Synthesis of Novel Two‐Dimensional Co–H ₃ BTC–4,4′‐BiPy Metal Organic Framework and Its Derived Cobalt‐Based Nanostructured Catalyst for Glycerol Electrooxidation

Glycerol can be upcycled to various value‐added chemicals like glyceric acid, glyceraldehyde, dihydroxyacetone, tartronic acid and formic acid by the process of oxidation. These products have wide application in the pharmaceutical, leather auxiliary, food processing and agricultural industries. Whereas the thermal approaches are quite energy intensive, electrochemical glycerol oxidation reaction (GOR) facilitates a mild operational condition to do so. Here, the synthesis of novel cobalt‐based metal‐organic framework, Co‐1,3,5‐benezenetricarboxylic acid (H 3 BTC)–4,4′‐Bipyridine (4,4′‐BiPy), was done via a solvothermal method using 4,4′‐BiPy and H 3 BTC as linkers. Its controlled carbonisation at 600°C under a H 2 /N 2 atmosphere yields a nitrogen‐doped carbon‐supported cobalt nanoparticle composite (Co NPs@NC‐600). This catalyst exhibits excellent electrocatalytic performance for GOR, achieving a current density of 10 mA.cm −2 at 1.28 V versus reversible hydrogen electrode (RHE) and a maximum Faradaic efficiency of ∼91.65%. The superior activity arises from its high surface area (150.65 m 2 .g −1 ) and microporous structure (∼1.85 nm). Density functional theory calculations reveal lower activation barriers for key reaction steps and C–C bond cleavage on Co (111) surfaces compared to Co 3 O 4 (311) surface, supporting the observed catalytic enhancement. These findings position Co NPs@NC‐600 as a highly efficient and durable electrocatalyst for selective GOR, with strong potential for integrated green energy and chemical valorisation applications.