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.

Regulating the Electronic Structure of Cu Single-Atom Catalysts toward Enhanced Electro-Fenton Degradation of Organic Contaminants via 1O2 and •OH.

Heterogeneous electro-Fenton degradation with 1O2 and •OH generated from O2 reduction is cost-effective for the removal of refractory organic pollutants from wastewater. As 1O2 is more tolerant to background constituents such as salt ions and a high pH value than •OH, tuning the production of 1O2 and •OH is important for efficient electro-Fenton degradation. However, it remains a great challenge to selectively produce 1O2 and improve the species yield. Herein, the electronic structure of atomically dispersed Cu-N4 sites was regulated by doping electron-deficient B into porous hollow carbon microspheres (CuBN-HCMs), which improved *O2 adsorption and significantly enhanced 1O2 selectivity in electro-Fenton degradation. Its 1O2 yield was 2.3 times higher than that of a Cu single-atom catalyst without B doping. Meanwhile, •OH was simultaneously generated as a minor species. The CuBN-HCMs were efficient for the electro-Fenton degradation of phenol, sulfamethoxazole, and bisphenol A with a high mineralization efficiency. Its kinetic constants showed insignificant changes under various anions and a wide pH range of 1-9. More importantly, it was energy-efficient for treating actual coking wastewater with a low energy consumption of 19.0 kWh kgCOD-1. The superior performance of the CuBN-HCMs was contributed from 1O2 and •OH and its high 1O2 selectivity.

Scaling-Free Cathodes: Enabling Electrochemical Extraction of High-Purity Nano-CaCO3 and -Mg(OH)2 in Seawater.

For electrochemical application in seawater or brine, continuous scaling on cathodes will form insulation layers, making it nearly impossible to run an electrochemical reaction continuously. Herein, we report our discovery that a cathode consisting of conical nanobundle arrays with hydrophobic surfaces exhibits a unique scaling-free function. The hydrophobic surfaces will be covered with microbubbles created by electrolytic water splitting, which limits scale crystals from standing only on nanotips of conical nanobundles, and the bursting of large bubbles formed by the accumulation of microbubbles will cause a violent disturbance, removing scale crystals automatically from nanotips. Benefiting from the scaling-free properties of the cathode, high-purity nano-CaCO3 (98.9%) and nano-Mg(OH)2 (99.5%) were extracted from seawater. This novel scaling-free cathode is expected to eliminate the inherent limitations of electrochemical technology and open up a new route to seawater mining.

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.

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.

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.

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.

Steering CO2 electroreduction toward ethanol production by a surface-bound Ru polypyridyl carbene catalyst on N-doped porous carbon.

Electrochemical reduction of CO2 to multicarbon products is a significant challenge, especially for molecular complexes. We report here CO2 reduction to multicarbon products based on a Ru(II) polypyridyl carbene complex that is immobilized on an N-doped porous carbon (RuPC/NPC) electrode. The catalyst utilizes the synergistic effects of the Ru(II) polypyridyl carbene complex and the NPC interface to steer CO2 reduction toward C2 production at low overpotentials. In 0.5 M KHCO3/CO2 aqueous solutions, Faradaic efficiencies of 31.0 to 38.4% have been obtained for C2 production at -0.87 to -1.07 V (vs. normal hydrogen electrode) with 21.0 to 27.5% for ethanol and 7.1 to 12.5% for acetate. Syngas is also produced with adjustable H2/CO mole ratios of 2.0 to 2.9. The RuPC/NPC electrocatalyst maintains its activity during 3-h CO2-reduction periods.

Enhancing anoxic denitrification of low C/N ratio wastewater with novel ZVI composite carriers.

External organic carbon sources are needed to provide electron donors for the denitrification of wastewater with a low COD/NO3--N (C/N) ratio, increasing the treatment cost. The economic strategy is to enhance the bioactivity and/or biodiversity of denitrifiers to efficiently utilize organic substances in wastewater. In this study, novel zero-valent iron (ZVI) composite carriers were prepared and implemented in a suspended carrier biofilm reactor to enhance the bioactivity and/or biodiversity of denitrifiers. At the influent C/N ratio of 4 (COD was 179.5 ± 5.0 mg/L and TN was 44.2 ± 0.8 mg/L), COD and TN removal efficiencies were 85.1% and 66.4%, respectively, in the reactors filled with 3 wt% ZVI composite carriers. In contrast, COD and TN removal efficiencies were 70.4% and 55.3%, respectively, in the reactor filled with conventional high-density polyethylene (HDPE) biofilm carriers. The biofilm formation on the 3 wt% ZVI composite carriers was optimized due to its higher roughness (surface square roughness increased from 76.0 nm to 93.8 nm) and favorable hydrophilicity (water contact angle dropped to 72.5° ± 1.4° from 94.3° ± 3.2°) compared with the HDPE biofilm carriers. In addition, heterotrophic denitrifiers, Thauera and Dechloromonas, were enriched, whereas autotrophic denitrifiers, Raoultella and Thiobacillus, exhibited high relative abundance in the biofilm of ZVI composite carriers. The coexistence of heterotrophic denitrifiers and autotrophic denitrifiers on the surface of ZVI composite carriers provided mixotrophic metabolism of denitrification (including heterotrophic and iron-based autotrophic), thereby ensuring effective denitrification for wastewater with a low C/N ratio without external organic carbon source addition.

Enhanced Chlorinated Pollutant Degradation by the Synergistic Effect between Dechlorination and Hydroxyl Radical Oxidation on a Bimetallic Single-Atom Catalyst.

Chlorinated organic pollutants are highly toxic and widespread in the environment, which cause ecological risk and threaten the human health. Chlorinated pollutants are difficult to degrade and mineralize by the conventional advanced oxidation process as the C-Cl bond is resistant to reactive oxygen species oxidation. Herein, we designed a bifunctional Fe/Cu bimetallic single-atom catalyst anchored on N-doped porous carbon (FeCuSA-NPC) for the electro-Fenton process, in which chlorinated pollutants are dechlorinated on single-atom Cu and subsequently oxidized by the ·OH radical produced from O2 conversion on single-atom Fe. Benefitting from the synergistic effect between dechlorination on single-atom Cu and ·OH oxidation on single-atom Fe, the chlorinated organic pollutants can be efficiently degraded and mineralized. The mass activity for chlorinated organic pollutant degradation by FeCuSA-NPC is 545.1-1374 min-1 gmetal-1, excessing the highest value of the reported electrocatalyst. Moreover, FeCuSA-NPC is demonstrated to be pH-universal, long-term stable, and environment friendly. This work provides a new insight into the rational design of a bifunctional electrocatalyst for efficient removal of chlorinated organic pollutants.

Electrokinetic Enhancement of Water Flux and Ion Rejection through Graphene Oxide/Carbon Nanotube Membrane.

Graphene oxide (GO) is promising for constructing next-generation high-performance membranes for water treatment and desalination. However, GO-based membranes are still subjected to low ion rejection or limited water flux. Herein, the electrokinetic effect is employed as a new strategy for the coenhancement of water flux and ion rejection through an ethylenediamine-polystyrenesulfonate intercalated graphene oxide/carbon nanotube (GO&EDA-PSS/CNT) asymmetric membrane. Benefiting from the external voltage applied across the GO&EDA-PSS layer, the electrokinetically driven water transport velocity is significantly increased from 0 to 23.7 µm s-1 with increasing the voltage from 0 to 3.0 V. As a result, the water flux is improved from 9.1 to 17.4 L m-2 h-1 under a transmembrane pressure of 1 bar. Simultaneously, the rejection rate for NaCl is increased from 52.4% to 78.3%. Numerical analysis reveals that the increased rejection rate is attributed to the electrokinetic enhancements of water transport through the membrane and ion partitioning between the membrane and bulk solution. These results indicate that the assistance of the electrokinetic effect is an effective means to improve membrane filtration performance, which provides a new perspective on the design of advanced membranes for achieving high water flux and rejection efficiency.

High-Efficiency Electrocatalysis of Molecular Oxygen toward Hydroxyl Radicals Enabled by an Atomically Dispersed Iron Catalyst.

Fenton catalysis represents the promising technology to produce super-active ·OH for tackling severe water environment pollution issues, whereas it suffers from low atomic efficiency, poor pH adaptability, and catalyst non-reusability in a homogeneous or heterogeneous system. Here, single-atom iron catalysis is creatively introduced to drive electrochemical ·OH evolution utilizing earth-abundant oxygen and water as raw materials. The atomically dispersed iron settled by defective three-dimensional porous carbon (AD-Fe/3DPC) with unique C, Cl unsaturated coordination can efficiently tune the multi-electron oxygen reduction process, enabling O2-to-·OH conversion. The mass activity in ·OH production by AD-Fe/3DPC is almost two-orders of magnitude higher as compared to that by nanoparticular iron oxide catalyst. Meanwhile, the AD-Fe/3DPC electro-Fenton system exhibits fast elimination of refractory toxic pollutants, surpassing nanoparticular iron oxides in kinetic rate by 59 times or homogeneous Fenton by 10 times under similar experimental conditions. Experimental and theoretical results demonstrate that the remarkable enhanced mass activity of AD-Fe/3DPC in catalyzing O2 to ·OH is contributed by the synergistic effects of the maximized catalysis of atomically dispersed iron and the unique unsaturated coordination environment. The AD-Fe/3DPC catalytic system is demonstrated to be pH-universal, long-term stable, and well recyclable, truly satisfying flexible, sustainable, and green application of wastewater purification. This study gives a new sight into local coordination modulation of single-atom catalysts for selective electrocatalytic oxygen reduction.

Mitigating Membrane Fouling Based on In Situ •OH Generation in a Novel Electro-Fenton Membrane Bioreactor.

A novel electro-Fenton membrane bioreactor was constructed to investigate the effect of electro-Fenton on mitigating membrane fouling. Herein, porous carbon (PC), carbon nanotubes (CNTs) and Fe2+ were spun into hollow fiber membranes (Fe-PC-CHFM), then served as cathode and filtration core simultaneously. The H2O2 can be in situ produced by O2 reduction with electro-assistance, and further induce hydroxyl radicals (•OH) generation with loaded Fe2+ on the surface of Fe-PC-CHFM. In addition, Fe3+/Fe2+ cycle can be realized effectively by the electro-assistance, avoiding ferrous iron addition. During over 100-day operation, the electro-Fenton membrane bioreactor achieved 93% of COD and 88% of NH4+-N removal at a HRT of 8 h. At the end of operation, the membranes in electro-Fenton membrane bioreactor still exhibited obviously mesh-like structure similarly to initial level. Importantly, merely 15 min with an operation voltage of -0.8 V was sufficient to completely recover permeate flux of the fouled Fe-PC-CHFM. The energy consumption used for membrane fouling control was barely 8.64 × 10-5 kW·h/m3. Therefore, this novel energy-saved electro-Fenton membrane bioreactor process could provide an envisaging prospective and promising method for practice wastewater membrane treatment.

Integrated Analysis of the Water-Energy-Environmental Pollutant Nexus in the Petrochemical Industry.

China has set high water-conservation, energy-saving, and pollutant-reduction goals for the petrochemical industry. This represents a challenge to petrochemical enterprises because of the complex coupling between water, energy, and environmental pollutant (WEE) subsystems, elements (different types of WEE), and production units. However, there has been little research on the element-level coupling relationship. The connection and difference between the coupling relationships of the system, element, and unit levels are not well understood. Therefore, an integrated analysis method was developed to quantify the petrochemical WEE nexus (WEEN) at these three levels, including a generic WEEN model, material and energy flow analysis, and a WEEN analysis matrix. Three indicators were proposed to analyze three-level coupling quantitatively and to formulate improvement strategies for water-conservation, energy-saving, and pollutant-reduction. A case study demonstrated significant three-level coupling. The coupled percentage of WEE subsystems were 95.87%, 61.97%, and 54.99%, respectively. The dominant energy subsystem was the root of high consumption and pollution. Based on synergies and trade-offs, we proposed element optimization priorities: High priority (deoxidized water and fuel), medium priority (steam, circulating water, and wastewater), and low priority (fresh water, demineralized water, waste gas, and electricity). The identified unit improvement potential revealed overestimation (hydrotreating and delayed coking units) and underestimation (crude distillation units) of conventional methods that overlook three-level coupling.

Cross-linked Graphene Oxide Framework Membranes with Robust Nano-Channels for Enhanced Sieving Ability.

It remains challenging for graphene oxide (GO) membranes to achieve highly efficient performance and sufficient stability for aqueous molecule/ion precise separations. Herein, a molecular-level rational structure design protocol was proposed to develop ceramic-based graphene oxide framework (GOF) membranes with significantly enhanced sieving performance and stability for efficient removal of salts and micropollutants. Via a molecular cross-linking strategy, interlayered nanochannels between GO nanosheets can be rationally designed, featuring precisely tailorable channel size, promising surface chemistries and remarkably robust stability suitable for aqueous separation. Due to a significantly decreased nanochannel size, cross-linking of TU (thiourea) molecule significantly improved monovalent salt rejection (95.6% for NaCl), outperforming existing state-of-the-art GO-based, commercial organic nanofiltration and emerging two-dimensional MoS2 membranes, while moderately decreasing water permeability. In comparison, the GOF membranes cross-linked with MPD (m-phenylenediamine) exhibited a simultaneous increase in permeability and rejection for both salts and micropollutants (21.0% and 53.3% enhancement for chloramphenicol (CAP) solution), breaking their conventional trade-off issue. Cross-linking mechanism indicates that more robust nanochannels were formed by stronger covalent bonds via dehydration condensation between amine (TU/MPD) and carboxyl groups (GO), and nucleophilic addition between amine (TU/MPD) and epoxy groups (GO). Molecule/ion separation mechanism involved size sieving (steric hindrance), electrostatic interaction, Donnan effect, and partial dehydration effect. This work provides a novel protocol for rationally designing size and surface chemistry of highly robust GO nanochannels at a subnanometer level to construct water-stable functional GOF membranes with enhanced sieving performance for water treatment applications.

Flexible Superhydrophobic Metal-Based Carbon Nanotube Membrane for Electrochemically Enhanced Water Treatment.

Treatment of highly saline wastewaters via conventional technology is a key challenging issue, which calls for efficient desalination membranes featuring high flux and rejection, low fouling, and excellent stability. Herein, we report a high-strength and flexible electro-conductive stainless steel-carbon nanotube (SS-CNT) membrane, exhibiting significantly enhanced anticorrosion and antifouling ability via a microelectrical field-coupling strategy during membrane distillation. The membrane substrates exhibited excellent mechanical strength (244.2 ± 9.8 MPa) and ductility, thereby overcoming the critical bottleneck of brittleness of traditional inorganic membranes. By employing a simple surface activation followed by self-catalyzed chemical vapor deposition, CNT was grown in situ on SS substrates via a tip-growth mechanism to finally form robust superhydrophobic SS-CNT membrane. To address the challenging issues of significant corrosion and fouling, using a negative polarization microelectrical field-coupling strategy, simultaneously enhanced antifouling and anticorrosion performance was realized for treatment of organic high salinity waters while exhibiting stable high flux and rejection via an electrostatic repulsion and electron supply mechanism. This application-oriented rational design protocol can be potentially used to extend toward high performance composite membranes derived from other electro-conductive metal substrates functionally decorated with CNT network and to other applications in water treatment.

Construction of a Microchannel Electrochemical Reactor with a Monolithic Porous-Carbon Cathode for Adsorption and Degradation of Organic Pollutants in Several Minutes of Retention Time.

A monolithic porous-carbon (MPC) electrode was fabricated to simultaneously intensify mass transfer and enhance reaction activity. The MPC involved channel arrays (about 50 µm of diameter for each channel) with mesopores and micropores in channel walls. The abundant surface pores may improve the reaction efficiency of the reduction of O2 to produce H2O2 and •OH. The function of channel arrays was to shorten the mass-transfer distance not only from O2 to the electrode surface but also from pollutants to the electrode surface and •OH. A microchannel electrochemical reactor was assembled to evaluate the performance of the MPC cathode. For 20 mg/L of phenol, sulfamethoxazole or atrazine, effluent concentration and total organic carbon (TOC) decreased down to 1.5 and 3 mg/L, respectively, in a retention time of only 100-300 s. Phenol removal was dominated by the MPC cathode, and the contribution of cathodic adsorption, cathodic degradation, and anodic reaction was 46, 33, and 8%, respectively. The proper working potential for the MPC cathode was +0.26 to +0.6 V versus reversible hydrogen electrode; in this potential range, no scaling was observed. For the real surface water (the initial TOC was 41.5 mg/L), TOC in effluent (the retention time was 335 s) was stable at 31.0 mg/L.

Effects of nanomaterials on metal toxicity: Case study of graphene family on Cd.

The risk of heavy metal cadmium (Cd) on aquatic organisms has drawn widespread attentions, but the effects of nanomaterials (e.g. graphene (G)) on Cd toxicity are rarely clarified. It was known that mixture of contaminants may exhibit more severe impact than the individual metal. Here, we conducted a study systematically on the effects of nanomaterials on the toxicity of Cd to Scenedesmus Obliquus (S. obliquus) with or without the presence of graphene family materials (GFMs) derived from G, such as graphene oxide (GO) and amine-modified graphene (GNH). Our results showed that the influence of GFMs on the acute toxicity of Cd to S. obliquus is in the order of GO > G > GNH based on their EC50 of Cd-GFMs. The effects of GFMs on the cytotoxicity and oxidative damage of Cd to S. obliquus are varied with the concentrations of GFMs. The differences between the effects of GFMs on Cd toxicity may attribute to their different surface oxygen-containing functional groups contained in the nanomaterials. The adsorption capacity of nanomaterials on metal ions, their dispersibility in water and their interaction mode with organisms, may dominate main contributions to their effects on Cd toxicity. Our study aids to clarify the interference of nanoparticles on the ecotoxicity of metals, to avoid the misunderstanding of the potential risk of metals in the complicate water environments.

Improvement of Antifouling and Antimicrobial Abilities on Silver-Carbon Nanotube Based Membranes under Electrochemical Assistance.

Excellent fouling resistance to various foulants is crucial to maintain the separation performance of membranes in providing potable water. Antimicrobial modification is effective for antibiofouling but fails to mitigate organic fouling. Improving surface charges can improve the resistance to charged foulants, but the lack of antimicrobial ability results in bacterial aggregation. Herein, a silver nanoparticle modified carbon nanotube (Ag-CNT)/ceramic membrane was prepared with enhanced antifouling and antimicrobial properties under electrochemical assistance. The presence of silver nanoparticles endows the composite membrane with antimicrobial ability by which biofilm formation is inhibited. Its steady-state flux is 1.9 times higher than that for an unmodified membrane in filtering bacterial suspension. Although the formation of organic fouling did weaken the biofouling resistance, the negatively charged bacteria and organic matter can be sufficiently repelled away from the cathodic membrane under electrochemical assistance. The flux loss under a low-voltage of 2.0 V decreased to <10% from >35% for the membrane alone when bacteria and organic matter coexisted in the feedwater. More importantly, silver dissolution was significantly inhibited via an in situ electroreduction process by which the Ag+ concentration in the effluent (<1.0 µg/L) was about 2 orders of magnitude lower than that without voltage. The integration of antimicrobial modification and electrochemistry offers a new prospect in the development of membranes with high fouling resistance in water treatment.