Carbon monoxide separation from industrial waste gases could contribute largely to carbon circularity. Traditional separation technologies are unable to separate CO from N₂ selectively. Instead, electroactive carriers show promise in selective separation of CO from N₂, where CO binds a complex in one oxidation state and releases in another oxidation state. We study Cu(i)/Cu(ii)-chloride complexes as potential carrier materials with high binding affinity to CO, good solubility and low energy consumption of the process. We show that the electrolyte composition of a copper chloride system affects the binding affinity and stability of the copper carrier (Cu⁺). Cyclic voltammetry measurements reveal that the CO binding constant increase from the previously reported 1600 M⁻¹ for 1 M KCl to 5500 M⁻¹ for 0.5 M CaCl₂. However, this increase in binding constant is not reflected to the same extent in the CO capture capacity, showing a smaller increase in CO capture. In general, the binding constant decreases with chloride concentration, while the Cu⁺ stability window increases. This highlights a trade-off that needs to be considered for electrolyte selection in electrochemical CO separation with copper chlorides.

A key challenge in capturing CO2 from postcombustion gases is humidity due to competitive adsorption between CO2 and H2O. Multivariate (MTV) metal-organic frameworks (MOFs) have been considered a promising option to address this problem, e.g., combining CO2-affinitive and hydrophobic groups. Here, we synthesized a series of amine and methyl cofunctionalized MTV MIL-53(Al)-xNH2(1 - x)CH3 and their parent materials. All the mixed linker MIL-53(Al)-xNH2(1 - x)CH3 showed amino linker enrichment compared to the synthesis ratio, yet the linkers were distributed relatively homogeneously from the bulk to the surface. Material hydrophobicity or hydrophilicity varied with methyl or amino group content, respectively. The single-component adsorption indicated that certain mixed linker MIL-53(Al)-xNH2(1 - x)CH3 might outcompete the parent materials. In CO2-H2O competitive adsorption, however, the hydrophobic parental MIL-53(Al)-CH3 outperformed the mixed linker MOFs. CO2 adsorption capacities of 5.4, 4.9, and 3.6 wt % were found for 0.3 bar of CO2 under 0, 5, and 10% RH, respectively. The results highlight that materials with enhanced hydrophobicity and tight-fitting pores can outperform groups with high CO2 affinity in the CO2 capture under humid conditions.

Large amounts of carbon monoxide are produced by industrial processes such as biomass gasification and steel manufacturing. The CO present in vent streams is often burnt, this produces a large amount of CO₂, e.g., oxidation of CO from metallurgic flue gasses is solely responsible for 2.7% of manmade CO₂ emissions. The separation of N₂ from CO due to their very similar physical properties is very challenging, meaning that numerous energy-intensive steps are required for CO separation, making the CO separation from many process streams uneconomical in spite of CO being a valuable building block in the production of major chemicals through C1 chemistry and the production of linear hydrocarbons by the Fischer-Tropsch process. The development of suitable processes for the separation of carbon monoxide has both industrial and environmental significance. Especially since CO is a main product of electrocatalytic CO₂ reduction, an emerging sustainable technology to enable carbon neutrality. This technology also requires an energy-efficient separation process. Therefore, there is a great need to develop energy efficient CO separation processes adequate for these different process streams. As such the urgency of separating carbon monoxide is gaining greater recognition, with research in the field becoming more and more crucial. This review details the principles on which CO separation is based and provides an overview of currently commercialised CO separation processes and their limitations. Adsorption is identified as a technology with the potential for CO separation with high selectivity and energy efficiency. We review the research efforts, mainly seen in the last decades, in developing new materials for CO separation via ad/bsorption and membrane technology. We have geared our review to both traditional CO sources and emerging CO sources, including CO production from CO₂ conversion. To that end, a variety of emerging processes as potential CO₂-to-CO technologies are discussed and, specifically, the need for CO capture after electrochemical CO₂ reduction is highlighted, which is still underexposed in the available literature. Altogether, we aim to highlight the knowledge gaps that could guide future research to improve CO separation performance for industrial implementation.