Electrochemical Reduction of Protic Supercritical CO on Copper Electrodes.

The electrochemical reduction of carbon dioxide is usually studied in aqueous solutions under ambient conditions. However, the main disadvantages of this method are high hydrogen evolution and low faradaic efficiencies of carbon-based products. Supercritical CO (scCO ) can be used as a solvent itself to suppresses hydrogen evolution and tune the carbon-based product yield; however, it has received little attention for this purpose.

Photoreduction of CO2 using [Ru(bpy)2(CO)L]n+ catalysts in biphasic solution/supercritical CO2 systems.

The reduction of CO2 in a biphasic liquid-condensed gas system was investigated as a function of the CO2 pressure. Using 1-benzyl-1,4-dihydronicotinamide (BNAH) as sacrificial electron donor dissolved in a dimethylformamide-water mixture and [Ru(bpy)2(CO)L](n+) as a catalyst and [Ru(bpy)3](2+) as a photosensitizer, the reaction was found to produce a mixture of CO and formate, in total about 250 μmol after just 2 h. As CO2 pressure increases, CO formation is greatly favored, being four times greater than that of formate in aqueous systems.

Steady-state macroscale voltammetry in a supercritical carbon dioxide medium.

The electrochemical oxidation and reduction of decamethylferrocene is demonstrated in supercritical carbon dioxide at a macro gold disc electrode at 100 bar and 313 K. Fast mass transport effects were exhibited and the corresponding steady-state voltammetry was observed at high scan rates. A highly lipophilic room temperature ionic liquid that readily dissolved in supercritical CO(2) with acetonitrile as a co-solvent was used as an electrolyte, allowing for a conducting supercritical single phase.

Artificial photosynthesis at soft interfaces.

The concept of artificial photosynthesis at a polarised liquid membrane is presented. It includes two photosystems, one at each interface for the hydrogen and oxygen evolution respectively. Both reactions involve proton coupled electron transfer reactions, and some ultrafast steps at the photosensitization stage.