Design of electrolyzer for carbon dioxide conversion to fuels and chemicals.

摘要

The stabilization of global atmospheric CO2 levels requires a transition towards a renewable energy based economy as well as methods for handling current CO2 output from fossil fuels. Challenges with renewable energy intermittency have thus far limited the use of these alternative energy sources to only a fraction of the current energy portfolio. To enable more widespread use of renewable energy systems, methods of large scale energy storage must be developed to store excess renewable energy when demand is low and allow for combined use of energy storage and renewable systems when demand is high. To date, no one technique has demonstrated energy storage methods on the gigawatt scale needed for integration with renewable sources; therefore the development of suitable energy storage technologies, such as CO2 electrolysis to fuels is needed. In this work, research efforts have focused on two major thrusts related to electrochemical methods of CO 2 conversion to fuels. The first thrust focuses on the synthesis and design of highly efficient anode and cathode catalysts with emphasis on understanding structure-property relationships. A second thrust focuses on the design of novel electrochemical devices for CO2 conversion and integration of synthesized materials into flow cell systems.;On the anode side, the synthesis of highly active catalysts using abundant transition metals is crucial to reducing capital costs and enabling widespread use of electrochemical CO2 conversion devices. Highly active mesoporous Co3O4 and metal-substituted Co3O4 water oxidation catalysts were designed to investigate the role of the spinel structure on water oxidation activity. Further analysis of metal substituted samples reveal the importance of the octahedral sites in the spinel structure, which was later used to design an Mg-Co3O4 sample with improved water oxidation activity.;The design of efficient cathode materials which can selectivity reduce CO2 to fuels and chemicals is critical to the widespread use of CO2 electrolysis. A nanoporous Ag material was synthesized through a dealloying technique able to operate with less than 0.5 V overpotential and high selectivity towards CO. CO is a valuable intermediate chemical which can used in Fischer-Tropsch or Gas-to-liquids technologies to produce liquids fuels. A detailed investigation of nanostructured Ag catalysts found stepped sites to be responsible for enhanced CO2 reduction activity due to improved stabilization of the COOH intermediate on the catalyst surface. In addition, an low-cost Zn dendrite electrocatalyst was developed using an electroplating technique. Low coordinated sites formed through electrodeposition demonstrated the suppression of hydrogen evolution while maintaining CO activity. The Zn dendrite electrocatalyst was further examined using a newly developed in situ X-ray absorption technique able to probe catalyst stability and crystalline structure under CO2 reduction operating conditions.;A final hurdle in the realization of CO2 electrolysis technologies is the integration of catalysts into working flow cell devices. To address this issue and enable testing in a practical system, a highly efficient and robust CO2 electrolysis flow cell was designed including the scale up of the previous nanoporous Ag synthesis procedure. Using the modified porous Ag catalyst, currents in the Amp regime were demonstrated approaching rates needed for energy storage applications. Stability on the order of days was successfully demonstrated due to use of robust system components and conditions suitable for process scale up.