Visible‐Light‐Activated Photocatalytic Films toward Self‐Cleaning Membranes

Membranes are among the most promising means of delivering increased supplies of fit‐for‐purpose water, but membrane fouling remains a critical issue restricting their widespread application. Coupling photocatalysis with membrane separation has been proposed as a potentially effective approach to reduce membrane fouling. However, commonly used materials in photocatalysis limit use of low‐cost sources such as sunlight due to their large bandgaps. There are few examples of in situ photocatalytic self‐cleaning of membranes, with removal from the filtration system and ex situ illumination being more common. In this work, a visible‐light‐activated photocatalytic film prepared by nitrogen doping into the lattice of TiO₂ is deposited on commercial ceramic membranes via atomic layer deposition. The synergy between membrane separation and redox reactions between organic pollutants and reactive oxygen species produced by the visible‐light‐activated layer offers a possibility for stable and sustainable membrane operation under in situ solar irradiation.     

Selective Defect‐Patching of Zeolite Membranes Using Chemical Liquid Deposition at Organic/Aqueous Interfaces

The elimination of possible defects is indispensable in making zeolite membranes popular in process industries. A novel counter‐diffusion chemical liquid deposition (CLD) technique is proposed and developed for selective defect‐patching of zeolite membranes. Dodecyltrimethoxysilane (DMS) is employed as the silane coupling agent, forming a protective layer on the membrane surface so that intracrystalline pores can be kept intact in the subsequent reparation step. By using tetraethoxy orthosilicate (TEOS) and (3‐chloropropyl)triethoxysilane (3CP‐TES), co‐hydrolysis and co‐condensation at the organic/aqueous interface fabricate the silsesquioxane/silicate hybrid on macro‐, meso‐ and even microdefects. The silicalite‐1 membrane before and after reparation is characterized using contact‐angle measurements, Fourier transform IR spectroscopy, and electron probe microanalysis. Permporometry is conducted to study the pore‐size distribution of the membrane before and after reparation. It is found that the silsesquioxane/silicate hybrid is only deposited at the pore‐mouth of the defects, and the defects can be plugged to less than 1.3 nm pores after patching. After reparation, the separation factor of a 50/50 n/i‐butane‐gas mixture through the membrane can be increased to 35.8 from 4.4, and the separation factor of a CO₂/N₂ gas mixture through the membrane can be increased to around 15 from 1, while keeping the two‐thirds CO₂ permeation flux of the synthesized membrane.     

High‐Performance Multifunctional TiO2 Nanowire Ultrafiltration Membrane with a Hierarchical Layer Structure for Water Treatment

A novel, multifunctional TiO₂ nanowire ultrafiltration (UF) membrane with a layered hierarchical structure is made via alkaline hydrothermal synthesis, followed by a filtration and hot‐press process. The TiO₂ UF membrane has high surface porosity (21.3%) and pore size values around 20 nm. The membrane possesses multifunctional capabilities under UV irradiation, such as anti‐fouling, anti‐bacterial, concurrent separation, and photocatalytic oxidation. The unique properties of the membrane indicate its potential in applications for environmental purification.     

N‐Doped Polypyrrole‐Based Porous Carbons for CO2 Capture

Highly porous N‐doped carbons have been successfully prepared by using KOH as activating agent and polypyrrole (PPy) as carbon precursor. These materials were investigated as sorbents for CO₂ capture. The activation process was carried out under severe (KOH/PPy = 4) or mild (KOH/PPy = 2) activation conditions at different temperatures in the 600–800 °C range. Mildly activated carbons have two important characteristics: i) they contain a large number of nitrogen functional groups (up to 10.1 wt% N) identified as pyridonic‐N with a small proportion of pyridinic‐N groups, and ii) they exhibit, in relation to the carbons prepared with KOH/PPy = 4, narrower micropore sizes. The combination of both of these properties explains the large CO₂ adsorption capacities of mildly activated carbon. In particular, a very high CO₂ adsorption uptake of 6.2 mmol·g^?1 (0 °C) was achieved for porous carbons prepared with KOH/PPy = 2 and 600 °C (1700 m²·g^?1, pore size ≈ 1 nm and 10.1 wt% N). Furthermore, we observed that these porous carbons exhibit high CO₂ adsorption rates, a good selectivity for CO₂‐N₂ separation and it can be easily regenerated.     

Biomimetic and Superwettable Nanofibrous Skins for Highly Efficient Separation of Oil‐in‐Water Emulsions

Developing a feasible and efficient separation membrane for the purification of highly emulsified oily wastewater is of significance but challenging due to the critical limitations of low flux and serious membrane fouling. Herein, a biomimetic and superwettable nanofibrous skin on an electrospun fibrous membrane via a facile strategy of synchronous electrospraying and electrospinning is created. The obtained nanofibrous skin possesses a lotus‐leaf‐like micro/nanostructured surface with intriguing superhydrophilicity and underwater superoleophobicity, which are due to the synergistic effect of the hierarchical roughness and hydrophilic polymeric matrix. The ultrathin, high porosity, sub‐micrometer porous skin layer results in the composite nanofibrous membranes exhibiting superior performances for separating both highly emulsified surfactant‐free and surfactant‐stabilized oil‐in‐water emulsions. An ultrahigh permeation flux of up to 5152 L m^?2 h^?1 with a separation efficiency of >99.93% is obtained solely under the driving of gravity (≈1 kPa), which was one order of magnitude higher than that of conventional filtration membranes with similar separation properties, showing significant applicability for energy‐saving filtration. Moreover, with the advantage of an excellent antioil fouling property, the membrane exhibits robust reusability for long‐term separation, which is promising for large‐scale oily wastewater remediation.     

Reversible Nanopatterning on Polypyrrole Films by Atomic Force Microscope Electrochemical Lithography

A reversible, erasable, and rewritable pattern at the nanoscale is inscribed on polypyrrole films doped with sodium dodecylbenzenesulfonate (PPy(DBS)) utilizing atomic force microscopy based electrochemical lithography. Nanopatterns are formed by applying a bias voltage between a conductive tip and the substrate. Afterward, the generated nanopatterns can be erased completely, followed by rewriting at the same location of the polymer film. Moreover, the alterations of PPy(DBS) during the lithography process are investigated by comparing the changes of the current intensity and surface potential depending on the lithography time.     

Stomata‐Inspired Membrane Produced Through Photopolymerization Patterning

The programmed movements of responsive functional hydrogels have received much attention because of their abundant functions and wide range of engineering applications. In this study, an innovative stomata‐inspired membrane (SIM) is fabricated by using a temperature‐responsive hydrogel through a simple, cost‐effective, and high‐throughput patterned photopolymerization. Polymerization‐induced diffusion on the macroscale surface results in formation of a double‐parted polymer membrane with fine pores after single illumination. After heating the SIM, the less deformable thick frame supports the whole structure and the highly deformable thin base regulates pore shape. Among various SIM types, the slit pores of monocot SIM, which are lined up in parallel, exhibit the largest radius deformation. The morphological configuration of the SIM can be easily controlled by changing the photomask for a given application. As the developed SIM features the sensing‐to‐activation functions of stimuli‐responsive hydrogels and can be easily fabricated, this membrane can be potentially used for numerous practical applications, such as filter membranes with adjustable pores, membrane‐based sensors, membrane‐based actuators, and multifunctional membranes.     

Organic/Inorganic Hybrid Nanochannels Based on Polypyrrole‐Embedded Alumina Nanopore Arrays: pH‐ and Light‐Modulated Ion Transport

Inspired by the asymmetric structure and responsive ion transport in biological ion channels, organic/inorganic hybrid artificial nanochannels exhibiting pH‐modulated ion rectification and light‐regulated ion flux have been constructed by introducing conductive polymer into porous nanochannels. The hybrid nanochannels are achieved by partially modifying alumina (Al₂O₃) nanopore arrays with polypyrrole (PPy) layer using electrochemical polymerization, which results in an asymmetric component distribution. The protonation and deprotonation of Al₂O₃ and PPy upon pH variation break the surface charge continuity, which contributes to the pH‐tunable ion rectification. The ionic current rectification ratio is affected substantially by the pH value of electrolyte and the pore size of nanochannels. Furthermore, the holes (positive charges) in PPy layer induced by the cooperative effect of light and protons are used to regulate the ionic flux through the nanochannels, which results in a light‐responsive ion current. The magnitude of responsive ionic current could be amplified by optimizing this cooperation. This new type of stimuli‐responsive PPy/Al₂O₃ hybrid nanochannels features advantages of unique optical and electric properties from conducting PPy and high mechanical performance from porous Al₂O₃ membrane, which provide a platform for creating smart nanochannels system.     

Self‐Supporting,Double Stimuli‐Responsive Porous Membranes From Polystyrene‐block‐poly(N,N‐dimethylaminoethyl methacrylate) Diblock Copolymers

Asymmetric membranes are prepared via the non‐solvent‐induced phase separation (NIPS) process from a polystyrene‐block‐poly(N,N‐dimethylaminoethyl methacrylate) (PS‐b‐PDMAEMA) block copolymer. The polymer is prepared via sequential living anionic polymerization. Membrane surface and volume structures are characterized by scanning electron microscopy. Due to their asymmetric character, resulting in a thin separation layer with pores below 100 nm on top and a macroporous volume structure, the membranes are self‐supporting. Furthermore, they exhibit a defect‐free surface over several 100 µm². Polystyrene serves as the membrane matrix, whereas the pH‐ and temperature‐sensitive minority block, PDMAEMA, renders the material double stimuli‐responsive. Therefore, in terms of water flux, the membranes are able to react on two independently applicable stimuli, pH and temperature. Compared to the conditions where the lowest water flux is obtained, low temperature and pH, activation of both triggers results in a seven‐fold permeability increase. The pore size distribution and the separation properties of the obtained membranes were tested through the pH‐dependent filtration of silica particles with sizes of 12–100 nm.     

High‐Performance CO2 Capture through Polymer‐Based Ultrathin Membranes

Thin film composite (TFC) membranes have attracted great research interest for a wide range of separation processes owing to their potential to achieve excellent permeance. However, it still remains challenging to fully exploit the superiority of thin selective layers when mitigating the pore intrusion phenomenon. Herein, a facile and generic interface‐decoration‐layer strategy collaborating with molecular‐scale organic–inorganic hybridization in the selective layer to obtain a high‐performance ultrathin film composite (UTFC) membrane for CO₂ capture is reported. The interface‐decoration layer of copper hydroxide nanofibers (CHNs) enables the formation of an ultrathin selective layer (≈100 nm), achieving a 2.5‐fold increase in gas permeance. The organic part in the molecular‐scale hybrid material contributes to facilitating CO₂‐selective adsorption while the inorganic part assists in maintaining robust membrane structure, thus remarkably improving the selectivity toward CO₂. As a result, the as‐prepared membrane shows a high CO₂ permeance of 2860 GPU, superior to state‐of‐the‐art polymer membranes, with a CO₂/N₂ selectivity of 28.2. The synergistic strategy proposed here can be extended to a wide range of polymers, holding great potential to produce high‐efficiency ultrathin membranes for molecular separation.     

Photocatalytic Nanofiltration Membranes with Self‐Cleaning Property for Wastewater Treatment

Membrane fouling is one of the most severe problems restricting membrane separation technology for wastewater treatment. This work reports a photocatalytic nanofiltration membrane (NFM) with self‐cleaning property fabricated using a facile biomimetic mineralization process. In this strategy, a polydopamine (PDA)/polyethyleneimine (PEI) intermediate layer is fabricated on an ultrafiltration membrane via a co‐deposition method followed by mineralization of a photocatalytic layer consisting of β‐FeOOH nanorods. The PDA–PEI layer acts both as a nanofiltration selective layer and an intermediate layer for anchoring the β‐FeOOH nanorods via strong coordination complexes between Fe³⁺ and catechol groups. In visible light, the β‐FeOOH layer exhibits efficient photocatalytic activity for degrading dyes through the photo‐Fenton reaction in the presence of hydrogen peroxide, endowing the NFM concurrently with effective nanofiltration performance and self‐cleaning capability. Moreover, the mineralized NFMs exhibit satisfactory stability under simultaneous filtration and photocatalysis processing, showing great potential in advanced wastewater treatment.     

Mesoporous Separation Membranes of Polymer‐Coated Copper Hydroxide Nanostrands

Extremely long and thin nanocomposite fibers are prepared by oxidative polymerization of pyrrole (or aniline) around the surfaces of copper hydroxide nanostrands. The individual nanostrands of 2.5 nm are uniformly coated with a polypyrrole layer of 3 to 4 nm, resulting in hybrid core/shell fibers of about 10 nm in diameter and a few micrometers in length, as confirmed by high‐resolution electron microscopy. The as‐prepared nanocomposite fibers are dispersive in water and can be converted into thin free‐standing films by simply filtering a small volume of the aqueous solution using a polycarbonate membrane filter. The films covering the submicrometer pores of the membrane filter have a thickness of a few tens of nanometers, and provide a mechanically stable nanofiber network with abundant pores of a few nanometers. The network is stable in acidic and basic media, and can be used for protein separation under pressures of at least 90 kPa. The permeation rates of cytochrome c, myoglobin, and ferritin were examined by changing the pH around their isoelectric points. It is seen that the nanofibrous free‐standing films on the polycarbonate membrane filter show clear size selectivity for the proteins, retaining extremely high filtration rates for water. We demonstrate herein durable mesoporous separation membranes made of organic–inorganic nanocomposite fibers and their outstanding performance.     

Solvent‐Induced Rearrangement of Ion‐Transport Channels: A Way to Create Advanced Porous Membranes for Vanadium Flow Batteries

Porous membranes with critically hydrophobic/hydrophilic phase‐separated‐like structures for use in vanadium flow battery application are first realized by solvent‐induced reassembly of a polymer blend system. Porous poly(ether sulfone) (PES)/sufonated poly(ether ether ketone) (SPEEK) blend membranes with tunable pore size are prepared via the phase inversion method. After solidification, isopropanol (IPA) is introduced to induce the reassembly of sulfonated groups and further form ion‐transport channels by using the interaction between IPA and functional groups in SPEEK. As a result, a highly phase separated membrane structure is created, composed of a highly stable hydrophobic porous PES matrix and hydrophilic interconnected small pores. The charged pore walls are highly beneficial to improving proton conductivity, while pores are simultaneously shrunk during the IPA treatment. Therefore, the resultant membranes show an excellent battery performance with a coulombic efficiency exceeding 99%, along with an energy efficiency over 91%, which is among the highest values ever reported. This article supplies an ease‐to‐operate and efficient method to create membranes with controlled ion‐transport channels.     

Intracellularly Degradable Hydrogen‐Bonded Polymer Capsules

The assembly of low‐fouling polymer capsules with redox‐responsive behavior and intracellular degradability is reported. Thiol‐containing poly(2‐ethyl‐2‐oxazoline) (PEtOxMA_SH) brushes are synthesized by atom transfer radical polymerization (ATRP) of oligo(2‐ethyl‐2‐oxazoline)methacrylate and glycidyl methacrylate (GMA) and subsequent ring‐opening reaction of the GMA. Sequential deposition of PEtOxMA_SH/poly(methacrylic acid) (PMA) multilayers onto silica (SiO₂) particle templates and crosslinking through disulfide formation yield stable capsules after the removal of the SiO₂ templates by buffered hydrofluoric acid (HF). The redox‐responsive nature of the disulfide crosslinking groups enables the degradation of these capsules under simulated intracellular conditions at pH 5.9 and 5 mm glutathione (GSH). Furthermore, capsule degradation is observed after incubation with dendritic (JAWS II) cells. Even at high capsule‐to‐cell ratios, PEtOxMA_SH capsules show only negligible cytotoxicity. Quartz crystal microgravimetry (QCM) studies, using 100% human serum, reveal that films prepared from PEtOxMA_SH exhibit low‐fouling properties. The degradation and low‐fouling properties are promising for application of PEtOxMA_SH films/capsules for the delivery and triggered release of therapeutics.     

Multi‐Length Scale Porous Polymers

Thin films with porosities spanning from the nanoscopic to the macroscopic are obtained by combining breath figures (BFs), micrometer‐sized surface cavities arising from the condensation of water on the surface of a film as solvent evaporates rapidly, with the nanoscopic morphology inherent to block copolymers. Using chloroform as a solvent for polystyrene‐b‐poly methyl methacrylate (PS‐b‐PMMA) block copolymers (BCPs), micrometer‐sized pores arise from the formation of the BFs, while nanoscopic pores are generated by the removal of the PMMA by deep UV‐irradiation, which also crosslinks the PS. Solvent retention, though, limits its utility. This is overcome using PS‐b‐poly(n‐butyl methacrylate) dissolved in dichloromethane where, again, multi‐length scales of porosity are achieved by a selective removal of one component of BCPs. Arrays of nanopores on the surface of a film can also be obtained by swelling the hydrophilic component block of PS‐b‐poly(ethyleneoxide) (PEO) with water vapor, under controlled humidity. Simultaneously, large pores can be obtained by macrophase separation between BCPs and water, which leads to multi‐length scale porous films.     

On the Origin of Ion Selectivity in Ultrathin Nanopores: Insights for Membrane‐Scale Osmotic Energy Conversion

Nanopores in ultrathin or atomically thin membranes attract broad interest because the infinitesimal pore depth allows selective transport of ions and molecules with ultimate permeability. Toward large‐scale osmotic energy conversion, great challenges remain in extrapolating the promising single‐pore demonstration to really powerful macroscopic applications. Herein, the origin of the selective ion transport in ultrathin nanopores is systematically investigated. Based on a precise Poisson and Nernst–Planck model calculation, it is found that the generation of net diffusion current and membrane potential stems from the charge separation within the electric double layer on the outer membrane surface, rather than that on the inner pore wall. To keep the charge selectivity of the entire membrane, a critical surface charged area surrounding each pore orifice is therefore highly demanded. Otherwise, at high pore density, the membrane selectivity and the overall power density would fall down instead, which explains the giant gap between the actual experimental achievements and the single‐pore estimation. To maximize the power generation, smaller nanopores (pore diameter ≈1–2 nm) are appropriate for large‐scale osmotic energy conversion. With a porosity of ≈10%, the total power density approaches more than 200 W m^‐2, anticipating a substantial advance toward high‐performance large‐scale nanofluidic power sources.     

Microporous Polypyrrole‐Coated Graphene Foam for High‐Performance Multifunctional Sensors and Flexible Supercapacitors

This study reports on the fabrication of pressure/temperature/strain sensors and all‐solid‐state flexible supercapacitors using only polydimethylsiloxane coated microporous polypyrrole/graphene foam composite (PDMS/PPy/GF) as a common material. A dual‐mode sensor is designed with PDMS/PPy/GF, which measures pressure and temperature with the changes of current and voltage, respectively, without interference to each other. The fabricated dual‐mode sensor shows high sensitivity, fast response/recovery, and high durability during 10 000 cycles of pressure loading. The pressure is estimated using the thermoelectric voltage induced by simultaneous increase in temperature caused by a finger touch on the sensor. Additionally, a resistor‐type strain sensor fabricated using the same PDMS/PPy/GF could detect the strain up to 50%. Flexible, high performance supercapacitor used as a power supply is fabricated with electrodes of PPy/GF for its high surface area and pseudocapacitance. Furthermore, an integrated system of such fabricated multifunctional sensors and a supercapacitor on a skin‐attachable flexible substrate using liquid–metal interconnections operates well, whereas sensors are driven by the power of the supercapacitor. This study clearly demonstrates that the appropriate choice of a single functional material enables fabrication of active multifunctional sensors for pressure, temperature, and strain, as well as the supercapacitor, that could be used in wirelessly powered wearable devices.     

Mesocylindrical Aluminosilica Monolith Biocaptors for Size‐Selective Macromolecule Cargos

Immobilization of biological macromolecules, such as protein, onto solid supports is an important method for diagnostic assays andgenetechnology. This present study reports the size‐selective adsorption/removal of virtual proteins that have different shapes, sizes, functions, and properties, such as insulin, cytochrome c, lysozyme, myoglobin, β‐lactoglobin, α‐amylase, hemoglobin, and myosin in aqueous water using mesobiocaptor monoliths. To prevent large proteins from adsorbing and remaining attached to adsorbent surfaces, large, open, cylindrical‐pored, three‐dimensional cubic aluminosilica mesostructures with large aluminum contents and micrometer‐sized monolith particles were fabricated. The unique physical properties and the surface functionality of the mesobiocaptors enhance protein adsorption characteristics in terms of loading capacity and quantity of the sample, ensuring a higher concentration of adsorbed proteins, interior pore diffusivity, and encapsulation in a short period. Thermodynamic studies indicate that protein adsorption into the mesobiocaptor pores is favorable and spontaneous. Theoretical models were used to investigate the major driving forces for the most optimal performance of the protein adsorption. The geometrical findings point to key factors, such as surface energy, intermolecular forces, charge distribution, hydrophobicity, and electrostatic interaction, which might control the adsorption into the interior large, open cylindrical mesobiocaptor cavities (sized 3–16 nm) without aggregation of these proteins on the exterior surfaces of monoliths. Indeed, the availability of adsorption of single proteins from mixtures based on size‐ and shape‐selective separation opens new avenues of research in encapsulation of proteins and bioanalysis.     

Biocompatible Electromechanical Actuators Composed of Silk‐Conducting Polymer Composites

Single‐component, metal‐free, biocompatible, electromechanical actuator devices are fabricated using a composite material composed of silk fibroin and poly(pyrrole) (PPy). Chemical modification techniques are developed to produce free‐standing films with a bilayer‐type structure, with unmodified silk on one side and an interpenetrating network (IPN) of silk and PPy on the other. The IPN formed between the silk and PPy prohibits delamination, resulting in a durable and fully biocompatible device. The electrochemical stability of these materials is investigated through cyclic voltammetry, and redox sensitivity to the presence of different anions is noted. Free‐end bending actuation performance and force generation within silk‐PPy composite films during oxidation and reduction in a biologically relevant environment are investigated in detail. These silk–PPy composites are stable to repeated actuation, and are able to generate forces comparable with natural muscle (>0.1 MPa), making them ideal candidates for interfacing with biological tissues.     

Zwitterionic Nanohydrogel Grafted PVDF Membranes with Comprehensive Antifouling Property and Superior Cycle Stability for Oil‐in‐Water Emulsion Separation

Fouling caused by oil and other pollutants is one of the most serious challenges for membranes used for oil/water separation. Aiming at improving the comprehensive antifouling property of membranes and thus achieving long‐term cyclic stability, it is reported in this work the design of a kind of zwitterionic nanosized hydrogels grafted poly(vinylidene fluoride) (PVDF) microfiltration membrane (ZNG‐g‐PVDF) with superior fouling‐tolerant property for oil‐in‐water emulsion separation. Sulfobetaine zwitterionic nanohydrogels with the diameter of ≈ 50 nm are synthesized by an inverse microemulsion polymerization process. They are then grafted onto the surface of PVDF microfiltration membrane, endowing the membrane a superhydrophilic and nearly zero oil adhesion property. This ZNG‐g‐PVDF membrane exhibits great tolerance and resistance to salts pH, especially an excellent antifouling property to oil‐in‐water emulsions containing various pollutants such as surfactants, proteins, and natural organic materials (e.g., humic acid). The comprehensive antifouling property of the membrane gives rise to the cyclic stability of the membrane greatly improved. A nearly 100% recovery ratio of permeating flux is achieved during several cycles of oil‐in‐water emulsion filtration. The ZNG‐g‐PVDF membrane shows great potential in treating practical oily wastewater containing complicated components in the effluent.