银纳米颗粒掺杂的活性微孔炭球：一种高效吸附/催化去除刚果红的双功能材料

以载银纳米颗粒壳聚糖溶液为前驱体,联合喷雾干燥法、高温碳化法和KOH活化法制备出银纳米颗粒掺杂的活性微孔炭球(Ag/AMCSs)。基于一系列表征和性能研究发现,银纳米颗粒均匀分布于Ag/AMCSs结构中,Ag/AMCSs不仅表现出优异的染料吸附性能,而且可以有效催化NaBH₄还原刚果红(CR)的反应。此外,通过研究pH值、接触时间和染料初始浓度对Ag/AMCSs吸附性能的影响,发现Ag/AMCSs对CR的吸附过程符合准二级动力学模型和Langmuir模型,最大吸附量(q_e)可达445mg·g^-1。Ag/AMCSs催化NaBH₄还原CR,反应速率常数k可达0.311min^-1,5次循环利用后,染料催化转化率仍可高达95%。     

γ-AlOOH/Al2O3修饰硅藻土的制备与Cs+、Pb2+吸附性能

以结晶氯化铝(AlCl₃·6H₂O)作为铝源,十二烷基苯磺酸钠(SDBS)为模板剂,采用水热法在硅藻土盘上制备了束状纳米结构γ-AlOOH/Al₂O₃复合吸附剂。采用XRD、SEM、TEM、TG/DSC、N₂吸脱附等对样品进行了表征。研究了样品对¹³³Cs⁺及Pb²⁺的吸附能力。研究表明,样品γ-AlOOH/硅藻土、γ-Al₂O₃/硅藻土,对Cs⁺及Pb²⁺均具有良好的吸附性能,两者对Cs⁺的去除率分别为98.9%和99.6%;对Pb²⁺的最大吸附量分别为357.1、416.7 mg·g^-1。两种样品对Pb²⁺的吸附均符合Langmuir吸附模型。     

一步热解法制备Cu/Fe双金属生物炭复合材料及其高效吸附Pb2+性能

使用一步热解法制备了 Cu/Fe双金属生物炭复合材料(BC@Cu/Fe-X,X=3、5、10)和 Fe生物炭复合材料(BC@Fe)。考察了Cu掺杂量对BC@Cu/Fe-X吸附Pb²⁺的影响,确定最佳掺杂比例。结果显示BC@Cu/Fe-5吸附Pb²⁺性能最好。考察了吸附时间、Pb²⁺浓度、pH、背景离子、空气中老化等实验条件对 BC@Cu/Fe-5 吸附 Pb²⁺的影响。通过动力学、热力学数据拟合分析了BC@Cu/Fe-5吸附Pb²⁺的行为,利用X射线粉末衍射(XRD)、X射线光电子能谱(XPS)、傅里叶变换红外光谱(FTIR)等表征手段解析了BC@Cu/Fe-5吸附Pb²⁺前后特征峰变化。BC@Cu/Fe-5吸附Pb²⁺的机理如下：大约42%的Pb²⁺被还原为Pb⁰,33%的Pb²⁺形成PbO/Pb(OH)₂,25%的Pb²⁺与O—H、C—O、C=O、COO、Fe—O等官能团形成配合物。Cu掺杂可以提高Fe还原Pb²⁺的能力。     

氧化铁改性蛭石的制备、表征及吸附氟的特性

采用共沉淀法制备了3种不同含铁量的氧化铁改性蛭石(Verm-Fe_x,x=5,10,20),研究了纯蛭石(Verm)和Verm-Fe_x的表面性质及吸附氟的特性。与样品Verm比较,3种Verm-Fe_x中Verm的d₍₀₀₂₎层间距略有升高;Verm-Fe_x的孔体积、表面积、表面分形度均随含铁量的增加而升高,其中微孔体积和外表面积的增加幅度更明显。4种样品的等电点(IEP)也随含铁量的增加而明显升高;初始pH＝5.0时,它们的表面ζ电位分别为-16.4,-6.1,10.5和28.4 mV。4种样品对氟的等温吸附数据用单吸附位Langmuir模型拟合(R²=0.973~0.995)时,Verm的R²最高;双吸附位Langmuir模型可很好地描述3种Verm-Fe_x样品的等温吸附过程(R²=0.991~0.998);Freundlich模型对4种样品吸附数据的拟合度较差(R²=0.835~0.937),但R²随样品含铁量的增加而略微升高。初始pH=5.0时,Verm和Verm-Fe_x(x=5,10,20)对氟的最大吸附容量(q_max)分别为3.18,6.76,9.27和12.43 mg·g^-1。可见,Verm-Fe_x(尤其含铁量较高的产物)对表生环境中氟的吸附固定性能明显高于Verm。     

聚合羟基铁改性蒙脱石的制备、表征及吸附Se（Ⅵ）的特性

采用共沉淀法制备了3种聚合羟基铁改性蒙脱石（Mt-Fe_x,x=1,2,3）,对比研究了纯蒙脱石（Mt）和Mt-Fe_x（x=1,2,3）的表面性质及吸附Se（Ⅵ）的特性。结果表明,Mt样品的d_（001）层间距为1.296nm,在Mt-Fe_x中升高至1.430nm以上;与Mt样品比较,Mt-Fe_x的孔体积、表面积、表面分形度均随含铁量的增加而升高,其中微孔体积和微孔表面积的变化尤为明显;Mt样品的等电点（IEP）低于3,而Mt-Fe₃的IEP升高至6.8;初始pH=5.0时,Mt和Mt-Fe_x（x=1,2,3）的表面ζ电位分别为-33.5,-11.7,9.9和33.2mV。单吸附位Langmuir模型能够很好地拟合Mt样品对Se（Ⅵ）的等温吸附数据（R²=0.993）,4种样品吸附数据的单吸附位Langmuir拟合判断系数（R²）随样品含铁量的增加而降低;3种Mt-Fe_x样品的吸附数据更适合用双吸附位Langmuir模型拟合（R²=0.993~0.997）;Freundlich模型对4种样品的吸附数据拟合度较低（R²=0.849~0.970）,其判断系数（R²）随样品含铁量的增加而升高。初始pH=5.0时,Mt和Mt-Fe_x（x=1,2,3）对Se（Ⅵ）的吸附容量分别为4.23,7.83,10.38和14.34mg·g^-1。可见,聚合羟基铁含量较高的Mt-Fe_x样品对土-水体系中Se（Ⅵ）的固定能力明显高于Mt。     

层状钴氧化物Bi2-xAgxSr2Co2O8-δ的高温热电性能及XPS研究

采用固相反应法制备了组成为Bi_2-xAg_xSr₂Co₂O_8-δ(x=0.0, 0.4, 0.8,略写为BAC-222)的层状钴氧化物陶瓷。利用X-射线光电子能谱考察该类化合物的电子结构,结果表明钴离子以Co³⁺和Co⁴⁺混合价态形式存在,n_Co⁴⁺/n_Co³⁺的比例随着Ag掺杂的量增加而增加。O1s光电子谱显示在所有样品中均存在点阵氧和吸附氧。热电性能测试结果显示,随着Ag掺杂量的增加,电导率显著增加而Seebeck系数几乎保持不变,Ag的引入极大的影响了BAC-222的电子输运性质,其功率因子在1 123 K时达到了1.23×10^-4 W·m^-1·K^-2,是一种具有很好应用前景的热电材料。     

用于高效去除水中孔雀石绿的三层结构磁性复合材料Fe3O4@聚丙烯酸@ZiF-8的制备

设计并合成了一种以磁性纳米粒子为核，聚合物为中间层，金属有机骨架材料为外层的三层结构磁性复合材料(Fe₃O₄@PAA@ZIF 8)。首先利用溶剂热法制备Fe₃O₄纳米粒子，然后通过蒸馏沉淀聚合法在Fe₃O₄纳米粒子表面包覆聚丙烯酸(PAA)层，最后通过原位沉积法在PAA外部包覆ZIF 8。在对Fe₃O₄@PAA@ZIF 8的组成和结构进行表征的基础上，深入研究其对孔雀石绿(MG)的吸附性能。透射电子显微镜(TEM)显示 Fe₃O₄@PAA@ZIF 8 具有明显的三层结构，Fe₃O₄的平均粒径为 117nm，PAA 层厚度约为 17 nm，ZIF 8层的厚度约为 14 nm。Fe₃O₄@PAA@ZIF 8对 MG 的吸附量随着 pH 的升高而增大，吸附过程符合准二阶动力学模型和 Langmuir等温吸附模型。此外，Fe₃O₄@PAA@ZIF 8还表现出良好的重复利用性能，8次循环利用后对MG(500 mg·L^-1)的最大吸附量仍可达982 mg·g^-1。     

Co2+含量对CoAl-LDHs焙烧产物结构、组成及其生长碳纳米管的影响

采用成核晶化隔离法将Co²⁺引入层状双金属氢氧化物(LDHs),得到了含不同Co²⁺/Al³⁺物质的量的比为1∶1,2∶1,3∶1的二元钴铝碳酸根型LDHs(CoAl-LDHs)。通过X射线衍射(XRD)、透射电镜(TEM)、扫描电镜-能量散射谱(SEM-EDS)、拉曼光谱(Raman)、程序升温还原(TPR)及X射线光电子能谱(XPS)等方法对CoAl-LDHs焙烧产物的结构、组成及其化学气相沉积(CCVD)催化生长多壁碳纳米管(CNTs)进行了研究。结果表明：CoAl-LDHs前体中钴的含量可以明显改变焙烧产物的组成分布和还原性能,并最终影响CNTs的生长,其中以n_Co²⁺/n_Al³⁺比为2/1的LDHs作为催化剂前体可以得到管径均匀和石墨化程度高的CNTs,这与还原得到的纳米活性Co颗粒均匀分散有关。     

Mn4+掺杂Co3O4纳米纤维的静电纺丝法制备及其电化学性能

通过静电纺丝法制备Mn⁴⁺掺杂的Co₃O₄复合纳米纤维,利用XRD、XPS、BET、SEM和电化学工作站等对材料的结构、成分、形貌和电化学性能进行表征与测试。研究发现,通过Mn⁴⁺掺杂,Co₃O₄复合纳米纤维的电化学性能得到明显改善。当n_Co∶n_Mn=20∶2时,相应的复合纤维具有较大比表面积68 m²·g^-1,而且该样品呈现出清晰的氧化还原峰,在1 A·g^-1的电流密度下,放电比电容量为585 F·g^-1,这比纯Co₃O₄纳米纤维的416 F·g^-1,有显著提高;循环500圈电容保持率达到82.6%,而纯Co₃O₄纳米纤维则是76.4%。     

ZnCr双金属层状材料对废水中酸性红14的吸附性能

采用共沉淀法制备性能优异的层状材料锌铬水滑石(Zn_xCr-LDHs, x=2, 3, 4), 并探究各种因素对吸附酸性红14(AR14)的影响。XRD、ICP、FTIR及BET表征结果表明:合成的Zn_xCr-LDHs晶型良好且稳定, 具备介孔结构。实验结果表明:最佳吸附剂为Zn₃Cr-LDHs, 比表面积为101 m²·g^-1, 对AR14的最大吸附容量为484.63 mg·g^-1。同时, 降低溶液pH值和提高溶液温度均可促进AR14的吸附。该吸附过程分别符合准二级动力学模型和Freundlich等温吸附模型。结合Materials Studio 5.5软件模拟, 推测该吸附机理主要以表面吸附为主, -SO₃^-基团是反应点。     

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%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

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.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

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.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.