Layered FeCoNi double hydroxides with tailored surface electronic configurations induced by oxygen and unsaturated metal vacancies for boosting the overall water splitting process.

Two-dimensional (2D) layered double hydroxides (LDH) with excellent hydrophilic ability and rapid hydroxyl insertion are regarded as one of the most promising electrocatalysts for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) for overall water splitting to produce hydrogen. However, the electrocatalytic HER/OER activities can be restricted by the inert basal plane due to the poor conductivity, deficient active sites and inferior durability despite there being efficient active sites in the material edge. Thus, capturing many more exposed reactive sites to facilitate the rapid reaction kinetics is a crucial strategy. In this paper, both oxygen and unsaturated metal vacancies with FeCoNi LDH materials are generated through a surface activation approach by pre-covering of fluoride and a post-boronizing process. Such a material is grown on Ni foam to form an F-FeCoNi-Ov LDH/NF electrocatalyst. The activated surface of the electrocatalyst with oxygen vacancies and unsaturated metal sites shows enhanced electroconductivity for regulating the surface electronic structure and optimizing the surface adsorption energy for intermediates during HER/OER processes. As a result, this electrocatalyst exhibits excellent electrocatalytic performance for both the HER and OER with low overpotentials, small Tafel slopes and long durability. The enhancement mechanism is also studied deeply for fundamental understanding. For performance validation, an F-FeCoNi-Ov LDH/NF∥F-FeCoNi-Ov LDH/NF water splitting cell is fabricated and needs only 1.54 V and 1.81 V to reach current densities of 10 and 100 mA cm -2 , respectively. This work provides a practicable strategy to develop 2D LDH nanomaterials with boosted electrocatalytic activity for sustainable and clean energy storage systems.