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Title: Engineering Substrate Interaction To Improve Hydrogen Evolution Catalysis of Monolayer MoS2 Films beyond Pt

Abstract

MoS2 holds great promise as a cost-effective alternative to Pt for catalyzing the hydrogen evolution reaction (HER) of water, but its reported catalytic efficiency is still worse than that of Pt, the best HER catalyst but too rare and expensive for mass production of hydrogen. Here, we report a strategy to enable the catalytic activity of monolayer MoS2 films that are even better than that of Pt via engineering the interaction of the monolayer with supporting substrates. The monolayer films were grown with chemical vapor deposition processes and controlled to have an optimal density (7–10%) of sulfur vacancies. We find that the catalytic activity of MoS2 can be affected by substrates in two ways: forming an interfacial tunneling barrier with MoS2 and modifying the chemical nature of MoS2via charge transfer (proximity doping). Following this understanding, we enable excellent catalytic activities at the monolayer MoS2 films by using substrates that can provide n-doping to MoS2 and form low interfacial tunneling barriers with MoS2, such as Ti. The catalytic performance may be further boosted to be even better than Pt by crumpling the films on Ti coated flexible polymer substrates, as the Tafel slope of the film is substantially decreased with themore » presence of crumpling-induced compressive strain. The monolayer MoS2 films show no degradation in catalytic performance after being continuously tested for over 2 months.« less

Authors:
 [1];  [2];  [3];  [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
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  1. North Carolina State Univ., Raleigh, NC (United States)
  2. Duke Univ., Durham, NC (United States)
  3. Univ. of Texas, Austin, TX (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Complex Materials from First Principles (CCM); Temple Univ., Philadelphia, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Welch Foundations
OSTI Identifier:
1608110
Grant/Contract Number:  
SC0012575; 1900039; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 14; Journal Issue: 2; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; MoS2; hydrogen evolution reaction; water splitting; 2D materials; substrate effects

Citation Formats

Li, Guoqing, Chen, Zehua, Li, Yifan, Zhang, Du, Yang, Weitao, Liu, Yuanyue, and Cao, Linyou. Engineering Substrate Interaction To Improve Hydrogen Evolution Catalysis of Monolayer MoS2 Films beyond Pt. United States: N. p., 2020. Web. doi:10.1021/acsnano.9b07324.
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Li, Guoqing, Chen, Zehua, Li, Yifan, Zhang, Du, Yang, Weitao, Liu, Yuanyue, & Cao, Linyou. Engineering Substrate Interaction To Improve Hydrogen Evolution Catalysis of Monolayer MoS2 Films beyond Pt. United States. https://doi.org/10.1021/acsnano.9b07324
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Li, Guoqing, Chen, Zehua, Li, Yifan, Zhang, Du, Yang, Weitao, Liu, Yuanyue, and Cao, Linyou. Thu . "Engineering Substrate Interaction To Improve Hydrogen Evolution Catalysis of Monolayer MoS2 Films beyond Pt". United States. https://doi.org/10.1021/acsnano.9b07324. https://www.osti.gov/servlets/purl/1608110.
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@article{osti_1608110,
title = {Engineering Substrate Interaction To Improve Hydrogen Evolution Catalysis of Monolayer MoS2 Films beyond Pt},
author = {Li, Guoqing and Chen, Zehua and Li, Yifan and Zhang, Du and Yang, Weitao and Liu, Yuanyue and Cao, Linyou},
abstractNote = {MoS2 holds great promise as a cost-effective alternative to Pt for catalyzing the hydrogen evolution reaction (HER) of water, but its reported catalytic efficiency is still worse than that of Pt, the best HER catalyst but too rare and expensive for mass production of hydrogen. Here, we report a strategy to enable the catalytic activity of monolayer MoS2 films that are even better than that of Pt via engineering the interaction of the monolayer with supporting substrates. The monolayer films were grown with chemical vapor deposition processes and controlled to have an optimal density (7–10%) of sulfur vacancies. We find that the catalytic activity of MoS2 can be affected by substrates in two ways: forming an interfacial tunneling barrier with MoS2 and modifying the chemical nature of MoS2via charge transfer (proximity doping). Following this understanding, we enable excellent catalytic activities at the monolayer MoS2 films by using substrates that can provide n-doping to MoS2 and form low interfacial tunneling barriers with MoS2, such as Ti. The catalytic performance may be further boosted to be even better than Pt by crumpling the films on Ti coated flexible polymer substrates, as the Tafel slope of the film is substantially decreased with the presence of crumpling-induced compressive strain. The monolayer MoS2 films show no degradation in catalytic performance after being continuously tested for over 2 months.},
doi = {10.1021/acsnano.9b07324},
journal = {ACS Nano},
number = 2,
volume = 14,
place = {United States},
year = {2020},
month = {1}
}
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https://doi.org/10.1021/acsnano.9b07324
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Works referenced in this record:

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

Recent developments of molybdenum and tungsten sulfides as hydrogen evolution catalysts
journal, January 2011

  • Merki, Daniel; Hu, Xile
  • Energy & Environmental Science, Vol. 4, Issue 10, 3878
  • DOI: 10.1039/c1ee01970h

Recent Development in Hydrogen Evolution Reaction Catalysts and Their Practical Implementation
journal, March 2015

  • Vesborg, Peter C. K.; Seger, Brian; Chorkendorff, Ib
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 6
  • DOI: 10.1021/acs.jpclett.5b00306

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
  • DOI: 10.1038/nmat4410

Multifunctional Mo-N/C@MoS 2 Electrocatalysts for HER, OER, ORR, and Zn-Air Batteries
journal, September 2017

  • Amiinu, Ibrahim Saana; Pu, Zonghua; Liu, Xiaobo
  • Advanced Functional Materials, Vol. 27, Issue 44
  • DOI: 10.1002/adfm.201702300

Self-optimizing, highly surface-active layered metal dichalcogenide catalysts for hydrogen evolution
journal, July 2017

Hydrogen-Evolution Catalysts Based on Non-Noble Metal Nickel-Molybdenum Nitride Nanosheets
journal, May 2012

  • Chen, Wei-Fu; Sasaki, Kotaro; Ma, Chao
  • Angewandte Chemie International Edition, Vol. 51, Issue 25
  • DOI: 10.1002/anie.201200699

Noble metal-free hydrogen evolution catalysts for water splitting
journal, January 2015

  • Zou, Xiaoxin; Zhang, Yu
  • Chemical Society Reviews, Vol. 44, Issue 15
  • DOI: 10.1039/C4CS00448E

2D Transition-Metal-Dichalcogenide-Nanosheet-Based Composites for Photocatalytic and Electrocatalytic Hydrogen Evolution Reactions
journal, December 2015

Earth-abundant catalysts for electrochemical and photoelectrochemical water splitting
journal, January 2017

  • Roger, Isolda; Shipman, Michael A.; Symes, Mark D.
  • Nature Reviews Chemistry, Vol. 1, Issue 1
  • DOI: 10.1038/s41570-016-0003

Benchmarking Hydrogen Evolving Reaction and Oxygen Evolving Reaction Electrocatalysts for Solar Water Splitting Devices
journal, March 2015

  • McCrory, Charles C. L.; Jung, Suho; Ferrer, Ivonne M.
  • Journal of the American Chemical Society, Vol. 137, Issue 13
  • DOI: 10.1021/ja510442p

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
  • DOI: 10.1073/pnas.0603395103

Hydrogen Production Technologies: Current State and Future Developments
journal, January 2013

  • Kalamaras, Christos M.; Efstathiou, Angelos M.
  • Conference Papers in Energy, Vol. 2013
  • DOI: 10.1155/2013/690627

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
  • DOI: 10.1021/nl400258t

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

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

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

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

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
  • DOI: 10.1038/nmat3439

Engineering stepped edge surface structures of MoS 2 sheet stacks to accelerate the hydrogen evolution reaction
journal, January 2017

  • Hu, Jue; Huang, Bolong; Zhang, Chengxu
  • Energy & Environmental Science, Vol. 10, Issue 2
  • DOI: 10.1039/C6EE03629E

High Electrochemical Selectivity of Edge versus Terrace Sites in Two-Dimensional Layered MoS 2 Materials
journal, November 2014

  • Wang, Haotian; Zhang, Qianfan; Yao, Hongbin
  • Nano Letters, Vol. 14, Issue 12
  • DOI: 10.1021/nl503730c

Controllable Growth and Transfer of Monolayer MoS 2 on Au Foils and Its Potential Application in Hydrogen Evolution Reaction
journal, September 2014

  • Shi, Jianping; Ma, Donglin; Han, Gao-Feng
  • ACS Nano, Vol. 8, Issue 10
  • DOI: 10.1021/nn503211t

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

Amorphous Molybdenum Sulfides as Hydrogen Evolution Catalysts
journal, July 2014

  • Morales-Guio, Carlos G.; Hu, Xile
  • Accounts of Chemical Research, Vol. 47, Issue 8
  • DOI: 10.1021/ar5002022

Defect-Rich MoS 2 Ultrathin Nanosheets with Additional Active Edge Sites for Enhanced Electrocatalytic Hydrogen Evolution
journal, August 2013

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
  • DOI: 10.1021/ja408329q

Defects Engineered Monolayer MoS 2 for Improved Hydrogen Evolution Reaction
journal, January 2016

All The Catalytic Active Sites of MoS 2 for Hydrogen Evolution
journal, December 2016

  • Li, Guoqing; Zhang, Du; Qiao, Qiao
  • Journal of the American Chemical Society, Vol. 138, Issue 51
  • DOI: 10.1021/jacs.6b05940

Efficient hydrogen evolution in transition metal dichalcogenides via a simple one-step hydrazine reaction
journal, June 2016

  • Cummins, Dustin R.; Martinez, Ulises; Sherehiy, Andriy
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11857

Triggering the electrocatalytic hydrogen evolution activity of the inert two-dimensional MoS 2 surface via single-atom metal doping
journal, January 2015

  • Deng, Jiao; Li, Haobo; Xiao, Jianping
  • Energy & Environmental Science, Vol. 8, Issue 5
  • DOI: 10.1039/C5EE00751H

Energy Level Engineering of MoS 2 by Transition-Metal Doping for Accelerating Hydrogen Evolution Reaction
journal, October 2017

  • Shi, Yi; Zhou, Yue; Yang, Dong-Rui
  • Journal of the American Chemical Society, Vol. 139, Issue 43
  • DOI: 10.1021/jacs.7b08881

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
  • DOI: 10.1021/nl403661s

Contributions of Phase, Sulfur Vacancies, and Edges to the Hydrogen Evolution Reaction Catalytic Activity of Porous Molybdenum Disulfide Nanosheets
journal, June 2016

  • Yin, Ying; Han, Jiecai; Zhang, Yumin
  • Journal of the American Chemical Society, Vol. 138, Issue 25
  • DOI: 10.1021/jacs.6b03714

Efficient Hydrogen Evolution by Mechanically Strained MoS 2 Nanosheets
journal, August 2014

  • Lee, Ji Hoon; Jang, Woo Soon; Han, Sun Woong
  • Langmuir, Vol. 30, Issue 32
  • DOI: 10.1021/la501349k

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
  • DOI: 10.1038/nmat3700

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
  • DOI: 10.1021/nl403620g

Engineering Substrate Interactions for High Luminescence Efficiency of Transition-Metal Dichalcogenide Monolayers
journal, May 2016

  • Yu, Yifei; Yu, Yiling; Xu, Chao
  • Advanced Functional Materials, Vol. 26, Issue 26
  • DOI: 10.1002/adfm.201600418

Fundamental limits of exciton-exciton annihilation for light emission in transition metal dichalcogenide monolayers
journal, May 2016

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

Tuning the Electronic and Chemical Properties of Monolayer MoS 2 Adsorbed on Transition Metal Substrates
journal, January 2013

  • Chen, Wei; Santos, Elton J. G.; Zhu, Wenguang
  • Nano Letters, Vol. 13, Issue 2
  • DOI: 10.1021/nl303909f

The role of electronic coupling between substrate and 2D MoS2 nanosheets in electrocatalytic production of hydrogen
journal, June 2016

  • Voiry, Damien; Fullon, Raymond; Yang, Jieun
  • Nature Materials, Vol. 15, Issue 9
  • DOI: 10.1038/nmat4660

Controlled Scalable Synthesis of Uniform, High-Quality Monolayer and Few-layer MoS2 Films
journal, May 2013

  • Yu, Yifei; Li, Chun; Liu, Yi
  • Scientific Reports, Vol. 3, Issue 1
  • DOI: 10.1038/srep01866

Surface-Energy-Assisted Perfect Transfer of Centimeter-Scale Monolayer and Few-Layer MoS 2 Films onto Arbitrary Substrates
journal, November 2014

  • Gurarslan, Alper; Yu, Yifei; Su, Liqin
  • ACS Nano, Vol. 8, Issue 11
  • DOI: 10.1021/nn5057673

Interfacial Properties of Monolayer MoSe 2 –Metal Contacts
journal, June 2016

  • Pan, Yuanyuan; Li, Sibai; Ye, Meng
  • The Journal of Physical Chemistry C, Vol. 120, Issue 24
  • DOI: 10.1021/acs.jpcc.6b02696

Interfacial Properties of Monolayer and Bilayer MoS2 Contacts with Metals: Beyond the Energy Band Calculations
journal, March 2016

  • Zhong, Hongxia; Quhe, Ruge; Wang, Yangyang
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep21786

Interfacial Thermal Transport in Monolayer MoS 2 - and Graphene-Based Devices
journal, July 2017

  • Yasaei, Poya; Foss, Cameron J.; Karis, Klas
  • Advanced Materials Interfaces, Vol. 4, Issue 17
  • DOI: 10.1002/admi.201700334

Activating MoS 2 for pH-Universal Hydrogen Evolution Catalysis
journal, November 2017

  • Li, Guoqing; Zhang, Du; Yu, Yifei
  • Journal of the American Chemical Society, Vol. 139, Issue 45
  • DOI: 10.1021/jacs.7b07450

Efficient hydrogen production on MoNi4 electrocatalysts with fast water dissociation kinetics
journal, May 2017

  • Zhang, Jian; Wang, Tao; Liu, Pan
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms15437

Reaction Mechanism for the Hydrogen Evolution Reaction on the Basal Plane Sulfur Vacancy Site of MoS 2 Using Grand Canonical Potential Kinetics
journal, November 2018

  • Huang, Yufeng; Nielsen, Robert J.; Goddard, William A.
  • Journal of the American Chemical Society, Vol. 140, Issue 48
  • DOI: 10.1021/jacs.8b10016

Transition-metal doped edge sites in vertically aligned MoS2 catalysts for enhanced hydrogen evolution
journal, January 2015

Bending Two-Dimensional Materials To Control Charge Localization and Fermi-Level Shift
journal, March 2016

Projector augmented-wave method
journal, December 1994

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865
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