Role of Sulfur Vacancies and Undercoordinated Mo Regions in MoS2 Nanosheets toward the Evolution of Hydrogen

Lei Li, Zhaodan Qin, Lucie Ries, Song Hong, Thierry Michel, Jieun Yang, Chrystelle Salameh, Mikhael Bechelany, Philippe Miele, Daniel Kaplan, Manish Chhowalla, Damien Voiry

Research output: Contribution to journalArticle

Abstract

Low-dimensional materials have been examined as electrocatalysts for the hydrogen evolution reaction (HER). Among them, two-dimensional transition metal dichalcogenides (2D-TMDs) such as MoS2 have been identified as potential candidates. However, the performance of TMDs toward HER in both acidic and basic media remains inferior to that of noble metals such as Pt and its alloys. This calls for investigating the influence of controlled defect engineering of 2D TMDs on their performance toward hydrogen production. Here, we explored the HER activity from defective multilayered MoS2 over a large range of surface S vacancy concentrations up to 90%. Amorphous MoS2 and 2H MoS2 with ultrarich S vacancies demonstrated the highest HER performance in acid and basic electrolytes, respectively. We also report that the HER performance from multilayered MoS2 can be divided into two domains corresponding to "point defects" at low concentrations of surface S vacancies (Stage 1) and large regions of undercoordinated Mo atoms for high concentrations of surface S vacancies (Stage 2). The highest performance is obtained for Stage 2 in the presence of undercoordinated Mo atoms with a TOF of ∼2 s-1 at an overpotential of 160 mV in 0.1 M KOH which compares favorably to the best results in the literature. Overall, our work provides deeper insight on the HER mechanism from defected MoS2 and provides guidance for the development of defect-engineered TMD-based electrocatalysts.

Original languageEnglish
JournalACS nano
DOIs
Publication statusPublished - Jan 1 2019

Fingerprint

Nanosheets
Sulfur
Vacancies
Hydrogen
sulfur
hydrogen
electrocatalysts
Electrocatalysts
Atoms
Defects
defects
hydrogen production
Point defects
Hydrogen production
Precious metals
noble metals
point defects
Electrolytes
Transition metals
atoms

Keywords

  • H-annealing
  • hydrogen evolution reaction
  • MoS
  • sulfur vacancies
  • undercoordinated Mo

ASJC Scopus subject areas

  • Materials Science(all)
  • Engineering(all)
  • Physics and Astronomy(all)

Cite this

Role of Sulfur Vacancies and Undercoordinated Mo Regions in MoS2 Nanosheets toward the Evolution of Hydrogen. / Li, Lei; Qin, Zhaodan; Ries, Lucie; Hong, Song; Michel, Thierry; Yang, Jieun; Salameh, Chrystelle; Bechelany, Mikhael; Miele, Philippe; Kaplan, Daniel; Chhowalla, Manish; Voiry, Damien.

In: ACS nano, 01.01.2019.

Research output: Contribution to journalArticle

Li, L, Qin, Z, Ries, L, Hong, S, Michel, T, Yang, J, Salameh, C, Bechelany, M, Miele, P, Kaplan, D, Chhowalla, M & Voiry, D 2019, 'Role of Sulfur Vacancies and Undercoordinated Mo Regions in MoS2 Nanosheets toward the Evolution of Hydrogen', ACS nano. https://doi.org/10.1021/acsnano.9b01583
Li, Lei ; Qin, Zhaodan ; Ries, Lucie ; Hong, Song ; Michel, Thierry ; Yang, Jieun ; Salameh, Chrystelle ; Bechelany, Mikhael ; Miele, Philippe ; Kaplan, Daniel ; Chhowalla, Manish ; Voiry, Damien. / Role of Sulfur Vacancies and Undercoordinated Mo Regions in MoS2 Nanosheets toward the Evolution of Hydrogen. In: ACS nano. 2019.
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AB - Low-dimensional materials have been examined as electrocatalysts for the hydrogen evolution reaction (HER). Among them, two-dimensional transition metal dichalcogenides (2D-TMDs) such as MoS2 have been identified as potential candidates. However, the performance of TMDs toward HER in both acidic and basic media remains inferior to that of noble metals such as Pt and its alloys. This calls for investigating the influence of controlled defect engineering of 2D TMDs on their performance toward hydrogen production. Here, we explored the HER activity from defective multilayered MoS2 over a large range of surface S vacancy concentrations up to 90%. Amorphous MoS2 and 2H MoS2 with ultrarich S vacancies demonstrated the highest HER performance in acid and basic electrolytes, respectively. We also report that the HER performance from multilayered MoS2 can be divided into two domains corresponding to "point defects" at low concentrations of surface S vacancies (Stage 1) and large regions of undercoordinated Mo atoms for high concentrations of surface S vacancies (Stage 2). The highest performance is obtained for Stage 2 in the presence of undercoordinated Mo atoms with a TOF of ∼2 s-1 at an overpotential of 160 mV in 0.1 M KOH which compares favorably to the best results in the literature. Overall, our work provides deeper insight on the HER mechanism from defected MoS2 and provides guidance for the development of defect-engineered TMD-based electrocatalysts.

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