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二氧化硅-共聚物杂化荧光纳米材料用于动物活体成像
张泽芳, 袁薇, 徐明, 易韬, 张善端, 李富友
2018, 34(11): 1943-1949  doi: 10.11862/CJIC.2018.250
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以氧化硅(SiO2)前驱体与三嵌段共聚物F108合成较小粒径的SiO2-共聚物杂化纳米体系(SNP),并与高效近红外发射的疏水染料M507自组装,构建了近红外发光纳米探针M507@SNP。同时,研究了M507@SNP的光物理性能和细胞毒性。动物成像实验证明该纳米成像探针可实现活体层次高信噪比的小动物全身成像和前哨淋巴结的指示。
CO2在氨基改性MIL-101(Cr)中吸附的分子模拟
王之婧, 王俊超, 赵行乐, 马正飞
2018, 34(11): 1966-1974  doi: 10.11862/CJIC.2018.258
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采用实验与分子模拟结合的方法研究298 K下CO2在氨基改性得到的MIL-101(Cr)-NH2和MIL-101(Cr)-ED(ED:乙二胺)上的吸附性能。比较MIL-101(Cr)、MIL-101(Cr)-NH2和MIL-101(Cr)-ED的吸附等温线与吸附热的结果,表明采用直接合成改性法得到的MIL-101(Cr)-NH2比采用合成后再改性得到的MIL-101(Cr)-ED有更高的CO2吸附容量。进一步比较密度分布图和径向密度分布曲线,分析CO2在氨基改性MIL-101(Cr)中的吸附位,表明在低压下CO2首先吸附在MIL-101(Cr)微孔的超级四面体中,随着吸附压力的增大逐渐填充到更大的孔中。氨基的存在增加了CO2的吸附位点,使MIL-101(Cr)-NH2具有较高CO2吸附容量;同时MIL-101(Cr)-ED中的ED分子的存在增加了CO2的吸附位点,使MIL-101(Cr)-ED也具有较高CO2吸附容量;但是MIL-101(Cr)-ED中的ED分子占据了MIL-101(Cr)中Cr的吸附位点,使Cr对CO2的吸附强度减弱,同时可吸附位点少于MIL-101(Cr)-NH2,导致其对CO2的吸附容量少于MIL-101(Cr)-NH2
Er3+, Yb3+共掺杂NaY(WO4)2上转换荧光粉的制备及其发光性能
史忠祥, 卢杨, 王晶, 关昕, 时军, 江豪
2018, 34(11): 1975-1982  doi: 10.11862/CJIC.2018.229
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应用传统水热法合成出具有四方白钨矿结构的NaY(WO42微米颗粒及一系列Er3+/Yb3+共掺杂NaY(WO42上转换荧光粉。利用XRD、SEM、TEM、HRTEM、粒度分布和上转换发光光谱对样品的物相、形貌及上转换发光性能进行分析表征。结果表明,pH值对于制备具有同一形貌的纯相NaY(WO42微米颗粒发挥重要作用。随着pH值的升高,可以完成从八面体到拟立方体再到片状颗粒的形貌转变。在980 nm近红外光激发下,观测到525及553 nm处的强绿光发射,对应Er3+2H11/24I15/24S3/24I15/2跃迁,以及650~680 nm范围内的弱红光发射,对应Er3+4F9/24I15/2跃迁,且绿、红光上转换发射均属于双光子过程。此外,通过调节NaY(WO42:Er3+,Yb3+荧光粉中Yb3+的浓度,可实现对绿光色度的有效控制。
CP@NiAl-LDH复合材料的制备及其超级电容器性能
普颖慧, 杜东峰, 于世凡, 邢伟
2018, 34(11): 1983-1990  doi: 10.11862/CJIC.2018.224
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通过采用简易温和的水热条件制备导电聚合物@镍铝层状双金属氢氧化物复合材料(CP@NiAl-LDH),构建电子/离子的高速传输纳米通道,利用SEM和XRD对复合材料结构形貌进行表征。电化学性能测试结果表明,导电聚合物为复合材料提供一定的赝电容,促进电荷的快速转移,使CP@NiAl-LDH的电容性能得以显著提升。PPy@LDH具有最好的电容性能,在1 A·g-1的电流密度下,其比容量高达3 010.3 F·g-1,当电流密度升高到20 A·g-1时,其比电容保持率为73.1%,表现出优异的倍率性能;同时,在10 A·g-1的电流密度下10 000次充放电循环后仍具有88.8%的比容量保持率,具有优异的循环稳定性。这主要归功于NiAl-LDH与导电聚合物之间的协同增强效应。
扫帚状氧化铈制备及其对Pt基阳极催化剂催化性能的影响
莫逸杰, 郭瑞华, 安胜利, 郭乐乐, 张捷宇, 周国治
2018, 34(11): 1991-1999  doi: 10.11862/CJIC.2018.247
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采用水热合成法,合成了比表面积为175 m2·g-1,孔径在2~4nm范围内的扫帚状CeO2。通过微波辅助乙二醇还原氯铂酸法制备了Pt-CeO2/RGO催化剂,探究扫帚状CeO2的添加对Pt基催化剂电催化性能的影响。利用X射线衍射仪(XRD)、扫描电镜(SEM)、N2吸附-脱附、X射线光电子能谱(XPS)对所制备的CeO2及催化剂进行表征。利用电化学工作站对催化剂进行电化学性能测试。结果表明,催化剂中CeO2保持原有扫帚状,Pt纳米粒子均匀分布于石墨烯载体表面;当mRGOmCeO2=1:2时,添加了扫帚状CeO2的Pt-CeO2/RGO催化剂的电催化性能最优,电化学活性表面积为102.83 m2·g-1,对乙醇氧化的峰值电流密度为757.17 A·g-1,1 000 s的稳态电流密度为108.17 A·g-1,对乙醇催化氧化反应的电荷转移电阻最小,活化能最低。
基于量子点涂料的柔性光阳极及碳基对电极的制备和优化
童晶, 方文娟, 嵇小荷, 赵卿飞, 张华
2018, 34(11): 2000-2008  doi: 10.11862/CJIC.2018.252
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首先制备出量子点(QDs)/TiO2涂料,分别采用丝网印刷法与刀刮法将涂料涂覆于ITO/PET柔性基底上,结果表明刀刮法制备量子点敏化太阳电池(QDSCs)效果更佳,且具有普适性。基于铜片对电极所组装的ZnCuInSe,CdSe和CdSeTe量子点半柔性QDSCs最高效率分别达2.83%,2.46%和1.99%。另外,我们对石墨纸进行表面化学修饰以提高亲水性,再通过简单的连续离子交换吸附法(SILAR)在石墨纸上负载CuxS纳米粒子,制备出CuxS/GP柔性对电极,进一步组装成全柔性QDSCs,获得了2.13%光电转化效率。
薄膜表面等离子体光催化剂Ag@AgBr/CNT/Ni的制备和性能
李爱昌, 赵娣, 卢艳红, 杨晓静, 王瑶, 刘建新
2018, 34(11): 2009-2018  doi: 10.11862/CJIC.2018.262
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用复合电沉积技术制备了Ag@AgBr/CNT/Ni表面等离子体薄膜催化剂,以扫描电镜(SEM)、X射线衍射(XRD)、拉曼光谱(Raman Spectra)、X射线光电子能谱(XPS)和紫外-可见漫反射光谱(UV-Vis DRS)对薄膜的表面形貌、晶体结构、化学组成和光谱特性进行了表征,在可见光照射下,用罗丹明B(RhB)作为模拟污染物对薄膜的光催化性质和稳定性进行测定,采用测定薄膜电化学阻抗谱(EIS)和向反应系统中加入活性物种捕获剂的方法对薄膜光催化机制进行探索。结果表明:最优工艺下制备的Ag@AgBr/CNT/Ni薄膜是由少量碳纳米管(CNT)和表面沉积纳米Ag粒子的AgBr晶体构成的复合薄膜。薄膜具有突出的表面等离子体共振效应、优异的光催化活性和良好的催化稳定性。光催化罗丹明B 20 min,Ag@AgBr/CNT/Ni薄膜的降解率是Ag@AgBr/Ni薄膜的1.32倍,是P25 TiO2/ITO多孔薄膜的21.6倍。在保持光催化性能基本不变的前提下可循环使用5次。CNT的存在使薄膜电荷传导性能和光催化还原溶解氧的性能大幅增加,是所制薄膜相对于Ag@AgBr/Ni薄膜光催化性能提高的主要原因。提出了薄膜光催化罗丹明B的反应机理。
MoS2/CNFs对电极膜厚对染料敏化太阳能电池性能影响
李玲, 王东阳, 张雪, 王启明, 付丽珊, 于敏思, 肖金冲, 赵晓辉
2018, 34(11): 2019-2024  doi: 10.11862/CJIC.2018.264
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通过静电纺丝技术和水热法成功获得了碳纳米纤维负载二维层状硫化钼(MoS2/CNFs),将其作为对电极组装的染料敏化太阳能电池(DSSCs)表现出优异的电化学特性。在DSSCs制备过程中,对电极膜厚对电池性能有很大影响,所以本文重点探究了喷涂法制备的对电极膜厚对其组装的染料敏化电池光电性能影响,获得最佳对电极膜厚。实验结果表明当MoS2/CNFs复合对电极材料膜厚为8 μm时,电池光电转换效率达到最大值7.78%。
“蒸汽相转化”法制备纳米晶组成的块状方钠石多级孔沸石催化材料
秦波, 孔庆岚, 刘芝平, 杨晓娜, 宁伟巍, 杜艳泽, 郑家军
2018, 34(11): 2025-2031  doi: 10.11862/CJIC.2018.240
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将实验室合成的聚苯乙烯乳胶微球(PS)加入制备方钠石(SOD)沸石的前驱体凝胶中,在45℃条件下制得干凝胶,随后采用"蒸汽相转化"法制备了大块状SOD沸石材料。对影响多级SOD沸石形成因素进行了详细讨论。采用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、N2吸附-脱附和压汞技术等表征手段对制备的材料进行了详细表征。结果表明通过"蒸汽相转化"法制备的大块状SOD沸石由球状多晶聚集体构成,这些球状多晶聚集体又是由粒径为50~100 nm的初级纳米晶粒组成,在初级纳米晶粒上和纳米晶粒之间形成了2~50 nm介孔结构以及由脱除PS微球形成的50~300 nm的大孔结构。
氮化钨-钨/掺氮有序介孔碳复合材料的制备及其氧还原性能
郭虎, 李玲慧, 王涛, 范晓莉, 宋力, 龚浩, 夏伟, 姜澄, 高斌, 何建平
2018, 34(11): 2032-2040  doi: 10.11862/CJIC.2018.263
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采用软模板法制备了氮化钨-钨/掺氮有序介孔碳复合材料(WN-W/NOMC), 作为一种高比表面积且价格低廉的阴极氧还原反应催化剂。通过适量添加尿素来改变复合材料中的氮含量, 在掺氮量为7%(w/w)时, 实验发现材料能够保持完整有序介孔结构, 测试其比表面积高达835 m2·g-1, 透射电子显微镜(TEM)测试结果显示其催化颗粒均匀地分散在氮掺杂有序介孔碳载体上。在O2饱和的0.1 mol·L-1 KOH溶液中测试了材料的氧还原催化性能(ORR), 显示其起始电位为0.87 V(vs RHE), 极限电流密度为4.49 mA·cm-2, 氧还原反应的转移电子数为3.4, 接近于20%(w/w)商业Pt/C的3.8, 说明该材料表现出近似4电子的氧还原反应途径。研究结果表明, WN-W/NOMC的催化性能虽然稍弱于商业铂碳(0.99 V, 5.1 mA·cm-2), 但其具有远超铂碳的循环稳定性和耐甲醇毒化能力。
Articles
Preparation, Photophysical and Photocatalytic Property Characterization of Sm2FeSbO7 during Visible Light Irradiation
Jing-Fei LUAN, Wen-Cheng TAN
2018, 34(11): 1950-1965  doi: 10.11862/CJIC.2018.245
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In order to efficiently degrade organic pollutants in water, a new photocatalyst Sm2FeSbO7 was prepared by a solid-state reaction method for the first time. The construction and photocatalytic property of Sm2FeSbO7 had been characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, transmission electron microscope and UV-visible spectrometer. Sm2FeSbO7 crystallized with a pyrochlore-type structure, a cubic crystal system and a space group Fd3m. The lattice parameter a of Sm2FeSbO7 was 1.035 434 nm. The band gap of Sm2FeSbO7 was estimated to be 2.46 eV. The photocatalytic degradation of indigo carmine was accomplished under visible light irradiation with Sm2FeSbO7 as a catalyst compared with nitrogen-doped TiO2. The results indicated that Sm2FeSbO7 displayed higher photocatalytic activity compared with nitrogen-doped TiO2 for the photocatalytic degradation of indigo carmine under visible light irradiation. The reduction of the total organic carbon, the gradual formation of inorganic products, SO42- and NO3-, and the evolution of CO2 revealed the continuous mineralization of indigo carmine during the photocatalytic process. Some intermediate products which came from the photocatalytic degradation of indigo carmine were detected, such as o-nitrobenzoic acid and o-nitrobenzaldehyde, and a possible photocatalytic degradation path of indigo carmine was acquired.
Synthesis and Performance of La2Mo2O7 with MWCNTs Composite Materials as Pt-Free Counter Electrodes for Dye Sensitized Solar Cells
Ke-Zhong WU, Jia-Jing ZHAO, Yuan-Yuan XIONG, Bei RUAN, Ming-Xing WU
2018, 34(11): 2041-2048  doi: 10.11862/CJIC.2018.249
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A Pt-free counter electrode (CE) composed of La2Mo2O7 (La2O3-2MoO2) was successfully synthesized via the simple pyrolysis of lanthanum acetate (C6H9O6La·xH2O) and hexaammonium heptamolybdate tetrahydrate ((NH4)6Mo7O24·4H2O) in a high-temperature solid-state reaction.Also, La2Mo2O7 and multiwall carbon nanotubes (MWCNTs) are combined using two methods.La2Mo2O7/MWCNTs was prepared by spray-coating La2Mo2O7 over the surface of MWCNTs, and La2Mo2O7@MWCNTs was synthesized by doping La2Mo2O7 into MWCNTs.The two types of composite materials were further used as Pt-free catalytic material in CEs in dye sensitized solar cells (DSSCs).The morphology and microstructure of La2Mo2O7/MWCNTs and La2Mo2O7@MWCNTs were determined using scanning electron microscopy and X-ray diffraction.The electrochemical performance of the La2Mo2O7/MWCNTs and La2Mo2O7@MWCNTs composite catalysts for CEs was determined using photocurrent-voltage measurements, cyclic voltammetry, electrochemical impedance spectroscopy, and Tafel polarization in encapsulation of DSSCs batteries.The experimental results show that power conversion efficiencies of 6.09% and 4.84% were obtained for La2Mo2O7/MWCNTs and La2Mo2O7@MWCNTs, respectively, as CEs toward the reduction of I3-/I- ions, and these values are superior to those of MWCNTs (3.94%) and the La2Mo2O7 (0.87%) electrode under the same conditions.The enhanced electrode performance was attributed to the relatively larger surface area and higher conductivity of the La2Mo2O7/MWCNTs composite catalysts.
Metal Ions Tuned Architectures Based on Diphenic Acid and 1,4-Bis(benzimidazol-1-ylmethyl)-benzene: Syntheses, Structures and Properties
Yu-Ting YANG, Chang-Zheng TU, Li-Feng YAO, Li-Li XU, Jun-Shi WANG, Hong-Ju YIN, Fan WANG
2018, 34(11): 2049-2056  doi: 10.11862/CJIC.2018.257
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Two novel complexes, [Cu2(bbix)(dpa)2(C2H5OH)2]n (1) and {[Cd(bbix)0.5(dpa)]·0.5H2O}n (2) (H2dpa=diphenic acid, bbix=1, 4-bis(benzimidazol-1-ylmethyl)-benzene), were synthesized and structurally characterized under solvothermal conditions.Both 1 and 2 exhibit two-dimensional (2D) architecture.Complex 1 has 63 wave-like layer consisting of Cu-dpa helical chains in which the Cu(Ⅱ) ions as 3-connecting nodes.While the layer structure of 2 consists of one-dimensional chains containing alternated 4-membered and 8-membered rings.Furthermore, the solid-state properties of thermal stability for all crystalline materials and the fluorescence property of 2 at room temperature have been investigated.
Syntheses, Crystal Structures and DNA-Binding Properties of Ni(Ⅱ)/Co(Ⅲ) Complexes with Pyrazine Thiosemicarbazone Ligand
Hao WU, Yuan WANG, Yu-Fei SONG, Ling ZHANG, Wei-Na WU
2018, 34(11): 2057-2062  doi: 10.11862/CJIC.2018.253
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Two complexes[Ni(L)(OAc)] (1) and[Co(L)2]Cl·4CH3OH (2) (HL=2-aceto-3-methylpyrazine N-(4-fluorophenyl)thiosemicarbazone) have been synthesized and structurally determined by single-crystal X-ray diffraction, elemental analysis and IR spectroscopy.X-ray diffraction analysis results show that the Ni(Ⅱ) ion in complex 1 with a distorted square planar geometry is surrounded by one anionic TSC ligand with NNS donor set and one monodentate acetate.By contrast, Co(Ⅲ) ion coordinates with two tridentate TSC ligands, and thus possessing a distorted octahedron coordination geometry.Moreover, the fluorescence spectra indicate that the interactions of complexes 1 and 2 with DNA are stronger than that of the ligand HL.
Halide Triggered Spin State Switching of Iron(Ⅱ) Tetrahedral Cages
Hai-Xia ZHANG, Wang-Kang HAN, Feng-Li ZHANG, Wei HE, Fang-Yuan GE, Ya-Qin WANG, Xiao-Dong YAN, Zhi-Guo GU
2018, 34(11): 2063-2072  doi: 10.11862/CJIC.2018.233
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Three iron(Ⅱ) tetrahedral cages 1~3 with solid state spin-crossover properties were rational constructed.Single crystal X-ray diffraction analysis confirmed the edge-capped capsule, which were assembled from six imidazole Schiff-base ligands and four iron(Ⅱ) ions.The metal centers occupy the vertices and each linker situates at the edges of the tetrahedron.The inner cavities of these cages are surrounded by imidazole groups, while the periphery is decorated by substituted phenyl rings.One of the counter anions is encapsulated at the central cavities and shows strong anion binding interactions with the cages.Interestingly, the iron(Ⅱ) cages in solution can change their spin states from low-spin (LS) to high-spin (HS) upon addition of halide, since tremendous change of solution color and absorption intensity of characteristic broad absorption MLCT bands when addition of halide (Cl- and Br-) to the CH3CN solution of the cages.
Effects of Hydroxyl Groups on Dispersibility of Silicon Nitride Powder in Aqueous Media
Qi CHEN, Bing-Jie XU, Bao-Song XU, Peng-Fei LIU, Zhao HAN, Ben QIU
2018, 34(11): 2073-2080  doi: 10.11862/CJIC.2018.244
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The surface of silicon nitride (Si3N4) powder was efficiently hydroxylated via application of nitric acid to improve dispersibility in aqueous media.Hydroxylated powder results in more stable colloidal dispersion in aqueous media compared to native powder.Results of Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy show that hydroxyl group content of Si3N4 powder significantly increased with hydroxyl modification.This is helpful in preventing Si3N4 powder from aggregating in aqueous media.In addition, thermogravimetric analysis indicates that hydroxyl group content of hydroxylated Si3N4 powder was 68.8% higher than that of native powder.Furthermore, surface hydrophilicity of Si3N4 powder is enhanced with hydroxyl modification, and powder dispersibility is improved with an increase in hydroxyl content.
Syntheses, Crystal Structures and Properties of Mn(Ⅱ) and Cu(Ⅱ) Complexes with 3, 3'-Thiodipropionic Acid Ligand
Ji-Wei LIU, Shu-Xia GUAN, Chang-Sheng GU
2018, 34(11): 2081-2087  doi: 10.11862/CJIC.2018.254
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A Mn(Ⅱ) coordination polymer, {[Mn(DPA)(4, 4'-bipy)]·H2O}n (1) was prepared with 3, 3'-thiodipropionic acid (DPA), 4, 4'-bipyridine (4, 4'-bipy) and Mn(NO3)2·4H2O by hydrothermal method, and a Cu(Ⅱ) coordination polymer, {[Cu(DPA)(bpp)(H2O)]·H2O}n (2) was hydrothermal synthesized by using 3, 3'-thiodipropionic acid (DPA), 1, 3-bis(4-pyridyl)propane (bpp) and Cu(NO3)2·3H2O. The coordination polymers were characterized by elemental analysis, thermal analysis, IR, XRD and X-ray single crystal diffraction. Complexes 1 and 2 have two-dimensional layer structures, Furthermore, there are hydrogen bonds and π-π stacking interactions contributing three-dimensional supramolecular structures of 1 and 2, respectively.
Preparation of Titania Doped SiO2 Nanotube Composites with Manganese Loadings for NH3-SCR Applications
Yong-Zhou YE, Fei SHEN, Hong-Ning WANG, Ruo-Yu CHEN, Lin SUN
2018, 34(11): 2088-2096  doi: 10.11862/CJIC.2018.260
[摘要]  (2) [HTML全文] (2) [PDF 4143KB] (0)
摘要:
Ti-containing SiO2 nanotubes (TiSNTs) were firstly synthesized via a sol-gel and co-polycondensation method. After that, a family of Mn doped TiSNTs (Mn/TiSNTs) catalysts with various Mn loading were prepared via the co-precipitation method. When Si/Ti molar ratio was more than 5, a worm-like tubular morphology was clearly observed. The NH3-TPD (NH3-temperature programmed desorption) results show that the Ti doping into the skeleton of the silica nanotubes greatly enhanced the acidic sites of the catalyst and promoted the adsorption and NH3-SCR (selective catalytic reduction) activation on the surface of the catalyst. Meanwhile, the results of H2-TPR (H2-temperature programmed reduction) also show that Ti doping enhanced the redox ability of the catalyst and the capacity of oxygen storage. Moreover, the doped Mn species was beneficial for reducing the reaction temperature. The results of SCR of NOx with NH3 show the catalyst with Si/Ti molar ratios of 10 (Mn/Ti(10)SNT) exhibited significant catalytic activity, and the NO conversion rate remained over 90% in the reactive temperature range of 135 to 325℃.
Binuclear Nickel(Ⅱ) and Zinc(Ⅱ) Complexes Based on 2-Amino-3-hydroxy-pyridine Schiff Base: Syntheses, Supramolecular Structures and Spectral Properties
Jian CHANG, Hong-Jia ZHANG, Hao-Ran JIA, Yin-Xia SUN
2018, 34(11): 2097-2107  doi: 10.11862/CJIC.2018.256
[摘要]  (3) [HTML全文] (3) [PDF 5539KB] (0)
摘要:
Two 2-amino-3-hydroxy-pyridine Schiff base binuclear Ni(Ⅱ) and Zn(Ⅱ) complexes, [Ni(L1)(DMF)]2 (1) (H2L1=4-hydroxy-3-((3-hydroxy-pyridin-2-ylimino)-methyl)-chromen-2-one) and[Zn(L2)(H2O)]2·2DMF (2) (H2L2=2-((3, 5-dibromo-2-hydroxy-benzylidene)-amino)-pyridin-3-ol) have been synthesized and characterized by elemental analyses, IR, UV-Vis, emission spectra and X-ray crystallography. X-ray crystallography analyses showed that complexes 1 and 2 all possess the binuclear structures, consisting of two metal ions, two ligand units and two coordinated solvent molecules, in which the difference is that complex 2 contains two solvent molecules. Complexes 1 and 2 crystallize in the monoclinic space group P21/c and the center Ni(Ⅱ) and Zn(Ⅱ) are all five-coordinated slightly distorted square pyramid geometry by four O atoms and one imine N atoms. Complex 1 (or 2) links some other molecules into an infinite 3D network supramolecular structure via intermolecular hydrogen bond, C-H…π or ππ stacking interactions. And the fluorescent properties of H2L1, H2L2 and their corresponding Ni(Ⅱ) and Zn(Ⅱ) complexes have been discussed. The ligands H2L1 and H2L2 exhibit blue emission with the maximum emission wavelength λem=457 and 473 nm, and complexes 1 and 2 show green emission with λem=543 and 538 nm.
Syntheses, Crystal Structures and Luminescence Properties of Two La(Ⅲ) Complexes Assembled by 3, 5-Dinitrosalicylic Acid and 1, 10-Phenanthroline
You-Zhu YU, Yu-Hua GUO, Yong-Sheng NIU, Xian-Li WU, Ya-Ting FANG, Na-Jie ZHUANG, Jun-Wei ZHANG, Hao LIANG, Fang WANG
2018, 34(11): 2108-2114  doi: 10.11862/CJIC.2018.248
[摘要]  (3) [HTML全文] (3) [PDF 2302KB] (0)
摘要:
Two new complexes based on 3, 5-dinitrosalicylic acid (H2dns) and 1, 10-phenanthroline (phen), namely[La2(dns)2(Hdns)2(phen)4] (1) and[La4(dns)6(phen)6] (2) have been synthesized and characterized by IR, elemental analyses, thermogravimetric analyses and X-ray diffraction technique. Single-crystal X-ray diffraction analyses revealed that two complexes all crystallize in the triclinic system and space group P1. For complexes 1, H2dns ligands adopt tridentate and didentate coordination modes to link La(Ⅲ) ions into dinuclear structure. However H2dns ligands adopt tridentate coordination mode to link La(Ⅲ) ions into tetranuclear structure. TG and fluorescence analysis show the thermal stability of 2 is higher than that of 1, and 1 and 2 have same maximum emission band of the fluorescence at 467 nm.
Distinct Role of La Doping in Regulating the Photo-Oxidation and Reduction of BiOBr Nanosheet
Qi-Zhe FAN, Chun-Fa LIAO, Zhi-Feng LI, Zhi-Wen ZHANG, Xin CHEN, Chang-Lin YU
2018, 34(11): 2115-2126  doi: 10.11862/CJIC.2018.255
[摘要]  (3) [HTML全文] (3) [PDF 7283KB] (0)
摘要:
Both organic cetyltrimethyl ammonium bromide (CTAB) and inorganic NaBr are served as the bromine source, the thylakoid-like La doped BiOBr photocatalysts were synthesized via a hydrothermal process. The obtained samples were first characterized by X-ray diffraction (XRD), N2 physical adsorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-visible spectroscopy, X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL) spectroscopy. Then, the effects of photo-oxidation and reduction properties of BiOBr with La doping were investigated by DFT calculation. The photo-oxidation and reduction activity of the pure and La doped BiOBr samples were evaluated by photo-catalytic degradation of acid orange Ⅱ, ammonia nitrogen and methylene blue reduction under visible light irradiation. The results showed that it could inhibit growth of BiOBr crystals and promote the stacking crystals when La doped. More importantly, the oxidation performances of BiOBr were promoted, where the reduction performances were inhibited in large part by La doping.
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论文
Ta3N5@Ta2O5的可控制备及可见光催化分解水析氢性能
张微, 姜洪泉
2018, 34(9): 1591-1599  doi: 10.11862/CJIC.2018.198
[摘要]  (88) [HTML全文] (88) [PDF 5908KB] (88)
摘要:
以水热法制备的Ta2O5纳米粒子为前驱体,利用高温氮化技术成功制备了核壳异质结构的Ta3N5@Ta2O5纳米光催化剂。采用XRD、XPS、TEM、N2吸附-脱附测试、DRS及电化学测试等分析手段,考察了氮化温度和氮化时间对样品的表面组成、晶粒尺寸、晶面结构、能带结构及载流子分离效率的影响规律。在NH3气流量50 mL·min-1的条件下,当氮化温度为750℃,控制氮化时间能够对纳米Ta2O5样品的带隙结构在3.86~2.08 eV间有效调控,相应地样品逐渐从Ta2O5经TaON@Ta2O5转化为Ta3N5@Ta2O5;当氮化时间为3 h,氮化温度由750℃升高到900℃,Ta3N5@Ta2O5样品的带隙窄化至2.04 eV;当氮化温度为850℃,氮化时间延长至12 h,Ta2O5完全氮化为Ta3N5,带隙进一步窄化至2.02 eV。经850℃氮化3 h样品,壳层Ta3N5界面转化为高活性(110)晶面,光生载流子分离效率最大,在可见光(λ>420 nm)照射下光解水析氢活性最高,达21.75 μmol·g-1·h-1
金纳米球和金纳米棒的制备及其光热催化性能
李健, 王菁华, 杨阿龙, 石振宁, 王江韦, 赵勤富, 张莹
2018, 34(9): 1610-1614  doi: 10.11862/CJIC.2018.189
[摘要]  (70) [HTML全文] (70) [PDF 1608KB] (70)
摘要:
以氯金酸(HAuCl4)为原料,硼氢化钠(NaBH4)为还原剂,聚乙烯吡咯烷酮K30(PVP)为稳定剂制备了尺寸5 nm的金纳米球;以阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)为模板剂和油酸钠(NaOL)稳定剂,用种子生长法制备了不同长径比(R=2.5~4)的金纳米棒。在2 W·cm-2的808 nm激光照射10 min条件下,C(0.4 mg·mL-1)浓度金纳米球溶液升温10.2℃,该溶液可催化血液中亚硝基硫醇释放NO,最大释放量可达1.42 nmol·L-1;相同光热及催化条件下,C(0.4 mg·mL-1)浓度金纳米棒(R=3.01)溶液升温41.3℃,该溶液催化血液中亚硝基硫醇释放NO最大释放量可达1.89 nmol·L-1。金纳米球和金纳米棒的光热及催化性能随着浓度增加而增强,金纳米棒的光热及催化性能要优于金纳米球。
萃取温度对无灰煤结构及煤基活性炭电化学性能的影响
郭秉霖, 侯彩霞, 樊丽华, 孙章
2018, 34(9): 1615-1624  doi: 10.11862/CJIC.2018.201
[摘要]  (61) [HTML全文] (61) [PDF 4961KB] (61)
摘要:
以内蒙古褐煤为原料,N-甲基吡咯烷酮为萃取剂,在不同温度下萃取制备无灰煤,进而利用KOH活化法制备活性炭,探究萃取温度对活性炭电化学性能的影响。结果表明,无灰煤萃取温度对煤基活性炭电化学性能有显著影响。对无灰煤及原料褐煤的灰分含量,表面官能团含量和对应活性炭的比表面积、孔结构及其电化学性能进行对比发现,330℃下萃取制备出的无灰煤在碱煤质量比3:1,活化温度650℃,活化时间2h的活化过程中具备最适宜的反应性,对应活性炭比表面积高达1 252 m2· g-1,表面官能团含量适中,在3 mol·L-1 KOH电解液中50 mA·g-1电流密度下比电容高达322 F·g-1,2 A·g-1的电流密度下比电容保持率仍可接近90%。
Co掺杂比例对ZnO热致变色变发射率性能的影响
徐晨, 方罡, 刘初阳, 徐国跃, 朱永梅, 张艳婷
2018, 34(9): 1625-1631  doi: 10.11862/CJIC.2018.203
[摘要]  (52) [HTML全文] (52) [PDF 3608KB] (52)
摘要:
利用固相烧结法制备了不同Co2+掺杂比例的ZnO,研究了Co2+掺杂比例对ZnO微观结构形貌,从而对变色变发射率性能的影响。结果表明,Co2+掺杂会取代ZnO中部分的Zn2+,但不改变ZnO的六方纤锌矿结构。掺杂比例达到7.5%和10%时,会形成杂相Co3O4。随着掺杂比例逐渐增加,ZnO的结晶质量下降、禁带宽度减小、而晶粒形貌尺寸基本不变。Co2+掺杂ZnO在室温下都呈绿色,随掺杂比例增加颜色先变深后变浅。当温度从室温升高到700℃,所有样品可变为黄褐色同时发射率逐渐提高。并且,随掺杂比例增加,颜色变化更为明显,发射率变化值增大。
基于水滑石的Zn-Cr-Cu复合金属氧化物的制备及其对罗丹明B的光催化降解性能
孟跃, 夏盛杰, 薛继龙, 倪生良, 倪哲明
2018, 34(9): 1632-1640  doi: 10.11862/CJIC.2018.208
[摘要]  (47) [HTML全文] (47) [PDF 4752KB] (47)
摘要:
采用共沉淀法一步组装获得席夫碱铜(Ⅱ)插层的Zn-Cr水滑石(ZnCr-SBCu-LDHs),再经500℃高温焙烧制得新颖的Zn-Cr-Cu复合金属氧化物(ZnCr-SBCu-LDO)光催化材料。通过X射线粉末衍射(XRD)、紫外-可见漫反射图谱(UV-Vis DRS)、扫描电子显微镜(SEM)、电感耦合等离子体原子发射光谱(ICP-AES)对催化材料的结构和性质进行分析表征。以较难被水滑石吸附的阳离子型染料罗丹明B(RhB)作为模型,研究材料的光催化活性,考察材料用量、RhB溶液的初始pH值、温度以及H2O2初始浓度等对光催化活性的影响。结果发现:ZnCr-SBCu-LDO具有优异的光催化活性,在初始pH值为7.40、温度为25℃以及H2O2初始浓度10 mmol·L-1的条件下,光照4 h后,1 g·L-1的催化材料对5 mg·L-1的RhB溶液的降解效率可达98.68%。此外,进一步对催化剂的再生能力进行了研究,并初步探讨了光催化降解的机理。
钠离子电池正极材料Na3V2(PO4)2O2F的控制合成与电化学性能优化
谷振一, 郭晋芝, 杨洋, 吕红艳, 赵欣欣, 席晓彤, 何晓燕, 吴兴隆
2018, 34(9): 1641-1648  doi: 10.11862/CJIC.2018.204
[摘要]  (126) [HTML全文] (126) [PDF 4185KB] (126)
摘要:
采用简单的水热合成法制备氟磷酸钒氧钠(Na3V2(PO42O2F,简写为NVPOF),通过调节水热反应溶液的pH值和反应温度等关键参数,有效调节NVPOF的颗粒尺寸和均匀性,优化其电化学性能。研究结果显示,性能最优的NVPOF的合成条件是:pH值为7.00±0.05,水热反应温度为170℃。在该条件下合成的NVPOF正极材料具有优异的电化学性能,表现为0.1C(1C=130 mA·g-1)的倍率下放电比容量可达123.2 mAh·g-1,且在20C的高倍率下仍可实现85.9 mAh·g-1的比容量,在1C下循环200圈后其容量保持率为96.2%,表明该材料具有高容量、优异的倍率和循环性能。所制备的NVPOF颗粒为纳米尺度且具有很高的均匀性,可缩短Na+的传输路径从而缩短其传输时间,且NVPOF晶体结构具有高稳定性,是一类具有高性能的钠离子电池正极材料。
以磷酸二氢根为轴向配体的铂(Ⅳ)前药的设计、合成和抗癌活性测试
高安丽, 熊庆丰, 姜婧, 余娟, 楼丽广, 刘伟平
2018, 34(9): 1649-1654  doi: 10.11862/CJIC.2018.211
[摘要]  (59) [HTML全文] (59) [PDF 1907KB] (59)
摘要:
以顺铂和奥沙利铂为原药,合成了2种以磷酸二氢根为配体的铂(Ⅳ)前药(代号:CPL-1501和CPL-1504),采用元素分析、红外光谱和核磁共振表征了其化学结构,通过循环伏安法测定了它们的还原电位。应用标准MTT法,测试了这2种铂(Ⅳ)前药对多种人癌细胞株生长的抑制活性。结果表明:CPL-1501作为顺铂的前药,水溶性好(10 mg·mL-1)、稳定,Ep值分别为0.16和-0.52 V,为不可逆的双电子还原过程,在癌细胞缺氧的微环境中易被还原激活。CPL-1501对多种癌细胞株的生长均有明显的抑制作用,抗癌活性与顺铂相当、明显高于水溶性Pt(Ⅱ)抗癌药物-卡铂。CPL-1504虽然水溶性(50 mg·mL-1)高于奥沙利铂,却未表现出明显的抗癌活性,这可能与其较低的还原电位(Ep值分别为-0.51和-0.76 V)有关。
籽晶层制备方式对氧化锌纳米棒阵列的影响
周菲迟, 袁龙, 冯守华, MartynA McLachlan, 张佳旗
2018, 34(9): 1655-1662  doi: 10.11862/CJIC.2018.210
[摘要]  (79) [HTML全文] (79) [PDF 3702KB] (79)
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采用3种不同的方式制备ZnO薄膜籽晶层:旋涂、喷雾热解和脉冲激光沉积。对于每一种制备方式,其薄膜的晶体结构、形貌、表面粗糙度等性能分别用X射线衍射(XRD)、扫描电子显微镜(SEM)和原子力显微镜(AFM)进行了表征。之后,通过水热合成方法,在3种籽晶层衬底上制备得到具有不同结构和形貌特征的ZnO纳米棒阵列。结果表明,ZnO纳米棒生长和籽晶层制备方式具有极强的相关性。最后,对两者相关性的生长机理进行了解释。
金属有机框架@介孔分子筛复合材料的构建和性质
马苗苗, 李梅, 柯福生
2018, 34(9): 1663-1669  doi: 10.11862/CJIC.2018.176
[摘要]  (61) [HTML全文] (61) [PDF 2634KB] (61)
摘要:
通过蒸汽诱导内部水解法(VIH)在介孔分子筛SBA-15孔壁上引入Al2O3,合成得到Al2O3@SBA-15复合物,随后与对二苯甲酸配体反应,从而制备得到金属有机框架化合物(MIL-53)与介孔分子筛(SBA-15)复合材料(MIL-53@SBA-15)。采用粉末X射线衍射(PXRD)、N2吸附-脱附测试、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等技术证明成功合成了MIL-53@SBA-15复合材料。染料吸附实验结果表明,MIL-53@SBA-15复合材料相比于SBA-15、MIL-53及其物理混合样品,表现出对丁基罗丹明染料更高效吸附特性。
α-氧化铁介孔纳米材料的制备及其在锂/钠离子电池中的电化学性能
李华梅, 陈宇杰, 赵晓辉, 邓昭
2018, 34(9): 1670-1676  doi: 10.11862/CJIC.2018.221
[摘要]  (58) [HTML全文] (58) [PDF 5163KB] (58)
摘要:
采用硬模板法合成了具有六方排列的平行圆柱形有序孔道介孔α-氧化铁(α-Fe2O3),并将其用作锂离子、钠离子电池的负极材料。所制备的介孔α-Fe2O3凭借其独特的有序介孔结构,有效缓解电极在充放电过程中的体积效应,提高了电解液浸润性,促进锂/钠离子的转移和传输,从而在锂离子及钠离子电池中均表现出优异的电化学性能。作为锂离子电池负极时,其首圈放电比容量为983.9 mAh·g-1。经过100次循环后,其放电比容量为1 188.0 mAh·g-1。在钠离子电池中,其首圈放电比容量为687.7 mAh·g-1。经过50次循环后,仍有316.9 mAh·g-1的放电比容量。
Articles
Syntheses, Structures and Luminescent Properties of 3D Ni(Ⅱ)-Ln(Ⅲ) Heterometallic Coordination Polymers Constructed from the Triazol-Based Ligand
Yu-Qing LIN, Min GAO, Hui ZHANG, Xue PENG, Wen GU, Xin LIU, Sheng-Yun LIAO
2018, 34(9): 1600-1609  doi: 10.11862/CJIC.2018.194
[摘要]  (59) [HTML全文] (59) [PDF 4968KB] (59)
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A series of Ni(Ⅱ)-Ln(Ⅲ) heterometallic isomers[Ln2Ni(tia)4(H2O)4]n (Ln=La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8) and Dy (9)), and {[Yb2Ni(tia)4(H2O)2]·2H2O}n (10) (tia=5-(1H-1, 2, 3-triazol-1-yl)isophthalate) have been constructed from the tritopic 1, 2, 3-trazol-based aromatic heterocyclic carboxylic ligand H3ctia (H3ctia=5-(4-carboxyl-1H-1, 2, 3-triazol-1-yl) isophthalic acid). The results of single crystal X-ray diffraction show that all of these complexes possess 3D microporous frameworks. Complexes 1~9 are isomorphic. The chemical composition of complex 10 is the same as those of 1~9, but the crystallographic structure is totally different from 1~9. In the visible region, complexes 5, 6, 8 and 9 exhibit the characteristic luminescent emissions of Sm(Ⅲ), Eu(Ⅲ), Tb(Ⅲ) and Dy(Ⅲ) with the long luminescent lifetime (234 μs for 6, 598 μs for 8 and 2.96 μs for 9). Complexes 4, 9 and 10 show characteristic emissions of Nd(Ⅲ), Dy(Ⅲ), and Yb(Ⅲ) in the near infrared region with the average lifetime of 4.25, 3.42 and 5.66 μs, respectively.
CNx Nanotube Support Platinum-CeOx as Highly Stable and Efficient Electrocatalyst for Oxygen Reduction Reaction
Yu FU, Hong-Liang AO, Ling-Xiao ZHANG, Yu-Meng GUO, Ju-Mei LIANG, Li-Juan ZHANG, Fan LI
2018, 34(9): 1677-1687  doi: 10.11862/CJIC.2018.206
[摘要]  (70) [HTML全文] (70) [PDF 9317KB] (70)
摘要:
A novel catalyst was synthesized using CNx nanotube (CNxNT) converted from polypyrrole nanotube as support and CeOx as co-catalyst. The as-prepared Pt-CeOx/CNxNT catalyst showed superior ORR activity compared to Pt/CNxNT and commercial Pt/C catalyst, which is attributed to the existence of CeOx, pyridine-like nitrogenin support and the unique hollow tube nanostructure of CNxNT support. Moreover, the presence of CeOx can significantly enhance the durability for both Pt nanoparticles and support.
Controllable Fabrication of Mono-Shelled Hollow Sphere CaCO3 Microspheres via CO2 Bubbling Method:Potential Dye Carrier for Cell Bio-imaging
Jiang LIU, Feng SHA, Ting-Yu YANG, Liang MA, Jian-Bin ZHANG
2018, 34(9): 1688-1700  doi: 10.11862/CJIC.2018.220
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摘要:
Mono-shelled hollow sphere CaCO3 microspheres were prepared in the presence of L-methionine (L-Met) via a CO2 bubbling method; after that, the effects of L-Met adding amount, CO2 flow rate, and temperature on morphology, size, and phase composition of CaCO3 have been systemically explored. As a potential guest molecule carrier, the as-synthesized hollow sphere CaCO3 microspheres could load with rhodamine B (RhB) to prepare a novel luminescent composite material (RhB@hollow-CaCO3). This luminescent composite material not only presented good biocompatibility to the A-549 lung cancer cells (A-549 LCCs) and HO8910 ovarian cancer cells (HO8910 OCCs), but also had the ability of luminescence in above cells.
Simple Way to Enhance the Photocatalytic Activity and Application in Antireflective Coatings for Amorphous TiO2
Yuan-Yang LI, Liang-Hong YAN, Bo JIANG
2018, 34(9): 1701-1709  doi: 10.11862/CJIC.2018.205
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Small-sized amorphous TiO2 nanoparticles were prepared and deposited on mesoporous SiO2 support via sol-gel method at room temperature. This structure greatly increases the surface areas of the amorphous TiO2 particles, which facilitates the enhancement of photocatalytic activity and preserved the optical performance of the films in the same time. The resultant SiO2&amorphous-TiO2 films afford glasses a maximum transmittance of 99.97% and show a much higher photocatalytic activity than the monolayer amorphous TiO2 film. Surprisingly, the SiO2&amorphous-TiO2 even shows a higher photocatalytic activity than the counterparts with anatase phase. This higher photocatalytic activity is attributed to abundant surface hydroxyl groups and relative loose structure of the amorphous TiO2 nanoparticles, which can help enhance photocatalytic activity through reducing recombination of electron-hole pairs and increase the migration rates of the photoexcited electrons and holes, respectively. And these characteristics may be preferable to crystal structure for enhancing photocatalytic activity. Meanwhile, the coating process is very simple, low cost and conducted at room temperature, which is feasible for polymer substrates.
Ti4+ Doped Perovskite for Efficient Perovskite Solar Cells by Grain Boundary Passivation
Hui TIAN, Qi XIONG, Peng LIU, Jing ZHANG, Lei HAN, Yu-Hao ZHANG, Yong-Jin ZHENG, Li-Shuang WU, Yue-Jin ZHU
2018, 34(9): 1710-1718  doi: 10.11862/CJIC.2018.200
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摘要:
The grain boundaries defect is solved by titanium ion (Ti4+) doping. Ti4+ has small radius which is proved to form at the grain boundary of polycrystalline perovskite. By control doping of titanium ion, grain size become more uniform, which leads to more continuous perovskite thin film. Studies suggest that the defects in grain boundary of polycrystalline perovskite are passivated by doping Ti4+, which results in the trap states concentration greatly decrease. And experimental test clearly exhibits more excellent performance of short-circuit current density (JSC=22.3 mA·cm-2), open-circuit voltage (VOC=1.10 V), fill factor (FF=72.4%) and photovoltaic conversion efficiency (PCE=17.4%) with low amount Ti4+ doping compared with pure planar heterojunction perovskite solar cells (AM1.5).
Cu(Ⅰ)Fe(Ⅱ) Heterobimetallic Complexes Based on Functionalized 6-Methoxycarbonyl-2, 2'-bipyridine Ligands
Rong HUANG, Xue-Hua ZENG, Wan-Man WANG, Meng-Li ZHANG, Jing-Lin CHEN, Jin-Sheng LIAO, Sui-Jun LIU, He-Rui WEN
2018, 34(9): 1719-1724  doi: 10.11862/CJIC.2018.188
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Two new Cu(Ⅰ)Fe(Ⅱ) heterobimetallic complexes, [Cu(mbpy)(dppf)]ClO4·CH2Cl2 (1) and[Cu(mmbpy)(dppf)]ClO4 (2), were synthesized by using[Cu(CH3CN)4]ClO4, 6-methoxycarbonyl-2, 2'-bipyridine (mbpy), 6-metho-xycarbonyl-4, 4'-dimethyl-2, 2'-bipyridine (mmbpy), and 1, 1'-bis(diphenylphosphino)ferrocene (dppf) as the starting materials. As revealed by single-crystal X-ray diffraction analysis, complexes 1 and 2 are all Cu(Ⅰ)Fe(Ⅱ) heterobimetallic species and exhibit tetra-coordinated and distorted tetrahedral configuration. Complexes 1 and 2 all show a weak low-energy broad absorption in the wavelength range of 330~520 nm, which is mainly assigned to metal-to-ligand charge-transfer (MLCT) transition. No emission is detected in solution and solid states at room temperature for 1 and 2, due to the introduction of 1, 1'-bis(diphenylphosphino)ferrocene.
Two Binuclear Cu(Ⅱ) Complexes of Reduced Schiff Base Ligand Containing Benzimidazole Ring:Syntheses, Structures and Electrochemical Properties
Hai-Yan ZHAO, Na LI, Xiao-Dong YANG
2018, 34(9): 1725-1732  doi: 10.11862/CJIC.2018.218
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Two binuclear copper(Ⅱ) complexes of the reduced Schiff base, namely, HL=2-(((2-(2-benzimidazyl) ethyl)aimino)methyl)phenol (HL) have been synthesized and characterized by C, H and N microanalyses, spectroscopic (FT-IR, UV-Vis) as well as electrochemical techniques and single-crystal X-ray diffraction. The crystal structures of[CuL(CH3OH)]2(BF4)2 (1) and[CuL(NO3)2]2 (2) show that the Cu(Ⅱ) atoms are bridged by two phenolato oxygen atoms in the dimers. The geometries around Cu(Ⅱ) atoms are distorted square pyramid with the Addison parameters (τ) of 0.31 and 0.35 for 1 and 2, respectively. Furthermore, the complex units in 1 and 2 are linked into 1D and 3D supramolecular networks by H-bonding in the solid state, respectively. The electrochemical studies of 1 and 2 show two quasi-reversible one electron reduction processes.
Syntheses, Characterization and Luminescent Properties of Two Silver(Ⅰ) Complexes Based on N-donor and P-donor Ligands
Xiao-Nan KUANG, Yu WANG, Ning ZHU, Min LIU, Yu-Ping YANG, Zhong-Feng LI, Hong-Liang HAN, Qiong-Hua JIN
2018, 34(9): 1733-1738  doi: 10.11862/CJIC.2018.193
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Two novel silver(Ⅰ) complexes, [Ag2(dppp)2(phen)2](CF3SO3)2 (1) and[Ag2(dppm)2(dpq)2](CF3SO3)2·3CH3OH (2) (dppp=bis(diphenylphosphino)propane, dppm=bis(diphenylphosphino)methane, phen=1, 10-phenan-throline, dpq=pyrazino[2, 3-f][1, 10]phenanthroline), have been synthesized in mixed solvent CH3OH and CH2Cl2 and characterized by IR, single-crystal X-ray diffraction, 1H NMR spectroscopy, fluorescence spectra and THz time domain spectroscopy (THz-TDS). Complex 1 is of a binuclear complex, which was generated by the reaction of AgCF3SO3 and dppp with phen in 1:1:1 molar ratio. In complex 1, the central Ag(Ⅰ) ion forms a ring by the bridging bisphosphine ligand (dppp) and chelating N-donor ligand (phen). Like 1, 2 is of a binuclear complex, which was obtained by the reaction of AgCF3SO3 and dppm with dpq in 1:1:1 molar ratio. The luminescent spectra show that all these emissions are assigned to ligand centered π-π* transition.
Crystal Structures and Fluorescence Properties of Cu(Ⅱ)/Ni(Ⅱ) Complexes with 4-(1, 2, 4-Triazol-1-yl)phenol Ligand
Hong-Kun ZHAO, Bo DING, Xiu-Guang WANG, Fang JIA, En-Cui YANG, Xiao-Jun ZHAO
2018, 34(9): 1739-1746  doi: 10.11862/CJIC.2018.219
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Two 4-(1, 2, 4-triazol-1-yl)phenol (hptrz)-based transition metal complexes, {[Ni(H2O)2(hptrz)2(tp)]·2DMF}n (1) and[Cu(hptrz)2(SCN)2]·2H2O (2) (H2tp=terephthalic acid), have been prepared and characterized by single-crystal and powder X-ray diffractions, elemental analysis, FT-IR spectra, thermogravimertric and luminescence spectra. X-ray diffraction analysis revealed that 1 is a one-dimensional linear chain with octahedral Ni(Ⅱ) ions extended by bis-unidentate tp2- anions; whereas 2 exhibits a centrosymmetric mononuclear entity. The neutral hptrz ligand in the both complexes serves as terminal ligands to complete the metal coordination sphere and to help to assemble the low-dimensional aggregates into a high-dimensional supramolecular architecture by O-H…O hydrogen-bonding interactions. Additionally, the complexes display strong emissions in UV region originated from intraligand electronic transfer.
Assembly and Properties of a 2D Layer Coordination Polymer Containing Linear Tetranuclear Cobalt-Cluster Unit Bridged by Tricarboxylic Acid Ligand
Peng-Fei WANG
2018, 34(9): 1747-1752  doi: 10.11862/CJIC.2018.207
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摘要:
The hydrothermal reaction of cobalt(Ⅱ) salts with 2-hydroxyl-1, 3, 5-benzenetricarboxylic acid (OH-H3BTC) in the presence of sodium hydroxide afforded a cobalt(Ⅱ) coordination polymer, namely[Co2(O-BTC)(H2O)5]n (1), which has been characterized by powder and single-crystal X-ray diffraction, infrared spectroscopy, elemental analysis, and thermogravimetric analysis. Compound 1 contains a linear tetranuclear unit[Co4O7] through the carboxylate oxygen and hydroxyl atoms, which are further linked to form a two-dimensional (2D) layered structure in the ab plane by the O-BTC4- organic ligands. Adjacent layers are packed along the c-axis with the hydrogen bond interactions dominating between the layers to form a three-dimensional (3D) supramolecular structure. Thermal analysis reveals that 1 begins to lose weight at ca. 100℃. Magnetic studies reveal that dominant antiferromagnetic interactions are dominated between the magnetic centers in 1.
Preparation and Properties for Aza-Micheal Addition Reaction of Magnetic Y-MOF@SiO2@Fe3O4 Catalysts
Jin-Cheng MU, Sai JIANG, Sheng-Fu JI
2018, 34(9): 1753-1760  doi: 10.11862/CJIC.2018.209
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The magnetic Y-MOF@SiO2@Fe3O4 catalysts with different Y-MOF contents were synthesized by encapsulating magnetic SiO2@Fe3O4 nanospheres into Y-MOF through an in-situ method. The structure of the catalyst was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), infrared spectroscopy (FT-IR), vibration sample magnetometer (VSM) and the N2 adsorption-desorption test. The performance of the catalyst for Aza-Micheal addition reaction with aniline and methyl acrylate was evaluated. The results showed that Y-MOF was uniformly coated on the surface of the SiO2@Fe3O4 nanospheres to form a core-shell magnetic Y-MOF@SiO2@Fe3O4 catalyst. The catalysts exhibited good superparamagnetism. When Y-MOF content was 43.3% (w/w), the Y-MOF@SiO2@Fe3O4 catalyst had better catalytic performance for the Aza-Micheal addition reaction. The conversion of methyl acrylate was 88.3% and the selectivity of N-(β-methoxycarbonylethyl) aniline was 99.8%. After reaction, the catalyst was recovered by magnetic recovery. It was reused five times, and still has high conversion and selectivity.
Synthesis, Structure and Magnetic Property of Dysprosium(Ⅲ) Complex Based on β-Diketonate and Tetramethylimidazolium Ligands
Jing-Yuan GE, Zhong-Yan CHEN, Jian-Ping MA, Shuai HUANG, Jia DU, Hai-Ou WANG, Kun-Peng SU, Hai-Ying WANG
2018, 34(9): 1761-1767  doi: 10.11862/CJIC.2018.202
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摘要:
A mononuclear dysprosium(Ⅲ) complex, namely (Tmim)[Dy(thd)4] (1), was synthesized by the combination of 2, 2, 6, 6-tetramethylheptanedione (thd-) anion ligand and a 1, 3, 4, 5-tetramethylimidazolium (Tmim+) cation balancing the charge. Complex 1 was structurally and magnetically characterized. The coordination geometry of Dy(Ⅲ) ion is ascribed to approximately square antiprismatic (D4d) symmetry with the SAPR-8 parameter of 0.316. In the solid state, every mononuclear[Dy(thd)4]- anion is separated by Tmim+ cations regularly and the shortest Dy…Dy distance is 1.229 8 nm. Magnetic studies suggest that complex 1 behaves as a single-ion magnet under 500 Oe dc-applied field with a high effective energy of 30.9 K.
Syntheses, Crystal Structures and Luminescent Properties of Dinuclear d10 Complexes Based on a Ligand Formed in Situ by 8-Hydroxyquinoline
Xiang GAO, Wei XU, Chang-Li WU, Xi-Miao ZHU, Yong-Cong OU, Jian-Zhong WU
2018, 34(9): 1768-1774  doi: 10.11862/CJIC.2018.213
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摘要:
Three novel d10 complexes[M2(HL)3] NO3·H2O (M=Cd (1), Zn (2, 3), H2L=7, 7'-(ethane-1, 1-diyl)diquinolin-8-ol) have been synthesized under solvothermal conditions. Single crystal X-ray diffraction analysis reveals that the complexes have the same coordination positive charged unit, [M2(HL)3]+, but different lattice structures due to the different places of the guest molecules. Complexes 1 and 3 crystallize in hexagonal system (P63/m) and complex 2 crystallizes in trigonal system (R3). The metal ions are six-coordinated with three oxygen atoms and three nitrogen atoms of three HL- ligands, presenting a slightly distorted octahedron geometry. There are abundant weak interactions between HL- ligands and guest molecule (NO3- and H2O), which play a vital role in the form of the crystal packing. These complexes show good thermal stabilities and exhibit green fluorescence. Further, the fluorescence of ligand H2L extracted from the complex 1 has also been studied firstly and blue light emission of it was observed.