Electrocatalytic Properties of 3D Hierarchical Graphitic Carbon-Cobalt Nanoparticles for Urea Oxidation

A 3D hierarchical graphitic carbon nanostructure encapsulating cobalt(0)/cobalt oxide nanoparticles (CoGC) has been prepared by solid-state pyrolysis of a mixture of anthracene and cobalt 2,2'-bipyridine terephthalate complex at 850 °C. Based on the Brunauer-Emmett-Teller (BET) and Barrett-Joyner-Halenda (BJH) methods, the prepared material has high surface area (186.8 m² g^-1) with an average pore width of 205.5 Å. XPS reveals the functionalization of carbon with different oxygen-containing groups, such as carboxylic acid groups. The presence of metallic cobalt nanoparticles with cubic and hexagonal crystalline structures encapsulated in graphitized carbon is confirmed using XRD and TEM. Raman spectroscopy indicates a graphitization degree of I _D/I _G = 1.02. CoGC was cast onto a glassy carbon electrode and used for urea electrooxidation in an alkaline solution. The electrochemical investigation shows that the newly prepared CoGC has a promising electrocatalytic activity toward urea. The specific activity is 128 mA cm^-1 mg^-1 for the electrooxidation of 0.3 M urea in 1 M KOH at a relatively low onset potential (0.31 V vs Ag/AgCl). It can be mainly attributed to the morphological structure of carbon and the high reactivity of cobalt nanoparticles. The calculated charge-transfer resistance, R _ct, of the modified electrode in the presence of urea (10.95 Ω) is significantly lower than that in the absence of urea (113.5 Ω), which indicates electrocatalytic activity. The value of charge-transfer rate constant, k _s, for the anodic reaction is 0.0058 s^-1. Electrocatalytic durability in 1000 s chronoamperometry of the modified electrode suggests high structure stability. The modified electrode retained about 60% of its activity after 100 cycles as indicated by linear sweep voltammetry.