Integrated electrochemical CO2 reduction and hydroformylation

The development of integrated multi-catalyst processes has become of high interest to transform abundant feedstocks or environmental pollutants to commodity chemicals in a one pot, one pass fashion. Specifically, CO2 poses a large environmental burden and would thus be a desirable, relatively abundant C1 source in multi-step synthetic chemistry. Herein we disclose the synthesis of aldehydes from CO2via the integration of electrochemical CO2 reduction (CO2RR) and hydroformylation, taking advantage of the typically unwanted concomitant hydrogen evolution (HER) to generate the necessary CO and H2 needed for hydroformylation. Though typical hydroformylation catalysts based on Rh would be deactivated under CO2RR conditions, we circumvent this limitation by spatially segregating our CO2RR and hydroformylation systems in a vial-in-vial reactor, while allowing CO and H2 transport between catalyst sites. In this manner, 97% aldehyde yield from CO2RR and styrene was achieved selectively using a classic homogeneous hydroformylation catalyst in HRh(CO)(PPh3)3, and 43% aldehyde yield was obtained using a heterogenized version of this Rh catalyst onto mesoporous silica. This work not only repurposes undesired HER in CO2RR and prepares aldehydes from CO2 without added H2, but expands the scope of processes that transform feedstocks all the way to commodity chemicals in a one pass manner.