Single-Phase Spinel NiCo2O4 as Highly Active and Stable Electrocatalysts for Urea Oxidation Reaction in Urea Electrolysis

Zhou, Tongxin; Zhang, Lihua; Deskins, N. Aaron; Teng, Xiaowei

doi:10.1021/acsomega.5c06513

Single-Phase Spinel NiCo₂O₄ as Highly Active and Stable Electrocatalysts for Urea Oxidation Reaction in Urea Electrolysis

Journal Article · Thu Sep 04 00:00:00 EDT 2025 · ACS Omega

DOI:https://doi.org/10.1021/acsomega.5c06513· OSTI ID:2589744

Zhou, Tongxin ^[1]; ^[2]; ^[1]; ^[1]

Worcester Polytechnic Institute, MA (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)

Exploring and designing a stable and active catalyst for the urea electro-oxidation reaction (UOR, CO(NH₂)₂ + 6OH^– → CO₂ + N₂ + 5H₂O + 6e^–) is crucial for the long-term sustainability of ecological systems and clean energy production. We found that spinel NiCo₂O₄ is a stable and active electrocatalyst for UOR at a relatively low anodic potential without triggering the competing oxygen evolution reaction (OER). A urea electrolysis cell (CO(NH₂)2 + H₂O → CO₂ + N₂ + 2H₂) utilizing a spinel NiCo₂O₄ anode and a commercial Pt cathode was further characterized through galvanostatic polarization tests, demonstrating excellent structural stability at various current densities. Post-mortem analysis of long-term urea electrolysis measurements suggested that NiCo₂O₄ electrocatalysts maintained a stable spinel structure. However, redistribution of Ni³⁺ to Ni²⁺ valence on the catalyst surface was observed, in contrast to the intact Co valence, indicating that (i) Ni sites are active toward urea adsorption and sequential electro-oxidation; (ii) while urea oxidation proceeds primarily through the direct electro-oxidation mechanism, chemical reactions between the Ni³⁺ site and urea occur during long-term electrochemical UOR operation. Density functional theory (DFT) simulations were used to calculate the adsorption energies of urea molecules on NiO, Co₃O₄, and NiCo₂O₄, revealing the importance of regulating the configuration of adsorbed urea molecules on the NiCo₂O₄ surface.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0012704

OSTI ID:: 2589744

Report Number(s):: BNL--228962-2025-JAAM

Journal Information:: ACS Omega, Journal Name: ACS Omega Journal Issue: 36 Vol. 10; ISSN 2470-1343

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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