The development of solid materials for CO2 reduction could improve upon the present state of the art in molecular catalysis by providing approaches to stabilizing catalysts against degradation and making separation of products more facile.1 In this work, we describe an electrode-attached, porous, conductive, and catalytically functionalized material for electrochemical carbon dioxide reduction to carbon monoxide, a fuel precursor. The approach relies on imbedding proven molecular CO2 reduction catalyst Mn(bipy)(CO)3Br 2 in a novel version of a known conductive coordination polymer consisting of rhodium diisocyanide sheets that stack with Rh-Rh bonding.3 The structure is grown from a gold electrodes via free isocyanide ligands, known to self-assemble on gold.4 The Mn catalyst is integrated directly in the coordination polymer by incorporating 5,5'-diisocyanide-2,2'-bipyridine in the coordination polymer, as indicated in the attached figure showing one coordination polymer sheet. Infrared reflection-absorption spectroscopy and electrochemical analysis is used to characterize the catalytically-functionalized, coordination polymer-modified electrodes. While the Rh coordination polymer host for the catalysts provides important proof of principle, our ongoing efforts involve preparation of conductive supports from more abundant materials, and these will also be described. 1G. Centi and S. Perathoner. Catalysis Today. 2009, 148, 191. 2 M.D. Sampson et al. Inorganic Chem. 2014, 136, 5460. 3 E.G. Carson et al. J Phys Chem B. 2007, 111, 14114. 4 J.I. Henderson et al. Langmuir. 2000, 16, 6183

Molecular catalyst incorporation in conductive coordination polymer scaffolds for heterogeneous electrocatalytic carbon dioxide reduction

251st National Meeting (2016)

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