Unique Reactivity of Transition Metal Atoms Embedded in Graphene to CO, NO, O2 and O Adsorption: A First-Principles Investigation

Molecules

Minmin Chu²  Xin Liu¹  Yanhui Sui¹  Jie Luo²  Changgong Meng¹ 

[1]School of Chemistry and State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China

关键词: graphene;    defects;    transition metal;    single atom catalysis;    CO oxidation;   

DOI  :  10.3390/molecules201019540

来源: mdpi

【 摘 要 】

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.

【 授权许可】

CC BY   
© 2015 by the authors; licensee MDPI, Basel, Switzerland.