title: Photocatalytic CO2 Reduction to Formate Using a Mn(I) Molecular Catalyst in a Robust Metal-Organic Framework.
abstract: A manganese bipyridine complex, Mn(bpydc)(CO)3Br (bpydc = 5,5'-dicarboxylate-2,2'-bipyridine), has been incorporated into a highly robust Zr(IV)-based metal-organic framework (MOF) for use as a CO2 reduction photocatalyst. In conjunction with [Ru(dmb)3](2+) (dmb = 4,4'-dimethyl-2,2'-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.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093, United States.
authors.forename: Honghan
authors.initials: H
authors.lastname: Fei
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093, United States.
authors.forename: Matthew D
authors.initials: MD
authors.lastname: Sampson
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093, United States.
authors.forename: Yeob
authors.initials: Y
authors.lastname: Lee
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093, United States.
authors.forename: Clifford P
authors.initials: CP
authors.lastname: Kubiak
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093, United States.
authors.forename: Seth M
authors.initials: SM
authors.lastname: Cohen