Synergistic engineering of heteroatom doping and heterointerface construction in V-doped Ni(OH)₂/FeOOH to boost both...

The exploitation of cost-effective and abundant non-noble metal electrocatalysts holds great significances in enhancing the efficiency of oxygen evolution reaction (OER) and/or urea oxidation reaction (UOR). Herein, we report an electrocatalyst with co-existing V-dopants and Ni(OH)₂/FeOOH interfaces (referred to as A-NiFeV/NF, with "A" indicating "activated"). The electron coupling between Ni, Fe and V, analyzed through X-ray photoelectron spectroscopy, indicates that Ni and Fe both receive electrons from the V. Additionally, the Fe can also lead to a bias toward a lower valence of the Ni centers in Ni(OH)₂. Further in situ Raman spectroscopy reveals that Ni²⁺(OH)₂ inevitably undergoes transformation into amorphous Ni³⁺OOH during the activation process, however, the synergistic effects of V-dopants and Ni(OH)₂/FeOOH interfaces keep the Ni centers mostly in a lower oxidation state of +2 even at high potential ranges. These low-valence Ni centers are proposed to be positively correlated with the optimized OER activity of the Ni-based electrocatalysts. As a result, the designed A-NiFeV/NF electrocatalyst exhibits low overpotentials of 234 and 313 mV to propel current densities of 10 and 100 mA/cm², and a small Tafel slope of 37.8 mV/dec for OER in 1.0 M KOH. The catalyst demonstrates a stable OER activity for over 100 h at 100 mA/cm². Additionally, it can be integrated with a solar cell to construct a solar-driven electrolytic OER device without additional electric input. Similarly, for the small molecule oxidation, UOR, only ∼1.33 and ∼1.39 V vs. RHE (RHE: reversible hydrogen electrode) are required to achieve 10 and 100 mA/cm², respectively, in an electrolyte composed of 1.0 M KOH with 0.33 M urea.