The origin of high activity of amorphous MoS2 in the hydrogen evolution reaction

Longfei Wu, Alessandro Longo, Nelson Y. Dzade, Akhil Sharma, Marco Hendrix, Ageeth Bol, Nora H. de Leeuw, Emiel Hensen (Corresponding author), Jan Philipp Hofmann (Corresponding author)

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Abstract

Molybdenum disulfide (MoS 2) and related transition metal chalcogenides can replace expensive precious metal catalysts such as Pt for the hydrogen evolution reaction (HER). The relations between the nanoscale properties and HER activity of well-controlled 2H and Li-promoted 1T phases of MoS 2, as well as an amorphous MoS 2 phase, have been investigated and a detailed comparison is made on Mo−S and Mo−Mo bond analysis under operando HER conditions, which reveals a similar bond structure in 1T and amorphous MoS 2 phases as a key feature in explaining their increased HER activity. Whereas the distinct bond structure in 1T phase MoS 2 is caused by Li + intercalation and disappears under harsh HER conditions, amorphous MoS 2 maintains its intrinsic short Mo−Mo bond feature and, with that, its high HER activity. Quantum-chemical calculations indicate similar electronic structures of small MoS 2 clusters serving as models for amorphous MoS 2 and the 1T phase MoS 2, showing similar Gibbs free energies for hydrogen adsorption (ΔG H*) and metallic character.

Original languageEnglish
Pages (from-to)4383-4389
Number of pages7
JournalChemSusChem
Volume12
Issue number19
DOIs
Publication statusPublished - 8 Oct 2019

Fingerprint

Hydrogen
hydrogen
Chalcogenides
Gibbs free energy
precious metal
transition element
Intercalation
Precious metals
molybdenum
Electronic structure
Transition metals
Molybdenum
catalyst
adsorption
Adsorption
Catalysts

Bibliographical note

front cover image: https://doi.org/10.1002/cssc.201902516
cover profile article highlighting the work and the cover: https://doi.org/10.1002/cssc.201902489

Keywords

  • bond structure
  • electrocatalysis
  • molybdenum
  • operando spectroscopy
  • polymorphism

Cite this

@article{6733d13010714ac5b154f4804dd43693,
title = "The origin of high activity of amorphous MoS2 in the hydrogen evolution reaction",
abstract = "Molybdenum disulfide (MoS 2) and related transition metal chalcogenides can replace expensive precious metal catalysts such as Pt for the hydrogen evolution reaction (HER). The relations between the nanoscale properties and HER activity of well-controlled 2H and Li-promoted 1T phases of MoS 2, as well as an amorphous MoS 2 phase, have been investigated and a detailed comparison is made on Mo−S and Mo−Mo bond analysis under operando HER conditions, which reveals a similar bond structure in 1T and amorphous MoS 2 phases as a key feature in explaining their increased HER activity. Whereas the distinct bond structure in 1T phase MoS 2 is caused by Li + intercalation and disappears under harsh HER conditions, amorphous MoS 2 maintains its intrinsic short Mo−Mo bond feature and, with that, its high HER activity. Quantum-chemical calculations indicate similar electronic structures of small MoS 2 clusters serving as models for amorphous MoS 2 and the 1T phase MoS 2, showing similar Gibbs free energies for hydrogen adsorption (ΔG H*) and metallic character.",
keywords = "bond structure, electrocatalysis, molybdenum, operando spectroscopy, polymorphism",
author = "Longfei Wu and Alessandro Longo and Dzade, {Nelson Y.} and Akhil Sharma and Marco Hendrix and Ageeth Bol and {de Leeuw}, {Nora H.} and Emiel Hensen and Hofmann, {Jan Philipp}",
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The origin of high activity of amorphous MoS2 in the hydrogen evolution reaction. / Wu, Longfei; Longo, Alessandro; Dzade, Nelson Y.; Sharma, Akhil; Hendrix, Marco; Bol, Ageeth; de Leeuw, Nora H.; Hensen, Emiel (Corresponding author); Hofmann, Jan Philipp (Corresponding author).

In: ChemSusChem, Vol. 12, No. 19, 08.10.2019, p. 4383-4389.

Research output: Contribution to journalArticleAcademicpeer-review

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AU - Bol, Ageeth

AU - de Leeuw, Nora H.

AU - Hensen, Emiel

AU - Hofmann, Jan Philipp

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N2 - Molybdenum disulfide (MoS 2) and related transition metal chalcogenides can replace expensive precious metal catalysts such as Pt for the hydrogen evolution reaction (HER). The relations between the nanoscale properties and HER activity of well-controlled 2H and Li-promoted 1T phases of MoS 2, as well as an amorphous MoS 2 phase, have been investigated and a detailed comparison is made on Mo−S and Mo−Mo bond analysis under operando HER conditions, which reveals a similar bond structure in 1T and amorphous MoS 2 phases as a key feature in explaining their increased HER activity. Whereas the distinct bond structure in 1T phase MoS 2 is caused by Li + intercalation and disappears under harsh HER conditions, amorphous MoS 2 maintains its intrinsic short Mo−Mo bond feature and, with that, its high HER activity. Quantum-chemical calculations indicate similar electronic structures of small MoS 2 clusters serving as models for amorphous MoS 2 and the 1T phase MoS 2, showing similar Gibbs free energies for hydrogen adsorption (ΔG H*) and metallic character.

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