Amorphization of MOFs with Rich Active Sites and High Electronic Conductivity for Hydrazine Oxidation

The applications of metal-organic frameworks (MOFs) in electrocatalysis are limited by the perfect crystalline nature with insufficient coordinatively unsaturated sites and low electronic conductivity. Here, we report an electrosynthesis method to induce rapid assembly of amorphous MOFs on carbon cloth (denoted as aMnFc’/CC), achieving the amorphization of MOFs with rich active sites and high electronic conductivity. The long-range disordered structure of aMnFc’/CC forms a large number of oxygen vacancies to modify the coordination and electronic structures of Mn sites. In the electrocatalytic hydrazine oxidation reaction (HzOR), the aMnFc’/CC electrocatalyst exhibits superior activity to its crystalline MOF counterparts. Density functional theory calculations reveal that the unsaturated Mn centers present in aMnFc’/CC facilitate efficient electron transfer while simultaneously lowering the free energy of the rate-determining step in the HzOR process.