Bismuth Vanadate Photoanode Research Articles

Photoelectrochemical performance of W-doped BiVO4 thin films deposited by spray pyrolysis

The effects of tungsten doping and hydrogen annealing on the photoelectrochemical (PEC) performance of bismuth vanadate (BiVO4) photoanodes for solar water splitting were studied. Thin films of BiVO4 were deposited on indium tin oxide-coated glass slides by ultrasonic spray pyrolysis of an aqueous solution containing bismuth nitrate and vanadium oxysulfate. Tungsten doping was achieved by adding either silicotungstic acid (STA) or ammonium metatungstate (AMT) to the precursor. The 1.7- to 2.2-μm-thick films exhibited a highly porous microstructure. Undoped films that were reduced at 375°C in 3% H2 exhibited the largest photocurrent densities under 0.1 W cm−2 AM1.5 illumination, where photocurrent densities of up to 1.3 mA cm−2 at 0.5 V with respect to Ag/AgCl were achieved. Films doped with 1% or 5% (atomic percent) tungsten from either STA or AMT exhibited reduced PEC performance and greater sample-to-sample performance variations. Powder x-ray diffraction data indicated that the films continue to crystallize in the monoclinic polymorph at low doping levels but crystallize in the tetragonal scheelite structure at higher doping. It is surmised that the phase and morphology differences promoted by the addition of W during the deposition process reduced the PEC performance as measured by photovoltammetry.

Optimization of amorphous silicon double junction solar cells for an efficient photoelectrochemical water splitting device based on a bismuth vanadate photoanode

A photoelectrochemical water splitting device (PEC-WSD) was designed and fabricated based on cobalt-phosphate-catalysed and tungsten-gradient-doped bismuth vanadate (W:BiVO4) as the photoanode. A simple and cheap hydrogenated amorphous silicon (a-Si:H) double junction solar cell has been used to provide additional bias. The advantage of using thin film silicon (TF-Si) based solar cells is that this photovoltaic (PV) technology meets the crucial requirements for the PV component in PEC-WSDs based on W:BiVO4 photoanodes. TF-Si PV devices are stable in aqueous solutions, are manufactured by simple and cheap fabrication processes and their spectral response, voltage and current density show an excellent match with the photoanode. This paper is mainly focused on the optimization of the TF-Si solar cell with respect to the remaining solar spectrum transmitted through the W:BiVO4 photoanode. The current matching between the top and bottom cells is studied and optimized by varying the thickness of the a-Si:H top cell. We support the experimental optimization of the current balance between the two sub-cells with simulations of the PV devices. In addition, the impact of the light induced degradation of the a-Si:H double junction, the so-called Staebler-Wronski Effect (SWE), on the performance of the PEC-WSD has been studied. The light soaking experiments on the a-Si:H/a-Si:H double junctions over 1000 hours show that the efficiency of a stand-alone a-Si:H/a-Si:H double junction cell is significantly reduced due to the SWE. Nevertheless, the SWE has a significantly smaller effect on the performance of the PEC-WSD.

Plasmonic enhancement of the optical absorption and catalytic efficiency of BiVO₄ photoanodes decorated with Ag@SiO₂ core-shell nanoparticles.

Recent progress in the development of bismuth vanadate (BiVO4) photoanodes has firmly established it as a promising material for solar water splitting applications. Performance limitations due to intrinsically poor catalytic activity and slow electron transport have been successfully addressed through the application of water oxidation co-catalysts and novel doping strategies. The next bottleneck to tackle is the modest optical absorption in BiVO4, particularly close to its absorption edge of 2.4 eV. Here, we explore the modification of the BiVO4 surface with Ag@SiO2 core-shell plasmonic nanoparticles. A photocurrent enhancement by a factor of ~2.5 is found under 1 sun illumination (AM1.5). We show that this enhancement consists of two contributions: optical absorption and catalysis. The optical absorption enhancement is induced by the excitation of localized surface plasmon resonances in the Ag nanoparticles, and agrees well with our full-field electromagnetic simulations. Far-field effects (scattering) are found to be dominant, with a smaller contribution from near-field plasmonic enhancement. In addition, a significant catalytic enhancement is observed, which is tentatively attributed to the electrocatalytic activity of the Ag@SiO2 nanoparticles.

Efficient solar water splitting by enhanced charge separation in a bismuth vanadate-silicon tandem photoelectrode

Metal oxides are generally very stable in aqueous solutions and cheap, but their photochemical activity is usually limited by poor charge carrier separation. Here we show that this problem can be solved by introducing a gradient dopant concentration in the metal oxide film, thereby creating a distributed n(+)-n homojunction. This concept is demonstrated with a low-cost, spray-deposited and non-porous tungsten-doped bismuth vanadate photoanode in which carrier-separation efficiencies of up to 80% are achieved. By combining this state-of-the-art photoanode with an earth-abundant cobalt phosphate water-oxidation catalyst and a double- or single-junction amorphous Si solar cell in a tandem configuration, stable short-circuit water-splitting photocurrents of ~4 and 3 mA cm(-2), respectively, are achieved under 1 sun illumination. The 4 mA cm(-2) photocurrent corresponds to a solar-to-hydrogen efficiency of 4.9%, which is the highest efficiency yet reported for a stand-alone water-splitting device based on a metal oxide photoanode.

Progress in bismuth vanadate photoanodes for use in solar water oxidation

Harvesting energy directly from sunlight as nature accomplishes through photosynthesis is a very attractive and desirable way to solve the energy challenge. Many efforts have been made to find appropriate materials and systems that can utilize solar energy to produce chemical fuels. One of the most viable options is the construction of a photoelectrochemical cell that can reduce water to H(2) or CO(2) to carbon-based molecules. Bismuth vanadate (BiVO(4)) has recently emerged as a promising material for use as a photoanode that oxidizes water to O(2) in these cells. Significant advancement in the understanding and construction of efficient BiVO(4)-based photoanode systems has been made within a short period of time owing to various newly developed ideas and approaches. In this review, the crystal and electronic structures that are closely related to the photoelectrochemical properties of BiVO(4) are described first, and the photoelectrochemical properties and limitations of BiVO(4) are examined. Subsequently, the latest efforts toward addressing these limitations in order to improve the performances of BiVO(4)-based photoanodes are discussed. These efforts include morphology control, formation of composite structures, composition tuning, and coupling oxygen evolution catalysts. The discussions and insights provided in this review reflect the most recent approaches and directions for general photoelectrode developments and they will be directly applicable for the understanding and improvement of other photoelectrode systems.

Efficient and Stable Photo-Oxidation of Water by a Bismuth Vanadate Photoanode Coupled with an Iron Oxyhydroxide Oxygen Evolution Catalyst

BiVO(4) films were prepared by a simple electrodeposition and annealing procedure and studied as oxygen evolving photoanodes for application in a water splitting photoelectrochemical cell. The resulting BiVO(4) electrodes maintained considerable photocurrent for photo-oxidation of sulfite, but generated significantly reduced photocurrent for photo-oxidation of water to oxygen, also decaying over time, suggesting that the photoelectrochemical performance of BiVO(4) for water oxidation is mainly limited by its poor catalytic ablity to oxidize water. In order to improve the water oxidation kinetics of the BiVO(4) electrode, a layer of FeOOH was placed on the BiVO(4) surface as an oxygen evolution catalyst using a new photodeposition route. The resulting BiVO(4)/FeOOH photoanode exhibitied significantly improved photocurrent and stability for photo-oxidation of water, which is one of the best among all oxide-based phoatoanode systems reported to date. In particular, the BiVO(4)/FeOOH photoanode showed an outstanding performance in the low bias region (i.e., E < 0.8 V vs RHE), which is critical in determining the overall operating current density when assembling a complete p-n photoelectrochemical diode cell. The photocurrent-to-O(2) conversion efficiency of the BiVO(4)/FeOOH photoanode is ca. 96%, confirming that the photogenerated holes in the BiVO(4)/FeOOH photoanode are indeed excusively used for O(2) evolution.