Unconventional molybdenum carbide phases with high electrocatalytic activity for hydrogen evolution reaction

Chaoyun Tang, Hui Zhang, Kuofeng Xu, Qianling Zhang, Jianhong Liu, Chuanxin He, Liangdong Fan, Teddy Asefa

Research output: Contribution to journalArticle

Abstract

The development of noble metal-free catalysts, which can replace noble metal ones, such as Pt, for various electrocatalytic processes in renewable energy devices is currently of huge interest. The β-phase of molybdenum carbide (i.e., β-Mo2C) has been reported to be one of the most active noble metal-free electrocatalysts for the hydrogen evolution reaction (HER) in electrolyzers, whereas the other phases, MoC and MoC1-x, have been widely regarded as weak electrocatalysts for HER. Herein, we report the synthesis of nanoporous substoichiometric α-MoC1-x and η-MoC nanosheets, named np-MoC NSs, that show comparable electrocatalytic activity toward HER as β-Mo2C does. The materials are synthesized using two-dimensional (2D) conjugated carbonitride and ammonium molybdate as precursors. Their structures contain N dopant atoms and nanopores. The pores create highly accessible catalytic sites and good mass and charge transport, and thereby excellent reaction kinetics for HER, in the materials. Theoretical calculations show that the N dopant atoms modulate the electronic properties of the catalytically active sites in the materials, leading to lower free energy of adsorption and desorption for the hydrogen species involved in the reaction and better catalytic activity for HER. This work demonstrates that, by simple structural design and electronic modulation, various phases of molybdenum carbides and related materials that have been traditionally considered inactive catalysts for HER can be made robust electrocatalysts for the reaction.

Original languageEnglish
Pages (from-to)18030-18038
Number of pages9
JournalJournal of Materials Chemistry A
Volume7
Issue number30
DOIs
Publication statusPublished - Jan 1 2019

Fingerprint

Molybdenum
Carbides
Hydrogen
Electrocatalysts
Precious metals
Doping (additives)
Atoms
Catalysts
Nanopores
Carbon nitride
Nanosheets
Phase modulation
molybdenum carbide
Structural design
Reaction kinetics
Electronic properties
Free energy
Charge transfer
Catalyst activity
Desorption

ASJC Scopus subject areas

  • Chemistry(all)
  • Renewable Energy, Sustainability and the Environment
  • Materials Science(all)

Cite this

Unconventional molybdenum carbide phases with high electrocatalytic activity for hydrogen evolution reaction. / Tang, Chaoyun; Zhang, Hui; Xu, Kuofeng; Zhang, Qianling; Liu, Jianhong; He, Chuanxin; Fan, Liangdong; Asefa, Teddy.

In: Journal of Materials Chemistry A, Vol. 7, No. 30, 01.01.2019, p. 18030-18038.

Research output: Contribution to journalArticle

Tang, Chaoyun ; Zhang, Hui ; Xu, Kuofeng ; Zhang, Qianling ; Liu, Jianhong ; He, Chuanxin ; Fan, Liangdong ; Asefa, Teddy. / Unconventional molybdenum carbide phases with high electrocatalytic activity for hydrogen evolution reaction. In: Journal of Materials Chemistry A. 2019 ; Vol. 7, No. 30. pp. 18030-18038.
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