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We report a bifunctional metal–organic layer (MOL) as a photocatalyst for CO2 reduction to CO under visible light irradiation with a turnover number of 6990 in 24 h and a CO selectivity of 99%. The fully accessible and modifiable Hf12 secondary building units and the coordinating porphyrin linkers of the MOL allow for the integration of both Ru photosensitizers and catalytic Fe-porphyrin sites into one single platform. The close distance (∼11 Å) between the Ru photosensitizer and the catalytic center leads to enhanced electron transfer and promotes photocatalytic CO2 reduction. This strategy leads to an increase of the CO2-to-CO turnover number for the bifunctional MOL catalyst over a combination of a homogeneous Ru photosensitizer and an Fe-porphyrin complex. The mechanism of MOL-catalyzed CO2 photoreduction was also studied by photophysical and electrochemical experiments.
Liao et al. (Fri,) studied this question.