pH‐Responsive Nanoporous Silica Colloidal Membranes

Free‐standing colloidal membranes (nanofrits) with varied thickness and nanopore size are fabricated and modified with pH‐responsive poly(2‐(dimethylamino)ethyl methacrylate) brushes. The polymer‐modified nanofrits demonstrate excellent gating behavior for molecular diffusion: in the presence of acid, the diffusion rate of positively charged species significantly decreases. Increasing the polymer length and membrane thickness and decreasing the nanopore size leads to the complete acid‐controlled gating of the membranes.     

Virus Filtration Membranes Prepared from Nanoporous Block Copolymers with Good Dimensional Stability under High Pressures and Excellent Solvent Resistance

We introduce a nanoporous membrane suitable for virus filtration with good dimensional stability under high pressures maintaining high selectivity. The membrane consists of a double layer: The upper layer is a nanoporous film with pore size of ～17 nm and a thickness of ～160 nm, which was prepared by polystyrene‐block‐poly(methyl methacrylate) copolymer (PS‐b‐PMMA) where PMMA block was removed by ultraviolet irradiation followed by rinsing with acetic acid. The nanoporous block copolymer film was combined with a conventional micro‐filtration membrane to enhance mechanical strength. The membrane employed in this study did not show any damage or crack even at a pressure of 2 bar, while high selectivity was maintained for the filtration of human rhinovirus type 14 which has a diameter of ～30 nm and is a major pathogen of the common cold in humans. Furthermore, due to crosslinked PS matrix during the UV irradiation, the nanoporous membrane showed excellent resistance to all organic solvents. This could be used under harsh filtration conditions such as high temperature and strong acidic (or basic) solution.     

聚乙二醇共水热合成TiO2纳米晶多孔薄膜

以钛酸丁酯为原料,在水热过程中加入聚乙二醇(分子量2 000)合成TiO2纳米晶,并制备多孔薄膜用于染料敏化太阳能电池(DSSCs)。采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、台阶仪、紫外-可见分光光度计(UV-vis)对纳米晶粒的晶体结构、薄膜的表面形貌、厚度和光学吸收性能以及电池的光电能量转换性能随聚乙二醇的加入量变化的规律进行了探索。结果表明,聚乙二醇的加入抑制了锐钛矿相TiO2晶粒的生长,诱导了金红石相的形成。当聚乙二醇的加入量为TiO2质量的5%时性能达到最佳,采用单层多孔薄膜以及不添加四-叔丁基吡啶的电解质组装的电池获得了2.86%的光电能量转换效率。     

Nanoporous Alumina Membranes as Diffusion Controlling Systems

This work describes the use of nanoporous alumina membranes for the diffusion of crystal violet molecules, encapsulated in the micelles of sodium dodecylsulfate (SDS), through pores ranging between 20 and 200 nm in diameter. The encapsulation of the crystal violet in SDS micelles is necessary in order to enlarge the size of the molecules to such an extent that the pore size becomes a speed‐controlling function. Superior results were obtained when the membrane‐containing capsule is placed into a water‐filled beaker, and carefully moved by means of a “tipping bridge” in order to prevent diffusion problems in the capsule. Free crystal violet was liberated following diffusion due to the low SDS concentration in the aqueous solution, which was far below the critical micelle concentration (CMC). Micelle formation and encapsulation of crystal violet is shown by UV‐visible and fluorescence spectroscopies. The experiments described herein serve as an exploratory test for developing novel drug delivery systems.     

Electrically Tunable Nanoporous Carbon Hybrid Actuators

A novel nanoporous carbon/electrolyte hybrid material is reported for use in actuation. The nanoporous carbon matrix provides a 3D network that combines mechanical strength, light weight, and low cost with an extremely high surface area. In contrast to lower dimensional nanomaterials, the nanoporous carbon matrix can be prepared in the form of macroscopic monolithic samples that can be loaded in compression. The hybrid material is formed by infiltrating the free internal pore volume of the carbon with an electrolyte. Actuation is prompted by polarizing the internal interfaces via an applied electric bias. It is found that the strain amplitude is proportional to the Brunauer‐Emmett‐Teller (BET) mass specific surface area, with reversible volume strain amplitudes up to the exceptionally high value of 6.6%. The mass‐specific strain energy density compares favorably to reported values for piezoceramics and for nanoporous metal actuators.     

Graphene‐Based Nanoporous Materials Assembled by Mediation of Polyoxometalate Nanoparticles

A kind of graphene‐based nanoporous material is prepared through assembling graphene sheets mediated through polyoxometalate nanoparticles. Owing to the strong interaction between graphene and polyoxometalate, 2D graphene sheets with honeycomb‐latticed carbon atoms could assemble into a porous structure, in which 3D polyoxometalate nanoparticles serve as the crosslinkers. Nitrogen and hydrogen sorption analysis reveal that the as‐prepared graphene‐based hybrid material possesses a specific surface area of 680 m² g^?1 and a hydrogen uptake volume of 0.8?1.3 wt%. Infrared spectrometry is used to probe the electron density changes of polyoxometalate particle in the redox‐cycle and to verify the interaction between graphene and polyoxometalate. The as‐prepared graphene‐based materials are further characterized by Raman spectroscopy, X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy.     

Bioinspired Large-Area Atomically-Thin Graphene Membranes

Nanoporous graphene membranes are attractive for molecular separations, but it remains challenging to maintain sufficient mechanical strength during scalable fabrication and module development. Inspired by the composite structure of cell membranes and cell walls, a large-area atomically thin nanoporous graphene membrane supported by a fiber-reinforced structure with strong interlamellar adhesion is designed. Compared with other graphene-based membranes of large scale, the fracture stress, fracture strength, and tensile stiffness of the composite membranes can be enhanced by a factor of 17, 67, and 94, respectively. This fiber-reinforced structure also confers stability of the composite membrane to different curvature states and repeated bending processes after 10 000 times, which provides an opportunity for modularization. The breathable function of such membrane with an ultrahigh gas permeance (≈8.6–23 L m⁻² d⁻¹ Pa⁻¹) and an ultralow water vapor transportation rate (WVTR) (≈23–129 g L m⁻² d⁻¹) is observed, superior to most commercial materials. This work provides a facile method to fabricate large-area graphene membranes and paves the road to practical application in the membrane separation field for other 2D films.     

Sub‐10 nm Wide Cellulose Nanofibers for Ultrathin Nanoporous Membranes with High Organic Permeation

There are increasing requirements for highly efficient and solvent‐resistant nanoporous membranes in various separation processes. Traditional membranes usually have a poor solvent resistance and a thick skin layer leading to a low permeation flux. Currently, the major challenge lies in fabrication of ultrathin few‐nanometers‐pore membranes for fast organic filtration. Herein, a facile approach is presented to prepare ultrafine cellulose nanofibers for fabrication of ultrathin nanoporous membranes. The obtained nanofibers have a uniform diameter of 7.5 ± 2.5 nm and are homogeneously dispersed in aqueous solutions that are favorable to the fabrication of ultrathin nanoporous membranes. The resulting cellulose nanoporous membranes have an adjustable thickness down to 23 nm and pore sizes ranging from 2.5 to 12 nm. They allow fast permeation of water and organics during pressure‐driven filtration. Typically, the 30 nm thick membrane has high fluxes of 1.14 and 3.96 × 10⁴ L h^?1 m^?2 bar^?1 for pure water and acetone respectively. Furthermore, the as‐prepared cellulose nanofibers are easily employed to produce a novel syringe filter with sub‐10 nm pores that have a wide application in fast separation and purification of nanoparticles on few‐nanometers scale.     

Dynamic Electrochemical Membranes for Continuous Affinity Protein Separation

A membrane system with nanometer‐scale thick electrodes is able to selectively bind genetically modified proteins and pump them across the membrane with sequential voltage pulses. The electrodes are located at the first 20 nm of pore entrances to specifically capture targeted proteins and block non‐specific protein transport through the pores during the binding cycle. During the release cycle, concentration of imidazole is controlled to keep the pore blocked while releasing proteins at the bottom edge of the electrode. A separation factor for GFP:BSA of 16 was achieved with observed GFP electrophoretic mobility of 2.54 × 10^?6 cm² V^?1 s^?1. This non‐optimized system with a membrane area of 0.75 cm² has the same throughput as 1 mL of commercially available chromatography columns showing viability as a continuous process. This system will enable continuous separation of expressed proteins directly from fermentation broths dramatically simplifying the separation process as well as reducing bio‐pharmaceutical production costs.     

Induced Chain Alignment of Conjugated Polymers Within Nanoporous Template

This work presents a simple method to generate ordered conjugated polymer nanoarrays through a pore‐filling process for nanoporous polymer templates so as to enhance the efficiency of photoluminescence (PL). PL results combined with the morphological evolution examined by scanning probe microscopy revealed that the enhanced PL reaches maximum intensity as the template pores are completely filled by conjugated polymers. Polarized PL spectroscopy and grazing incidence Fourier transform infrared spectroscopy were used to determine the chain orientation of templated conjugated polymer; the spectroscopic results indicate a parallel chain orientation along the cylindrical direction of nanopores. The induced alignment of the polymer chains is attributed to a nanoscale spatial effect that increases the PL intensity and the lifetime of the conjugated polymer. The enhanced luminescence of nanostructured conjugated polymers is highly promising for use in designing luminescent nanodevices.     

Core/Shell and Hollow Ultra High Molecular Weight Polyethylene Nanofibers and Nanoporous Polyethylene Prepared by Mesoscopic Shape Replication Catalysis

Polyvinyl alcohol (PVA) nanofibers, produced by electrospinning, represent attractive high‐surface‐area supports for olefin polymerization catalysts. Tethered with metal alkyls, PVA nanofibers immobilize a great variety of transition metal compounds, thus producing highly active nanofiber‐supported Ziegler‐, metallocene‐, and post‐metallocene catalysts. Whereas most conventional heterogeneous polymerization catalysts form particles, PVA‐nanofiber‐supported catalysts enable polyolefin nanofiber and nanostructure formation by mesoscopic shape replication using electrospun nanofibers as templates. At low ethylene pressure, linear correlation between average PE/PVA core/shell fiber diameter and polymerization time are made. At elevated pressure, this control is lost, accounting for the formation of reactor blends consisting of PE granules and built‐in PE/PVA nanofibers. Whereas conventional catalysts produce micrometer‐sized particles of ultrahigh molecular weight PE (UHMWPE), PVA‐nanofiber supported chromium catalysts afford new families UHMWPE materials. They range from UHMWPE/PVA core/shell nanofibers and nonwovens to hollow UHMWPE fibers and nanoporous UHMWPE, obtained by removing the PVA component.     

Size‐Selective Binding of Sodium and Potassium Ions in Nanoporous Thin Films of Polymerized Liquid Crystals

The development of a nanoporous material from a columnar liquid crystalline complex between a polymerizable benzoic acid derivative and a 1,3,5‐tris(1H‐benzo[d]imidazol‐2‐yl)benzene template molecule is described. The morphology of the liquid crystalline complex is retained upon polymerization and quantitative removal of the template molecule affords a nanoporous material with the same lattice parameters. The nanoporous material selectively binds cations from aqueous solution, with selectivity for sodium and potassium ions over lithium and barium ions, as shown with FT‐IR. Binding is also quantified gravimetrically with a quartz crystal microbalance with dissipation monitoring, a technique that is used for this purpose for the first time here.     

量子系统的纠缠探测与纠缠测量

在回顾了量子系统中有关纠缠探测的各种方法和纠缠度不同定义的基础上,总结了探测两体或多体纠缠的几种分离判据;分析了它们与正映射之间及其相互之间的关系;重点分析了纠缠目击者这种特殊的分离判据,包括它的定义以及构造方法,并且从实验观点分析了它的应用。在已提出的公理化假设的纠缠测量思想的基础上,讨论了理论上各种两体纠缠度和多体纠缠度的定义并且讨论了各种纠缠度在实验中的估计问题。最后对各种非线性分离判据进行了分析。     

Streptavidin‐Functionalized Three‐Dimensional Ordered Nanoporous Silica Film for Highly Efficient Chemiluminescent Immunosensing

A novel biofunctionalized three‐dimensional ordered nanoporous SiO₂ film is designed for construction of chemiluminescent analytical devices. The nanoporous SiO₂ film is prepared with self‐assembly of polystyrene spheres as a template and 5‐nm SiO₂ nanoparticles on a glass slide followed by a calcination process. Its functionalization with streptavidin is achieved by using 3‐glycidoxypropyltrimethoxysilane as a linker. Based on the high‐selectivity recognition of streptavidin to biotin‐labeled antibody a novel immunosensor is further constructed for highly efficient chemiluminescent immunoassay. The surface morphologies and fabrication processes of both the biofunctionalized film and the immunosensor are characterized using scanning electron microscopy, atomic‐force microscopy, X‐ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy. The three‐dimensional ordered nanopores have high capacity for loading of streptavidin and antibody and promote the mass transport of immunoreagents for immunoreaction, thus the resulting chemiluminescent immunosensor shows wide dynamic range for fast immunoassay, and good reproducibility and stability. Using carbohydrate antigen 125 (CA 125) as a model, the highly efficient chemiluminescent immunosensing shows a linear range of three orders of magnitude, from 0.5 to 400 U mL^?1. This work provides a biofunctionalized porous nanostructure for promising biosensing applications.     

Electrochemical Control of Charge Current Flow in Nanoporous Graphene

During the last decade, on-surface fabricated graphene nanoribbons (GNRs) have gathered enormous attention due to their semiconducting π-conjugated nature and atomically precise structure. A significant breakthrough is the recent fabrication of nanoporous graphene (NPG) as a 2D array of laterally bonded GNRs. This covalent integration of GNRs could enable complex electronic functionality at the nanoscale; however, for that, it is crucial to externally control the electronic coupling between GNRs within NPGs, which, to date, has not been possible. Using quantum chemical calculations and large-scale transport simulations, this study demonstrates that such control is enabled in a newly designed quinone-NPG (q-NPG) thanks to its GNRs inter-connections based on electroactive para-benzoquinone units. As a result, the spatial distribution of injected currents in q-NPG may be tuned, with sub-nanometer precision, via the application of external electrostatic gates and electrochemical means. These results thus provide a fundamental strategy to design organic nanodevices with built-in externally tunable electronics and spintronics, which is key for future applications such as bio-chemical nanosensing and carbon nanoelectronics.     

Synthesis of Thin,Oriented Zeolite A Membranes on a Macroporous Support

Continuous, thin, oriented zeolite A membranes are produced by a two‐step synthesis on macroporous α‐Al₂O₃ supports. In the first step, zeolite A nano‐cubes with ～350‐nm edges are prepared as a native impurity phase in zeolite Y synthesis dispersions, the support surface is pre‐modified with a cationic polymer having a selective affinity for zeolite A. The thus‐treated support is contacted with a colloidally stable dispersion of zeolite A and Y mixture in water, which results in selective, dense‐packed deposition of the zeolite A cubes with one face aligned to the average support surface. In a second step of hydrothermal epitaxial growth, the seed layer grows epitaxially into a continuous, meso‐defect free, ～1 µm thick zeolite A layer, already after 1 h of treatment. This microstructure of the membrane compares very favorably to what is commonly obtained. The pH value of the zeolite mixture suspension is found to have a major influence on seed layer morphology, and thereby, on the quality and orientation of zeolite A membrane after short synthesis times. The final zeolite A membrane thickness and morphology is controlled by varying secondary growth synthesis time. The approach presented is thought to be of generic use for the preparation of oriented zeolite membranes.     

Membranes in Solar-Driven Evaporation: Design Principles and Applications

Solar-driven evaporation process brings exciting opportunities to recover clean water and resources in a sustainable way from diverse sources like seawater and wastewater. Separation membranes, as a vital material in many environmental and energy applications, can contribute significantly to this process owing to their structural features. However, the unique roles of membranes in solar evaporator construction and process design are seldom recognized and not summarized yet from scientific principles and application demands, which forms the motivation of this review. Herein, the roles of membranes in different processes based on solar-driven evaporation are focused and the design principles of membrane materials and devices to meet the requirements of these applications are discussed. Fabrication strategies for photothermal membranes are introduced primarily, followed by a discussion on how to design membrane materials, devices, and processes to pursue optimal performance and realize advanced functions accompanied by evaporation. Furthermore, the future of this field is forecast with both challenges and opportunities.     

A Simple Template‐Free Strategy to Synthesize Nanoporous Manganese and Nickel Oxides with Narrow Pore Size Distribution,and Their Electrochemical Properties

A facile method has been developed to synthesize nanoporous manganese and nickel oxides with polyhedron particle morphologies, high surface areas and narrow pore distributions by controlled thermal decomposition of the oxalate precursors. This method can be extended to using other kinds of salt precursors to prepare a series of nanoporous metal oxides. The heating rate, calcination temperature and controlled particle size of the oxalate precursors are important factors to get well‐defined pore structures. XRD, TG‐DTA, TEM, SEM, XPS, wet chemical titration and N₂ sorption isotherm techniques are employed for morphology and structure characterizations. High surface area microporous manganese oxide (283 m² g^?1) and mesoporous nickel oxide (179 m² g^?1) with narrow pore distribution at around 1.0 nm and 6.0 nm, respectively, are obtained. Especially, we can tune the pore size of manganese oxides from microscope to mesoscope by controlling the thermal procedure. Electrochemical properties of manganese and nickel oxides are studied by cyclic voltammetry measurements in a mild aqueous electrolyte, which shows a high specific capacitance of 309 F g^?1 of microporous manganese oxide and a moderately high specific capacitance of 165 F g^?1 of mesoporous NiO due to their nanoporous structure, presenting the promising candidates for super capacitors (SC).     

Lignin-Derived Ionic Conducting Membranes for Low-Grade Thermal Energy Harvesting

Wood-based ionic conductive membranes have emerged as a new paradigm for low-grade thermal energy harvesting applications due to their unique andtailorable structures. Herein, a lignin-derivedionic conducting membrane with hierarchical aligned channels is synthesized viaa double network crosslinking approach. Their excellent thermal stability andsuperior swelling ratio allow their optimization as low-grade heat recovery technologies. Several vertically aligned nanoscaleconfinements are found in the synthesized membranes, contributing towardenhanced ionic diffusion. Among all the combinations, the membrane comprising69.2 wt.% of lignin and infiltrated with 0.5 m KOH exhibits anexceptional ionic figure of merit (ZTi) of 0.25, relatively higher ionic conductivity(51.5 mS cm^‒1), lower thermal conductivity(0.195 W m^‒1·K), and a remarkable ionic Seebeck coefficientof 5.71 mV K^‒1 under the application of an axialtemperature gradient. A numerical model is also utilized to evaluate theveracity of experimental observations and to gain a better understanding of thefundamental mechanisms involved in attaining such values. These results displaythe potential of lignin-basedmembranes for future thermal energy harvesting applications and are a new facetin thermoelectric energy conversion which is certain to pave the way forfurther investigations on sustainable ionic conductive membranes.