Immobilization of Ru(II)(salen)(PPh3)2 on Mesoporous MCM-41/SBA-15: Characterization and Catalytic Applications

Ru(II)(salen)(PPh₃)₂ immobilized on MCM-41 and SBA-15 modified with aminopropyl groups as linkers has been synthesized and characterized by elemental analysis, TEM, FTIR, BET, and TGA. Elemental analysis shows that the grafted samples contain 0.7–0.8 wt.% Ru. The retaining of long range ordering of the mesoporous MCM-41 and SBA-15 supporting materials after grafting is evident from TEM and N₂ adsorption/desorption measurements. FTIR and TGA spectra show the formation of metal salen complexes with the amino groups acting as connectors to the SiO₂ surface. Both grafted materials were successfully applied as catalysts for the olefination of various aldehydes with very good yields and high E-selectivity. The catalyst materials are recyclable for several catalytic runs.     

Investigation of chromium oxide clusters grafted on SBA-15 using Cr-polycation sol

A comparative study of chromium oxide clusters grafted on mesoporous silica SBA-15 was carried out using samples synthesized by one-pot, impregnation and Cr-polycation sol grafting methods. The nature of CrO_x species incorporated into SBA-15 by direct hydrothermal one-pot method as well as impregnation of Cr(NO₃)₃·9H₂O and Cr-polycation precursors was characterized by XRD, BET isotherms, UV–Vis DRS, FTIR, TGA, O1s XPS, ²⁹Si-MAS NMR, H₂-TPR, NH₃-TPD, SEM and TEM. Powder XRD did not show the presence of Cr₂O₃ in the calcined samples obtained by one-pot method. It, however, shows the rhombohedral clusters of α-Cr₂O₃ dispersed over SBA-15 for CrO_x/SBA-15 samples prepared by impregnation and polycation sol grafting methods. The absorption band at 296 nm, observed for Cr³⁺ in solution, is absent for the aqueous Cr-polycation sol. There is evidence that the presence of chromium precursor in the reaction medium can influence the morphology of SBA-15 as seen in the SEM micrographs. Charge transfer transitions demonstrate the insertion of CrO_x species on SBA-15 matrix synthesized by one-pot method. Cr-polycation grafted SBA-15 sample shows unique vibrational features at 573 and 624 cm^?1 attributed to extra-framework CrO_x species. The ratio of Cr⁶⁺/Cr³⁺ species present in CrO_x/SBA-15 samples depends on the Cr-precursor employed for grafting on SBA-15. One-pot synthesized samples predominantly contain coordinated water (δ_H–O–H at 1,635 cm^?1) on SBA-15 while impregnated samples show water molecules associated with CrO_x species (δ_H–O–H at 1,594 cm^?1).     

Influence of initial Si/Al ratios on the structural,acidic and catalytic properties of nanosized-ZSM-5/SBA-15 analog composites prepared from ZSM-5 precursors

Nano-ZSM-5/SBA-15 analog composites (ZSC) were prepared in a two-step process from ZSM-5 precursors with different Si/Al molar ratios (10–50) via high-temperature synthesis in mildly acidic media (200 °C, pH 3.5) aiming to evaluate the influence of the initial Si/Al ratio on their structural, acidic and catalytic properties. The resulting materials were characterized by SAXS, XRD, FTIR, TEM, N₂ sorption, ²⁷Al solid state-NMR, NH₃-TPD, FTIR spectroscopy of adsorbed pyridine, AAS and ICP-AES. Under the applied synthesis conditions, a ZSC material with controlled distribution of nano-ZSM-5 and SBA-15 analog phases can be prepared from ZSM-5 precursors by adjusting the initial Si/Al ratio in the range of 20–30. Increasing the initial Si/Al ratio to 50, only ZSM-5 nanocrystals were obtained whereas reducing the initial Si/Al ratio to 10 led to the formation of a disordered mesoporous SBA-15 analog. The total acidity increases with the crystallinity of the ZSM-5 phase as varying the Si/Al ratio from 10 to 30 despite the decreased amount of incorporated aluminum. However, the acidity declines slightly when raising the Si/Al ratio to 50 because of the low incorporated aluminum. The catalytic performance of the ZSC materials compared to the reference materials, i.e. purely mesoporous Al-SBA-15 and purely microporous H-ZSM-5 was assessed in the gas phase cracking of cumene and 1,3,5-tri-isopropylbenzene (TIPB) as test reactions. The results show that a balanced ratio of nano-ZSM-5 and SBA-15 analog phases obtained by tuning the initial Si/Al ratio is crucial to achieve superior catalytic performance of the ZSC materials in the cracking of both cumene and TIPB.     

Saponin-loaded SBA-15: release properties and cytotoxicity to Panc-I cancer cells

In this study, first time a nanoformulation, saponin-loaded SBA-15 has been developed for an improved and continuous release. The SBA-15 nanopowder was synthesized by a hydrothermal process. Saponin was introduced into the mesoporous channels of SBA-15 and its concentration in SBA-15 was measured by UV–visible spectrophotometry. The pristine SBA-15 and saponin-loaded SBA-15 were characterized by small-angle XRD, FESEM, HRTEM, TGA, FTIR. N₂ adsorption–desorption isotherms were used to measure the specific surface area and pore channel structure parameters of pristine and loaded SBA-15. Saponin release was studied in phosphate buffered saline (pH 7.4), which revealed that the release rate could be effectively controlled. The controlled drug release is highly desired for cancer treatment. The cytotoxicity of pristine and loaded SBA-15 was analyzed on Panc-I cancer cells. Both the pristine SBA-15 and saponin-loaded SBA-15 nanoparticles showed specific toxicity on the cancer cells. The preliminary results showed that saponin-loaded SBA-15 could be an effective therapeutic agent for Panc-I cancer cells.     

In-vitro drug release kinetics studies of mesoporous SBA-15-azathioprine composite

The mesoporous silica (or SBA-15) was loaded with azathioprine drug. Azathioprine drug was incorporated into mesoporous silica by post impregnation method to reduce its toxic effects by controlling the drug release property. The synthesized pure SBA-15 and SBA-15-azathioprine composite were characterized by UV–visible spectrophotometry, thermo-gravimetric analysis, small and large angle powder X-ray diffraction, field emission scanning electron microscopy, high resolution transmission electron microscopy, Fourier transform infrared spectroscopy and nitrogen adsorption–desorption analysis. The successful inclusion of azathioprine drug in host material SBA-15 was confirmed by the reduced surface area (114 m²/g) and pore diameter (6.5 nm) of the organic–inorganic composite material. The drug entrapment efficiency of 90.67 % and loading efficiency of 72.67 % was achieved. The azathioprine drug release process from the mesoporous silica to simulated gastric, intestinal and body fluid were examined and the controlled release effect of the azathioprine drug in all fluids were studied. The Korsmeyer–Peppas model fits well the drug release data with the non-Fickian diffusion model and zero order kinetics for produced mesoporous silica. The controlled drug release enhanced the bioavailability and reduces its repeated administration. Hence, the composite drug can reduce the toxicity and side effects of the azathioprine.     

Preparation of bimodal mesoporous silica containing cerious salt and its application as catalyst for the synthesis of biodiesel by esterification

A kind of bimodal mesoporous silica catalyst modified with ammonium cerous sulfate (ACS/BMMS) was synthesized and applied in the esterification of free fatty acid and alcohol. The characterization results including XRD, N₂ adsorption and desorption, FTIR, ²⁹Si-NMR and TEM showed that ACS/BMMS has orderly arranged bimodal mesopores, the small mesopore diameter is about 4.0–6.0 nm and the large mesopore diameter is in the range of 7.0–9.0 nm. The chemical interaction existed between silica group Si (OH)₂(OSi)₂ and the NH₄ ⁺, SO₄ ^2? and Ce-O groups of cerious salt. When the loading is not more than 10%, cerious salt dispersed finely on the supports. Oleic acid and methanol were used as the raw material of probe reaction; ACS/BMMS had significantly better activity than the ACS/SBA-15, ACS/SBA-16, ACS/MCM-41, BMMS and bulk ACS. The optimum loading of ACS is 10%, the optimum reaction conditions are reaction temperature 140 °C, reaction time 2 h, mole ratio of methanol to oleic acid 2.0 and the dosage of catalyst 4.0%, in above situation the conversion of oleic acid is about 94.0%, the reusability of ACS/BMMS is much better than bulk ACS. The kinetic study showed that the esterification of oleic acid and methanol on ACS/BMMS match Eley–Rideal model very well.     

Pt-Promoted Cu/SBA-15 Catalysts with Excellent Performance for Chemoselective Hydrogenation of Dimethyl Oxalate to Ethylene Glycol

Cu/SBA-15 catalysts containing a small amount of Pt (Cu–Pt/SBA-15) were prepared by sequential adsorption–reduction method and examined for chemoselective hydrogenation of dimethyl oxalate (DMO) to ethylene glycol (EG). The Cu–Pt/SBA-15 catalyst with an optimal Cu/Pt atomic ratio of 10 showed a DMO conversion close to 100 % with a 98 % selectivity to EG at a temperature as low as 463 K. The results showed that the best Cu–Pt/SBA-15 enhanced the space time yield of EG by about 1.47 times compared with Cu/SBA-15. The introduction of Pt with stronger ability for H₂ adsorption and activation substantially enhanced the reducibility of the Cu²⁺ species and further promoted the chemisorption capacity of H₂. After reduction, a portion of Cu was alloyed with Pt, which was beneficial for the generation and stabilization of a balanced Cu⁺/Cu⁰ ratio during the hydrogenation process.     

Removal of Cu (II) from water pollutant with Tunisian activated lignin prepared by phosphoric acid activation

Activated lignin with a relative high BET surface area and a well-developed porosity has been prepared from Tunisian deposit lignin, by H₃PO₄ activation at various process conditions. Physical and chemical properties of activated carbons produced, implying BET surface area, Boehm titration, Fourier Transform Infrared Spectroscopy (FTIR) and thermogravimetric analysis (TGA), were investigated. It was found that the maximum surface area reached at the carbonization temperature of 500 °C in H₃PO₄ activation, and that the activated lignin prepared from lignin acidic activation, showed a surface area of 463 m²/g. The potential application of these carbons for the removal of heavy metal contaminant, has been investigated by measuring their adsorption capacities for Cu (II) as representative of main local toxic contaminant found in industrial wastewaters. The results obtained compare well and even favourably with those reported in literature for other unconventional materials.     

Synthesis and NMR Characterization of Titanium and Zirconium Oxides Incorporated in SBA-15

Single oxides of Ti and Zr incorporated SBA-15 were prepared and characterized by N₂ adsorption, NMR, and XPS techniques. ²⁹Si MAS NMR results suggest the formation of Si–O–X linkages (X: Ti or Zr) by an increase in the ratio of Q ³/Q ⁴ in the presence of Ti or Zr. XPS analysis of Ti–SBA-15 catalysts indicate the presence of Ti–O–Si bonds in addition to Ti–O–Ti and Si–O–Si bonds, supporting the NMR evidence.     

CuO Impregnated mesoporous silica KIT-6: a simple and efficient catalyst for benzene hydroxylation by C–H activation and styrene epoxidation reactions

Copper oxide doped mesoporous KIT-6 materials were synthesized by ultrasonication as impregnation method. The highly ordered nature of mesoporous CuO-KIT-6 materials analyzed by low angle X-ray diffraction. The high surface area, pore diameter and mesoporous nature of synthesized materials were confirmed by BET surface area analysis. Si–O–Si, Si–OH and Cu–O–Si bonds in the framework of CuO-KIT-6 were verified by FTIR spectroscopy. The Cu²⁺ ← O^2? charge-transfer transitions and d–d transitions of dispersed Cu²⁺ on ordered mesoporous KIT-6 were identified by DRS UV–Vis spectroscopy. The morphology of the synthesized CuO-KIT-6 materials was analyzed by HR-SEM. The 3D ordered nature of CuO-KIT-6 confirmed by TEM analysis. The highly ordered 3D mesoporous CuO-KIT-6 materials are excellent catalyst for benzene hydroxylation reaction through C-H activation and styrene epoxidation reaction with 30 % aqueous H₂O₂. The catalyst CuO-KIT-6 itself showed a good conversion towards both reactions.     

Adsorption of Eu(III), Th(IV), and U(VI) by mesoporous solid materials bearing sulfonic acid and sulfamic acid functionalities

ABSTRACT

SBA-15 mesoporous materials modified by sulfonic acid and sulfamic acid functionalities, abbreviated as SBA-15/SO₃H and SBA-15/NHSO₃H, were synthesized and applied for the removal–separation of Eu(III), Th(IV), and U(VI). SBA-15/NHSO₃H showed an excellent selectivity toward U(VI), while SBA-15/SO₃H was more efficient adsorbent for Eu(III) and Th(IV). It was found that in the presence of KNO₃ (1 mol L^?1), the separation of Eu(III)/Th(IV) from their mixtures is possible. The results of the sorption behavior indicated a high adsorption capacity toward U(VI) and Th(IV) ions (140.5 and 106.7 mg g^?1, respectively) and ultrafast kinetics (15 min) in Eu(III) adsorption.     

A chromotropic acid modified SBA-15 as a highly sensitive fluorescent probe for determination of Fe<Superscript>3+</Superscript> and I<Superscript>−</Superscript> ions in water

A novel organic–inorganic hybrid nanomaterial (SBA-15-CA) was prepared by covalent immobilization of chromotropic acid onto the surface of mesoporous silica material SBA-15. Different techniques such as XRD, TEM, FT-IR, N₂ adsorption–desorption and TGA analyses were employed to characterize the grafting process. The data showed that the organic moiety (0.41 mmol g^?1) was successfully grafted to the SBA-15 and the primary hexagonally ordered mesoporous structure of SBA-15 was preserved after the grafting procedure. SBA-15-CA has been realized as a highly sensitive and selective fluorescent probe towards Fe³⁺ and I^? ions in aqueous media. SBA-15-CA exhibited a remarkable fluorescent quenching in the presence of Fe³⁺ ion over other competitive cations including Na⁺, Mg²⁺, Al³⁺, K⁺, Ca²⁺, Cr³⁺, Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺, and Pb²⁺ as well as I^? ion among a series of anions including F^?, Cl^?, Br^?, CO₃^2?, HCO₃^?, CN^?, NO₃^?, NO₂^?, SCN^?, SO₄^2?, H₂PO₄^?, HPO₄^2?, and CH₃COO^?. A good linear response was observed between the concentration of the quenchers (Fe³⁺ and I^? ions) and fluorescence intensity of SBA-15-CA with detection limits of 1.5?×?10^?7 M for Fe³⁺ and 0.2?×?10^?7 M for I^?. Moreover, the effects of various pH values on the sensing ability of SBA-15-CA were investigated. Finally, the proposed method was successfully utilized for the determination of Fe³⁺ and I^? ions in river water, well water and tap water samples.     

Co3O4 and Mn3O4 Nanoparticles Dispersed on SBA-15: Efficient Catalysts for Methane Combustion

Co₃O₄ and Mn₃O₄ nanoparticles were successfully impregnated on SBA-15 mesoporous silica. A high dispersion of these metal oxide particles was achieved while using a “two-solvents” procedure, allowing a proper control of the metal oxides loading (7 wt%) and size (10–12 nm). These Co₃O₄ and Mn₃O₄ supported oxides on SBA-15 were characterised by means of XRD, BET and TEM techniques. The influence of the nature of the silica support was investigated in terms of porosity and specific surface area. Since, an improved catalytic activity was achieved over SBA-15 mesoporous silica; it appears that its organised porous meso-structure creates a confinement medium which permits a high dispersion of metal oxide nanoparticles. Supported Co₃O₄/SBA-15 (7 wt%) showed the highest catalytic performance in the combustion of methane under lower explosive limit conditions, comparable to perovskites. These materials become therefore novel efficient combustion catalysts at low metal loading.     

AuPd bimetal immobilized on amine-functionalized SBA-15 for hydrogen generation from formic acid: The effect of the ratio of toluene to DMF

The volume ratio of toluene to N,N-dimethylformamide (DMF) was adjusted during the amine functionalization of SBA-15 to change the amine content of SBA-15. XPS, FTIR, and TGA analyses indicated that under the experimental synthetic conditions the number of amine groups varies with the ratio of toluene/DMF, and the highest content of amine could be obtained with a volume ratio of toluene/DMF = 3:2. The hydrogen production experiment of formic acid decomposition showed that the hydrogen production efficiency over the Au-Pd-SBA-15-NH₂ catalysts increased with the increase in the surface amine content of the Au-Pd-SBA-15-NH₂. The optimal Au-Pd-SBA-15-NH₂-TD (toluene/DMF = 3:2) catalyst proved to have the smallest Au-Pd bimetal nanoparticle size and exhibited a turnover frequency (TOF) = 631 hours⁻¹ and an activation energy (Ea) = 20.8 kJ · mol⁻¹ at 25°C. The catalytic performance of hydrogen generation from the formic acid was improved due to the synergistic effect between the amine-functionalized SBA-15 and the Au-Pd bimetal (metal-support interactions).     

Preparation,characterization and testing of Cr/AlSBA-15 ethylene polymerization catalysts

Ethylene polymerization catalysts have been prepared by grafting chromium(III) acetylacetonate onto AlSBA-15 (Si/Al = ∞, 156, 86 and 30) mesoporous materials. A combination of XRD, nitrogen adsorption, TEM, ICP-atomic emission spectroscopy, H₂-TPR, TGA, UV–vis and FT-IR spectroscopy, were used to characterize the prepared Cr–AlSBA-15 catalysts. By reducing the Si/Al ratio of the AlSBA-15 supports increases the amount of chromium anchored, promotes the stabilization of chromium species as chromate and decreases the reduction temperature of Cr⁶⁺ ions determined by H₂-TPR. Attachment of Cr species onto AlSBA-15 surface results from the interaction of hydroxyl groups with the acetylacetonate ligands through H-bonds. On the contrary, a ligand exchange reaction may occur over siliceous SBA-15.The polymerization activity of Cr–AlSBA-15 catalysts is significantly improved by increasing aluminium content of the AlSBA-15 supports. Particularly, the chromium catalyst prepared with AlSBA-15 (Si/Al = 30) support is almost four times more active than a conventional Cr/SiO₂ Phillips catalyst. Polymers obtained with all the catalysts showed melting temperatures, bulk densities and high load melt indexes indicating the formation of linear high-density polyethylene.     

Sulfonic acid functionalized mesoporous SBA-15 for selective synthesis of 4-phenyl-1,3-dioxane

Mesoporous SBA-15 silica has been functionalized with propylsulfonic acid groups post-synthetically using 3-mercaptopropyltrimethoxysilane as sulfur source. The materials before and after functionalization have been characterized by BET surface area and pore size distribution by BJH method, powder X-ray diffraction and temperature programmed desorption (TPD) of NH₃. The resultant mesoporous material (solid acid catalyst) exhibited hexagonal mesoscopic ordering, which possess 1.3 meq H⁺ g⁻¹ SiO₂ exchange capacity, 96 Å mesopore size diameter, and 660 m² g⁻¹surface area. Sulfonic acid groups anchored to SBA-15 silica pore surfaces are thermally stable up to 653 K, hydrothermally robust in boiling water and resistant to leaching in organic and aqueous solvents under mild conditions. XRD results indicate that there is no change in the structure after anchoring SBA-15 with SO₃H group. SBA-15-SO₃H catalyst has been found to be highly active and selective for the Prins condensation of styrene with formaldehyde. Both the conversion of styrene and the selectivity to 4-phenyl-1,3-dioxane are nearly 100%. Presence of more number of acid sites in SBA-15-SO₃H catalyst helps in achieving high yields. Furthermore, the conversion and the selectivity to 4-phenyl-1,3-dioxane are found to be consistent in four repeated cycles.     

Preparation and characterization of polyhedral oligomeric silsesquioxane–titania aerogels

The novel polyhedral oligomeric silsesquioxane (POSS)–titania aerogels which contain different contents of titania were successfully prepared by the sol–gel process and subsequently supercritical drying with carbon dioxide. All the aerogels are monolithic and the densities of those aerogels are low. The FTIR spectra of the aerogels showed the resulting POSS–TiO₂ composite aerogels had homogeneous Si–O–Ti bonds. The microstructure, surface composition and thermal stability were measured by FESEM, XPS and TGA. With the increasing of titania contents, the aggregated particles of the aerogels in the microstructure got larger and larger. The texture of the aerogels was measured by XRD and nitrogen adsorption/desorption and showed that they were amorphous and had high surface area (>500 m²/g).     

A biomimetic mesoporous silica–polymer composite scaffold for bone tissue engineering

A biomimetic organic–inorganic composite system comprising of microspheres fabricated from combination of a biodegradable polymer poly(lactide-co-glycolide) (PLGA) and bioactive mesoporous silica (SBA-15) has been developed through sintering technique for bone regeneration applications. The morphological and structural properties of the SBA-15/PLGA composite scaffold were evaluated using electron microscopy and fourier transform infrared spectroscopy and the results showed spherical morphology and composite nature. The presence of mesopores in the silica was confirmed through nitrogen adsorption–desorption isotherms. The surface area and pore size of mesoporous silica were found to be 792 m² g^?1 and 3.7 nm, respectively. The thermal characteristics of the SBA-15/PLGA composites studied using thermogravimetry analysis shows a weight loss of around 80% with the degradation occurring at 324?°C. The prepared scaffold is also found to support the adhesion and proliferation of osteoblast cells. The expression of specific bone markers is significantly enhanced in the SBA-15/PLGA composite scaffold when compared with the pristine polymeric scaffold indicating the positive effect of mesoporous silica. Hence, these SBA-15/PLGA composite scaffolds can be explored further for bone regeneration applications.     

Effect of lignin on mechanical,biodegradability, morphology,and thermal properties of polypropylene/polylactic acid/lignin biocomposite

ABSTRACT

The effects of lignin on mechanical, biodegradability, morphology, and thermal properties of PP/PLA/lignin were investigated. PP/PLA/lignin film were manufactured by adding PP, PLA, lignin and compatibilizer into rheomix at 200°C, at 70?rev?min^?1 for 30?minthen pressed using Hydraulic Hot Press at 200°C–210°C, at 6 bar for 20?min. The functional groups of PP/PLA/lignin were analyzed using FTIR. The surface morphology, mechanical properties and thermal stability was measured by SEM, tensile strenght and TGA respectively. TThe FTIR intensity of vibration peak of –CH₃?cm^-1 from PP/lignin and PP/PLA/lignin at 997–993, 1458–1451 and 2966–2904?cm^-1 was lower than neat PP. The addition of lignin into PP/lignin, PLA/lignin and PP/PLA/lignin can reduce tensile strength and elongation at break. The thermal stability PP/PLA/lignin was lower than the PP/lignin but higher compared to PP/PLA biocomposites. The biodegradability of PP/PLA/lignin biocomposites was two times higher than that of PP/lignin.     

Hydrogenation of CO<Subscript>2</Subscript> to methanol over Au–CuO/SBA-15 catalysts

A series of Au–CuO/SBA-15 catalysts with 1–3 wt% Au and 30 wt% CuO were successfully prepared for CO₂ hydrogenation to methanol by chemical reduction and the following impregnation. The influence of Au content on the physicochemical properties of Au–CuO/SBA-15 catalysts was investigated in terms of ICP-AES, N₂ physisorption, XRD, TEM, N₂O titration, XPS and H₂–TPR technique. The results showed that the as-prepared Au–CuO/SBA-15 catalysts exhibited higher catalytic activity than CuO/SBA-15 catalyst. 2 % Au–CuO/SBA-15 catalyst showed the best catalytic activity with 13.5 % methanol selectivity and 24.2 % CO₂ conversion for CO₂ hydrogenation to methanol. The addition of Au NPs played an important role in improving the catalytic activity for CO₂ hydrogenation to methanol, which may be attributed to the interaction between Au and CuO.