Metal–metalloid compounds have been paid much attention as new high‐performance water oxidation catalysts due to their exceptional durability for water oxidation in alkaline media originating from the multi‐dimensional covalent bonding of the metalloid with the surrounding metal atoms. However, compared to the excellent stability, a relatively low catalytic activity of metal‐metalloids often limits their practical application as high‐performance water oxidation catalysts. Here, for the first time, disclosed is a novel self‐templating strategy combined with atomic layer deposition (ALD) to design the electrochemically active and stable quaternary metal boride (vanadium‐doped cobalt nickel boride, VCNB), hollow nanoprism by inducing electronic double layers on the surface. The incorporation of V in a double‐layered structure can substantially increase the number of surface active sites with unsaturated electronic structure. Furthermore, the induced electronic double layers of V can effectively protect the dissolution of the surface active sites. In addition, density functional theory (DFT) calculations reveal that the impressive water oxidation properties of VCNB originate from the synergetic physicochemical effects of the different metal elements, Co and B as active sites, Ni as a surface electronic structure modifier, and V as a charge carrier transporter and supplier.

No abstract

Metal–fluoride possesses a high potential as new high-performance water oxidation catalysts due to a highly polarized electronic configuration. However, low conductivity, related to high iconicity in metal–fluorine bonds, and instability of metal–fluoride in alkaline solution act as major roadblocks for using metal–fluoride as a highly efficient electrocatalyst. Here, we first disclose a novel strategy to design the electrochemically active and stable metal–fluoride electrocatalysts, nickel–cobalt fluoride oxide (NCFO), for water oxidation. The incorporation of F leads to substantial increase of the number of surface active sites with unsaturated electronic structure, which is beneficial for boosting electrocatalytic activity.