CO2 Chemistry

Two catalytic approaches will be used for CO2 conversion into high-value organic chemicals, namely organic (cyclic) carbonates (OCCs) and carbonyls and acid derivatives. Traditionally, OCCs are synthesized via cycloaddition of CO₂ to epoxides or via reaction of phosgene with alcohols [HXJ24]. These approaches raise serious concerns due to the acute toxicity of epoxides [HEL03] and of phosgene. As a safer and more sustainable alternative, we propose catalytic coupling of alcohols, easyto-handle renewable substrates, with CO2 to produce OCCs. Similarly, toxic CO, widely used in catalytic carbonylation to yield carbonyls and acid derivatives, can be replaced by in situ CO₂ reduction. Though pivotal to industrial processes for producing a wide range of chemicals (e.g. polymers, pharmaceuticals, and agrochemicals) [BRS07], these processes largely rely on costly and scarce noble metal-based homogeneous catalysts and pure CO2. This task answers the need for developing reductive carbonylation strategies from high purity of bio-CO2, using environmental-friendly recyclable heterogeneous catalysts (contributing to O2.1 and O2.2). These new methods will also be used for the synthesis of isotopically labelled high-value compounds using bio-CO2 as a source of 14CO and 11C for preclinical drug metabolic studies, radiopharmaceuticals for CO2 neural cancer treatment, and diagnostic applications – a multibillion-dollar market.

In addition, CO2 copolymerization into polycarbonates offers a direct route to incorporating CO2 as a building block into engineering thermoplastics. However, this approach suffers from competing side reactions, in particular the formation of cyclic carbonates resulting in low yields and low Mw. The catalysts, typically organometallic compounds, play a decisive role in selectivity and regioselectivity, but currently fail to quantitatively convert CO2 into polycarbonates. Therefore, we will confine the catalytic sites densely onto well-crafted porous matrix to enhance (regio)selectivity and by developing matching chain-extenders to link polycarbonates to produce high Mw polymers suitable for composite use.

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