Demonstration of Scalable Water Splitting into H and O by a Flow-Type Photocatalysis-Electrolysis Hybrid System Using a Highly Stable Photocatalyst.

Water splitting via a photocatalysis-electrolysis hybrid system has been investigated as a potentially scalable and economically feasible means of producing renewable H. However, there are no reports demonstrating a scalable system for stoichiometric water splitting using an efficient and stable photocatalyst, and the key operating conditions for efficiently driving the entire system have not been established. Herein, we address the issues required to efficiently drive the entire system of a Cs, Fe, and H ion-modified WO (denoted as H-Fe-Cs-WO) photocatalyst fixed reactor combined with a polymer electrolyte membrane (PEM)-type electrolyzer.

Simultaneous production of hydrogen and chlorine through overall brine splitting with a particulate photocatalyst.

Sunlight-driven photocatalytic water splitting shows promise for green H production. In an attempt to achieve seawater splitting, we constructed a new stoichiometric brine splitting system that produces H along with Cl instead of O. Cl-a more potent high-value-added oxidant than O-was obtained with 100% selectivity over 10 h by adjusting the solution pH to acidic using a UV-light-driven Pt-loaded TiO photocatalyst.

Surface-modified, dye-sensitized niobate nanosheets enabling an efficient solar-driven Z-scheme for overall water splitting.

While dye-sensitized metal oxides are good candidates as H evolution photocatalysts for solar-driven Z-scheme water splitting, their solar-to-hydrogen (STH) energy conversion efficiencies remain low because of uncontrolled charge recombination reactions. Here, we show that modification of Ru dye-sensitized, Pt-intercalated HCaNbO nanosheets (/Pt/HCaNbO) with both amorphous AlO and poly(styrenesulfonate) (PSS) improves the STH efficiency of Z-scheme overall water splitting by a factor of ~100, when the nanosheets are used in combination with a WO-based O evolution photocatalyst and an I/I redox mediator, relative to an analogous system that uses unmodified /Pt/HCaNbO. By using the optimized photocatalyst, PSS//AlO/Pt/HCaNbO, a maximum STH of 0.

HO production on a carbon cathode loaded with a nickel carbonate catalyst and on an oxide photoanode without an external bias.

Efficient HO production both on a carbon cathode modified with various metal salts and on an oxide photoanode was investigated. The cathodic current density and faradaic efficiency for HO production (FE(HO)) on a carbon cathode in KHCO aqueous solution were significantly improved by the loading of an insoluble nickel carbonate basic hydrate catalyst. This electrode was prepared by a precipitation method of nickel nitrate and KHCO aqueous solution at ambient temperature.

Solar-to-Pharmaceutical Raw Material Production: Photoelectrochemical Naphthoquinone Formation Using Stabilized BiVO Photoanodes in Acid Media.

In the quest for efficient use of solar energy to produce high-value-added chemicals, we first achieved the photoelectrochemical (PEC) diketonization of naphthalene, using a BiVO/WO photoanode, to obtain naphthoquinone, an important pharmaceutical raw material with excellent efficiency by solar energy conversion. In the electrochemical (EC) reaction using F-doped SnO (FTO) substrates and a 0.5 M HSO HO-acetone (60 vol %) mixed solution containing 5 mM naphthalene, we produced a small amount of naphthoquinone evolution in the dark.

Acid-Resistant BiVO Photoanodes: Insolubility Control by Solvents and Weak W Diffusion in the Lattice.

We have revealed for the first time that BiVO photoanodes can be used even in strong acid media by mixing organic solvents into the electrolyte and depositing multilayers with a WO bottom layer. In general, the BiVO photoanodes are photocorrosive, especially in acid solutions. However, this shortcoming has been overcome using a combination of the two aforementioned modifications.

Functions of MnO 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, O and HClO production in aqueous solution containing Cl on photoanodes modified with various metal oxides was investigated.

An Artificial Z-Scheme Constructed from Dye-Sensitized Metal Oxide Nanosheets for Visible Light-Driven Overall Water Splitting.

Sensitization of a wide-gap oxide semiconductor with a visible-light-absorbing dye has been studied for decades as a means of producing H from water. However, efficient overall water splitting using a dye-sensitized oxide photocatalyst has remained an unmet challenge. Here we demonstrate visible-light-driven overall water splitting into H and O using HCaNbO nanosheets sensitized by a Ru(II) tris-diimine type photosensitizer, in combination with a WO-based water oxidation photocatalyst and a triiodide/iodide redox couple.

PINO/NHPI-mediated selective oxidation of cycloalkenes to cycloalkenones via a photo-electrochemical method.

The selective photo-electrochemical oxidation of cyclohexene to 2-cyclohexene-1-one was successfully performed with excellent Faraday efficiency (>99%) via indirect oxidation with a PINO/NHPI mediator and O on a BiVO/WO photoanode under low applied bias.

Photo-Electrochemical C-H Bond Activation of Cyclohexane Using a WO Photoanode and Visible Light.

The photo-electrochemical C-H bond activation of cyclohexane to produce cyclohexanol and cyclohexanone (KA oil) with high partial oxidation selectivity (99 %) and high current utilization ratio (76 %) was achieved in air at room temperature at atmospheric pressure. The production rate of KA oil was accelerated by applying a bias. The incident photon to current efficiencies at 365 and 420 nm were 57 % and 24 %, respectively.

Photoelectrochemical Hydrogen Peroxide Production from Water on a WO /BiVO Photoanode and from O on an Au Cathode Without External Bias.

The photoelectrochemical production and degradation properties of hydrogen peroxide (H O ) were investigated on a WO /BiVO photoanode in an aqueous electrolyte of hydrogen carbonate (HCO ). High concentrations of HCO species rather than CO species inhibited the oxidative degradation of H O on the WO /BiVO photoanode, resulting in effective oxidative H O generation and accumulation from water (H O). Moreover, the Au cathode facilitated two-electron reduction of oxygen (O ), resulting in reductive H O production with high current efficiency.

Discovery of Overcoating Metal Oxides on Photoelectrode for Water Splitting by Automated Screening.

We applied an automated semiconductor synthesis and screen system to discover overcoating film materials and optimize coating conditions on the BiVO4/WO3 composite photoelectrode to enhance stability and photocurrent. Thirteen metallic elements for overcoating oxides were examined with various coating amounts. The stability of the BiVO4/WO3 photoelectrode in a highly concentrated carbonate electrolyte aqueous solution was significantly improved by overcoating with Ta2O5 film, which was amorphous and porous when calcined at 550 °C.

Photocatalytic reduction of carbon dioxide over Ag cocatalyst-loaded ALa4Ti4O15 (A = Ca, Sr, and Ba) using water as a reducing reagent.

Ag cocatalyst-loaded ALa(4)Ti(4)O(15) (A = Ca, Sr, and Ba) photocatalysts with 3.79-3.85 eV of band gaps and layered perovskite structures showed activities for CO(2) reduction to form CO and HCOOH by bubbling CO(2) gas into the aqueous suspension of the photocatalyst powder without any sacrificial reagents.

Water splitting over new niobate photocatalysts with tungsten-bronze-type structure and effect of transition metal-doping.

Photophysical properties and photocatalytic activities for water splitting over KM(2)Nb(5)O(15) (M = Sr and Ba) and K(2)LnNb(5)O(15) (Ln = La, Pr, Nd, and Sm) with tungsten bronze-type structure were investigated. Single phases of KM(2)Nb(5)O(15) and K(2)LnNb(5)O(15) were successfully prepared by solid-state reaction (SSR) method and polymerizable complex (PC) method. The band gaps of these niobates were estimated to be 3.

Combinatorial search for iron/titanium-based ternary oxides with a visible-light response.

A combinatorial approach has been carried out to systematically investigate visible-light responsiveness of Fe-Ti-M (M: various metal elements) oxides for photoelectrochemical water splitting. Among the 25 elements tested, strontium was the most effective. A ternary metal oxide with the composition Fe(86.

Heterogeneous photocatalyst materials for water splitting.

This critical review shows the basis of photocatalytic water splitting and experimental points, and surveys heterogeneous photocatalyst materials for water splitting into H2 and O2, and H2 or O2 evolution from an aqueous solution containing a sacrificial reagent. Many oxides consisting of metal cations with d0 and d10 configurations, metal (oxy)sulfide and metal (oxy)nitride photocatalysts have been reported, especially during the latest decade. The fruitful photocatalyst library gives important information on factors affecting photocatalytic performances and design of new materials.