Local Structure of Sulfur Vacancies on the Basal Plane of Monolayer MoS2

Garcia-Esparza, Angel T.; Park, Sangwook; Abroshan, Hadi; Paredes Mellone, Oscar A.; Vinson, John; Abraham, Baxter; Kim, Taeho R.; Nordlund, Dennis; Gallo, Alessandro; Alonso-Mori, Roberto; Zheng, Xiaolin; Sokaras, Dimosthenis

doi:10.1021/acsnano.2c01388

Title: Local Structure of Sulfur Vacancies on the Basal Plane of Monolayer MoS₂

Journal Article · 04 April 2022 · ACS Nano

DOI: https://doi.org/10.1021/acsnano.2c01388 · OSTI ID:1876003

^[1]; Park, Sangwook ^[2];

^[3]; Paredes Mellone, Oscar A. ^[1];

^[4]; Abraham, Baxter ^[1]; Kim, Taeho R. ^[2]; Nordlund, Dennis ^[1];

^[5]; Alonso-Mori, Roberto ^[6];

^[2]; Sokaras, Dimosthenis ^[5]

SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Stanford University, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States); Georgia Institute of Technology, Atlanta, GA (United States); University of Arizona, Tucson, AZ (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)

We report the nature of the S-vacancy is central to controlling the electronic properties of monolayer MoS₂. Understanding the geometric and electronic structures of the S-vacancy on the basal plane of monolayer MoS₂ remains elusive. Here, operando S K-edge X-ray absorption spectroscopy shows the formation of clustered S-vacancies on the basal plane of monolayer MoS₂ under reaction conditions (H₂ atmosphere, 100–600 °C). First-principles calculations predict spectral fingerprints consistent with the experimental results. The Mo K-edge extended X-ray absorption fine structure shows the local structure as coordinatively unsaturated Mo with 4.1 ± 0.4 S atoms as nearest neighbors (above 400 °C in an H₂ atmosphere). Conversely, the 6-fold Mo–Mo coordination in the crystal remains unchanged. Electrochemistry confirms similar active sites for hydrogen evolution. The identity of the S-vacancy defect on the basal plane of monolayer MoS₂ is herein elucidated for applications in optoelectronics and catalysis.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; Seoul National University

Grant/Contract Number:: AC02-76SF00515; AC02-05CH11231

OSTI ID:: 1876003

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 4 Vol. 16; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
monolayer molybdenum disulfide
operando
X-ray absorption spectroscopy
sulfur vacancy
hydrogen evolution reaction
DFT

Title: Local Structure of Sulfur Vacancies on the Basal Plane of Monolayer MoS2

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Title: Local Structure of Sulfur Vacancies on the Basal Plane of Monolayer MoS₂