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SCIENCE CHINA Materials, Volume 61, Issue 6: 895-904(2018) https://doi.org/10.1007/s40843-017-9237-2

A dual-electrolyte system for photoelectrochemical hydrogen generation using CuInS2-In2O3-TiO2 nanotube array thin film

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  • ReceivedNov 7, 2017
  • AcceptedFeb 26, 2018
  • PublishedApr 4, 2018

Abstract

The utilization of Na2S/Na2SO3 mixture as the electrolyte solution to stabilize sulfide anode in a photoelectrochemical cell for hydrogen evolution generally compromises the current-to-hydrogen efficiency (ηcurrent) of the system. Here, the employment of a dual-electrolyte system, that is, Na2S/Na2SO3 mixture and pH-neutral Na2SO4 as the respective electrolyte solutions in the anode and cathode chambers of a water splitting cell is demonstrated to suppress the photocorrosion of CuInS2-In2O3-TiO2 nanotube (CIS-In2O3-TNT) heterostructure, while simultaneously boosts the ηcurrent. Although n-type CIS and In2O3 nanoparticles can be easily formed on TNT array via facile pulse-assisted electrodeposition method, conformal deposition of the nanoparticles homogeneously on the nanotubes wall with preservation of the TNT hollow structure is shown to be essential for achieving efficient charge generation and separation within the heterostructure. In comparison to Na2S/Na2SO3 solution as the sole electrolyte in both the anode and cathode chambers, introduction of dual electrolyte is shown to not only enhance the photostability of the CIS-In2O3-TNT anode, but also lead to near-unity ηcurrent as opposed to the merely 20% ηcurrent of the single-electrolyte system.


Funded by

the Australian Research Council(DP170102895)


Acknowledgment

This work was supported by the Australian Research Council (DP170102895). We thank the UNSW Mark Wainwright Analytical Centre for providing access to all analytical facilities.


Interest statement

The authors declare no conflict of interest.


Contributions statement

Ng C and Yun JH fabricated the electrodes and conducted the photoelectrochemical measurements. Tan HL and Wu H performed characterizations on the samples. Amal R and Ng YH supervised this work. All authors analyzed the data and completed the paper.


Author information

Charlene Ng is currently an Alexander von Humboldt Postdoctoral Fellow at Leibniz-Institut für Polymerforschung Dresden. She received her PhD in Chemical Engineering from UNSW Australia and was awarded for a 3-year OCE Postdoctoral Fellowship from Year 2014--2017 at the Commonwealth Scientific and Industrial Research Organization in Melbourne, Australia. Her primary research interests are aimed at addressing challenges associated with the conversion of solar energy into chemical fuels.


Yun Hau Ng received his PhD from Osaka University in 2009. After a brief research visit to the University of Notre Dame, he joined UNSW with the Australian Postdoctoral Fellowship (APD) in 2011. He is currently a senior lecturer in the School of Chemical Engineering at UNSW. His research is focused on the development of novel photoactive semiconductors (particles and thin films) for solar energy conversion.


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  • Figure 1

    XRD spectra of CIS-In2O3-TNT1 and TNT1 anodized for 1 h.

  • Figure 2

    SEM images of (a) CIS-In2O3-TNT1, (b) CIS-In2O3-TNT3, (c) CIS-In2O3-TNT7 and (d) UV-vis diffuse reflectance spectra of the CIS-In2O3-TNT heterostructures. The inset in (a) presents the SEM image of TNT1.

  • Figure 3

    (a) Amperometric photocurrent densities of CIS-In2O3 and CIS-In2O3-TNT arrays with different lengths of TNT arrays under visible light irradiation (λ>435 nm) in Na2S/Na2SO3 electrolyte solution. (b) Schematic diagram on energy band gap and different photoexcited electron pathways within the CIS-In2O3-TNT composite photoelectrode. (c) Photocurrent density comparison of the TNT arrays and CIS-In2O3-TNT electrodes with different lengths under UV illumination.

  • Figure 4

    (a) Current-to-hydrogen efficiency of CIS-In2O3-TNT1 array in Na2S/Na2SO3 & Na2SO4 dual electrolyte and Na2S/Na2SO3 electrolyte in a two-electrode photoelectrochemical water splitting system for H2 generation, (b) photocurrent of CIS-In2O3-TNT1 array in Na2S/Na2SO3 & Na2SO4 dual electrolyte system and Na2SO4 electrolyte, (c) schematic diagram of the photoelectrochemical H2 generation reactor featuring dual-electrolyte system and (d) photoelectrochemical H2 evolution of CIS-In2O3-TNT1 array in Na2S/Na2SO3 & Na2SO4 dual-electrolyte system.

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