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Fabrication of Hybrid Materials Containing Keggin-Type Polyoxometalates Units and 2-Picolinic Acid: Synthesis, Structures and Properties
Yang-Zheng CAO, Hao XU, Wei PAN, Xiang-Hua ZENG, Jun-Yong ZHANG, Hai-Yang GUO, Jin-Sheng LIAO, Sui-Jun LIU, Jing-Li XIE
2020, 36(9): 1613-1619  doi: 10.11862/CJIC.2020.196
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摘要:
2-Picolinic acid (2-PA) has been integrated with Keggin-type[SiW12O40]4- and[PMo12O40]3- polyoxometalates units to achieve final products:H2[(CH3)4N]6[Cu(2-PA)2(SiW12O40)2] (1) and (H3O)[Cu6(2-PA)9(PMo12O40)(NO3)] (2). These two inorganic-organic hybrid compounds have been characterized by single-crystal X-ray diffraction, infrared spectroscopy and powder X-ray diffraction. Compound 1 crystalizes in monoclinic system with space group P21/c, and the asymmetric unit is composed of one Cu(Ⅱ) ion, two 2-PA ligands and two[SiW12O40]4- Keggin-type polyoxometalate anions. Compound 1 is a zero-dimensional structure. The cyclic voltammogram of 1-CPE(the bulk-modified carbon paste electrode) showed that the half-wave potentials (E1/2=(Ecp+Eap)/2) of Ⅰ-Ⅰ', Ⅱ-Ⅱ' and Ⅲ-Ⅲ' were -270, -516 and -708 mV, respectively, when the sweep speed was 100 mV·s-1. Compound 2 crystallizes in trigonal system with space group R3c, there are two crystallographically independent Cu ions with two kinds of coordination modes in 2 and it is a two-dimensional networks containing hexanuclear clusters.
Syntheses, Crystal Structures, and Luminescent Property of Two 1D Cadmium(Ⅱ) Coordination Polymers Assembled from an Ether-Bridged Tetracarboxylic Acid
Yu LI, Zhen-Yu ZHAO, Xun-Zhong ZOU, An-Sheng FENG, Wen-Da QIU
2020, 36(9): 1728-1734  doi: 10.11862/CJIC.2020.181
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摘要:
Two 1D cadmium(Ⅱ) coordination polymers, namely[Cd2(μ5-L)(phen)2]n (1) and {[Cd2(μ4-L)(2, 2'-bipy)2 (H2O)2]·2H2O}n (2), have been constructed hydrothermally using H4L (H4L=2, 3, 3', 4'-diphenyl ether tetracarboxylic acid), phen (phen=1, 10-phenanthroline), 2, 2'-bipy (2, 2'-bipy=2, 2'-bipyridine), and cadmium chloride. Single-crystal X-ray diffraction analyses reveal that two polymers crystallize in the monoclinic or triclinic systems, space groups P21/c or P1. Polymers 1 and 2 show 1D chains composed of Cd4 or Cd2 units. The luminescent properties for two compounds were also investigated.
Co(Ⅱ) Coordination Polymer Based on Bis(carboxyl) Dibenzylamine and Bis(imidazole) Biphenyl Ligands: Synthesis, Crystal Structure and Detection for Fe3+ Ions in Water
Tian-Yang XU, Ya-Li ZHAO, Jia-Ming LI, Zhong-Feng SHI
2020, 36(9): 1735-1743  doi: 10.11862/CJIC.2020.183
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摘要:
A new Co(Ⅱ)-based coordination polymer (CP), namely {[Co(H3bcba)(bdmi)]·H2O}n (1), where H3bcba is 4, 4'-biscarboxyl-N, N-dibenzylamine and bdmi is 4, 4'-bis(2-methyl-1H-imidazol-1-yl)-1, 1'-biphenyl, has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis, thermogravimetric and Hirshfeld surface analyses. X-ray diffraction crystallographic analyses show that the partly deprotonated H3bcba ligand coordinates two Co (Ⅱ) ions with two carboxylate groups bending bidentate chelate modes, while bdmi serves as a μ2-bridging ligand in 1, result in a 2D polymeric grid frameworks with a 4-connected (4, 4) topology. In the crystal, a 3D supramolecular architecture is further formed by O-H…O and N-H…O hydrogen bonds, C-H…O and C-H…N interactions, as well as C-H…π stacking in 1. Complex 1 showed intense luminescence in the solid state, and exhibited a high selectivity and sensitivity for Fe3+ ions through the fluorescence quenching effect in aqueous solution at room temperature.
Nitric Acid Assisted Synthesis of Water-Soluble Green Fluorescent Carbon Dots for pH Measurement and Fe3+ Ions Detection
Ya-Chao KANG, Yuan-Yuan HUANG, Hua-Zhen SUN, Wan-Li ZHENG, Xian-Li MA, Dong-Li JIANG
2020, 36(9): 1744-1752  doi: 10.11862/CJIC.2020.194
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摘要:
A green fluorescent carbon dots (CDs) was synthesized from citric acid, formamide and concentrated nitric acid. The phase compositions, morphologies and fluorescence properties were characterized. The applications of the as-prepared CDs in ion detection and fluorescence imaging were studied as well. The results show that the as-synthesized CDs presented a good water-solubility and emitted bright green fluorescence with an excitation-independent photoluminescence (PL) behavior when the excitation wavelength ranged from 360 to 460 nm. The quantum yield was as high as 44.2%. Meanwhile, the green fluorescent CDs was pH sensitive and the normalized fluorescence intensity was linearly proportional to the pH values of solutions in a range of 4.5~8.5. Furthermore, the CDs also exhibited excellent selective response to Fe3+ with a good linear relationship between the fluorescence quenching efficiency (I0/I) and the Fe3+ concentration in a range of 0~1 000 μmol·L-1, and the detection limit was calculated to be 9.8 μmol·L-1.
Effect of Decorating Au with Different Sizes on Visible Light Photocatalytic Performance of Bi6Fe1.9Co0.1Ti3O18 Nanosheets
Wen GE, Kong LIU
2020, 36(9): 1753-1762  doi: 10.11862/CJIC.2020.191
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摘要:
In this work, we synthesized visible-light-driven Bi6Fe1.9Co0.1Ti3O18/Au (BFCTO/Au) nanocomposite photo-catalysts by a facile assembly method. The photocatalytic activity of BFCTO was enhanced by introducing Au nanoparticles with different sizes (~23 nm, ~36 nm, ~55 nm and~80 nm) into the BFCTO nanoplates. In particular, the BFCTO/Au-1 sample that was loaded with~23 nm Au nanoparticles exhibited the strongest photocatalytic activity under visible light irradiation.
Synthesis, Spectroscopic and Electrochemical Properties of Ruthenium(Ⅱ) Polypyridyl Complexes with Dimethyl-bibenzimidazolate Ligands
Man-Li CAO, Mei-Jie SHANG, Wen-Ting LIU, Wei YIN, Su-Yang YAO, Bao-Hui YE
2020, 36(9): 1763-1773  doi: 10.11862/CJIC.2020.204
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摘要:
A family of ruthenium(Ⅱ) polypyridyl complexes, namely[Ru(bpy)2(DMBbimHx)]y+ (bpy=2, 2'-bipyridine, DMBbimH2=7, 7'-dimethyl-2, 2'-bibenzimidazole, 1-A:x=2, y=2; 1-B:x=1, y=1; 1-C:x=0, y=0), were synthesized and determined by 1H NMR, UV-Vis absorption and electrochemical measurements. With the deprotonation of N-H in DMBbimHx ligands, the spectroscopic and electrochemical properties of complexes showed evident differences. Interestingly, the electrochemical properties of mono-deprotonated 1-B behaved very differently in dichloromethane and acetonitrile, which is due to different polarities of the solvents. In dichloromethane, mononuclear complex 1-B underwent a two-step oxidation. This is because[Ru(bpy)2(DMBbimH)]+ cations are bonded by hydrogen bonds to form dimers in weakly polar solvent, and proton-coupled electron transfer (PCET) exists between the[Ru(bpy)2 (DMBbimH)]+ cations. Single crystals of[Ru(bpy)2(DMBbimH)]PF6·2CH2Cl2 (2) were obtained from the solution of complex 1-B in dichloromethane. Crystal structure analysis shows that[Ru(bpy)2(DMBbimH)]+ cations are bonded by hydrogen bonds to form dimers, which is consistent with the result of the electrochemical measurements. However, hydrogen-bonded dimers couldn't exist stably in the more polar acetonitrile, therefore only one peak existing in the CV curve.
Synthesis, Structure and Hydrogen-Bonding Interaction of Three Metal-Orotic Acid Complexes
Pei-Pei CUI, Yue ZHAO, Peng WANG, Rui JIN, De-Jie JIAO, Xiu-Ling ZHANG, Wen-Ning YAN
2020, 36(9): 1774-1782  doi: 10.11862/CJIC.2020.205
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Orotic acid as a pyrimidine derivative was less studied in the synthesis of metal-organic complexes. In this article, reactions of orotic acid as ligand with transition metal salts under solvothermal conditions gave rise to three new complexes, namely {[Cu(HOr)2]·2NH2(CH3)2}n (R-1), [Co2(HOr)2(bipy)(H2O)6]·2H2O (R-2) and {[Ni2(HOr)2 (1, 3-dpp)2(H2O)2] [Ni(HOr)(1, 3-dpp)(H2O)]2·(1, 3-dpp)·2H2O}n (R-3) (H3Or=orotic acid, bipy=4, 4'-bipyridine, 1, 3-dpp=1, 3-di(4-pyridyl)propane). All the complexes have been structurally characterized by single-crystal X-ray diffraction analyses and characterized by elemental analysis, infrared spectra (IR) and thermogravimetric analysis (TGA). X-ray crystallography analysis reveals that R-1 is mononuclear complex with 2D sheet structure, R-2 is a simple monomolecular complex, and R-3 is a complicated sandwich structure containing layers and chains. All the complexes are linked to form 3D framework through intermolecular hydrogen bonding interaction.
Synthesis, Structure, DNA interaction and Cytotoxicity of Pyridine-Based Mononuclear Cobalt(Ⅱ) Complex
Chun-Yan GAO, Pei-Pei QIAO, Huang-Ze YANG, Peng-Fei ZHANG, Yun-Bo LEI, Yong-Po ZHANG, Min WANG, Ai-Qin YUE, Jin-Zhong ZHAO, Wei-Jun DU
2020, 36(9): 1783-1790  doi: 10.11862/CJIC.2020.208
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A new mononuclear complex[Co(L)Cl2] (L=4-methyl-N, N-bis(pyridin-2-ylmethyl) aniline) was synthesized and characterized by infrared spectroscopy, elemental analysis and X-ray single crystal diffraction. The results show that the Co(Ⅱ) center of the complex is a distorted trigonal-bipyramidal configuration with N3Cl2 donor sets. The interaction between the complex and DNA was studied by the electron absorption, emission spectroscopy and gel electrophoresis. The results reveal that the complex bind to CT-DNA by partial intercalation binding mode, and in the presence of hydrogen peroxide as a inducer, the DNA cleavage abilities of the complex are significantly improved. The Oxidative mechanism has been demonstrated via the pathway involving both hydroxyl radicals (·OH) and singlet oxygen (1O2) as ROS, and the binding site between the complex and DNA may be in the large groove. In addition, in vitro cytotoxicity of the drug has been tested by MTT against HeLa, BGC-823 and NCI-H460 cell lines.
Preparation of Boron and Fluorine Doped ZSM-5 Zeolites for Methanol to Propylene Reaction
Rui FENG, Xiao-Yan HU, Xin-Long YAN, Jian-Jun WU
2020, 36(9): 1791-1803  doi: 10.11862/CJIC.2020.209
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A series of boron and/or fluorine containing ZSM-5 zeolites were synthesized and used for the methanol to propylene (MTP) reaction. The as-synthesized ZSM-5 were characterized by X-ray diffraction, N2 adsorption-desorption, 29Si solid nuclear magnetic resonance, Fourier transform infrared spectroscopy, scanning electron micro-scope, and ammonia temperature-programmed desorption methods. The ZSM-5 molecular sieve with higher crystal-linity can be synthesized under the conditions of boron and fluorine doping. The heteroatom doping improves the SiO2/Al2O3 ratio (nSiO2/nAl2O3) of the molecular sieve. Boron and fluorine doped ZSM-5 possessed reduced Lewis acid sites but increased Brønsted acid sites. Besides, the particle size of ZSM-5 decreased with both boron and fluorine doping. In the MTP reaction, the enhanced catalyst lifetime could be attributed to the low content of Lewis acid sites and less strong Brønsted acid sites on the ZSM-5 catalysts. NH4BF4 modified ZSM-5 catalyst (Z5-BF2) with reduced Lewis acid sites and appropriate Brønsted acid sites exhibited relatively high propylene selectivity and long catalyst lifetime.
论文
K3ZrF7:Mn4+红色荧光粉的溶剂热合成及发光性质
赵春梅, 宁德鹏, 李雪艳, 冀银豪, 温婷
2020, 36(9): 1620-1624  doi: 10.11862/CJIC.2020.184
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用溶剂热法制备了K3ZrF7,并利用离子交换法对其进行Mn4+掺杂,获得了发光强度较高的红色荧光粉。分别用X射线衍射仪(XRD)和扫描电子显微镜(SEM)对材料的结构和形貌进行了表征。考察了掺杂浓度(物质的量分数)对材料发光强度的影响。通过对比2种锰掺杂材料的发光行为,发现在掺杂浓度相同的条件下,K3ZrF7:Mn4+的发光强度是K2ZrF6:Mn4+的10倍多。通过对二者晶体结构和掺杂离子配位环境进行分析,从晶体场理论的角度解释了发光强度差异机制。
一种五元羧酸与Eu(Ⅲ)、Tb(Ⅲ)配合物的结构及光致发光性质
王磊, 何盼盼, 王宏胜
2020, 36(9): 1625-1630  doi: 10.11862/CJIC.2020.182
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摘要:
水热条件下利用一种五元有机羧酸分别与稀土铕和铽的高氯酸盐反应合成了二维配位聚合物{[Eu4(HL)2(ox)2(H2O)10]·3H2O}n1)和{[Tb2(HL)(ox)(H2O)5]·2H2O}n2)(H5L=4-(4-羧基苯基)吡啶-2,3,5,6-四羧酸;ox=草酸根离子)。X射线单晶衍射结构分析表明这2个配合物为同构化合物,属单斜晶系,P21/c空间群。草酸根离子可能是由于部分五元羧酸在水热反应过程中发生分解而产生。稀土离子与五元酸及草酸根配体配位,形成了二维平面结构。配合物12分别发射铕或铽离子的红色或绿色特征荧光,其绝对量子产率分别为45%和38%。铕配合物中5D0激发态的寿命为1.83 ms,铽配合物中5D4激发态的寿命为1.07 ms。
双吡啶酰腙Schiff碱HgⅡ/Cd(Ⅱ)配合物的合成及其对甲醇蒸气的吸附
刘红娟, 魏小康, 易瑞, 黄超, 朱必学
2020, 36(9): 1631-1638  doi: 10.11862/CJIC.2020.203
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合成了双吡啶酰腙Schiff碱配体(L),并采用核磁共振氢谱、质谱、红外光谱和元素分析等手段对其结构进行了表征。进一步采用溶剂挥发法合成了2个配合物{[Cd(L2Cl2]·2DMF·6H2O}n1)和[Hg(L)Cl2]n2)。通过X射线单晶衍射技术测定了配体及2个配合物的单晶结构,并对配合物的热稳定性及其在常温下对甲醇蒸气的吸附进行了考察。实验结果表明,2个配合物均为1D配位聚合物,配合物1对甲醇蒸气有较好的吸附能力。
MOFs自牺牲模板法制备ZnO及其对NO2的气敏性能
陈沭璇, 贾丽华, 郭祥峰, 赵振龙, 杨瑞, 王欣
2020, 36(9): 1639-1648  doi: 10.11862/CJIC.2020.187
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以硝酸锌和2,5-二羟基对苯二甲酸为原料,采用溶剂热法制备了Zn-MOF-74,并利用MOFs自牺牲模板法制备了ZnO纳米材料。利用热重-差示扫描量热法(TG-DSC)、X射线衍射(XRD)、红外光谱测试(FT-IR)、X射线光电子能谱测试(XPS)、氮气吸附-脱附、扫描电镜(SEM)和高倍透射电镜(HRTEM)等方法对合成的样品进行了结构表征。研究了煅烧温度对产物结构、形貌和组成的影响,以及材料的气敏传感性能。结果表明,450℃煅烧Zn-MOF-74制备的六方柱状介孔氧化锌(ZnO450)是由直径约为20 nm的粒子组成的纳米片堆叠形成的,表面残留部分有机官能团,且吸附氧含量明显高于350和550℃处理的样品。基于ZnO 450的气敏传感器选择性响应NO2气体,对100 mL·m-3的NO2气体响应值达到了77.40,是所测试的其他气体响应值的6~105倍,检出限为0.1 mL·m-3;并且在有SO2等气体共存时,对NO2的响应值基本不变,抗干扰能力强。该传感器对NO2优异的响应能力是由于材料表面吸附氧含量高、比表面积及孔径较大,这些有利于NO2的吸附、表面反应和扩散。
RuO2修饰纳米多孔Ni-Mo复合电极及其电催化析氢性能
周琦, 黎新宝, 李志洋
2020, 36(9): 1649-1658  doi: 10.11862/CJIC.2020.186
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采用脱合金化结合胶体聚沉的方法制备了纳米多孔Ni/RuO2、Ni-Mo/RuO2复合电极材料。通过X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电镜(SEM)、透射电镜(TEM)对电极材料的物相、元素组态、形貌结构、孔径大小和结晶度进行表征,并通过线性扫描伏安、交流阻抗以及循环伏安等方法测试多孔电极的电催化析氢性能。分析结果显示:RuO2由于聚沉作用包覆在Ni基合金的骨架表面。Mo的加入使Ni-Mo合金非晶化的同时,促使其骨架细化,形成双连续的纳米多孔结构。Mo与RuO2的加入以及Mo含量的增加均提高了电催化析氢性能。纳米多孔Ni2.5Mo2.5/RuO2复合电极在50 mA·cm-2的电流密度下析氢过电位为182 mV。
高光效高热稳定性蓝色荧光粉Ca2-ySrySiO4:Ce3+, Li+的组成筛选和发光机理
征雪, 陈悦, 贾英华, 陈轩锋, 穆哲, 王小芳, 马驰, 周文理, 廉世勋
2020, 36(9): 1659-1668  doi: 10.11862/CJIC.2020.185
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采用高温固相法合成了一系列Ca2-x-ySry-xSiO4xCe3+xLi+蓝色固溶体荧光粉。XRD结果表明,所合成的固溶体荧光粉均为单一物相。随着Sr2+成分的增加,Ca2-ySrySiO4物相从单斜晶系β-Ca2SiO4向正交晶系α'-Ca2SiO4转变,发射光谱逐渐红移。组成为Ca1.75Sr0.25SiO4时,荧光粉的发射波长最长(454 nm),Stokes位移最大。基质为Ca1.1Sr0.9SiO4的晶体结构可诱导掺杂离子Ce3+取代SrO10格位、Li+取代CaO8格位。优化的荧光粉Ca1.05Sr0.85SiO4:0.05Ce3+,0.05Li+(CS0.85SO:CeLi)在375 nm紫外光激发下,发射445 nm的蓝光,内量子效率(IQE)达到91.18%,200℃时发射强度保持室温发光强度的98.70%。根据晶体结构、晶体场分裂和掺杂离子质心位移等理论,讨论了CS0.85SO:CeLi综合发光效应最佳的内在原因。
蒎烯类苯酚基吡啶氟硼发光材料的合成与性质
吕光宇, 王庭玮, 汪文源, 张蕤, 刘建
2020, 36(9): 1669-1674  doi: 10.11862/CJIC.2020.189
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将天然刚性结构单元蒎烯引入到苯酚基吡啶氟硼配合物体系中,制备了一系列具有蓝光发射性质的手性氟硼配合物。研究结果表明,蒎烯基团的引入可以提高配合物的荧光量子效率。此外,辅助取代基的变化也能进一步调控配合物的发光性质。基于蒎烯基团的手性,我们还研究了这类氟硼发光配合物对映体的圆二色谱。
基于CoP纳米笼的高效无酶葡萄糖电化学传感器
吕雪义, 刘俊果, 朱艳艳
2020, 36(9): 1675-1682  doi: 10.11862/CJIC.2020.193
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采用水热法和煅烧结合的方法制备过渡金属磷化钴(CoP)纳米笼,并利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、扫描透射电子显微镜(STEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)表征CoP的形貌、结构和元素组成。研究发现,所合成的CoP具有中空纳米笼的结构,该结构有利于提供更多可接触的催化活性位点,促进电子或离子的传输,加快催化反应过程。采用循环伏安法(CV)和计时电流法研究表明CoP纳米笼对葡萄糖具有优异的电催化氧化活性。基于CoP纳米笼修饰的玻碳电极构建的无酶葡萄糖电化学传感器显示出优异的性能。该传感器具有宽的线性范围(0.04~3 mmol·L-1和3~8 mmol·L-1)、低的检测限(3.8 μmol·L-1)和高的灵敏度,以及良好的选择性、重复性、重现性和稳定性。另外,该传感器能够实现人体血清中葡萄糖的快速检测。
金属-有机框架薄膜衍生的CoSe2/N共掺杂碳膜作DSSC对电极
欧金花, 胡波年, 何塞玉, 韩瑜
2020, 36(9): 1683-1689  doi: 10.11862/CJIC.2020.195
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摘要:
针对粉体MOF衍生材料存在制备工艺复杂、薄膜厚度难以控制等问题,我们通过液相外延分步生长法制备了一种金属有机框架薄膜(PIZA-1),然后以其作牺牲模板,在惰性氛围中制备了一种CoSe2和N共掺杂的碳膜(CoSe2/N-CF),并用作DSSC对电极,其具有制备简单、粘结力强、厚度可调等优势。系统表征了CoSe2/N-CF形貌特点、结构性质及电化学性能,并深入研究了不同厚度薄膜、CoSe2颗粒大小对DSSC的光伏性能的影响。结果表明,CoSe2/N-CF-15电极具有优异的催化活性,所组装的DSSC获得了8.68%的光电转化效率(PCE),高于相同条件下Pt电极组装电池的PCE(7.97%)。
酸洗处理对NaEuTiO4的结构、形貌以及电化学性能影响
朱德澄, 陈亦新, 季崇星, 朱贤雨, 李德成
2020, 36(9): 1690-1700  doi: 10.11862/CJIC.2020.201
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摘要:
采用溶胶-凝胶法合成了具有层状钙钛矿结构的NaEuTiO4(NETO),并利用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)、循环伏安(CV)和充放电循环测试等方法对用稀硝酸溶液酸洗处理后的NETO在结构、形貌和电化学性能方面的变化做了表征。研究结果表明,对于NETO而言,除了文献报道的Na+→Li+离子交换路径外,还存在着Na+→H+→Li+的离子交换路径,即NETO中的Na+可以跟稀酸中的H+发生离子交换。交换后得到的化合物HEuTiO4可以在电池中通过电化学反应的方式转化为LiEuTiO4。通过这样的路径得到的LETO具有相同优异的电化学性能,其中酸洗12 h的NETO具有最佳的电化学性能,经过300次循环后,其可逆容量约为213.2 mAh·g-1,而且表现出良好的倍率性能。
高容量有机正极材料杯[4]醌在离子液体中的储锂性能
孙会民, 周文君, 黄苇苇, 王丽秋
2020, 36(9): 1701-1706  doi: 10.11862/CJIC.2020.199
[摘要]  (34) [HTML全文] (34) [PDF 3188KB] (0)
摘要:
选用理论容量高达446 mAh·g-1的杯[4]醌(calix[4]quinone,C4Q)作为正极材料,研究其储锂性能。由于C4Q在常规有机电解液中的溶解问题会在一定的程度上限制其性能最大化,我们选用Li[TFSI]/[PY13][TFSI]([PY13][TFSI]:1-丙基-1-甲基吡咯烷鎓双三氟甲基磺酰亚胺)离子液体电解液与C4Q进行匹配组装锂离子电池,较大程度地提升了其循环稳定性和倍率性能。在0.1C的电流密度下,循环100圈后的放电比容量为280 mAh·g-1,1 000圈后的容量保持率高达72%。当电流密度增加至1C时,放电容量仍有154 mAh·g-1
氮掺杂HTi2NbO7纳米片的制备及其可见光催化性能
孟承启, 吕洪杰, 董鹏玉, 刘超, 陈小卫, 高欣, 程婷, 刘银, 李建军, 奚新国
2020, 36(9): 1707-1716  doi: 10.11862/CJIC.2020.170
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摘要:
首先,采用高温固相法制备层状前驱体CsTi2NbO7,再通过与硝酸进行质子交换形成层状HTi2NbO7;其次,在四丁基氢氧化铵(TBAOH)中剥离层状HTi2NbO7以获得HTi2NbO7纳米片;然后与尿素混合并高温焙烧;最后成功地得到了氮掺杂的HTi2NbO7纳米片光催化剂。使用粉末X射线衍射(XRD)、扫描电子显微镜(SEM)、高分辨透射电子显微镜(HRTEM)、X射线光电子能谱(XPS)、紫外-可见漫反射吸收光谱(UV-Vis DRS)以及N2吸附-脱附测试等方式对所制备样品的晶体结构、形貌、比表面积、孔分布和光吸收能力等进行详细的表征。研究表明,氮掺杂后减小了HTi2NbO7的禁带宽度,从而使光响应范围扩展到可见光区域;掺杂的氮原子主要位于Ti2NbO7-薄片的间隙位置,并与氢离子化学键合;与N掺杂的层状HTi2NbO7相比,N掺杂的HTi2NbO7纳米片具有更大的比表面积和更丰富的介孔结构,这是由于钛铌酸纳米片相对松散且不规则的排列。因此,在降解罗丹明B(RhB)溶液时,N掺杂的HTi2NbO7纳米片比N掺杂的层状HTi2NbO7具有更加优异的可见光催化活性。
铁电极化对层状Bi2MoO6光催化性能的增强
邹晨涛, 张志, 廖文静, 杨水金
2020, 36(9): 1717-1727  doi: 10.11862/CJIC.2020.190
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摘要:
通过对铁电光催化剂Bi2MoO6和聚甲基丙烯酸甲酯(PMMA)构建的有机-无机复合膜材料施加电场极化,来探究铁电极化对Bi2MoO6光催化剂活性提升的影响。未极化的Bi2MoO6在光照40 min时降解罗丹明B(RhB)的效率为57.6%,在光照150 min时对双酚A(BPA)的降解效率为33.4%。在15 V电压下极化1.5 h的Bi2MoO6材料在相同条件下降解罗丹明B和双酚A的效率分别达到98.1%和79.2%,光催化活性得到了较大的提升。光催化活性提升的原因归因于内部电场的增强。未极化的Bi2MoO6的内电场的铁电畴是无序、分布不均匀的,光生载流子非常容易发生体内复合。当外加电场极化Bi2MoO6时,Bi2MoO6的铁电畴趋于有序,极化方向趋于同一方向,表面一侧(C+区)产生正电荷,在另一侧(C-区)产生负电荷,从C-区指向C+区的极化电场推动光生电子和空穴分别迁移到C+和C-区域。这一过程促使光生电荷载流子快速从体内迁移至表面,提高和延长了光生载流子的分离效率和寿命,导致光催化活性的提升。
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论文
蝴蝶形单分子配合物的合成、晶体结构及其对水溶液中有害离子的检测
汤泉, 单贵谦, 王新悦, 王舒桐, 王举棋, 陈斌, 梁丽丽, 陈明功
2020, 36(2): 201-209  doi: 10.11862/CJIC.2020.039
[摘要]  (717) [HTML全文] (717) [PDF 5276KB] (717)
摘要:
用苯并咪唑基配体5,5'-二(2-苯并咪唑基)-2,2'-联吡啶(H2L)与镍、锌离子溶剂热合成了配合物[Ni(HL)(HCOO)(H2O)](1)和[Zn(H2L)(H2O)2](NO322)。X射线单晶测试表明镍与锌配合物的晶体结构是只含一个配体和一个金属离子的蝴蝶形单分子。配合物分子之间存在大量分子间氢键,配合物1通过分子间氢键连接成了二维层状结构,配合物2通过分子间氢键连接成了三维超分子结构。配合物12在水溶液中很稳定,且能够微溶于水。荧光测试表明配合物2的固体及在水溶液中都具有很强的荧光性质,且能够在水溶液中高选择性、高灵敏度检测有害重金属离子Hg2+及氧化性阴离子Cr2O72-
碳纤维表面羰基铁的原位生长及吸波性能
刘渊, 贾瑛, 李茸
2020, 36(2): 210-216  doi: 10.11862/CJIC.2020.041
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摘要:
以Fe(CO)5为前驱体,通过金属有机化学气相沉积(MOCVD),在碳纤维(CF)表面构筑厚度为纳米级的羰基铁(CI)壳层,通过改变沉积温度,调控核壳粉体的形貌结构和吸波性能。用X射线衍射仪、扫描电子显微镜和矢量网络分析仪对粉末的结构及电磁性能进行表征并对其吸波性能进行研究。结果表明:随着沉积温度升高(210~240℃),沉积到CF表面的羰基铁颗粒互相“吞并-融合”,此时CF-CI形成了完整的薄膜包覆型核壳结构;沉积温度太高时(270℃)会造成CF表面羰基铁壳层形貌的恶化。通过调节沉积温度,在纳米尺度上可以有效调控CI壳层的形貌,从而调节CF-CI核壳粒子的电磁性能。以核壳形貌及吸波性能为考察指标,最终确定最佳的沉积温度为240℃。以沉积温度为240℃时所获样品的电磁参数,模拟计算出涂层厚度为0.9 mm时,小于-10 dB的吸波带宽最大为4.6 GHz(13.4~18 GHz);涂层厚度为2.0 mm时,反射率达到最小值为-21.5 dB;厚度为0.9~3.9 mm时,在2~18 GHz均能实现吸波强度低于-10 dB。
Pt2+/Pt0掺杂g-C3N4光催化降解环丙沙星和偶氮染料
马小帅, 陈范云, 余长林, 杨凯, 黄微雅, 李韶雨
2020, 36(2): 217-225  doi: 10.11862/CJIC.2020.040
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摘要:
以三聚氰胺和氯铂酸(H2PtCl6·6H2O)为原材料,采用简单一步煅烧法制备了不同含量的Pt2+/Pt0掺杂石墨相氮化碳(Pt2+/Pt0-CN)。运用扫描电镜、透射电子显微镜、X射线光电子能谱、X射线粉末衍射、N2物理吸附-脱附、紫外-可见漫反射光谱和光电流测试等技术对制备的样品的形貌、化学组成、晶体结构、比表面积和光电性能等物理化学性质进行了表征。由XPS可知Pt粒子以二价Pt和零价Pt掺杂在催化剂的表面和内部,其中Pt0与Pt2+的比约为1:7.26。与g-C3N4相比,Pt2+/Pt0-CN表现出高效的光催化降解活性。当Pt2+/Pt0理论负载质量分数为0.02%时,对环丙沙星、罗丹明B、酸性橙Ⅱ、甲基橙和亚甲基蓝的降解效率分别提升了43%、64%、39%、42%和52%。Pt2+/Pt0掺杂使催化剂的比表面积大幅度增加,同时增强光催化剂对光的吸收能力,并抑制光生电子(e-)和空穴(h+)的复合。
基于原位脱羧3-硝基邻苯二甲酸构筑的金属配合物的合成、晶体结构及物理性质
吴国志, 汪鹏飞, 李善青, 方霄龙
2020, 36(2): 226-232  doi: 10.11862/CJIC.2020.035
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摘要:
利用水热反应以3-硝基邻苯二甲酸(3-NPAH2)和菲咯啉(phen)或1,2,4-三氮唑(Htrz)分别与ZnSO4·7H2O和Pb(NO32反应,成功组装了2个配合物:[Zn(3-NBA)(trz)]n1)、[Pb(3-NBA)(phen)2]NO32)。在反应过程中3-硝基邻苯二甲酸发生了原位脱羧反应而产生3-硝基苯甲酸(3-HNBA),理论计算也证实了实验结果。利用红外光谱、粉末XRD、元素分析和热重分析等方法对2个配合物进行了表征。单晶结构解析结果显示:配合物1具有二维层状结构,层与层之间存在N-O…π弱相互作用。配合物2具有零维单核结构,这些单核单元通过π…π弱相互作用进一步形成了三维超分子结构。此外,还研究了2个配合物室温条件下的固体荧光性质。
配体尺度对配合物结构及光催化降解活性的调节:从零维到一维的Cu(Ⅱ)配合物
王其宝, 李响, 王海英, 卢文欣, 王鹏
2020, 36(2): 233-240  doi: 10.11862/CJIC.2020.043
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摘要:
合成了桥联吡啶类配体2,6-二(3'-吡啶乙炔基)-4-甲基苯胺(L1)和未见文献报道的尺度更短的桥联吡啶配体2,6-二(3'-吡啶基)-4-甲基苯胺(L2),在常温下分别将其与一水合醋酸铜(Cu(OAc)2·H2O,OAc-=CH3CO2-)进行配位反应获得零维的配位大环分子[Cu2(L1)(OAc)4]21)和一维的配位聚合物{[Cu2(L2)(OAc)4]·2CH2Cl2·CH3CN}n2)。对获得的2个配合物进行了X射线单晶衍射、傅里叶红外光谱、元素分析等方面的结构表征。对比其结构可以发现,配合物12中均存在{Cu2(OAc)4}的二核铜簇,不同的是2个配合物中配体的配位取向不同:配位大环化合物1中的配体L1以U型构型与二核铜簇形成了“2+2”的平面配位大环结构,而化合物2中的配体L2则以Z型构型连接相邻的二核铜簇形成一维链状结构。2个化合物的结构差异是由于配体的尺度导致的,更短的尺度使得配位氮原子取向发生改变而产生不同的配位构型,这显示了结构调控中配体尺度的影响作用。通过测定配体与配合物在固态下的荧光发射性质,证实了铜的引入会猝灭配体自身的荧光发射;同时,采用亚甲基蓝(MB)为底物的光催化降解实验证明,大环配位分子的光催化降解活性明显优于一维配位聚合物,两者的催化活性均远远强于醋酸铜本身的催化活性。
CuCo/BNNSs纳米催化剂对固态储氢材料氨硼烷水解的催化性能
翟佳欣, 李国华, 甘思平, 张雪明, 朱萌萌, 张晓蕊, 胡恩言
2020, 36(2): 241-252  doi: 10.11862/CJIC.2020.018
[摘要]  (781) [HTML全文] (781) [PDF 10151KB] (781)
摘要:
采用共还原法将CuCo双金属负载到通过聚乙烯吡咯烷酮(PVP)辅助离子插层法制备的少层氮化硼纳米片(BNNSs)上,获得了平均粒径为2.7 nm且高度分散的铜钴/氮化硼纳米片(CuCo/BNNSs)纳米催化剂。通过原子力显微镜(AFM)、X射线衍射(XRD)、傅里叶转换红外光谱(FTIR)、拉曼光谱(Raman)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)和高分辨率透射电镜(HRTEM)对载体及催化剂的结构及形貌进行表征,并研究了CuCo/BNNSs的催化性能。研究发现,由于Cu、Co、BNNSs和OH-之间高效的四重效应协同使得Cu0.5Co0.5/BNNSs纳米催化剂在室温、pH=14条件下对氨硼烷(AB,NH3BH3)水解释氢具有极高的催化活性。转化频率(TOF)值达到104.52 molH2·molmetal-1·min-1,且CuCo/BNNSs纳米催化剂具有良好的稳定性,6次循环利用后仍保持较高催化活性。
可见光高催化活性GO/Ag3PO4/Ni复合薄膜的制备和性能
赵娣, 刘洪燕, 李桂花, 刘宇阳, 崔子硕
2020, 36(2): 253-260  doi: 10.11862/CJIC.2020.012
[摘要]  (638) [HTML全文] (638) [PDF 3913KB] (638)
摘要:
以磷酸铵和氧化石墨烯悬浊液的混合液为电解液,采用电化学共沉积法制备了Ag3PO4基GO/Ag3PO4/Ni复合薄膜。运用扫描电子显微镜(SEM)、能量色散谱(EDS)、X射线衍射(XRD)、拉曼光谱(Raman)和紫外可见漫反射光谱(UV-Vis DRS)等对其形貌、物相和光谱特性进行分析。最佳工艺制备的GO/Ag3PO4/Ni复合薄膜呈现出GO包覆在直径为100 nm左右的Ag3PO4纳米球外的表面形貌。GO片与Ag3PO4纳米球之间存在强电荷相互作用。与单独的Ag3PO4纳米球相比,GO片的附着导致带隙缩小,可见光区的吸收率增强。可见光下考察了复合薄膜降解罗丹明B的光催化活性和稳定性,并利用荧光光谱和捕获剂法对薄膜的光催化机理进行了探索。结果表明,GO片的加入不仅显著提高了Ag3PO4的光催化活性,而且提高了Ag3PO4的结构稳定性。光催化降解罗丹明B 60 min时,GO/Ag3PO4/Ni复合薄膜的降解率是Ag3PO4/Ni薄膜的1.32倍。在保持薄膜光催化活性基本不变的前提下可循环使用7次。GO优异的电荷传导性能,以及Ag3PO4纳米球与GO片之间的正协同效应是提高复合薄膜光催化性能的主要原因。
离子热处理合成氮缺陷石墨相氮化碳及其光解水制氢性能
崔言娟, 杨传锋, 祝玉鑫, 宋艳华, 滕伟, 唐盛
2020, 36(2): 261-268  doi: 10.11862/CJIC.2020.019
[摘要]  (677) [HTML全文] (677) [PDF 6759KB] (677)
摘要:
以尿素和二氰二胺为原料热聚合得到石墨相氮化碳,分别采用直接二次煅烧和熔盐离子热后热处理在不同温度下对产物进行后热处理,得到氮缺陷氮化碳CN和CNS。利用X射线衍射(XRD)、紫外-可见漫反射光谱(UV-Vis DRS)、透射电镜(TEM)等手段对所制备样品进行表征和分析,探讨了不同热处理温度和加热方法对催化剂微观聚合结构的影响;同时以光解水制氢为测试方法,考察了催化剂的可见光催化性能。结果表明,熔盐离子热更有利于氮化碳的层间聚合,得到高结晶度材料;在面内七嗪聚合单元中引入氮缺陷,产生末端氰基,优化电荷密度分布,增强电荷流动性;克服粒子尺寸效应,扩展催化剂的光吸收范围;当后热处理温度为500℃时,制备的CNS-500表现出优异的光解水制氢活性,是同温度下直接热处理得到的催化剂的3.84倍。
高容量锂离子电池正极复合材料pillar[5]quinone/CMK-3的制备
熊文旭, 掌学谦, 黄苇苇
2020, 36(2): 269-275  doi: 10.11862/CJIC.2020.033
[摘要]  (595) [HTML全文] (595) [PDF 5205KB] (595)
摘要:
以有机醌类化合物柱[5]醌(pillar[5]quinone,P5Q)作为锂离子电池的正极材料,探索了其储锂性能。实验结果表明,P5Q首圈放电容量达到了431 mAh·g-1,显示出100%的活性位点利用率。然而,P5Q在电解液中的溶解会导致循环过程中容量的衰减。采用超声法将P5Q填入有序介孔碳CMK-3的孔道,制备了P5Q/CMK-3复合材料,以此减少P5Q与电解液的接触,从而减缓了P5Q的溶解速率,提高了电池的循环稳定性。P5Q/CMK-3复合材料100次充放电循环后容量为300 mAh·g-1,保持率高达71%,说明了该优化方法效果显著,提高了P5Q在锂离子电池中的实际应用价值。
Eu3+掺杂的LaBO3荧光粉制备及发光性能
侯晓飞, 赵婉男, 马晶, 孙继强, 李艳红
2020, 36(2): 276-282  doi: 10.11862/CJIC.2020.016
[摘要]  (622) [HTML全文] (622) [PDF 2842KB] (622)
摘要:
采用水热法合成前驱体,后经热处理方式制备不同晶相的LaBO3:Eu3+荧光粉。通过X射线衍射(XRD)、电子扫描电镜(SEM)、红外光谱和荧光光谱对样品的结构、形貌和发光性能进行了研究。并研究了硼酸用量、热处理温度及初始溶液pH等对晶相结构和发光性能的影响。XRD研究结果表明:合成样品具有单斜结构、正交结构及单斜和正交两相混合结构。适当的硼酸用量、较高的热处理温度及较高的初始溶液pH值易于获得正交结构的荧光粉。红外光谱显示:pH值和硼酸用量影响前驱体成分,热处理温度影响晶相的转变。SEM结果显示:LaBO3:Eu3+荧光粉的晶粒尺寸随着pH值的增加逐渐减小,与XRD计算结果相一致。荧光光谱结果表明:正交结构的LaBO3:Eu3+发光粉具有较高的紫外吸收和较为纯正的红色发射强度。
多巴胺用量对Fe3O4@PDA@PAMAM磁性纳米吸附材料的微观结构及吸附性能的影响
孙一鸣, 李冬云, 孙玉坤, 徐扬, 申亚强, 葛洪良
2020, 36(2): 283-288  doi: 10.11862/CJIC.2020.025
[摘要]  (561) [HTML全文] (561) [PDF 2856KB] (561)
摘要:
以自制的Fe3O4磁性纳米材料为核,多巴胺(DA)为表面修饰剂,成功地将2.0 G聚酰胺-胺(PAMAM)树状大分子接枝在Fe3O4磁核表面,制备出了一系列不同DA含量的Fe3O4@PDA@PAMAM磁性纳米吸附材料。采用X射线衍射仪(XRD)、红外光谱仪(IR)、振动样品磁强计(VSM)、透射电子显微镜(TEM)和电感耦合等离子体发射光谱仪(ICP-OES)等分析测试手段对材料组成、微观结构、磁性能和对重金属Cd(Ⅱ)离子的吸附性能进行了测试和表征。研究了修饰剂DA用量对Fe3O4@PDA@PAMAM磁性纳米吸附材料的相组成、微观结构、磁性能和吸附性能的影响。实验结果表明,Fe3O4@PDA@PAMAM磁性纳米吸附材料均呈典型的核-壳结构,材料晶型均呈现尖晶石结构,且壳层厚度随DA用量增加而增厚;材料的饱和磁化强度(Ms)均比Fe3O4的小,且随着DA用量的增加而降低,并且材料的矫顽力(Hc)和剩余磁化强度(Mr)均较低,其磁响应特性适合于做为可回收磁性纳米吸附材料。材料对Cd(Ⅱ)离子的平衡吸附容量随着DA用量的增加呈先增加后减小趋势。当Fe3O4和DA的质量比为8:4时,吸附剂对Cd(Ⅱ)离子的吸附容量达到最大值165.13 mg·g-1
高岭土原位无溶剂法合成小粒径ZSM-5分子筛
张培青, 刘思成, 郑淑琴
2020, 36(2): 289-294  doi: 10.11862/CJIC.2020.028
[摘要]  (665) [HTML全文] (665) [PDF 2954KB] (665)
摘要:
结合原位水热法和无溶剂法的优点,在不添加有机模板剂和溶剂的基础上,以高岭土为原料通过晶种诱导绿色高效地合成出ZSM-5分子筛。运用X射线衍射、N2吸附-脱附、扫描电镜、透射电镜和NH3程序升温脱附(TPD-NH3)等技术对ZSM-5分子筛进行表征。表征结果与原位水热法合成的ZSM-5分子筛相比,原位无溶剂法合成ZSM-5分子筛的结晶度较高、晶体粒径较小、酸强度略高、孔结构相似。
用于低浓度三聚氰胺选择性检测的铝/银纳米传感器的组装及其SERS性能
曹琳, 陈前, 姜飞, 秦利霞, 康诗钊, 高峰, 李向清
2020, 36(2): 295-301  doi: 10.11862/CJIC.2020.050
[摘要]  (656) [HTML全文] (656) [PDF 4456KB] (656)
摘要:
通过置换法在铝板上快速制备了一种即插即用型的Al/Ag纳米表面增强拉曼光谱(SERS)活性基底。结果表明该SERS基底较好地解决了银纳米颗粒在支撑物质上的吸附问题,能够快速实现对三聚氰胺的检测,而且具有操作简单、成本低、无损伤检测等优点,最低检测浓度能达到10-7 mol·L-1,满足国家食品安全要求的最低标准。另外,Al/Ag活性基底对三聚氰胺检测具有较高的拉曼测试重现性,连续测定15 h的过程中拉曼强度波动不大;且该Al/Ag活性基底能够在三乙醇胺、NN-二甲基甲酰胺和1,2-丙二胺等胺类物质中实现对三聚氰胺的选择性检测。
甲醇热还原法制备高分散Cu2O微米立方体及其光催化性能
陈小平, 魏源送, 范敏, 石金明, 桂双林, 陈泊宏, 黄顺楠
2020, 36(2): 302-308  doi: 10.11862/CJIC.2020.027
[摘要]  (647) [HTML全文] (647) [PDF 5918KB] (647)
摘要:
通过简单的甲醇热还原法制备高分散Cu2O微米立方体,制备过程中无需添加表面活性剂。利用X射线衍射(XRD)、场发射扫描电镜(FESEM)、高分辨透射电镜(HRTEM)、X射线光电子能谱(XPS)等分析测试手段对样品的物相及形貌进行表征;通过紫外可见漫反射(UV-Vis)及光致发光光谱(PL)对样品的光化学性能进行表征;样品的光催化性能通过可见光(λ>400 nm)催化降解罗丹明B染料(RhB)脱色活性进行测试表征。同时,对样品光催化性能与物理化学性能之间的内在联系进行了研究。结果表明:制备温度对样品的形态及光催化性能有着重要影响,当制备温度为140℃时,可制备得到高分散Cu2O微立方体并且其显示出最优的光催化活性;当制备温度进一步提高时,得到的样品为超细铜粉,样品的光催化性能迅速降低。
一维Ga2O3/SnO2纳米纤维的制备及其气敏性能
吴海燕, 干正强, 储向峰, 梁士明, 何利芳
2020, 36(2): 309-316  doi: 10.11862/CJIC.2020.021
[摘要]  (697) [HTML全文] (697) [PDF 5224KB] (697)
摘要:
通过静电纺丝法制备了一维Ga2O3/SnO2纳米纤维,采用X射线衍射(XRD)、扫描电镜(SEM)、紫外可见漫反射光谱(UV-Vis DRS)等方法对材料进行了表征,测试了不同Ga2O3质量分数(0、40%、50%、60%、70%、100%)的Ga2O3/SnO2纳米纤维(650℃,5 h)对应元件对三甲胺、丙酮、乙醛、乙酸、氨气、乙醇、甲醛7种气体的气敏性能。结果表明:在室温(25℃)时,60%(w/w)Ga2O3-40%(w/w)SnO2纳米纤维对三甲胺气体具有较高的灵敏度和较短的响应/恢复时间。对1 000 μL·L-1三甲胺的灵敏度达到51;检出限达到0.8 μL·L-1,其灵敏度为1.3。
混晶海胆状TiO2空心球多级结构的制备及其对亚甲基蓝的光催化降解
刘顺强, 解明江, 郭学锋, 季伟捷
2020, 36(2): 317-323  doi: 10.11862/CJIC.2020.037
[摘要]  (587) [HTML全文] (587) [PDF 4128KB] (587)
摘要:
用简单的无模板水热法可控合成了金红石相锥刺和锐钛矿相空心球的海胆状TiO2多级结构。研究了制备介质pH值和反应时间对形貌的影响。空心球上锥刺的密度可以通过改变反应条件加以调控。对海胆状TiO2多级结构可能的形成机理进行了研究。将不同锥刺密度的TiO2空心球应用于亚甲基蓝降解的光催化研究,结果表明低锥刺密度的TiO2空心球的光催化效果优于P25-TiO2,更优于锥刺多和无锥刺的光滑TiO2空心球。
CdS纳米晶@碳点复合物膜的电致化学发光
胡佳杰, 朱媛, 宋华菊, 王颖, 单云
2020, 36(2): 324-332  doi: 10.11862/CJIC.2020.034
[摘要]  (745) [HTML全文] (745) [PDF 5541KB] (745)
摘要:
采用热解柠檬酸法制备碳点(CDs),并将之与表面无包裹剂的CdS纳米晶(CdS NCs)超声复合制备CdS纳米晶@碳点(CdS NCs@CDs)复合物。研究了复合物膜阴极电致化学发光(ECL),探讨了CDs对CdS纳米晶膜ECL增强的机理。CDs分散性良好、尺寸在1.5~4 nm之间;与粒径约为4 nm的CdS纳米晶按体积比2:3复合后,在360 nm光激发下复合物具有最强的荧光发射且表现为CDs的荧光。同时,复合物膜产生归属于激发态CdS纳米晶的最强的ECL发射,且ECL发光峰起置电势正移至-1.05 V。复合物膜的ECL发射是pH依赖的,在pH值为6时,复合物膜具有最大的ECL强度,为CdS纳米晶膜ECL强度的19倍。这种ECL增强源于CDs能束缚大量电子产生局域电场从而促进近邻CdS纳米晶激发态的形成与弛豫。
Articles
Facile Solvothermal Synthesis of Porous Persimmon-like BiOBr Photocatalyst
Huang-Gen YANG, Yuan CHEN, Zhi-Wei WANG, Jia-Tian YANG, Li-Gang ZHU, Li-Qin QIN, Hong-Xing DAI
2020, 36(2): 333-344  doi: 10.11862/CJIC.2020.007
[摘要]  (734) [HTML全文] (734) [PDF 6054KB] (734)
摘要:
Porous nanosheet-aggregated persimmon-like bismuth oxybromide (BiOBr) were successfully prepared for the first time using polyvinyl pyrrolidone (PVP)-assisted solvothermal strategy with bismuth nitrate and cetyltrimethyl ammonium bromide (CTAB) as Bi and Br sources. Physicochemical properties of the hierarchical microstructure BiOBr materials were characterized by means of numerous analytical techniques, and their photocatalytic activities were evaluated for the removal of methylene blue (MB) under visible-light illumination. It is found that the solvothermal time and PVP addition had a significant influence on the particle morphology and crystallinity of the product. The porous sheet-aggregated persimmon-like BiOBr sample could be obtained after solvothermal treatment at 120℃ for 12 h in the presence of 0.7 g PVP. The porous persimmon-like BiOBr sample with a surface area of 4 m2·g-1 and a bandgap energy of 2.64 eV possessed good optical absorption property in visible-light regions and showed excellent visible-light-driven photocatalytic activity and stability for MB degradation. It is concluded that the high visible-light-driven catalytic performance of the porous sheet-aggregated persimmon-like BiOBr sample is associated with its high surface area, porous structure, and low bandgap energy as well as the unique particle morphology.
Syntheses, Crystal Structures and Magnetic Properties of Two Copper(Ⅱ) Coordination Compounds Based on 5-Bromoisophthalic Acid and 2, 2'-Bipyridine
Yu LI, Xun-Zhong ZOU, An-Sheng FENG, Zhen-Yu ZHAO
2020, 36(2): 345-351  doi: 10.11862/CJIC.2020.002
[摘要]  (594) [HTML全文] (594) [PDF 2145KB] (594)
摘要:
Zero-dimensional mononuclear copper(Ⅱ) coordination compound and 1D chain copper(Ⅱ) coordination polymer, namely [Cu(BIPA)(2, 2'-bipy)(H2O)2]·H2O (1) and[Cu3(μ3-BIPA)2(μ-OH)2(2, 2'-bipy)2]n (2), were constructed hydrothermally using H2BIPA (H2BIPA=5-bromoisophthalic acid), 2, 2'-bipy (2, 2'-bipy=2, 2'-bipyridine), and copper chloride at the nNaOH:nH2 BIPA (molar ratio) of 2:1 or 3:1, respectively. Single-crystal X-ray diffraction analyses reveal that both compounds crystallize in the monoclinic system, space groups P21/c or P21/n, respectively. Compound 1 discloses a discrete monomer structure, which is assembled to a 2D sheet through O-H…O hydrogen bonds. Compound 2 has a chain structure based on Cu3 unit. The chains are further extended into a 2D sheet by π-π stacking interactions. Structural differences between compounds 1 and 2 are attributed to the different molar ratio between NaOH and H2BIPA. Magnetic studies for compound 2 demonstrate an antiferromagnetic coupling between the adjacent Cu(Ⅱ) centers within Cu3 unit.
Syntheses and Spectroscopic Properties of Chiral Dinuclear Eu(Ⅲ) Complexes
Li-Li WANG, Qian-Ying YANG, Li-Zhi HAN, Xiao-Peng ZHANG, Xin-Han CHEN, Zai-Feng SHI
2020, 36(2): 352-360  doi: 10.11862/CJIC.2020.020
[摘要]  (613) [HTML全文] (613) [PDF 2936KB] (613)
摘要:
Circularly polarized luminescence materials based on emissive Eu(Ⅲ) complexes have attracted considerable attention in 3D-displays and bioresponsive imaging. In this work, we design and report the syntheses of a pair of chiral carboxylic-containing 2, 2'-bipyridine ligands ((+)-L and (-)-L). Through reaction with highly emissive β-diketone Eu(Ⅲ) complexes[Eu(TTA)3]·2H2O (TTA=2-thenoyltrifluoroacetone), a couple of chiral dinuclear Eu(Ⅲ) enantiomers, [Eu2((+)-L)2(TTA)2(C2H5OH)2] ((+)-1) and[Eu2((-)-L)2(TTA)2(C2H5OH)2] ((-)-1), were prepared, and the structure of (+)-1 was confirmed by single-crystal X-ray diffraction. The absorption, emission and chiroptical properties of (+)-1 and (-)-1 were investigated, and distinct CPL activities were clearly detected.
A Chiral Ag(Ⅰ) Coordination Polymer Based on an α, α-L-Diaryl Prolinol-Pyridine Derivative: Circular Dichroism, SHG Response and Luminescent Property
Lin CHENG, Jing-Hua YANG, Qing-Chao ZHAI, Qing-Song ZHANG
2020, 36(2): 361-367  doi: 10.11862/CJIC.2020.013
[摘要]  (684) [HTML全文] (684) [PDF 1921KB] (684)
摘要:
A chiral α, α-L-diaryl prolinol-pyridine derivative, (S)-bis(4-(pyridin-4-yl)phenyl)(pyrrolidin-2-yl)methanol (L), was synthesized and used to construct a chiral coordination polymer, {[Ag4(L)4](NO3)4·1.5CH3OH·1.25H2O}n (1), with Ag(Ⅰ). The polymer displayed a one-dimensional ladder-like chain structure, which was characterized by single crystal XRD, PXRD, IR spectra, TGA and luminescent spectra. CD spectra and SHG response of the compounds confirmed that the bulk sample was of structural chirality.
Syntheses, Structures and Properties of Ni(Ⅱ)/Cd(Ⅱ)/Zn(Ⅱ) Complexes with Flexible Homophthalic Acid and Diimidazolyl-Type Ligands
Feng-Yang JU, Yun-Ping LI, Guang-Zhen LIU
2020, 36(2): 368-376  doi: 10.11862/CJIC.2020.044
[摘要]  (594) [HTML全文] (594) [PDF 3129KB] (594)
摘要:
Based on flexible homophthalic acid (H2hmph) and diimidazolyl-type ligands, three novel coordination polymers with the formulas determined as {[Ni2(hmph)2(bib)2(H2O)2]·3H2O}n (1), [Cd(hmph)(bib)]n (2) and {[Zn(hmph)(bip)]·H2O}n (3) (bib=1, 4-bis(1-imidazolyl)benzene; bip=3, 5-bis(1-imidazolyl)pyridine) have been solvothermally synthesized. Complex 1 displays a 2D mono-layer structure featuring Ni-carboxylate chains cross-linked further by bib co-ligands. Complex 2 exhibits a 2D bilayer structure containing double-stranded Cd-carboxylate chains bridged by bib co-ligands, wherein there are carboxyl-bridged dinuclear kernels. Complex 3 is double-stranded chain featuring Zn-carboxylate binuclear units extended further by bip co-ligands. TGA experiments show that all three complexes have high thermal stabilities. And the magetic data indicate there is typical ferromagnetic exchange coupling in complex 1. Furthermore, the fluorescent properties of both complexes 2 and 3 show significant blue-shift compared with the free ligands.
Syntheses, Crystal Structures, Luminescent and Magnetic Properties of 2D Manganese(Ⅱ) and Zinc(Ⅱ) Coordination Polymers Based on an Ether-Bridged Tetracarboxylic Acid
Yu LI, Zhen-Yu ZHAO, Xun-Zhong ZOU, An-Sheng FENG, Jin-Zhong GU
2020, 36(2): 377-384  doi: 10.11862/CJIC.2020.042
[摘要]  (592) [HTML全文] (592) [PDF 2452KB] (592)
摘要:
Two 2D manganese(Ⅱ) and zinic(Ⅱ) coordination polymers, namely {[Mn2(μ6-L)(phen)2]·5H2O}n (1) and {[Zn2(μ7-L)(py)]·H2O}n (2), have been constructed hydrothermally using H4L (H4L=3, 3', 4, 5'-diphenyl ether tetra-carboxylic acid), phen (phen=1, 10-phenanthroline), py (py=pyridine), and manganese or zinc chlorides. Single-crystal X-ray diffraction analyses revealed that two complexes crystallize in the triclinic or monoclinic systems, space groups P1 or I2/a. Both complexes feature a 2D sheet structure based on Mn4 or Zn2 subunits. The luminescent and magnetic properties for two complexes were also investigated. The results of fluorescence and magnetic studies show that complex 2 can emit blue fluorescence at room temperature, and antiferromagnetic interactions exist between adjacent Mn(Ⅱ) ions in polymer 1.
Synthesis and Catalytic Performance for Oxidative Cyclization Reaction of Oil-Dispersible Core-Shell Fe3O4@MnO Nanocomposites
Qing-Xiang YANG, Li-Ling LEI, Qing-Qing WANG, Fang-Cao WANG, Cong WANG, Meng-Guo DONG, Yin-Ping LI, Zhi-Jun CHEN
2020, 36(2): 385-391  doi: 10.11862/CJIC.2020.032
[摘要]  (635) [HTML全文] (635) [PDF 2683KB] (635)
摘要:
A new type oil-soluble core-shell structure Fe3O4@MnO nanocomposites with diameter about 15 nm was prepared through two-phase seed mediate method with Mn-oleate precursors. The as-prepared nanocomposites with core-shell structure were monodispersed and uniform. The products exhibited high and recyclable catalytic activity for the oxidative cyclization reaction of 2-hydroxyacetophenone and 1, 2-diaminobenzene. Compared with other reported catalysts used in this kind of cyclization reaction, the as-prepared Fe3O4@MnO nanocomposites are green, cheap and more suitable for large scale industrial applications.