Ein neuer Weg zu kolloidalen,UV‐lumineszenten Silicium‐Nanopartikeln

For the last decade, there has been a growing interest in silicon nanoparticles smaller than 5 nm in diameter because of their luminescence properties. Here, we present a new approach for the fabrication of such particles. Starting with larger nanoparticles from industrial production, a combined treatment with anhydrous hydrogen fluoride and 1‐alkenes leads to alkylated Silicon nanoparticles in the size range necessary for luminescence. In nonpolar solvents, these particles are colloids, which do not precipitate for a long time. During one‐pot reactions, the size decrease of the crystalline silicon core is mediated by the intermediary presence of H₂O₂. In this paper, we describe the reaction conditions of this new path to colloidal silicon nanoparticles and discuss their structure as seen in TEM images, their surface chemistry and luminescence properties.     

Easy synthesis of iron doped ordered mesoporous carbon with tunable pore sizes

Precise control of the pore sizes for porous carbon materials is of importance to study the confinement effect of metal particles because the pore size in nanosize range will decide the physical and chemical properties of the metal nanoparticles.In this paper,we report a new approach for the synthesis of iron doped ordered mesoporous carbon materials with adjustable pore size using Fe-SBA-15 as hard template and boric acid as the pore expanding reagent.The pore size can be precisely adjusted by a step of 0.4 nm in the range of 3-6 nm.The carbonization temperature can be lowered to 773 K due to the catalytic role of the doped iron.The present approach is suitable for facile synthesis of metal imbedded porous carbon materials with tunable pore sizes.     

Rigid nanoscopic containers for highly dispersed, stable metal and bimetal nanoparticles with both size and site control

We demonstrate a novel strategy for the preparation of mesoporous silica-supported, highly dispersed, stable metal and bimetal nanoparticles with both size and site control. The supporting mesoporous silica, functionalized by polyaminoamine (PAMAM) dendrimers, is prepared by repeated Michael addition with methyl acrylates (MA) and amidation reaction with ethylenediamine (EDA), by using aminopropyl-functionalized mesoporous silica as the starting material. The encapsulation of metal nanoparticles within the dendrimer-propagated mesoporous silica is achieved by the chemical reduction of metal-salt-impregnated dendrimer-mesoporous silica by using aqueous hydrazine. The site control of the metal or bimetal nanoparticles is accomplished by the localization of inter- or intradendrimeric nanoparticles within the mesoporous silica tunnels. The size of the encapsulated nanoparticles is controlled by their confinement to the nanocavity of the dendrimer and the mesopore. For Cu and Pd, particles locate at the lining of mesoporous tunnels, and have diameters of less than 2.0 nm. For Pd/Pt, particles locate at the middle of mesoporous tunnels and have diameters in the range of 2.0-4.2 nm. The Pd and Pd/Pt nanoparticles are very stable in air, whereas the Cu nanoparticles are stable only in an inert atmosphere.     

Meso- to Macro-Porous Oxides as Semiconductor Gas Sensors

The present article reviews our latest studies directed to improving gas sensing properties of semiconductor metal oxides, SnO₂ and TiO₂, by controlling their porous structure in the range of nano- to micro-meter size. Thermally stable mesoporous oxide powders and submicron-size porous thick films were fabricated by a templating method employing supramolecular surfactants or polymethylmethacrylate microspheres and also by a sol–gel process in a polyethylene glycol matrix. Advantages of these methods in improving the sensing properties are overviewed and then remaining problems are discussed.     

Mesoporous PtCu Alloy Nanoparticles with Tunable Compositions and Particles Sizes Using Diblock Copolymer Micelle Templates

A simple, scalable route for the generation of mesoporous Rh particles by chemical reduction on self-assembled block-copolymer micelle templates was reported recently (Nat. Commun. 2017 , 8, 15581). Here, this concept is extended to generate mesoporous PtCu alloy nanoparticles through the same approach. The PtCu alloy particles possess high-surface-area nanoporous architectures and good chemical stability for applications in catalysis. Both the composition and diameter of the bimetallic PtCu nanoparticles can be controlled by adjusting the amount of precursor in the reaction, which affects the electrochemical properties of the material. The combination of the mesoporous structure with the synergistic bimetallic electronic effects of PtCu gives rise to enhanced activity for the catalytic oxidation of methanol compared with commercial Pt black.     

Advances in the Interfacial Assembly of Mesoporous Silica on Magnetite Particles

Interfacing magnetic particles with ordered mesoporous materials is an effective direction for the development of functional porous composite materials with rationally designed core–shell structures. Owing to the combined properties of magnetic nanoparticles and mesoporous silica (high surface area, large pore volume, porosity, and biocompatibility), core–shell magnetic mesoporous silica materials have generated tremendous interest in various disciplines, including chemistry, materials, bioengineering, and biomedicine. Interfacial assembly strategies enable the rational construction of magnetic mesoporous silica materials with well‐defined core–shell structure, morphology, pore parameters, and surface wettability, which can decisively influence their physical and chemical properties and thus improve their application performance. This Minireview summarizes recent progress in the synthesis of core–shell magnetic mesoporous silica and the adjustment of key parameters, including pore size, morphology, and pore orientation.     

Molecularly imprinted polymeric shell coated monodisperse‐porous silica microspheres as a stationary phase for microfluidic boronate affinity chromatography

Molecular imprinting of cis‐diol functionalized agents via boronate affinity interaction has been usually performed using nanoparticles as a support which cannot be utilized as a stationary phase in continuous microcolumn applications. In this study, monodisperse‐porous, spherical silica particles in the micron‐size range, with bimodal pore diameter distribution were selected as a new support for the synthesis of a molecularly imprinted boronate affinity sorbent, using a cis‐diol functionalized agent as the template. A specific surface area of 158 m²/g was achieved with the imprinted sorbent by using monodisperse‐porous silica microspheres containing both mesoporous and macroporous compartments as the support. High porosity originating from the macroporous compartment and sufficiently high particle size provided good column permeability to the imprinted sorbent in microcolumn applications. The mesoporous compartment provided a large surface area for the parking of imprinted molecules while the macroporous compartment facilitated the intraparticular diffusion of imprinted target within the microsphere interior. A microfluidic boronate affinity system was first constructed by using molecularly imprinted polymeric shell coated monodisperse‐porous silica microspheres as a stationary phase. The synthetic route for the imprinting process, the reversible adsorption/ desorption behavior of selected target and the selectivity of imprinted sorbent in both batch and microfluidic boronate affinity chromatography systems are reported.     

Polyurethane‐mesoporous silica gas separation membranes

The concept of mixed matrix membrane comprising dispersed inorganic fillers into a polymer media has revealed appealing to tune the gas separation performance. In this work, the membranes were prepared by incorporation of mesoporous silica into polyurethane (PU). Mesoporous silica particles with different pore size and structures, MCM‐41, cubic MCM‐48 and SBA‐16, were synthesized by templating method and functionalized with 3‐aminopropyltriethoxysilane (APTES). High porosity and aminated surface of the mesoporous silica enhance the adhesion of the particles to the PU matrix. The SEM and FTIR results showed strong interactions between the particles and the PU chains. Moreover, the thermal stability of the hybrid PUs improved compared to the pure polymer. Gas transport properties of the membranes were measured for pure CO₂, CH₄, O₂, and N₂ gases at 10 bar and 25°C. The results showed that the gas permeabilities enhanced with increasing in the loading of modified mesoporous silica particles. High porosity and amine‐functionalized particles render opportunities to enhance the gas diffusivity and solubility through the membranes. The enhanced gas transport properties of the mixed matrix membranes reveal the advantages of mesoporous silica to improve the gas permeability (CO₂ permeability up to ~70) without scarifying the gas selectivity (α(CO₂/N₂)~ 30 for 5 wt% SBA‐16 content).     

The formation of palladium nanocomposite catalysts on the porous silicon used as anodes of fuel cells

Palladium nanoparticles on the porous silicon were synthesized by radiation-chemical reduction in the solution of reversed micelles. The Pd nanoparticles obtained are electron deficient. The porosity, the type of conductivity, the silicon matrix pore geometry, and precursor parameters influence the size, the shape and the charge state of palladium catalysts. The mechanism of H₂ and HCOOH electrooxidation on porous silica in the presence of Pd+/Pd redox pair is proposed.     

Silicone composites containing stabilized silver clusters or nanoparticles

Silver nanoparticles are of high importance due to their electrical, magnetic, and optical properties, as well as catalytic and biocidal activity that are superior to the bulk silver and other metals. To prepare certain devices, generally, silver is incorporated into a matrix either as preformed or in situ‐generated particles. Silver nanoparticles were generated in situ into a silicone matrix formed by cohydrolysis of the mixture of silanes, each of them having a certain role: dimethyldiethoxysilane (DMDES) as a precursor for highly flexible polydimethylsiloxane, methyltriethoxysilane (MTES) as a cross‐linker highly compatible with polydimethylsiloxane, and 3‐aminopropyltriethoxysilane as a stabilizer, since it can readily complex to silver atoms through its amine functionality. Dimethylformamide (DMF) was used as a solvent for the silver nitrate and reducing agent. The samples were investigated both in sol state and as aged coating films deposited on glass substrate. The complexation of the silver and the matrix formation were emphasized by FTIR. The size of the formed silicone particles encapsulating silver was estimated by dynamic light scattering (DLS) (about 100 nm) in sol and by AFM in film (about 90 nm). The formation of the clusters or nanoparticles depending on the ratio between the reducing and complexing agents was evidenced by UV–Vis absorption spectra. Thus, it would create conditions to stop and isolate clusters at the desired size by precise control of the experimental conditions. The composites could be used alone as antibacterial‐coating materials but also, porous silica having incorporated silver clusters with potential applicability in catalysis may result after their calcination. Copyright © 2010 John Wiley & Sons, Ltd.     

Effects of Co-Solvent Nature and Acid Concentration in the Size and Morphology of Wrinkled Mesoporous Silica Nanoparticles for Drug Delivery Applications

Hierarchically porous materials, such as wrinkled mesoporous silica (WMS), have gained interest in the last couple of decades, because of their wide range of applications in fields such as nanomedicine, energy, and catalysis. The mechanism of formation of these nanostructures is not fully understood, despite various groups reporting very comprehensive studies. Furthermore, achieving particle diameters of 100 nm or less has proven difficult. In this study, the effects on particle size, pore size, and particle morphology of several co-solvents were evaluated. Additionally, varying concentrations of acid during synthesis affected the particle sizes, yielding particles smaller than 100 nm. The morphology and physical properties of the nanoparticles were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and dynamic light scattering (DLS). Homogeneous and spherical WMS, with the desired radial wrinkle morphology and particle sizes smaller than 100 nm, were obtained. The effect of the nature of the co-solvents and the concentration of acid are explained within the frame of previously reported mechanisms of formation, to further elucidate this intricate process.     

Textural manipulation of mesoporous materials for hosting of metallic nanocatalysts

The preparation and stabilization of nanoparticles are becoming very crucial issues in the field of so-called "nanocatalysis". Recent developments in supramolecular self-assembled porous materials have opened a new way to get nanoparticles hosted in the channels of such materials. In this paper, a new approach towards monodisperse and thermally stable metal nanoparticles by confining them in ordered mesoporous materials is presented, and three aspects are illustrated. Firstly, the recent progress in the functional control of mesoporous materials will be briefly introduced, and the rational tuning of the textures, pore size, and pore length is demonstrated by controlling supramolecular self-assembly behavior. A novel synthesis of short-pore mesoporous materials is emphasized for their easy mass transfer in both biomolecule absorption and the facile assembly of metal nanocomposites within their pore channels. In the second part, the different routes for encapsulating monodisperse nanoparticles inside channels of porous materials are discussed, which mainly includes the ion-exchange/conventional incipient wetness impregnation, in situ encapsulation routes, organometallic methodologies, and surface functionalization schemes. A facile in situ autoreduction route is highlighted to get monodisperse metal nanoparticles with tunable sizes inside the channels of mesoporous silica. Finally, confinement of mesoporous materials is demonstrated to improve the thermal stability of monodisperse metal nanoparticles catalysts and a special emphasis will be focused on the stabilization of the metal nanoparticles with a low Tammann temperature. Several catalytic reactions concerning the catalysis of nanoparticles will be presented. These uniform nanochannels, which confine monodisperse and stable metal nanoparticles catalysts, are of great importance in the exploration of size-dependent catalytic chemistry and further understanding the nature of catalytic reactions.     

酸浸蚀Al-Si合金制备锂离子电池高性能多孔硅负极材料

本文首次提出利用酸浸蚀Si-Al（含Al 80%）合金粉末的方法制备多孔硅材料. 分析表明制得的多孔硅材料为晶体,并具有由纳米颗粒结集成的海绵状多孔结构,其粒径约20 μm,比表面102.7 m²·g^-1. 多孔硅电极按多孔硅:导电碳:粘结剂 = 1:1:1（by mass）涂成. 在添加15%氟化碳酸乙烯酯（FEC）的1 mol·L^-1 LiPF₆/EC + DMC（1:1,by volume）电解液,在100 mA·g^-1电流密度充放电,多孔硅电极的首次放电比容量2072 mAh·g^-1 Si. 经237次充放电循环后,其放电容量仍可保持在1431 mAh·g^-1 Si,显示了相当高的充放电稳定性. 这归因于其海绵状多孔结构有足够的微空间以承受充电过程中硅的急剧膨胀. 硅微粒的纳米尺寸有利于锂在Li-Si合金中的扩散. 纳米硅微粒可牢固地联成一整体,不易因膨胀、收缩而粉化断裂. 这种构筑多孔硅负极材料的新方法操作简便、成本低廉,有着很好的应用前景.     

Low-Temperature Plasma-Chemical Deposition of Nanocomposite Antifriction Molybdenum Disulfide (Filler)–Silicon Oxide (Matrix) Coatings

It was demonstrated experimentally that the spatial separation of two processes of chemical vapor deposition, one of which provides synthesis of filler (MoS₂) nanoparticles and the other yields the matrix (SiO₂) of the nanocomposite coating, performed ina common reactor, enables an independent control over two process rates and makes it possible to widely vary the composition of the films deposited in this way. The deposition was performed in a double-zone vertical tubular quartz reactor. Molybdenum disulfide particles were produced by pyrolysis of aerosols of ammonium thiomolybdate solutions in dimethylformamide in the upper zone of the reactor, and the plasma-chemical deposition of a nanocomposite coating occurred in the lower zone into which MoS₂ nanoparticles were transported by the gas flow and tetraethoxysilane was delivered. It was shown that the nanocomposite coatings composed of molybdenum disulfide (filler) and silicon oxide (matrix) possess improve the antifriction properties as compared with the matrix (SiO₂ layers), these properties being determined by the relative amounts of MoS₂ nanoparticles in the layer and by their average size.     

Synthesis and characterization of stimuli‐responsive porous/hollow nanoparticles by self‐assembly of chitosan‐based graft copolymers and application in drug release

In this research, stimuli‐responsive porous/hollow nanoparticles were prepared by the self‐assembly method. First, chitosan‐graft‐poly(N‐isopropylacrylamide) (CS‐g‐PNIPAAm) copolymers were synthesized through polymerization of N‐isopropylacrylamide (NIPAAm) monomer in the presence of chitosan (CS) solution using ceric ammounium nitrate as the initiator. Then, the CS‐g‐PNIPAAm copolymers were dissolved in the acetic acid aqueous solution and heated to 40 °C to induce their self‐assembly. After CS‐g‐PNIPAAm assembled to form micelles, a cross‐linking agent was used to reinforce the structure to form nanoparticles. The molecular weight of grafted PNIPAAm on CS chains was changed to investigate its effect on the structure, morphology, thermo‐, and pH‐responsive properties of the nanoparticles. TEM images showed that a porous or hollow structure in the interior of nanoparticles was developed, depending on the medium temperature. The synthesized nanoparticles carried positive charges on the surface and exhibited stimuli‐responsive properties, and their mean diameter thus could be manipulated by changing the pH value and temperature of the environment. The nanoparticles showed a continuous release of the encapsulated doxycycline hyclate up to 10 days during an in vitro release experiment. These porous/hollow particles with environmentally sensitive properties are expected to be used in hydrophilic drug delivery system. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2377–2387, 2010     

Copper nanoparticles incorporated on a mesoporous carbon nitride,an excellent catalyst in the Huisgen 1,3‐dipolar cycloaddition and N‐arylation of N‐heterocycles

Cu nanoparticles with average particles size around 10 nm were incorporated on the surface of a mesoporous carbon nitride support. The XRD and N₂ adsorption isotherms show that it maintains a hexagonal mesoporous structure with a high surface area (600.03 m² g^?1). The embedded Cu nanoparticles exhibit extremely high catalytic performance in two different kinds of organic reactions. The Huisgen 1,3‐dipolar cycloaddition and N‐arylation of N‐heterocycles were all accomplished.     

A Robust Mesoporous Al2O3-Based Nanocomposite Catalyst for Abundant NOx Storage with Rational Design of Pt and Ba Species

The nanostructural design of heterogeneous catalysts has often been demanded for assessing synergetic effects, which should be developed further by using high-surface-area porous metal oxide supports. However, such opportunities have been undermined by the poor stability of ordered mesoporous structures. Herein, rational design is demonstrated to obtain nanocomposite catalysts showing improved NO_x storage properties owing to the presence of Ba species over a well-designed mesoporous alumina (Al₂O₃) support. It is found that Ba species are impregnated successfully only after the stabilization of the mesoporous structure by full crystallization of Al₂O₃ frameworks to the γ-phase, with the formation of Pt nanoparticles coinciding with complete removal of organic components. All the insights during this synthetic procedure are essential for designing high-performance catalysts to purify and recover NO_x molecules, and are applied for designing a variety of cutting-edge mesoporous nanocomposite catalysts.     

Gemini Surfactants Templated Mesoporous Silica Microparticles: from Solid to Hollow Mesoporous Spheres

We synthesized a series of mesoporous silica microparticles (MSs) using cationic gemini surfactants C_14–2‐n (n = 2, 6, 10, 14) as templates. The porous structures and pore size of these MSs can be tuned by varying the length of alkyl chain in gemini surfactant templates. These MSs showed effective doxorubicin (DOX) loading and a pH‐responsive drug release characteristics. These results indicate that the MSs, especially the hollow mesoporous silica nanoparticles, have great potential for biomedical applications.     

One-step conversion of Mg2Si into hydrogen-terminated porous silicon nanostructures

A simple, fast, and low-cost acid-treatment method is proposed for the conversion of magnesium silicide (Mg₂Si) into hydrogen-terminated mesoporous silicon nanostructured material (M-pSi). The formation of porosity in M-pSi is attributed to the generation of gas species during the acid treatment, providing a large number of active sites. The adsorption and the photocatalytic performances of M-pSi toward the degradation of methyl orange are investigated. It is found that the mesoporous Si material exhibits an unusual and high photocatalytic ability toward the dye degradation in acidic conditions, outperforming the performance of commercially available Si nanoparticles. This unusual photocatalytic performance is related to the presence of hydrogen-terminated silicon nanostructures with a high surface area of 203 m²/g. The article proposes an alternative way of producing porous silicon materials with enhanced photocatalytic activity.     

Highly transparent silica monoliths embedded with high concentration oxide nanoparticles

Silica monoliths embedded with high concentration of γ-Fe₂O₃ or TiO₂ nanoparticles were prepared by a sol–gel procedure designed according to the inherent properties of oxide colloids. In the first step, highly dispersible oxide nanoparticles were produced using an in situ modification sol–gel strategy. Then, these particles were re-dispersed in silicon alkoxide-containing solution to form a stable colloidal solution. The hydrolysis and condensation reactions of alkoxide were catalyzed by an organic base (morpholine). Due to the large molecule size of morpholine, the electric double layer on the surface of colloidal particles was not compressed by the ionized morpholine molecules. The colloidal solution thus remained stable during the gelation process. Through this procedure, oxide nanoparticles could be immobilized homogeneously in the pores of a silica matrix, forming highly transparent and crack-free monoliths.