There has been growing interest in the photoelectrochemical conversion of carbon dioxide to useful carbon-based fuels or chemicals. Given the fact that the CO₂ molecule is very stable, its electroreduction processes are characterized by large overpotentials. It is often postulated that, during electroreduction, the rate limiting step is the protonation of the adsorbed CO product to form the CHO adsorbate. In this respect, the proton availability and its mobility at the photo(electro)chemical interface has to be addressed. On the other hand, competition between such parallel processes as hydrogen evolution and carbon dioxide reduction has also to be considered.

Recently, we have concentrated on the development of hybrid materials by utilizing combination of metal oxide semiconductors thus capable of effective photoelectrochemical reduction of carbon dioxide. For example, the combination of titanium (IV) oxide and copper (I) oxide has been considered before and after sunlight illumination. Application of the hybrid system composed of both above-mentioned oxides resulted in high current densities originating from photoelectrochemical reduction of carbon dioxide mostly to methanol (CH₃OH) as demonstrated upon identification of final products. Among important issue is intentional stabilization, activation, and functionalization of the mixed-metal-oxide-based photoelectrochemcal interface toward better long-term performance and selectivity production of small organic molecules (C1-C4) and other chemicals. In this respect, ultra-thin films of conducting polymers (simple or polyoxometallate-derivatized) and supramolecular complexes (with nitrogen containing ligands and certain transition metal sites), sub-monolayers of metals (Cu, Au), networks of noble metal (Au, Ag) nanoparticles or layers of robust bacterial biofilms have been considered.

We are also going to demonstrate that the photoinduced electron from semiconductor conduction band is capable of activation of the active center of the metalo-enzyme molecule. Here the.nanostructured silicon material has been chosen as the substrate for the enzyme adsorption. In this case the p-type Si(111) was etched toward formation of the bunched steps on the surface. The photo-biocathode with Cu-containing enzyme has induced the reduction of not only oxygen but carbon dioxide as well, under illuminations with photon energies higher than silicon band gap.

In the presentation, special attention will be paid to mechanistic aspects of electroreduction of carbon dioxide, fabrication and characterization of highly selective and durable semiconductor photoelectrode materials and to importance of the reaction conditions.