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合成气直接制C2含氧化合物Rh基催化剂中金属-助剂(载体)界面的构建
陈维苗, 宋宪根, 丁云杰
2020, 36(11): 2005-2013  doi: 10.11862/CJIC.2020.234
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摘要:
由煤、天然气或生物质经合成气直接制取乙醇等C2含氧化合物可以替代传统的石油和粮食路线,其意义重大。负载型助剂促进的金属Rh是实现该过程最有效的催化剂,其中Rh-助剂(载体)接触界面是发生目标反应的活性位,其面积的大小直接决定了该催化剂的性能,因此,近些年来人们尝试多种物理或化学方法来改进Rh基催化剂的制备过程,以最大化金属-助剂界面。我们简要介绍和评述了涂覆法、形成复合氧化物或合金、强静电吸附法、控制表面反应法和原子层沉积法等的原理、过程以及优缺点。通过结合上述合成方法,可制备出均一分布的、界面活性位结构确定的催化剂。
Articles
Syntheses, Structures and Optical Band Gaps of Three Zn(Ⅱ)/Co(Ⅱ) Coordination Polymers
Qi-Hui DING, Yao-Yao LIU, Lu-Chao LI, Yong-Qing HUANG, Yue ZHAO
2020, 36(11): 2014-2022  doi: 10.11862/CJIC.2020.245
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Three new coordination polymers with formulas[Zn(L1)(L2)0.5Cl]n (1), [Co(L1)(L2)0.5Cl]n (2) and {[Zn(L1) (L3)]ClO4·1.7H2O}n (3) have been prepared via the combination of zwitterionic carboxylic ligand with Zn(Ⅱ) and Co (Ⅱ) salts under the participation of two bridging imidazole-based isomers, where L1, L2 and L3 are 4-carboxy-1-(4-carboxybenzyl)-pyridinium, 1, 4-bis(imidazole-1-ylmethyl)benzene and 1, 3-bis(imidazole-1-ylmethyl)benzene, respectively. Complexes 1 and 2 are isostructural and feature an undulated 2D herringbone layer structure with (6, 3) topology, exhibiting a rare 2D→3D inclined polycatenated structure. Compared with 1 and 2, complex 3 displays 1D catenated chain structure, which are further assembled into 2D layer via abundant π-π interactions. It is noteworthy that 1~3 can all be considered as consisting of 1D[M(L1)]n chains and bridging bis-imidazole-based ligands. For 1 and 2, the 1D[M(L1)]n chains take helical form and bridging L2 ligands adopting Z-shape. In contrast, the 1D[M(L1)]n chains in 3 exhibit zigzag form and bridging L3 ligands having C-configuration. The results reveal that different N-donor ancillary ligands and anions have a subtle effect on the final structures. The study of optical band gaps showed that the band gaps of 1~3 were 2.96, 1.72 and 3.16 eV, respectively, which indicates that 1~3 have properties of potential wide-band-gap semiconductors.CCDC: 1973985, 1; 1973986, 2; 1973987, 3.
Syntheses, Crystal Structures, Luminescence and Photocatalytic Activity of Cu(Ⅱ), Zn(Ⅱ) and Mn(Ⅱ) Coordination Polymers Based on Ether-Bridged Carboxylic Acids
Yu LI, Fu-Ran ZENG, Feng ZHOU, Shan-Ji LI
2020, 36(11): 2124-2134  doi: 10.11862/CJIC.2020.243
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Two 2D coordination polymers, namely {[Cu3(μ4-dpna)2(2,2'-bipy)2]·4H2O}n (1) and {[Zn3(μ4-dpna)2(2,2'-bipy)2(H2O)2]·6H2O}n (2) as well as two 1D coordination polymers, namely {[M2(μ4-deta)(phen)2(H2O)]·3H2O}n (M=Mn (3), Zn (4)) have been constructed hydrothermally using H3dpna (H3dpna=5-(3',4'-dicarboxylphenoxy)nicotic acid) or H4deta (H4deta=2,3,2',3'-diphenyl ether tetracarboxylic acid) as a principal building block, 2,2'-bipy (2,2'-bipy=2,2'-bipyridine) or phen (phen=1,10-phenanthroline) as a auxiliary ligand, and copper, zinc or manganese chlorides. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses (TGA), and single-crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that compounds 1 and 2 crystallize in the monoclinic system, space groups P21/c or C2/c. Compounds 1 and 2 disclose two different 2D sheet structures. The structural difference of compounds 1 and 2 is driven by the Cu(Ⅱ)/Zn(Ⅱ) nodes. Compounds 3 and 4 are isostructural and crystallize in the monoclinic system, space group P21/n. Both compounds show a 1D chain structure. The luminescent and photocatalytic properties of the compounds were investigated, showing that compounds 2 and 4 can effectively degrade methylene blue as a model organic dye pollutant.CCDC: 2004109, 1; 2004110, 2; 2004481, 3; 2004482, 4.
Crystal Structure, Electrochemistry and Spectral Properties of Two 2-Substituted-4, 6-di(2-pyridyl)-1, 3, 5-triazine Bridged Dinuclear Ruthenium Complexes
Man-Li CAO, Yu-Qi HE, Wen-Ting LIU, Wei YIN, Su-Yang YAO
2020, 36(11): 2135-2144  doi: 10.11862/CJIC.2020.242
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Two new dinuclear Ru(Ⅱ) complexes of 2-substituted 4, 6-di(2-pyridyl)-1, 3, 5-triazine, [Ru2(OBPT)(bpy)4] (PF6)3·3H2O·0.5CH3CH2OH (1) and[Ru2(HABPT)(bpy)4](PF6)4·0.5H2O (2), where bpy=2, 2'-bipyridine, HOBPT=4, 6-bi(2-pyridyl)-1, 3, 5-triazin-2-ol, HABPT=2-amino-4, 6-bi(2-pyridyl)-1, 3, 5-triazine, were synthesized and characterized. The X-ray crystal structures of the complexes have been determined, which show that 1 crystallizes in the monoclinic C2/c space group and in the rac-(ΔΔ) stereoisomeric form, while 2 in the orthorhombic Pca21 space group and in the meso-(ΔΛ) stereoisomeric form. Single-crystal structures indicate that the bridging ligand HOBPT in 1 is deprotonated while the ligand HABPT in 2 is not. The electrochemical and spectral properties of two complexes are significantly different. All data indicate the presence of electronic coupling between the individual metal centers bridged by the ligands in the complexes.CCDC: 2026074, 1; 2026075, 2.
Effect of Calcination Temperature on Three-Way Catalytic Performance of Pd/Ce0.65Zr0.35O2 Prepared by Soft-Hard Template Method
Li-Hua HUANG, Yao-Qiang CHEN
2020, 36(11): 2145-2156  doi: 10.11862/CJIC.2020.227
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High thermal stability Ce0.65Zr0.35O2(CeZr) was prepared by soft-hard template method. The influence of calcination temperature on properties of Ce0.65Zr0.35O2 and its corresponding Pd based three-way catalyst (TWC) was investigated. The samples were analyzed by X-ray diffraction, surface area analysis, Raman spectrum, X-ray photoelectron spectroscopy, oxygen storage capacity and H2-temperature-programmed reduction. The results indicate that the structure and redox properties are strongly influenced by calcination temperature. The structure properties, for instance, BET (Brunaner-Emmett-Teller) surface area declined along with the rise of temperature, but the BET surface area of the sample calcinated at 1 000℃ was 61 m2·g-1, which was significantly higher than that calcinated direct in air at the same temperature. The OSC and reduction property of Ce0.65Zr0.35O2 increased with the rise of calcination temperature because of phase rearrangement at high temperature. The redox property of their corresponding catalysts decreased due to descending of Pd dispersion, which results in decline of three-way catalytic activity at last. Although high temperature sintering led to decrease of catalytic performance, the catalyst prepared by soft-hard template method calcinated at 1 000℃ still had excellent activity. The light-off temperature for C3H8, CO and NO was 274, 175 and 133℃, respectively, which was significantly lower than catalyst calcined direct in air at the same temperature. Redox property and dispersity of Pd are significant factors affecting activity of catalyst.
Verifying Principle of Electroneutrality by NBO Charge Calculations
Jia-Wei XU, Li-Ke DENG, Hao-Zhe ZHANG, Huan-Yu ZHANG, Yu-Chen LUO, Xin-Ya YAN, Jian-Chun Bao, Min FANG, Yong WU
2020, 36(11): 2157-2168  doi: 10.11862/CJIC.2020.236
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NBO charges of[M(H2O)6]3+ (M=Sc~Co), [Co (Ⅲ) L6] (L=F-, H2O, NH3, CN-), Al3O(OH)7(H2O)5 (Al3) and Al6O6(OH)6(H2O)5 (Al6) created based on α-Al2O3 were calculated at B3LYP/6-31++G(d, p) level of density functional theory (DFT). Except for[Co(NH3)6]3+, they all violate the principle of electroneutrality (EN) by having charges out-side the range of +1 to -1. In addition, the charge for the central metal ion is drastically influenced by the type of the coordination atoms, which is not included in the current EN principle. The charges of Co3+ in[CoF6]3- and[Co(CN)6]3- were found to be 1.639 and -1.360, respectively. When the ionic potential of the central atom increases, its charge would decrease. Based on our calculation, we predict the charge of Al in α-Al2O3 is 2.1±0.1.
Chiral Discrimination Tyrosine Enantiomers Based on N-Acetyl-L-cysteine Modified ZnFe2O4@SiO2 Nanoparticles
Shao-Kai CHEN, Xin LI, Chen-Chen GUO, Yi-Xuan WEI, Sai-Wei YUAN, Hui-Hua SONG
2020, 36(11): 2169-2178  doi: 10.11862/CJIC.2020.235
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N-acetyl-L-cysteine (NALC) functionalized ZnFe2O4@SiO2 (ZnFe2O4@SiO2-NALC) was synthesized and exhibited simplicity, rapidity and high selectivity in the separation of chiral tyrosine (Tyr) enantiomers. The chiral nanocomposite of ZnFe2O4@SiO2-NALC was characterized by X-ray powder diffraction (XRD), infrared spectroscopy (FT-IR), energy dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM) and vibrating sample magnetometer (VSM). This is the first synthesis of ZnFe2O4@SiO2-NALC for chiral recognition. The proposed optical spectroscopic techniques (UV-Vis spectrum and fluorescence spectra) showed excellent enantiospecificity for Tyr enantiomers. Furthermore, the experimental parameters such as the Tyr concentration and the pH values were optimized.
Fabrication of ZnIn2S4/Au Nanosheet Arrays for Visible-Light-Response Photoelectrochemical N2 Fixation
Kun LI, Xiao-Yan CAI, Yu-Long ZHAO, Xiu-Quan GU, Liang MAO
2020, 36(11): 2179-2188  doi: 10.11862/CJIC.2020.240
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In this study, single-crystal ZnIn2S4 nanosheet arrays (NSAs) were synthesized via a facile hydrothermal route for photoelectrochemical (PEC) N2 fixation under a visible light irradiation. The Au nanoparticles (NPs) with average size of 5 nm were deposited onto the edges of ZnIn2S4 nanosheets through a photodeposition method, leading to both the enhancements of visible light harvesting and carrier separation. After optimizing the Au loading amounts, the PEC N2 fixation activity was enhanced significantly from 1.09 to 2.26 μg·cm-2·h-1, which is attributed to the enhancements of visible light absorption and carrier separation. Furthermore, a schematic model was used to clarify the mechanism as had been demonstrated by the photoluminescence (PL) and PEC results, respectively.
Ordered Mesoporous and Complete Amorphous Ce-Ti Catalytic Filter for Particle Separation and NOx Removal
Dan LI, Hui WANG, Liu-Ping CHEN, Na ZHU
2020, 36(11): 2189-2196  doi: 10.11862/CJIC.2020.233
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A complete amorphous and highly ordered Ce-Ti catalytic membrane was prepared for simultaneously removing the particulates and NOx. Results showed that the presence of Ce species suppressed the phase transformation of the anatase TiO2, consolidated the pore framework and well retained the ordered hexagonal pore structure. As a result, the highly ordered Ce0.2TiOx catalyst presented approximately 100% NO conversion in a wide temperature of 175~350℃ and satisfactory SO2 tolerance because of large surface and formation of the Ce-O-Ti species. Furthermore, the prepared Ce0.2TiOx catalytic membrane slightly enhanced the operating pressure drop and delivered an almost similar selective catalytic reduction (SCR) activity for NOx with the catalyst powder.
Syntheses, Crystal Structures and Properties of Two Zn(Ⅱ) Complexes Constructed from Flexible 1, 5-Bis(imidazol-2-methyl)pentane Ligand
Chun-Hua ZHANG, Ying WANG, Hai-Jun TANG, Yi-Fang DENG, Man-Sheng CHEN
2020, 36(11): 2197-2204  doi: 10.11862/CJIC.2020.250
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Hydrothermal assembly reactions of Zn(NO3)2·6H2O, 1, 5-bis-(2-methyl-imidazol)pentane (BMIP) and 5-hydroxyisophthalic acid (5-OHH2IP) or 5-bromoisophthalic acid (5-BrH2IP) ligands resulted in the formation of complexes[Zn(5-OHIP)(BMIP)]n (1) and[Zn(5-BrIP)(BMIP)]n (2), respectively. The resulting complexes were characterized by IR spectrum, elemental analysis and single-crystal X-ray diffraction. Crystal structure analysis shows that complex 1 crystallizes in the monoclinic system, space group P21/n with β=101.363(10)°. Complex 1 displays a two-dimensional layer net constructed by 5-hydroxyisophthalic acid and 1, 5-bis-(2-methyl-imidazol)pentane. For 2, 5-bromoisophthalic acid and 1, 5-bis-(2-methyl-imidazol)pentane link Zinc ion into a two-dimensional layers, which are pillared by the other BMIP ligands to result in the three-dimensional framework from another direction. Finally, it exhibits a fascinating three-fold interpenetrating net with dmp topology. Both complexes exhibit a strong photolu-minescence in the solid state at room temperature. Moreover, two complexes present good photocatalytic activities in methylene blue (MB) degradation reactions.CCDC: 1502156, 1; 1502157, 2.
论文
含氟菲咯啉的设计合成及其杂配铜配合物的光解水性能
刘雪粉, 俞哲健, 徐良轩, 陈浩, 王天琦, 杨鹏, 罗书平
2020, 36(11): 2023-2030  doi: 10.11862/CJIC.2020.248
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设计合成新型含氟菲咯啉二齿配体,与六氟磷酸四乙腈合铜及磷配体Xantphos进行配位,得到相应的铜基配合物(CP1~CP4),再以此配合物作为光敏剂用于光催化水解制氢,发现其在均相光解水体系中表现出较好的光敏活性,制氢总转换数(TON)可达896。结合对所选的配合物进行吸收光谱和荧光发射光谱的测试结果可知,此配合物在溶液中也具有很好的稳定性,不会发生配体的重组现象。荧光淬灭实验表明,氧化淬灭为光解水过程中主要的淬灭途径。此外,对这类配合物作为光敏剂的构效关系及其内在机理进行了初步的解释与探讨。
高比表面积介孔网状氧化镁的制备、表征及对废水中Pb(Ⅱ)的吸附性能和机理
黄建翠, 凌观爽, 武艳妮, 翟俊, 宗俊
2020, 36(11): 2031-2040  doi: 10.11862/CJIC.2020.238
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以天然水菱镁矿为原料,通过"煅烧-水化-煅烧"的简单方法制备了高比表面积介孔网状MgO,且实验过程中无须加入任何试剂。系统性研究了氧化镁用量、吸附时间、吸附温度及pH对氧化镁吸附模拟废水中铅离子吸附性能的影响,揭示了吸附机理,并考察了氧化镁对多种离子的吸附效果。结果表明:该氧化镁吸附剂具有188 m2·g-1的高比表面积和0.85 cm3·g-1的高孔体积,平均孔径为12.33 nm,其吸附动力学和等温线数据与伪二级模型和Langmuir模型高度吻合,表明重金属离子在氧化镁上为单层化学吸附。MgO介孔网状结构表现出对Pb(Ⅱ)的高吸附性能,最大吸附量为7 431.5 mg·g-1,该数值远高于其他报道的基于MgO吸附剂的数值,铅去除率高达99.8%以上。介孔网状MgO的吸附机理主要是羟基官能团以及Mg(Ⅱ)与MgO表面重金属离子之间的离子交换所致。另外,该氧化镁可同时吸附多种离子,对Cd、Cr、Ni、As、Co、P、Se、Be、Bi、Cu、Fe、Mn、Ⅴ、Zn、Al离子均具有优异的吸附性能。
HA/ZnO/SiO2梯度涂层材料的制备及其体外抗菌活性测试
钟欣, 黄紫洋, 赵梦阳
2020, 36(11): 2041-2047  doi: 10.11862/CJIC.2020.210
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采用区带电泳法电泳羟基磷灰石(HA)、壳聚糖(CS)、ZnO和SiO2悬浊液,接着施予反向电场进行电泳沉积从而在钛基材表面获得HA/CS/ZnO/SiO2复合涂层材料,而后经710℃焙烧2 h后得到HA/ZnO/SiO2涂层材料(Z1)。同时也仅用电泳沉积法直接制得HA/ZnO/SiO2涂层材料(E1)作为对比。X射线能谱分析发现Si和Zn两种元素在Z1的径向上均呈现梯度分布,初步说明Z1具有一定的梯度。结合扫描电子显微镜、粉末X射线衍射、傅里叶红外光谱等手段对2种材料进行表征,发现Z1的各种性能较E1更为优异,主要表现在Z1与钛基材表面的结合强度达31.2 MPa,且在HEPES模拟体液中培养14 d后Z1表面碳磷灰石化程度更加完全。另外,抑菌实验发现Z1粉末对大肠杆菌和金黄色葡萄球菌的抑菌率分别为81.7%和89.4%。
Ag负载KTa1-xNbxO3-BaTiO3颗粒掺杂P(VDF-TrFE-CTFE)复合材料的制备及介电性能
张钊, 沈达, 熊晓英, 杨辉, 张启龙, 申乾宏
2020, 36(11): 2048-2054  doi: 10.11862/CJIC.2020.228
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通过光照还原法制备了银颗粒负载的铌钽酸钾-钛酸钡复合粉体(Ag/KTN-BT),并将其与聚偏氟乙烯-三氟乙烯-三氟氯乙烯(P(VDF-TrFE-CTFE))聚合物复合,获得Ag/KTN-BT聚合物基复合材料。研究发现,Ag/KTN-BT填料颗粒在聚合物基体中分散均匀,复合材料结构致密,无明显气孔和裂纹,且具有较好的柔韧性。银纳米颗粒的负载,一方面在复合材料中引入了额外的界面,导致界面极化作用增强,明显提高复合材料的介电常数;另一方面银纳米颗粒的量子尺寸效应和库伦阻塞效应使得复合材料保持较低的介电损耗。当填充体积分数为20%的Ag/KTN-BT颗粒时,聚合物基复合材料的介电常数大幅提升,从聚合物的37提升到125(100 Hz),介电损耗仅为0.12。与KTN-BT基复合材料对比,Ag/KTN-BT基复合材料也显示出较好的介电性能。
荧光碳点的制备及银离子辅助的点亮型识别青霉胺
李玲芳, 王琦
2020, 36(11): 2055-2062  doi: 10.11862/CJIC.2020.232
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以半胱氨酸为原料,通过一步热解法制备了荧光碳点(CDs),并采用透射电镜(TEM)、动态光散射(DLS)、X射线能谱分析(XPS)、紫外可见吸收光谱(UV-Vis)和荧光光谱(FL)对其进行了表征。结果表明该碳点平均尺寸为3.12 nm,且表现出了良好的荧光特性。银离子能够与碳点结合进而通过光诱导的电子转移有效猝灭碳点的荧光。青霉胺得益于其与重金属离子的配位作用,能够与银离子结合使得后者离开碳点表面从而实现荧光恢复。基于此,我们建立了银离子辅助的碳点荧光点亮型识别青霉胺的新方法。该方法的线性范围为8~500 μmol·L-1,检出限为5.62 μmol·L-1。该荧光体系用于尿液样品测定,回收率在97.17%~102.05%范围内。
基于羟乙氧基间苯二甲酸配体的Cd(Ⅱ)和Pb(Ⅱ)金属有机框架的合成、晶体结构及荧光性质
张齐, 张广威, 程军妍, 卢文欣, 王鹏
2020, 36(11): 2063-2070  doi: 10.11862/CJIC.2020.247
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以5-(2-羟乙氧基)-1,3-苯二甲酸二甲酯(Me2L)为配位前驱物分别与二水合醋酸镉和三水合醋酸铅在水热条件下发生原位水解-配位反应,得到2个基于5-(2-羟乙氧基)-1,3-苯二甲酸配体和Cd(Ⅱ)或Pb(Ⅱ)的三维金属有机框架化合物{[Cd(L)(H2O)2]·1.5H2O}n1)和[Pb(L)·H2O]n2)。对这2个化合物进行了红外、元素分析和X射线单晶衍射分析,获得了其单晶结构并进一步使用X射线粉末衍射技术证明了所获得的产物具有单一晶相。对比固态下配体和2个金属有机框架化合物的荧光发射性质,能发现金属有机框架化合物较配体有了较大的红移,且红移程度与金属离子种类有关,Pb(Ⅱ)离子构建的金属有机框架化合物具有更大的红移程度。
硼、铝和镓掺杂对硅纳米管电子结构和光电性质的影响
秦成龙, 罗祥燕, 谢泉
2020, 36(11): 2071-2079  doi: 10.11862/CJIC.2020.229
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基于密度泛函理论的第一性原理计算,研究了本征硅纳米管(SiNTs)的几何结构,以及Ⅲ族元素B、Al、Ga掺杂对单壁锯齿型(14,0)SiNTs稳定性、电子结构和光学性质的影响。结果表明,褶皱型SiNTs为SiNTs稳定存在的结构,B、Al、Ga掺杂能够提高SiNTs的稳定性。本征(14,0)SiNTs属于窄带隙金属材料,通过B、Al、Ga的分别掺杂,SiNTs的带隙变宽,实现了SiNTs从金属性向半导体性质的转变。随着Ⅲ族元素原子序数的增大,其掺杂体系的稳定性不断降低,相应的带隙也不断减少。B、Al、Ga掺杂的单壁锯齿型(14,0)SiNTs具有近乎一致的光学性质,对于紫外光有着很强的吸收特性,并且对于红外和可见光吸收也有着不错的提升。
铕掺杂的一维钛氧簇合物Ti4Eu2O4(OOCC6H5)14的制备、晶体结构及表征
吴念念, 赵明明, 刘胜军, 刘波
2020, 36(11): 2080-2086  doi: 10.11862/CJIC.2020.231
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摘要:
采用完全羧基配位和铕离子掺杂钛氧簇策略,通过溶剂热法制备得到单晶Ti4Eu2O4(OOCC6H514(记为POTi4Eu2)。通过元素分析、热重分析、固态紫外可见吸收光谱、红外光谱等技术对POTi4Eu2进行表征,通过液相荧光光谱和固态荧光寿命等技术来研究其光学性质。POTi4Eu2结构包含4个TiO6八面体、2个EuO8十二面体和14个桥联的二齿苯甲酸配体。簇核Ti4Eu2是由14个苯甲酸配体稳定的,14个苯甲酸配体均采用双齿桥配位,分布于钛氧簇的核簇四周,相邻的簇之间通过苯甲酸配体桥联,形成一维链结构。热重分析数据显示单晶POTi4Eu2的结构在空气中256℃以内可以保持稳定。单晶POTi4Eu2的平均荧光寿命为1.63 ms。
2个具有四重穿插框架和dia网络的5-羟甲基间苯二甲酸类Zn(Ⅱ)配位聚合物的合成、结构和荧光性质
徐中轩, 李立凤, 徐仕菲, 陈雪婷
2020, 36(11): 2087-2092  doi: 10.11862/CJIC.2020.230
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摘要:
在溶剂热条件下,5-羟甲基间苯二甲酸(5-(hydroxymethyl)isophthalic acid,H2HIPA)和锌离子分别与1,4-双(2-甲基-1氢-咪唑-1-基)苯(1,4-bis(2-methyl-1H-imidazol-1-yl)benzene,1,4-BMIB)以及1,2-二(吡啶-4-基)乙烯(1,2-di(pyridin-4-yl)ethene,dpee)反应得到2个三维的配位聚合物[Zn(HIPA)(1,4-BMIB)]n1)和{[Zn(HIPA)(dpee)]·0.5dpee}n2)。单晶衍射揭示在配合物1中,锌离子中心呈现一个略微变形的四面体配位构型,而HIPA2-和1,4-BMIB为简单连接体,构建出具有四重穿插和dia网络的框架。在2中,锌离子中心以五角双锥构型作为四连接节点分别连接2个HIPA2-和dpee配体,仍然是一个具有dia网络的四重穿插框架。此外,dpee不仅作为辅助配体参与构建配合物2,而且还以客体分子的形式存在。固体紫外-可见光谱显示12在紫外区有强的吸收,同时固体荧光测试揭示它们具有蓝色荧光特征,分别在414和440 nm附近有强的荧光发射峰。
CuInS2量子点阻变效应
邵雅洁, 沈杰, 龚少康, 陈文, 周静
2020, 36(11): 2093-2099  doi: 10.11862/CJIC.2020.225
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摘要:
采用改进的热分解法制备了具有半导体效应的CuInS2量子点,量子点尺寸均匀、大小为4.2 nm。组装的Au/CuInS2/FTO阻变存储器件表现出典型的双极性阻变特点,其开态电压为-3.8 V,关态电压为4 V,ON/OFF开关比约为103。对器件的I-V特性曲线线性拟合发现,器件的阻变机制在高阻态时表现为空间限制电荷(SCLC)传导机制,在低阻态时表现为欧姆传导机制。器件的阻变特性主要是由于电荷被CuInS2薄膜中的缺陷产生的势阱捕获导致。通过调节陷阱势垒高度引起电荷在陷阱中移动,导致导电通路的产生和断裂,使器件处于高阻态和低阻态。
原位光化学还原法制备Ag-UiO-66-NH2复合物以增强其光催化性能
周云彩, 王崇臣, 王鹏, 付会芬, 赵晨
2020, 36(11): 2100-2112  doi: 10.11862/CJIC.2020.207
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摘要:
采用原位光化学还原沉积法,通过大功率氙灯照射AgNO3和UiO-66-NH2混合溶液制备了系列Ag-UiO-66-NH2复合材料(X min-Ag-UiO-66-NH2X为照射时间)。以粉末X射线衍射(PXRD)、傅里叶变换红外光谱(FTIR)、扫描电镜(SEM)、透射电镜(TEM)、高倍透射电镜(HRTEM)、紫外-可见漫反射(UV-Vis DRS)、X射线光电子能谱(XPS)等手段对X-Ag-UiO-66-NH2的形貌和结构进行了表征。在低功率LED可见光下照射下,对X-Ag-UiO-66-NH2光催化还原六价铬(Cr(Ⅵ))的性能进行了探究。其中,30min-Ag-UiO-66-NH2在低功率LED照射40 min对应的Cr(Ⅵ)(初始浓度为10 mg·L-1)的还原效率为94%,照射60 min可将Cr(Ⅵ)彻底还原。同时,还研究了不同pH值(pH=2,3,4,6,8)、小分子有机酸(草酸、柠檬酸和酒石酸)和外来离子(湖水、自来水和模拟海水)对30 min-Ag-UiO-66-NH2光催化还原Cr(Ⅵ)的影响。30 min-Ag-UiO-66-NH2经过5次光催化还原Cr(Ⅵ)循环实验后仍能在照射80 min内实现100% Cr(Ⅵ)还原,表明其具有良好的可重复利用性和稳定性。通过光致发光技术(PL)、电化学测试、电子自旋共振(ESR)和活性物质捕获实验,对光催化还原Cr(Ⅵ)的机理进行了研究和验证。总之,原位光化学还原沉积形成的Ag纳米颗粒有助于改善Ag-UiO-66-NH2复合材料界面上的电荷转移,从而促进光催化效率的提升。
ZnO纳米颗粒锚定的亚微米碳纤维的制备及其吸波性能
龚雷, 刘敏, 向军
2020, 36(11): 2113-2123  doi: 10.11862/CJIC.2020.226
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摘要:
使用静电纺丝技术结合水热法制备了表面锚定ZnO纳米颗粒的亚微米碳纤维(ZnO/SDCFs)复合物,并详细研究了反应溶液的pH值对复合物的结构、组成、电磁特性和吸波性能的影响。结果显示,随着pH值的升高,ZnO的含量增加,介电常数、介电损耗以及电磁衰减能力均下降,但阻抗匹配程度提高。相比于纯碳纤维,所有ZnO/SDCFs复合物的吸波性能均得到不同程度的加强。其中,pH值等于8时所制备的ZnO/SDCFs-8复合物拥有最好的吸波性能,主要归因于电磁衰减能力和阻抗匹配间的更好平衡。当ZnO/SDCFs-8的填充量仅为2.5%(质量分数)、厚度为1.7 mm时,相应吸波涂层的最小反射损耗达到-44.1 dB,低于-10 dB的有效吸收带宽为6.1 GHz,频率范围为11.9~18 GHz;当厚度为3.0 mm时,有效吸收带宽可提高到11.8 GHz(6.2~18 GHz)。
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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]  (863) [HTML全文] (863) [PDF 5276KB] (863)
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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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
[摘要]  (1018) [HTML全文] (1018) [PDF 3040KB] (1018)
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
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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]  (768) [HTML全文] (768) [PDF 3913KB] (768)
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]  (830) [HTML全文] (830) [PDF 6759KB] (830)
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]  (716) [HTML全文] (716) [PDF 5205KB] (716)
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]  (771) [HTML全文] (771) [PDF 2842KB] (771)
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]  (715) [HTML全文] (715) [PDF 2856KB] (715)
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]  (815) [HTML全文] (815) [PDF 2954KB] (815)
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]  (823) [HTML全文] (823) [PDF 4456KB] (823)
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]  (806) [HTML全文] (806) [PDF 5918KB] (806)
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]  (832) [HTML全文] (832) [PDF 5224KB] (832)
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]  (764) [HTML全文] (764) [PDF 4128KB] (764)
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]  (931) [HTML全文] (931) [PDF 5541KB] (931)
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]  (860) [HTML全文] (860) [PDF 6054KB] (860)
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]  (747) [HTML全文] (747) [PDF 2145KB] (747)
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]  (750) [HTML全文] (750) [PDF 2936KB] (750)
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]  (821) [HTML全文] (821) [PDF 1921KB] (821)
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]  (740) [HTML全文] (740) [PDF 3129KB] (740)
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
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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]  (800) [HTML全文] (800) [PDF 2683KB] (800)
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.