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

• Published in: Chemistry : a European journal Vol. 29; no. 44; pp. e202301028 - n/a
• Main Authors: Jiang, Wen‐qiang, Wang, Hong‐juan, Su, Yaqiong
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 04.08.2023
• Subjects: black phosphorus; Catalysts; Catalytic activity; Chemistry; Copper; density functional theory; Direct conversion; Dynamic stability; Electronic structure; Hydrogen bonds; Iron; Mathematical analysis; Methane; methane oxidation; Methanol; Nitrous oxide; Oxidation; Phosphorus; single atom catalyst; Single atom catalysts; Thermal stability; Transition metals; methanol; black phosphorus; single atom catalyst; density functional theory; methane oxidation
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202301028

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. Fe, Co, Ni, and Cu single metal atoms anchored on black phosphorus are designed as efficient and low‐price catalysts for converting methane to methanol. First‐principles calculations show that Cu@BP exhibits the best methane activation performance 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.