Cobalt-Doping Induced Formation of Five-Coordinated Nickel Selenide for Enhanced Ethanol Assisted Overall Water Splitting.

To overcome the low efficiency of overall water splitting, highly effective and stable catalysts are in urgent need, especially for the anode oxygen evolution reaction (OER). In this case, nickel selenides appear as good candidates to catalyze OER and other substitutable anodic reactions due to their high electronic conductivity and easily tunable electronic structure to meet the optimized adsorption ability. Herein, an interesting phase transition from the hexagonal phase of NiSe (H-NiSe) to the rhombohedral phase of NiSe (R-NiSe) induced by the doping of cobalt atoms is reported. The five-coordinated R-NiSe is found to grow adjacent to the six-coordinated H-NiSe, resulting in the formation of the H-NiSe/R-NiSe heterostructure. Further characterizations and calculations prove the reduced splitting energy for R-NiSe and thus the less occupancy in the t2g orbits, which can facilitate the electron transfer process. As a result, the Co2 -NiSe/NF shows a satisfying catalytic performance toward OER, hydrogen evolution reaction, and (hybrid) overall water splitting. This work proves that trace amounts of Co doping can induce the phase transition from H-NiSe to R-NiSe. The formation of less-coordinated species can reduce the t2g occupancy and thus enhance the catalytic performance, which might guide rational material design.

Porous Indium Tin Oxide-Supported NiFe LDH as a Highly Active Electrocatalyst in the Oxygen Evolution Reaction and Flexible Zinc-Air Batteries.

The oxygen evolution reaction (OER) is crucial for hydrogen production from water splitting and rechargeable metal-air batteries. However, the four-electron mechanism results in slow reaction kinetics, which needed to be accelerated by efficient catalysts. Herein, a hybrid catalyst of novel nickel-iron layered double hydroxide (NiFe LDH) on porous indium tin oxide (ITO) is presented to lower the overpotential of the OER. The as-prepared NiFe LDH@ITO catalyst showed superior catalytic activity toward the OER with an overpotential of only 240 mV at a current density of 10 mA/cm2. The catalyst also offered high stability with almost no activity decay after more than 200 h of chronopotentiometry test. Furthermore, the applications of NiFe LDH@ITO in (flexible) rechargeable zinc-air batteries exhibited a better performance than commercial RuO2 and can remain stable in cycling tests. It is supposed that the superior catalytic behavior originates from the ITO conductive framework, which prevents the agglomeration and facilitates the electron transfer during the OER process.