A pilot scale of electrochemical integrated treatment technology and equipment driven by solar energy for decentralized domestic sewage treatment.

Based on the natural air diffusion electrode (NADE) cathode, a solar-driven electrochemical integrated sewage treatment technology and equipment in a pilot scale was developed to treat dispersed rural wastewater. The non-aeration NADE had efficient and stable H2O2 production performance, maintaining the H2O2 output between 1474 and 1535 mg h-1 within 50 h with the current efficiency of 77.4%-80.6%. This electrochemical integrated wastewater treatment system was coupled with technologies such as dual-cathode electro-Fenton, peroxi-coagulation and photoelectro-Fenton, which effectively improved the conversion and utilization efficiency of H2O2. It integrated Fenton-like oxidation, electro-oxidation and UV/H2O2, as well as Fe(OH)3-dominated flocculation, which could effectively remove various pollutants in wastewater. The integrated sewage treatment equipment (500 L d-1) realized the effective treatment of a rural decentralized domestic sewage, achieving simultaneous removal of chemical oxygen demand (COD), NH3-N, total phosphorus (TP) and bacteria. Driven by solar energy, its application feasibility, superiority and stability have been proved, providing theoretical and technical support for the efficient and low-consumption treatment of dispersed organic wastewater.

FeMo@porous carbon derived from MIL-53(Fe)@MoO3 as excellent heterogeneous electro-Fenton catalyst: Co-catalysis of Mo.

An ultra-efficient electro-Fenton catalyst with porous carbon coated Fe-Mo metal (FeMo@PC), was prepared by calcining MIL-53(Fe)@MoO3. This FeMo@PC-2 exhibited impressive catalytic performance for sulfamethazine (SMT) degradation with a high turnover frequency value (7.89 L/(g·min)), much better than most of reported catalysts. The mineralization current efficiency and electric energy consumption were 83.2% and 0.03 kWh/gTOC, respectively, at low current (5 mA) and small dosage of catalyst (25.0 mg/L). The removal rate of heterogeneous electro-Fenton (Hetero-EF) process catalyzed by FeMo@PC-2 was 4.58 times that of Fe@PC/Hetero-EF process. Because the internal-micro-electrolysis occurred between PC and Fe0, while the co-catalysis of Mo accelerated the rate-limiting step of the Fe3+/Fe2+ cycle and greatly improved the H2O2 utilization efficiency. The results of radical scavenger experiments and electron paramagnetic resonance confirmed the main role of surface-bound hydroxyl radical oxidation. This process was feasible to remove diverse organic contaminants such as phenol, 2,4-dichlorophenoxyacetic acid, carbamazepine and SMT. This paper enlightened the importance of the doped Mo, which could greatly improve the activity of the iron-carbon heterogeneous catalyst derived from metal-organic frameworks in EF process for efficient removal of organic contaminants.

Revisiting UV/sulfite exposed to air: A redox process for reductive dechlorination and oxidative mineralization.

2,4-Dichlorophenol (2,4-DCP) widely exists in many industrial wastewaters and is considered a priority pollutant due to its high toxicity. In this work, we proposed a UV/sulfite process without aeration for high-efficiency dechlorination and enhanced mineralization. The UV/sulfite system significantly improved the removal of 2,4-DCP (93.33 % in 60 min) and dechlorination rate (85.13 % in 60 min) compared with UV alone and sulfite alone, and the synergistic factor was 6.59. The UV/sulfite system without aeration improved the mineralization rate (49.80 %) compared with the nitrogen aeration system. UV/sulfite was a reduction-oxidation coupled process and was more suitable for neutral and alkaline conditions. Reducing species (hydrated electrons and H•) made 2,4-DCP dechlorinate to form dechlorination products such as p-chlorophenol (4-CP), o-chlorophenol (2-CP), and phenol, which were further mineralized by oxidized species (SO4•-). UV/sulfite remained highly efficient in the presence of coexisting ions and under different water quality conditions. This process was also suitable for removing a wide range of chlorinated organic compounds. The UV/sulfite process without aeration can achieve high dechlorination and enhanced mineralization with simple operation and low cost (1.78 $·m-3 order-1), which has a broad and cost-effective application prospect in removing refractory halogenated organic pollutants.

Floating sandwich-type electro-Fenton: A feasible process to remove micro-pollutants through adsorption enrichment and enhanced oxidation efficiency.

To improve the removal efficiency of low-concentration organic pollutants and enhance the oxidation efficiency of electro-Fenton (EF) process, a floating sandwich-type EF system (N/(A)/D-EF) without aeration was constructed for the first time. This EF system electro-synthesized H2O2 through the floating natural air diffusion electrode (NADE) without aeration, and regenerated Fe(II) effectively by the activated carbon fiber (ACF) interlayer, which significantly enhanced the process oxidation capacity since its •OH yield was 8.7 times that of the conventional EF system. In addition, the ACF interlayer could adsorb and enrich micro-pollutants and the generated •OH directly oxidize the pollutants adsorbed on the ACF, which enabled regeneration of ACF and maintained removal stability in 20 consecutive experiments. The removal rate constant (k) of carbamazepine by N/(A)/D-EF process was 7.6 times and 2.1 times higher than that of conventional EF and ACF adsorption process, respectively. This process could efficiently remove mixed low-concentration organic pollutants (0.1 mg L-1) in domestic sewage and lake water with rate constant 1.6-7.1 times that of the conventional EF process but lower energy consumption. Meanwhile, the N/(A)/D-EF process had a wider application range of sewage pH and conductivity, which was a promising process for removing low-concentration pollutants in wastewater.

An efficient Fe2+ assisted UV/electrogenerated-chlorine process for carbamazepine degradation: The role of Fe(IV).

To improve the performance and solve the restrictions of UV/chlorine process (e.g., the narrow pH application range and high disinfection by-products (DBPs) formation), a Fe2+ assisted advanced oxidation process with electrochemically generated chlorine (UV/E-Cl/Fe2+) was proposed for carbamazepine (CBZ) degradation, which eliminated CBZ (5 mg/L) within 4 min under the optimal conditions. Compared with UV/electro-generated chlorine (UV/E-Cl) and anodic oxidation-chlorination/Fe2+ (AO-Cl/Fe2+) processes, the apparent first-order kinetics constant in UV/E-Cl/Fe2+ increased by 2.56 and 3.18 times respectively, and the energy consumption was lower (1.15 kWh/m3-log). Simultaneously, the pH application range could be expanded to 9, and DBPs formed in this process were 17.1% less than those in UV/E-Cl. Through quenching tests, electron paramagnetic resonance (EPR) experiments, measurement of •OH concentration, quantification of methyl phenyl sulfoxide (PMSO) and benzosulfone (PMSO2) and processes comparison, possible CBZ degradation pathways and mechanism of UV/E-Cl/Fe2+ were proposed, in which Fe(IV) played the dominant role in the early stage, while the production of radicals (i.e., •OH and Cl•) was enhanced with the increase of chlorine generation, accelerating the CBZ removal. Furthermore, this process demonstrated wide application prospect in treating various contaminants and real wastewaters. In conclusion, this study offers an effective and energy-efficient method for organic pollutants degradation.

Building dual active sites Co3O4/Cu electrode to break scaling relations for enhancement of electrochemical reduction of nitrate to high-value ammonia.

The electrochemical reduction of nitrate to ammonia (ERNA) has become a green treatment technology for nitrate wastewater. However, strong adsorption for product caused high activation energy for product desorption in scaling relations, blocking activity of electrocatalyst in ERNA. Density functional theory (DFT) calculations indicated that constructing dual active sites (Cu and Co3O4) could achieve strong adsorption of nitrate (-2.91 eV) with low desorbing energy barrier of ammonia (0.13 eV), breaking scaling relations. This dual active sites Co3O4/Cu electrode achieved a high ammonia yield rate of 684 µg mgcat-1 h-1 with 94.6% faradic efficiency, surpassing single active site Co3O4 and Cu electrodes. For mechanism, In-situ electrochemical characterization found the vital intermediates of *NH and *NH2, demonstrating that indirect reduction was the main pathway on Co3O4/Cu electrode. Thus, it is believed that building dual active sites on electrode is a reliable strategy to enhance ERNA for purifying industrial wastewater polluted by nitrate.

Enhanced degradation of 2,4-dichlorophenoxyacetic acid by electro-fenton in flow-through system using B, Co-TNT anode.

A flow-through system was constructed for 2,4-dichlorophenoxyacetic acid (2,4-D) degradation for the first time using efficient boron and cobalt co-doped TiO2 nanotubes (B, Co-TNT) as the anode and carbon black doped carbon felt (CB-CF) that had a high H2O2 yield as the cathode. Compared with dimensionally stable anode (DSA), whether in anodic oxidation (AO) or AO-electro-Fenton (EF) system, 2,4-D degradation in B, Co-TNT anode system was more efficient accompanying with a lower energy consumption (Ec). Different operating parameters including applied current density, initial pH and flow rate were explored, supporting that the optimal Fe2+ dosage was 0.5 mM while decreasing the initial pH and increasing the current intensity and flow rate were beneficial to 2,4-D removal. In this AO-EF system, the involved mechanisms for 2,4-D degradation were anodization and Fenton oxidation, possessing the comprehensive effect of •OH and SO4•- with their contribution of 92.7% and 4.8%, respectively. This flow-through AO-EF system performed a stable performance, and an efficient degradation performance with low Ec (5.8-29.5 kWh (kg TOC)-1) was obtained for different kinds of contaminants (methylene blue, phenol, p-nitrophenol and sulfamethazine). Therefore, B, Co-TNT anode coupled with CB-CF cathode in flow-through system was effective for contaminants degradation.

S-doped MIL-53 as efficient heterogeneous electro-Fenton catalyst for degradation of sulfamethazine at circumneutral pH.

The reduced S-modified MIL-53(Fe) was prepared by sulfurizing MIL-53(Fe) at low temperature, which was an efficient electro-Fenton catalyst at wide pH range (3-9) for sulfamethazine (SMT) degradation. The best temperature and MIL-53(Fe)/S ratio were 350 °C and 1:2, at which the BET surface area was much enlarged. The MIL-53(Fe) surface was etched by S to many 2D nanosheets with the thickness of ~50 nm, while S2-2 replaced OH- to coordinate with Fe2+ and increased the Fe2+ content, which improved the catalytic performance. Even at initial pH of 7.0, the SMT removal was 95.8%, and the rate constant (k) in the Hetero-EF process was 16-folds of that in the Homo-EF process. The turnover frequency (TOFd) value of MIL-53(Fe)/S(1:2)-350 was 0.48 L g-1 min-1, which was 6.8 times that of commercial FeS2. The S2-2in catalyst adjusted the pH superfast, and promoted the generation of Fe2+ and thus efficiently activating H2O2 to form surface ·OH, which was verified to be the main radical by EPR and radical scavenger experiments. This catalyst showed promising prospect for environmental application and could be regenerated by sulfidation method. S-doped MIL-53(Fe) was an excellent pH regulator, thus promoting promising application in Hetero-EF processes.

Synergistic Effect of Co(III) and Co(II) in a 3D Structured Co3O4/Carbon Felt Electrode for Enhanced Electrochemical Nitrate Reduction Reaction.

As nitrate contamination causes serious environmental problems, it is necessary to develop stable and efficient electrocatalysts for efficient electrochemical nitrate reduction reaction (ENRR). Here, a nonprecious Co3O4/carbon felt (CF) electrode with a 3D structure was prepared by integrating electrodeposition with calcination methods. This 3D structured Co3O4/CF electrode exhibits a high-rate constant of 1.18 × 10-4 s-1 cm-2 for the ENRR, surpassing other Co3O4 electrodes in previous literature. Moreover, it also has an excellent stability with a decrease of 6.4% after 10 cycles. Density functional theory calculations, electron spin resonance analysis, and cyclic voltammetry were performed to study the mechanism of the ENRR on the Co3O4/CF electrode, proving that atomic H* (indirect pathway) plays a prominent role in NO3- reduction and clarifying the synergistic effect of Co(III) and Co(II) in the Co(II)-Co(III)-Co(II) redox cycle for the ENRR: Co(III) prefers the adsorption of NO3- and Co(II) favors the production of H*. Based on this synergy, a relatively large amounts of Co(II) on the surface of the Co3O4/CF electrode (1.3 Co(II)/Co(III) ratio) was maintained by controlling the temperature of calcination to 200 °C with a lower energy barrier of H* formation of 0.46 eV than other ratios, which is beneficial for forming H* and enhancing the performance of the ENRR. Thus, this study suggests that building 3D structure and optimizing Co(II)/Co(III) ratio are important for designing efficient Co3O4 electrocatalyst for ENRR.

The radical and non-radical oxidation mechanism of electrochemically activated persulfate process on different cathodes in divided and undivided cell.

Electrochemically activated persulfate (PS) employing stainless steel (SS), carbon felt (CF) and carbon black modified CF (CB-CF) as the cathode, in the divided and undivided cell, respectively, for degradation of atrazine (ATZ) was first investigated using novel B, Co-doped TiO2 nanotubes (B, Co-TNT) anode. In undivided cell, ATZ degradation was followed the order of CF

Enhancement of hydrogen peroxide production by electrochemical reduction of oxygen on carbon nanotubes modified with fluorine.

It is vital to synthesis hydrogen peroxide via electrochemical reduction of oxygen since it is a green process to produce oxidant with wide applications including water/wastewater treatment. In this work, fluorine (F) was employed to modify carbon nanotube (CNT), and the obtained F doped CNT (F-CNT) catalyst was used to fabricate gas diffusion electrode (GDE). It was found that F doping could improve oxygen reduction activity and H2O2 selectivity, and then enhanced the H2O2 production. After modification, F-CNT prepared with 0.6 M HF (CNT-F-0.6) had much higher H2O2 production (47.6 mg L-1) and current efficiency (89.5%) than that of CNT (29.6 mg L-1, 70.1%) at bias voltage of -1.3 V (vs SCE) and pH 7. Moreover, the high catalytic activity of CNT-F-0.6 could maintain in 5 consecutive reaction cycles. The material characterization and electrochemical test indicated that F doping had no significant effects on the surface area of CNT, but improved the defect degree of CNT. The enhanced H2O2 production performance could be ascribed to the formation of CF2 and CF3 on the surface of F-doped CNT, which rendered the potential for practical application of novel carbon catalyst for GDE.

Highly efficient electrosynthesis of hydrogen peroxide on a superhydrophobic three-phase interface by natural air diffusion.

Hydrogen peroxide (H2O2) synthesis by electrochemical oxygen reduction reaction has attracted great attention as a green substitute for anthraquinone process. However, low oxygen utilization efficiency (<1%) and high energy consumption remain obstacles. Herein we propose a superhydrophobic natural air diffusion electrode (NADE) to greatly improve the oxygen diffusion coefficient at the cathode about 5.7 times as compared to the normal gas diffusion electrode (GDE) system. NADE allows the oxygen to be naturally diffused to the reaction interface, eliminating the need to pump oxygen/air to overcome the resistance of the gas diffusion layer, resulting in fast H2O2 production (101.67 mg h-1 cm-2) with a high oxygen utilization efficiency (44.5%-64.9%). Long-term operation stability of NADE and its high current efficiency under high current density indicate great potential to replace normal GDE for H2O2 electrosynthesis and environmental remediation on an industrial scale.

Comprehensive treatment of marine aquaculture wastewater by a cost-effective flow-through electro-oxidation process.

The effective treatment of marine aquaculture wastewater is of great significance to protect marine environment and marine organisms. This study validated the feasibility of the comprehensive removal of NH4+-N, NO2--N, COD and P, as well as disinfection and antibiotics removal from marine aquaculture wastewater by electrochemical oxidation (EO), comparing the performance and energy consumption with that by electro-peroxone (EP) and electro-Fenton (EF) process. Due to the formation of more free chlorine, the removal of NH4+-N and COD was in order of EO â‰« EP > EF. A new flow-through EO reactor was adopted, which was found enhanced the formation rate of free chlorine and degradation rate of pollutants, and thus performed better than that of flow-by reactor and batch reactor. By this flow-through EO process, the removal of NH4+-N and NO2--N could reach >90% and their concentrations after treatment both meet the Water Drainage Standard for Sea Water Mariculture (SC/T 9103-2007). Meanwhile, the process had a good bactericidal performance with a lg(c/c0) of -5.6. At the same time, antibiotics such as sulfadimidine (SMT) and norfloxacin (NOR) could be completely removed. The energy consumption was only 0.054 kWh/g NH4+-N (0.27 kWh/m3), which was far more cost-effective than other oxidative processes. The new flow-through EO process has great practical application prospects for the comprehensive removal of multiple pollutants and sterilization from marine aquaculture wastewater.

A highly efficient flow-through electro-Fenton system enhanced with nitrilotriacetic acid for phenol removal at neutral pH.

Low pH requirement is one of the biggest limitations of the application of traditional Fenton and electro-Fenton (EF) process because FeII/FeIII would precipitate at high pH. In this study, a flow-through EF system operated in batch recirculation mode was constructed. Nitrilotriacetic acid (NTA) was used as a chelating agent in the EF system (NTA/EF) to keep iron soluble at high pH values, producing OH by reaction of H2O2 generated in situ with FeIINTA that obtained by the reduction of FeIIINTA at the cathode. This flow-through NTA/EF system accelerated the mass transfer of target molecules to the electrode surface and showed high efficiency for phenol removal at pH 5-8 with rate constants (k) at around 0.26 min-1, higher than that of the batch test (k = 0.15 min-1) and EF process without NTA (k = 0.16 min-1). The influences of aeration rate, current, flow rate, Fe dose, the ratio of NTA to Fe, pH, and initial phenol concentration on the phenol removal were investigated. The system could be used for at least 3 times for phenol removal without obvious efficiency decline. The flow-through NTA/EF system is promising for the removal of organic contaminants in a wide pH range.

Cost-efficient improvement of coking wastewater biodegradability by multi-stages flow through peroxi-coagulation under low current load.

Cost-effective pretreatment of the highly concentrated and biorefractory coking wastewater to improve biodegradability is of significant importance, while green electrochemical technologies without external chemicals addition are charming but still challenging due to its high energy consumption. In this work, a novel multi-stages flow through peroxi-coagulation (PC) was for the first time developed with graphite felt cathode modified by graphene, showing an excellent performance in removal of 71.5% COD, 72.3% phenol and 59.4% NH3-N and significant biodegradability enhancement with a low energy consumption as 1.2 kWh/m3. Compared with conventional flow PC, this process was more cost-effective due to more intensive .OH production and higher utilization of generated active species. Through UV spectrophotometry and GC-MS analysis, the improvement of biodegradability was attributed to the reduction of both low and high molecular weight compounds content in the coking wastewater. Comparing to the electro-Fenton, electrocoagulation and ozonation process, the proposed PC process was highly cost-effective, providing a promising and new alternative for pretreatment of coking wastewater.

Simultaneous removal of tetracycline and disinfection by a flow-through electro-peroxone process for reclamation from municipal secondary effluent.

Pharmaceutical and personal care products as one of the micropollutants and bacteria in secondary effluent restrict the water reuse from municipal secondary effluent. Electro-peroxone (EP) process where H2O2 is generated in-situ by electrolysis is an emerging advanced oxidation process and an improvement of traditional peroxone method (O3/H2O2). In this work, a flow-through EP process was compared with ozonation and electrolysis for simultaneous disinfection and degradation of tetracycline (TC). The disinfection effect by EP was higher than the sum of standalone ozone and electrolysis and the coupling coefficient of ozonation and electrolysis in EP process was 1.2. The flow-through EP system presented similar efficiency for separately and simultaneously treating E. coli and TC. For the actual secondary effluent treatment, trihalomethanes, haloacetonitrile and halonitromethanes, the main disinfection by-products, were much lower than the WHO's thresholds for drinking water. TOC and COD removal was 44% and 65%, respectively, at flow rate of 35 mL/min. BOD5, bacteria, pH and other parameters in the effluent could satisfy the recreational landscape water quality standard, and the required energy consumption was 0.47 kW h/m3 at the flow rate 35 mL/min. Most of the degradation products were small-molecule organic acids, and possible degradation pathway of TC was suggested.