Oxidative carboxylation of olefins with CO2 in continuous-flow
Marcileia Zanatta a, Victor Sans a, Diego Iglesias a
a Institute of Advanced Materials (INAM), Universitat Jaume I, Avda Sos Baynat s/n, 12071, Castellón, Spain
Materials for Sustainable Development Conference (MATSUS)
Proceedings of Materials for Sustainable Development Conference (MAT-SUS) (NFM22)
#Suschem- Materials and electrochemistry for sustainable fuels and chemicals
Barcelona, Spain, 2022 October 24th - 28th
Organizers: Marta Costa Figueiredo and Raffaella Buonsanti
Poster, Marcileia Zanatta, 347
Publication date: 11th July 2022

Carbon dioxide is the largest contributor to greenhouse gas emission, one of the responsible for the global warming and the climate change. However, the abundance of CO2 can be also viewed as an opportunity to source the C1 building block of the future for fuels and chemicals. Regarding the CO2 reuse, one of the most studied added-value products is the cyclic carbonate. This because the cycloaddition of CO2 to epoxide presents an advantage because the CO2 is directly incorporated to the substrate without the necessity of breaking bonds of this gas. In addition, cyclic carbonates are widely applied as polar aprotic solvents, organic synthesis intermediates, electrolytes in lithium-ion batteries, cosmetic formulations, and monomers. The one-pot synthesis of cyclic carbonates from styrene employing the same or combined catalytic system for the alkene oxidation to form epoxides followed by cycloaddition of CO2 is a very cost-efficient method to generate functional cyclic carbonates. This route requires a multifunctional catalyst, which is able to promote the oxidation of alkenes to epoxides and the following reaction of the latter with CO2 to yield carbonates. In this context, the use of continuous-flow process appears as a smart methodology to connect different type of reactions in an efficient and sustainable processes to produce the cyclic carbonate. [1,2]   

Ionic liquids (ILs) and their covalently supported (SILs) or polymeric (PILs) analogues are multifunctional materials with great catalytic ability, due to the possibility to modulate their properties according to combination of the cation/anion.[3] Here, we successfully demonstrated an oxidative carboxylation of olefins with CO2 to produce cyclic carbonate in continuous-flow using IL-based catalyst (Figure 1). The system combines sequentially the olefins oxidation and the CO2 cycloaddition. Different parameters in the electrochemical oxidation were evaluated (e.g. solvent, electrode, electrolyte, concentrations and current intensity). Complete conversion and high selectivity (>60%) to the formation of epoxide were observed. The consecutive CO2 cycloaddition reaction were also evaluated and a global conversion of 88 % with 80% of selectivity to cyclic carbonate was observed.[4] 

This project has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No 101026335. 

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