INVESTIGATIONS OF COPPER CATALYZED CO2 REDUCTION WITH MOLECULAR COPPER MODELS, TECHNOECONOMICS, AND GREEN POLICY
Organometallic Copper Complexes
Decarbonizing the chemical sector, which is responsible for 8% of annual greenhouse gas emissions, is an acute challenge. The reduction of carbon dioxide (CO2) to multi-carbon products by copper heterogenous electrocatalysts offers an avenue to produce high value chemicals at low carbon intensi-ties. State of the art copper catalysts are unselective and inefficient, preventing their commercializa-tion. However, adding electronegative dopants on the copper surface and Lewis acid additives to reaction conditions can increase the selectivity of copper catalysts for multi-carbon products. Herein, we examine these chemical strategies using non-catalytic molecular dinuclear copper complexes as models for the copper surface. With voltammetry, high pressure electrochemistry, and spectroelectro-chemistry, we measure kinetic and thermodynamic parameters of key elementary steps in the CO2 reduction pathway. Our results suggest that additives and electron-withdrawing dopants increase the affinity of copper with CO – an intermediate in CO2 reduction. We also ask what performance targets do copper photoelectrocatalysts and electrocatalysts need to achieve to become market viable and answer this question using a technoeconomic analysis. The thesis concludes by looking at re-tooling existing financial mechanisms to support equitable deployment of emergent green technologies, such as CO2 electrochemical and photochemical reduction systems.
Mallouk, Thomas, E