Engineering the Inhomogeneity of Metal-Insulator-Semiconductor Junctions for Photoelectrochemical Methanol Oxidation.

Si-based inhomogeneous metal-insulator-semiconductor (MIS) junctions with a discontinuous metal nanostructure on the Si/insulator layer are expected to be efficient photoelectrodes for solar energy conversion. However, the formation of a metal nanostructure with an optimized arrangement on semiconductors for efficient charge carrier collection is still a big challenge. Herein, we report a method for the in situ formation of an n-Si inhomogeneous MIS junction with well-dispersed metal nanocontacts through a self-assembly process during photoelectrochemical (PEC) methanol oxidation. The photovoltage shows a strong dependence on the inhomogeneity of the n-Si MIS junction, which can be precisely tuned by the applied electrode potential and operation time. The appropriate inhomogeneity of the Schottky junction as well as the high barrier regions induced by the metal oxide/(oxy)hydroxide layer synergistically produces a large photovoltage of 500 mV for the n-Si inhomogeneous MIS junction. Finally, the n-Si-based photoanode is coupled with a CO2-to-formate reaction to realize the production of formate at both electrodes, resulting in a high faradic efficiency (FE) of 86 and 93% for anode and cathode reactions at an operational current of 30 mA/cm2, respectively. These findings provide important insights into the design of highly efficient inhomogeneous MIS junctions through an in situ self-assembly route for solar energy conversion and storage.

Coupling CO2-to-Ethylene Reduction with the Chlor-Alkaline Process in Seawater through In Situ-Formed Cu Catalysts.

The overall commercial value of a CO2 electroreduction system is hindered by the valueless product and high energy consumption of the oxygen evolution reaction (OER) at the anode. Herein, with an in situ-formed copper catalyst, we employed the alternative chlorine evolution reaction for OER, and high-speed formation of both C2 products and hypochlorite in seawater can be realized. The EDTA in the sea salt electrolyte can trigger an intense dissolution and deposition of Cu on the surface of the electrode, resulting in the in situ formation of dendrites of Cu with high chemical activity. In this system, a faradaic efficiency of 47% can be realized for C2H4 production at the cathode and a faradaic efficiency of 85% can be realized for hypochlorite production at the anode with an operation current of 100 mA/cm2. This work presents a system for designing a highly efficient coupling system for the CO2 reduction reaction and alternative anodic reactions toward value-added products in a seawater environment.