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.

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.

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.

Structurally Stable, Antifouling, and Easily Renewable Reduced Graphene Oxide Membrane with a Carbon Nanotube Protective Layer.

The excellent permeability and selectivity of reduced graphene oxide (rGO) membranes have been demonstrated both theoretically and experimentally; however, strategies for the fabrication of highly stable, antifouling rGO membranes with facile recovery after fouling have rarely been investigated. In this work, we report a structurally durable rGO-based hollow fiber membrane that allows high-pressure (at least 1 bar) back-flushing. This is achieved by sandwiching the rGO layer between a carbon nanotube (CNT) protective layer and a polyacrylonitrile (PAN) support. The CNT layer could also function as a prefiltration and pre-adsorption microsystem and endow a higher resistance against fouling. This is experimentally confirmed by the much higher normalized permeance (0.82-0.92) of the CNT/rGO/PAN membranes than the simple rGO/PAN membranes (0.42-0.53) under the same operating conditions. Additionally, under a low cathode potential (0.9 V), the membrane could easily be renewed after fouling by simple back-flushing with a flux recovery ratio of ∼96%. An investigation of the mechanism indicates that electrostatic repulsive forces promote the desorption of charged organic foulants (e.g., humic acid and dyes) from the rGO and CNT layers, and they can subsequently be removed from the membrane with water.

Aqueous OH Radical Reaction Rate Constants for Organophosphorus Flame Retardants and Plasticizers: Experimental and Modeling Studies.

Aqueous ·OH reaction rate constants ( kOH) for organophosphate esters (OPEs) are essential for assessing their environmental fate and removal potential in advanced oxidation processes (AOPs). Herein experimental and in silico approaches were adopted to obtain kOH values for a variety of OPEs. The determined kOH for 18 OPEs varies from 4.0 × 108 M-1 s-1 to 1.6 × 1010 M-1 s-1. Based on the experimental kOH values, a quantitative structure-activity relationship model that involves molecular structural information on the number of heavy atoms, content index, and the most negative charge of C atoms was developed for predicting kOH of other OPEs. Furthermore, appropriate density functional theory (DFT) and solvation models were selected, which together with transition state theory were employed to predict kOH of three representative OPEs. The deviation between the DFT calculated and the experimental kOH values ( kcal/ kexp) is within 2. Half-lives of the OPEs were estimated to be 0.5-22791.3 days in natural waters and 0.044-19.7 s in AOPs, indicating the OPEs are potentially persistent in natural waters and can be quickly eliminated by AOPs. The determined kOH values and the in silico methods offer a scientific base for assessing OPEs fate in aquatic environments.

Combined Effects of Surface Charge and Pore Size on Co-Enhanced Permeability and Ion Selectivity through RGO-OCNT Nanofiltration Membranes.

Nanofiltration (NF) has received much attention for wastewater treatment and desalination. However, NF membranes generally suffer from the trade-off between permeability and selectivity. In this work, the coenhancement of permeability and ion selectivity was achieved through tuning the surface charge and pore size of oxidized carbon nanotube (OCNT) intercalated reduced graphene oxide (RGO) membranes. With the increase of OCNT content from 0 to 83%, the surface charge and the pore size were increased. The permeability increased to 10.6 L m-2 h-1 bar-1 and rejection rate reached 78.1% for Na2SO4 filtration at a transmembrane pressure of 2 bar, which were 11.8 and 1.3 times higher than those of pristine RGO membrane. The composite membrane also showed 11.1 times higher permeability (11.1 L m-2 h-1 bar-1) and 2.9 times higher rejection rate (35.3%) for NaCl filtration. The analyses based on Donnan steric pore model suggest that the increased permeability is attributed to the combined effects of enlarged pore size and increased surface charge, while the enhanced ion selectivity is mainly dependent on the electrostatic interaction between the membrane and target ions. This finding provides a new insight for the development of high-performance NF membranes in water treatment and desalination.

Constructing all carbon nanotube hollow fiber membranes with improved performance in separation and antifouling for water treatment.

Manipulating carbon nanotubes (CNTs) through engineering into advanced membranes with superior performance for disinfection and decontamination of water shows great promise but is challenging. In this paper, a facile assembly of CNTs into novel hollow fiber membranes with tunable inner/outer diameters and structures is developed for the first time. These free-standing membranes composed entirely of CNTs feature a porosity of 86±5% and a permeation flux of about 460±50 L m(-2) h(-1) at a pressure differential of 0.04 MPa across the membrane. The randomly oriented interwoven structure of CNTs endows the membranes considerable resistance to pore blockage. Moreover, the adsorption capability of the CNT hollow fiber membranes, which is crucial in the efficient removal of small and trace contaminant molecules, is about 2 orders of magnitude higher than that of commercial polyvinylidene fluoride hollow fiber membranes. The unique advantage of the CNT hollow fiber membranes over other commercial membranes is that they can be in situ electrochemically regenerated after adsorption saturation.

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.

Conductive MXene ultrafiltration membrane for improved antifouling ability and water quality under electrochemical assistance.

Membrane fouling is a major challenge for the membrane separation technique in water treatment. Herein, an MXene ultrafiltration membrane with good electroconductivity and hydrophilicity was prepared and showed excellent fouling resistance under electrochemical assistance. The fluxes under negative potential were 3.4, 2.6 and 2.4 times higher than those without external voltage during treatment of raw water containing bacteria, natural organic matter (NOM), and coexisting bacteria and NOM, respectively. During the treatment of actual surface water with 2.0 V external voltage, the membrane flux was 1.6 times higher than that without external voltage and the TOC removal was improved from 60.7% to 71.2%. The improvement is mainly attributed to the enhanced electrostatic repulsion. The MXene membrane presents good regeneration ability after backwashing under electrochemical assistance with the TOC removal remaining stable at around 70.7%. This work demonstrates that the MXene ultrafiltration membrane under electrochemical assistance possesses excellent antifouling ability and has great potential in advanced water treatment.

Highly Permeable Sulfonated Graphene-Based Composite Membranes for Electrochemically Enhanced Nanofiltration.

A sulfophenyl-functionalized reduced graphene oxide (SrGO) membrane is prepared. The SrGO membranes have a high charge density in water and could provide many atomically smooth nanochannels, because of their strong ionized-SO3H groups and low oxygen content. Therefore, the SrGO membranes have an excellent performance in terms of high permeance and high rejection ability. The permeance of SrGO membranes could be up to 118.2 L m−2 h−1 bar−1, which is 7.6 times higher than that of GO membrane (15.5 L m−2 h−1 bar−1). Benefiting from their good electrical conductivity, the SrGO membranes could also function as an electrode and demonstrate a significantly increased rejection toward negatively charged molecules and positively charged heavy metal ions such as Cu2+, Cr3+ and Cd2+, if given an appropriate negative potential. The rejection ratios of these metal ions can be increased from <20% at 0 V to >99% at 2.0 V. This is attributed to the enhanced electrostatic repulsion between the SrGO membrane and the like-charged molecules, and the increased electrostatic adsorption and electrochemical reduction in these heavy metal ions on the membranes. This study is expected to contribute to efficient water treatment and the advance of graphene-based membranes.

Turning Tissue Waste into High-Performance Microfiber Filters for Oily Wastewater Treatment.

Developing low-cost, durable, and high-performance materials for the separation of water/oil mixtures (free oil/water mixtures and emulsions) is critical to wastewater treatment and resource recovery. However, this currently remains a challenge. In this work, we report a biopolymer microfiber assembly, fabricated from the recovery of tissue waste, as a low-cost and high-performance filter for oily wastewater treatment. The microfiber filters demonstrate superhydrophilicity (water contact angle of 28.8°) and underwater superoleophobicity (oil contact angle of 154.2°), and thus can achieve separation efficiencies of >96% for both free oil/water mixtures and surfactant-stabilized emulsions even in highly acidic (pH 2.2)/alkaline (pH 11.8) conditions. Additionally, the prepared microfiber filters possess a much higher resistance to oil fouling than conventional membranes when filtering emulsions, which is because the large-sized 3D interconnected channels of the filters can delay the formation of a low-porosity oil gel layer on their surface. The filters are expected to practically apply for the oily wastewater treatment and reduce the amount of tissue waste entering the environment.

Colloidal biliquid aphron demulsification using polyaluminum chloride and density modification of DNAPLs: optimal conditions and common ion effect.

Dense non-aqueous phase liquids (DNAPLs) entrapped and pooled in aquifers serve as a long term source of groundwater contamination because of their low solubility and high density. Density modification displacement (DMD) with colloidal biliquid aphrons (CBLAs) is a promising approach to prevent DNAPL downward migration during surfactant-based remediation processes. CBLA demulsification and quick release of internal light organic matter is the key to density modification of DNAPLs. In this work, it is reported for the first time that polyaluminum chloride (PAC) could destabilize CBLAs efficiently. The optimum conditions for demulsification of CBLAs by PAC were obtained; the effects of several specific ions in groundwater on demulsification of CBLAs by PAC were investigated. The results indicated that the CBLA was completely demulsified by PAC within 10 minutes and released light organic matter. It recorded the highest demulsification efficiency when the addition ratio (VPAC/VCBLA) was 2 : 1, concentration of PAC was 0.7 g L-1 and the PVR of CBLAs was 8. Most cations (sodium, magnesium and calcium ions) had inhibitory effects on demulsification of CBLAs by PAC with increasing ion concentration, but iron ions had no effect on it. Sulfate anions showed a stronger inhibitory effect on demulsification of CBLAs by PAC compared to chloride ions. With PAC as the demulsifier, CBLAs could be demulsified efficiently, irreversibly modifying the density of trichloroethylene in 5 minutes.

Quantitative structure-activity relationship models for predicting singlet oxygen reaction rate constants of dissociating organic compounds.

As singlet oxygen (1O2) is ubiquitous in the environment, 1O2-involved oxidation may play an important role in the transformation and fate of organic pollutants. Accordingly, the reaction rate constants (k1O2) of organic compounds with 1O2 are important to determine the environmental fate and persistence assessment of organic pollutants. However, currently there are limited k1O2 data available, especially for organic chemicals with different charged (deprotonated/protonated) forms. Herein three quantitative structure-activity relationship (QSAR) models (one comprehensive model and two models for neutral and deprotonated molecules) were created for predicting aqueous k1O2 values for diversely dissociating molecules. The models include larger datasets (180 chemicals) and have wider applicability domain than previous ones. Molecular structural characteristics (only half-wave potential is present in both models) determining the 1O2 reaction rate of neutral and deprotonated molecules vary greatly. The comparison results of predicting k1O2 values of organic compounds at certain pH conditions show that the combination of the QSAR models for neutral and deprotonated molecules has advantages over the comprehensive QSAR model. This work is the first study to predict k1O2 for a wide variety of neutral and deprotonated molecules and provides an important tool for assessing the fate of organic pollutants in aquatic environments.

Superpermeable Atomic-Thin Graphene Membranes with High Selectivity.

Theoretical permeability of membrane is inversely proportional to its thickness, which indicates ultrathin membranes will be extremely permeable. Inspired by the atomic thickness of graphene, herein we report a four-layered graphene membrane with a thickness of about 2 nm. The ultrathin membrane is facilely fabricated by directly punching a complete graphene sheet through selective removal of some carbon atoms with metal oxide nanoparticles at high temperature. Their perpendicular pore channels spanning the whole thickness could, to a great extent, reduce hydrodynamic resistance for water transport. Experimental tests have revealed a flux of up to 4600 L m-2 h-1 of the membranes with a pore size of 50 nm and pore density of 1.0 × 107 cm-2 at a pressure of 0.2 bar. This flux is 40-400 times higher than those of conventional ceramic membranes and track-etched membranes. The enhancement in water permeance is attributed to their atomic thickness and straight pore channels. High selectivity is also evidenced by selective separation of nanospheres with their narrowly distributed pores. These atomic-thin graphene membranes, in view of their outstanding permeability and selectivity, possess great potential as future advanced membranes and may inspire the design and development of other innovative membranes.

Voltage-Gated Transport of Nanoparticles across Free-Standing All-Carbon-Nanotube-Based Hollow-Fiber Membranes.

Understanding the mechanism underlying controllable transmembrane transport observed in biological membranes benefits the development of next-generation separation membranes for a variety of important applications. In this work, on the basis of common structural features of cell membranes, a very simple biomimetic membrane system exhibiting gated transmembrane performance has been constructed using all-carbon-nanotube (CNT)-based hollow-fiber membranes. The conductive CNT membranes with hydrophobic pore channels can be positively or negatively charged and are consequently capable of regulating the transport of nanoparticles across their pore channels by their "opening" or "closing". The switch between penetration and rejection of nanoparticles through/by CNT membranes is of high efficiency and especially allows dynamic control. The underlying mechanism is that CNT pore channels with different polarities can prompt or prevent the formation of their noncovalent interactions with charged nanoparticles, resulting in their rejection or penetration by/through the CNT membranes. The theory about noncovalent interactions and charged pore channels may provide new insight into understanding the complicated ionically and bimolecularly gated transport across cell membranes and can contribute to many other important applications beyond the water purification and resource recovery demonstrated in this study.