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Title: Mo 6S 8-based single-metal-atom catalysts for direct methane to methanol conversion

Abstract

The single atom catalysts have been attracting much attention for catalysis. Here, the significant influence of single-metal-atom (M = K, Ti, Fe, Co, Ni, Cu, Rh) doping on a Mo 6S 8 cluster was revealed for the direct methane to methanol conversion in water stream using density functional theory calculations. It was found that all single atom dopants help to facilitate the conversion via the steam reforming of methane (SRM). The single Fe atom on Mo 6S 8 (Fe—Mo 6S 8) exhibits the most significant promoting effect, which is followed by Ni, Co, Rh—Mo 6S 8 > K, Ti, Cu—Mo 6S 8 > Mo 6S 8 in a decreasing sequence. The enhanced activity by single atom doping on Mo 6S 8 is mainly associated with the interplay between the ensemble effect via the direct participation of an active M dopant and the site confinement imposed by doping of a single M atom, in tuning the methane conversion and methanol selectivity. It generates the new active center, M, which confines the SRM to occur at the M—Mo bridge sites and facilitates the selective production of methanol. An adequate single-atom promoter should not only bind *OH or *O moderately, being strongly enoughmore » to help water dissociation and weakly enough to allow the oxidation of methane, but also impose the confinement effect to facilitate the C—O bond association and production of methanol. Our results highlight the importance of the interplay among ligand, ensemble, and confinement effects in promoting the complex SRM over single atom catalysts.« less

Authors:
 [1];  [2]; ORCiD logo [3];  [1]
  1. Michigan Technological Univ., Houghton, MI (United States)
  2. Yangzhou Univ. (China)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1530524
Report Number(s):
BNL-211823-2019-JAAM
Journal ID: ISSN 0021-9606
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 2; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; single-atom catalyst; methane reforming; methanol synthesis; molybdenum sulfide; DFT

Citation Formats

Zhang, Hao-Tian, Liu, Cheng, Liu, Ping, and Hu, Yun Hang. Mo6S8-based single-metal-atom catalysts for direct methane to methanol conversion. United States: N. p., 2019. Web. doi:10.1063/1.5110875.
Zhang, Hao-Tian, Liu, Cheng, Liu, Ping, & Hu, Yun Hang. Mo6S8-based single-metal-atom catalysts for direct methane to methanol conversion. United States. doi:10.1063/1.5110875.
Zhang, Hao-Tian, Liu, Cheng, Liu, Ping, and Hu, Yun Hang. Wed . "Mo6S8-based single-metal-atom catalysts for direct methane to methanol conversion". United States. doi:10.1063/1.5110875.
@article{osti_1530524,
title = {Mo6S8-based single-metal-atom catalysts for direct methane to methanol conversion},
author = {Zhang, Hao-Tian and Liu, Cheng and Liu, Ping and Hu, Yun Hang},
abstractNote = {The single atom catalysts have been attracting much attention for catalysis. Here, the significant influence of single-metal-atom (M = K, Ti, Fe, Co, Ni, Cu, Rh) doping on a Mo6S8 cluster was revealed for the direct methane to methanol conversion in water stream using density functional theory calculations. It was found that all single atom dopants help to facilitate the conversion via the steam reforming of methane (SRM). The single Fe atom on Mo6S8 (Fe—Mo6S8) exhibits the most significant promoting effect, which is followed by Ni, Co, Rh—Mo6S8 > K, Ti, Cu—Mo6S8 > Mo6S8 in a decreasing sequence. The enhanced activity by single atom doping on Mo6S8 is mainly associated with the interplay between the ensemble effect via the direct participation of an active M dopant and the site confinement imposed by doping of a single M atom, in tuning the methane conversion and methanol selectivity. It generates the new active center, M, which confines the SRM to occur at the M—Mo bridge sites and facilitates the selective production of methanol. An adequate single-atom promoter should not only bind *OH or *O moderately, being strongly enough to help water dissociation and weakly enough to allow the oxidation of methane, but also impose the confinement effect to facilitate the C—O bond association and production of methanol. Our results highlight the importance of the interplay among ligand, ensemble, and confinement effects in promoting the complex SRM over single atom catalysts.},
doi = {10.1063/1.5110875},
journal = {Journal of Chemical Physics},
number = 2,
volume = 151,
place = {United States},
year = {2019},
month = {7}
}

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Works referenced in this record:

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Hydrogen production by methane decomposition: A review
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