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C2N负载的过渡金属三聚体催化剂用于CO2电催化还原制CH4：第一性原理研究
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Abstract:
三原子催化剂(TACs)在二氧化碳还原反应(CO2RR)中展现了巨大潜力，设计新型三原子催化剂具有重要意义。本工作利用第一性原理，建立了单层多孔氮化石墨烯(C2N)负载的过渡金属三聚体(3TM-C2N, TM = Mn, Mo, Ru, Ti)催化剂用于将二氧化碳(CO2)还原为甲烷(CH4)。计算结果表明，3TM-C2N催化剂结构稳定，不但能有效吸附和活化CO2，而且对析氢反应(HER)有良好的抑制性。吉布斯自由能分布图显示，CO2RR在3TM-C2N上会以不同的反应路径生成CH4。极限电势(UL)分析显示，3Mn-C2N表现出了最好的催化性能，对应的UL为？0.44 V。这些发现不仅为实验上调控C2N基催化剂提供了理论依据，还对开发其他高效的CO2RR电催化剂有一定的指导意义。
Triple-Atom Catalysts (TACs) have shown great potential in carbon dioxide reduction reactions (CO2RR). It is of great significance to design new Triple-Atom Catalysts. In this work, a monolayer porous nitrogen-doped graphene (C2N) supported transition metal trimers (3TM-C2N, TM = Mn, Mo, Ru, Ti) catalyst models were established to catalyze the reduction of carbon dioxide (CO2) to me-thane (CH4) using first-principles. The results show that the structure of the 3TM-C2N catalyst is stable, not only can effectively adsorb and activate CO2, but also has good inhibition of Hydrogen Evolution Reaction (HER). The Gibbs free energy profiles show that the CO2RR produces CH4 products in different reaction paths on 3TM-C2N. The limiting potential (UL) analysis showed that 3Mn-C2N ex-hibited the best catalytic performance, UL of ？0.44 V. These findings not only provide a theoretical basis for the experimental regulation of C2N-based catalysts, but also provide guidance for the development of other efficient CO2RR electrocatalysts.
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