Nonionic surfactant-templated mesoporous carbon as an electrocatalyst support for methanol oxidation

Two carbons were synthesized for use as platinum electrocatalyst supports for methanol oxidation. For both materials, furfuryl alcohol was used as the carbon precursor; however, one (CPEG) was made using poly ethylene glycol as the pore former, while the other (CSRF) was produced using Pluronic^® F127 as the soft template by organic–organic self-assembly. The CPEG and CSRF carbons were estimated from nitrogen physisorption experiments to be micro- and mesoporous, respectively. Platinum nanoparticles were deposited on each carbon as well as on Vulcan XC-72 carbon by the formic acid reduction method. The physicochemical properties of electrocatalysts were studied using X-ray diffraction (XRD), transmission electron microscopy (TEM), and energy dispersive X-ray analysis (EDX), and their electrochemical features were examined using cyclic voltammetry, chronoamperometry, and impedance spectroscopy. It was found that higher methanol oxidation peak current densities as well as lesser charge transfer resistance at electrode/electrolyte interface were obtained for Pt supported on CSRF as compared to those on Vulcan XC-72 carbon, owing to the higher specific surface area and larger total pore volume (696 m² g⁻¹ and 0.60 cm³ g⁻¹, respectively) together with superior electrical conductivity of mesoporous CSRF. On the other hand, the lower surface area and pore volume of microporous CPEG substrate confined Pt nanoparticles deposition and thus made CPEG-supported Pt an inefficient methanol oxidation electrocatalyst.     

Multi-Dimensional Molecular Self-Assembly Strategy for the Construction of Two-Dimensional Mesoporous Polydiaminopyridine and Carbon Materials

Two-dimensional (2D) mesoporous polymers, combining the advantages of organic polymers, porous materials, and 2D materials, have received great attention in adsorption, catalysis, and energy storage. However, the synthesis of 2D mesoporous polymers is not only challenged by the complex 2D structure construction, but also by the low yield and difficulty in controlling the dynamics of the assembly during the generation of mesopores. Herein, a facile multi-dimensional molecular self-assembly strategy is reported for the preparation of 2D mesoporous polydiaminopyridines (MPDAPs), which features tunable pore sizes (17–35 nm) and abundant N content up to 18.0 at%. Benefitting from the abundant N sites, 2D nanostructure, and uniform-large mesopores, the 2D MPDAPs exhibit excellent catalytic performance for the Knoevenagel condensation reaction. After calcination under N₂ atmosphere, the obtained 2D N-doped mesoporous carbon (NMCs) with large and uniform pore sizes, high surface areas, abundant N content (up to 23.1%), and a high ratio of basic N species (57.0% pyridinic N and 35.9% pyrrolic N) can show an excellent CO₂ uptake density (11.7 µmol m⁻² at 273 K), higher than previously reported porous materials.     

Enhanced dehydrogenation of nanoscale MgH2 confined by ordered mesoporous silica

Nanoscale MgH₂ was synthesized through loading di-n-butylmagnesium (MgBu₂) solution into the pores of ordered mesoporous silicas (SBA-15) with a pore diameter in a range of 5–10 nm, followed by freeze drying and hydrogenation treatment. The MgBu₂ inside the pore channels of SBA-15 decomposed into MgH₂ upon hydrogenation at 493 K under 6 MPa hydrogen. The nanoconfined MgH₂ exhibited greatly decreased desorption temperature of 540 K, a reduction of 146 K in comparison with that of commercial MgH₂, or 65 K reduction relative to that of MgH₂ obtained from MgBu₂ without confinement. Moreover, lower desorption temperature for the MgH₂ supported by SBA-15 with smaller pore diameter. The improvement on the dehydrogenation properties of MgH₂ was attributed to the nanosizing effect induced by the nanoconfinement of mesoporous silica.     

Conditions and features of matrix and bulk carbonization of the organic precursors

Comparative research of matrix and bulk carbonization of some organic precursors (sucrose, acetonitrile) in silica mesoporous materials SBA-15 and KIT-6 was conducted. X-ray diffraction, nitrogen adsorption analysis, Raman spectroscopy were used for determination of the structural-sorption characteristics of the obtained materials. It was shown that the carbon mesoporous materials CMK-8 obtained in the mesopores of KIT-6 had higher adsorption characteristics because of features of three-dimensional cubic structure, larger pore volume and framework’s wall thickness. It was established that partially graphitized spatially well-organized carbon materials were formed as a result of pyrolysis of acetonitrile in the silica matrices SBA-15 and KIT-6. It was conditioned by the absence of considerable spatial limitations for growth of graphite structures on the initial stage of the synthesis when the pores of the matrix were not filled up with the organic precursor. Product of bulk carbonization of sucrose is compact carbon microporous framework with low sorption characteristics (micropore volume is 0.09 cm³/g).     

Sol–gel synthesis and characterization of mesoporous yttria-stabilized zirconia membranes with graded pore structure

Mesoporous yttria-stabilized zirconia (YSZ) membranes can be used for liquid phase applications in harsh environments and as supports for ultra-thin dense ceramic, carbonate, or metallic membranes. This article reports on the synthesis and characterization of three-layer mesoporous ceramic membranes consisting of a mesoporous YSZ layer, a macroporous YSZ intermediate layer, and macroporous α-alumina support. The macroporous YSZ intermediate layer was coated on the alumina support using a suspension of submicron-sized YSZ powders, and the mesoporous YSZ layer was obtained by dip-coating with diluted zirconia sol doped with yttrium nitrate. The mesoporous YSZ layer has desired cubic phase structure. Crack-free mesoporous YSZ membranes could be obtained by multiple dip-coating, drying, and calcination using a dilute YSZ sol at a concentration of 0.014 M with the help of using a drying control chemical additive. The 5 times dip-coated mesoporous YSZ membranes were about 1 μm in thickness with an average pore diameter of 3 nm. The mesoporous YSZ membranes exhibited Knudsen separation factor. The characteristics of the dip-coating process for the mesoporous YSZ membranes on the macroporous YSZ support are similar to those on the macroporous alumina support.     

Synthesis of Fe-Ti-MCM-48 from silatrane precursor via sol-gel process and its hydrothermal stability

A series of bimetallic Fe–Ti-MCM-48 materials was successfully synthesized via sol–gel method using cetyltrimethylammonium bromide (CTAB) as a template and silatrane, iron (III) chloride, and titanium (IV) isopropoxide as silica, iron, and titanium sources, respectively. Scanning electron microscopy (SEM) showed the truncated octahedron morphology of Fe–Ti-MCM-48.X-ray diffraction (XRD) patterns showed well-defined, order cubic mesoporous structures. X-ray fluorescence (XRF) revealed the total metal content of the final product. UV–visible absorption spectra confirmed both iron (Fe³⁺) and cerium (Ti⁴⁺) species highly dispersed in the framework, while N₂ adsorption/desorption measurements indicated a high specific surface area. As metal content increased, the mesoporous order and surface area decreased. The synthesized Fe–Ti-MCM-48 with 0.01Fe/Si and 0.01Ti/Si ratio still retained a cubic structure after hydrothermal treatment at 100 °C for 72 h.     

A solvothermal approach for the size-, shape- and phase-controlled synthesis and properties of CuInS2

In this work, Copper Indium disulfide (CIS) nanoparticles of size ∼ 5 nm were prepared via solvothermal approach in ethanol under the nitrogen atmosphere using copper chloride, indium chloride and thiourea (Tu) as starting materials, without any assistance through organic ligands at the reaction temperature of 150 °C. The factors which might affect the morphology, structure, phase of the product during the synthesis were discussed. It was found that the products were significantly affected by the reaction time and solvent. The morphology, structure, phase constituents and optical properties of the as prepared CIS powders were characterized by X-ray diffraction (XRD), Energy dispersive Spectroscopy (EDS), scanning electron microscopy (SEM) and ultraviolet–visible (UV–Vis) spectrometry respectively. The result shows that the CIS nanoparticles can be synthesized by solvothermal method at a reaction time of 2 h and shows that when the reaction time was increased from 2 h to 48 h, CIS porous flower like nanoparticles were obtained as we increase the reaction time. We also observed that in this process, the phase selection of WZ-CIS or CH-CIS is greatly influence by solvent. We also observed that, in this process sulfur source did not influence the phase but participated in the growth of the nanoparticles.     

High-performance carbon nanotube-implanted mesoporous carbon spheres for supercapacitors with low series resistance

Carbon nanotube-implanted mesoporous carbon spheres were prepared by an easy polymerization-induced colloid aggregation method using gelatin as a soft template. Scanning electron microscopy, transmission electron microscopy and nitrogen adsorption–desorption measurements reveal that the materials are mesoporous carbon spheres, with a diameter of ∼0.5–1.0 μm, a specific surface area of 284 m²/g and average pore size of 3.9 nm. Using the carbon nanotube-implanted mesoporous carbon spheres as electrode material for supercapacitors in an aqueous electrolyte solution, a low equivalent series resistance of 0.83 Ω cm² and a maximum specific capacitance of 189 F/g with a measured power density of 8.7 kW/kg at energy density of 6.6 Wh/kg are obtained.     

Novel silica/bis(3-aminopropyl) polyethylene glycol inorganic/organic hybrids by sol–gel chemistry

Biomaterials are needed for tissue regeneration applications that provide control of mechanical properties and enhanced toughness compared to conventional bioceramics. New sol–gel hybrids were developed with interpenetrating networks of silica and bis(3-aminopropyl) polyethylene glycol. Covalent coupling between the organic and the inorganic components was used to control mechanical properties of the hybrids. The objective was to synthesise and characterise a bis(3-aminopropyl) polyethylene glycol silica hybrid material with 35 wt% organic and 65 wt% inorganic and covalent coupling between the components. A coupling agent, 3-glycidopropyltrimethoxysilane (GPTMS) was used to form the covalent links. The hypothesis was that the epoxy ring of the GPTMS would react with the polymer, leaving a polymer functionalised with siloxane groups. In a sol of hydrolysed tetraethyl orthosilicate (TEOS) the siloxanes from the GPTMS form –Si–O–Si– bonds between the functionalised polymer and the silica network. Bis(3-aminopropyl) polyethylene glycol contains two terminal amino groups available for the covalent functionalisation with the epoxy group of GPTMS. Hybrids with 35 wt% organic and 65 wt% inorganic with a ratio of GPTMS:PEG of 1:4 were proven to have an excellent balance between strain to failure (10%) and compressive strength (20 MPa). However, the functionalisation of the polymer was followed by liquid NMR as a function of the aging time and temperature and the expected reaction of nucleophilic attack of the epoxy ring by the amino group of the polymer did not happen until the water was removed from the system during drying. Increasing the amount of GPTMS decreased rate of weight loss during immersion in TRIS buffer solution.     

Mesoporous niobium oxides with tailored pore structures

Novel thermally stable and 2D mesoporous niobia phases were prepared by the evaporation induced self-assembly (EISA) with high surface areas (up to 211 m²/g). The pore size of these novel mesoporous niobium oxides was tuned in a wide range from 4.6 to 21 nm by increasing the aging temperature, aging time, and humidity of aging atmosphere. Mixtures of two nonionic surfactants, Pluronic P123 and Brij 35, were for the first time used to tune the pore structure of resultant mesoporous niobia phases which showed that the mesopore shape may be switched from cylindrical to ink-bottle. The niobia mesostructures obtained in this study were thermally stable up to 500 °C. These novel mesoporous niobium oxides with tunable pore sizes are highly promising as catalytic supports and a major component in the synthesis of porous Nb-containing mixed metal oxides, such as MoVTeNbO _x catalysts for selective (amm)oxidation of propane.     

Generation of mesoporosity in MOR zeolites synthesized under perturbation conditions

The hydrothermal synthesis of various mesoporous materials with mordenite (MOR) structures is performed under perturbation conditions involving varying-temperature crystallizations and the use of ternary organic templates, and at least three types of mesoporous materials are obtained from the same starting gel containing the ternary organic templates. The greater structural diversities of these materials are found to correlate remarkably with the second-staged crystallization temperature and time. Among these materials, the two mesoporous materials crystallized incompletely over low temperature periods are differently structural composites consisting of MOR crystallites within disordered mesoporous phases, whereas the mesoporous mordenite crystallized completely over relatively high temperature period possesses the intrinsic microporosity and hierarchical mesoporosity. TEM morphological investigations on the mesoporous mordenite crystals demonstrate the formation of intracrystalline mesopores. Furthermore, an entirely new approach to synthesize mesoporous MOR zeolites is proposed based on the pore-inducing role of MOR structure defects and the adequate perturbation towards synthesis conditions.     

Terahertz time-domain spectroscopy response of amines and amino acids intercalated smectites in far-infrared region

Layered clay minerals from the smectite group with different chemical composition and resulting layer charge (e.g. pyrophyllite, illite, hectorite and montmorillonite) were characterised for their dielectric properties in the far-infrared region using terahertz-time domain spectroscopy (THz-TDS). Samples with distinct cation exchange capacity such as hectorite and montmorillonite were modified using cation exchange reaction with alkylamines or amino acids. The presence of these species in 2D gallery was proved by X-ray diffraction and Fourier transform infrared spectroscopy. The frequency-dependent refractive index of these minerals was determined in the experimentally accessible range of 0.1–3.0 THz (3–100 cm⁻¹) using THz-TDS. Pristine samples revealed their refractive indices to be 1.82–2.15 at about 1 THz while the modified montmorillonite samples had their refractive indices changed by organic molecules used for their modification to 1.70–2.35 for amines and 1.97–2.36 for amino acids. The presence of organic substances in 2D gallery of clays was detectable despite the relatively high absorption of smectites with magnitude of 100 cm⁻¹.     

Electron transport properties of some new 4-tert-butylcalix[4]arene derivatives in thin films

Temperature dependences of electric conductivity and thermoelectric power of some recently synthesized organic compounds, 4-tert-butylcalix[4]arene derivatives, are studied. Thin-film samples (d = 0.10–0.40 μm) spin-coated from chloroform solutions onto glass substrates were used. Organic films with reproducible electron transport properties can be obtained if, after deposition, they are submitted to a heat treatment within temperature range of 295–575 K.     

Confined palladium colloids in mesoporous frameworks for carbon nanotube growth

Palladium colloidal nanoparticles with an average size of approximately 2.4 nm have been incorporated into mesoporous inorganic thin films following a multistep approach. This involves the deposition of mesoporous titania thin films with a thickness of 200 nm by spin-coating on titanium plates with a superhydrophilic titania outer layer and activation by calcination in a vacuum furnace at 573 K. Nanoparticles have been confined within the porous titania network by dip-coating noble metal suspensions onto these mesoporous thin films. Finally, the resulting nanoconfined systems were used as substrates for the growth of oriented carbon nanotubes (CNTs) using plasma-enhanced chemical vapour deposition at 923 K in order to enhance their surface area. These CNTs were tested in the hydrogenation of phenylacetylene by hydrogen in a batch reactor. The initial reaction rate observed on a CNT/TiO₂ structured catalyst was considerably higher than that on 1 wt% Pd/TiO₂ thin films.     

介孔硫化锌的合成与表征

以表面活性剂十二胺( Dodecylamine,DDA)为模板剂, 在中性条件下合成了ZnS颗粒的介孔(mesoporous)结构, 结合N2 吸附脱附曲线、透射电子显微分析(TEM)和X射线衍射(XRD)对所得样品进行了表征。结果表明,采用溶剂萃取的方法除去模板剂后得到了高纯度、立方相的ZnS 介孔结构颗粒,产品具有较高比表面积(223m2/g)和较窄孔径分布(4.9nm)。此外,借助傅立叶红外分析(FTIR)和热失重分析(TGA),讨论了有机模板剂在不同样品中的存在和作用。     

Rapid synthesis of ordered hexagonal mesoporous silica and their incorporation with Ag nanoparticles by solution plasma

Rapid synthesis of silica with ordered hexagonal mesopore arrangement was obtained using solution plasma process (SPP) by discharging the mixture of P123 triblock copolymer/TEOS in acid solution. SPP, moreover, was utilized for Ag nanoparticles (AgNPs) incorporation in silica framework as one-batch process using silver nitrate (AgNO₃) solution as precursor. The turbid silicate gel was clearly observed after discharge for 1 min and the white precipitate formed at 3 min. The mesopore with hexagonal arrangement and AgNPs were observed in mesoporous silica. Two regions of X-ray diffraction patterns (2θ < 2° and 2θ = 35–90°) corresponded to the mesoporous silica and Ag nanocrystal characteristics. Comparing with mesoporous silica prepared by a conventional sol–gel route, surface area and pore diameter of mesoporous silica prepared by solution plasma were observed to be larger. In addition, the increase in Ag loading resulted in the decrease in surface area with insignificant variation in the pore diameter of mesoporous silica. SPP could be successfully utilized not only to enhance gelation time but also to increase surface area and pore diameter of mesoporous silica.     

Novel mesoporous composites based on natural rubber and hexagonal mesoporous silica: Synthesis and characterization

The present study is the first report on the synthesis and characterization of mesoporous composites based on natural rubber (NR) and hexagonal mesoporous silica (HMS). A series of NR/HMS composites were prepared in tetrahydrofuran via an in situ sol–gel process using tetraethylorthosilicate as the silica precursor. The physicochemical properties of the composites were characterized by various techniques. The effects of the gel composition on the structural and textural properties of the NR/HMS composites were investigated. The Fourier-transform infrared spectroscopy (FTIR) and ²⁹Si magic angle spinning nuclear magnetic resonance (²⁹Si MAS NMR) results revealed that the surface silanol groups of NR/HMS composites were covered with NR molecules. The powder X-ray diffraction (XRD) and transmission electron microscopy (TEM) data indicated an expansion of the hexagonal unit cell and channel wall thickness due to the incorporation of NR molecules into the mesoporous structure. NR/HMS composites also possessed nanosized particles (∼79.4 nm) as confirmed by scanning electron microscopy (SEM) and particle size distribution analysis. From N₂ adsorption–desorption measurement, the NR/HMS composites possessed a high BET surface area, large pore volume and narrow pore size distribution. Further, they were enhanced hydrophobicity confirmed by H₂O adsorption–desorption measurement. In addition, the mechanistic pathway of the NR/HMS composite formation was proposed.     

Synthesis,structural characterization,and magnetic property of nanostructured ferrite spinel oxides (AFe2O4, A = Co,Ni and Zn)

Nanostructured ferrite spinels AFe₂O₄ (A = Co, Ni, Zn) were successfully synthesized via a co-precipitation method using oxalate salt as a precursor in an anionic surfactant system in combination with a simple calcination process. High crystallinity samples of nanoparticle spinels in a grain size range of 15–100 nm were obtained by varying the calcination temperature (300–700 °C) and time (1–5 h). Their pore sizes were controlled in a range of 3 nm up to a hundred nm by tailoring the calcination conditions. Raising the calcination temperature was found to decrease the Brunauer–Emmett–Teller (BET) surface area, and broaden the pore structure due to enhanced crystal growth and agglomeration of interparticles of spinels. Transmission electron microscopy (TEM) images of ferrite spinels calcined at 300 °C showed mesoporous structures with narrow pore size distribution, and the maximum BET surface area of CoFe₂O₄, NiFe₂O₄ and ZnFe₂O₄ were found at 201 (Co), 315 (Ni), and 273 (Zn) m² g⁻¹, respectively. The magnetic hysteresis loops of the ferrite spinels at room temperature demonstrated ferromagnetism in CoFe₂O₄, superparamagnetism–ferromagnetism in NiFe₂O₄, and paramagnetism in ZnFe₂O₄. The highest saturation magnetization (M_s), remanent magnetization (M_r), and coercivity (H_c) were obtained from high crystallinity spinels calcined at 700 °C. Nanostructured AFe₂O₄ with high surface area and mesoporosity promises potentials as novel magnetic catalysts.     

Mesoporous TiO2 thin films embedded with Au nanoparticles for the enhancement of the photocatalytic properties

Mesoporous TiO₂ thin films were prepared by hydrothermal-oxidation of titanium metal thin films, which were obtained by DC magnetron sputtering technique. Gold nanoparticles, which were prepared by reduction of HAuCl₄, were embedded into the holes of the mesoporous TiO₂ films by capillary method followed by annealing in air up to 400 °C. The size of pore of TiO₂ films is about 100 nm and that of Au nanoparticles is about 10 nm in average. The morphology of the films was analyzed by field emission scanning electron microscope (FE-SEM) and scanning probe microscopes (SPMs). Subsequently, the photocatalytic performances of the obtained nanosystems in the decomposition of methylene blue solution are discussed. The obtained results show that the dispersion of Au nanoparticles on the mesoporous TiO2 matrix will help enhancing the photocatalytic activity with respect to pure TiO₂ under visible light irradiation.