Screening performance of methane activation over atomically dispersed metal catalysts on defective boron nitride monolayers:A density functional theory study

Methane(CH_4) controllable activation is the key process for CH_4 upgrading,which is sensitive to the surface oxygen species.The high thermal conductivity and superb thermal stability of the hexagonal boron nitride(h-BN) sheet makes a single transition metal atom doped hexagonal boron nitride monolayer(TM-BN) possible to be a promising material for catalyzing methane partial oxidation.The performances of 24 TM-BNs for CH_4 activation are systematically investigated during the CH_4 oxidation by means of first-principles computation.The calculation results unravel the periodic va riation trends for the stability of TM-BN,the adsorption strength and the kind of O_2 species,and the resulting CH_4 activation performance on TM-BNs.The formed peroxide O_2~(2-)of which the O-O bond could be broken and O-anions are found to be reactive oxygen species for CH_4 activation under the mild conditions.It is found that the redox potential of TM center,including its valence electron number,coordination environment,and the work function of TM-BN,is the underlying reason for the formation of different oxygen species and the resulting activity for CH_4 oxidative dehydrogenation.