Contributions of Phase, Sulfur Vacancies, and Edges to the Hydrogen Evolution Reaction Catalytic Activity of Porous Molybdenum Disulfide Nanosheets
Abstract
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 weremore »
- Authors:
-
- Department of Chemistry, University of Wisconsin—Madison, 1101 University Avenue, Madison, Wisconsin 53706, United States
- School of Materials Science and Engineering, Dalian Jiaotong University, Dalian 116028, China
- Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
- Publication Date:
- Research Org.:
- Univ. of Wisconsin, Madison, WI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- 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. https://doi.org/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. Tue .
"Contributions of Phase, Sulfur Vacancies, and Edges to the Hydrogen Evolution Reaction Catalytic Activity of Porous Molybdenum Disulfide Nanosheets". United States. https://doi.org/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 = {Tue Jun 21 00:00:00 EDT 2016},
month = {Tue Jun 21 00:00:00 EDT 2016}
}
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Works referenced in this record:
A high-porosity carbon molybdenum sulphide composite with enhanced electrochemical hydrogen evolution and stability
journal, January 2013
- Laursen, Anders B.; Vesborg, Peter C. K.; Chorkendorff, Ib
- Chemical Communications, Vol. 49, Issue 43
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
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
Powering the planet: Chemical challenges in solar energy utilization
journal, October 2006
- Lewis, N. S.; Nocera, D. G.
- Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735
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
Site-specific catalytic activity in exfoliated MoS 2 single-layer polytypes for hydrogen evolution: basal plane and edges
journal, January 2014
- Fan, Xiao-Li; Yang, Yi; Xiao, Pin
- J. Mater. Chem. A, Vol. 2, Issue 48
Highly Active Electrocatalysis of the Hydrogen Evolution Reaction by Cobalt Phosphide Nanoparticles
journal, April 2014
- Popczun, Eric J.; Read, Carlos G.; Roske, Christopher W.
- Angewandte Chemie International Edition, Vol. 53, Issue 21
Defect identification in semiconductors with positron annihilation: Experiment and theory
journal, November 2013
- Tuomisto, Filip; Makkonen, Ilja
- Reviews of Modern Physics, Vol. 85, Issue 4
Tuning the electrical property via defect engineering of single layer MoS 2 by oxygen plasma
journal, January 2014
- Islam, Muhammad R.; Kang, Narae; Bhanu, Udai
- Nanoscale, Vol. 6, Issue 17
High-Performance Electrocatalysis Using Metallic Cobalt Pyrite (CoS 2 ) Micro- and Nanostructures
journal, June 2014
- Faber, Matthew S.; Dziedzic, Rafal; Lukowski, Mark A.
- Journal of the American Chemical Society, Vol. 136, Issue 28
Theoretical insights into the hydrogen evolution activity of layered transition metal dichalcogenides
journal, October 2015
- Tsai, Charlie; Chan, Karen; Nørskov, Jens K.
- Surface Science, Vol. 640
Earth-abundant inorganic electrocatalysts and their nanostructures for energy conversion applications
journal, January 2014
- Faber, Matthew S.; Jin, Song
- Energy Environ. Sci., Vol. 7, Issue 11
Two-Dimensional Nanosheets Produced by Liquid Exfoliation of Layered Materials
journal, February 2011
- Coleman, J. N.; Lotya, M.; O'Neill, A.
- Science, Vol. 331, Issue 6017, p. 568-571
Bioinspired molecular co-catalysts bonded to a silicon photocathode for solar hydrogen evolution
journal, April 2011
- Hou, Yidong; Abrams, Billie L.; Vesborg, Peter C. K.
- Nature Materials, Vol. 10, Issue 6
Facile synthesis of few-layer-thick carbon nitride nanosheets by liquid ammonia-assisted lithiation method and their photocatalytic redox properties
journal, January 2014
- Yin, Ying; Han, Jiecai; Zhang, Xinghong
- RSC Adv., Vol. 4, Issue 62
Defect-Rich MoS 2 Ultrathin Nanosheets with Additional Active Edge Sites for Enhanced Electrocatalytic Hydrogen Evolution
journal, August 2013
- Xie, Junfeng; Zhang, Hao; Li, Shuang
- Advanced Materials, Vol. 25, Issue 40
Efficient hydrogen evolution catalysis using ternary pyrite-type cobalt phosphosulphide
journal, September 2015
- Cabán-Acevedo, Miguel; Stone, Michael L.; Schmidt, J. R.
- Nature Materials, Vol. 14, Issue 12
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
Conducting MoS 2 Nanosheets as Catalysts for Hydrogen Evolution Reaction
journal, November 2013
- Voiry, Damien; Salehi, Maryam; Silva, Rafael
- Nano Letters, Vol. 13, Issue 12
A first-principles examination of conducting monolayer 1T′-MX 2 (M = Mo, W; X = S, Se, Te): promising catalysts for hydrogen evolution reaction and its enhancement by strain
journal, January 2015
- Putungan, Darwin Barayang; Lin, Shi-Hsin; Kuo, Jer-Lai
- Physical Chemistry Chemical Physics, Vol. 17, Issue 33
Interfacial processes involving electrocatalytic evolution and oxidation of H2, and the role of chemisorbed H
journal, August 2002
- Conway, B. E.; Tilak, B. V.
- Electrochimica Acta, Vol. 47, Issue 22-23, p. 3571-3594
Synthesis of MoS2 and MoSe2 Films with Vertically Aligned Layers
journal, February 2013
- Kong, Desheng; Wang, Haotian; Cha, Judy J.
- Nano Letters, Vol. 13, Issue 3, p. 1341-1347
Lineshapes of ESR signals and the nature of paramagnetic species in amorphous molybdenum sulfides
journal, January 1991
- Deroide, B.; Bensimon, Y.; Belougne, P.
- Journal of Physics and Chemistry of Solids, Vol. 52, Issue 7
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
Monolayer-Precision Synthesis of Molybdenum Sulfide Nanoparticles and Their Nanoscale Size Effects in the Hydrogen Evolution Reaction
journal, February 2015
- Seo, Bora; Jung, Gwan Yeong; Sa, Young Jin
- ACS Nano, Vol. 9, Issue 4
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
Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis
journal, October 2012
- Kibsgaard, Jakob; Chen, Zhebo; Reinecke, Benjamin N.
- Nature Materials, Vol. 11, Issue 11, p. 963-969
Controllable Disorder Engineering in Oxygen-Incorporated MoS 2 Ultrathin Nanosheets for Efficient Hydrogen Evolution
journal, November 2013
- Xie, Junfeng; Zhang, Jiajia; Li, Shuang
- Journal of the American Chemical Society, Vol. 135, Issue 47
Amorphous Molybdenum Sulfides as Hydrogen Evolution Catalysts
journal, July 2014
- Morales-Guio, Carlos G.; Hu, Xile
- Accounts of Chemical Research, Vol. 47, Issue 8
Growth and Activation of an Amorphous Molybdenum Sulfide Hydrogen Evolving Catalyst
journal, August 2013
- Vrubel, Heron; Hu, Xile
- ACS Catalysis, Vol. 3, Issue 9
Will Solar-Driven Water-Splitting Devices See the Light of Day?
journal, September 2013
- McKone, James R.; Lewis, Nathan S.; Gray, Harry B.
- Chemistry of Materials, Vol. 26, Issue 1
Raman study and lattice dynamics of single molecular layers of
journal, August 1991
- Jiménez Sandoval, S.; Yang, D.; Frindt, R. F.
- Physical Review B, Vol. 44, Issue 8
Theoretical and experimental study of positron annihilation with core electrons in solids
journal, July 1996
- Alatalo, M.; Barbiellini, B.; Hakala, M.
- Physical Review B, Vol. 54, Issue 4
Etude par resonance paramagnetique electronique de sulfures de molybdene et de tungstene
journal, January 1987
- Deroide, B.; Belougne, P.; Zanchetta, J. V.
- Journal of Physics and Chemistry of Solids, Vol. 48, Issue 12
Enhanced catalytic activity in strained chemically exfoliated WS2 nanosheets for hydrogen evolution
journal, July 2013
- Voiry, Damien; Yamaguchi, Hisato; Li, Junwen
- Nature Materials, Vol. 12, Issue 9
Layer-Dependent Electrocatalysis of MoS 2 for Hydrogen Evolution
journal, January 2014
- Yu, Yifei; Huang, Sheng-Yang; Li, Yanpeng
- Nano Letters, Vol. 14, Issue 2
Electrochemical tuning of vertically aligned MoS2 nanofilms and its application in improving hydrogen evolution reaction
journal, November 2013
- Wang, H.; Lu, Z.; Xu, S.
- Proceedings of the National Academy of Sciences, Vol. 110, Issue 49
High-Performance Electrocatalysis for Hydrogen Evolution Reaction Using Se-Doped Pyrite-Phase Nickel Diphosphide Nanostructures
journal, September 2015
- Zhuo, Junqiao; Cabán-Acevedo, Miguel; Liang, Hanfeng
- ACS Catalysis, Vol. 5, Issue 11
Molybdenum Sulfide Supported on Crumpled Graphene Balls for Electrocatalytic Hydrogen Production
journal, May 2014
- Smith, Alexander J.; Chang, Yung-Huang; Raidongia, Kalyan
- Advanced Energy Materials, Vol. 4, Issue 14
Highly active hydrogen evolution catalysis from metallic WS 2 nanosheets
journal, January 2014
- Lukowski, Mark A.; Daniel, Andrew S.; English, Caroline R.
- Energy Environ. Sci., Vol. 7, Issue 8
1T-MoS 2 , a new metallic modification of molybdenum disulfide
journal, January 1992
- Wypych, Fernando; Schöllhorn, Robert
- J. Chem. Soc., Chem. Commun., Issue 19
High sensitivity of positron-annihilation induced Auger-electron spectroscopy to surface impurities
journal, July 1996
- Ohdaira, Toshiyuki; Suzuki, Ryoichi; Mikado, Tomohisa
- Applied Surface Science, Vol. 100-101
Nanostructured hydrotreating catalysts for electrochemical hydrogen evolution
journal, January 2014
- Morales-Guio, Carlos G.; Stern, Lucas-Alexandre; Hu, Xile
- Chemical Society Reviews, Vol. 43, Issue 18
First-row transition metal dichalcogenide catalysts for hydrogen evolution reaction
journal, January 2013
- Kong, Desheng; Cha, Judy J.; Wang, Haotian
- Energy & Environmental Science, Vol. 6, Issue 12
Monolayer MoS 2 Films Supported by 3D Nanoporous Metals for High-Efficiency Electrocatalytic Hydrogen Production
journal, October 2014
- Tan, Yongwen; Liu, Pan; Chen, Luyang
- Advanced Materials, Vol. 26, Issue 47
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
Preparation and isochronal sintering behaviour of molybdenum disulphide compound
journal, December 1990
- Viswanath, R. N.; Ramasamy, S.
- Journal of Materials Science, Vol. 25, Issue 12
Activating and tuning basal planes of MoO 2 , MoS 2 , and MoSe 2 for hydrogen evolution reaction
journal, January 2015
- Lin, Shi-Hsin; Kuo, Jer-Lai
- Physical Chemistry Chemical Physics, Vol. 17, Issue 43
PALS study of point defects in Fe-Al and Fe-Al-Cr alloys
journal, November 2009
- Kansy, Jerzy; Hanc, Aneta; Paja��k, Lucjan
- physica status solidi (c), Vol. 6, Issue 11
Structure of single-molecular-layer
journal, May 1991
- Yang, D.; Sandoval, S. Jiménez; Divigalpitiya, W. M. R.
- Physical Review B, Vol. 43, Issue 14
Nanostructured Nickel Phosphide as an Electrocatalyst for the Hydrogen Evolution Reaction
journal, June 2013
- Popczun, Eric J.; McKone, James R.; Read, Carlos G.
- Journal of the American Chemical Society, Vol. 135, Issue 25
Vacancy Associates-Rich Ultrathin Nanosheets for High Performance and Flexible Nonvolatile Memory Device
journal, February 2015
- Liang, Lin; Li, Kun; Xiao, Chong
- Journal of the American Chemical Society, Vol. 137, Issue 8
Edge-terminated molybdenum disulfide with a 9.4-Å interlayer spacing for electrochemical hydrogen production
journal, July 2015
- Gao, Min-Rui; Chan, Maria K. Y.; Sun, Yugang
- Nature Communications, Vol. 6, Issue 1