Highly Efficient Porphyrin-Driven CO<SUB>2</SUB> Reduction via Hetero-Collisional Electron Transfer Route between Homogeneous Porphyrin and TiO<SUB>2</SUB> Semiconductor
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A zinc porphyrin complex (ZnP) was applied as visible-light photosensitizer in solution to the selective CO2 reduction to CO in the presence of an electron donor (BIH) and a hybrid catalyst (TiO2/ReC) prepared by anchoring of Re(4,4′-Y2-bpy)(CO)3Cl (Y = CH2PO(OH)2) on TiO2 particles. LED irradiation in N,N-dimethylformamide (DMF) at ＞500 nm resulted in the successful reduction of CO2 to CO. The systems efficiently proceeded CO2 to CO conversion during photocatalysis. Under lower energy irradiation (＞500 nm) with added 3 vol% water in DMF solvent, the ZnP hybrid showed a TONRe of ~2000 over an extended time-period of 50 h. It was found via in-situ UV-Vis absorption spectroscopy that the added porphyrin photosensitizers experience a significant photomodification during photolysis. Detailed in-situ mass analysis of supernatant after photocatalysis revealed that the original structure of porphyrin derivatives was significantly modified.