Photo- and electro-active molecular systems for fuel production
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BENNISTON, Andrew. Photo- and electro-active molecular systems for fuel production. In: Physical Methods in Coordination and Supramolecular Chemistry, 8-9 octombrie 2015, Chişinău. Chisinau, Republic of Moldova: 2015, XVIII, p. 8.
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Physical Methods in Coordination and Supramolecular Chemistry
XVIII, 2015
Conferința ""Physical Methods in Coordination and Supramolecular Chemistry""
Chişinău, Moldova, 8-9 octombrie 2015

Photo- and electro-active molecular systems for fuel production


Pag. 8-8

Benniston Andrew
 
Newcastle University
 
 
Disponibil în IBN: 17 aprilie 2020


Rezumat

The production of fuels from sunlight remains as one of the main challenges for the scientific community. In recent years, various steps towards efficient systems have been taken although no example having the desired properties of stability and price has been discovered. The main components of a full device for light-driven water splitting can be divided as catalysts for oxidation and reduction reactions, light-harvesting compounds, semiconducting electrodes for electron and hole transport and a membrane for conducting protons and separate the generated gases. Many examples of molecular catalysts have appeared in the literature for water oxidation and proton reduction, some of them exhibiting incredible performances. However, there are not many examples of sensitisers for water oxidation, limited mainly by the high oxidation potential needed to drive the reaction and their stability in aqueous media. Molecular sensitizers for water splitting are restricted to ruthenium(II) tris(bipyridine) and porphyrin derivatives. In both cases, the molecules are directly attached to a semiconductor and fast recombination reactions from the injected electrons are observed. On the other hand, the use of 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (Bodipy) as a chromophore has become very popular owing to its exceptional optical properties, photostability, and ease of preparation and purification. Very complicated structures have been prepared based on dendritic scaffolds, cassette light harvester or multi-dyad showing the versatility of such dyes. They can be easily functionalised to tune redox and optical properties to meet the demands for the water oxidation reaction. Recently, Bodipy dyes have been published as sensitizers for light-driven hydrogen production although no examples in photochemical oxidation reactions have appeared so far. In view of such considerations, we envisioned the possibility to designing Bodipy-ruthenium dyads with directional control of electron and hole transport within the sensitizer to minimise recombination reactions and improve the performance of the system. Both subunits are bridged by a triazole linker to avoid coupling between the Bodipy and the ruthenium. Moreover, the dyad BDR2 has an ethylene-bipyridyl ligand that is easier to reduce than bipyridine and should direct the electron towards this end of the molecule. The two targeted molecules are shown in Scheme 1 and this talk will discuss the progress made so far in the field of artificial photosynthesis.Scheme