Molecular Catalysis ( IF 3.9 ) Pub Date : 2023-03-13 , DOI: 10.1016/j.mcat.2023.113033 Zongxing Tu , Guangyao Zhang , Luliang Liao , Hongming Wang
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Metal-organic frameworks (MOFs) has shown promising applications in electrocatalytic CO2 reductions due to their high specific surface area, abundant active sites and clear structure, but the conductivity of MOFs is a great challenge. Herein, a two-dimensional (2D) coordination network materials M3(2,3,6,7,10,11-hexahydroxytriphenylene)2 (M3(HHTP)2) with a good conductivity were systematically investigated and theoretical screened as promising electrocatalysts for the electrocatalytic carbon dioxide reduction reactions (CO2RR) combining density function theory (DFT) calculations and experimental validation. The theoretical calculations show that CH4 is the main reduction product for CO2RR catalyzed by Cu3(HHTP)2 and Ti3(HHTP)2. However, favorable product by Sc3(HHTP)2, Co3(HHTP)2, Ni3(HHTP)2 and Zn3(HHTP)2 is CO. For V3(HHTP)2 and Mn3(HHTP)2, HCHO is dominant product, but the reaction of V3(HHTP)2 catalyst required a high overpotential above 1.69 V. HCOOH is primarily produced from Cr3(HHTP)2 and Fe3(HHTP)2. Furthermore, the electrochemical CO2RR catalyzed by Cu3(HHTP)2 and Ni3(HHTP)2 were completed to validate theoretical screening. It is found that Cu3(HHTP)2 hold excellent CO2RR activity with 42.88% Faraday efficiency (FE) of CH4 with 107.92 mA cm−2 at -1.30 V vs RHE, and Ni3(HHTP)2 has 68.27% CO FE with a current density of 59.92 mA cm−2 at -0.50 V vs RHE. This work showed that theoretical screening work can provide a highly effective approach to investigate the reaction mechanism and can aid in designing novel catalysts for CO2RR, and would greatly promote design of MOF catalysts for CO2RR.
中文翻译：
M3(2,3,6,7,10,11-六羟基苯并菲)2 用于电催化 CO2 还原的理论筛选和实验验证
金属有机骨架材料(MOFs)以其高比表面积、丰富的活性位点和清晰的结构在电催化CO 2还原中显示出广阔的应用前景，但MOFs的电导率是一个巨大的挑战。在此，系统地研究了具有良好导电性的二维 (2D) 配位网络材料 M 3 (2,3,6,7,10,11-六羟基苯并菲) 2 (M 3 (HHTP) 2 )用于结合密度函数理论 (DFT) 计算和实验验证的电催化二氧化碳还原反应 (CO 2 RR) 的电催化剂。理论计算表明CH 4是由Cu 3 (HHTP) 2和Ti 3 (HHTP) 2催化的CO 2 RR的主要还原产物。然而，Sc 3 (HHTP) 2、Co 3 (HHTP) 2、Ni 3 (HHTP) 2和Zn 3 (HHTP) 2的有利产物是CO。对于V 3 (HHTP) 2和Mn 3 (HHTP) 2， HCHO 是主要产物，但 V 3 (HHTP) 2催化剂的反应需要高于 1.69 V 的高过电势。HCOOH 主要由 Cr 产生3 (HHTP) 2和Fe 3 (HHTP) 2。此外，完成了由Cu 3 (HHTP) 2和Ni 3 (HHTP) 2催化的电化学CO 2 RR，以验证理论筛选。结果发现，Cu 3 (HHTP) 2具有优异的 CO 2 RR 活性，CH 4的法拉第效率 (FE) 为 42.88% ，107.92 mA cm -2在 -1.30 V vs RHE 下，而 Ni 3 (HHTP) 2具有 68.27%电流密度为 59.92 mA cm -2的 CO FE在 -0.50 V 相对于 RHE。这项工作表明，理论筛选工作可以提供一种高效的方法来研究反应机理，并有助于设计新型 CO 2 RR 催化剂，并将极大地促进 MOF 催化剂的 CO 2 RR 设计。
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