The effect of TiO2 particle size on the characteristics of Au–Pd/TiO2 catalysts

The nanocrystalline TiO₂ materials with average crystallite sizes of 9 and 15 nm were synthesized by the solvothermal method and employed as the supports for preparation of bimetallic Au/Pd/TiO₂ catalysts. The average size of Au–Pd alloy particles increased slightly from sub-nano (< 1 nm) to 2–3 nm with increasing TiO₂ crystallite size from 9 to 15 nm. The catalyst performances were evaluated in the liquid-phase selective hydrogenation of 1-heptyne under mild reaction conditions (H₂ 1 bar, 30 °C). The exertion of electronic modification of Pd by Au–Pd alloy formation depended on the TiO₂ crystallite size in which it was more pronounced for Au/Pd on the larger TiO₂ (15 nm) than on the smaller one (9 nm), resulting in higher hydrogenation activity and lower selectivity to 1-heptene on the former catalyst.     

Ru/SBA-15 catalysts for partial hydrogenation of benzene to cyclohexene: Tuning the Ru crystallite size by Ba

Ru–Ba/SBA-15 catalysts with different Ba/Ru molar ratios were prepared by the ‘two solvents’ method, which can readily introduce the active components into the channels of SBA-15. Characterizations revealed that the crystallite size of Ru was tuned smoothly from 3.6 to 7.5 nm by increasing the Ba/Ru ratio from 0.1 to 1.0. In liquid phase hydrogenation of benzene, the maximum yield of cyclohexene was obtained on the Ru–Ba/SBA-15 catalyst with Ru crystallite size of 5.6 nm, which is interpreted as the presence of the highest population of the active sites favorable for the production of cyclohexene on such Ru crystallites.     

Effects of Fe addition on the structure and catalytic performance of mesoporous Mn/Al–SBA-15 catalysts for the reduction of NO with ammonia

Mesoporous Al–SBA-15 has been synthesized by a hydrothermal method and used as a support for Mn/Al–SBA-15, Fe/Al–SBA-15, and Mn–Fe/Al–SBA-15 catalysts. XRD, N₂ sorption, XPS, H₂-TPR and activity tests have been used to assess the properties of catalysts. The Mn–Fe/Al–SBA-15 catalyst exhibited a higher SCR activity than Mn/Al–SBA-15 or Fe/Al–SBA-15 due to a synergistic effect between Mn and Fe. After the addition of Fe, the binding energy of Mn 2p_3/2 on Mn–Fe/Al–SBA-15(573) decreased by about 0.4 eV and the Mn^4 +/Mn^3 + ratio decreased to 1.10. The appropriate Mn^4 +/Mn^3 + ratio may have a great effect on the reduction of NO over Mn–Fe/Al–SBA-15(573) catalyst.     

An efficient microwave-assisted Suzuki reaction using Pd/MCM-41 and Pd/SBA-15 as catalysts in solvent-free condition

Palladium catalysts, Pd/MCM-41 and Pd/SBA-15 were prepared by impregnation of an aqueous solution of [Pd(NH₃)₄]Cl₂ on MCM-41 and SBA-15. Palladium contents of Pd/MCM-41 and Pd/SBA-15 are 8.4% and 8.7%, respectively. It has been shown that these catalysts are very suitable to microwave-assisted Suzuki reactions under solvent-free condition. It is also found that the base additives for this reaction are K₂CO₃, Cs₂CO₃ or CsF. Thus, phenylboronic acid and phenyl iodide with Pd/MCM-41 produce biphenyl by microwave irradiation for 10 min in 97.4% yield. Phenyl bromide, instead of phenyl iodide, also proceeds the reaction with phenylboronic acid using Pd/MCM-41 or Pd/SBA-15 yielding biphenyl by microwave irradiation for 10 min in excellent yield. Whereas the reaction of phenyl chloride with phenylboronic acid gives poor yield in same condition. Various aryl iodides and aryl bromides are tested. In this paper our recent results of microwave-assisted Suzuki reaction using Pd/MCM-41 and Pd/SBA-15 under solvent-free condition are described.     

Epoxidation of propene on vanadium species supported on silica supports of different structure

Silica supports such as mesoporous materials (SBA-3, SBA-15 and MCM-41), silicalite and amorphous silica were used for accommodation of vanadium species introduced on the support surface by means of impregnation, with vanadium concentration from 1 to 7 wt.%. Catalysts were characterised by means of XRD, low temperature adsorption/desorption of nitrogen, DR UV–vis and Raman spectra and also H₂-TPR measurements. Isolated vanadium species dispersed in the channels of mesoporous SBA-3 with pores diameter related to micropores range, seems to be the most active for propene epoxidation.     

In situ hydrothermally synthesized mesoporous LaCoO3/SBA-15 catalysts: High activity for the complete oxidation of toluene and ethyl acetate

Mesoporous yLaCoO₃/SBA-15 (y = 10–50 wt%) catalysts were prepared and characterized for the combustion of toluene and ethyl acetate (EA). The results show that well-ordered mesoporous LaCoO₃/SBA-15 catalysts of high surface areas (338–567 m²/g) could be fabricated by a facile in situ method of hydrothermal treatment. The particles of perovskite-type LaCoO₃ were highly dispersed on the walls of pore channels. The ordered mesoporous structure and high dispersion of LaCoO₃ are beneficial to the adsorption and activation of toluene and EA molecules. We found that in terms of specific activity, the in situ fabricated 35LaCoO₃/SBA-15 and 40LaCoO₃/SBA-15 is, respectively, superior to 35LaCoO₃/SBA-15_imp (generated by incipient wetness impregnation method) and bulk LaCoO₃ (prepared by sol–gel method) in catalytic performance. Based on the above results, we conclude that the excellent performance can be attributed to the good dispersion of highly reducible LaCoO₃ species in yLaCoO₃/SBA-15.     

Self-oscillations of methane oxidation rate over Pd/Al2O3 catalysts: Role of Pd particle size

Oscillations of the methane oxidation rate were studied under methane-rich conditions on Pd/Al₂O₃ catalysts differing in Pd particle size. It was demonstrated that the temperature interval where oscillations occur narrows from 300–360 °C for the catalyst with Pd particle aggregates from 50–100 nm to 345–355 °C for the catalyst with isolated Pd particles of ~ 5 nm in size. At the same time, the period of oscillations showed ~ 6-fold increase. Structural transformations of Pd in the oscillation cycle were similar to those observed on bulk Pd used as a catalyst in the same reaction.     

Diesel-like hydrocarbons obtained by direct hydrodeoxygenation of sunflower oil over Pd/Al-SBA-15 catalysts

Hydrodeoxygenation of sunflower oil was performed in an autoclave over 5.0 wt.% Pd/Al-SBA-15 (Si/Al molar ratios from 22 to 300) and Pd/HZSM-5(22). The effects of acidity of the catalysts and the reaction temperatures on the activity of the catalysts were investigated. Pd/Al-SBA-15(Si/Al = 300) showed a high activity as 74.4% liquid yield and 72.9% C15–C18 diesel-like hydrocarbons yield at 250 °C. At 300 °C, the higher activity over Pd/Al-SBA-15(Si/Al = 50, 100 and 300) catalysts compared with that over Pd/Al-SBA-15(22) and Pd/HZSM-5(22) indicated that strong acidity of the catalysts was not favorable for converting sunflower oil into C15–C18 diesel-like hydrocarbons at a high temperature.     

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.     

An excellent support of Pd–Fe–Ox catalyst for low temperature CO oxidation: CeO2 with rich (200) facets

Pd–Fe–O_x catalysts for low temperature CO oxidation were supported on SBA-15, CeO₂ nano-particles with rich (111) facets and CeO₂ nano-rod with rich (200) facets, and characterized by X-ray diffraction, low-temperature nitrogen adsorption, transmission electron microscopy and temperature-programmed reduction. The results showed that when CeO₂ nano-rod was used as a support, Pd–Fe–O_x catalyst exhibits higher activity (T₁₀₀ = 10 °C), resulting from the rich (200) facets of CeO₂ nano-rod, which leads to a formation of large numbers of the oxygen vacancies on the surface of Pd–Fe–O_x catalysts.     

Potassium-modified molybdenum-containing SBA-15 catalysts for highly efficient production of acetaldehyde and ethylene by the selective oxidation of ethane

Mo-incorporated SBA-15 (Mo-SBA-15) catalysts with different Mo:Si molar ratios were synthesized by a direct hydrothermal method, and SBA-15-supported Mo catalysts (Mo/SBA-15 and K-Mo/SBA-15) were prepared by an incipient-wetness impregnation method. The structures of the catalysts were characterized by means of N₂ adsorption–desorption, XRD, TEM, FT-IR, and UV-Raman, and their catalytic performance for the oxidation of ethane was tested. Turnover frequency and product selectivity are strongly dependent on the molybdenum content and catalyst preparation method. Furthermore, the addition of potassium promotes the formation of isolated tetra-coordination molybdenum species and potassium molybdate. The K/Mo-SBA-15 catalysts possess much higher catalytic selectivity to acetaldehyde in the selective oxidation of ethane than the supported molybdenum catalysts (Mo/SBA-15 or K-Mo/SBA-15). The highest selectivity of CH₃CHO + C₂H₄ 68.3% is obtained over the K/Mo-SBA-15 catalyst. Analysis of kinetic results supports the conclusion that ethane oxidation is the first-order reaction and ethane activation may be the rate-determining step for the oxidation of ethane. Ethylene is a possible intermediate for acetaldehyde formation.     

Effective Pd/C catalyst for chlorobenzene and hexachlorobenzene hydrodechlorination by direct pyrolysis of sawdust impregnated with palladium nitrate

Two Pd/C catalysts were prepared by pyrolysis of Pd(NO₃)₂ impregnated sawdust. At equal pyrolysis time slow ramping with shorter isothermal heating resulted in 0.9 wt.% Pd/C-S1 sample comprising carbon support with some oxygen-containing moieties and Pd⁰ with 2.6 nm average particle size (APS) partially decorated with carbon shell, whereas fast temperature ramping and long isothermal heating provided 0.6 wt.% Pd/C-S2 containing Pd⁰ with 3.7 nm APS, with larger fraction of carbon decorated particles. Pd/C-S1 is slightly more efficient than Pd/C-S2 in gas phase chlorobenzene hydrodechlorination to benzene at 100–250 °C. Only Pd/C-S1 provides hexachlorobenzene hydrodechlorination in liquid phase due to lower APS and probably smaller PdC_x content.     

Highly selective hydrogenation of phenol and derivatives over Pd catalysts supported on SiO2 and γ-Al2O3 in aqueous media

Pd/Al₂O₃ and Pd/SiO₂ catalysts containing Pd nanoparticles in the size range of 3–13 nm were prepared and investigated in direct selective hydrogenation of phenol to cyclohexanone. Catalysts with 3 nm Pd nanoparticles present highly active and promoted the selective formation of cyclohexanone under atmospheric pressure of hydrogen in aqueous media without additives. Conversion of 99% and a selectivity higher than 99% were achieved within 3 h at 333 K. The generality of Pd/Al₂O₃ catalyst with 3 nm Pd nanoparticles for this reaction was demonstrated by selective hydrogenation of other hydroxylated aromatic compounds with similar performance.     

Nitrogen-doped ordered mesoporous carbons based on cyanamide as the dopant for supercapacitor

Nitrogen-doped ordered mesoporous carbons (N-doped OMCs) with a high surface area of 1741 m²/g and nitrogen content up to 15 wt.% have been synthesized by nanocasting approach by using SBA-15 as a hard template, phenolic resin (resol) as a carbon source and high nitrogen-containing cyanamide as the nitrogen dopant. The introduction of cyanamide not only incorporates high-content nitrogen into the carbon matrix in the primary forms of pyridinic and quaternary species, but also greatly increases the surface area of materials. The obtained N-doped OMCs have large surface area with mesoporosity up to 92%, uniform and appropriate pore size (3.6–4.1 nm), large pore volume (1.2–1.81 cm³/g). These merits together with high nitrogen enrichment lead to a specific capacitance (230 F/g at 0.5 A/g) and good rate capability (175 F/g at 20 A/g with capacitance retention of 77.4%) in 6 M KOH aqueous electrolytes.     

SBA-15-supported ionic liquid compounds containing silver salts: Novel mesoporous π-complexing sorbents for separating polyunsaturated fatty acid methyl esters

Novel π-complexing sorbents were prepared by covalently immobilizing ionic liquids (ILs) onto mesoporous SBA-15 using a one-pot sol–gel process followed by coating these SBA-15-supported IL compounds with silver salts. The mesoporous π-complexing sorbents were characterized by small angle X-ray scattering (SAXS), FTIR, TEM, SEM, nitrogen adsorption desorption isotherm, NMR, and nitrogen elemental analysis. Two advantages were obtained using these novel mesoporous π-complexing sorbents versus the traditional π-complexing sorbents formed by directly anchoring silver salts onto silica gel. (1) Higher extraction capacities were found. The extraction capacity for the polyunsaturated fatty acid methyl ester (PUFAME), methyl all-cis-5,8,11,14,17-eicosapentaenoate (20:5 or EPA), was 195 mg/g sorbent using the mesoporous AgBF₄/SBA-15 · IL · PF₆ sorbent. The capacity decreased to 121 mg/g sorbent with microporous complexing sorbent AgBF₄/SiO₂ · IL · PF₆. (2) Better reusability was also achieved. The supported IL phase immobilized and retained silver salt on SBA-15 due to the interaction between the ionic liquid’s imidazolium cations and silver ions. Eight successive sorption runs with the AgBF₄/SBA-15 · IL · PF₆ sorbent showed a satisfactory reusability. The traditional π-complexing sorbent has a silver salt directly anchored on silica without the supported ionic liquid phase. Higher silver leaching into organic solution occurred from the AgBF₄/SBA-15 sorbent determined by ICP-AES. The combined percentage (wt%) of the omega-3 PUFAMEs: 20:5 and methyl all-cis-4,7,10,13,16,19-docosahexaenoate (22:6 or DHA) stripped from the AgBF₄/SBA-15 · IL · PF₆ by 1-hexene was significantly enriched from 18% in the original cod liver oil to 90.5%.     

Control of amine functionality distribution in polyvinylamine/SBA-15 hybrid catalysts for Knoevenagel condensation

Poly(N-vinylformamide) was deposited on the surface of highly ordered hexagonal mesoporous silica SBA-15 by in situ polymerization. Acid-catalyzed hydrolysis followed by neutralization with NaOH (pH = 7.0–10.0) allowed obtaining the poly(vinylamine)/SBA-15 hybrid materials with various distributions of N-containing species, which were determined by XPS and DRIFT spectroscopy. The changes in the form of deposited polymer as well as its interaction with the silica support were discussed. The poly(vinylamine)/SBA-15 materials were tested as catalysts of Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate, ethyl acetoacetate and diethyl malonate. It was found that the sample neutralized at pH = 9.0 showed the best catalytic performance, which was attributed to a high content of accessible NH₂ groups.     

Synthesis and catalytic application of Pd nanoparticles in graphite oxide

Pd nanoparticles of 1–6 nm were synthesized in graphite oxide (GO) via cation exchange. The synthesis procedure involved immobilization of the precursor Pd(NH₃)₄(NO₃)₂ in GO, followed by reduction in flowing H₂. The resulting low-loaded Pd–GO material was characterized by X-ray diffraction (XRD), infrared (IR) spectroscopy and transmission electron microscopy (TEM). Structural characterization revealed that intercalation of the precursor took place in GO and the reduced Pd nanoparticles were situated both on the external surface and in the interlamellar space of the GO lamellae. The catalytic behaviour of Pd–GO was investigated in the liquid-phase hydrogenations of 3-hexyne and 4-octyne under standard conditions. For both reactants, marked turnover frequencies (18–36 s^?1) and pronounced (Z)-alkene stereoselectivities (93–98.4%) were obtained, indicating that Pd–GO was a highly active and stereoselective catalyst. For the stereoselective hydrogenation of 3-hexyne, Pd–GO exhibited an outstanding catalytic performance: at reactant:Pd (S:Pd) ratios ? 5000, complete conversions were achieved in 8–15 min and the (Z)-alkene stereoselectivities exceeded 98%.     

Palladium metal nanoparticles on organically modified thin hybrid films

Hybrid thin films containing palladium nanoparticles in different concentrations (0.5% and 1%) with and without nanoparticle stabiliser agent [mercaptopropyl trimethoxysilane, MPTMS] were prepared using a sol–gel process. Pd nanoparticles were found to be highly dispersed on the thin films with particles ranging from 7 to 10 nm. The catalytic properties of the thin films supported Pd nanoparticles were investigated in the Heck reaction of iodobenzene and methyl acrylate. Films containing Pd MNP (with and without MPTMS) gave quantitative conversion and complete selectivity to the targeted product (methyl cinnamate) in a short time of reaction (<15 min) under microwave irradiation. While Pd containing films without MPTMS were highly active and reusable after 3 runs, MPTMS containing films were found to be inactive after the first use. Such phenomenon was correlated to the steric hindrance round the Pd MNP due to the adsorption of species on the surface that render the catalysts inactive.     

Novel synthesis of mesoporous hydroxyapatite using carbon nanorods as a hard-template

A novel hard-template synthesis approach for the fabrication of mesoporous hydroxyapatite (HAP) is described herein. Carbon nanorods, synthesised using mesoporous silica (SBA-15) and an acidified sucrose solution, are used as a hard template, after which, they are utilised to synthesise mesoporous HAP. Transmission electron microscopy (TEM), X-ray diffraction (XRD) energy-dispersive X-ray spectroscopy (EDX) and nitrogen adsorption/Brunauer–Emmett–Teller (BET), are all employed to characterise the synthesised materials. We demonstrate that this approach allows for the successful fabrication of single phase HAP with surface area 242.20±2.27 m² g⁻¹ and average pore diameter 3.5 nm and 18.9 nm. This work proposes for the first time a bespoke innovative procedure that employs carbon nanorods as a template for the synthesis of mesoporous HAP via a hard templating protocol.     

Powder XRD analysis and catalysis characterization of ultra-small gold nanoparticles deposited on titania-modified SBA-15

Ultra-small gold nanoparticles (0.8–1 nm) are successfully deposited on titania-modified SBA-15 via a deposition–precipitation method. A comparison of experimental X-ray diffraction (XRD) patterns with theoretical ones shows that gold exists as Au³⁺ and Au⁰ in the as-synthesized and reduced catalyst, respectively. The XRD analyses also suggest that Au nanoparticles are more developed along the 〈1 1 1〉 direction forming a raft-type structure. Z-contrast transmission electron microscopy analyses indicate that the ultra-small gold nanoparticles are uniformly dispersed on the surface of the substrate. The material is found to possess high catalytic activity for low-temperature CO oxidation.