纳米氧化镍、氧化锌的合成新方法

以草酸和醋酸盐为原料,用室温固相化学反应首先合成出前驱配合物二水合草酸镍和二水合草酸锌,进而二水合草酸镍和二水合草酸锌分别在380℃和460℃热分解2 h,得到产物纳米氧化镍和氧化锌。用X-射线粉末衍射、透射电镜对产物的组成、大小、形貌进行表征。结果表明,产物纳米氧化镍为球形立方晶系结构,平均粒径均为40 nm左右,产物氧化锌为粒度分布均匀的球形六角晶系结构,平均粒径约为20 nm。     

低共熔溶剂中纳米氧化锌的制备及形貌调控

分别以工业氧化锌、氯化锌和草酸锌为锌源,氯化胆碱-尿素低共熔溶剂为溶剂,通过沉淀法制备了不同结构和形貌的纳米氧化锌。通过X射线衍射仪(XRD)、扫描电子显微镜(SEM)和甲基橙光催化降解对样品进行了表征,分析了锌源变化对产物形貌的影响以及不同形貌氧化锌形成过程中前驱体的调控作用及反应机理。并将制备的不同形貌氧化锌应用于光催化降解甲基橙。结果表明制备的由纳米晶组装而成的厚块状Zn O纳米结构对甲基橙有良好的光催化性能。     

无机纳米粒子/丁苯胶乳复合技术的研究

研究了无机纳米粒子／丁苯胶乳的复合材料，用脂肪酸对纳米粒子进行了表面改性，使之均匀分散在丁苯胶乳中，用红外、吸油性，润湿试验等方法对改性纳米微粒进行了表征，纸张涂布和老化试验证明，纳米碳酸钙和纳米氧化锌具有优良的隔热效果，纳米氧化锌还有很好的防紫外老化功能，对以纳米TiO2为核，包覆苯丙共聚物的乳液矣合也作了初步研究。     

表面活性剂种类对纳米氧化锌形貌的影响

利用简单的水热法,以Zn(Ac)2.2H2O为锌源,通过调整表面活性剂的种类及碱源,制备了一系列不同形貌的纳米结构氧化锌;利用场发射扫描电子显微镜和X射线粉末衍射仪分析了产物的形貌和晶体结构,并探讨了多种表面活性剂和醋酸钠碱源对氧化锌纳米结构的影响.结果表明,以NaOH作为碱源时,在不添加任何表面活性剂的情况下,产物的形貌结构与氢氧化钠的加入量有关,当n(Zn2+)∶n(OH-)为1∶2.5、1∶10及1∶20时,分别得到片状、棒状及海胆状纳米结构的氧化锌;产物均为六方相氧化锌.     

纳米氧化锌的合成及表面改性

以硫酸锌、尿素为原料,采用均相沉淀法合成了纳米氧化锌.研究了硬脂酸对所制的纳米氧化锌粉体表面改性的机理及其对粉体亲油性的影响.实验结果表明,硬脂酸中的羧基与纳米氧化锌粉体颗粒表面的羟基发生了酯化反应,并在表面形成单分子膜.经过表面改性的纳米氧化锌由亲水性转化为亲油性.同时,就纳米氧化锌粉体硬脂酸表面改性反应,探讨了反应摩尔分数、反应温度和反应时间对产物的影响,从而筛选出粉体亲油性最大的反应条件为:硬脂酸质量分数为7%;反应温度为50℃;反应时间为1h.     

矿物药炉甘石成分分析及其纳米形态的抑菌活性研究

用差示热重等方法分析了矿物中药炉甘石的成分,合成纳米碱式碳酸锌和纳米氧化锌,制备了纳米炉甘石.用激光粒度分析仪测定了炉甘石及其成分的粒径分布,用透射电镜观察纳米氧化锌的形貌.采用杯碟法,以四环素为对照品,测试纳米炉甘石及其成分的抑菌活性.结果显示,氧化锌的含量与粒径大小决定了炉甘石的抑菌活性,纳米炉甘石抑菌活性显著提高.     

燃烧合成法制备纳米氧化锌

采用燃烧合成法制备氧化锌纳米粉体，DTA结果表明用柠檬酸作为燃烧剂比用尿素为燃烧剂时进行燃烧反应放出的热量少，更易制得纳米级氧化物．利用XRD和TEM表征样品，确定了生产纳米氧化锌粉体的最佳条件：硝酸锌与柠檬酸按9：1．5(物质的量比)形成前驱体，600℃进行反应．得到球形粉体粒径为16．4nm。     

Fe_3O_4纳米棒和Fe_2O_3纳米线的热氧化制备与表征

以铁单质和草酸溶液为原料,将0.75mol/L的草酸溶液滴在铁片上,于空气中200~600℃范围内加热1h,制备了Fe3O4纳米棒和Fe2O3纳米线,用扫描电镜(SEM)、X射线衍射仪(XRD)和透射电子显微镜(TEM)对产物进行表征,并研究了反应温度对产物形貌的影响.结果表明,在200~500℃下空气中反应1h在铁片上直接生长出矩形截面的多晶的立方相Fe3O4纳米棒,其直径范围约为0.5~0.8μm.当反应温度为600℃,得到的产物为六方相的Fe2O3纳米线.研究表明,C2H2O4对纳米棒的形成起关键作用,并提出了可能生长机理.     

Fe3O4纳米棒和Fe2O3纳米线的热氧化制备与表征

以铁单质和草酸溶液为原料,将0.75mol/L的草酸溶液滴在铁片上,于空气中200-600℃范围内加热1h,制备了Fe3O4纳米棒和Fe2O3纳米线,用扫描电镜（SEM）、X射线衍射仪（XRD）和透射电子显微镜（TEM）对产物进行表征,并研究了反应温度对产物形貌的影响.结果表明,在200-500℃下空气中反应1h在铁片上直接生长出矩形截面的多晶的立方相Fe3O4纳米棒,其直径范围约为0.5-0.8μm.当反应温度为600℃,得到的产物为六方相的Fe2O3纳米线.研究表明,C2H2O4对纳米棒的形成起关键作用,并提出了可能生长机理.     

均相沉淀法合成纳米ZnO及其光催化性能研究

以ZnSO_4、尿素为原料，采用均相沉淀法在90 ℃合成出了纳米ZnO，并就反应 温度、反应时间、反应物浓度及物料配比等条件对产物的影响进行了探讨。XRD物 相分析，产物为六方晶系；TEM形貌观察，粒子基本为球形，平均粒径20 nm；并用 IR，TG-DTA等测试手段对其进行了表征。利用紫外-可见分光光度计测试了光吸收 性能，发现纳米氧化锌对200～380 nm波长范围的光有很强吸收性，在可见光范围 内，也有较强的吸收。利用纳米氧化锌作为光催化剂对有机染料溶液进行了降解实 验，发现在日光照射60 min后，对酸性大红4BE的降解率可达100%。     

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.