2590 J . Phys. Chem.

1989, 93, 2590-2595

spectra of adsorbed CO may be assessed. Magic-angle spinning
yields precise isotropic shifts and thus could detect subtle changes
in the properties of the adsorption site caused by, for example,
promoters or coadsorbates. However, magic-angle spinning spectra
of adsorbed CO should not be used to exclude the existence of
some species. As noted above, the bridge-bonded species do not
appear and could be overlooked if the lack of agreement between
the center of mass of the broad-line and high-resolution spectra
was not noted. The I3C N M R spectra of CO on Rh/silica il-
lustrate another caveat; similar isotropic shifts of the dicarbonyl
and linearly bonded CO caused two species to appear as one. To
separate these components, it was necessary to decompose the
spectra by using sideband intensities predicted from fits to the
broad-line spectra. Also, it is tenuous to extract relative site
populations from the magic-angle spinning spectra, as seen by
comparing the broad-line and high-resolution results in Table I.
Measuring both high-resolution and broad-line spectra aids the
assignment of component peaks. For example, CO on Ru has at
least three isotropic peaks in the range 200-175 ppm, which this
study identifies as 199, 195, and 180 ppm. The peak at 199 ppm
can be correlated to the Lorentzian peak in the broad-line spectrum
by its atypical sharpness (cf. Figure 7) and its lack of sidebands.
The other two peaks have sidebands whose intensities and range
correspond to linearly bonded CO species. We note that these
assignments are inconsistent with an earlier study of CO on Ru/Y
~ e o l i t e which
,~ proposed the following peaks and assignments:
dicarbonyl (168 ppm), linearly bonded CO (1 80 ppm), and bridge
bonded (203 ppm). On the basis of the results obtained here, we
propose alternate assignments: multicarbonyl (203 ppm), linearly
bonded (180 ppm), and linearly bonded (168 ppm). The
bridge-bonded species is predicted to lie upfield of 203 ppm and
we believe was not resolved, for reasons discussed in preceding
sections.
V. Summary
High-resolution and broad-line I3C N M R spectra of CO on
silica-supported Ru and Rh corroborate previous assignments and
provide additional information on the adsorbed states. The
high-resolution spectra obtained by magic-angle spinning reveal
isotropic shifts consistent with the broad-line components proposed
previously to be linearly bonded CO and multicarbonyls formed
on isolated metal atoms. In addition, experimental evidence
suggests two types of linearly bonded CO on Ru/silica. The
sharpness of the linear peaks suggests that some Ru and Rh
aggregates have negligible magnetic susceptibility, consistent with
raftlike structures.
Quantitative comparison of the high-resolution and broad-line
spectra of adsorbed CO reveals possible pitfalls of relying on
magic-angle spinning spectra alone. First, bridge-bonded CO,
whose presence is indicated by the quantitatively correct broad-line
spectra, is not sufficiently narrowed to be observed in magic-angle
spinning spectra. If the I3CNMR spectrum of the bridge-bonded
species is broadened by chemical inhomogeneity, then improved
resolution (for example, to resolve 2-fold and 3-fold bridged CO)
lies in the realm of sample preparation and not N M R metho-
dology. Second, species whose line shapes are distinctly different
in the broad-line spectra, such as the Lorentzian of the Rh di-
carbonyl and the powder pattern of the linearly bonded CO, may
have the same isotropic shift and be unresolved in magic-angle
spinning spectra. While in principle they may be separated by
analysis of sideband intensities, this is not practical to do without
constraints provided by other techniques. Finally, the relative site
populations in the high-resolution spectra are inconsistent with
the independently calibrated broad-line spectra. Avoiding these
and other traps by using the strengths of several techniques-
resolution of species and accurate determination of isotropic shifts
from magic-angle spinning, and anisotropies and quantitative
measurement of all species from wide-line spectroscopy-to
compensate for the weaknesses of the other gives more reliable
results.
Registry No. CO, 630-08-0; Rh, 7440-16-6; Ru, 7440-18-8.

Solid-state NMR Study Using Trimethylphosphine as a Probe of Acid Sites in Normal

and Dealuminated Zeolite Y

Jack H. Lunsford,*,t Pierre N. Tutunjian,*-* Po-jen Chu,+ Eshan B. Yeh,? and David J. Zalewsk?
Department of Chemistry, Texas A & M University, College Station, Texas 77843, and Shell Development
Company, Houston, Texas 77001 (Received: July 22, 1988)

31PMAS-NMR spectra of trimethylphosphine adsorbed in normal and dealuminated zeolite Y have been used to provide
both qualitative and quantitative information on their acidic properties. Interaction of the (CH3)3Pwith Bransted acid sites
gives rise to the protonated adduct having chemical shifts in the range -1 to -4 ppm. In a partially oxidized sample the
protonated form of trimethylphosphine oxide exhibits a resonance at 64.6 ppm. The integrated spectra of these two protonated
species provide a reasonably reliable quantitative determination of the Brernsted site concentration provided the concentration
is 233/uc (unit cell). Trimethylphosphine also interacts with Lewis acid sites in steam-dealuminated zeolites which were
dehydrated at 400 "C, but the Lewis-bound form is in rapid chemical exchange with the liquidlike (CH3)3P. The resulting
resonance is at -62 ppm. When the zeolites were heated to 600 'C, additional resonances were observed in the range -31
to -58 ppm. These are attributed to (CH&P at other Lewis acid sites which develop as the aluminum oxyhydroxide in the
large cavities progressively dehydroxylates. In the presence of oxygen the Lewis-bound and liquidlike species are rapidly
oxidized to the corresponding oxides, which exhibit resonances at 56.4 and 43.5 ppm, respectively.

Introduction to structural factors such as the silicon-to-aluminum ratio, it is

The protonic forms of zeolites exhibit acidic properties which important to develop methods for determining the acidity of both
are largely responsible for the catalytic importance of this class the Brernsted and Lewis acid sites. Jacobs] has reviewed several
of material. In order to relate acidity to catalytic activity and of the techniques that have been employed to determine acidity.

'Texas A & M University. ( 1 ) Jacobs, P. A. In Characterization of Heterogeneous Catalysu: Della-

'Shell Development Co. ney, F., Ed.; Marcel Dekker: New York, 1986; pp 367-404.

0022-3654/89/2093-2590$01.50/00 1989 American Chemical Society

Trimethylphosphine Adsorbed in Zeolite Y
Recently, solid-state NMR spectroscopy of basic probe molecules
has emerged as a promising approach for evaluating not only the
types of acid sites on alumina and aluminosilicates but also the
number of acid sites. Nitrogen-15 bases, including ammonia,
pyridine, and trimethylamine, have been effectively used; however,
the small magnetogyric ratio of I5N results in sensitivity prob-
l e m ~ . ~ -These
~ difficulties have been overcome by adopting
)IP-containing probe molecules such as trimethylph~sphine.~-*In
addition to being a highly sensitive nucleus, 31Pchemical shifts
are relatively large, which enables one to obtain information on
the types of acid sites that are present in the catalysts.
A variety of phosphorus bases, including trialkylphosphines and
phosphine oxides, have now been used to characterize acid sites.
Among these, trimethylphosphine has one important advantage
in that the spectrum of the protonated adduct exhibits
coupling, which enables one to probe Bransted acidity with con-
fidence.5s6 Moreover, there is some indication from earlier studies
that the chemical shift differences from -2 to -4 ppm might reflect
differences in Bransted acid ~ t r e n g t h .Dehydroxylation
~ of H-Y
zeolites at elevated temperatures is known to produce Lewis acid
sites, and indeed resonances in the region from -32 to -58 ppm
suggest that several types of Lewis acid adducts are f ~ r m e d . ~
In the present study it was of interest to examine dealuminated
Y-type zeolites because of their importance in petroleum refining
as cracking catalysts. Partial removal of framework aluminum
reduces the concentration of acid sites in the zeolite, but mea-
surements of catalytic activity indicate that the acid strength
increasesg During the removal process part of the extracted
aluminum remains in the cavities as oxides and oxyhydroxides.
This extraframework aluminum dehydroxylates when heated, and
the resulting Lewis acid sites may result in catalyst deactivation
via the formation of nonvolatile carbonaceous residues known as
coke.I0
Evaluation of )'P N M R as a quantitative technique for de-
termining acid sites in zeolites also was a goal of this research.
In earlier studies Haw et al." adopted titration methods to estimate
the numbers of Bransted and Lewis sites on an amorphous sili-
ca-alumina. In one study n-butylamine was used to displace
I5N-enriched pyridine, a weaker base, from the Bransted and
Lewis sites. Estimates of the amount of Bransted acidity were
obtained from the equivalents of n-butylamine required to com-
pletely displace pyridine from the Brernsted acid sites. On a similar
acid catalyst trimethylphosphine, triethylphosphine, and tri-
butylphosphine were added until no further increase in the signal
of the protonated adduct was observed.6 For the pyridine and
the three trialkylphosphines the end points occurred at 0.17, 0.23,
0.19 and 0.15 mmol of H+ per gram of catalyst. Several reasons
were offered for the observed discrepancies, but in the absence
of a material of known proton concentration it was not possible
to distinguish between the alternatives. Unlike the amorphous
aluminosilicates, for which the proton concentration is unknown,
the proton concentration in the H-Y zeolite, at least in principle,
is known from the framework aluminum content. Thus, one has
(2) Earl, W. L.; Fritz, P. 0.;Gibson, A. A. V.; Lunsford, J. H . J . Phys.
Chem. 1987, 91, 2091.
( 3 ) Ripmeester, J. A. J . Am. Chem. SOC.1983, 105, 2925.
(4) Maciel, G. E.; Haw, J. F.; Chuang, I.&; Hawkins, B. L.; Early, T. E.;
McKay, D. R.; Petrakis, L. J . Am. Chem. SOC.1983, 105, 5529.
(5) Lunsford, J. H.; Rothwell, W. P.; Shen, W. J . A m . Chem. SOC.1985,
107, 1540. Rothwell, W. P.; Shen, W.; Lunsford, J . H. J . A m . Chem. SOC.
1984, 106, 2452.
(6) Baltusis, L.; Frye, J. S.;Maciel, G. E. J . A m . Chem. SOC.1987, 109,
40.
(7) Bein, Th.; Chase, D. B.; Farlee, R. D.; Stucky, G. D. In New Deuel-
opments in Zeolife Science Technology; Murakami, Y . ;Iijima, A,, Ward, J .
W., Eds.; Kodansha Ltd.: Tokyo, 1986; pp 311-318.
(8) Baltusis, L.; Frye, J. S.; Maciel, G. E. J . A m . Chem. SOC.1986, 108,
71 19.
(9) DeCanio, S. J.; Sohn, J. R.; Fritz, P. 0.;Lunsford, J. H. J . Carol. 1986,
101, 132. Sohn,J . R.; DeCanio, S. J.; Fritz, P. 0.;Lunsford, J . H. J . Phys.
Chem. 1986, 90, 4847.
(101 Nock. A.: Rudham. R. Zeolites 1987. 7 . 481.
~I
( 1 1 ) Haw,'J. F.; Chuang, I.-S.; Hawkins,'B:L.; Maciel, G. E. J . Am.
Chem. SOC.1983, 105, 7206.
The Journal of Physical Chemistry, Vol. 93, No. 6, 1989 2591
a standard material for comparison with N M R results.
Experimental Section
Zeolite Samples. All of the zeolite samples used in this study
were prepared from Union Carbide's LZ-Y62 (Si/Al = 2 . 5 5 ) or
LZ-Y52 (Si/Al = 2.38). The Na+ cations were replaced with
NH4+ cations by treatment with a solution of either (NH4)2S04
or NH4N03. A typical ion exchange consisted of stirring 5 g of
zeolite with approximately 15 equiv of NH4+ in 500 mL of dis-
tilled, deionized water. The solution was maintained at 80 OC
for 2 h. After washing the sample, the procedure was repeated
an additional two times. The last exchange solution was allowed
to equilibrate for 12 h before collecting the zeolite. Samples
containing various amounts of Na, designated as NaH-Y, were
prepared by a single ion-exchange step. The desired amount of
N H 4 N 0 , was added to 2 g of zeolite in 500 mL of water. After
heating the solution to 80 OC for 6 h, the zeolite was collected
and washed with distilled, deionized water. The final Na con-
centration was determined by inductively coupled plasma (ICP)
analysis.
Three methods were used to extract aluminum atoms from the
framework of the zeolites, thus altering the silicon-to-aluminum
ratio. The dealumination was achieved by steaming, by dehy-
droxylation, and by reaction of the zeolite with SiC14.
The steamed zeolite was prepared by heating an NH4-Y zeolite
under flowing N 2 / H 2 0 to 600 OC for either 1 or 3 h. The sample
was then cooled under steam and ion exchanged with NH4+ (1
M N H 4 N 0 3 , 60 "C, 12 h) to remove residual Na+ ions. This
material, referred to as SDY for steam-dealuminated Y-type
zeolite, was crystalline and contained 38 and 28 Al/uc for the
samples steamed for 1 and 3 h, respectively. An ICP analysis of
the SDY (3 h) zeolite indicated that the material contained a total
of 53 Al/uc. Thus, the majority of the A1 atoms removed by the
steaming process remained inside the zeolite cavities as extra-
framework AI. Unless otherwise stated, this and subsequent
dealuminated samples were heated under vacuum to 400 O C and
maintained at that temperature for 2 h.
A method that involves dehydroxylation of the zeolite at elevated
temperatures was introduced by McDaniel and Maher.', Fol-
lowing the method B, a Na-Y zeolite was ion exchanged twice
with NH4+ in a solution of (NH4)2S04. The zeolite was washed
free of sulfate ions and heated in air to 815 OC for 3 h. After
cooling, the zeolite was again ion exchanged twice with NH4+ at
100 "C for 1 h, washed free of sulfate ions, and then dried.
According to powder X-ray diffraction analysis the zeolite was
crystalline and contained 33 Al/uc. As with the SDY zeolite,
essentially all of the A1 removed from the framework remained
in the cavities. This material is referred to as USY for ultrastable
Y-type zeolite.
The SiC1,-dealuminated zeolite (DY) was prepared by first
heating ca. 2 g of NH4-Y zeolite to 375 OC at a rate of 0.9 "C
min-I under flowing N z (100 mL min-'). The sample was
maintained at 375 "C overnight. Subsequently, the sample was
exposed to SiCl, vapor in flowing N, at 50 OC. The sample
temperature was raised to 275 OC at a rate of 4 "C min-I, the
SiC1, was interrupted, and the sample was maintained under
flowing N2 for 4 h at 275 OC. After cooling to 25 OC the zeolite
was exchanged three times with NH4+ions. The sample was then
deamminated at 400 "C, as described previously. The DY zeolite
contained 38 Al/uc.
Trimethylphosphine (Strem) was adsorbed from the vapor phase
(20 Torr) on the zeolite samples (0.5 g) which were at 25, 50,
or 80 "C. For all quantitative experiments the trimethylphosphine
was added to the zeolite at 80 "C and the zeolite was cooled to
25 OC in 20 Torr of gas. In some cases excess and weakly adsorbed
trimethylphosphine was removed by heating the sample under
vacuum. Normally, the zeolite was then transferred to the NMR
rotor in a glovebox or dry bag filled with either dry nitrogen or
argon; however, several samples were sealed in glass ampules which
(12) McDaniel, C. V.; Maher, P. K. In Proceedings of the Conference on
Molecular Seiues, 1967; Society of Chemical Industry: London, 1986; p 186.
2592 The Journal of Physical Chemistry, Vol. 93, No. 6, 1989
a
-1 I a
, . . . . , . . . .
100 50 0 -sa
PPI4
Figure 1. Proton-decoupled, 90" pulse ,lP MAS-NMR spectra of
(CH,),P in zeolites which were dehydrated at 400 "C: (a) H-Y, (b) DY,
(c) SDY. Excess (CH3),P was added to the samples at 80 "C, and
spectra were obtained at 25 "C. denotes spinning sidebands.
were inserted into the N M R rotors.
N M R Experiments. The N M R results reported here were
obtained with a Bruker CXP-200 spectrometer that was equipped
with a Chemagnetics probe or with a Bruker MSL-300 spec-
trometer and probe. Unless otherwise noted, magic angle spinning
(MAS) at 3-4 kHz was employed along with either cross-po-
larization or 90" pulse methods. The spectra were collected with
and without proton decoupling. Quantitative spectra were obtained
by using a 90" pulse-and-acquire sequence. Standards consisting
of various amounts of (NH4),HP04 physically mixed with
N H 4 N 0 3were used to determine the absolute number of 31Pspins.
By varying the time between successive pulses, it was found that
both the standards and the samples had T I less than 5 s. Chemical
shifts are reported relative to 85% H3P04 with negative shifts
reflecting greater shielding (i.e., higher external field required).
Results and Discussion
Lewis Acidity in Zeolites. Proton-decoupled spectra of H-Y,
DY, and SDY samples, all of which contained excess tri-
methylphosphine, are shown in Figure 1. The spectra of the H-Y
and DY zeolites are remarkably similar. Notably absent from
the spectrum of the DY sample are resonances in the -30 to -60
ppm region from Lewis-bound trimethylphosphine. Although the
reaction of the zeolite with SiCI, removes part of the aluminum
as volatile AICI,, it is evident from previous studies that part of
the aluminum remains within the zeolite cavities9 By contrast,
in the SDY zeolite essentially all of the aluminum removed from
the framework resides in the cavities. Characterization of this
extraframework material by Shannon et aI.l3 has led to the
conclusion that it is present as y-A100H (boehmite). The res-
onance at -62.6 ppm in Figure I C is distinctly at a lower field than
the resonance at -67.4 ppm for liquidlike (CH,),P in the zeolite
c a ~ i t i e s . ' Also,
~ it is significant that there is no resonance at -67.4
(13) Shannon, R. D.; Gardner, K. H.; Staley, R. H.; Bergeret, G.;
Gallezot,
P.;Auroux, A. J . Phys. Chem. 1985, 89, 4778.
Lunsford et al.
40 20 0 -20 -44 -60
P PM
I .
-LOO Figure 2. I'P MAS-NMR spectra of (CH3),P in a SDY zeolite which
had been dehydrated at 400 "C: spectra obtained with the sample at (a)
25, (b) -28, and (c) -63 "C. The concentration of (CH,),P in the zeolite
was approximately equivalent to that of the framework aluminum atoms.
denotes spinning sidebands.
ppm in Figure IC, which is surprising since excess (CH,),P was
present in the zeolite. The width of the resonance for the pro-
tonated adduct also is considerably greater in the SDY sample
than in the DY sample (12 ppm vs 3 ppm). Moreover, as the
temperature of the SDY sample was lowered the resonances
sharpened up. This behavior in the SDY sample is consistent with
a rapid chemical exchange between two phosphine species. When
a sample of SDY was degassed at 100 "C following the addition
of trimethylphosphine, the only resonance was that of the pro-
tonated adduct at -4 ppm.
An additional manifestation of the exchange process was ob-
served when (CHJ3P was adsorbed on a SDY zeolite in an amount
which was approximately equivalent to the framework aluminum
content, Le., approximately equal to 24 (CH,),P molecules/uc.
At this loading the large cavities were only partially filled. Oxygen
was rigorously excluded from this sample. The resulting room-
temperature spectrum shown in Figure 2a exhibited a single, broad
resonance at -19.4 ppm. No spinning sidebands were observed
in this spectrum. Upon cooling the sample to -28 "C two reso-
nances at -3.7 and -59.9 ppm were observed (Figure 2b), but both
lines wcre rather broad. Further cooling to -63 "C resulted in
the spectrum of Figure 2c, which was similar to, but better resolved
than, that of Figure IC. The resonance at -3.6 ppm, assigned to
[ (CH3)3P-H]+,possesses spinning sidebands, which indicates that
the protonated adduct is no longer undergoing a rapid chemical
exchange process. The remaining resonance at -60.2 ppm does
not have any spinning sidebands associated with it. Moreover,
the chemical shift value of -60.2 ppm is between that of Lewis-
bound (see below) and liquidlike (CH3),P. The effect of tem-
perature was completely reversible. These results suggest that,
in a partially loaded sample, chemical exchange is occurring not
only between the liquidlike and Lewis-bound trimethylphosphine
(14) Previ~usly,~
the resonance at -67 ppm was attributed to physisorbed
(CH3),P, but here we make the distinction between liquidlike and several
forms of the Lewis-bound base, all of which could be referred to as physi-
sorbed.
Trimethylphosphine Adsorbed in Zeolite Y
b
h
1 . . . . I . . . . I . . . . I
100 0 -so
so PPY
Figure 3. Spectra obtained 5 days after those of Figure 1: (a) SDY, (b)
DY. denotes spinning sidebands.
but also between the Lewis-bound base and the protonated adduct.
The former gives rise to the resonance at -60.2 ppm and the latter
to the resonance at -19.4 ppm. Even at -63 OC it was not possible
to slow down the exchange between Lewis-bound and liquidlike
(CH,),P such that two resonances could be resolved. These
exchange processes, however, become slower when the zeolite is
fully loaded with (CH,),P.
Although the oxidation of trimethylphosphine in zeolites will
be reported more fully in a subsequent paper, the spectrum de-
picted in Figure 3a reveals some of the salient features of the
process. After 5 days in the rotor, sufficient oxygen leaked into
the SDY sample to form trimethylphosphine oxide (TMPO),
which gives rise to the resonances at 43-65 ppm. In agreement
with the assignments of Baltusis et a1.6, we attribute the resonances
at 43.5, 56.4, and 64.6 ppm to physisorbed, Lewis-bound, and
protonated TMPO, respectively. The sharp resonance at 26.9 ppm
has not been assigned at this time. It is evident from this spectrum
and related studies that the weakly bound (CH3),P is much more
easily oxidized than the protonated adduct.
The DY zeolite after 5 days in the rotor exhibited the spectrum
of Figure 3b. Here the resonance of the liquidlike (CH,),P has
decreased relative to that of the protonated adduct, and the
principal form of TMPO is physisorbed. Only a small amount
of protonated TMPO was detected, and none of the Lewis-bound
form was observed.
The nature of Lewis acid sites in these dealuminized zeolites
has been explored further by dehydroxylating the samples at 600
OC. In the previous study of H-Y zeolite^,^ it was demonstrated
that Lewis sites began to form upon dehydroxylation of the zeolite
at temperatures greater than 400 OC. But this process is com-
plicated by the fact that dehydroxylation is accompanied by
dealumination. In the present study the SDY zeolite was already
dealuminated; therefore, the higher temperature (600 "C) mainly
resulted in the dehydroxylation of the zeolite as well as the ex-
traframework alumina.
Whereas H-Y zeolites begin to dehydroxylate significantly only
at temperatures >400 0C,15*16 alumina progressively dehydrox-
ylates as the temperature is increased above 100 OC. As reported
by Peril' for y-A1203, 56% of the water (present as hydroxyl
groups) is removed at 400 O C and 84% is removed at 600 O C .
Peril* has developed a model that shows the evolution of oxide
(15) Uytterhoeven, J.; Christner, L. G.; Hall, W. K. J . Phys. Chem. 1965,
69,21 17.
(16) Ward, J. W. J. Catal. 1967, 9, 225.
(17) Peri, J. B. J . Phys. Chem. 1965, 69,211.
The Journal of Physical Chemistry, Vol. 93, No. 6,1989 2593
- 58.6
a
-
28.7
IAJ
-
.54.5
b
C
- 61.7
. . . . I .
-100
200 100 0 -lw
PPM
Figure 4. 3'P MAS-NMR spectra of (CH3)3Pin zeolites which were
dehydroxylated 10 h at 600 OC: (a) H-Y, (b) SDY after several minutes
in the probe, (c) SDY after 2 h in the probe. denotes spinning side-
bands.
ions and oxide vacancies on the surface. Oxide vacancies and,
thus, exposed aluminum ions begin to occur at temperatures as
low as 250 "C, but two or more adjacent oxide vacancies occur
only at temperatures above 450 "C. From this model it is evident
that the types of Lewis acid sites change with the extent of surface
dehydroxylation. Although there are undoubtedly differences
between an extended alumina surface and the small particles in
the zeolite, the qualitative effects are believed to be similar. In
a previous study it was demonstrated that (CH,),P adsorbed on
y-A1203which had been degassed at 500 "C gave rise to a single
resonance at -56.3 p ~ m . ~
The spectra of (CH3),P in H-Y and SDY zeolites, after the
samples had been heated in vacuo to 600 OC for ca. 10 h, are
shown in Figure 4. The spectrum of Figure 4a obtained with
the H-Y zeolite is similar to that which was reported previously
for a H-Y zeolite that had been dehydroxylated 2 h at 700 O C 5
The most prominent feature is the resonance at -58.5 ppm. The
proton coupled spectrum (not shown) was almost identical, except
that the resonance at -3.7 ppm was significantly broadened. Even
in the static mode the resonance at -58.5 ppm was relatively
narrow, which suggests that the coordinated (CH,),P is mobile
on the N M R time scale. As observed with the SDY sample
(Figure IC), the spectrum exhibited no resonance at -67 ppm even
though the zeolite contained excess trimethylphosphine.
The 31Pspectrum of the analogous SDY sample, dehydroxylated
at 600 OC, is shown in Figure 4b. In many respects the spectrum
resembles that of an H-Y zeolite which had been dehydroxylated
for 2 h at 600 O C ; only the [(CH,),P-H]+ resonance is consid-
erably weaker in the SDY sample. The resonances from -3 1.1
to -54.5 ppm, attributed to Lewis-bound trimethylphosphine, are
clearly evident. This rotor, however, was not sealed well, and it
is evident that air slowly leaked into the sample. As indicated
by the spectrum of Figure 4c, after 2 h in the probe oxidation
products were formed, and the intensity of both the protonated
TMPO and trimethylphosphine resonances increased at the ex-
(18) Peri, J. B. J . Phys. Chem. 1965, 69,220.
2594 The Journal of Physical Chemistry, Vol. 93, No. 6, 1989 Lunsford et al.

pense of the Lewis-bound trimethylphosphine. The reversible TABLE I: Quantitative Evaluation of Bransted Acid Sites in Zeolite
conversion of Lewis acid to Brernsted acid sites upon addition water Y
has been noted previously with ze01ites.l~ In addition, a new
[(CH3)3- %[(CH3)-
resonance becomes apparent at -61.7 ppm, which is near the [(CH,),P-H]+/ P-HI+/ P-HI+/ total
position of the high field resonance of Figure IC. Upon longer Al/uc" gX uc A1 P/uc
exposure to air this peak also disappeared. H-Y 54 (2.6)b 17 24.6 46 37
The latter result provides a clue to the origin of the resonance SDY(1 h) 38 (4.0) 8.6c 15.4 41 38
at -61 to -63 ppm. As water is adsorbed by the highly hydroscopic SDY(3 h ) 28 (6.9) 9.5' 20.6 74 33
sample, it is evident that the zeolite framework is partially re- USY 33 (5.8) 13.5' 28.6 87 45
hydroxylated, and one would expect that the alumina in the cavities DY 38 (4.0) 9.9 20.5 54 33
also would be rehydroxylated. We tentatively assign the resonance
a Framework AI per unit cell (uc). *%/AI ratio given in parentheses.
at -60 to -63 ppm to (CH3),P which is weakly adsorbed on 'Obtained from [(CH3),P-H]+ plus [(CH3)3PO-H]+.
partially hydroxylated alumina in the zeolite cavities. This form
of trimethylphosphine is undergoing rapid exchange with liquidlike
molecules that also must be present in the sample. Here it should TABLE 11: Effect of Sodium Ion and Proton Concentrations on the
Forms of Trimethylphosphine in Zeolite Yo
be noted that (CH3),P in a Na-Y zeolite exhibits a resonance
at -59.5 ppm, which demonstrates that noncoordinating ions also [(CH3!,- [(CH,),- 7% H'
promote a 31Pchemical shift. The extraframework aluminum in P-H1 P-Nal' (CHd,P TMPO detected
the DY material perhaps is in the small cages and thus is inac- NaSl-Y 0 24
cessible to the probe molecule. Na49H8-Y 5 22 62
Trimethylphosphine is a soft base and therefore does not interact Na31H20-Y 16 16 1 2 80
strongly with hard acids such as tricoordinate aluminum. Even NaZ2H3,-Y 24 13 69
when Lewis acids are present in the zeolite, the coordinated Na, ,H,,-Y 21 13 63
Na6H4*-Y 25 12 52
(CH3),P is often characterized by relatively small chemical shifts
and rapid chemical exchange. Thus, the demarcation in the NMR "All concentrations expressed as molecules per unit cell
spectrum between Lewis-bound and other weakly bound forms
of trimethylphosphine is not always obvious. The (CH3),P and The results obtained for five samples are summarized in Table
(CH,),PO spectra complement one another in that (CH3),P is I. It is evident from these data that the concentration of the
more sensitive with respect to Brolnsted acidity; whereas (CHJ3P0 protonated adduct is less than that of the framework aluminum.
provides a more definitive test of Lewis acidity. For example, the When trimethylphosphine was adsorbed on the H-Y zeolite de-
resonance at -62.6 ppm in Figure I C does not provide conclusive hydrated at 400 "C, the concentration of [(CH,),P-H]+ was
evidence for Lewis acidity, but the resonance at 56.4 ppm in Figure determined to be 24.6 Al/uc. This value represents only 46% of
3a, obtained after partial oxidation of the (CHJ3P, confirms the that expected from the aluminum content. This material contained
presence of Lewis acidity in this sample. Consistent with this 6.3 Na+/uc; therefore there were actually 48 H+/uc. Hence, 52%
interpretation, almost no resonance was observed at -62.6 ppm of the protons were detected by NMR. With respect to repro-
in the spectrum of (CH3),P on DY (Figure lb) and the spectrum ducibility it is interesting to note that a second sample, run on
for Lewis-bound TMPO is not present in Figure 3b. a different instrument by a different operator, gave a value of 23.5
These results, together with the spectrum of (CH,),P on H-Y [( C H ~ ) ~ P - H ] + / U C .
(Figure la), confirm that for samples which have been carefully The inability of the probe molecule to sample all of the protons
degassed to 400 "C Lewis acidity is present neither in a H-Y in this zeolite appears to be the result of filling and steric factors.
zeolite nor in a DY zeolite, but it abounds in a SDY zeolite. For The filling of (CH3),P in the large cavities was determined by
samples dehydroxylated at T L 600 "C Lewis acidity is present several methods, and it is evident that the maximum loading is
in all protonated Y zeolites, and the extent of dehydroxylation about 40 molecules/uc or 5 molecules per large cavity. Bein et
alters the nature of the Lewis acid site. al. arrived at an identical number.' This value is consistent with
Quantitative Determination of Brolnsted Acidity. For the pure a measured liquid density of 0.70 g/mL for (CH3)3P. A H-Y
H-Y zeolite each framework aluminum atom is charge-balanced sample was weighed before and after exposure to (CH3),P, and
by a proton; thus, from the number of A1 atoms per unit cell one the amount adsorbed was determined to be 38 molecules/uc, which
can determine the number of H+ ions per unit cell. A calculation is in good agreement with the value of 37 molecules/uc determined
of the number of protons in a dealuminated zeolite is not nearly from the N M R spectrum (protonated adduct plus liquidlike
so straightforward as some of the extraframework aluminum may material). As indicated in Table I, all of the zeolites had a total
be present in the cationic form which cannot be removed by loading of 33-38 molecules/uc with the exception of the USY
ion-exchange techniques. For example, the cationic aluminum sample, which contained somewhat more phosphine. This rela-
may be located in the small cavities in the same manner that tively constant loading, even in the dealuminated zeolites, suggests
lanthanide ions are present in a Y-type zeolite after dehydration that partial blocking of the cavities of extraframework aluminum
at elevated temperature^.'^ In addition, it is possible that ex- is not a serious problem.
traframework aluminum, present as oxybydroxides, may physically If one considers a model of faujasite containing 54 Al/uc, it
block certain acid sites by partially filling the large cavities. becomes evident that a substantial number of aluminum ions are
The value of trimethylphosphine as a quantitative probe of present as next-nearest TO., tetrahedra, along with their
Brernsted acidity in zeolites was evaluated by absorbing the base charge-balancing protons.20 There is insufficient volume for two
at 80 "C, cooling the sample to 25 "C, and determining the trimethylphosphine molecules to exist adjacent to these proximal
number of [(CH,),P-H]+ species from the resonance at -1 to -4 acid sites. Thus, even though there is adequate volume for ca.
ppm. In those cases where partial oxidation of the phosphine five molecules per large cavity, only three of these are sufficiently
occurred, the integral of the resonance at 64.6 ppm, which resulted near to the acid sites for protonation in the normal H-Y zeolite.
from protonated TMPO, was added to the integral of the reso- In order to further explore this limitation on the use of (CH3),P
nance for [(CH,),P-H]+. It should be noted that the oxidation to evaluate quantitatively the number of protons in a zeolite, a
of the physisorbed (CH,),P was much more rapid than that of series of NaH-Y zeolites were investigated, and the results are
the protonated adduct. Thus, the potential problem introduced given in Table I1 and Figure 5. As the H+ concentration in-
by chemical exchange in the SDY sample could be avoided by creased, the loading level of (CH,),P generally increased. At a
determining the Brernsted acid concentration from the spectrum level of 20 protons/uc (Na3,Hzo-Y) 80% of the protons were
of Figure 2a, rather than Figure IC.
(20) Beagley, B.; Dwyer, J.; Fitch, F. R.; Mann, R.; Waiters, J. J . Phys.
(19) Marynen. P.; Maes, A.: Cremers, A. Zeolires 1984, 4, 287. Chem. 1984, 88. 1744.
Trimethylphosphine Adsorbed in Zeolite Y
50 0
P PM
- 50
Figure 5. ,'P MAS-NMR spectra of (CH,),P in NaH-Y zeolites which
had been dehydrated at 400 "C. denotes spinning sidebands.
accounted for by the [(CH,),P-H]+ adduct, but at a level of 48
protons/uc (Na6H48-Y) only 52% of the protons were accounted
for. The results of Table I1 show that the concentration of the
protonated adduct increased to a level of ca. 25 molecules/uc and
subsequently remained essentially constant. In the Na-rich zeolites
the total amount of (CH3),P was less than in the protonated
zeolites, which may reflect the presence of the rather large Na+
ion in the site I1 positions.21 That is, Na+ ions partially occupy
(2 I ) Mortier, W. Compilation of Extraframework Sites in Zeolites;
Butterworth Scientific Limited: Guildford, 1982; pp 19-31.
The Journal of Physical Chemistry, Vol. 93, No. 6, 1989 2595
the volume of the large cavities. As depicted in Figure 5 , the
resonance observed for (CH,),P in Na5,-Y (-59.5 ppm) is much
broader than the resonance observed in Na6H48-Y (-67.5 ppm),
with the peak width at half-height being 438 and 146 Hz, re-
spectively. This broadening may result from a weak interaction
between the base and Na+ ions ( I = 3 / 2 ) .
The effect of diluting the protons in the zeolite is further il-
lustrated with the dealuminated samples of Table I: The number
of framework A1 atoms having no next-nearest aluminum tet-
rahedra reaches a maximum at about 33 Al/uc. It is not sur-
prising, therefore, that the SDY(3 h) and USY samples, which
had 28 and 33 framework Al/uc, respectively, exhibited the
maximum percentage of [(CH,),P-H]+/Al. The value for SDY( 1
h) is anomalously small, and this may reflect the incomplete
development of acid sites after short periods of steaming. As noted
previously, some of the extraframework aluminum may be present
in a cationic form which reduces the number of protons required
for charge compensation. The concentrations of protonated ad-
ducts measured in the SDY(3 h) and USY samples may indeed
reflect the true concentration of protons in these materials.
Conclusions
Trimethylphosphine is an effective probe molecule for studying
both Brernsted and Lewis acid sites in acidic Y-type zeolites.
Normal H-Y zeolites and samples prepared by dealumination with
SiC14 exhibited almost no Lewis acidity after dehydration and
deammination at 400 OC, but a steam-dealuminated zeolite had
Lewis acid sites which adsorbed (CH3),P weakly. These Lewis
acid sites apparently are associated with the extraframework
aluminum which is present in the large cavities as an oxyhydroxide
species. There is rapid chemical exchange between the phosphine
adsorbed at Lewis acid sites and the liquidlike phase. In these
same zeolites chemical exchange also occurs at 25 "C between
the Lewis-bound (CH3)3Pand the protonated adduct.
The determination of Brmsted acid site concentrations in
zeolites using trimethylphosphine is limited by both the capacity
of the large cavities and the steric effects of probe molecules at
adjacent acid sites. The technique is most accurate when the
proton concentration is 133/uc, and even in this case the estimated
error is approximately 20%. In general, the method underestimates
the proton concentration.
Acknowledgment. This research was supported in part with
funds provided by the Board of Reagents of Texas A&M Univ-
ersity and the U S . Army Research Office. We thank Dr. W.
P. Rothwell for his valuable comments and discussions.
Registry No. (CH3)3P,594-09-2.