Looking for highly stable and efficient electrocatalysts for CO2 reduction is quite crucial, but a big challenge in community. In this paper, the catalytic performance of the first transition metal series-porphyrin (TM-PP) monolayers as single atom catalysts for the electrochemical reduction of CO2 has been studied using density functional theory. The results show that the TM-PP monolayers have excellent catalytic stability and CO2 electrochemical reduction selectivity. The primary reduction product of Sc-PP, Mn-PP and Ni-PP is CO, the primary reduction product of Ti-PP and V-PP is CH4, and the primary reduction product of the other five monolayers is HCOOH. Ti-PP, V-PP, Ni-PP, and Cu-PP have an overpotential >0.7 V, while the overpotentials of the other monolayers are all less than 0.5 V. In particular, the overpotentials for Mn-PP and Co-PP are very low (∼0.13 V). Therefore, TM-PP monolayers are promising systems for experimental research on electrochemical catalysts for CO2 reduction.
Bibliographical noteFunding Information:
J.-H. L and L.-M. Y. gratefully acknowledge support from the National Natural Science Foundation of China (21673087 and 21873032), and startup fund (2006013118 and 3004013105) and independent innovation research fund (0118013090) from Huazhong University of Science and Technology. The authors thank the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for supercomputing resources.
© 2019 The Royal Society of Chemistry.