Highly efficient activation of periodate by a manganese-modified biochar to rapidly degrade methylene blue.

In this study, the manganese oxide/biochar composites (Mn@BC) were synthesized from Phytolacca acinosa Roxb. The Mn@BC was analyzed via techniques of Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X-ray diffraction analysis (XRD). The results show that MnOx is successfully loaded on the surface of BC, and the load of MnOx can increase the number of surface functional groups of BC. X-ray photoelectron spectroscopy (XPS) shows that MnOx loaded on BC mainly exists in three valence forms: Mn(Ⅱ), Mn(Ⅲ), and Mn(Ⅳ). The ability of Mn@BC to activate periodate (PI) was studied by simulating the degradation of methylene blue (MB) dye. The degradation experiment results showed that the MB removal rate by the Mn@BC/PI system reached 97.4% within 30 min. The quenching experiment and electron paramagnetic resonance (EPR) analysis confirmed that Mn@BC can activate PI to produce iodate (IO3•), singlet oxygen (1O2), and hydroxyl radical (•OH), which can degrade MB during the reaction. Response surface methodology (RSM) based on Box-Behnken Design (BBD) was used to determine the interaction between pH, Mn@BC and PI concentration in the Mn@BC/PI system, and the optimum technological parameters were determined. When pH = 5.4, Mn@BC concentration 0.56 mg/L, PI concentration 1.1 mmol/L, MB removal rate can reach 98.05%. The cyclic experiments show that Mn@BC can be reused. After four consecutive runs, the removal rate of MB by the Mn@BC/PI system is still 82%, and the Mn@BC/PI system also shows high performance in treating MB in actual water bodies and degrading other pollutants. This study provides a practical method for degrading dyes in natural sewage.

Shallow Graph Convolutional Network for Skeleton-Based Action Recognition.

Graph convolutional networks (GCNs) have brought considerable improvement to the skeleton-based action recognition task. Existing GCN-based methods usually use the fixed spatial graph size among all the layers. It severely affects the model's abilities to exploit the global and semantic discriminative information due to the limits of receptive fields. Furthermore, the fixed graph size would cause many redundancies in the representation of actions, which is inefficient for the model. The redundancies could also hinder the model from focusing on beneficial features. To address those issues, we proposed a plug-and-play channel adaptive merging module (CAMM) specific for the human skeleton graph, which can merge the vertices from the same part of the skeleton graph adaptively and efficiently. The merge weights are different across the channels, so every channel has its flexibility to integrate the joints. Then, we build a novel shallow graph convolutional network (SGCN) based on the module, which achieves state-of-the-art performance with less computational cost. Experimental results on NTU-RGB+D and Kinetics-Skeleton illustrates the superiority of our methods.

A new strategy for enhanced electrochemically activation of persulfate on B and Co co-modified carbon felt in flow-through system for efficient organic pollutants degradation.

Electrochemical activation of persulfate (EA-PS) is gradually attracting attention as an emerging method for wastewater treatment. In this study, a novelty flow-through EA-PS system was first attempted for pollutants degradation using boron and cobalt co-doping carbon felt (B, Co-CF) as the cathode. SEM images, XPS and XRD spectra of B, Co-CF were investigated. The optimal doping ration between B and Co was 1:2. Increasing current density, PS concentration and flow rate, decreasing initial pH accelerated the removal of AO7. The mechanism involved in EA-PS were the comprehensive effect of DET, •OH and SO4•-. B, Co-CF cathode for flow-through system was stable with five cycles efficient AO7 decay performance. EA-PS in flow-through system was an efficient method with low cost and efficient pollutants degradation. This work provides a feasible strategy for synergistically enhancing PS activation and promoting the degradation of organic pollutants.

Methane emission reduction oriented extracellular electron transfer and bioremediation of sediment microbial fuel cell: A review.

Sediment is the internal and external source of water environment pollution, so sediment remediation is the premise of water body purification. Sediment microbial fuel cell (SMFC) can remove the organic pollutants in sediment by electroactive microorganisms, compete with methanogens for electrons, and realize resource recycling, methane emission inhibiting and energy recovering. Due to these characteristics, SMFC have attracted wide attention for sediment remediation. In this paper, we comprehensively summarized the recent advances of SMFC in the following areas: (1) The advantages and disadvantages of current applied sediment remediation technologies; (2) The basic principles and influencing factors of SMFC; (3) The application of SMFC for pollutant removal, phosphorus transformation and remote monitoring and power supply; (4) Enhancement strategies for SMFC in sediments remediation such as SMFC coupled with constructed wetland, aquatic plant and iron-based reaction. Finally, we have summarized the drawback of SMFC and discuss the future development directions of applying SMFC for sediment bioremediation.

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.

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

Degradation of 2,4-dichlorophenoxyacetic acid by a novel photoelectrocatalysis/photoelectro-Fenton process using Blue-TiO2 nanotube arrays as the anode.

2,4-dichlorophenoxyacetic acid (2,4-D)'s removal was studied in the photoelectrocatalysis/photoelectro-Fenton (PEC-PEF) process with Blue-TiO2 nanotube (Blue-TNTs) and modified carbon felt as the anode and cathode, respectively. Polytetrafluoroethylene and carbon black were used to modify the carbon felt to improve the efficiency of H2O2 production. The impact factors of 2,4-D degradation in the PEC-PEF process were investigated, including Fe2+ dose, bias potential, light intensity and the concentration of 2,4-D. It was found that the removal of 2,4-D increased firstly and then decreased with the increase of Fe2+ dose. Bias potential and light intensity played a positive role on 2,4-D removal, while the opposite was right for the impact of 2,4-D initial concentration. Compared with stainless steel, the modified carbon felt was found more efficient for 2,4-D removal as it could generate more H2O2. Reactive species for 2,4-D degradation was studied and it was proved that •OH radical rather than holes was mainly responsible for the removal. Such PEC-PEF process offered a promising alternative for herbicide-containing wastewater treatment.

Stable boron and cobalt co-doped TiO2 nanotubes anode for efficient degradation of organic pollutants.

Anode materials are crucial to anodic oxidation for wastewater treatment. In this regard, stable boron and cobalt co-doped TiO2 nanotube (B, Co-TNT) was prepared for the first time, and its lifetime was found increased significantly while electrocatalytic activity decreased with the increase of Co(NO3)2 in preparation from 1 to 10 mM. Characterized by scanning electron microscope (SEM), X-Ray Diffraction (XRD) and X-ray Photo-electronic Spectroscopy (XPS), B and Co content were optimized and successfully doped on TNT, which was more smooth without ripple with Co content of 0.038 mg/cm2 in a valence of +2, and B atomic content of 2.17 at.% in form of Ti-B-O. This optimized anode enhanced electrode lifetime 122.8 times while the electrochemical activity decreased slightly when compared to the undoped TNT. The effects of current density, initial pH and initial 2,4-dichlorophenoxyacetic acid (2,4-D) concentration were investigated, and the mainly responsible radical for degradation was confirmed to be the surface OH on B, Co-TNT anode. This anode had better performance on the TOC removal, mineralization current density (MCE) and energy consumption (Ec) when compared with BDD, PbO2, DSA and Pt anodes, and it also presented a very stable degradation for 10 cycles oxidation of 20 mg/L 2,4-D with allowable Co leaching. Therefore, B, Co-TNT anode is a promising, stable, safety and cost-effective anode for application in electrochemical advanced oxidation processes (EAOPs).

Photoelectrochemical degradation of 2,4-dichlorophenoxyacetic acid using electrochemically self-doped Blue TiO2 nanotube arrays with formic acid as electrolyte.

Blue TiO2 nanotube arrays (Blue-TNTs) were fabricated via an electrochemical reduction method with formic acid as the electrolyte. The optimum reduction conditions were obtained as bias potential of -1.3 V, reduction time of 5 min and formic acid of 3 M. Blue-TNTs were remarkably corroded compared with the intact TNTs. Similar crystal structures of the two catalysts were observed using X-ray diffraction, while red-shift was observed for Blue-TNTs using Raman spectra. X-ray photoelectron spectroscopy indicated of the presence of Ti3+ in Blue-TNTs that resulted from the reduction of Ti4+ and reduced the resistance of the catalyst. Blue-TNTs exhibited much stronger light-absorption than intact TNTs over the entire ultraviolet-visible region, especially in the visible region. The catalyst was used toward the photoelectrochemical oxidation of 2,4-dichlorophenoxyacetic acid (2,4-D) for the first time where the influencing factors were studied. Photoelectrocatalysis with Blue-TNTs presented a 2,4-D degradation rate constant (0.0295 min-1) more than twice the sum of that of electrocatalysis (0.0055 min-1) and photocatalysis (0.0089 min-1). Blue-TNTs fabricated in formic acid showed a better photoelectrocatalytic performance for 2,4-D removal compared with that prepared in ethylene glycol, Na2SO4 and NaNO3 solution. Blue-TNTs is considered to be a promising photoelectric anode for contaminant degradation.

Pre-magnetized Fe0 as heterogeneous electro-Fenton catalyst for the degradation of p-nitrophenol at neutral pH.

Pre-magnetized Fe0 (Pre-Fe0) was for the first time applied as heterogeneous catalyst to enhance the oxidation efficiency of electro-Fenton (EF) for the degradation of p-nitrophenol (PNP). The parameters including current, initial pH and pre-Fe0 dosage of Pre-Fe0/EF process were optimized and compared with other two processes (conventional Fe0/EF and electro-oxidation) to confirm its advantage. The rate constants of PNP removal were 1.40-3.82 folds of those by Fe0/EF process under various experimental conditions. The application of pre-Fe0 as catalyst could extend the working pH range from 3.0 to neutral conditions for PNP removal and reduce the Fe0 dosage from 2 to 0.5 mM corresponding to Fe0/EF, avoiding the second pollution of iron sludge. The superiority of Pre-Fe0/EF process was also verified to improve the degradation and mineralization of other phenols and antibiotics. Furthermore, a possible pathway of PNP degradation was revealed by the identification of intermediates and organic acids, and the possible mechanism of pre-Fe0 efficiently enhanced the EF efficiency was proposed. This work demonstrated that such a novel heterogeneous EF process using pre-Fe0 catalyst was clean and promising for the degradation of refractory organic pollutants.

Kinetic and mechanism study of UV/pre-magnetized-Fe0/oxalate for removing sulfamethazine.

In this study, UV irradiated photochemical reactions of oxalate (Ox) with premagnetized-Fe0 (pre- Fe0) as the catalyst was used to degrade sulfamethazine (SMT). Magnetic field promoted the release of iron ion from Fe0 thus enhanced SMT and Ox removal in UV/pre- Fe0/Ox process. X-ray photoelectron spectroscopy demonstrated that the presence of UV and Ox promoted the transformation of Fe3+ to Fe2+ on Fe0, which enhanced the surface bound •OH (•OHsurf) generation. Ox inhibited the formation of iron (hydro)xides and enhanced the hydroxylation of Fe0 surface. •OHsurf was mainly responsible for SMT removal (44%), while UV direct photolysis and •OH in the solution both caused around 28% SMT removal. The process with Ox exhibited much higher efficiency in SMT degradation than that added with H3PO4, citric acid and ethylenediaminetetraacetic acid, which greatly expanded the chelate-modified Fenton processes and their treatment efficiency.

EDTA, oxalate, and phosphate ions enhanced reactive oxygen species generation and sulfamethazine removal by zero-valent iron.

The activation rate of oxygen by zero-valent iron (Fe°) was very low. In this study, ethylenediaminetetraacetic acid (EDTA), oxalate (Ox), and phosphate ions (Na2HPO4) were used to enhance the oxygen activation by Fe° for sulfamethazine (SMT) removal. The addition of these ligands could significantly enhance the SMT degradation. SMT removal was improved from 10.5 % in the Fe° system (360 min) to 70.3 %, 85.2 % and 77.8 % in the Fe°/EDTA (60 min), Fe°/Ox (180 min) and Fe°/phosphate (360 min) systems, respectively. Scanning electron microscopy with energy dispersive X-ray (SEM-EDX), Fourier transform infrared reflection (FTIR), contact angle and X-ray photoelectron spectra (XPS) of Fe° in different systems were recorded. The presence of chelating agents hydroxylated Fe°, inhibited the iron oxide formation on the Fe° surface and promoted iron ion release from the solid. Moreover, the agents improved the recovery of surface Fe2+ which could subsequently enhance the activation of O2 to produce more H2O2 and reactive oxygen radicals for SMT removal. OH radical produced mainly through H2O2 decomposition was primarily responsible for removing SMT in all three systems. The Fe° system added with chelating agents is a new and promising approach for treating wastewaters containing ligands.

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.

Enhanced removal of antibiotics from secondary wastewater effluents by novel UV/pre-magnetized Fe0/H2O2 process.

Antibiotics have been frequently detected in the aquatic environment and are of emerging concern due to their adverse effect and potential of inducing antibiotic resistance. In this study, we developed an UV/pre-magnetized Fe0/H2O2 process (UV/pre-Fe0/H2O2) valid for neutral pH conditions, which could remove sulfamethazine (SMT) completely within only 30 min and enhance 1.8 times of SMT removal. Meanwhile, this process demonstrated outstanding mineralization capability with the TOC removal of 92.1%, while for UV/H2O2 and UV/Fe0/H2O2 system it was 53.9% and 72.1%, respectively. Better synergetic effect between UV irradiation and pre-Fe0/H2O2 system was observed, and the value of synergetic factor was 6.3 in the presence of both ions and humic acid, which was much higher than that in deionized water (4.4), humic acid (5.5) and ions (1.5). Moreover, the process could efficiently remove various antibiotics (800 µg L-1 oxytetracycline (OTC); 800 µg L-1 tetracycline (TC); 400 µg L-1 sulfadiazine (SD) and 400 µg L-1 SMT) in the secondary wastewater effluent. After optimization of Fe0 and H2O2 dosage, these antibiotics could be removed within 10 min (kapp (103) = 288.6 min-1) with a very low treatment cost of 0.1 USD m-3, and the EE/O value was only 1.22 kWh m-3. Compared with O3, UV/Fe2+/PDS, VUV/UV/Fe2+ and other US-based processes, the degradation rates by this process could enhance as high as 22.3 folds while the treatment cost or EE/O value could reduce greatly. Therefore, UV/pre-Fe0/H2O2 process is promising and cost-effective for the treatment of antibiotics in secondary wastewater effluents.

Indirect electrochemical oxidation of 2,4-dichlorophenoxyacetic acid using electrochemically-generated persulfate.

This research investigated persulfate electrosynthesis using a boron-doped diamond anode and a chemical reaction of persulfate in its activated form with an herbicide, 2,4-Dichlorophenoxyacetic acid (2,4-D). The first part of this research is dedicated to the influence of the applied current density on the electrosynthesis of persulfate. The first part shows that for a 2 M sulfuric acid, the current efficiency reached 96% for 5 mA/cm2 and dropped to 52% for a higher current density (100 mA cm-2). This fall cannot be explained by mass transfer limitations: an increase in temperature (from 9 to 30 °C) during electrolysis leads to the decomposition of 23% of the persulfate. The second part of this research shows that a quasi-complete degradation of the target herbicide can be reached under controlled operating conditions: (i) a high ratio of initial concentrations [Persulfate]/[2,4-D], (ii) a minimum temperature of 60 °C that produces sulfate radicals by heat decomposition of persulfate, and (iii) a sufficient contact time between reactants is required under dynamic conditions.

Degradation and mechanism of 2,4-dichlorophenoxyacetic acid (2,4-D) by thermally activated persulfate oxidation.

The chlorinated phenoxy herbicide of 2,4-dichlorophenoxyacetic acid (2,4-D) was oxidized by thermally activated persulfate (TAP). This herbicide was studied for different persulfate dosages (0.97-7.29 g L-1), for varying initial pH levels (3-12) and temperatures (25-70 °C). Compared with Fe2+/PS, TAP could achieve a higher total organic carbon (TOC) removal under wider pH ranges of 3-12. Increasing the mole ratio of PS to 2,4-D favored for the decay of 2,4-D and the best performance was achieved at the ratio of 50. The 2,4-D degradation rate constant highly depended on the initial pH and temperature, in accordance with the Arrhenius model, with an apparent activation energy of 135.24 kJ mol-1. The study of scavenging radicals and the EPR confirmed the presence of both SO4- and OH. However, SO4- was the predominant oxidation radical for 2,4-D decay. The presence of both Cl- and CO32- inhibited the degradation of 2,4-D, whereas the effect of NO3- could be negligible. Verified by GC/MS, HPLC and ion chromatography, a possible degradation mechanism was proposed.