Mapping Catalytically Relevant Edge Electronic States of MoS2

Abhishek Parija, Yun Hyuk Choi, Zhuotong Liu, Justin L. Andrews, Luis R. De Jesus, Sirine C. Fakra, Mohammed Al-Hashimi, James D. Batteas, David Prendergast, Sarbajit Banerjee

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

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 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.

Original languageEnglish
Pages (from-to)493-503
Number of pages11
JournalACS Central Science
Volume4
Issue number4
DOIs
Publication statusPublished - 25 Apr 2018

Fingerprint

Electronic states
Electronic structure
Microscopic examination
Scanning
Imaging techniques
X rays
X ray absorption spectroscopy
Desulfurization
Hydrocarbons
Conduction bands
Sulfur
Molybdenum
Transition metals
Hydrogen
Nanostructures
Catalyst activity
Current density
Catalysts
molybdenum disulfide

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Parija, A., Choi, Y. H., Liu, Z., Andrews, J. L., De Jesus, L. R., Fakra, S. C., ... Banerjee, S. (2018). Mapping Catalytically Relevant Edge Electronic States of MoS2 ACS Central Science, 4(4), 493-503. https://doi.org/10.1021/acscentsci.8b00042

Mapping Catalytically Relevant Edge Electronic States of MoS2 . / 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.

In: ACS Central Science, Vol. 4, No. 4, 25.04.2018, p. 493-503.

Research output: Contribution to journalArticle

Parija, A, Choi, YH, Liu, Z, Andrews, JL, De Jesus, LR, Fakra, SC, Al-Hashimi, M, Batteas, JD, Prendergast, D & Banerjee, S 2018, 'Mapping Catalytically Relevant Edge Electronic States of MoS2 ', ACS Central Science, vol. 4, no. 4, pp. 493-503. https://doi.org/10.1021/acscentsci.8b00042
Parija A, Choi YH, Liu Z, Andrews JL, De Jesus LR, Fakra SC et al. Mapping Catalytically Relevant Edge Electronic States of MoS2 ACS Central Science. 2018 Apr 25;4(4):493-503. https://doi.org/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 In: ACS Central Science. 2018 ; Vol. 4, No. 4. pp. 493-503.
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