Silicon microwire arrays decorated with amorphous heterometal-doped molybdenum sulfide for water photoelectrolysis

Chih Jung Chen, Kai Chih Yang, Chi Wei Liu, Ying Rui Lu, Chung Li Dong, Da Hua Wei*, Shu Fen Hu, Ru Shi Liu

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

57 Citations (Scopus)


Silicon is a promising photocathode material for solar hydrogen evolution because of its small band gap, negative conduction band position, and ideal theoretical current density. In this study, p-type Si microwire (p-Si MW) arrays were prepared as photocathodes because of the large surface area and high light-harvesting capability. However, Si MWs suffered from low photocatalytic activity because of slow photo-induced carriers during driving of water-splitting reaction. Therefore, molybdenum sulfide (MoS2) with appropriate band alignment with p-Si material was employed for surface modification to function as a co-catalyst for collecting photo-generated minority carriers and reducing recombination possibility. The onset potential and current density at 0 V versus reversible hydrogen electrode (RHE) of Si@MoS2 MWs were +0.122 V and −8.41 mA cm−2. Heterometal atoms were employed to dope MoS2 co-catalyst and expose more sulfur-terminated active sites to further boost photoelectrochemical performance. Optimal activity of Si@MMoSx (M = Fe, Co, Ni) was achieved by doping Co heteroatoms, and its turn-on voltage and photocurrent density at 0 V (vs. RHE) were respectively increased to +0.192 V and −17.2 mA cm−2. X-ray absorption spectroscopy was applied to demonstrate that Fe ions of FeMoSx were dichalcogenide materials, forming a composite with MoS2 and contributing better photoelectrolytic efficiency. By contrast, two-valent heteroatoms of CoMoSx and NiMoSx substituted the Mo4+ ions in MoS2. For charge compensation, more defects and edges were revealed as active sites of solar hydrogen production by adding Co or Ni dopants in MoS2 co-catalyst, which led to lower overpotential.

Original languageEnglish
Pages (from-to)422-432
Number of pages11
JournalNano Energy
Publication statusPublished - 2017 Feb 1


  • Co-catalyst
  • Molybdenum sulfide
  • Silicon microwire array
  • Solar hydrogen evolution
  • Water splitting

ASJC Scopus subject areas

  • Renewable Energy, Sustainability and the Environment
  • General Materials Science
  • Electrical and Electronic Engineering


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