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Title: Rational design of stable sulfur vacancies in molybdenum disulfide for hydrogen evolution

Abstract

Sulfur (S) vacancies in MoS2 have been found to act as a new active center, which shows an unprecedented intrinsic HER activity under elastic strain. However, such S-vacancies are unstable and the activities are very sensitive to the vacancy concentration. A strategy to stabilize these abundant active sites is thus highly desirable. Herein, we rationally design a catalyst system to stabilize S-vacancies in the basal plane of $2H-$MoS2 supported on defective vertical graphene network (VGN). The energetically favorable line-shaped S-vacancies in MoS2 shows a consistently high HER activity that is insensitive to S-vacancy concentration. Moreover, the defective graphene support effectively stabilizes these S-vacancies. The optimized catalyst exhibits a superior HER activity with overpotential of 128 mV at 10 mA cm-2 and Tafel slope of 50 mV dec-1. Most importantly, the catalyst shows greatly increased stability over 500 h; benchmarking the most stable nonprecious HER catalyst in acidic media to date.

Authors:
 [1];  [2];  [3];  [3]; ORCiD logo [4];  [5];  [6]; ORCiD logo [7]
+ Show Author Affiliations
  1. Nanyang Technological Univ. (Singapore); Chinese Academy of Sciences (CAS), Ningbo (China)
  2. Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis
  3. Chinese Academy of Sciences (CAS), Ningbo (China)
  4. CSIRO Manufacturing, Lindfield, NSW (Australia); Univ. of New South Wales, Sydney, NSW (Australia)
  5. Technical Univ. of Denmark, Lyngby (Denmark)
  6. Sun Yat-Sen Univ., Guangzhou (China)
  7. Nanyang Technological Univ. (Singapore)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1580683
Alternate Identifier(s):
OSTI ID: 1591954
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Catalysis
Additional Journal Information:
Journal Volume: 382; Journal Issue: C; Journal ID: ISSN 0021-9517
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 2D heterostructure; hydrogen evolution; stabilization function; vacancies; long-term stability

Citation Formats

Zhao, Yunxing, Tang, Michael T., Wu, Sudong, Geng, Jing, Han, Zhaojun, Chan, Karen, Gao, Pingqi, and Li, Hong. Rational design of stable sulfur vacancies in molybdenum disulfide for hydrogen evolution. United States: N. p., 2020. Web. doi:10.1016/j.jcat.2019.12.028.
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Zhao, Yunxing, Tang, Michael T., Wu, Sudong, Geng, Jing, Han, Zhaojun, Chan, Karen, Gao, Pingqi, & Li, Hong. Rational design of stable sulfur vacancies in molybdenum disulfide for hydrogen evolution. United States. https://doi.org/10.1016/j.jcat.2019.12.028
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Zhao, Yunxing, Tang, Michael T., Wu, Sudong, Geng, Jing, Han, Zhaojun, Chan, Karen, Gao, Pingqi, and Li, Hong. Sat . "Rational design of stable sulfur vacancies in molybdenum disulfide for hydrogen evolution". United States. https://doi.org/10.1016/j.jcat.2019.12.028. https://www.osti.gov/servlets/purl/1580683.
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@article{osti_1580683,
title = {Rational design of stable sulfur vacancies in molybdenum disulfide for hydrogen evolution},
author = {Zhao, Yunxing and Tang, Michael T. and Wu, Sudong and Geng, Jing and Han, Zhaojun and Chan, Karen and Gao, Pingqi and Li, Hong},
abstractNote = {Sulfur (S) vacancies in MoS2 have been found to act as a new active center, which shows an unprecedented intrinsic HER activity under elastic strain. However, such S-vacancies are unstable and the activities are very sensitive to the vacancy concentration. A strategy to stabilize these abundant active sites is thus highly desirable. Herein, we rationally design a catalyst system to stabilize S-vacancies in the basal plane of $2H-$MoS2 supported on defective vertical graphene network (VGN). The energetically favorable line-shaped S-vacancies in MoS2 shows a consistently high HER activity that is insensitive to S-vacancy concentration. Moreover, the defective graphene support effectively stabilizes these S-vacancies. The optimized catalyst exhibits a superior HER activity with overpotential of 128 mV at 10 mA cm-2 and Tafel slope of 50 mV dec-1. Most importantly, the catalyst shows greatly increased stability over 500 h; benchmarking the most stable nonprecious HER catalyst in acidic media to date.},
doi = {10.1016/j.jcat.2019.12.028},
journal = {Journal of Catalysis},
number = C,
volume = 382,
place = {United States},
year = {2020},
month = {2}
}
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https://doi.org/10.1016/j.jcat.2019.12.028
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Works referenced in this record:

A comprehensive review on PEM water electrolysis
journal, April 2013

  • Carmo, Marcelo; Fritz, David L.; Mergel, Jürgen
  • International Journal of Hydrogen Energy, Vol. 38, Issue 12, p. 4901-4934
  • DOI: 10.1016/j.ijhydene.2013.01.151

Solar Water Splitting Cells
journal, November 2010

  • Walter, Michael G.; Warren, Emily L.; McKone, James R.
  • Chemical Reviews, Vol. 110, Issue 11, p. 6446-6473
  • DOI: 10.1021/cr1002326

Building MoS2/S-doped g-C3N4 layered heterojunction electrocatalysts for efficient hydrogen evolution reaction
journal, July 2019

Hydrogen the future transportation fuel: From production to applications
journal, March 2015

Hydrogen production by alkaline water electrolysis
journal, January 2013

Electrocatalyst performance in industrial water electrolysers
journal, January 1985

Hydrogen Production From Water Electrolysis: Current Status and Future Trends
journal, February 2012

Addressing the terawatt challenge: scalability in the supply of chemical elements for renewable energy
journal, January 2012

  • Vesborg, Peter C. K.; Jaramillo, Thomas F.
  • RSC Advances, Vol. 2, Issue 21
  • DOI: 10.1039/c2ra20839c

Biomimetic Hydrogen Evolution:  MoS 2 Nanoparticles as Catalyst for Hydrogen Evolution
journal, April 2005

  • Hinnemann, Berit; Moses, Poul Georg; Bonde, Jacob
  • Journal of the American Chemical Society, Vol. 127, Issue 15
  • DOI: 10.1021/ja0504690

Identification of Active Edge Sites for Electrochemical H2 Evolution from MoS2 Nanocatalysts
journal, July 2007

  • Jaramillo, T. F.; Jorgensen, K. P.; Bonde, J.
  • Science, Vol. 317, Issue 5834, p. 100-102
  • DOI: 10.1126/science.1141483

Enhanced Hydrogen Evolution Catalysis from Chemically Exfoliated Metallic MoS 2 Nanosheets
journal, May 2013

  • Lukowski, Mark A.; Daniel, Andrew S.; Meng, Fei
  • Journal of the American Chemical Society, Vol. 135, Issue 28
  • DOI: 10.1021/ja404523s

Electrochemical generation of sulfur vacancies in the basal plane of MoS2 for hydrogen evolution
journal, April 2017

  • Tsai, Charlie; Li, Hong; Park, Sangwook
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms15113

Monolayer MoS 2 with S vacancies from interlayer spacing expanded counterparts for highly efficient electrochemical hydrogen production
journal, January 2016

  • Xu, Yuzi; Wang, Longlu; Liu, Xia
  • Journal of Materials Chemistry A, Vol. 4, Issue 42
  • DOI: 10.1039/C6TA06534A

Sulfur-Depleted Monolayered Molybdenum Disulfide Nanocrystals for Superelectrochemical Hydrogen Evolution Reaction
journal, September 2016

Activating and optimizing MoS2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies
journal, November 2015

  • Li, Hong; Tsai, Charlie; Koh, Ai Leen
  • Nature Materials, Vol. 15, Issue 1
  • DOI: 10.1038/nmat4465

Activating basal-plane catalytic activity of two-dimensional MoS2 monolayer with remote hydrogen plasma
journal, December 2016

Substoichiometric Molybdenum Sulfide Phases with Catalytically Active Basal Planes
journal, October 2016

  • Bao, Yang; Yang, Ming; Tan, Sherman Jun Rong
  • Journal of the American Chemical Society, Vol. 138, Issue 42
  • DOI: 10.1021/jacs.6b09042

MoS2 Nanoparticles Grown on Graphene An Advanced Catalyst for the Hydrogen Evolution Reaction
journal, May 2011

  • Li, Yanguang; Wang, Hailiang; Xie, Liming
  • Journal of the American Chemical Society, Vol. 133, Issue 19, p. 7296-7299
  • DOI: 10.1021/ja201269b

Kinetic Study of Hydrogen Evolution Reaction over Strained MoS 2 with Sulfur Vacancies Using Scanning Electrochemical Microscopy
journal, April 2016

  • Li, Hong; Du, Minshu; Mleczko, Michal J.
  • Journal of the American Chemical Society, Vol. 138, Issue 15
  • DOI: 10.1021/jacs.6b01377

Optoelectronic crystal of artificial atoms in strain-textured molybdenum disulphide
journal, June 2015

  • Li, Hong; Contryman, Alex W.; Qian, Xiaofeng
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8381

Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation
journal, June 2012

Tuning the MoS 2 Edge-Site Activity for Hydrogen Evolution via Support Interactions
journal, February 2014

  • Tsai, Charlie; Abild-Pedersen, Frank; Nørskov, Jens K.
  • Nano Letters, Vol. 14, Issue 3
  • DOI: 10.1021/nl404444k

Molybdenum Sulfides and Selenides as Possible Electrocatalysts for CO 2 Reduction
journal, July 2014

The adhesion and shape of nanosized Au particles in a Au/TiO2 catalyst
journal, July 2004

On the Role of Surface Modifications of Palladium Catalysts in the Selective Hydrogenation of Acetylene
journal, October 2008

  • Studt, Felix; Abild-Pedersen, Frank; Bligaard, Thomas
  • Angewandte Chemie International Edition, Vol. 47, Issue 48
  • DOI: 10.1002/anie.200802844

Influence of H 2 O and H 2 S on the composition, activity, and stability of sulfided Mo, CoMo, and NiMo supported on MgAl 2 O 4 for hydrodeoxygenation of ethylene glycol
journal, February 2018

  • Dabros, Trine Marie Hartmann; Gaur, Abhijeet; Pintos, Delfina Garcia
  • Applied Catalysis A: General, Vol. 551
  • DOI: 10.1016/j.apcata.2017.12.008

Probing the Active Sites of MoS 2 Based Hydrotreating Catalysts Using Modulation Excitation Spectroscopy
journal, January 2019

  • Gaur, Abhijeet; Hartmann Dabros, Trine Marie; Høj, Martin
  • ACS Catalysis, Vol. 9, Issue 3
  • DOI: 10.1021/acscatal.8b04778

Line Defects in Molybdenum Disulfide Layers
journal, May 2013

  • Enyashin, Andrey N.; Bar-Sadan, Maya; Houben, Lothar
  • The Journal of Physical Chemistry C, Vol. 117, Issue 20
  • DOI: 10.1021/jp403976d

Intrinsic Structural Defects in Monolayer Molybdenum Disulfide
journal, May 2013

  • Zhou, Wu; Zou, Xiaolong; Najmaei, Sina
  • Nano Letters, Vol. 13, Issue 6, p. 2615-2622
  • DOI: 10.1021/nl4007479

Single-Layer MoS 2 with Sulfur Vacancies: Structure and Catalytic Application
journal, March 2014

  • Le, Duy; Rawal, Takat B.; Rahman, Talat S.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 10
  • DOI: 10.1021/jp411256g

Band Engineering in Graphene with Superlattices of Substitutional Defects
journal, February 2011

  • Casolo, S.; Martinazzo, R.; Tantardini, G. F.
  • The Journal of Physical Chemistry C, Vol. 115, Issue 8
  • DOI: 10.1021/jp109741s

MoS2-coated vertical graphene nanosheet for high-performance rechargeable lithium-ion batteries and hydrogen production
journal, May 2016

  • Wang, Ye; Chen, Bo; Seo, Dong Han
  • NPG Asia Materials, Vol. 8, Issue 5
  • DOI: 10.1038/am.2016.44

Wetting of Mono and Few-Layered WS 2 and MoS 2 Films Supported on Si/SiO 2 Substrates
journal, February 2015

  • Chow, Philippe K.; Singh, Eklavya; Viana, Bartolomeu Cruz
  • ACS Nano, Vol. 9, Issue 3
  • DOI: 10.1021/nn5072073

Growth and Tunable Surface Wettability of Vertical MoS 2 Layers for Improved Hydrogen Evolution Reactions
journal, August 2016

  • Bhimanapati, Ganesh R.; Hankins, Trevor; Lei, Yu
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 34
  • DOI: 10.1021/acsami.6b05848

Ultradispersed and Single-Layered MoS 2 Nanoflakes Strongly Coupled with Graphene: An Optimized Structure with High Kinetics for the Hydrogen Evolution Reaction
journal, October 2017

  • Huang, Haoliang; Huang, Junying; Liu, Weipeng
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 45
  • DOI: 10.1021/acsami.7b12038

Molybdenum sulfides—efficient and viable materials for electro - and photoelectrocatalytic hydrogen evolution
journal, January 2012

  • Laursen, Anders B.; Kegnæs, Søren; Dahl, Søren
  • Energy & Environmental Science, Vol. 5, Issue 2
  • DOI: 10.1039/c2ee02618j

Catalyzing the Hydrogen Evolution Reaction (HER) with Molybdenum Sulfide Nanomaterials
journal, October 2014

  • Benck, Jesse D.; Hellstern, Thomas R.; Kibsgaard, Jakob
  • ACS Catalysis, Vol. 4, Issue 11
  • DOI: 10.1021/cs500923c

Amorphous Molybdenum Sulfide on Graphene–Carbon Nanotube Hybrids as Highly Active Hydrogen Evolution Reaction Catalysts
journal, February 2016

  • Pham, Kien-Cuong; Chang, Yung-Huang; McPhail, David S.
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 9
  • DOI: 10.1021/acsami.5b09690

Vertical nanosheet array of 1T phase MoS2 for efficient and stable hydrogen evolution
journal, June 2019

Potential-Cycling Synthesis of Single Platinum Atoms for Efficient Hydrogen Evolution in Neutral Media
journal, August 2017

  • Zhang, Lihan; Han, Lili; Liu, Haoxuan
  • Angewandte Chemie International Edition, Vol. 56, Issue 44
  • DOI: 10.1002/anie.201706921

Facile synthesis of low crystalline MoS2 nanosheet-coated CNTs for enhanced hydrogen evolution reaction
journal, January 2013

Chemically activating MoS2 via spontaneous atomic palladium interfacial doping towards efficient hydrogen evolution
journal, May 2018

Ultrathin MoS 2 Nanoplates with Rich Active Sites as Highly Efficient Catalyst for Hydrogen Evolution
journal, December 2013

  • Yan, Ya; Xia, BaoYu; Ge, Xiaoming
  • ACS Applied Materials & Interfaces, Vol. 5, Issue 24
  • DOI: 10.1021/am404843b

Amorphous Molybdenum Sulfide Catalysts for Electrochemical Hydrogen Production: Insights into the Origin of their Catalytic Activity
journal, August 2012

  • Benck, Jesse D.; Chen, Zhebo; Kuritzky, Leah Y.
  • ACS Catalysis, Vol. 2, Issue 9, p. 1916-1923
  • DOI: 10.1021/cs300451q
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