| Illustration of the microfluidic flow cell architecture. a, Exploded view of the microfluidic cell 13 used in this study. b, Scheme of the flow of species at the cathode electrocatalyst. Reactant CO gas flows 14 through the gas diffusion electrode (GDE) for its reduction to various products. KOH catholyte furnishes 15 an alkaline environment at the cathode and transports gaseous and liquid products to the reservoir for 16 analysis by GC or 1 H NMR, respectively. The flow of CO and KOH catholyte are indicated in black dash 17 line. The molecular structure of CO, C2H4 and AcO -are shown. (red, oxygen; grey, carbon; white, 18 hydrogen) 19 20

| Illustration of the microfluidic flow cell architecture. a, Exploded view of the microfluidic cell 13 used in this study. b, Scheme of the flow of species at the cathode electrocatalyst. Reactant CO gas flows 14 through the gas diffusion electrode (GDE) for its reduction to various products. KOH catholyte furnishes 15 an alkaline environment at the cathode and transports gaseous and liquid products to the reservoir for 16 analysis by GC or 1 H NMR, respectively. The flow of CO and KOH catholyte are indicated in black dash 17 line. The molecular structure of CO, C2H4 and AcO -are shown. (red, oxygen; grey, carbon; white, 18 hydrogen) 19 20

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The highest performance flow cells capable of electrolytically converting CO2 into higher value chemicals and fuels pass a concentrated hydroxide electrolyte across the cathode. A major problem for CO2 electrolysis is that this strongly alkaline medium converts the majority of CO2 into unreactive HCO3– and CO32– rather than CO2 reduction reaction (...

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Direct electrochemical reduction of CO2 to C2 products such as ethylene is more efficient in alkaline media, but it suffers from parasitic loss of reactants due to (bi)carbonate formation. A two-step process where the CO2 is first electrochemically reduced to CO and subsequently converted to desired C2 products has the potential to overcome the limitations posed by direct CO2 electroreduction. In this study, we investigated the technical and economic feasibility of the direct and indirect CO2 conversion routes to C2 products. For the indirect route, CO2 to CO conversion in a high temperature solid oxide electrolysis cell (SOEC) or a low temperature electrolyzer has been considered. The product distribution, conversion, selectivities, current densities, and cell potentials are different for both CO2 conversion routes, which affects the downstream processing and the economics. A detailed process design and techno-economic analysis of both CO2 conversion pathways are presented, which includes CO2 capture, CO2 (and CO) conversion, CO2 (and CO) recycling, and product separation. Our economic analysis shows that both conversion routes are not profitable under the base case scenario, but the economics can be improved significantly by reducing the cell voltage, the capital cost of the electrolyzers, and the electricity price. For both routes, a cell voltage of 2.5 V, a capital cost of $10,000/m², and an electricity price of <$20/MWh will yield a positive net present value and payback times of less than 15 years. Overall, the high temperature (SOEC-based) two-step conversion process has a greater potential for scale-up than the direct electrochemical conversion route. Strategies for integrating the electrochemical CO2/CO conversion process into the existing gas and oil infrastructure are outlined. Current barriers for industrialization of CO2 electrolyzers and possible solutions are discussed as well.