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合成低碳混合醇铜基催化剂中助剂K作用的XPS研究

THE ROLE OF POTASSIUM MODIFIER IN COPPER-BASED CATALYST FOR MIXED ALCOHOL SYNTHESIS STUDIED BY XPS

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【作者】 陈宝树; 赵九生; 张鎏; 熊国兴; 盛世善;

【Author】 Chen Bao-shu, Zhao Jiu-sheng, Chang Liu, (Department of Chemical Engineering, Tianjin University, Tianjin 300072)Xiong Guo-xing and Sheng Shi-shan(Laboratory for Catalysis, Dalian Institute of Chemical Physics, Academia Sinica, Dalian 116023)

【机构】 天津大学化学工程系; 中国科学院大连化学物理研究所催化基础研究开放实验室; 中国科学院大连化学物理研究所催化基础研究开放实验室 天津 300072; 天津 300072; 大连 116023; 大连 116023;

【摘要】 用XPS考察了低碳混合醇合成用CuO-ZnO-Al2O3-K2CO3催化剂在反应条件下的表面状态及助剂K的作用。结果表明,在还原及反应后,表面没有稳定的Cu+和Cu2+存在,仅能检测到Cu0物种,Cu0是催化剂的活性组分之一。在表面存在着混合醇合成活性单元(□为氧空位)和甲醇合成活性单元,助剂K被稳定地联结在Al2O3上。当Al2O3不存在时,K会大量富集在催化剂表面。未还原催化剂中,K与CuO之间存在着强的电子相互作用,K作为施主把电子传递给CuO。但在反应条件下,未检测到K与Cu0之间明显的电子相互作用。K的存在可适当提高高级醇的选择性。

【Abstract】 The surface states of CuO-ZnO-Al2O3-K2CO3 catalysts for mixed alcohol synthesis and the role of modifier potassium v ere studied by XPS measurement under simulated reaction conditions. After reduction and reaction, no stable Cu+ and Cu2+ ions were found, only Cu0 v as detected. Cu0 is believed to be dispersed in oxygen-deficient species ZnOx(x≤1 )and A12O3 in the form of microcr -stallites. It is proposed that Cu?is one of the active components on the surface,the active units exist as Cu- Zn-O-K("□" is oxygen vacancy) for mixed alcoholas well as Cu - Zn-O for CH3OH synthesis.The potassium was bonded to Al2O3. In the absence of Al2O3, surface enrichment in K was observed. There exists strong elecironic interaction between K and reduced CuO with K acting as a donor and transferring electrons to CuO. But no obvious electronic interaction between K and Cu0 v, as detected during reaction. It is suggested that besides the possible action of neutralizing the acidit of Al2O3, K can act on Cu through ZnO to stabilize ox gen-containing intermediates, promoting C-C chain grov, th and improving higher alcohol selectivity .

【基金】 国家自然科学基金;中国科学院大连化学物理研究所催化基础研究开放实验室基金
  • 【文献出处】 催化学报 ,Chinese Journal of Catalysis , 编辑部邮箱 ,1990年04期
  • 【被引频次】23
  • 【下载频次】137
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