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Title: Mapping Catalytically Relevant Edge Electronic States of MoS 2

Molybdenum disulfide (MoS 2) is a semiconducting transition metal dichalcogenide that is known to be a catalyst for both the hydrogen evolution reaction (HER) as well as for hydro-desulfurization (HDS) of sulfur-rich hydrocarbon fuels. Specifically, the edges of MoS 2 nanostructures are known to be far more catalytically active as compared to unmodified basal planes. However, in the absence of the precise details of the geometric and electronic structure of the active catalytic sites, a rational means of modulating edge reactivity remain to be developed. Here in this paper we demonstrate using first-principles calculations, X-ray absorption spectroscopy, as well as scanning transmission X-ray microscopy (STXM) imaging that edge corrugations yield distinctive spectroscopic signatures corresponding to increased localization of hybrid Mo 4d states. Independent spectroscopic signatures of such edge states are identified at both the S L 2,3 and S K-edges with distinctive spatial localization of such states observed in S L 2,3-edge STXM imaging. The presence of such low-energy hybrid states at the edge of the conduction band is seen to correlate with substantially enhanced electrocatalytic activity in terms of a lower Tafel slope and higher exchange current density. These results elucidate the nature of the edge electronic structure andmore » provide a clear framework for its rational manipulation to enhance catalytic activity.« less
Authors:
 [1] ; ORCiD logo [2] ;  [2] ;  [2] ;  [2] ;  [3] ;  [4] ; ORCiD logo [2] ;  [5] ; ORCiD logo [2]
  1. Texas A & M Univ., College Station, TX (United States). Dept. of Chemistry and Dept. of Materials Science and Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry and Advanced Light Source
  2. Texas A & M Univ., College Station, TX (United States). Dept. of Chemistry and Dept. of Materials Science and Engineering
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source
  4. Texas A & M Univ., College Station, TX (United States). Dept. of Chemistry
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
Publication Date:
Grant/Contract Number:
AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
ACS Central Science
Additional Journal Information:
Journal Volume: 4; Journal Issue: 4; Journal ID: ISSN 2374-7943
Publisher:
American Chemical Society (ACS)
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1460312

Parija, Abhishek, Choi, Yun-Hyuk, Liu, Zhuotong, Andrews, Justin L., De Jesus, Luis R., Fakra, Sirine C., Al-Hashimi, Mohammed, Batteas, James D., Prendergast, David, and Banerjee, Sarbajit. Mapping Catalytically Relevant Edge Electronic States of MoS2. United States: N. p., Web. doi:10.1021/acscentsci.8b00042.
Parija, Abhishek, Choi, Yun-Hyuk, Liu, Zhuotong, Andrews, Justin L., De Jesus, Luis R., Fakra, Sirine C., Al-Hashimi, Mohammed, Batteas, James D., Prendergast, David, & Banerjee, Sarbajit. Mapping Catalytically Relevant Edge Electronic States of MoS2. United States. doi:10.1021/acscentsci.8b00042.
Parija, Abhishek, Choi, Yun-Hyuk, Liu, Zhuotong, Andrews, Justin L., De Jesus, Luis R., Fakra, Sirine C., Al-Hashimi, Mohammed, Batteas, James D., Prendergast, David, and Banerjee, Sarbajit. 2018. "Mapping Catalytically Relevant Edge Electronic States of MoS2". United States. doi:10.1021/acscentsci.8b00042. https://www.osti.gov/servlets/purl/1460312.
@article{osti_1460312,
title = {Mapping Catalytically Relevant Edge Electronic States of MoS2},
author = {Parija, Abhishek and Choi, Yun-Hyuk and Liu, Zhuotong and Andrews, Justin L. and De Jesus, Luis R. and Fakra, Sirine C. and Al-Hashimi, Mohammed and Batteas, James D. and Prendergast, David and Banerjee, Sarbajit},
abstractNote = {Molybdenum disulfide (MoS2) is a semiconducting transition metal dichalcogenide that is known to be a catalyst for both the hydrogen evolution reaction (HER) as well as for hydro-desulfurization (HDS) of sulfur-rich hydrocarbon fuels. Specifically, the edges of MoS2 nanostructures are known to be far more catalytically active as compared to unmodified basal planes. However, in the absence of the precise details of the geometric and electronic structure of the active catalytic sites, a rational means of modulating edge reactivity remain to be developed. Here in this paper we demonstrate using first-principles calculations, X-ray absorption spectroscopy, as well as scanning transmission X-ray microscopy (STXM) imaging that edge corrugations yield distinctive spectroscopic signatures corresponding to increased localization of hybrid Mo 4d states. Independent spectroscopic signatures of such edge states are identified at both the S L2,3 and S K-edges with distinctive spatial localization of such states observed in S L2,3-edge STXM imaging. The presence of such low-energy hybrid states at the edge of the conduction band is seen to correlate with substantially enhanced electrocatalytic activity in terms of a lower Tafel slope and higher exchange current density. These results elucidate the nature of the edge electronic structure and provide a clear framework for its rational manipulation to enhance catalytic activity.},
doi = {10.1021/acscentsci.8b00042},
journal = {ACS Central Science},
number = 4,
volume = 4,
place = {United States},
year = {2018},
month = {4}
}