Abstract

CO2 activation and conversion are of significant interest. Here we report a mono-alkyl pyrocarbonate-bipyridinium salt intermediate to activate CO2 for synthesizing ethyl formate as a value-added product via tandem esterification and hydrogenation. The required basic bipyridine sites for CO2 activation and metallic Pd nanoparticles for hydrogenation were assembled in the same nano-cavity of a designer metal–organic framework (MOF). This MOF hybrid exhibits a high catalytic activity to generate ethyl formate (HCO2Et) (1333 μmol/gcat/h) with 93.5% selectivity at 412 K. The turnover frequency of HCO2Et based on the number of exposed Pd atoms is up to 22.2 h−1, higher than those of other catalysts previously reported for generating alkyl formates from CO2 under similar conditions.

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