Ferrate (K2FeO4) is a powerful oxidant and up to 3 mol of electrons could be captured by 1 mol of ferrate in the theoretical conversion of Fe­(VI)–Fe­(V)–Fe­(IV)–Fe­(III). However, it is reported that the utilization efficiency of the ferrate oxidation capacity is quite low because of the rapid autodecomposition of intermediate iron species, which negatively influences the potential of ferrate on organic pollutants control. We accidentally found that for the ferrate oxidation of carbamazepine (CBZ), bisphenol S (BPS), diclofenac (DCF), and ciprofloxacin (CIP), the determined reaction rate constants were 1.7–2.4 times lower in phosphate buffer than those in borate buffer at pH 8.0. For the reaction of ferrate with 2,2′-azino-bis­(3-ethylbenzothiazoline-6-sulfonate) (ABTS) at pH 7.0, the determined reaction stoichiometries were 1:1.04 in 100 mM phosphate buffer, 1:1.18 in 10 mM phosphate buffer, and 1:1.93 in 10 mM borate buffer, respectively. The oxidation ability of ferrate seems depressed in phosphate buffer. A kinetic model involving the oxidation of ABTS by Fe­(VI), Fe­(V) and Fe­(IV) species was developed and fitted the ABTS•+ formation kinetics well under different buffer conditions. The results showed that phosphate exhibited little influence on the oxidation ability of Fe­(VI) and Fe­(IV) species, but decreased the specific rate constants of ABTS with Fe­(V) species by 1–2 orders of magnitude, resulting in the outcompeting of Fe­(V) autodecomposition pathway. The complexation between phosphate anions and Fe­(V) species may account for the inhibition effect of phosphate buffer. Considering that many studies regarding ferrate oxidation were carried out in phosphate buffer, the actual oxidation ability of ferrate may be underestimated.

Ubiquitous oxygen vacancies (Vo) existing in metallic compounds can activate peroxymonosulfate (PMS) for water treatment. However, under environmental conditions, especially oxygenated surroundings, the interactions between Vo and PMS as well as the organics degradation mechanism are still ambiguous. In this study, we provide a novel insight into the PMS activation mechanism over Vo-containing Fe−Co layered double hydroxide (LDH). Experimental results show that Vo/PMS is capable of selective degradation of organics via a single-electron-transfer nonradical pathway. Moreover, O 2 is firstly demonstrated as the most critical trigger in this system. Mechanistic studies reveal that, with abundant electrons confined in the vacant electron orbitals of Vo, O 2 is thermodynamically enabled to capture electrons from Vo to form O 2•− under the imprinting effect and start the activation process. Simultaneously, Vo becomes electron-deficient and withdraws the electrons from organics to sustain the electrostatic balance and achieve organics degradation (32% for Bisphenol A without PMS). Different from conventional PMS activation, under the collaboration of kinetics and thermodynamics, PMS is endowed with the ability to donate electrons to Vo as a reductant other than an oxidant to form 1 O 2 . In this case, 1 O 2 and O 2•− act as the indispensable intermediate species to accelerate the circulation of O 2 (as high as 14.3 mg/L) in the micro area around Vo, and promote this nanoconfinement electron-recycling process with 67% improvement of Bisphenol A degradation. This study provides a brand-new perspective for the nonradical mechanism of PMS activation over Vo-containing metallic compounds in natural environments.

A novel synergetic mechanism of hydroxyl radical (•OH) oxidation and an intra-electron-transfer nonradical reaction was found in the catalytic ozonation of ketoprofen (KTP) with the in situ N-doped hollow sphere carbon (NHC). Outperforming the conventional •OH-based catalytic ozonation process, O3/NHC not only realized an enhancement of the pseudo-first-order rate constant of 11 times in comparison with that of O3 alone, but was also endowed with a high stability over a wide pH (4–9) and temperature (15–35 °C) range for the degradation of KTP. The high graphitization degree (I D/I G = 0.78–0.88) and low unsaturated oxygen content (0.10–1.38%) of NHC highlighted the dominant role of N-heteroatoms in the O3/NHC system. The specific effects of different N species were confirmed by a relationship study (N property vs catalytic activity) and X-ray photoelectron spectroscopy characterization. The graphitic N forming in the bulk of the graphitic structure served as the “electron-mobility” region to promote KTP degradation with the transfer of electrons from the KTP molecule to O3 via a nonradical reaction process. The pyrrolic and pyridinic N located at defects of the graphitic structure acted as the “radical-generation” region to decompose O3 into •OH for degrading KTP by a radical oxidation process. This finding provided a brand new insight into engineering N-doped carbonaceous catalysts precisely in the catalytic ozonation process for the efficient treatment of organic-contaminated water.

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