Developing catalysts for the photochemical reduction of carbon dioxide is of great interest in the field of renewable energy because of the potential implications for the creation of carbon feedstocks from abundant sources and remediation of combustion emissions. Catalysts of the type [Re(bpy)(CO)3X]n (n = +1, 0; X = P(OEt)3, CH3CN, Cl�, OTf�; bpy = 2,2'  -bipyridyl and analogues thereof) have been studied extensively in recent decades for their capacity to catalytically reduce CO2, a greenhouse gas, into more valuable industrial feedstocks such as CO, which may be used in Fischer-Tropsch processes. These complexes are both competent electrocatalysts and photocatalysts for the reduction of carbon dioxide by two electrons. The proposed electrocatalytic mechanism centers on a single Re(bpy)-based catalyst which, when reduced by two electrons, can perform a concerted reduction of CO2 to CO and H2O. The proposed photocatalytic mechanism to generate CO requires an interspecies charge transfer between two singly photoreduced catalyst molecules to yield an active species similar to the electrocatalytic mechanism. The efficiency of the photocatalytic pathway has been improved by modification of the bipyridine with flexible hydrogen bonding groups. These hydrogen bonding groups favor the formation of dimers by two equivalents of the singly reduced complex, accelerating the interspecies charge transfer pathway. Interestingly, both pathways may be interrogated during electrochemical studies based on choice of solvent and scan rate.

Harnessing hydrogen-bonding interactions to improve the photocatalytic reduction of CO<sub>2</sub> by Re(2,2'-bipyridyl) complexes

248th National Meeting (2014)

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Harnessing hydrogen-bonding interactions to improve the photocatalytic reduction of CO2 by Re(2,2'-bipyridyl) complexes

Harnessing hydrogen-bonding interactions to improve the photocatalytic reduction of CO₂ by Re(2,2'-bipyridyl) complexes