Electrodissolution-Coupled Hafnium Alkoxide Synthesis with High Environmental and Economic Benefits

The conventional thermal method of preparing hafnium alkoxides [Hf(OR)₄ , R=alkyl] - excellent precursors for gate-dielectric HfO₂ on semiconductors - is severely hindered by its unsatisfactory environmental and economic burdens. Herein, we propose a promising electrodissolution-coupled Hf(OR)₄ synthesis (EHS) system for green and efficient electrosynthesis of Hf(OR)₄ . The operational principle of the electrically driven system consists of two simultaneous heterogeneous reactions of Hf dissolution and alcohol dehydrogenation, plus a spontaneous solution-based combination reaction. In applying ethanol as solvent and Hf metal as electrodissolution medium, we achieved waste-free production of high-purity hafnium ethoxide [Hf(OEt)₄ ] with an equivalent "a concomitant" reduction in CO₂ emission of 187.33 g CO₂ per kg Hf(OEt)₄ and a high net profit of 30 477 USD per kg Hf(OEt)₄ . This system is very competitive with the thermal process, which unavoidably releases substantial waste and CO₂ for a net profit of 27 700 USD per kg Hf(OEt)₄ . We anticipate that the environmental and economic benefits of the EHS process could pave the way for its practical application.