As energy systems across the globe transition toward net-zero emissions, the decarbonization of hard-to-decarbonize sectors, e.g., industry and transportation, is becoming more crucial. Renewable power-driven carbon dioxide (CO₂) electrolysis has the potential to facilitate this transition by (1) substituting carbon-intensive petrochemical and fuel production and (2) using CO₂ otherwise emitted from industrial processes or CO₂ from the atmosphere; however, because of existing technical and economic challenges, the industrial deployment of this technology is not yet imminent. Here, we present an overview of CO₂ electrolysis technologies to identify key hurdles in view of the industrial deployment of this technology in net-zero emissions energy systems. From the technology standpoint, catalysts should be developed with enhanced activity, selectivity, and stability/durability as well as membranes and reactors that prevent carbonate formation or crossover, achieve higher reaction rates, e.g., >1 A/cm², and demonstrate long-term stability, e.g., >5 years. Conversely, from the system integration standpoint, impurity-tolerant CO₂ electrolysis systems need to be developed and tested under relevant conditions, e.g., CO₂ streams with traces of impurities (NO_x, SO_x, O₂, N₂, H₂S, etc.). Additionally, the quantification of pros and cons of different integration pathways for CO₂ capture and CO₂ electrolysis requires further research. Moreover, the integration with variable renewable power sources—e.g., wind and solar photovoltaic power—and electricity markets requires a better understanding. For instance, the value of CO₂ electrolysis flexibility in view of variable renewable power supply or dynamic electricity prices is not well understood.

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Defossilizing the chemical industry using air-to-chemical processes offers a promising solution to driving down the emission trajectory to net-zero by 2050. Syngas is a key intermediate in the chemical industry, which can be produced from electrolytic H2 and air-sourced CO2. To techno-economically assess possible emerging air-to-syngas routes, we develop detailed process simulations of direct air CO2 capture, proton exchange membrane water electrolysis, and CO2 electrolysis. Our results show that renewable electricity prices of ≤$15 per MW h enable the replacement of current syngas production methods with CO2 electrolysis at CO2 avoidance costs of about $200 per t-CO2. In addition, we identify necessary future advances that enable economic competition of CO2 electrolysis with traditional syngas production methods, including a reverse water gas shift. Indeed, we find an improved CO2 electrolysis process (total current density = 1.5 A cm−2, CO2 single-pass conversion = 54%, and CO faradaic efficiency = 90%) that can economically compete with the reverse water gas shift at an optimal cell voltage of about 2.00 V, an electricity price of $28–42 per MW h, a CO2 capture cost of $100 per t-CO2, and CO2 taxes of $100–300 per t-CO2. Finally, we discuss the integration of the presented emerging air-to-syngas routes with variable renewable power systems and their social impacts in future deployments. This work paints a holistic picture of the targets required to economically realize a defossilized syngas production method that is in alignment with net-zero goals.@en