Recent Developments in Graphene‐Based Membranes: Structure,Mass‐Transport Mechanism and Potential Applications

Significant achievements have been made on the development of next‐generation filtration and separation membranes using graphene materials, as graphene‐based membranes can afford numerous novel mass‐transport properties that are not possible in state‐of‐art commercial membranes, making them promising in areas such as membrane separation, water desalination, proton conductors, energy storage and conversion, etc. The latest developments on understanding mass transport through graphene‐based membranes, including perfect graphene lattice, nanoporous graphene and graphene oxide membranes are reviewed here in relation to their potential applications. A summary and outlook is further provided on the opportunities and challenges in this arising field. The aspects discussed may enable researchers to better understand the mass‐transport mechanism and to optimize the synthesis of graphene‐based membranes toward large‐scale production for a wide range of applications.     

Characterization and manipulation of the electroosmotic flow in porous anodic alumina membranes

Porous anodic alumina membranes (PAAMs) have uniform and high-density nanopores, and the dimension and interval of the pores can be easily controlled by varying the anodization conditions. The application of PAAMs could widely impact the cost and efficiency of the liquid-based nanoscale separations. We report here the property of electroosmotic flow in PAAMs, which plays a significant role in the mass transport across these membranes that have charged pore surfaces. By controlling the solution pH and the magnitude and sign of the applied current, the mass transport through these nanoporous membranes can be spatially and temporally manipulated. The effects of electrosurface properties and electrolyte ionic strength on electroosmotic flow were studied. The anion incorporation and adsorption cause the variation of the electrosurface properties of PAAMs, which in turn influence the rate and direction of the mass transport. As compared to the membrane with fixed surface charge, this diversity makes it possible for the PAAMs to be used in various conditions.     

Characterisation of pore structures in nanoporous materials for advanced bionanotechnology

Porous materials are potential candidates for applications in various fields, such as bionanotechnology, gas separation, catalysts and micro-electronics. In particular, their applications in bionanotechnology include biosensors, biomedical implants and microdevices, biosupporters, bio-encapsules, biomolecule separations and biomedical therapy. All these bionanotechnology applications utilise the shape, size and size distribution of pores in porous materials. Therefore the controlled creation of pores with desired shape, size and size distribution is most important in the development of nanoporous materials. Accordingly, the accurate evaluation of pore structure is necessary in the development of nanoporous materials and their applications. This article reviews recent developments in analytical techniques to characterise the pore structures of nanoporous materials.     

Purification of Nano‐Porous Silicon for Biomedical Applications

Recently, various bio‐medical applications of nanoporous silicon (np‐Si) have been suggested. This work investigates the biocompatibility of np‐Si particles taking into account hazardous residua confined in the pores after preparation. The emphasis is on the potential application of such particles as oxygen photosensitizer for photodynamic therapy of cancer, which requires both negligible toxicity of np‐Si particles in darkness and a high photo‐cyto‐toxic effect due to generation of singlet oxygen under illumination. Considerable amounts of water soluble toxic impurities are found to be present in the nanoporous shell of micrometer‐sized np‐Si particles immediately after their preparation by chemical etching of bulk silicon powder. The effects of several ordinary cleaning treatments are investigated by using thermal effusion mass‐spectroscopy and FTIR spectroscopy. A particular purification procedure is developed, capable to reduce the concentration of residual impurities to levels acceptable for bio‐medical applications while preserving the required photo‐activity of the np‐Si particles.     

3D Porous Hydrogel/Conducting Polymer Heterogeneous Membranes with Electro‐/pH‐Modulated Ionic Rectification

Heterogeneous membranes composed of asymmetric structures or compositions have enormous potential in sensors, molecular sieves, and energy devices due to their unique ion transport properties such as ionic current rectification and ion selectivity. So far, heterogeneous membranes with 1D nanopores have been extensively studied. However, asymmetric structures with 3D micro‐/nanoscale pore networks have never been investigated. Here, a simple and versatile approach to low‐costly fabricate hydrogel/conducting polymer asymmetric heterogeneous membranes with electro‐/pH‐responsive 3D micro‐/nanoscale ion channels is introduced. Due to the asymmetric heterojunctions between positively charged nanoporous polypyrrole (PPy) and negatively charged microscale porous hydrogel poly (acrylamide‐co‐acrylic acid) (P(AAm‐co‐AA)), the membrane can rectify ion transmembrane transport in response to both electro‐ and pH‐stimuli. Numerical simulations based on coupled Poisson and Nernst–Plank equations are carried out to explain the ionic rectification mechanisms for the membranes. The membranes are not dependent on elaborately fabricated 1D ion channel substrates and hence can be facilely prepared in a low‐cost and large‐area way. The hybridization of hydrogel and conducting polymer offers a novel strategy for constructing low‐cost, large‐area and multifunctional membranes, expanding the tunable ionic rectification properties into macroscopic membranes with micro‐/nanoscale pores, which would stimulate practical applications of the membranes.     

Ordered nanoporous polymer-carbon composites

Nanostructured organic materials, particularly those constructed with uniform nanopores, have been sought for a long time in materials science. There have been many successful reports on the synthesis of nanostructured organic materials using the so-called, 'supramolecular liquid crystal templating' route. Ordered nanoporous polymeric materials can also be synthesized through a polymerization route using colloidal or mesoporous silica templates. The organic pore structures constructed by these approaches, however, are lower in mechanical strength and resistance to chemical treatments than nanoporous inorganic, silica and carbon materials. Moreover, the synthesis of the organic materials is yet of limited success in the variation of pore sizes and structures, whereas a rich variety of hexagonal and cubic structures is available with tunable pore diameters in the case of the inorganic materials. Here we describe a synthesis strategy towards ordered nanoporous organic polymers, using mesoporous carbon as the retaining framework. The polymer-carbon composite nanoporous materials exhibit the same chemical properties of the organic polymers, whereas the stability of the pores against mechanical compression, thermal and chemical treatments is greatly enhanced. The synthesis strategy can be extended to various compositions of hydrophilic and hydrophobic organic polymers, with various pore diameters, connectivity and shapes. The resultant materials exhibiting surface properties of the polymers, as well as the electric conductivity of the carbon framework, could provide new possibilities for advanced applications. Furthermore, the synthesis strategy can be extended to other inorganic supports such as mesoporous silicas.     

Facile Synthesis of Macrocellular Mesoporous Foamlike Ce–Sn Mixed Oxides with a Nanocrystalline Framework by Using Triblock Copolymer as the Single Template

Macrocellular mesoporous foamlike cerium–tin mixed oxide materials with well‐defined porous structure and nanocrystalline frameworks are synthesized through a simple one‐step self‐assembly process using an amphiphilic triblock copolymer as the single template. The macrocellular pores are synthesized without the addition of any swelling agent or hazardous acids. The final mixed oxide possesses a hierarchically porous structure including macrocellular foam with ultralarge cell size, closed windows, and mesopores on the walls. This indicates that the porous structure can be notably stabilized and improved by the incorporation of Sn in the CeO₂. The materials are expected to be good candidates in catalysis, since the hierarchical porosity enables high surface areas and hence more chemically active sites associated with the mesopores, combined with the high efficiency of mass transport from the macrocellular foam. The catalytic characteristics are discussed in relation to the architectures of the materials, and it is revealed that the macrocellular/mesoporous materials would be an efficient catalyst for CO oxidation.     

A Tunable 3D Nanostructured Conductive Gel Framework Electrode for High‐Performance Lithium Ion Batteries

This study develops a tunable 3D nanostructured conductive gel framework as both binder and conductive framework for lithium ion batteries. A 3D nanostructured gel framework with continuous electron pathways can provide hierarchical pores for ion transport and form uniform coatings on each active particle against aggregation. The hybrid gel electrodes based on a polypyrrole gel framework and Fe₃O₄ nanoparticles as a model system in this study demonstrate the best rate performance, the highest achieved mass ratio of active materials, and the highest achieved specific capacities when considering total electrode mass, compared to current literature. This 3D nanostructured gel‐based framework represents a powerful platform for various electrochemically active materials to enable the next‐generation high‐energy batteries.     

Bioinspired Flexible and Tough Layered Peptide Crystals

One major challenge of functional material fabrication is combining flexibility, strength, and toughness. In several biological and artificial systems, these desired mechanical properties are achieved by hierarchical architectures and various forms of anisotropy, as found in bones and nacre. Here, it is reported that crystals of N‐capped diphenylalanine, one of the most studied self‐assembling systems in nanotechnology, exhibit well‐ordered packing and diffraction of sub‐Å resolution, yet display an exceptionally flexible nature. To explore this flexibility, the mechanical properties of individual crystals are evaluated, assisted by density functional theory calculations. High‐resolution scanning electron microscopy reveals that the crystals are composed of layered self‐assembled structures. The observed combination of strength, toughness, and flexibility can therefore be explained in terms of weak interactions between rigid layers. These crystals represent a novel class of self‐assembled layered materials, which can be utilized for various technological applications, where a combination of usually contradictory mechanical properties is desired.     

Effect of ultraviolet illumination and ambient gases on the photoluminescence and electrical properties of nanoporous silicon layer for organic vapor sensor

The purpose of this research, the nanoporous silicon layer were fabricated and investigated the physical properties such as photoluminescence and the electrical properties in order to develop organic vapor sensor by using nanoporous silicon. The Changes in the photoluminescence intensity of nanoporous silicon samples are studied during ultraviolet illumination in various ambient gases such as nitrogen, oxigen and vacuum. In this paper, the nanoporous silicon layer was used as organic vapor adsorption and sensing element. The advantage of this device are simple process compatible in silicon technology and usable in room temperature. The structure of this device consists of nanoporous silicon layer which is formed by anodization of silicon wafer in hydrofluoric acid solution and aluminum electrode which deposited on the top of nanoporous silicon layer by evaporator. The nanoporous silicon sensors were placed in a gas chamber with various organic vapor such as ethanol, methanol and isopropyl alcohol. From studying on electrical characteristics of this device, it is found that the nanoporous silicon layer can detect the different organic vapor. Therefore, the nanoporous silicon is important material for organic vapor sensor and it can develop to other applications about gas sensors in the future.     

Micro‐Macroporous Composite Materials – Preparation Techniques and Selected Applications: A Review

Pores, on several orders of magnitude in size, control the properties of a solid material to a large extent. This is just as true for materials containing pores in the sub‐nanometer range like zeolites as for cellular foam structures with pores of several millimeters in size. All these porous materials have their distinct potential application ranging from heterogeneous catalysis to metal melt filtration. In many cases, the (hierarchical) combination of pores with different size regimes can improve the performance of the respective porous material or can lead to entirely new properties and applications. This review addresses the preparation and properties of microporous‐macroporous composite materials based on cellular foam supports (ceramic, metal, polymer) with a coating of a microporous compound (zeolite, zeotype framework, metal‐organic framework). The manufacturing of these materials can either be performed by dispersion‐based techniques, where the microporous coating is applied from a dispersion onto the cellular support (ex situ), or in situ by crystallization of the microporous compound directly onto the struts of the foam structure. In both cases, the general procedure can be modified by a pretreatment of the cellular support in order to improve the coating layer adherence, the overall amount of deposited material, or to control of the crystal morphology of the microporous compound.

     

Engineering Gyroid‐Structured Functional Materials via Templates Discovered in Nature and in the Lab

In search of optimal structures for functional materials fabrication, the gyroid (G) structure has emerged as a promising subject of widespread research due to its distinct symmetry, 3D interconnected networks, and inherent chiral helices. In the past two decades, researchers have made great progress fabricating G‐structured functional materials (GSFMs) based on G templates discovered both in nature and in the lab. The GSFMs demonstrate extraordinary resonance when interacting with light and matter. The superior properties of GSFMs can be divided into two categories based on the dominant structural properties, namely, dramatic optical performances dominated by short‐range symmetry and well‐defined texture, and effective matter transport due to long‐range 3D interconnections and high integrity. In this review, G templates suitable for fabrication of GSFMs are summarized and classified. State‐of‐the‐art optical applications of GSFMs, including photonic bandgap materials, chiral devices, plasmonic materials, and matamaterials, are systematically discussed. Applications of GSFMs involved in effective electron transport and mass transport, including electronic devices, ultrafiltration, and catalysis, are highlighted. Existing challenges that may hinder the final application of GSFMS together with possible solutions are also presented.     

Scalable synthesis of nanoporous boron for high efficiency ammonia electrosynthesis

Three-dimensional bicontinuous nanoporosity fabricated by dealloying can provide unique chemical properties in catalytic materials, which conventional nanoparticulate catalysts do not have. Although many solid elements in the periodic table have been fabricated as nanoporous materials by dealloying, technically important nanoporous boron has not been realized because of the poor diffusivity and high chemical stability of boron. Here we report a scalable top–down method to produce three-dimensional nanoporous boron by selectively leaching a less stable metal compound phase from rapidly solidified two-phase metal–boron alloys. The metalloid boron phase with relatively high chemical stability remains as the skeleton of a nanoporous structure. The resultant nanoporous boron with tunable pore sizes, and porosities, shows superior catalytic activities towards ammonia electrosynthesis. This work provides a new approach to fabricate nanoporous metalloids for a wide range of functional applications and brings boron, an important functional material, to the family of dealloyed nanoporous materials.     

The Confinement Effect of Angstrom‐Sized Pores in Asymmetrical Membrane Constructed by Zeolitic Imidazolate Frameworks: Partially Dehydrated Ion Transport Performance

The confinement effect in asymmetrical biological ion channels makes the state of molecules and ions differs from that in the external environment, and the mass transfer confined in the biological ion channels is in a single strand form. Herein, an asymmetrical membrane with angstrom‐sized pores is constructed by growth of ZIF‐90 membrane on the porous anodic aluminum oxide film. Due to the confinement effect of angstrom‐sized pores of ZIF‐90, ions transport through the pores of ZIF‐90 suffer from multiple dehydration‐hydration‐dehydration process in the form of a single ionic chain. Molecular dynamics simulations imply that ions inside the pores of ZIF‐90 are partially dehydrated. In alkaline condition, high rectification ratios of 237, 295, and 357 can be achieved in 10 × 10^?3 m KCl, NaCl, and LiCl electrolyte, respectively. Besides, the strong electrostatic interaction between ions and the confined ZIF‐90 pores makes the ions transport through the asymmetrical membrane suffer from an energy barrier, and the energy barrier is different with different ion species. This work helps to understand the ions transfer mechanism through angstrom‐sized pores, which can provide guidance for the design of asymmetrical membrane and boost their applications.     

Tuning Surface Structure of 3D Nanoporous Gold by Surfactant‐Free Electrochemical Potential Cycling

3D dealloyed nanoporous metals have emerged as a new class of catalysts for various chemical and electrochemical reactions. Similar to other heterogeneous catalysts, the surface atomic structure of the nanoporous metal catalysts plays a crucial role in catalytic activity and selectivity. Through surfactant‐assisted bottom‐up synthesis, the surface‐structure modification has been successfully realized in low‐dimensional particulate catalysts. However, the surface modification by top‐down dealloying has not been well explored for nanoporous metal catalysts. Here, a surfactant‐free approach to tailor the surface structure of nanoporous gold by surface relaxation via electrochemical redox cycling is reported. By controlling the scan rates, nanoporous gold with abundant {111} facets or {100} facets can be designed and fabricated with dramatically improved electrocatalysis toward the ethanol oxidation reaction.     

Hierarchical nanoporous metals as a path toward the ultimate three-dimensional functionality

Abstract

Nanoporous metals prepared via dealloying or selective leaching of solid solution alloys and compounds represent an emerging class of materials. They possess a three-dimensional (3D) structure of randomly interpenetrating ligaments/nanopores with sizes between 5 nm and several tens of micrometers, which can be tuned by varying their preparation conditions (such as dealloying time and temperature) or additional thermal coarsening. As compared to other nanostructured materials, nanoporous metals have many advantages, including their bicontinuous structure, tunable pore sizes, bulk form, good electrical conductivity, and high structural stability. Therefore, nanoporous metals represent ideal 3D materials with versatile functionality, which can be utilized in various fields. In this review, we describe the recent applications of nanoporous metals in molecular detection, catalysis, 3D graphene synthesis, hierarchical pore formation, and additive manufacturing (3D printing) together with our own achievements in these areas. Finally, we discuss possible ways of realizing the ultimate 3D functionality beyond the scope of nanoporous metals.     

Mesoporous structures confined in anodic alumina membranes

The synthesis of nanoporous membranes based on different concepts and materials is a field of active research. This review focuses on the synthesis strategies, mesophase evolution mechanisms and potential applications of mesoporous materials confined within anodic alumina membranes (AAM). Following a rapid evolution of synthetic techniques, a significant number of different mesoporous materials (e.g., silica, titania, and carbon) with highly regular structures can now be prepared within these membranes. In recent years, efforts have also been made to understand the formation mechanisms of these hierarchical mesophases. The resulting organized nanoporous membranes open up a wide range of potential applications in fields such as templating oriented nanowires and controlled separation and release of molecules. For example, while various synthesis strategies can be used for the preparation of membrane-embedded nanowires, the latter can also be obtained as isolated objects after dissolution of the alumina host matrix. The review also discusses issues such as control of structural defects or integrity of interfaces that should be addressed in future research in order to fully exploit the potential of these hierarchical mesoporous channel structures.     

3D‐Printed Biomimetic Super‐Hydrophobic Structure for Microdroplet Manipulation and Oil/Water Separation

Biomimetic functional surfaces are attracting increasing attention for various technological applications, especially the superhydrophobic surfaces inspired by plant leaves. However, the replication of the complex hierarchical microstructures is limited by the traditional fabrication techniques. In this paper, superhydrophobic micro‐scale artificial hairs with eggbeater heads inspired by Salvinia molesta leaf was fabricated by the Immersed surface accumulation three dimensional (3D) printing process. Multi‐walled carbon nanotubes were added to the photocurable resins to enhance the surface roughness and mechanical strength of the microstructures. The 3D printed eggbeater surface reveals interesting properties in terms of superhydrophobilicity and petal effect. The results show that a hydrophilic material can macroscopically behave as hydrophobic if a surface has proper microstructured features. The controllable adhesive force (from 23 μN to 55 μN) can be easily tuned with different number of eggbeater arms for potential applications such as micro hand for droplet manipulation. Furthermore, a new energy‐efficient oil/water separation solution based on our biomimetic structures was demonstrated. The results show that the 3D‐printed eggbeater structure could have numerous applications, including water droplet manipulation, 3D cell culture, micro reactor, oil spill clean‐up, and oil/water separation.     

Surface‐Mounted Metal–Organic Frameworks: Crystalline and Porous Molecular Assemblies for Fundamental Insights and Advanced Applications

Metal–organic frameworks (MOFs) are crystalline coordination polymers, assembled from inorganic nodes connected by organic linker molecules. An enormous surface area, huge compositional variety, regular structure, and favorable mechanical properties are among their outstanding properties. Monolithic MOF thin films, i.e., surface‐mounted metal–organic frameworks (SURMOFs), with high degree of structural order and adjustable defect density, can be prepared on solid substrates using layer‐by‐layer techniques. Recent studies where SURMOFs served as model systems for quantitative studies of molecular interactions in porous media, including diffusion, are reviewed. Moreover, SURMOFs are ideally suited for the incorporation of photoactive molecules as well as to study electrical transport through crystalline molecular assemblies. Recent work has demonstrated that the realization of crystalline chromophore assemblies via the SURMOF approach allows the study of fundamental aspects of exciton transport, exciton channeling, and photon upconversion at internal interfaces in organic semiconductor materials. Due to their crystalline nature, MOF materials are well suited for quantitative comparisons with theoretical results; especially, since defect densities and types can be characterized and varied in a straightforward fashion. The active role of these nanoporous films in advanced applications, like for remote‐controlled release of molecules, membranes with photoswitchable selectivity, and ion‐conductors with adjustable conductivity, are also emphasized.     

Progress in the Physisorption Characterization of Nanoporous Gas Storage Materials

Assessing the adsorption properties of nanoporous materials and determining their structural characterization is critical for progressing the use of such materials for many applications, including gas storage. Gas adsorption can be used for this characterization because it assesses a broad range of pore sizes, from micropore to mesopore. In the past 20 years, key developments have been achieved both in the knowledge of the adsorption and phase behavior of fluids in ordered nanoporous materials and in the creation and advancement of state-of-the-art approaches based on statistical mechanics, such as molecular simulation and density functional theory. Together with high-resolution experimental procedures for the adsorption of subcritical and supercritical fluids, this has led to significant advances in physical adsorption textural characterization. In this short, selective review paper, we discuss a few important and central features of the underlying adsorption mechanisms of fluids in a variety of nanoporous materials with well-defined pore structure. The significance of these features for advancing physical adsorption characterization and gas storage applications is also discussed.