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首页> 外文期刊>The journal of physical chemistry, C. Nanomaterials and interfaces >Quantum Effects in the Kinetics of H2O Dissociative Adsorption on Pt(111), Cu(111), Rh(111), and Ni(111)
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Quantum Effects in the Kinetics of H2O Dissociative Adsorption on Pt(111), Cu(111), Rh(111), and Ni(111)

机译:H2O在Pt(111),Cu(111),Rh(111)和Ni(111)上的离解吸附动力学中的量子效应

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摘要

Quantum effects on the rate constant and on the activation energy of the water dissociation reaction on (111) metal surfaces (Pt, Cu, Ru, and Rh) are described using an approach based on 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 Br0nsted-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 on 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 on metal. The reaction paths and mechanism of the water activation on a catalyst surface are interpreted on three-dimensional and two-dimensional pictures. Results of calculations are compared with published data.
机译:使用基于绝热势能表面(APES)的近似结构的方法描述了对(111)金属表面(Pt,Cu,Ru和Rh)上水分解反应的速率常数和活化能的量子效应)。构造APES需要有关反应物和产物的吸附特性的信息。绘制了计算出的活化能和相应的反应能之间的布朗斯台德-埃文斯-波兰尼(BEP)关系,两者都考虑了量子效应。与通过ZPE校正的经典量子点相比,隧穿可导致零点能量(ZPE)校正的量子活化能减少,其中Cu,Rh和Ru的系数分别为1.50、1.64和1.99。铂的校正幅度很小(1.02-1.09,取决于氢产物的吸附部位)。考虑了系统中可能存在的氘动力学同位素效应(KIE)。取决于金属,此效果的值估计为3.4到7.6。在三维和二维图中解释了催化剂表面水活化的反应路径和机理。将计算结果与发布的数据进行比较。

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