Currently, the conventional halide synthesis method of preparing hafnium alkoxides [Hf(OR)₄, R is an alkyl] has problems of inefficiency, a heavy CO₂ emission footprint, and substantial solid and gas waste, which severely hinders its wide deployment. Herein, we propose an electrodissolution-coupled Hf(OR)₄ synthesis system using an alcohol solvent and Hf metal as feedstock for the efficient, low-carbon and waste-free electro-synthesis of Hf(OR)₄. The electrochemical behavior of the tetraethylammonium-hydrogen sulfate (Et₄NHSO₄)-based EHS process is investigated by cyclic voltammetry, linear sweep voltammetry, Tafel, and electrochemical impedance spectroscopy, complemented with SEM observation. The anodic hafnium dissolution/corrosion occurs inside the passive film while the cathodic ethanol dehydrogenation occurs in a two-stage pathway. Tafel extrapolation and numerical fitting analysis acquires important kinetics parameters, such as corrosion current density, exchange current density, and apparent activation energy as well as solution, polarization and “Warburg” resistances, etc. This work can provide theoretical guidance for the efficient operation of EHS.

目前，制备醇铪[Hf(OR) ₄，R为烷基]的传统卤化物合成方法存在效率低、CO ₂排放足迹大、固体和气体浪费大等问题，严重阻碍了其广泛应用。在此，我们提出了一种使用醇溶剂和 Hf 金属作为原料的电溶解耦合 Hf(OR) ₄合成系统，用于高效、低碳和无浪费地电合成 Hf(OR) ₄。四乙基硫酸氢铵（Et ₄ NHSO _{4 ）的电化学行为}) 为基础的 EHS 过程通过循环伏安法、线性扫描伏安法、Tafel 和电化学阻抗谱进行研究，并辅以 SEM 观察。阳极铪溶解/腐蚀发生在钝化膜内部，而阴极乙醇脱氢发生在两阶段路径中。Tafel外推和数值拟合分析获得了重要的动力学参数，如腐蚀电流密度、交换电流密度、表观活化能以及溶液、极化和“Warburg”电阻等。这项工作可以为高效运行提供理论指导。环境、健康和安全。