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Title: Rapid flame doping of Co to WS 2 for efficient hydrogen evolution

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 WS 2/W 18O 49 nanotubes with a tunable amount of Co. Our combined density functional theory (DFT) calculations and experiments demonstrate that the HER activity of basal plane WS 2 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 WS 2 nanotubes.
Authors:
ORCiD logo [1] ;  [2] ;  [3] ; ORCiD logo [2] ;  [4] ; ORCiD logo [1] ;  [2] ; ORCiD logo [2] ;  [3] ;  [2] ; ORCiD logo [1]
  1. Stanford Univ., CA (United States). Dept. of Mechanical Engineering
  2. Stanford Univ., CA (United States). Dept. of Chemical Engineering
  3. Stanford Univ., CA (United States). Dept. of Material Science and Engineering
  4. Stanford Univ., CA (United States). Dept. of Chemical Engineering; SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Grant/Contract Number:
AC02-76SF00515; ECCS-1542152
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
Research Org:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 08 HYDROGEN
OSTI Identifier:
1476298

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., 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. 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., and Zheng, Xiaolin. 2018. "Rapid flame doping of Co to WS2 for efficient hydrogen evolution". United States. doi:10.1039/c8ee01111g.
@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 = {2018},
month = {6}
}

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