The Origin of High Activity of Amorphous MoS2 in the Hydrogen Evolution Reaction

Longfei Wu; Alessandro Longo; Nelson Y. Dzade; Akhil Sharma; Marco M.R.M. Hendrix; Ageeth A. Bol; Nora H. de Leeuw; Emiel J.M. Hensen; Jan P. 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 M.R.M. Hendrix, Ageeth A. Bol, Nora H. de Leeuw, Emiel J.M. Hensen^*, Jan P. Hofmann

^*Corresponding author for this work

Research output: Contribution to journal › Comment/Letter to the editor › Academic › peer-review

Abstract

Molybdenumdisulfide(MoS2)and related transition metal chal-cogenides can replace expensive preciousmetal catalysts suchas Pt for the hydrogen evolution reaction(HER). The relationsbetween the nanoscale properties and HER activity of well-controlled 2H and Li-promoted1Tphases of MoS2,aswell asan amorphous MoS2phase, have been investigated and ade-tailed comparison is made on Mo@Sand Mo@Mo bond analysisunder operando HER conditions, which reveals asimilar bondstructure in 1T and amorphous MoS2phases as akey feature inexplaining their increased HER activity.Whereasthe distinctbond structure in 1T phase MoS2is caused by Li+intercalationand disappears under harsh HER conditions, amorphous MoS2maintainsits intrinsic short Mo@Mo bond feature and, withthat, its high HER activity.Quantum-chemical calculations indi-cate similarelectronic structures of small MoS2clusters servingas modelsfor amorphous MoS2and the 1T phase MoS2,show-ing similarGibbs free energies for hydrogen adsorption (DGH*)and metalliccharacter.

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

Funding

We acknowledge the cover art design by Joost van der Meijs, Bart Zijlstra, and Dr. Ivo Filot of Eindhoven University of Technology. The cover art has been designed using Blender 2.80 (http://www.blender.org).

Keywords

bond structure
electrocatalysis
molybdenum
operando spectroscopy
polymorphism

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10.1002/cssc.201901811

cssc.201901811Final published version, 1.7 MB

Cite this

@article{05b8bf4110d34c3ea6c3e97cd8fc4657,

title = "The Origin of High Activity of Amorphous MoS2 in the Hydrogen Evolution Reaction",

abstract = "Molybdenumdisulfide(MoS2)and related transition metal chal-cogenides can replace expensive preciousmetal catalysts suchas Pt for the hydrogen evolution reaction(HER). The relationsbetween the nanoscale properties and HER activity of well-controlled 2H and Li-promoted1Tphases of MoS2,aswell asan amorphous MoS2phase, have been investigated and ade-tailed comparison is made on Mo@Sand Mo@Mo bond analysisunder operando HER conditions, which reveals asimilar bondstructure in 1T and amorphous MoS2phases as akey feature inexplaining their increased HER activity.Whereasthe distinctbond structure in 1T phase MoS2is caused by Li+intercalationand disappears under harsh HER conditions, amorphous MoS2maintainsits intrinsic short Mo@Mo bond feature and, withthat, its high HER activity.Quantum-chemical calculations indi-cate similarelectronic structures of small MoS2clusters servingas modelsfor amorphous MoS2and the 1T phase MoS2,show-ing similarGibbs free energies for hydrogen adsorption (DGH*)and metalliccharacter.",

keywords = "bond structure, electrocatalysis, molybdenum, operando spectroscopy, polymorphism",

author = "Longfei Wu and Alessandro Longo and Dzade, \{Nelson Y.\} and Akhil Sharma and Hendrix, \{Marco M.R.M.\} and Bol, \{Ageeth A.\} and \{de Leeuw\}, \{Nora H.\} and Hensen, \{Emiel J.M.\} and Hofmann, \{Jan P.\}",

year = "2019",

month = oct,

day = "8",

doi = "10.1002/cssc.201901811",

language = "English",

volume = "12",

pages = "4383--4389",

journal = "ChemSusChem",

issn = "1864-5631",

publisher = "Wiley",

number = "19",

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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 M.R.M.

AU - Bol, Ageeth A.

AU - de Leeuw, Nora H.

AU - Hensen, Emiel J.M.

AU - Hofmann, Jan P.

PY - 2019/10/8

Y1 - 2019/10/8

N2 - Molybdenumdisulfide(MoS2)and related transition metal chal-cogenides can replace expensive preciousmetal catalysts suchas Pt for the hydrogen evolution reaction(HER). The relationsbetween the nanoscale properties and HER activity of well-controlled 2H and Li-promoted1Tphases of MoS2,aswell asan amorphous MoS2phase, have been investigated and ade-tailed comparison is made on Mo@Sand Mo@Mo bond analysisunder operando HER conditions, which reveals asimilar bondstructure in 1T and amorphous MoS2phases as akey feature inexplaining their increased HER activity.Whereasthe distinctbond structure in 1T phase MoS2is caused by Li+intercalationand disappears under harsh HER conditions, amorphous MoS2maintainsits intrinsic short Mo@Mo bond feature and, withthat, its high HER activity.Quantum-chemical calculations indi-cate similarelectronic structures of small MoS2clusters servingas modelsfor amorphous MoS2and the 1T phase MoS2,show-ing similarGibbs free energies for hydrogen adsorption (DGH*)and metalliccharacter.

AB - Molybdenumdisulfide(MoS2)and related transition metal chal-cogenides can replace expensive preciousmetal catalysts suchas Pt for the hydrogen evolution reaction(HER). The relationsbetween the nanoscale properties and HER activity of well-controlled 2H and Li-promoted1Tphases of MoS2,aswell asan amorphous MoS2phase, have been investigated and ade-tailed comparison is made on Mo@Sand Mo@Mo bond analysisunder operando HER conditions, which reveals asimilar bondstructure in 1T and amorphous MoS2phases as akey feature inexplaining their increased HER activity.Whereasthe distinctbond structure in 1T phase MoS2is caused by Li+intercalationand disappears under harsh HER conditions, amorphous MoS2maintainsits intrinsic short Mo@Mo bond feature and, withthat, its high HER activity.Quantum-chemical calculations indi-cate similarelectronic structures of small MoS2clusters servingas modelsfor amorphous MoS2and the 1T phase MoS2,show-ing similarGibbs free energies for hydrogen adsorption (DGH*)and metalliccharacter.

KW - bond structure

KW - electrocatalysis

KW - molybdenum

KW - operando spectroscopy

KW - polymorphism

U2 - 10.1002/cssc.201901811

DO - 10.1002/cssc.201901811

M3 - Comment/Letter to the editor

AN - SCOPUS:85074202976

SN - 1864-5631

VL - 12

SP - 4383

EP - 4389

JO - ChemSusChem

JF - ChemSusChem

IS - 19

ER -