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)

Research output: Contribution to journalArticleAcademicpeer-review

Abstract

Molybdenum disulfide (MoS2) and related transition metal chalcogenides can replace expensive precious metal catalysts such as Pt for the hydrogen evolution reaction (HER). We investigated the relation between the nanoscale properties and HER activity of well‐controlled 2H and Li‐promoted 1T phases of MoS2 as well as an amorphous MoS2 phase. Our detailed comparison based on a Mo‐S and Mo‐Mo bond analysis under operando HER conditions reveals a similar bond structure in 1T and amorphous MoS2 phases as a key feature in explaining their increased HER activity. Whereas the distinct bond structure in 1T phase MoS2 is caused by Li+ intercalation and disappears under harsh HER conditions, amorphous MoS2 maintains its intrinsic short Mo‐Mo bond feature and, with that, its high HER activity. Quantum‐chemical calculations point at similar electronic structures of small MoS2 clusters serving as models for amorphous MoS2 and the 1T phase MoS2 showing similar Gibbs free energies for hydrogen adsorption (ΔGH*) and metallic character.
LanguageEnglish
Pages4383-4389
JournalChemSusChem
Volume12
DOIs
StateAccepted/In press - 2019

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

Cite this

@article{6733d13010714ac5b154f4804dd43693,
title = "The origin of high activity of amorphous MoS2 in the hydrogen evolution reaction",
abstract = "Molybdenum disulfide (MoS2) and related transition metal chalcogenides can replace expensive precious metal catalysts such as Pt for the hydrogen evolution reaction (HER). We investigated the relation between the nanoscale properties and HER activity of well‐controlled 2H and Li‐promoted 1T phases of MoS2 as well as an amorphous MoS2 phase. Our detailed comparison based on a Mo‐S and Mo‐Mo bond analysis under operando HER conditions reveals a similar bond structure in 1T and amorphous MoS2 phases as a key feature in explaining their increased HER activity. Whereas the distinct bond structure in 1T phase MoS2 is caused by Li+ intercalation and disappears under harsh HER conditions, amorphous MoS2 maintains its intrinsic short Mo‐Mo bond feature and, with that, its high HER activity. Quantum‐chemical calculations point at similar electronic structures of small MoS2 clusters serving as models for amorphous MoS2 and the 1T phase MoS2 showing similar Gibbs free energies for hydrogen adsorption (ΔGH*) and metallic character.",
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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year = "2019",
doi = "10.1002/cssc.201901811",
language = "English",
volume = "12",
pages = "4383--4389",
journal = "ChemSusChem",
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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, 2019, p. 4383-4389.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - The origin of high activity of amorphous MoS2 in the hydrogen evolution reaction

AU - Wu,Longfei

AU - Longo,Alessandro

AU - Dzade,Nelson Y.

AU - Sharma,Akhil

AU - Hendrix,Marco

AU - Bol,Ageeth

AU - de Leeuw,Nora H.

AU - Hensen,Emiel

AU - Hofmann,Jan Philipp

N1 - 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

PY - 2019

Y1 - 2019

N2 - Molybdenum disulfide (MoS2) and related transition metal chalcogenides can replace expensive precious metal catalysts such as Pt for the hydrogen evolution reaction (HER). We investigated the relation between the nanoscale properties and HER activity of well‐controlled 2H and Li‐promoted 1T phases of MoS2 as well as an amorphous MoS2 phase. Our detailed comparison based on a Mo‐S and Mo‐Mo bond analysis under operando HER conditions reveals a similar bond structure in 1T and amorphous MoS2 phases as a key feature in explaining their increased HER activity. Whereas the distinct bond structure in 1T phase MoS2 is caused by Li+ intercalation and disappears under harsh HER conditions, amorphous MoS2 maintains its intrinsic short Mo‐Mo bond feature and, with that, its high HER activity. Quantum‐chemical calculations point at similar electronic structures of small MoS2 clusters serving as models for amorphous MoS2 and the 1T phase MoS2 showing similar Gibbs free energies for hydrogen adsorption (ΔGH*) and metallic character.

AB - Molybdenum disulfide (MoS2) and related transition metal chalcogenides can replace expensive precious metal catalysts such as Pt for the hydrogen evolution reaction (HER). We investigated the relation between the nanoscale properties and HER activity of well‐controlled 2H and Li‐promoted 1T phases of MoS2 as well as an amorphous MoS2 phase. Our detailed comparison based on a Mo‐S and Mo‐Mo bond analysis under operando HER conditions reveals a similar bond structure in 1T and amorphous MoS2 phases as a key feature in explaining their increased HER activity. Whereas the distinct bond structure in 1T phase MoS2 is caused by Li+ intercalation and disappears under harsh HER conditions, amorphous MoS2 maintains its intrinsic short Mo‐Mo bond feature and, with that, its high HER activity. Quantum‐chemical calculations point at similar electronic structures of small MoS2 clusters serving as models for amorphous MoS2 and the 1T phase MoS2 showing similar Gibbs free energies for hydrogen adsorption (ΔGH*) and metallic character.

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