Visible-Light-Driven Conversion of CO ₂ to CH ₄ with an Organic Sensitizer and an Iron Porphyrin Catalyst

Using a phenoxazine-based organic photosensitizer and an iron porphyrin molecular catalyst, we demonstrated photochemical reduction of CO 2 to CO and CH 4 with turnover numbers (TONs) of 149 and 29, respectively, under visible-light irradiation (λ > 435 nm) with a tertiary amine as sacrificial electron donor. This work is the first example of a molecular system using an earth-abundant metal catalyst and an organic dye to effect complete 8e – /8H + reduction of CO 2 to CH 4, as opposed to typical 2e – /2H + products of CO or formic acid. The catalytic system continuously produced methane even after prolonged irradiation up to 4 days. Using CO as the feedstock, the same reactive system was able to produce CH 4 with 85% selectivity, 80 TON and a quantum yield of 0.47%. The redox properties of the organic photosensitizer and acidity of the proton source were shown to play a key role in driving the 8e – /8H + processes.