In this study, we report the electrocatalytic behavior of a neutral, monomeric Zn(II) complex, ZnL1, for the metal ligand cooperativity and ligand-centered carbon dioxide reduction in methanol to formate. ZnL1, exhibits a maximum TOF of 185.5 s-1, or 6.678 x 105 h-1 at an E1/2 of -2.08V vs Fc/Fc+, or an overpotential of -1.45V. The rate law is second-order in catalyst and first order in proton concentration. 1H NMR of of the controlled potential electrolysis confirms ZnL1 as a carbon dioxide reduction catalyst and formate as the main product with a TON of 9.54 and a faradaic efficiency of 75%, with not sign of degradation over 24h. The catalyst was also shown to react with other hydride sources such as platinum and sodium borohydride. The catalyst was is also shown to react with small concentrations of carbon dioxide with full conversion to the methylcarbonate intermediate at 1,000 ppm CO2. Catalyst reactions were also done using atmospheric pressures of CO2 and binding was also shown as well, via UV/vis and IR. Bulk electrolysis at these pressures also resulted in a TON of 3.88. Catalytically important intermediates were identified using 1H NMR, X-Ray photoelectron, IR-spectroscopy, and UV-visible spectroscopy.

Homogeneous reduction of atmospheric carbon dioxide by a neutral zinc complex

2019 Fall National Meeting

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