Differentiating the reaction mechanism of three-dimensionally electrocatalytic system packed with different particle electrodes: Electro-oxidation versus electro-fenton

Abstract

Recently, there are still some controversial mechanisms of the 3D electrocatalytic oxidation system, which would probably confound its industrial application. From the conventional viewpoint, the Ti₄O₇ material may be the desired particle electrodes in the 3D system since its high oxygen evolution potential favors the production of ^•OH via H₂O splitting reaction at the anode side of Ti₄O₇ particle electrodes. In fact, the incorporation of Ti₄O₇ particles showed phenol degradation of 88% and COD removal of 51% within 120 min, under the optimum conditions at energy consumption of 0.668 kWh g^-1 COD, the performance of which was much lower than those in many previous literatures. In contrast, the prepared carbon black-polytetrafluoroethylene composite (CB-PTFE) particles with abundant oxygen-containing functional groups could yield considerable amounts of H₂O₂ (200 mg L^-1) in the 3D reactor and achieved a complete degradation of phenol and COD removal of 80% in the presence of Fe²⁺, accompanying a low energy consumption of only 0.080 kWh g^-1 COD. It was estimated that only 20% of Ti₄O₇ particles near the anode attained the potential over 2.73 V/SCE at 30 mA cm^-2 based on the potential test and simulation, responsible for the low yield of ^•OH via the H₂O splitting on Ti₄O₇ (1.74 × 10^-14 M), and the main role of Ti₄O₇ particle electrodes in phenol degradation was through direct oxidation. For the CB-PTFE-based 3D system, current density of 10 mA cm^-2 was sufficient for all the CB-PTFE particles to attain cathodic potential of -0.67 V/SCE, conducive to the high yield of H₂O₂ and ^•OH (9.11 × 10^-14 M) in the presence of Fe²⁺, and the ^•OH-mediated indirect oxidation was mainly responsible for the phenol degradation. Generally, this study can provide a deep insight into the 3D electrocatalytic oxidation technology and help to develop the high-efficiency and cost-efficient 3D technologies for industrial application.

Keywords: Carbon black; Electro-Fenton; Particle electrodes; Three-dimensional electrochemical system; Ti(4)O(7).