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

Title: Rhenium-Doped and Stabilized MoS2 Atomic Layers with Basal-Plane Catalytic Activity

Abstract

The development of stable and efficient hydrogen evolution reaction (HER) catalysts is essential for the production of hydrogen as a clean energy resource. A combination of experiment and theory demonstrates that the normally inert basal planes of 2D layers of MoS2 can be made highly catalytically active for the HER when alloyed with rhenium (Re). The presence of Re at the ≈50% level converts the material to a stable distorted tetragonal (DT) structure that shows enhanced HER activity as compared to most of the MoS2-based catalysts reported in the literature. More importantly, this new alloy catalyst shows much better stability over time and cycling than lithiated 1T-MoS2. Density functional theory calculations find that the role of Re is only to stabilize the DT structure, while catalysis occurs primarily in local Mo-rich DT configurations, where the HER catalytic activity is very close to that in Pt. The study provides a new strategy to improve the overall HER performance of MoS2-based materials via chemical doping.

Authors:
 [1];  [2];  [3];  [4];  [5];  [6];  [6];  [7];  [5];  [1]; ORCiD logo [8]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Rice Univ., Houston, TX (United States); Beihang Univ., Beijing (China)
  3. Vanderbilt Univ., Nashville, TN (United States)
  4. Vanderbilt Univ., Nashville, TN (United States); Chinese Academy of Sciences (CAS), Beijing (China)
  5. Rice Univ., Houston, TX (United States)
  6. Univ. of Science and Technology, Hefei Anhui (China)
  7. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Vanderbilt Univ., Nashville, TN (United States)
  8. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Chinese Academy of Sciences (CAS), Beijing (China)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Vanderbilt Univ., Nashville, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1490572
Alternate Identifier(s):
OSTI ID: 1479536; OSTI ID: 1597917
Grant/Contract Number:  
AC05-00OR22725; FG02-09ER46554; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 51; Journal ID: ISSN 0935-9648
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Yang, Shi-Ze, Gong, Yongji, Manchanda, Priyanka, Zhang, Yu-Yang, Ye, Gonglan, Chen, Shuangming, Song, Li, Pantelides, Sokrates T., Ajayan, Pulickel M., Chisholm, Matthew F., and Zhou, Wu. Rhenium-Doped and Stabilized MoS2 Atomic Layers with Basal-Plane Catalytic Activity. United States: N. p., 2018. Web. doi:10.1002/adma.201803477.
Yang, Shi-Ze, Gong, Yongji, Manchanda, Priyanka, Zhang, Yu-Yang, Ye, Gonglan, Chen, Shuangming, Song, Li, Pantelides, Sokrates T., Ajayan, Pulickel M., Chisholm, Matthew F., & Zhou, Wu. Rhenium-Doped and Stabilized MoS2 Atomic Layers with Basal-Plane Catalytic Activity. United States. doi:10.1002/adma.201803477.
Yang, Shi-Ze, Gong, Yongji, Manchanda, Priyanka, Zhang, Yu-Yang, Ye, Gonglan, Chen, Shuangming, Song, Li, Pantelides, Sokrates T., Ajayan, Pulickel M., Chisholm, Matthew F., and Zhou, Wu. Thu . "Rhenium-Doped and Stabilized MoS2 Atomic Layers with Basal-Plane Catalytic Activity". United States. doi:10.1002/adma.201803477. https://www.osti.gov/servlets/purl/1490572.
@article{osti_1490572,
title = {Rhenium-Doped and Stabilized MoS2 Atomic Layers with Basal-Plane Catalytic Activity},
author = {Yang, Shi-Ze and Gong, Yongji and Manchanda, Priyanka and Zhang, Yu-Yang and Ye, Gonglan and Chen, Shuangming and Song, Li and Pantelides, Sokrates T. and Ajayan, Pulickel M. and Chisholm, Matthew F. and Zhou, Wu},
abstractNote = {The development of stable and efficient hydrogen evolution reaction (HER) catalysts is essential for the production of hydrogen as a clean energy resource. A combination of experiment and theory demonstrates that the normally inert basal planes of 2D layers of MoS2 can be made highly catalytically active for the HER when alloyed with rhenium (Re). The presence of Re at the ≈50% level converts the material to a stable distorted tetragonal (DT) structure that shows enhanced HER activity as compared to most of the MoS2-based catalysts reported in the literature. More importantly, this new alloy catalyst shows much better stability over time and cycling than lithiated 1T-MoS2. Density functional theory calculations find that the role of Re is only to stabilize the DT structure, while catalysis occurs primarily in local Mo-rich DT configurations, where the HER catalytic activity is very close to that in Pt. The study provides a new strategy to improve the overall HER performance of MoS2-based materials via chemical doping.},
doi = {10.1002/adma.201803477},
journal = {Advanced Materials},
number = 51,
volume = 30,
place = {United States},
year = {2018},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 27 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Structure of RexMo1-xS2 alloy monolayers at different Re concentrations. a-d, Experimental STEM-ADF images (left) paired with the corresponding atom mapping images (right). The Re and Mo atoms are identified by image intensities. S atoms are omitted from the atom mapping images for clarity. Re concentrations are determined directlymore » from the atom mapping image. Scale bars: 2 nm.« less

Save / Share:

Works referenced in this record:

Interfacial properties of semiconducting transition metal chalcogenides
journal, January 1988


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

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

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

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
  • DOI: 10.1002/anie.201402646

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


Structural destabilization induced by lithium intercalation in MoS 2 and related compounds
journal, January 1983

  • Py, M. A.; Haering, R. R.
  • Canadian Journal of Physics, Vol. 61, Issue 1
  • DOI: 10.1139/p83-013

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

Work function, electronegativity, and electrochemical behaviour of metals
journal, September 1972


Core–shell MoO3–MoS2 Nanowires for Hydrogen Evolution A Functional Design for Electrocatalytic Materials
journal, October 2011

  • Chen, Zhebo; Cummins, Dustin; Reinecke, Benjamin N.
  • Nano Letters, Vol. 11, Issue 10, p. 4168-4175
  • DOI: 10.1021/nl2020476

Pure and stable metallic phase molybdenum disulfide nanosheets for hydrogen evolution reaction
journal, February 2016

  • Geng, Xiumei; Sun, Weiwei; Wu, Wei
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms10672

In Situ Detection of Active Edge Sites in Single-Layer MoS 2 Catalysts
journal, July 2015

  • Bruix, Albert; Füchtbauer, Henrik Gøbel; Tuxen, Anders K.
  • ACS Nano, Vol. 9, Issue 9
  • DOI: 10.1021/acsnano.5b03199

Understanding catalysis in a multiphasic two-dimensional transition metal dichalcogenide
journal, October 2015

  • Chou, Stanley S.; Sai, Na; Lu, Ping
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9311

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


Electrochemical Tuning of MoS 2 Nanoparticles on Three-Dimensional Substrate for Efficient Hydrogen Evolution
journal, April 2014

  • Wang, Haotian; Lu, Zhiyi; Kong, Desheng
  • ACS Nano, Vol. 8, Issue 5
  • DOI: 10.1021/nn500959v

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

Recent advances in transition metal phosphide nanomaterials: synthesis and applications in hydrogen evolution reaction
journal, January 2016

  • Shi, Yanmei; Zhang, Bin
  • Chemical Society Reviews, Vol. 45, Issue 6, p. 1529-1541
  • DOI: 10.1039/C5CS00434A

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

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

The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets
journal, April 2013

  • Chhowalla, Manish; Shin, Hyeon Suk; Eda, Goki
  • Nature Chemistry, Vol. 5, Issue 4, p. 263-275
  • DOI: 10.1038/nchem.1589

The Hydrogen Evolution Reaction on Rhenium Metallic Electrodes: A Selected Review and New Experimental Evidence
journal, November 2014


Density functional theory calculations for the hydrogen evolution reaction in an electrochemical double layer on the Pt(111) electrode
journal, January 2007

  • Skúlason, Egill; Karlberg, Gustav S.; Rossmeisl, Jan
  • Phys. Chem. Chem. Phys., Vol. 9, Issue 25
  • DOI: 10.1039/B700099E

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

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

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


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
  • DOI: 10.1021/ja403440e

Origin of Structural Transformation in Mono- and Bi-Layered Molybdenum Disulfide
journal, May 2016

  • Sun, Xiaoli; Wang, Zhiguo; Li, Zhijie
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep26666

Molybdenum Sulfide/N-Doped CNT Forest Hybrid Catalysts for High-Performance Hydrogen Evolution Reaction
journal, February 2014

  • Li, Dong Jun; Maiti, Uday Narayan; Lim, Joonwon
  • Nano Letters, Vol. 14, Issue 3
  • DOI: 10.1021/nl404108a

Electrochemistry of Nanostructured Layered Transition-Metal Dichalcogenides
journal, October 2015


Atomic-Scale Structure of Co–Mo–S Nanoclusters in Hydrotreating Catalysts
journal, January 2001

  • Lauritsen, J. V.; Helveg, S.; Lægsgaard, E.
  • Journal of Catalysis, Vol. 197, Issue 1
  • DOI: 10.1006/jcat.2000.3088

Band Gap Engineering and Layer-by-Layer Mapping of Selenium-Doped Molybdenum Disulfide
journal, December 2013

  • Gong, Yongji; Liu, Zheng; Lupini, Andrew R.
  • Nano Letters, Vol. 14, Issue 2
  • DOI: 10.1021/nl4032296

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

    Works referencing / citing this record:

    Doping of Two-Dimensional Semiconductors: A Rapid Review and Outlook
    journal, January 2019


    Doping of Two-Dimensional Semiconductors: A Rapid Review and Outlook
    journal, January 2019


      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.