Unique interfacial thermodynamics of few-layer 2D MoS 2 for (photo)electrochemical catalysis
Abstract
The electronic structure of few-layer MoS2 is studied by in-situ and operando spectroelectrochemistry in conditions relevant to its use as an electrocatalyst. We show that electron injection into the conduction band is coupled with a redshift of the exciton resonance, the magnitude of which depends on the number of vertical MoS2 layers. In addition, the applied electric field/electronic doping imparts uniaxial tensile strain evidenced by broadening Raman signals, indicating that under conditions of electrocatalysis, the system is structurally different from equilibrium. We demonstrate that field/carrier induced changes to the electronic structure of MoS2 alter the band edge positions which changes the fundamental thermodynamic driving force for charge transfer. This property is a function of the applied potential, an effect unique to 2D semiconductors. The dynamic band edge potentials change the relevant interfacial energetics for charge transfer and has strong implications for the mechanistic understanding of (photo)catalytic fuel-forming reactions using two-dimensional systems.
- Publication Date:
- Research Org.:
- National Renewable Energy Laboratory (NREL), Golden, CO (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1512676
- Alternate Identifier(s):
- OSTI ID: 1508417
- Report Number(s):
- NREL/JA-5900-73687
Journal ID: ISSN 1754-5692; EESNBY
- Grant/Contract Number:
- AC36-08GO28308
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Energy & Environmental Science
- Additional Journal Information:
- Journal Volume: 12; Journal Issue: 5; Journal ID: ISSN 1754-5692
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; electronic structure; electrochemistry; electrocatalysts
Citation Formats
Carroll, Gerard, Zhang, Hanyu, Dunklin, Jeremy R., Link, Elisa M, Neale, Nathan R., and Van De Lagemaat, Jao. Unique interfacial thermodynamics of few-layer 2D MoS 2 for (photo)electrochemical catalysis. United States: N. p., 2019.
Web. doi:10.1039/C9EE00513G.
Carroll, Gerard, Zhang, Hanyu, Dunklin, Jeremy R., Link, Elisa M, Neale, Nathan R., & Van De Lagemaat, Jao. Unique interfacial thermodynamics of few-layer 2D MoS 2 for (photo)electrochemical catalysis. United States. https://doi.org/10.1039/C9EE00513G
Carroll, Gerard, Zhang, Hanyu, Dunklin, Jeremy R., Link, Elisa M, Neale, Nathan R., and Van De Lagemaat, Jao. Fri .
"Unique interfacial thermodynamics of few-layer 2D MoS 2 for (photo)electrochemical catalysis". United States. https://doi.org/10.1039/C9EE00513G. https://www.osti.gov/servlets/purl/1512676.
@article{osti_1512676,
title = {Unique interfacial thermodynamics of few-layer 2D MoS 2 for (photo)electrochemical catalysis},
author = {Carroll, Gerard and Zhang, Hanyu and Dunklin, Jeremy R. and Link, Elisa M and Neale, Nathan R. and Van De Lagemaat, Jao},
abstractNote = {The electronic structure of few-layer MoS2 is studied by in-situ and operando spectroelectrochemistry in conditions relevant to its use as an electrocatalyst. We show that electron injection into the conduction band is coupled with a redshift of the exciton resonance, the magnitude of which depends on the number of vertical MoS2 layers. In addition, the applied electric field/electronic doping imparts uniaxial tensile strain evidenced by broadening Raman signals, indicating that under conditions of electrocatalysis, the system is structurally different from equilibrium. We demonstrate that field/carrier induced changes to the electronic structure of MoS2 alter the band edge positions which changes the fundamental thermodynamic driving force for charge transfer. This property is a function of the applied potential, an effect unique to 2D semiconductors. The dynamic band edge potentials change the relevant interfacial energetics for charge transfer and has strong implications for the mechanistic understanding of (photo)catalytic fuel-forming reactions using two-dimensional systems.},
doi = {10.1039/C9EE00513G},
journal = {Energy & Environmental Science},
number = 5,
volume = 12,
place = {United States},
year = {Fri Apr 12 00:00:00 EDT 2019},
month = {Fri Apr 12 00:00:00 EDT 2019}
}
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