Single-Site Photocatalytic H-2 Evolution from Covalent Organic Frameworks with Molecular Cobaloxime Co-Catalysts

Banerjee, Tanmay; Haase, Frederik; Savasci, Goekcen; Gottschling, Kerstin; Ochsenfeld, Christian and Lotsch, Bettina V. (2017): Single-Site Photocatalytic H-2 Evolution from Covalent Organic Frameworks with Molecular Cobaloxime Co-Catalysts. In: Journal of the American Chemical Society, Vol. 139, No. 45: pp. 16228-16234

Abstract

We demonstrate photocatalytic hydrogen evolution using COF photosensitizers with molecular proton reduction catalysts for the first time. With azine-linked N2-COF photosensitizer, chloro(pyridine)cobaloxime co-catalyst, and TEOA donor, H-2 evolution rate of 782,mu mol h(-1) g(-1) and TON of 54.4 has been obtained in a water/acetonitrile mixture. PXRD, solid-state spectroscopy, EM analysis, and quantum-chemical calculations suggest an outer sphere electron transfer from the COF to the co-catalyst which subsequently follows a monometallic pathway of H-2 generation from the Co-III-hydride and/or Co-II-hydride species.

• Item Type: Journal article
• EU Funded Grant Agreement Number: 639233
• EU Projects: Horizon 2020 > ERC Grants > ERC Starting Grant > ERC Grant 639233: Fuel from sunlight: Covalent organic frameworks as integrated platforms for photocatalytic water splitting and CO2 reduction
• Faculties: Chemistry and Pharmacy > Department of Chemistry
• Subjects: 500 Science > 540 Chemistry
• ISSN: 0002-7863
• Language: English