Effect of the thermal and hydrothermal treatment on textural properties of Zr-MCM-41 mesoporous molecular sieve

Zr-containing mesoporous molecular sieves were synthesized by hydrothermal method using cetyltrimethyl ammonium bromide as a template and sodium silicate and zirconium sulfate as raw materials. The structure and morphology of the synthesized samples were characterized via various physicochemical methods, including X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, solid state nuclear magnetic resonance (²⁹Si MAS-NMR) techniques, thermal gravimetric-differential scanning calorimeter (TG-DSC) and N₂ physical adsorption, respectively. The effect of the different initial ZrO₂:SiO₂ molar ratio, the different thermal treatment temperature and the different hydrothermal treatment time on textural property was investigated. The experimental results reveal that the as synthesized samples possess a typical mesoporous structure of MCM-41. On the other hand, the specific surface area and pore volume of the synthesized Zr-MCM-41 mesoporous molecular sieve decrease with the increase of the amount of zirconium incorporated in the starting material, the rise of thermal treatment temperature and the prolonging of hydrothermal treatment time, the mesoporous ordering becomes poor. Also, when the molar ratio of ZrO₂:SiO₂ in the starting material is 0.1, the mesoporous structure of the Zr-MCM-41 mesoporous molecular sieve still retains after calcination at 750 °C for 3 h or hydrothermal treatment at 100 °C for 6 d, and have specific surface areas of 423.9 and 563.9 m²/g, respectively.     

Effect of the Si/Ce molar ratio on the textural properties of rare earth element cerium incorporated mesoporous molecular sieves obtained room temperature

Rare earth Ce-incorporated MCM-41 mesoporous molecular sieves (CeMCM-41) were synthesized via a direct and nonhydrothermal method at room temperature from sodium silicate and ammonium cerium (IV) nitrate as raw materials. Cetyltrimethyl ammonium bromide (CTAB) was used as a template. The resultant samples were characterized by means of powder X-ray diffraction (XRD), transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR), diffuse reflectance ultraviolet–visible spectroscopy (UV–vis) and N₂ physical adsorption, respectively. The effect of the Si/Ce molar ratio on the crystalline structure and textural properties of CeMCM-41 was also investigated. The experimental results show that ordered CeMCM-41 mesoporous molecular sieves were successfully synthesized at room temperature and the resultant mesoporous materials have specific surface areas in the range of 594–1369 m²/g and average pore sizes in the range of ca. 2.5–2.8 nm. It has been found that the structural properties are strongly related to the amounts of cerium incorporation. When the cerium content increased in the samples, the intensity of the peak (1 0 0) was gradually reduced, and the surface area and structural regularity were diminished.     

Comparative studies of Zr-based MCM-41 and MCM-48 mesoporous molecular sieves: Synthesis and physicochemical properties

Two surfactant-templated synthetic routes are developed for the preparation of new types of mesoporous molecular sieves, Zr-MCM-41 and Zr-MCM-48, using different Si sources but keeping the same zirconium precursor (zirconium-n-propoxide). When fumed silica was used as Si precursor, a Zr-MCM-48 material of cubic structure was formed with a surface area of 654.8 m²/g and an unimodal pore diameter distribution. It shows low stability: after calcination at 600 °C, the ordered structure was transformed into a relatively disordered worm-like mesostructure with many defects and silanol groups. The use of tetraethyl orthosilicate as Si source led to the formation of a Zr-MCM-41 mesoporous solid, which had good thermal stability and a highly ordered hexagonal arrangement, with a surface area 677.9 m²/g and an uniform pore diameter distribution. Fourier transform infrared (FT-IR) characterization and ²⁹Si NMR analysis confirm that zirconium ions indeed incorporated into the framework of the solid. The in situ FT-IR spectroscopy of pyridine adsorption reveals that both, Lewis and Brönsted acid sites, were formed on the surface of these mesoporous materials. The strength and number of the Brönsted acid sites of the Zr-MCM-48 solid were greater than those of the Zr-MCM-41, due to a lower degree of condensation reaction during the synthesis that led to more structural defects in the framework and more silanol groups stretching from the solid surface.     

Stability and textural properties of cobalt incorporated MCM-48 mesoporous molecular sieve

Transition metal cobalt incorporated MCM-48 mesoporous molecular sieves (CoMCM-48) with different Co contents were synthesized hydrothermally at 120 °C for 24 h by directly adding fluoride ions to the initial gel. The resulting materials were characterized by means of XRD, TEM, FT-IR, UV-vis, TPR and N₂ physical adsorption, respectively. The effect of various factors, such as the Si/Co molar ratio, calcination temperature and hydrothermal treatment time, on the crystalline structure and textural properties of CoMCM-48 was investigated in detail. The results show that the CoMCM-48 mesoporous materials with high specific surface area were successfully synthesized. A small amount substitution of Co for Si in MCM-48 did not significantly change the textural properties while the higher cobalt incorporated leads to decrease of the surface area and deterioration of structural regularity. Furthermore, the resulting CoMCM-48 still retained the cubic mesoporous framework even after calcination at 800 °C for 4 h or hydrothermal treatment at 100 °C for 24 h.     

Synthesis and catalytic-isomerization performance of Al-MCM-41 mesoporous sieves]

Al-MCM-41 mesoporous sieves were synthesized at the ambient temperature by using TEOS as silica source, Al(NO)3 x 9H2O as Al source, and cetyl trimethylammonium bromide as templating agent. The framework and surface structures of the synthesized samples were characterized by XRD, N2-adsorption/desorption isotherms, FTIR and SEM etc. The results showed that the samples were the typical Al-MCM-41 mesoporous sieves with the higher ordered-degree and specific surface area (up to 816 m2 x g(-1)) and the narrower pore diameter distribution. Controlling the highest value of Al/Si with the range of 0.06-0.13, and taking temperature programmed calcination would be beneficial to the formation of the highly ordered Al-MCM-41 mesoporous sieves. The evaluating results showed that the synthesized Al-MCM-41 molecular sieves have a higher catalytic activity for isomerization of endo-tetrahydrodicyclo-pentadiene (endo-TCD) into exo-tetrahydrodicyclo-pentadiene (exo-TCD) and adamantane.     

Fabrication and application of highly ordered mesoporous Co3O4, NiO, and their metals

Highly ordered mesoporous Co₃O₄, NiO, and their metals were synthesized by nanocasting method using there corresponding mesoporous SBA-15 silica as a template. The obtained porous metal oxides have high surface areas, large pore volume, and a narrow pore size distribution. The N₂-adsorption data for mesoporous metal oxides have provided the BET area of 257.7 m² g⁻¹ and the total pore volume of 0.46 cm³ g⁻¹. The mesoporous metals were employed as a catalyst in the synthesis of (S)-3-pyrrolidinol from chiral (S)-4-chloro-3-hydroxybutyronitrile, and a high yield to (S)-3-pyrrolidinol-salt was obtained on the mesoporous Co metal catalyst.     

Catalytic activity of Fe, Co and Fe-Co-MCM-41 for the growth of carbon nanotubes by chemical vapour deposition method

Iron, cobalt and a mixture of iron and cobalt incorporated mesoporous MCM-41 molecular sieves were synthesised by hydrothermal method and used to investigate the rules governing their nanotube producing activity. The catalysts were characterised by XRD and N₂ sorption studies. The effect of the catalysts has been investigated for the production of carbon nanotubes at an optimised temperature 750 °C with flow rate of N₂ and C₂H₂ is 140 and 60 ml/min, respectively for a reaction time 10 min. Fe-Co-MCM-41 catalyst was selective for carbon nanotubes with low amount of amorphous carbon with increase in single-walled carbon nanotubes (SWNTs) yield at 750 °C. Formation of nanotubes was studied using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. Transmission electron microscope and Raman spectrum was used to follow the quality and nature of carbon nanotubes formed and the graphitic layers and disordered band, which shows the clear evidence for the formation of SWNTs, respectively. The result propose that the diameter of the nanotubes in the range of 0.78-1.35 nm. Using our optimised conditions for this system, Fe-Co-MCM-41 showed the best results for selective SWNTs with high yield when compared with Fe-MCM-41 and Co-MCM-41.     

Stability and characterization of mesoporous molecular sieve using natural clay as a raw material obtained by microwave irradiation

Mesoporous molecular sieve was synthesized via microwave irradiation method, and using natural clay, sodium silicate and aluminum chloride as raw materials and cetyl trimethyl ammonium bromide (CTAB) as a template agent under alkaline condition. The samples were characterized by various analytic and spectroscopic tools such as XRD, FT-IR, TEM, TG-DSC and N₂ physical adsorption, respectively. The results show that the synthesized sample has typical mesoporous structure and exhibits good mesoporous ordering. On the other hand, the as synthesized sample after calcination at 550 °C for 10 h has a surface area of 576.0 m²/g and an average pore size of 4.83 nm. Furthermore, the synthesized mesoporous molecular sieve still exhibits good mesoporous ordering after calcination at 750 °C for 3 h or hydrothermal treatment at 100 °C for 10 days.     

Highly selective epoxidation of styrene over mesoporous Au-Ti-SBA-15 via photocatalysis process: Synthesis, characterization, and catalytic application

Highly ordered Au-Ti-SBA-15 mesoporous molecular sieves were successfully synthesized by one-pot hydrothermal synthesis in acid medium, and were characterized by XRD, UV-vis, SEM, element-mapping, HRTEM, N₂ adsorption, XPS, ²⁹Si MAS NMR, NH₃-TPD and FT-IR. The as-prepared Au-Ti-SBA-15 samples were possessed of highly ordered mesostructures with larger pore diameter, pore volume and uniform mesopore size distribution. In the oxidation of styrene with H₂O₂ as the oxidant over Au-Ti-SBA-15 catalyst under photo-irradiation, reaction parameters, such as molar ratio of H₂O₂ to styrene, reaction time, solvent, the amount of catalyst, catalyst species, and the amount of 3% NaOH, were conditioned at length. As a result, highly selective epoxidation of styrene over catalyst was carried out perfectly for 10 min with high TOF of 4.75 × 10³ min⁻¹.     

Synthesis of multi-wall carbon nanotubes by the pyrolysis of ethanol on Fe/MCM-41 mesoporous molecular sieves

Ordered hexagonal arrangement MCM-41 mesoporous molecular sieves were synthesized by the traditional hydrothermal method, and Fe-loaded MCM-41 mesoporous molecular sieves (Fe/MCM-41) were prepared by the wet impregnation method. Their mesoporous structures were testified by X-ray diffraction (XRD) and the N₂ physical adsorption technique. Carbon nanotubes (CNTs) were synthesized by the chemical vapor deposition (CVD) method via the pyrolysis of ethanol at atmospheric pressure using Fe/MCM-41 as a catalytic template. The effect of different reaction temperatures ranging from 600 to 800 ^°C on the formation of CNTs was investigated. The resulting carbon materials were characterized by various physicochemical techniques such as transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and Raman spectroscopy. The results show that multi-wall carbon nanotubes (MWCNTs) with an internal diameter of ca. 7.7 nm and an external diameter of ca. 16.9 nm were successfully obtained by the pyrolysis of ethanol at 800 ^°C utilizing Fe/MCM-41 as a catalytic template.     

Structure of water in mesoporous organosilica by calorimetry and inelastic neutron scattering

In this paper, we describe the preparation of mesoporous organosilica samples with hydrophilic or hydrophobic organic functionality inside the silica channel. We synthesized mesoporous organosilica of identical pore sizes based on two different organic surface functionality namely hydrophobic (based on octyltriethoxysilane OTES) and hydrophilic (3-aminopropyltriethoxysilane ATES) and MCM-41 was used as a reference system. The structure of water/ice in those porous silica samples have been investigated over a range temperatures by differential scanning calorimetry (DSC) and inelastic neutron scattering (INS). INS study revealed that water confined in hydrophobic mesoporous organosilica shows vibrational behavior strongly different than bulk water. It consists of two states: water with strong and weak hydrogen bonds (with ratio 1:2.65, respectively), compared to ice-Ih. The corresponding O-O distances in these water states are 2.67 and 2.87 ?, which strongly differ compared to ice-Ih (2.76 ?). INS spectra for water in hydrophilic mesoporous organosilica ATES show behavior similar to bulk water, but with greater degree of disorder.     

Synthesis of silica-pillared clay (SPC) with ordered mesoporous structure by one-step method without preswelling process

The simultaneous intercalation of surfactants and TEOS into clay interlayers and subsequent intragallery ammonia-catalyzed hydrolysis of TEOS resulted in mesoporous silica-pillared clay (SPC). These SPC materials exhibited refractions corresponding to a basal spacing of 3.7-4.3 nm, a uniform pore size of 2.5-3.16 nm and large surface areas of 567-576 m²/g. Our results indicate that surfactants play a decisive role in pore formation, because they act as micelle-like template during the hydrolysis of TOES. Moreover, the pore size of SPC derivatives is controllable by the molecular length of surfactant. All of the SPC materials reported here exhibit high catalytic activity and selectivity for coker gas oil (CGO) cracking reaction in comparison to parent MCM-41 and Al-MCM-41. The excellent acid catalytic activity, together with their sable, well-organized porous structure, opens up new opportunities for applications in catalysis.     

Thermal diffusivity of electrodeposited Ni and Co nanowires using infrared thermography

One-dimensional nanostructures such as Ni and Co nanowires (NWs) show anisotropic thermal properties in a direction parallel and perpendicular to the NW axis. Thermal diffusivity of Ni and Co NWs embedded in a 100-nm pore anodic alumina (AAO) template has been measured in a direction perpendicular to the NW axis, using an infrared thermography-based non-contact approach. The measured thermal diffusivity values in the radial direction are 0.728×10⁻⁶ and 0.732×10⁻⁶ m²s⁻¹, respectively, for the Ni and Co nanocomposites. The changes in the thermal diffusivity of the synthesized NWs alone were estimated using a first-order lower bound model (FOLBM). A nearly seven- and sixfold reduction, respectively, of thermal diffusivity in a direction perpendicular to the NW axis is estimated for the synthesized Ni and Co NWs.     

The influence of hydrogen on the electronic and magnetic structures of TM(0 0 1) (TM=Fe, Co, Ni, and Cu) surfaces and interfaces: Ab-initio calculations

We present ab-initio investigation of the electronic and magnetic structure of TM(0 0 1) surfaces and TM/Cu(0 0 1) systems (TM=Fe, Co, Ni, Cu) with and without hydrogen adsorbed layer. The adsorption energy of hydrogen atom is found to be energetically more stable above the surface layer of Ni(0 0 1) surface than other TM(0 0 1) surfaces. The adsorption energies of hydrogen on TM/Cu(0 0 1) systems are larger than those on TM(0 0 1) surfaces. The relaxed geometries show that hydrogen has a strong influence on the interlayer distance. Furthermore, a marked reduction of Fe, Co, and Ni surface magnetic moments to 2.54, 1.41 and 0.25 μ_B, respectively, is obtained due to the presence of hydrogen.     

Adsorption characterization of surfactant-templated ordered mesoporous silicas synthesized with and without hydrothermal treatment

This work reports a systematic study of ordered mesoporous silicas (OMSs) synthesized with and without hydrothermal treatment at 373 K for a series of surfactants of different alkyl chain length (from C10 to C18). For these samples nitrogen adsorption and small angle X-ray scattering (SAXS) data were measured to characterize their adsorption and surface properties. Namely, nitrogen adsorption isotherms were used to evaluate their specific surface area, pore volume and pore size distribution, whereas SAXS data provided information about their structural ordering. It is shown that while the room temperature synthesis afforded OMS samples with cubic MCM-48 structure, an additional 5-day hydrothermal treatment of these samples at 373 K caused their transformation to MCM-41 (two-dimensional hexagonal structure) and improved their pore uniformity, which was manifested by reducing the width of pore size distribution.     

High specific surface area TEOS-based aerogels with large pore volume prepared at an ambient pressure

The experimental results on the synthesis of tetraethoxysilane (TEOS)-based silica aerogel with high specific surface area and large pore volume, via ambient pressure drying (APD) route, are reported. The silica aerogels were prepared by the acid-base sol-gel polymerization of TEOS precursor followed by the drying of the alcogels at an ambient pressure. The solvent present in the alcogel (i.e. ethanol) was replaced by a non-polar solvent such as hexane prior to the surface modification step. In order to minimize the drying shrinkage, the surface of the gels was modified using trimethylchlorosilane (TMCS) before the APD. The FTIR spectra of the surface modified aerogels showed Si-CH₃ peaks at 2965 and 850 cm⁻¹. The effect of the base catalyst (NH₄OH) addition to the sol, at different time intervals (T), on the physical and textural properties of the resulting aerogels has been investigated. It has been observed that the surface area and the cumulative pore volume of the aerogels enhanced considerably from 819 to 1108 m² g⁻¹ and 2.65 to 4.7 cm³ g⁻¹, respectively with an increase in the T value from 6 to 48 h. Silica aerogels with very low bulk density (0.06 g cm⁻³), extremely high specific surface area (1108 m² g⁻¹) and large cumulative pore volume (4.7 cm³ g⁻¹) could be synthesized by drying the alcogels at the ambient pressure. The aerogels were mesoporous solids with the average pore size ranging from 12 to 17 nm. The results have been discussed by taking into consideration the hydrolysis and condensation reactions during the sol-gel polymerization of the TEOS precursor.     

Laser cladding of copper with molybdenum for wear resistance enhancement in electrical contacts

Laser cladding of Mo on Cu has been attempted with the aim of enhancing the wear resistance and hence increasing the service life of electrical contacts made of Cu. In order to overcome the difficulties arising from the large difference in thermal properties and the low mutual solubility between Cu and Mo, Ni was introduced as an intermediate layer between Mo and Cu. The Ni and Mo layers were laser clad one after the other to form a sandwich layer of Mo/Ni/Cu. Excellent bonding between the clad layer and the Cu substrate was ensured by strong metallurgical bonding. The hardness of the surface of the clad layer is seven times higher than that of the Cu substrate. Pin-on-disc wear tests consistently showed that the abrasive wear resistance of the clad layer was also improved by a factor of seven as compared with untreated Cu substrate. The specific electrical contact resistance of the clad surface was about 5.6 × 10⁻⁷ Ω cm².     

Growth and sacrificial oxidation of transition metal nanolayers

Growth and oxidation of Au, Pt, Pd, Rh, Cu, Ru, Ni and Co layers of 0.3-4.3 nm thickness on Mo have been investigated with ARPES and AFM. Co and Ni layers oxidize while the Mo remains metallic. For nobler metals, the on top O and oxidation state of subsurface Mo increase, suggesting sacrificial e⁻ donation by Mo. Au and Cu, in spite of their significantly lower surface free energy, grow in islands on Mo and actually promote Mo oxidation. Applications of the sacrificial oxidation in nanometer thin layers exist in a range of nanoscopic devices, such as nano-electronics and protection of e.g. multilayer X-ray optics for astronomy, medicine and lithography.     

An alternative method to remove PEO-PPO-PEO template in organic-inorganic mesoporous nanocomposites by sulfuric acid extraction

Sulfuric acid is used as an extraction agent to remove PEO-PPO-PEO templates in the organic-inorganic mesoporous nanocomposites from the triconstituent co-assembly which includes the low-polymerized phenolic resins, TEOS and triblock copolymer F127. The XRD and TEM results show well ordered mesostructure after extraction with sulfuric acid. As followed from the N₂ sorption isotherms the extracted composites possess high surface areas (332-367 m²/g), large pore volumes (0.66-0.78 cm³/g), and large pore sizes (about 10.7 nm). The FT-IR analysis reveals almost complete elimination of triblock copolymer F127, and the maintenance of organic groups. This method shows potentials in removing templates from nanocomposites containing functional moieties.     

Pillaring and photocatalytic properties of mesoporous α-Fe2O3/titanate nanocomposites via an exfoliation and restacking route

Mesoporous α-Fe₂O₃-pillared titanate nanocomposites have been successfully synthesized through an exfoliation−restacking route. Powder X-ray diffraction and N₂ adsorption-desorption isotherms revealed that the α-Fe₂O₃ pillared titanate has an interlayer distance of 3.27 nm, a specific surface area of 66 m²/g and an average pore size of 7.6 nm, suggesting the formation of a mesoporous pillared structure. UV-vis diffuse reflectance spectra show a red shift, indicative of a narrow band gap energy of ∼2.1 eV compared to the host layered titanate, which is essential in creating a visible light photocatalytic activity. The results of degradation of rhodamine B reveal that the present pillared mesoporous composites exhibit better photocatalytic activities than those of the pristine materials under visible irradiation, based on the band gap excitement and the dye-sensitized path, originated from their high surface area, mesoporosity and the electronic coupling between the host and the guest components.