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

• Published in: Chinese chemical letters Vol. 32; no. 6; pp. 1972 - 1976
• Main Authors: Cao, Xiao-Ming, Zhou, Haijin, Zhao, Liyang, Chen, Xuning, Hu, Peijun
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.06.2021; School of Chemistry and Chemical Engineering,The Queen's University of Belfast,Belfast BT95AG,United Kingdom; Joint International Research Laboratory for Precision Chemistry and Molecular Engineering,Centre for Computational Chemistry and Research Institute of Industrial Catalysis,School of Chemistry and Molecular Engineering,East China University of Science and Technology,Shanghai 200237,China%Joint International Research Laboratory for Precision Chemistry and Molecular Engineering,Centre for Computational Chemistry and Research Institute of Industrial Catalysis,School of Chemistry and Molecular Engineering,East China University of Science and Technology,Shanghai 200237,China
• Subjects: Boron nitride monolayer; Density functional theory; Methane activation; Surface reactive oxygen species; Transition metal center; Boron nitride monolayer; Density functional theory; Transition metal center; Methane activation; Surface reactive oxygen species
• ISSN: 1001-8417; 1878-5964
• DOI: 10.1016/j.cclet.2020.09.015

The single transition metal atom anchored on defective boron nitride monolayers would exhibit the periodic trend for the electronic structure of the formed oxygen species and the resultant performance of methane activation. The modulation of the valence electron number and work function of the material could improve the activity of methane oxidative dehydrogenation. [Display omitted] Methane (CH4) controllable activation is the key process for CH4 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 CH4 activation are systematically investigated during the CH4 oxidation by means of first-principles computation. The calculation results unravel the periodic variation trends for the stability of TM-BN, the adsorption strength and the kind of O2 species, and the resulting CH4 activation performance on TM-BNs. The formed peroxide O22− of which the OO bond could be broken and O− anions are found to be reactive oxygen species for CH4 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 CH4 oxidative dehydrogenation.