Electrocatalytic chemical oxidation (ECO) is an energy-efficient anodic reaction alternative to the oxygen evolution reaction (OER). ECO lowers the reaction potential and yields higher-value fine chemicals at the anode. The catalyst material plays a crucial role in influencing and determining ECO performance. Enhancing catalyst performance encompasses aspects such as activity, stability, selectivity, and cost. Nickel-based electrocatalysts have garnered significant attention for their exceptional performance and widespread use in ECO applications. By modifying Nickel-based electrocatalysts, the formation of NiOOH active centers can be encouraged. Strategies such as adjusting size and morphology, doping, introducing defects, and constructing heterojunctions are advantageous for enhancing performance. Given the rapid advancements in related research fields, it is imperative to comprehend the mechanisms of nickel-based electrocatalysts in ECO and develop innovative catalysts. This article provides an overview of the modification strategies of nickel-based electrocatalysts, as well as their applications and mechanisms in ECO.

Ammonia plays a vital role in the development of modern agriculture and industry. Compared to the conventional Haber–Bosch ammonia synthesis in industry, electrocatalytic nitrogen reduction reaction (NRR) is considered as a promising and environmental friendly strategy to synthesize ammonia. Here, inspired by biological nitrogenase, we designed iron doped tin oxide (Fe-doped SnO₂) for nitrogen reduction. In this work, iron can optimize the interface electron transfer and improve the poor conductivity of the pure SnO₂, meanwhile, the synergistic effect between iron and Sn ions improves the catalyst activity. In the electrocatalytic NRR test, Fe-doped SnO₂ exhibits a NH₃ yield of 28.45 μg·h⁻¹·mg_cat⁻¹, which is 2.1 times that of pure SnO₂, and Faradaic efficiency of 6.54% at −0.8 V vs. RHE in 0.1 M Na₂SO₄. It also shows good stability during a 12-h long-term stability test. Density functional theory calculations show that doped Fe atoms in SnO₂ enhance catalysis performance of some Sn sites by strengthening N–Sn interaction and lowering the energy barrier of the rate-limiting step of NRR. The transient photovoltage test reveals that electrons in the low-frequency region are the key to determining the electron transfer ability of Fe-doped SnO₂.