Synthesis,characterization of SiO2 supported-industrial phosphoric acid catalyst for hydrolysis of NaBH4 solution

Abstract

Tunisian industrial phosphoric acid H₃PO₄ was supported on silica gel SiO₂ (SIPA) to catalyze the hydrolysis reaction of aqueous alkaline sodium borohydride (NaBH₄). The SiO₂ was produced from purified quartz sand using alkali fusion-acidification chemical process. The BET surface area results indicate that the prepared silica gel could reach a specific surface area up to 585 m²/g. The addition of PO₃H₂ functional groups resulted in an increase of surface acidity of SiO₂ catalyst as shown by FT-IR and DTA-DTG spectra. The total acidity of SIPA catalyst was determined by titration to be 2.8?mmol H⁺/g. SEM/EDS maps reveal the distribution of heavy metals on the silica surface. The effect of supported PO₃H₂ functional groups and heavy metals on the NaBH₄ hydrolysis reaction was studied for different ratios of SIPA catalyst to NaBH₄. The sample 12SIPA/NaBH₄ leads to a very high hydrogen generation rate (up to 90%). The activation energy of hydrogen generation by NaBH₄ hydrolysis was 25.7?kJ mol^?1.     

Hydrosilylation Catalyzed with Rh(PPh3)3Cl/Ionic-Liquid–Functionalized SiO2

Ionic liquid–modified silica has been prepared by a “one-pot” reaction of activated silica, 3-chloropropyltriethoxysilane, and alkylimidazole or pyridine. It was found that the catalytic activity and β-adduct selectivity of the supported catalyst Rh(PPh₃)₃Cl/ionic-liquid–modified-SiO₂ for the hydrosilylation reaction of alkenes with triethoxysilane was significantly improved. Furthermore, the catalyst system could be recovered easily.     

Sulfonic Acid–Functionalized Silica (SiO2-Pr-SO3H) as a Solid and a Heterogeneous Catalyst in Green Organic Synthesis: Recent Advances

The application of sulfonic acid–functionalized silica (SBA-Pr-SO₃H) as a catalyst in organic synthesis has become an efficient and green strategy for the selective construction of organic motifs. Therefore, the great efforts have been made by scientists to replace the conventional acid catalysts by sulfonic acid–functionalized silica used as solid, heterogeneous catalyst in various organic transformations. The sustainable advantage of sulfonic acid–functionalized silica is that it can be recovered and reused several times without loss of its efficiency. In this tutorial review, we attempt to give an overview about the use of sulfonic acid–functionalized silica as a catalyst in the synthesis of various organic compounds having industrial as well as pharmaceutical applications.     

Ultrasound-promoted green approach for the synthesis of multisubstituted pyridines using stable and reusable SBA-15@ADMPT/H5PW10V2O40 nanocatalyst at room temperature

ABSTRACT

A facile one-pot protocol for the synthesis of 2-amino-3-cyanopyridins using SBA-15@Triazine/H₅PW₁₀V₂O₄₀ as an efficient catalyst under ultrasonic conditions has been developed. The nanohybrid catalyst was prepared by the chemical anchoring of Keggin heteropolyacid H₅PW₁₀V₂O₄₀ onto the surface of SBA-15 mesoporous silica modified with 2-APTS -4,6-bis(3,5-dimethyl-1H-pyrazol- 1-yl)-1,3,5-triazine (ADMPT) linker. Then the nanohybrid was used as a green, efficient, eco-friendly, and highly recyclable catalyst for the one-pot and multi-component synthesis of 2-amino-3-cyanopyridin derivatives from the reaction of aldehydes, malononitrile, cyclic ketones and ammonium acetate under ultrasound waves with good to excellent yields (79–95%) and in a short span of time. This nanocatalyst was characterized by using FT-IR, XRD, SEM, TEM, BET, and EDX techniques.     

AlCl3/PCC-SiO2-Promoted Oxidation of Azaindoles and Indoles

Abstract

A simple and efficient method is described for the oxidation of 7-azaindoles and indoles to 7-azaisatins and isatins using pyridinium chlorochromate–silica gel (PCC-SiO₂) with the aid of Lewis acid catalyst aluminium chloride (AlCl₃) in dichloroethane. Simplicity of the reaction conditions, easy workup procedure, and good yields are the key features of this protocol.     

Synthesis of one-pot pyrazolo[4′,3′:5,6]pyrano[2,3-c]phenazin-15-yl) methanone derivatives via a multi-component using Fe3O4@TiO2-SO3H as a recoverable magnetic catalyst under microwave irradiation

ABSTRACT

A new one-pot method for the synthesis four-component of pyrazolo[4′,3′:5,6]pyrano[2,3-c]phenazin-15-yl)methanone derivatives has been developed in the presence of nano Fe₃O₄@TiO₂-SO₃H catalysts (heterogeneous acid) under microwave conditions and in a solvent-free environment at 180?W. One of the benefits of using this catalyst was its re-use in subsequent stages of its reaction without much loss in its activity, which was carried out by an external magnet and recovered. The catalyst was synthesized and characterized by XRD, EDX, TEM, FESEM, TGA-DTA, BET, VSM and AFM. The productivity of the products obtained from this protocol (MAOS) is significantly high and the shorter reaction time in the synthesis process over the reflux method. These results showed advantages for synthesis, such as mild reaction conditions, no use of toxic catalysts in the laboratory, solvent-free environment, low energy consumption and Economically Affordable.     

Sulfonic Acid Functionalized Nano Γ-Al2O3: a New,Efficient, and Reusable Catalyst for Synthesis of Thioamides

Abstract

Sulfonic acid functionalized nano γ-Al₂O₃ is easily prepared by the reaction of nano γ-Al₂O₃ with 1,3-propane sulfone. This reagent can be used as an eficient catalyst for the synthesis of thioamides. This new method consistently has the advantages of excellent yields and short reaction times. Further, the catalyst can be recovered for several times.     

TsOH-SiO2 as an efficient and eco-friendly catalyst for Knoevenagel condensation

Tosic acid on silica gel (TsOH-SiO₂) was synthesized and characterized using microscopic and spectroscopic techniques such as powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and FT-IR spectroscopy. Thermal behaviour of the catalyst was investigated by differential scanning calorimetry (DSC) and thermogravimetric (TG) analysis. TsOH-SiO₂ showed excellent catalytic activity for the Knoevenagel condensation and was recyclable for six cycles.     

Deactivation and regeneration of the B2O3/TiO2-ZrO2 catalyst in the vapor phase Beckmann rearrangement of cyclohexanone oxime

The deactivation and regeneration of B₂O₃/TiO₂-ZrO₂ catalyst for the vapor phase Beckmann rearrangement of cyclohexanone oxime to -caprolactam were studied. The fresh, deactivated and regenerated catalysts were characterized by using adsorption of nitrogen, X-ray diffraction (XRD), thermogravimetry (TG) and NH₃-temperature-programmed desorption (NH₃-TPD) techniques. The crystal structure and pore size distribution of the catalyst were retained after reaction, but the number of acid sites decreased significantly. There was a relationship between the amount of coke deposited on the catalyst and the decline in catalytic activity. These results suggest that the coke deposition on the surface of catalyst is mainly responsible for the catalyst deactivation. The catalytic activity can be recovered completely after calcining the deactivated catalyst in air flow at 600 °C for 8 h.     

Nano-Fe3O4–Supported,Hydrogensulfate Ionic Liquid–Catalyzed,One-Pot Synthesis of Polysubstituted Pyridines

Abstract

Anchoring 1-methyl-3-(triethoxysilylpropyl) imidazolium chloride onto silica-coated magnetic Fe₃O₄ particles afforded the corresponding supported ionic liquid. Exchanging the Cl^? anion by treating with H₂SO₄ gave Brønsted ionic liquid 1-methyl-3-(triethoxysilylpropyl) imidazolium hydrogensulfate. The synthesized catalyst was characterized by various techniques such as infrared, x-ray diffraction, scanning electron microscopy, thermogravimetric analysis, and elemental analyses. The results indicated that the prepared catalyst had a nanostructure. The catalytic activity of the supported ionic liquid was examined in the synthesis of the polysubstituted pyridines by reaction of aromatic aldehydes with acetophenones and ammonium acetate in moderate to good yields under solvent-free conditions. The catalyst can be easily recovered by applying an external magnetic field and reused for at least seven runs without deterioration in catalytic activity.     

Co或Ni促进的Cu/SiO2-Al2O3催化剂上丙三醇和苯胺气相合成3-甲基吲哚

对丙三醇和苯胺在Co或Ni促进的Cu/SiO2-Al2O3催化剂上气相合成3-甲基吲哚进行了研究.采用N2吸附、氢气程序升温还原(H2-TPR)、电感耦合等离子体(ICP)发射光谱、X射线衍射(XRD)、透射电子显微镜(TEM)、氨程序升温脱附(NH3-TPD)及热重(TG)分析等技术对催化剂进行了表征.结果表明,向Cu/SiO2-Al2O3催化剂加入钴或镍助剂改善了催化剂的催化性能,钴比镍更加有效.在催化剂Cu-Co/SiO2-Al2O3和Cu-Ni/SiO2-Al2O3上,反应第3 h,3-甲基吲哚收率分别达到47%和45%,而且催化剂经过6次再生收率仍能达到44%和42%.各种表征表明,向Cu/SiO2-Al2O3催化剂加入钴或镍助剂能增强铜和载体之间的相互作用,其结果不仅促进了铜粒子在载体表面的分散度,而且有效减少了反应过程中铜组分的流失.另外,加入钴或镍助剂还能减少催化剂的中强酸中心数,从而提高3-甲基吲哚的选择性,并且抑制积炭的形成.此外,钴助剂还能增加催化剂的弱酸中心数,促进3-甲基吲哚的生成.提出了金属铜与弱酸中心共同促进3-甲基吲哚合成的催化反应机理.     

Selective oxidation of octadecan-1-ol to octadecanoic acid over Co3O4/SiO2 catalysts

Factors (reaction temperature, reaction time, flow rate of oxygen, amount of catalyst, etc.) influencing the catalytic properties of Co₃O₄/SiO₂catalyst in the oxidation octadecan-1-ol to octadecanoic acid were investigated. The catalysts were characterized by means of XRD, FT-IR and N₂-adsorption. The experimental results indicate that under the optimal condition the selectivity to octadecanoic acid reached 97.5 % over 5 % Co₃O₄/SiO₂ catalyst.This revised version was published online in December 2005 with corrections to the Cover Date.     

The effects of silica gel (carrier) on the activity (hydrogen yield) of photocatalytic decomposition of water over [pol-Ti(OBu)4 + CH3OH]-complex

A significant effect of pore size has been found on the yield of photolysis of water to hydrogen, ozone (oxidising product) and methane (decomposing product of catalyst or solvent) using [pol-Ti(OBu)₄ + CH₃OH]-complex/SiO₂. The pore structure of silica gel has been found to provide good conditions for forming this type of catalyst.     

Reverse Atom Transfer Radical Polymerization of Acrylonitrile Catalyzed by FeCl3/Lactic Acid

Reverse atom transfer radical polymerization (RATRP) of acrylonitrile (AN) was carried out using azobisisobutyronitrile (AIBN) as initiator, ferric trichloride anhydrous (FeCl₃)/lactic acid (LA) as catalyst system; a ratio of FeCl₃/LA was 1:2 gave the best control. RATRP of AN with N,N-dimethylformamide (DMF) as solvent gave the moderate polymerization rate and the narrowest polydispersity index (PDI). When FeCl₃ was replaced by CuBr₂, RATRP of AN showed a longer induction period. When Cu was added to the CuBr₂-based catalyst system, the induction period was reduced. ¹H-NMR spectra of PAN verified the possibility of controlled/living polymerization for future chain extension.     

Expeditious,Nano-BF3 · SiO2-Catalyzed Michaelis–Arbuzov Reaction in an Ionic Liquid: Synthesis of Privileged Aryl/Heterocyclic Phosphonates

An expeditious, simple, and green method was developed for the synthesis of privileged aryl/heterocyclicphosphonates, 8(a–c) to 13(a–c) through Michaelis–Arbuzov reaction of aryl/heterocyclic halides (Br), 1–6, and trialkylphosphites, 7(a–c), in room-temperature ionic liquid [bbim]Br using heterogeneous Lewis catalyst, nano-silica-supported boron trifluoride (BF₃-SiO₂). The advantages of this protocol are simplicity, good yield of the products, less reaction time (20–38 min), mild reaction conditions, easy workup, and reusability of the catalyst and ionic liquid. It is demonstrated that nano-BF₃-SiO₂ is a recoverable and easy accessible catalyst for the formation of C(sp²)-P bond in an ionic liquid.     

Preparation and characterization of CuO/SiO2 and NiO/SiO2 with bimodal pore structure by sol-gel method

CuO/SiO₂ and NiO/SiO₂ with bimodal pore structure were prepared by sol-gel reactions of Tetra-methoxysilane (TMOS) and the respective metal nitrate in the presence of poly (ethylene oxide) (PEO) with an average molecular weight of 10 000 and the catalyst of acetic acid. In this process, the interconnected macroporous morphology was formed when transitional structures of spinodal decomposition were frozen by the sol-gel transition of silica. The addition of copper and nickel into the silica-PEO system had a negligible effect on the morphology formation. In gel formation, it was found that NiO crystalline sizes in the samples increased with decreasing Si/Ni molar ratio. It was considered that PEO interacted with both silica and nickel cations. In the CuO/SiO₂ with the presence of PEO_, CuO crystalline sizes were larger than those of NiO/SiO_2. It was considered that there was no obvious interaction between the Cu cation and PEO, most of the copper ions in wet silica gel were present in the outer solution. They easily aggregated as copper salts in the drying process of wet gel and decomposed into CuO particles in heating. While in the CuO/SiO₂ with the absence of PEO, the Cu was selectively entrapped as small particles in the gel skeleton due to the interaction between Cu aqua complex and silica gel network.     

Rh(PPh3)3Cl/Tetrakis(Dialkylamino)Phosphonium Salts as Thermoregulated and Recyclable Catalytic System for Hydrosilylation Reaction

Abstract

Eleven tetrakis(dialkylamino)phosphonium salts have been prepared and were used as “soft” catalyst supports for the hydrosilylation reaction of styrene with triethoxysilane catalyzed by Rh(PPh₃)₃Cl. Among the Rh(PPh₃)₃Cl/tetrakis(dialkylamino)phosphonium salts tested, the best catalytic activity and selectivity in favor of the β-adduct were obtained when {[(C₄H₉)₂N]₃[(C₈H₁₇)₂N]P}PF₆ was used as the support, and Rh(PPh₃)₃Cl/ {[(C₄H₉)₂N]₃[(C₈H₁₇)₂N]P}PF₆ catalyst system can be reused more than 10 times without noticeable loss of catalytic activity and selectivity.

GRAPHICAL ABSTRACT      

H2SO4-SiO2: Highly Efficient and Reusable Catalyst for per-O-Acetylation of Carbohydrates Under Solvent-Free Conditions

Sulfuric acid immobilized on silica gel (H₂SO₄-SiO₂) was used as an efficient promoter for per-O-acetylation of carbohydrates with acetic anhydride under solvent-free conditions. The substrates include not only monosaccharides and disaccharides, but also glycosides. The catalyst is recyclable and stable at room temperature, and the reaction protocol is simple, is cost-effective, and gives good isolated yield with high purity. The large-scale reactions also proceeded conveniently and in high yields.