介孔分子筛CsxH3-xPW12O40-SBA-15催化合成丙烯酸正丁酯[

采用溶胶-凝胶方法，以P123为模板剂、正硅酸乙酯为硅源，合成出含有杂多酸铯盐的介孔分子筛Cs_xH_3-xPW₁₂O₄₀-SBA-15。XRD表征结果表明，改性后的催化剂具有纯硅SBA-15分子筛晶体结构。将该催化剂用于合成丙烯酸正丁酯，并考察了不同Cs/P物质的量的比对反应活性的影响，其中Cs_2.5H_0.5PW₁₂O₄₀-SBA-15的催化活性最好。采用正交设计方法确定出各因素对反应结果的影响顺序为反应时间＞反应温度＞原料组成＞催化剂用量，确定最佳操作条件为反应温度130 ℃，酸醇物质的量的比1∶1.2，反应时间5　h，催化剂用量为总原料质量的5%(每克的物料催化剂用量为0.05 g)。重复试验表明Cs_2.5H_0.5PW₁₂O₄₀- SBA-15具有良好的稳定性。     

负载杂多酸(盐)的表征及其在苹果酯合成反应中的催化性能

用浸渍法制备了一系列负载型磷钨酸及其铯盐催化剂,载体包括超稳Y沸石（USY）、脱铝超稳Y沸石（DUSY）、SiO₂和SBA-15,测定了催化剂的比表面积和酸强度,并在乙酰乙酸乙酯与乙二醇液相缩合制取苹果酯反应中考察了催化剂的性能.结果表明,这些负载型杂多化合物催化剂都表现出较高的催化活性.然而,催化剂在水中的溶脱性能实验表明,负载型磷钨酸催化剂存在严重的活性组分流失现象,不能重复使用,而DUSY负载的磷钨酸铯盐催化剂不仅表现出较高的催化活性,而且显示出较好的重复使用性能.在优化的反应条件下30% (质量分数) Cs_2.5H_0.5PW/DUSY催化剂上乙酰乙酸乙酯的转化率可达98.7%,苹果酯的选择性大于97%.     

载体对Ni基催化剂催化蒽醌加氢活性的影响

研究了载体对Ni基催化剂用于蒽醌法制备H₂O₂加氢活性的影响,同时对比了骨架镍的催化活性,考察Ni负载量对催化剂活性的影响。结果表明,负载在SiO₂上的催化剂比负载在γ-Al₂O₃上的催化活性高,对于Ni/SiO₂催化剂,Ni负载质量分数28.57%～50%时,加氢活性较高,按单位质量纯Ni上H₂O₂产量计算,Ni/SiO₂优于骨架镍催化剂,Ni负载量过高时,加氢活性降低。2-乙基蒽醌在Ni/SiO₂催化剂上的加氢为结构敏感型反应,当Ni在SiO₂的分散度达到约18%时,催化活性较佳。     

KNaHC4H4O6·4H2O/Al2O3固体碱催化制备生物柴油

采用酒石酸钾钠（KNaHC₄H₄O6·4H₂O）和Al₂O₃制备了负载型KNaHC₄H₄O₆·4H₂O/Al₂O₃固体碱催化剂,将其应用于菜籽油和甲醇的酯交换反应制备生物柴油,并以生物柴油的转化率作为评价其催化活性的指标。分别考察了催化剂制备条件和酯交换反应条件对催化剂活性的影响。结果表明,在催化剂用量为菜籽油质量的3.5％、醇油物质的量比为9∶1、反应温度65 ℃和反应时间3 h时,转酯化反应的转化率达96.3%。     

负载型铁基高温变换催化剂的制备和性能研究

分别以镁铝尖晶石和活性炭作为载体制备了负载型铁基高温变换催化剂，通过XRD、TEM和活性评价测试，考察了催化剂的结构和催化反应性能。以镁铝尖晶石负载γ-Fe₂O₃制得的催化剂，其催化活性明显高于负载α-Fe₂O₃催化剂，当催化剂组成为：Fe₂O₃ 26%，K2O 2%，MgO 0.05%，Cr₂O₃ 0.7%时，400℃下CO转化率为92%，350℃为84%（汽/气=1， 空速=2000 h^-1）；经氧化处理的活性炭作为催化剂载体时，低铬条件下也具有较好的催化活性，当负载量为40%时，相同变换反应条件下CO的转化率在400℃和350℃下分别为88%和80%。两种催化剂在低Cr₂O₃含量时都保持了与传统铁铬系变换催化剂(B117型)相当的催化活性，对于改善环境具有很大意义。     

载体和制备方法对铜系一步法合成

以甲醇与乙醇一步反应合成异丁醛反应为基础，研究了不同载体对铜基催化剂反应性能的影 响。分别以SiO₂、SiO_2-ZrO₂、SiO_2-Al₂O₃、Al₂O₃和SiO₂-TiO₂为载体，采用溶胶-凝胶和 浸渍法制备催化剂。采用TPR、XRD和BET等技术对催化剂进行表征。结果表明，复合氧 化物特别是SiO₂-ZrO₂和SiO₂-TiO₂作载体能提高催化剂的比表面积，活性组分分散 好，催化剂的催化性能较好。     

修饰剂对磷霉素环氧化催化剂的影响

采用原位法制备活性炭负载磷钨酸催化剂,制备过程中加入环氧丙基磷酸盐（顺丙烯磷酸盐的环氧化产物）作为修饰剂,获得活性炭负载修饰型PW/C催化剂,并用于顺丙烯磷酸的环氧化反应。结果表明,加入5%的修饰剂可以使该催化剂环氧化收率提高58.4%,重复使用稳定性也明显改善。采用BET、IR和XRD方法表征证明,在活性炭负载催化剂上主要催化活性成分为H₃PW₁₂O₄₀磷钨杂多酸。     

纳米γ-Fe2O3复合氧化物的制备与气敏性质

用溶胶-凝胶法制备了纳米γ-Fe₂O₃及γ-Fe₂O₃/SiO₂复合氧化物,用热重-差热分析 (TG-DTA)、X射线衍射 (XRD)、透射电镜 (TEM)和二次粒度分布对纳米粒子进行表征,并考察了γ-Fe₂O₃、γ-Fe₂O₃/SiO₂敏感材料对CO、H₂、C₂H₄、C₆H₆等气体的敏感系数及其焙烧温度对敏感系数的影响,并选择了敏感材料对气体检测的最佳工作温度.结果表明,γ-Fe₂O₃/SiO₂纳米复合氧化物中SiO₂对提高γ-Fe₂O₃的相变温度、加强热稳定性及提高催化和气体敏感系数起很大作用.     

纳米粒子Al2O3 催化剂在制备n-DOP增塑剂反应中的催化活性

用改进了的溶胶2凝胶法新工艺在不同条件下制备出不同结构的纳米粒子A l₂O₃ 催化剂。采用在纳米A l₂O₃ 催化作用下苯酐与正辛醇反应生成n-DOP 增塑剂的方法考察了不同纳米A l₂O₃ 的催化活性。结果表明, 由于制备条件对纳米A l₂O₃ 前驱体组成结构的影响, 使制得的纳米A l₂O₃ 催化性能各异。以C 型纳米G₂A l₂O₃ 的催化活性较高。B 型纳米C₂H₂A l₂O₃ 催化剂具有较高的比活性。反应转化率随温度升高而逐渐增大, 而纳米A l₂O₃ 催化活性在低温时也随温度升高而增大, 高温时则不明显, 相反, 随反应时间增长, 催化活性急剧下降。     

TiO2复合氧化物的制备及其在加氢脱硫中的应用

对TiO₂、TiO₂-Al₂O₃、TiO₂-SiO₂和TiO₂-ZrO₂载体的制备技术及其在加氢脱硫中的应用进行了综述。研究表明，以TiO₂调变的Al₂O₃、SiO₂和ZrO₂载体能影响MoO₃与Al₂O₃、MoO₃与SiO₂及MoO₃与ZrO₂之间的相互作用，改善MoO₃在载体表面的分散，促进其还原，有利于提高催化剂表面活性组分的数量，提高催化剂的加氢脱硫活性。     

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.     

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.     

Catalytic decomposition of 2,3-dihydrobenzofuran to monomeric cyclic compounds over Pd/XCs2.5H0.5PW12O40/OMC (ordered mesoporous carbon) (X = 10–30 wt.%) catalysts

A series of Pd/XCs_2.5H_0.5PW₁₂O₄₀/OMC (ordered mesoporous carbon) (X = 10, 15, 20, 25, and 30 wt.%) catalysts with different Cs_2.5H_0.5PW₁₂O₄₀ contents (X, wt%) were prepared by a sequential incipient wetness impregnation method for use in the catalytic decomposition of 2,3-dihydrobenzofuran to monomeric cyclic compounds. 2,3-Dihydrobenzofuran was used as a lignin model compound for representing β-5 linkage of lignin. Acidity of Pd/XCs_2.5H_0.5PW₁₂O₄₀/OMC catalysts served as an important factor determining the catalytic performance in the reaction. Conversion of 2,3-dihydrobenzofuran and total yield for main products (2-ethylphenol and ethylcyclohexane) increased with increasing acidity of Pd/XCs_2.5H_0.5PW₁₂O₄₀/OMC catalysts.     

An inorganic/organic self-humidifying composite membranes for proton exchange membrane fuel cell application

With an aim to operate the proton exchange membrane fuel cells (PEMFCs) with dry reactants, an inorganic/organic self-humidifying membrane based on sulfonated polyether ether ketone (SPEEK) hybrid with Cs_2.5H_0.5PW₁₂O₄₀ supported Pt catalyst (Pt-Cs2.5 catalyst) has been investigated. The Pt-Cs2.5 catalysts incorporated in the SPEEK matrix provide the site for catalytic recombination of permeable H₂ and O₂ to form water, and meanwhile avoid short circuit through the whole membrane due to the insulated property of Cs_2.5H_0.5PW₁₂O₄₀ support. Furthermore, the Pt-Cs2.5 catalyst can adsorb the water and transfer proton inside the membrane for its hygroscopic and proton-conductive properties. The structure of the SPEEK/Pt-Cs2.5 composite membrane was characterized by XRD, FT-IR, SEM and EDS. Comparison of the physicochemical and electrochemical properties, such as ion exchange capacity (IEC), water uptake and proton conductivity between the plain SPEEK and SPEEK/Pt-Cs2.5 composite membrane were investigated. Additive stability measurements indicated that the Pt-Cs2.5 catalyst showed improved stability in the SPEEK matrix compared to the PTA particle in the SPEEK matrix. Single cell tests employing the SPEEK/Pt-Cs2.5 self-humidifying membrane and the plain SPEEK membrane under wet or dry operation conditions and primary 100 h fuel cell stability measurement were also conducted in the present study.     

Catalytic decomposition of benzyl phenyl ether to aromatics over cesium-exchanged heteropolyacid catalyst

Cesium-exchanged Cs _x H_3.0−x PW₁₂O₄₀ (X=2.0–3.0) heteropolyacid catalysts were prepared and applied to the decomposition of benzyl phenyl ether to aromatics. Benzyl phenyl ether was chosen as a lignin model compound for representing α-O-4 bond in lignin. Phenol, benzene, and toluene were mainly produced by the decomposition of benzyl phenyl ether. Conversion of benzyl phenyl ether and total yield for main products (phenol, benzene, and toluene) were closely related to the surface acidity of Cs _x H_3.0−x PW₁₂O₄₀ (X=2.0–3.0) heteropolyacid catalyst. Conversion of benzyl phenyl ether and total yield for main products increased with increasing surface acidity of the catalyst. Among the catalysts tested, Cs_2.5H_0.5PW₁₂O₄₀ with the largest surface acidity showed the highest conversion of benzyl phenyl ether and total yield for main products.     

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 (Cs2 5H0 5PW1 2 O4 0 )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Cs2 5H0 5PW1 2 O4 0 作为醚化催化剂的催化活性 结果表明 ,大孔硅胶是Cs2 5H0 5PW1 2 O4 0 的适宜载体 ,硅胶的钠含量越低制备的Cs2 5H0 5PW1 2 O4 0 SiO2 催化剂的活性越高 .采用一步法和二步法制备的Cs2 5H0 5PW1 2 O4 0 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     

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.     

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.     

溶胶-凝胶法制备H3PW12O40/SiO2及催化合成三羟甲基丙烷三庚酸酯

H3PW12O40/SiO2 (PW/SiO2) was prepared by the sol-gel method and trimethylolpropane triheptanoate (TMH) was synthesized by trimethylolpropane (TMP) and heptylic acid (HA) in the presence of H3PW12O40/SiO2. The results showed that the catalyst with 50% (mass) PW had good activity and stability. The optimal esterification conditions were as follows: nTNP：nHA = 1：4, 2%(mass) PW/SiO2, reaction temperature 120-200℃ and 3 h. The structure of TMH was characterized by GC, IR, ^1HNMR spectra and the rate of esterification was up to 95%.     

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.