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In order to catalytically degrade organic pollutants, a CoAl-layered double hydroxide catalytic membrane (CoAl-LDH-M) was fabricated for the activation of peroxymonosulfate (PMS). Notably, at the dosage of 50 mg/L PMS and flow rate of 1.0 mL/min, 99.7% removal of Rhodamine B (RhB) was obtained. The corresponding removal efficiency of total organic carbon (TOC) was 59.9%. This demonstrated that CoAl-LDH-M possessed high efficiency for PMS activation. Inductively coupled plasma (ICP) results showed that the leached amount of cobalt and aluminum were 0.13 and 0.04 mg/L, indicating the high stability of CoAl-LDH-M. The CoAl-LDH-M /PMS system could also effectively degrade several other contaminants, obtaining removal efficiencies of 92.7–99.6%. The effects of pH and co-existing ions were investigated as well. Reusability of the catalytic membrane was evaluated in both distilled water and synthetic wastewater. Mechanism studies showed that both reactive oxidative species (ROSs) and non-radical electron transfer were involved. The non-radical electron transfer played the primary role. The degradation pathway of RhB was unraveled by liquid chromatography-mass spectrometry measurements and theoretical calculations. Furthermore, the ecotoxicity of the reaction intermediates was evaluated by utilizing quantitative structure activity relationship (QSAR) calculations. [ABSTRACT FROM AUTHOR]

The advancement of technologies for producing chemicals and materials from non‐fossil resources is of critical importance. An illustrative example is the dehydrogenation of glucose, to yield gluconic acid, a specialty chemical. In this study, we propose an innovative production route for gluconic acid while generating H2 as a co‐product. Our concept involves a dual‐function membrane, serving both as a catalyst for glucose dehydrogenation into gluconic acid and as a means to efficiently remove the produced H2 from the reaction mixture. To achieve this two membranes were developed, one catalytically active and one dense aimed at H2 removal. The catalytic membrane showed significant activity, yielding 16 % gluconic acid (t=120 min) with a catalyst selectivity of 93 % and stable performance over five consecutive cycles. Incorporating the H2 separating membrane showed the significance of H2 removal in driving the reaction forward. Its inclusion led to a twofold increase in gluconic acid yield, aligning with Le Chatelier's principles. As a future prospect the two layers can be combined into a dual‐layer membrane which opens the way for a new production route to simultaneously produce gluconic acid and H2, using high‐throughput reactors such as hollow‐fiber systems. [ABSTRACT FROM AUTHOR]

The present study is focused on the synthesis of zero-valent iron/cellulose acetate (Fe0-x/CA) membranes by phase inversion route for the activation of peroxymonosulfate (PMS). The generated •OH and SO4•− effectively degraded methylene blue (MB) dye in water to give comparatively non-toxic byproducts. The SEM investigations revealed that Fe0 nanoparticles are evenly dispersed into the CA membrane resulting in decline of agglomeration and enhancing the roughness of the composite surface. Moreover, the catalytic degradation of MB demonstrated that M5-alone showed 85% and was further boosted to 97% when coupled with PMS (M5/HSO5−). The catalytic degradation of degradation of MB by M5/HSO5− membrane system in acidic, neutral, and basic media indicated that the degradation was 99.5%, 98.0%, 97.0%, 86.0% and 70.0% when the pH of the medium was 3, 5, 7, and 11, respectively. Furthermore, the degradation performance of M5/HSO5− membrane system was evaluated in de-ionized water (DIW), tape water (TPW) and industrial wastewater (IWW) and the results indicated that MB catalytic degradation was in the order of DIW (97%) > TPW (84%) > IWW (68%). Besides, various parameters like water flux permeability, contact angle, porosity, and fouling performance were also investigated. In addition, the degradation products were evaluated, and the degradation pathways were proposed accordingly. [ABSTRACT FROM AUTHOR]

Engineering a catalytic membrane capable of efficiently removing emerging organic microcontaminants under ultrahigh flux conditions is of significance for water purification. Herein, drawing inspiration from the functional attributes of lymphatic vessels involved in immunosurveillance and fluid transport with minimal energy consumption, a novel hierarchical porous catalytic membrane is engineered. This membrane, based on an innovative nitrogen‐rich conjugated microporous polymer (polytripheneamine, PTPA), is synthesized using an electrospinning coupled in situ polymerization approach. The resulting bioinspired membrane with hierarchical channels comprises a thin layer (≈1.7 µm) of crosslinked PTPA nanoparticles covering the interconnected electrospun nanofibers. This unique design creates an intrinsic microporous angstrom‐confined system capable of activating peroxymonosulfate (PMS) to generate 98.7% singlet oxygen (1O2), enabling durable and highly efficient degradation of microcontaminants. Additionally, the presence of a thin layer of mesoporous structure between PTPA nanoparticles and macroporous channels within the interwoven nanofibers enhances mass transfer efficiency and facilitates high flux rates. Notably, the prepared hierarchical porous organic catalytic membrane demonstrates enduring high‐efficiency degradation performance with a superior permeance (>95% and >2500 L m−2 h−1 bar−1) sustained over 100 h. This work introduces an innovative pathway for the design of high‐performance catalytic membranes for the removal of emerging organic microcontaminants. [ABSTRACT FROM AUTHOR]

As typical pharmaceuticals and personal care products (PPCPs), metronidazole (MNZ) and bisphenol A (BPA) normally presented in sewage effluent and surface water. The nitrogen-doped multi-walled carbon nanotube (NCNT) membrane was prepared and utilized as a peroxymonosulphate (PMS) catalyst to degrade MNZ and BPA. Within the NCNT membrane/PMS catalytic system, MNZ and BPA can be efficiently degraded, while different catalytic degradation mechanism exists related with their structure, adsorption properties and even PMS dosage. The optimal conditions for the degradation of MNZ and BPA were investigated. Quenching tests and electron paramagnetic resonance examination demonstrated that •OH radicals and ¹O2 played roles in MNZ degradation, while surface-bound radicals and ¹O2 dominated BPA degradation within the NCNT membrane catalytic PMS system. Electrochemical tests proved that an electron-transfer process between NCNT membrane and PMS during MNZ degradation, and the electron-transfer process was further verified with the degradation experiment in the binary-solute system (BPA and MNZ). PMS dosage had little influence on the degradation mechanism of MNZ and BPA. [ABSTRACT FROM AUTHOR]

Different drying methods were used to prepare catalytic membranes for the simultaneous removal of dust and NO to explore their effect on the distribution of active components, with the structural properties, filtration performance, catalytic performance, and working mechanism of the preferred prepared catalytic membrane systematically investigated. The results indicated that microwave drying, in contrast to traditional electric drying with blasting, effectively inhibited the migration of the precursor solution to achieve uniform loading of active components, thus endowing the catalytic membrane with excellent catalytic activity. Meanwhile, the pore structure of the fibrous ceramic substrate was not almost affected by the loaded catalyst and still exhibited high porosity. These characteristics contributed to the development of a catalytic membrane with good filtration and catalytic performance, as well as superior adaptable NO concentration and filtration velocity properties. Therefore, fibrous ceramic-based catalytic membranes prepared using microwave assistance offer considerable application prospects for integrated purification of high-temperature flue gases. Furthermore, the removal of dust and NO was determined to follow the Eley–Rideal reaction mechanism and surface filtration mechanism of the residual dust cake, respectively. [ABSTRACT FROM AUTHOR]

In this research, the CuFeS2/MXene-modified polyvinylidene fluoride (PVDF) membrane was prepared to activate peroxymonosulfate (PMS) to remove moxifloxacin (MOX) and its morphology; surface functional groups and hydrophilicity were also studied. The parameters of the catalytic membrane/PMS system were optimized, with an optimal loading of 4 mg/cm2 and a PMS dosage of 0.20 mM. High filtration pressure, alkaline conditions, and impurities in water could inhibit MOX removal. After continuous filtration, the removal efficiency of MOX using the catalytic membrane/PMS system and PVDF membrane was 68.2% and 9.9%, respectively. Batch filtration could remove 87.8% MOX by the extra 10 min contact time between the catalytic membrane and solution. During the filtration process, CuFeS2/MXene on the surface of the catalytic membrane activated PMS to produce SO4•−, HO•, and 1O2, and MOX was removed through adsorption and degradation. Taking humic acid (HA) as the model foulant, reversible fouling resistance in the catalytic membrane/PMS system was 22.8% of the PVDF membrane. The catalytic membrane/PMS system weakened the formation of the cake layer by oxidizing HA into smaller pollutants and followed the intermediate blocking cake filtration model. The novelty of this research was to develop a CuFeS2/MXene–PVDF membrane-activated PMS system and explore its application in antibiotics removal. [ABSTRACT FROM AUTHOR]

Abstract Engineering a catalytic membrane capable of efficiently removing emerging organic microcontaminants under ultrahigh flux conditions is of significance for water purification. Herein, drawing inspiration from the functional attributes of lymphatic vessels involved in immunosurveillance and fluid transport with minimal energy consumption, a novel hierarchical porous catalytic membrane is engineered. This membrane, based on an innovative nitrogen‐rich conjugated microporous polymer (polytripheneamine, PTPA), is synthesized using an electrospinning coupled in situ polymerization approach. The resulting bioinspired membrane with hierarchical channels comprises a thin layer (≈1.7 µm) of crosslinked PTPA nanoparticles covering the interconnected electrospun nanofibers. This unique design creates an intrinsic microporous angstrom‐confined system capable of activating peroxymonosulfate (PMS) to generate 98.7% singlet oxygen (1O2), enabling durable and highly efficient degradation of microcontaminants. Additionally, the presence of a thin layer of mesoporous structure between PTPA nanoparticles and macroporous channels within the interwoven nanofibers enhances mass transfer efficiency and facilitates high flux rates. Notably, the prepared hierarchical porous organic catalytic membrane demonstrates enduring high‐efficiency degradation performance with a superior permeance (>95% and >2500 L m−2 h−1 bar−1) sustained over 100 h. This work introduces an innovative pathway for the design of high‐performance catalytic membranes for the removal of emerging organic microcontaminants.

In this work, a gold nanoparticle (AuNP)-embedded composite polymer membrane for dip-catalysis is developed. Primarily, a polyvinylpyrrolidone-stabilized AuNP (PVP-AuNP) with an average size of 6.50 nm was synthesized by the reduction of a composite solution of Au salt and PVP. Next, the composite membrane was fabricated by simply depositing the PVP-AuNP on the Nylon membrane followed by UV cross-linking. The composite membrane having the cross-linked PVP-AuNP was utilized as a dip-catalyst for the aerobic oxidation of alcohols to carbonyl compounds under oxygen and clean reaction conditions. The catalyst was further tested for performing cross-aldol reactions. The PVP-AuNP-catalyzed oxidation reaction also has other noteworthy characteristics, such as a low catalyst loading (Au, 1.2 mol %), high yield, and selectivity with a broad substrate scope (aliphatic, aromatic, biphenyl, and heterocyclic alcohols). The turnover number (TON) and turnover frequency (TOF) for the oxidation reaction of the alcohol are calculated to be 74.5 and 12.41 h–1, respectively. The P4VP-AuNP dip-catalysts are highly stable under the reaction conditions without significant leaching of Au into the solution. The dip-catalyst demonstrates outstanding reusability up to 10 catalytic cycles while maintaining high catalytic performance and structural features. It can be easily recovered by simply pulling it out from the reaction mixture once the reaction is complete, followed by washing and drying. The practical usefulness of the suggested method was further demonstrated by the PVP-AuNP-catalyzed gram-scale synthesis of high-value chemicals like acetophenone. Although the AuNPs are already used for different reactions, their integration into dip-catalysts for oxidation of alcohols and cross-aldol reactions with a wide substrate scope is rare. Overall, these findings demonstrate that developing composite dip-catalyst systems is a realistic strategy for creating high-value chemicals in a sustainable and environmentally friendly way. [ABSTRACT FROM AUTHOR]

In this work, CoFe 2 O 4 (CFO)−PVDF catalytic membrane was fabricated by coupling CFO into PVDF membrane. It can activate peroxomonosulfate (PMS) to oxidize contaminants. Therefore, the catalytic membrane can realize filtration and catalytic oxidation of dyes simultaneously. The single rejection rate of the CFO 2 −PVDF membrane is about 70% and catalysis alone can remove 62.37% AR18 within 110 min. In comparison with filtration and catalytic oxidation separately, the removal rate of the catalytic membrane has a visible increase which can reach 100% within 70 min. The mechanism reveals that hydroxyl radical (·OH), sulfate radical (SO 4 · −) and 1O 2 nonradical played about 13% parts, 27% parts and 60% parts in catalytic oxidation of dyes, respectively. The mechanism includes both radical and nonradical oxidation. The catalytic membrane has a good application for different type of dyes. The removal rate can still maintain at 86% after reused for five times since the catalyst CFO can renew from Co3+ to Co2+ through self recovery. Furthermore, the results confirm that the catalytic membrane has a good anti-fouling ability and low metal ions leaching risk. [Display omitted] • Membrane filtration coupled with catalytic degradation. • ·OH, SO 4 · − and 1O 2 is the main active substance. • The catalyst can renew from Co3+ to Co2+ by self recovery. • A new path for rapid water purification. [ABSTRACT FROM AUTHOR]

The use of the nano zero-valent iron (nZVI) nanoparticle-based advanced oxidation systems in conjunction with an activator such as peroxymonosulfate (PMS) to generate hydroxyl and sulfate radicals for the degradation of organic pollutants has been extensively used in recent studies. In this study, a nZVI-modified polyethersulfone (PES) membrane (nZVI@PES) was produced successfully by attaching the nZVI catalytic nanoparticles on the surface of a commercial microporous polymeric membrane material using a simple and easy filter press coating method. The presence of nZVI nanoparticles on the nZVI@PES membrane was confirmed by XRD, SEM, and EDS analyses. The nZVI@PES membrane was applied in the dead-end filtration system in the presence of the PMS activator to treat the reactive black 5 (RB5) dye solution. The effect of catalyst loading, RB5 dye concentration, PMS dosage, and pH level on the nZVI@PES membrane/PMS system was investigated. Quenching experiments were carried out to identify the reactive species responsible, and reusability tests were conducted on the membrane. The highest decolorization efficiency (96.8%) was obtained at 20 mg/L RB5 dye solution, initial pH of 3, the nZVI loading of 5 mg/cm2, and the PMS dosage of 300 mg/L at the end of a reaction time of 30 min. The formation of HO•, SO 4 ∙ - , O 2 ∙ - and, 1O2 was confirmed by quenching experiments. The results indicate that the nZVI@PES membrane/PMS system could successfully treat wastewater contaminated with an organic dye. [ABSTRACT FROM AUTHOR]

In this research, the CuFeS2/MXene-modified polyvinylidene fluoride (PVDF) membrane was prepared to activate peroxymonosulfate (PMS) to remove moxifloxacin (MOX) and its morphology; surface functional groups and hydrophilicity were also studied. The parameters of the catalytic membrane/PMS system were optimized, with an optimal loading of 4 mg/cm2 and a PMS dosage of 0.20 mM. High filtration pressure, alkaline conditions, and impurities in water could inhibit MOX removal. After continuous filtration, the removal efficiency of MOX using the catalytic membrane/PMS system and PVDF membrane was 68.2% and 9.9%, respectively. Batch filtration could remove 87.8% MOX by the extra 10 min contact time between the catalytic membrane and solution. During the filtration process, CuFeS2/MXene on the surface of the catalytic membrane activated PMS to produce SO4•−, HO•, and 1O2, and MOX was removed through adsorption and degradation. Taking humic acid (HA) as the model foulant, reversible fouling resistance in the catalytic membrane/PMS system was 22.8% of the PVDF membrane. The catalytic membrane/PMS system weakened the formation of the cake layer by oxidizing HA into smaller pollutants and followed the intermediate blocking cake filtration model. The novelty of this research was to develop a CuFeS2/MXene–PVDF membrane-activated PMS system and explore its application in antibiotics removal.

Carbon nanotube catalysts encapsulating cobalt-iron (CoFe) alloy nanoparticles (CoFe@Cs) were synthesized by calcination of cobalt-iron bimetallic Prussian Blue analogs (CoFe PBA), and further assembled on polyethersulfone (PES) membrane support by vacuum filtration to prepare composite catalytic membranes for catalytic activation of peroxymonosulfate and efficient degradation of tetracycline (TC). The morphology and structure of the samples were analyzed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The composition was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Based on the morphology, composition and performance, carbon nanotube catalysts (CoFe@Cs-900) were selected from the prepared series of CoFe@Cs, and further the reactive oxygen species (ROS) in the catalytic process was analyzed by reactive oxygen quenching experiments and electron paramagnetic resonance (EPR). The stability of the carbon nanotube catalytic membrane under long-term operation was tested under optimized conditions. The results showed that the calcination temperature played an important role in regulating the morphology and composition of the catalysts. Among them, the carbon nanotube catalyst prepared by calcination at 900 ℃ can produce the reactive oxygen species, including sulfate radicals (·SO4 −) and singlet oxygen (1O2), for the rapid removal of tetracycline. The carbon nanotube catalytic membrane achieved more than 99% removal of TC in continuous 24 h cross-flow filtration, and the water flux was maintained at 172 L/(m2·h). Overall, the catalytic membrane showed excellent degradation performances and potential application. [ABSTRACT FROM AUTHOR]

Abstract Increasing both clean water and green energy demands for survival and development are the grand challenges of our age. Here, we successfully fabricate a novel multifunctional 3D graphene-based catalytic membrane (3D-GCM) with active metal nanoparticles (AMNs) loading for simultaneously obtaining the water purification and clean energy generation, via a “green” one-step laser scribing technology. The as-prepared 3D-GCM shows high porosity and uniform distribution with AMNs, which exhibits high permeated fluxes (over 100 L m−2 h−1) and versatile super-adsorption capacities for the removal of tricky organic pollutants from wastewater under ultra-low pressure-driving (0.1 bar). After adsorption saturating, the AMNs in 3D-GCM actuates the advanced oxidization process to self-clean the fouled membrane via the catalysis, and restores the adsorption capacity well for the next time membrane separation. Most importantly, the 3D-GCM with the welding of laser scribing overcomes the lateral shear force damaging during the long-term separation. Moreover, the 3D-GCM could emit plentiful of hot electrons from AMNs under light irradiation, realizing the membrane catalytic hydrolysis reactions for hydrogen energy generation. This “green” precision manufacturing with laser scribing technology provides a feasible technology to fabricate high-efficient and robust 3D-GCM microreactor in the tricky wastewater purification and sustainable clean energy production as well.

Advanced oxidation processes (AOPs) have attracted increased attention in the abatement of refractory organic pollutants from wastewater due to its high reactivity and oxidative capability. Catalytic membrane-coupled oxidation process exhibits excellent wastewater treatment efficiency in the filtration process through an integrated system, largely improving the utilization of oxidants. This article reviews the recent research processes on an important category of catalytic membranes (i.e., the catalytic membranes based on transition metal catalysts) used for the activation of oxidants including persulfate, hydrogen peroxide and ozone. In addition, the catalytic membrane substrates, active components in different oxidation systems, and the enhanced mechanism of the nanoconfined effect on oxidants activation in catalytic membrane-coupled AOPs are also summarized. Finally, the perspectives on the enhancement oxidation activation by transition metal-based catalytic membrane and their practical application in wastewater treatment are also proposed. [ABSTRACT FROM AUTHOR]

The photocatalytic degradation of pollutants in wastewater shows promise as a potential sustainable water treatment technology. The main challenges in the application of nanocatalysts are catalyst recovery and toxic effects. In this paper, a simple vacuum filter was used to fix a photocatalyst on a membrane surface, which alleviated the problem of catalyst recovery. These synthetic membranes were able to filter and degrade contaminants, alleviating the problems of reduced separation efficiency and shortened membrane life. In this work, K-birnessite MnO2 photocatalyst was prepared by a simple hydrothermal reaction, and K-birnessite MnO2 photocatalytic film was prepared by a simple vacuum filtration method. This membrane showed excellent catalytic activity for the degradation of methylene blue (MB). The photocatalytic membrane prepared in this paper was able to catalyze the oxidation of peroxymonosulfate (PMS) to degrade organic dyes in aqueous solution at a constant flow rate of 1 ml/min under simulated sunlight. Furthermore, the membrane also showed good performance under dark conditions. A mechanism analysis showed that the OH. and SO4.− produced by PMS interacting with the different oxidation states of Mn were the main causes of dye degradation. The catalytic filtration process using the K-birnessite MnO2 catalytic membrane provides a new method for wastewater purification with high efficiency and low energy consumption. [ABSTRACT FROM AUTHOR]

Catalytic membrane reactors have the advantages of allowing the selective removal of products, avoiding the separation procedure of powder catalysts from the reaction mixture, intensifying the diffusion of reactants in the catalytic region, and integrating different reactions in one unit. Catalytic membrane reactors have been widely applied in the fields related to carbon peaking and carbon neutrality, including the capture and utilization of carbon dioxide, hydrogen production, and hydrogenation reaction. This review summarizes the design and fabrication of catalytic membrane reactors, with the focus on the capture and efficient utilization of carbon dioxide, hydrogen production and efficient liquid-phase hydrogenation. The design of membrane materials, catalyst materials and catalytic membranes, and the operation of catalytic membrane reactors are discussed respectively. Finally, the perspectives and future challenges of catalytic membrane reactors for carbon peaking and carbon neutrality are forecasted. [ABSTRACT FROM AUTHOR]

Highlights: A novel multifunctional three-dimensional graphene-metal frame film for the combination of water purification and hydrolysis hydrogen production, which has excellent purification efficiency and extremely low energy consumption. A “green” one-step laser scribing technology without any organic solvent in the whole preparation process. Metal nanoparticles as the active site can be loaded in a graphene film and wrapped by graphene, preventing undesirable aggregation and increasing catalytic active sites.Increasing both clean water and green energy demands for survival and development are the grand challenges of our age. Here, we successfully fabricate a novel multifunctional 3D graphene-based catalytic membrane (3D-GCM) with active metal nanoparticles (AMNs) loading for simultaneously obtaining the water purification and clean energy generation, via a “green” one-step laser scribing technology. The as-prepared 3D-GCM shows high porosity and uniform distribution with AMNs, which exhibits high permeated fluxes (over 100 L m−2 h−1) and versatile super-adsorption capacities for the removal of tricky organic pollutants from wastewater under ultra-low pressure-driving (0.1 bar). After adsorption saturating, the AMNs in 3D-GCM actuates the advanced oxidization process to self-clean the fouled membrane via the catalysis, and restores the adsorption capacity well for the next time membrane separation. Most importantly, the 3D-GCM with the welding of laser scribing overcomes the lateral shear force damaging during the long-term separation. Moreover, the 3D-GCM could emit plentiful of hot electrons from AMNs under light irradiation, realizing the membrane catalytic hydrolysis reactions for hydrogen energy generation. This “green” precision manufacturing with laser scribing technology provides a feasible technology to fabricate high-efficient and robust 3D-GCM microreactor in the tricky wastewater purification and sustainable clean energy production as well. [ABSTRACT FROM AUTHOR]

Herein, we developed a trimetallic CoFeCu-layered double hydroxide (LDH) assembled nanoconfined catalytic membrane, innovatively combining membrane filtration and advanced oxidation processes (AOPs). The CoFeCu-LDH nanoconfined catalytic membrane was shown to directly oxidize and mineralize micropollutants, rather than concentrating them within the brine, while also maintaining high water permeability with harmless membrane permeate. The first-order rate constant for 100% degradation of endocrine disrupting chemicals (bisphenol A), and pharmaceuticals (ranitidine, carbamazepine, oxytetracycline) (e.g., 2.40 ms−1 for ranitidine) by the CoFeCu-LDH catalytic membrane and its ultra-high water permeance of 2378.4 LMH/bar, were 1–3 orders of magnitude and 2−2000-fold higher than that of other state-of-the-art catalytic membranes, respectively. This study provides a reference for the development of sustainable and efficient catalytic membranes for water purification. [Display omitted] • CoFeCu-LDH membrane achieves 100 % removal of diverse organic pollutants. • The degradation rate is 101−3 times higher than the reported AOP systems. • CoFeCu-LDH membrane demonstrates ultra-high water permeance of 2378.4 LMH/bar. • The CoFeCu-LDH membrane/PMS system has a negative E ads value (-5.034 eV). • DFT calculations elucidate the mechanism of electron transfer and PMS activation. [ABSTRACT FROM AUTHOR]

Finding new class of materials to overcome limitation in conventional membranes is a challenging task. Use of naturally stable and sustainable alternative materials stock is an emerging task. In this direction, a novel iron-zirconium hybrid aminoclay (FZ-AC) has emerged as a promising catalyst effectively employed to alleviate fouling concerns within the framework of a biopolymer-based thin film composite (TFC), constructed on a cellulose acetate (CA) support. Notably, FZ-AC exhibits remarkable catalytic activity in the degradation of foulants through potential free radicals generated from Fe and Zr active centres in synergy with oxidising agent. The optimised catalytic membrane (FZ-TFC-1) exhibited an ultrafast degradation of congo red (CR), eriochrome black-T (EBT), crystal violet (CV), methylene blue (MB), red-brown dye (RBn), bisphenol-A (BPA), azithromycin (AZC), and Cr(VI) within 4 min. The cooperative action of redox centres of Fe and Zr metal ions synergistically accelerated the swift production of reactive species and facilitated the efficient degradation of pollutants within a notably short timeframe. Furthermore, >95% of above dyes rejection was achieved with >67 L m−2.h−1 of flux. The results of a long-term study demonstrated that FZ-TFC membranes exhibit exceptional stability, retaining their performance for a duration up to 150 h. This extended period of stability underscores the superiority of these membranes over alternative counterparts, suggesting their robustness and reliability for sustained operation in various applications. This strategic utilization of FZ-AC representing a promising avenue for enhancing the efficacy and longevity of nanofiltration membranes, thereby advancing the frontier of membrane-based separation technologies. [Display omitted] • A biopolymer-based catalytic TFC membrane was fabricated to mitigate limitations in NF process. • A novel Fe–Zr hybrid aminoclay-based functional catalytic membrane (FZ-TFC) was prepared. • Optimised membrane (FZ-TFC-1) has excellent degradation property for all emerging organic pollutants. • Synergic Fe–Zr centres generated free-radicals, facilitating ultrafast pollutant degradation & self-cleaning. • FZ-TFC membranes showed exceptional stability by performing under elevated test conditions (150 h). [ABSTRACT FROM AUTHOR]

[Display omitted] • Ni2+ to solid nanorods in casting solution with carbon particles and polyethersulfone. • Film casting cum phase separation directly yields porous catalytic membranes. • NiO to Ni(0) shifts persulfate activation to non-radical and mitigates Ni leaching. • Diclofenac oxidation coupled with adsorption of degradation products within membrane. • Up to 98 % organic carbon removal in flow-through at residence time of only 1.6 s. We introduce a novel all-in-one fabrication method for porous catalytic polyethersulfone (PES) membranes containing NiO nanorods and carbon nanoparticles. This method is based on the sonochemical in situ solidification of a metal salt with NaBH 4 in presence of carbon particles in a PES-containing casting-reaction solution, directly followed by membrane preparation via film casting cum phase separation. In the catalytic flow-through degradation of 20 mg/L aqueous diclofenac with persulfate as oxidant, an as-prepared NiO-carbon-PES membrane achieved a 99 % aromatic content removal degree at a residence time of only 1.6 s. In comparison, NiO and CuO membranes without carbon particles exhibited < 40 % aromatic removal degrees. The high performance was attributed to a degradation-induced adsorption, with a diclofenac removal capacity of 950 mg/g of incorporated carbon particles. We demonstrated that diclofenac is catalytically mineralized in the membrane at incorporated NiO nanorods, followed by adsorption of remaining degradation products at nearby carbon particles. Our data further suggests that reducing NiO to Ni(0) via a membrane pretreatment shifts the catalytic persulfate activation from a radical to a non-radical pathway, and that HCO 3 – can function as sacrificial electron donor for Ni(0). This completely mitigated nickel leaching from the membrane in contact to persulfate. Moreover, even in the presence of NaHCO 3 and NaCl, a Ni(0)–carbon–PES membrane consistently eliminated ∼ 90 % of the total organic carbon (TOC) from a 2 mg/L diclofenac feed containing persulfate in single-pass flow-through mode (continuously for 5 h, respectively for 500 L/m2 permeate volume), with no detectable release of degradation products or any nickel leaching. [ABSTRACT FROM AUTHOR]

Schematic diagram of CSMT-3 catalytic membrane for oily PM capture and decomposition. [Display omitted] • MnO 2 @Zr-TiO 2 catalytic membrane with a core–shell structure was firstly fabricated. • MnO 2 nanosheets enhance oily PM capture and accelerate its decomposition. • CSMT-3 catalytic membrane exhibited excellent performance for purifying oily PM. • The CSMT-3 catalytic membrane achieves sustained low pressure drop filtration. Oily particulate matter (PM) filtration faces the problems of high pressure drop and difficult regeneration. Herein, vertical arrays of MnO 2 nanosheets was assembled on Zr doped TiO 2 (Zr-TiO 2) nanofibers to construct a core–shell structure MnO 2 @Zr-TiO 2 (CSMT-x) catalytic membranes for highly efficient oily PM filtration and decomposition. The confining effect of the ultrathin MnO 2 nanosheets enhances PM capture efficiency, and the increase of effective contact area between MnO 2 and oily PM accelerate the decomposition of oily PM. The optimized CSMT-3 catalytic membrane exhibited high gas permeability and redox capacity, outperforming the Zr-TiO 2 (Bare T) membrane with over 99.97 % PM filtration efficiency and a low pressure drop at the temperatures of 25–425 °C. The catalytic decomposition of PM prevented the accumulation of particles on the membrane surface, which inhibited the formation of cake layer. Therefore, the CSMT-3 membrane exhibited a slight increase in pressure drop (less than 120 Pa) even after 120 h long-term filtration. This work may contribute to the development of advanced multifunctional membranes for purification of oily PM. [ABSTRACT FROM AUTHOR]

[Display omitted] • A system was first constructed to degrade organic pollutants in membrane distillation by activating PMS with γ-FeOOH@PVDF. • In-situ OCT verified the superior antifouling performance of γ-FeOOH@PVDF. • Self-cleaning mechanism of the γ-FeOOH@PVDF/PMS system was elucidated. • Quinone substances were involved in the Fe(Ⅲ)/Fe(Ⅱ) redox cycle preferentially. • Both free radical (SO 4 •-, O 2 •- and •OH) and non-free radical (1O 2) pathways participated in the degradation of TAP. The resolution of membrane fouling issues is crucial for the commercial application of membrane distillation (MD) ammonia recovery. The peroxymonosulfate-based advanced oxidation process (PMS-AOP) exhibited conspicuous degradation of organic pollutants, and in-situ coupling with the MD process could probably achieve desirable antifouling performance. In this research, a novel γ-FeOOH@PVDF catalytic membrane was fabricated by gas–liquid self-deposition method and fluorination treatment. The γ-FeOOH nanosheets arrayed on the substrate membrane endowed the catalytic membrane with superhydrophobicity. The MD ammonia recovery of the digestate achieved a high recovery rate (97.3%), and no membrane fouling or wetting phenomena were detected by real-time monitoring by optical coherence tomography (OCT). The batch degradation experiments of thiamphenicol (TAP) validated the γ-FeOOH@PVDF/PMS system with superior degradation performance and stability. The electron paramagnetic resonance (EPR) coordinated free radical quenching experiment determined the active substance (SO 4 •-, 1O 2 , O 2 •- and •OH) in the degradation process. In addition, the potential self-cleaning mechanism of the radical and non-radical pathways of γ-FeOOH@PVDF was elucidated via density functional theory (DFT) calculation. The quinone groups in the organic pollutants facilitated the redox of Fe(Ⅲ)/Fe(Ⅱ) and accelerated the activation of PMS. Hence, the catalytic membrane developed in this research provided a novel instructive strategy for membrane fouling control and also exhibited significant potential of coupling catalysis and membrane technology for water treatment. [ABSTRACT FROM AUTHOR]

[Display omitted] • Fabrication of NiFe 2 O 4 /carbon loaded porous polymer membranes. • Photocatalytic flow-through degradation of tetracycline in presence of persulfate. • NiFe 2 O 4 changes to Fe x O y during continuous use due to Ni leaching. • Fe x O y has no mineralization activity but retains a high conversion activity. • Radical scavengers inhibit tetracycline degradation by blocking the catalyst surface. We synthesized NiFe 2 O 4 /carbon composite nanoparticles through a straightforward co-precipitation method, and incorporated these particles into porous polyethersulfone (PES) membranes via casting solution blending and film casting cum phase separation. The resulting photocatalytic membranes were used for the oxidative degradation of tetracycline (TC) in flow–through. We could demonstrate a higher catalytic activity in acidic conditions, a photocatalytic enhancement under visible light irradiation, and a 3x higher TC removal by persulfate (PS) in comparison to H 2 O 2. Moreover, we observed the leaching of all Ni from the incorporated NiFe 2 O 4 after using a membrane for 30 h in the flow-through degradation of 5 ppm TC with PS. This was accompanied by a loss of the total organic carbon removal activity, suggesting that Ni plays an important role as mineralization promoter. However, no Fe leaching occurred and the in situ formed Fe x O y retained the high TC conversion activity of NiFe 2 O 4 after 30 h contact to acidic conditions, highlighting an exceptional long-term stability. We further identified that substrate desorption, catalyst complexation, and metal leaching can be facilitated by the presence of radical scavengers. This significantly contributed to their inhibitory effects, illustrating that an altered substrate-catalyst interaction may frequently be overlooked during the detection of radical species. [ABSTRACT FROM AUTHOR]

A carbon-based catalytic membrane reactor in a contactor (interfacial) configuration has been used as an approach to control selectivity in the reduction of NO 3 - in water. Water and hydrogen fed to the reactor circulate tangentially on opposite sides of the membrane, which acts as a separator and contactor, enabling hydrogen transfer to the water phase. Powdered carbons (carbon black, carbon nanofiber, and activated carbon) were used to prepare catalytic membranes that also acted as contactors to transfer H 2 from the gas phase to water. The membranes based on the Pd-Cu/carbon black catalyst showed lower selectivity towards unwanted NH 4 + than the Pd-Cu and Pd-Sn catalysts supported on carbon nanofibers and activated carbon, due to a good balance among conductivity, external surface area, and particle size. Sensitivity analysis for H 2 partial pressure demonstrated that the contactor membrane reactor can be operated with control of H 2 mass transfer, hence enabling enhanced control of the selectivity to NH 4 +. Additional control of selectivity was achieved by reducing the catalytic layer thickness of the membrane, which improved NO 3 - transport and decreased the H/N ratio at the active centers. With these approaches, NO 3 - conversion values above 40 % with negligible NH 4 + production and NO 3 - conversions close to 60 % with NH 4 + selectivity values around 3 % were achieved. [Display omitted] • Novel approach to control selectivity in NO 3 - reduction in H 2 O based on ICMR • NH 4 + was undetected up to 40 % of NO 3 - conversion • Pd-Cu/carbon black catalytic membranes showed good stability in 24 h tests [ABSTRACT FROM AUTHOR]

Membranes for wastewater treatment should ideally exhibit sustainable high permeate production, enhanced pollutant removal, and intrinsic physical rejection. In this study, CoFe 2 O 4 /MoS 2 serves as a non-homogeneous phase catalyst; it is combined with polyether sulfone membranes via liquid-induced phase separation to simultaneously sustain membrane permeability and enhance antibiotic pollutant degradation. The prepared catalytic membranes have higher pure water flux (329.34 L m−2 h−1) than pristine polyethersulfone membranes (219.03 L m−2 h−1), as well as higher mean pore size, porosity, and hydrophilicity. Under a moderate transmembrane pressure (0.05 MPa), tetracycline (TC) in synthetic and real wastewater was degraded by the optimal catalytic membrane by 72.7 % and 91.2 %, respectively. Owing to the generation of the reactive oxygen species (ROS) during the Fenton-like reaction process, the catalytic membrane could exclude the natural organics during the H 2 O 2 backwash step and selectively promote fouling degradation in the membrane channel. The irreversible fouling ratio of the catalyzed membrane was significantly reduced, and the flux recovery rate increased by up to 91.6 %. A potential catalytic mechanism and TC degradation pathways were proposed. This study offers valuable insights for designing catalytic membranes with enhanced filtration performance. [Display omitted] • Nano-sized CoFe 2 O 4 /MoS 2 embedded onto membrane stably by facile method • The prepared membrane has enhanced permeability and can significantly suppress fouling • The catalytic membrane can instantly degrade TC in the cross-flow mode • A fenton-like reaction was initiated by simple H 2 O 2 backwashing to alleviate irreversible fouling [ABSTRACT FROM AUTHOR]

[Display omitted] • A novel MnO 2 @CS coated ultrafiltration membrane was synthesized. • The mesoporous MnO 2 @CS guaranteed adequate water channels and active sites. • MnO 2 @CS-UF showed superior water purification and anti-fouling performance. • High-valent metal-oxo species dominated in sequential oxidation-filtration process. • Standard blocking became the dominant fouling pattern for MnO 2 @CS-UF/PMS. The integration of advanced oxidation process and ultrafiltration membrane has been regarded as an effective method to improve pollutants removal and mitigate membrane fouling simultaneously in the field of wastewater treatment. Hence, a novel catalytic membrane microreactor, referred to as MnO 2 @CS-UF, was synthesized via coupling MnO 2 modified carbon spheres (MnO 2 @CS) with membrane. The mesoporous structure of MnO 2 @CS guaranteed adequate water transfer channels and also contributed to more exposure of active sites. With MnO 2 @CS uniformly dispersed, the MnO 2 @CS-UF membrane showed increased hydrophilicity, higher permeability and superior peroxymonosulfate (PMS)-activation capability. With synergistic effect of pore interception and catalytic degradation, MnO 2 @CS-UF showed excellent organic pollutants removal (MB removal of about 100 % in 5 min), and had a prominent mitigation effect on membrane fouling caused by model NOM. In addition, MnO 2 @CS-UF/PMS system showed excellent catalytic filtration performance in the treatment of actual secondary effluent (SE). MnO 2 @CS-UF/PMS system could effectively remove fluorescent organics, and the removal rates of I - V region were 36.3 %, 72.3 %, 67.7 %, 73.5 % and 71.4 %, respectively. The permeance decline of MnO 2 @CS-UF was also effectively alleviated, with irreversible and reversible resistances reduced by 61.0 % and 23.2 % than UF membranes, individually. High-valent manganese-oxo species and singlet oxygen played a leading role in contaminants elimination, whereas radical oxidation acted as auxiliary contributors. Standard blocking became the dominant fouling pattern for MnO 2 @CS-UF/PMS, demonstrating that the MnO 2 @CS catalytic layer ensured the synthesis of vast active substances, prevented foulant adhesion on pore walls and alleviated the growth of cake layer. These results illustrated that the integration of MnO 2 @CS catalytic degradation and membrane filtration was feasible to improve the permeate quality and mitigate membrane fouling in wastewater reclamation. [ABSTRACT FROM AUTHOR]

• Weakly hydrophobic GO-HT@PBA confined catalytic membrane was developed. • The GO-HT@PBA membrane achieved the degradation rate constant with 0.46 ms−1. • The GO-HT@PBA membrane exhibited superior and contaminant resistance. • The GO-HT@PBA membrane reached near-total p -ASA and arsenic immobilization over 107 h. Enhancing the peroxymonosulfate (PMS) activation in powder Fe-based metal–organic frameworks (MOFs) for addressing insufficient mass transfer and reactivity loss in humid environments remains a significant challenge. In response to this issue, we proposed a novel approach involving the creation of a weakly hydrophobic microenvironment-assisted confined strategy for the fabrication of a mixed dimensional GO-HT@ bimetallic Prussian blue analogues (PBA) confined catalytic membrane through low-temperature treatment (GO-HT). This innovative method has demonstrated improved mass transfer capabilities for the safe treatment of organoarsenic compounds. The optimized GO-HT@PBA confined membrane exhibited a marked improvement in the removal efficiency of p-arsanilic acid (p -ASA) compared to its unconfined counterpart, showing a substantial increase in the reaction kinetic constant by 6–7 orders of magnitude (0.46 ms−1) compared to unconfined GO-HT@PBA/PMS system. Additionally, the GO-HT@PBA membrane exhibited superior pH tolerance, and resistance to inorganic ions, humic acid, and complex water matrices. Notably, the membrane achieved nearly complete degradation of p -ASA and immobilization of total arsenic over a continuous operation period of 107 h, highlighting its exceptional reactivity and stability. Overall, our research will inform the development of MOF-based composites, with the potential to enhance the reactivity of the catalytic component and mitigate its inherent limitations by leveraging the host's properties. [ABSTRACT FROM AUTHOR]

The eliminate of antibiotic resistance genes (ARGs) is pivotal in mitigating the proliferation of antibiotic resistance. In this study, a PMS/CM-UV system was engineered, combining a Co 3 O 4 -modified carbon nanotubes catalytic membrane with LED-UV lamps, to effectively eliminate intracellular ARGs (iARGs). Leveraging the synergistic effect of singlet oxygen ( 1 O 2 ) and UV irradiation, this process requires only a brief hydraulic retention time of a few minutes and standard UV disinfection irradiation intensity. The cellular physiological function and transcriptomic analysis indicated that reactive oxygen species (ROS) and UV irradiation compromised the cell membrane integrity of E. coli MG1655-SD, as indicated by the down-regulation of the feoB gene, leading to an increased concentration of 1 O 2 within the intracellular environment. The synergistic effect of 1 O 2 and UV irradiation resulted in the down-regulation of btuE, thereby curtailing the SOS and oxidative stress responses. Additionally, UV irradiation down-regulated ftsK, uvrB, and uvrA genes, involved in DNA replication, damage site recognition, and self-repair. These processes collectively contribute to the oxidative damage of iARGs by 1 O 2 before their release into the extracellular environment. This work provided a strategy to develop advanced oxidation disinfection technology aimed at ARGs removal., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The application of homogeneous catalysts in water remediation is limited by their excessive chemical and energy input, weak regenerability, and potential leaching. Heterogeneous catalytic membranes (CMs) offer a new approach to facilitate efficient, selective, and continuous pollutant degradation. Thus, integrating membranes and continuous filtration with heterogeneous advanced oxidation processes (AOPs) can promote thermodynamic and kinetic mass transfers in spatially confined intrapores and facilitate diffusion-reaction processes. Despite the remarkable advantages of heterogeneous CMs, their engineering application is practically restricted due to the fuzzy design criteria for specific applications. Herein, the recent advances in CMs for advanced water remediation are critically reviewed and the design flow for tempospatially confined CMs is proposed. Further, state-of-the-art CM materials and their catalytic mechanisms are reviewed, after which the tempospatial confinement mechanisms comprising the nanoconfinement effect, interface effect, and kinetic mass transfer are emphasized, thus clarifying their roles in the construction and performance optimization of CMs. Additionally, the fabrication methods for CMs based on their catalysts and pore sizes are summarized and an overview of their application and performance evaluations is presented. Finally, future directions for CMs in materials research and water treatment, are presented., (© 2024 Wiley‐VCH GmbH.)

Fenton-like membrane reactors applied to water purification provide a broad solution to address the challenges of catalyst recovery, low reaction efficiency, and high mass transfer resistance in heterogeneous batch reactions. Zeolites as nanocatalyst carriers are promising candidates for advanced purification membranes. Herein, we report a composite catalytic membrane (4A-Cu/PES) for Fenton-like degradation of phenol wastewater, fabricated by in-situ growth of copper nanoflowers on a 4A zeolite/polyethersulfone (PES) mixed matrix membrane, forming a three-dimensional core-shell nanostructured catalyst. Compared with the conventional method, the in-situ growth prevents the copper catalyst from being covered by the polymer and significantly increases the copper loading (3.97 %), thus ensuring efficient catalytic reactions within the membrane pores. Meanwhile, the porous structure of zeolite provides a large specific surface area, facilitating uniform dispersion of copper ions during in situ growth of the catalyst and providing abundant active sites. The membrane exhibited a phenol degradation rate of 93.9 % at pH 6, significantly broadening the pH applicability of the Fenton reaction. Hydroxyl radicals (·OH) were identified as the primary active species in the 4A-Cu/PES-H 2 O 2 system. Moreover, the membrane retained high catalytic activity after five cycles, demonstrating excellent stability. This work provides important insights for designing efficient and stable Fenton-like zeolite catalytic membranes. [Display omitted] • In-situ growth increases copper content to 3.97 %, enhancing catalytic efficiency. • Copper nanoflowers are in-situ grown on zeolite, forming a 3D core-shell structure. • The 4A-Cu/PES membrane extends the pH range for Fenton-like reactions. • The membrane stays highly active after five cycles, demonstrating excellent stability. [ABSTRACT FROM AUTHOR]

The significance of addressing arsenic contamination is huge, given its widespread environmental impact and detrimental effects on human health. Herein, we developed a double-confined catalytic membrane capable of activating peroxymonosulfate (PMS) by integrating hollow Prussian blue analogues (H-PBA) with a unique void-confinement effect into graphene oxide (GO) laminates. This delicately designed H-PBA/GO membrane displayed 98.8 % p-arsanilic acid (p -ASA) removal with a 9.03 s retention time, surpassing most reported studies. Our experiments underscored that the dual-confined architecture not only drove mass transfer but also bolstered reactant concentration, thereby multiplying catalytic activities. Remarkably, this double-confinement conduced to a sustained dominance of surface-radicals (SO 4 −) and singlet oxygen (1O 2), bolstering p -ASA degradation across a broad pH spectrum and numerous aqueous realms, inclusive of high salinity waters pertinent to desalination pre-treatment processes. Crucially, the H-PBA/GO membrane demonstrated over 90 % degradation of p -ASA and immobilized total As, unfaltering over 80 h of continuous operation. This signified an evolution in membrane technology, promising enhanced and steadfast performance. This innovation bore profound implications for devising double-confined efficacious and robust catalysts, poised to revolutionize advanced wastewater treatment, notably augmenting desalination systems by fortifying pre-treatment and safeguarding reverse osmosis membranes from organic and arsenic fouling. [ABSTRACT FROM AUTHOR]

The removal of antibiotic resistance genes (ARGs) is crucial to prevent the proliferation of antibiotic resistance. In this study, we successfully removed intracellular ARGs using the PMS/Co@CM system, which involved activating peroxymonosulfate (PMS) with a catalytic membrane composed of Co 3 O 4 and carbon nanotubes. In the PMS/Co@CM system, 1O 2 was the primary reactive oxygen species (ROS) responsible for intracellular ARGs removal. However, the presence of sulfamethoxazole (SMX) in the water samples significantly reduced the efficiency of removing intracellular ARGs in the PMS/Co@CM system although SMX was degraded by •SO 4 −. This can be attributed to the selective pressure of SMX, which elevated intracellular Superoxide Dismutase (SOD) levels while decreasing Propidium Iodide (PI) levels in cells. Consequently, this led to heightened antioxidant defense and reduced membrane permeability, thereby enhancing cell resistance to 1O 2 generated by the PMS/Co@CM system. Encouragingly, a typical UV disinfection process facilitated the removal of residual intracellular ARGs in the effluent of the PMS/Co@CM system, attributed to decreased SOD levels and increased intracellular 1O 2 by UV irradiation. These findings contribute to the theoretical understanding of effective ARGs removal and aid in the development of more efficient removal technologies. [Display omitted] • The PMS/Co@CM system can effectively remove sul1, intI1 , and 16Sr RNA genes. • The presence of SMX reduced the efficiency of removing intracellular ARG. • Different ROS are involved in SMX degradation and intracellular ARGs removal. • SMX makes E. coli more resistant to external stimuli. • UV disinfection removed residual intracellular ARGs in the effluent from the PMS/Co@CM system. [ABSTRACT FROM AUTHOR]

Developing efficient and eco-friendly technologies for treating the antibiotic wastewaters is crucial. At present, the catalysts with metal-nitrogen (M-N x) coordination showed excellent Fenton-like performance but were always difficult to realize practical antibiotics degradation because of their complicated preparation methods and inferior stability. In this work, the Co-N x configuration was facilely reconstructed on the surface of Co 3 O 4 (Co-N x /Co 3 O 4), which exhibited superior catalytic activity and stability towards various antibiotics. DFT results indicated that stronger ETP oxidation will be triggered by the electron-donating pollutants since more electrons can be easily migrated from these pollutants to the Co-N x /Co 3 O 4 /PMS complex. The Co-N x /Co 3 O 4 /PMS system could maintain superior oxidation capacity, high catalytic stability and anti-interference due to (i) the strong nonradical ETP oxidation with superior degradation selectivity in Co-N x /Co 3 O 4 /PMS system, and (ii) the synchronously enhanced radical oxidation with high populations of non-selective radicals generated via activating PMS by the Co-N x /Co 3 O 4. As a result, the synergies of synchronously enhanced dual oxidation pathways guaranteed the self-cleaning properties, maintaining 98 % of activity after eight cycles and stability across a wide pH range. Basically, these findings have significant implications for developing technologies for purifying antibiotic wastewater. [Display omitted] • Co-N x configuration was facilely reconstructed on surface of Co 3 O 4 (Co-N x /Co 3 O 4); • The Co-N x /Co 3 O 4 exhibited superior catalytic activity and catalytic stability; • Synergies of synchronously enhanced dual oxidation pathways were observed; • Unveiling the contributions of radical/nonradical oxidation towards different antibiotics. [ABSTRACT FROM AUTHOR]

[Display omitted] • MXene@h-BN was firstly assembled into membrane for advanced wastewater treatment. • Emerging pollutants removed by synergetic chemisorption and photocatalytic process. • Membrane self-cleaning driven by solar without extra chemicals addition. • Unequal Fermi level in conductor-semiconductor junction trigged enhanced photocatalysis. • Functionalized membrane was reliable in durability and practical application. Membrane filtration is regarded as one of the promising technologies for water treatment. However, insufficient micropollutants removal and membrane fouling still limited the further application. Herein, this study engineered a novel membrane hybrid system integrating typical pharmaceuticals removal and membrane self-cleaning by assembled layered MXene and hexagonal boron nitride (h-BN). By doping a small amount of MXene into h-BN (mass ratio of 1 to 10), the synergetic process of adsorption and photocatalytic degradation were achieved. Based on experimental and density functional theory (DFT) calculation results, the chemisorption-photodegradation performance of the membrane hybrid system assembled with 1/10 MXene@h-BN was significantly enhanced due to the termination group and conductive property of MXene. In addition, trimethoprim (TMP) degradation by the above membrane followed the Langmuir–Hinshelwood model, indicating pollutants removal initiated not only on the membrane surface but also in the bulk solution under simulated solar irradiation. This phenomenon was attributed to the generation of •OH and 1O 2 by forming Ohmic contact with altered internal band structure. The durability and practical experiments with secondary effluent from local wastewater treatment were also tested. The exceptional self-cleaning performance of the membrane hybrid system assembled with 1/10 MXene@h-BN was demonstrated by lower membrane fouling and maintaining durability even after five cycles. Furthermore, the performance (both pollutants removal and flux) of the modified membrane for secondary effluent treatment was also considerable, validating its potential for practical application. Owing to the excellent features, the membrane assembled with MXene@h-BN is anticipated to be an ideal candidate for advanced wastewater treatment. [ABSTRACT FROM AUTHOR]

Fe and N co-doped walnut shell biochar (Fe,N-BC) was prepared through a one-pot pyrolysis procedure by using walnut shells as feedstocks, melamine as the N source, and iron (III) chloride as the Fe source. Moreover, pristine biochar (BC), nitrogen-doped biochar (N-BC), and α-Fe 2 O 3 -BC were synthesized as controls. All the prepared materials were characterized by different techniques and were used for the activation of peroxymonosulfate (PMS) for the degradation of sulfamethoxazole (SMX). A very high degradation rate for SMX (10 mg/L) was achieved with Fe,N-BC/PMS (0.5 min−1), which was higher than those for BC/PMS (0.026 min−1), N-BC/PMS (0.038 min−1), and α-Fe 2 O 3 -BC/PMS (0.33 min−1) under the same conditions. This is mainly due to the formation of Fe 3 C and iron oxides, which are very reactive for the activation of PMS. In the next step, Fe,N-BC was employed for the formation of a composite membrane structure by a liquid-induced phase inversion process. The synthesized ultrafiltration membrane not only exhibited high separation performance for humic acid sodium salt (HA, 98%) but also exhibited improved self-cleaning properties when applied for rhodamine B (RhB) filtration combined with a PMS solution cleaning procedure. Scavenging experiments revealed that 1O 2 was the predominant species responsible for the degradation of SMX. The transformation products of SMX and possible degradation pathways were also identified. Furthermore, the toxicity assessment revealed that the overall toxicity of the intermediate was lower than that of SMX. [Display omitted] • Fe and N co-doped biochar demonstrated an excellent degradation efficiency for SMX. • The synergistic effects of Fe and N co-doping on biochar properties were discussed. • 1O 2 are the main active species for the degradation of SMX in the Fe,N-BC/PMS system. • The separation and self-cleaning performances of the Fe,N-BC membrane were evaluated. [ABSTRACT FROM AUTHOR]

[Display omitted] • Fe-doped CoTiO 3 /TiO 2 /Ti catalytic membrane (FCTT) was synthesized. • FCTT catalytic membrane was employed in a continuous flow-through mode. • The FCTT/PMS system achieved a SMX degradation efficiency of 98.6%. • The synergy of Co and Fe contributed to efficient redox cycles. In heterogeneous catalysis of the sulfate radical (SO 4 ∙ -)-based advanced oxidation processes, the limited availability of exposed active sites and the inert membrane substrate that does not participate in redox reactions pose challenges to the pollutant degradation efficiencies. This study fabricated a Fe-doped CoTiO 3 /TiO 2 /Ti (FCTT) catalytic membrane to initiate peroxymonosulfate (PMS) activation in a continuous flow-through reactor for the degradation of sulfamethoxazole (SMX). Fe doped into the lattice of CoTiO 3 significantly improved the conversion efficiency between Co2+ and Co3+, promoting the degradation rate of SMX by 12.17 %. Additionally, we employed TiO 2 nanotubes featured with highly accessible porous structures and a large surface area (7.78 m2/g) as a substrate in the system. The formation of Co-O-Ti bond signally reduced the Co ion leaching (43 μg/L after 10 h of use) while ensuring the reusability (>90.42 % in 24 h) of FCTT. The species of SO 4 ∙ - , •OH, O 2 ∙ - and 1O 2 were involved in FCTT/PMS system, jointly participated the degradation of SMX in the FCTT/PMS system. Theoretical calculations revealed the nitrogen on amino groups was the most susceptible site to be attacked. This research provides valuable insights and approaches for developing highly efficient catalysts in heterogeneous catalytic oxidation. [ABSTRACT FROM AUTHOR]

The immobilization of heterogeneous catalysts on membrane supports can realize highly efficient degradation of organic pollutants to alleviate membrane fouling through in situ catalytic oxidation. In this work, a polyacrylonitrile (PAN)-based catalytic membrane was prepared via a phase inversion method in the presence of core-shell structured perovskite catalysts. Following this, a controlled alkali-induced strategy was employed to simultaneously hydrolyze the –CN groups on the membrane surface and the core-shell structured perovskite catalysts anchored in the membrane matrix. Correspondingly, improved hydrophilicity, permeability, and catalytic efficiency via activating peroxymonosulfate were achieved compared with pristine PAN membrane. Rapid tetracycline (TC) elimination (10 ppm, 500 mL) can be realized (99 % in 30 min) under a flux of 334.5 L/m2h (0.02 MPa). Besides, owing to the intrinsic size sieving of the membrane, favorable TC degradation efficiency can also be accomplished in the presence of humic acid. Furthermore, the accumulation of pollutants on the membrane surface was released owing to the massive generation of sulfate radicals and singlet oxygen, enabling self-cleaning properties. More importantly, the as-prepared catalytic membrane possessed attractive stability with the cobalt leaching below 0.013 mg/L. This work provides a method to synergistically enhance permeability, catalytic activity and anti-fouling performance of the membranes, which shows potential application in wastewater decontamination. [Display omitted] • Core-shell structured perovskite catalyst was incorporated in the membrane matrix. • Alkaline modification was used to improve hydrophilicity and catalytic activity. • Membrane filtration and catalytic oxidation were integrated effectively. • Rapid TC degradation was realized more efficiently by enhanced mass transfer. • Membrane possessed attractive stability and self-cleaning properties. [ABSTRACT FROM AUTHOR]

The effective removal of micropollutants by water treatment technologies remains a significant challenge. Herein, we develop a CoFe layered double hydroxide (CoFeLDH) catalytic membrane for peroxymonosulfate (PMS) activation to achieve efficient micropollutant removal with improved mass transfer rate and reaction kinetics. This study found that the CoFeLDH membrane/PMS system achieved an impressive above 98% degradation of the probe chemical ranitidine at 0.1 mM of PMS including five more micropollutants (Sulfamethoxazole, Ciprofloxacin, Carbamazepine, Acetaminophen and Bisphenol A) at satisfactory level (above 80%). Moreover, significant improvements in water flux and antifouling properties were observed, marking the membrane as a specific advancement in the removal of membrane fouling in water purification technology. The membrane demonstrated consistent degradation efficiency for several micropollutants and across a range of pH (4–9) as well as different anionic environments, thereby showing it suitability for scale-up application. The key role of reactive species such as SO 4 •–, and O 2 • − radicals in the degradation process was elucidated. This is followed by the confirmation of the occurrence of redox cycling between Co and Fe, and the presence of CoOH+ that promotes PMS activation. Over the ten cycles, the membrane could be operated with a flux recovery of up to 99.8% and maintained efficient performance over 24 h continuous operation. Finally, the efficiency in degrading micropollutants, coupled with reduced metal leaching, makes the CoFeLDH membrane as a promising technology for application in water treatment. [Display omitted] • CoFeLDH membrane achieves >98% micropollutant degradation. • Works across diverse pH and anionic conditions. • SO 4.•–, and O 2 • − radicals key to degradation. • Redox cycling between Co and Fe enhances performance. • Maintains 99.8% flux recovery over ten cycles. [ABSTRACT FROM AUTHOR]

The catalytic membrane, combining confinement effect with advanced oxidation processes, exhibits great potential as an efficient technology for removing contaminants and mitigating membrane fouling. Herein, the Prussian blue analogues (PBAs) functionalized graphene oxide (GO) membranes, referred as PGMs, was successfully fabricated. It exhibited a package-like confined structure where Co–Fe PBAs were encapsulated within interconnected GO nanosheets. The surface properties, internal structure as well as the catalytic performance of PGMs were controlled by adjusting the amount of Co–Fe PBAs anchored on GO nanosheets. The designed PGM as efficient peroxymonosulfate activator exhibited exceptional catalytic performance, achieving complete removal of bisphenol A (BPA) with a retention time of 31 ms. The corresponding first-order rate constant was 6000 min−1, which surpassed conventional batch system by four orders of magnitude (0.2194 min−1). Moreover, the redox cycle involving Fe2+ and Co3+, coupled with the effective suppression of ion leaching from Co–Fe PBAs nanoparticles (<10 μg/L) through GO protective layers, ensured the stable catalytic performance of PGM over 144 h. This study employs a novel approach to confine catalytic nanoparticles within two-dimensional nanosheets, demonstrating the potential applications of the resulting confined membrane in water treatment. [Display omitted] • Co–Fe PBAs functionalized GO catalytic membrane (PGM) for PMS activation was built. • The PGM membrane exhibited adjustable surface properties and internal structure. • The PGM/PMS system exhibited a 100 % BPA removal with a retention time of 31 ms. • The degradation of BPA was achieved through confined oxidation by reactive spices. • The PGM exhibited stable catalytic performance for 144 h of operation. [ABSTRACT FROM AUTHOR]

A novel Co@CM catalytic membrane was fabricated by loading Co on the polydopamine modified multi-channel ceramic membrane and pyrolyzing under Ar atmosphere. Fine regulation of the dopamine concentration, cobalt nitrate concentration and pyrolysis temperature is in favor of achieving the Co@CM catalytic membrane with abundant Co nanoparticles, high surface Co content, and rich graphitic N, thereby intensifying the continuous reduction of p -nitrophenol to p -aminophenol in a flow-through catalytic membrane reactor. [Display omitted] • A Co@CM multi-channel ceramic catalytic membrane was designed and constructed. • The modification with dopamine can capture, reduce and protect Co via a CN layer. • The dopamine and Co concentrations obviously affect the microstructures of Co@CM. • The pyrolysis temperature significantly affects the microstructures of Co@CM. • Co@CM-3.0–0.1–700 can continuously, stably and fully convert 4-NP to 4-AP. The hydrogenation of p -nitrophenol (4-NP) to p -aminophenol (4-AP) transforms a detrimental pollutant into a valuable chemical, while conventional powder catalysts face challenges in continuous operation due to the limitations in separation and recovery processes. Here, we developed a catalytic membrane by loading Co onto a polydopamine (PDA)-modified multi-channel ceramic membrane (CM) with subsequent pyrolysis. PDA plays a crucial role in capturing Co ions, facilitating the reduction of Co ions, and preventing the leaching of Co nanoparticles (NPs) from the membrane. Fine-tuning the DA and cobalt nitrate concentrations, along with the pyrolysis temperature, results in the catalytic membrane with abundant Co NPs, enriched surface Co content, and sufficient graphitic N, which significantly enhances the reduction of 4-NP to 4-AP in a flow-through catalytic membrane reactor. The Co@CM-3.0–0.1–700 demonstrates a remarkable activity of converting 4-NP at a rate of 67.4 h−1, maintaining stability for a continuous operation of 300 min. This study pioneers highly efficient catalytic membrane for the transformation of detrimental pollutant 4-NP to a valuable chemical 4-AP. [ABSTRACT FROM AUTHOR]

[Display omitted] • Cu-MnO@PDA@PVDF electrospinning catalytic membrane was prepared. • Favorable SMX removal was obtained by Cu-MnO@PDA@PVDF membrane/H 2 O 2 filtration. • Catalytic membrane/H 2 O 2 scheme showed membrane fouling mitigation ability. • Hydroxyl radicals played a vital role in SMX degradation. • Mn-Cu bimetallic centers endow the membrane with high reactivity towards H 2 O 2. Heterogeneous catalyst reuse and the effectiveness of hydrogen peroxide (H 2 O 2)-based advanced oxidation processes under near-neutral conditions remain an obstacle in wastewater remediation. Herein, we put forward a versatile catalytic membrane with Cu-doped MnO active layer anchoring on the polydopamine-modified electrospinning polyvinylidene fluoride (PDA@PVDF) base. The Cu-MnO@PDA@PVDF membrane was conferred admirable sulfamethoxazole (SMX) reduction (over 90% within 90 min) and clogging alleviation (relative flux recovery to 0.98) capabilities via in situ H 2 O 2 activation at pH 8, which was slightly affected by actual water background. Electron paramagnetic resonance (EPR) and trapping tests unveiled the joint contribution of •OH, O 2 •− and 1O 2 , with •OH exerting the supreme role in SMX oxidation. The inherent characteristics of dual Mn-Cu centers on the membrane surface for facilitation of electron transfer, H 2 O 2 adsorption and barrierless dissociation to •OH were further elucidated by electrochemical measurements and density functional theory (DFT) computation. Comprehensively, this study proposes a facile procedure and insights into engineering catalytic membrane coupled H 2 O 2 strategy for refractory organic treatment at ambient conditions. [ABSTRACT FROM AUTHOR]

Catalytic degradation of organic foulants using cost-effective and light-independent catalyst in membrane system is a promising technology in advancing the self-cleaning membranes. In this work, we report AIP-clay as an efficient light-independent catalyst in membrane system to degrade the organic foulants. The characterization of AIP-clay and membrane was performed using FE-SEM, ATR-IR, DLS, XPS, AFM, zeta potential, and contact angle measurements. The optimised AIP-clay loaded membrane (0.1AIP-PAN) showed an efficient Fenton-based insitu degradation of fouled dyes and SWW both in dark and light condition. Although, membrane exhibited significant self-cleaning capabilities in presence of light, the efficiency was nearly equivalent in dark condition as well, indicating minimal disparity in performance. The membranes remained stable even after multiple cycles of self-cleaning, with no notable loss in flux or rejection ability. The 0.1AIP-PAN membrane performance was further assessed based on the removal capacity of various salts (18% of NaCl and 38% of MgSO 4), dyes (MB, MG, CR, EBT and RBr), SWW (>90%) and pharmaceuticals (>80%). In addition, the AIP-clay loaded membrane was studied for its anti-fouling property via long-term study for SWW with 97.7% FRR while retaining the membrane stability even after 216 h. Therefore, these studies demonstrate the potential self-cleaning in both dark and light, long-term stability and high separation performance of the AIP-clay membranes for diverse applications. [ABSTRACT FROM AUTHOR]

Heterogeneous catalyst/persulfate advanced oxidation process has been widely used in antibiotic wastewater treatment. As-designed MIL-88A(Fe)/g-C 3 N 4 composite catalyst firstly activated peroxydisulfate (PDS) to degrade tetracycline (TC) in this work. Activating PDS by MIL-88A(Fe)/g-C 3 N 4 has a higher efficiency and rate toward TC degradation compared with MIL-88A(Fe) and g-C 3 N 4. After 60 min, the optimal MIL-88A(Fe)/g-C 3 N 4 -5 activated PDS to degrade about 80% of TC in water. The existence of g-C 3 N 4 increases the specific surface area and active Fe2+ content of MIL-88(Fe), promotes PDS adsorption and utilization, thus showing an excellent catalytic performance for PDS activation. MIL-88A(Fe)/g-C 3 N 4 activated PDS oxidation process synergistically removed TC by free radicals (O 2 •−, •OH and SO 4 •−) with non-free radicals (1O 2), and the effect of some important operating factors on TC removal, the TC degradation pathways and toxicity of TC intermediates were analyzed. Moreover, the MIL-88A(Fe)/g-C 3 N 4 -5 powdered catalyst was designed into a catalytic membrane, which could remove 96% of TC in a short time (<10 min). The cycle tests confirm that powdered MIL-88A(Fe)/g-C 3 N 4 composite catalyst and its catalytic membrane have a good recyclability and stability, demonstrating that this catalyst possesses a practical application potential in the treatment of TC polluted wastewater. [Display omitted] • MIL-88A(Fe)/g-C 3 N 4 catalyst efficiently activated PDS to remove TC from water. • The content of active Fe2+ on MIL-88A(Fe) is increased in the presence of g-C 3 N 4. • The g-C 3 N 4 can improve the adsorption ability of MIL-88A(Fe) toward PDS. • The toxicity of TC-containing wastewater was reduced after treatment. • MIL-88A(Fe)/g-C 3 N 4 and its catalytic membrane have a good recyclability. [ABSTRACT FROM AUTHOR]

An Fe 3 O 4 -impregnated catalytic ceramic membrane (CCM) was fabricated through a facile ethylene glycol-gel-assisted wet impregnation method. Ethylene glycol played a dual role, acting as a reducing agent for iron (III) nitrate salt and a chelating agent to disperse catalyst uniformly in the CCM. The resulting 5xFe 3 O 4 -CCM efficiently activated peroxymonosulfate (PMS) to generate reactive oxygen species (ROS), achieving a 99% removal of atrazine (ATZ) within a short hydraulic retention time (HRT) of 5.7 s. This was facilitated by the spatial confinement effect in CCMs, enhancing the interaction among ATZ, ROS and CCM. The versatile 5xFe 3 O 4 -CCM could also effectively activate H 2 O 2 and peroxydisulfate (PDS). It demonstrated robustness in real wastewater matrices (settled water and RO-reject) collected from local water reclamation and treatment plants. The 5xFe 3 O 4 -CCM exhibited self-cleaning properties in reducing fouling of CCM by humic acid. ROS scavenging experiments and electron paramagnetic resonance (EPR) spectroscopy revealed the pivotal role of SO 4 •-, •OH, and 1O 2 in ATZ removal. The co-existing anion species HCO 3 - showed a strong inhibitory effect on ATZ degradation compared to other ionic species (NO 3 - and Cl-), attributed to different scavenging reaction rate of both SO 4 •- and •OH by anions in generating less reactive species. Possible degradation pathways of 5xFe 3 O 4 -CCM/PMS were proposed based on the LC-QTOF analysis, including oxidation, dealkylation, dealkylation-hydroxylation, dechlorination-hydroxylation of both s-triazine ring and side chain. The toxicity of the ATZ by-products was assessed, revealing reduced toxicity after treatment. With optimized operating parameters, Fe 3 O 4 -CCM can be utilized effectively in different advanced oxidation processes (AOPs) and real wastewater matrices. [Display omitted] • Catalytic ceramic membranes impregnated with Fe 3 O 4 oxide were fabricated by ethylene-glycol gel. • 5xFe 3 O 4 -CCM/PMS could remove 99% of ATZ removal within 5.7 s HRT. • Fe 3 O 4 -CCM exhibited catalytic activity with various advanced oxidation process systems. • Fe 3 O 4 -CCM showed robustness and self-cleaning properties when applied in real wastewater and humic acid. • Reactive oxygen species (ROS) generated shows selective efficacy in degrading pollutant. [ABSTRACT FROM AUTHOR]

[Display omitted] • A Co 3 O 4 -Bi 2 O 3 -Ti catalytic membrane was facilely fabricated. • The membrane efficiently activated PMS to degrade organic pollutants continuously. • Reactive oxidative species and non-radical electron transfer were involved. • The catalytic membrane showed excellent reusability. In this study, a functionalized Co 3 O 4 -Bi 2 O 3 -Ti catalytic membrane (CBO-Ti-M) was prepared and applied for removing organic pollutants via activating peroxymonosulfate (PMS) in the dead-end filtration mode. Characterizations including scanning electron microcopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) showed that the Co 3 O 4 -Bi 2 O 3 catalyst was successfully supported on the Ti membrane. The CBO-Ti-M /PMS system could efficiently remove various organic pollutants such as sulfamethoxazole, methyl orange, bisphenol A and methylene blue, achieving removal efficiencies of 98.0%-99.5%. The effects of PMS concentration, flow rate and solution environment on degradation efficiency were investigated in detail. Furthermore, quenching experiments, electron spin resonance (ESR) and in-situ open circuit potential (OCP) tests collectively demonstrated that singlet oxygen as well as the non-radical electron transfer pathway mainly contributed in the reaction mechanism. The synergistic effect of Co and Bi was illustrated according to XPS results, and the possible degradation pathway of MB was proposed based on LC-MS analysis. Reusability test showed that pollutant removal efficiency with the CBO-Ti-M /PMS system remained stable in four runs and limited metal leaching was observed. [ABSTRACT FROM AUTHOR]

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