Hydrogen Production Coupled to Hydrocarbon Oxygenation from Photocatalytic Water Splitting

Abstract

On the sunny side: A homogeneous system for H2 production and hydrocarbon oxidation was developed in the absence of any sacrificial reagent. This system consists of [Ru(TPA)(H2O)2]2+ and [Fe3(CO)12] as catalysts and [Ru(bpy)3]2+ and [Ir(bpy)(ppy)2]+ as photosensitizers (PS). Water is the oxygen source as well as the source for H2 formation (see picture; Sub=organic substrate).

Artificial photosynthesis: opportunities and challenges of molecular catalysts

“…In this review, we mainly focused on water splitting and CO 2 reduction reactions. However, it should be noted that the production of other types of fuels and highvalue-added chemicals can also be achieved with AP by driving the corresponding reactions, 10 such as ammonia production from nitrogen fixation, 11 epoxide production from hydrocarbon oxygenation, [12][13][14] hydrogen peroxide production from oxygen reduction, 15 and polymer production from biomass related 5-hydroxymethylfurfural (HMF) conversion reactions. 16 Two types of devices have been designed for the production of solar fuels, the photoelectrochemical (PEC) cell ( Fig.…”

H2 generation and sulfide to sulfoxide oxidation with H2O and sunlight with a model photoelectrosynthesis cell

“…Furthermore, a large excess of sacrificial molecules can be used to favor the desired reaction. So far, only one example can be found in which oxidation and reduction reactions are coupled together in a fully homogeneous molecular system for the oxidation of organic substrates and hydrogen [30].…”

Photochemical Hydrogen Generation Initiated by Oxidative Quenching of the Excited Ru(bpy)32+* by a Bio‐Inspired [2Fe2S] Complex

“…[5] An alternative is photocatalytic hydrogen generation coupled with hydrocarbon oxygenation with water as an oxygen source, in which the oxygen atom of a water molecule would be transferred to an organic substrate through two-electron water oxidation. [6] Recently, photocatalytic oxygenation of organic substrates with water as an oxygen source has been achieved by non-heme iron(IV)-oxo species using Ru(bpy) 3 2 + as photosensitizer in the presence of a sacrificial electron acceptor. [7] In that case, oxidative quenching of the excited Ru(bpy) 3 2 + * by a bio-inspired [2Fe2S] complex instead of the terminal electron acceptor, in principle, would generate strong oxidant Ru(bpy) 3 3 + , providing a chance to develop a photo water-splitting system employing Fe-based catalysts in the both reduction and oxidation semi-reactions.…”

“…Here, we report the intermolecular electron transfer from the excited Ru(bpy) 3 2 + * to the synthetic diiron dithiolate complex NAHFe 2 S 2 (CO) 6 (1) Figure S1 in the Supporting Information). It should be noted that complex 1 possesses the most positive reduction potentials among the [FeFe] hydrogenase model analogues reported so far.…”