Bimetallic 2D Metal−Organic Framework Precatalysts That Enable Electrochemical Glycerol Oxidation

Abstract Electrochemical glycerol oxidation is considered a promising route to convert the glycerol by-product from biodiesel generation into valuable chemicals. Nevertheless, there is a need to develop effective alternatives to the commonly used noble metal electrocatalysts. Herein, we show that a Zr-BTB 2D-MOF could be post-synthetically metalated to construct bimetallic Co:Ni and Fe:Ni glycerol oxidation precatalysts. The as-formed precatalysts were then electrochemically converted into their corresponding active oxyhydroxide species, as confirmed by detailed Raman spectroscopy characterizations. Detailed electrocatalytic analysis showed that the Co:Ni modified Zr-BTB precatalyst exhibited high catalytic kinetics toward two key GOR products, formate and glycerate. Additionally, the Co:Ni modified Zr-BTB also revealed promising electrocatalytic and chemical stability, maintaining its product selectivity under prolonged operation periods. Hence, these results might pave the way for the design of active and selective electrocatalytic systems for a wide range of organic transformation reactions.