Highly Efficient Electrochemical Degradation of Dyes via Oxygen Reduction Reaction Intermediates on N-Doped Carbon-Based Composites Derived from ZIF-67

Abstract

A cobalt-containing zeolitic imidazolate framework (ZIF-67) was carbonized by different routes to composite materials (cZIFs) composed of metallic Co, Co3O4, and N-doped carbonaceous phase. The effect of the carbonization procedure on the water pollutant removal properties of cZIFs was studied. Higher temperature and prolonged thermal treatment resulted in more uniform particle size distribution (as determined by nanoparticle tracking analysis, NTA) and surface charge lowering (as determined by zeta potential measurements). Surface-governed environmental applications of prepared cZIFs were tested using physical (adsorption) and electrochemical methods for dye degradation. Targeted dyes were methylene blue (MB) and methyl orange (MO), chosen as model compounds to establish the specificity of selected remediation procedures. Electrodegradation was initiated via an intermediate reactive oxygen species formed during oxygen reduction reaction (ORR) on cZIFs serving as electrocatalysts. The adsorption test showed relatively uniform adsorption sites at the surface of cZIFs, reaching a removal of over 70 mg/g for both dyes while governed by pseudo-first-order kinetics favored by higher mesoporosity. In the electro-assisted degradation process, cZIF samples demonstrated impressive efficiency, achieving almost complete degradation of MB and MO within 4.5 h. Detailed analysis of energy consumption in the degradation process enabled the calculation of the current conversion efficiency index and the amount of charge associated with O2•−/•OH generation, normalized by the quantity of removed dye, for tested materials. Here, the proposed method will assist similar research studies on the removal of organic water pollutants to discriminate among electrode materials and procedures based on energy efficiency.