title: Wide Range pH-Tolerable Silicon@Pyrite Cobalt Dichalcogenide Microwire Array Photoelectrodes for Solar Hydrogen Evolution.
abstract: This study employed silicon@cobalt dichalcogenide microwires (MWs) as wide range pH-tolerable photocathode material for solar water splitting. Silicon microwire arrays were fabricated through lithography and dry etching technologies. Si@Co(OH)2 MWs were utilized as precursors to synthesize Si@CoX2 (X = S or Se) photocathodes. Si@CoS2 and Si@CoSe2 MWs were subsequently prepared by thermal sulfidation and hydrothermal selenization reaction of Si@Co(OH)2, respectively. The CoX2 outer shell served as cocatalyst to accelerate the kinetics of photogenerated electrons from the underlying Si MWs and reduce the recombination. Moreover, the CoX2 layer completely deposited on the Si surface functioned as a passivation layer by decreasing the oxide formation on Si MWs during solar hydrogen evolution. Si@CoS2 photocathode showed a photocurrent density of -3.22 mA cm(-2) at 0 V (vs RHE) in 0.5 M sulfuric acid electrolyte, and Si@CoSe2 MWs revealed moderate photocurrent density of -2.55 mA cm(-2). However, Si@CoSe2 presented high charge transfer efficiency in neutral and alkaline electrolytes. Continuous chronoamperometry in acid, neutral, and alkaline solutions was conducted at 0 V (vs RHE) to evaluate the photoelectrochemical durability of Si@CoX2 MWs. Si@CoS2 electrode showed no photoresponse after the chronoamperometry test because it was etched through the electrolyte. By contrast, the photocurrent density of Si@CoSe2 MWs gradually increased to -5 mA cm(-2) after chronoamperometry characterization owing to the amorphous structure generation.
authors: Department of Chemistry, National Taiwan University , Taipei 10617, Taiwan.
authors: Chih-Jung
authors: CJ
authors: Chen
authors: Department of Physics, National Taiwan Normal University , Taipei 11677, Taiwan.
authors: Kai-Chih
authors: KC
authors: Yang
authors: Department of Chemistry, National Taiwan University , Taipei 10617, Taiwan.
authors: Mrinmoyee
authors: M
authors: Basu
authors: Department of Chemistry, National Taiwan University , Taipei 10617, Taiwan.
authors: Tzu-Hsiang
authors: TH
authors: Lu
authors: National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan.|Program for Science and Technology of Accelerator Light Source, National Chiao Tung University , Hsinchu 30010, Taiwan.
authors: Ying-Rui
authors: YR
authors: Lu
authors: National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan.|Department of Physics, Tamkang University , Tamsui 25137, Taiwan.
authors: Chung-Li
authors: CL
authors: Dong
authors: Department of Physics, National Taiwan Normal University , Taipei 11677, Taiwan.
authors: Shu-Fen
authors: SF
authors: Hu
authors: Department of Chemistry, National Taiwan University , Taipei 10617, Taiwan.|Department of Mechanical Engineering and Graduate Institute of Manufacturing Technology, National Taipei University of Technology , Taipei 10608, Taiwan.
authors: Ru-Shi
authors: RS
authors: Liu
keywords: co-catalyst; cobalt dichalcogenide; hydrogen evolution; silicon microwire arrays; solar water splitting; wide range pH toleration