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Enhanced photochemical performance of hexagonal WO3 by metal-assisted S–O coupling for solar-driven water splitting

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  • ReceivedJul 3, 2017
  • AcceptedSep 20, 2017
  • PublishedNov 16, 2017

Abstract

Hybrid density functional calculations was used to comprehensively study the electronic structure of S-, Sn- and Pb-monodoped and (Sn, S)- and (Pb, S)-codoped hexagonal WO3 (h-WO3) in order to improve their visible light photocatalytic activity. Results indicate that the (Sn, S)- and (Pb, S)-codoped h-WO3 can realize a significant band gap reduction and prevent the formation of empty states in the valence band of h-WO3, while Sn/Pb-monodoped h-WO3 cannot, because in (Sn, S)- and (Pb, S)-codoping, the S-doping introduces the fully occupied S 3p states in the forbidden band gap of h-WO3 and the acceptor metals (Sn and Pb) would assist the coupling of the introduced S with its nearest O. In particular, the (Sn, S)-codoped h-WO3 has the narrowest band gap of 1.85 eV and highest reducing ability among the doped case. Moreover, the calculated optical absorption spectra show that (Sn, S)-codoping can improve the visible light absorption. In short, these results indicate that the (Sn, S)-codoped h-WO3 is a promising material in solar-driven water splitting.


Funded by

the National Key Technology Support Program(2014BAE12B01)

the National Natural Science Foundation of China(21476024)

the Fundamental Research Funds for the Central Universities(PYCC1705)

and the “Chemical Grid Project” of BUCT.

Beijing Municipal Science and Technology Project(Z151100003315005)


Acknowledgment

This research is supported by the National Natural Science Foundation of China (21476024, 21576008, 91334203 and 91634116), the National Key Technology Support Program (2014BAE12B01), Beijing Municipal Science and Technology Project (Z151100003315005), the Fundamental Research Funds for the Central Universities (PYCC1705), and the “Chemical Grid Project” of BUCT.


Interest statement

The authors declare that they have no conflict of interest.


Contributions statement

Chen JF proposed and guided the project. Yang C performed the first principle calculations and wrote the paper. Zeng X and Cheng D supervised the project and revised the paper. The final version of the manuscript was approved by all authors.


Author information

Chenxi Yang received his PhD degree in 2016 from Beijing University of Chemical Technology. He is currently a postdoctoral fellow in the Sinopec Beijing Research Institute of Chemical Industry. His research interests focus on the catalysis of metals and oxides.

Jian-Feng Chen is a professor at the Department of Chemical Engineering, Beijing University of Chemical Technology, China. His research focuses on high-gravity technology, particularly on the application of high-gravity technology in reaction and separation process, synthesis of nanomaterials. He has authored more than 300 scientific publications, two monographs and 120 patents.

Xiaofei Zeng is a professor at the Department of Chemical Engineering, Beijing University of Chemical Technology, China. Her research focuses on nanotechnology, particularly on the preparation of inorganic nanoparticles, nanodispersion and their application in organic materials. She has published more than 80 scientific papers and has 20 patents.

Daojian Cheng is currently a professor at the Department of Chemical Engineering, Beijing University of Chemical Technology, China. He is interested in theoretical study, computational design and experimental synthesis of metal clusters and nanoalloys as catalysts for renewable clean energy and environmental protection applications. He has published 100 peer review papers.

Supplement

Supporting data are available in the online version of the paper.


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  • Figure 1

    Perspective view of the 2 × 2 × 1 supercell of h-WO3. The red and light blue spheres represent O and W atom, respectively. O1 is replaced by S atom and W1 is substituted by Sn (Pb) atom in S-containing and Sn (Pb)-containing systems, respectively.

  • Figure 2

    Inner part of the optimized structures of (a) pure h-WO3, (b) S-, (c) Sn- and (d) Pb-monodoped and (e) (Sn, S)- and (f) (Pb, S)-codoped h-WO3. The red, yellow, gray, deep green and light blue spheres represent O, S, Sn, Pb and W atoms, respectively.

  • Figure 3

    The caculated band structres of (a) pure h-WO3, (b) S-, (c) Sn- and (d) Pb-monodoped and (e) (Sn, S)- and (f) (Pb, S)-codoped h-WO3. The red dashed horizontal lines represent the Fermi levels.

  • Figure 4

    The calculated TDOS and PDOS of (a) pure h-WO3, (b) S-monodoped, and (c) (Sn, S)- and (d) (Pb, S)-codoped h-WO3. Only the O 2p and W 5d states of the nearest O and W atoms are presented downward for clarification in (Sn, S)- and (Pb, S)-codoped WO3. The black dashed vertical lines represent the Fermi levels.

  • Figure 5

    Part of charge density profile of the (a) pure h-WO3, (b) S-monodoped, and (c) (Sn, S)- and (d) (Pb, S)-codoped h-WO3 plotted at (001) plane.

  • Figure 6

    Schematic plot of the bonding mechanism for the S atom and its neighboring O atom in (Sn, S)- and (Pb, S)-codoped h-WO3.

  • Figure 7

    Band alignment of undoped, S-monodoped and (Sn, S)- and (Pb, S)-codoped h-WO3. The horizontal dashed lines and plus sign (+) represent the water redox potential levels and upshift of VBM or CBM, respectively.

  • Figure 8

    The calculated optical absorption spectra for pure, S-monodoped and (Sn, S)-codoped h-WO3.

  • Table 1   The calculated lattice parameters (a, b, and c), formation energy (Ef) of pure and S-, Sn-, Pb-monodoped, and (Sn, S)- and (Pb, S)-codoped h-WO3

    a (Å)

    b (Å)

    c (Å)

    EfO-rich (eV)

    EfW-rich (eV)

    Pure h-WO3 (experimental [44])

    Pure h-WO3 (theoretical [45])

    Pure h-WO3 (this work)

    7.298

    7.438

    7.453

    7.298

    7.438

    7.453

    3.899

    3.827

    3.833

    -

    -

    0

    -

    -

    0

    S-monodoped

    7.579

    7.579

    3.806

    2.736

    −0.541

    Sn-monodoped

    7.507

    7.474

    3.847

    −2.943

    6.888

    Pb-monodoped

    7.539

    7.499

    3.861

    −0.871

    5.683

    (Sn, S)-codoped

    7.521

    7.646

    3.793

    −3.756

    2.798

    (Pb, S)-codoped

    7.584

    7.645

    3.797

    −1.565

    4.988

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