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Acta Phys. Chim. Sin.  2012, Vol. 28 Issue (01): 170-176    DOI: 10.3866/PKU.WHXB201228170
Preparation of CuO-ZnO-ZrO2 by Citric Acid Combustion Method and Its Catalytic Property for Methanol Synthesis from CO2 Hydrogenation
GUO Xiao-Ming1,2, MAO Dong-Sen2, LU Guan-Zhong1,2, WANG Song2
1. Research Institute of Industrial Catalysis, East China University of Science and Technology, Shanghai 200237, P. R. China;
2. Research Institute of Applied Catalysis, Shanghai Institute of Technology, Shanghai 200235, P. R. China
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Abstract  CuO-ZnO-ZrO2 (CZZ) catalysts for methanol synthesis from CO2 hydrogenation were prepared by a citric acid combustion method. The combustion reactions were analyzed in terms of propellant chemistry and the combustion behavior was recorded by thermo-gravimetric/differential thermal analysis (TG-DTA). The as-prepared CZZ powders were investigated with X-ray diffraction (XRD), N2 adsorption, temperature-programmed reduction (TPR), and reactive N2O adsorption techniques and the catalytic activities were evaluated for methanol synthesis from CO2 hydrogenation. The results show that the influence of citric acid quantity on the physicochemical and catalytic properties of CZZ is subtle, and the reason is related to the characteristics of the combustion reaction. Furthermore, the relationship between the quantity of fuel (citric acid, urea, and glycine) and the properties of the catalysts was determined. The citric acid combustion method exhibits better controllability and it is a simple, fast, and valuable route for the preparation of the CZZ catalyst for methanol synthesis from CO2 hydrogenation.

Key wordsCombustion synthesis      Citric acid      CuO-ZnO-ZrO2      CO2 hydrogenation      Methanol     
Received: 29 August 2011      Published: 03 November 2011
MSC2000:  O643  

The project was supported by the Science and Technology Commission of Shanghai Municipality, China (08520513600), Leading Academic Discipline Project of Shanghai Education Committee, China (J51503), and Science and Technology Development Fund of Shanghai Institute of Science and Technology, China (KJ2010-05).

Corresponding Authors: MAO Dong-Sen, LU Guan-Zhong     E-mail:;
Cite this article:

GUO Xiao-Ming, MAO Dong-Sen, LU Guan-Zhong, WANG Song. Preparation of CuO-ZnO-ZrO2 by Citric Acid Combustion Method and Its Catalytic Property for Methanol Synthesis from CO2 Hydrogenation. Acta Phys. Chim. Sin., 2012, 28(01): 170-176.

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(1) Zhang, J. X.; Zhao, Y. Q.; Chen, J. X.;Wang, R. J.; Zhang, J. Y. Natural Gas Chem. Ind. 2004, 29, 43. [张建祥, 赵彦巧, 陈吉祥, 王日杰, 张继炎. 天然气化工, 2004, 29, 43.]
(2) Olah, G. A. Catal. Lett. 2004, 93, 1.  
(3) Arena, F.; Barbera,K.; Italiano, G.; Bonura, G.; Spadaro, L.; Frusteri, F. J. Catal. 2007, 249, 185.  
(4) S?oczyński, J.; Grabowski, R.; Koz?owska, A.; Olszewski, P.; Lachowska, M.; Skrzypek, J.; Stoch, J. Appl. Catal. A-Gen. 2003, 249, 129.  
(5) Ma, Y.; Sun, Q.;Wu, D.; Fan,W. H.; Zhang, Y. L.; Deng, J. F. Appl. Catal. A-Gen. 1998, 171, 45.  
(6) Raudaskoski, R.; Niemelä, M. V.; Keiski, R. L. Top. Catal. 2007, 45, 57.  
(7) S?oczyński, J.; Grabowski, R.; Koz?owska, A.; Olszewski, P.; Stoch, J.; Skrzypek, J.; Lachowska, M. Appl. Catal. A-Gen. 2004, 278, 11.  
(8) Zhuang, H. D.; Bai, S. F.; Liu, X. M.; Yan, Z. F. J. Fuel Chem. Technol. 2010, 38, 462. [庄会栋, 白绍芬, 刘欣梅, 阎子峰. 燃料化学学报, 2010, 38, 462.]  
(9) Zhu, P. F.; Li, J.; Zuo, S. F.; Zhou, R. X. Appl. Surf. Sci. 2008, 255, 2903.  
(10) Zhu, Y. Q.; Ma, Y. F.; Lin, X. P.;Wang, Z. H. Chin. J. Catal. 1998, 19, 393. [朱毅青, 马延风, 林西平, 王占华. 催化学报, 1998, 19, 393.]
(11) Cong, Y.; Tin, K. C.;Wang, N. B.; Xu, C. H.; Zhang, T.; Sun, X. Y.; Guan,W.; Liang, D. B. Chin. J. Catal. 2000, 21, 247. [从昱, 田金忠, 黄宁表, 徐长海, 张涛, 孙孝英, 关文, 梁东白. 催化学报, 2000, 21, 247.]
(12) Agrell, J.; Boutonnet, M.; Melian-Cabrera, I.; Fierro, J. L. G. Appl. Catal. A-Gen. 2003, 253, 201.  
(13) Wang, L. C.; Liu, Y. M.; Chen, M.; Cao, Y.; He, H. Y.;Wu, G. S.; Dai,W. L.; Fan, K. N. J. Catal. 2007, 246, 193.  
(14) Su, X. T.; Yan, Q. Z.; Ge, C. C. Progress Chem. 2005, 17, 430. [宿新泰, 燕青芝, 葛昌纯. 化学进展, 2005, 17, 430.]
(15) Patil, K. C.; Aruna, S. T.; Mimani, T. Curr. Opin. Solid State Mater. Sci. 2002, 6, 507.  
(16) Wang, Q. G.; Peng, R. R.; Xia, C. R.; Zhu,W.;Wang, H. T. Ceram. Int. 2008, 34, 1773.  
(17) Ribeiro, N. F. P.; Souza, M. M. V. M.; Schmal, M. J. Power Sources 2008, 179, 329.  
(18) Avgouropoulos, G.; Ioannides, T. Appl. Catal. A-Gen. 2003, 244, 155.  
(19) Toniolo, J. C.; Lima, M. D.; Takimi, A. S.; Bergmann, C. P. Mater. Res. Bull. 2005, 40, 561.  
(20) Guo, X. M.; Mao, D. S.; Lu, G. Z.;Wang, S.;Wu, G. S. J. Catal. 2010, 271, 178.  
(21) Guo, X. M.; Mao, D. S.;Wang, S.;Wu, G. S.; Lu, G. Z. Catal. Commun. 2009, 10, 1661.  
(22) Chinchen, G. C.; Hay, C. M.; Vandervell, H. D.;Waugh, K. C. J. Catal. 1987, 103, 79.  
(23) Jain, S. R.; Adiga, K. C.; Pai Verneker, V. R. Combust. Flame 1981, 40, 71.  
(24) Dean, J. A. Lange ' s Handbook of Chemistry, 13th ed.; McGraw-Hill: New York, 1985; pp 9-14, 9-19, 9-25, 9-66, 9-67, 9-93.
(25) Zhang, Y. P.; Fei, J. H.; Yu, Y. M.; Zheng, X. M. Energy Convs. Manage. 2006, 47, 3360.  
(26) Melián-Cabrera, I.; López Granados, M.; Fierro, J. L. G. J. Catal. 2002, 210, 273.  
(27) Lin, M. G.; Yang, C.;Wu, G. S.;Wei,W.; Li,W. H.; Shan, Y. K.; Sun, Y. H.; He, M. Y. Chin. J. Catal. 2004, 25, 591. [林明桂, 杨成, 吴贵升, 魏伟, 李文怀, 单永奎, 孙予罕, 何鸣元. 催化学报, 2004, 25, 591.]
(28) Yang, Z. Q.; Mao, D. S.; Guo, Q. S.; Gu, L. Acta Phys. -Chim. Sin. 2010, 26, 3278. [杨志强, 毛东森, 郭强胜, 顾蕾. 物理化学学报, 2010, 26, 3278]
(29) Purohit, R. D.; Sharma, B. P.; Pillai, K. T.; Tyagi, A. K. Mater. Res. Bull. 2001, 36, 2711.  
(30) Andrade de Jesus, F. A.; Silva, R. S.; Hernandes, A. C.; Macedo, Z. S. J. Eur. Ceram. Soc. 2009, 29, 125.  
(31) Chinchen, G. C.;Waugh, K. C.; Whan, D. A. Appl. Catal. 1986, 25, 101.  
(32) Sun, Q.; Zhang, Y. L.; Chen, H. Y.; Deng, J. F.;Wu, D.; Chen, S. Y. J. Catal. 1997, 167, 92.  
(33) Zhang, Z. L.; Zhang, Y. X.; Mu, Z. G.; Yu, P. F.; Ni, X. Z.; Wang, S. L.; Zheng, L. S. Appl. Catal. B-Enviro. 2007, 76, 335.  
(34) Deganello, F.; Marcì, G.; Deganello, G. J. Eur. Ceram. Soc. 2009, 29, 439.  
(35) Zhang, J. R.; Gao, L. Mater. Lett. 2004, 58, 2730.  
(36) Singh, K. A.; Pathak, L. C.; Roy, S. K. Ceram. Int. 2007, 33, 1463.  
(37) Chandramouli, V.; Anthonysamy, S.; Vasudeva Rao, P. R. J. Nucl. Mater. 1999, 265, 255.  
(38) Li, F.; Hu, K. A.; Li, J. L.; Zhang, D.; Chen, G. J. Nucl. Mater. 2002, 300, 82.  
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