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


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 Natural Science Foundation of China(21476024,21576008,91334203,91634116)

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.


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.


Supplementary information

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


[1] Kudo A, Miseki Y. Heterogeneous photocatalyst materials for water splitting. Chem Soc Rev, 2009, 38: 253-278 CrossRef PubMed Google Scholar

[2] Tao J, Luttrell T, Batzill M. A two-dimensional phase of TiO2 with a reduced bandgap. Nat Chem, 2011, 3: 296-300 CrossRef PubMed ADS Google Scholar

[3] Chen X, Shen S, Guo L, et al. Semiconductor-based photocatalytic hydrogen generation. Chem Rev, 2010, 110: 6503-6570 CrossRef PubMed Google Scholar

[4] Liu Y, Shrestha S, Mustain W. Synthesis of nanosize tungsten oxide and its evaluation as an electrocatalyst support for oxygen reduction in acid media. ACS Catal, 2012, 2: 456-463 CrossRef Google Scholar

[5] Ping Y, Rocca D, Galli G. Electronic excitations in light absorbers for photoelectrochemical energy conversion: first principles calculations based on many body perturbation theory. Chem Soc Rev, 2013, 42: 2437-2469 CrossRef PubMed Google Scholar

[6] Liu F, Chen X, Xia Q, et al. Ultrathin tungsten oxide nanowires: oleylamine assisted nonhydrolytic growth, oxygen vacancies and good photocatalytic properties. RSC Adv, 2015, 5: 77423-77428 CrossRef Google Scholar

[7] Zheng H, Ou J, Strano M, et al. Nanostructured tungsten oxide-properties, synthesis, and applications. Adv Funct Mater, 2011, 21: 2175-2196 CrossRef Google Scholar

[8] Zheng J, Haider Z, Van T, et al. Tuning of the crystal engineering and photoelectrochemical properties of crystalline tungsten oxide for optoelectronic device applications. CrystEngComm, 2015, 17: 6070-6093 CrossRef Google Scholar

[9] Miseki Y, Kusama H, Sugihara H, et al. Cs-modified WO3 photocatalyst showing efficient solar energy conversion for O2 production and Fe (III) ion reduction under visible light. J Phys Chem Lett, 2010, 1: 1196-1200 CrossRef Google Scholar

[10] Liu Y, Li J, Li W, et al. Enhancement of the photoelectrochemical performance of WO3 vertical arrays film for solar water splitting by gadolinium doping. J Phys Chem C, 2015, 119: 14834-14842 CrossRef Google Scholar

[11] Phuruangrat A, Ham D, Hong S, et al. Synthesis of hexagonal WO3 nanowires by microwave-assisted hydrothermal method and their electrocatalytic activities for hydrogen evolution reaction. J Mater Chem, 2010, 20: 1683-1690 CrossRef Google Scholar

[12] Wang N, Wang D, Li M, et al. Photoelectrochemical water oxidation on photoanodes fabricated with hexagonal nanoflower and nanoblock WO3. Nanoscale, 2014, 6: 2061-2066 CrossRef PubMed ADS Google Scholar

[13] Khajeh Aminian M, Hakimi M. Surface modification by loading alkaline hydroxides to enhance the photoactivity of WO3. Catal Sci Technol, 2014, 4: 657-664 CrossRef Google Scholar

[14] Rao P, Cai L, Liu C, et al. Simultaneously efficient light absorption and charge separation in WO3/BiVO4 core/shell nanowire photoanode for photoelectrochemical water oxidation. Nano Lett, 2014, 14: 1099-1105 CrossRef PubMed ADS Google Scholar

[15] Chang X, Sun S, Zhou Y, et al. Solvothermal synthesis of Ce-doped tungsten oxide nanostructures as visible-light-driven photocatalysts. Nanotechnology, 2011, 22: 265603 CrossRef PubMed ADS Google Scholar

[16] Janáky C, Rajeshwar K, de Tacconi N, et al. Tungsten-based oxide semiconductors for solar hydrogen generation. Catal Today, 2013, 199: 53-64 CrossRef Google Scholar

[17] Muthu Karuppasamy K, Subrahmanyam A. The electrochromic and photocatalytic properties of electron beam evaporated vanadium-doped tungsten oxide thin films. Sol Energ Mater Sol Cells, 2008, 92: 1322-1326 CrossRef Google Scholar

[18] Vernardou D, Drosos H, Spanakis E, et al. Electrochemical and photocatalytic properties of WO3 coatings grown at low temperatures. J Mater Chem, 2011, 21: 513-517 CrossRef Google Scholar

[19] Liu Y, Li Y, Li W, et al. Photoelectrochemical properties and photocatalytic activity of nitrogen-doped nanoporous WO3 photoelectrodes under visible light. Appl Surf Sci, 2012, 258: 5038-5045 CrossRef ADS Google Scholar

[20] Sun Y, Murphy C, Reyes-Gil K, et al. Photoelectrochemical and structural characterization of carbon-doped WO3 films prepared via spray pyrolysis. Int J Hydrogen Energ, 2009, 34: 8476-8484 CrossRef Google Scholar

[21] Upadhyay S, Mishra R, Sahay P. Structural and alcohol response characteristics of Sn-doped WO3 nanosheets. Sensors Actuators B-Chem, 2014, 193: 19-27 CrossRef Google Scholar

[22] Zhang T, Zhu Z, Chen H, et al. Iron-doping-enhanced photoelectrochemical water splitting performance of nanostructured WO3: a combined experimental and theoretical study. Nanoscale, 2015, 7: 2933-2940 CrossRef PubMed ADS Google Scholar

[23] Wang F, Di Valentin C, Pacchioni G. Doping of WO3 for photocatalytic water splitting: hints from density functional theory. J Phys Chem C, 2012, 116: 8901-8909 CrossRef Google Scholar

[24] Modak B, Ghosh S. Enhancement of visible light photocatalytic activity of SrTiO3 : a hybrid density functional study. J Phys Chem C, 2015, 119: 23503-23514 CrossRef Google Scholar

[25] Liew S, Zhang Z, Goh T, et al. Yb-doped WO3 photocatalysts for water oxidation with visible light. Int J Hydrogen Energ, 2014, 39: 4291-4298 CrossRef Google Scholar

[26] Guo C, Yin S, Dong Q, et al. Near-infrared absorption properties of RbxWO3 nanoparticles. CrystEngComm, 2012, 14: 7727-7732 CrossRef Google Scholar

[27] Wu X, Yin S, Xue D, et al. A CsxWO3/ZnO nanocomposite as a smart coating for photocatalytic environmental cleanup and heat insulation. Nanoscale, 2015, 7: 17048-17054 CrossRef PubMed ADS Google Scholar

[28] Li W, Da P, Zhang Y, et al. WO3 nanoflakes for enhanced photoelectrochemical conversion. ACS Nano, 2014, 8: 11770-11777 CrossRef PubMed Google Scholar

[29] Chen Z, Wang Q, Wang H, et al. Ultrathin PEGylated W18O49 nanowires as a new 980 nm-laser-driven photothermal agent for efficient ablation of cancer cells in vivo. Adv Mater, 2013, 25: 2095-2100 CrossRef PubMed Google Scholar

[30] Zhao J, Zhang L, Xing W, et al. A novel method to prepare B/N codoped anatase TiO2. J Phys Chem C, 2015, 119: 7732-7737 CrossRef Google Scholar

[31] Fang Y, Cheng D, Wu W. Understanding electronic and optical properties of N–Sn codoped anatase TiO2. Comp Mater Sci, 2014, 85: 264-268 CrossRef Google Scholar

[32] Fang Y, Cheng D, Niu M, et al. Tailoring the electronic and optical properties of rutile TiO2 by (Nb+Sb, C) codoping from DFT+U calculations. Chem Phys Lett, 2013, 567: 34-38 CrossRef ADS Google Scholar

[33] Gai Y, Li J, Li S, et al. Design of narrow-gap TiO2: a passivated codoping approach for enhanced photoelectrochemical activity. Phys Rev Lett, 2009, 102: 036402 CrossRef PubMed ADS Google Scholar

[34] Belošević-Čavor J, Batalović K, Koteski V, et al. Enhancing photocatalytic properties of rutile TiO2 by codoping with N and metals – ab initio study. Int J Hydrogen Energ, 2015, 40: 9696-9703 CrossRef Google Scholar

[35] Ma X, Wu Y, Lu Y, et al. Effect of compensated codoping on the photoelectrochemical properties of anatase TiO2 photocatalyst. J Phys Chem C, 2011, 115: 16963-16969 CrossRef Google Scholar

[36] Yin W, Tang H, Wei S, et al. Band structure engineering of semiconductors for enhanced photoelectrochemical water splitting: the case of TiO2. Phys Rev B, 2010, 82: 045106 CrossRef ADS Google Scholar

[37] Niu M, Xu W, Shao X, et al. Enhanced photoelectrochemical performance of rutile TiO2 by Sb–N donor-acceptor coincorporation from first principles calculations. Appl Phys Lett, 2011, 99: 203111 CrossRef ADS Google Scholar

[38] Wang J, Meng Q, Huang J, et al. Band structure engineering of anatase TiO2 by metal-assisted P–O coupling. J Chem Phys, 2014, 140: 174705 CrossRef PubMed ADS Google Scholar

[39] Niu M, Cheng D, Cao D. Understanding photoelectrochemical properties of B–N codoped anatase TiO2 for solar energy conversion. J Phys Chem C, 2013, 117: 15911-15917 CrossRef Google Scholar

[40] Kresse G, Furthmüller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B, 1996, 54: 11169-11186 CrossRef ADS Google Scholar

[41] Vanderbilt D. Soft self-consistent pseudopotentials in a generalized eigenvalue formalism. Phys Rev B, 1990, 41: 7892-7895 CrossRef ADS Google Scholar

[42] Hammer B, Hansen L, Nørskov J. Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals. Phys Rev B, 1999, 59: 7413-7421 CrossRef ADS Google Scholar

[43] Monkhorst H, Pack J. Special points for Brillouin-zone integrations. Phys Rev B, 1976, 13: 5188-5192 CrossRef ADS Google Scholar

[44] Heyd J, Scuseria G, Ernzerhof M. Hybrid functionals based on a screened Coulomb potential. J Chem Phys, 2003, 118: 8207-8215 CrossRef ADS Google Scholar

[45] Paier J, Marsman M, Hummer K, et al. Screened hybrid density functionals applied to solids. J Chem Phys, 2006, 124: 154709-154709 CrossRef PubMed ADS Google Scholar

[46] Cole B, Marsen B, Miller E, et al. Evaluation of nitrogen doping of tungsten oxide for photoelectrochemical water splitting. J Phys Chem C, 2008, 112: 5213-5220 CrossRef Google Scholar

[47] Liu K, Foord D, Scipioni L. Easy growth of undoped and doped tungsten oxide nanowires with high purity and orientation. Nanotechnology, 2005, 16: 10-14 CrossRef ADS Google Scholar

[48] Magrasó A, Haugsrud R. Effects of the La/W ratio and doping on the structure, defect structure, stability and functional properties of proton-conducting lanthanum tungstate La28−xW4+xO54+δ. A review. J Mater Chem A, 2014, 2: 12630-12641 CrossRef Google Scholar

[49] Liu P, Nisar J, Pathak B, et al. Hybrid density functional study on SrTiO3 for visible light photocatalysis. Int J Hydrogen Energ, 2012, 37: 11611-11617 CrossRef Google Scholar

[50] Gerand B, Nowogrocki G, Guenot J, et al. Structural study of a new hexagonal form of tungsten trioxide. J Solid State Chem, 1979, 29: 429-434 CrossRef ADS Google Scholar

[51] Migas D, Shaposhnikov V, Rodin V, et al. Tungsten oxides. I. Effects of oxygen vacancies and doping on electronic and optical properties of different phases of WO3. J Appl Phys, 2010, 108: 093713-093713 CrossRef ADS Google Scholar

[52] Prévot M, Sivula K. Photoelectrochemical tandem cells for solar water splitting. J Phys Chem C, 2013, 117: 17879-17893 CrossRef Google Scholar

[53] Yang C, Chen J, Zeng X, et al. Design of the alkali-metal-doped WO3 as a near-infrared shielding material for smart window. Ind Eng Chem Res, 2014, 53: 17981-17988 CrossRef Google Scholar

[54] Yang K, Dai Y, Huang B, et al. Density functional characterization of the band edges, the band gap states, and the preferred doping sites of halogen-doped TiO2. Chem Mater, 2008, 20: 6528-6534 CrossRef Google Scholar

[55] Niu M, Cheng D, Cao D. Enhanced photoelectrochemical performance of anatase TiO2 by metal-assisted S–O coupling for water splitting. Int J Hydrogen Energ, 2013, 38: 1251-1257 CrossRef Google Scholar

[56] Szilágyi I, Fórizs B, Rosseler O, et al. WO3 photocatalysts: influence of structure and composition. J Catal, 2012, 294: 119-127 CrossRef Google Scholar

  • 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 (, , and ), formation energy () of pure and S-, Sn-, Pb-monodoped, and (Sn, S)- and (Pb, S)-codoped h-WO

    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)


































    (Sn, S)-codoped






    (Pb, S)-codoped






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