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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

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 (MoSx) 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 MoS3 and remains unmodified under functional conditions (pH = 2 aqueous HNO3) 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 MoS2 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. In conclusion, these results show the implication of terminal disulfidemore » 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]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Synchrotron SOLEIL, Gif-sur-Yvette (France)
  2. Ecole Polytechnique Federale Lausanne (Switzlerland)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
OSTI Identifier:
1165886
Grant/Contract Number:
AC02-05CH11231
Type:
Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 137; Journal Issue: 1; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY