To alleviate the greenhouse effect and maintain the sustainable development, it is of great significance to find an efficient and low-cost catalyst to reduce carbon dioxide(CO_(2)) and generate formic acid(FA). In thi...To alleviate the greenhouse effect and maintain the sustainable development, it is of great significance to find an efficient and low-cost catalyst to reduce carbon dioxide(CO_(2)) and generate formic acid(FA). In this work, based on the first-principles calculation, the catalytic performance of a single transition metal(TM)(TM = Cr, Mn, Fe, Co, Ni, Cu, Zn,Ru, Rh, Pd, Ag, Cd, Ir, Pt, Au, or Hg) atom anchored on C_(9)N_(4) monolayer(TM@C_(9)N_(4)) for the hydrogenation of CO_(2) to FA is calculated. The results show that single TM atom doping in C_(9)N_(4) can form a stable TM@C_(9)N_(4) structure, and Cu@C_(9)N_(4) and Co@C_(9)N_(4) show better catalytic performance in the process of CO_(2) hydrogenation to FA(the corresponding maximum energy barriers are 0.41 eV and 0.43 e V, respectively). The partial density of states(PDOS), projected crystal orbital Hamilton population(p COHP), difference charge density analysis and Bader charge analysis demonstrate that the TM atom plays an important role in the reaction. The strong interaction between the 3d orbitals of the TM atom and the non-bonding orbitals(1πg) of CO_(2) allows the reaction to proceed under mild conditions. In general, our results show that Cu@C_(9)N_(4) and Co@C_(9)N_(4) are a promising single-atom catalyst and can be used as the non-precious metals electrocatalyst for CO_(2) hydrogenation to formic acid.展开更多
基金Project supported by the National Natural Science Foundation of China (Grant No. 51871126)the K.C.Wong Magna Fund in Ningbo University。
文摘To alleviate the greenhouse effect and maintain the sustainable development, it is of great significance to find an efficient and low-cost catalyst to reduce carbon dioxide(CO_(2)) and generate formic acid(FA). In this work, based on the first-principles calculation, the catalytic performance of a single transition metal(TM)(TM = Cr, Mn, Fe, Co, Ni, Cu, Zn,Ru, Rh, Pd, Ag, Cd, Ir, Pt, Au, or Hg) atom anchored on C_(9)N_(4) monolayer(TM@C_(9)N_(4)) for the hydrogenation of CO_(2) to FA is calculated. The results show that single TM atom doping in C_(9)N_(4) can form a stable TM@C_(9)N_(4) structure, and Cu@C_(9)N_(4) and Co@C_(9)N_(4) show better catalytic performance in the process of CO_(2) hydrogenation to FA(the corresponding maximum energy barriers are 0.41 eV and 0.43 e V, respectively). The partial density of states(PDOS), projected crystal orbital Hamilton population(p COHP), difference charge density analysis and Bader charge analysis demonstrate that the TM atom plays an important role in the reaction. The strong interaction between the 3d orbitals of the TM atom and the non-bonding orbitals(1πg) of CO_(2) allows the reaction to proceed under mild conditions. In general, our results show that Cu@C_(9)N_(4) and Co@C_(9)N_(4) are a promising single-atom catalyst and can be used as the non-precious metals electrocatalyst for CO_(2) hydrogenation to formic acid.
