3D self-supported Ni nanoparticle@N-doped carbon nanotubes anchored on NiMoN pillars for the hydrogen evolution reaction with high activity and anti-oxidation ability

Abstract

A 3D self-supported hierarchical architecture composed of Ni nanoparticle@nitrogen-doped carbon nanotube modified NiMoN micro-pillar arrays grown on Ni foam (Ni@NCNT/NiMoN/NF) was synthesized. Benefiting from the protection by N-doped carbon layers, and the well-designed hierarchical structure with a large surface area, high electrical conductivity and convenient mass/electron transfer paths, this composite shows excellent activity and durability under both acidic and alkaline conditions. It demands extremely low overpotentials of 15 mV and 156 mV in 1.0 M KOH, and 31 and 96 mV in 0.5 M H₂SO₄ to achieve current densities of 10 and 200 mA cm⁻², respectively, which are superior to those for commercial Pt/C and other control samples. DFT calculations prove that the synergetic effect between N-doped carbon, Ni, and NiMoN enhances H₂O adsorption and decreases hydrogen adsorption free energy (|ΔG_H*|) to facilitate the HER process. Furthermore, the composite possesses extraordinary antioxidation ability under the conditions of the cyclic current pulse and power-off–on state. This work suggests an effective pathway to enhance the catalytic activity and oxidation resistance by building a hierarchical structure encapsulated by thin N-doped carbon layers, showing promising potency as the HER electrode in practical energy conversion and storage systems of wind power and solar power.