Single-Site Photocatalytic H2 Evolution from Covalent Organic Frameworks with Molecular Cobaloxime Co-Catalysts

Tanmay Banerjee; Frederik Haase; Gökcen Savasci; Kerstin Gottschling; Christian Ochsenfeld; Bettina V Lotsch

doi:10.1021/jacs.7b07489

Single-Site Photocatalytic H₂ Evolution from Covalent Organic Frameworks with Molecular Cobaloxime Co-Catalysts

J Am Chem Soc. 2017 Nov 15;139(45):16228-16234. doi: 10.1021/jacs.7b07489. Epub 2017 Nov 3.

Authors

Tanmay Banerjee¹, Frederik Haase^{1

2}, Gökcen Savasci^{1

2}, Kerstin Gottschling^{1

2}, Christian Ochsenfeld^{2

3}, Bettina V Lotsch^{1

2

3

4}

Affiliations

¹ Max Planck Institute for Solid State Research , Heisenbergstraße 1, 70569 Stuttgart, Germany.
² Department of Chemistry, University of Munich (LMU) , Butenandtstraße 5-13, 81377 München, Germany.
³ Center for Nanoscience , Schellingstraße 4, 80799 München, Germany.
⁴ Nanosystems Initiative Munich (NIM) , Schellingstraße 4, 80799 München, Germany.

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, H₂ evolution rate of 782 μmol 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 H₂ generation from the Co^III-hydride and/or Co^II-hydride species.

Publication types

Research Support, Non-U.S. Gov't