Single Step Preparation of Novel Hydrophobic Composite Films for Low‐k Applications

Composite films with low dielectric constants (k) containing micro‐ and mesopores are synthesized from precursor solutions for the preparation of mesoporous silica and ethanolic suspensions of silicalite‐1 nanoparticles. The material contains silicalite‐1 nanoparticles (include nanocrystals and nanoslabs/intermediates) embedded in a randomly oriented matrix of highly porous mesoporous silica. Micropores result from the incorporated silicalite‐1 nanoparticles, while decomposition of the porogen F127 leads to additional mesopores. The porosity of the composite films increases from 9 to 60% with the increase in porogen loading, while in parallel the elastic modulus and hardness decrease. The elastic moduli of the films are in the range of 13–20 GPa. Hydrophobic surfaces of the composite films are obtained by introducing methyl triethoxysilane during the preparation of both precursor solutions, leading to the incorporation of ? CH₃ groups in the final composite films. These methyl groups are stable up to at least 500 °C. A low k value of approximately 2 is observed for films cured at 400 °C in N₂ flow, which is ideal for removing templates without decomposing methyl groups. Due to the intrinsic hydrophobicity of the material, post‐silylation is not required rendering the composite films attractive candidates for future low k materials.     

Templated Synthesis of Mesoporous Superparamagnetic Polymers

We present a novel synthetic strategy for fabricating superparamagnetic nanoparticles randomly dispersed in a mesoporous polymeric matrix. This method is based on the use of mesoporous silica materials as templates. The procedure used to obtain these mesoporous magnetic polymers consisted in: a) generating iron oxide ferrite magnetic nanoparticles (FMNP) of size ～ 7–8 nm within the pores of the silica, b) loading the porosity of the silica/FMNP composite with a polymer (Polydivinylbenzene), c) selectively removing the silica framework from the resulting silica/FMNP/polymer composite. Such magnetic porous polymeric materials exhibit large surface areas (up to 630 m² g^–1), high pore volumes (up to 0.73 cm³ g^–1) and a porosity made up of mesopores. In this way, it is possible to obtain superparamagnetic mesoporous hybrid nanocomposites that are easily manipulated by an external magnetic field and display different magnetic behaviours depending on the textural properties of the template employed.     

Porous Ti4O7 Particles with Interconnected‐Pore Structure as a High‐Efficiency Polysulfide Mediator for Lithium–Sulfur Batteries

Multifunctional Ti₄O₇ particles with interconnected‐pore structure are designed and synthesized using porous poly(styrene‐b ‐2‐vinylpyridine) particles as a template. The particles can work efficiently as a sulfur‐host material for lithium–sulfur batteries. Specifically, the well‐defined porous Ti₄O₇ particles exhibit interconnected pores in the interior and have a high‐surface area of 592 m² g^?1; this shows the advantage of mesopores for encapsulating of sulfur and provides a polar surface for chemical binding with polysulfides to suppress their dissolution. Moreover, in order to improve the conductivity of the electrode, a thin layer of carbon is coated on the Ti₄O₇ surface without destroying its porous structure. The porous Ti₄O₇ and carbon‐coated Ti₄O₇ particles show significantly improved electrochemical performances as cathode materials for Li–S batteries as compared with those of TiO₂ particles.     

Magnetically Induced Large Mesoporous Single‐Domain Monoliths Using a Mineral Liquid Crystal as a Template

In this paper, we report on how the properties of the suspensions of a lyotropic nematic mineral liquid crystal (MLC) based on V₂O₅ ribbons are exploited to synthesize single‐domain mesostructured inorganic–inorganic composites, aligned at the centimeter length scale by application of a relatively small magnetic field (0.85 T). In addition, the removal of the mineral template from the inorganic matrix leaves aligned empty channels, fingerprints of the V₂O₅ ribbons. Large colorless and birefringent mesoporous material is obtained where the orientational order of the channel director has retain the magnetic‐field alignment of its mineral template up to the centimeter length scale within the porous macroscopic silica matrix. A representative material exhibits slit‐like pores with cross‐sectional dimensions of 2 × 20 nm over 600 nm, and has a specific surface area of 207 m² g^–1.     

Mesocellular Silica Foam as an Epoxy Polymer Reinforcing Agent

A new type of mechanically improved rubbery epoxy composite is demonstrated based on the use of a mesocellular silica foam, denoted MSU‐F, as the reinforcement agent. The silica exhibits a surface area of 540 m² g^–1, a cell size of 26.5 nm (14.9 nm window size) and a pore volume of 2.2 cm³ g^–1. Most notably, the silica foam particles readily disperse in the epoxy matrix without the need for an organic surface modifier or dispersing agent. Relative to the pristine polymer, the tensile modulus, strength, strain‐at‐break, and toughness for the mesocomposites are systematically enhanced at relatively low silica loading over the range 1–9 wt %. Moreover, all of these benefits are realized without a sacrifice in thermal stability or optical transparency of the polymer. The results demonstrate that silica in mesocellular foam form can provide polymer reinforcement far beyond the level realized for non‐porous silica or silica with small mesopores at the same weight loading.     

Colloidal Suspensions of Nanometer‐Sized Mesoporous Silica

Nanometer‐sized surfactant‐templated materials are prepared in the form of stable suspensions of colloidal mesoporous silica (CMS) consisting of discrete, nonaggregated particles with dimensions smaller than 200 nm. A high‐yield synthesis procedure is reported based on a cationic surfactant and low water content that additionally enables the adjustment of the size range of the individual particles between 50 and 100 nm. Particularly, the use of the base triethanolamine (TEA) and the specific reaction conditions result in long‐lived suspensions. Dynamic light scattering reveals narrow particle size distributions in these suspensions. Smooth spherical particles with pores growing from the center to the periphery are observed by using transmission electron microscopy, suggesting a seed‐growth mechanism. The template molecules could be extracted from the nanoscale mesoporous particles via sonication in acidic media. The resulting nanoparticles give rise to type IV adsorption isotherms revealing typical mesopores and additional textural porosity. High surface areas of over 1000 m² g^–1 and large pore volumes of up to 1 mL g^–1 are obtained for these extracted samples.     

Evaporation‐Induced Coating and Self‐Assembly of Ordered Mesoporous Carbon‐Silica Composite Monoliths with Macroporous Architecture on Polyurethane Foams

A facile approach of solvent‐evaporation‐induced coating and self‐assembly is demonstrated for the mass preparation of ordered mesoporous carbon‐silica composite monoliths by using a polyether polyol‐based polyurethane (PU) foam as a sacrificial scaffold. The preparation is carried out using resol as a carbon precursor, tetraethyl orthosilicate (TEOS) as a silica source and Pluronic F127 triblock copolymer as a template. The PU foam with its macrostructure provides a large, 3D, interconnecting interface for evaporation‐induced coating of the phenolic resin‐silica block‐copolymer composites and self‐assembly of the mesostructure, and endows the composite monoliths with a diversity of macroporous architectures. Small‐angle X‐ray scattering, X‐ray diffraction and transmission electron microscopy results indicate that the obtained composite monoliths have an ordered mesostructure with 2D hexagonal symmetry (p6m) and good thermal stability. By simply changing the mass ratio of the resol to TEOS over a wide range (10–90%), a series of ordered, mesoporous composite foams with different compositions can be obtained. The composite monoliths with hierarchical macro/mesopores exhibit large pore volumes (0.3–0.8 cm³ g^?1), uniform pore sizes (4.2–9.0 nm), and surface areas (230–610 m² g^?1). A formation process for the hierarchical porous composite monoliths on the struts of the PU foam through the evaporation‐induced coating and self‐assembly method is described in detail. This simple strategy performed on commercial PU foam is a good candidate for mass production of interface‐assembly materials.     

“Brain‐Coral‐Like” Mesoporous Hollow CoS2@N‐Doped Graphitic Carbon Nanoshells as Efficient Sulfur Reservoirs for Lithium–Sulfur Batteries

Hollow carbon materials are considered promising sulfur reservoirs for lithium–sulfur batteries owing to their internal void space and porous conductive shell, providing high loading and utilization of sulfur. Since the pores in carbon materials play a critical role in the infusion of sulfur, access of the electrolyte, and the passage of lithium polysulfides (LPSs), the creation and tuning of hierarchical pore structures is strongly required to improve the electrochemical properties of sulfur/porous carbon composites, but remains a major challenge. Herein, a “brain‐coral‐like” mesoporous hollow carbon nanostructure consisting of an in situ‐grown N‐doped graphitic carbon nanoshell (NGCNs) matrix and embedded CoS₂ nanoparticles as an efficient sulfur host is presented. The rational synthetic design based on metal–organic framework chemistry furnishes unusual multiple porosity in a carbon scaffold with a macrohollow in the core and microhollows and mesopores in the shell, without the use of any surfactant or template. The CoS₂@NGCNs/S composite electrode facilitates high sulfur loading (75 wt%), strong adsorption of LPSs, efficient reaction kinetics, and stable cycle performance (903 mAh g^?1 at 0.1 C after 100 cycles), derived from the synergetic effects of the dual hollow features, chemically active CoS₂, and the conductive and mesoporous N‐doped carbon matrix.     

Preparation of Secondary Mesopores in Mesoporous Anatase–Silica Nanocomposites with Unprecedented‐High Photocatalytic Degradation Performances

In this article, a simple and mild preparation of secondary pores are reported, for the first time, with uniform and tunable sizes (in a wide range of 0.9–4.8 nm) in the walls highly connecting the primary mesochannels in 3D mesopore networks. The uniform secondary pores are obtained by using ordered 2D hexagonal mesoporous anatase TiO₂–SiO₂ nanocomposites as precursors, NaOH as an etchant via an “extracting SiO₂” approach. The strategy here adopts diluted NaOH solution, appropriate extraction temperature, and solid/liquid ratio. The photocatalytic degradation rates of Rhodamine B (0.347 min^–1), Acid Red 1 (0.0487 min^–1), microcystin–LR (1.66 min^–1) on the representative resultant nanocomposite are very high, which are 4.63, 11.7, 1.84 times that of the precursor without secondary mesopores; even up to 18.9, 8.21, 4.66 times that of P25, respectively. These results clearly demonstrate that the secondary mesopores play an overwhelming role to the increments of activities. The mesoporous anatase–silica nanocomposites with secondary mesopores present unprecedented‐high degradation activities to various organic pollutants in the mesoporous metal‐oxides‐based materials reported up to now and are considerably stable and reusable. It is believed that the fundamentals in this study will provide new insights for rational design and preparation of 3D highly interconnected mesoporous metal‐oxides‐based materials with super‐high performances.     

Synthesis of Hierarchically Porous Carbon Monoliths with Highly Ordered Microstructure and Their Application in Rechargeable Lithium Batteries with High‐Rate Capability

In this paper, we report on Li storage in hierarchically porous carbon monoliths with a relatively higher graphite‐like ordered carbon structure. Macroscopic carbon monoliths with both mesopores and macropores were successfully prepared by using meso‐/macroporous silica as a template and using mesophase pitch as a precursor. Owing to the high porosity (providing ionic transport channels) and high electronic conductivity (ca. 0.1 S cm^–1), this porous carbon monolith with a mixed conducting 3D network shows a superior high‐rate performance if used as anode material in electrochemical lithium cells. A challenge for future research as to its applicability in batteries is the lowering of the irreversible capacity.     

Transparent and Robust Silica Coatings with Dual Range Porosity for Enzyme‐Based Optical Biosensing

Hierarchically porous transparent silica coatings combine large specific surface area with enhanced pore accessibility for optical biosensing. This paper describes a versatile approach to fabricate optically transparent silica coatings with multiscale porosity. Thin films (around 1 μm in thickness) of an aqueous suspension of primary silica aggregates form a mesoporous, interconnected matrix, and sacrificial polymer particles template well‐defined, discrete macropores with high structural integrity. The total surface area achieved is around 200 m² g^?1 with mesopore sizes of 20–40 nm and macropores of 250 nm, with a total porosity of 84%. The macro/meso dual range of porosity allows enhanced biocatalyst loadings of l ‐lactate dehydrogenase for detection of lactate. The functionalized films showed a linear response within the range of interest of 1–20 × 10^?3m of lactate. These biosensing coatings therefore strongly enhance sensitivity, speed and reliability of optically based lactate detection as compared to classical thin films with monomodal mesopore structure. Particle‐based simulations and experiments reveal that both the location and connectivity of the macropores control the biosensing performance. The coatings and procedure presented here are versatile, scalable, inexpensive, and are therefore compatible with a wide range of deposition techniques suitable for industrial and health care applications.     

The Preparation and Characterization of Small Mesopores in Siloxane‐Based Materials That Use Cyclodextrins as Templates

Porous thin films containing very small closed pores (～ 20 Å) with a low dielectric constant (～ 2.0) and excellent mechanical properties have been prepared using the mixture of cyclic silsesquioxane (CSSQ) and a new porogen, heptakis(2,3,6‐tri‐O‐methyl)‐β‐cyclodextrin (tCD). The pore sizes vary from 16.3 Å to 22.2 Å when the content of tCD in the coating mixture increases to 45 wt.‐% according to positronium annihilation lifetime spectroscopy (PALS) analysis. It has also been found that the pore percolation threshold (the onset of pore interconnectivity) occurs as the ～ 50 % tCD porogen load. The dielectric constants (k = 2.4 ～ 1.9) and refractive indices of these porous thin films decreased systematically as the amount of porogen loading increased in the coating mixture. The electrical properties and mechanical properties of such porous thin films were fairly good as interlayer dielectrics.     

Reinforcement of a Rubbery Epoxy Polymer by Mesostructured Silica and Organosilica with Wormhole Framework Structures

Mesostructured forms of silica (denoted MSU‐J) and aminopropyl‐functionalized silica (denoted AP‐MSU‐J) with wormhole framework structures are effective reinforcing agents for a rubbery epoxy polymer. At loadings of 2.0–10 wt %, MSU‐J silica with an average framework pore size of 14 nm (65 °C assembly temperature) provides superior reinforcement properties in comparison to MSU‐J silica with a smaller average framework pore size of 5.3 nm (25 °C assembly temperature), even though the surface area of the larger pore mesostructure (670 m² g^?1) is substantially lower than the smaller pore mesostructure (964 m² g^?1). The introduction of 5.0 and 10 mol % aminopropyl groups in the wormhole framework walls decreases the textural properties in comparison to the pure silica analogs. AP‐MSU‐J organosilicas increase the tensile strength as well as the strain‐at‐break of the rubbery epoxy mesocomposites in comparison to MSU‐J silica as a reinforcing agent. The improved toughness provided by the aminopropyl functionalized mesostructures is attributable in part to covalent bond formation between the mesostructured silica walls and the cured epoxy matrix and to a more ductile mesostructure framework in comparison to a pure silica framework. An organosilica derivative containing 20 mol % aminopropyl groups, but lacking a mesostructured framework, provides little or no improvement in polymer tensile properties, demonstrating that an ordered porous network is essential for polymer reinforcement. In general, the reinforcement benefits provided by mesostructures with larger framework pores are superior to those provided by smaller pore derivatives, most likely because of more efficient polymer impregnation of the particle mesopores. The presence of a mesostructured form of the organosilica is essential for improving the mechanical properties of the epoxy polymer.     

Designed Multifunctional Nanocomposites for Biomedical Applications

The assembly of multifunctional nanocomposite materials is demonstrated by exploiting the molecular sieving property of SBA‐16 nanoporous silica and using it as a template material. The cages of the pore networks are used to host iron oxide magnetic nanoparticles, leaving a pore volume of 0.29 cm³ g^?1 accessible for drug storage. This iron oxide–silica nanocomposite is then functionalized with amine groups. Finally the outside of the particle is decorated with antibodies. Since the size of many protein molecules, including that of antibodies, is too large to enter the pore system of SBA‐16, the amine groups inside the pores are preserved for drug binding. This is proven using a fluorescent protein, fluorescein‐isothiocyanate‐labeled bovine serum albumin (FITC‐BSA), with the unreacted amine groups inside the pores dyed with rhodamine B isothiocyanate (RITC). The resulting nanocomposite material offers a dual‐targeting drug delivery mechanism, i.e., magnetic and antibody‐targeting, while the functionalization approach is extendable to other applications, e.g., fluorescence–magnetic dual‐imaging diagnosis.     

Synthesis of Hierarchically Porous Hydrogen Silsesquioxane Monoliths and Embedding of Metal Nanoparticles by On‐Site Reduction

A facile synthesis of a new class of reactive porous materials is reported: hierarchically porous hydrogen silsesquioxane (HSiO_1.5, HSQ) monoliths with well‐defined macropores and mesopores. The HSQ monoliths are prepared via sol‐gel accompanied by phase separation in a mild condition, and contain micrometer‐sized co‐continuous macropores and high specific surface area reaching up to 800 m² g^?1 because of the small mesopores. A total preservation of Si–H, which is always an issue of HSQ materials, is confirmed by ²⁹Si solid‐state NMR. The HSQ monolith has then been subjected to reduction of noble metal ions to their corresponding metal nanoparticles in simple aqueous solutions under an ambient condition. The nanoparticles produced in this manner are immobilized on the HSQ monolith and are characterized by X‐ray diffraction (XRD) and high angle annular dark‐field scanning transmission electron microscopy (HAADF‐STEM). Both the bare HSQ and nanoparticles‐embedded HSQ are promising as heterogeneous catalysts, exhibiting reusability and recyclability.     

Macroscopic Nanotemplating of Semiconductor Films with Hydrogen‐Bonded Lyotropic Liquid Crystals

Aqueous gel‐like lyotropic liquid crystals with extensive hydrogen bonding and nanoscale hydrophilic compartments have been used to define the growth of macroscopic nanotemplated CdS and CdTe thin films. These mesoporous semiconductor films contain a hexagonal array of 2.5 nm pores, 7 nm center‐to‐center, that extend in an aligned fashion perpendicular to the substrate. The CdS is deposited on a polypropylene substrate by a reaction between Cd(NO₃)₂ dissolved in the liquid crystal and H₂S transported via diffusion through the substrate. The CdTe is electrodeposited on indium‐tin‐oxide‐coated glass from TeO₂ and Cd(NO₃)₂, both of which are dissolved in the liquid‐crystal template. The porous nature of the CdTe films enables chemical transformations of the entire bulk of the film. As electrodeposited, the CdTe films are Te rich and, in contrast to a non‐templated film, the excess Te could be removed via a chemical treatment, proving the continuity of the pores in the nanotemplated films. These results suggest that liquid‐crystal lithography with hydrogen‐bonding amphiphiles may be a useful approach to create materials with nanoscale features over macroscopic dimensions.     

Hierarchical Porosity in Self‐Assembled Polymers: Post‐Modification of Block Copolymer–Phenolic Resin Complexes by Pyrolysis Allows the Control of Micro‐ and Mesoporosity

It is shown that self‐assembled hierarchical porosity in organic polymers can be obtained in a facile manner based on pyrolyzed block‐copolymer–phenolic resin nanocomposites and that a given starting composition can be post‐modified in a wide range from monomodal mesoporous materials to hierarchical micro‐mesoporous materials with a high density of pores and large surface area per volume unit (up to 500–600 m² g^–1). For that purpose, self‐assembled cured composites are used where phenolic resin is templated by a diblock copolymer poly(4‐vinylpyridine)‐block‐polystyrene (P4VP‐b‐PS). Mild pyrolysis conditions lead only to monomodal mesoscale porosity, as essentially only the PS block is removed (length scale of tens of nanometers), whereas during more severe conditions under prolonged isothermal pyrolysis at 420 °C the P4VP chains within the phenolic matrix are also removed, leading to additional microporosity (sub‐nanometer length scale). The porosity is analyzed using transmission electron microscopy (TEM), small‐angle X‐ray scattering, electron microscopy tomography (3D‐TEM), positron annihilation lifetime spectroscopy (PALS), and surface‐area Brunauer–Emmett–Teller (BET) measurements. Furthermore, the relative amount of micro‐ and mesopores can be tuned in situ by post modification. As controlled pyrolysis leaves phenolic hydroxyl groups at the pore walls and the thermoset resin‐based materials can be easily molded into a desired shape, it is expected that such materials could be useful for sensors, separation materials, filters, and templates for catalysis.     

Highly Conductive Organosilica Hybrid Films Prepared from a Liquid‐Crystal Perylene Bisimide Precursor

Significant anisotropic electrical conduction in organosilica films is achieved by long‐range orientation of electroactive perylene bisimide (PBI) moieties in the silica scaffold. A new PBI‐based organosilane precursor is designed with lyotropic liquid‐crystalline properties. The PBI precursor with triethoxysilylphenyl groups exhibits a hexagonal columnar phase in the presence of organic solvents. The lyotropic liquid‐crystalline behavior of the precursor enables the preparation of dip‐coated films consisting of uniaxially aligned columnar aggregates of the PBI precursor on the centimeter scale. The oriented structure is successfully fixed by in situ polycondensation, which yields insoluble, thermally stable PBI–silica hybrid films. The oriented organosilica films doped with hydrazine exhibit high electrical conductivities on the order of 10^?2 S cm^?1, which are at the highest level for organosilica materials, and are comparable to those of all‐organic PBI assemblies. Definite anisotropy of conductivities is also found for these films. The present results suggest that the induction of significant electrical properties in organic molecular assemblies is compatible with the structural stabilization by inorganic–organic hybridization.     

Synthesis of Self‐Supported Ordered Mesoporous Cobalt and Chromium Nitrides

Herein, we demonstrate an ammonia nitridation approach to synthesize self‐supported ordered mesoporous metal nitrides (CoN and CrN) from mesostructured metal oxide replicas (Co₃O₄ and Cr₂O₃), which were nanocastly prepared by using mesoporous silica SBA‐15 as a hard template. Two synthetic routes are adopted. One route is the direct nitridation of mesoporous metal oxide nanowire replicas templated from SBA‐15 to metal nitrides. By this method, highly ordered mesoporous cobalt nitrides (CoN) can be obtained by the transformation of Co₃O₄ nanowire replica under ammonia atmosphere from 275 to 350 °C, without a distinct lose of the mesostructural regularity. Treating the samples above 375 °C leads to the formation of metallic cobalt and the collapse of the mesostructure due to large volume shrinkage. The other route is to transform mesostructured metal oxides/silica composites to nitrides/silica composites at 750–1000 °C under ammonia. Ordered mesoporous CrN nanowire arrays can be obtained after the silica template removal by NaOH erosion. A slowly temperature‐program‐decrease process can reduce the influence of silica nitridation and improve the purity of final CrN product. Small‐angle XRD patterns and TEM images showed the 2‐D ordered hexagonal structure of the obtained mesoporous CoN and CrN nanowires. Wide‐angle XRD patterns, HRTEM images, and SAED patterns revealed the formation of crystallized metal nitrides. Nitrogen sorption analyses showed that the obtained materials possessed high surface areas (70–90 m² g^?1) and large pore volumes (about 0.2 cm³ g^?1).     

Single‐Source Precursors For Synthesizing Bifunctional Periodic Mesoporous Organosilicas

A new class of bifunctional periodic mesoporous organosilicas (PMOs) composed of organosilicate building blocks with two different silicon sites have been synthesized from the single‐source bifunctional organosilica precursors tris(triethoxysilylethyl)ethoxysilane and bis(triethoxysilylethyl)diethoxysilane, respectively denoted MT³‐PMO and DT²‐PMO. The synthesis of these PMOs is achieved by the co‐assembly of a triblock‐copolymer Pluronic P123 template with the bifunctional organosilica precursor under acid‐catalyzed and inorganic‐salt‐assisted conditions. After template removal through solvent extraction, the MT³‐PMO and DT²‐PMO so obtained show well‐ordered mesopores and display large pore diameters (6–7 nm) and pore volumes (0.6–0.8 cm³ g^–1) with a narrow pore‐size distribution and high surface areas (700–800 m³ g^–1).