Computational design of BC_(3)N_(2) based single atom catalyst for dramatic activation of inert CO_(2) and CH4 gasses into CH_(3)COOH with ultralow CH_(4) dissociation barrier

The production of CH_(3)COOH from CO_(2)and CH_(4) has stimulated much interest due to the high energy density of C2 species.Various kinds of catalysts have been developed while the high dissociation barrier of CH_(4) and low selectivity still hinders the efficiency of the reaction.We have herein proposed a novel catalyst with single metals loaded on 2D BC_(3)N_(2) substrate(M@2D-BC_(3)N_(2))based on density functional theory.Among numerous candidates,Pt@2D-BC_(3)N_(2) possesses the most favorable reactivity with an ultralow barrier of CH_(4) splitting(0.26 e V),which is due to the efficient capture ability of CH_(4) on Pt site.Besides,the selectivity for CH_(3)COOH is also very high,which mainly stems from the unique electronic properties of molecules and substrate:The degenerated states,including s,px,pyand pz,in CO_(2)reflects the existence of delocalizedπbonds between C and O.This can interact with states of Pt(s),Pt(pz),Pt(dxz),Pt(dyz),and Pt(z2)in Pt@2D-BC_(3)N_(2).The kinetics model also proves that our system can promote CH_(3)COOH production via simply increasing the temperature or the coverage of CH_(4) and CO_(2).Our results provide a reasonable illustration in clarifying mechanism and propose promising candidates with high reactivity for further study.