Mo3+ hydride as the common origin of H2 evolution and selective NADH regeneration in molybdenum sulfide electrocatalysts

Jeremy A. Bau; Abdul Hamid Emwas; Pavlo Nikolaienko; Areej A. Aljarb; Vincent Tung; Magnus Rueping

doi:10.1038/s41929-022-00781-8

Mo³⁺ hydride as the common origin of H₂ evolution and selective NADH regeneration in molybdenum sulfide electrocatalysts

Jeremy A. Bau^*, Abdul Hamid Emwas, Pavlo Nikolaienko, Areej A. Aljarb, Vincent Tung, Magnus Rueping^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

53 Scopus citations

Abstract

Hydride transfers are key to a number of economically and environmentally important reactions, including H₂ evolution and NADH regeneration. The electrochemical generation of hydrides can therefore drive the electrification of chemical reactions to improve their sustainability for a green economy. Catalysts containing molybdenum have recently been recognized as among the most promising non-precious catalysts for H₂ evolution, but the mechanism by which molybdenum confers this activity remains debated. Here we show the presence of trapped Mo³⁺ hydride in amorphous molybdenum sulfide (a-MoS_x) during the hydrogen evolution reaction and extend its catalytic role to the selective hydrogenation of the biologically important energy carrier NAD to its active 1,4-NADH form. Furthermore, this reactivity applies to other HER-active molybdenum sulfides. Our results demonstrate a direct role for molybdenum in heterogeneous H₂ evolution. This mechanistic finding also reveals that molybdenum sulfides have potential as economic electrocatalysts for NADH regeneration in biocatalysis. [Figure not available: see fulltext.]

Original language	English (US)
Pages (from-to)	397-404
Number of pages	8
Journal	Nature Catalysis
Volume	5
Issue number	5
DOIs	https://doi.org/10.1038/s41929-022-00781-8
State	Published - May 2022

Bibliographical note

Funding Information:
This work has been supported by King Abdullah University of Science and Technology (KAUST). J.A.B. acknowledges S. Sioud from KAUST Analytical Core Labs for assistance with UHPLC/MS, and D. Renn of KAUST for assistance with procuring materials, images and equipment for biocatalytic experiments. V.T. and A.A. are indebted to the support from the King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research (OSR) under award no. OSR-2018-CARF/CCF-3079.

Publisher Copyright:
© 2022, The Author(s), under exclusive licence to Springer Nature Limited.

ASJC Scopus subject areas

Catalysis
Bioengineering
Biochemistry
Process Chemistry and Technology

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10.1038/s41929-022-00781-8

Cite this

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title = "Mo3+ hydride as the common origin of H2 evolution and selective NADH regeneration in molybdenum sulfide electrocatalysts",

abstract = "Hydride transfers are key to a number of economically and environmentally important reactions, including H2 evolution and NADH regeneration. The electrochemical generation of hydrides can therefore drive the electrification of chemical reactions to improve their sustainability for a green economy. Catalysts containing molybdenum have recently been recognized as among the most promising non-precious catalysts for H2 evolution, but the mechanism by which molybdenum confers this activity remains debated. Here we show the presence of trapped Mo3+ hydride in amorphous molybdenum sulfide (a-MoSx) during the hydrogen evolution reaction and extend its catalytic role to the selective hydrogenation of the biologically important energy carrier NAD to its active 1,4-NADH form. Furthermore, this reactivity applies to other HER-active molybdenum sulfides. Our results demonstrate a direct role for molybdenum in heterogeneous H2 evolution. This mechanistic finding also reveals that molybdenum sulfides have potential as economic electrocatalysts for NADH regeneration in biocatalysis. [Figure not available: see fulltext.]",

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AU - Rueping, Magnus

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N2 - Hydride transfers are key to a number of economically and environmentally important reactions, including H2 evolution and NADH regeneration. The electrochemical generation of hydrides can therefore drive the electrification of chemical reactions to improve their sustainability for a green economy. Catalysts containing molybdenum have recently been recognized as among the most promising non-precious catalysts for H2 evolution, but the mechanism by which molybdenum confers this activity remains debated. Here we show the presence of trapped Mo3+ hydride in amorphous molybdenum sulfide (a-MoSx) during the hydrogen evolution reaction and extend its catalytic role to the selective hydrogenation of the biologically important energy carrier NAD to its active 1,4-NADH form. Furthermore, this reactivity applies to other HER-active molybdenum sulfides. Our results demonstrate a direct role for molybdenum in heterogeneous H2 evolution. This mechanistic finding also reveals that molybdenum sulfides have potential as economic electrocatalysts for NADH regeneration in biocatalysis. [Figure not available: see fulltext.]

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