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Title: Evidence from in Situ X-ray Absorption Spectroscopy for the Involvement of Terminal Disulfide in the Reduction of Protons by an Amorphous Molybdenum Sulfide Electrocatalyst

Abstract

The reduction of protons into dihydrogen is important because of its potential use in a wide range of energy applications. The preparation of efficient and cheap catalysts for this reaction is one of the issues that need to be tackled to allow the widespread use of hydrogen as an energy carrier. In this paper, we report the study of an amorphous molybdenum sulfide (MoS x ) proton reducing electrocatalyst under functional conditions, using in situ X-ray absorption spectroscopy. We probed the local and electronic structures of both the molybdenum and sulfur elements for the as prepared material as well as the precatalytic and catalytic states. The as prepared material is very similar to MoS 3 and remains unmodified under functional conditions (pH = 2 aqueous HNO 3 ) in the precatalytic state (+0.3 V vs RHE). In its catalytic state (-0.3 V vs RHE), the film is reduced to an amorphous form of MoS 2 and shows spectroscopic features that indicate the presence of terminal disulfide units. These units are formed concomitantly with the release of hydrogen, and we suggest that the rate-limiting step of the HER is the reduction and protonation of these disulfide units. These results show themore » implication of terminal disulfide chemical motifs into HER driven by transition-metal sulfides and provide insight into their reaction mechanism.« less

Authors:
 [1];  [2];  [2];  [3];  [3];  [2];  [3]
+ Show Author Affiliations
  1. Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States, Synchrotron SOLEIL, L’Orme des Merisiers, Saint-Aubin, 91191 Gif-sur-Yvette, France
  2. Laboratory of Inorganic Synthesis and Catalysis, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne (EPFL), EPFL-ISIC-LSCI, BCH 3305, Lausanne, CH 1015, Switzerland
  3. Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1165886
Alternate Identifier(s):
OSTI ID: 1257354; OSTI ID: 1407325
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Name: Journal of the American Chemical Society Journal Volume: 137 Journal Issue: 1; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lassalle-Kaiser, Benedikt, Merki, Daniel, Vrubel, Heron, Gul, Sheraz, Yachandra, Vittal K., Hu, Xile, and Yano, Junko. Evidence from in Situ X-ray Absorption Spectroscopy for the Involvement of Terminal Disulfide in the Reduction of Protons by an Amorphous Molybdenum Sulfide Electrocatalyst. United States: N. p., 2014. Web. doi:10.1021/ja510328m.
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Lassalle-Kaiser, Benedikt, Merki, Daniel, Vrubel, Heron, Gul, Sheraz, Yachandra, Vittal K., Hu, Xile, & Yano, Junko. Evidence from in Situ X-ray Absorption Spectroscopy for the Involvement of Terminal Disulfide in the Reduction of Protons by an Amorphous Molybdenum Sulfide Electrocatalyst. United States. https://doi.org/10.1021/ja510328m
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Lassalle-Kaiser, Benedikt, Merki, Daniel, Vrubel, Heron, Gul, Sheraz, Yachandra, Vittal K., Hu, Xile, and Yano, Junko. Fri . "Evidence from in Situ X-ray Absorption Spectroscopy for the Involvement of Terminal Disulfide in the Reduction of Protons by an Amorphous Molybdenum Sulfide Electrocatalyst". United States. https://doi.org/10.1021/ja510328m.
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@article{osti_1165886,
title = {Evidence from in Situ X-ray Absorption Spectroscopy for the Involvement of Terminal Disulfide in the Reduction of Protons by an Amorphous Molybdenum Sulfide Electrocatalyst},
author = {Lassalle-Kaiser, Benedikt and Merki, Daniel and Vrubel, Heron and Gul, Sheraz and Yachandra, Vittal K. and Hu, Xile and Yano, Junko},
abstractNote = {The reduction of protons into dihydrogen is important because of its potential use in a wide range of energy applications. The preparation of efficient and cheap catalysts for this reaction is one of the issues that need to be tackled to allow the widespread use of hydrogen as an energy carrier. In this paper, we report the study of an amorphous molybdenum sulfide (MoS x ) proton reducing electrocatalyst under functional conditions, using in situ X-ray absorption spectroscopy. We probed the local and electronic structures of both the molybdenum and sulfur elements for the as prepared material as well as the precatalytic and catalytic states. The as prepared material is very similar to MoS 3 and remains unmodified under functional conditions (pH = 2 aqueous HNO 3 ) in the precatalytic state (+0.3 V vs RHE). In its catalytic state (-0.3 V vs RHE), the film is reduced to an amorphous form of MoS 2 and shows spectroscopic features that indicate the presence of terminal disulfide units. These units are formed concomitantly with the release of hydrogen, and we suggest that the rate-limiting step of the HER is the reduction and protonation of these disulfide units. These results show the implication of terminal disulfide chemical motifs into HER driven by transition-metal sulfides and provide insight into their reaction mechanism.},
doi = {10.1021/ja510328m},
journal = {Journal of the American Chemical Society},
number = 1,
volume = 137,
place = {United States},
year = {Fri Dec 19 00:00:00 EST 2014},
month = {Fri Dec 19 00:00:00 EST 2014}
}
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