聚合氯化铝制备球形拟薄水铝石和γ-Al_2O_3的研究Ⅰ——制备条件探讨

采用实验室自制的聚合氯化铝为原料,结合溶胶-凝胶法和油滴法制备球形拟薄水铝石及其衍生物γ-Al2O3,采用XRD,TEM和N2吸附法对样品进行了分析表征,探讨了不同pH值、不同铝形态含量的聚合氯化铝、不同煅烧温度及不同表面活性剂对产物结构性质的影响。结果表明:pH值在8.5附近合成的水合氧化铝以拟薄水铝石为主;高Alc含量的聚合氯化铝有利于形成高比表面积的球形产物;在450～750℃下煅烧产物为球形γ-Al2O3,并且随温度升高,产物比表面积下降、孔径增大,孔容变化不明显,在1000℃下煅烧产物为球形θ-Al2O3与γ-Al2O3的混合物;随着聚乙二醇表面活性剂分子量的增加,所得球形γ-Al2O3的孔容和孔径增大,聚乙二醇10000的扩孔效果最好,450℃下煅烧所得球形γ-Al2O3的比表面积、孔容分别达326m2·g-1、0.55cm3·g-1。     

面向异丁烷脱氢介孔γ-Al_2O_3基催化剂的合成及其高催化性能

采用溶剂蒸发自组装法调控载体形貌及孔道结构,成功制备了有序介孔氧化铝载体。以铬氧物种为活性组分,碱金属钾为助剂,采用浸渍法制备负载型催化剂,用于异丁烷催化脱氢反应,研究了反应温度、原料流速、催化剂粒径等因素对催化性能的影响。采用X射线粉末衍射、透射电子显微镜、N_2物理吸附、氢气程序升温还原及热重等表征方法探讨了载体形貌、孔道结构与催化性能的构效关系,结果表明,低温下有利于控制异丙醇铝的水解和缩合及介孔γ-Al_2O_3的研制。与常规的γ-Al_2O_3相比,所制备的介孔γ-Al_2O_3的有更大的比表面积和良好的有序性,在600℃、101.325kPa、GHSV=1 000 h~(-1)的条件下,10%(w/w)Cr_2O_3/γ-Al_2O_3催化剂性能最佳,异丁烷的转化率达63.1%,异丁烯的选择性达到85.5%。与传统的催化剂相比,介孔Cr_2O_3/γ-Al_2O_3催化剂具有大的比表面积,高度分散的活性组分,优良的催化性能和良好的抗积碳能力。     

聚合氯化铝制备拟薄水铝石及γ-Al2O3的研究Ⅱ——表面活性剂影响探讨

本实验采用自制的聚合氯化铝溶液为原料,利用溶胶-凝胶法制备拟薄水铝石及其衍生物γ-Al2O3,采用XRD、TEM和N2吸附法对样品进行表征和分析,探讨了不同pH值、不同合成温度以及不同pluronic表面活性剂对产物结构性质的影响。结果表明:当pH值为8.5时水合氧化铝以拟薄水铝石为主;当温度为70℃时制备的产物为拟薄水铝石晶相。随着表面活性剂L64、L65和F68分子量的增加,生成的拟薄水铝石及其衍生物γ-Al2O3的物相结晶度升高,但产物的晶相没有改变。所制备的拟薄水铝石在500℃焙烧6 h后均得到γ-Al2O3,其中表面活性剂为L65时扩孔效果最佳,比表面积、孔容和孔径分别为231 m2.g-1、0.28 cm3.g-1和4.52 nm。     

水热改性对铝基载体孔结构及异丁烷脱氢性能的影响

分别以两种水热介质对γ-Al_2O_3载体进行水热改性,并将改性后的载体负载CrO_x后应用于异丁烷催化脱氢,考察了水热温度对载体物化性质以及水热改性对催化脱氢性能的影响。通过XRD、N_2吸附-脱附及H_2-TPR对载体结构进行表征。结果表明,水热改性使γ-Al_2O_3发生再水合过程,焙烧后,结晶度变好,活性组分与载体的相互作用增加,CrO_x/Al_2O_3催化剂的异丁烷脱氢性能得到改善。以盐溶液水热改性载体,140℃处理4h,CrO_x/Al_2O_3催化剂表现出较好的异丁烷脱氢性能,10h内异丁烷脱氢平均转化率为43.04%,平均选择性86.34%,失活参数13.7%。     

CuMnCeLa-O/γ-Al2O3催化剂助燃脱硝性能研究

采用等体积浸渍法制备了Cu Mn-O/γ-Al_2O_3、Cu Mn Ce-O/γ-Al_2O_3和Cu Mn Ce La-O/γ-Al_2O_3催化剂.用XRD、BET、SEM、XPS和H_2-TPR技术对其物相和表面性质进行了表征.在连续固定床微反装置上评价了催化剂的CO+O_2和CO+NO反应性能.结果表明,催化剂样品中观测不到Cu O、Mn O_x、Ce O_2和La_2O_3的XRD晶相峰,活性组分在γ-Al_2O_3载体表面呈高度分散状态.Ce、La的引入对催化剂的比表面积、孔容和孔径分布影响不大.SEM谱图中未观测到活性组分的形貌,金属氧化物在载体表面均匀分布.Ce~(3+)!Ce~(4+)之间的可变价转换,引起Cu Mn Ce-O/γ-Al_2O_3催化剂表相Cu O中具有非完整结构的[Cu~(2+)_(1-x)Cu_x~+][O_(1-2)1_x□1_(2x)]增多,Cu~+/Cu~(2+)比例增大,表相氧空位增多,H_2-TPR还原峰温度向低温区偏移.Ce~(4+)、La~(3+)之间不平衡电荷以及共生过程中Cu-Mn-Ce-La-O之间的强相互作用,加大了Cu O和Mn O_x结构的不完整性,导致Cu Mn Ce La-O/γ-Al_2O_3催化剂样品表相产生更多的Cu~+、Mn~(2+)、Mn~(3+)和氧空位,相应的H_2-TPR还原峰温度进一步向低温区偏移.催化氧化CO和CO催化还原NO实验结果表明,在反应空速20 000 h~(-1),350℃反应温度下,Cu Mn Ce La-O/γ-Al_2O_3催化剂CO催化还原NO反应的CO转化率达到88.2%,NO转化率达到了96.1%,表现出了较好的氧化还原活性.     

微波辐射下KF/nano-γ-Al2O3催化合成二硫代氨基甲酸酯类化合物

本文报道以缺电子烯烃、胺类和二硫化碳为原料,以PEG-400为溶剂,在固体碱KF/nano-γ-Al_2O_3催化下,经微波辅助的Michael加成反应高效地合成二硫代氨基甲酸酯类化合物,收率为76.5%～91.6%。对催化剂、溶剂、微波功率、反应时间等影响因素进行了考察,确定了优化的反应条件。该方法具有反应时间短、收率高和环境友好等特点。另外,本文还报道了苯甲醛、酮类、胺类与二硫化碳四组分在PEG-400溶液中,在固体碱KF/nano-γ-Al_2O_3催化下,经微波辐射"一锅法"合成二硫代氨基甲酸酯类化合物的反应,收率为73.4%～82.8%。     

活性氧化铝的衍射线宽化和结构缺陷

从不同的氧化铝水合物加热脱水制备的γ和η型氧化铝,广泛用作催化剂和催化剂载体。它们具有不同的物化性质,其微观结构已进行了很多研究。γ-和η-Al_2O_3的x射线衍射有两个特征:一是其整个衍射图非常类似于尖晶石类结构的衍射图;二是各衍射线具不同的宽化特征:即所有衍射线可分成宽散线和较尖锐线两大组。根据前者,γ-和η-Al_2O_3被认为是具有畸变尖晶石结构,由于η-Al_2O_3的(400)和(440)单线在γ-Al_2O_3中变为双线,因而二     

高比表面大中孔拟薄水铝石和γ-Al2O3的制备研究

大中孔γ-Al₂O₃作为重要的催化剂载体、吸附剂和分离材料，尤其对重油和渣油转化催化剂的研制具有十分重要的意义，但传统大中孔γ-Al₂O₃的制备方法往往以牺牲其比表面积为代价。本文分别从控制拟薄水铝石的析出过程和后处理方法以及添加扩孔剂、助烧结剂扩孔等角度出发，评述了近年来国内外高比表面大中孔γ-Al₂O₃及其前驱物拟薄水铝石的制备方法和扩孔机制，这些方法包括pH摆动法、有机溶剂合成法、表面活性剂组装法、微波加热法、水热处理法、有机溶剂置换法、非常规干燥法和扩孔剂或助烧结剂扩孔法等。最后，还对高比表面大中孔拟薄水铝石和γ-Al₂O₃制备方法的发展趋势进行了展望。     

助剂Ni与载体的相互作用及其对NiMo/γ-Al_2O_3催化剂加氢脱硫性能的影响

以γ-Al_2O_3为载体,制备了一系列不同NiO负载量的NiMo/γ-Al_2O_3催化剂,利用XRD、~(27)Al-MAS NMR、Py-FTIR和HRTEM等技术对其进行了表征;在高压微反装置对该系列催化剂的加氢脱硫性能进行了评价,研究了助剂Ni与载体γ-Al_2O_3中不饱和铝间的相互作用及其对催化剂活性相结构形貌和催化活性的影响。结果表明,助剂Ni优先作用于γ-Al_2O_3表面的四配位不饱和铝原子位置;随着NiO负载量的增加,硫化态NiMo/γ-Al_2O_3催化剂中MoS_2活性相的长度变短、堆垛层数增加。Ni的引入能明显提高NiMo/γ-Al_2O_3催化剂的加氢脱硫活性,但其加氢选择性则有所降低。     

NiO-Fe_2O_3/PG-γ-Al_2O_3催化剂的制备及其在秸秆热解中的应用

通过沉积沉淀法与均匀沉淀法制备以坡缕石与伽马氧化铝(Palygorskite-Gamma Alumina,PG-γ-Al_2O_3)为复合载体的负载型NiO-Fe_2O_3/PG-γ-Al_2O_3催化剂,采用了EDX、XRD、SEM、N2等温吸附-脱附等手段对催化剂进行了表征与分析。同时利用管式炉考察了NiO-Fe_2O_3/PG-γ-Al_2O_3催化剂在作物秸秆热解中的催化性能和再生使用寿命及抗积炭能力,并与两种单载体催化剂(NiO-Fe_2O_3/PG,NiO-Fe_2O_3/γ-Al_2O_3)进行了比较。结果表明,PG-γ-Al_2O_3复合载体比表面积达134.21 m2/g,平均孔径为39.65 nm。NiO-Fe_2O_3/PG-γ-Al_2O_3催化剂活性组分负载均匀,分散较好且催化剂中同时存在镍铁合金与镍铝尖晶石结构。催化剂活性测试显示,NiO-Fe_2O_3/PG-γ-Al_2O_3催化剂用于作物秸秆热解具有极高的催化活性,能够显著提高产品燃气品质、燃气中的CO与H2含量和燃气热值;相比单载体催化剂其催化活性好,再生效果佳,抗积炭能力较强。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.