Cluster Models for Studying CO2 Reduction on Semiconductor Photoelectrodes
Cluster Models for Studying CO2 Reduction on Semiconductor Photoelectrodes
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DOI：
10.1007/s11244-014-0341-1
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发表时间：
2015-02-01
影响因子：
3.6
通讯作者：
Carter, Emily A.
中科院分区：
文献类型：
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作者：
Keith, John A.;Munoz-Garcia, Ana B.;Carter, Emily A.
太阳光驱动的CO2光电还原是一种有前途的和潜在的可持续的路线，将CO2副产品回收到能量密集的液体燃料中。迄今为止已知的最有趣的过程之一是P型GaP光电极上的吡啶催化的CO2还原，其中转化为甲醇的法拉第效率接近100%。模拟这种反应环境需要了解半导体电极上不同带电物种的能量，因此我们开发了一个簇模型和基准结合能，从它到那些采用周期性边界条件的Kohn-Sham密度泛函理论计算。然后，我们使用这个集团模型，理论上预测的结构和结合能的带电和中性吸附在差距（110）表面上的货车的存在和不存在的范德华相互作用和隐式溶剂化。我们讨论了结合能贡献的相对大小不同的吸附物认为相关的CO2还原过程中，并提供细节显示陷阱时，使用集群模型。
Sunlight-powered CO2-photoelectroreduction is a promising and potentially sustainable route to recycle CO2 byproducts back into energy-dense liquid fuels. One of the most intriguing processes known to date is the pyridinium-catalyzed CO2 reduction on p-type GaP photoelectrodes, where conversion to methanol has reported faradaic efficiencies nearing 100 %. Modeling this reactive environment requires understanding energetics of differently charged species at semiconductor electrodes, so we develop a cluster model and benchmark binding energies from it to those from Kohn-Sham density functional theory calculations that employ periodic boundary conditions. We then use this cluster model to theoretically predict structures and binding energies for charged and neutral adsorbates on the GaP(110) surface with and without the presence of van der Waals interactions and implicit solvation. We discuss the relative magnitudes of binding energy contributions for different adsorbates considered relevant in this CO2 reduction process and provide details showing pitfalls when using cluster models.