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Chem. Mater. 2000, 12, 2442-2447
Water-Assisted Tetragonal-to-Monoclinic Phase Transformation of ZrO2 at Low Temperatures Shuibo Xie, Enrique Iglesia,* and Alexis T. Bell* Chemical and Materials Sciences Divisions, Lawrence Berkeley National Laboratory, and Department of Chemical Engineering, University of California, Berkeley, California 94720-1462 Received March 7, 2000. Revised Manuscript Received June 10, 2000
In-situ Raman spectroscopy has been used to characterize the transformation of amorphous zirconium oxyhydroxide to tetragonal ZrO2 and then to monoclinic ZrO2 in both the absence and presence of water vapor. In the absence of H2O vapor, t-ZrO2 forms when zirconium oxyhydroxide is treated in air above 673 K and the tetragonal-to-monoclinic transformation occurs at temperatures above 950 K. Treatment at progressively higher temperatures is accompanied by loss of surface area. The tetragonal-to-monoclinic transformation occurs when the size of the zirconia particles is equal to or greater than a critical size determined from an analysis of the thermodynamic stability of small particles of t- and m-ZrO2. Exposure of t-ZrO2 to 3 kPa of H2O or immersion in liquid water at 298 K results in its extensive (∼80%) transformation to m-ZrO2 without a loss in surface area. This observation is attributed to a decrease in the difference between the surface free energy of m-ZrO2 and that of t-ZrO2 caused by the adsorption of H2O. Treatment in water vapor at 623 K induces the tetragonal-to-monoclinic transformation as well, but it is accompanied by a significant decrease in surface area. Only 80% of the t-ZrO2 is transformed to m-ZrO2 at 298 K because of the apparent presence of some crystallites with lattice strain, which increases the temperature for the tetragonal-to-monoclinic phase transformation. The results of this study demonstrate that m-ZrO2 with high surface areas can be prepared by exposing t-ZrO2 to water vapor at room temperature.
Introduction Zirconium oxide has attracted considerable attention recently as both a catalyst and a catalyst support because of its high thermal stability and the amphoteric character of its surface hydroxyl groups. Zirconia catalyzes the hydrogenation of olefins,1-4 the isomerization of olefins5 and epoxides,6,7 and the dehydration of alcohols.8,9 When zirconia is used as a support, various reactions such as Fischer-Tropsch synthesis,10,11 methanol synthesis,12-15 and hydrodesulfurization16 have been * To whom correspondence should be addressed at University of California, Berkeley. E-mail:
[email protected]; bell@ cchem.berkeley.edu. Fax: (510) 642-4778. (1) Yamaguchi, T.; Hightower, J. J. Am. Chem. Soc. 1977, 99, 4201. (2) Tanaka, Y.; Hattori, H.; Tanabe, K. Bull. Chem. Soc. Jpn. 1978, 51, 3641. (3) Nakano, Y.; Yamaguchi, T.; Tanabe, K. J. Catal. 1983, 80, 307. (4) Bird, R.; Kemball, C.; Leach, H. F. J. Chem. Soc., Faraday Trans. 1987, 1, 3069. (5) Nakano, Y.; Iizuka, T.; Hattori, H.; Tanabe, K. J. Catal. 1979, 57, 1. (6) Arata, K.; Akutagawa, S.; Tanabe, K. Bull. Chem. Soc. Jpn. 1976, 49, 390. (7) Arata, K.; Kato, K.; Tanabe, K. Bull. Chem. Soc. Jpn. 1976, 49, 563. (8) Yamaguchi, T.; Sasaki, H.; Tanabe, K. Chem. Lett. 1973, 1017. (9) Davis, B. H.; Ganesan, P. Ind. Eng. Chem. Prod. Res. Dev. 1979, 18, 191. (10) Bruce, L.; Mathews, J. F. Appl. Catal. 1982, 4, 353. (11) Bruce, L.; Hope, G. J.; Mathews, J. F. Appl. Catal. 1983, 8, 349. (12) Amenomiya, Y. Appl. Catal. 1987, 30, 57. (13) Denise, B.; Sneedon, R. P. A. Appl. Catal. 1986, 28, 235. (14) Fisher, I.; Bell, A. T., J. Catal. 1997, 172, 222.
reported to proceed with higher rates and selectivity than with other supports. The catalytic applications of zirconia mentioned above have stimulated research aimed at understanding the factors controlling the structural and textural properties of ZrO2, such as the distribution of ZrO2 among amorphous, tetragonal, and monoclinic phases, the BET surface area, and the pore size distribution.17-31 Aqueous precipitation or sol-gel methods are often used to (15) Fisher, I.; Bell, A. T. J. Catal. 1998, 178, 153. (16) Hamon, D.; Vrinat, M.; Breysse, M.; Durand, B.; Jebrouni, M.; Roubin, M.; Magnoux, P.; des Courieres, T. Catal. Today 1991, 10, 613. (17) Srinivasan, R.; Davis; B. H.; Cavin, O. B.; Hubbard, C. R. J. Am. Ceram. Soc. 1992, 75, 1217. (18) Ward, D. A.; Ko, E. I. Chem. Mater. 1993, 5, 956. (19) Clearfield, A.; Serrette; G. P. D.; Khazi-Syed, A. H. Catal. Today 1994, 20, 295. (20) Coma, A.; Fornes; V. Juan-Rajadel; M. I.; Lopez Nieto, J. M. Appl. Catal. A: Genl. 1994, 116, 151. (21) Inoue, M.; Koninami, H.; Inui, T. Appl. Catal. A: Genl. 1995, 121, L1. (22) Bedilo, A. F.; Klabunde, K. J. NanoStruct. Matl. 1997, 8, 119. (23) Collins, D. E.; Bowman, K. J. J. Mater. Res. 1997, 13, 1230. (24) Zhan, Z.; Zeng, H. C. J. Mater. Res. 1997, 13, 2174. (25) Navı´o, J. A.; Colo´n, G.; Sa´nchez-Soto, P. J.; Macias, M. Chem. Mater. 1997, 9, 1256. (26) Stichert, W.; Schuth, F. Chem. Mater. 1998, 10, 2020. (27) Chuah, G. K.; Jaenicke, S.; Pong, B. K. J. Catal. 1998, 175, 80. (28) Chuah, G. K. Catal. Today 1999, 49, 131. (29) Afanasiev, P.; Thiollier, A.; Breysse, M.; Dubois, J. L. Topics Catal. 1999, 8, 147. (30) Barton, D. G.; Soled, S. L.; Meitzner, G. D.; Fuentes, G. A.; Iglesia, E.; J. Catal. 1999, 181, 57. (31) Srinivasan, R.; Davis, B. H. In Materials Synthesis and Characterization; Perry, D. L., Ed.; Plenum: New York, 1994; p 147.
10.1021/cm000212v CCC: $19.00 © 2000 American Chemical Society Published on Web 08/04/2000
Phase Transformation of ZrO2
produce zirconia powders (see ref 31 and references therein). The initial product is an amorphous zirconium oxyhydroxide or a mixture of amorphous and tetragonal ZrO2 (a-ZrO2 and t-ZrO2, respectively). Calcination of the initial product at progressively higher temperatures leads to the conversion of all of the a-ZrO2 to t-ZrO2, and at higher temperatures to the conversion of t-ZrO2 to monoclinic ZrO2 (m-ZrO2). Since treatments also lead to a decrease in surface area, m-ZrO2 is usually obtained with much lower surface area than t-ZrO2. The attainment of high surface area m-ZrO2 requires methods for inducing the tetragonal to monoclinic transformation at low temperature. The possibility of using water vapor to achieve this goal has been reported in the literature.32,33 At temperatures above 673 K, the presence of water vapor was found to promote the tetragonal-tomonoclinic phase transformation of ZrO2, but with concurrent growth in the crystallite size of both phases. The present work was undertaken in order to determine whether the tetragonal-to-monoclinic transformation can be carried out near room temperatures in order to minimize particle growth. Experimental Section Zirconium oxyhydroxide, ZrOx(OH)4-2x, was prepared by the precipitation of an aqueous solution of ZrOCl2 at a constant pH of 10.29 The precipitate was washed with deionized water until the rinse solution was free of chloride ions, and the filter cake was then dried overnight at 393 K. The N2 BET surface area of the powders was 412 m2/g. Raman spectra were recorded using a HoloLab 5000 Raman spectrometer (Kaiser Optical) equipped with a Nd:YAG laser that is frequency doubled to 532 nm. The laser was operated at a power level of 45 mW. The resolution of the spectrometer is 5 cm-1. The samples were loaded as powders into a stationary cell that could be heated to 1023 K.34 The sample could then be treated in the Raman cell with 20% O2/He or with a mixture of 20% O2/He saturated with H2O vapor at 298 K. Powder X-ray diffraction (XRD) patterns were recorded using a Siemens D5000 diffractometer. Cu (KR) radiation was used together with a scanning rate of 0.02 deg s-1. Samples were prepared by spreading a thin layer of powder in Vaseline on a glass plate holder. For a limited number of samples, XRD patterns were also recorded without exposure of the sample to room air. In these cases, the pretreated samples were transferred into a glovebox where they were mixed with a small amount of Vaseline and then spread onto the sample holder. Preparation in this manner ensured that water vapor in the air would not affect the smaples. The volume fraction of m-ZrO2 was determined via the method described by Toraya et al.35 Thermal analysis was carried out with an SDT 2960 Simultaneous DSC-TGA (TA Instruments). Weight loss and heat flows were measured while samples (∼ 0.02 g) were heated from 293 to 1273 K at 10 K/min in flowing O2. These measurements were used to determine the temperature at which the amorphous-to-tetragonal and the tetragonal-tomonoclinic phase transitions occurred and the amount of heat released during each transformation.
Results Figure 1 shows Raman spectra taken as a function of time as amorphous zirconium oxyhdroxide was heated (32) Murase, Y.; Kato, E. J. Am. Ceram. Soc. 1979, 62, 527. (33) Murase, Y.; Kato, E. J. Am. Ceram. Soc. 1983, 66, 196. (34) Xie, S.; Rosynek, M. P.; Lunsford, J. H. Appl. Spectrosc. 1999, 53, 1183. (35) Toraya, H.; Yoshimura, M.; Somiya, S. J. Am. Ceram. Soc. 1984, 67, C-119.
Chem. Mater., Vol. 12, No. 8, 2000 2443
Figure 1. Raman spectra for amorphous ZrOx(OH)2-2x recorded at 623 K in 20% O2/He. Spectra were recorded at intervals of 10 min. Temperature was increased from 298 K at 10 K/min.
in flowing 20% O2/He at 623 K. Spectra acquired for heating times of 50% m-ZrO2 resemble very closely those of pure m-ZrO2. This conclusion is based on measurements of CO and CO2 adsorption and on the dynamics of D2 exchange of Zr-OH groups.45 The net result is that high surface area ZrO2 supports with the properties of pure m-ZrO2 can be prepared by water treatment of t-ZrO2 under ambient conditions. Conclusions In situ Raman spectroscopy can be used to follow the tetragonal-to-monoclinic transformation of ZrO2. In the (44) Mitsuhashi, T.; Ichihara, M.; Tatsuke, U. J. Am. Ceram. Soc., 1974, 57, 97. (45) Jung, K. D.; Bell, A. T. J. Catal., in press.
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absence of water vapor, t-ZrO2 prepared by calcination of amorphous zirconium oxyhydroxide at 623 K has a surface area of 204 m2/g. This material is stable up to calcination temperatures of 823 K; above that it starts to transform into m-ZrO2. The tetragonal-to-monoclinic transformation occurs when the size of the t-ZrO2 particles reaches a critical value, which is determined by thermodynamics (see eq 1). Exposure of t-ZrO2 calcined at 623 K to 3 kPa H2O vapor or immersion in liquid H2O at 298 K results in the conversion of nearly 80% of the t-ZrO2 to m-ZrO2 without a loss in surface area. This transformation is attributed to a preferential lowering of the surface free energy of the m-ZrO2 relative to t-ZrO2 upon adsorption of water. Failure to achieve complete transformation to m-ZrO2 is attributed to strain stabilization in some t-ZrO2 particles. Treatment of t-ZrO2 in water vapor at elevated temperature causes the tetragonal-to-monoclinic transformation to occur concurrently with a significant loss in surface area.
Acknowledgment. The authors would like to thank Kyle Fujdala for carrying out the thermal analysis reported here. This work was supported by the Director, Office of Energy Sciences, Chemical Sciences Division, of the U.S. Department of Energy under contract DE-AC03-76SF00098. CM000212V
