【摘要】 电催化二氧化碳还原反应（CO₂RR）被认为是一种潜在的碳循环技术,因为它可以利用CO₂作为资源在温和条件下生产高附加值燃料和化学品.因此,开发高效的二氧化碳还原反应催化剂极其重要.本文设计了一系列TM-N₂O₂C_x （TM=Sc,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,Zn）单原子催化剂,并利用密度函数理论研究了其对CO₂RR的催化活性.这些TM-N₂O₂C_x催化剂在相对较低的过电位下对三种不同的产物,包括CH₄、CO和HCOOH,表现出优异的CO₂RR产品选择性,其中ScN2O₂Cx、Mn-N₂O₂C_x、Zn-N₂O₂C_x的CO₂RR产品是CO,V-N₂O₂Cx的产品是CH₄,而其他六种催化剂会产生HCOOH.此外,该研究还揭示了CH₄形成的最佳途径,即^*+CO₂→C^*OOH→C^*O+H₂O→C^*HO→C^*HOH→C^*H+H₂0→C^*H₂→C^*H₃→^*+CH₄.总之,TMN₂O₂C_x催化剂对电催化CO₂RR表现出较高的催化活性,这为实验合成这些有前景的CO₂RR催化剂提供了有价值的信息.更多还原

【Abstract】 Electrocatalytic CO₂ reduction reaction（CO₂RR） has been extensively considered as a potential carbon cycle technology because it can use CO₂ as resources to produce high value-added fuels and chemicals under mild conditions.Therefore,developing highly efficient CO₂RR catalysts is extremely significant.Here,we designed a series of TM-N₂O₂Cx（TM=Sc,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,and Zn）single-atom catalysts and investigated their catalytic activities for CO₂RR by using the density functional theory.Interestingly,these TM-N₂O₂C_x catalysts exhibit excellent CO₂RR selectivity towards three kinds of different products,including CH₄,CO,and HCOOH at relatively low overpotentials,where the CO₂RR product of Sc-N₂O₂C_x,Mn-N₂O₂C_x,and Zn-N₂O₂C_x is CO,and that of V-N₂O₂C_x is CH₄,while the other six catalysts would produce HCOOH.Moreover,the best pathway for CH₄ formation is also unveiled,that is,^*+CO₂→C^*OOH→C^*O+H₂O→C^*HO→C^*HOH→C^*H+H₂O→C^*H₂→C^*H₃→^*CH₄.In short,TM-N₂O₂Cx catalysts exhibit high catalytic activity for electrocatalytic CO₂RR,which provides useful information for experimental scientists to synthesize these promising CO₂ RR catalysts.更多还原