Trends in electrochemical CO2 reduction activity for open and close-packed metal surfaces
Trends in electrochemical CO2 reduction activity for open and close-packed metal surfaces
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DOI：
10.1039/c3cp54822h
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发表时间：
2014-01-01
影响因子：
3.3
通讯作者：
Norskov, Jens K.
中科院分区：
文献类型：
--
作者：
Shi, Chuan;Hansen, Heine A.;Norskov, Jens K.
我们提出了一种基于密度泛函理论计算的电催化CO2还原过电位趋势的理论分析。这种分析是基于对中间体自由能变化的理解，并绘制出不同基本步骤作为催化活性的一种度量所对应的势能。我们研究了不同的表面结构，并引入了一个简单的模型来考虑吸附物-吸附物相互作用的影响。我们发现在典型的反应条件下，对于反应性较强的过渡金属，CO的高覆盖率会影响对CO2还原反应的催化活性，但金属活性的顺序不会改变。对于析氢反应，高CO覆盖率将最大活性转移到比Pt更活泼的金属上。
We present a theoretical analysis of trends in overpotentials for electrocatalytic CO2 reduction based on density functional theory calculations. The analysis is based on understanding variations in the free energy of intermediates and mapping out the potential at which different elementary steps are exergonic as a measure of the catalytic activity. We study different surface structures and introduce a simple model for including the effect of adsorbate-adsorbate interactions. We find that high coverages of CO under typical reaction conditions for the more reactive transition metals affect the catalytic activity towards the CO2 reduction reaction, but the ordering of metal activities is not changed. For the hydrogen evolution reaction, a high CO coverage shifts the maximum activity towards more reactive metals than Pt.