Activated carbon fiber as an efficient co-catalyst toward accelerating Fe2+/Fe3+ cycling for improved removal of antibiotic cefaclor via electro-Fenton process using a gas diffusion electrode.

The electro-Fenton (EF) based on gas-diffusion electrodes (GDEs) reveals promising application prospective towards recalcitrant organics degradation because such GDEs often yields superior H2O2 generation efficiency and selectivity. However, the low efficiency of Fe2+/Fe3+ cycle with GDEs is always considered to be the limiting step for the EF process. In this study, activated carbon fiber (ACF) was firstly employed as co-catalyst to facilitate the performance of antibiotic cefaclor (CEC) decomposition in EF process. It was found that the addition of ACF co-catalyst achieved a rapid Fe2+/Fe3+ cycling, which significantly enhanced Fenton's reaction and hydroxyl radicals (•OH) generation. X-ray photoelectron spectroscopy (XPS) results indicated that the functional groups on ACF surface are related to the conversion of Fe3+ into Fe2+. Moreover, DMSO probing experiment confirmed the enhanced •OH production in EF + ACF system compared to conventional EF system. When inactive BDD and Ti4O7/Ti anodes were paired to EF system, the addition of ACF could significantly improve mineralization degree. However, a large amount of toxic byproducts, including chlorate (ClO3-) and perchlorate (ClO4-), were generated in these EF processes, especially for BDD anode, due to their robust oxidation capacity. Higher mineralization efficiency and less toxic ClO4- generation were obtained in the EF + ACF process with Ti4O7/Ti anode. This presents a novel alternative for efficient chloride-containing organic removal during wastewater remediation.

Insights into the efficient mineralization of antibiotic trimethoprim in aqueous media by Fe2+ catalytically enhanced vacuum-UV irradiation: Kinetics, mechanisms, and toxicity evaluation.

The widespread existence of antibiotics in the environment has attracted growing concerns regarding the potential adverse effects on aquatic organisms, ecosystems, and human health even at low concentrations. Extensive efforts have been devoted to developing new methods for effective elimination of antibiotics from wastewater. Herein, a novel process of Fe2+ catalytically enhanced vacuum ultraviolet (VUV) irradiation was proposed as a promising approach for the removal of antibiotic trimethoprim (TMP) in water. Compared with UVC photolysis, VUV photolysis, and UVC/Fe2+, VUV/Fe2+ could increase the pseudo-first-order reaction rate constant of TMP removal by 6.6-38.4 times and the mineralization rate by 36.5%-59.9%. The excellent performance might originate from the synergistic effect of VUV and Fe2+, i.e., VUV irradiation could effectively split water and largely accelerate the Fe3+/Fe2+ cycle to generate more reactive oxygen species (ROS). EPR results indicated that •OH and O2•- were identified as the main ROS in the UVC/Fe2+ and VUV/Fe2+ processes, while •OH, O2•-, and 1O2 were involved in the VUV process. The operating parameters, such as Fe2+ dosage and initial TMP contents, were evaluated and optimized. Up to 8 aromatic intermediates derived from hydroxylation, demethylation, carbonylation, and methylene group cleavage were identified by UPLC-QTOF-MS/MS technique, the possible pathways of TMP degradation were proposed. Finally, the acute and chronic toxicity of intermediates formed during TMP degradation in the VUV/Fe2+ process were also evaluated.

Flow-through heterogeneous electro-Fenton system using a bifunctional FeOCl/carbon cloth/activated carbon fiber cathode for efficient degradation of trimethoprim at neutral pH.

The synthesis of multifunctional cathode with high-efficiency and stable catalytic activity for simultaneously producing and activating H2O2 is an effective way for promoting the performance of heterogeneous electro-Fenton process (HEF). In addition, accelerating mass transfer by adopting a flow-through reactor is also great importance because of its better utilization of catalysts and adequate contact of the contaminant with the oxidants generated on the electrode surface. Herein, a novel flow-through HEF (FHEF) system was designed for the degradation of trimethoprim (TMP) using bifunctional cathode with a sandwich structure FeOCl nanosheets loaded onto carbon cloth (CC) and activated carbon fiber (ACF) (FeOCl/CC/ACF). The cathode exhibited excellent performance in activating H2O2 for the in-situ generation of hydroxyl radicals (•OH). The electron spin resonance (ESR) measurements and radical quenching tests proved that the high production of •OH in the FHEF process was favorable to the high catalytic efficiency. 25 mg L-1 TMP was entirely degraded after 60 min, with the TOC removal of 62.6% (180 min) at pH 6.8, 9.0 mA cm-2, and flux rate 210 mL min-1. Moreover, the degradation rate still could reach 83% (60 min) after 10 cycles without obvious valence and crystal phase changes. Simultaneously, the current utilization rate has also been greatly enhanced, with an average current efficiency of 69.9% and a low energy consumption of 0.28 kWh kg-1. The reasonable degradation pathways for TMP were proposed based on the UPLC-QTOF-MS/MS results. Finally, the results of toxicological simulation showed a declining trend in the toxicity of the samples during TMP degradation. These results claim that the FeOCl/CC/ACF-FHEF system is an efficient and economical technology for the treatment of organic contaminants in effluents.

Insights into antibiotic cefaclor mineralization by electro-Fenton and photoelectro-Fenton processes using a Ti/Ti4O7 anode: Performance, mechanism, and toxic chlorate/perchlorate formation.

A comparative degradation of antibiotic cefaclor (CEC) between Ti/Ti4O7 and Ti/RuO2 anodes, in terms of degradation kinetics, mineralization efficiency, and formation of toxic chlorate (ClO3-) and perchlorate (ClO4-), was performed with electrochemical-oxidation (EO), electro-Fenton (EF), and photoelectro-Fenton (PEF) processes. Besides, CEC degradation by EF with boron-doped diamond (BDD) anode was also tested. Results showed CEC decays always followed pseudo-first-order kinetics, with increasing apparent rate constants in the sequence of EO < EF < PEF. The mineralization efficiency of the processes with Ti/Ti4O7 anode was higher than that of Ti/RuO2 anode, but slightly lower than that of BDD anode. Under the optimal conditions, 94.8% mineralization was obtained in Ti/Ti4O7-PEF, which was much higher than 64.4% in Ti/RuO2-PEF. The use of Ti/RuO2 gave no generation of ClO3- or ClO4-, while the use of Ti/Ti4O7 yielded a small amount of ClO3- and trace amounts of ClO4-. Conversely, the use of BDD led to the highest generation of ClO3- and ClO4-. The reaction mechanism was studied systematically by detecting the generated H2O2 and •OH. The initial N of CEC was released as NH4+ and, in smaller proportion, as NO3-. Four short-chain carboxylic acids and nine aromatic intermediates were also detected, a possible reaction sequence for CEC mineralization was finally proposed.

Facile synthesis of bimetallic ACF/CC@FeOCl-Cu composite cathode for efficient degradation of sulfamethoxazole at neutral pH by a flow-through heterogeneous electro-Fenton process.

Flow-through heterogeneous electro-Fenton (FHEF) process shows a broad prospect for refractory organic pollutants removal. However, maintaining a long-term service life of higher catalytic cathode is crucial for the development of cathode materials, especially for iron-functionalized cathode operated under harsh conditions. In this study, a novel bimetallic CC@FeOCl-Cu composite was synthesized through one-step calcination, coupled with a series of microstructure characterization methodology, including XRD, SEM-EDS, XPS, and FTIR. The superior catalytic activity of CC@FeOCl-Cu could be ascribed to Fe-Cu synergy and better dispersion of FeOCl nanosheets. With the optimal Cu:Fe ratio of 1:60, the bifunctional ACF/CC@FeOCl-Cu cathode was employed in FHEF process, exhibiting an outstanding performance for sulfamethoxazole (SMX) removal over a wide pH range (3.0-9.0). Comparison of experimental results indicated that the ACF/CC@FeOCl-Cu-FHEF process showed higher performance than ACF/CC@FeOCl-FHEF and homogeneous EF processes. The average SMX removal efficiency was 98% and TOC removal efficiency was more than 57% even after 10 cycles. Radical quenching experiments and electron spin resonance test confirmed that •OH was the primary active species. More •OH was generated in the ACF/CC@FeOCl-Cu-FHEF process because the doping of Cu could enhance catalytic activity of cathode. In addition, the satisfactory performance could be observed in the ACF/CC@FeOCl-Cu-FHEF process for the treatment of real landfill leachate, indicating its potential for practical application in wastewater treatment.

Impact of vacuum ultraviolet (VUV) intensity on the performance of VUV irradiation for the mineralization of trimethoprim in neutral media: Kinetics, mechanisms, and by-products formation.

A comparative study on the mineralization of antibiotic trimethoprim (TMP) in neutral medium was investigated by applying irradiation with five types of ultraviolet lamps. Among these lamps, the whole envelope of one lamp contained ordinary quartz, which could only transmit ultraviolet-C (UVC) light. For the other four lamps, approximately one tenth, a quarter, a half, and full of envelopes were comprised of high-purity synthetic quartz, which can transmit both vacuum ultraviolet (VUV) and UVC light. TMP decay was well fitted to pseudo-first-order reaction kinetics and occurred more quickly as the VUV intensity increased. Poor mineralization was achieved in the absence of VUV light, whereas the mineralization efficiency was also enhanced with increasing VUV intensity. The presence of hydroxyl radicals (•OH), superoxide radicals (O2•-) and singlet oxygen (1O2) during VUV photolysis of water was confirmed by electron paramagnetic resonance (EPR) analysis. Appropriate radical quenching experiments and fluorescent molecular probe detection provided the evidence that •OH played a significant role in TMP mineralization. Higher VUV intensity favored the generation of H2O2 and •OH. The evolution of NH4+ and NO3- as well as carboxylic acids (formic, acetic, oxalic, and oxamic acids) released in the treated solution were quantified. Ten aromatic intermediates were also identified by UPLC-QTOF-MS. Thereby, a plausible reaction sequence for TMP mineralization in VUV/UVC photolysis was finally proposed.

Mineralization of cefoperazone in acid medium by the microwave discharge electrodeless lamp irradiated photoelectro-Fenton using a RuO2/Ti or boron-doped diamond anode.

The mineralization of 125 mL of 50-300 mg L-1 cefoperazone (CFPZ) has been comparatively studied by electrochemical advanced oxidation processes (EAOPs) like anodic oxidation (AO), electro-Fenton (EF) and photoelectro-Fenton (PEF) with a RuO2/Ti or boron-doped diamond (BDD) anode and an activated carbon fiber (ACF) cathode. A microwave discharge electrodeless lamp (MDEL) was used as the UV source in PEF process. CFPZ decays always followed pseudo-first-order kinetics and their constant rates increased in the order: AO < EF < MDEL-PEF, regardless of anode types. Higher mineralization was achieved in all methods using BDD instead of RuO2/Ti, while the most potent BDD-MDEL-PEF gave 88% mineralization under its optimum conditions of 0.36 A, pH 3.0 and 1.0 mmol L-1 Fe2+. The synergistic mechanisms were explored by quantifying the electrogenerated H2O2 and formed •OH, in which 2.27 and 2.58 mmol L-1 H2O2 were accumulated in AO-H2O2 with RuO2/Ti or BDD anode, respectively, while 92.0 and 263.5 µmol L-1 •OH were generated in EF with RuO2/Ti or BDD anode, respectively. The oxidation power of EAOPs with different anodes was also compared by measuring the evolutions of NO3- and NH4+ as well as four generated carboxylic acids including oxalic, oxamic, formic and fumaric acids.

Effect of surface properties of activated carbon fiber cathode on mineralization of antibiotic cefalexin by electro-Fenton and photoelectro-Fenton treatments: Mineralization, kinetics and oxidation products.

Solutions of 200 mg L-1 cefalexin (CLX), an antibiotic with high usage frequency and biodegradation resistance, have been comparatively degraded by electro-Fenton (EF) and photoelectro-Fenton (PEF) processes using two kinds of activated carbon fiber (ACF) cathodes with different physical properties. These two ACFs shared similar pore volumes and pore diameters but varied BET surface areas, which were confirmed to be 0.5210 cm3 g-1, 2.26 nm and 921 m2 g-1 for ACF1, while 0.6508 cm3 g-1, 2.16 nm and 1206 m2 g-1 for ACF2, respectively. Their oxidation abilities were comparatively assessed in terms of degradation kinetics and mineralization rates, which increased in the order: ACF1-EF < ACF2-EF < ACF1-PEF < ACF2-PEF. These results confirmed the superiority of ACF with higher surface area, which was correlated to faster H2O2 and OH accumulation in more reaction sites provided. After 120 min electrolysis, ACF1 exhibited 1510 µM H2O2 and 37 µM OH accumulation, while ACF2 generated 1934 µM H2O2 and 85 µM OH. Moreover, ACF cathode with more developed pore structure also revealed faster formation of degradation by-products like inorganic ions (NH4+ and NO3- ions) and short-chain carboxylic acids (acetic, formic, oxamic and oxalic acids), as well as enhanced removal for partial acids. In order to gain a deeper understanding of degradation mechanisms for ACF2-PEF system, evolutions of six aromatic by-products generated from sulfoxidation, hydroxylation and decarboxylation were confirmed by UPLC-QTOF-MS/MS determination. Based on the above identifications of the degradation intermediates, a plausible reaction pathway for CLX removal was proposed.