Rational Design of Covalent Cobaloxime–Covalent Organic Framework Hybrids for Enhanced Photocatalytic Hydrogen Evolution
| Autor: | Hugo A. Vignolo-González, Tanmay Banerjee, Christian Ochsenfeld, Sandra Schmidt, Gökcen Savasci, Petra Rovó, Kerstin Gottschling, Philipp Mauker, Bettina V. Lotsch |
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| Jazyk: | angličtina |
| Rok vydání: | 2020 |
| Předmět: |
Chemistry
Rational design General Chemistry 010402 general chemistry Solar fuel 7. Clean energy 01 natural sciences Biochemistry Combinatorial chemistry Catalysis Article 0104 chemical sciences Colloid and Surface Chemistry Covalent bond Photocatalysis Reactivity (chemistry) Thermal stability Covalent organic framework |
| Zdroj: | Journal of the American Chemical Society |
| ISSN: | 1520-5126 0002-7863 |
| Popis: | Covalent organic frameworks (COFs) display a unique combination of chemical tunability, structural diversity, high porosity, nanoscale regularity, and thermal stability. Recent efforts are directed at using such frameworks as tunable scaffolds for chemical reactions. In particular, COFs have emerged as viable platforms for mimicking natural photosynthesis. However, there is an indisputable need for efficient, stable, and economical alternatives for the traditional platinum-based cocatalysts for light-driven hydrogen evolution. Here, we present azide-functionalized chloro(pyridine)cobaloxime hydrogen-evolution cocatalysts immobilized on a hydrazone-based COF-42 backbone that show improved and prolonged photocatalytic activity with respect to equivalent physisorbed systems. Advanced solid-state NMR and quantum-chemical methods allow us to elucidate details of the improved photoreactivity and the structural composition of the involved active site. We found that a genuine interaction between the COF backbone and the cobaloxime facilitates recoordination of the cocatalyst during the photoreaction, thereby improving the reactivity and hindering degradation of the catalyst. The excellent stability and prolonged reactivity make the herein reported cobaloxime-tethered COF materials promising hydrogen evolution catalysts for future solar fuel technologies. |
| Databáze: | OpenAIRE |
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