Oxidation of metallic Cu by supercritical CO₂ and control synthesis of amorphous nano-metal catalysts for CO₂ electroreduction

Amorphous nano-metal catalysts often exhibit appealing catalytic properties, because the intrinsic linear scaling relationship can be broken. However, accurate control synthesis of amorphous nano-metal catalysts with desired size and morphology is a challenge. In this work, we discover that Cu(0) could be oxidized to amorphous Cu_xO species by supercritical CO₂. The formation process of the amorphous Cu_xO is elucidated with the aid of machine learning. Based on this finding, a method to prepare Cu nanoparticles with an amorphous shell is proposed by supercritical CO₂ treatment followed by electroreduction. The unique feature of this method is that the size of the particles with amorphous shell can be easily controlled because their size depends on that of the original crystal Cu nanoparticles. Moreover, the thickness of the amorphous shell can be easily controlled by CO₂ pressure and/or treatment time. The obtained amorphous Cu shell exhibits high selectivity for C2+ products with the Faradaic efficiency of 84% and current density of 320 mA cm⁻². Especially, the FE of C2+ oxygenates can reach up to 65.3 %, which is different obviously from the crystalline Cu catalysts.