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; Jan Philipp Hofmann

doi:10.1002/cssc.201901811

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 language	English
Pages (from-to)	4383-4389
Number of pages	7
Journal	ChemSusChem
Volume	12
Issue number	19
DOIs	https://doi.org/10.1002/cssc.201901811
Publication status	Published - 8 Oct 2019

Keywords

bond structure
electrocatalysis
molybdenum
operando spectroscopy
polymorphism

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10.1002/cssc.201901811Licence: CC BY

Publishers versionFinal published version, 1.7 MBLicence: CC BY

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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}",

year = "2019",

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doi = "10.1002/cssc.201901811",

language = "English",

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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

PY - 2019/10/8

Y1 - 2019/10/8

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.

AB - 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.

KW - bond structure

KW - electrocatalysis

KW - molybdenum

KW - operando spectroscopy

KW - polymorphism

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

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Keywords

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

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