Projektbeschreibung
Stabilere Elektrokatalysetechnologie unterstützt chemische Umwandlungen
Das Ziel des vom Europäischen Forschungsrat finanzierten Projekts MOFcat besteht darin, für die Energieerzeugung relevante metallorganische Redox-Katalysatoren in metallorganische Gerüstverbindungen einzugliedern. Dieser Ansatz dürfte die Katalysatoren stabilisieren sowie ihre Langlebigkeit und Wiederverwertbarkeit gewährleisten. Die geregelte Umgebung innerhalb von metallorganischen Gerüstverbindungen ermöglicht die Erforschung entscheidender Faktoren wie Konformationsflexibilität, Diffusion und Ladungstransport, die in homogenen Lösungen normalerweise nicht realisierbar sind. Die Auswirkungen der Umgebung mit metallorganischen Gerüstverbindungen auf die Katalyse werden anhand elektrochemischer Messungen untersucht. Zudem werden lichtinduzierte Elektronentransferprozesse genutzt, um die Reaktivität der resultierenden Katalysatoren zu erkunden. Das vorgeschlagene Forschungsvorhaben soll das Verständnis der Chemie und Katalyse metallorganischer Gerüstverbindungen verbessern und zur Entwicklung effizienterer Elektroden und neuartiger Designs für Farbstoff-Solarbrennstoffvorrichtungen führen.
Ziel
Organometallic redox-catalysts of energy relevance, i.e. water and hydrogen oxidation, and proton and carbon dioxide reduction catalysts, will be incorporated into metal-organic frameworks (MOFs). Immobilization and spatial organization of the molecular catalysts will stabilize their molecular integrity and ensure longevity and recyclability of the resulting MOFcats. The organized environment provided by the MOF will enable the control of conformational flexibility, diffusion, charge transport, and higher coordination sphere effects that play crucial roles in enzymes, but cannot be addressed in homogenous solution and are thus largely unexplored. The effect that the MOF environment has on catalysis will be directly probed electrochemically in MOFcats that are immobilized or grown on electrode surfaces. In combination with spectroscopic techniques in spectroelectrochemical cells, intermediates in the catalytic cycles will be detected and characterized. Kinetic information of the individual steps in the catalytic cycles will be obtained in MOFs that contain both a molecular photosensitizer (PS) and a molecular catalyst (PS-MOFcats). The envisaged systems will allow light-induced electron transfer processes to generate reduced or oxidized catalyst states the reactivity of which will be studied with high time resolution by transient UV/Vis and IR spectroscopy. The acquired fundamental mechanistic knowledge is far beyond the current state-of-the-art in MOF chemistry and catalysis, and will be used to prepare MOFcat-based electrodes that function at highest possible rates and lowest overpotentials. PS-MOFcats will be grown on flat semiconductor surfaces, and explored as a novel concept to photoanode and -cathode designs for dye-sensitized solar fuel devices (DSSFDs). The design is particularly appealing as it accommodates high PS concentrations for efficient light-harvesting, while providing potent catalysts close to the solvent interface.
Wissenschaftliches Gebiet
Not validated
Not validated
- natural scienceschemical scienceselectrochemistryelectrolysis
- natural sciencesphysical scienceselectromagnetism and electronicssemiconductivity
- natural scienceschemical sciencescatalysis
- natural sciencesbiological sciencesbiochemistrybiomoleculesproteinsenzymes
- natural sciencesphysical sciencesopticsspectroscopy
Programm/Programme
Thema/Themen
Finanzierungsplan
ERC-COG - Consolidator GrantGastgebende Einrichtung
751 05 Uppsala
Schweden