Photocatalytic CO2 Reduction to Formate Using a Mn(I) Molecular Catalyst in a Robust Metal鈥揙rganic Framework

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• 作者：Honghan Fei ; Matthew D. Sampson ; Yeob Lee ; Clifford P. Kubiak ; Seth M. Cohen
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：July 20, 2015
• 年：2015
• 卷：54
• 期：14
• 页码：6821-6828
• 全文大小：458K
• ISSN：1520-510X

文摘

A manganese bipyridine complex, Mn(bpydc)(CO)₃Br (bpydc = 5,5鈥?dicarboxylate-2,2鈥?bipyridine), has been incorporated into a highly robust Zr(IV)-based metal鈥搊rganic framework (MOF) for use as a CO₂ reduction photocatalyst. In conjunction with [Ru(dmb)₃]²⁺ (dmb = 4,4鈥?dimethyl-2,2鈥?bipyridine) as a photosensitizer and 1-benzyl-1,4-dihydronicotinamide (BNAH) as a sacrificial reductant, Mn-incorporated MOFs efficiently catalyze CO₂ reduction to formate in DMF/triethanolamine under visible-light irradiation. The photochemical performance of the Mn-incorporated MOF reached a turnover number of approximately 110 in 18 h, exceeding that of the homogeneous reference systems. The increased activity of the MOF-incorporated Mn catalyst is ascribed to the struts of the framework providing isolated active sites, which stabilize the catalyst and inhibit dimerization of the singly reduced Mn complex. The MOF catalyst largely retained its crystallinity throughout prolonged catalysis and was successfully reused over several catalytic runs.