Rapid flame doping of Co to WS2 for efficient hydrogen evolution
Abstract
Transition metal sulfides have been widely studied as electrocatalysts for the hydrogen evolution reaction (HER). Though elemental doping is an effective way to enhance sulfide activity for the HER, most studies have only focused on the effect of doping sulfide edge sites. Few studies have investigated the effect of doping the basal plane or the effect of doping concentration on basal plane activity. Probing the dopant concentration dependence of HER activity is challenging due to experimental difficulties in controlling dopant incorporation. We overcome this challenge by first synthesizing doped transition metal oxides and then sulfurizing the oxides to sulfides, yielding core/shell Co-doped WS2/W18O49 nanotubes with a tunable amount of Co. Our combined density functional theory (DFT) calculations and experiments demonstrate that the HER activity of basal plane WS2 changes non-monotonically with the concentration of Co due to local changes in the binding energy of H and the formation energy of S-vacancies. At an optimal Co doping concentration, the overpotential to reach -10 mA cm-2 is reduced by 210 mV, and the Tafel slope is reduced from 122 to 49 mV per decade (mV dec-1) compared to undoped WS2 nanotubes.
- Authors:
-
[1];
[2];
[1];
[2];
[1]
- Stanford Univ., CA (United States). Dept. of Mechanical Engineering
- Stanford Univ., CA (United States). Dept. of Chemical Engineering
- Stanford Univ., CA (United States). Dept. of Material Science and Engineering
- Stanford Univ., CA (United States). Dept. of Chemical Engineering; SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1476298
- Grant/Contract Number:
- AC02-76SF00515; ECCS-1542152
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Energy & Environmental Science
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 8; Journal ID: ISSN 1754-5692
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 08 HYDROGEN
Citation Formats
Shi, Xinjian, Fields, Meredith, Park, Joonsuk, McEnaney, Joshua M., Yan, Hongping, Zhang, Yirui, Tsai, Charlie, Jaramillo, Thomas F., Sinclair, Robert, Nørskov, Jens K., and Zheng, Xiaolin. Rapid flame doping of Co to WS2 for efficient hydrogen evolution. United States: N. p., 2018.
Web. doi:10.1039/c8ee01111g.
Shi, Xinjian, Fields, Meredith, Park, Joonsuk, McEnaney, Joshua M., Yan, Hongping, Zhang, Yirui, Tsai, Charlie, Jaramillo, Thomas F., Sinclair, Robert, Nørskov, Jens K., & Zheng, Xiaolin. Rapid flame doping of Co to WS2 for efficient hydrogen evolution. United States. https://doi.org/10.1039/c8ee01111g
Shi, Xinjian, Fields, Meredith, Park, Joonsuk, McEnaney, Joshua M., Yan, Hongping, Zhang, Yirui, Tsai, Charlie, Jaramillo, Thomas F., Sinclair, Robert, Nørskov, Jens K., and Zheng, Xiaolin. Tue .
"Rapid flame doping of Co to WS2 for efficient hydrogen evolution". United States. https://doi.org/10.1039/c8ee01111g. https://www.osti.gov/servlets/purl/1476298.
@article{osti_1476298,
title = {Rapid flame doping of Co to WS2 for efficient hydrogen evolution},
author = {Shi, Xinjian and Fields, Meredith and Park, Joonsuk and McEnaney, Joshua M. and Yan, Hongping and Zhang, Yirui and Tsai, Charlie and Jaramillo, Thomas F. and Sinclair, Robert and Nørskov, Jens K. and Zheng, Xiaolin},
abstractNote = {Transition metal sulfides have been widely studied as electrocatalysts for the hydrogen evolution reaction (HER). Though elemental doping is an effective way to enhance sulfide activity for the HER, most studies have only focused on the effect of doping sulfide edge sites. Few studies have investigated the effect of doping the basal plane or the effect of doping concentration on basal plane activity. Probing the dopant concentration dependence of HER activity is challenging due to experimental difficulties in controlling dopant incorporation. We overcome this challenge by first synthesizing doped transition metal oxides and then sulfurizing the oxides to sulfides, yielding core/shell Co-doped WS2/W18O49 nanotubes with a tunable amount of Co. Our combined density functional theory (DFT) calculations and experiments demonstrate that the HER activity of basal plane WS2 changes non-monotonically with the concentration of Co due to local changes in the binding energy of H and the formation energy of S-vacancies. At an optimal Co doping concentration, the overpotential to reach -10 mA cm-2 is reduced by 210 mV, and the Tafel slope is reduced from 122 to 49 mV per decade (mV dec-1) compared to undoped WS2 nanotubes.},
doi = {10.1039/c8ee01111g},
journal = {Energy & Environmental Science},
number = 8,
volume = 11,
place = {United States},
year = {Tue Jun 05 00:00:00 EDT 2018},
month = {Tue Jun 05 00:00:00 EDT 2018}
}
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Figures / Tables:
Fig. 1: Free energy of hydrogen adsorption ($ΔG$H) to 2H- and 1T-WS2 with increasing Co-dopant concentration. Stable geometry (left, Win turquoise. Co in light pink, and S in yellow) and colored $ΔG$H activity map (right) for 4 x 4 (a) 2H - phase and (b) lT-phase WS2 basal planes asmore »
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