title: Unique Reactivity of Transition Metal Atoms Embedded in Graphene to CO, NO, O₂ and O Adsorption: A First-Principles Investigation.
abstract: Taking the adsorption of CO, NO, O₂ and O as probes, we investigated the electronic structure of transition metal atoms (TM, TM = Fe, Co, Ni, Cu and Zn) embedded in graphene by first-principles-based calculations. We showed that these TM atoms can be effectively stabilized on monovacancy defects on graphene by forming plausible interactions with the C atoms associated with dangling bonds. These interactions not only give rise to high energy barriers for the diffusion and aggregation of the embedded TM atoms to withstand the interference of reaction environments, but also shift the energy levels of TM-d states and regulate the reactivity of the embedded TM atoms. The adsorption of CO, NO, O₂ and O correlates well with the weight averaged energy level of TM-d states, showing the crucial role of interfacial TM-C interactions on manipulating the reactivity of embedded TM atoms. These findings pave the way for the developments of effective monodispersed atomic TM composites with high stability and desired performance for gas sensing and catalytic applications.
authors.affiliation: School of Chemistry and State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China. molisa0618@mail.dlut.edu.cn.
authors.forename: Minmin
authors.initials: M
authors.lastname: Chu
authors.affiliation: School of Chemistry and State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China. xliu@dlut.edu.cn.
authors.forename: Xin
authors.initials: X
authors.lastname: Liu
authors.affiliation: School of Chemistry and State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China. free@mail.dlut.edu.cn.
authors.forename: Yanhui
authors.initials: Y
authors.lastname: Sui
authors.affiliation: School of Chemistry and State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China. zhuxuanlvluojie@mail.dlut.edu.cn.
authors.forename: Jie
authors.initials: J
authors.lastname: Luo
authors.affiliation: School of Chemistry and State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China. cgmeng@dlut.edu.cn.
authors.forename: Changgong
authors.initials: C
authors.lastname: Meng
mesh_terms: D000327:Adsorption; D002248:Carbon Monoxide / Q000737:chemistry; D004581:Electronics; D006108:Graphite / Q000737:chemistry*; D008958:Models, Molecular; D009569:Nitric Oxide / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry; D011789:Quantum Theory; D028561:Transition Elements / Q000737:chemistry*
chemical_list: D028561:Transition Elements; D009569:Nitric Oxide; D006108:Graphite; D002248:Carbon Monoxide; D010100:Oxygen
keywords: CO oxidation; defects; graphene; single atom catalysis; transition metal