磷钨酸盐催化转化葡萄糖合成乙酰丙酸

制备了一系列金属离子修饰的磷钨酸盐(M_XH_3-2XPW₁₂O₄₀,M=Zn,Cu,Cs,Ag)催化剂,并将磷钨酸银盐(Ag₃PW₁₂O₄₀)用于水解葡萄糖制备乙酰丙酸的实验中。采用FTIR、XRD、SEM和EPMA等技术对磷钨酸盐性能进行了表征,并分析了磷钨酸银盐催化剂在反应前后结构和表面元素相对含量的变化。考察了反应温度、反应时间、催化剂用量和葡萄糖浓度等对乙酰丙酸得率的影响。结果表明:合成的磷钨酸盐具有磷钨酸的Keggin结构,并且Ag₃PW₁₂O₄₀催化剂在多次使用后Keggin结构没有被破坏。在催化合成反应中,在反应温度200℃、反应时间2 h、Ag₃PW₁₂O₄₀催化剂用量0.7 g和葡萄糖浓度40 g·L^-1的条件下,乙酰丙酸的最大得率可达到81.61%,催化剂可重复利用。     

Highly active and selective Cs2.5H0.5PW12O40/SBA-15 composite material in the oxidation of cyclopentane-1,2-diol to glutaric acid by aqueous H2O2

In the present work, for the first time the Cs_2.5H_0.5PW₁₂O₄₀/SBA-15 catalysts were prepared as highly efficient catalysts for the direct production of glutaric acid (GAC) via selective oxidation of cyclopentane-1,2-diol by using aqueous hydrogen peroxide as the green oxidant. The yield of GAC is higher than 88%. The fresh catalyst and the recovered ones were all characterized by XRD, FT-IR, Raman and ³¹P MAS NMR to reveal the structure change during the reaction. XRD results revealed that the Cs_2.5H_0.5PW₁₂O₄₀/SBA-15 catalysts keep the crystalline structure of the as-prepared Cs_2.5H_0.5PW₁₂O₄₀. And it is found that the structure of the Cs_2.5H_0.5PW₁₂O₄₀/SBA-15 catalysts was retained after the reaction, as determined by Raman, FT-IR and ³¹P MAS NMR. The new Cs_2.5H_0.5PW₁₂O₄₀/SBA-15 catalyst can be easily recycled after reaction and can be reused six times, indicating its excellent stability.     

负载型Cs2.5H0.5PW12O40醚化催化剂的制备与催化性能

制备了负载型磷钨酸铯(Cs_2.5H_0.5PW₁₂O₄₀)催化剂，考察了载体种类、载体性质、制备方法和制备条件对催化剂性能的影响,对制备的催化剂进行了表征，并考察了负载型Cs_2.5H _0.5PW₁₂O₄₀作为醚化催化剂的催化活性.结果表明,大孔硅胶是Cs_2.5H_0.5PW₁₂O₄₀的适宜载体，硅胶的钠含量越低制备的Cs_2.5H_0.5PW₁₂O₄₀/SiO₂催化剂的活性越高.采用一步法和二步法制备的Cs_2.5H_0.5PW₁₂O₄₀/SiO₂催化剂均具有较强的酸性、催化活性以及良好的稳定性,可以替代液体酸和阳离子交换树脂,成为一种环境友好的固体酸催化剂.     

Mesoporous H3PW12O40-silica composite: Efficient and reusable solid acid catalyst for the synthesis of diphenolic acid from levulinic acid

Mesoporous H₃PW₁₂O₄₀-silica composite catalysts with controllable H₃PW₁₂O₄₀ loadings (4.0–65.1%) were prepared by a direct sol–gel–hydrothermal technique in the presence of triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) copolymer. Powder X-ray diffraction (XRD) patterns and nitrogen sorption analysis indicate the formation of well-defined mesoporous materials. With H₃PW₁₂O₄₀ loading lower than 20%, the materials exhibit larger BET surface area (604.5–753.0 m² g⁻¹), larger and well-distributed pore size (6.1–8.6 nm), larger pore volume (0.75–1.2 cm³ g⁻¹), and highly dispersed Keggin unit throughout the materials. Raman scattering spectroscopy studies confirm that the primary Keggin structure remained intact after formation of the composites. As a novel kind of reusable solid acid catalyst, as-prepared H₃PW₁₂O₄₀-silica composite was applied for the synthesis of diphenolic acid (DPA) from biomass platform molecule, levulinic acid (LA), under solvent-free condition, and remarkably high catalytic activity and stability were observed.     

Kinetic study of cellulose hydrolysis with tungsten-based acid catalysts

Tungsten plays an important role in transforming cellulose to C2 C3 polyols. In previous reports, the research focus was mainly on the C C cleavage reactions of cellulose catalyzed by various tungsten-containing catalysts, but less on its catalytic role in cellulose hydrolysis although it is usually considered as the rate-determining step in cellulose conversion. In this article, the method of determining kinetics parameters for hydrolyzing cellulose into glucose was developed. The effects of reaction temperature, different tungsten-based acid catalysts, and H⁺ concentration on reaction rate of hydrolyzing cellulose into glucose were quantitatively addressed. The relevant reaction rate equations with using H₃O₄₀PW₁₂, H₄O₄₀SiW₁₂, and H₂WO₄ as tungsten acid catalysts were obtained in developed batch continuous stirred tank reactors and validated by experimental data. The simulating analysis indicates that the reaction mechanism of cellulose hydrolysis can change with the temperature. H₃O₄₀PW₁₂ is the best candidate catalyst for obtaining the maximum glucose concentration.     

Transesterification of Vegetable Oil to Biodiesel using a Heteropolyacid Solid Catalyst

A clean, facile, and ecologically friendly method for the production of biodiesel has been developed. A solid acid, namely the heteropolyacid (HPA) Cs_2.5H_0.5PW₁₂O₄₀, has been used as a heterogeneous catalyst for the production of biodiesel from Eruca sativa Gars. oils (ESG oil) with methanol at a certain temperature. A study for optimizing the reaction conditions such as the reaction time, temperature, the oil to methanol ratio, the amount of catalyst, and the usage times of the catalyst, has been performed. The Cs_2.5H_0.5PW₁₂O₄₀ heterogeneous acid catalyst shows almost the same activity under the optimized reaction conditions as compared to a conventional homogeneous catalyst such as sodium hydroxide or sulfuric acid, and can easily be separated from the products and can be used for several more runs. The most important features of this catalyst are that the catalytic activity is not effected by the content of free fatty acids and content of water in the vegetable oil and that the esterification can occur at a lower temperature (room temperature) and be finished within a shorter time. The results illustrate that the Cs_2.5H_0.5PW₁₂O₄₀ is an excellent, water‐tolerant and environmentally benign solid acid catalyst for the production of biodiesel. The fuel properties of ESG biodiesel were found to be in agreement with the ASTM standard.     

A comparison of cesium-containing heteropolyacid and sulfated zirconia catalysts for isomerization of light alkanes

The heteropolyacid H₃PW₁₂O₄₀ and its cesium salts Cs_xH_3-x PW₁₂O₄₀ (x = 1, 2, 2.5, 3) were synthesized, characterized and tested as catalysts for hydrocarbon reactions. All samples were characterized by a variety of techniques including elemental analysis, X-ray diffraction, dinitrogen adsorption, thermal gravimetric analysis and ammonia sorption. Results from these methods confirmed that pure cesium salts were prepared without significant contamination by amorphous oxide phases. Incorporation of cesium into the heteropolyacid decreased the acidic protons available for catalysis, increased the specific surface area, and increased the thermal stability. The heteropolyacids were tested as catalysts for butane skeletal isomerization, pentane skeletal isomerization and 1-butene double bond isomerization. For comparison, the activity of sulfated zirconia, a well-studied strong acid catalyst, was also evaluated for the three probe reactions. On a per gram basis, the Cs₂HPW₁₂O₄₀ sample was the most active heteropolyacid, presumably due to its high surface area. This sample was more active than sulfated zirconia for pentane skeletal isomerization and 1-butene double bond isomerization. However, sulfated zirconia was more effective for butane skeletal isomerization. Since the pentane and 1-butene reactions were monomolecular in nature, whereas butane isomerization was bimolecular, restrictions inside the micropores of the heteropolyacid may inhibit the formation of long chain intermediates. Interestingly, trace butenes were required to initiate butane isomerization reactions on sulfated zirconia, whereas heteropolyacids catalyzed the reaction in the absence of butenes. This revised version was published online in June 2006 with corrections to the Cover Date.     

H3PW12O40 acid dispersed on its Cs salt: improvement of its catalytic properties by mechanical mixture and grinding

Acidic cesium salts Cs_x H_3-xPW₁₂O₄₀ have been prepared by grinding together amounts of H₃PW₁₂O₄₀ and porous Cs₃PW₁₂O₄₀ compounds in varying stoichiometries. It is shown that this procedure leads to a dispersion of the acid on top of the high surface area Cs₃PW₁₂O₄₀ salt (160 m² g^-1), and, subsequently, yields high surface area materials which exhibit a much higher catalytic activity for n-butane isomerisation at 473 K when compared with samples prepared directly by chemical precipitation. This improvement holds particularly true with low Cs content (x < 2). This revised version was published online in July 2006 with corrections to the Cover Date.     

Regeneration of H<Subscript>3</Subscript>PW<Subscript>12</Subscript>O<Subscript>40</Subscript> catalyst in the direct preparation of dichloropropanol (DCP) from glycerol and hydrochloric acid gas

Methods for regenerating H₃PW₁₂O₄₀ catalyst in the solvent-free direct preparation of dichloropropanol (DCP) from glycerol and hydrochloric acid gas were investigated. Regenerated H₃PW₁₂O₄₀ catalyst was then applied to the solvent-free direct preparation of DCP. In the solvent-free direct preparation of DCP, selectivity for DCP over H₃PW₁₂O₄₀ catalyst regenerated by method I (recovery of solid H₃PW₁₂O₄₀ catalyst by evaporating homogeneous liquidphase product solution) significantly decreased with increasing recycling run, while that over H₃PW₁₂O₄₀ catalyst regenerated by method II (regeneration of H₃PW₁₂O₄₀ catalyst by oxidative calcination of solid product recovered by method I) was slightly decreased with no significant catalyst deactivation with respect to recycling run. On the other hand, selectivity for DCP over H₃PW₁₂O₄₀ catalyst regenerated by method III (regeneration of H₃PW₁₂O₄₀ catalyst by recrystallization and subsequent oxidative calcination of solid product recovered by method II) was the same as that over fresh catalyst without any catalyst deactivation with respect to recycling run. Thus, method III was found to be the most efficient method for the regeneration of H₃PW₁₂O₄₀ catalyst.     

On the active site in H3PW12O40/SiO2 catalysts for fine chemical synthesis

The surface environment and structural evolution of silica supported phosphotungstic acid (H₃PW₁₂O₄₀) catalysts have been investigated as a function of acid loading. H₃PW₁₂O₄₀ clusters are deposited intact upon the silica surface, adopting a Stranksi-Krastanov growth mode forming a two-dimensional adlayer which saturates at 45wt% acid. Intimate contact with the silica support perturbs the local chemical environment of three tungstate centres, which become inequivalent with those in the remaining cluster, suggesting an adsorption mode involving three terminal W==O groups. Above the monolayer, H₃PW₁₂O₄₀ clusters form three-dimensional crystallites with physico-chemical properties indistinguishable from those in the bulk heteropoly acid. These H₃PW₁₂O₄₀/SiO₂ materials are efficient for the solventless isomerisation of α-pinene under mild reaction conditions. Activity scales directly with the number of accessible perturbed tungstate sites at the silica interface; these are the active species.     

Heterogeneous amino acid-based tungstophosphoric acids as efficient and recyclable catalysts for selective oxidation of benzyl alcohol

A series of organic-inorganic composite catalysts, prepared by modifying tungstophosphoric acid (TPA; H₃PW₁₂O₄₀) with different amino acids such as phenylalanine (Phe), alanine (Ala), and glycine (Gly) were synthesized. The physicochemical and acidic properties of these (MH) _x H_3?x PW₁₂O₄₀ (M=Phe, Ala, and Gly; x=1–3) composite materials were characterized by a variety of different analytical and spectroscopic techniques, namely TGA, XRD, FT-IR, XPS, and NMR, and exploited as heterogeneous catalysts for selective oxidation of benzyl alcohol (BzOH) with hydrogen peroxide (H₂O₂). Among them, the [PheH]H₂PW₁₂O₄₀ catalyst exhibited the best oxidative activity with an excellent BzOH conversion of 99.0% and a desirable benzaldehyde (BzH) selectivity of 99.6%. Further kinetic studies and model analysis by response surface methodology (RSM) revealed that the oxidation of BzOH with H₂O₂ follows a second-order reaction with an activation energy of 56.7 kJ·mol^?1 under optimized experimental variables: BzOH/H₂O₂ molar ratio=1 : 1.5 mol/mol, amount of catalyst=6.1 wt%, reaction time (x₃)=3.8 h, and amount of water (x₄)=30.2 mL.     

Effect of CsxH3?xPW12O40 addition on the catalytic performance of ZnFe2O4 in the oxidative dehydrogenation of n-butene to 1,3-butadiene

Oxidative dehydrogenation of n-butene to 1,3-butadiene over ZnFe₂O₄ catalyst mixed with Cs _x H_3−x PW₁₂O₄₀ heteropolyacid (HPA) was performed in a continuous flow fixed-bed reactor. The effect of Cs _x H_3−x PW₁₂O₄₀ addition on the catalytic performance of ZnFe₂O₄ was investigated. Cs _x H_3−x PW₁₂O₄₀ itself showed very low catalytic performance in the oxidative dehydrogenation of n-butene. However, addition of small amount of Cs _x H_3−x PW₁₂O₄₀ into ZnFe₂O₄ enhanced the catalytic performance of ZnFe₂O₄ catalyst. The catalytic performance of ZnFe₂O₄-Cs _x H_3−x PW₁₂O₄₀ mixed catalysts was closely related to the surface acidity of Cs _x H_3−x PW₁₂O₄₀. Among the catalysts tested, ZnFe₂O₄-Cs_2.5H_0.5 PW₁₂O₄₀ mixed catalyst showed the best catalytic performance. Strong acid strength and large surface acidity of Cs_2.5H_0.5PW₁₂O₄₀ was responsible for high catalytic performance of ZnFe₂O₄-Cs_2.5H_0.5PW₁₂O₄₀ mixed catalyst. Thus, Cs_2.5H_0.5PW₁₂O₄₀ could be utilized as an efficient promoter and diluent in formulating ZnFe₂O₄ catalyst for the oxidative dehydrogenation of n-butene.     

Production of middle distillate through hydrocracking of paraffin wax over Pd0.15CsxH2.7?xPW12O40 catalysts: Effect of cesium content and surface acidity

Palladium-exchanged heteropolyacid (Pd_0.15Cs _x H_2.7−x PW₁₂O₄₀) catalysts were prepared by an ion-exchange method with a variation of cesium content (x=2.0, 2.2, 2.5, and 2.7) for use in the production of middle distillate through hydrocracking of paraffin wax. Surface acidity of Pd_0.15Cs _x H_2.7−x PW₁₂O₄₀ catalysts determined by NH₃-TPD experiments showed a volcano-shaped trend with respect to cesium content. Surface acidity of the catalysts played an important role in determining the catalytic performance in the hydrocracking of paraffin wax. Conversion of paraffin wax increased with increasing surface acidity of the catalyst, while yield for middle distillate showed a volcano-shaped curve with respect to surface acidity of the catalyst. Among the catalysts tested, Pd_0.15Cs_2.7PW₁₂O₄₀ catalyst with moderate surface acidity showed the best catalytic performance.     

Effects of Brønsted and Lewis Acidities on Catalytic Activity of Heteropolyacids in Transesterification and Esterification Reactions

Some salts of H₃PW₁₂O₄₀‐M_x/nH_3–xPW₁₂O₄₀ (abbreviated as M_x/nH_3–xPW) were prepared and used as acid catalysts for transesterification and esterification reactions. These catalysts have double acidity properties, i.e., Lewis acidity and Brønsted acidity, that are suitable for the conversion of waste cooking oil into biodiesel. The highest efficiency was 59.2 % and 94.7 % corresponding to transesterification and esterification reactions by Ti_0.6H_0.6PW with moderate Lewis acidity. The relationship between the acidic properties and the catalytic activity is discussed in detail.     

A pronounced catalytic activity of heteropoly compounds supported on dealuminated USY for liquid-phase esterification of acetic acid with n-butanol

12-Phosphotungstic acid and its cesium salts supported on a dealuminated ultra-stable Y zeolite were prepared, and showed the high catalytic activity in the liquid-phase esterification of acetic acid with n-butanol. The supported Cs_2.5H_0.5PW₁₂O₄₀ catalyst gave a high conversion of n-butanol of 94.6% and a selectivity for n-butyl acetate of 100%, accompanying the high water-tolerance and catalytic reusability without regeneration.     

One-pot generation of mesoporous carbon supported nanocrystalline H3PW12O40 heteropoly acid with high performance in microwave esterification of acetic acid and isoamyl alcohol

Ordered mesoporous carbon-supported H₃PW₁₂O₄₀ heteropoly acid materials (HPW/OMCs) have been rationally synthesized for the first time. The method is based on the evaporation-induced triconstituent co-assembly effect using the sol–gel process, wherein soluble resol polymer is used as an organic precursor, and triblock copolymer F127 is used as a template. The ordered mesoporous carbon-supported H₃PW₁₂O₄₀ heteropoly acid materials were analyzed and characterized by X-ray diffraction, N₂ adsorption and desorption (BET), and transmission electron microscope. The mesoporous carbon-supported H₃PW₁₂O₄₀ materials possess an ordered mesostructure, narrow pore size distributions (around 2.8–3.6 nm), high pore volumes (up to 0.49 cm³ g^?1), high specific BET surface areas (up to 590 m² g^?1), tailorable HPW content (up to 30 wt%), and well dispersion of HPW particles. Moreover, the resultant mesoporous ordered mesoporous carbon-supported H₃PW₁₂O₄₀ materials exhibit high catalytic activity in microwave esterification of acetic acid and isoamyl alcohol. The obtained 20 % HPW/OMC catalyst exhibits high catalytic performance with 96.7 % of isoamyl acetate yield at temperature of 120 °C, alcohol/acid molar ratio of 2, catalyst amount of 0.2 g, microwave irradiation power of 800 W, and reaction time of 18 min. It was believed that the concentration of H₃PW₁₂O₄₀ have a crucial effect on the HPW/OMCs’ porosity, mesostructure and catalytic performance.     

Direct synthesis of hydrogen peroxide from hydrogen and oxygen over palladium-exchanged insoluble heteropolyacid catalysts

Palladium-exchanged insoluble heteropolyacid (Pd_0.15Cs_xH_2.7?xPW₁₂O₄₀) catalysts were prepared with a variation of cesium content (x = 2.0, 2.2, 2.5, and 2.7), and were applied to the direct synthesis of hydrogen peroxide from hydrogen and oxygen. Pd_0.15Cs_xH_2.7?xPW₁₂O₄₀ showed high catalytic performance even in the absence of H₂SO₄ additive, indicating that Pd_0.15Cs_xH_2.7?xPW₁₂O₄₀ acted as an efficient catalyst and served as an alternate acid source in the reaction. The catalytic performance of Pd_0.15Cs_xH_2.7?xPW₁₂O₄₀ increased with increasing surface acidity of the catalyst. Among the catalysts tested, Pd_0.15Cs_2.5H_0.2PW₁₂O₄₀ catalyst with the largest surface acidity showed the highest yield for hydrogen peroxide.     

Direct preparation of dichloropropanol from glycerol and hydrochloric acid gas using heteropolyacid (HPA) catalyst by heterogeneous gas phase reaction

Direct preparation of dichloropropanol (DCP) from glycerol and hydrochloric acid gas was carried out in a heterogeneous gas phase reactor using H₃PMo_12?XW_XO₄₀ (X = 0, 3, 6, 9, and 12), H₄SiW₁₂O₄₀, and H₄SiMo₁₂O₄₀ heteropolyacid (HPA) catalysts. Acid property of the HPA catalyst was determined by NH₃-TPD measurement in order to correlate the catalytic activity with the acid property of the catalyst. Acid strength of the HPA catalyst played a key role in determining the catalytic performance in the reaction. Yield for DCP increased with increasing acid strength of the catalyst. Among the catalysts tested, H₃PW₁₂O₄₀ with the highest acid strength showed the highest yield for DCP.     

Catalytic synthesis of N-alkylacrylamide from acrylonitrile and 1-adamantanol with a novel solid heteropoly compound

Catalytic synthesis of N-adamantylacrylamide from acrylonitrile and 1-adamantanol has been studied over various solid and liquid acids. Solid acids such as Cs_2.5H_0.5PW₁₂O₄₀, Amberlyst 15, Nafion, and Nafion–SiO₂ composite gave yields higher than 97% at 373 K, and were superior in yield to liquid acids like p-toluenesulfonic acid, H₃PW₁₂O₄₀, and H₂SO₄. It was further demonstrated that Cs_2.5H_0.5PW₁₂O₄₀ exhibited the highest catalytic performance for this reaction in the presence of excess water. This revised version was published online in July 2006 with corrections to the Cover Date.     

Calcium Salts of Tungstophoric Acid Supported on Silica as Novel Catalysts for Tetrahydrofuran Polymerization

Abstract  

The 12-tungstophoric acid (HPW) and its calcium salts Ca_x/2H_3−xPW₁₂O₄ with the calcium content in the range 0 < x < 3 supported on silica were synthesized, and their catalytic properties were also studied in the polymerization of tetrahydrofuran under mild conditions. These catalysts were characterized by isothermal nitrogen adsorption/desorption, infrared spectroscopy, n-butylamine electrometric titration, and thermal analysis. The calcium salts presented strong acidity and high catalytic performance. When x = 2.0, the supported calcium salt CaHPW₁₂O₄₀/SiO₂ calcined at 300 °C gave the highest catalytic activity. However, a poor catalytic activity was only obtained over the Ca_1.5PW₁₂O₄₀/SiO₂ catalyst substituting all protons of phosphotungstic acid, which was due to its weakest acidity. The CaHPW₁₂O₄₀/SiO₂ sample showed better reusability than normal HPW/SiO₂ catalyst, and reacted as a recyclable and effective catalyst for tetrahydrofuran polymerization.