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化学学报
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化学学报 ›› 2006, Vol. 64 ›› Issue (10): 1017-1021. 上一篇    下一篇

研究论文

Cu/ZrO2催化剂中的氢和水逆溢流效应及其对甲醇分解反应的影响

吴贵升，王路存，刘永梅，曹勇*, 戴维林，贺鹤勇，范康年*   

  1. (复旦大学化学系 上海市分子催化和功能材料重点实验室 上海 200433)
  • 投稿日期:2005-09-25 修回日期:2006-01-18 发布日期:2006-05-25
  • 通讯作者: 范康年

Research on the Role of Reverse Hydrogen and Water Spillover in Methanol Decomposition over Cu/ZrO2 Catalyst

WU Gui-Sheng, WANG Lu-Cun, LIU Yong-Mei, CAO Yong*, DAI Wei-Lin, HE He-Yong, FAN Kang-Nian*   

  1. (Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials at Department of Chemistry,
    Fudan University, Shanghai 200433)
  • Received:2005-09-25 Revised:2006-01-18 Published:2006-05-25
  • Contact: FAN Kang-Nian

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应用漫反射红外和质谱在线技术对H2, H2O及甲醇在ZrO2及Cu/ZrO2上的程序升温脱附(TPD)及程序升温反应(TPSR)行为进行了研究. 结果表明, Cu/ZrO2催化剂中铜锆组分间表现出显著的氢和水组分“逆溢流”效应. 对Cu/ZrO2催化体系中ZrO2表面线式及桥式羟基物种浓度随还原预处理温度变化的进一步分析表明, 由于氢和水“逆溢流效应”的存在, 使得Cu/ZrO2在较低的还原温度下活化的同时, 在铜锆界面处形成较丰富的氧阴离子和氧空穴活性位, 而后者的形成与存在直接影响并决定了甲醇在Cu/ZrO2催化剂上的低温催化分解行为.

关键词: 氢溢流, 逆溢流, ZrO2, Cu/ZrO2, 甲醇分解

The interaction of H2, H2O and CH3OH with pure ZrO2 or Cu/ZrO2 catalyst has been investigated by temperature programmed desorption and reaction to understand the nature of the surface sites and the mechanism involved in methanol decomposition. The results show that methanol decomposition over Cu/ZrO2 occured primarily on ZrO2 with the aid of surface oxygen anions and oxygen vacancies. The primary function of surface oxygen anions and oxygen vacancies was suggested to facilitate the dissociated adsorption of methanol, with the main role of metallic Cu to provide sites for H2 removal by efficiently recombining the hydrogen atoms formed during the dehydrogenation of species located on zirconia.

Key words: hydrogen spillover, reverse spillover, ZrO2, Cu/ZrO2, methanol decomposition