Kyoung-Shin Choi

Nanoporous BiVO4 photoanodes with dual-layer oxygen evolution catalysts for solar water splitting.

A Boost for Bismuth Vanadate In theory, given its light-absorption spectrum, bismuth vanadate should be an effective photoanode for solar water-splitting. However, in prior studies, few of the “holes” generated upon photoexcitation have persisted long enough to strip electrons from water. Kim and Choi (p. 990, published online 13 February) now show that the use of a hydrophobic vanadium source in the semiconductors synthesis results in a high-surface-area morphology with substantially enhanced hole lifetimes. Deposition of two successive catalyst layers enhanced the proportion of holes that reacted with water at the surface, thereby raising the efficiency of the oxygen evolution reaction. A high-surface-area morphology of bismuth vanadate enhances the proportion of photogenerated holes that can oxidize water. Bismuth vanadate (BiVO4) has a band structure that is well-suited for potential use as a photoanode in solar water splitting, but it suffers from poor electron-hole separation. Here, we demonstrate that a nanoporous morphology (specific surface area of 31.8 square meters per gram) effectively suppresses bulk carrier recombination without additional doping, manifesting an electron-hole separation yield of 0.90 at 1.23 volts (V) versus the reversible hydrogen electrode (RHE). We enhanced the propensity for surface-reaching holes to instigate water-splitting chemistry by serially applying two different oxygen evolution catalyst (OEC) layers, FeOOH and NiOOH, which reduces interface recombination at the BiVO4/OEC junction while creating a more favorable Helmholtz layer potential drop at the OEC/electrolyte junction. The resulting BiVO4/FeOOH/NiOOH photoanode achieves a photocurrent density of 2.73 milliamps per square centimenter at a potential as low as 0.6 V versus RHE.

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.

Photochemical deposition of cobalt-based oxygen evolving catalyst on a semiconductor photoanode for solar oxygen production

This study describes the photochemical deposition of Co-based oxygen evolution catalysts on a semiconductor photoanode for use in solar oxygen evolution. In the photodeposition process, electron-hole pairs are generated in a semiconductor upon illumination and the photogenerated holes are used to oxidize Co2+ ions to Co3+ ions, resulting in the precipitation of Co3+-based catalysts on the semiconductor surface. Both photodeposition of the catalyst and solar O2 evolution are photo-oxidation reactions using the photogenerated holes. Therefore, photodeposition provides an efficient way to couple oxygen evolution catalysts with photoanodes by naturally placing catalysts at the locations where the holes are most readily available for solar O2 evolution. In this study Co-based catalysts were photochemically deposited as 10–30 nm nanoparticles on the ZnO surface. The comparison of the photocurrent-voltage characteristics of the ZnO electrodes with and without the presence of the Co-based catalyst demonstrated that the catalyst generally enhanced the anodic photocurrent of the ZnO electrode with its effect more pronounced when the band bending is less significant. The presence of Co-based catalyst on the ZnO photoanode also shifted the onset potential of the photocurrent by 0.23 V to the negative direction, closer to the flat band potential. These results demonstrated that the cobalt-based catalyst can efficiently use the photogenerated holes in ZnO to enhance solar O2 evolution. The photodeposition method described in this study can be used as a general route to deposit the Co-based catalysts on any semiconductor electrode with a valence band edge located at a more positive potential than the oxidation potential of Co2+ ions.

Photocurrent Enhancement of n-Type Cu2O Electrodes Achieved by Controlling Dendritic Branching Growth

Cu(2)O electrodes composed of dendritic crystals were produced electrochemically using a slightly acidic medium (pH 4.9) containing acetate buffer. The buffer played a key role for stabilizing dendritic branching growth as a pH drop during the synthesis prevents formation of morphologically unstable branches and promotes faceted growth. Dendritic branching growth enabled facile coverage of the substrate with Cu(2)O while avoiding growth of a thicker Cu(2)O layer and increasing surface areas. The resulting electrodes showed n-type behavior by generating anodic photocurrent without applying an external bias (zero-bias photocurrent under short-circuit condition) in an Ar-purged 0.02 M K(2)SO(4) solution. The zero-bias photocurrent of crystalline dendritic electrodes was significantly higher than that of the electrodes containing micrometer-size faceted crystals deposited without buffer. In order to enhance photocurrent further a strategy of improving charge-transport properties by increasing dendritic crystal domain size was investigated. Systematic changes in nucleation density and size of the dendritic Cu(2)O crystals were achieved by altering the deposition potential, Cu(2+) concentration, and acetate concentration. Increasing dendritic crystal size consistently resulted in the improvement of photocurrent regardless of the method used to regulate crystal size. The electrode composed of dendritic crystals with the lateral dimension of ca. 12000 microm(2) showed more than 20 times higher zero-bias photocurrent than that composed of dendritic crystals with the lateral dimension of ca. 100 microm(2). The n-type nature of the Cu(2)O electrodes prepared by this study were confirmed by linear sweep voltammetry with chopped light and capacitance measurements (i.e., Mott-Schottky plots). The flatband potential in a 0.2 M K(2)SO(4) solution (pH 6) was estimated to be -0.78 vs Ag/AgCl reference electrode. The IPCE measured without applying an external bias was approximately 1% for the visible region. With appropriate doping studies and surface treatment to improve charge transport and interfacial kinetics more efficient n-type Cu(2)O electrodes will be prepared for use in various photoelectrochemical and photovoltaic devices.

P-type Cu--Ti--O nanotube arrays and their use in self-biased heterojunction photoelectrochemical diodes for hydrogen generation.

Copper and titanium remain relatively plentiful in the earths crust; hence, their use for large-scale solar energy conversion technologies is of significant interest. We describe fabrication of vertically oriented p-type Cu-Ti-O nanotube array films by anodization of copper rich (60% to 74%) Ti metal films cosputtered onto fluorine doped tin oxide (FTO) coated glass. Cu-Ti-O nanotube array films 1 mum thick exhibit external quantum efficiencies up to 11%, with a spectral photoresponse indicating that the complete visible spectrum, 380 to 885 nm, contributes significantly to the photocurrent generation. Water-splitting photoelectrochemical pn-junction diodes are fabricated using p-type Cu-Ti-O nanotube array films in combination with n-type TiO 2 nanotube array films. With the glass substrates oriented back-to-back, light is incident upon the UV absorbing n-TiO 2 side, with the visible light passing to the p-Cu-Ti-O side. In a manner analogous to photosynthesis, photocatalytic reactions are powered only by the incident light to generate fuel with oxygen evolved from the n-TiO 2 side of the diode and hydrogen from the p-Cu-Ti-O side. To date, we find under global AM 1.5 illumination that such photocorrosion-stable diodes generate a photocurrent of approximately 0.25 mA/cm (2), at a photoconversion efficiency of 0.30%.

Electrochemical Synthesis of Photoelectrodes and Catalysts for Use in Solar Water Splitting.

This review focuses on introducing and explaining electrodepostion mechanisms and electrodeposition-based synthesis strategies used for the production of catalysts and semiconductor electrodes for use in water-splitting photoelectrochemical cells (PECs). It is composed of three main sections: electrochemical synthesis of hydrogen evolution catalysts, oxygen evolution catalysts, and semiconductor electrodes. The semiconductor section is divided into two parts: photoanodes and photocathodes. Photoanodes include n-type semiconductor electrodes that can perform water oxidation to O2 using photogenerated holes, while photocathodes include p-type semiconductor electrodes that can reduce water to H2 using photoexcited electrons. For each material type, deposition mechanisms were reviewed first followed by a brief discussion on its properties relevant to electrochemical and photoelectrochemical water splitting. Electrodeposition or electrochemical synthesis is an ideal method to produce individual components and integrated systems for PECs due to its various intrinsic advantages. This review will serve as a good resource or guideline for researchers who are currently utilizing electrochemical synthesis as well as for those who are interested in beginning to employ electrochemical synthesis for the construction of more efficient PECs.

A new electrochemical synthesis route for a BiOI electrode and its conversion to a highly efficient porous BiVO4 photoanode for solar water oxidation

A new electrodeposition condition utilizing p-benzoquinone reduction was developed to produce BiOI electrodes composed of extremely thin 2D BiOI crystals. These electrodes served as precursors to form porous BiVO4 electrodes via mild chemical and thermal treatments. The resulting porous BiVO4 electrodes showed outstanding photoelectrochemical performance for sulfite oxidation reaching 1.25 mA cm−2 at 0.5 V vs. RHE in 0.1 M potassium phosphate buffer (pH 7) containing 0.1 M sodium sulfite. When a ca. 100 nm thick FeOOH layer was deposited on the surface of BiVO4 as an oxygen evolution catalyst, the kinetics of water oxidation was improved to the level of sulfite oxidation and the maximum power point for solar water oxidation was achieved at a bias as low as 0.55 V vs. RHE with a photocurrent density of 1.17 mA cm−2. The remarkable solar water oxidation performance achieved by the porous BiVO4–FeOOH system strongly encourages further morphological and compositional optimizations of the BiVO4-based photoanode systems to realize highly efficient and practical solar water oxidation.

Simultaneous enhancements in photon absorption and charge transport of bismuth vanadate photoanodes for solar water splitting

n-Type bismuth vanadate has been identified as one of the most promising photoanodes for use in a water-splitting photoelectrochemical cell. The major limitation of BiVO4 is its relatively wide bandgap (∼2.5 eV), which fundamentally limits its solar-to-hydrogen conversion efficiency. Here we show that annealing nanoporous bismuth vanadate electrodes at 350 °C under nitrogen flow can result in nitrogen doping and generation of oxygen vacancies. This gentle nitrogen treatment not only effectively reduces the bandgap by ∼0.2 eV but also increases the majority carrier density and mobility, enhancing electron–hole separation. The effect of nitrogen incorporation and oxygen vacancies on the electronic band structure and charge transport of bismuth vanadate are systematically elucidated by ab initio calculations. Owing to simultaneous enhancements in photon absorption and charge transport, the applied bias photon-to-current efficiency of nitrogen-treated BiVO4 for solar water splitting exceeds 2%, a record for a single oxide photon absorber, to the best of our knowledge.

Electrochemical Synthesis of Spinel Type ZnCo2O4 Electrodes for Use as Oxygen Evolution Reaction Catalysts.

A new electrochemical synthesis route was developed to prepare spinel-type ZnCo2O4 and Co3O4 as high quality thin film-type electrodes for use as electrocatalysts for oxygen evolution reaction (OER). Whereas Co3O4 contains Co(2+) in the tetrahedral sites and Co(3+) in the octahedral sites in the spinel structure, ZnCo2O4 contains only Co(3+) in the octahedral sites; Co(2+) in the tetrahedral sites is replaced by Zn(2+). Therefore, by comparing the catalytic properties of ZnCo2O4 and Co3O4 electrodes prepared with comparable surface morphologies and thicknesses, it was possible to examine whether Co(2+) in Co3O4 is catalytically active for OER. The electrocatalytic properties of ZnCo2O4 and Co3O4 for OER in both 1 M KOH (pH 13.8) and 0.1 M phosphate buffer (pH 7) solutions were investigated and compared. The results suggest that the Co(2+) in Co3O4 is not catalytically critical for OER and ZnCo2O4 can be a more economical and environmentally benign replacement for Co3O4 as an OER catalyst.

Electrochemical Synthesis of p-Type CuFeO2 Electrodes for Use in a Photoelectrochemical Cell

A new electrodeposition route was developed to prepare p-type CuFeO2 as a thin film-type electrode for use as a photocathode in a solar water splitting cell. The resulting p-CuFeO2 film has a bandgap energy of ca. 1.55 eV, with its conduction band edge located at a more negative potential than the reduction potential of water. Various photoelectrochemical properties of the p-CuFeO2 electrode were investigated, and its photoelectrochemical hydrogen production in 1 M NaOH solution was confirmed by gas chromatography. The incident photon-to-current conversion efficiency plot confirmed that p-CuFeO2 has the ability to utilize the entire range of visible light.