Rational design of graphyne-based dual-atom site catalysts for CO oxidation

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.

Interplay between invasive single atom Pt and native oxygen vacancy in rutile TiO_(2)(110)surface:A theoretical study

Oxygen vacancy(O_(v))as well as Ov migration in metal oxide are of great importance in structural evolution of active center in single-atom catalysts(SACs).Here,the interplay between invasive single Pt atom and native O_(v) in SA-Pt/rutile TiO_(2)(110)surface,as well as their synergetic effect on water dissociation are investigated by density functional theory(DFT)calculations.We show that importing Pt atom as Pt-ads,Pt_(2c),Pt_(5c) and Pt6c modes could decelerate the O_(v) migration effectively,especially in Pt6c mode.Under oxygen-rich conditions,Pt6c substitution could make oxygen Ov formation easier,but migration harder.On Pt_(6c)/Ti_(1-y)O_(2-x1)(110)surface,as a bimetal center,Pt_(4c)-Ti_(5c) concave could not make water dissociation process easier;however,the O2c closed to Pt become a good proton acceptor to make water dissociation on Ti_(5c)-O_(2c) more convenient with the aid of topmost Ti_(5c).