RESUMO
Electrochemical CO2 reduction can convert CO2 to value-added chemicals, but its selectivity toward C3+ products are very limited. One possible solution is to run the reactions in hybrid processes by coupling electrocatalysis with other catalytic routes. In this contribution, we report the cascade electrocatalytic and thermocatalytic reduction of CO2 to propionaldehyde. Using Cu(OH)2 nanowires as the precatalyst, CO2 /H2 O is reduced to concentrated C2 H4 , CO, and H2 gases in a zero-gap membrane electrode assembly (MEA) reactor. The thermochemical hydroformylation reaction is separately investigated with a series of rhodium-phosphine complexes. The best candidate is identified to be the one with the 1,4-bis(diphenylphosphino)butane diphosphine ligand, which exhibits a propionaldehyde turnover number of 1148 under a mild temperature and close-to-atmospheric pressure. By coupling and optimizing the upstream CO2 electroreduction and downstream hydroformylation reaction, we achieve a propionaldehyde selectivity of ~38 % and a total C3 oxygenate selectivity of 44 % based on reduced CO2 . These values represent a more than seven times improvement over the best prior electrochemical system alone or over two times improvement over other hybrid systems.
RESUMO
Ionic liquids (ILs) have been widely used in transition metal-catalyzed processes, but the precise behavior of ILs and catalysts in these reactions is unknown. Herein, the role of ILs and the interaction pattern between Shvo's catalyst and ILs have been revealed with characterization by 1H NMR and crystallography based on the catalytic hydrogenation of CO2. ILs promote the dissociation of Shvo's catalyst and enhance the rate of production of CO. The CO that is produced is subsequently used in the tandem hydroformylation-reduction of alkenes to produce valuable alcohols. In the absence of ILs, formamides can be obtained by N-formylation of most primary or secondary amines.