纳米WO3的制备工艺探讨与结构表征

通过气液反应制备了纳米WO₃光催化剂,并用紫外吸收光谱、粉末X射线衍射(XRD)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、能量散射谱(EDS)等手段对催化剂进行了表征.讨论了乙二醇加入量和表面活性剂十二烷基苯磺酸钠对催化剂粒度大小和形貌的影响.结果表明:当水和乙二醇的比例为25:75时所得WO₃粒径为30 nm左右.在此比例条件下加入0.1 g表面活性剂十二烷基苯磺酸钠,可制得片状WO₃,粒径约为80 nm.对自制的两种纳米WO₃光催化剂在紫外光照射时降解苯酚的活性进行了初步探讨,两者的催化性能均明显优于商品WO₃.     

改性SiO2载体对邻菲咯啉钌荧光特性及氧敏感荧光膜性能的影响

为提高极性荧光指示剂Ru(dpp)₃Cl₂在非极性硅橡胶中的分散性,以沉淀白炭黑、气相白炭黑和甲基MQ树脂,载负荧光指示剂Ru(dpp)₃Cl₂,再填充到二甲基硅橡胶(PDMS)中,制备氧敏感荧光膜.以分光光度计和荧光光谱仪,研究载体种类对Ru(dpp)₃Cl₂的吸附性、荧光特性及氧敏感荧光膜性能的影响.白炭黑载负Ru(dpp)₃Cl₂的荧光发射光谱相对其稀溶液约红移20 nm.载体表面的甲基可减弱SiO₂载体对Ru(dpp)₃Cl₂分子的吸附性和相互作用,减少荧光发射光谱的红移12 nm,提高荧光强度近10倍.白炭黑有助改善Ru(dpp)₃Cl₂在PDMS中的分散性和氧敏感荧光膜的荧光输出和猝灭比,尤以MQ树脂的效果最为显著.     

亚微米级多刺状星形氧化铜的制备

在阳离子gemini表面活性剂[C₁₆H₃₃(CH₃)₂N^＋(CH₂)₄N^＋(CH₃)₂C₁₆H₃₃]•2Br^－ (16-4-16)存在条件下, 以六次甲基四胺为沉淀剂, 利用水热合成法制备了大量多刺状星形亚微米级氧化铜. 用X射线衍射(XRD), X射线光电子能谱(XPS), 扫描电子显微镜(SEM)和透射电子显微镜(TEM)等多种手段对制备产物的表征结果表明, 所得产物是具有单斜结构多刺状星形氧化铜. 考察了表面活性剂浓度、温度以及铜源对产物物相及其形貌的影响.     

电活性铁氰化镍膜电极对稀土钇的电控离子分离

通过电沉积方法分别在镀铂石英晶片和铂基底上制备了电活性铁氰化镍膜,并考察了膜电极在含钇离子溶液中的电控离子交换性能. 在0.1 mol·L^-1的硝酸钇溶液中,使用循环伏安法及石英晶体微天平技术测试考察了铁氰化镍膜对钇离子的置入释放性能及对应的质量变化,同时比较了铁氰化镍膜电极在Y(NO₃)₃和Sr(NO₃)₂溶液中的电化学性能. 在0.1 mol·L^-1 [Y(NO₃)₃ + Sr(NO₃)₂]混合溶液中,通过循环伏安法分析了薄膜对Y³⁺/Sr²⁺离子的选择性. 用扫描电子显微镜观察了铁氰化镍膜的表面形貌,并通过X射线光电子能谱仪测定了膜在氧化和还原状态下的元素组成. 结果表明,铁氰化镍膜在含Y³⁺溶液中具有良好的离子交换行为,其中氧化过程薄膜质量减少,对应着钇离子的释放;还原过程薄膜质量增加,对应钇离子的置入;在0.0 V或0.9 V调控膜电极的氧化还原状态实现对钇离子的有效分离.     

Sn(MSA)2电镀液体系表面活性剂性能优化的模拟研究

在本工作中,我们利用粗粒化分子动力学(MD)模拟方法,研究了两亲性表面活性剂构型及浓度对Sn(MSA)₂类电镀液体相溶液与铜基板周围电镀液微观结构的影响,从分子水平系统考察了主盐离子、表面活性剂与甲醛添加剂的分布和聚集情况,及其与铜基板的相互作用.研究表明,A₄B₁₂型表面活性剂的疏水链段(A₄)协同效应较强,易在溶液中形成胶束,在基板上吸附能力有限;A₂B₁₂A₂疏水链较短,B₆A₄B₆疏水链居中,该两种表面活性剂在溶液中难以聚集,易充分吸附于基板之上;(AB₃)₄型表面活性剂在体相溶液中充分分散,在基板上的吸附能力有限.A₂B₁₂A₂及B₆A₄B₆型表面活性剂的充分吸附,有助于金属离子及甲醛添...     

CuO-WO3-ZrO2的结构和性质对苯甲醛加氢反应催化性能的影响

采用共沉淀法制备了不同CuO和WO₃含量的CuO-WO₃-ZrO₂催化剂. 利用X射线衍射(XRD)、 扫描电子显微镜(SEM)、 X射线荧光光谱(XRF)、 N₂气物理吸附、 氢气程序升温还原(H₂-TPR)、 X射线光电子能谱(XPS)及程序升温脱附(TPD)等手段对催化剂的结构和表面性质进行了表征. 结果表明, WO₃的引入可以调变ZrO₂的晶型, 从而使催化剂的比表面积和孔径发生变化, 促进CuO在催化剂表面的分散, 并影响催化剂的酸碱性. 在苯甲醛加氢制备苯甲醇反应中, 以CuO质量分数为18%, WO₃质量分数为10%的CuO-WO₃-ZrO₂为催化剂时苯甲醛单程转化率达到92.03%, 产物苯甲醇的选择性为94.76%.     

具有强吸附与可见光催化活性的红细胞状Bi3OXy (WO6)1-y (X=Cl、Br、I)固溶体

采用简单的两步水热法,成功制备了Bi₃OX_y(WO₆)_1-y(X=Cl、Br、I)固溶体材料,在改变形貌的同时,增强了吸附与光催化性能。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、紫外可见漫反射光谱(UV-Vis DRS)、X射线光电子能谱(XPS)、光致发光光谱(PL),对3种复合材料的结构和性质进行了详细的表征,推测了固溶体的形成原理。与BW单体相比,BI固溶体的形成使得带隙减小,可见光吸收能力增强,同时光生电子-空穴的复合率也减小。Bi₃OX_y(WO₆)_1-y对于罗丹明B(RhB)阳离子染料具有很强的吸附能力。通过高浓度下的吸附实验,研究了不同材料的吸附动力学。     

化学沉淀法制备BaTiO3纳米粉体的研究

以正钛酸(H₄TiO₄)、硝酸钡[Ba(NO₃)₂]为原料, 以双氧水、氨水为溶剂, 采用化学沉淀法制备出晶粒尺寸约20 nm的钛酸钡粉体. 研究了原料种类、煅烧温度、加料方式、反应温度对钛酸钡粉体性能的影响, 确定了最佳的制备条件. 结果表明: 当正钛酸(g)∶双氧水(mL)∶氨水(mL)＝1∶5∶3, 且采用正钛酸的双氧水-氨水溶液缓慢滴加到硝酸钡溶液中的加料方式时, 溶解完全, 制得的BaTiO₃粉体粒径小、纯度高. 用X射线衍射(XRD)和扫描电子显微镜(SEM)表征了颗粒的晶体结构、晶型转变机理以及颗粒的形貌|结果显示: 前驱体的起始晶型转变温度为500, 800 ℃煅烧获得的粒子晶型完整, 形貌呈规则的球形, 当煅烧温度升高到900 ℃时, 粉体晶体结构由立方相转变为四方相.     

表面活性剂辅助合成LiNi0.8Co0.1Mn0.1O2正极材料

通过添加烷基季铵盐类表面活性剂来调控材料形貌和粒径的改性方法,在LiNi_0.8Co_0.1Mn_0.1O₂前驱体合成过程中添加表面活性剂十二烷基三甲基溴化铵(DTAB)和十六烷基三甲基溴化铵(CTAB),利用尿素作为配合剂和沉淀剂,采用溶剂热法合成LiNi_0.8Co_0.1Mn_0.1O₂前驱体。最后,高温混锂煅烧合成椭球形的空心多孔材料。相比于不添加表面活性剂的样本,改性的材料有着更小的粒径和更加规整的形貌。电化学测试表明,添加DTAB和CTAB之后,首次充电容量分别达到223与251 mAh·g^-1(0.1C)。其中,添加CTAB的样品首次放电容量达到216 mAh·g^-1(0.1C),100次循环后容量保持率为85.1%,高于LiNi_0.8Co_0.1Mn_0.1O₂的81.7%(0.1C)。表面活性剂的改性显著提高了材料的电化学性能,为高镍三元正极材料的改性提供了一种新的思路。     

Ni2P/Cu(OH)2催化剂的制备及其全解水性能研究

通过化学处理法在泡沫铜基底表面生成Cu(OH)₂纳米线,大大增加了基底材料的表面积和导电性.采用水热法在Cu(OH)₂纳米线表面制备片状Ni-CH/Cu(OH)₂前驱体,对Ni-CH/Cu(OH)₂前驱体进行低温磷化得到多级结构Ni₂P/Cu(OH)₂催化剂.通过扫描电子显微镜(SEM)、X射线光电子能谱仪(XPS)和X射线衍射仪(XRD)对催化剂的物质结构和表面形貌进行了表征.采用线性伏安法、恒电位等技术对催化剂的电化学性能进行测试.在1.0 mol·L^-1 KOH碱性溶液中,当电流密度为10 mA·cm^-2时,Ni₂P/Cu(OH)₂的析氢反应(HER)和析氧反应(OER)过电位分别为133和333 mV,且均具有较好的稳定性.将这种多级结构Ni₂P/Cu(OH)₂催化剂分别用作阳极和阴极进行全解水电解,电流密度达到10 ...     

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.