Photochemical splitting of water into H2 and O2 using solar energy is a process of great economic and environmental interest. Since the discovery of the first water splitting system based on TiO2 and Pt in 1972 by Fujishima and Honda, over 130 inorganic materials have been discovered as catalysts for this reaction. This review discusses the known inorganic catalysts with a focus on structure–activity relationships.

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Inorganic Materials as Catalysts for Photochemical Splitting of Water

In view of the diminishing oil resources and the ongoing climate change, the use of efficient and environmentally benign technologies for the utilization of renewable resources has become indispensible. Therein, hydrogenolysis reactions offer a promising possibility for future biorefinery concepts. These reactions result in the cleavage of C-C and C-O bonds by hydrogen and allow direct access to valuable platform chemicals already integrated in today's value chains. Thus, hydrogenolysis bears the potential to bridge currently available technologies and future biomass-based refinery concepts. This Review highlights past and present developments in this field, with special emphasis on the direct utilization of cellulosic feedstocks.

Hydrogenolysis Goes Bio: From Carbohydrates and Sugar Alcohols to Platform Chemicals

In this review, for a variety of metals and semiconductors, an attempt is made to generalize observations in the literature on the effect of process conditions applied during photodeposition on (i) particle size distributions, (ii) oxidation states of the metals obtained, and (iii) consequences for photocatalytic activities. Process parameters include presence or absence of (organic) sacrificial agents, applied pH, presence or absence of an air/inert atmosphere, metal precursor type and concentration, and temperature. Most intensively reviewed are studies concerning (i) TiO2; (ii) ZnO, focusing on Ag deposition; (iii) WO3, with a strong emphasis on the photodeposition of Pt; and (iv) CdS, again with a focus on deposition of Pt. Furthermore, a detailed overview is given of achievements in structure-directed photodeposition, which could ultimately be employed to obtain highly effective photocatalytic materials. Finally, we provide suggestions for improvements in description of the photodeposition methods applied when included in scientific papers.

Methods, Mechanism, and Applications of Photodeposition in Photocatalysis: A Review.

Although the use of CO as a reductant had been in the past confined to few reactions, its use in organic synthesis, especially in the reductive carbonylation of nitro aromatics and the oxidative carbonylation of aromatic amines, has increased dramatically. Since the discovery of CO-induced reduction of nitro groups, there has been a wide spread increase of interest in the application and mechanistic understanding of this reaction. In a major review published in 1988 it was noted, that in practice no studies of the mechanism of N-carbonylation of aromatic nitro compounds with alcohols leading to carbamates have been carried out. This review clearly shows a major change since that publication. Indeed, metal-catalyzed reductive carbonylation of nitro aromatics using CO as reducing agent has been in the past 10 years the subject of intense investigation both in academia and in the chemical industry. Several articles and reviews have covered the subject up to the late 1980s. The authors will concentrate on more recent literature, but sometimes older data will be used to establish an understanding of these reactions. 127 refs.

A Review of the Selective Catalytic Reduction of Aromatic Nitro Compounds into Aromatic Amines, Isocyanates, Carbamates, and Ureas Using CO.

Nitrogen dioxide and carbonate radical anion: two emerging radicals in biology.

Phase transfer-catalysed transfer hydrogenation of ketones using iron carbonyls as catalysts

The in situ deposition of Pt and Ir on CdS during the photocatalytic decomposition of aqueous sulfide results in the formation of an effective bifunctional photocatalyst (MS/CdS/M, where MS is Pt or Ir sulfide and M is Pt or Ir) which is more active than CdS and metallized CdS. In situ metallization provides a convenient method for the preparation of metal- and metal-sulfide-deposited CdS. The order of reactivity for the in situ metallization of CdS in the case of the photocatalytic decomposition of aqueous sulfide is Rh > Pt > Ru = Ir > Co ≃ Ni ≃ Fe. Based on the observed results a mechanism for the photocatalytic decomposition of aqueous sulfide is proposed.

J. C. Kuriacose

Papers

Phase transfer-catalysed transfer hydrogenation of ketones using iron carbonyls as catalysts

Cadmium sulfide with iridium sulfide and platinum sulfide deposits as a photocatalyst for the decomposition of aqueous sulfide

Reactions of the carbonate radical with aliphatic amines

Ruthenium(III)-catalysed oxidation of secondary alcohols by N-methylmorpholine N-oxide (NMO)

RuCl2(PPh3)3-catalyzed transfer hydrogenation of d-glucose