Nafion–Carbon Nanocomposite Membranes Prepared Using Hydrothermal Carbonization for Proton‐Exchange‐Membrane Fuel Cells

Nafion–carbon (NC) composite membranes were prepared by hydrothermal treatment of Nafion membrane impregnated with glucose solution. The carbon loading of the NC membrane was tuned by controlling the hydrothermal carbonization time. X‐ray diffraction, Fourier‐transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, and positron annihilation lifetime spectroscopy were used to characterize plain Nafion and NC composite membranes. Nafion–carbon composite membranes exhibited better proton conductivity and reduced methanol permeability than those of the plain Nafion membrane. A single cell prepared with the NC composite membrane with a carbon loading of 3.6 wt% exhibited the highest cell performance. Compared with the cell performance of plain Nafion membrane, the maximum power density of the new cell improved by 31.7% for an H₂/O₂ fuel cell at room temperature, and by 44.0% for a direct methanol fuel cell at 60 °C.     

Neutron Reflectivity and Performance of Polyamide Nanofilms for Water Desalination

The structure and hydration of polyamide (PA) membranes are investigated with a combination of neutron and X‐ray reflectivity, and their performance is benchmarked in reverse osmosis water desalination. PA membranes are synthesized by the interfacial polymerization of m‐phenylenediamine (MPD) and trimesoyl chloride (TMC), varying systematically reaction time, concentration, and stoichiometry, to yield large‐area exceptionally planar films of ≈10 nm thickness. Reflectivity is employed to precisely determine membrane thickness and roughness, as well as the (TMC/MPD) concentration profile, and response to hydration in the vapor phase. PA film thickness is found to increase linearly with reaction time, albeit with a nonzero intercept, and the composition cross‐sectional profile is found to be uniform, at the conditions investigated. Vapor hydration with H₂O and D₂O from 0 to 100% relative humidity results in considerable swelling (up to 20%), but also yields uniform cross‐sectional profiles. The resulting film thickness is found to be predominantly set by the MPD concentration, while TMC regulates water uptake. A favorable correlation is found between higher swelling and water uptake with permeance. The data provide quantitative insight into the film formation mechanisms and correlate reaction conditions, cross‐sectional nanostructure, and performance of the PA active layer in RO membranes for desalination.     

Use of Elastic,Porous, and Ultrathin Co-Culture Membranes to Control the Endothelial Barrier Function via Cell Alignment

Porous membranes used in co-culture enable the in vitro partitioning of cellular microenvironments, while still permitting physical and biochemical crosstalk between cells. Thus, features of the co-culture membrane are crucial for recapitulating the physiological functions of co-cultured cells. This study presents elastic, porous, and ultrathin membranes (EPUMs), which enhance cell–cell interactions and control cell alignment with surface topology created by stretching the membranes. The EPUM is fabricated using poly(lactide-co-caprolactone) as the base material, and the porous feature is endowed by a vapor-induced phase separation process induced by the presence of hygroscopic salt. Owing to its elastic property, the membrane can be stretched, and the deformed porous structures on the membrane surfaces act as nanostructured topographical cues, resulting in cell alignment. By co-culturing human mesenchymal stem cells (hMSCs) and human umbilical vein endothelial cells (HUVECs) on the opposite sides of the membrane, rapid endothelialization occurs through the membranes, as compared to the commercial membranes. Furthermore, the stretched membranes induce the alignment of hMSCs and HUVECs and ultimately exhibit enhanced endothelial barrier function. The co-culture membrane developed in this study may provide an effective tool for recapitulating endothelial basement membranes with a controllable endothelial barrier function.     

All‐Carbon Nanoarchitectures as High‐Performance Separation Membranes with Superior Stability

The application of graphene‐based membranes is hindered by their poor stability under practical hydrodynamic conditions. Here, nanocarbon architectures are designed by intercalating surface‐functionalized, small‐diameter, multi‐walled carbon nanotubes (MWCNTs) into reduced graphene oxide (rGO) sheets to create highly stable membranes with improved water permeability and enhanced membrane selectivity. With the intercalation of 10 nm diameter MWCNTs, the water permeability reaches 52.7 L m^?2 h^?1 bar^?1, which is 4.8 times that of pristine rGO membrane and five to ten times higher than most commercial nanofiltration membranes. The membrane also attains almost 100% rejection for three organic dyes of different charges. More importantly, the membrane can endure a turbulent hydrodynamic flow with cross‐flow rates up to 2000 mL min^?1 and a Reynolds number of 4667. Physicochemical characterization reveals that the inner graphitic walls of the MWCNTs can serve as spacers, while nanoscale rGO foliates on the outer walls interconnect with the assimilated rGO sheets to instill superior membrane stability. In contrast, intercalating with single‐walled nanotubes fails to reproduce such stability. Overall, this nanoarchitectured design is highly versatile in creating both graphene‐rich and CNT‐rich all‐carbon membranes with engineered nanochannels, and is regarded as a general approach in obtaining stable membranes for realizing practical applications of graphene‐based membranes.     

Ultraselective and Highly Permeable Polyamide Nanofilms for Ionic and Molecular Nanofiltration

Membranes with ultrahigh ion selectivity and high liquid permeance are needed to produce high-quality product water with increased recovery and process efficiency in water desalination. The narrow pore size distribution and controlled surface charge in the separation layer of nanofiltration membranes significantly improve the ion selectivity through molecular sieving and Donnan exclusion of co-ions. Here, the ultraselective and yet highly water permeable polyamide nanofilm composite nanofiltration membranes developed by precisely controlling the kinetics of the interfacial polymerization reaction by maintaining the stoichiometric equilibrium at the interface is reported. The kinetically favorable stoichiometric equilibrium condition prohibits the formation of aggregate pores in the nanofilm and leads to the formation of narrow network pores with a high surface negative charge. Nanofilms are designed with a controlled degree of crosslinking and made as thin as ≈7 nm to achieve increased water permeance. The ultraselective membranes exhibit up to 99.99% rejection of divalent salt (Na₂SO₄) and demonstrate monovalent to divalent ion selectivity of >4000. The selectivity of these nanofilm composite membranes is beyond the permeance–selectivity upper-bound line of the state-of-the-art nanofiltration membranes and one to two orders of magnitude higher than the commercially available membranes with pure water permeances of up to 23 L m⁻² h⁻¹ bar⁻¹. The fabrication process is scalable for membrane manufacturing.     

Inside Front Cover: Nanocrystalline TiO2 Photocatalytic Membranes with a Hierarchical Mesoporous Multilayer Structure: Synthesis,Characterization, and Multifunction (Adv. Funct. Mater. 8/2006)

The inside cover shows a hierarchical, mesoporous, multilayer TiO2 photocatalytic membrane synthesized via a novel sol–gel dip‐coating process employing surfactant templates reported by Dionysiou and co‐workers on p. 1067. The resulting asymmetric mesoporous TiO2 membrane supported onto a porous Al2O3 substrate exhibited hierarchical changes in pore diameter and materials porosity from the top to the bottom layer. The TiO2 membrane has multiple simultaneous functions, including photocatalysis, disinfection, separation, and anti‐biofouling. A novel sol–gel dip‐coating process to fabricate nanocrystalline TiO₂ photocatalytic membranes with a robust hierarchical mesoporous multilayer and improved performance has been studied. Various titania sols containing poly(oxyethylenesorbitan monooleate) (Tween 80) surfactant as a pore‐directing agent to tailor‐design the porous structure of TiO₂ materials at different molar ratios of Tween 80/isopropyl alcohol/acetic acid/titanium tetraisopropoxide = R:45:6:1 have been synthesized. The sols are dip‐coated on top of a homemade porous alumina substrate to fabricate TiO₂/Al₂O₃ composite membranes, dried, and calcined, and this procedure is repeated with varying sols in succession. The resulting asymmetric mesoporous TiO₂ membrane with a thickness of 0.9 μm exhibits a hierarchical change in pore diameter from 2–6, through 3–8, to 5–11 nm from the top to the bottom layer. Moreover, the corresponding porosity is incremented from 46.2, through 56.7, to 69.3 %. Compared to a repeated‐coating process using a single sol, the hierarchical multilayer process improves water permeability significantly without sacrificing the organic retention and photocatalytic activity of the TiO₂ membranes. The prepared TiO₂ photocatalytic membrane has great potential in developing highly efficient water treatment and reuse systems, for example, decomposition of organic pollutants, inactivation of pathogenic microorganisms, physical separation of contaminants, and self‐antifouling action because of its multifunctional capability.     

Nanocrystalline TiO2 Photocatalytic Membranes with a Hierarchical Mesoporous Multilayer Structure: Synthesis,Characterization, and Multifunction

A novel sol–gel dip‐coating process to fabricate nanocrystalline TiO₂ photocatalytic membranes with a robust hierarchical mesoporous multilayer and improved performance has been studied. Various titania sols containing poly(oxyethylenesorbitan monooleate) (Tween 80) surfactant as a pore‐directing agent to tailor‐design the porous structure of TiO₂ materials at different molar ratios of Tween 80/isopropyl alcohol/acetic acid/titanium tetraisopropoxide = R:45:6:1 have been synthesized. The sols are dip‐coated on top of a homemade porous alumina substrate to fabricate TiO₂/Al₂O₃ composite membranes, dried, and calcined, and this procedure is repeated with varying sols in succession. The resulting asymmetric mesoporous TiO₂ membrane with a thickness of 0.9 μm exhibits a hierarchical change in pore diameter from 2–6, through 3–8, to 5–11 nm from the top to the bottom layer. Moreover, the corresponding porosity is incremented from 46.2, through 56.7, to 69.3 %. Compared to a repeated‐coating process using a single sol, the hierarchical multilayer process improves water permeability significantly without sacrificing the organic retention and photocatalytic activity of the TiO₂ membranes. The prepared TiO₂ photocatalytic membrane has great potential in developing highly efficient water treatment and reuse systems, for example, decomposition of organic pollutants, inactivation of pathogenic microorganisms, physical separation of contaminants, and self‐antifouling action because of its multifunctional capability.     

Fabrication of a “Soft” Membrane Electrode Assembly Using Layer‐by‐Layer Technology

A new type of thin‐film electrode that does not utilize conducting polymers or traditional metal or chemical vapor deposition methods has been developed to create ultrathin flexible electrodes for fuel cells. Using the layer‐by‐layer (LbL) technique, carbon–polymer electrodes have been assembled from polyelectrolytes and stable carbon colloidal dispersions. Thin‐film LbL polyelectrolyte–carbon electrodes (LPCEs) have been successfully assembled atop both metallic and non‐metallic, porous and non‐porous substrates. These electrodes exhibit high electronic conductivities of 2–4 S cm^–1, and their porous structure provides ionic conductivities in the range of 10^–4 to 10^–3 S cm^–1. The electrodes show remarkable stability towards oxidizing, acidic, or delaminating basic solutions. In particular, an LPCE consisting of poly(diallyldimethyl ammonium chloride)/poly(2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid)/carbon–platinum assembled on a porous stainless steel support yields an open‐circuit potential similar to that of a pure platinum electrode. With LbL carbon–polymer electrodes, the membrane‐electrode assembly (MEA) in a fuel cell can be made several times thinner, assume multiple geometries, and hence be more compact. The mechanism for LPCE deposition, electrode structure, and miniaturization will be presented and discussed, and demonstrations of the LbL electrodes in a traditional Nafion‐based proton fuel cell and the first demonstration of a thin‐film hydrogen–air “soft” fuel cell fully constructed using multilayer assembly are described.     

An Ultrathin Flexible 2D Membrane Based on Single‐Walled Nanotube–MoS2 Hybrid Film for High‐Performance Solar Steam Generation

Solar steam generation is achieved by localized heating system using various floating photothermal materials. However, the steam generation efficiency is hindered by the difficulty in obtaining a photothermal material with ultrathin structure yet sufficient solar spectrum absorption capability. Herein, for the first time, an ultrathin 2D porous photothermal film based on MoS₂ nanosheets and single‐walled nanotube (SWNT) films is prepared. The as‐prepared SWNT–MoS₂ film exhibits an absorption of more than 82% over the whole solar spectrum range even with an ultrathin thickness of ≈120 nm. Moreover, the SWNT–MoS₂ film floating on the water surface can generate a sharp temperature gradient due to the localized heat confinement effect. Meanwhile, the ultrathin and porous structure effectively facilitates the fast water vapor escaping, consequently an impressively high evaporation efficiency of 91.5% is achieved. Additionally, the superior mechanical strength of the SWNT–MoS₂ film enables the film to be reused for atleast 20 solar illumination cycles and maintains stable water productivity as well as high salt rejection performance. This rational designed hybrid architecture provides a novel strategy for constructing 2D‐based nanomaterials for solar energy harvesting, chemical separation, and related technologies.     

Large‐Area Flexible Core–Shell Graphene/Porous Carbon Woven Fabric Films for Fiber Supercapacitor Electrodes

New porous materials are of great importance in many technological applications. Here, the direct synthesis of multi‐layer graphene and porous carbon woven composite films by chemical vapor deposition on Ni gauze templates is reported. The composite films integrate the dual advantages of graphene and porous carbon, having not only the excellent electrical properties and flexibility of graphene but also the porous characteristics of amorphous carbon. The multi‐layer graphene/porous carbon woven fabric film creates a new platform for a variety of applications, such as fiber supercapacitors. The designed composite film has a capacitance of 20 μF/cm², which is close to the theoretical value and a device areal capacitance of 44 mF/cm².     

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.     

Designing a New Generation of Proton‐Exchange Membranes Using Layer‐by‐Layer Deposition of Polyelectrolytes

All fuel cells utilizing the membrane‐electrode assembly have their ion‐conductive membrane sandwiched between bipolar plates. Unfortunately, applying conventional techniques to isolated polyelectrolyte membranes is challenging and difficult. A more practical alternative is to use the layer‐by‐layer assembly technique to fabricate a membrane‐electrode assembly that is technologically relatively simple, economic, and robust. The process presented here paves the way to fabricate ion‐conductive membranes tailored for optimum performance in terms of controlled thickness, structural morphology, and catalyst loading. Composite membranes are constructed through the layered assembly of ionically conductive multilayer thin films atop a porous polycarbonate membrane. Under ambient conditions, a fuel cell using a poly(ethylene oxide)/poly(acrylic acid) (PEO/PAA) composite membrane delivers a maximum power density of 16.5 mW cm^–2 at a relative humidity of 55 %, which is close to that of some commercial fuel cells operating under the same conditions. Further optimization of these systems may lead to new, ultrathin, flexible fuel cells for portable power and micropower applications.     

Photoswitchable Superabsorbency Based on Nanocellulose Aerogels

Chemical vapor deposition of a thin titanium dioxide (TiO₂) film on lightweight native nanocellulose aerogels offers a novel type of functional material that shows photoswitching between water‐superabsorbent and water‐repellent states. Cellulose nanofibrils (diameters in the range of 5–20 nm) with native crystalline internal structures are topical due to their attractive mechanical properties, and they have become relevant for applications due to the recent progress in the methods of their preparation. Highly porous, nanocellulose aerogels are here first formed by freeze‐drying from the corresponding aqueous gels. Well‐defined, nearly conformal TiO₂ coatings with thicknesses of about 7 nm are prepared by chemical vapor deposition on the aerogel skeleton. Weighing shows that such TiO₂‐coated aerogel specimens essentially do not absorb water upon immersion, which is also evidenced by a high contact angle for water of 140° on the surface. Upon UV illumination, they absorb water 16 times their own weight and show a vanishing contact angle on the surface, allowing them to be denoted as superabsorbents. Recovery of the original absorption and wetting properties occurs upon storage in the dark. That the cellulose nanofibrils spontaneously aggregate into porous sheets of different length scales during freeze‐drying is relevant: in the water‐repellent state they may stabilize air pockets, as evidenced by a high contact angle, in the superabsorbent state they facilitate rapid water‐spreading into the aerogel cavities by capillary effects. The TiO₂‐coated nanocellulose aerogels also show photo‐oxidative decomposition, i.e., photocatalytic activity, which, in combination with the porous structure, is interesting for applications such as water purification. It is expected that the present dynamic, externally controlled, organic/inorganic aerogels will open technically relevant approaches for various applications.     

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.     

Battery Electrode Materials with Omnivalent Cation Storage for Fast and Charge‐Efficient Ion Removal of Asymmetric Capacitive Deionization

Capacitive deionization (CDI) that engages porous carbon electrodes constitutes one of the well‐established energy‐efficient desalination methods. However, improvement in desalination performance, including ion removal capacity, ion removal rate, and charge efficiency remains requisite for a wide range of applications. Herein, an ion‐exchange membrane‐free asymmetric CDI is introduced by pairing a metal organic framework (MOF), namely, K_0.03Cu[Fe(CN)₆]_0.65·0.43H₂O and porous carbon. The exclusive intercalation of cations into the MOF prevents the reverse adsorption of co‐ions (anions), thus significantly improving ion removal capacity (23.2 mg g^?1) and charge efficiency (75.8%). Moreover, by utilizing the advantage of the MOF that diverse mono‐ and divalent cations can be stored in the narrow redox potential range, the asymmetric CDI allows simultaneous capture of mono‐ and divalent cations, thus achieving omnivalent cation removal. Moreover, cations are intercalated in the hydrated forms without a discrete phase transition of the host structure, facilitating rapid desalination by reducing the desolvation energy penalty, which results in a high ion removal rate of 0.24 mg g^?1 s^?1. This study offers a new design principle in CDI: the integration of a crystal structure with large ionic channels that enable hydrated intercalation of multivalent ions in a fast and exclusive manner.     

Dynamically Gas‐Phase Switchable Super(de)wetting States by Reversible Amphiphilic Functionalization: A Powerful Approach for Smart Fluid Gating Membranes

In nature, cellular membranes perform critical functions such as endocytosis and exocytosis through smart fluid gating processes mediated by nonspecific amphiphilic interactions. Despite considerable progress, artificial fluid gating membranes still rely on laborious stimuli‐responsive mechanisms and triggering systems. In this study, a room temperature gas‐phase approach is presented for dynamically switching a porous material from a superhydrophobic to a superhydrophilic wetting state and back. This is realized by the reversible attachment of bipolar amphiphiles, which promote surface wetting. Application of this reversible amphiphilic functionalization to an impermeable nanofibrous membrane induces a temporary state of superhydrophilicity resulting in its pressure‐less permeation. This mechanism allows for rapid smart fluid gating processes that can be triggered at room temperature by variations in the environment of the membrane. Owing to the universal adsorption of volatile amphiphiles on surfaces, this approach is applicable to a broad range of materials and geometries enabling facile fabrication of valve‐less flow systems, fluid‐erasable microfluidic arrays, and sophisticated microfluidic designs.     

Atomic Layer Deposition Inducing Integration of Co,N Codoped Carbon Sphere on 3D Foam with Hierarchically Porous Structures for Flexible Hydrogen Producing Device

Integration of metal–organic frameworks on deformation tolerant substrates exhibits a promising prospect in flexible electrode applications. A straightforward synthesis utilizing atomic layer deposition pretreating to induce the growth of a zeolitic imidazolate framework‐67 (ZIF‐67) layer on carbon foam (CF), which maintains high ZIF‐67 loading with a hierarchically porous structure and large surface area of 453 m² g^?1 is presented. With a subsequent pyrolysis process, three‐dimensional composite structures are obtained with Co, N codoped carbon spheres attached firmly on the CF framework, and CF bridges the individual carbon spheres to construct a conductive pathway. The composites are used as a flexible electrode for hydrogen production both in acid and alkaline electrolytes. The advances in the composite structure, such as the hierarchically porous structure, large surface area, and high loading of active material, lead to excellent electrochemical performance in terms of low overpotential of 142 mV and low Tafel slope of 73 mV dec^?1 in 0.5 m H₂SO₄. Most importantly, the composite structure with outstanding flexible property shows good catalytic performance under remarkable deformation, and after 100 repeated compression–recovery cycles, the performance degrades slightly. This work provides a new design of flexible electrode, which is promising for the hydrogen production industry.     

Hierarchical Graphene–Carbon Fiber Composite Paper as a Flexible Lateral Heat Spreader

As a low dimensional crystal, graphene attracts great attention as heat dissipation material due to its unique thermal transfer property exceeding the limit of bulk graphite. In this contribution, flexible graphene–carbon fiber composite paper is fabricated by depositing graphene oxide into the carbon fiber precursor followed by carbonization. In this full‐carbon architecture, scaffold of one‐dimensional carbon fiber is employed as the structural component to reinforce the mechanical strength, while the hierarchically arranged two‐dimensional graphene in the framework provides a convenient pathway for in‐plane acoustic phonon transmission. The as‐obtained hierarchical carbon/carbon composite paper possesses ultra‐high in‐plane thermal conductivity of 977 W m^?1 K^?1 and favorable tensile strength of 15.3 MPa. The combined mechanical and thermal performances make the material highly desirable as lateral heat spreader for next‐generation commercial portable electronics.     

A Multifunctional Polymeric Periodontal Membrane with Osteogenic and Antibacterial Characteristics

Periodontitis is a prevalent chronic, destructive inflammatory disease affecting tooth‐supporting tissues in humans. Guided tissue regeneration strategies are widely utilized for periodontal tissue regeneration generally by using a periodontal membrane. The main role of these membranes is to establish a mechanical barrier that prevents the apical migration of the gingival epithelium and hence allowing the growth of periodontal ligament and bone tissue to selectively repopulate the root surface. Currently available membranes have limited bioactivity and regeneration potential. To address such challenges, an osteoconductive, antibacterial, and flexible poly(caprolactone) (PCL) composite membrane containing zinc oxide (ZnO) nanoparticles is developed. The membranes are fabricated through electrospinning of PCL and ZnO particles. The physical properties, mechanical characteristics, and in vitro degradation of the engineered membrane are studied in detail. Also, the osteoconductivity and antibacterial properties of the developed membrane are analyzed in vitro. Moreover, the functionality of the membrane is evaluated with a rat periodontal defect model. The results confirmed that the engineered membrane exerts both osteoconductive and antibacterial properties, demonstrating its great potential for periodontal tissue engineering.     

Autonomously Responsive Membranes for Chemical Warfare Protection

Stimuli‐responsive materials offer new opportunities to resolve long‐standing material challenges and are rapidly gaining pivotal roles in diverse applications. For example, smart protective garments that rapidly transport water vapor and autonomously block chemical threats are expected to enable an effective new paradigm of adaptive personal protection. However, the incorporation of these seemingly incompatible properties into a single responsive system remains elusive. Herein, a bistable membrane that can rapidly, selectively, and reversibly transition from a highly breathable state in a safe environment to a chemically protective state when exposed to organophosphate threats such as sarin is demonstrated. Dynamic response to chemical stimuli is achieved through the physical collapse of an ultrathin copolymer layer on the membrane surface, which efficiently gates transport through membrane pores composed of single‐walled carbon nanotubes (SWNTs). The adoption of nanometer‐wide SWNTs for ultrafast moisture conduction enables a simultaneous boost in size‐sieving selectivity and water‐vapor permeability by decreasing nanotube diameter, thereby overcoming the breathability/protection trade‐off that limits conventional membrane materials. Adaptive multifunctional membranes based on this platform greatly extend the active use of a protective garment and present exciting opportunities in many other areas including separation processes, sensing, and smart delivery.