Framework nitrogen atoms of carbon nitride (C3N4) can coordinate with and activate metal sites for catalysis. In this study, C3N4 was employed to harvest visible light and activate Co2+ sites, without the use of additional ligands, in photochemical CO2 reduction. Photocatalysts containing single Co2+ sites on C3N4 were prepared by a simple deposition method and demonstrated excellent activity and product selectivity toward CO formation. A turnover number of more than 200 was obtained for CO production using the synthesized photocatalyst under visible-light irradiation. Inactive cobalt oxides formed at relatively high cobalt loadings but did not alter product selectivity. Further studies with X-ray absorption spectroscopy confirmed the presence of single Co2+ sites on C3N4 and their important role in achieving selective CO2 reduction.

In the presence of a molecular Co(II) catalyst, CO2 reduction occurred at much less negative potentials on Si photoelectrodes than on an Au electrode. The addition of 1 % H2 O significantly improved the performance of the Co(II) catalyst. Photovoltages of 580 and 320 mV were obtained on Si nanowires and a planar Si photoelectrode, respectively. This difference likely originated from the fact that the multifaceted Si nanowires are better in light harvesting and charge transfer than the planar Si surface.

The CO-reduction activity of two Re(i)-NHC complexes is investigated employing a silicon nanowire photoelectrode to drive catalysis. Photovoltages greater than 440 mV are observed along with excellent selectivity towards CO over H formation. The observed selectivity towards CO production correlates with strong adsorption of the catalysts on the photoelectrode surface.