热涨落对电催化金属表面性质和CO结合趋势的关键作用
The Critical Role of Thermal Fluctuations for Electrocatalytic Metal Surface Properties and CO Binding Trends
摘要：
这项工作解决了一个长期存在的理论差异，使用密度泛函理论（DFT）与实验观察的CO结合趋势的电催化相关金属的CO2还原反应（CO2 RR）。通过使用适当的统计力学NVT和NPT系综引入热涨落，我们表明，具有普遍色散相互作用的DFT产生了定性上更好的金属表面应变趋势和CO结合能，一致地预测了所有金属的正确位置偏好，这是由于热诱导的表面扭曲优先暴露Cu（111）和Pt（111）的配位不足的顶部位置，而对于弱结合的Ag（111）和Au（111）表面，在有限温度下，CO-金属相互作用是化学吸附和物理吸附的混合物。这项研究更好地将理论作为实验多相催化的平等伙伴，证明需要充分考虑有限的温度波动，使接触表面科学实验。
英文摘要：
This work addresses a longstanding theoretical discrepancy using Density Functional Theory (DFT) with experimental observations of CO binding trends on electrocatalytically relevant metals for the CO2 reduction reaction (CO2RR). By introducing thermal fluctuations using appropriate statistical mechanical NVT and NPT ensembles, we show that DFT with universal dispersion interactions yields qualitatively better metal surface strain trends and CO binding energetics, consistently predicts the correct site preference for all metals due to thermally induced surface distortions that preferentially exposes the undercoordinated atop site for Cu(111) and Pt(111), and for the weak binding Ag(111) and Au(111) surfaces at finite temperatures shows CO-metal interactions that are a mixture of chemisorbed and physisorbed species. This study better places theory as an equal partner to experimental heterogeneous catalysis by demonstrating the need to fully account for finite temperature fluctuations to make contact with surface science experiments.
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