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金属钯CO中毒机理的热力学研究

Thermodynamic study of the poisoning mechanism of CO on metal palladium

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【作者】 阮文罗文浪张莉蒙大桥朱正和傅依备

【Author】 RUAN Wen~(1,2), LUO Wen-Lang~(1,2), ZHANG Li~1, MENG Da-Qiao~(1,3),ZHU Zheng-He~1, FU Yi-Bei~1(1. Institute of Atomic and Molecular Physics,Sichuan University, Chengdu 610065 China;2. College of Mathematics and Physics, Jinggangshan University, Ji’an 343009, China;3. State Key Laboratory of Physics and Chemistry, CAEP, Mianyang 621907, China)

【机构】 四川大学原子与分子物理研究所井冈山大学数理学院中国工程物理研究院表面物理与化学国家重点实验室

【摘要】 采用密度泛函方法和相对论有效原子实势分别对PdCO、PdOC及PdH的几何构型进行了优化,得到PdCO和PdOC分子电子状态均为(X1+),对于PdCO分子,RPdC=0.1834 nm,RCO=0.1140 nm,∠PdCO=180°;对于PdOC分子,RPdO=0.2157 nm,RCO=0.1133,nm,∠PdOC=180°;PdH分子基态为2∑,RPdH=0.1526 nm。根据电子-振动近似理论计算了不同温度下金属Pd与CO及H2分子反应的生成热力学函数,导出了反应平衡压力随温度的变化关系,分析认为CO引起Pd合金膜中毒主要是由于CO的C原子与Pd原子结合而使CO分子吸附在膜表面所致。

【Abstract】 The different structures of PdCO, PdOC, and PdH were optimized by the relativistic effective core potential (RECP) and the density functional method B3P86. The results showed that Pd and CO of stable Pd—CO molecule were in the same plane. The ground state of PdCO was (X1+) of C∞v, and the bond length (RPdC) was 0.1834 nm, (RCO) was 0.1140 nm, bond angle(∠PdCO)was 180.0°. For PdOC molecule, the ground state was also (X1+), the structure parameters RPdO, RCO, and ∠PdOC were 0.2157 nm, 0.1133 nm, and 180°, respectively. The ground state of PdH was 2∑, and the bond length was 0.1526 nm. Furthermore, the thermodynamic functions of PdCO, PdOC, and PdH were also calculated according to electronic-vibration approximation, and the relationship of the equilibrium pressures with temperatures was obtained. From the results, it was deduced that the poisoning effect of CO was mainly due to the adsorption of CO on palladium surface by combining C atom with Pd atom.

【关键词】 PdCOPdOCPdH热力学函数中毒
【Key words】 PdCOPdOCPdHthermodynamic functionpoisoning
【基金】 国家自然科学基金(10676022,10847138);江西省教育厅科技研究项目([赣教技字2007]325,326,[2005]263);江西省科技厅工业攻关项目(200621);中物院表面物理与化学国家重点实验室基金(08H0135)
  • 【文献出处】 四川大学学报(自然科学版) ,Journal of Sichuan University(Natural Science Edition) , 编辑部邮箱 ,2009年02期
  • 【分类号】O643.3
  • 【被引频次】2
  • 【下载频次】52
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