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Title: Nanoscale mapping of hydrogen evolution on metallic and semiconducting MoS2 nanosheets

Abstract

Hydrogen evolution reaction (HER) on molybdenum disulfide (MoS2) nanosheets is enhanced for the metallic (1T) phase relative to the thermodynamically stable semiconducting (2H) phase. To measure this difference, we employ scanning electrochemical microscopy (SECM) for high-resolution mapping (<20 nm spatial resolution) of surface reactivity for mixed-phase and pure 2H-only MoS2 nanosheets. For mixed-phase MoS2 nanosheets, we find major differences in reactivity of the two phases for electron transfer involving ferrocenemethanol, allowing us to locate 1T and 2H regions and directly map the corresponding HER activity. In our measurements, we find that HER is immeasurably slow on the 2H basal plane and much faster on edges, whereas 1T portions are highly reactive across the entire portion. We also use scanning transmission electron microscopy-electron energy loss spectroscopy and scanning Kelvin probe microscopy to corroborate the phase domains and local workfunctions (surface potentials) within the MoS2 nanosheets; the mixed-phase MoS2 has a shallower workfunction compared to 2H MoS2, which could enable a greater driving force for H2 generation. As a result, this powerful combination of techniques for spatially mapping surface reactivity and correlated phase domains should be applicable to a broad range of materials for HER and other catalysis reactions.

Authors:
 [1]; ORCiD logo [2];  [1];  [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [2]
  1. Queens College-CUNY, Flushing, NY (United States); Graduate Center of CUNY, New York, NY (United States)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1524319
Alternate Identifier(s):
OSTI ID: 1484536
Report Number(s):
NREL/JA-5900-71993
Journal ID: ISSN 2055-6756; NHAOAW
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Nanoscale Horizons
Additional Journal Information:
Journal Volume: 4; Journal Issue: 3; Journal ID: ISSN 2055-6756
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; electron energy levels; electron energy loss spectroscopy; electron scattering; energy dissipation; high resolution transmission electron microscopy; hydrogen; layered semiconductors; mapping; nanosheets; scanning; scanning electron microscopy; scanning probe microscopy; sulfur compounds

Citation Formats

Sun, Tong, Zhang, Hanyu, Wang, Xiang, Liu, Jun, Xiao, Chuanxiao, Nanayakkara, Sanjini U., Blackburn, Jeffrey L., Mirkin, Michael V., and Miller, Elisa M. Nanoscale mapping of hydrogen evolution on metallic and semiconducting MoS2 nanosheets. United States: N. p., 2018. Web. doi:10.1039/C8NH00346G.
Sun, Tong, Zhang, Hanyu, Wang, Xiang, Liu, Jun, Xiao, Chuanxiao, Nanayakkara, Sanjini U., Blackburn, Jeffrey L., Mirkin, Michael V., & Miller, Elisa M. Nanoscale mapping of hydrogen evolution on metallic and semiconducting MoS2 nanosheets. United States. doi:10.1039/C8NH00346G.
Sun, Tong, Zhang, Hanyu, Wang, Xiang, Liu, Jun, Xiao, Chuanxiao, Nanayakkara, Sanjini U., Blackburn, Jeffrey L., Mirkin, Michael V., and Miller, Elisa M. Thu . "Nanoscale mapping of hydrogen evolution on metallic and semiconducting MoS2 nanosheets". United States. doi:10.1039/C8NH00346G. https://www.osti.gov/servlets/purl/1524319.
@article{osti_1524319,
title = {Nanoscale mapping of hydrogen evolution on metallic and semiconducting MoS2 nanosheets},
author = {Sun, Tong and Zhang, Hanyu and Wang, Xiang and Liu, Jun and Xiao, Chuanxiao and Nanayakkara, Sanjini U. and Blackburn, Jeffrey L. and Mirkin, Michael V. and Miller, Elisa M.},
abstractNote = {Hydrogen evolution reaction (HER) on molybdenum disulfide (MoS2) nanosheets is enhanced for the metallic (1T) phase relative to the thermodynamically stable semiconducting (2H) phase. To measure this difference, we employ scanning electrochemical microscopy (SECM) for high-resolution mapping (<20 nm spatial resolution) of surface reactivity for mixed-phase and pure 2H-only MoS2 nanosheets. For mixed-phase MoS2 nanosheets, we find major differences in reactivity of the two phases for electron transfer involving ferrocenemethanol, allowing us to locate 1T and 2H regions and directly map the corresponding HER activity. In our measurements, we find that HER is immeasurably slow on the 2H basal plane and much faster on edges, whereas 1T portions are highly reactive across the entire portion. We also use scanning transmission electron microscopy-electron energy loss spectroscopy and scanning Kelvin probe microscopy to corroborate the phase domains and local workfunctions (surface potentials) within the MoS2 nanosheets; the mixed-phase MoS2 has a shallower workfunction compared to 2H MoS2, which could enable a greater driving force for H2 generation. As a result, this powerful combination of techniques for spatially mapping surface reactivity and correlated phase domains should be applicable to a broad range of materials for HER and other catalysis reactions.},
doi = {10.1039/C8NH00346G},
journal = {Nanoscale Horizons},
number = 3,
volume = 4,
place = {United States},
year = {2018},
month = {11}
}

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