Efficient electro-catalyzed PMS activation on a Fe-ZIF-8 based BTNAs/Ti anode: An in-depth investigation on anodic catalytic behavior

Phenanthrene (PHE), mainly released from coal tar and petroleum distillation, is an important kind of prevalent polycyclic aromatic hydrocarbons (PAHs) contamination in China (up to 2.38 ± 0.02 mg/kg in soil and 8668 ng/L in surface water) and other countries in the world. Metal-organic frameworks (MOFs) show promising application prospects in the decontamination field, however, suffering from the intrinsic fragility and fine powder forms. Therefore, macroscopic MOFs architecture-sandwich-like Fe-ZIF-8/blue TiO₂ nanotube arrays (BTNAs)/Ti substrate (FBTT) anode with strong interfacial bonding (Fe-O-Ti and Fe-2-MIM-Ti coordination) was constructed using innovative in situ growth, condensation-crystallization-deposition, and pyrolysis methods, aiming at exploring the feasibility of MOFs-based anode/peroxymonosulfate (PMS) mediated PHE elimination, revealing the in-depth mechanisms, simultaneously overcoming the intrinsic drawbacks of MOFs. The FBTT-4 (doping content of 30 %) efficiently degraded PHE by 90.01 % and 74.5 % within 10 min at 350 μg/L and 3 mg/L, respectively, mediated by the ^·OH compared to the SO₄^·-, ¹O₂, and O₂^·-. Post-optimized range of anodic potential enabled (i) anodic oxidation, (ii) activation of water and PMS molecules to produce active species, (iii) capture of electrons in reactants to reduce Fe³⁺/Ti⁴⁺ to Fe²⁺/Ti³⁺, maintaining the proportion of Fe/Ti with low valence and thus stable PMS activation capacity, and (iv) regulation of the Fe/Ti d-band center to modulate the anode adsorption capacity. The further increment in anodic potential could promote "dark photocatalysis" with a Z-scheme-like mechanism. Thus, it is proposed that the development of macroscopic MOFs-based anode, especially those with small band gaps, represents vast potentials in electrocatalytic contamination elimination. Simultaneously, the MOFs-based anode is expected to fully exploit their catalytic capacities and solve their intrinsic defects as well.