Periodic Reporting for period 2 - CARBOFLOW (Streamlined carbon dioxide conversion in ionic liquids – a platform strategy for modern carbonylation chemistry)
Berichtszeitraum: 2022-07-01 bis 2023-12-31
Carbon dioxide from the combustion of fossil sources is regarded as the most significant greenhouse gas; hence, carbon dioxide capture and utilization (CCU) has attracted considerable attention in the past years. As an abundant, nontoxic, non-flammable and renewable carbon resource, carbon dioxide is attractive as a feedstock for making fine chemicals and materials. Since the discovery in the nineteenth century, carbonylation chemistry has found broad applicability in chemical industries and become now key technology for bulk and fine chemical synthesis. Despite its substantial toxicity, carbon monoxide (CO) is commonly used as carbonyl source causing considerable safety issues, particularly when transported and used on bulk scale. The replacement of this hazardous gas with more benign surrogates would be highly desirable, and recent ideas focus on the valorization of carbon dioxide as abundant, non-toxic and renewable carbon resource.
However, few industrial processes utilize carbon dioxide as a raw material, and potent catalysts are required to overcome its thermodynamic and kinetic barrier.
The ERC-funded project CARBOFLOW focuses on the photocatalytic reduction of carbon dioxide in ionic liquids and its successive conversion into high value carbonyl compounds. Several goals need to be realized, including fundamental studies and optimization of the ionic liquid co-catalysed photocatalytic reduction of carbon dioxide to produce CO as building block under mild conditions. The reactivity of formed CO in carbon dioxide with various organic substrates needs to be explored before finally developing a streamlined and continuous process for the direct formation of carbonyl compounds from carbon dioxide.
Overall, we expect that the photocatalytic activation of carbon dioxide may overcome problems currently associated with carbon dioxide utilization, eventually replacing the long-standing bastion of CO-based carbonylation chemistry with novel solutions.
However, few industrial processes utilize carbon dioxide as a raw material, and potent catalysts are required to overcome its thermodynamic and kinetic barrier.
The ERC-funded project CARBOFLOW focuses on the photocatalytic reduction of carbon dioxide in ionic liquids and its successive conversion into high value carbonyl compounds. Several goals need to be realized, including fundamental studies and optimization of the ionic liquid co-catalysed photocatalytic reduction of carbon dioxide to produce CO as building block under mild conditions. The reactivity of formed CO in carbon dioxide with various organic substrates needs to be explored before finally developing a streamlined and continuous process for the direct formation of carbonyl compounds from carbon dioxide.
Overall, we expect that the photocatalytic activation of carbon dioxide may overcome problems currently associated with carbon dioxide utilization, eventually replacing the long-standing bastion of CO-based carbonylation chemistry with novel solutions.
Within the first period, the project CARBOFLOW has been running very well without significant deviations from the original plan. One PhD student and one undergraduate student have been working on the synthesis of different ionic liquids as co-catalysts and of photocatalysts, specifically Ru/Re and Ni/Ir systems. Together with two post-doctoral research fellows, the set-up for photocatalytic reactions, and specifically for carbon dioxide reduction in liquid and gas phase, was set-up and analytics were validated. First results on the photocatalytic reduction of carbon dioxide were successfully performed and show that CO can be produced under mild conditions with high selectivity.
In parallel, a second postdoctoral fellow was working on the development of carbonylation processes in pre-formed CO/carbon dioxide mixtures. So far, different reactions were successfully performed in batchwise mode and in continuous flow at ambient pressure, including alkoxycarbonylations, amidations, carbonylative cross couplings and formation of redox active esters.
In parallel, a second postdoctoral fellow was working on the development of carbonylation processes in pre-formed CO/carbon dioxide mixtures. So far, different reactions were successfully performed in batchwise mode and in continuous flow at ambient pressure, including alkoxycarbonylations, amidations, carbonylative cross couplings and formation of redox active esters.
So far, novel catalysts for photocatalytic carbon dioxide reduction could be developed featuring photosensitizer, photocatalyst and ionic liquids as co-catalysts These polymer conjugates showed high selectivity for the reduction of carbon dioxide to CO and can be used in solution,. but also as heterogeneous catalysts for continuous flow applications.
Additionally, a novel cooperation with the electrochemistry department enabled electrochemical carbon dioxide reduction in continous flow as alternative to photochemical reduction. Ultimately, novel photochemical reactions were developed that gave new input and widened product range for the utilization of captures carbon dioxide (CCU).
We expect that these results and findings can be fit together until the end of the project, thus providing a mild, reliable and continous way to utilize carbon dioxide for the production of fuels , bulk and fine chemicals.
Additionally, a novel cooperation with the electrochemistry department enabled electrochemical carbon dioxide reduction in continous flow as alternative to photochemical reduction. Ultimately, novel photochemical reactions were developed that gave new input and widened product range for the utilization of captures carbon dioxide (CCU).
We expect that these results and findings can be fit together until the end of the project, thus providing a mild, reliable and continous way to utilize carbon dioxide for the production of fuels , bulk and fine chemicals.