Bandgap widening through doping for improving the photocatalytic oxidation ability of narrow-bandgap semiconductors.

The trade-off relationship between narrowing the bandgap and achieving sufficient redox potentials accounts for the hindrance to the development of an efficient photocatalyst. Most of the previous researchers attempt to narrow the bandgap of semiconductors by impurity doping to achieve visible-light sensitivity, but this approach causes the losses of their oxidation and/or reduction ability. Conversely, this study presents a bandgap widening strategy by doping to improve the redox potential of photogenerated carriers. Employing first-principles simulations, we propose the lanthanum-doped bismuth vanadate (La-BiVO4) photocatalyst as a wider-bandgap semiconductor exhibiting stronger oxidation ability compared to pristine BiVO4, and the results revealed that the bismuth orbital in the valence band (VB) was diluted by lanthanum-ion doping, while the VB shifted to a higher potential (positively shifted). Thereafter, a La-BiVO4 powder was synthesized via a solid-state reaction, after which its activity was evaluated in the photocatalytic oxidation of 2-propanol (IPA). La-BiVO4 exhibited bandgap widening; thus, the number of absorbed photons under visible-light irradiation was lower than that of pristine BiVO4. However, the quantum efficiency (QE) of La-BiVO4 for the oxidation of IPA was higher than that of the pristine BiVO4. Consequently, the photocatalytic reaction rate of La-BiVO4 was superior to that of pristine BiVO4 under the same visible-light irradiation conditions. Although the bandgap of La-BiVO4 is widened, it is still sensitive to the cyan-light region, which is the strongest in the sunlight spectrum. These results demonstrate that the orbital dilution strategy by impurity elemental doping is effective for bandgap widening and contributes to improving the oxidation and/or reduction ability of the photogenerated charge carriers. This study elucidates the possibility of boosting photocatalytic performances via bandgap widening.

Photocatalytic solar hydrogen production from water on a 100-m2 scale.

The unprecedented impact of human activity on Earth's climate and the ongoing increase in global energy demand have made the development of carbon-neutral energy sources ever more important. Hydrogen is an attractive and versatile energy carrier (and important and widely used chemical) obtainable from water through photocatalysis using sunlight, and through electrolysis driven by solar or wind energy1,2. The most efficient solar hydrogen production schemes, which couple solar cells to electrolysis systems, reach solar-to-hydrogen (STH) energy conversion efficiencies of 30% at a laboratory scale3. Photocatalytic water splitting reaches notably lower conversion efficiencies of only around 1%, but the system design is much simpler and cheaper and more amenable to scale-up1,2-provided the moist, stoichiometric hydrogen and oxygen product mixture can be handled safely in a field environment and the hydrogen recovered. Extending our earlier demonstration of a 1-m2 panel reactor system based on a modified, aluminium-doped strontium titanate particulate photocatalyst4, we here report safe operation of a 100-m2 array of panel reactors over several months with autonomous recovery of hydrogen from the moist gas product mixture using a commercial polyimide membrane5. The system, optimized for safety and durability, and remaining undamaged on intentional ignition of recovered hydrogen, reaches a maximum STH of 0.76%. While the hydrogen production is inefficient and energy negative overall, our findings demonstrate that safe, large-scale photocatalytic water splitting, and gas collection and separation are possible. To make the technology economically viable and practically useful, essential next steps are reactor and process optimization to substantially reduce costs and improve STH efficiency, photocatalyst stability and gas separation efficiency.

Charge carrier mapping for Z-scheme photocatalytic water-splitting sheet via categorization of microscopic time-resolved image sequences.

Photocatalytic water splitting system using particulate semiconductor materials is a promising strategy for converting solar energy into hydrogen and oxygen. In particular, visible-light-driven 'Z-scheme' printable photocatalyst sheets are cost-effective and scalable. However, little is known about the fundamental photophysical processes, which are key to explaining and promoting the photoactivity. Here, we applied the pattern-illumination time-resolved phase microscopy for a photocatalyst sheet composed of Mo-doped BiVO4 and Rh-doped SrTiO3 with indium tin oxide as the electron mediator to investigate photo-generated charge carrier dynamics. Using this method, we successfully observed the position- and structure-dependent charge carrier behavior and visualized the active/inactive sites in the sheets under the light irradiation via the time sequence images and the clustering analysis. This combination methodology could provide the material/synthesis optimization methods for the maximum performance of the photocatalyst sheets.

Functions of MnOx in NaCl Aqueous Solution for Artificial Photosynthesis.

Photoelectrochemical water splitting has been intensively investigated as artificial photosynthesis technology to convert solar energy into chemical energy. The use of seawater and salted water has advantages for minimum environmental burden; however, the oxidation of Cl- ion to hypochlorous acid (HClO), which has toxicity and heavy corrosiveness, should occur at the anode, along with the oxygen evolution. Here, O2 and HClO production in aqueous solution containing Cl- on photoanodes modified with various metal oxides was investigated. The modification of MnOx resulted in the promotion of the O2 evolution reaction (OER) specifically without HClO production over a wide range of conditions. The results will contribute not only to the practical application of artificial photosynthesis using salted water but also to the elucidation of substantial function of manganese as the element for OER center in natural photosynthesis.

Z-Scheme Water Splitting under Near-Ambient Pressure using a Zirconium Oxide Coating on Printable Photocatalyst Sheets.

Sunlight-driven water splitting systems operating under ambient pressure are essential for practical renewable hydrogen production. Printable photocatalyst sheets, composed of a hydrogen evolution photocatalyst (HEP), an oxygen evolution photocatalyst (OEP), and conductive metal nanoparticles, are cost-effective and scalable systems. However, the decrease in water splitting activity under ambient pressure due to reverse reactions hampers their practical application. In this study, coating zirconium oxide (ZrOx ) by facile drop-casting onto a printed photocatalyst sheet, which consists of SrTiO3 : Rh, BiVO4 : Mo, and Au nanocolloids as the HEP, OEP, and electron mediator, respectively, effectively maintains the water splitting activity at elevated pressure. The ZrOx -coated photocatalyst sheet retains 90 % and 84 % of the base performance (the pristine sheet at 10 kPa) at 50 and 90 kPa, respectively. Achieving efficient water splitting at the ambient pressure by inexpensive and extensible processes is an important step toward solar hydrogen production.

Green light active photocatalyst for complete oxidation of organic molecules.

Photocatalytic organic decomposition is an effective method to combat environmental pollution, a growing public health concern worldwide. Here we report that Fe(iii) nanocluster grafted BiVO4 shows high activity for complete decomposition of organic molecules even under green light. This study is the first investigation to utilize green light for complete gas phase organic decomposition.

Green fabrication of nanoporous BiVO4 films on ITO substrates for photoelectrochemical water-oxidation.

A new green method was developed to prepare nanoporous BiVO4 films on ITO substrates for photoelectrochemical (PEC) water-oxidation under visible light irradiation. The films can be prepared by simple drop-casting of a stable aqueous solution of Bi3+ and V5+ complexes with tartaric acid and ethylenediaminetetraacetic acid, followed by drying and calcination in air. Thanks to these ligands, the aqueous precursor solution is remarkably stable over a wide range of pH (pH 4-9). The BiVO4 films on ITO substrates possess a 3D-network structure comprised of nanoparticles with a scheelite-monoclinic phase and a diameter of ca. <100 nm, after calcination at 450-500 °C for 1 h. The PEC performance clearly depended on the film thickness that can be controlled by coating times, and calcination conditions (temperature and time). The CoPi-loaded BiVO4 electrodes exhibited relatively high performance for PEC water oxidation (ABPE of 0.35% at 0.8 V vs. RHE) under simulated sunlight irradiation.

Preparation and function of poly(acrylic acid)s modified by supramolecular complex composed of porphinatoiron and a cyclodextrin dimer that bind diatomic molecules (O2 and CO) in aqueous solution.

Poly(acrylic acid) (PAA) is modified by 5-(4-ß-alanylaminophenyl)-10,15,20-tris(4-sulfonatophenyl) porphinatoiron(III) to yield iron porphyrin-bearing PAAs (FeP(n)s) through a condensation reaction. FeP(n)s were further functionalized by Py3CD, which is a per-O-methylated ß-cyclodextrin (CD) dimer with a pyridine linker and includes the porphyrin pendants to form ferric hemoCD-P(n)s. Ferrous hemoCD-P(3), having three porphyrin chromophores in a polymer chain, is shown to bind molecular oxygen (P(1/2)=7.9±1.4 Torr) in aqueous solution at pH 7.0 and 25 °C, affording oxy-hemoCD-P(3). Oxy-hemoCD-P(3) is biphasically autoxidized to ferric hemoCD-P(3), with 27% of the dioxygen adducts being rapidly oxidized. The rate of autoxidation of oxy-hemoCD-P(15), having 15 porphyrin chromophores in a polymer chain, was much faster than that of oxy-hemoCD-P(3), thus suggesting self-catalyzed autoxidation of oxy-hemoCD-P(n)s. Oxy-hemoCD-P(n)s are markedly stabilized by catalase, thereby indicating that hydrogen peroxide generated from oxy-hemoCD-P(n) accelerates the autoxidation. Most of the hemoCD-P(3) molecules injected into the femoral vein of a rat remained in the body, though about 16% of the hemoCD-P(3) molecules were excreted in the urine as a carbon monoxide adduct.