There are increasing concerns about the environmental impact of rising atmospheric carbon monoxide concentrations,thus it is necessary to develop new catalysts for efficient CO oxidation.Based on first-principles calc...There are increasing concerns about the environmental impact of rising atmospheric carbon monoxide concentrations,thus it is necessary to develop new catalysts for efficient CO oxidation.Based on first-principles calculations,the potential ofγ-graphyne(GY)as substrate for metals in the 4th and 5th periods under single-atom and dual-atoms concentration modes has been systematically investigated.It was found that single-atom Co,Ir,Rh,and Ru could effectively oxidate CO molecules,especially for single Rh.Furthermore,proper atoms concentration could boost the CO oxidation activity by supplying more reaction centers,such as Rh^(2)/GY.It was determined that two Rh atoms in Rh^(2)/GY act different roles in the catalytic reaction:one structural and another functional.Screening tests suggest that substituting the structural Rh atom in the center of acetylenic ring by Co or Cu atom is a possible way to maintain the reaction performance while reducing the noble metal cost.This systemic investigation will help in understanding the fundamental reaction mechanisms on GY-based substrates.We emphasize that properly exposed frontier orbital of functional metal atom is crucial in adsorption configuration as well as entire catalytic performance.This study constructs a workflow and provides valuable information for rational design of CO oxidation catalysts.展开更多
基金This work was supported by the National Natural Science Foundation of China(Nos.22101029 and 21703219)Beijing Municipal Natural Science Foundation(No.2222006)+1 种基金Beijing Municipal Financial Project BJAST Scholar Programs B(No.BS202001)Beijing Municipal Financial Project BJAST Young Scholar Programs B(No.YS202202).
文摘There are increasing concerns about the environmental impact of rising atmospheric carbon monoxide concentrations,thus it is necessary to develop new catalysts for efficient CO oxidation.Based on first-principles calculations,the potential ofγ-graphyne(GY)as substrate for metals in the 4th and 5th periods under single-atom and dual-atoms concentration modes has been systematically investigated.It was found that single-atom Co,Ir,Rh,and Ru could effectively oxidate CO molecules,especially for single Rh.Furthermore,proper atoms concentration could boost the CO oxidation activity by supplying more reaction centers,such as Rh^(2)/GY.It was determined that two Rh atoms in Rh^(2)/GY act different roles in the catalytic reaction:one structural and another functional.Screening tests suggest that substituting the structural Rh atom in the center of acetylenic ring by Co or Cu atom is a possible way to maintain the reaction performance while reducing the noble metal cost.This systemic investigation will help in understanding the fundamental reaction mechanisms on GY-based substrates.We emphasize that properly exposed frontier orbital of functional metal atom is crucial in adsorption configuration as well as entire catalytic performance.This study constructs a workflow and provides valuable information for rational design of CO oxidation catalysts.
