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 Photocatalytic water splitting and H2 evolution using abundant compounds as electron donors are expected to contribute to construction of a clean and simple system for solar hydrogen production, and a solution of global energy and environmental issues in the future (361 references)

Heterogeneous photocatalyst materials for water splitting

2.3. Evaluation of Photocatalytic Water Splitting 6507 2.3.1. Photocatalytic Activity 6507 2.3.2. Photocatalytic Stability 6507 3. UV-Active Photocatalysts for Water Splitting 6507 3.1. d0 Metal Oxide Photocatalyts 6507 3.1.1. Ti-, Zr-Based Oxides 6507 3.1.2. Nb-, Ta-Based Oxides 6514 3.1.3. W-, Mo-Based Oxides 6517 3.1.4. Other d0 Metal Oxides 6518 3.2. d10 Metal Oxide Photocatalyts 6518 3.3. f0 Metal Oxide Photocatalysts 6518 3.4. Nonoxide Photocatalysts 6518 4. Approaches to Modifying the Electronic Band Structure for Visible-Light Harvesting 6519

Semiconductor-based Photocatalytic Hydrogen Generation

The absolute energy positions of conduction and valence band edges were compiled for about 50 each semiconducting metal oxide and metal sulfide minerals. The relationships between energy levels at mineral semiconductor-electrolyte interfaces and the activities of these minerals as a catalyst or photocatalyst in aqueous redox reactions are reviewed. The compilation of band edge energies is based on experimental flatband potential data and complementary empirical calculations from electronegativities of constituent elements. Whereas most metal oxide semiconductors have valence band edges 1 to 3 eV below the H2O oxidation potential (relative to absolute vacuum scale), energies for conduction band edges are close to, or lower than, the H2O reduction potential. These oxide minerals are strong photo-oxidation catalysts in aqueous solutions, but are limited in their reducing power. Non-transition metal sulfides generally have higher conduction and valence band edge energies than metal oxides; therefore, valence band holes in non-transition metal sulfides are less oxidizing, but conduction band electrons are exceedingly reducing. Most transition-metal sulfides, however, are characterized by small band gaps (<1 eV) and band edges situated within or close to the H2O stability potentials. Hence, both the oxidizing power of the valence band holes and the reducing power of the conduction band electrons are lower than those of non-transition metal sulfides.

The absolute energy positions of conduction and valence bands of selected semiconducting minerals

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.

https://science.sciencemag.org/content/sci/early/2014/02/12/science.1246913.full.pdf

Nanoporous BiVO4 Photoanodes with Dual-Layer Oxygen Evolution Catalysts for Solar Water Splitting

The production of clean and renewable hydrogen through water splitting using photocatalysts has received much attention due to the increasing global energy crises. In this study, a high efficiency of the photocatalytic H2 production was achieved using graphene nanosheets decorated with CdS clusters as visible-light-driven photocatalysts. The materials were prepared by a solvothermal method in which graphene oxide (GO) served as the support and cadmium acetate (Cd(Ac)2) as the CdS precursor. These nanosized composites reach a high H2-production rate of 1.12 mmol h–1 (about 4.87 times higher than that of pure CdS nanoparticles) at graphene content of 1.0 wt % and Pt 0.5 wt % under visible-light irradiation and an apparent quantum efficiency (QE) of 22.5% at wavelength of 420 nm. This high photocatalytic H2-production activity is attributed predominantly to the presence of graphene, which serves as an electron collector and transporter to efficiently lengthen the lifetime of the photogenerated charge carrier...

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Highly efficient visible-light-driven photocatalytic hydrogen production of CdS-cluster-decorated graphene nanosheets.

An efficient hydrogen production can be achieved by irradiated suspensions of platinized CdS in solutions of S/sup 2 -/ and/or SO/sub 3//sup 2 -/ ions. However, the photocatalytic activity of CdS powders strongly depends on their specific surface area. However, coprecipitation of CdS with about 0.5-3 wt% silver sulfide or surface modification of CdS with a large specific surface area by silver ions permitted preparation of very active platinized photocatalysts. The enhancement of activity is not limited to the absorption range of CdS, but also results from a significant extension of the spectral response up to about 620 nm. Further improvement of the photoactivity can be achieved by doping the Ag/sub 2/S activated CdS powders with zinc sulfide. 77 references, 17 figures.

Photochemical hydrogen production with platinized suspensions of cadmium sulfide and cadmium zinc sulfide modified by silver sulfide

Active photocatalysts for photochemical hydrogen production have been prepared by platinum deposition on microcrystals of CdS powders. Hydrogen produced by irradiating suspensions of platinized CdS in various electrolyte solutions (S/sup 2 -/, SO/sub 3//sup 2 -/, H/sub 2/PO/sup 2 -/) has been shown to be significantly improved by photoetching the CdS microcrystals. The efficiency of hydrogen formation in solutions containing S/sup 2 -/ is low due to the formation of disulfide ions. Additional of reducing agents such as sulfite or hypophosphite ions, which efficiently suppresses disulfide formation, allows hydrogen to evolve at a surprisingly high rate. In the case of a solution containing both S/sup 2/ and SO/sub 3//sup 2 -/ ions, the formation of thiosulfate is observed with a quantum yield of 0.25. In mixtures of sulfide and hypophosphite ions, phosphite and phosphate ions are the oxidation products. Hydrogen formation occurs in solutions containing SO/sub 3//sup 2 -/ ions only when the platinized CdS particles have previously been photoetched. Concomitant to the proton reduction, SO/sub 3//sup 2 -/ ions are oxidized to sulfate and dithionate. In 12 days, 9 L of H/sub 2/ was generated by irradiating 1 g of CdS/Pt suspended in an Na/sub 2/SO/sub 3/ solution. Aftermore » this period, the efficiency of the photocatalyst dropped to about 60% of the initial rate. The reaction parameters and the formation of the oxidation products have been investigated in detail. 57 references, 10 figures, 4 tables.« less

Photochemical hydrogen production with cadmium sulfide suspensions

Hydrogen has been produced efficiently by the irradiation of suspensions of metalized ZnS powders in the presence of hole scavengers such as S/sup 2 -/ and SO/sub 3//sup 2 -/ions, mixtures of these two, or S/sup 2 -/ and hypophosphite ions. Results of investigation of the properties of active ZnS photocatalysts, the reaction parameters, and the formation of the reaction products are reported. The rate of the reaction was found to be strongly dependent on the amount of ZnS, and ZnS produced 5 times as much hydrogen as CdS.

Photochemical production of hydrogen with zinc sulfide suspensions

A process is described for the selective production of hydrogen by means of heterogeneous photoredox catalysis, in which mixtures of water and alkali metal sulfites or sulfides, alkaline earth metal sulfites or sulfides or ammonium sulfites or sulfides are reacted under the action of light in a suspension of a cadmium sulfide, cadmium sulfoselenide or titanium dioxide/semiconductor powder which is at least partially coated with Cu, Cr, Ni, Co or a noble metal or mixtures thereof. The catalysts which can be employed in this process (coated semiconductor powders) are in some cases novel.

Jean Francois Dr Reber

Papers

Photochemical hydrogen production with platinized suspensions of cadmium sulfide and cadmium zinc sulfide modified by silver sulfide

Photochemical hydrogen production with cadmium sulfide suspensions

Photochemical production of hydrogen with zinc sulfide suspensions

Process for the production of hydrogen by means of heterogeneous photoredox catalysis

Photochemical Hydrogen Production with Platinized Suspensions of Cadmium Sulfide and Cadmium Zinc Sulfide Modified by Silver Sulfide.