Development of Nanostructured Hybrid Materials for Electrocatalytic and Photoelectrocatalytic Reduction of Carbon Dioxide
Because reduction of CO2 can effectively occur by hydrogenation, to optimize the conventional electrocatalytic approach, we propose such a model catalytic system as nanostructured metallic palladium capable of absorbing reactive hydrogen in addition to the ability to adsorb monoatomic hydrogen at the interface. Under such conditions, the two-electron reduction of CO2 typically to CO is favored. To produce highly dispersed and reactive nanoparticles, we generate them by electrodeposition from N-coordination complexes of palladium(II). The resulting metallic Pd nanoparticles, rather than Pd cationic species, are stabilized and activated by nitrogen coordination centers from the macromolecular matrix. In the present research, we demonstrate that stabilization and activation of highly dispersed nanostructured metallic Pd centers with a supramolecular architecture of “privileged ligands” results in the electrocatalytic enhancement of the CO2 reduction. Reduction of carbon dioxide begins now at less negative potentials and is accompanied by significant enhancement of the CO2-reduction current densities. Among important issues are specific interactions between nitrogen coordinating centers and metallic palladium sites at the electrocatalytic interface.
Another possibility to enhance electroreduction of carbon dioxide is to explore direct transformation of solar energy to chemical energy using transition metal oxide semiconductor materials. We show here that, by intentional and controlled combination of metal oxide semiconductors, we have been able to drive effectively photoelectrochemical reduction of carbon dioxide. The combination of titanium (IV) oxide (TiO2) and copper (I) oxide (Cu2O) has been explored toward the reduction of carbon (IV) oxide (CO2) 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 using conventional and mass-spectrometry assisted gas chromatography. On mechanistic grounds, the role of TiO2 seems to be not only stabilizing: the oxide is also expected to prevent the recombination of charge carriers.