Organic Non-Nucleophilic Electrolyte Resists Carbonation during Selective CO Electroreduction.

The spontaneous reaction of CO with water and hydroxide to form (bi)carbonates in alkaline aqueous electrolytes compromises the energy and carbon efficiency of CO electrolyzers. We hypothesized that electrolyte carbonation could be mitigated by operating the reaction in an aprotic solvent with low water content, while also employing an exogenous non-nucleophilic acid as the proton donor to prevent parasitic capture of CO by its conjugate base. However, it is unclear whether such an electrolyte design could simultaneously engender high CO reduction selectivity and low electrolyte carbonation.

Highly Active NiO Photocathodes for HO Production Enabled via Outer-Sphere Electron Transfer.

Tandem dye-sensitized photoelectrosynthesis cells are promising architectures for the production of solar fuels and commodity chemicals. A key bottleneck in the development of these architectures is the low efficiency of the photocathodes, leading to small current densities. Herein, we report a new design principle for highly active photocathodes that relies on the outer-sphere reduction of a substrate from the dye, generating an unstable radical that proceeds to the desired product.