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05 July 2021
Manipulating metal-oxygen local atomic structures in single-junctional p-Si/WO3 photocathodes for efficient solar hydrogen generation
Shaohua Shen1(
)
)
Topics:
Charge transferHydrogen productionOxygenPhotocathodesPhotocurrents Photoelectrochemical cellsSiliconSilicon compoundsTungsten compounds
Cite this article:
Zhou W, Dong C-L, Wang Y, et al.
Manipulating metal-oxygen local atomic structures in single-junctional p-Si/WO3 photocathodes for efficient solar hydrogen generation.
Nano Research,
2021, 14(7): 2285-2293.
https://doi.org/10.1007/s12274-020-3223-9
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Self-passivation in aqueous solution and sluggish surface reaction kinetics significantly limit the photoelectrochemical (PEC) performances of silicon-based photoelectrodes. Herein, a WO3 thin layer is deposited on the p-Si substrate by pulsed laser deposition (PLD), acting as a photocathode for PEC hydrogen generation. Compared to bare p-Si, the single-junctional p-Si/WO3 photoelectrodes exhibit excellent and stable PEC performances with significantly increased cathodic photocurrent density and exceptional anodic shift in onset potential for water reduction. It is revealed that the WO3 layer could reduce the charge transfer resistance across the electrode/electrolyte interface by eliminating the effect of Fermi level pinning on the surface of p-Si. More importantly, by varying the oxygen pressures during PLD, the collaborative modulation of W-O bond covalency and WO6 octahedral structure symmetry contributes to the promoted charge carrier transport and separation. Meanwhile, a large band bending at the p-Si/WO3 junction, induced by the optimized O vacancy contents in WO3, could provide a photovoltage as high as ~ 500 mV to efficiently drive charge transfer to overcome the water reduction overpotential. Synergistically, by manipulating W-O local atomic structures in the deposited WO3 layer, a great improvement in PEC performance could be achieved over the single- junctional p-Si/WO3 photocathodes for solar hydrogen generation.
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Manipulating metal-oxygen local atomic structures in single-junctional p-Si/WO3 photocathodes for efficient solar hydrogen generation
Shaohua Shen1(
)
)
Abstract
Self-passivation in aqueous solution and sluggish surface reaction kinetics significantly limit the photoelectrochemical (PEC) performances of silicon-based photoelectrodes. Herein, a WO3 thin layer is deposited on the p-Si substrate by pulsed laser deposition (PLD), acting as a photocathode for PEC hydrogen generation. Compared to bare p-Si, the single-junctional p-Si/WO3 photoelectrodes exhibit excellent and stable PEC performances with significantly increased cathodic photocurrent density and exceptional anodic shift in onset potential for water reduction. It is revealed that the WO3 layer could reduce the charge transfer resistance across the electrode/electrolyte interface by eliminating the effect of Fermi level pinning on the surface of p-Si. More importantly, by varying the oxygen pressures during PLD, the collaborative modulation of W-O bond covalency and WO6 octahedral structure symmetry contributes to the promoted charge carrier transport and separation. Meanwhile, a large band bending at the p-Si/WO3 junction, induced by the optimized O vacancy contents in WO3, could provide a photovoltage as high as ~ 500 mV to efficiently drive charge transfer to overcome the water reduction overpotential. Synergistically, by manipulating W-O local atomic structures in the deposited WO3 layer, a great improvement in PEC performance could be achieved over the single- junctional p-Si/WO3 photocathodes for solar hydrogen generation.
Keywords:
silicon, water splitting, hydrogen generation, local atomic structure, photocathodes
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Publication history
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Acknowledgements
Publication history
Received: 28 August 2020
Revised: 15 October 2020
Accepted: 02 November 2020
Published:
05 July 2021
Issue date: July 2021
Copyright
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020
Acknowledgements
The authors acknowledge the financial support from the National Key Research and Development Program of China (Nos. 2018YFB1502003 and 2017YFE0193900), the National Natural Science Foundation of China (Nos. 51961165103 and 21875183), the National Program for Support of Top-notch Young Professionals, and "The Youth Innovation Team of Shaanxi Universities". C. L. D. would like to acknowledge the financial support under contracts MoST 107-2112-M-032-004-MY3 and 108-2218-E-032-003-MY3.
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