The electrochemical CO2 reduction reaction (ERCO2) is a promising technology for converting waste CO2 into chemicals which could be used as feedstock for the chemical industry or as synthetic fuels. The development of catalysts for the electrochemical reduction of carbon dioxide (ERCO2) with high activity and selectivity remains a grand challenge to render the technology useably. In this work, we studied the electrocatalysis CO2 reduction process of metal-nitrogen-carbon (M-NC) catalysts using metal atoms as the active center (M-NC, M = Fe, Os and Ru) as a model, and performing density functional (DFT) calculations. The calculation shows that the limiting potential required for methane formation over Fe-NC catalyst is the minimum (* + CO2+ 8H+ → C*OOH + 7H+ → C*O + 6H+ → *CHO + 5H+ → CH2O* + 4H+ → CH3O* + 3H+ → CH3O*H + 2H+→ *CH3 + H+ → * + CH4). At the same time, we use the d-band center theory to study the accuracy of the reaction steps. The d-band center value of Fe-NC is closer to EF than Os-NC and Ru-NC. This in-depth understanding of ERCO2 activity and selectivity based on metal morphology in NC provides guidance for the rational design of ERCO2 by M-NC catalysts for its application in high-performance equipment. Electrocatalytic reduction of CO2 to CH4 on Fe@d-NC cluster.

中文翻译：

---

锚定在掺氮碳上的过渡金属的电催化 CO2 还原活性：密度泛函理论研究

电化学 CO2 还原反应 (ERCO2) 是一种很有前景的技术，可将废 CO2 转化为可用作化学工业原料或合成燃料的化学品。开发具有高活性和选择性的用于电化学还原二氧化碳 (ERCO2) 的催化剂仍然是使该技术可用的巨大挑战。在这项工作中，我们研究了以金属原子为活性中心 (M-NC, M = Fe, Os 和 Ru) 为模型的金属-氮-碳 (M-NC) 催化剂的电催化 CO2 还原过程，并执行密度函数 (DFT) 计算。计算表明，在 Fe-NC 催化剂上形成甲烷所需的极限电位是最小的 (* + CO2+ 8H+ → C*OOH + 7H+ → C*O + 6H+ → *CHO + 5H+ → CH2O* + 4H+ → CH3O* + 3H+ → CH3O*H + 2H+→ *CH3 + H+ → * + CH4）。同时，我们利用d-band中心理论来研究反应步骤的准确性。Fe-NC 的 d 波段中心值比 Os-NC 和 Ru-NC 更接近 EF。这种基于NC中金属形态对ERCO2活性和选择性的深入理解为M-NC催化剂的ERCO2在高性能设备中的应用的合理设计提供了指导。Fe@d-NC 簇上 CO2 电催化还原为 CH4。