H2-Generation from Alcohols by the MOF-Based Noble Metal-Free Photocatalyst Ni/CdS/TiO2@MIL-101

The synthesis of important classes of chemical compounds from alcohols helps to conserve Earth’s fossil carbon resources, since alcohols can be obtained from indigestible and abundantly available biomass. The utilisation of visible light for the activation of alcohols permits alcohol-based C–N and C–C bond formation under mild conditions inaccessible with thermally operating hydrogen liberation catalysts. Herein, we report on a noble metal-free photocatalyst able to split alcohols into hydrogen and carbonyl compounds under inert gas atmosphere without the requirement of electron donors, additives, or aqueous reaction media. The reusable photocatalyst mediates C–N multiple bond formation using the oxidation of alcohols and subsequent coupling with amines. The photocatalyst consists of a CdS/TiO2 heterojunction decorated with co-catalytic Ni nanoparticles and is prepared on size-optimised colloidal metal–organic framework (MOF) crystallites.

CO2-based hydrogen storage – hydrogen liberation from methanol/water mixtures and from anhydrous methanol

New strategies for the reforming of methanol under mild conditions on the basis of heterogeneous and molecular catalysts have raised the hopes and expectations on this fuel. This contribution will focus on the progress achieved in the production of hydrogen from aqueous and anhydrous methanol with molecular and heterogeneous catalysts. The report entails thermal approaches, as well as light-triggered dehydrogenation reactions. A comparison of the efficiency and mechanistic aspects will be made and principles of catalytic pathways operating in biological systems will be also addressed.