Direct incorporation of vanadium into three-dimensional KIT-6: 1. Optimization of synthesis conditions

Three dimensional (3-D) cubic KIT-6 with directly incorporated vanadium was hydrothermally synthesized by using Pluronic P123 and n-butanol as the structure-directing mixture, tetraethyl orthosilicate (TEOS) as the silica source and NH₄VO₃ as the vanadium source. The molar composition was varied in the range of 0.017 P123/0.08–2.4 V/1.0–2.0 TEOS/1.31–1.70 BuOH/1.83–3.00 HCl/195 H₂O. The orderness of mesopore structure was estimated by X-ray diffraction, N₂ adsorption, and TEM analysis. The effects of the amount of HCl, TEOS and BuOH on the structure of KIT-6 were discussed. The time and temperature for the synthesis of KIT-6 were also optimized. The amount of vanadium content influenced the framework structure and crystallinity of the Ia3d phase significantly.     

Direct synthesis of vanadium incorporated three-dimensional KIT-6: A systematic study in the oxidation of cyclohexane

The direct synthesis of three-dimensional (3-D) cubic V-KIT-6 was prepared using a Pluronic P123 triblock copolymer as the structure directing agent and n-butanol as the co-surfactant. The material obtained therein showed a very high specific surface area 1000 m²/g with pore diameters that could be tuned within a narrow size distribution of 5.7–6.0 nm. After calcination, Raman and UV–vis analysis revealed the presence of V⁵⁺ species in a highly dispersed state with much less crystalline V₂O₅ formation. ⁵¹V-NMR analysis showed that the vanadium species interacted directly with the silica framework in an almost symmetrical tetrahedral environment. NH₃-TPD analysis for V-KIT-6 showed a wide distribution of acid sites at temperatures ranging from 200 to 800 °C. The calcined V-KIT-6 materials showed excellent catalytic activity in the direct oxidation of cyclohexane using dilute aqueous H₂O₂ as the oxidant.     

Direct incorporation of tungsten into ultra-large-pore three-dimensional mesoporous silicate framework: W-KIT-6

Tungsten was incorporated into ultra-large-pore silicate, KIT-6, via hydrothermal synthesis method using a Pluronic P123 triblock copolymer as the structure directing agent and n-butanol as additive. The Si/W ratio in the synthesis gel was varied from 10 to 100. Calcined W-KIT-6 samples were characterized by XRD, elemental analysis, N₂ sorption, HR-TEM, XPS, DR-UV-Vis, H₂-TPR and NH₃-TPD. These samples possess surface areas ranging from 625 to 927?m²/g with corresponding pore volumes from 1.09 to 1.44?cm³/g and narrow pore size distributions from 6.3 to 6.9?nm. In all the samples, the framework incorporation of tungsten is evident from low angle XRD and DR-UV-Vis analyses. In samples with higher tungsten content, extra-framework WO₃ species were also evident from high angle XRD, Laser Raman and DR-UV-Vis studies. NH₃-TPD study revealed the presence of low to medium acid strength sites in these samples.     

Cobalt oxide species supported on SBA-15, KIT-5 and KIT-6 mesoporous silicas for ethyl acetate total oxidation

Cobalt oxide modified SBA-15, KIT-5 and KIT-6 mesoporous silicas with different pore size/pore entrances have been synthesized by a conventional wet impregnation method using cobalt nitrate as the precursor. The modified materials were characterized by N₂-physisorption, XRD, TEM-EDX, XPS, FT-IR, UV–vis and TPR-TG with hydrogen. Their catalytic activities in total oxidation of ethyl acetate were evaluated. A good correlation was observed between the catalytic activity, and the presence of spinel-type Co₃O₄ in the materials. Supports with larger mesopores facilitated the formation of such easily reducible spinel particles. However, the interconnectivity of the mesopores and the uniformity of the channel dimensions also had an influence on the catalytic activity, implying that mass-transfer effects, especially in the case of supports with cage-like mesopores.     

Effects of incorporation of ions into Au/TiO2 catalysts for carbon monoxide oxidation

A number of anions and cations have been incorporated into TiO₂ as support for gold catalysts and also into as-prepared Au/TiO₂ catalysts at levels of 0.4 mol% and 2.5 mol% with respect to the support. The activities of the catalysts for CO oxidation reveal that the at the higher concentration level of the ions, in all cases, a decrease in activity compared with unmodified Au/TiO₂. However, and more interestingly, addition of only 0.4 mol% of the ions to the support, prior to gold addition, in most cases resulted in activity enhancement whilst similar addition to Au/TiO₂ resulted in decrease in activity. Attempts have been made to understand the origin of these effects.     

CeO2-ZnO/KIT-6催化剂在光催化吸附脱硫中的应用

光催化吸附脱硫技术在油品脱硫领域引起了极大的关注,具有高光催化活性和有机硫化物吸附能力的双功能材料的开发是关键。首次合成了3D介孔二氧化铈-氧化锌/KIT-6（CeO₂-ZnO/KIT-6）催化剂,并应用于二苯并噻吩（DBT）的光催化吸附脱硫。通过X射线衍射（XRD）、氮气吸附-脱附和透射电子显微镜（TEM）等手段对催化剂进行表征,并研究了催化剂在光照下对DBT的转化性能。实验结果表明,在没有额外添加氧化剂（例如氧气、过氧化氢或有机氧化剂）的情况下,CeO₂-ZnO/KIT-6具有很好的光催化脱硫能力,当二氧化铈质量分数为10%、氧化锌质量分数为15%时,催化剂CeO₂-ZnO/KIT-6对DBT的转化率可达90%,最大吸附量（以硫计）为8.1 mg/g。无氧化剂体系对于燃料的后续处理非常有利,并且可以明显降低脱硫成本。     

以KIT-6为模板制备有序介孔氧化铈催化剂

为了制备介孔氧化铈,并研究其对CO的催化氧化活性,本文以介孔氧化硅(KIT-6)为模板,采用硬模板法制备了有序介孔氧化铈。利用X-射线衍射、透射电镜、氮气吸脱附、傅里叶红外光谱、拉曼光谱和X-射线荧光光谱等技术对介孔氧化铈催化剂的结构进行了表征,并考察了该催化剂催化氧化CO的性能。实验结果表明:所制备的催化剂为萤石结构的有序介孔氧化铈,平均孔径约为3.4 nm,比表面积高达123.9 m2/g,平均晶粒尺寸为8.2 nm,表面存在质量分数3.3%的氧化硅。介孔氧化铈对CO的催化氧化实验表明,CO转化率达到50%时的温度即t50为284℃,明显优于沉淀法制备的普通氧化铈的催化性能(t50为320℃)。     

Bi2SiO5/SiO2催化剂上苯乙烯制苯甲醛催化性能研究

以甲醇为溶剂、过氧化氢为氧化剂,考察Bi_2SiO_5/SiO_2催化氧化苯乙烯制苯甲醛的反应温度、反应时间和V(苯乙烯):V(过氧化氢)对氧化反应的影响。通过动力学数据和模型分析,进行模型筛选及参数拟合,发现以过氧化氢和甲醇吸附形成五元环结构,苯乙烯吸附在活性位上,表面反应为控制步骤时,导出模型较好符合苯乙烯氧化制备苯甲醛的实验数据。     

Preparation of ZSM-5 containing vanadium and Brønsted acid sites with high promoting of styrene oxidation using 30% H2O2

Design and synthesis of low cost and efficacious industrial catalyst for the oxidation of styrene has been an important research project. Herein, ZSM-5 zeolite containing tetrahedral vanadium(V) and Br?nsted acid sites(V-H-ZSM-5)was prepared, and identified by characterizations such as XRD, SEM, UV–vis, NH_3-TPD, H_2-TPR N_2-adsorption/desorption and FTIR. V-H-ZSM-5 performed extremely enhanced catalytic activity for the oxidation of styrene with 30% H_2O_2 at 40 °C. Moreover, in-situ FTIR spectrum was used to investigate the catalytic mechanism. The results demonstrate that Br?nsted acid site could not only increase the adsorption concentration of styrene in the micropores of V-H-ZSM-5 via the π complex interaction between double bond of styrene and Br?nsted acid sites, but also increase the oxidation potential of H_2O_2. The synergetic action of tetrahedral vanadium(V) and Br?nsted acid enhanced the catalytic activity for the oxidation of styrene with 30% H_2O_2. Impressively, V-H-ZSM-5 performed high reusability within five runs at a low reaction temperature(40 °C) for the first time.     

Absorption of dietary cholesterol oxidation products and incorporation into rat lymph chylomicrons

Cholesterol oxidation products (oxysterols) induce macrophage lipid loading and accumulate in early arterial fatty streaks. The origin of lesion oxysterols has not been elucidated. The absorption of oxysterols from the diet and transport to the arterial wall by postprandial lipoprotein remnants may be a significant source. This study aimed to investigated the extent of oxysterol absorption and the effect on chylomicron composition. Cholesterol was heat-treated, causing 30% oxidation; the major oxidation products were 7β-hydroxycholesterol, 7-ketocholesterol, 5α,6α-epoxycholesterol, and 5β,6β-epoxycholesterol. Conscious lymph-cannulated rats were given a bolus gastric infusion of 50 mg oxidized cholesterol or 50 mg purified cholesterol in a vehicle of triglyceride. In the rats given the oxidized cholesterol, 6% of the oxysterol load was absorbed and incorporated into lymph chylomicrons. Rats given pure cholesterol had no increase in oxysterols above baseline levels. The incorporation of oxysterols into lymph chylomicrons differed over time with 7β-hydroxycholesterol, having peak absorption at 3 h, followed by 7-ketocholesterol at 4 h and 5α,6α-epoxycholesterol at 5 h. The absorption of oxysterols in animals given the oxidized cholesterol gastric infusate was associated with lymph chylomicron compositional changes at 2–4 h. The oxidized cholesterol-treated group has a twofold increase in the cholesterol (890±84 μg vs. 440±83 μg at 3 h) and triglyceride content (19.76±3.4 μg vs. 8.49±3.8 μg at 3 h). This led to a doubling of chylomicron size over this postprandial period, with particles having a mean diameter of 294 nm in the oxidized cholesterol-treated animals, compared to 179 nm in the purified cholesterol group. In conclusion, dietary oxysterols appear to influence postprandial lipoprotein particle size and composition. These changes may have effects on the clearance of chylomicrons from plasma, arterial delivery of oxysterols, and possible deposition in arterial lesions.     

Dietary lipid,fatty acid oxidation and incorporation of carbon into cholesterol

Female rats (200 g) were fed a nutritionally adequate diet containing 1% by weight of corn oil (low-fat, LF), 21% of corn oil (CO) or 20% of beef tallow plus 1% of corn oil (BT) for two weeks. Food was removed for 8–12 hr, then each rat was refed for 1 hr. Each rat was injected ip with Na-³H-acetate and U-¹⁴C-Na-palmitate, (P),-oleate (O) or-linoleate (L). Expired CO₂ was collected for 2 hr. Liver, heart and serum were obtained for analysis of total lipid¹⁴C and³H and cholesterol¹⁴C and³H. Oxidation of L was twice as great as O or P when the LF diet was fed. CO and BT diets doubled oxidation of O to equal L, and increased oxidation of P, 50%. In liver and serum P was retained to a greater extent than O or L on BT and CO diets. Incorporation of acetate into total lipid was highest on LF diet and reduced by feeding either CO or BT. Incorporation of acetate into cholesterol was greater when BT or CO was fed than for LF.¹⁴C was incorporated into cholesterol in such small amounts that it was barely detectable and could not be counted accurately. Conclusions are that (a) dietary fat affects rate of oxidation of uniformly labeled palmitate and oleate, but not linoleate, (b) acetate is a more ready precursor to cholesterol than is fatty acid carbon, and (c) the acetate incorporated into cholesterol when polyunsaturated fat is fed is not derived directly from fatty acid carbon. The failure of incorporation of fatty acid carbon into cholesterol within 2 hr of administration opens the question of compartmentation of acetate as to its metabolic source. Colorado Agricultural Experiment Station Scientific Series Paper No. 1510.     

离子液体功能化salen Mn催化苯乙烯与CO2一锅合成碳酸苯乙烯酯

合成了咪唑离子液体功能化salen Mn配合物（IL-salen Mn）,并作为唯一催化剂成功应用于苯乙烯与二氧化碳一锅合成碳酸苯乙烯酯反应中。首先,以尿素过氧化氢（UHP）为氧化剂、吡啶氮氧化物（PyNO）为助剂,催化苯乙烯高效制备环氧苯乙烷,继而催化环氧苯乙烷与二氧化碳发生环加成反应合成碳酸苯乙烯酯。分别考察了催化剂的种类和用量、助剂用量、氧化剂种类和用量、反应时间以及反应温度等因素对上述反应的影响。当催化剂用量为8 mol%（以反应物总的物质的量记）,n(苯乙烯)∶n(UHP)∶n(PyNO)=1.0∶3.0∶0.2,环氧化反应温度和时间分别为30 ℃和5 h,环加成反应温度和时间分别为80 ℃和12 h,二氧化碳压力为1 MPa时,苯乙烯的转化率为90%,碳酸苯乙烯酯收率达到32%。结合前期研究与反应时间动力学结果,推测了该串联反应可能的机理。     

离子液体功能化salen Mn催化苯乙烯与CO2一锅合成碳酸苯乙烯酯

合成了咪唑离子液体功能化salen Mn配合物(IL-salen Mn),并作为催化剂应用于苯乙烯与CO2一锅合成碳酸苯乙烯酯反应中.以尿素过氧化氢(UHP)为氧化剂、吡啶氮氧化物(PyNO)为助剂,催化苯乙烯高效制备环氧苯乙烷,继而催化环氧苯乙烷与CO2发生环加成反应合成碳酸苯乙烯酯.考察了催化剂种类和用量、助剂用量、氧化剂种类和用量、反应时间、反应温度及CO2压力对上述反应的影响.结果表明,当催化剂IL-salen Mn用量为苯乙烯物质的量的8％、n(苯乙烯):n(UHP):n(PyNO)=1.0:3.0:0.2、环氧化反应温度和时间分别为30℃和5 h、环加成反应温度和时间分别为80℃和12 h、CO2压力为1.0 MPa时,苯乙烯的转化率为90％,碳酸苯乙烯酯收率达到32％.结合前期研究与反应时间动力学结果,推测了该一锅反应的可能机理.     

离子液体功能化salen Mn催化苯乙烯与CO2一锅合成碳酸苯乙烯酯

合成了咪唑离子液体功能化salen Mn配合物(IL-salen Mn),并作为催化剂应用于苯乙烯与CO2一锅合成碳酸苯乙烯酯反应中.以尿素过氧化氢(UHP)为氧化剂、吡啶氮氧化物(PyNO)为助剂,催化苯乙烯高效制备环氧苯乙烷,继而催化环氧苯乙烷与CO2发生环加成反应合成碳酸苯乙烯酯.考察了催化剂种类和用量、助剂用量、氧化剂种类和用量、反应时间、反应温度及CO2压力对上述反应的影响.结果表明,当催化剂IL-salen Mn用量为苯乙烯物质的量的8％、n(苯乙烯):n(UHP):n(PyNO)=1.0:3.0:0.2、环氧化反应温度和时间分别为30℃和5 h、环加成反应温度和时间分别为80℃和12 h、CO2压力为1.0 MPa时,苯乙烯的转化率为90％,碳酸苯乙烯酯收率达到32％.结合前期研究与反应时间动力学结果,推测了该一锅反应的可能机理.     

Direct oxidation of H2S into S. New catalysts and processes based on SiC support

Nickel sulphide, supported on SiC, exhibits a very high activity and selectivity for the direct oxidation of H₂S into S at medium temperatures (100–120°C) or at room temperature (20–40°C). Iron oxide, also supported on SiC, is highly reactive, and selective, for the same reaction at higher temperatures (210–240°C). This support is very stable, insensitive to steam and to any sulphur compounds in this range of temperature.     

离子液体功能化salen Mn催化苯乙烯与CO2一锅合成碳酸苯乙烯酯

合成了咪唑离子液体功能化salen Mn配合物(IL-salen Mn),并作为催化剂应用于苯乙烯与CO2一锅合成碳酸苯乙烯酯反应中.以尿素过氧化氢(UHP)为氧化剂、吡啶氮氧化物(PyNO)为助剂,催化苯乙烯高效制备环氧苯乙烷,继而催化环氧苯乙烷与CO2发生环加成反应合成碳酸苯乙烯酯.考察了催化剂种类和用量、助剂用量、氧化剂种类和用量、反应时间、反应温度及CO2压力对上述反应的影响.结果表明,当催化剂IL-salen Mn用量为苯乙烯物质的量的8％、n(苯乙烯):n(UHP):n(PyNO)=1.0:3.0:0.2、环氧化反应温度和时间分别为30℃和5 h、环加成反应温度和时间分别为80℃和12 h、CO2压力为1.0 MPa时,苯乙烯的转化率为90％,碳酸苯乙烯酯收率达到32％.结合前期研究与反应时间动力学结果,推测了该一锅反应的可能机理.     

Sulfated niobia supported on KIT-6 as a catalyst for transesterification of groundnut oil

Mesoporous 3D cubic KIT-6 was synthesised hydrothermally via organic template route. Different weight percentages (1, 2 and 3 %) of sulfated niobia were supported on KIT-6 by wet impregnation method and are abbreviated as 1SNK, 2SNK and 3SNK. The synthesised materials were characterized by XRD, FT-IR, BET surface area, DRS-UV Visible and TG techniques. The morphology of pure KIT-6 and SNKs were studied by SEM and HR TEM techniques. Experiments were performed with SNK catalysts for the transesterification reaction to convert the groundnut oil to fatty acid methyl ester (FAME). The product was confirmed by GC–MS. The parameters were optimized to increase the yield of FAME by altering the reaction temperature, reaction time, catalyst loading. Among the synthesized catalysts, 3SNK showed high activity than others due to high density of acid sites. Hence sulphated niobia supported KIT-6 may be better choice of catalyst for the conversion of groundnut oil to FAME.     

Progress of vanadium phosphorous oxide catalyst for n-butane selective oxidation

The utilization of lighter alkanes into useful chemical products is essential for modern chemistry and reducing the CO₂ emission. Particularly, n-butane has gained special attention across the globe due to the abundant production of maleic anhydride (MA). Vanadium phosphorous oxide (VPO) is the most effective catalyst for selective oxidation of n-butane to MA so far. Interestingly, the VPO complex exists in more or less fifteen different structures, each one having distinct phase composition and exclusive surface morphology and physiochemical properties such as valence state, lattice oxygen, acidity etc., which relies on precursor preparation method and the activation conditions of catalysts. The catalytic performance of VPO catalyst is improved by adding different promoters or co-catalyst such as various metals dopants, or either introducing template or structural-directing agents. Meanwhile, new preparation strategies such as electrospinning, ball milling, hydrothermal, barothermal, ultrasound, microwave irradiation, calcination, sol–gel method and solvothermal synthesis are also employed for introducing improvement in catalytic performance. Research in above-mentioned different aspects will be ascribed in current review in addition to summarizing overall catalysis activity and final yield. To analyze the performance of the catalytic precursor, the reaction mechanism and reaction kinetics both are discussed in this review to help clarify the key issues such as strong exothermic reaction, phosphorus supplement, water supplement, deactivation, and air/n-butane pretreatment etc. related to the various industrial applications of VPO.     

Heterogeneous catalysts obtained by incorporation of polymer-supported phosphonates into silica used in oxidation reactions

Summary The synthesis of copolymers functionalized with phosphonate groups, incorporation of them into ordered meso-macroporous silica, characterization and evaluation of the obtained materials as catalysts in oxidation of cyclohexene are presented. The catalysts obtained are very active and selective in epoxidation of cyclohexene using hydrogen peroxide as an environmentally friendly oxidant.