Pd metal and Pd-based alloys are ideal catalysts that allow for the electrochemical conversion of CO 2 to HCOO − at almost zero-overpotential with high selectivity, but catalyst degradation caused by concurrent CO poisoning limits their practical implementation. Here, we demonstrate that cyclic two-step electrolysis, by applying the reduction and oxidation potentials alternately, achieves 100% current density stability and 97.8% selectivity toward HCOO − production for at least 45 h. The key idea for achieving the reliability is based on the selective removal of CO by controlling the parameters during the oxidation step, which utilizes the different reversibility of HCOO − and CO production reactions. Furthermore, it is found that potentiostatic electrolysis causes CO adsorption and subsequent dehydridation, which in turn lowers HCOO − selectivity. Our work provides a system-level strategy for solving the poisoning issue that is inevitable in many electrocatalytic reactions.

The severe increase in the CO2 concentration is a causative factor of global warming, which accelerates the destruction of ecosystems. The massive utilization of CO2 for value-added chemical production is a key to commercialization to guarantee both economic feasibility and negative carbon emission. Although the electrochemical reduction of CO2 is one of the most promising technologies, there are remaining challenges for large-scale production. Herein, an overview of these limitations is provided in terms of devices, processes, and catalysts. Further, the economic feasibility of the technology is described in terms of individual processes such as reactions and separation. Additionally, for the practical implementation of the electrochemical CO2 conversion technology, stable electrocatalytic performances need to be addressed in terms of current density, Faradaic efficiency, and overpotential. Hence, the present review also covers the known degradation behaviors and mechanisms of electrocatalysts and electrodes during electrolysis. Furthermore, strategic approaches for overcoming the stability issues are introduced based on recent reports from various research areas involved in the electrocatalytic conversion.

Carbon capture and utilization technology has been studied for its practical ability to reduce CO2 emissions and enable economical chemical production. The main challenge of this technology is that a large amount of thermal energy must be provided to supply high-purity CO2 and purify the product. Herein, we propose a new concept called reaction swing absorption, which produces synthesis gas (syngas) with net-zero CO2 emission through direct electrochemical CO2 reduction in a newly proposed amine solution, triethylamine. Experimental investigations show high CO2 absorption rates (>84%) of triethylamine from low CO2 concentrated flue gas. In addition, the CO Faradaic efficiency in a triethylamine supplied membrane electrode assembly electrolyzer is approximately 30% (@−200 mA cm−2), twice higher than those in conventional alkanolamine solvents. Based on the experimental results and rigorous process modeling, we reveal that reaction swing absorption produces high pressure syngas at a reasonable cost with negligible CO2 emissions. This system provides a fundamental solution for the CO2 crossover and low system stability of electrochemical CO2 reduction.