磷酸锡铝分子筛(SnAPO-5)的合成及性能研究

水热法合成了磷酸锡铝分子筛,并用X荧光分析其组成,X射线粉末衍射测定其晶胞参数。通过电子探针、穆斯堡尔谱、X射线光电子能谱及红外光谱等进行了结构分析。同时,研究了物化及催化性能。结果表明,读分子筛属于AlPO_(4-)5型分子筛的结构类型,Sn~(4+)位于分子筛骨架中。     

以粉煤灰为原料制备NaP分子筛及其吸附性能

以粉煤灰为原料,经对粉煤灰高温焙烧活化和酸浸除杂后,提取其中硅铝组分作为制备分子筛的硅源和铝源,采用水热合成法制备NaP分子筛.通过优化除杂参数和合成制备参数调控NaP分子筛的晶体生长,得到了制备NaP分子筛的适宜条件为:SiO_2∶Al_2O_3∶Na_2O∶H_2O=1∶0. 5∶1. 66∶136,晶化温度和时间分别为120℃和8 h.通过XRD、SEM等表征测试手段研究分子筛的结构特征,并且采用Ni~(2+)和Ca~(2+)吸附实验对NaP分子筛进行性能评价,Ni~(2+)的去除率最大可达99.58%,Ca~(2+)交换能力达到373 mg/g.     

原位合成的Cu-SSZ-13催化剂：结晶时间对NH3-SCR性能的影响

通过一步法原位合成Cu-SSZ-13分子筛催化剂,考察了结晶反应时间对NH3选择性催化还原(NH3-SCR)催化性能的影响,利用H2程序升温还原(H2-TPR)、X射线衍射(XRD)、电子顺磁共振光谱(EPR)和X射线电子能谱(XPS)等分析手段表征催化剂。结果表明,结晶时间不同会影响到Cu-SSZ-13分子筛中活性Cu物种的含量和分布,结晶时间为4 d时Cu-SSZ-13分子筛的NH3-SCR催化性能最佳。高温水热条件下,Cu-SSZ-13分子筛中不稳定的Cu~(2+)A物种会发生迁移而形成相对稳定的Cu~(2+)B物种;Cu~(2+)物种发生团聚而造成分子筛结构破坏,部分Cu~(2+)物种也因分子筛骨架坍塌而被包埋,这是导致催化活性下降的主要原因。     

磷酸镁铝分子筛的交换与催化性能研究

用红外与程序升温脱附氨法考察了磷酸镁铝分子筛的酸性,测定了94℃时Ni~(2+)与其进行离子交换的等温线,并在不同温度考察交换上Ni~(2+)后分子筛的催化加氢、裂解活性。     

交换有La^3＋离子的NaA型分子筛的交流电导研究

本文用X—光射线衍射、原子吸收光谱及热重等方法测定了交换有La~(3+)离子的NaA分子筛LaNaA的组成,用交流阻抗谱测定了其离子电导,由电导率随温度的变化,得到了NaA和LaNaA的电导表观活化能分别为54.9KJ/mol和37.6KJ/mol。讨论了交换有La~(3+)离子后对分子筛骨架结构中Na~+离子分布、落位以及扩散迁移的影响。     

离子交换超稳Y型(USY)分子筛的红外光谱研究

用红外光谱法考察了HY,CaHY,LaHY及相应的经超稳化处理的USY,CaUSY,LaUSY分子筛。也对比了HY,USY及其进一步用NH_4~+交换的USYH分子筛。USY的3700cm~(-1)特征谱带强度不仅与Na~+含量有关,也与其它阳离子如Ca~(2+),La~(3+)的含量有关。从OH基伸缩振动区的谱带看到,La有稳定结构羟基和抑制脱铝的作用。观察了各超稳化分子筛的各个OH基谱带及它们在不同吡啶脱附温度下的变化。HY,USY刚USYH的酸量及其强度有很大差别,它们的B酸强度不同,USYH的L酸强度出乎预料地高。正癸烷裂化活性与B酸有较好对应关系。讨论了超稳化处理、阳离子性质、后NH_4~+交换等因素对分子筛的酸性、稳定性和酸中心可接近性的影响。     

Cr~(3+)改性NaY分子筛的吸附脱氮性能

对Cr~(3+)离子改性NaY分子筛的实验条件进行了研究,通过XRD、FT-IR、N_2吸附-脱附等方法对改性后的CrY分子筛进行表征,确定最佳改性条件为温度40℃,Cr~(3+)浓度0.5 mol/L,改性两次。FT-IR谱图表明,CrY分子筛波数1 147 cm~(-1)处峰明显消失,且波数1 024 cm~(-1)峰与标准的NaY分子筛相比发生了蓝移现象,可以判定Cr~(3+)交换到分子筛骨架上。考察了吸附时间和温度对CrY分子筛吸附脱除模拟燃料中喹啉的影响。结果表明,吸附温度对吸附影响不大,可在室温下进行。CrY对喹啉的吸附主要为化学吸附,且吸附类型为配位吸附和π络合吸附,最佳吸附时间为30 min,吸附等温线线性回归表明,CrY分子筛对喹啉吸附动力学模型为L型和F型混合吸附。     

Cu~(2+)在胱氨酸-氨基乙酸溶液中的极谱吸附波

示波极谱法测定Cu~(2+),通常在氨-氯化铵介质中进行。利用Cu~(2+)与某些络合剂生成的络合物在滴汞电极上的吸附富集作用,常可提高Cu~(2+)的灵敏度。我们曾研究了胱氨酸在Cu~(2+)-乙二胺和Cu~(2+)-氨基乙酸溶液中的示波极谱行为,发现在乙二胺或氨基乙酸缓冲液中,在一定量Cu~(2+)存在下,由于胱氨酸与Cu~(2+)的共存,可产生某些灵敏度较高的极谱吸附波,并用于测定微量胱氨酸。进一步试验发现,在同样的缓冲液中,在一定量胱氨酸存在下,微量Cu~(2+)也可产     

Fe—Si—ZSM—12分子筛的表征

本文用红外光谱研究了Fe-Si-ZSM-12分子筛,观察到其结构单元的骨架振动谱带在545cm~(-1)、580cm~(-1)和630cm~(-1),而表示Si—O—Fe键的对称伸缩振动谱带在660cm~(-1)和780cm~(-1),且随铁含量增加向高波数位移。Fe-Si-ZSM-12分子筛的穆斯堡尔谱的结果表明,骨架铁的IS值很小,IS=0.086(-0.17)mm/s,且QS=0.0mm/s,这明显不同于非骨架铁IS=0.53mm/s。在Fe-Si-ZSM-12分子筛的ESR谱图上,观察到骨架铁的顺磁信号(g=4.3),样品焙烧后顺磁信号减弱,骨架铁向非骨架位迁移。IR、Mossbauer、ESR结果证明,Fe~(3+)进入了骨架。     

铜锌与邻苯二酚紫的络合吸附波研究——血清中微量铜锌的同时测定

汪尔康等人曾报导过邻苯二酚紫(简称PV)及其与某些金属络合物的极谱研究。我们较详细地研究了Cu~(2+)、Zn~(2+)与PV络合物的极谱行为。发现在HAc-NaHCO_3(pH_6.4)缓冲介质中当有8×10~(-4)％PV存在下,Cu~(2+)、Zn~(2+)均会产生灵敏的导数极谱波,峰电位分别为-0.50V和-1.20V(相对于银汞齐电极,下同)。研究了络合物的组成、极谱波的性质及其机理。并提出了同时测定血清中微量铜锌的方法。     

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%.     

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.     

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.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.