The increasing human need for clean and renewable energy has stimulated research in artificial photosynthesis, and in particular water photoelectrolysis as a pathway to hydrogen fuel. Nanostructured devices are widely regarded as an opportunity to improve efficiency and lower costs, but as a detailed analysis shows, they also have considerably disadvantages. This article reviews the current state of research on nanoscale-enhanced photoelectrodes and photocatalysts for the water splitting reaction. The focus is on transition metal oxides with special emphasis of Fe2O3, but nitrides and chalcogenides, and main group element compounds, including carbon nitride and silicon, are also covered. The effects of nanostructuring on carrier generation and collection, multiple exciton generation, and quantum confinement are also discussed, as well as implications of particle size on surface recombination, on the size of space charge layers and on the possibility of controlling nanostructure energetics via potential determining ions. After a summary of electrocatalytic and plasmonic nanostructures, the review concludes with an outlook on the challenges in solar fuel generation with nanoscale inorganic materials.

Inorganic nanostructures for photoelectrochemical and photocatalytic water splitting

The future of energy supply depends on innovative breakthroughs regarding the design of cheap, sustainable, and efficient systems for the conversion and storage of renewable energy sources, such as solar energy. The production of hydrogen, a fuel with remarkable properties, through sunlight-driven water splitting appears to be a promising and appealing solution. While the active sites of enzymes involved in the overall water-splitting process in natural systems, namely hydrogenases and photosystem II, use iron, nickel, and manganese ions, cobalt has emerged in the past five years as the most versatile non-noble metal for the development of synthetic H(2)- and O(2)-evolving catalysts. Such catalysts can be further coupled with photosensitizers to generate photocatalytic systems for light-induced hydrogen evolution from water.

Splitting water with cobalt.

Artificial photosynthesis: molecular systems for catalytic water oxidation.

Cost-effective production of solar fuels requires robust and earth-abundant oxygen evolution reaction (OER) catalysts. Herein, we report that ultrathin nanoplates of cobalt–manganese layered double hydroxide (CoMn LDH) are a highly active and stable oxygen evolution catalyst. The catalyst was fabricated by a one-pot coprecipitation method at room temperature, and its turnover frequency (TOF) is more than 20 times higher than the TOFs of Co and Mn oxides and hydroxides, and 9 times higher than the TOF of a precious IrO2 catalyst. The activity of the catalyst was promoted by anodic conditioning, which was proposed to form amorphous regions and reactive Co(IV) species on the surface. The stability of the catalyst was demonstrated by continued electrolysis.

Ultrathin Cobalt–Manganese Layered Double Hydroxide Is an Efficient Oxygen Evolution Catalyst

Molecular Catalysts for Water Oxidation

Water oxidation in all oxygenic photosynthetic organisms is catalysed by the Mn₄CaO₄ cluster of Photosystem II. This cluster has inspired the development of synthetic manganese catalysts for solar energy production. A photoelectrochemical device, made by impregnating a synthetic tetranuclear-manganese cluster into a Nafion matrix, has been shown to achieve efficient water oxidation catalysis. We report here in situ X-ray absorption spectroscopy and transmission electron microscopy studies that demonstrate that this cluster dissociates into Mn(II) compounds in the Nafion, which are then reoxidized to form dispersed nanoparticles of a disordered Mn(III/IV)-oxide phase. Cycling between the photoreduced product and this mineral-like solid is responsible for the observed photochemical water-oxidation catalysis. The original manganese cluster serves only as a precursor to the catalytically active material. The behaviour of Mn in Nafion therefore parallels its broader biogeochemistry, which is also dominated by cycles of oxidation into solid Mn(III/IV) oxides followed by photoreduction to Mn²⁺.

Lan Yun Chang

Papers

Water-oxidation catalysis by manganese in a geochemical-like cycle