Multiple-perspective design of hollow-structured cerium-vanadium-based nanopillar arrays for enhanced overall water electrolysis.

It is critical and challenging to develop highly active and low cost bifunctional electrocatalysts for the hydrogen/oxygen evolution reaction (HER/OER) in water electrolysis. Herein, we propose cerium-vanadium-based hollow nanopillar arrays supported on nickel foam (CeV-HNA/NF) as bifunctional HER/OER electrocatalysts, which are prepared by etching the V metal-organic framework with Ce salt and then pyrolyzing. Etching results in multidimensional optimizations of electrocatalysts, covering substantial oxygen vacancies, optimized electronic configurations, and an open-type structure of hollow nanopillar arrays, which contribute to accelerating the charge transfer rate, regulating the adsorption energy of H/O-containing reaction intermediates, and fully exposing the active sites. The reconstruction of the electrocatalyst is also accelerated by Ce doping, which results in highly active hydroxy vanadium oxide interfaces. Therefore, extremely low overpotentials of 170 and 240 mV under a current density of 100 mA cm^-2 are achieved for the HER and OER under alkaline conditions, respectively, with long-term stability for 300 h. An electrolysis cell with CeV-HNA/NF as both the cathode and anode delivers a small voltage of 1.53 V to achieve water electrolysis under 10 mA cm^-2, accompanied by superior durability for 150 h. This design provides an innovative way to develop advanced bifunctional electrocatalysts for overall water electrolysis.