Conformal Coating of Co/N‐Doped Carbon Layers into Mesoporous Silica for Highly Efficient Catalytic Dehydrogenation–Hydrogenation Tandem Reactions

To maximize the utilizing efficiency of cobalt (Co) and optimize its catalytic activity and stability, engineering of size and interfacial chemical properties, as well as controllable support are of ultimate importance. Here, the concept of coating uniform thin Co/N‐doped carbon layers into the mesopore surfaces of mesoporous silica is proposed for heterogeneous aqueous catalysis. To approach the target, a one‐step solvent‐free melting‐assisted coating process, i.e., heating a mixture of a cobalt salt, an amino acid (AA), and a mesoporous silica, is developed for the synthesis of mesoporous composites with thin Co/N‐doped carbon layers uniformly coated within mesoporous silica, high surface areas (250–630 m² g⁻¹), ordered mesopores (7.0–8.4 nm), and high water dispersibility. The strong silica/AA adhesive interactions and AA cohesive interactions direct the uniform coating process. The metal/N coordinating, carbon anchoring, and mesopore confining lead to the formation of tiny Co nanoclusters. The carbon intercalation and N coordination optimize the interfacial properties of Co for catalysis. The optimized catalyst exhibits excellent catalytic performance for tandem hydrogenation of nitrobenzene and dehydrogenation of NaBH₄ with well‐matched reaction kinetics, 100% conversion and selectivity, high turnover frequencies, up to ≈6.06 mol_nitrobenzene mol_Co⁻¹ min⁻¹, the highest over transition‐metal catalysts, and excellent stability and magnetic separability.     

Mesoporous‐Silica‐Coated Up‐Conversion Fluorescent Nanoparticles for Photodynamic Therapy

Near‐infrared (NIR)‐to‐visible up‐conversion fluorescent nanoparticles have potential to be used for photodynamic therapy (PDT) in deep tissue because NIR light can penetrate thick tissue due to weak absorption in the optical window. Here a uniform layer of mesoporous silica is coated onto NaYF₄ up‐converting nanocrystals, with a large surface area of ≈770 m² g^?1 and an average pore size of 2 nm. A photosensitizer, zinc phthalocyanine, is incorporated into the mesoporous silica. Upon excitation by a NIR laser, the nanocrystals convert NIR light to visible light, which further activates the photosensitizer to release reactive singlet oxygen to kill cancer cells. The photosensitizer encapsulated in mesoporous silica is protected from degradation in the harsh biological environment. It is demonstrated that the photosensitizers loaded into the porous silica shell of the nanoparticles are not released out of the silica while they continuously produce singlet oxygen upon excitation by a NIR laser. The nanoparticles are reusable as the photosensitizers encapsulated in the silica are removed by soaking in ethanol.     

The size modulation of hollow mesoporous carbon spheres synthesized by a simplified hard template route

Hollow mesoporous carbon spheres (HMCSs) have been prepared by a simplified replication route from a solid silica core/mesoporous silica shell aluminosilicate (SCMS-Al) template, which was synthesized by directly incorporating aluminum species into the mesoporous framework during template synthesis. The size of HMCSs can be tuned between 80 and 470 nm by simply changing the diameters of SCMS-Al. The HMCSs have uniform mesopores with a narrow pore size distribution (3.4-4.1 nm), and high surface area, (890-1150 m²/g) and total pore volumes (0.75-1.15 cm³/g). The techniques of N₂ sorption isotherms, TEM, EDX and SEM were used to characterize the as-synthesized spheres.     

Multilayer Amorphous‐Si‐B‐C‐N/γ‐Al2O3/α‐Al2O3 Membranes for Hydrogen Purification

The hydrogen and carbon monoxide separation is an important step in the hydrogen production process. If H₂ can be selectively removed from the product side during hydrogen production in membrane reactors, then it would be possible to achieve complete CO conversion in a single‐step under high temperature conditions. In the present work, the multilayer amorphous‐Si‐B‐C‐N/γ‐Al₂O₃/α‐Al₂O₃ membranes with gradient porosity have been realized and assessed with respect to the thermal stability, geometry of pore space and H₂/CO permeance. The α‐Al₂O₃ support has a bimodal pore‐size distribution of about 0.64 and 0.045 µm being macroporous and the intermediate γ‐Al₂O₃ layer—deposited from boehmite colloidal dispersion—has an average pore‐size of 8 nm being mesoporous. The results obtained by the N₂‐adsorption method indicate a decrease in the volume of micropores—0.35 vs. 0.75 cm³ g^?1—and a smaller pore size ?6.8 vs. 7.4 Å—in membranes with the intermediate mesoporous γ‐Al₂O₃ layer if compared to those without. The three times Si‐B‐C‐N coated multilayer membranes show higher H₂/CO permselectivities of about 10.5 and the H₂ permeance of about 1.05 × 10^?8 mol m^?2 s^?1 Pa^?1. If compared to the state of the art of microporous membranes, the multilayer Si‐B‐C‐N/γ‐Al₂O₃/α‐Al₂O₃ membranes are appeared to be interesting candidates for hydrogen separation because of their tunable nature and high‐temperature and high‐pressure stability.     

Synthesis and characterization of ordered and cubic mesoporous silica crystals under a moderately acidic condition

Ordered and cubic mesoporous silica materials were synthesized by using poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) triblock copolymer as template under a moderately acidic condition of 0.5 mol/l HCl solution. These mesoporous materials were characterized by Fourier transform (FT) IR spectroscopy, thermo-gravimetric analysis (TGA), X-ray diffraction (XRD) pattern, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and nitrogen adsorption–desorption measurements. The three-dimensional cage-like microporosity of the prepared mesoporous silica having ordered hexagonal mesoporous structure was evidenced by the well-defined XRD patterns combined with TEM photographs. SEM observation shows a highly regular cubic crystal structure for the prepared mesoporous silica. The size of these crystallites was maintained within the range between 4 and 6 μm, which is fairly important for the application to the stationary phase for separation. The nitrogen adsorption–desorption analysis reveals that the prepared mesoporous silica possesses a small pore diameter of 3.68 nm, a total surface area of 363.648 m²/g, a total pore volume of 0.379 cm³/g, and a pore-wall thickness of 6.63 nm. These features may lead to higher thermal and hydrothermal stability, excellent microporosity, and good connectivity. The mesoporous silica prepared in this study exhibits potential applications to catalysis, sensoring, and separation.     

Defect-sealing synthesis of vertically oriented ordered mesoporous silica membranes

Vertically oriented ordered mesoporous silica membranes have been successfully synthesized in our laboratory in the form of silica plugs filling the macron-sized straight pores of hydrophobic track-etched polycarbonate membrane support. However, these membranes have shown gaps between the plugs and support pore wall which make the membranes unfeasible for use. This paper reports on techniques of synthesis of defect-free ordered mesoporous silica membranes by filling the gaps with microporous silica. Here, the elimination of defects is achieved by filling the membrane gaps with an alkoxysilane followed by exposure to humid air to allow controlled hydrolysis and condensation resulting in the formation of microporous silica within the gaps. Molecular probing gas permeation and helium/nitrogen (or oxygen) binary separation tests, coupled with surface characterization methods, show that the final membranes contain ordered mesopores of about 2.7 nm pore diameter, running through the membrane, with gaps sealed by microporous silica having a pore size <0.55 nm.     

New mesoporous silica/carbon composites by in situ transformation of silica template in carbon/silica nanocomposite

Hard template-based fabrication of mesoporous carbon unavoidably goes through the removal process of the template to generate template-free carbon replica, including troublesome disposal of template waste often accompanied by toxic etchant, which not only increases the fabrication cost of materials but also raises serious environmental concerns. As a novel strategy to overcome such problem, a direct in situ synthesis approach using silica waste in carbon/silica nanocomposite as a silica source and cetyltrimethylammonium bromide as a porogen under basic condition is reported in this study for the generation of a new composite composed of mesoporous MCM-41 silica and hollow carbon capsule. The resultant MCM-41/carbon capsule composite offers a 3-D interconnected multimodal pore system, which discloses a wide pore range of ordered uniform mesopores (ca 2.3?nm) resulting from MCM-41 silica and disordered uniform mesopores (ca 3.8?nm) and macropores (ca 300?nm) from hollow mesoporous carbon, respectively. The composite has a high specific surface area (ca 909?m²/g) and large pore volume (ca 0.73?cm³/g). The in situ transformation approach of silica waste into valuable mesoporous silica is considered as a promising scalable route for efficient new multi-functional composites useful for a wide range of applications such as adsorption of volatile organic compounds and radioactive wastes produced in a nuclear facility.     

Core‐Cone Structured Monodispersed Mesoporous Silica Nanoparticles with Ultra‐large Cavity for Protein Delivery

A new type of monodispersed mesoporous silica nanoparticles with a core–cone structure (MSN‐CC) has been synthesized. The large cone‐shaped pores are formed by silica lamellae closely packed encircling a spherical core, showing a structure similar to the flower dahlia. MSN‐CC has a large pore size of 45 nm and a high pore volume of 2.59 cm³ g⁻¹. MSN‐CC demonstrates a high loading capacity of large proteins and successfully delivers active β‐galactosidase into cells, showing their potential as efficient nanocarriers for the cellular delivery of proteins with large molecular weights.     

Silica‐Templated Synthesis of Ordered Mesoporous Tungsten Carbide/Graphitic Carbon Composites with Nanocrystalline Walls and High Surface Areas via a Temperature‐Programmed Carburization Route

Ordered mesostructured tungsten carbide and graphitic carbon composites (WC/C) with nanocrystalline walls are fabricated for the first time by a temperature‐programmed carburization approach with phosphotungstic acid (PTA) as a precursor and mesoporous silica materials as hard templates. The mesostructure, crystal phase, and amount of deposited graphitic carbon can be conveniently tuned by controlling the silica template (SBA‐15 or KIT‐6), carburizing temperature (700–1000 °C), the PTA‐loading amount, and the carburizing atmosphere (CH₄ or a CH₄/H₂ mixture). A high level of deposited carbon is favorable for connecting and stabilizing the WC nanocrystallites to achieve high mesostructural regularity, as well as promoting the carburization reaction. Meanwhile, large pore sizes and high mesoporosity of the silica templates can promote WC‐phase formation. These novel, ordered, mesoporous WC/C nanocomposites with high surface areas (74–169 m² g^?1), large pore volumes (0.14–0.17 cm³ g^?1), narrow pore‐size distributions (centered at about 3 nm), and very good oxidation resistance (up to 750°C) have potential applications in fuel‐cell catalysts and nanodevices.     

Templated synthesis of nanosized mesoporous carbons

Mesoporous carbon materials formed by nanosized particles have been synthesized by means of a nanocasting technique based on the use of mesostructured silica materials as templates. We found that the modification of the chemical characteristics of the surfactant employed allows mesostructured silica materials with particle sizes <100 nm to be synthesised. The mesoporous carbons obtained from these silica materials retain the structural properties of the silica used as template and consequently they have a particle size in the 20-100 nm range. These carbons exhibit large BET surfaces areas (up to 1300 m² g⁻¹) and high pore volumes (up to 2.5 cm³ g⁻¹), a framework confined porosity made up of uniform mesopores (3.6 nm) and an additional textural porosity arising from the interparticle voids between the sub-micrometric particles. The main advantage of nanometer-sized mesoporous carbons in relation to the micrometer-sized carbons is that they have enhanced mass transfer rates, which is important for processes such as adsorption or catalysis.     

Preparation and electrochemical characteristics of mesoporous carbon spheres for supercapacitors

Mesoporous carbon spheres serving as electrode materials for supercapacitors were synthesized by a facile polymerization-induced colloid aggregation method using melamines as a carbon precursor and commercial colloidal silica as a silica source for hard template. After the carbonization of as-formed resins-template composites at 1000 °C and the removal of the silica template by hydrofluoric acid, the resulting mesoporous carbon spheres with a diameter size of ∼5 μm, specific surface area (up to 1280 m²/g) and uniform pore size as large as 30 nm could be obtained. Due to the enriched nitrogen content and the large pore size of the mesoporous carbon spheres affecting the surface wettability, resistance, and ion diffusion process in the pores, the mesoporous carbon spheres showed a high specific capacitance of 196 F/g in 5 mol/l H₂SO₄ electrolytes at a discharge current density of 1 A/g.     

Organic-templating approach to synthesis of nanoporous silica composite membranes (l): TPA-templating and CO2 separation

Nanoporous silica composite membranes for gas separation have been synthesized by dip-coating the tetrapropylammonium (TPA)-templating silica sols on tubular alumina supports (pore size 2.8–100 nm), followed by eliminating the template via heat-treating at 550–600°C. The NMR spectroscopy of TPABr-silica hybrid composites obtained from the templated silica sols confirmed that TPA molecules (i.e., final pores) were uniformly distributed in the silica matrix. The average pore size and the specific surface area of an unsupported membrane prepared by firing the TPABr (6 wt%)-silica hybrid composite at 600°C were below 18 Å and 830 m²/g, respectively. Any defects such as cracks or pin-holes on the surface of amorphous silica composite membranes were not observed. The CO₂/N₂ separation factor of their composite membranes varied from 3.2 to 10.3 and their gas permeability from 10^–8 to 10^–9 mol/m² · s · Pa depending on the microstructure of aluminar supports.     

Facile Synthesis of Yolk–Shell‐Structured Triple‐Hybridized Periodic Mesoporous Organosilica Nanoparticles for Biomedicine

The synthesis of mesoporous nanoparticles with controllable structure and organic groups is important for their applications. In this work, yolk–shell‐structured periodic mesoporous organosilica (PMO) nanoparticles simultaneously incorporated with ethane‐, thioether‐, and benzene‐bridged moieties are successfully synthesized. The preparation of the triple‐hybridized PMOs is via a cetyltrimethylammonium bromide‐directed sol–gel process using mixed bridged silsesquioxanes as precursors and a following hydrothermal treatment. The yolk–shell‐structured triple‐hybridized PMO nanoparticles have large surface area (320 m² g^–1), ordered mesochannels (2.5 nm), large pore volume (0.59 cm³ g^–1), uniform and controllable diameter (88–380 nm), core size (22–110 nm), and shell thickness (13–45 nm). In vitro cytotoxicity, hemolysis assay, and histological studies demonstrate that the yolk–shell‐structured triple‐hybridized PMO nanoparticles have excellent biocompatibility. Moreover, the organic groups in the triple‐hybridized PMOs endow them with an ability for covalent connection of near‐infrared fluorescence dyes, a high hydrophobic drug loading capacity, and a glutathione‐responsive drug release property, which make them promising candidates for applications in bioimaging and drug delivery.     

One-pot synthesis of thermally stable gold@mesoporous silica core-shell nanospheres with catalytic activity

A facile one-pot method has been developed to synthesize uniform gold@mesoporous silica nanospheres (Au@MSNs), which have a well-defined core-shell structure with ordered mesoporous silica as a shell. The resulting Au@MSNs have a high surface area (～521 m2/g) and uniform pore size (～2.5 nm) for the mesoporous silica shell. The diameter of the gold core can be regulated by adjusting the amount of HAuCl₄. The catalytic performance of the Au@MSNs was investigated using the reduction of 4-nitrophenol as a model reaction. The mesopores of the silica shells provide direct access for the reactant molecules to diffuse and subsequently interact with the gold cores. In addition, the Au@MSNs display the great advantage of sintering-resistance to 950 °C because the mesoporous silica shells inhibit aggregation or deformation of the gold cores. The high thermal stability enables the Au@MSNs to be employed in high-temperature catalytic reactions.      

High Efficiency Poly(acrylonitrile) Electrospun Nanofiber Membranes for Airborne Nanomaterials Filtration

The potential of poly(acrylonitrile) electrospun membranes with tuneable pore size and fiber distributions were investigated for airborne fine‐particle filtration for the first time. The impact of solution concentration on final membrane properties are evaluated for the purpose of designing separation materials with higher separation efficiency. The properties of fibers and membranes are investigated systematically: the average pore distribution, as characterized by capillary flow porometry, and thermo‐mechanical properties of the mats are found to be dependent on fiber diameter and on specific electrospinning conditions. Filtration efficiency and pressure drop are calculated from measurement of penetration through the membranes using potassium chloride (KCl) aerosol particles ranging from 300 nm to 12 μm diameter. The PAN membranes exhibited separation efficiencies in the range of 73.8–99.78% and a typical quality factor 0.0224 (1 Pa^?1) for 12 wt% PAN with nanofibers having a diameter of 858 nm. Concerning air flow rate, the quality factor and filtration efficiency of the electrospun membranes at higher face velocity are much more stable than for commercial membranes. The results suggest that the structure of electrospun membranes is the best for air filtration in terms of filtration stability at high air flow rate.

     

Ordered Mesoporous Carbons

Ordered mesoporous carbons have recently been synthesized using ordered mesoporous silica templates. The synthesis procedure involves infiltration of the pores of the template with appropriate carbon precursor, its carbonization, and subsequent template removal. The template needs to exhibit three‐dimensional pore structure in order to be suitable for the ordered mesoporous carbon synthesis, otherwise disordered microporous carbon is formed. MCM‐48, SBA‐1, and SBA‐15 silicas were successfully used to synthesize carbons with cubic or hexagonal frameworks, narrow mesopore size distributions, high nitrogen Brunauer–Emmett–Teller (BET) specific surface areas (up to 1800 m² g^–1), and large pore volumes. Ordered mesoporous carbons are promising in many applications, including adsorption of large molecules, chromatography, and manufacturing of electrochemical double‐layer capacitors.     

Modulating Ion Diffusivity and Electrode Conductivity of Carbon Nanotube@Mesoporous Carbon Fibers for High Performance Aluminum–Selenium Batteries

Selenium (Se)‐based rechargeable aluminum batteries (RABs), known as aluminum–selenium (Al–Se) batteries, are an appealing new battery design that holds great promise for addressing the low‐capacity problem of current RAB technology. However, their applications are hindered by mediocre high‐rate capacity (≈100 mAh g^?1 at 0.5 A g^?1) and insufficient cycling life (50 cycles). Herein, the synthesis of mesoporous carbon fibers (MCFs) by coating mesoporous carbon with short‐length mesopores and tunable mesopore sizes (2.7 to 8.9 nm) coaxially on carbon nanotubes (CNT) is reported. When compositing MCFs with Se for Al–Se batteries, a positive correlation between mesopore size and electrolyte ion diffusivity is observed, however when pore size is increased to 8.9 nm, large voids are created at the interface of CNT core and mesoporous carbon shell, leading to decreased electrode conductivity. The trade‐off between ion diffusivity and interfacial connectivity/conductivity determines MCF with pore size of 7.1 nm as the best host material for Al–Se batteries. The composite cathode delivers high specific capacities (366 and 230 mAh g^?1 at 0.5 and 1 A g^?1), good rate performance, and excellent cycling stability (152 mAh g^?1 after 500 cycles at 2 A g^?1), superior over previously reported Se cathodes and other cathodes for RABs.     

Degradation‐Restructuring Induced Anisotropic Epitaxial Growth for Fabrication of Asymmetric Diblock and Triblock Mesoporous Nanocomposites

A novel degradation‐restructuring induced anisotropic epitaxial growth strategy is demonstrated for the synthesis of uniform 1D diblock and triblock silica mesoporous asymmetric nanorods with controllable rod length (50 nm to 2 µm) and very high surface area of 1200 m² g^?1. The asymmetric diblock mesoporous silica nanocomposites are composed of a 1D mesoporous organosilicate nanorod with highly ordered hexagonal mesostructure, and a closely connected dense SiO₂ nanosphere located only on one side of the nanorods. Furthermore, the triblock mesoporous silica nanocomposites constituted by a cubic mesostructured nanocube, a nanosphere with radial mesopores, and a hexagonal mesostructured nanorod can also be fabricated with the anisotropic growth of mesopores. Owing to the ultrahigh surface area, unique 1D mesochannels, and functionality asymmetry, the obtained match‐like asymmetric Au‐NR@SiO₂&EPMO (EPMO = ethane bridged periodic mesoporous organosilica) mesoporous nanorods can be used as an ideal nanocarrier for the near‐infrared photothermal triggered controllable releasing of drug molecules.     

The morphology and size of nanostructured Au in Au/SBA-15 affected by preparation conditions

Template-free mesoporous silica SBA-15 was reacted with TPTAC to generate positively charged functional groups PTA⁺ on the pore surface. Through ion exchange, a uniform distribution of anionic metal complexes on the intrachannel surface of host silica was achieved. In this study, ethanol and water were used as solvent for HAuCl₄ precursor solutions impregnated on SBA-15 mesoporous silica. The solvent used can affect the size and location of the resulting nanoparticles. Large Au nanoparticles (15–43 nm) were found on the as-prepared Au/SBA-15 as observed by PXRD, XAS, UV–vis and TEM. This may have originated through Si–OH reduction of chloroaurate complexes generated in the aqueous solution of HAuCl₄, and such particles were not present when ethanolic solution was used. After NaBH₄ and H₂ reduction, the average size of Au nanoparticles, which was incorporated into the channels of SBA-15, was found to be limited to ≤  7 nm.     

Controlling the Pore Size of Mesoporous Carbon Thin Films through Thermal and Solvent Annealing

Herein an approach to controlling the pore size of mesoporous carbon thin films from metal‐free polyacrylonitrile‐containing block copolymers is described. A high‐molecular‐weight poly(acrylonitrile‐block‐methyl methacrylate) (PAN‐b‐PMMA) is synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization. The authors systematically investigate the self‐assembly behavior of PAN‐b‐PMMA thin films during thermal and solvent annealing, as well as the pore size of mesoporous carbon thin films after pyrolysis. The as‐spin‐coated PAN‐b‐PMMA is microphase‐separated into uniformly spaced globular nanostructures, and these globular nanostructures evolve into various morphologies after thermal or solvent annealing. Surprisingly, through thermal annealing and subsequent pyrolysis of PAN‐b‐PMMA into mesoporous carbon thin films, the pore size and center‐to‐center spacing increase significantly with thermal annealing temperature, different from most block copolymers. In addition, the choice of solvent in solvent annealing strongly influences the block copolymer nanostructure and the pore size of mesoporous carbon thin films. The discoveries herein provide a simple strategy to control the pore size of mesoporous carbon thin films by tuning thermal or solvent annealing conditions, instead of synthesizing a series of block copolymers of various molecular weights and compositions.