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Title: BiVO4–Liquid Junction Photovoltaic Cell with 0.2% Solar Energy Conversion Efficiency

Journal Article · · Journal of the American Chemical Society

BiVO4 is an important photoanode material for water oxidation, but its photoelectrochemistry regarding the triiodide/iodide redox couple is not well understood. Here, we use a combination of open circuit potential measurements, photoelectrochemical scans, and liquid surface photovoltage spectroscopy (SPS) to confirm that BiVO4/triiodide/iodide electrolyte contacts produce up to 0.55 V photovoltage under 23 mW/cm–2 illumination from a 470 nm LED. Inspired by these results, we construct FTO/BiVO4/KI(I2)aq/Pt sandwich photoelectrochemical cells from electrochemically grown 0.5 × 0.5 cm2 BiVO4 and Mo-doped BiVO4 films. Under AM 1.5 illumination, the devices have up to 0.22% energy conversion efficiency, 0.32 V photovoltage, and 1.8 mA cm–2 photocurrent. Based on SPS, hole transfer to iodide is sufficiently fast to prevent the competing water oxidation reaction. Mo doping increases the incident photon-to-current efficiency to up to 55% (at 425 nm under front illumination) by improving the BiVO4 conductivity, but this comes at the expense of a lower photovoltage resulting from recombination at the Mo defects and a detrimental Schottky junction at the interface with FTO. Additional photovoltage losses are caused by the offset between the BiVO4 valence band edge and the triiodide/iodide electrochemical potential and by electron back transfer to iodide at the FTO back contact (shunting). Overall, this work provides the first example of a BiVO4–liquid photovoltaic cell and an analysis of its limitations. Finally, even though the larger band gaps of metal oxides constrain their solar energy conversion efficiency, their transparency to visible light and deep valence bands makes them suitable for tandem photovoltaic devices.

Research Organization:
Michigan State Univ., East Lansing, MI (United States); Univ. of California, Davis, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
SC0015329; SC0017342
OSTI ID:
2341755
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 47 Vol. 145; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (44)

Efficient BiVO 4 Thin Film Photoanodes Modified with Cobalt Phosphate Catalyst and W-doping journal November 2012
13.6% Efficient Organic Dye-Sensitized Solar Cells by Minimizing Energy Losses of the Excited State journal March 2019
Recent theoretical progress in the development of photoanode materials for solar water splitting photoelectrochemical cells journal January 2015
Redox-Based Visible-Light-Driven Z-Scheme Overall Water Splitting with Apparent Quantum Efficiency Exceeding 10% journal November 2018
Progress in bismuth vanadate photoanodes for use in solar water oxidation journal January 2013
The renaissance of dye-sensitized solar cells journal February 2012
Adaptive semiconductor/electrocatalyst junctions in water-splitting photoanodes journal December 2013
Particulate Photocatalyst Sheets Based on Carbon Conductor Layer for Efficient Z-Scheme Pure-Water Splitting at Ambient Pressure journal January 2017
Principles of Photoelectrochemical Cells book January 2011
Efficient and Stable Photo-Oxidation of Water by a Bismuth Vanadate Photoanode Coupled with an Iron Oxyhydroxide Oxygen Evolution Catalyst journal January 2012
The effect of co-catalyst for Z-scheme photocatalysis systems with an Fe3+/Fe2+ electron mediator on overall water splitting under visible light irradiation journal October 2008
Photochemical Charge Separation and Dye Self-Oxidation Control Performance of Fluorescein, Rose Bengal, and Triphenylamine Dye-Sensitized Solar Cells journal November 2020
The Origin of Slow Carrier Transport in BiVO 4 Thin Film Photoanodes: A Time-Resolved Microwave Conductivity Study journal July 2013
Fermi Level Pinning Controls Band Bending and Photochemical Charge Separation in Particles of n -SrTiO 3 , n -SrTiO 3 :Al, and n -GaAs:Te journal July 2020
Use of Surface Photovoltage Spectroscopy to Measure Built-in Voltage, Space Charge Layer Width, and Effective Band Gap in CdSe Quantum Dot Films journal August 2016
Surface photovoltage spectroscopy observes junctions and carrier separation in gallium nitride nanowire arrays for overall water-splitting journal October 2020
Current and Voltage Limiting Processes in Thin Film Hematite Electrodes journal March 2011
Photoelectrolysis of water in cells with TiO2 anodes journal October 1975
Hydrogen evolution with fluorescein-sensitized Pt/SrTiO3 nanocrystal photocatalysts is limited by dye adsorption and regeneration journal September 2020
Combined Charge Carrier Transport and Photoelectrochemical Characterization of BiVO 4 Single Crystals: Intrinsic Behavior of a Complex Metal Oxide journal July 2013
Semiconductors' Photoelectrochemistry:  A Kinetic and Thermodynamic Analysis in the Light of Equilibrium and Nonequilibrium Models journal June 2001
Nanoporous BiVO4 Photoanodes with Dual-Layer Oxygen Evolution Catalysts for Solar Water Splitting journal February 2014
Efficient Photocatalytic Degradation of Phenol over Co 3 O 4 /BiVO 4 Composite under Visible Light Irradiation journal October 2006
Band Edge Electronic Structure of BiVO 4 : Elucidating the Role of the Bi s and V d Orbitals journal February 2009
Photoinduced charge transfer processes at semiconductor electrodes and particles book January 1994
The end of iodide? Cobalt complex redox shuttles in DSSCs journal January 2012
Visible Light Induced Photoelectrochemical Properties of n-BiVO 4 and n-BiVO 4 /p-Co 3 O 4 journal January 2008
Contactless measurement of the photovoltage in BiVO4 photoelectrodes journal January 2023
Construction of Z-scheme Type Heterogeneous Photocatalysis Systems for Water Splitting into H 2 and O 2 under Visible Light Irradiation journal October 2004
Near-Complete Suppression of Surface Recombination in Solar Photoelectrolysis by “Co-Pi” Catalyst-Modified W:BiVO 4 journal November 2011
Elaborately Modified BiVO 4 Photoanodes for Solar Water Splitting journal December 2018
Photoelectrochemical hydrogen evolution and water photolyzing semiconductor suspensions: properties of platinum group metal catalyst-semiconductor contacts in air and in hydrogen journal November 1983
Surface Interrogation Scanning Electrochemical Microscopy (SI-SECM) of Photoelectrochemistry at a W/Mo-BiVO 4 Semiconductor Electrode: Quantification of Hydroxyl Radicals during Water Oxidation journal May 2013
Photoelectrochemical Water Splitting System—A Study of Interfacial Charge Transfer with Scanning Electrochemical Microscopy journal January 2016
Kinetics of Regeneration and Recombination Reactions in Dye-Sensitized Solar Cells Employing Cobalt Redox Shuttles journal December 2015
A Novel Aqueous Process for Preparation of Crystal Form-Controlled and Highly Crystalline BiVO 4 Powder from Layered Vanadates at Room Temperature and Its Photocatalytic and Photophysical Properties journal December 1999
Highly Improved Quantum Efficiencies for Thin Film BiVO 4 Photoanodes journal August 2011
Advancing beyond current generation dye-sensitized solar cells journal January 2008
Semiconductor Electrodes: VI . A Photoelectrochemical Solar Cell Employing a Anode and Oxygen Cathode journal July 1976
Textured nanoporous Mo:BiVO 4 photoanodes with high charge transport and charge transfer quantum efficiencies for oxygen evolution journal January 2016
Ln10S14O (Ln = La, Pr, Nd, Sm) Oxysulfides: A Series of Direct n-Type Semiconductors journal August 2022
Effect of charge selective contacts on the quasi Fermi level splitting of CuGa3Se5 thin film photocathodes for hydrogen evolution and methylviologen reduction journal January 2023
Photocatalytic O2 evolution under visible light irradiation on BiVO4 in aqueous AgNO3 solution journal January 1998
Development of New Photocatalytic Water Splitting into H 2 and O 2 using Two Different Semiconductor Photocatalysts and a Shuttle Redox Mediator IO 3 - /I - journal August 2005