Degradation of emerging pollutants on bifunctional ZnFeV LDH@graphite felt cathode through prominent catalytic activity in heterogeneous electrocatalytic processes

The heterogeneous Electro-Fenton (EF) process is a promising wastewater treatment technology that can generate onsite H₂O₂, and operate in a wide pH range without generating a metal sludge. However, the heterogeneous EF process needs bifunctional cathode electrodes that can have high activity in 2e⁻ oxygen reduction reaction and H₂O₂ decomposition. Herein, ZnFeV layered double hydroxide (LDH), as a heterogeneous catalyst, was coated on the graphite felt (ZnFeV LDH@GF) cathode using the electrophoretic deposition method. ZnFeV LDH@GF cathode was able to generate 59.8 ± 5.9 mg L⁻¹ H₂O₂ in 90 min under a constant supply of O₂. EF process with ZnFeV LDH@GF cathode exhibited 89.8 ± 6.8% removal efficiency for pharmaceutical (ciprofloxacin) at neutral pH. Remarkably, the apparent reaction rate constant (k_app) of the ZnFeV LDH@GF-EF was 2.14 times that of the EF process with pristine GF. ZnFeV LDH coating increased the hydroxyl radical (^•OH) production of the EF process from 1.74 mM to 3.65 mM. The pathway of ^•OH production is thought to be a single electron transfer from redox couples of Fe²⁺/Fe³⁺ and V⁴⁺/V⁵⁺ to H₂O₂. After 10 reuse cycles, the ZnFeV LDH@GF cathode retained 90.2% of its efficiency. Eight intermediate compounds were identified by GC-MS including cyclic compounds and aliphatic compounds.