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SCIENCE CHINA Materials, Volume 60, Issue 3: 193-207(2017) https://doi.org/10.1007/s40843-016-5168-0

Promoting charge carrier utilization by integrating layered double hydroxide nanosheet arrays with porous BiVO4 photoanode for efficient photoelectrochemical water splitting

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  • ReceivedDec 9, 2016
  • AcceptedDec 28, 2016
  • PublishedJan 22, 2017

Abstract

The increasing exploration of renewable and clean power sources have driven the development of highly active materials for photoelectrochemical (PEC) water splitting. However, it is still a great challenge to enhance the charge utilization. Herein, we report a facile method to fabricate composite photoanode with porous BiVO4 film as the photon absorber and layered double hydroxide (LDH) nanosheet arrays as the oxygen-evolution cocatalysts (OECs). The as-prepared BiVO4/NiFe-LDH photoanode shows an excellent performance for PEC water splitting benefitting from the synergistic effect of the superior charge separation efficiency facilitated by porous BiVO4 film and the excellent water oxidation activity resulting from LDH nanosheet arrays. A photocurrent density is 4.02 mA cm−2 at 1.23 V vs. the reversible hydrogen electrode (RHE). Furthermore, the O2 evolution rate at the surface of BiVO4/NiFe-LDH photoanode is as high as 29.6 µmol h−1 cm−2 and the high activity for water oxidation is maintained for over 30 h. Impressively, the performance of the as-fabricated composite photoanode for PEC water splitting can be further enhanced through incorporating a certain amount of Co2+ cation into NiFe-LDH as OEC. The photocurrent density is achieved up to 4.45 mA cm−2 at 1.23 V vs. RHE. This value is the highest yet reported for un-doped BiVO4-based photoanodes so far.


Funded by

National Natural Science Foundation of China(21422104)


Acknowledgment

This work was supported by the National Natural Science Foundation of China (21422104) and the Key Project of Natural Science Foundation of Tianjin City (16JCZDJC30600).


Interest statement

The authors declare that they have no conflict of interest.


Contributions statement

Huang Y and Zhang B designed and performed the series of synthesis and characterization experiments. Huang Y wrote the paper with support from Zhang B. All authors analyzed the experimental results and contributed to the general discussion.


Supplement

Experimental details and supporting data are available in the online version of the paper.


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  • Figure 1

    Schematic illustration for the fabrication of BiVO4/NiFe-LDH photoanode, its charge separation process and PEC water splitting mechanism.

  • Figure 2

    Morphology and structure characterization. (a, b) Top view and (c, d) cross-section view SEM images of the porous BiVO4 (a and c) and BiVO4/NiFe-LDH (b and d). The inset of (b) is the high magnification top view SEM image of BiVO4/NiFe-LDH. The white arrows in (d) indicate the positions where the NiFe-LDH nanosheets are grown on the internal part of porous BiVO4 film. (e, f) TEM images of BiVO4/NiFe-LDH. The insets of (f) are the HRTEM images of BiVO4 (bottom) and NiFe-LDH (upper right), respectively. The white square in (e) implies the position where the HAADF-STEM image is obtained. (g) HAADF-STEM image and the associated STEM-EDS elemental mapping images of BiVO4/NiFe-LDH.

  • Figure 3

    UV-vis absorption spectra measured at different sides of samples: (a) front-side, (b) back-side. The insets in (a) and (b) are the corresponding schematic illustration of illumination, respectively. The blue arrows represent incident solar irradiation.

  • Figure 4

    Effect of NiFe-LDH on PEC performance of the porous BiVO4 photoanode. (a) The LSV curves, (b) ABPE curves of BiVO4 and BiVO4/NiFe-LDH photoanodes under the front-side and back-side illumination. (c) LSV behavior chopped light illumination, (d) I-t curves at a potential of 1.0 V vs. RHE under chopped light illumination, (e) EIS spectra measured at the open-circuit potential under illumination and (f) IPCE curves measured at a potential of 1.0 V vs. RHE for the pristine BiVO4 and BiVO4/NiFe-LDH photoanodes.

  • Figure 5

    Charge separation efficiency of BiVO4/NiFe-LDH photoanode. (a) LSV curves of the pristine BiVO4 and BiVO4/NiFe-LDH photoanode measured in 0.1 mol L−1 KHCO3 with (solid lines) and without (dashed lines) 0.1 mol L−1 Na2SO3 as a hole scavenger under AM 1.5G irradiation. (b) The charge separation efficiency (ηsurf) on the surface of pristine BiVO4 and BiVO4/NiFe-LDH photoanodes.

  • Figure 6

    Effect of the electrolyte on the PEC performance of the BiVO4/NiFe-LDH photoanode. (a) The LSV curves, (b) I-t curves at a potential of 1.0 V vs. RHE under light illumination for the BiVO4/NiFe-LDH photoanode in 0.1 mol L−1 KHCO3 (black), 0.1 mol L−1 K2SO4 (red) and 0.1 mol L−1 NaOH (blue). (c) The optical photographs of the BiVO4/NiFe-LDH photoanode after PEC test for 3 h in different electrolytes: (I) reference sample without test; (II) 0.1 mol L−1 KHCO3; (III) 0.1 mol L−1 K2SO4; (IV) 0.1 mol L−1 KOH. (d–f) The LSV curves of the BiVO4/NiFe-LDH photoanode before and after PEC test for 3 h in (d) 0.1 mol L−1 KHCO3, (e) 0.1 mol L−1 K2SO4 and (f) 0.1 mol L−1 KOH.

  • Figure 7

    Water photoelectrolysis on the BiVO4/NiFe-LDH photoanode. (a) Detection of O2 and H2 in initial 3 h, (b) I-t curve at a potential of 1.0 V vs. RHE under light illumination for the BiVO4/NiFe-LDH photoanode. Dashed line in (a) is the theoretical result based on the number of transferred electrons. The insert of (b) is the cross-section view SEM image of the BiVO4/NiFe-LDH photoanode after 30 h PEC test.

  • Figure 8

    Effect of ternary NiFeCo-LDH on porous BiVO4 photoanode. (a) The LSV curves, (b) ABPE curves, (c) LSV behavior under chopped light illumination, (d) I-t curves at a potential of 1.0 V vs. RHE under chopped light illumination for the pristine BiVO4, BiVO4/NiFe-LDH and BiVO4/NiFeCo-LDH photoanodes.

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