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author:

Zhou, Shuyun (Zhou, Shuyun.) [1] | Lin, Xinying (Lin, Xinying.) [2] | Li, Juan (Li, Juan.) [3] | Jiang, Rong (Jiang, Rong.) [4] | Lin, Sen (Lin, Sen.) [5]

Indexed by:

EI Scopus SCIE

Abstract:

The catalytic conversion of methane (CH4) has garnered significant interest due to its potential to mitigate the greenhouse effect and produce high-value chemicals. In this work, we employ density functional theory (DFT) calculations to investigate the performance of TM-doped Ag(111) dilute alloys in CH4 activation. The results demonstrate that Rh- and Pt-doped Ag(111) single-atom alloys (SAAs) exhibit high activity for direct CH4 activation, while Cr-, Mn-, and Cu-doped SAAs display activity in oxygen (O2) dissociation rather than CH4 activation. However, the pre-adsorption of an oxygen atom (O*) is found to inhibit CH4 activation on Rh- and Pt- doped Ag(111) surfaces, while promoting it on Au-, Cu-, Pd-, Mn-, and Cr-doped Ag(111) surfaces. Electronic structure analysis reveals the existence of a distinct two-site, five-center transition state (TS) in the O*-assisted C-H activation pathway, where dipole-dipole interactions play a crucial role in stabilizing the TS. Furthermore, it is found that the closer the 2p-band center of O* is to the Fermi level, the stronger the Lewis basicity of O*, which in turn facilitates the C-H bond activation of CH4. This work provides insights into the efficient CH4 activation through the design of dilute alloys with tunable O* adsorption characteristics, paving the way for the development of efficient catalysts for CH4 conversion.

Keyword:

Adsorption CH4 activation Density functional theory Dilute alloys Reaction mechanism

Community:

  • [ 1 ] [Zhou, Shuyun]Fuzhou Univ, Coll Chem, State Key Lab Photocatalysis Energy & Environm, Fuzhou 350002, Peoples R China
  • [ 2 ] [Lin, Xinying]Fuzhou Univ, Coll Chem, State Key Lab Photocatalysis Energy & Environm, Fuzhou 350002, Peoples R China
  • [ 3 ] [Li, Juan]Fuzhou Univ, Coll Chem, State Key Lab Photocatalysis Energy & Environm, Fuzhou 350002, Peoples R China
  • [ 4 ] [Jiang, Rong]Fuzhou Univ, Coll Chem, State Key Lab Photocatalysis Energy & Environm, Fuzhou 350002, Peoples R China
  • [ 5 ] [Lin, Sen]Fuzhou Univ, Coll Chem, State Key Lab Photocatalysis Energy & Environm, Fuzhou 350002, Peoples R China

Reprint 's Address:

  • [Jiang, Rong]Fuzhou Univ, Coll Chem, State Key Lab Photocatalysis Energy & Environm, Fuzhou 350002, Peoples R China;;[Lin, Sen]Fuzhou Univ, Coll Chem, State Key Lab Photocatalysis Energy & Environm, Fuzhou 350002, Peoples R China

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Source :

APPLIED SURFACE SCIENCE

ISSN: 0169-4332

Year: 2025

Volume: 688

6 . 3 0 0

JCR@2023

Cited Count:

WoS CC Cited Count:

SCOPUS Cited Count:

ESI Highly Cited Papers on the List: 0 Unfold All

WanFang Cited Count:

Chinese Cited Count:

30 Days PV: 4

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