Understanding low-pressure CO 2 insertion chemistry in epoxide–CO 2 copolymerization catalysis

Journal article

Despite many CO2 use strategies being reliant on fast and selective CO2 insertion reactions into metal-alkoxide bonds, in-depth studies into this chemistry remain rare. Here the effect of CO2 pressure on the CO2 insertion chemistry is studied using epoxide–CO2 copolymerizations. Five high-performance literature catalysts are investigated under systematically varied CO2 pressures, revealing kinetic profiles indicative of CO2 insertion equilibria. For each catalyst, two key parameters describing the CO2 insertion chemistry are determined: the equilibrium constant, Keq, and the saturation CO2 pressure above which catalytic performance is maximized, Pthreshold. Generalizable correlations between copolymerization activity, Keq and Pthreshold are uncovered and used to predict performances for four further catalyst–monomer combinations. These correlations are a direct link between CO2 insertion chemistry and process operating conditions, providing a mechanistic framework and testing protocols to accelerate future catalyst development. These results should help deliver efficient scalable CO2 use technologies, operating with minimal energy.

Authors: Thorogood, R; Eisenhardt, KHS; Smith, ML; Williams, CK

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: Nature Research
• Journal: Nature Chemistry
• Volume: 18
• Issue: 5
• Pages: 931-938
• Publication date: 2026-04-30
• Acceptance date: 2026-02-11
• DOI: 10.1038/s41557-026-02098-6
• EISSN: 1755-4349
• ISSN: 1755-4330
• Language: English
• Keywords: Copolymer; Polymer; Monomer; Catalysis; Polymerization