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Biomimetic Copper Complexes for Energy Conversion Reactions

Descrizione del progetto

Catalizzatori naturali per migliorare le celle a combustibile solare

Lo sfruttamento dell’energia solare per produrre forme sostenibili di combustibile, come l’idrogeno, richiede fotocatalizzatori in grado di utilizzare in modo efficiente la luce visibile per scindere le molecole d’acqua attraverso l’elettrolisi. Allo stesso modo, per ridurre l’ossigeno in acqua e produrre energia elettrica nelle celle a combustibile è fondamentale la presenza di catalizzatori efficienti in grado di accelerare la reazione con perdite energetiche minime. Finanziato dal Consiglio europeo della ricerca, il progetto Cu4Energy studierà dei catalizzatori naturali come l’enzima di rame Laccase, caratterizzato da funzionamento rapido e bassi requisiti energetici. I ricercatori assoceranno la struttura del catalizzatore all’attività catalitica e analizzeranno il paesaggio energetico del ciclo di reazione. I risultati del progetto dovrebbero migliorare le conoscenze fondamentali e fornire catalizzatori di rame altamente attivi per le reazioni di scissione e riduzione dell’ossigeno.

Obiettivo

Water oxidation (WO) and oxygen reduction (OR) are crucial reactions to produce and to consume solar fuels. It is important that WO and OR occur with very high catalytic rates with only a very small thermodynamic driving force (i.e. a small overpotential). In these terms, natural catalysts perform significantly better than the artificial systems. Especially the copper enzyme Laccase operates fast at a low overpotential. In principle one could use the same design principles used in the enzymatic systems to produce artificial catalysts for OR and WO. It is envisioned that for the most ideal OR and WO catalysts:

1. all redox reactions within the catalytic cycle should occur as close as possible to the thermodynamic potential where OR and WO become accessible.

2. Equilibria that are not coupled to redox reactions need to be biased for product formation.

3. Proton shuttles are necessary to manage proton transfer concerted with electron-transfer and electron-transfer coupled to O–O bond cleavage or O–O bond formation.

In this proposal molecular copper catalysts for OR and WO are studied by means of a combined electrochemical and computational approach, taking in account the design principles above. Experiments will be carried out wherein the structure of the catalyst is linked to the observed catalytic activity and the potential energy surface of the catalytic cycle. The proposal is in particular focused on the rate-determining step of the catalytic reaction, as improvements here will directly lead to enhanced catalytic rates. A functional model system of Laccase will be designed to study the rate limiting proton-and-electron-coupled O–O bond scission reaction, which is the rate limiting step in OR by Laccase.
The aim of the proposal is to significantly increase of fundamental understanding of the design principles for molecular OR and WO catalysts and to deliver new and very active molecular copper catalysts for OR and WO at the end of the project.

Meccanismo di finanziamento

ERC-STG - Starting Grant
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Coordinatore

UNIVERSITEIT LEIDEN
Contribution nette de l'UE
€ 1 500 000,00
Indirizzo
Rapenburg 70
2311 EZ Leiden
Paesi Bassi

Mostra sulla mappa

Regione
West-Nederland Zuid-Holland Agglomeratie Leiden en Bollenstreek
Tipo di attività
Higher or Secondary Education Establishments
Collegamenti
Altri finanziamenti
€ 0,00

Beneficiari (1)