Computational Study of Single Metal Atom Anchored on Black Phosphorus for Methane Oxidation to Methanol by Nitrous Oxide.

Direct conversion of methane to the high-value-added transportable chemicals is of great challenge, which requires high energy input to break the strong C-H bond. Developing efficient catalysts for methane oxidation to methanol under mild conditions is of vital importance. In this work, the single transition metal atoms (TM = Fe, Co, Ni, Cu) anchored on black phosphorus (TM@BP) were studied as catalysts to assist the methane oxidation to methanol by means of first-principles calculations. The results indicate that Cu@BP exhibits an outstanding catalytic activity through the radical reaction pathways and the formation of the Cu-O active site is the rate-determining with an energy barrier of 0.48 eV. Meanwhile, electronic structure calculations and dynamic simulations show that Cu@BP offer excellent thermal stability. Our calculations provide a new approach for the rational design of single atom catalysts for methane oxidation to methanol.