Selective and Efficient Gd-Doped BiVO4 Photoanode for Two-Electron Water Oxidation to H2O2

Photoelectrochemical oxidation of water presents a pathway for sustainable production of hydrogen peroxide (H2O2). Two-electron water oxidation toward H2O2, however, competes with the popular four-electron process to form oxygen and one-electron water oxidation to form OH radical. To date, bismuth vanadate (BiVO4) has been shown to exhibit promising selectivity toward H2O2, especially under illumination, but it suffers from high overpotential and notoriously poor stability. Herein, using density functional theory calculations, we predict that doping BiVO4 with optimal concentrations of gadolinium (Gd) not only enhances its activity for H2O2 production but also improves its stability. Experimentally, we demonstrate that intermediate amounts of Gd doping (6–12%) reduce the onset potential of BiVO4 for H2O2 production by ∼110 mV while achieving a Faradaic efficiency of ∼99.5% under illumination and prolonging the catalytic lifetime by more than a factor of 20 at 2.0 V vs RHE under illumination.

[1]  Yi Xie,et al.  Electronic Supplementary Information Synthetic Loose-packed Monoclinic Bivo 4 Nanoellipsoids with Novel Multiresponses to Visible Light, Trace Gas and Temperature , 2022 .

[2]  J. Fierro,et al.  Hydrogen peroxide synthesis: an outlook beyond the anthraquinone process. , 2006, Angewandte Chemie.

[3]  Xiaolin Zheng,et al.  Light‐Driven BiVO4–C Fuel Cell with Simultaneous Production of H2O2 , 2018, Advanced Energy Materials.

[4]  Y. Ando,et al.  Proposal for a new system for simultaneous production of hydrogen and hydrogen peroxide by water electrolysis , 2004 .

[5]  Xiaolin Zheng,et al.  Enabling silicon photoanodes for efficient solar water splitting by electroless-deposited nickel , 2018, Nano Research.

[6]  F. d’Acapito,et al.  Doping porous silicon with erbium: pores filling as a method to limit the Er-clustering effects and increasing its light emission , 2017, Scientific Reports.

[7]  Kyoung-Shin Choi,et al.  Enhancing long-term photostability of BiVO4 photoanodes for solar water splitting by tuning electrolyte composition , 2018 .

[8]  Kazuhiro Sayama,et al.  Photoelectrochemical Hydrogen Peroxide Production from Water on a WO3 /BiVO4 Photoanode and from O2 on an Au Cathode Without External Bias. , 2017, Chemistry, an Asian journal.

[9]  Andreas Greiner,et al.  Unusual complex chemistry of rare-Earth elements: large ionic radii-small coordination numbers. , 2003, Angewandte Chemie.

[10]  M. Matsumura,et al.  Quantitative analysis of superoxide ion and hydrogen peroxide produced from molecular oxygen on photoirradiated TiO2 particles , 2004 .

[11]  Edward Sanville,et al.  Improved grid‐based algorithm for Bader charge allocation , 2007, J. Comput. Chem..

[12]  Jens K Nørskov,et al.  Selective Electrochemical Generation of Hydrogen Peroxide from Water Oxidation. , 2015, The journal of physical chemistry letters.

[13]  Guoqiang Tan,et al.  A comprehensive investigation of tetragonal Gd-doped BiVO4 with enhanced photocatalytic performance under sun-light , 2016 .

[14]  John Kitchin,et al.  Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces , 2011 .

[15]  S. Beg,et al.  Study of electrical conductivity and phase transition in Bi2O3–V2O5 system , 2010 .

[16]  G. Henkelman,et al.  A fast and robust algorithm for Bader decomposition of charge density , 2006 .

[17]  Hyun Suk Jung,et al.  CaSnO3: An Electrocatalyst for Two-Electron Water Oxidation Reaction to Form H2O2 , 2018, ACS Energy Letters.

[18]  Tao Yu,et al.  Solar hydrogen generation from seawater with a modified BiVO4 photoanode , 2011 .

[19]  Jens K Nørskov,et al.  One- or Two-Electron Water Oxidation, Hydroxyl Radical, or H2O2 Evolution. , 2017, The journal of physical chemistry letters.

[20]  F. Abdi,et al.  Spray-deposited Co-Pi Catalyzed BiVO 4 : a low-cost route towards highly efficient photoanodes , 2012 .

[21]  Yusuke Yamada,et al.  Efficient Photocatalytic Production of Hydrogen Peroxide from Water and Dioxygen with Bismuth Vanadate and a Cobalt(II) Chlorin Complex , 2016 .

[22]  A. Kudo,et al.  Selective Preparation of Monoclinic and Tetragonal BiVO4 with Scheelite Structure and Their Photocatalytic Properties , 2001 .

[23]  Yang Li,et al.  Facile fabrication of tetragonal scheelite (t-s) BiVO4/g-C3N4 composites with enhanced photocatalytic performance , 2018 .

[24]  D. Macfarlane,et al.  Low overpotential water oxidation to hydrogen peroxide on a MnOx catalyst , 2012 .

[25]  K. P. Kepp.  A Quantitative Scale of Oxophilicity and Thiophilicity. , 2016, Inorganic chemistry.

[26]  Y. Ping,et al.  Simultaneous enhancements in photon absorption and charge transport of bismuth vanadate photoanodes for solar water splitting , 2015, Nature Communications.

[27]  Thomas F. Jaramillo,et al.  Understanding activity trends in electrochemical water oxidation to form hydrogen peroxide , 2017, Nature Communications.

[28]  G. Wallace,et al.  Sustained solar hydrogen generation using a dye-sensitised NiO photocathode/BiVO4 tandem photo-electrochemical device , 2012 .

[29]  T. Furtak,et al.  Cobalt-phosphate (Co-Pi) catalyst modified Mo-doped BiVO4 photoelectrodes for solar water oxidation , 2011 .

[30]  Kazuhiro Sayama,et al.  Enhanced Oxidative Hydrogen Peroxide Production on Conducting Glass Anodes Modified with Metal Oxides , 2016 .

[31]  G. Henkelman,et al.  A grid-based Bader analysis algorithm without lattice bias , 2009, Journal of physics. Condensed matter : an Institute of Physics journal.

[32]  N. Wang,et al.  Visible light driven overall water splitting using cocatalyst/BiVO4 photoanode with minimized bias. , 2013, Physical chemistry chemical physics : PCCP.

[33]  F. Toma,et al.  Bismuth Vanadate as a Platform for Accelerating Discovery and Development of Complex Transition-Metal Oxide Photoanodes , 2017 .

[34]  Y. Nosaka,et al.  Photocatalytic reactivity for O2•- and OH• radical formation in anatase and rutile TiO2 suspension as the effect of H2O2 addition , 2007 .

[35]  Matthew R. Shaner,et al.  Mechanistic insights into chemical and photochemical transformations of bismuth vanadate photoanodes , 2016, Nature Communications.

[36]  N. Lewis,et al.  Improved Stability of Polycrystalline Bismuth Vanadate Photoanodes by Use of Dual-Layer Thin TiO_2/Ni Coatings , 2014 .