Layered Organic–Inorganic Materials: A Way towards Controllable Magnetism

The search for new materials for tailor‐made applications and new devices involves not only solid‐state chemists, physicists or materials engineers, but also the area molecular and organo‐metallic chemistry, and even biochemistry. This is especially clear in the field of organic–inorganic multifunctional materials, whose design necessitates to investigate new concepts and principles developed in these different disciplines. Here, the authors review the structure‐magnetic property relationships in layered structures, made of organic and inorganic subunits.     

Fracture of nanoporous thin-film glasses

Fracture of nanoporous thin-film glasses is a significant challenge for the integration of these mechanically fragile materials in emerging microelectronic and biological technologies. In particular, the integration of these materials has been limited by accelerated cracking rates in moist environments leading to premature failure. Here, we demonstrate how cracking is affected by aqueous solution chemistry, and reveal anomalously high crack-growth rates in hydrogen peroxide solutions frequently encountered during device processing or when in use. Kinetic mechanisms involving the transport and steric hindrance of reactive hydrogen peroxide molecules at the crack tip are proposed. Thin-film design strategies that involve energy dissipation by local plasticity in thin ductile layers on increasing the resistance to cracking of nanoporous glass layers is demonstrated. Understanding how aqueous solutions influence cracking and associated device reliability is a fundamental challenge for these promising materials to be viable candidates for new technologies.     

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.     

Silica nanocasting of lyotropic surfactant phases and organized organic matter: material science or an analytical tool?

The synthesis of porous inorganic films and materials by templating organized organic matter with nanosized structural elements is an actual field in the cross-section of inorganic chemistry, materials chemistry and surfactant science. This discussion article will review recent experiments in this area on a variety of systems and try to evaluate the outcome of both material applications and the basic understanding of self-assembly processes of organic self-organization.     

Design and deposition of vacuum-ultraviolet narrow-bandpass filters for analytical chemistry applications

Vacuum-ultraviolet (VUV) narrow-bandpass filters with central wavelengths at 177.5, 180.7, and 193 nm are necessary for analytical chemistry applications and for atomic emission spectrum separation. The emission spectra are so close that the required passbands of these filters are 1 to 2 nm with a maximum of 2 nm. We first investigated the designs based on the Fabry-Perot model with fluoride materials and second the deposition of narrow-bandpass filter components by using evaporation deposition. VUV spectral characterizations show that the filter components meet the requirements for analytical chemistry applications.     

Directed Self‐Assembly of Liquid‐Crystalline Molecular Building Blocks for Sub‐5 nm Nanopatterning

The thin‐film directed self‐assembly of molecular building blocks into oriented nanostructure arrays enables next‐generation lithography at the sub‐5 nm scale. Currently, the fabrication of inorganic arrays from molecular building blocks is restricted by the limited long‐range order and orientation of the materials, as well as suitable methodologies for creating lithographic templates at sub‐5 nm dimensions. In recent years, higher‐order liquid crystals have emerged as functional thin films for organic electronics, nanoporous membranes, and templated synthesis, which provide opportunities for their use as lithographic templates. By choosing examples from these fields, recent progress toward the design of molecular building blocks is highlighted, with an emphasis on liquid crystals, to access sub‐5 nm features, their directed self‐assembly into oriented thin films, and, importantly, the fabrication of inorganic arrays. Finally, future challenges regarding sub‐5 nm patterning with liquid crystals are discussed.     

纳米电子器件呼唤真空化学研究

纳米电子器件是微电子器件发展的下一代 ,现有微电子器件的主要材料是极纯的硅、锗和镓砷等晶体半导体。纳米电子器件有可能是以有机或有机 /无机复合晶体薄膜为主要材料 ,要求纯度更高 ,结构更完善。真空制备的清洁环境 ,有希望加工组装出纳米电子器件所要求的结构。故本文建议开展真空化学研究     

Antimicrobial and anticorrosive efficacy of inorganic nanoporous surfaces

The relationship between microbe populations that are active on engineered-product surfaces and their relationship to surface corrosion or human health is increasingly being recognized by the materials engineering community as a critically important study-direction. Microbial contamination from biofilms and germ colonies leads to costs that are reported to be extremely high every year in infection control, epidemics, corrosion loss and energy/infrastructure materials loss throughout the world. Nanostructured surfaces, particularly those that are hard-surface nanoporous (pore radii between 2 and 1000 nm), are an emerging class of surfaces that have recently been recognized as important for the prevention of microbial colony growth and biofilm formation. Such nanostructured/nanoporous surfaces, whether made with deposited nanoparticles (welded nanoparticles), or formed by ion-assisted growth on a surface have been found to display biocidal activity with varying efficacy that depends on both the microbe and the nanosurface features. The rate of mortality from common pathogens that are resident in ubiquitous bio-films when attached to common engineering surfaces made of steels, titanium and zirconium appears to be increasing. In this short review, we look at methods of manufacture of durable (i.e., highly scratch resistant) nanostructuring on commonly used engineering surfaces. The microstructures, energy dispersive X-ray analysis, X-ray photo-electron spectroscopy and other types of characterization of a few such surfaces are presented. Simple tests are required by the surface engineering community for understanding the efficacy of a surface for antimicrobial action. These are reviewed. The surface drying rate and the dynamics of the droplet spread have been proposed in the literature as quick methods that correlate well with the residual antimicrobial activity efficacy even after some surface abrasion of the nanostructured surface. A categorization of a surface against short-term antimicrobial action and long-term action is proposed in this review article. Test periods that span time-frames greater than 5 years have demonstrated a high efficacy of the nanoporous nanostructures for preventing bio-film formation. New comparative results for diamond- and graphite-containing surfaces are presented. A brief discussion on a recently developed plasma application technique for creating durable nanoporous surfaces is presented. Although considerable information is now available regarding tunable surface nanofeatures for antimicroabial efficacy, there is a need for more research activity, particularly directed toward the low cost manufacture and rapid characterization of durable (wear and chemical resistant) surfaces that display permanent antimicrobial behavior.     

溶胶-凝胶法制备有机/无机杂化材料研究进展

综述了溶胶-凝胶法制备有机／无机杂化材料的途径和产物的结构特征,并对有机／无机杂化材料进行了分类;阐述了溶胶-凝胶法制备有机／无机杂化材料的基本原理和步骤。     

Beating Thermal Coarsening in Nanoporous Materials via High-Entropy Design

Controlling the feature sizes of 3D bicontinuous nanoporous (3DNP) materials is essential for their advanced applications in catalysis, sensing, energy systems, etc., requiring high specific surface area. However, the intrinsic coarsening of nanoporous materials naturally reduces their surface energy leading to the deterioration of physical properties over time, even at ambient temperatures. A novel 3DNP material beating the universal relationship of thermal coarsening is reported via high-entropy alloy (HEA) design. In newly developed TiVNbMoTa 3DNP HEAs, the nanoporous structure is constructed by very fine nanoscale ligaments of a solid-solution phase due to enhanced phase stability by maximizing the configuration entropy and suppressed surface diffusion. The smallest size of 3DNP HEA synthesized at 873 K is about 10 nm, which is one order of magnitude smaller than that of conventional porous materials. More importantly, the yield strength of ligament in 3DNP HEA approaches its theoretical strength of G/2π of the corresponding HEA alloy even after thermal exposure. This finding signifies the key benefit of high-entropy design in nanoporous materials—exceptional stability of size-related physical properties. This high-entropy strategy should thus open new opportunities for developing ultrastable nanomaterials against its environment.     

Patterned ion beam implantation of Co ions into a SiO2 thin film via ordered nanoporous alumina masks

Spatially patterned ion beam implantation of 190 keV Co(+) ions into a SiO(2) thin film on a Si substrate has been achieved by using nanoporous anodic aluminum oxide with a pore diameter of 125 nm as a mask. The successful synthesis of periodic embedded Co regions using pattern transfer is demonstrated for the first time using cross-sectional (scanning) transmission electron microscopy (TEM) in combination with analytical TEM. Implanted Co regions are found at the correct relative lateral periodicity given by the mask and at a depth of about 120 nm.     

Layer-by-layer deposition of all-nanoparticle multilayers in confined geometries

Nanofluidic arrays containing high-aspect-ratio nanochannels were used as a platform for the deposition of all nanoparticle multilayers. LbL assembly of 6 nm titania and 15 nm silica nanoparticles resulted in conformal multilayers of uniform thickness throughout the nanochannels. These multilayers are inherently nanoporous with void volume fractions of about 0.5. Compared to unconfined assembly of the same materials on flat substrates, thinner multilayer films were observed for the case of deposition within confined channel geometries because of surface charge-induced electrostatic depletion of the depositing species. Additionally, systematic and reproducible bridging of the nanochannels occurred as multilayer assembly progressed, a phenomenon not seen in our earlier work involving polyelectrolytes. This behavior was attributed to relatively weak nanoparticle adsorption and the resulting formation of large aggregates. These results demonstrate a new route by which confined geometries can be coated and even bridged with a nanoporous multilayer without the need for calcination or other postassembly steps to introduce porosity into the conformal coating.     

Functionalization of Porous Carbon Materials with Designed Pore Architecture

Recent progress in syntheses of porous carbons with designed pore architecture has rejuvenated the field of carbon chemistry and promises to provide new advanced materials. In order to reap the full benefit of designer carbons, it is necessary to develop chemistries for functionalizing the porous carbon surfaces. This Review examines methods of functionalizing porous carbon through direct incorporation of heteroatoms in the carbon synthesis, surface oxidation and activation, halogenation, sulfonation, grafting, attachment of nanoparticles and surface coating with polymers. Methods of characterizing the functionalized carbon materials and applications that benefit from functionalized nanoporous carbons with designed architecture are also highlighted.     

Fabrication of Homogeneous Nanoporous Structure on 4H-/6H-SiC Wafer Surface via Efficient and Eco-Friendly Electrolytic Plasma-Assisted Chemical Etching

Nanoporous single-crystal silicon carbide (SiC) is widely used in various applications such as protein dialysis, as a catalyst support, and in photoanodes for photoelectrochemical water splitting. However, the fabrication of nano-structured SiC is challenging owing to its extreme chemical and mechanical stability. This study demonstrates a highly-efficient, open-circuit electrolytic plasma-assisted chemical etching (EPACE) method without aggressive fluorine-containing reactants. The EPACE method enables the nano-structuring of SiC via a plasma-enveloped microtool traversing over the target material in an electrolyte bath. Through process design, EPACE readily produces a uniform nanoporous layer on a 4H-SiC wafer in KOH aqueous solution, with adjustable pore diameters in the range 40–130 nm. Plasma diagnosis by optical emission spectrometry (OES) and surface microanalysis reveal that EPACE realizes a nanoporous structure by electrolytic plasma-assisted oxidation and subsequent thermochemical reduction of an oxide. An increase in voltage or a decrease in etch gap intensifies the plasma and improves the etching efficiency. The maximum etch rate and depth reach 540 nm min⁻¹ and 10 µm, respectively, demonstrating the significant potential of the approach as a time-saving and sustainable nanofabrication method for industrial applications. Further, the effectiveness of the fabricated SiC nanoporous structure for application in photoelectrochemical water splitting is demonstrated.     

In2O3纳米孔材料的制备及其甲醛气敏性能研究

以In(NO3)3·4.5H2O为主要原料,采用溶剂热法成功地制备出In2O3纳米孔材料.采用X射线粉末衍射、透射电子显微镜等对样品的物相和形貌进行了表征和分析,并系统研究了其气敏性能.结果表明,成功合成的六方相In2O3纳米孔材料,其孔径小于17nm,孔道形状复杂且相互连通,以该材料制成的气敏元件对甲醛有很好的气敏性能,对50×10-6甲醛的灵敏度高达23.6.     

Nanoscale porosity in polymer films: fabrication and therapeutic applications

This review focuses on current developments in the field of nanostructured bulk polymers and their application in bioengineering and therapeutic sciences. In contrast to well-established nanoscale materials, such as nanoparticles and nanofibers, bulk nanostructured polymers combine nanoscale structure in a macroscopic construct, which enables unique application of these materials. Contemporary fabrication and processing techniques capable of producing nanoporous polymer films are reviewed. Focus is placed on techniques capable of sub-100 nm features since this range approaches the size scale of biological components, such as proteins and viruses. The attributes of these techniques are compared, with an emphasis on the characteristic advantages and limitations of each method. Finally, application of these materials to biofiltration, immunoisolation, and drug delivery are reviewed.     

Preparation of Inorganic Materials Using Ionic Liquids

Conventional synthesis of inorganic materials relies heavily on water and organic solvents. Alternatively, the synthesis of inorganic materials using, or in the presence of, ionic liquids represents a burgeoning direction in materials chemistry. Use of ionic liquids in solvent extraction and organic catalysis has been extensively studied, but their use in inorganic synthesis has just begun. Ionic liquids are a family of non‐conventional molten salts that can act as templates and precursors to inorganic materials, as well as solvents. They offer many advantages, such as negligible vapor pressures, wide liquidus ranges, good thermal stability, tunable solubility for both organic and inorganic molecules, and much synthetic flexibility. In this Review, the use of ionic liquids in the preparation of several categories of inorganic and hybrid materials (i.e., metal structures, non‐metal elements, silicas, organosilicas, metal oxides, metal chalcogenides, metal salts, open‐framework structures, ionic liquid‐functionalized materials, and supported ionic liquids) is summarized. The status quo of the research field is assessed, and some future perspectives are furnished.     

Nanoporous Carbons Derived from Metal‐Organic Frameworks as Novel Matrices for Surface‐Assisted Laser Desorption/Ionization Mass Spectrometry

Surface‐assisted laser desorption/ionization mass spectrometry (SALDI‐MS) represents a powerful tool for the analysis of biomolecules, synthetic polymers, and even small organic compounds; its performances largely depend on the type of matrix materials utilized. Here, for the first time the employment of nanoporous carbons derived from metal‐organic frameworks (MOFs) as novel matrices for SALDI‐MS is demonstrated. The nanoporous carbons derived from MOFs not only circumvent the shortcomings of existing matrix materials but also demonstrate much higher efficiency of laser desorption/ionization for various compounds than any other nanoporous carbons reported so far. A new perspective for the development of matrix materials for SALDI‐MS application is therefore provided.     

Sensitive Detection of Human Insulin Using a Designed Combined Pore Approach

A unique combined pore approach to the sensitive detection of human insulin is developed. Through a systematic study to understand the impact of pore size and surface chemistry of nanoporous materials on their enrichment and purification performance, the advantages of selected porous materials are integrated to enhance detection sensitivity in a unified two‐step process. In the first purification step, a rationally designed large pore material (ca. 100 nm in diameter) is chosen to repel the interferences from nontarget molecules. In the second enrichment step, a hydrophobically modified mesoporous material with a pore size of 5 nm is selected to enrich insulin molecules. A low detection limit of 0.05 ng mL^?1 in artificial urine is achieved by this advanced approach, similar to most antibody‐based analysis protocols. This designer approach is efficient and low cost, and thus has great potential in the sensitive detection of biomolecules in complex biological systems.