Passivation-Free, Liquid-Metal-Based Electrosynthesis of Aluminum Metal–Organic Frameworks Mediated by Light Metal Activation

The production of aluminum (Al) metal-organic frameworks (MOFs) by electrosynthesis using solid-state Al electrodes always faces significant challenges due to the formation of a passivating aluminum oxide layer in the process. Here, we developed a liquid-metal-based method to electrosynthesize an aluminum Al-MOF (MIL-53). This method uses a liquid-state gallium (Ga) anode as a reservoir and activator for a light metal, Al, in the form of Al-Ga alloys that releases Al³⁺ for the electrosynthesis of Al-MOFs. Introducing Ga into the system inhibits the formation of aluminum oxide passivation layer and promotes the electrochemical reaction for Al-MOF synthesis. The electrosynthesis using liquid Al-Ga alloy is conducted at ambient temperatures for long durations without requiring pretreatment for aluminum oxide removal. We show that the Al-MOF products synthesized from 0.40 wt % Al in liquid Ga lead to the highest crystallinity and possess a specific surface area greater than 800 m² g^-1 and a low capacity for CO₂ adsorption that can be used as a potential matrix for CO₂/N₂ separation. This work provides evidence that employing liquid-metal electrodes offers a viable pathway to circumvent surface passivation effects that inevitably occur when using conventional solid metals. It also introduces an efficient electrosynthesis method based on liquid metals for producing atomically porous materials.