Anomalous C-C Coupling on Under-Coordinated Cu (111): A Case Study of Cu Nanopyramids for CO2 Reduction Reaction by Molecular Modelling
Anomalous C-C Coupling on Under-Coordinated Cu (111): A Case Study of Cu Nanopyramids for CO2 Reduction Reaction by Molecular Modelling
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DOI：
10.1002/cssc.202002036
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发表时间：
2020-11-24
期刊：
影响因子：
8.4
通讯作者：
Qiao, Shi-Zhang
中科院分区：
文献类型：
--
作者：
Chen, Ling;Tang, Cheng;Qiao, Shi-Zhang
通过CO2还原反应将CO2转化为高附加值的C-2碳氢化合物由于能量密度较高、易于运输以及已建立的利用基础设施而引起人们的关注。本文证明，通过形成纳米金字塔来定制铜催化剂形态提供了促进 C-2 生产的替代途径。利用密度泛函理论计算，研究了五种具有不同取向、形状和暴露面的多晶铜纳米金字塔。由于异常的 C-C 耦合行为，三个研究的纳米金字塔在不同程度上有利于 C-2 的产生。这种 C-C 耦合的根本原因是纳米金字塔对欠配位 Cu (111) 表面的金字塔效应。金字塔效应包括改进的 *CO 吸附、C-C 耦合的几何优选位点以及增强的电子转移。基于这些结果，开发了C-2活性位点筛选原理：扩展的“方形”原理，可以作为高效催化剂开发的新形貌设计规则。
Converting CO2 to high value-added C-2 hydrocarbons by CO2 reduction reaction attracted attention due to higher energy density, readiness for transportation, and established utilization infrastructure. Herein, it was demonstrated that tailoring the copper catalyst morphology by forming nanopyramids offers alternative routes to promote C-2 production. Using density functional theory calculations, five polycrystalline Cu nanopyramids with various orientations, shapes, and exposing facets were investigated. Three investigated nanopyramids favored the C-2 production to different extents due to anomalous C-C coupling behaviors. The underlying reason for such C-C coupling was the pyramidal effect on under-coordinated Cu (111) surface from the nanopyramids. The pyramidal effect includes improved *CO adsorption, geometrically preferable sites for C-C coupling, and enhanced electron transfer. Based on these results, a C-2 active site screening principle was developed: an extended "square" principle, which can serve as a new morphology design rule for efficient catalyst development.