Author: diyan.wang

Boosted Urea Electrooxidation Activity by Dynamic Steady Blending CoOOH-Ni(OH)₂ Nanoclusters for H₂ Production in a pH-asymmetric Electrolyzer

Shih-Mao Peng,^1,2# Shu-Ting Chang,^2# Chia-Che Chang,^3# Priyadarshini HN,² Chun-Chih Chang,⁴* Kuan-Chang Wu,² Yung-Hung Huang,⁵ Yi-Chia Chen,⁵ Tsung-Rong Kuo,⁶ Chih-Wen Pao,³ Jeng-Lung Chen,³ Di-Yan Wang⁵*

https://doi.org/10.1039/D4TA04241G

Electrochemical urea oxidation reaction (UOR) is a promising alternative to the oxygen evolution reaction for reducing the overall potential of the hydrogen evolution reaction during water electrolysis. The theoretical potential for the UOR is only 0.37 V versus reversible hydrogen electrode (RHE). However, the kinetics of the six-electron transfer process involved in the UOR are inherently sluggish, resulting in high overpotential during the reaction. This study designed an active catalyst with a lower kinetic barrier in the UOR by fabricating blending CoOOH–Ni(OH)₂ nanoclusters through the structural transformation of amorphous Co–Ni hydroxide films. This structural transformation was investigated using high-angle annular dark-field scanning transmission electron microscopy, corresponding energy-dispersive X-ray spectroscopy, and in situ X-ray absorption spectra. The blending CoOOH–Ni(OH)₂ nanoclusters exhibited superior electrocatalytic activity in the UOR in an alkaline environment, achieving a low onset potential of 1.24 V (vs. RHE) in 1 M KOH with 0.5 M urea. We employed the CoOOH–Ni(OH)₂ nanoclusters as anodic electrocatalysts in a two-cell electrolyzer for asymmetric electrocatalysis. Hydrogen could be produced at a remarkable current density of 10 mA/cm² at a low applied potential of only 0.45 V. Density functional theory calculations revealed that blending CoOOH–Ni(OH)₂ nanoclusters with more oxygen vacancies exhibited a lower Gibbs free energy for the intermediate reaction pathway of NCONH₂ → NCONH, compared with the fine structure of CoNiOx (x = 2–3). This study lays down a novel pathway for developing new blending electrocatalysts to be used in electrochemical reactions.