An effective aza-Michael addition of aromatic amines to electron-deficient alkenes in alkaline Al2O3

Aza-Michael addition of aromatic or aliphatic amines with various electron-deficient alkenes was performed using alkaline Al₂O₃ as solid media at room temperature afforded the corresponding Michael addition products in good to excellent yields. The alkaline Al₂O₃ can be easily recovered and reused.     

KF/Al2O3 mediated 1,3-dipolar cycloaddition of azomethine ylides: a novel and convenient procedure for the synthesis of highly substituted pyrrolidines

The regio- and diastereoselective synthesis of pyrrolidine derivatives through 1,3-dipolar cycloaddition of an azomethine ylide and dipolarophile mediated by KF/Al₂O₃, a versatile solid supported reagent, is reported. KF/Al₂O₃ is sufficiently basic such that it can deprotonate α-imino esters to generate azomethine ylides and it also functions as a solid supported catalyst leading to the cycloadduct rather than the Michael adduct.     

Preparation of MoO3/g-Al2O3 catalyst by the reaction of a-boehmite with MoO3/H2O slurry - dual role of MoO3 as active phase and texture stabilizer during calcination

Summary Catalyst MoO₃/g-Al₂O₃ was prepared by the reaction of a-boehmite with molybdic acid in slurry MoO₃/H₂O followed by calcination. The deposited MoO₃ functioned as thermal stabilizer and inhibited sintering of Al₂O₃ phase during calcination. After calcination at 550 and 650^oC the surface area of Al₂O₃ obtained from a-boehmite was 207 and 172 m² g^-1, respectively, and of MoO₃/Al₂O₃ obtained from MoO₃/a-boehmite was 323 and 285 m² g^-1, respectively. On the other hand, molybdic acid did not work as peptization agent and the mechanical strength of MoO₃/Al₂O₃ was not higher than of Al₂O₃. The catalyst was sulfided and its activity in thiophene hydrodesulfurization was tested; it exhibited about the same activity as reference industrial MoO₃/Al₂O₃ catalyst.     

TPR studies on steam reforming of 2-propanol on Rh/Al2O3, Ru/Al2O3 and Pd/Al2O3

Reaction pathways for steam reforming of 2-propanol (isopropyl alcohol, IPA) on Rh/Al₂O₃, Ru/Al₂O₃ and Pd/Al₂O₃ have been studied by temperature-programmed reactions (TPRs) of IPA and acetone in the presence of steam. The results of TPRs suggest that that of IPA on Rh/Al₂O₃ and Ru/Al₂O₃ proceeds via acetone, while the steam reforming of IPA on Pd/Al₂O₃ takes place via propene from acetone. This revised version was published online in August 2006 with corrections to the Cover Date.     

Direct synthesis of hydrogen peroxide from H2/O2 using Pd/Al2O3 catalysts

Pd/Al₂O₃ catalysts were prepared by the impregnation method and were used for the direct formation of hydrogen peroxide from H₂ and O₂. The H₂O₂ concentration and selectivity were strongly dependent on the solubility of hydrogen in the reaction medium. The modification of the support by halogenate has a beneficial effect on the selectivity. The state of the active Pd on Pd/Al₂O₃ catalysts was studied using X-ray photoelectron spectroscopy, and Pd(0) was found to be active.     

Microwave-assisted deformylation of N-aryl formamide by KF on basic Al2O3

The formyl group was successfully removed from N-aryl formamide by KF on a solid support of basic Al₂O₃ in 4-20 min with microwave irradiation. The conditions mimic base-catalyzed hydrolysis of formamide and are compatible with carbamates and t-butyl esters, but not methyl, ethyl, and benzyl esters.     

High-temperature X-ray diffraction and specific heat studies on GdAlO3, Gd3Al5O12 and Gd4Al2O9

Gadolinium aluminates, GdAlO₃, Gd₃Al₅O₁₂ and Gd₄Al₂O₉ were synthesized by the solution combustion method. Very fine particles in the nanoparticle range of ∼10-20 nm could be prepared by this method as evidenced by surface area measurement by multipoint BET method. Thermal studies on these compounds were carried out using high-temperature X-ray diffraction (HT-XRD) and differential scanning calorimetry (DSC) methods. The thermal expansion coefficients of GdAlO₃, Gd₃Al₅O₁₂ and Gd₄Al₂O₉ were calculated from the lattice parameter data and specific heats were calculated from DSC data. The lattice parameters of GdAlO₃ and Gd₃Al₅O₁₂ were found to increase linearly with temperature whereas Gd₄Al₂O₉ did not show a linear trend. The specific heats of these compounds show an increasing trend with increase in aluminum atom fraction. Based on the thermodynamic data available in the literature and the specific heat data obtained in this study, oxygen potential diagram was constructed at 1000 K.     

Catalytic activity of NiMo/TiO2?Al2O3 systems in thiophene hydrodesulfurization

A correlation exists between the number of surface acid sites and the catalytic activity of NiMo/TiO₂–Al₂O₃ systems in thiophene hydrodesulfurization. The catalytic activity for thiophene hydrodesulfurization and surface concentration of Brönsted acid sites increase with the titania content in the TiO₂–Al₂O₃ support.     

The support and characterization of C60 and MoO3 on Al2O3

A new type of catalyst from supporting C₆₀ on MoO₃ and Al₂O₃ has been prepared. The effect of different order of impregnation and calcination atmosphere on catalyst are investigated by the solution test in toluene, UV-VIS spectroscopy and temperature programmed reduction (TPR). The results show that when the catalyst was prepared by supporting MoO₃ on C₆₀/Al₂O₃ and calcined in N₂, there is a stronger interaction between C₆₀, MoO₃ and Al₂O₃, but when supporting C₆₀ on MoO₃/Al₂O₃, the interaction is relatively weak. We consider that in the former method a new complex, Mo–C₆₀–O–Al, is formed.     

ZrO4/SiO2-Al2O3催化肉桂醛MPV转移加氢性能

以九水合硝酸铝（Al（NO₃）₃·9H₂O）与正硅酸乙酯（TEOS）为前驱盐,采用溶胶-凝胶法制备一系列不同Al₂O₃含量的SiO₂-Al₂O₃复合氧化物,并通过浸渍硝酸氧锆引入ZrO₂,制备ZrO₂/SiO₂-Al₂O₃复合氧化物催化剂,考察催化剂在肉桂醛（CAL）MPV转移加氢中的催化性能,并结合N₂物理吸附、X射线粉末衍射（XRD）、傅里叶变换红外光谱（FTIR）、NH₃-程度升温脱附（NH₃-TPD）、Py-原位红外（Py-IR）等技术,研究催化剂结构、织构以及表面性质与其催化性能间的构效关系.研究表明,所制备的催化剂均以L酸为主,并含有少量B酸中心,这使得加氢产物以肉桂醇（COL）为主,并含有少量1-苯丙烯-2-丙基醚（CPE）.Al₂O₃含量不仅影响催化剂表面的酸中心数量,而且对催化剂的织构参数有较大影响.随Al₂O₃含量的增加,催化剂表面L酸与B酸中心均有所增加,而孔径则持续变小,这使得催化反应呈现CAL转化率先增加后减少、目标产物COL选择性先稍有减小后有所增加的趋势.在Si/Al比为2时,催化剂具有最优的催化性能,优化反应条件下,CAL转化率达96%,目标产物COL选择性达90%.     

过渡金属修饰Fe2O3/Al2O3氧载体的Redox性能研究

采用冷冻干燥法分别制备了经Cu、Co、Mn、Ni修饰的Fe₂O₃/Al₂O₃氧载体。利用化学吸附仪,通过程序升温还原(H₂-TPR)和程序升温氧化(TPO)来研究经不同过渡金属修饰的Fe₂O₃/Al₂O₃与H₂和O₂的反应性能。实验发现,在Fe₂O₃/Al₂O₃中加入Cu、Co、Ni以后,氧载体与H₂的反应性都有提高,但是当在Fe₂O₃/Al₂O₃中加入Mn以后,氧载体的反应性和载氧能力反而下降。经Cu修饰的Fe₂O₃/Al₂O₃与H₂的反应性最高,且具有很好的反应稳定性,适合用于化学链燃烧。     

Selective Catalytic Reduction of NO with Propene over Au/Fe2O3/Al2O3 Catalysts

A series of Au/Fe₂O₃/Al₂O₃ catalysts were prepared by the homogeneous deposition-precipitation method. The catalytic activity of the catalyst samples for selective catalytic reduction of NO by propene under oxygen-rich atmosphere was evaluated. The results showed that 2%Au/10%Fe₂O₃/Al₂O₃ exhibited good low-temperature activity. The maximum of NO conversion reached 43% at 300 °C, while it was only 21% over the 2%Au/Al₂O₃ catalyst at the same temperature. The addition of 2% steam to the feed gas had little effect on the catalytic activity. X-ray diffraction results indicated that both Au and Fe₂O₃ particles were highly dispersed over Al₂O₃. H₂-temperature-programmed reduction results indicated that there was strong interaction between Au and Fe₂O₃, which made the reduction of Fe₂O₃ easy. The synergistic effect between Au and Fe₂O₃ was probably responsible for the good catalytic performance of the Au/Fe₂O₃/Al₂O₃ catalyst at low temperature.     

Cu修饰的Fe2O3/Al2O3氧载体的循环反应稳定性研究

采用冷冻干燥法制备了经Cu修饰（10%）的Fe₂O₃/Al₂O₃氧载体。利用热重分析仪分别在850、900和950 ℃等温环境下,使氧载体交替接触还原气体和氧化气体,来模拟氧载体在化学链燃烧中的循环过程。结果表明,经Cu修饰的Fe₂O₃/Al₂O₃氧载体在850和900 ℃下的等温循环过程中反应性能都很稳定,在950 ℃时的循环反应前期有微量烧结,但在循环后期反应性能也很稳定。随着反应温度的升高,氧载体氧化速率增大,还原速率和载氧率先减小后增大。与未经修饰的Fe₂O₃/Al₂O₃氧载体相比较,在900 ℃下作等温循环实验,经Cu修饰的Fe₂O₃/Al₂O₃氧载体具有较高的载氧能力和还原速率,但氧化速率较低;两者都具有较好的循环稳定性。     

Effect of inert components (Y2O3, Al2O3, and Ga2O3) on the chemistimulating effect of the Sb2O3 activator of GaAs thermal oxidation

Chemistimilated thermal oxidation of gallium arsenide was studied using Sb₂O₃ activator oxide in compositions with Ga₂O₃, Al₂O₃, and Y₂O₃ inert components. For Sb₂O₃-Y₂O₃ compositions, the thickness of the resulting oxide layer on GaAs was found to be a linear function of composition over the enter range of the compositions. For antimony oxide compositions with Ga₂O₃ and Al₂O₃ inert components, nonadditivities were observed near the component ordinates. For the Sb₂O₃-Ga₂O₃ system, the chemistimulating efficiency noticeably weakened at low concentrations of the inert component. The linear trend observed for this system within 0–60 mol % Sb₂O₃ is additively determined by the oxide layer thickness on GaAs in the presence of Sb₂O₃ and in the absence of activator. In the presence of inert Al₂O₃, the chemistimulating effect was enhanced near the Al₂O₃ ordinate and the resulting function was nonadditive with respect to the thicknesses reached in the presence of the individual components.     

P改性对Mo-Ni/Al2O3煤焦油加氢脱氮性能的影响

在磷含量1.34%下,采用分步浸渍法按磷添加顺序不同制备了3种改性催化剂:MoP-Ni/Al₂O₃、Mo-NiP/Al₂O₃、Mo-Ni/PAl₂O₃.通过X射线衍射(XRD)、程序升温脱附(NH₃-TPD)、程序升温还原(H₂-TPR)、氮气吸附等技术对催化剂进行了表征.以新疆中低温煤焦油为原料,考察了不同磷改性方式对催化剂加氢脱氮(HDN)性能的影响.结果表明,适宜的磷添加方式能够改变催化剂的酸性分布,提高10~13 nm加氢脱氮有效孔的比例,并且减弱活性组分与载体的相互作用,同时使得活性组分更易被还原,进而提高催化剂加氢脱氮性能.加氢脱氮活性顺序为Mo-Ni/PAl₂O₃(74.36%)>Mo-NiP/Al₂O₃(72.74%)>Mo-Ni/Al₂O₃(71.72%)>MoP-Ni/Al₂O₃(56.13%).     

KF/Al2O3: an efficient solid heterogeneous base catalyst in one-pot synthesis of benzimidazoles and bis-benzimidazoles at room temperature

Abstract  

KF/Al₂O₃ is an efficient solid heterogeneous base catalyst in the one-pot synthesis of 2-substituted benzimidazoles and 2,2′-disubstituted bis-benzimidazoles from 1,2-phenylenediamines or 3,3′-diaminobenzidines and acid chlorides, anhydrides, and esters at room temperature.     

柠檬酸添加方式对Mo-Ni-P/Al_2O_3催化剂加氢活性的影响

以Mo、Ni为活性组分,Al_2O_3为载体,采用不同柠檬酸添加方法制备了Mo-Ni-P/Al_2O_3催化剂.通过氢气程序升温还原(H2-TPR)、X射线衍射(XRD),透射扫描电镜(TEM)、XPS等表征方法研究催化剂的物化性质.结果表明:催化剂经柠檬酸的后处理,改善了载体氧化铝表面羟基基团的分布,促使Mo物种以八面体配位多核聚钼酸的形态存在,有效地减弱了载体与活性金属之间的强相互作用,提高了Mo物种的分散度与硫化度,使得催化剂形成更多"Mo-Ni-S"加氢活性相,提高了催化剂的加氢活性.与其他处理方法相比,柠檬酸后处理的催化剂对VGO具有更高的加氢脱硫、脱氮与芳烃饱和性能.     

Characterization and evaluation of Fe2O3/Al2O3 oxygen carrier prepared by sol–gel combustion synthesis

The sol-gel combustion synthesis (SGCS) for oxygen carrier (OC) to be used in chemical looping combustion (CLC) was first designed and experimented in this work, which is a new method of OC synthesis by combining sol-gel technique and solution combustion synthesis. Cheap hydrated metal nitrates and urea were adopted as precursors to prepare Fe₂O₃/Al₂O₃ OC at the molar ratio to unity (Fe1Al1), which was characterized through various means, including Fourier transforms infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), differential thermal analysis (DTA), X-ray diffractor (XRD), and N₂ isothermal adsorption/desorption method. FTIR analysis on the chemical structure of the dried gel of Fe1Al1 indicated that urea was partly hydrolyzed and the hydrated basic carbonate was formed by the combination of groups such as (Fe(_1−yAl_y)_1−xO_1−3x, CO₃²⁻ and -OH-. By analyzing the staged products during SGCS, calcination was found as a necessary step to produce Fe₂O₃/Al₂O₃ OC with separate phases of α-Fe₂O₃ and α-Al₂O₃. Through TGA-DTA, the decomposition of the dried gel was found to undergo five stages. The analysis of the evolved gases from the gel decomposition using FTIR partially confirmed the staged decomposition and assisted a better understanding of the mechanism of SGCS. XRD identification further substantiated the necessity of calcination to synthesize Fe₂O₃/Al₂O₃ OC with separate phases of α-Fe₂O₃ and α-Al₂O₃, though it was not necessary for the synthesis of single phase α-Fe₂O₃ and α-Al₂O₃. Structural characterization performed on N₂ adsorption analyzer displayed that the pore shape of Fe1Al1 particles was heterogeneous. Finally, H₂ temperature-programmed reduction (TPR) of Fe1Al1 products in TGA indicated that the reduction reaction of Fe1Al1 OC after calcination was a single step reaction from α-Fe₂O₃ to Fe, and calcination benefited to improve the transfer rate of the lattice oxygen from the OC to fuel H₂. Furthermore, four times of reduction and oxidization (redox) reaction by alternating with H₂ and air demonstrated the synthesized OC had good reactivity and sintering-resistance, much suitable to be used in the realistic CLC. Overall, the SGCS method was found superior to other existent methods to prepare Fe₂O₃/Al₂O₃ OC for CLC application.     

Two-stage catalytic system of Sn/Al2O3 and Pt/Al2O3for NO reduction by propene in lean conditions

The Pt/Al₂O₃, Sn/Al₂O₃catalysts were prepared by the single sol-gel method. The two-stage Sn/Al₂O₃and Pt/Al₂O₃catalyst in series for NO reduction with propene were investigated. The coexistance of water vapor enhanced the activity at medium temperature of 300-400^oC, and the NO conversion was above 50% at 225 to 500^oC even in the presence of water vapor and SO₂. This revised version was published online in August 2006 with corrections to the Cover Date.     

Photodegradation of 2,4-D over PdO/Al2O3-Nd2O3 photocatalysts prepared by the sol-gel method

The photocatalytic activity of 1.0 wt% PdO supported on Al₂O₃-Nd₂O₃ binary oxides prepared by the sol-gel method was studied in the photodegradation of 2,4-dichlorophenoxyacetic acid (2,4-D). The photocatalysts were characterized by N₂ physisorption, XRD and UV-vis spectroscopy. PdO supported on γ-Al₂O₃ photo-degrades the 2,4-D, however the addition of Nd₂O₃ to γ-Al₂O₃ notably improves the photocatalytic activity. As the concentration of Nd₂O₃ in the binary oxide increases from 2 to 10 wt%, the photodegradation of 2,4-D is highly enhanced. The catalytic test for PdO supported on pure Nd₂O₃ showed scarce photocatalytic activity. Total organic carbon (TOC) analysis showed that the 2,4-D has been completely destroyed on the PdO/Al₂O₃-Nd₂O₃ photocatalysts after 6 h under irradiation.