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Title: Electrochemical generation of sulfur vacancies in the basal plane of MoS2 for hydrogen evolution

Abstract

Recently, sulfur (S)-vacancies created on the basal plane of 2H-molybdenum disulfide (MoS 2) using argon plasma exposure exhibited higher intrinsic activity for the electrochemical hydrogen evolution reaction than the edge sites and metallic 1T-phase of MoS 2 catalysts. But, a more industrially viable alternative to the argon plasma desulfurization process is needed. In this work, we introduce a scalable route towards generating S-vacancies on the MoS 2 basal plane using electrochemical desulfurization. We found that they can be electrochemically reduced under accessible applied potentials, even though sulfur atoms on the basal plane are known to be stable and inert. This can be done on various 2H-MoS 2 nanostructures. Furthermore, by changing the applied desulfurization potential, the extent of desulfurization and the resulting activity can be varied. The resulting active sites are stable under extended desulfurization durations and show consistent HER activity.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3];  [4];  [3];  [1];  [3];  [1]
  1. Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis; SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis
  2. Stanford Univ., CA (United States). Dept. of Mechanical Engineering; Nanyang Technological Univ. (Singapore). School of Mechanical and Aerospace Engineering
  3. Stanford Univ., CA (United States). Dept. of Mechanical Engineering
  4. Stanford Univ., CA (United States). Dept. of Material Science and Engineering
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1360913
Grant/Contract Number:
AC02-76SF00515
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
70 PLASMA PHYSICS AND FUSION TECHNOLOGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemical engineering; electrocatalysis; hydrogen fuel

Citation Formats

Tsai, Charlie, Li, Hong, Park, Sangwook, Park, Joonsuk, Han, Hyun Soo, Nørskov, Jens K., Zheng, Xiaolin, and Abild-Pedersen, Frank. Electrochemical generation of sulfur vacancies in the basal plane of MoS2 for hydrogen evolution. United States: N. p., 2017. Web. doi:10.1038/ncomms15113.
Tsai, Charlie, Li, Hong, Park, Sangwook, Park, Joonsuk, Han, Hyun Soo, Nørskov, Jens K., Zheng, Xiaolin, & Abild-Pedersen, Frank. Electrochemical generation of sulfur vacancies in the basal plane of MoS2 for hydrogen evolution. United States. doi:10.1038/ncomms15113.
Tsai, Charlie, Li, Hong, Park, Sangwook, Park, Joonsuk, Han, Hyun Soo, Nørskov, Jens K., Zheng, Xiaolin, and Abild-Pedersen, Frank. Fri . "Electrochemical generation of sulfur vacancies in the basal plane of MoS2 for hydrogen evolution". United States. doi:10.1038/ncomms15113. https://www.osti.gov/servlets/purl/1360913.
@article{osti_1360913,
title = {Electrochemical generation of sulfur vacancies in the basal plane of MoS2 for hydrogen evolution},
author = {Tsai, Charlie and Li, Hong and Park, Sangwook and Park, Joonsuk and Han, Hyun Soo and Nørskov, Jens K. and Zheng, Xiaolin and Abild-Pedersen, Frank},
abstractNote = {Recently, sulfur (S)-vacancies created on the basal plane of 2H-molybdenum disulfide (MoS2) using argon plasma exposure exhibited higher intrinsic activity for the electrochemical hydrogen evolution reaction than the edge sites and metallic 1T-phase of MoS2 catalysts. But, a more industrially viable alternative to the argon plasma desulfurization process is needed. In this work, we introduce a scalable route towards generating S-vacancies on the MoS2 basal plane using electrochemical desulfurization. We found that they can be electrochemically reduced under accessible applied potentials, even though sulfur atoms on the basal plane are known to be stable and inert. This can be done on various 2H-MoS2 nanostructures. Furthermore, by changing the applied desulfurization potential, the extent of desulfurization and the resulting activity can be varied. The resulting active sites are stable under extended desulfurization durations and show consistent HER activity.},
doi = {10.1038/ncomms15113},
journal = {Nature Communications},
number = ,
volume = 8,
place = {United States},
year = {Fri Apr 21 00:00:00 EDT 2017},
month = {Fri Apr 21 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 5works
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  • As a promising non-precious catalyst for the hydrogen evolution reaction, molybdenum disulphide (MoS 2) is known to contain active edge sites and an inert basal plane. Activating the MoS 2 basal plane could further enhance its HER activity but is not often a strategy for doing so. Herein, we report the first activation and optimization of the basal plane of monolayer 2H-MoS 2 for HER by introducing sulphur (S) vacancies and strain. Our theoretical and experimental results show that the S-vacancies are new catalytic sites in the basal plane, where gap states around the Fermi level allow hydrogen to bindmore » directly to exposed Mo atoms. The hydrogen adsorption free energy (ΔG H) can be further manipulated by straining the surface with S-vacancies, which fine-tunes the catalytic activity. Furthermore, proper combinations of S-vacancy and strain yield the optimal ΔG H = 0 eV, which allows us to achieve the highest intrinsic HER activity among molybdenum-sulphide-based catalysts.« less
  • Molybdenum disulfide (MoS 2) is a promising nonprecious catalyst for the hydrogen evolution reaction (HER) that has been extensively studied due to its excellent performance, but the lack of understanding of the factors that impact its catalytic activity hinders further design and enhancement of MoS 2-based electrocatalysts. Here, by using novel porous (holey) metallic 1T phase MoS 2 nanosheets synthesized by a liquid-ammonia-assisted lithiation route, we systematically investigated the contributions of crystal structure (phase), edges, and sulfur vacancies (S-vacancies) to the catalytic activity toward HER from five representative MoS 2 nanosheet samples, including 2H and 1T phase, porous 2H andmore » 1T phase, and sulfur-compensated porous 2H phase. Superior HER catalytic activity was achieved in the porous 1T phase MoS 2 nanosheets that have even more edges and S-vacancies than conventional 1T phase MoS 2. A comparative study revealed that the phase serves as the key role in determining the HER performance, as 1T phase MoS 2 always outperforms the corresponding 2H phase MoS 2 samples, and that both edges and S-vacancies also contribute significantly to the catalytic activity in porous MoS 2 samples. Then, using combined defect characterization techniques of electron spin resonance spectroscopy and positron annihilation lifetime spectroscopy to quantify the S-vacancies, the contributions of each factor were individually elucidated. Furthermore, this study presents new insights and opens up new avenues for designing electrocatalysts based on MoS 2 or other layered materials with enhanced HER performance.« less
    Cited by 103