1436

Langmuir 1991, 7 , 1436-1440

Adsorption of Chloroplatinic Acid and Chloroiridic Acid on Composite Oxides

S. Subrammiant and J. A. Schwarz'
Department of Chemical Engineering and Materials Science, Syracuse University, Syracuse, New York 13244 Received October 1, 1990. I n Final Form: December 19, 1990 The objective of the present study is to investigate the adsorption of chloroplatinicacid and chloroiridic acid on alumina, titania, and composite oxides formed from alumina and titania. The adsorption results were analyzed by using the Langmuir equation. The adsorption kinetics and adsorption equilibrium amounts indicate that the metal ions have a higher affinity for alumina compared to titania; the difference is more significant in the case of Ir. It was also observed that the presence of titania inhibits aluminum dissolution when the TiOzAl2Oa supports are brought in contact with acidic impregnationsolutions. The adsorption results suggest that the metal ion can be selectivelypartitioned to alumina present in a &Os-Ti02 composite oxide. This selective adsorption process was explored by using temperature-programmed reduction. Our results suggest that the metal weight loading determines the selectivity of this partitioning.

Introduction
Supported platinum and iridium catalysts are used in systems of industrial interest such as, automobile catalytic converters and reformers.lP2 A critical step in the preparation of supported catalysts is the impregnation of the active ingredient onto the support. Scientific interest in the impregnation step developed after itwas demonstrated that certain acids and salts contributed to the distribution of the active ingredient within a porous catalyst pelletS3p4 The investigation of the adsorption process during the wet impregnation of H2PtCLJA1203 became the subject of interest in subsequent studies.b** The impregnation step for several other precursor/support systems has been studieda7-l2 But no information is reported on the adsorption of HzIrCh. Also, the adsorption of catalytic precursors on more complex supports such as composite oxides has not been studied to date. Composite oxides form a class of supports for the potential design of supported metal catalysts with unique properties.13-18 The strength, number, and type of acid

* To whom correspondence should be addressed. 'Present address: Ford Motor Co., P.O. Box 2053, 2162 SRL, Dearborn, MI 48121. (1) Kummer, J. T. h o g . Energy Combust. Sci. 1980,6, 177. (2).Sinfelt, J. H. Bimetallic Catalysts: Discoveries, Concepts, and Apphcationu; John Wiley: New York, 1983. (3) Maatman, R. W.; Prater, C. D. Ind. Eng. Chem. 1957,49, 253. (4) Maatman, R. W. Ind. Eng. Chem. 1969,51,913. ( 5 )Santacasaria, E.; Canna, S.;Adami, I. Ind. Eng. Chem. R o d . Res. Dev. 1977, 16, 41. (6) Santacesaria, E.; Galli, C.; Canna, React. Kinet. Catal. Lett.

63, 35. (13) Jin, T.; Hattori, H.; Tanabe, K. Bull. Chem. Soe. Jpn. 1982,55, 2279.

Preparation of Catalysts I. Studies in Surface Science and Catalysis; Delmon, B., Grange, P., Jacobs, P., Poncelet, G., Ed.; Elsevier: Amstardam, 1976; Vol. 2, p 251. (11) Hegedus, L. L.; Chou, T. S.; Summers, J. C.; Potter, N. M. In Preparation of Catalysts II. Studies in Surface Science and Catalysis; Delmon, B., Grange, P., Jacobs, P., Poncelet, G., E&.; Elsevier: Amsterdam, 1979; Vol. 3, p 171. (12) Komiyama, M.; Merrill, R. P.; Harnsberger, H. F. J. Catal. 1980,

1977,6, 301. (7) Chen, H. C.;Anderson,R.B. Ind. Eng. Chem. R o d . Res. Deu. 1973, 12, 122. (8) Chen, H. C.; Anderson, R. B. J. Catal. 1976,43,200. (9) Cervello, J.; Garcia dela Banda, J. F.;Hermana, E.; Jimenez,J. F. Chem. Eng. Technol. 1967,48,520. (10) Cervello, J.; Chou, T. S.; Summers, J. C.; Potter, N. M. In

F.

a sites in a composite oxide can be controlled by varying t composition.13-ls Dumesic and co-workers have repon !d on the acidic DroDerties of a series of model binary oxic ?S formed by mou&ing a metal oxide at low concentrations onto the surface of a second metal oxide. Since the physical properties of the newly formed adsorbent are different from either of the pure components, we would expect that their adsorption properties during impregnation would also be different from that of the pure phases. In particular, the partitioning of the supported metal between the two phases of a composite oxide would be controlled by the adsorption kinetics on each phase. The objective of the present study is to investigate the adsorption of chloroplatinic and chloroiridic acid on pure and composite oxides formed from alumina and titania. Titania is of the strong metal-support interaction (SMSI) type and thus provides a unique anchor for catalytic However, pure titania is a low surface area support and alumina-titania composite oxides provide a convenient method for increasing the surface area of the supported titania phase.23 The rate of adsorption of the hexachlorinate Pt and Ir ions (MCh2-, where M = Pt or Ir) on AlzOs, TiO2, and TiOz/Al203composite oxides was measured and the results were analyzed by using the Langmuir equation.s Temperature-programmed reduction (TPRd) was used to assess the distribution of the metal species in the composite oxide supported precursors. The transient and equilibrium adsorption data and TPRd results suggest that, a t relatively low metal weight loadings, the selective adsorption of the hexachlorinate ion on alumina in a TiO2A1203 composite oxide is achieved.
B., Jacobs, P. A., Poncelet, G.,Ede.;Elsevier: Amsterdam, 1976; p 65. (15) Shibata, K.; Koyoura, K.; Kitagawa, J.; Samiyoahi, T.; Tanabe, K. Bull. Chem. SOC. Jpn. 1973,46, 2986. (16) Connell, G.; Dumesic, J. A. J. Catal. 1986, 101, 103. (17) Connell, G.; Dumesic, J. A. J . Catal. 1986, 102, 216. (18) Connell, G.; Dumesic, J. A. J . Catal. 1987, 105, 285. (19) Tauster, S. J.; Fung, S. C. J. Catal. 1978, 55, 29. (20) Tauster, S. J.; Fung,S.C.; Garten, R. L.J. Am. Chem. Soc. 1978,
of Catalysts; Delmon,
105, 170.

(14) Tanabe, K.; Itoh, M.; Morahige, K.; Hattori, H. In Preparation

(21) Vannice, M. A.; Garten, R. L. J. Catal. 1979,56, 236. (22) Vannice, M. A,; Twu, C. C.; Moon, S. H. J. Catal. 1983, 79, 70. (23) McVicker, G. B.; Ziemiak, J. J. J. Catal. 1985,95,473.

0743-7463/91/2407-1436$02.50/0 0 1991 American Chemical Society

Adsorption of Acids on Composite Oxides

Langmuir, Vol. 7, No. 7 , 1991 1437 were centrifuged (International Clinical Centrifuge, Model No. 19963H)and care was taken to avoid pipeting the solid with the solution. The metal concentration in the solution phase was determined with a Perkin-Elmer Model 2380 atomic absorption spectrophotometer. The instrument was calibrated by using iridium and platinum standard solutions. A three-point calibration was used. Each aliquot was diluted with air-saturated distilled water in flasks to ensure that the concentration of iridium and platinum were in the range, 100-500 and 60-360 ppm, respectively. The diluted solutions were filtered to remove traces of support particles that may be present. Estimation of Dissolved Aluminum. The concentration of aluminum dissolved in the impregnation solution at equilibrium was measured witha Perkin-Elmer Model 2380 atomic absorption spectrophotometer. The instrument was calibrated by using an aluminum standard solution (Fisher SA442-500). The threepoint calibration procedure was used. The aliquots were diluted (using air-saturated distilled water) to adjust the aluminum concentration between 100 and 600 ppm. Preparation a n d Characterization of Catalytic Precursors. One gram of oxide was contacted with 0.5 cm3 of the impregnation solution of desired concentration to attain a metal weight loading of 0.7 % and 3 % . The precursors were dried overnight at room temperature under darkness. The precursors were further dried in air at 423 K for a period of 1 h. These precursors were characterized by TPRd. The schematic diagram of the TPRd apparatus and the experimental procedures are reported elsewhere.%

Theoretical Section The adsorption of a charged species onto a charged site may be described by a reaction of the form
A + [active site] = A,, (1) Santacesaria et al.s have used the Langmuir equation to study the adsorption of chloroplatinic acid on alumina. In the present study, the adsorption of chloroplatinic and chloroiridic acid on A1203, TiO2, and TiOz/AlzOs was analyzed by using the Langmuir equation. According to the Langmuir equation, a t short adsorption times (t << tequiljbriu), the kinetics of the adsorption reaction can be expressed ass

where q is the amount (gmol) of metal adsorbed per gram of support, qe is the amount (gmol) of metal adsorbed a t equlibrium per gram of support, kl (s-l) and k-1 (g.mol/ L-s)are the forward and backward reaction rate constants, respectively. Using the initial condition C M e = 0 at t = 0, integration of eq 2 results in

t=-

[2cq + u - (-M)/2] 1 log (-M)I2 [2cq + u + (-M)/2]

where (-M) = m2 - ~ U C u , = klR1 (CMe)o, u = -[kl (k-lRl/qe) + (kl(CMe)dZl/qe)l,c = kl/qe, R1 = Vml/g, and t (8) is the time of adsorption.

Experimental Section
Materials. The pure supports used in this study, A1203(pore volume 0.5 cmS/g, BET area 195 m2/g) and Ti02 (nonporous, BET area 50 m2/g) were obtained from American Cyanamid and Degussa Corp., respectively. The supports were conditioned to have a particle size of 40-80 mesh and were calcined at 873 K for 24 h. Two types of composite oxides, 0.87 % AlzOa-TiOz and 11.4% TiO2-AlzO3, were prepared. [It may be noted that in the 0.87 5% AlSOa-Ti02 composite oxide, Al2Osis the secondary phase that is supported on TiO2. Likewise, in the 11.4% TiO2-Al203 composite oxide, Ti02 is the secondary phase that is supported on A1203.1 The procedure used for preparing the compositeoxides was identical with that used by Subramanian et These investigators have used point of zero charge (pzc) measurements to show that the surface area contributed by the secondary phase (i.e., Al2O3in the 0.87% A1203-Ti02 composite oxide and Ti02 in the 11.4 % Ti02-Al203 composite oxide) is approximately 50%. Preparation of Impregnation Solutions. The impregnation solutions were prepared by using air-saturated distilled water (pH = 5.6). The pH values for the Pt and Ir impregnation solutions were adjusted to 0.54 and 0.63, respectively, by the addition of 4 N HN03. These values were measured with a Corning pH meter calibrated at pH values 1 and 2. The concentrations of the impregnation solutions were adjusted to and 3.509 X 1 t 2 gmol/L for Ir and Pt, respectively; 3.295 X these correspond to solutions required for mounting 0.3 % metal by weight using the dry impregnation procedure. Adsorption Rate Measurement. Two grams of the support was contacted with 25 cma of the impregnation solution. The suspensions were periodically agitated. Aliquots 1 cm3 (or 0.5 cm3) were periodically drawn with a Kimble Pyrex disposable serologicalpipet (2 i 0.005 cm3). Typically, samples were drawn after 1,5,10,30,60, and 120 min. The loss of the impregnation solution, due to periodic sampling, was considered in the analysis used to estimate the amount of metal adsorbed. The solutions
(24)Subramanian, S . ;Noh, J. S.; Schwarz, J. A. J. Catal. 1988, 114, 433.

Results In the following analysis, the term support refers to a pure oxide and the term composite oxide refers to a material (e.g., 0.87 % A1203-Ti02) prepared by depositing a secondary phase (e.g., A1203) on a primary phase (e.g., TiO2). The total amount of metal mounted on the support or composite oxide is the sum of the adsorbed component and the pore filling component.26 Here the adsorbed component refers to the amount of metal adsorbed or exchanged on the support/composite oxide. The impreg nation solution remains trapped with in the pores of the porous material. When the solution evaporates, the metal is deposited inside the pores leading to the pore filling component. Titania is a nonporous support and, hence, the pore filling component in the case of Ti02 and the A1203-Ti02 composite oxide is zero. The pore filling component in the case of A1203 was estimated from its void volume of 0.5 cm3/g. The results reported by Subramanian et al.24 indicate that the secondary phase, TiO2, in a Ti02-Al203 composite oxide is highly dispersed. Therefore, it is reasonable to assume the void volume for the Ti02-Al203 composite oxide to be the same as that of the alumina substrate, Le., 0.5 cm3/g. The total amount of metal mounted on the support or composite oxide at equilibrium as well as the adsorbed component is presented in Table I. The equilibrium pH of the impregnation solutions and the amount of AP+ ions (gmol) in solution are presented in Table 11. It should noted that the amount of A13+ions released into the chloroiridic acid impregnation solution is higher than that released into the chloroplatinic acid solution when alumina is used as the support. Yet, the amount of Ir adsorbed on alumina is less than the amount of platinum adsorbed on alumina. This effect is an inherent property of the system and might be due to the differences in the buffering properties of the hexachlorinate Pt and Ir ions.
(25)Subramanian,S . ;Schwarz, J. A. J. Catal. 1991, 127, 201. (26) H u g , Y. J.; Barrett, B. R.; Schwarz, J. A. Appl. Catal. 1986,24, 241.

1438 Langmuir, Vol. 7, No. 7, 1991

Table I. Equilibrium Metal Adsorption Data amt of amt of metal adsorbed, metal mounted, g.mol/g of gmol/g of system support ( X W ) support (Xlor)
KIO-

Subramanian and Schwarz

Pt/Al20s Pt/ TiOrAl20a Pt/A120a-Ti02 Pt/TiOz Ir/AlZOa Ir /Ti02-A1203 Ir/AlZOa-TiOz Ir/TiOz

2.9 1.8 0.3 0.3 2.2 2.1 0.7 0.4

3.0 1.9 0.3 0.3 2.2 2.2 0.7 0.4

A

Table 11. Equilibrium Solution pH and Dissolved A1 Concentration (Bash: 2 g of oxide)

system

8
0

amt of Ala+ amt of Ala+ 7 % available equil dissolved, available, aluminum pH pmol ( X W ) g-mol (NOS) dissolved
3.4 1.9 0.7 0.6 3.6 3.2 0.7 0.7 2.0 1.1 0.1 0.0 3.9 2.3 0.2 0.0 39.2 34.9 0.3
0.0

603

I200
Time ( s )

1 800

YO6

IA

Pt/A1203 Pt/TiOz-A120~ Pt/AlzOa-Ti02 Pt/TiOz Ir/AlaOs Ir/TiOrAlgOs

Ir/Al2OrTiOz

5.1 3.1 20.6 10.0 6.6 44.1

Figure 1. Plot of amount of Pt adsorbed (gmol/g of support) versus impregnation time (a). The solid line representsthe Langmuir equation.
a KJ+

Ir/TiOz

39.2 34.9 0.3 0.0

The transient data, amount of metal adsorbed (a) as a function of time, for pure as well as composite oxides are shown in Figures 1and 2. In these figures, the ordinates were obtained by subtracting the pore filling component from the total amount of metal mounted on the support or composite oxide. The pore fiiing component (calculated from the pore volume and concentration of the metal solution inside the pores) is zero in the case of nonporous supports and composite oxides. At t << tequilibrium, eq 2 can be used to assess the forward and backward adsorption rate constants. The model parameters kl and k-1 (Table 111) were obtained by using the simplex optimization procedure for nonlinear equation^.^^*^ Experimental data points collected for time, t C 600 s, were used in this analysis. The solid lines shown in these figures were obtained from eq 3.

Time ( r l

Figure 2. Plot of amount of Ir adsorbed (gmol/g of support) versus impregnation time (e). The solid line representsthe Langmuir equation. Table 111. Langmuir Equation Parameten system Wkl, 8-1 Wk-1, pmol/L.s Pt/TiOrAlzOs Pt/ AlzO3-TiO2 Pt/ Ti02 Ir/&Os Ir/TiOrAlzOa Ir/AlaOs-TiOz
Ir/TiOz

Discussion Titania is considered to be insoluble in acidic solutions.29 It is interesting to note (Table 11) that the amount of A1203 dissolved in the case of composite oxides is lower than that observed in the case of pure Al2O3; the presence of Ti02 in the composite oxide appears to provide a protective coating and inhibit the dissolution of A&. The percentage of A1203 dissolved in the case of A1203-Ti02 is higher. The percentage of available aluminum that is released into solution in the different metal/oxide systems 1 . These values vary from a is presented in Table 1 maximum of 44.12% in the case of Ir/0.87% Al203-Ti02 to a minimum of 3.12% in the case of Pt/11.4% T i O p Al2O3. The dissolution equilibrium limits the maximum amount of AP+ ions that can go into solution. The impregnation of the aqueous precursor was conducted a t pH values less than 1.0. Anions, PtCb2- and IrCls2-, are adsorbed on the positively charged sites of the support. The pzcs of Ti02 and A1203 are 6.20 and 8.30, re~pectively.~~ Surface charge considerations suggest that
(27) Spendley, W.; Hext, G. R.; Hinsworth, F. R. Technometrics 1962, 4, 441. (28) Nelder, J. A.; Mead, R. Computer J. 1966, 7, 308. (29) Grant, F. A. Rev. Mod. Phys. 1959, 31, 646.

Pt/&Os

4.2 1.8 1.9 1.0 6.0 4.7 1.5 0.4

3.8 1.6 1.5 0.9 1.7 3.3 0.9 2.5

the metal ions w i l l have a stronger affinity for alumina compared to titania. A comparison of the forward adsorption rate constant, kl, on alumina and titania (Table I) indicates that the metal ions, PtCb2- and IrCb2-, have a higher affinity for alumina compared to titania. Furthermore, the amount of both Pt and Ir adsorbed a t equilibrium is higher in the case of alumina compared to titania. A comparison of the kl values on Ti02 and 0.87% A1203-Ti02 indicates that the presence of alumina as a secondary phase in the composite oxide increases the adsorption rate. Likewise, a comparison of the kl values on A1203 and 11.4% T i O r A1203 indicates that the presence of Ti02 as a secondary phase in the composite oxide lowers the adsorption rate. These considerations indicate that the hexachlorinate ions have a preference for adsorption on alumina over adsorp-

Adsorption of Acids on Composite Oxides

I

Langmuir, Vol. 7, No. 7 ,1991 1439

-I

400

600
Tempemlua(I0

800

200

403

600
Temperature ( K )

BCO

Figure 3. Temperature-programmed reductionprofile for 0.7 % Ir/&03, 0.7% Ir/TiOz, and 0.7% Ir/0.87% A120s-Ti02 precursors.
Table IV. TPRd Peak Temperature and Hydrogen Consumption Values

Figure 4. Temperature-programmedreduction profile for 3 % Ir/A1203,3% Ir/TiO2, and 3 % Ir/0.87 % AlzOs-Ti02 precursors. selective exchange process, iridium precursors were characterized by TPRd. I t is important to note that the precursors were not calcined; the changes occurring during this high temperature treatment are dependent on the nature of the support and the TPRd profiles of calcined precursors cannot be interpreted easi1y.m In this study, the peak temperature obtained during the TPRd of dried precursors was used as a "fingerprint" to identify the iridium distribution in a composite oxide supported precursor. Figure 3 shows the TPRd spectra of the Al2O3, TiOz, and0.87 % A1203-Ti02 supported Ir precursors. The peak temperatures and hydrogen consumption values are reported in Table IV. In these cases the metal weight loading was adjusted to 0.7 5%. At metal weight loadings significantly lower than 0.7% (i.e., 0.05%), the TPRd signal was insignificant. It is interesting to note that at the 0.7 % level weight loading, the TPRd spectrum for the 0.7% Ir/0.87 % A1203-Ti02 precursor qualitatively resembles the TPRd spectrum of the 0.7 9% Ir/A1203precursor. The peak temperatures for these spectra are similar. Comparison of the reduction spectra for Ir/TiOz and Ir/0.87 % Ti02-Al203 precursors suggests that the peak a t 355 K in the case of the 0.875% A1203-Ti02 supported Ir precursor originates from the fraction of Ir distributed on TiOz. Figure 4 shows the TPRd spectra of the TiOz, A1203, and 0.87% A1203-Ti02 supported Ir precursors with a metal weight loading of 3%. The peak temperatures and hydrogen consumption values are reported in Table IV. It is interesting to note that the TPRd spectrum of the composite oxide supported precursors is qualitatively similar to that obtained for the Ti02 supported precursors. The similarity in peak temperatures is striking. The amount of metal distributed on A1203 is negligible in comparison to the amount of metal distributed on TiOz. This confirms the assertion that, at relatively high metal weight loadings, the metal is essentially distributed on Ti02 in the 0.87% A1203-Ti02 composite oxide. These studies illustrate that selective partitioning of the metal species can be achieved if the ion under consideration has a significant affinity for one of the oxides. The variable that determines the selectivity of the exchange process is the metal weight loading. The concept of selectively adsorbing metal ions on one of the compoents of a composite oxide can be extended to cations as well as anions. The selective adsorption process is of particular interest in low metal weight loading systems where the metal may be selectively distributed on the secondary phase (the minor component on a weight basis) of the composite oxide.
NY,1989.
(30) Subramanian,S. PbD. Dissertation,SyracuseUniversity,Syracuee

Metal Loading: 0.7 %

system

Ir/Al*Os Ir/A1203-Ti02 Ir/TiOz

~

peak temp, K 352,479,600-800 355, 375,493,600-800 379,484,600-800

consumed, rcmol/a of precursor

118.2 122.4 129.9

hydrogen

Metal Loading: 3.0%

~ ~~ ~

system

Ir/A120s Ir/ALOs-TiOz Ir/TiOz

peak temp, K 379,495,600-800 340-380,477,600-800 353, 462,600-800

hydrogen consumed, pmollg of precursor 349.6 356.4 348.9

tion on titania. The aforementioned considerations suggest that the metal component may be directed to selectively adsorb on the alumina present in the composite oxide. The 0.87% A1203-Ti02 composite is of particular interest. Here Al2O3, the component on which adsorption is favored, is present as the secondary phase. One may consider the following "idealized" scenario assuming that metal will be directed toward Ti02 only after A1203reaches adsorption equilibrium with the metal. At extremely low metal loadings, the metal ions' preference for A1203 will direct the metal exclusively toward A1203. For example, at a 0.05% total metal loading, the weight loading on A1203 will be only 5.75%, if all the available metal is present on A1203. At relatively high metal loadings, A1203 will be "saturated" with the metal and the remaining available metal will be present on TiOz. For example, a t a 3 % total metal loading, the weight loading on A1203 w i l lbe 344.82 % , if all the available metal is present on A1203. A metal loading of 344.85% is unrealistic. In this case, the metal will be distributed on Ti02 once A1203attains adsorption equilibrium with the metal. It appears that selective metal exchange on alumina may be achieved a t reasonably low metal loadings. For completeness, in the 11.4% TiOzA1203composite, A1203 is the primary component. Since the adsorption on the primary component is favored, it is not possible to direct the metal component toward Ti02 at reasonable metal loadings. The ratio of the forward adsorption rate constants on alumina and titania is higher in the case of iridium (5.96 X 1Om3/O.36 X 10-3 = 16.56) compared to platinum (4.17 X 10-3/1.03 X 10-3 = 4.05). These kinetic considerations favor the selective adsorption process in the case of iridium compared to platinum. Therefore Ir precursors were chosen for further study. In order to investigate the

1440 Langmuir, Vol. 7, No. 7, 1991

Subramanian and Schwarz (3) The selective adsorption process has been explored by using TPRd and the results suggest that the metal may be selectively dispersed on one of the components of the composite oxide, if the metal ion has a higher affinity for that component. The metal weight loading determines the selectivity of the exchange process.

Conclusions The findings of the study may be summarized as follows: (1) The adsorption kinetics observed for the composite oxide systems can be described in terms of the Langmuir equation. The model parameters, kl and k-1, have been estimated by using the simplex optimization procedure. (2) The adsorption kinetics and adsorption equilibrium indicate that the metal ion has a preference for adsorption on alumina compared to adsorption on titania. Titania in the Ti02-Al203 composite oxide appears to provide a protective coating and inhibit the amount of A13+dissolving into acidic impregnation solutions.

Acknowledgment. Portions of this work were supported under Department of Energy Grant DE-FGOB87ER-13650and National Science Foundation Grant CTS 8900514.