Quantum Effects in the Kinetics of H2O Dissociative Adsorption on Pt(111), Cu(111), Rh(111), and Ni(111)
Quantum Effects in the Kinetics of H2O Dissociative Adsorption on Pt(111), Cu(111), Rh(111), and Ni(111)
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DOI：
10.1021/jp910328g
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发表时间：
2010-02-25
影响因子：
3.7
通讯作者：
Sheintuch, M.
中科院分区：
文献类型：
--
作者：
German, Ernst D.;Sheintuch, M.
用近似构造绝热势能面的方法，研究了量子效应对Pt、Cu、Ru和Rh金属（111）表面水解离反应速率常数和活化能的影响.构建APES需要关于反应物和产物的吸附特性的信息。Bronsted-Evans-Polanyi（BEP）之间的关系计算的活化能和相应的反应能量，都占量子效应，绘制。Tunnel被示出导致的零点能（ZPE）校正的量子活化能的减少，相比于ZPE校正的经典的，由因子1.50，1.64，和1.99的Cu，Rh，和Ru，而对于铂的校正是边际的（1.02-1.09，取决于油的吸附位点的氢产品）。一个可能的氘动力学同位素效应（KIE）在系统中被认为是。这种影响的值估计为3.4至7.6，取决于石油金属。用三维和二维图象解释了水活化催化剂表面的反应途径和机理。计算结果与公布的数据进行比较。
Quantum effects on the rate constant and oil the activation energy of the water dissociation reaction oil (111) metal surfaces (Pt, Cu, Ru, and Rh) are described using an approach based oil the approximate construction of an adiabatic potential energy Surface (APES). Information about adsorption characteristics of the reactant and products is required to construct the APES. The Bronsted-Evans-Polanyi (BEP) relation between the calculated activation energies and the corresponding reaction energies, both accounting for quantum effects, is plotted. Tunneling is shown to lead to a decrease of the zero point energies (ZPE) corrected quantum activation energy, as compared to the ZPE-corrected classical one, by factors of 1.50, 1.64, and 1.99 for Cu, Rh, and Ru, while for platinum the correction is marginal (1.02-1.09, depending oil the adsorption site for the hydrogen product). A possible deuterium kinetic isotope effect (KIE) in the system is considered. The value of this effect is estimated from 3.4 to 7.6 depending oil metal. The reaction paths and mechanism of the water activation Oil a Catalyst surface are interpreted on three-dimensional and two-dimensional Pictures. Results Of Calculations are compared with published data.