Development of a simple aqueous solution based chemical method for synthesis of mesoporous γ-alumina powders with disordered pore structure

A technically simple chemical method for the synthesis of mesoporous γ-alumina has been reported. Mesoporous γ-aluminas with different pore structure and surface area were synthesized by using aluminium nitrate as a source of aluminum. Supramolecular liquid crystalline phase of acid soap template synthesized via reaction of different carboxylic acids (stearic acid, oliec acid and lactic acid) with excess of triethanolamine (TEA) acts as a structure directing agent and water was used as solvent. Precursors were calcined at 550 °C in air for 2 h to obtain mesoporous alumina powders. Synthesized γ-alumina powders were characterized by using thermogravimetric analysis, X-ray diffraction, high resolution transmission electron microscope and N₂ adsorption–desorption surface area and pore size analyzer. Pore size and ordering of pores were influenced by the chain length of carboxylic acids. Surface area of synthesized alumina powders varied from 214 to 376 m²/g and average pore diameter from 3.3 to 6.5 nm depending upon the chain length of the carboxylic acid.     

Preparation and characterization of nanocrystalline and mesoporous strontium titanate thin films at room temperature

The low temperature perovskite-type strontium titanate (SrTiO₃) thin films and powders with nanocrystalline and mesoporous structure were prepared by a straightforward particulate sol–gel route. The prepared sol had a narrow particle size distribution with hydrodynamic diameter of about 17 nm. X-ray diffraction (XRD) revealed that the synthesized powders had a perovskite-SrTiO₃ structure with preferable orientation growth along the (1 0 0) direction. TEM images showed that the average crystallite size of the powders annealed in the range 300–800°C was around 8 nm. FE-SEM analysis and AFM images revealed that the deposited thin films had mesoporous and nanocrystalline structure with the average grain size of 25 nm at 600°C. Based on Brunauer–Emmett–Taylor (BET) analysis, the synthesized powders showed mesoporous structure with BET surface area in the range 92–75 m²/g at 400–600°C. One of the smallest crystallite sizes and one of the highest surface areas reported in the literature were obtained, which can be used in many applications, such as photocatalysts.     

The effect of glucose on the formation of the nanocrystalline transition alumina phases

Series of alumina powders were synthesized starting from sodium aluminate solution prepared from Bayer liquor. The neutralisation of sodium aluminate solution was performed with the use of sulphuric acid. The influence of glucose as a non-surfactant additive on the structure of alumina powders at moderate pH was investigated. The results show that the properties of the powders are influenced by the initial pH value of the solution, as well as the duration of the neutralisation step. High pHs lead to the formation of powders with heterogeneous structure with bayerite as a dominant phase, which during calcinations converts to η-alumina with high surface area. Addition of glucose to the starting aluminate solution leads to the formation of nanocrystalline boehmite with estimated average crystallite size less than 3 nm and high surface area (above 300 m²/g). After calcinations, boehmite transforms to γ-alumina. The results have shown that during the heat treatment, structural transformations proceeded simultaneously with the significant changes in the textural properties of the obtained mesoporous γ- and η-alumina powders.     

Synthesis of hard mesoporous macro-spheres with silicate and aluminosilicate compositions

This study reports the synthesis mechanism and the influence of different variables in the preparation of mesoporous macro-spheres having silicate and aluminosilicate compositions. The spheres possess sizes in the range 200–1000 μm with a narrow particle size distribution and a significant mechanical resistance (hard macro-spheres). In addition, the presence of a highly regular mesoporosity (around 3 nm) and of a high surface area (normally about 1000 m²/g) make these materials as very interesting self-supported adsorbents or catalysts that could be directly applied without no binder, which is a great advantage compared to materials in powder form. The synthesis of the hard mesoporous spheres takes place in a biphasic system, generated by the use of tetrabutoxysilane as silica source, which is reacted with water and NaOH leading to the formation of small primary particles which initially do not present any mesoscopic ordering. However, after about 5 h of synthesis, the presence of cetyltrimethylammonium chloride, as surfactant, gives rise to the detection of a mesostructured silica material. Subsequently, after 9 h of synthesis the small mesostructured particles, with sizes in the micrometer range, acquire a spherical shape. Finally, the reorganization and fusion of these particles cause the formation of the silica macrospheres, with a particle size of several hundreds of micrometers. When the synthesis is carried in the presence of an aluminium source, the aluminosilicate materials so obtained exhibit smaller surface area and pore volume and greater particle size than the pure silica ones.     

A comparative study on the thermal stability,textural, and structural properties of mesostructured γ-Al2O3 granules in the presence of La,Sn, and B additives

Mesoporous γ-alumina is widely used as catalyst support in various catalytic reactions of industrial interest. However, due to the instability of γ-alumina at elevated temperatures, many efforts have been reported to inhibit the α-alumina phase transition through doping with suitable metalloids, as well as transition, post-transition, or rare-earth elements. In the present study, undoped and La-, Sn-, and B-doped alumina granules were synthesized via sol-gel/oil drop method with the aim to clarify the role of the additives and their content on the porous structure as well as on the chemical, structural, and microstructural behavior of γ-alumina. XRD and DTA/TG results demonstrated that thermal stability of transition aluminas increases more than 100 °C by 3 wt% lanthanum and tin doping; however, boron doping seems to have only negligible effect on the thermal stability. On the other hand, based on nitrogen adsorption-desorption analysis, tin and boron-doped aluminas showed a higher surface area at 750 °C (between 214.74 m²/g to 245.97 m²/g) but higher loss in the surface area after calcination at 1200 °C (between 25.45 m²/g to 8.57 m²/g). On the contrary, the 3 wt% La-doped alumina sample, with a relatively high surface area at 750 °C (227.17 m²/g), exhibited the highest surface area after calcination at 1200 °C (53.07 m²/g). ²⁷Al MAS NMR and HRTEM studies indicated that the presence of 3 wt% La in alumina structure leads to thermal and mesoporous structure stability up to 1200 °C by inhibiting oxygen lattice restructuring. These results provide a comparative perspective of La, B, and Sn additives' behavior in γ-alumina.     

Control of mesoporous properties of carbon cryogels prepared from wattle tannin and furfural

Wattle tannin–furfural (TFu) carbon cryogels are synthesized by sol–gel polycondensation of wattle tannin with furfural by using sodium hydroxide (NaOH) as a catalyst, dried by freeze-drying technique and then pyrolyzed under inert atmosphere, respectively. The amounts of wattle tannin (T), furfural (Fu), NaOH (C) and distilled water (W) are changed for preparing the mesoporous TFu carbon cryogels. The mole ratio of tannin to catalyst T/C plays a crucial role for the synthesis of TFu organic and carbon cryogels. The results suggest that the T/C ratio should be above 0.25 but <1.0 to prepare the mesoporous and homogeneous cryogels. Although TFu carbon cryogels have the broad mesopore size distribution, the mesoporous structure is controllable by the synthesis conditions. The carbon cryogels possess the mesopore volume less than 0.56 cm³/g and the BET surface area less than 600 m²/g. Moreover, the ratio of catalyst to water C/W can be used to prepare the homogeneous and mesoporous carbon cryogels, and to control the mesopore radius of carbon cryogels in the range of 1.6–9.6 nm.     

Synthesis of mesoporous alumina by using a cost-effective template

A salt of stearic acid, i.e., magnesium stearate [(C₁₇H₃₅COO)₂Mg], can be used as a chemical template for the formation of mesoporous alumina, and is a less expensive reagent than stearic acid. Mesoporous alumina prepared using this cost-effective surfactant shows similar pore properties with respect to pore size (3.5 nm) and surface area (above 300 m²Vg) to that prepared using stearic acid. In addition, textural porosity, arising from non-crystalline intraaggregate voids and spaces, was effectively removed by the addition of magnesium nitrate. The entire transformation from aluminum hydroxide to active alumina was performed at 550 °C, and the crystallinity of the product was confirmed by powder XRD analysis.²⁷A1 MAS NMR result shows the phase of mesoporous alumina is the γ-alumina form.     

Novel MgO–SnO<Subscript>2</Subscript> Solid Superbase as a High-Efficiency Catalyst for One-Pot Solvent-Free Synthesis of Polyfunctionalized 4<Emphasis Type="Italic">H</Emphasis>-pyran Derivatives

Abstract  

We report for the first time the hydrothermal synthesis of MgO–SnO₂ solid superbase using P123 as template. The basicity of the materials was determined by two approaches of Hammett indicators method and temperature-programmed desorption using CO₂ as adsorbate (CO₂-TPD). It was found that Mg/Sn molar ratio has an effect on MgO–SnO₂ basicity, and superbasicity was observed only at Mg/Sn molar ratio of 1. With variation of Mg/Sn molar ratio, superbase strength (H _-) was in the 26.5–33.0 range, showing superbasic value up to 0.939 mmol/g. The structure and texture of the as-prepared materials were studied by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and N₂ physio-adsorption methods. We detected particles of spherical morphology having diameter of ca. 150 nm. N₂ adsorption–desorption results suggested that the materials are of mesoporous structure, having specific surface area of 115.2 m²/g and average pore diameter of 6 nm. The superbase was found to exhibit excellent catalytic activity towards the one-pot synthesis of polyfunctionalized 4H-pyrans through the condensation of aldehydes, malononitrile, and an active methylene compound. Its excellent catalytic efficiency is related to its superbasicity of the MgO–SnO₂. The results provide a new route for the design and preparation of composite oxide superbases. Furthermore, the solid superbases will facilitate a strategy for high-efficiency synthesis of polyfunctionalized 4H-pyrans.     

Synthesis of mesoporous alumina with CO2 expanded carbonation and its catalytic oxidation of cyclohexanone

A CO₂ expanded carbonation technique is proposed for direct synthesis of alumina powders that does not require structure directing substances or templates. Mesoporous amorphous flower-like alumina was synthesized at relatively low volume expansions (lower ethanol to water volume ratio), whereas mesoporous crystalline honey-comb-like alumina was synthesized at high volume expansions. The alumina powders exhibited high surface area and pore size with small crystallite sizes. The alumina structures were stable from 400 to 800 °C. Experimental tests showed that the alumina powders could catalytically convert cyclohexanone to ɛ-caprolactone efficiently. The use of the calcined catalysts (at 400 and 800 °C; flower-like alumina) at equal ethanol to water volume ratio avoids the usual and inevitable hydrolysis of ɛ-caprolactone to ɛ-hydroxyhexanoic acid. The catalyst was recyclable and stable for up to five reaction cycles.     

Synthesis of composite materials of carbon nanofibres and ceramic monoliths with uniform and tuneable nanofibre layer thickness

Composite materials consisting of ceramic monoliths and carbon nanofibres (CNFs) have been synthesized by catalytic growth of CNFs on the γ-alumina washcoating layer covering the walls of a ceramic monolith. The composites possess a relatively uniform mesoporous layer of CNFs of relatively small diameter. The thin alumina washcoating (ca. 0.1 μm) prevents the CNFs from being trapped inside the alumina pores and hence the CNFs grow freely throughout the washcoating layer to form a uniform layer of CNFs that completely covers the surface of the monolith walls. The growth temperature is found to control the thickness of the CNF layer (2-4 μm), the growth rate of the nanofibres, and the mechanical strength of the resulting CNF-monolith composite. At ideal conditions, a complete adhesion of the CNF layer and higher mechanical strength than the original cordierite monolith can be obtained. The CNF layer has an average pore size of 17 nm with absence of microporosity which renders these monoliths promising candidates for the use as catalyst supports, especially for liquid phase reactions. The CNFs have small diameters (5-30 nm) due to the high dispersion of Ni particles in the growth catalyst and the CNFs exhibit an unusual branched structure.     

Using modified Pechini method to synthesize α-Al2O3 nanoparticles of high surface area

A modified Pechini method for the preparation of a high surface area α-alumina is proposed. The synthesis of these nanoparticles was carried out using a polymer as a chelating agent. The polymer was prepared from citric acid and acrylic acid by the melt blending method. The resulting α-alumina (98.16%) after calcination at 900 °C consisted of cylindrical nanoparticles of 100–200 nm in length and <25 nm in diameter with a relatively high surface area (18 m² g^?1).     

Periodic Mesoporous Organosilica Nanorice

A periodic mesoporous organosilica (PMO) with nanorice morphology was successfully synthesized by a template assisted sol–gel method using a chain-type precursor. The PMO is composed of D and T sites in the ratio 1:2. The obtained mesoporous nanorice has a surface area of 753 m² g⁻¹, one-dimensional channels, and a narrow pore size distribution centered at 4.3 nm. The nanorice particles have a length of ca. 600 nm and width of ca. 200 nm.     

Trypsin immobilization on mesoporous silica with or without thiol functionalization

The effects of pore size, structure, and surface functionalization of mesoporous silica on the catalytic activity of the supported enzyme, trypsin, were investigated. For this purpose, SBA-15 with 1-dimensional pore arrangement and cubic Ia3d mesoporous silica with 3-dimensional pores were prepared and tested as a support. Materials with varying pore diameters in the range 5–10 nm were synthesized using a non-ionic block copolymer by controlling the synthesis temperature. Thiol-group was introduced to the porous materials via siloxypropane tethering either by post synthesis grafting or by direct synthesis. These materials were characterized using XRD, SEM, TEM, N₂ adsorption, and elemental analysis. Trypsin-supported on the solids prepared was active and stable for hydrolysis of N-α-benzoyl-DL-arginine-4-nitroanilide (BAPNA). Without applying thiol-functionalization, cubic Ia3d mesoporous silica with ca. 5.4 nm average pore diameter was found to be superior to SBA-15 for trypsin immobilization and showed a better catalytic performance. However, enzyme immobilized on the 5% thiol-functionalized SBA-15 prepared by directly synthesis was found to be the most promising and was also found recyclable.     

Controllable synthesis of mesoporous alumina with large surface area for high and fast fluoride removal

Gamma phase of mesoporous alumina (MA) with large surface area was successfully synthesized by a facile hydrothermal method followed by thermal treatment for fluoride removal. The as-synthesized MA nanoparticles with average size of 20 nm–150 nm have ordered wormhole-like mesoporous structure. The pore size is 5 nm with a narrow distribution, and the specific surface area reaches 357 m² g⁻¹ while the bulk density is 0.45 cm³ g⁻¹. Glucose as a small-molecule template plays an important role on the morphology, surface area and pore diameter of the MA. As an ionic adsorbent for fluoride removal, the maximum adsorption capacity of MA is 8.25 mg g⁻¹, and the remove efficiency reaches 90% in several minutes at pH of 3. The Langmuir equilibrium model is found to be suitable for describing the fluoride sorption on MA and the adsorption behavior follows the pseudo-second-order equation well with a correlation coefficient larger than 0.99. The larger surface area and relatively narrow pore size of MA are believed to be responsible for improving the adsorption efficiency for fluoride in aqueous solution.     

Effect of pH in preparation and properties of mesoporous sieve from montmorillonite

Mesoporous material with dual mesoporous size distribution had been synthesized with montmorillonite as precursor. The materials exhibited two kinds of mesopores: one is mesopore in interlayers of montmorillonite with mean sizes of 2.9 nm, the other is mesopore out of layers of montmorillonite with mean sizes of 3.9 nm. With the increasing of pH values (8.0–11.0), the specific surface area and pore volume of two kinds of mesopores changed regularly. The samples were characterized by XRD, TEM and Nitrogen adsorption/desorption isotherms. The results indicated that higher pH benefits the synthesis of mesoporous montmorillonite with smaller pore and the TOT of montmorillonite had been present as porous wall.     

Hydrophobic inorganic membranes for water/gas separation

Macroporous or mesoporous hydrophobic inorganic membranes are prepared by a simple one-pot synthesis method coupling the sol–gel process with fluorinated silanes as precursors and the use of alumina powders as fillers. The porosity of these intrinsically hydrophobic membranes can be tuned by the particle size distribution of the dispersed alumina powder. These membranes developed for water/gas separation applications are characterized in term of gas permeance and water breakthrough pressure. A value of air permeance equal to 1800 L min⁻¹ bar⁻¹ m⁻² associated with a water breakthrough pressure larger than 10 bar are measured for the effective sample.     

Synthesis of macroporous ZrO2–Al2O3 mixed oxides with mesoporous walls, using polystyrene spheres as template

Macroporous ZrO₂–Al₂O₃ mixed oxides with mesoporous walls were synthesized. The three-dimensional interconnected macroporous structures, of inorganic zirconia–alumina mixed oxides containing different alumina compositions (25, 50, 100 wt%), were prepared by sol–gel method from inorganic precursors and using polystyrene microspheres with diameters of 685 and 1520 nm as templates. The final porous arrays with controllable pore size in the submicrometer range could be obtained by calcination of the organic template. The structural characteristics are discussed. The physicochemical characterization of the samples was carried out by N₂ physisorption (S_BET), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The shrinkage of pore diameter was approximately 35%, and the wall thickness of inorganic framework varied between 135 and 154 nm. The specific surface areas, of the samples, were between 123 and 287 m²/g, obtaining the largest surface area with the highest alumina contents and the smallest templates.     

Preparation of high pure α-Al2O3 nanoparticles at low temperatures using Pechini method

A Pechini process was successfully used to synthesize alpha-alumina (98.95% mass fraction) at relatively low calcination temperature (925 °C). The synthesis of these nanoparticles was carried out using a polymer prepared from citric acid and ethylene glycol by the melt blending method. This polymer worked as a chelating agent for aluminum cations. The final products were produced after a dual-stages thermal treatment. The resulting α-alumina consisted of nanoparticles of 8–16 nm in diameters with a surface area (～8 m² g^?1). The mass fraction of α-alumina was dependent on the concentration of aluminum salt and polymer precursor's solutions, while the surface area of the final product was dependent on the mass fraction of θ-alumina.     

Alumina Over-coating on Pd Nanoparticle Catalysts by Atomic Layer Deposition: Enhanced Stability and Reactivity

Abstract  

ALD Alumina was utilized as a protective layer to inhibit the sintering of supported nano-sized ALD Pd catalysts in the methanol decomposition reaction carried out at elevated temperatures. The protective ALD alumina layers were synthesized on Pd nanoparticles (1–2 nm) supported on high surface area alumina substrates. Up to a certain over-coat thickness, the alumina protective layers preserved or even slightly enhanced the catalytic activity and prevented sintering of the Pd nanoparticles up to 500 °C.     

Catanionic-surfactant templated synthesis of organized mesoporous γ-alumina by double hydrolysis method

Organized mesoporous γ-alumina samples were prepared by cationic-anionic double hydrolysis (CADH) method using the mixture of cationic and anionic surfactants as template. The intermediate aluminum oxyhydroxides were characterized by XRD, SEM, TEM, FT-IR and TG. Boehmite could easily form under the given synthetic conditions, where an increase in the crystallization temperature favored the formation of well-crystallized boehmite. After the calcination, organized mesoporous γ-Al₂O₃ was obtained by dehydroxylation between AlOOH octahedron structures. After being characterized by N₂ adsorption–desorption, the obtained γ-Al₂O₃ was of excellent textural properties, i.e., large pore volume (0.79 cm³ g⁻¹), and large pore size (12.1 nm) with narrow pore size distribution which can be used as good candidates for catalyst support in the processing of heavy petroleum. In this modified CADH method, the mixture of cationic and anionic surfactants plays a key role in the formation of relatively large mesopore.