Chemical and phase evolution of amorphous molybdenum sulfide catalysts for electrochemical hydrogen production [Chemical and phase evolution of amorphous molybdenum sulfide catalysts for electrochemical hydrogen production directly observed using environmental transmission electron microscopy]

Lee, Sang Chul; Benck, Jesse D.; Tsai, Charlie; Park, Joonsuk; Koh, Ai Leen; Abild-Pedersen, Frank; Jaramillo, Thomas F.; Sinclair, Robert

doi:10.1021/acsnano.5b05652

Title: Chemical and phase evolution of amorphous molybdenum sulfide catalysts for electrochemical hydrogen production [Chemical and phase evolution of amorphous molybdenum sulfide catalysts for electrochemical hydrogen production directly observed using environmental transmission electron microscopy]

Journal Article · Tue Dec 01 04:00:00 UTC 2015 · ACS Nano

DOI: https://doi.org/10.1021/acsnano.5b05652 · OSTI ID:1253168

Lee, Sang Chul ^[1]; Benck, Jesse D. ^[1]; Tsai, Charlie ^[2]; Park, Joonsuk ^[1]; Koh, Ai Leen ^[1]; Abild-Pedersen, Frank ^[3]; Jaramillo, Thomas F. ^[2]; Sinclair, Robert ^[1]

Stanford Univ., Stanford, CA (United States)
Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)

Amorphous MoS_x is a highly active, earth-abundant catalyst for the electrochemical hydrogen evolution reaction. Previous studies have revealed that this material initially has a composition of MoS₃, but after electrochemical activation, the surface is reduced to form an active phase resembling MoS₂ in composition and chemical state. However, structural changes in the Mo_Sx catalyst and the mechanism of the activation process remain poorly understood. In this study, we employ transmission electron microscopy (TEM) to image amorphous MoS_x catalysts activated under two hydrogen-rich conditions: ex situ in an electrochemical cell and in situ in an environmental TEM. For the first time, we directly observe the formation of crystalline domains in the MoS_x catalyst after both activation procedures as well as spatially localized changes in the chemical state detected via electron energy loss spectroscopy. Using density functional theory calculations, we investigate the mechanisms for this phase transformation and find that the presence of hydrogen is critical for enabling the restructuring process. Our results suggest that the surface of the amorphous MoS_x catalyst is dynamic: while the initial catalyst activation forms the primary active surface of amorphous MoS₂, continued transformation to the crystalline phase during electrochemical operation could contribute to catalyst deactivation. Finally, these results have important implications for the application of this highly active electrocatalyst for sustainable H₂ generation.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center on Nanostructuring for Efficient Energy Conversion (CNEEC); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0001060; AC02-76SF00515

OSTI ID:: 1253168

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 1 Vol. 10; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
density functional theory
electrocatalysis
environmental transmission electron microscopy
hydrogen evolution
molybdenum sulfide

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