单原子位点光催化共价有机框架分子型钴配合物协同析氢

Max Planck Institute for Solid State Research , Heisenbergstraße 1, 70569 Stuttgart, Germany.

Department of Chemistry, University of Munich (LMU) , Butenandtstraße 5-13, 81377 München, Germany.

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

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 evolution rate of 782 μmol h g 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 generation from the Co-hydride and/or Co-hydride species.

我们首次展示了使用 COF 敏化剂和分子质子还原催化剂进行光催化制氢。在嗪基连接的 N2-COF 敏化剂、氯（吡啶）钴配合物共催化剂和 TEOA 供体的作用下，在水/乙腈混合物中，H2 的生成速率达到了 782 μmol h g，TON 达到了 54.4。PXRD、固态光谱、EM 分析和量子化学计算表明，从 COF 到共催化剂的外层电子转移，随后遵循 Co-氢化物和/或 Co-氢化物物种生成 H2 的单金属途径。