Mamiko Nakabayashi

Surface Modification of CoOx Loaded BiVO4 Photoanodes with Ultrathin p-Type NiO Layers for Improved Solar Water Oxidation

Photoelectrochemical (PEC) devices that use semiconductors to absorb solar light for water splitting offer a promising way toward the future scalable production of renewable hydrogen fuels. However, the charge recombination in the photoanode/electrolyte (solid/liquid) junction is a major energy loss and hampers the PEC performance from being efficient. Here, we show that this problem is addressed by the conformal deposition of an ultrathin p-type NiO layer on the photoanode to create a buried p/n junction as well as to reduce the charge recombination at the surface trapping states for the enlarged surface band bending. Further, the in situ formed hydroxyl-rich and hydroxyl-ion-permeable NiOOH enables the dual catalysts of CoO(x) and NiOOH for the improved water oxidation activity. Compared to the CoO(x) loaded BiVO4 (CoO(x)/BiVO4) photoanode, the ∼6 nm NiO deposited NiO/CoO(x)/BiVO4 photoanode triples the photocurrent density at 0.6 V(RHE) under AM 1.5G illumination and enables a 1.5% half-cell solar-to-hydrogen efficiency. Stoichiometric oxygen and hydrogen are generated with Faraday efficiency of unity over 12 h. This strategy could be applied to other narrow band gap semiconducting photoanodes toward the low-cost solar fuel generation devices.

A Complex Perovskite-Type Oxynitride: The First Photocatalyst for Water Splitting Operable at up to 600 nm†

One of the simplest methods for splitting water into H2 and O2 with solar energy entails the use of a particulate-type semiconductor photocatalyst. To harness solar energy efficiently, a new water-splitting photocatalyst that is active over a wider range of the visible spectrum has been developed. In particular, a complex perovskite-type oxynitride, LaMg(x)Ta(1-x)O(1+3x)N(2-3x)(x≥1/3), can be employed for overall water splitting at wavelengths of up to 600 nm. Two effective strategies for overall water splitting were developed. The first entails the compositional fine-tuning of a photocatalyst to adjust the bandgap energy and position by forming a series of LaMg(x)Ta(1-x)O(1+3x)N(2-3x) solid solutions. The second method is based on the surface coating of the photocatalyst with a layer of amorphous oxyhydroxide to control the surface redox reactions. By combining these two strategies, the degradation of the photocatalyst and the reverse reaction could be prevented, resulting in successful overall water splitting.

Enhancement of Solar Hydrogen Evolution from Water by Surface Modification with CdS and TiO2 on Porous CuInS2 Photocathodes Prepared by an Electrodeposition–Sulfurization Method

Porous films of p-type CuInS2, prepared by sulfurization of electrodeposited metals, are surface-modified with thin layers of CdS and TiO2. This specific porous electrode evolved H2 from photoelectrochemical water reduction under simulated sunlight. Modification with thin n-type CdS and TiO2 layers significantly increased the cathodic photocurrent and onset potential through the formation of a p-n junction on the surface. The modified photocathodes showed a relatively high efficiency and stable H2 production under the present reaction conditions.

Photoelectrochemical oxidation of water using BaTaO2N photoanodes prepared by particle transfer method.

A photoanode of particulate BaTaO2N fabricated by the particle transfer method and modified with a Co cocatalyst generated a photocurrent of 4.2 mA cm(-2) at 1.2 V(RHE) in the photoelectrochemical water oxidation reaction under simulated sunlight (AM1.5G). The half-cell solar-to-hydrogen conversion efficiency (HC-STH) of the photoanode reached 0.7% at 1.0 V(RHE), which was an order of magnitude higher than the previously reported photoanode made from the same material. The faradaic efficiency for oxygen evolution from water was virtually 100% during the reaction for 6 h, attesting to the robustness of the oxynitride.

Mg–Zr Cosubstituted Ta3N5 Photoanode for Lower-Onset-Potential Solar-Driven Photoelectrochemical Water Splitting

In p/n photoelectrochemical (PEC) cell systems, a low onset potential for the photoanode, as well as a high photocurrent, are critical for efficient water splitting. Here, we report a Mg-Zr cosubstituted Ta3N5 (Ta3N5:Mg+Zr) photoanode, designed to provide a more negative onset potential for PEC water splitting. The anodic photocurrent onset on Ta3N5:Mg+Zr was 0.55 V(RHE) under AM 1.5G-simulated sunlight, which represented a negative shift from the ca. 0.8 V(RHE) for pure Ta3N5. This negative shift in the onset potential of PEC water splitting was attributed to the change in the bandgap potential due to partial substitution by the foreign ions Mg(2+) and/or Zr(4+).

Positive onset potential and stability of Cu2O-based photocathodes in water splitting by atomic layer deposition of a Ga2O3 buffer layer

The Cu2O-based photocathode is considered as one of the most promising photocathodes for high performance water splitting under sunlight. However, the relatively negative onset potential for H2 production of these photocathodes impedes further optimization of the solar-to-fuel conversion efficiency. Here, a thin Ga2O3 buffer layer is introduced between the Cu2O absorber layer and the TiO2 protective layer by atomic layer deposition to increase the photovoltage. For the optimized TiO2 deposition temperature, the Pt/TiO2/Ga2O3/Cu2O electrode achieves a high cathodic photocurrent of −2.95 mA cm−2 at 0 V vs. RHE and an extremely positive onset potential of 1.02 V vs. RHE (defined as the potential where photocathodic current reaches 20 μA cm−2 under air-mass 1.5 global illumination), benefiting from a buried p–n junction and a favorable band alignment. The Pt/TiO2/Ga2O3/Cu2O electrodes exhibit a stable cathodic current for 2 h under continuous illumination of a 500 W Xe lamp for the TiO2 deposition temperatures below 180 °C.

Fabrication of a Core–Shell-Type Photocatalyst via Photodeposition of Group IV and V Transition Metal Oxyhydroxides: An Effective Surface Modification Method for Overall Water Splitting

The design of optimal surface structures for photocatalysts is a key to efficient overall water splitting into H2 and O2. A unique surface modification method was devised for a photocatalyst to effectively promote overall water splitting. Photodeposition of amorphous oxyhydroxides of group IV and V transition metals (Ti, Nb, Ta) over a semiconductor photocatalyst from corresponding water-soluble metal peroxide complexes was examined. In this method, amorphous oxyhydroxide covered the whole surface of the photocatalyst particles, creating a core-shell structure. The water splitting behavior of the novel core-shell-type photocatalyst in relation to the permeation behavior of the coating layer was investigated in detail. Overall water splitting proceeded successfully after the photodeposition, owing to the prevention of the reverse reaction. The photodeposited oxyhydroxide layers were found to function as molecular sieves, selectively filtering reactant and product molecules. By exploiting the selective permeability of the coating layer, redox reactions on the photocatalyst surface could be suitably controlled, which resulted in successful overall water splitting.

Highly Active GaN‐Stabilized Ta3N5 Thin‐Film Photoanode for Solar Water Oxidation

Ta3 N5 is a very promising photocatalyst for solar water splitting because of its wide spectrum solar energy utilization up to 600 nm and suitable energy band position straddling the water splitting redox reactions. However, its development has long been impeded by poor compatibility with electrolytes. Herein, we demonstrate a simple sputtering-nitridation process to fabricate high-performance Ta3 N5 film photoanodes owing to successful synthesis of the vital TaOδ precursors. An effective GaN coating strategy is developed to remarkably stabilize Ta3 N5 by forming a crystalline nitride-on-nitride structure with an improved nitride/electrolyte interface. A stable, high photocurrent density of 8 mA cm-2 was obtained with a CoPi/GaN/Ta3 N5 photoanode at 1.2 VRHE under simulated sunlight, with O2 and H2 generated at a Faraday efficiency of unity over 12 h. Our vapor-phase deposition method can be used to fabricate high-performance (oxy)nitrides for practical photoelectrochemical applications.

Band engineering of perovskite-type transition metal oxynitrides for photocatalytic overall water splitting

It has recently been discovered that LaMgxTa1−xO1+3xN2−3x solid solutions act as photocatalysts for water splitting under a wide range of visible wavelengths. In the present study, a detailed characterization of the crystal structure, optical properties, and electronic band structure of these photocatalysts was performed. It was found that increasing the Mg content decreased the N content in the solid solution as a result of co-substitution of Mg2+ for Ta5+ and O2− for N3−, and enabled fine tuning of the bandgap energy and position. The bandgap increased due to a shift in the valence band maximum towards the positive electrode potential, rather than a change in the conduction band minimum. This facilitated water oxidation, and thus overall water splitting. On the basis of this finding, overall water splitting was also achieved for another series of solid solutions, LaScxTa1−xO1+2xN2−2x (x ≥ 0.5).

Enhanced Hydrogen Evolution under Simulated Sunlight from Neutral Electrolytes on (ZnSe)0.85(CuIn0.7Ga0.3Se2)0.15 Photocathodes Prepared by a Bilayer Method

A (ZnSe)0.85 (CuIn0.7 Ga0.3 Se2 )0.15 photocathode with a bilayer structure was fabricated and found to exhibit a photocurrent almost twice that of a photocathode with a monolayer structure during hydrogen evolution from water. The cathodic photocurrent reached maximum values of 12 and 4.9 mA cm-2 at 0 and 0.6 VRHE in a neutral phosphate buffer under simulated sunlight, while the half-cell solar-to-hydrogen conversion efficiency was 3.0 % at 0.6 VRHE , with a maximum value of 3.6 % at 0.45 VRHE . Cross-sectional mapping of the electron-beam-induced current established that the increased photocurrent can be attributed to improved uniformity at the solid-liquid junction in the bilayer sample, which results in enhanced carrier collection.