Protsenko Vyacheslav
Department of Physical Chemistry, Ukrainian State University of Science and Technologies, Dnipro, Ukraine.
R Soc Open Sci. 2025 Jul 23;12(7):250156. doi: 10.1098/rsos.250156. eCollection 2025 Jul.
This study presents a comparative thermodynamic analysis of various pathways for electrochemical hydrogen production coupled with the anodic oxidation of urea, offering a sustainable alternative to the conventional oxygen evolution reaction. For the first time, the feasibility and efficiency of these processes were evaluated using integrated green chemistry metrics, including atom economy and a newly proposed metric, electricity economy, which quantifies the theoretical minimum electrical energy required for the equilibrium formation of reaction products. The analysis demonstrated that urea-oxidation pathways generally require significantly less energy input than water electrolysis. Among the examined reactions, the oxidation of urea to gaseous nitrogen and carbonate ions was identified as the most efficient, with an electricity economy of -4650.83 J mol and an atom economy of 6.4%. However, practical application is hindered by issues such as low product selectivity and high anodic potentials dictated by the redox thermodynamics of commonly used nickel-based catalysts. These findings underscore the need for next-generation electrocatalysts with enhanced selectivity and lower overpotentials to fully exploit the energetic advantages of urea oxidation for green hydrogen production.
本研究对电化学产氢与尿素阳极氧化耦合的各种途径进行了比较热力学分析，为传统析氧反应提供了一种可持续的替代方案。首次使用包括原子经济性和新提出的电经济性在内的综合绿色化学指标评估了这些过程的可行性和效率，电经济性量化了反应产物平衡形成所需的理论最小电能。分析表明，尿素氧化途径通常比水电解所需的能量输入显著更少。在所研究的反应中，尿素氧化为气态氮和碳酸根离子被确定为最有效，电经济性为-4650.83 J/mol，原子经济性为6.4%。然而，实际应用受到诸如产物选择性低和常用镍基催化剂的氧化还原热力学所决定的高阳极电位等问题的阻碍。这些发现强调需要具有更高选择性和更低过电位的下一代电催化剂，以充分利用尿素氧化在绿色制氢方面的能量优势。
