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

Title: All the catalytic active sites of MoS 2 for hydrogen evolution

Abstract

MoS 2 presents a promising low-cost catalyst for the hydrogen evolution reaction (HER), but the understanding about its active sites has remained limited. Here we present an unambiguous study of the catalytic activities of all possible reaction sites of MoS 2, including edge sites, sulfur vacancies, and grain boundaries. We demonstrate that, in addition to the well-known catalytically active edge sites, sulfur vacancies provide another major active site for the HER, while the catalytic activity of grain boundaries is much weaker. Here, the intrinsic turnover frequencies (Tafel slopes) of the edge sites, sulfur vacancies, and grain boundaries are estimated to be 7.5 s –1 (65–75 mV/dec), 3.2 s –1 (65–85 mV/dec), and 0.1 s –1 (120–160 mV/dec), respectively. We also demonstrate that the catalytic activity of sulfur vacancies strongly depends on the density of the vacancies and the local crystalline structure in proximity to the vacancies. Unlike edge sites, whose catalytic activity linearly depends on the length, sulfur vacancies show optimal catalytic activities when the vacancy density is in the range of 7–10%, and the number of sulfur vacancies in high crystalline quality MoS 2 is higher than that in low crystalline quality MoS 2, which may be related withmore » the proximity of different local crystalline structures to the vacancies.« less

Authors:
 [1];  [2]; ORCiD logo [3];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [2];  [1];  [1];  [3];  [2]; ORCiD logo [1]
  1. North Carolina State Univ., Raleigh, NC (United States)
  2. Duke Univ., Durham, NC (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1347369
Report Number(s):
BNL-113649-2017-JA
Journal ID: ISSN 0002-7863; R&D Project: MA015MACA; KC0201010
Grant/Contract Number:  
SC00112704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 138; Journal Issue: 51; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Li, Guoqing, Zhang, Du, Qiao, Qiao, Yu, Yifei, Peterson, David, Zafar, Abdullah, Kumar, Raj, Curtarolo, Stefano, Hunte, Frank, Shannon, Steve, Zhu, Yimei, Yang, Weitao, and Cao, Linyou. All the catalytic active sites of MoS2 for hydrogen evolution. United States: N. p., 2016. Web. doi:10.1021/jacs.6b05940.
Li, Guoqing, Zhang, Du, Qiao, Qiao, Yu, Yifei, Peterson, David, Zafar, Abdullah, Kumar, Raj, Curtarolo, Stefano, Hunte, Frank, Shannon, Steve, Zhu, Yimei, Yang, Weitao, & Cao, Linyou. All the catalytic active sites of MoS2 for hydrogen evolution. United States. doi:10.1021/jacs.6b05940.
Li, Guoqing, Zhang, Du, Qiao, Qiao, Yu, Yifei, Peterson, David, Zafar, Abdullah, Kumar, Raj, Curtarolo, Stefano, Hunte, Frank, Shannon, Steve, Zhu, Yimei, Yang, Weitao, and Cao, Linyou. Tue . "All the catalytic active sites of MoS2 for hydrogen evolution". United States. doi:10.1021/jacs.6b05940. https://www.osti.gov/servlets/purl/1347369.
@article{osti_1347369,
title = {All the catalytic active sites of MoS2 for hydrogen evolution},
author = {Li, Guoqing and Zhang, Du and Qiao, Qiao and Yu, Yifei and Peterson, David and Zafar, Abdullah and Kumar, Raj and Curtarolo, Stefano and Hunte, Frank and Shannon, Steve and Zhu, Yimei and Yang, Weitao and Cao, Linyou},
abstractNote = {MoS2 presents a promising low-cost catalyst for the hydrogen evolution reaction (HER), but the understanding about its active sites has remained limited. Here we present an unambiguous study of the catalytic activities of all possible reaction sites of MoS2, including edge sites, sulfur vacancies, and grain boundaries. We demonstrate that, in addition to the well-known catalytically active edge sites, sulfur vacancies provide another major active site for the HER, while the catalytic activity of grain boundaries is much weaker. Here, the intrinsic turnover frequencies (Tafel slopes) of the edge sites, sulfur vacancies, and grain boundaries are estimated to be 7.5 s–1 (65–75 mV/dec), 3.2 s–1 (65–85 mV/dec), and 0.1 s–1 (120–160 mV/dec), respectively. We also demonstrate that the catalytic activity of sulfur vacancies strongly depends on the density of the vacancies and the local crystalline structure in proximity to the vacancies. Unlike edge sites, whose catalytic activity linearly depends on the length, sulfur vacancies show optimal catalytic activities when the vacancy density is in the range of 7–10%, and the number of sulfur vacancies in high crystalline quality MoS2 is higher than that in low crystalline quality MoS2, which may be related with the proximity of different local crystalline structures to the vacancies.},
doi = {10.1021/jacs.6b05940},
journal = {Journal of the American Chemical Society},
number = 51,
volume = 138,
place = {United States},
year = {2016},
month = {11}
}

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

Citation Metrics:
Cited by: 47 works
Citation information provided by
Web of Science

Save / Share:

Works referencing / citing this record:

The Role of Supported Atomically Distributed Metal Species in Electrochemistry and How to Create Them
journal, May 2019

  • Ding, Yuxiao; Schlögl, Robert; Heumann, Saskia
  • ChemElectroChem, Vol. 6, Issue 15
  • DOI: 10.1002/celc.201900598

Electrodeposition of amorphous molybdenum sulfide thin film for electrochemical hydrogen evolution reaction
journal, July 2019


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


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

Basal plane oxygen exchange of epitaxial MoS 2 without edge oxidation
journal, July 2019

  • Grønborg, Signe S.; Thorarinsdottir, Kristbjörg; Kyhl, Line
  • 2D Materials, Vol. 6, Issue 4
  • DOI: 10.1088/2053-1583/ab2d00