Electrostatic-induced ion-confined partitioning in graphene nanolaminate membrane for breaking anion-cation co-transport to enhance desalination.

Constructing nanolaminate membranes made of two-dimensional graphene oxide nanosheets has gained enormous interest in recent decades. However, a key challenge facing current graphene-based membranes is their poor rejection for monovalent salts due to the swelling-induced weak nanoconfinement and the transmembrane co-transport of anions and cations. Herein, we propose a strategy of electrostatic-induced ion-confined partitioning in a reduced graphene oxide membrane for breaking the correlation of anions and cations to suppress anion-cation co-transport, substantially improving the desalination performance. The membrane demonstrates a rejection of 95.5% for NaCl with a water permeance of 48.6 L m-2 h-1 bar-1 in pressure-driven process, and it also exhibits a salt rejection of 99.7% and a water flux of 47.0 L m-2 h-1 under osmosis-driven condition, outperforming the performance of reported graphene-based membranes. The simulation and calculation results unveil that the strong electrostatic attraction of membrane forces the hydrated Na+ to undergo dehydration and be exclusively confined in the nanochannels, strengthening the intra-nanochannel anion/cation partitioning, which refrains from the dynamical anion-cation correlations and thereby prevents anions and cations from co-transporting through the membrane. This study provides guidance for designing advanced desalination membranes and inspires the future development of membrane-based separation technologies.

Efficient electro-Fenton degradation of organic pollutants via the synergistic effect of 1O2 and •OH generated on single FeN4 sites.

The electro-Fenton with in situ generated 1O2 and •OH is a promising method for the degradation of micropollutants. However, its application is hindered by the lack of catalysts that can efficiently generate 1O2 and •OH from electrochemical oxygen reduction. Herein, N-doped stacked carbon nanosheets supported Fe single atoms (Fe-NSC) with FeN4 sites were designed for simultaneous generation of 1O2 and •OH to enhance electro-Fenton degradation. Due to the synergistic effect of 1O2 and •OH, a variety of contaminants (phenol, 2,4-dichlorophenol, sulfamethoxazole, atrazine and bisphenol A) were efficiently degraded with high kinetic constants of 0.037-0.071 min-1 by the electro-Fenton with Fe-NSC as cathode (-0.6 V vs Ag/AgCl, pH 6). Moreover, the superior performance for electro-Fenton degradation was well maintained in a wide pH range from 3 to 10 even with interference of various inorganic salt ions. It was found that FeN4 sites with pyridinic N coordination were responsible for its good performance for electro-Fenton degradation. Its 1O2 yield was higher than •OH yield, and the contribution of 1O2 was more significant than •OH for pollutant degradation.

Effectiveness of Intelligent Control Strategies in Robot-Assisted Rehabilitation-A Systematic Review.

This review aims to provide a systematic analysis of the literature focused on the use of intelligent control systems in robotics for physical rehabilitation, identifying trends in recent research and comparing the effectiveness of intelligence used in control, with the aim of determining important factors in robot-assisted rehabilitation and how intelligent controller design can improve them. Seven electronic research databases were searched for articles published in the years 2015 - 2022 with articles selected based on relevance to the subject area of intelligent control systems in rehabilitation robotics. It was found that the most common use of intelligent algorithms for control is improving traditional control strategies with optimization and learning techniques. Intelligent algorithms are also commonly used in sensor output mapping, model construction, and for various data learning purposes. Experimental results show that intelligent controllers consistently outperform non-intelligent controllers in terms of transparency, tracking accuracy, and adaptability. Active participation of the patients and lowered interaction forces are consistently mentioned as important factors in improving the rehabilitation outcome as well as the patient experience. However, there are limited examples of studies presenting experimental results with impaired participants suffering limited range of motion, so the effectiveness of therapy provided by these systems is often difficult to quantify. A lack of universal evaluation criteria also makes it difficult to compare control systems outside of articles which use their own comparison criteria.

Highly Efficient Acidic Electrosynthesis of Hydrogen Peroxide at Industrial-Level Current Densities Promoted by Alkali Metal Cations.

Acidic H2O2 synthesis through electrocatalytic 2e- oxygen reduction presents a sustainable alternative to the energy-intensive anthraquinone oxidation technology. Nevertheless, acidic H2O2 electrosynthesis suffers from low H2O2 Faradaic efficiencies primarily due to the competing reactions of 4e- oxygen reduction to H2O and hydrogen evolution in environments with high H+ concentrations. Here, we demonstrate the significant effect of alkali metal cations, acting as competing ions with H+, in promoting acidic H2O2 electrosynthesis at industrial-level currents, resulting in an effective current densities of 50‒421 mA cm‒2 with 84‒100% Faradaic efficiency and a production rate of 856‒7842 µmol cm-2 h-1 that far exceeds the performance observed in pure acidic electrolytes or low-current electrolysis. Finite-element simulations indicate that high interfacial pH near the electrode surface formed at high currents is crucial for activating the promotional effect of K+. In situ attenuated total reflection Fourier transform infrared spectroscopy and ab initio molecular dynamics simulations reveal the central role of alkali metal cations in stabilizing the key *OOH intermediate to suppress 4e- oxygen reduction through interacting with coordinated H2O.

Promoting CO2 Electroreduction to Ethane by Iodide-Derived Copper with the Hydrophobic Surface.

Electrochemical reduction of CO2 to value-added products provides a feasible pathway for mitigating net carbon emissions and storing renewable energy. However, the low dimerization efficiency of the absorbed CO intermediate (*CO) and the competitive hydrogen evolution reaction hinder the selective electroreduction of CO2 to ethane (C2H6) with a high energy density. Here, we designed hydrophobic iodide-derived copper electrodes (I-Cu/Nafion) for reducing CO2 to C2H6. The Faradaic efficiency of C2H6 reached 23.37% at -0.7 V vs RHE over the I-Cu/Nafion electrode in an H-type cell, which was about 1.7 times higher than that of the I-Cu electrode. The hydrophobic properties of the I-Cu/Nafion electrodes led to an increase in the local CO2 concentration and stabilized the Cu+ species. In situ Raman characterizations and density functional theory calculations indicate that the enhanced performances could be ascribed to the strong *CO adsorption and decreased the formation energy of *COOH and *COCOH intermediates. This study highlights the effect of the hydrophobic surface on Cu-based catalysts in the electroreduction of CO2 and provides a promising way to adjust the selectivity of C2 products.

Surface-surface contacted direct Z-scheme TiO2-BiVO4-PI heterostructure for enhanced photoelectrocatalytic degradation of bisphenols under solar driven.

Bisphenols (BPs) are a series of widely used endocrine disruptors, which potentially harm the environment and human health. In this work, a novel Z-scheme TiO2-BiVO4-PI heterostructure was synthesized, characterized, and used for the simulated sunlight-driven photoelectrocatalytic degradation of BPs. Due to the existence of surface-surface contacted direct Z-scheme between BiVO4 and PI, holes were concentrated on the valence band of BiVO4 and electrons were concentrated on the conduction band of PI, resulting in a stronger redox activity. All six BPs exhibited appreciable degradation following the order of bisphenol A (BPA, 93.5%) > bisphenol B (BPB, 92.7%) > bisphenol AP (BPAP, 85.6%) > bisphenol F (BPF, 75.9%) > bisphenol AF (BPAF, 69.8%) > bisphenol S (BPS, 39.2%), within 120 min under the optimal condition. In the process of degradation, superoxide radicals (·O2-) and hydroxyl radicals (·OH) played dominant roles, and the intermediates of BPs degradation were mainly formed via the substituent shedding or C-C bond breaking of phenol ring, hydroxylation, and ring opening of phenol ring. The ECOSAR program was used to analyze the changes in the toxicity of the intermediates, and it was proved that the toxicity showed a decrease trend during the degradation process. This study provides a Z-scheme mechanism for TiO2-BiVO4-PI, which can degrade BPs and reduce their toxicity effectively.

Toxic effect of copper ions on anammox in IFFAS process filled with ZVI-10 modified carriers.

The inhibitory effects of heavy metals on anammox bacteria (AnAOB) have attracted attention worldwide. However, most are conducted in activated sludge rather than biofilm systems. The toxic effect and resistance response of anammox biofilm are not predictable from those of free-living AnAOB. Zero valent iron (ZVI) has been demonstrated to enhance anammox performance, but whether ZVI can promote AnAOB resistance to heavy metal stress remains unclear. Herein, the toxic effect of copper ions (Cu(II)) on anammox in integrated floating-film activated sludge (IFFAS) process filled with 10 wt% ZVI modified carriers (R1) was investigated. Results indicated half inhibiting concentration (IC50) of Cu(II) in R1 was 9.13 mg/L, which was much higher than that in R0 filled with conventional carriers made of high density polyethylene (HDPE) (3.94 mg/L). Long-term effect of Cu(II) demonstrated that Cu(II) concentrations less than 1.0 mg/L could not inhibit anammox biofilm significantly, whereas R1 performed better anammox process than R0 under the stress of 0.1-1.0 mg/L Cu(II). The ZVI modified carriers induced more extracellular polymeric substances (EPS) to trap Cu(II) to attenuate the toxicity to AnAOB. Besides, the activities of functional enzymes related to anammox (NIR and HDH), as well as heme-c contents, were always higher in R1 than R0 regardless of the Cu(II) dosage. Candidatus Kuenenia was identified as the predominant AnAOB, which had stronger resistance to Cu(II) stress compared to other genera in the IFFAS process. Metal resistance genes (MRGs) analysis identified AnAOB induced multi-responses to resist Cu(II) stress, such as the up-regulation of copC, cutA, cutC, cutF, cueR and cueO, to synthesize more proteins with functions of copper exocytosis, conjugation and oxidation.

Enhanced electrochemical-activation of H2O2 to produce •OH by regulating the adsorption of H2O2 on nitrogen-doped porous carbon for organic pollutants removal.

The heterogeneous Fenton oxidation is regarded as a promising technology for refractory organic pollutants removal relying on highly active •OH generated via the decomposition of H2O2 catalyzed by iron-based catalyst that overcomes the issues of pH limitation and iron sludge discharge encountered in conventional Fenton reaction. However, the efficiency of •OH production in heterogeneous Fenton remains low as the limited mass transfer between H2O2 and catalysts caused by the poor H2O2 adsorption. Here, a nitrogen-doped porous carbon (NPC) catalyst with tunable N configuration was prepared for electrochemical-activation of H2O2 to •OH by enhancing the H2O2 adsorption on catalysts. The resultant •OH production yield on NPC reached 0.83 mM in 120 min. Notably, the NPC catalyst could be more energy-efficient for actual coking wastewater treatment with an energy consumption of 10.3 kWh kgCOD-1 than other electro-Fenton catalysts reported (20-29.7 kWh kgCOD-1). Density function theory (DFT) revealed that highly efficient •OH production was ascribed to the graphitic N which enhances the adsorption energy of H2O2 on NPC catalyst. This study provides new insight into the fabrication of efficient carbonaceous catalysts by rationally modulating electronic structures for refractory organic pollutants degradation.

Simultaneous removal of refractory organic pollutants and nitrogen using electron shuttle suspended biofilm carriers in an integrated hydrolysis/acidification-anoxic/aerobic process.

Azo dyes wastewater contains refractory pollutant and nitrogen, which threatens human health and ecological environment when discharged into environment directly. Electron shuttle (ES) is able to participate in the extracellular electron transfer, and thus enhances the removal efficiency of refractory pollutant. However, the continuous dosing of soluble ES would rise operation cost and cause contamination inevitably. In this study, a type of insoluble ES (carbonylated graphene oxide (C-GO)) was developed and melt blended into polyethylene (PE) to prepare novel C-GO-modified suspended carriers. Compared to those of conventional carrier (31.60%), the surface active sites of novel C-GO-modified carrier increased to 52.95%. An integrated hydrolysis/acidification (HA, filled with C-GO-modified carrier) - anoxic/aerobic (AO, filled with clinoptilolite-modified carrier) process was applied to remove azo dye acid red B (ARB) and nitrogen simultaneously. ARB removal efficiency was significantly improved in the reactor filled with C-GO-modified carriers (HA2) compared to the reactor filled with conventional PE carriers (HA1) or activated sludge (HA0). Total nitrogen (TN) removal efficiency of the proposed process increased by 25.95-32.64% compared to the reactor filled with activated sludge. Moreover, the intermediates of ARB were identified by liquid chromatograph-mass spectrometer (LC-MS), and the degradation pathway of ARB through ES was proposed. C-GO-modified carriers induced ARB-removal-related bacterial enrichment (such as Chloroflexi, Lactivibrio, Longilinea, Bacteroidales and Anaerolineaceae). Besides, the relative abundance of denitrifiers and nitrifiers in the AO reactor filled with clinoptilolite-modified carrier was increased by 11.60% compared with activated sludge. Copy numbers of genes related to membrane transport, carbon/energy metabolism and nitrogen metabolism increased significantly on the surface-modified carriers. This study proposed an efficient approach for simultaneous azo dyes and nitrogen removal, showing potential in actual application.

Electroregulation of graphene-nanofluid interactions to coenhance water permeation and ion rejection in vertical graphene membranes.

Graphene oxide (GO) membranes with nanoconfined interlayer channels theoretically enable anomalous nanofluid transport for ultrahigh filtration performance. However, it is still a significant challenge for current GO laminar membranes to achieve ultrafast water permeation and high ion rejection simultaneously, because of the contradictory effect that exists between the water-membrane hydrogen-bond interaction and the ion-membrane electrostatic interaction. Here, we report a vertically aligned reduced GO (VARGO) membrane and propose an electropolarization strategy for regulating the interfacial hydrogen-bond and electrostatic interactions to concurrently enhance water permeation and ion rejection. The membrane with an electro-assistance of 2.5 V exhibited an ultrahigh water permeance of 684.9 L m-2 h-1 bar-1, which is 1-2 orders of magnitude higher than those of reported GO-based laminar membranes. Meanwhile, the rejection rate of the membrane for NaCl was as high as 88.7%, outperforming most reported graphene-based membranes (typically 10 to 50%). Molecular dynamics simulations and density-function theory calculations revealed that the electropolarized VARGO nanochannels induced the well-ordered arrangement of nanoconfined water molecules, increasing the water transport efficiency, and thereby resulting in improved water permeation. Moreover, the electropolarization effect enhanced the surface electron density of the VARGO nanochannels and reinforced the interfacial attractive interactions between the cations in water and the oxygen groups and π-electrons on the VARGO surface, strengthening the ion-partitioning and Donnan effect for the electrostatic exclusion of ions. This finding offers an electroregulation strategy for membranes to achieve both high water permeability and high ion rejection performance.

Electromotive force induced by dynamic magnetic field electrically polarized sediment to aggravate methane emission.

As a primary driving force of global methane production, methanogens like other living organisms are exposed to an environment filled with dynamic electromagnetic waves, which might induce electromotive force (EMF) to potentially influence the metabolism of methanogens. However, no reports have been found on the effects of the induced electromotive force on methane production. In this study, we found that exposure to a dynamic magnetic field enhanced bio-methanogenesis via the induced electromotive force. When exposed to a dynamic magnetic field with 0.20 to 0.40 mT of intensity, the methane emission of the sediments increased by 41.71%. The respiration of methanogens and bacteria was accelerated by the EMF, as the ratios of F420H2/F420 and NAD+/NADH of the sediment increased by 44.12% and 55.56%, respectively. The respiratory enzymes in respiration chains might be polarized with the EMF to accelerate the proton-coupled electron transfer to enhance microbial metabolism. Together with the enriched exoelectrogens and electrotrophic methanogens, as well as the increased sediment electro-activities, this study indicated that the EMF could enhance the electron exchange among extracellular respiratory microorganisms to increase the methane emission from sediments.

Co3O4 with upshifted d-band center and enlarged specific surface area by single-atom Zr doping for enhanced PMS activation.

In this work, single-atom Zr doping is demonstrated to be an effective strategy to enhance the catalytic performance of Co3O4 toward peroxymonosulfate (PMS) by modulating electronic structure and enlarging specific surface simultaneously. The d-band center of Co sites upshifts owing to different electronegativity of Co and Zr in the bonds of Co-O-Zr confirmed by density functional theory calculations, leading to enhanced adsorption energy of PMS and strengthened electron transfer from Co(II) to PMS. The specific surface area of Zr-doped Co3O4 increases by 6 times due to the decrease of crystalline size. Consequently, the kinetic constant of phenol degradation with Zr-Co3O4 is 10 times higher than that with Co3O4 (0.31 vs. 0.029 min-1). The relative surface specific kinetic constant of Zr-Co3O4 for phenol degradation is still 2.29 times higher than that of Co3O4 (0.00660 vs. 0.00286 g m-2 min-1). In addition, the potential practical applicability of 8Zr-Co3O4 was also confirmed by practical wastewater treatment. This study provides deep insights into modifying electronic structure and enlarging specific surface area to enhance the catalytic performance.

Metal-free electro-Fenton degradation of perfluorooctanoic acid with efficient ordered mesoporous carbon catalyst.

Heterogeneous electro-Fenton with in situ generated H2O2 and •OH is a cost-effective method for the degradation of refractory organic pollutants, in which the catalyst is an important factor affecting its degradation performance. Metal-free catalysts can avoid the potential risk of metal dissolution. However, it remains great challenge to develop efficient metal-free catalyst for electro-Fenton. Herein, ordered mesoporous carbon (OMC) was designed as a bifunctional catalyst for efficient H2O2 and •OH generation in electro-Fenton. The electro-Fenton system showed fast perfluorooctanoic acid (PFOA) degradation with kinetics constant of 1.26 h-1 and high total organic carbon (TOC) removal efficiency of 84.0 % after 3 h reaction. The •OH was the main species responsible for PFOA degradation. Its generation was promoted by the abundant oxygen functional groups such as C-O-C and the nano-confinement effect of mesoporous channels on OMCs. This study indicated that OMC is an efficient catalyst for metal-free electro-Fenton system.

Electrochemical Opening of Impermeable Nanochannels in Laminar Graphene Membranes for Ultrafast Nanofiltration.

Reduced graphene oxide (rGO) could be theoretically used to construct highly permeable laminar membranes with nearly frictionless nanochannels for water treatment. However, their pristine (sp2 C-C) regions usually restack into impermeable channels as a result of van der Waals interactions, resulting in a much low permeance. In this study, we demonstrate that the restacked regions could be electrochemically expanded to form ultrafast water transport nanochannels by providing a low positive potential (e.g., +1.00 V vs SCE) to the rGO membrane. Experimental investigations indicate that the structural expansion is attributed to the intercalation of water molecules into the restacked regions, driven by hydrogen bond interactions between water molecules and hydroxyl groups that are electrochemically produced on edges of rGO nanosheets. The structural expansion could be promoted by weakening the graphene-OH- interactions through intermittent application of the potential. As a result of more ultrafast water transport nanochannels available, the electrochemically treated rGO membranes could have a permeance 2 orders of magnitude higher than that of the pristine one and ∼3 times higher than that of graphene oxide membranes. Because of their smaller average pore size, the rGO membranes also have a higher ionic/molecular rejection performance than graphene oxide membranes.

Highly Efficient Hydroxyl Radicals Production Boosted by the Atomically Dispersed Fe and Co Sites for Heterogeneous Electro-Fenton Oxidation.

The heterogeneous electro-Fenton (hetero-e-Fenton)-coupled electrocatalytic oxygen reduction reaction (ORR) is regarded as a promising strategy for ·OH production by simultaneously driving two-electron ORR toward H2O2 and stepped activating the as-generated H2O2 to ·OH. However, the high-efficiency electrogeneration of ·OH remains challengeable, as it is difficult to synchronously obtain efficient catalysis of both reaction steps above on one catalytic site. In this work, we propose a dual-atomic-site catalyst (CoFe DAC) to cooperatively catalyze ·OH electrogeneration, where the atomically dispersed Co sites are assigned to enhance O2 reduction to H2O2 intermediates and Fe sites are responsible for activation of the as-generated H2O2 to ·OH. The CoFe DAC delivers a higher ·OH production rate of 2.4 mmol L-1 min-1 gcat-1 than the single-site catalyst Co-NC (0.8 mmol L-1 min-1 gcat-1) and Fe-NC (1.0 mmol L-1 min-1 gcat-1). Significantly, the CoFe DAC hetero-e-Fenton process is demonstrated to be more energy-efficient for actual coking wastewater treatment with an energy consumption of 19.0 kWh kg-1 COD-1 than other electrochemical technologies that reported values of 29.7∼68.0 kW h kg-1 COD-1. This study shows the attractive advantages of efficiency and sustainability for ·OH electrogeneration, which should have fresh inspiration for the development of new-generation wastewater treatment technology.

Metal single-site catalyst design for electrocatalytic production of hydrogen peroxide at industrial-relevant currents.

Direct hydrogen peroxide (H2O2) electrosynthesis via the two-electron oxygen reduction reaction is a sustainable alternative to the traditional energy-intensive anthraquinone technology. However, high-performance and scalable electrocatalysts with industrial-relevant production rates remain to be challenging, partially due to insufficient atomic level understanding in catalyst design. Here we utilize theoretical approaches to identify transition-metal single-site catalysts for two-electron oxygen reduction using the *OOH binding energy as a descriptor. The theoretical predictions are then used as guidance to synthesize the desired cobalt single-site catalyst with a O-modified Co-(pyrrolic N)4 configuration that can achieve industrial-relevant current densities up to 300 mA cm-2 with 96-100% Faradaic efficiencies for H2O2 production at a record rate of 11,527 mmol h-1 gcat-1. Here, we show the feasibility and versatility of metal single-site catalyst design using various commercial carbon and cobalt phthalocyanine as starting materials and the high applicability for H2O2 electrosynthesis in acidic, neutral and alkaline electrolytes.

Highly efficient electro-Fenton process on hollow porous carbon spheres enabled by enhanced H2O2 production and Fe2+ regeneration.

Electro-Fenton (e-Fenton) is a promising method for wastewater treatment that relies on powerful ·OH generated via the decomposition of electro-generated H2O2 catalyzed by Fe2+. In this regard, developing a catalyst capable of simultaneously producing H2O2 and accelerating Fe2+ regeneration is of considerable importance; however, this remains a challenge because of the difficulty in modulating the electronic microenvironment. Herein, a hollow porous carbon sphere catalyst (HPCS) is developed to synchronously enhance H2O2 generation and accelerate Fe3+/Fe2+ cycling by constructing an electron-rich microenvironment via surface curvature regulation. The Fe2+ regeneration efficiency reaches 35.5% on HPCS featuring a larger curvature structure (HPCS-TPOS), which is 1.6 times higher than the smaller curvature HPCS-S catalyst (22.8%). Density functional theory reveals that the electron-rich microenvironment on the outer surface of high curvature structure promotes Fe2+ regeneration. The H2O2 production rate on HPCS-TPOS is 47.2 mmol L-1 h-1, exceeding the state-of-the-art e-Fenton catalysts reported. Benefiting from the concurrent high-efficiency of H2O2 production and Fe2+ regeneration, HPCS-TPOS e-Fenton is demonstrated to be efficient for sulfamethoxazole removal with the kinetic rate of 0.30-0.72 min-1 at pH 3-7. This work offers new insight into the design of efficient catalysts by rationally regulating curvature structures for wastewater treatment.

Improving the Performance of the Lamellar Reduced Graphene Oxide/Molybdenum Sulfide Nanofiltration Membrane through Accelerated Water-Transport Channels and Capacitively Enhanced Charge Density.

Graphene is promising in the construction of next-generation nanofiltration membranes for wastewater treatment and water purification. However, the application of graphene-based membranes has still been prohibited by their deficiencies in permeability and ion rejection. Herein, regulating the 2D channel and enhancing the charge density are co-adopted for simultaneous enhancement of the water flux and salt rejection of reduced graphene oxide (rGO) membranes through the intercalation of molybdenum sulfide (MoS2) nanosheets and external electrical assistance. The fabricated rGO/MoS2 membranes possess expanded nanochannels with less friction and a higher water molecule transport velocity gradient (from 8.57 to 14.07 s-1) than those of rGO membranes. Consequently, their water permeance increases from 0.92 to 34.9 L m-2 h-1 bar-1. Meanwhile, benefiting from the high capacitance and negative potential of -1.1 V versus the saturated calomel electrode given to the membranes, their rejection rates toward NaCl reach 87.2% and those toward Na2SO4 reach 93.7%. The Donnan steric pore model analysis indicates that the capacitively and electrically increased surface charge density make great contributions to the higher ion rejection rate. This work gives new insights into membrane design for high water flux and salt rejection efficiency.

Polyaniline derived carbon membrane and its in-situ membrane fouling mitigation performance in MBR based on metal-free electro-Fenton.

An electro-enhanced membrane bioreactor (EMBR) was constructed with polyaniline-based carbon (PAC) separation membrane as the membrane-electrode, which could realize the in-situ electro-generation and activation of H2O2 to ·OH depending on the graphitic and pyridinic N as active sites without metal catalyst. After the continuous operation of the bioreactor for 74 days, approximately 77.41% irreversible membrane fouling occurred on the electrochemically enhanced membrane, which was less than that on the control membrane (85.96%). The ·OH oxidation combined with electrostatic barrier formed by -1.0 V enhanced PAC membrane suppressed the extracellular polymeric substances deposition on membrane. After operation, the strength of total cell, proteins, ß-polysaccharides and α-polysaccharides on the membrane without bias were 5.17, 4.32, 9.65 and 16.31, respectively. In EMBR, the corresponding strength were 2.03, 3.35, 2.15 and 6.73. After calculation, the unblocked pores accounted for 35.3% and 78.5% of the total membrane surface in MBR and EMBR, respectively, indicating the fouling was alleviated obviously. Meanwhile, the EMBR owned a satisfactory wastewater treatment effect with average effluent chemical oxygen demand and NH4+-N around 18.98 mg/L and 0.68 mg/L. The successful implementation of this strategy achieved a green and metal-free method for ·OH production with electrochemical effect for membrane fouling control in MBR.

Enhancing anaerobic methane production in integrated floating-film activated sludge system filled with novel MWCNTs-modified carriers.

Conductive materials can enhance anaerobic methane production by accelerating interspecies electron transfer between electroactive bacteria and methanogens. However, the daily loss or less specific surface area of small/big size of conductive materials always limits their application in anaerobic digestion. In this study, the conductive multi-walled carbon nanotubes (MWCNTs) (15 wt% and 20 wt%) were mixed with high-density polyethylene (HDPE) and novel conductive suspended carriers were prepared. Results showed the conductivity of the novel conductive suspended carriers increased by 1-2 orders of magnitude comparing with HDPE carriers, as well as the attached biomass improved from 3.93 g/m2 (HDPE carriers) to 5.82 g/m2 (15 wt% MWCNTs-modified carriers) and 6.67 g/m2 (20 wt% MWCNTs-modified carriers). Integrated floating-film activated sludge (IFFAS) filled with MWCNT-modified carriers showed significant advantages in chemical oxygen demand (COD) removal (removal efficiency increased by 3.6-37.2%) and methanogenic performance (cumulative methane increased by 12.28-62.91%) compared with the control reactor filled with conventional HDPE carriers when treating sodium propionate wastewater at the organic loading rates (OLR) of 11.3-26.3 kg COD/(m³âˆ™d). SEM images and high-throughput sequencing results proved potential direct interspecies electron transfer (DIET) had been established successfully on the MWCNTs-modified carriers. The syntrophic electroactive bacteria (Geobacter, Thauera) and Methanotrix were enriched by 2.28-4.58% and 9.41-16.80% respectively owning to the addition of novel conductive carriers. This study proved IFFAS process filled with novel MWCNTs-modified suspended carriers showed great potential in establishing DIET to enhance anaerobic digestion in practical application.