J. Phys. Chem.

1995,99,14437-14443

14437

Silica-Supported Zirconia. 1. Characterization by Infrared Spectroscopy, Temperature-Programmed Desorption, and X-ray Diffraction
Z. Dang,P B. G. Anderson, Y. Amenomiya, and B. A. Morrow*
Department of Chemistry, University of Ottawa, Ottawa, Ontario, Canada KIN 6N5 Received: May I, 1995;In Final Form: July 22, 1995@

Silica-supported zirconia samples have been prepared by aqueous impregnation of a nonporous fumed silica with zirconyl nitrate giving 5, 10, or 20 wt % ZrO2 on Si02 after calcining at 450 "C. The surface areas were comparable to that of the parent silica (200 m2/g), and IR spectra showed OH peaks characteristic of Si02 and of monoclinic ZrOz. The intensity of the SiOH peak decreased with Zr02 loading, and a new IR band near 945 cm-' was attributed to the formation of ZrOSi linkages. The ZrO2 is dispersed as clusters on SiOz, and free SiOH is still available even at the highest Zr02 loading. X-ray diffraction shows either that SiOd ZrO2 is amorphous or that the Z r 0 2 crystallites are too small to be detected. Infrared spectroscopy of adsorbed ammonia and pyridine have shown that sites for coordination exist on all mixed oxides and on pure Zr02. The number of sites for coordination of NH3 increases as the ZrOz loading increases. Moreover, there are very weak Bronsted acid sites on SiOdZrO2 which can protonate NH3; these are absent on ZrOz. Temperatureprogrammed desorption of adsorbed NH3 has shown that the number of sites available for coordination, protonation, or H-bonding to ZrOH is about 2.5-3-fold greater.than the number of sites for H-bonding to SiOH groups on pure Si02. Finally, IR of adsorbed C02 (a probe of surface basicity) has shown that Si02/ ZrO2 is less basic than of pure Zr02.

Introduction
Zirconium dioxide has received considerable attention as a catalyst because it has moderate strength acid and base sites, as well as reducing and oxidizing properties.'-3 Therefore, it is suitable for a wide variety of catalytic and its surface properties have been c h a r a c t e r i ~ e d . ~ *Particular ~-~ attention has been directed to sulfated zirconia which is claimed to exhibit superacid properties which can make this material suitable for CH activation and alkane i s o m e r i ~ a t i o n . ' ~ - ~ ~ Zirconia is difficult to produce in a high surface area form,3 and it is relatively more expensive than the more common oxide materials such as alumina or silica. Accordingly, we have prepared some silica-supported zirconia catalysts with the view that (a) silica is a very thermally stable support and is readily available as a nonporous material of high surface area and (b) a binary Si02/ZrO2 oxide catalyst would be expected to be more acidic than either material alone according to theoretical considerations.I In this paper, we describe the surface characterization of Si021 Z r 0 2 catalysts which contain 5, 10, and 20 wt % zirconia which have been prepared by wet impregnation of zirconyl nitrate on a nonporous fumed silica. The catalysts have been characterized using infrared spectroscopy and X-ray diffraction, and the acid properties have been studied using IR spectroscopy of adsorbed ammonia and pyridine and temperature-programmed desorption of ammonia. In a subsequent paper,24the acid properties of the 10% zirconia catalyst after sulfation with varying quantities of sulfate will be described, and its potential as a catalyst for the direct coupling between olefins and methane will be assessed. Although the methods used in this paper have been previously used to study pure zirconia and sulfated zirconia, and several other groups have prepared ZrO~/Si02 mixed o ~ i d e s , ~ ~ - ~ O this
s2

is the first characterization of supported ZrO2 on Si02 catalysts using IR spectroscopy of adsorbed base probe molecules. Miejers et al.25have studied some Si02/ZrO2 catalysts prepared by incipient wetness impregnation of zirconyl nitrate on silica and of SiOz/ZrOz prepared by the deposition of zirconium ethoxide on silica, but their study was mainly concemed with the precursor stages during the calcining steps leading to the final product. The same g r o ~ p has~ also ~studied the ~ , ~ deposition of ZrO2 on thin films deposited in Si02/Si(100) surfaces. Sohn and JangI8 have also carried out a limited characterization of some SiO2/ZrO2 catalysts prepared by coprecipitation, and they studied its activity for 2-propanol dehydration and cumene dealkylation.

Experimental Section
The silica support was Cab-0-Si1grade M-5 and was provided by the Cabot Corp. Zirconia-impregnatedsilicas were prepared by mixing 2 g of silica with 6 mL of an aqueous solution of zirconyl nitrate, followed by drying in air ovemight at 110 "C and then calcining in air for 24 h at 450 "C. The calcined samples were ground into a fine powder using a mortar and pestle and were stored for further use. The solution concentration was chosen so as to give 5, 10, or 20 wt % ZrO2 after calcining. Pure zirconia was provided by Degussa. For infrared investigation, about 30 mg of the pure or mixed oxide was compacted at about lo7 Pa in a 25 mm diameter stainless steel die, and the resulting disk was mounted in a previously described 300 mL volume quartz celL3' All samples were heated for 1 h under vacuum at 450 "C prior to use. IR spectra were recorded using a Bomem Michelson MBlOO instrument (DTGS detector) at a resolution of 4 cm-I. The BET surface areas of disks of SiOz,ZrO2, and the various Si02/ZrO2 samples after vacuum activation for 1 h at 450 "C are shown in Table 1. For temperature-programmed desorption (TPD) studies, sample disks of the type which were used for the IR studies were broken up and sieved; granules ranging from 16 to 32 mesh (0.5-1.0

On leave from Lanzhou Institute of Chemical Physics, P.O. Box 97, Lanzhou, Gansu 73000, P. R. China. Abstract published in Advance ACS Absrracts, September 1, 1995.
@

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0022-3654/95/2099-14437$09.00/0 0 1995 American Chemical Society

14438 J. Phys. Chem., Vol. 99, No. 39, I995

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TABLE 1: BET Surface Areas (m2/g) after Vacuum Activation at 450 "C sample BET area (m2/g) sample BET area (m2/g) Si02 205 SiO?/Zr0?-20% 189 Si02/ZrO2-5% 20 1 ZrO? 45 SiO2/ZrOZ-l0% 190
mm) were used. The sample holder consisted of a 3/g in. diameter stainless steel tube into which 100 mg of the sieved particles was placed on top of a glass wool support. The resulting bed was 1 cm deep. Samples were typically activated under vacuum at 450 "C for 1 h prior to cooling to room temperature under vacuum. In a typical experiment, the reactant was allowed to contact the evacuated sample at a given pressure for times from 5 to 60 min; then the excess gas was condensed into a liquid nitrogen trap. Helium was then passed through the catalyst bed (30 mL/ min) at room temperature for 30 min. In the TPD experiment, the same flow rate of He was used, and the temperature was increased linearly with time at a rate of 15 "C/min. Desorbing products were detected using a thermal conductivity detector. In some cases the products desorbed were trapped by condensation in a liquid N2 trap placed after the TCD detector. The quantity desorbed was measured from the pressure after the products were expanded into a known volume. In a second method for quantitatively measuring the desorption products, integration of the TPD curves was compared with those obtained when known quantities of effluent were passed through the system. In this way a calibration curve was developed. When both methods were used (integration and expansion), the agreement was within &lo%, which we will take as the accuracy of our quantitative results. In order to compare the rates at which products are removed in the IR and the TPD experiments, it is important to realize that the experimental arrangements are quite different. In the IR experiment, a small sample disk is contained in a large free volume (300 mL), and this is connected by a 20 cm length of 5 mm i.d. Pyrex tubing to a large volume vacuum manifold. Evacuation is fast and efficient. In the TPD apparatus, the reactor is connected by 2 m of '/g in. 0.d. (about '/I6 in. i.d.) stainless steel tubing having multiple bends and constrictions of less than '/I6 in. i.d. where Swagelok fittings are located. Vacuum conductance is about 100-fold lower than that of the IR cell. X-ray diffraction analysis was performed using a Philips Analytical Model PW3710 powder X-ray diffractometer using Cu K a radiation.

-1

3900

3800
cm-1

3700

3600

Figure 1. Infrared spectra in the OH stretching region after evacuation for 1 h at 450 "C under vacuum: A, silica; B, C, D, 5%, 1076, and 20% ZrOz on SO?, respectively; E, Degussa ZrO2. The boxed inset shows IR spectra of SiOz/ZrO?-lO% a function of vacuum activation as for 1 h at, from top to bottom, 450,550,650, and 750 "C, respectively.
The IR spectrum of the ZrO2-impregnated samples after activation at 450 "C are shown in Figure 1, B, C, and D, for 5, 10, and 20 wt % ZrO2. Relative to pure Si02 the isolated silanol peak is of reduced intensity, and relative to pure ZrOz the two OH peaks are somewhat broadened but at approximately the same wavenumber. The lower wavenumber 3680-3670 cm-' peak is particularly broadened and is barely evident for the 5% sample. Infrared spectra of SiOz/ZrOz-lO% as a function of the temperature of activation from 450 to 750 "C are shown in the inset of Figure 1. It can be seen th& the 3675 cm-l ZrOz OH peak is practically eliminated after activation at 750 "C whereas that near 3775 cm-' is still evident but of reduced intensity relative to 450 "C activation. Addition of H20 to any of the samples resulted in broadening and shifting of the peaks to lower wavenumber. Reactivation of each sample at 450 "C completely restored the original spectrum. Exchange with D20 resulted in shifts to low wavenumber of all bands, to 2758 cm-' in the case of the silica OH peak, and to 2785 and 2705 cm-' in the case of the OH peaks on the SiO2/ZrO2 samples. These OWOD shifts are well documented in other studies of pure Z ~ O Z and ~ - ~ ~ ~ Si0232.33 samples. Self-supported silica disks are opaque37between about 1250 and 1000 cm-' and between 850 and 750 cm-I. Pure zirconia is opaque3' below about 800 cm-' and exhibits no distinct features between 800 and 3675 cm-I. IR spectra of Si02 and of the SiO2/ZrOz samples in the window of partial transparency between 1000 and 850 cm-' are shown in Figure 2A. There is an increase in the absorbance of the zirconia loaded samples near 950 cm-l, and this increases with zirconia content. The effect can be more clearly shown by subtracting the silica background spectrumfrom those of the Si02/ZrO~ samples, and these spectra are shown in Figure 2B. There is a distinct broad peak centered near 945 cm-'. This peak is absent in the spectrum of pure ZrO2, and its origin will be discussed in more detail later. XRD. The Degussa fumed zirconia is reported by the manufacturer to be mainly monoclinic, but our XRD results

Results
Basic IR Spectra of Si02 and SiOdZrOz. Infrared spectra of 450 "C vacuum-activated silica and zirconia in the OH stretching region (3900-3600 cm-') are shown in Figure 1, A and E, respectively. The silica spectrum is dominated by an intense sharp peak at 3747 cm-' due to isolated noninteracting surface silanol groups (single SiOH and geminal Si(OH)2) which have been characterized p r e v i o ~ s l y . ~ ~the ~ In . ~ spectrum of Z r O 2 there is a broad peak near 3775 cm-' which is unique to the monoclinic phase and another broad band with maxima at 3680 and 3670 cm-I which are characteristic of the tetragonal or monoclinic phases, r e s p e c t i ~ e l y . ~ , ~For < ~ ~ - ~ ~ - ~ the monoclinic phase, the higher wavenumber band is generally attributed to single ZrOH surface species, whereas the lower wavenumber band has been assigned to OH species which are bonded to multiple surface Zr atoms, but other interpretations of the spectrum of Zr02 have been a d ~ a n c e d . ~

Silica-Supported Zirconia Catalysts. 1

\
A

J. Phys. Chem., Vol. 99, No. 39, I995 14439

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f!

u ul m
0

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950
" 1

900

)O

1600
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Figure 2. (A) Infrared spectra of Si02 and SiO2/ZrO2 samples in the region of partial transparency between 100 and 850 cm-I. (B) Difference spectra as in (A) after subtraction of the background spectrum (0%) from'each of the indicated ZrO2 loaded samples.

Figure 3. (top)Infrared spectra of ZrO2 (A), Si02/ZrO2-10%(B), and Si02 (C) in contact with an equilibrium pressure of 3 Torr of NH3.

showed that the as-received material was approximately an equal mixture of the tetragonal and monoclinic phases. Upon calcining in air at 500 "C for 3 h, the quantity of the tetragonal phase decreased by about 50% with a corresponding increase in the monoclinic phase. As is known,3 the monoclinic phase is the more stable phase at temperatures below 1170 "C. The fumed silica, being an amorphous material, showed no distinct XRD peaks apart from a very broad weak feature between 2 0 = 20" to 40". All of the air-calcined SiO2/ZrO2 samples also showed the same broad feature. Ammonia Adsorption. Ammonia has been extensively used as a probe of oxide surface^,^*.^^ and the spectral region associated with NH, angle deformation modes between 1700 and 1300 cm-' is most diagnostic insofar as IR bands characteristic of strongly adsorbed species such as coordinated NH3 (1620-1600 cm-I, coordinated to Lewis acid sites) or N h f (1450-1400 cm-I, protonation from Bronsted acid sites) may be observed after evacuation of physically adsorbed (1628 cm-I) and/or H-bonded NH3 (1635 cm-I). The IR spectrum of ammonia adsorbed on silica has been well d o ~ u m e n t e d .As~shown in Figure 3C, in the presence of ~ 3 Torr of NH3 there is a band at 1635 cm-' due to H-bonded NH3 accompanied by a weaker one at 1555 cm-' due to SiNH2 which arises from the chemisorption of NH3 on silica when it has been activated at temperatures above about 400 " C 4 I Figure 3B shows the spectrum for lO%-Si02/ZrO2 in contact with 3 Torr of NH3. In addition to the 1555 cm-' band noted above, there is a new prominent peak at 1606 cm-I, with a shoulder to higher wavenumber near 1635 cm-I, and a broad band centered near 1450 cm-I. Finally, Figure 3A shows the spectrum under the same conditions for NH3 in contact with pure ZrO2; the strongest peak is now at 1600 cm-I, there is a weak peak at 1505 cm-', and the broad peak centered at 1450 cm-' for Si02/ZrO2-10% is absent. (In al cases, the background l spectrum of the solid and the gas phase spectrum of NH3 has been subtracted.)

(middle) Infrared spectra of chemisorbed NH3 on the same samples which were used in the top portion of the figure (A', B', and C', respectively),recorded after evacuation of the gas phase for 30 min at room temperature. (bottom) Infrared spectra of chemisorbed NH3 on the indicated SiOdZrO2 samples. The spectra observed after evacuation for 30 min following contact of 3 Torr of NH3 on ZrO2, Si02/ZrO2-10%, and Si02 are shown in Figure 3, A', B', and C', respectively. In all cases, the band or shoulder near 1635 cm-' due to H-bonded ammonia was removed, and the resulting spectra are, therefore, due to irreversibly held species (that is, strongly adsorbed) on each oxide. These are the species which provide information regarding the strong adsorption sites on a given catalyst. IR spectra of such irreversibly held species as a function of ZrOz loading are shown at the bottom of Figure 3. These spectra are also difference spectra observed after spectral subtraction of the background spectrum of the oxide; in each case 8 Torr of NH3 was added for about 30 min, followed by evacuation at room temperature for 30 min. (In all cases the spectra in the presence of excess gaseous NH3 also showed a single additional shoulder at 1635 cm-' due to H-bonded N H 3 , and this was removed after 1 min evacuation at room temperature.) In addition to the 1555 cm-' SiNH2 peak, coordinated ammonia (1606 cm-') and protonated NH3 (1450 cm-I) are in evidence, the quantity of the coordinated NH3 apparently increasing with ZrO2 loading. The IR results show that, in addition to reversibly held H-bonded NH3, the ZrO2-loaded samples also exhibit Lewis and Bronsted acidity. In order to more fully characterize these samples, we have carried out TDP experiments of adsorbed ammonia. TPD spectra of NH3 adsorbed at room temperature as a function of ZrO2 loading are shown in Figure 4. For pure silica, there is a sharp desorption peak near 90,whereas for the ZrO2 loaded samples this was accompanied by a broad hightemperature tail having an inflection near 245 "C. The quantity of NH3 desorbed from each sample is listed in Table 2. There was about a 3.5-fold increase in the quantity desorbed upon going from pure Si02 to Si02/ZrO2-5% and a slight increase thereafter.

14440 J. Phys. Chem., Vol. 99, No. 39, 1995

Dang et al.

d,
A

L 400 / io0 200 300

T('C)

Figure 4. (I) TPD spectra of NH3 as a function of ZrO2 loading: A, Si02; B, C, and D are for 5%, lo%, and 20% ZrO2 loading, respectively. (11) TPD spectrum of NH3 adsorbed on Degussa ZrO2.

1600

1500
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1400

TABLE 2: Quantity of NH3 Desorbed during TPD (Heating 25-450 "C) composition, amount desorbed, composition, amount desorbed, wt % Zr02 pmoVg of oxide wt % Zr02 pmoUg of oxide 0 (Si02) 110 20 450 5 390 100 (Zr02)u 250 10 410 a Degussa ZrO2, surface area 45 m2/g; see Table 1.

Figure 5. Infrared spectra of pyridine adsorbed on Si02 (I) and ZrO2 (11): A, in contact with 2 Torr of pyridine; B, evacuation for 1 min at room temperature; C, evacuation for 40 min at room temperature; D, evacuation for 40 min at 200 "C.

For comparative purposes, the TPD spectrum of N H 3 from Degussa ZrO2 is shown in Figure 411. There is not a distinct maximum which can be attributed to either H-bonded or coordinated NH3, the former presumably lying near 100-130 "C by analogy with the TPD spectrum of NH3 on Si02 or SiOd Zr02. However, given the lower surface area of ZrO2 relative to the other oxides, no particular significance should be attributed to the data in Table 2. Pyridine Adsorption. The infrared spectrum of pyridine adsorbed on metal oxides shows characteristic J bands in the R spectral region between 1700 and 1300 cm-' which are indicative of the mode of interaction with the s ~ r f a c e . ~ ~ , ~ ~ IR Ill spectra of pyridine adsorbed on silica (450 "C activation) are 5% shown in Figure 51. The main strong peaks at 1595 and 1447 cm-' (Yga and Y19b modes, respectively) and weaker bands near 1576 and 1480 cm-' are well-known to be due to H-bonded ~ y r i d i n e . ~ ~ . ~ ~ for 1 min reduced the intensity of these Evacuation bands slightly, and this was much greater for 40 min evacuation. In this respect, H-bonded pyridine is much more tenaciously 1600 1500 held to silica than NH3; the latter was removed after 1 min cm-' evacuation at room temperature. All adsorbed pyridine was Figure 6. Infrared spectra of pyridine adsorbed on 5 % (I), 10% (II), removed only after evacuation at 200 "C. For comparison, and 20% (111) Z O loaded Si02 samples. Curves A, B, and C (only r2 indicated for (I) but in the same order for the other spectra) are for 2 Figure 5II shows a similar series of spectra for pyridine adsorbed Torr of pyridine present (A), evacuation at room temperature for 40 on pure zirconia. In this case, even after evacuation at 200 "C, min (B), and evacuation for 40 min at 200 "C (C). peaks remain at 1607, 1490, and 1447 cm-I. The Y8a mode of coordinated pyridine generally lies at or interacting with gaseous pyridine. On the other hand, it is above 1600 cm-', and the mode at 1487 cm-' is of considerably evident that coordinated species strongly adhere to the surface greater intensity than that which is observed for H-bonded of pure zirconia (Figure 5II), although there is no evidence for ~yridine.~~,~~ On the other hand, protonated pyridine exhibits Bronsted acid sites (no band at 1540 cm-I). a unique band near 1540 cm-I which is absent in the spectra of A series of I spectra of pyridine adsorbed on the three Si021 R other forms of adsorbed pyridine, including physically adsorbed ZrO2 samples are shown in Figure 6, I, 11, and 111, for 20%, lo%, and 5% zirconia loadings, respectively. In each case, pyridine. Therefore, as is well-known, pure Si02 (activated at <450 "C)has no Lewis or Bronsted sites which are capable of curve A corresponds to the equilibrium pressure of 2 Torr of

Silica-Supported Zirconia Catalysts. 1 pyridine in the cell, curve B after evacuation for 40 min at room temperature, and curve C after evacuation at 200 "C for 40 min. In all cases, there is a distinct band at 1606 cm-', accompanied to varying degrees in curves A and B with IR bands due to . H-bonded pyridine near 1595 cm-I. In curves C, all traces of H-bonded pyridine are removed, and these spectra correspond to the known spectrum of strongly coordinated pyridine.42 The quantity of coordinated pyridine appears to be greater for the 10% and 20% samples than for the 5% sample. For a given Z r O 2 loading, the quantity of coordinated pyridine was independent of the temperature of activation (200,450, or 700 "C), and in no case was there a band near 1540 cm-' indicative of the formation of protonated pyridine.

J. Phys. Chem., Vol. 99, No. 39, I995 14441

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Discussion Physical Properties. The BET results (Table 1) show that there is not a significant decrease in surface area relative to pure silica for any of the silica-supported zirconia preparations. The XRD results suggest that the SiOz/ZrO2 samples are amorphous or that the Zr02 crystallites are very small. The IR results in the OH stretching region show that peaks typical of both silica and zirconia are present insofar as we can observe the typical OH stretching modes characteristic of both phases separately. At the very least, not all SiOH groups on the support are covered or interact with ZrO2. We will consider this in relation to the number of deposited ZrO2 units and the number of isolated silanol groups. It is well e ~ t a b l i s h e d ~that amorphous silicas of whatever ~*~~-~~ origin contain about 4.6-5 OH groups per nm2 when fully hydroxylated and that the surface silicon atom density is 7-8 per nm2. After vacuum activation33at 450 "C, the OH density drops to about 1.2-1.4 per nm2. The number of ZrO2 units deposited per nm2 for each Si02/ZrOz is as follows: 5% (1.3), 10% (2.6), and 20% (5.2). Therefore, the ratio of ZrO2:SiOH for the 5%, lo%, and 20% ZrO2 loaded samples is about 1, 2, or 4, respectively. Although there is a progressive decrease in the intensity of the SiOH peak relative to that of pure Si02 as the ZrO2 loading is increased (40%, 50%, and 60% decrease respectively for 5%, IO%, and 20% ZrO2 loading; see Figure l), not all SiOH groups interact with ZrO2 even at the highest loading. Therefore, the dispersion would not be expected to be very high. However, note that even for Si02/ZrO2-20% the number of deposited ZrO2 units per nm2 is still less than the density of surface Si atoms. Meijers et a1.26studied some silica-supported zirconia catalysts calcined in air at 680 "C which were prepared by an incipient wetness method and by deposition of zirconium ethoxide on a silica gel. Although IR spectroscopy of the OH region was not used, XPS measurements suggested that the dispersion was about 6-10 times greater for the ethoxide deposited catalyst, it being of the order of 12% for a 8 wt % zirconia catalyst prepared by the incipient wetness method. Marquez-Alvarez et aL30examined two 11.7 wt % Si02/ZrO2 catalysts, calcined in air at 550 "C, which had been prepared by deposition of zirconium tetra-tert-butoxide on silica. They observed XRD peaks of the cubic phase of zirconia (spectrum and details not shown). In the OH region of the IR spectrum, no peaks characteristic of ZrOH vibrations were observed, but the silanol peak after deposition of the ZrOz was reduced in intensity by 60% or 40% for two samples prepared by slightly different methods, compared to 50% in the present work for our 10% sample. The absence of ZrOH peaks might support their contention of high dispersion (no clear ZrO2 phase), but the observation of XRD peaks would suggest that relatively large particles were formed.

Figure 7 Infrared spectra after reacting ZrO2 with hexamethyldisi. lazane [HMDS] (A) or HMDS-dls (B) followed by evacuation at 200 "C. The bands marked with an asterisk are due to CH3 or CD3 angle

deformation modes. Our SiO2/ZrO2 samples probably have a higher dispersion than that found by Meijers et a1.26(they contended that the impregnated catalysts had large isolated particles of ZrO2 dispersed over the support), possibly closer to that studied by Marques-Alvarez et For example, we observed a new IR band near 945 cm-I which grew in intensity as the zirconia loading was increased (Figure 2). This band is probably due to the formation of a Si-0-Zr bond. A similar band near 960940 cm-' has been reported for the Si-0-Ti linkage in Si02/ Ti02 catalysts or Ti-substituted zeolite^.^-^^ Further, producing ZrOSi(CH& linkages on ZrO2 by reacting the ZrOH groups with hexamethyldisilazane (HMDS) gave a unique new band at 966 cm-' (Figure 7A) or at 958 cm-I for ZrOSi(CD3)3 (Figure 7B); neither band is present in the IR spectrum of HMDS or HMDS-dlg. (The bands marked with an asterisk in Figure 7 are due to the antisymmetric and symmetric CH3 or CD3 angle deformation modes and are present in the spectrum of pure HMDS.) Therefore, for SiO2/ZrO;. there must be a chemical attachment to the underlying silica network. The acidity measurement to be discussed below also supports this notion; the acidity of the present binary oxides is enhanced relative to that of Si02 or ZrO2 alone, and this enhanced acidity would only arise from a direct interaction between the silica support and the deposited zirconium. To summarize, our SiO2/ZrOz samples have a surface area which is similar to that of the support, and they possibly do not have a dispersion as high as can be achieved by deposition of zirconium alkoxides on s i l i ~ a s . ~However, the absence of ~-~~ an XRD pattern suggests either that the surface layer is amorphous or that the average particle size is still relatively small. On the other hand, that distinct ZrOH peaks are observed suggests that the particle size is of sufficient size to give rise to surface domains which resemble pure ZrO2. Given the increasing disappearance of the silanol peak with increasing ZrO2 loading, and the corresponding increase in the ZrOH and ZrOSi peaks, this suggests that there are relatively isolated clusters of ZrO2 on the surface and that the size of each cluster increases with zirconia loading such that there is an increasing number of both ZrOH groups and ZrOSi linkages. In an idealized model, we consider a hemisphere of zirconia deposited on the surface such that its height and surface diameter increase with increasing ZrOz content. Surface Acidity. Although silica is not known to exhibit either Lewis or Bronsted acidity at the gas-solid interface (at least with respect to adsorption of probes such as pyridine and ammonia and others of similar pK,), zirconia is a relatively weak acidic oxide having Lewis acid sites3 This is clearly borne

14442 J. Phys. Chem., Vol. 99, No. 39, 1995

Dang et al.

out in the present work; both ammonia and pyridine give rise to the typical IR bands attributable to coordinated species on ZrOz, as has been found by others. As expected, there is no evidence of Bronsted acidity on pure ZrOz. According to Tanabe's model's2 of a mixed Zroz-SiOz, there should be an enhanced acidity relative to either component. Although the present preparations are not true mixed oxides, being prepared by impregnation of Si02 with a zirconium salt, nonetheless there are obviously surface regions where Zr-OSi linkages have formed (Figure 2), and at this interface one could expect that Bronsted acid centers will be This could be expected to manifest itself in the IR spectra of adsorbed pyridine or ammonia. In the case of pyridine, an IR band near 1540 cm-' characteristic of the protonated pyridinium ion is absent in all spectra, and we conclude that Bronsted sites of sufficient strength to protonate pyridine do not exist on the mixed oxides. (As will be discussed in the following paper,24this was not the case for sulfated SiO2/ZrO2.) For adsorbed NH3, an IR band characteristic of the N&+ ion is expected near 1450-1400 cm-I, the lower the wavenumber generally indicating a stronger degree of protonation and, hence, by implication, a stronger acid site. In ionic solids (NH4C1, etc.) the antisymmetric N& stretching frequency near is 1400 cm-I, and the band is sharp. When the Bronsted acid site is weak such that proton transfer is less than complete and the interaction is more of the type M D * *I+ *NH3,the antisymmetric deformation mode lies near 1450 cm-I. In the present work, we observe a weak broad band near 1450 cm-' for adsorbed NH3 on all SiO2/ZrO2 samples, which is absent in the case o pure ZrO2. We conclude that the mixed f oxides may have a very weak Bronsted acidity. To anticipate the results of the second paper in this series relative to sulfated S i 0 2 / Z r O ~ very strong Bronsted acid sites were generated ,~~ following sulfation, and the wavenumber of the IR band of protonated ammonia shifted to lower wavenumber. Finally, it is apparent from the IR spectra shown at the bottom of Figure 3 that the number of sites for coordination of NH3 (1606 cm-' band) increases with ZrOz loading. However, the TPD results suggest that there is only a small increase in the quantity of strongly adsorbed species (Table 2 ) as a function of Zr02 loading. The TPD results are misleading because the broad peak starting at about 110 "C probably includes coordinated and strongly H-bonded ammonia (see Figure 411 for pure ZrOz) and, for SiOz/ZrI2, weakly protonated ammonia (IR band at 1450 cm-I). Therefore, the TPD spectra lack the resolution to give an accurate measure of the quantity of coordinated NH3 alone. Surface Basicity. It is relevant to compare the basicity of the SiOz/ZrOZ samples with the known weak basicity of pure ZrOz in order to complete the acidhase chara~terization.~ Accordingly, we have adsorbed COz, a well-established probe of base sites on these samples. The base sites are characterized by IR bands between 1800 and 1200 due to the formation of adsorbed carbonate and hydrogen carbonate species5'-53 After activation at 450 "C, each oxide was contacted with excess C02 for an hour, and then the gas phase was evacuated for 1 min. The relevant IR spectra are shown in Figure 8A for ZrO2 and in Figure 8B,C,D for 20%, lo%, and 5% ZrOz on SiOz, respectively. (Further evacuation for 1 h at room temperature resulted in a quasi-uniform decrease in all band intensities by about 30%.) Carbon dioxide does not chemisorb on Si02 at room temperature so in all cases the IR bands are due to adsorbed species associated with the presence of ZrOz. The spectrum

.2

1600
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1400

Figure 8. Infrared spectra following adsorption of excess CO2 and evacuation for 1 min at room temperature on (A) ZrOz, (B) SiO2/ZrO*20%, (C) Si02/ZrO2-10%,and (D) SiO*/Zr02-5%.

for COz/ZrO;? is virtually identical to that shown in the literature5 for polycrystallineZrOz powder, having IR bands at 1562 and 1319 cm-' due to bidentate carbonate species and a shoulder at 1620 cm-' and a strong band at 1435 cm-I due to hydrogen carbonates, HCO3-. Although not shown in Figure 8, the carbonate species and the HC03- species were also accompanied by known IR bands at 1056 and 1220/3610cm-I, respe~tively.~*.~3 For the SiOz/ZrOz samples, only the characteristic IR spectrum of HCO3- is observed (the spectral region below 1300 cm-' is opaque but the OH stretch at 3610 cm-' was observed), and the intensities diminish with decreasing zirconia loading for identical reaction conditions. Therefore, the weak base sites necessary for the formation of HCO3- species are present on pure ZrO2 and on SiOz/Zr02, but the stronger base sites necessary for the formation of adsorbed carbonate species are absent. It is apparent that the basicity of SiO2/ZrO2 is lower than that of pure Zr02.

Conclusions
Silica-supported zirconia samples that have many of the desirable characteristics of pure zirconia can be prepared by impregnation of silica with zirconyl nitrate. These materials have surface areas which are comparable to that of the support and are considerably greater than that typically found for pure ZrOz. Bronsted acid sites are absent on pure ZrOz, but weak Bronsted sites exist on SiOdZr02, and both materials have Lewis acid sites. Therefore, SiOz/ZrO2 appears to be slightly more acidic than pure Z r O 2 , and a potential catalyst having most of the desirable characteristics of pure ZrO2 can be prepared by supporting Zr02 on SiOz, at a fraction of the cost of pure zirconia itself. The basicity of the SiO2/ZrO2 is less than that of pure ZrO2.

Acknowledgment. We are grateful to the Natural Sciences and Engineering Research Council of Canada and to Esso Petroleum, Canada, for financial support. References and Notes
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