Rational Design of Covalent Cobaloxime−Covalent Organic Framework Hybrids for Enhanced Photocatalytic Hydrogen Evolution
2020-06-20
Kerstin Gottschling, Gökcen Savasci, Hugo Vignolo-González, Sandra Schmidt, Philipp Mauker, Tanmay Banerjee, Petra Rovó, Christian Ochsenfeld, Bettina V. Lotsch
J. Am. Chem. Soc., 2020, 142, 12146–12156
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.
Speaker: Prof. Dr. Thomas Carell
Ludwig-Maximilians-Universität München
Institut für Chemische Epigenetik (ICEM)
Department of Chemistry
Office:
Würmtalstrasse 201
81377 Munich
Germany
Mailing address:
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Phone: +49 (0)89 2180-77750
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Secretary: Birgit Carell
Institute for Chemical Epigenetics Munich (ICEM)
Office:
Würmtalstrasse 201, Haus L - EG / Room: 007
81377 Munich
Germany
Mailing address:
Butenandtstr. 5 - 13
81377 Munich
Germany
Phone: +49 (0)89 2180-77751
Fax: +49 (0)89 2180-77881
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Prof. Dr. Lena Daumann
LMU Munich
Department of Chemistry
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Dr. Sabine Schneider
LMU Munich
Institute for Chemical Epigenetics
Butenandtstr. 5 - 13
House L
81377 Munich, Germany
Phone: +49 89 2180 77716
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Dr. Martin Sumser (Coordinator)
LMU Munich
Institute for Chemical Epigenetics
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81377 Munich, Germany
Phone: +49 89 2180 77765
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