Solar-driven proton and carbon dioxide reduction to fuels — lessons from metalloenzymes

Carbon nitride–TiO2 hybrid modified with hydrogenase for visible light driven hydrogen production

“…Ideally, the distance from the CN x –TiO 2 surface to the [Fe 4 S 4 ] electron transport chain should be minimised and an improved orientation of the enzyme would allow trapping of CB TiO 2 electrons more efficiently for maximised turnover. 19 …”

Methodologies for “Wiring” Redox Proteins/Enzymes to Electrode Surfaces

“…Electrodes constructed of metal oxide semiconductors have become increasingly important in both PFE studies and metalloenzyme biotechnological device development. In particular, n‐type metal oxide semiconductors such as TiO 2 , indium tin oxide (ITO) and CdS were used for solar fuel applications and NADH recycling . TiO 2 electrode surfaces are rough, porous structures consisting of aggregated nanoparticles .…”

“…In particular, n‐type metal oxide semiconductors such as TiO 2 , indium tin oxide (ITO) and CdS were used for solar fuel applications and NADH recycling . TiO 2 electrode surfaces are rough, porous structures consisting of aggregated nanoparticles . The CdS surface topology is similar, comprising a highly porous three‐dimensional network of CdS sheets .…”

“…TiO 2 electrode surfaces are rough, porous structures consisting of aggregated nanoparticles . The CdS surface topology is similar, comprising a highly porous three‐dimensional network of CdS sheets . ITO electrodes with porous architectures suitable for redox‐protein immobilization can also be constructed and, along with PGE and TiO 2 , present negatively charged oxide functionalities for adsorbing protein or enzyme molecules at neutral pH .…”

Photobiokatalyse: Aktivierung von Redoxenzymen durch direkten oder indirekten Transfer photoinduzierter Elektronen

“…Hydrogenasen als Fe-Cluster-haltige Metalloenzyme katalysieren die Reduktion von Protonen zu molekularem Wasserstoff (oder die entgegengesetzte Reaktion) und wurden in den letzten Jahren intensiv als Katalysatoren für die solargetriebene Brennstoffherstellung erforscht, da ihre Aktivitäta nd ie anorganischer Katalysatoren wie Pt heranreicht. Aktuelle Forschungsansätze beschäftigen sich damit, Wege zur direkten Photoaktivierung von Hydrogenasen zu finden, in dem durch spezifische/nicht-spezifische Wechselwirkungen mittels kovalenter Bindung oder physikalischer Adsorption Kontakte zwischen organischen (oder anorganischen) Photosensibilisatoren und Hydrogenasen hergestellt werden [34,[88][89][90][91][92][93][94][95]. Die Eisen-Schwefel-Cluster, wie beispielsweise 4Fe-4S,b ilden hierbei die Elektronentransferkette,w elche die bençtigten Elektronen an das ins Innere des Enzyms eingebettete aktive Zentrum liefert.…”