t t r e r a n g e c o n s i d e r e d ) .
T h e s e resuhs are in a g r e e m e m with th(>se obt,titled
I))' X-rax '17 ((;anles<>n ~'/al.) and llenlr<)n I~+ (Wright i'/
a/.) diffractiota+ which sh()xxed that the prisms a r e the
p r e f e r r e d ads()rpti<)n cenlers at very low t e m p e r , l t t w e
(7"< - I I()°C), but that the.v are mnch less +WCUlfied ;it
h i g h e r telnl)eralttre (7(1~ <)cciq)ati<+n at -61)°(i).
E f f e c t o f n~ at 2 6 ° C
T h e above resuhs t]|;ike it p<)ssible I() I()lh)w the
n u m l ) e r o f a t o m s h)cated ill the cages ;u)(I prisuls as , ,
is varied at ~6°(:. We have seen Ihal the Sl)et'll';.t in
F i g , re 1 C()l]sist o f two lines: c, char;lcleristic o f Ihc
at(ires wilh a long r e s i d e n c e time iH the ('ages: :rod/',
d u e to the coalescence (d" IW() lilies 1~ a n d c',
characteristic o f at()lnS e x c h a n g i n g sites r a p i d l y with
5.~0~0 n
Figure 7 Structure of zeolite H-Rho. Xenon is adsorbed in
octogonal prisms and t~-cages
 Characterization of void spaces and location of cations in zeolite Rho: T. Ito and J. Fraissard
p o p u l a t i o n s .p a n d ,,, in the prisms a n d cages,
respectively. Ctmsequen~ly, m given l i l l e , file total
p o p u l a t i o n s in the pl'isn~s a n d cages are "1, a n d ,,.; =
, , + ,,,, respectively. A s s t m l i n g thai site exclaange is
r a p i d , o n e can easily d e t e r n l i n e nl, a n d ,,, [•r4ml the
value i5, a n d the theoretical shifts 6/, and 6,,, in the
absence o f exchalage. In this case:
IIe = lip + II d
6,.- 6,' "I'
81, - b,. .,,
therefore
Ill, ~" l"ll~' I1,' : _ _
l+r
whellce
lip ~ 11¢ - - II~'
ll~.t = II~ + lit'
For this calcuhllion, w e have taken For hI, Ihe value
b, = 230 I)pln at - 5 5 ° ( ; when tt = 1.8 x 1()'-"'. ""lilt"
Mild b/, sh41uld not c h a n g e very much with , , sitlce
each octog4,1al pl'iSln Callll()l "h4dd IllOl'C IhHII lille
x e n o n at4)lll. F o r b,,, wc have lakcn Ihe v,due b, given
experinaelmllly .uld characteristic 4~1' the I)t)l)ul,tlion
oJ alOlns in cages. I"iffltre 6 shows I}l;.ll at 21i°(; with ,~
sin;ill, in41st o f al4)lns ;11"C ill tile 4ages. (:onvel'sely, li~l
h i g h e r vahtes 41t IIt t h e r e ,Irc ,tl)ottt as altar< ill lilt"
cages ;IS ill the I)l'iSlnS.
Cs-Rho
T h e case 4d (:s-Rh4> is d i l R : l e n t I+ronl thal o f I-I-Rh4)
bec,luse o1 tile Cs + c,tlions. 'I'he single line d e l c c l e d
can lie d u e only 14) Xe ;II4)lI~S in tile cages. Sincc the
t e m p e r a t u r e e[l%cl is negligible, lhis lille C;UlllC~tresuh
tl4)nl the c4)alcscelwe ()t IW4) sigtuds C4)l'resp()nding I0
al(mlS e x c h a n g i n g r a p i d l y I)etwecn two adS()l'ptic)n
z4)nes, Furthel'm4)le, since Ille accessil)ilitv ()1 these
volunleS a n d the ale:in free p:lth o f Xe ill e:lch 4)I"
t h e m a r e n l a x h m l l fol- l l - R h o , l h c c h e n l i c a l s h i l i o f
x e l l O l l ;ttJStil'J)ed hl e;ich oJ" l h e JallC'l llltlSl be g1-l:;itel-
Ihan o r al le;isl equal It) the I)revi4)us values 6/, :l,ltl
b,. -'''-'t T h e Cs + cati4,1s are dleveF4~le re,lilly, in the
prisnls. Since they have almul 1lie s,une ra41ius as
xe,14m atoms, they prevent tllen~ fl'Oln b e i n g ill the
prislns.
T h i s rcsuh is c4ml]l-lned by study o f the Cs-Rho a n d
H-Rh4I is41thernls al 26°C. F4n- l)ressurcs I)el4~w 111)4)111
IO "l'ol'r. that is. when tile xe114)11 ;ids4nl)ed ¢)n l I-Rho
is entirely in tile cages, tile two isothevnls coincide.
T h e d i f f e r e n c e between them, which increases at the
e x p e n s e 41t Cs-Rh4) when 1' is raised, is hi;tinily (Itlc t4)
Ihe fact that x e n o n ;ill)IllS :ll'e nol IocatecI in tile
i)rislns o f this s4did, w h e r e a s ill H-Rh4,, the x e n o n
goes tall41 both Ille I)l'iSlllS and d i e cages.
1-h)wever. how ¢loes Ihe xe111111 d i f l u s e 11"o111 41lie
cage Io an4~ther if Ihe I~l'islns are o c c u p i e d by Cs?
A d l n i t t e d l y , all tile prisms a r e not oCCUlfied, I)ul t h e r e
would have to I)e at le,lsl 2()t/~ e m p t y a n d diSllil)uted
h o n l o g e n e o u s l y to allow d i f f u s i o n t l u ' o u g h the prisms
not c o n t a i n i n g Cs. In tiffs case the line o f shift 61,
would be visible. It l'nust be a s s u m e d , t h e r e f o r e , that
the Cs + cations can be d i s p l a c e d m o m e n t a r i l y fi-om
their equilibriunl positions by the x e n o n to allow t h e
latter to diffuse.
Finally, what causes the increase, c o m p a r e d to
H - R h o , o f the shift 6~ o f Xe a t o m s located in the
Cs-Rho cages? It has been shown that t h e t e t r a h e d r a l
d i s t o r t i o n o f these cages is even g r e a t e r than that for
H-Rho. Is''':s H o w e v e r , the d e c r e a s e in the lattice
c o n s t a n t to 14.6 ,~. does not a p p e a r sufficient to
explaill COlnplelely an increase in b, o f a b o u t 20 p p m .
Doubtless, one must also a d d the steric effect o f the
Cs + cation that sticks out fi'Oln the prisms a n d ,
i)articulal'ly, daeir polarizability, as has been seen in
the case o f zeolites K-Y a n d Rb-Y. H~
CONCLUSIONS
T h i s study is a f u r t h e r e x a m p l e o f the interest o f
I).111.I'. ille~lgLll-enleFlts on a d s o r b e d r-':'Xe in the
c h a r a c t e r i z a t i o n o f l h e void spaces o f zeolites a n d the
localization o f cations. W e have d e m o n s t r a t e d that in
H - R h o the d i s t r i b u t i o n o f x e n o n a t o l l s between the
cages a n d the prislns d e p e n d s 4m the e x p e r i m e n t a l
t e n q ) e r a t u r e , T, a n d on the total COl~cenu'ati,m o f
adsorl)ed xenola, n,. At 260( ` a n d low c o n c e n t r a t i o n ,
most o f the x e n o n a t o m s a r e in the cages, but theil"
r e s i d e n c e time in the I)rislns increases with ,¢ a n d
with lowerin~ o f the adsorptiola t e m p e r a t u r e . F o r
e x a l n p l e , w h e n "t -- 1.8 × - 1 (i'm " at 9(-o.,
,)~_., t h e r e a r e
1.2 × 10 "-'¢~a t o m s in t h e cages a n d 0.6 × 10"" r a p i d l y
e x c h a n g i n g between ads,,rpli4)l] zones; at - 5 5 ° C ,
thel'e are a p p r o x i m a t e l y as nlany a t o m s in the prisms
mad in the cages.
ACKNOWLEDGEMENT
' l ' h e a u t h o r s t h a n k Dr. Klinowski for tile samples.
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Characterization o f void spaces and location o f cations in zeolite Rho: 7". Ito and J. Fraissard
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