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Title: Self-optimizing, highly surface-active layered metal dichalcogenide catalysts for hydrogen evolution [Surface-active metal dichalcogenide electrocatalysts with self-improving performance for hydrogen evolution]

Low-cost, layered transition-metal dichalcogenides (MX 2) based on molybdenum and tungsten have attracted substantial interest as alternative catalysts for the hydrogen evolution reaction (HER). These materials have high intrinsic per-site HER activity; however, a significant challenge is the limited density of active sites, which are concentrated at the layer edges. Here we unravel electronic factors underlying catalytic activity on MX 2 surfaces, and leverage the understanding to report group-5 MX 2 (H-TaS 2 and H-NbS 2) electrocatalysts whose performance instead mainly derives from highly active basal-plane sites, as suggested by our first-principles calculations and performance comparisons with edge-active counterparts. Beyond high catalytic activity, they are found to exhibit an unusual ability to optimize their morphology for enhanced charge transfer and accessibility of active sites as the HER proceeds, offering a practical advantage for scalable processing. In conclusion, the catalysts reach 10 mA cm –2 current density at an overpotential of ~50–60 mV with a loading of 10–55 μg cm –2, surpassing other reported MX 2 candidates without any performance-enhancing additives.
Authors:
ORCiD logo [1] ;  [2] ;  [2] ; ORCiD logo [2] ;  [3] ;  [2] ;  [2] ;  [4] ;  [3] ; ORCiD logo [2] ;  [2] ;  [2] ;  [3] ;  [5]
  1. Rice Univ., Houston, TX (United States); California Inst. of Technology (CalTech), Pasadena, CA (United States)
  2. Rice Univ., Houston, TX (United States)
  3. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  4. San Diego State Univ., San Diego, CA (United State)
  5. Rice Univ., Houston, TX (United States
Publication Date:
Report Number(s):
LLNL-JRNL-659614
Journal ID: ISSN 2058-7546; 780651
Grant/Contract Number:
AC52-07NA27344
Type:
Accepted Manuscript
Journal Name:
Nature Energy
Additional Journal Information:
Journal Volume: 2; Journal Issue: 9; Journal ID: ISSN 2058-7546
Publisher:
Nature Publishing Group
Research Org:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org:
USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; 36 MATERIALS SCIENCE; 30 DIRECT ENERGY CONVERSION
OSTI Identifier:
1461742

Liu, Yuanyue, Wu, Jingjie, Hackenberg, Ken P., Zhang, Jing, Wang, Y. Morris, Yang, Yingchao, Keyshar, Kunttal, Gu, Jing, Ogitsu, Tadashi, Vajtai, Robert, Lou, Jun, Ajayan, Pulickel M., Wood, Brandon C., and Yakobson, Boris I.. Self-optimizing, highly surface-active layered metal dichalcogenide catalysts for hydrogen evolution [Surface-active metal dichalcogenide electrocatalysts with self-improving performance for hydrogen evolution]. United States: N. p., Web. doi:10.1038/nenergy.2017.127.
Liu, Yuanyue, Wu, Jingjie, Hackenberg, Ken P., Zhang, Jing, Wang, Y. Morris, Yang, Yingchao, Keyshar, Kunttal, Gu, Jing, Ogitsu, Tadashi, Vajtai, Robert, Lou, Jun, Ajayan, Pulickel M., Wood, Brandon C., & Yakobson, Boris I.. Self-optimizing, highly surface-active layered metal dichalcogenide catalysts for hydrogen evolution [Surface-active metal dichalcogenide electrocatalysts with self-improving performance for hydrogen evolution]. United States. doi:10.1038/nenergy.2017.127.
Liu, Yuanyue, Wu, Jingjie, Hackenberg, Ken P., Zhang, Jing, Wang, Y. Morris, Yang, Yingchao, Keyshar, Kunttal, Gu, Jing, Ogitsu, Tadashi, Vajtai, Robert, Lou, Jun, Ajayan, Pulickel M., Wood, Brandon C., and Yakobson, Boris I.. 2017. "Self-optimizing, highly surface-active layered metal dichalcogenide catalysts for hydrogen evolution [Surface-active metal dichalcogenide electrocatalysts with self-improving performance for hydrogen evolution]". United States. doi:10.1038/nenergy.2017.127. https://www.osti.gov/servlets/purl/1461742.
@article{osti_1461742,
title = {Self-optimizing, highly surface-active layered metal dichalcogenide catalysts for hydrogen evolution [Surface-active metal dichalcogenide electrocatalysts with self-improving performance for hydrogen evolution]},
author = {Liu, Yuanyue and Wu, Jingjie and Hackenberg, Ken P. and Zhang, Jing and Wang, Y. Morris and Yang, Yingchao and Keyshar, Kunttal and Gu, Jing and Ogitsu, Tadashi and Vajtai, Robert and Lou, Jun and Ajayan, Pulickel M. and Wood, Brandon C. and Yakobson, Boris I.},
abstractNote = {Low-cost, layered transition-metal dichalcogenides (MX2) based on molybdenum and tungsten have attracted substantial interest as alternative catalysts for the hydrogen evolution reaction (HER). These materials have high intrinsic per-site HER activity; however, a significant challenge is the limited density of active sites, which are concentrated at the layer edges. Here we unravel electronic factors underlying catalytic activity on MX2 surfaces, and leverage the understanding to report group-5 MX2 (H-TaS2 and H-NbS2) electrocatalysts whose performance instead mainly derives from highly active basal-plane sites, as suggested by our first-principles calculations and performance comparisons with edge-active counterparts. Beyond high catalytic activity, they are found to exhibit an unusual ability to optimize their morphology for enhanced charge transfer and accessibility of active sites as the HER proceeds, offering a practical advantage for scalable processing. In conclusion, the catalysts reach 10 mA cm–2 current density at an overpotential of ~50–60 mV with a loading of 10–55 μg cm–2, surpassing other reported MX2 candidates without any performance-enhancing additives.},
doi = {10.1038/nenergy.2017.127},
journal = {Nature Energy},
number = 9,
volume = 2,
place = {United States},
year = {2017},
month = {7}
}

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