skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Contributions of Phase, Sulfur Vacancies, and Edges to the Hydrogen Evolution Reaction Catalytic Activity of Porous Molybdenum Disulfide Nanosheets

Abstract

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 and 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 tomore » 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

Authors:
; ; ; ; ; ;  [1]; ; ;  [2];  [3];  [3]; ;  [1]
  1. Department of Chemistry, University of Wisconsin—Madison, 1101 University Avenue, Madison, Wisconsin 53706, United States
  2. School of Materials Science and Engineering, Dalian Jiaotong University, Dalian 116028, China
  3. Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
Publication Date:
Research Org.:
Univ. of Wisconsin-Madison, Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1258504
Alternate Identifier(s):
OSTI ID: 1260963
Grant/Contract Number:  
FG02-09ER46664
Resource Type:
Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Name: Journal of the American Chemical Society Journal Volume: 138 Journal Issue: 25; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Yin, Ying, Han, Jiecai, Zhang, Yumin, Zhang, Xinghong, Xu, Ping, Yuan, Quan, Samad, Leith, Wang, Xianjie, Wang, Yi, Zhang, Zhihua, Zhang, Peng, Cao, Xingzhong, Song, Bo, and Jin, Song. Contributions of Phase, Sulfur Vacancies, and Edges to the Hydrogen Evolution Reaction Catalytic Activity of Porous Molybdenum Disulfide Nanosheets. United States: N. p., 2016. Web. doi:10.1021/jacs.6b03714.
Yin, Ying, Han, Jiecai, Zhang, Yumin, Zhang, Xinghong, Xu, Ping, Yuan, Quan, Samad, Leith, Wang, Xianjie, Wang, Yi, Zhang, Zhihua, Zhang, Peng, Cao, Xingzhong, Song, Bo, & Jin, Song. Contributions of Phase, Sulfur Vacancies, and Edges to the Hydrogen Evolution Reaction Catalytic Activity of Porous Molybdenum Disulfide Nanosheets. United States. doi:10.1021/jacs.6b03714.
Yin, Ying, Han, Jiecai, Zhang, Yumin, Zhang, Xinghong, Xu, Ping, Yuan, Quan, Samad, Leith, Wang, Xianjie, Wang, Yi, Zhang, Zhihua, Zhang, Peng, Cao, Xingzhong, Song, Bo, and Jin, Song. Wed . "Contributions of Phase, Sulfur Vacancies, and Edges to the Hydrogen Evolution Reaction Catalytic Activity of Porous Molybdenum Disulfide Nanosheets". United States. doi:10.1021/jacs.6b03714.
@article{osti_1258504,
title = {Contributions of Phase, Sulfur Vacancies, and Edges to the Hydrogen Evolution Reaction Catalytic Activity of Porous Molybdenum Disulfide Nanosheets},
author = {Yin, Ying and Han, Jiecai and Zhang, Yumin and Zhang, Xinghong and Xu, Ping and Yuan, Quan and Samad, Leith and Wang, Xianjie and Wang, Yi and Zhang, Zhihua and Zhang, Peng and Cao, Xingzhong and Song, Bo and Jin, Song},
abstractNote = {Molybdenum disulfide (MoS2) 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 MoS2-based electrocatalysts. Here, by using novel porous (holey) metallic 1T phase MoS2 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 MoS2 nanosheet samples, including 2H and 1T phase, porous 2H and 1T phase, and sulfur-compensated porous 2H phase. Superior HER catalytic activity was achieved in the porous 1T phase MoS2 nanosheets that have even more edges and S-vacancies than conventional 1T phase MoS2. A comparative study revealed that the phase serves as the key role in determining the HER performance, as 1T phase MoS2 always outperforms the corresponding 2H phase MoS2 samples, and that both edges and S-vacancies also contribute significantly to the catalytic activity in porous MoS2 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 MoS2 or other layered materials with enhanced HER performance.},
doi = {10.1021/jacs.6b03714},
journal = {Journal of the American Chemical Society},
number = 25,
volume = 138,
place = {United States},
year = {2016},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/jacs.6b03714

Citation Metrics:
Cited by: 103 works
Citation information provided by
Web of Science

Save / Share:

Works referencing / citing this record:

The rise of two-dimensional MoS2 for catalysis
journal, July 2018


Defect engineering of molybdenum disulfide through ion irradiation to boost hydrogen evolution reaction performance
journal, April 2019


Lithiation-induced amorphization of Pd3P2S8 for highly efficient hydrogen evolution
journal, May 2018


Self‐Templated Conversion of Metallogel into Heterostructured TMP@Carbon Quasiaerogels Boosting Bifunctional Electrocatalysis
journal, July 2019

  • Guo, Hele; Feng, Qichun; Xu, Kaiwen
  • Advanced Functional Materials, Vol. 29, Issue 34
  • DOI: 10.1002/adfm.201903660

The Holy Grail in Platinum‐Free Electrocatalytic Hydrogen Evolution: Molybdenum‐Based Catalysts and Recent Advances
journal, June 2019


Engineering Two-Dimensional Materials and Their Heterostructures as High-Performance Electrocatalysts
journal, May 2019


Systematic design of superaerophobic nanotube-array electrode comprised of transition-metal sulfides for overall water splitting
journal, June 2018


In-situ visualization of hydrogen evolution sites on helium ion treated molybdenum dichalcogenides under reaction conditions
journal, July 2019

  • Mitterreiter, Elmar; Liang, Yunchang; Golibrzuch, Matthias
  • npj 2D Materials and Applications, Vol. 3, Issue 1
  • DOI: 10.1038/s41699-019-0107-5

Interfacial N–Cu–S coordination mode of CuSCN/C 3 N 4 with enhanced electrocatalytic activity for hydrogen evolution
journal, January 2019

  • Zhao, Ziming; Yang, Haidong; Zhu, Yan
  • Nanoscale, Vol. 11, Issue 27
  • DOI: 10.1039/c9nr02860a

Recent progress in Co 9 S 8 -based materials for hydrogen and oxygen electrocatalysis
journal, January 2019

  • Dong, Dongqi; Wu, Zexing; Wang, Jie
  • Journal of Materials Chemistry A, Vol. 7, Issue 27
  • DOI: 10.1039/c9ta04972j

Sensing behavior of flower-shaped MoS 2 nanoflakes: case study with methanol and xylene
journal, January 2018

  • Barzegar, Maryam; Berahman, Masoud; Iraji zad, Azam
  • Beilstein Journal of Nanotechnology, Vol. 9
  • DOI: 10.3762/bjnano.9.57

Self‐Templated Conversion of Metallogel into Heterostructured TMP@Carbon Quasiaerogels Boosting Bifunctional Electrocatalysis
journal, July 2019

  • Guo, Hele; Feng, Qichun; Xu, Kaiwen
  • Advanced Functional Materials, Vol. 29, Issue 34
  • DOI: 10.1002/adfm.201903660

The Holy Grail in Platinum‐Free Electrocatalytic Hydrogen Evolution: Molybdenum‐Based Catalysts and Recent Advances
journal, June 2019


The rise of two-dimensional MoS2 for catalysis
journal, July 2018


Defect engineering of molybdenum disulfide through ion irradiation to boost hydrogen evolution reaction performance
journal, April 2019


Engineering Two-Dimensional Materials and Their Heterostructures as High-Performance Electrocatalysts
journal, May 2019


Systematic design of superaerophobic nanotube-array electrode comprised of transition-metal sulfides for overall water splitting
journal, June 2018


In-situ visualization of hydrogen evolution sites on helium ion treated molybdenum dichalcogenides under reaction conditions
journal, July 2019

  • Mitterreiter, Elmar; Liang, Yunchang; Golibrzuch, Matthias
  • npj 2D Materials and Applications, Vol. 3, Issue 1
  • DOI: 10.1038/s41699-019-0107-5

Lithiation-induced amorphization of Pd3P2S8 for highly efficient hydrogen evolution
journal, May 2018


Interfacial N–Cu–S coordination mode of CuSCN/C 3 N 4 with enhanced electrocatalytic activity for hydrogen evolution
journal, January 2019

  • Zhao, Ziming; Yang, Haidong; Zhu, Yan
  • Nanoscale, Vol. 11, Issue 27
  • DOI: 10.1039/c9nr02860a

Recent progress in Co 9 S 8 -based materials for hydrogen and oxygen electrocatalysis
journal, January 2019

  • Dong, Dongqi; Wu, Zexing; Wang, Jie
  • Journal of Materials Chemistry A, Vol. 7, Issue 27
  • DOI: 10.1039/c9ta04972j

Sensing behavior of flower-shaped MoS 2 nanoflakes: case study with methanol and xylene
journal, January 2018

  • Barzegar, Maryam; Berahman, Masoud; Iraji zad, Azam
  • Beilstein Journal of Nanotechnology, Vol. 9
  • DOI: 10.3762/bjnano.9.57