Development of a 3D Ni-Mn binary oxide anode for energy-efficient electro-oxidation of organic pollutants

The depletion of clean water resources and the consequent accumulation of contaminants in aquatic systemsmust be urgently addressed by means of innovative solutions. Electro-oxidation (EO) is considered a promisingtechnology, prized for its versatility and eco-friendliness. However, the excessively high prices and the toxicityassociated with some of the materials currently employed for EO impede its broader application. This studyintroduces cost-effective Ni-Mn binary oxide anodes prepared on Ni foam (NF) substrate. A scalable synthesisroute that enables a 35-fold increase in the production of active material through a single optimization step hasbeen devised. The synthesized binary oxide material underwent electrochemical characterization, and itseffectiveness was assessed in an electrochemical flow-through cell, benchmarked against single Ni or Mn oxidesand more conventional alternatives like boron-doped diamond (BDD) and dimensionally-stable anode (DSA). Thenovel binary oxide anode demonstrated exceptional performance, achieving complete removal of phenol at verylow current density of 5 mA cm-2, along with an 80% of chemical oxygen demand (COD) decay within only60 min. The NF/NiMnO3 anode outperformed the BDD and DSA when using comparable projected surface areas,owing to its high porosity and ability to produce hydroxyl radicals, as confirmed from the degradation profiles inthe presence of radical scavengers. Furthermore, GC/MS analysis served to elucidate the degradation pathwaysof phenol

Evidence of cathodic peroxydisulfate activation via electrochemical reduction at Fe(II) sites of magnetite-decorated porous carbon: Application to dye degradation in water

Peroxydisulfate (PDS, S2O82−)-based advanced oxidation processes have been developed as an alternative to those based on *OH, as PDS activation yields a much more stable radical like SO4* − that can maintain the oxidation ability of water treatment systems for longer time. Here, the electrochemical PDS activation has been investigated using reticulated vitreous carbon (RVC) substrate modified with Fe3O4 nanoparticles (NPs) as cathode. The NPs were exhaustively characterized by different surface analysis techniques (TEM, SEM) and Mössbauer spectroscopy. Cyclic voltammetry and linear sweep voltammetry with a rotating disk electrode allowed concluding that the main electrocatalytic role in the cathodic PDS activation to SO4 *− corresponded to the Fe(II) active sites continuously promoted upon cathodic polarization. These sites were less catalytic for O2 reduction reaction, although it was still feasible with n = 2.7 electrons as determined from Koutecky-Levich analysis. Both cathodic reactions followed an inner-sphere reaction mechanism. The Fe3O4- modified RVC cathodes were employed to electrolyze Methylene Blue aqueous solutions at pH 3.5, employing different current values and PDS concentrations. Dissolved O2 was purged to impede the competitive cathodic H2O2 production and Fenton's reaction. The occurrence of dye adsorption/electrosorption on the cathode reduced the mass transport limitations, enhancing the reaction between SO4 *− and organic molecules. The best operation conditions to reach total and fast color removal at 18 min were 2 mM PDS and 10 mA, yielding > 80% TOC abatement at 45 min. Reproducible degradation profiles were found after 5 runs, thereby ensuring the stability of the Fe3O4-modified RVC, with no iron sludge production