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

Direct conversion of methane to high‐value‐added transportable methanol is a 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, 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 rate‐determining with an energy barrier of 0.48 eV. Meanwhile, electronic structure calculations and dynamic simulations show that Cu@BP offers excellent thermal stability. Our calculations provide a new approach for the rational design of single atom catalysts for methane oxidation to methanol. [ABSTRACT FROM AUTHOR]