物理化学学报 >> 1993, Vol. 9 >> Issue (03): 311 -318 .doi: 10.3866/PKU.WHXB19930307

研究论文 上一篇    下一篇

Fe2O3在ZrO2上的分散状态及其对催化性能的影响

季伟捷; 沈师孔; 李树本; 王弘立   

  1. 中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室,兰州 730000
  • 收稿日期:1991-10-18 修回日期:1992-03-23 发布日期:1993-06-15
  • 通讯作者: 季伟捷

Dispersion State of Ferric Oxide on ZrO2 and its Influence on the Catalytic Performance

Ji Wei-Jie; Shen Shi-Kong; Li Shu-Ben; Wang Hong-Li   

  1. State Key Laboratory of Oxo-Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academic of Sciences, Lanzhou 730000
  • Received:1991-10-18 Revised:1992-03-23 Published:1993-06-15
  • Contact: Ji Wei-Jie

摘要: 用多种物理化学手段, 对用不同方法制备的在ZrO_2上分散的氧化铁体系进行了细致的表征和比较. 对氧化铁在ZrO_2上分散的结构状态及其对催化性能的影响有了较为全面的了解.

关键词: 氧化铁, 氧化锆, 分散状态, 表面化学, 催化性能

Abstract: Three methods, dipping of support into an excess of aqueous solution of (NH_4)_3[Fe(C_2O_4)_3]·xH_2O, incipient wetness impregnation of Fe(NO_3)_3 solution and batch adsorption of Fe(AcAc)_3 in toluene were adopted to prepare supported ferric oxide on ZrO_2. Extensive characterization has been done on the physico-chemical properties of the system. The results indicated that monolayer dispersion of the supported component can be realized using the dipping and adsorption methods. It is difficult to obtain a full coverage of FeO_x on ZrO2. In order to get monolayer dispersion, it is importment that the adsorbed particles should be fully washed with pure toluene in adsorption method or the remained solution on the support particles should be carefully removed in dipping method. The monolayer FeO_x, espically the "quasi-isolated" Fe—O polyhedrons are difficultly detected by FTIR-DRS, LRS as well as XRD. TEM and HEED techniques were adopted to further comfirm the observation. The monolayer dispersed Fe~(3+) is at high spin state and located in a site with distorted rhombic symmetry. The monolayer FeO_x on ZrO_2 is easily reduced to ferrous state as compared with the unsupported bulk ferric oxide or even those monolayer FeO_x species on TiO_2(A) and γ-Al_2O_3. However, further reduction of ferrous ion is still difficult. The microcrystal of ferric oxide on ZrO_2 is reduced through an intermediate compound during the reduction process. The results of pulse reaction of 2-C_4H_8 with or without gas oxygen showed that even the monolayer "quasi-isolated" polyhedrons are still effective to catalyse the ODH of the reactant. Different from the bulk ferric oxide, the monolayer catalysts are sensitive to the presence of gas oxygen for the formation of surface residues and CO_x. In addition, the monolayer FeO_x species are not active for the methanation reaction.

Key words: Ferric oxide, Zirconium oxide, Dispersion state, Surface chemistry, Catalytic performance