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综述
多孔硅纳米材料的制备及在高能锂电池中的应用
孙林, 谢杰, 刘涛, 黄松超, 张磊, 陈智栋, 姜瑞雨, 金钟
2020, 36(3): 393-405  doi: 10.11862/CJIC.2020.062
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摘要:
多孔硅纳米材料具有巨大的比表面积,可调控的物理化学性质,在药物治疗、传感、能源储存与转化等领域拥有巨大的应用前景。尤其在高能量密度锂离子电池领域,多孔硅由于其丰富的孔道结构能有效释放充放电过程中硅体积变化带来的巨大应力以及大大地缩短锂离子传输距离,而引起了人们的广泛研究兴趣。但是,开发简便快速的方法来合成结构可调变的多孔硅纳米材料仍是当前研究的挑战。近年来,一些用来合成多孔硅纳米材料的方法已有报道。我们基于本课题组最近的研究进展和近年来相关文献,比较详细综述了近年来多孔硅纳米材料的制备方法以及重点关注其在高能锂电池领域的应用。最后,对多孔硅纳米材料的未来发展方向做了进一步的展望。
论文
咪唑-氰基合铁(Ⅲ)氢键型超分子晶体的合成、相变及介电性质
郑晓媛, 刘洋, 刘懿, 秦刘磊, 王乐, 刘尊奇
2020, 36(3): 406-414  doi: 10.11862/CJIC.2020.049
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摘要:
通过溶剂蒸发法,咪唑、18-冠醚-6和铁氰酸在甲醇溶液内反应,获得了氰基合铁配合物氢键型笼状超分子晶体材料(C3H5N23[Fe(CN)6]·2(18-crown-6)·2H2O(1)。通过变温X射线单晶衍射、红外光谱、元素分析、热重分析(TG)、差示扫描量热法(DSC)和变温-介电常数测试等对该晶体进行了结构、热能及电性能分析。该晶体的空间群为P21/c,属于单斜晶系,结构显示氰基合铁阳离子、水分子和咪唑阳离子在空间内通过氢键的相互作用形成以铁原子为顶点的三维笼状结构。温度变化触发笼状结构突变,同时引起[Fe(CN)6]3-框架内超分子发生动态摆动,从而引起晶体结构发生相变,该结构相变温度区间伴随介电物理特性阶梯状变化,从220到280 K,介电常数由38变为43,且可逆。温度在270 K之后的介电突然跃升是水汽影响导致。
熔盐锌热法制备三维多孔碳用于高性能钾离子电池负极材料
马凯, 林宁
2020, 36(3): 415-420  doi: 10.11862/CJIC.2020.058
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采用熔盐锌热法,以蔗糖为前驱体成功制备了三维多孔碳材料,并将其用作钾离子电池负极材料。所制备的三维多孔碳具有大量相互贯通的孔道,有效地缓解了电极在充放电循环过程中的体积效应,提高了电解液对电极的浸润性,缩短了钾离子的扩散路径,从而展现出优异的循环稳定性和倍率性能。三维多孔碳电极在0.5 A·g-1的电流密度下,经过2 500次循环后仍展现174.6 mAh·g-1的比容量,甚至在4.4 A·g-1的高倍率下容量仍保持在170 mAh·g-1
基于普鲁士蓝/二氧化锰复合材料修饰电极上的无酶过氧化氢传感器
刘玉革, 李志果, 陈伟珍
2020, 36(3): 421-425  doi: 10.11862/CJIC.2020.065
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合成了一种普鲁士蓝/二氧化锰(PB/MnO2)复合材料。表征结果显示两者成功地复合在一起。电化学测试结果表明复合材料比单独的PB具有更好的电化学活性。由修饰玻碳电极(GCE)构建的传感器对过氧化氢(H2O2)的还原具有良好的稳定性、重现性和选择性。
富表面氧空位Fe2O3/ZnO催化剂在光催化合成氨中的应用
陈琦, 周煜, 朱继秀, 梁甜甜, 黄荣斌, 陈爱民
2020, 36(3): 426-434  doi: 10.11862/CJIC.2020.063
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摘要:
光催化合成氨是一种绿色节能的合成氨技术,设计制造丰富的表面氧空位和异质结构是促进氮分子活化和抑制电子-空穴复合的重要方法。我们以乙二醇作为还原剂,采用溶剂热法制备合成了Fe2O3/ZnO光催化剂,利用X射线衍射(XRD)、透射电镜(TEM)、电子顺磁共振(EPR)、紫外-可见漫反射(UV-Vis DRS)、荧光光谱(PL)及光电流(PC)对Fe2O3/ZnO催化剂进行表征,并考察了Fe2O3/ZnO催化剂在常温、常压下的光催化合成氨的性能。4% Fe2O3/ZnO催化剂在无牺牲剂下用于光催化合成氨,有较好的光催化效率和稳定性,其合成氨效率达到2 059 μmol·L-1·g-1·h-1。其高催化效率归因于:可见光区域吸收的提高、氮分子在表面氧空位与Fe3+活性中心上的协同活化及光生电子与空穴的高分离效率。
咔咯锰(Ⅲ)配合物催化RNA磷酸二酯类似物HpPNP的水解断裂反应机理
李皎, 徐艳, 许旋, 徐志广, 刘海洋
2020, 36(3): 435-442  doi: 10.11862/CJIC.2020.064
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采用密度泛函B3LYP方法研究了咔咯锰(Ⅲ)配合物催化水解断裂RNA磷酸二酯类似物2-羟丙基-4-硝基苯基磷酸酯(HpPNP)的反应机理以及中位取代基的性质和数目对反应能垒的影响。计算结果表明:断裂反应以特殊碱催化(SBC)机理进行,咔咯锰(Ⅲ)配合物与HpPNP形成双氢键和双配位独特的过渡态结构,经由P-O键断裂后形成产物。与无催化剂时相比,带吸电子取代基的咔咯锰(Ⅲ)配合物的催化能使反应能垒下降4%~34%。咔咯锰(Ⅲ)配合物中位的吸电子取代基效应能显著降低反应能垒,促进水解断裂反应的进行。
碳量子点在八面双锥和纳米片TiO2上的光催化
吴冰钊, 黄红琴, 蒋彩英, 王惠钢, 郑旭明
2020, 36(3): 443-450  doi: 10.11862/CJIC.2020.061
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依次用溶剂热法和水热法制备得到暴露(101)晶面的八面双锥体二氧化钛OBP-TiO2和不同碳负载量的N-CDs/OBP-TiO2复合催化剂,以及暴露(001)晶面的纳米片二氧化钛TNS和不同碳负载量的N-CDs/TNS复合催化剂。利用TEM、XRD、XPS等表征手段对这2类复合催化剂的形貌结构、化学成分等作了鉴定。系统研究了碳量子点负载量对可见光降解RhB的光催化性能影响。实验发现,由于N-CDs的加入,均能较大提高2类复合催化剂的光催化性能。(101)高裸露晶面N-CDs/OBP-TiO2比(001)高裸露晶面N-CDs/TNS的光催化活性高。
层状CuyFe6-yAl2Ox催化剂的制备及其在罗丹明B降解反应中的应用
赖楚钧, 任骁湑, 何天衢, 岳林海, 侯昭胤
2020, 36(3): 451-457  doi: 10.11862/CJIC.2020.057
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以铜铁铝水滑石为前驱体,经焙烧后得到了一系列不同组成的层状铜铁铝混合氧化物催化剂。将其应用于中性条件下高浓度罗丹明B(450 mg·L-1)的类芬顿降解反应中,考察了催化剂中铜铁比例及焙烧温度对其降解性能的影响。实验结果表明,当铜铁物质的量之比为5:1、焙烧温度为500℃时所得到的Cu5FeAl2Ox-500催化剂对罗丹明B的降解效率最高,能够在150 min内将罗丹明B完全降解。表征结果发现,Cu5FeAl2Ox-500催化剂中生成了新的CuFe2O4物相,而且具有较大的比表面积和介孔体积,因而有利于罗丹明B的降解。同时还发现该催化剂对多种污染物的降解均有很好的效果。
三维海胆状二氧化锰微球对电催化氧还原反应的晶型效应
陈丽雅, 程高, 刘冠良, 韩佳锡, 符淑钗, 韩胜博, 孙明, 蓝邦, 余林
2020, 36(3): 458-466  doi: 10.11862/CJIC.2020.048
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采用水热法和高温煅烧法制备出了3种纯相(αγβ)的三维海胆状结构的MnO2微球,并系统地研究了它们的氧还原反应(ORR)性能。研究结果表明,3种MnO2微球的ORR活性依次为:α-MnO2 > γ-MnO2 > β-MnO2α-MnO2微球具有最优的ORR性能,其起始电位为0.92 V(vs RHE),在电流密度为-3 mA·cm-2处的电位为0.77 V(vs RHE)。α-MnO2微球优异的ORR活性主要归因于其具有更多的表面Mn3+和氧空位和更好的导电性。
双金属氮化物Co3W3N/CNTs纳米复合材料的制备及其室温常压氮还原性能
姜澄, 郭虎, 李玲慧, 王涛, 范晓莉, 宋力, 龚浩, 夏伟, 高斌, 何建平
2020, 36(3): 467-474  doi: 10.11862/CJIC.2020.047
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采用水热法并经氨气保护热处理制备了双过渡金属氮化物Co3W3N/CNTs复合材料,得到了价格低廉且拥有良好氮电化学还原性能(NRR)的催化剂。通过调节已经预氧化的CNTs与过渡金属氮化物前驱体CoWO4的比例以及氨气热处理温度,实现了Co3W3N在CNTs表面的均匀负载。扫描电子显微镜(SEM)及透射电子显微镜(TEM)测试结果显示该电化学活性纳米微粒均匀地分散于CNTs表面,表明经预氧化的CNTs由于表面富集了较多的活性基团,有利于双过渡金属氮化物的分散生长。热处理后CNTs表面的Co3W3N微粒尺寸约为20 nm,相较于无载体的Co3W3N尺寸(100 nm)有明显减小。室温条件下,在N2饱和的0.01 mol·L-1 H2SO4溶液中测试了该纳米复合材料在不同过电位下的NRR,该材料在-0.3 V(vs RHE)时的产氨率及法拉第效率分别可达12.73 μg·h-1·cm-2和13.59%,对比同样条件下,纯相Co3W3N的产氨率及法拉第效率仅为1.08 μg·h-1·cm-2和1.76%。结果表明,通过水热反应和氨气保护热处理的Co3W3N/CNTs纳米复合材料具有良好的NRR性能。
球磨干湿环境对原位硫掺杂氮化碳可见光催化性能的影响
谭杰, 李志锋, 杨晓飞, 李杰, 张婷婷
2020, 36(3): 475-484  doi: 10.11862/CJIC.2020.052
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以硫脲为原料,通过简单绿色的球磨法提高原位硫掺杂g-C3N4的光催化活性。利用X射线衍射、扫描电子显微镜、元素分析、X射线光电子能谱、紫外-可见漫反射光谱及光致发光光谱等测试方法对其结构和光学特性进行表征。以亚甲基蓝为目标污染物,评价了在不同物料溶剂比下球磨的硫掺杂g-C3N4的可见光催化性能。结果表明,湿式球磨后的硫掺杂g-C3N4光催化剂比表面积增大,反应活性位点的数量增加,带隙宽度也适当增大,氧化还原能力增强。另外,湿式球磨后样品的表面缺陷减少,聚合度增加,促进了光生电子-空穴的有效分离和转移,从而降低其复合率,协同提高了硫掺杂g-C3N4的可见光催化性能。湿式球磨后的样品在可见光照射下对亚甲基蓝的降解速率分别比未球磨的样品和干式球磨后的样品提高了1.5和3.6倍。
自生长镍基MOF材料的结构调控及其电化学性能
胡文明, 马倩, 何勇强, 刘洪波, 刘军强, 夏笑虹
2020, 36(3): 485-493  doi: 10.11862/CJIC.2020.060
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以六水合氯化镍(NiCl2·6H2O)为金属盐,对苯二甲酸(PTA)为有机配体,通过改变溶剂的类型,采用一步溶剂热法在泡沫镍表面自生长高负载量的镍基MOF材料(Ni-MOF/NF)。溶剂对PTA的溶解性越好或pH值越高,PTA在溶液中的去质子速率越快,材料的形核速率越快。自生长镍基MOF材料在不同溶剂体系下表现出球簇、片状和块体状三类形貌,同时负载量也随之改变。当采用三元混合溶剂(NN-二甲基甲酰胺、水和乙醇的体积比为1:1:1)时,Ni-MOF/NF材料在泡沫镍表面的负载量达到10 mg·cm-2,在3 mol·L-1 KOH电解液中1 mA·cm-2的电流密度下的面积容量达到8 780 mF·cm-2。在5 mA·cm-2电流密度下,面积容量仍达到5 544 mF·cm-2,容量保持率为63%,表现出优良的倍率性能。经过1 000次充放电循环后容量保持率为56%,具有良好的循环稳定性能。
Articles
Influence of Spirofluorene on Photoelectric Properties of Iridium Complexes Containing Tridentate Phosphite Ligands
Man CHEN, Yue WANG, Yue-Yue ZHOU, Ping WANG, Bi-Hai TONG, Man-Keung FUNG, Song WANG
2020, 36(3): 494-502  doi: 10.11862/CJIC.2020.045
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A cyclometalated iridium(Ⅲ) complex Ir(tpit)(sb)Cl (tpitH2=triphenyl phosphite) containing 4, 5-diazo-9, 9-spirobifluorene (sb) ligand was successfully synthesized and characterized by NMR spectroscopy and high resolution mass spectrometry. X-ray single crystal diffraction analysis showed that the existence of sb ligand distorted the structure of complex, which is beneficial for reducing the molecular aggregation and luminescent quenching. The photoelectric properties of complex Ir(tpit)(sb)Cl has been studied in comparison with those of the model complex Ir(tpit)(bpy)Cl (bpy=2, 2'-bipyridine) existing intramolecular π-π stacking. The results show that the luminescence wavelength of complex Ir(tpit)(sb)Cl in polymethyl methacrylate (mass fraction 1%) was 512 nm, and had a blue shift of 8 nm compared to that of complex Ir(tpit)(bpy)Cl (520 nm). The quantum efficiency of the complex Ir(tpit)(sb)Cl was 30%, which is significantly lower than that of the complex Ir(tpit)(bpy)Cl (94%), indicating the radiative transition rate is reduced by spirofluorene. Based on the complex Ir(tpit)(sb)Cl, the maximum current efficiency and external quantum efficiency of OLED device are 14 cd·A-1 and 4.5%, respectively. The maximum current efficiency and external quantum efficiency of Ir(tpit)(bpy)Cl-based device are up to 60 cd·A-1 and 18.2%, respectively.
Synthesis, Crystal Structure and Spectral Properties of Binuclear Ni(Ⅱ) and Cubane-like Cu4(μ3-O)4 Cored Tetranuclear Cu(Ⅱ) Complexes Based on Coumarin Schiff Base
Shu-Zhen ZHANG, Jian CHANG, Hong-Jia ZHANG, Ya WU, Yin-Xia SUN, Yan-Bin WANG
2020, 36(3): 503-514  doi: 10.11862/CJIC.2020.056
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Dinuclear Ni(Ⅱ) and cubane-like Cu4(μ3-O)4 cored tetranuclear Cu(Ⅱ) complexes, [Ni(L1)(DMF)(H2O)]2 (1) (H2L1=3-((5-bromo-2-hydroxy-benzylidene)-amino)-4-hydroxy-benzopyran-2-one), [Cu4(L2)4]·DMF·CH3OH·2H2O (2) (H2L2=4-hydroxy-3-((2-hydroxy-3-methoxy-benzylidene)-amino)-benzopyran-2-one) based on 3-amino-4-hydroxy-coumarin Schiff base ligands were synthesized and characterized by elemental analysis, IR, UV-Vis, emission spectra and X-ray single crystal diffraction analysis. The X-ray single crystal diffraction analysis results show that complex 1 has a binuclear structure composed of two metal ions and two ligand units, and complex 2 has a tetranuclear structure composed of four metal ions and four ligand units. Complex 1 crystallizes in monoclinic system, C2/c space group, whereas complex 2 crystallizes in tetragonal system, I41/a space group. The spatial configurations of the central metal Ni(Ⅱ) and Cu(Ⅱ) ions are all six-coordinated distorted octahedron in complexes 1 and 2, respectively. In addition, complex 1 forms a one-dimensional (1D) supramolecular chain through intermolecular hydrogen bonding, C-H…π and ππ stacking interactions, while complex 2 formed three-dimensional(3D) supramolecular network structure via intramolecular hydrogen bonding and ππ stacking interactions.
Synthesis, Crystal Structure, and Antibacterial Activity of Copper(Ⅱ) Complexes Based on Norfloxacin
Yan-Ju HUANG, Mei-Ling XU, Jun ZHANG
2020, 36(3): 515-520  doi: 10.11862/CJIC.2020.054
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Two copper complexes[Cu2(HNOR)2Cl]n (1) and[Cu2Cl3]·H3NOR·H2O (2) (H2NOR=norfloxacin) were prepared by hydrothermal process and their structures were determined by single-crystal X-ray diffraction. The results showed that although the reactants are the same, the complexes with different structures are formed under acidic and basic conditions. Through the hydrogen bonding interactions and π-π interactions, two complexes form stable two-dimensional structure. At the same time, Escherichia coli and Staphylococcus aureus were selected as Gram positive and Gram negative for antibacterial activity experiments. Bacteriostatic activity showed that both complexes had a good inhibitory effect on Escherichia coli and Staphylococcus aureus.
Hydrothermal Preparation and Properties of Ag3PO4/HAP Composite Photocatalysts
Cui SONG, Li-Hua ZHAO, Ming-Ying QI, Rong-Wei SUN, Qian ZHU
2020, 36(3): 521-528  doi: 10.11862/CJIC.2020.067
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High-purity hydroxyapatite (HAP) was prepared from oyster-shell waste by a hydrothermal method and was used as the carrier for Ag3PO4, resulting in the preparation of a nanorod-like Ag3PO4/HAP composite photocatalyst. Scanning electron microscopy (SEM), high-resolution transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) were used to characterize the prepared photocatalyst and to explore the effect of different preparation parameters on the catalytic activity of the photocatalyst toward the degradation of a methylene blue solution. The results shows that the 1:2-Ag3PO4/HAP catalyst exhibited the best performance, achieving 50% degradation in 10 min and complete degradation in 40 min. The 1:2-Ag3PO4/HAP catalyst was a highly efficient composite photocatalyst.
Syntheses, Crystal Structures and Luminescent Properties of Zn(Ⅱ) Complexes Based on 3, 4-Pyrazoledicarboxylic Acid
Meng-Na QIN, Li-Dong WANG, Mei-Ling CHENG, Lu LIU, Qi LIU, Xiao-Yan TANG
2020, 36(3): 529-535  doi: 10.11862/CJIC.2020.046
[摘要]  (29) [HTML全文] (29) [PDF 1866KB] (0)
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Treatment of H3pdc with Zn(NO3)2·6H2O under different reaction conditions afforded two complexes, [Zn(H2pdc)2(H2O)2]·2H2O (1) and[Zn2(Hpdc)2(H2O)6]·2H2O (2) (H3pdc=3, 4-pyrazoledicarboxylic acid). X-ray diffraction analyses reveal that 1 and 2 contain mono-and dinuclear Zn(Ⅱ) components, respectively. The partly deprotonated H3pdc ligand anions in 1 and 2 adopt N, O-chelating fashion (H2pdc-) and μ2-κN, O:κN' bridging mode (Hpdc2-), respectively. In both complexes, the adjacent zero-dimensional components are connected by intermolecular hydrogen bonds (O-H…O, N-H…O and C-H…O) to form a three-dimensional supramolecular architecture. The thermal and luminescent properties of complexes 1 and 2 have also been investigated.
Role of Process Parameters on Phase Purity of o-LiMnO2 and Synthesis of Li1.6Mn1.6O4 as Lithium Ion-Sieve
Yu-Yao FU, Xi-Yun YANG, Hai-Qiang HUANG, Yuan-Yuan WANG, Ji-Shen LI
2020, 36(3): 536-546  doi: 10.11862/CJIC.2020.038
[摘要]  (30) [HTML全文] (30) [PDF 3911KB] (1)
摘要:
Spinel Li1.6Mn1.6O4 was synthesized by hydrothermal oxidation of MnSO4 with KMnO4 to form LiMnO2 following solid-phase roasting. Acid pickling transforms Li1.6Mn1.6O4 to lithium ion-sieve. The effects of hydrothermal temperature, oxygen and molar ratio of MnO4- to Mn2+ (nMnO4-:nMn2+) on LiMnO2 composition and the dissolution percentage of manganese from Li1.6Mn1.6O4 during acid pickling were investigated. Open circuit potential measurement and chemical analysis indicate that oxygen in the air has involved in the hydrothermal reaction to produce LiMnO2 accompanied by formation of Li2MnO3 and LiMn2O4 impurities at a theoretical nMnO4-:nMn2+ of 1:4. Pure orthogonal LiMnO2 (o-LiMnO2) was obtained with a molar ratio of MnO4-to Mn2+ of 1:6 at 160℃. The Li+ adsorption capacity in salt lake brine was 42.87 mg·g-1. The lithium ion-sieve showed excellent adsorption selectivity toward Li+ in salt lake brine and followed a chemical adsorption process. The adsorption capacity remained at 37.21 mg·g-1 and the dissolution percentage of manganese decreased to 0.34% after 5 cycles.
Substrate-Selectivity of Strecker Reaction Based on Amino-Functionalized Ga-MIL-53 Catalyst
Peng-Cheng WANG, Shu-Jie WU, Liang SHAN, Yan-Song JIANG, Yong FAN, Li WANG, Xiao-Dong CHEN, Jia-Ning XU
2020, 36(3): 547-554  doi: 10.11862/CJIC.2020.036
[摘要]  (29) [HTML全文] (29) [PDF 466KB] (1)
摘要:
This work focuses on Strecker reactions catalyzed by metal-organic framework (MOF) of amino-functionalized Ga-MIL-53 (NH2-Ga-MIL-53) in regard to substrates of a series of N-Ph aldimines, and the results showed that:(1) NH2-Ga-MIL-53 exhibited excellect catalytic activity and good univisality among various substrates; (2) the electronic effect of substituents for substrates primarily affects the catalytic reaction rate, and the electron-donating substituted groups (i.e., MeO, Ph) and electron-withdrawing substituted groups (i.e., CF3, NO2) show promotion and suppression effects on the reaction, respectively; (3) the substituted position of substituents in respect of substrates secondarily influences the reaction rate, and the ortho-substituted MeO group perform the strongest promotion effects on the reaction; (4) as a heterogeneous catalyst, NH2-Ga-MIL-53 can be reused for 9 runs without obvious loss of conversion efficiencies and collapse of MOF structure; (5) contrasting the catalytic performances between NH2-Ga-MIL-53 and Ga-MIL-53, it is indicated that the amino groups of NH2-Ga-MIL-53 can be served as Lewis base moieties, facilating the reaction according to Lewis acid-base synergistic mechanism. Furthermore, comparing the catalytic effects among NH2-Ga-MIL-53, Ga(NO3)3·6H2O and 2-aminoterephthalic acid, it is concluded that the pore structure of NH2-Ga-MIL-53 framework plays a significant role in avoiding the side reactions with respect to Strecker reaction.
Highly Activated Polyporous Silver Film: Preparation by Voltammetric Etching with Chloride Ion Promotion and Electrochemical Determination of Trichloroacetic Acid
You-Qun CHU, Ling-Qiao WANG, Zhang-Kao HUANG, Ying-Hua XU, Feng-Ming ZHAO
2020, 36(3): 555-565  doi: 10.11862/CJIC.2020.059
[摘要]  (22) [HTML全文] (22) [PDF 4638KB] (1)
摘要:
A highly activated polyporous silver film was constructed on the outer ring of silver wire by voltammetric etching using halogen anions. In particular, chloride ion etching can promote the formation of self-supported porous channel structure on silver wire surface via microcell reactions. Appling a continuous positive potential to the silver wire electrode contributes to form a thin film of AgCl. After electrochemical reduction, chloride ions are stripped from AgCl and the AgCl spontaneously transformed to self-supported polyporous silver film. The as prepared self-supported polyporous silver film electrode (p-Ag film) reveals substantial electrocatalytic activity for the selective and sensitive sensing of trichloroacetic acid. The p-Ag film electrode displays 174 and 3.7 times enhancement in electrochemical active surface area and the dechlorination reaction, relative to the pristine silver wire electrode (r-Ag wire). The novel electrodes exhibited a low detection limit of 70 nmol·L-1 (fitting correlation coefficient R2=0.998 3) with the trichloroacetic acid concentration range of 0.1~518.1 μmol·L-1.
Constructing and Photocatalytic Performance of g-C3N4/Ag/TiO2 Composites
Ping LI, Xiao-Xian ZHANGA, Ying SI, Ting-Ting LIANG, Huan LIU, Ling-Fang QIU, Shu-Qi DUAN, Shu-Wang DUO, Zhong CHEN
2020, 36(3): 566-574  doi: 10.11862/CJIC.2020.055
[摘要]  (45) [HTML全文] (45) [PDF 5517KB] (2)
摘要:
g-C3N4/Ag/TiO2 ternary photocatalysts were successfully constructed by a mechanical agitation method with as-synthesized Ag/TiO2 hollow microspheres and g-C3N4 nanosheets as the raw materials. The photocatalysts were systematically characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), and photoluminescence spectra (PL). The results showed that g-C3N4/Ag/TiO2 was assembled by Ag/TiO2 microspheres and g-C3N4 nanosheets. Compared with TiO2, the resultant g-C3N4/Ag/TiO2 heterojunctions possessed longer visible-light response range and faster photo-induced carrier separation rate. At room temperature, the visible-light photocatalytic activity of g-C3N4/Ag/TiO2 was investigated by photodegradation of rhodamine B (RhB). The results showed that the highest visible-light-driven photocatalytic efficiency of g-C3N4 (0.5%)/Ag/TiO2 with 180 min of light irradiation was 91.9%, which was nearly 7.5 and 1.8 times higher than pure TiO2 and two-component Ag/TiO2, respectively. The enhanced photocatalytic activity could be mainly attributed to the reasonably designed heterojunctions and the electrical conductivity of Ag.
V2O5 Hollow Spheres as High Efficient Sulfur Host for Li-S Batteries
Pei-Feng PAN, Ping CHEN, Ya-Nan FANG, Qi SHAN, Ning-Na CHEN, Xiao-Miao FENG, Rui-Qing LIU, Pan LI, Yan-Wen MA
2020, 36(3): 575-583  doi: 10.11862/CJIC.2020.051
[摘要]  (30) [HTML全文] (30) [PDF 5754KB] (4)
摘要:
The V2O5 hollow spheres were used as a high efficient sulfur host for Li-S batteries, which was used for the storage of sulfur and restricting the shuttle effect of polysulfides. The hollow spheres had an average diameter around 500 nm, providing more space for storing sulfur, accommodating volumetric change of sulfur electrode. At the same time, V2O5 has a strong chemical adsorption of polysulfides, which can effectively limit the shuttle effect of polysulfides. The high capacity and excellent stability of Li-S batteries have been realized simultaneously due to the increasing of the storage of sulfur by the hollow structure and strong chemical adsorption for polysulfides by chemical bonding. The Li-S batteries with as-prepared V2O5/S cathode showed a high reversible capacity of 1 439 mAh·g-1 at 0.1C and stable cycling performance with a capacity of~600 mAh·g-1 after 300 cycles at 1C.
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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]  (113) [HTML全文] (113) [PDF 5276KB] (113)
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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
[摘要]  (34) [HTML全文] (34) [PDF 4390KB] (34)
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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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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
[摘要]  (36) [HTML全文] (36) [PDF 3255KB] (36)
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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]  (222) [HTML全文] (222) [PDF 3040KB] (222)
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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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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]  (33) [HTML全文] (33) [PDF 3913KB] (33)
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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]  (26) [HTML全文] (26) [PDF 6759KB] (26)
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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]  (35) [HTML全文] (35) [PDF 5205KB] (35)
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]  (33) [HTML全文] (33) [PDF 2842KB] (33)
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]  (37) [HTML全文] (37) [PDF 2856KB] (37)
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]  (45) [HTML全文] (45) [PDF 2954KB] (45)
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]  (27) [HTML全文] (27) [PDF 4456KB] (27)
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]  (30) [HTML全文] (30) [PDF 5918KB] (30)
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]  (28) [HTML全文] (28) [PDF 5224KB] (28)
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]  (40) [HTML全文] (40) [PDF 4128KB] (40)
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]  (28) [HTML全文] (28) [PDF 5541KB] (28)
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]  (29) [HTML全文] (29) [PDF 6054KB] (29)
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]  (28) [HTML全文] (28) [PDF 2145KB] (28)
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]  (37) [HTML全文] (37) [PDF 2936KB] (37)
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]  (29) [HTML全文] (29) [PDF 1921KB] (29)
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]  (31) [HTML全文] (31) [PDF 3129KB] (31)
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]  (31) [HTML全文] (31) [PDF 2452KB] (31)
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]  (27) [HTML全文] (27) [PDF 2683KB] (27)
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.