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综述
Li7P3S11电解质的合成、传导及应用
廖聪, 余创, 彭林峰, 李莉萍, 程时杰, 谢佳
2022, 38(6): 977-992  doi: 10.11862/CJIC.2022.122
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固态电解质是固态电池中的关键材料,开发具有高离子电导率、高化学/电化学稳定性、电极兼容性良好的固态电解质正成为研究热点。硫化物固态电解质相较其它固态电解质具有更高的离子电导率和良好的机械加工性能等优势,是最有前景实现实用化的固态电解质之一。在众多硫化物固态电解质中,Li7P3S11因其高的离子电导率和较低的原料成本而极具研究意义。本文首先介绍了Li7P3S11电解质的结构、Li+传导机理及合成路径;其次,针对该电解质的电导率提高、空气/水稳定性提升、固固界面稳定性及电解质自身稳定性改善等问题,综述了目前常用的改性策略研究;再次,总结了基于Li7P3S11电解质的全固态锂离子电池和全固态锂硫电池的构筑;最后,本文分析了Li7P3S11电解质的研究和应用面临的挑战,并指出该电解质未来发展的趋势。
二维过渡金属硫族化合物缺陷工程
李景涛, 马洋, 李绍先, 何业鸣, 张永哲
2022, 38(6): 993-1015  doi: 10.11862/CJIC.2022.120
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摘要:
二维过渡金属硫族化合物(two-dimensional transition metal dichalcogenides,TMDs)具有厚度在原子级别、禁带宽度随层数在1~2 eV内变化、高载流子迁移率(如MoS2载流子迁移率达到了200 cm2·V-1·s-1)等特点,在光学、电学等领域具有广泛应用。TMDs的超薄特性使此类材料与块体材料相比,更容易受到缺陷调控的影响,改变材料原有性能。在本综述中,首先介绍了TMDs的晶体结构和相结构,并根据维度特征对缺陷的类型进行了分类;接着从缺陷的抑制和修复,以及缺陷的制造两方面出发,总结了缺陷调控TMDs材料性能的最新研究进展;在此基础上,介绍了缺陷工程在电学、光学、磁学、电催化等领域的具体应用;最后,本综述讨论了缺陷工程在应用过程中面临的实际问题,并对其未来的研究及发展方向进行了展望。
论文
Li4SrCa(SiO4)2∶Eu3+红色荧光粉的合成及其发光性能
樊霞霞, 高志翔, 屈文山, 田翠锋, 李建刚, 李伟, 董丽娟, 石云龙
2022, 38(6): 1016-1022  doi: 10.11862/CJIC.2022.123
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采用硅酸盐作为基质材料,通过高温固相法合成了Li4SrCa(SiO4)2∶Eu3+红色荧光粉。通过X射线粉末衍射、X射线光电子能谱、透射电镜和荧光光谱,对所得样品的物相、形貌及其发光性能进行了表征分析。结果表明,掺入Eu3+后,Li4SrCa(SiO4)2的晶体结构并没有发生改变。在393 nm光激发下,荧光粉的荧光光谱中693 nm处发射峰强度最强。以693 nm作为监测波长,荧光激发峰分别为361 nm (7F05D4)、375 nm (7F05G3)、413 nm (7F05D3)、393 nm (7F05L6)和464 nm (7F05D2),即样品对近紫外和蓝光有较好的吸收。利用发射光谱研究了Eu3+掺杂浓度(物质的量分数)对荧光粉发光强度的影响。当Eu3+的掺杂浓度x= 0.10时,样品发射强度最强,发射红光,其色坐标为(0.637 5,0.353 7)。通过Dexter强度与浓度关系分析了浓度猝灭机制。
CL-b-PNIPAM配位Eu(Ⅲ)构筑的超小尺寸稀土配合物荧光纳米探针用于肿瘤细胞双色成像
关晓琳, 丁媛媛, 来守军, 杨学琴, 韦镜玉, 张家铭, 张丽媛, 童金辉, 雷自强
2022, 38(6): 1023-1036  doi: 10.11862/CJIC.2022.097
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依次采用开环聚合(ROP)和原位引发聚合方法,分别在四苯乙烯(TPE)分子的不同苯环位置上共价键合嵌段共聚物PCL-b-PNIPAM(PCL=聚己内酯,PNIPAM=聚(N-异丙基丙烯酰胺)),并通过与Eu(Ⅲ)配位,合成含有单、双、四臂的3种双亲性嵌段共聚物-Eu(Ⅲ)配合物,再自组装构筑出粒径分别为4.8、4.3和2.7 nm的小尺寸非半导体型聚合物量子点(Pdots)。测试结果表明:单、双、四臂Pdots均具有蓝光(430 nm)和红光(615 nm)的双荧光发射性能,且由TPE发射的蓝光具有聚集诱导发光性能和温度响应特性,最低临界溶解温度分别为32、36和37 ℃,接近人体正常体温。同时,3种Pdots均表现出极低的细胞毒性,并展现出优异的蓝/红双色荧光成像能力和可逆双色荧光切换功能。此外,对3种Pdots进行对比发现,四臂Pdots具有最小的粒径、最优的双荧光性能和最佳的细胞成像效果。
多孔碳纳米纤维负载Pd纳米颗粒用于增强电催化氧还原性能
莫志勇, 宋诗竹, 力文玉, 何学龙, 谌璐, 高晓红, 李奇
2022, 38(6): 1037-1048  doi: 10.11862/CJIC.2022.110
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采用溶剂热法合成了以锆为金属核心、2-氨基为配体的锆基金属有机骨架(UiO -66)纳米材料,通过静电纺丝技术制备出UiO-66自由分散的聚丙烯腈(PAN/UiO-66)纤维,可控热解得到多孔碳纳米纤维(porous carbon nanofibers,PCNFs),结合湿化学还原法在PCNFs表面沉积Pd纳米颗粒,得到PCNFs@Pd复合材料。通过扫描电子显微镜、透射电子显微镜、X射线衍射技术对其形貌、组成、结构进行表征;采用电化学工作站分别测试了PCNFs@Pd在0.1 mol·L-1 KOH和0.1 mol·L-1 HClO4电解质中氧还原性能(oxygen reduction reaction,ORR)。结果表明,在PAN纤维中添加UiO-66显著提高了PCNFs@Pd(Pd负载量为0.34%)复合材料的ORR性能。相比40%Pt/C,在碱性电解质中,PCNFs@Pd复合材料展示出更低的Tafel斜率、更优异的循环稳定性和耐甲醇中毒性。在酸性电解质中也表现出类似20%Pt/C的催化活性和循环稳定性。
钒氮共掺杂多孔碳催化剂上苄胺氧化偶联合成亚胺
吴晓雪, 齐妍妍, 王盈懿, 王丽, 涂高美, 傅仰河, 陈德利, 朱伟东, 张富民
2022, 38(6): 1049-1058  doi: 10.11862/CJIC.2022.112
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本工作以生物质壳聚糖作为牺牲模板,乙酰丙酮钒为金属钒源,ZnCl2为造孔剂,采用高温热解结合酸洗的策略制备出一种钒氮共掺杂多孔碳(V-N-C)催化剂。表征结果表明,V-N-C催化剂的比表面积高达1 470 m2·g-1,孔容为1.06 cm3·g-1,质量分数为0.19% 的钒物种可能以单原子VNx形式高度分散在载体上。在苄胺氧化偶联合成亚胺的反应中,V-N-C表现出高催化性能,底物苄胺的转化率和产物亚胺的选择性均为99%,性能明显优于均相VO(acac)2和多相V2O5催化剂。此外V-N-C催化剂连续重复使用9次也未出现任何活性衰减的问题,且对一系列含有不同官能团的底物也具有优良的普适性。机理研究表明,苄胺和氧气首先分别在催化剂VNx和缺陷位点活化成苄基亚胺和H2O2中间体,然后苄基亚胺与苄胺缩合脱NH3生成目标产物亚胺。
AgIn5S8/碳量子点/ZnIn2S4的多途径电子迁移与光催化性能
祖雯琳, 李莉, 黄继玮, 孙英茹, 马凤延, 曹艳珍
2022, 38(6): 1059-1072  doi: 10.11862/CJIC.2022.113
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首先,借助碳量子点(CQDs)的上转换光致发光(UCPL)特性对ZnIn2S4进行了表面改性,再结合离子交换法制备了复合材料AgIn5S8/CQDs/ZnIn2S4。采用X射线衍射(XRD)、X射线光电子能谱(XPS)、紫外可见漫反射吸收光谱(UV-Vis DRS)、扫描电镜(SEM)、透射电镜(TEM)、氮气吸附-脱附、光致发光(PL)和电化学阻抗(EIS)等测试手段对复合材料的组成、结构、形貌以及表面物理化学性质等进行了表征。结果表明,该复合材料中不同组分间的协同作用导致其呈现宽光谱响应(250~800 nm)。与对比体系相比,复合材料AgIn5S8/CQDs/ZnIn2S4表现出明显增强的光电流密度,更小的电荷转移阻抗,较长的光生载流子寿命。以甲基橙为模型分子,在不同光源作用下进行的光催化活性研究结果显示,AgIn5S8/CQDs/ZnIn2S4呈现增强的光催化降解活性。同时,该复合材料在光解水性能研究中不仅表现较高的光解水制氢速率(312.09 μmol·h-1·g-1),而且呈现良好的稳定性。
植物补光用非晶态La2Ti2O7∶Eu3+荧光粉的燃烧合成及性能
张义, 周翠平, 张启凤, 冯馨丹
2022, 38(6): 1073-1080  doi: 10.11862/CJIC.2022.114
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采用燃烧法合成了非晶态La2Ti2O7∶Eu3+荧光粉,利用X射线衍射、扫描电镜、荧光光谱表征了材料的结构、形貌和发光性能,并进一步制成了LED(light-emitting diode)光源,探讨了补光对小麦生长速率和光合色素含量的影响。与固相法合成的晶态La2Ti2O7∶Eu3+相比,非晶态La2Ti2O7∶Eu3+荧光粉中Eu3+离子配位环境的对称性减小,因而显著提高了7F2能级相对于7F1能级的发射强度,使得红光相对橙光成分明显增加,色坐标位于(0.661,0.339),色纯度从90.9% 提高为95.9%,适用于植物补光LED。同时,该非晶态荧光粉克服了一般非晶基质中Eu3+发光较弱的问题,荧光内量子效率可高达79.8%,用其制成的LED灯能有效促进小麦的生长,使得叶片中叶绿素和胡萝卜素含量提高了约28%。
两个取代苄基锡配合物的合成、抗癌活性及其与DNA相互作用
陈乐, 邓欣, 谭宇星, 张复兴, 邝代治, 蒋伍玖
2022, 38(6): 1081-1089  doi: 10.11862/CJIC.2022.124
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利用二(2,4-二氯苄基)二氯化锡分别与对甲基苯甲酰肼或对叔丁基苯甲酰肼、丙酮酸钠在甲醇中发生反应,合成了2个二(2,4-二氯苄基)锡配合物(C1C2),通过元素分析、IR、1H NMR、13C NMR、119Sn NMR、HRMS以及X射线单晶衍射表征了配合物结构。测试了配合物C1C2的热稳定性以及配合物对NCI-H460(人肺癌细胞)、HepG2(人肝癌细胞)和MCF7(人乳腺癌细胞)的体外抑制活性,发现配合物C1对癌细胞均表现较好的抑制作用。利用UV-Vis光谱、荧光光谱以及黏度法研究了2个配合物与ct-DNA之间的相互作用,结果表明配合物是以经典的嵌入模式与DNA结合。
ZSM-5催化丙烯芳构化反应构效关系及反应特性
任坤, 张亮亮, 李忠, 付廷俊
2022, 38(6): 1090-1102  doi: 10.11862/CJIC.2022.115
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甲醇两步制芳烃反应中低碳烯烃芳构化反应稳定性优异,为分析其内在机制,制备了不同硅铝比(nSiO2/nAl2O3)及Zn负载量的ZSM-5催化剂,以丙烯芳构化为模型反应,分析ZSM-5表面酸性对低碳烯烃芳构化反应性能的影响规律,并探究反应微观特性。发现当硅铝比由150降至75时,增加的酸密度促进了烯烃氢转移芳构化过程,使芳烃选择性由31.0% 增至34.4%,但丙烯直接参与的氢转移过程也被强化,使丙烷产物选择性由28.2% 增至36.0%。引入Zn助剂可将部分Brønsted酸转变为Zn-Lewis酸,强化烯烃脱氢芳构化过程,使芳烃选择性进一步显著增加到62.4%。丙烯芳构化过程中芳烃烷基化深度比甲醇芳构化过程低,提升总芳烃选择性的同时,也明显抑制了难溶性积碳的形成,使反应稳定性明显提升。由此得出,甲醇两步制芳烃过程中甲醇制低碳烯烃过程对甲醇的预先消耗,抑制了低碳烯烃芳构化反应芳烃产物的深度烷基化,是该反应表现出优异稳定性的重要原因。
Articles
A Dy2 Complex Showing Outstanding Single⁃Molecule Magnet Behavior
Xiao-Yan XIN, Xue-Jin ZHANG, Feng-Jiao CHEN, Yu WANG, Chen YANG, Na QIAO, Ying SHI, Wen-Min WANG
2022, 38(6): 1103-1111  doi: 10.11862/CJIC.2022.125
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Two new binuclear Ln(Ⅲ)-based complexes with the formula [Ln2(dbm)2(L)2(C2H5OH)2] (Ln=Dy (1), Nd (2); dbm-=1, 3-dioxo-1, 3-diphenylpropan-2-ide) have been synthesized via the solvothermal method by using a polydentate Schiff base ligand (H2L=(E)-N′-(3-ethoxy-2-hydroxybenzylidene)-3-hydroxypicolinohydrazide) reacting with Ln(dbm)3·2H2O. Single-crystal X-ray structures reveal that complexes 1 and 2 are mainly composed of two Ln(Ⅲ) ions, two dbm-ions, two L2-ions, and two C2H5OH molecules, and the two central Ln(Ⅲ) ions are connected by two μ2-O atoms forming a "parallelogram-shaped" Ln2O2 core. Magnetic studies show that the ferromagnetic interaction exists between the adjacent two Dy(Ⅲ) ions and single-molecule magnet behavior occurs in 1. CCDC: 2100188, 1; 2133336, 2.
Structure, Thermostability, Fluorescence, and Dye Adsorption Properties of a Copper(Ⅱ) Coordination Polymer Based on (+)-Di-p-toluoyl-D-tartaric Acid
Huan ZHENG, Yan-Xiao CHU, Si-Si FENG, Cai-Xia YUAN
2022, 38(6): 1112-1120  doi: 10.11862/CJIC.2022.109
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A coordination polymer, formulated as {[Cu(HDTTA)2(DMF)(H2O)]·DMF·H2O}n (1) (D-H2DTTA=(+) -di-p-toluoyl-D-tartaric acid, DMF=N, N-dimethylformamide), has been synthesized. Its structure was characterized by IR spectrum, elemental analysis, X-ray single-crystal diffraction, and powder X-ray diffraction. Complex 1 features a 1D chain structure along the a-axis and forms a 2D layered structure in the ab plane through weak intermolecular interactions. The thermal decomposition process of 1 included the loss of solvent molecules below 197 ℃ and follow-up decomposition of the main structure. Under the excitation of 300 nm, the fluorescence of the ligand was quenched by the coordinated Cu2+ cation. In addition, complex 1 exhibited a good and specific adsorption effect on methylene blue dye in an aqueous solution with an adsorption rate of 81% after 49 min.
Organometallic Gels Based on Metal Ion Exchange for the Detection of Antibiotics and Nitroaromatic Compounds
Yi-Zhen YUAN, Yun-Shang YANG, Yu-Chen ZHAO, Ying-Peng ZHANG
2022, 38(6): 1121-1132  doi: 10.11862/CJIC.2022.126
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Rapid detection of organic compounds in wastewater has always been an important issue. Fluorescent Tb-based metal- organic gel MOG(Tb) was prepared by the metal ion exchange method. The studies have shown that trace amounts of furazolidone (FZD), metronidazole (MDZ), 2, 4-dinitrotoluene (2, 4-DNT), and 4-nitrophenol (4-NP) could effectively quench the fluorescence emission of MOG(Tb) even in the presence of other analytes, demonstrat-ing that the MOG(Tb) xerogels could effectively detect antibiotics (FZD, MDZ) and nitroaromatic compounds (2, 4-DNT, 4-NP). However, penicillin G potassium salt (PCLP) could enhance the fluorescence of MOG(Tb). In addi-tion, the recyclability and water stability tests of the MOG(Tb) xerogels were also carried out, and satisfactory results were obtained.
Syntheses, Crystal Structures and Properties of Coordination Polymers Based on 4, 4'-Bis(imidazol-l-yl)-phenyl Sulphone or 4, 4'-Bis(imidazol-l-yl)diphenyl Thioether
Han XU, Zhao-Rui PAN, Rong JIANG
2022, 38(6): 1133-1145  doi: 10.11862/CJIC.2022.111
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Three new coordination polymers based on V-shaped ligands, namely {[Cd(BIDPS)(PA)(H2O)]·CH3OH}n (1), {[Zn(BIDPS)(p-bdc)]·H2O}n (2) and [Mn(BIDPT)(NBA)]n (3) (BIDPS=4, 4' -bis(imidazol-l-yl)-phenyl sulphone, H2PA=pamoic acid, p - H2bdc= p - phthalic acid, BIDPT=4, 4' - bis(imidazol - l - yl)diphenyl thioether, H2NBA=4, 4' - azanediyl dibenzoic acid) have been hydrothermally synthesized and structurally characterized. Compounds 1 and 2 feature an undulate 2D layer structure. Compound 1 exhibits a rare 2D→3D inclined polycatenated structure, while compound 2 is further joined by intermolecular hydrogen bondings to form a 3D network. Compound 3 displays a 3-connected hexagonal layer hcb topology (honeycomb network) and is further assembled into a 3D network via C—H … π interaction. Compounds 1 and 2 showed excellent water stability and fluorescence, which were further con-firmed as bifunctional fluorescent sensors for Fe3+ and Cr2O72- with high selectivity, sensitivity, and anti-interference ability in the water. The mechanisms of fluorescence quenching were also studied in detail. CCDC: 1919698, 1; 2085947, 2; 2117923, 3.
A Water Stable Luminescent Zn-Complex Sensor for Detection of PO43- Ion, Fe3+ Ion, and Nitroaromatic Explosives
Yue-Jiao JIA, Xiao-Yu LIANG, Ming HU
2022, 38(6): 1146-1158  doi: 10.11862/CJIC.2022.108
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A luminescent Zn-complex based on the 3-(2, 4-dicarboxylphenyl)-6-carboxylpyridine (H3dpcp), namely [Zn(H2dpcp)2(H2O)2]·H2O (1), was successfully fabricated by the solvothermal process. Complex 1 features a mono-nuclear butterfly-like structure, which further extends to the 3D supramolecular architecture via ππ interactions. It is found that complex 1 exhibited excellent luminescent stability in a pH range of 1-10 in an aqueous solution. It should be noted that complex 1 can not only detect PO43- ion based on the turn-on effect with high selectivity and recyclability but also serve as a remarkably selective sensing material with the fluorescence quenching for Fe3+ ion. The examination of nitroaromatic compounds demonstrated that complex 1 also behaved as a functional probe with high selectivity, sensitivity, and the low detection limit of 2, 4, 6-trinitrophenol (TNP). Furthermore, the luminescent sensing mechanisms for the above analytes were also investigated in detail. CCDC: 2010615.
Non-enzyme Glucose Biosensor Based on Bimetallic Pt-Au Nanoparticles Decorated Acupuncture Needle
Qi XIAO, Guang-Xian LIU, Jian-Dan CHEN, Zheng-Zhi YIN, Chun-Chuan GU, Hong-Ying LIU
2022, 38(6): 1159-1170  doi: 10.11862/CJIC.2022.119
[摘要]  (23) [HTML全文] (23) [PDF 13445KB] (0)
摘要:
An electrochemical biosensor for non-enzyme glucose detection was constructed based on the synergistic action of gold (Au) nanoparticles and platinum (Pt) nanoparticles on the surface of a stainless steel acupuncture needle (AN), which was achieved by respectively electrodepositing. The functional interface (Pt/Au/AN) was characterized by a scanning electron microscope, showing that cabbage-like nanomaterials were uniformly and densely distributed on the surface of AN. Pt/Au/AN electrode also possessed outstanding electrochemical characteristics, which were studied by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Significantly, Pt/Au/AN electrode exhibited remarkably electrocatalytic activity toward glucose oxidation compared with Au/AN or Pt/AN electrode. The results indicated that the contact interface of bimetallic Pt/Au was the vital electrocatalytic site for glucose oxidation. A further study proved that the contact interface exhibited intrinsic features and distinct selectivity for sensing glucose. The prepared sensor showed a wide linear range from 0.1 to 35 mmol·L-1, and the detection limit of glucose was 0.076 3 mmol·L-1. The sensor showed great stability, excellent selectivity, and miniaturization. Furthermore, the sensor was successfully used for the detection of glucose in human serum.
Solvothermal Synthesis, Structure, and Fluorescence Properties of Four Organotin Complexes Based on m-Phthaloyl Bis(substituted salicylaldehyde acylhydrazone)
Yong-Lan FENG, Wu-Jiu JIANG, Fu-Xing ZHANG, Dai-Zhi KUANG
2022, 38(6): 1171-1179  doi: 10.11862/CJIC.2022.105
[摘要]  (23) [HTML全文] (23) [PDF 3683KB] (0)
摘要:
Four new organotin complexes based on m-phthaloyl bis(substituted salicylaldehyde acylhydrazone) (H4L), (SnR2)2L (1-4), were synthesized by solvothermal reaction of H4L with R32SnOH, or one-pot solvothermal reaction of m-phthaloyl hydrazide, 3-tert-butyl salicylaldehyde, and tricyclohexyltin hydroxide, where H4L=m-Ph (CONH—N=CH(o-OH)PhR1)2; R1=NEt2, R2=Ph (1); R1=3, 5-di-tert-butyl=3, 5-t-2Bu, R2=Ph (2); R1=3, 5-t-2Bu, R2=Cy (3); R1=3-tert-butyl=3-t-Bu, R2=Cy (4). And they were characterized by elemental analysis, IR, and (1H, 13C, and 119Sn) NMR. The structures of complexes 1-4 were confirmed by X-ray diffraction. Three"inward E-type"complexes 1-3 were formed by the inward orientation of two substituted salicylaldehyde acylhydrazone chains of H4L and coordination with tin atoms. And two substituted salicylaldehyde acylhydrazone chains were oriented outward and coordinated with tin atoms to form an"outward E-type"complex 4. Complexes 1, 2, and 4 belong to the triclinic P1 space group and complex 3 belongs to the monoclinic P21/c space group. The central tin and the coordination atom form a five-coordinate distorted triangular bipyramids configuration. The fluorescence properties of the ligands and the complexes-chloroform solution showed that when free ligand m-Ph(CONH—N=CH(o-OH)PhNEt2)2 (H4L1) with weak fluorescence and ligand m-Ph(CONH—N=CH(o-OH)Ph(3, 5-t-2Bu))2 (H4L2) without fluorescence coordinated with phenyltin or cyclohexyltin, the chloroform solution of the complexes emitted strong fluorescence.
Three Zn(Ⅱ)-MOFs Based on Imidazole Derivatives and 2, 5-Dimethoxyterephthalic Acid: Syntheses, Crystal Structures, and Fluorescence Properties
Ming-Feng SHI, Jiang-Hong GU, Yi WAN, Zhong-Xuan XU
2022, 38(6): 1180-1188  doi: 10.11862/CJIC.2022.121
[摘要]  (28) [HTML全文] (28) [PDF 15999KB] (0)
摘要:
In the presence of 2, 5-dimethoxyterephthalic acid (H2DTA), three 3D metal-organic frameworks, namely {[Zn(DTA)(1, 2, 4, 5-TIB)0.5]·1.5H2O}n (1), [Zn(DTA)(1, 4-BMIB)0.5(H2O)]n (2), and {[Zn(DTA)(1, 4-BMIN)]·H2O}n (3), have been synthesized by using imidazole derivatives 1, 2, 4, 5-tetra(1H-imidazol-1-yl)benzene (1, 2, 4, 5-TIB), 1, 4-bis(4-methyl-1H-imidazol-1-yl)benzene (1, 4-BMIB), and 1, 4-bis(4-methyl-1H-imidazol-1-yl)naphthalene (1, 4-BMIN) as ligands to react to zinc ions, respectively. Their structures and fluorescent properties were studied. Single crystal X-ray diffraction analysis reveals that all complexes belong to the monoclinic crystal system. Among them, complex 1 based on four-coordinated 1, 2, 4, 5-TIB is a four-connected framework with a point symbol of (62.84). Compared with complex 1, slim 1, 4-BMIB and 1, 4-BMIN ligands with low coordination numbers caused that complexes 2 and 3 are 2-fold interpenetration pcu-type and 3-fold interpenetration dia-type networks, respectively. Furthermore, the fluorescent properties of complexes 1-3 were also studied, and their emission spectra had a significant enhancement and blue shift compared to the emission peak of the ligands.
Rapid Construction of Two-Dimensional N, S-Co-doped Porous Carbon for Realizing High-Performance Lithium-Sulfur Batteries
Lin SUN, Jie XIE, Feng CHENG, Ruo-Yu CHEN, Qing-Li ZHU, Zhong JIN
2022, 38(6): 1189-1198  doi: 10.11862/CJIC.2022.116
[摘要]  (27) [HTML全文] (27) [PDF 8226KB] (0)
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In this work, based on the industrial refinery product of pitch, we have developed a simple method for the production of metal-free, nitrogen, and sulfur co-doping porous carbon nanosheets (NSPC). The obtained NSPC exhibited a high specific surface area (339 m2·g-1) and puissant adsorbability for sulfur fixation. At the same time, the co-doping of N and S can effectively improve the electrical conductivity of carbon nanomaterials, and further improve the adsorption and conversion reaction of lithium polysulfides (LIPSs). The NSPC/S electrode delivered superior cycling performance (762 mAh·g-1 at 0.6C after 200 cycles). This work represents a rapid and massive production of two-dimensional porous carbon materials with high content of N and S as the cathode for advanced lithium-sulfur batteries.
Anionic Modification of the Cu-Tb Single-Molecule Magnets Based on the Compartmental Schiff-Base Ligand
Wen-Jie JI, Cheng-Cai XIA, Xin-Yu ZHANG, Xin-Yi WANG
2022, 38(6): 1199-1208  doi: 10.11862/CJIC.2022.117
[摘要]  (25) [HTML全文] (25) [PDF 6453KB] (0)
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By using different anions, three Cu-Tb metal complexes, namely [Cu2(vanophen)2TbCl2(MeOH)2]Cl· 3MeOH (1), [Cu2(vanophen)2TbCl2(MeOH)2](TCNQ)1.5·2MeOH (2), and [Cu2(vanophen)2Tb2(N3)6]·2MeOH (3), based on the compartmental Schiff-base ligand H2vanophen (H2vanophen=N, N′-bis(2-oxy-3-methoxybenzylidene)-1, 2-phenylenediamine, TCNQ=7, 7, 8, 8-tetracyanoquinodimethane) have been synthesized and characterized structurally and magnetically. Except for the different charge-balancing anions, complexes 1 and 2 have a very similar trinuclear [CuTbCu] structure, where the Cu(Ⅱ) ions are in the [N2O4] coordination pockets of the ligands, while the Tb(Ⅲ) ion is coordinated by all or some of the oxygen atoms from the [O4] pocket of the ligands. The charge-balancing anion is a Cl- ion in 1, while the positive charge is balanced by one TCNQ-0.5 radical and a half of the TCNQ- radical in 2. As for complex 3, it has a tetranuclear [CuTb]2 structure, where two [CuTb] units are bridged by end-end and end-on azides. Magnetic studies revealed that both 1 and 2 are field-induced SMMs while 3 is a zero-field SMM. The energy barriers of 1 and 3 were estimated to be (11.1±0.3) cm-1 and (20.2±0.3) cm-1, respectively. As for complex 2, its energy barrier was lower than that of 1, which might be due to the weak magnetic interaction between the [CuTbCu] unit and the paramagnetic radical anions.

  

综述
介孔碳纳米材料的制备与改性
朱胜, 盛建, 贾国栋, 刘汉鼎, 李彦
2022, 38(1): 1-13  doi: 10.11862/CJIC.2022.006
[摘要]  (574) [HTML全文] (574) [PDF 34796KB] (574)
摘要:
介孔碳纳米材料因具有快速传输通道、优异的导电性、极高的比表面积和出色的化学稳定性在众多领域受到广泛关注。实现介孔碳纳米材料的可控制备和精准改性是当前的研究热点和重点。基于此,本文分析总结了这类材料的制备和改性方法,并讨论了存在的问题和未来研究方向。
论文
TiO2掺杂用于调变α-Al2O3中空纤维膜烧结性能与表面性质
刘华, 高雪超, 彭莉, 顾学红
2022, 38(1): 14-20  doi: 10.11862/CJIC.2022.014
[摘要]  (308) [HTML全文] (308) [PDF 12447KB] (308)
摘要:
利用相转化-高温烧结技术制备α-Al2O3中空纤维膜,系统研究了TiO2掺杂调变中空纤维膜的烧结性能与表面性质。结果表明,TiO2α-Al2O3之间的固相反应能够促进中空纤维的烧结,当TiO2掺杂量(物质的量分数)为1%~2%时,其烧结温度可以降到1 400℃,且机械强度保持不变;TiO2掺杂增加了中空纤维表面的羟基活性位点浓度,从而有利于CHA分子筛膜的生长;使用物质的量分数1%~3% TiO2掺杂的α-Al2O3中空纤维制备出高质量CHA分子筛膜,其用于乙醇/水(9∶1,w/w)溶液渗透汽化脱水时的分离因子均超过10 000。
还原氧化石墨烯负载球形金属酞菁电催化阴极氧还原反应性能
谭阿敏, 何洋, 刘布雷, 杨正超, 田敏, 张改
2022, 38(1): 21-30  doi: 10.11862/CJIC.2022.023
[摘要]  (299) [HTML全文] (299) [PDF 13364KB] (299)
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针对阴极氧还原反应(ORR)动力学缓慢和Pt/C类贵金属催化剂成本高等关键难题,我们设计、合成了醛基取代的球形金属酞菁M2Pc2(TA)4(M=Zn、Co、Fe),采用“π-π组装”技术将其负载到还原氧化石墨烯(rGO)上得到复合催化剂M2Pc2(TA)4/rGO,并对其形貌和结构进行表征。结果表明:通过“π-π堆积”作用将球形金属酞菁负载在rGO表面上后,金属酞菁的团聚现象得到明显改善。利用循环伏安法和线性扫描伏安法对材料催化ORR活性进行评价。结果表明:rGO能与球形金属酞菁产生协同效应,促进ORR过程中电子的转移,有效提升电催化活性。机理研究发现催化ORR过程为4电子过程且催化活性与中心金属d电子有关,催化ORR反应活性顺序为Fe2Pc2(TA)4/rGO>Zn2Pc2(TA)4/rGO>Co2Pc2(TA)4/rGO。
絮状三元镍钴铁氢氧化物电极材料的制备及其电化学储能性能
谢登奎, 范爱玲, 庞伟, 郭亚奇, 高殿超
2022, 38(1): 31-38  doi: 10.11862/CJIC.2022.024
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采用一步溶剂热法在泡沫镍(NF)基底上合成了镍钴氢氧化物、镍铁氢氧化物及镍钴铁氢氧化物3种电极材料,并对其电化学性能进行测试,结果表明:三元镍钴铁金属电极的储能性能要远大于其他2种二元金属电极,其在2 mA·cm-2电流密度下能达到5.11 F·cm-2的面积比电容,并且构筑的非对称超级电容器在功率密度为46.814 W·m-2时所能达到的最大能量密度为5.994 Wh·m-2。研究发现三元镍钴铁金属电极的优异储能性能可归因于其疏松的絮状结构使其在单位体积内具有更大的比表面积,能储存更多的电荷,同时掺杂钴、铁元素后,可增强电极内部电子转移,降低活性物质和电解液之间的接触电阻,提高导电性。
咔咯锰(Ⅴ)氧配合物与苯乙烯的氧原子转移反应机理
曾琪, 徐艳, 陈华彬, 许旋, 徐志广, 刘海洋
2022, 38(1): 39-45  doi: 10.11862/CJIC.2022.005
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采用密度泛函理论B3LYP方法研究了咔咯锰(Ⅴ)氧配合物(MnO corrole)与苯乙烯氧原子转移(oxygen atom transfer,OAT)反应途径和吸电子取代基的影响。计算结果发现氧原子进攻苯乙烯中双键的β碳原子形成过渡态,结合内禀反应坐标法(intrinsic reaction coordinate method,IRC)和最小能量交叉点(minimum-energy crossing point,MECP)计算,给出该反应发生直接氧转移的机理。咔咯大环中位连的吸电子五氟苯基可通过改变锰原子的亲电性,加大取代基与氧原子的静电排斥作用,增加MnO corrole的氧化性。反应能垒随五氟苯基数目的增加而降低,且三重态的反应能垒明显低于单重态。体系可从单重态反应物开始,在MECP处易发生自旋翻转并形成三重态,然后以能量更低的三重态过渡态反应路径进行氧转移反应直至生成产物。
两个三(邻溴苄基)锡羧酸酯的合成、结构及抗肿瘤活性
刘熙, 张复兴, 何丽芳, 李达伟, 曾维鸿, 江叔沄, 贺霞, 盛良兵, 朱小明
2022, 38(1): 46-52  doi: 10.11862/CJIC.2022.016
[摘要]  (248) [HTML全文] (248) [PDF 5369KB] (248)
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合成了2个有机锡羧酸酯化合物三(邻溴苄基)锡噻吩2-甲酸酯(1)和三(邻溴苄基)锡肉桂酸酯(2)。通过元素分析、红外光谱、核磁共振谱(1H、13C和119Sn)、差热分析、X射线单晶衍射方法对12进行了结构表征,对其结构进行了量子化学从头计算。结果显示,化合物12均为单锡核结构,锡原子均为四配位的畸变四面体构型。体外抗癌活性研究表明化合物12对人乳腺癌细胞(MCF-7)、人非小细胞肺癌细胞(A549)和人大细胞肺癌细胞(H460)均显示出较强的抑制活性。
CeTiO4/g-C3N4复合材料的制备及其高效的光催化染料降解性能
李中钦, 陈小卫, 王艳, 程婷, 黄毅, 董鹏玉, 王勿忧, 张蓓蓓, 奚新国
2022, 38(1): 53-62  doi: 10.11862/CJIC.2022.009
[摘要]  (314) [HTML全文] (314) [PDF 28404KB] (314)
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采用简单固相法成功制备了CeTiO4/g-C3N4-x(CTO/CN-xx g为g-C3N4的添加量)复合材料,并通过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)、N2吸附-脱附测试、紫外可见吸收光谱(UV-Vis)及电化学测试对材料进行表征。研究发现:CeTiO4与g-C3N4层状纳米片紧密复合,并成功构建了界面异质结结构;形成CTO/CN-x复合相的光催化材料具有良好的可见光光响应性能,且光生空穴-电子对的分离和迁移率明显提高;通过太阳光模拟不同样品光催化降解有机污染物罗丹明B,降解140 min后复合材料CTO/CN-6表现出最高的光催化活性,反应速率常数为0.020 2 min-1。其活性增强的主要原因是异质结结构的构筑降低了CTO光生载流子的复合几率,提高了光生载流子的迁移速率。
氮掺杂碳纤维负载镍钴硒化物的制备及其电催化析氢性能
于静, 张婷, 刘琦, 刘婧媛, 王君
2022, 38(1): 63-72  doi: 10.11862/CJIC.2022.021
[摘要]  (261) [HTML全文] (261) [PDF 15848KB] (261)
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以静电纺丝制备的纤维为前驱体,通过煅烧、硒化处理等工艺合成了负载双金属硒化物纳米粒子的氮掺杂碳纤维(NCF)材料((Ni,Co)Se2/NCF),并对其进行了一系列相关的表征,研究了其在酸性和碱性条件下的析氢性能。(Ni,Co)Se2纳米粒子被锚定于NCF中,有效地阻止了纳米粒子的聚集,提供了更多的催化活性位点。电催化析氢性能测试的结果表明:在1 mol·L-1KOH溶液中,(Ni,Co)Se2/NCF在10 mA·cm-2电流密度下所需的过电位为102.3 mV,塔菲尔斜率为144.0 mV·dec-1。在0.5 mol·L-1 H2SO4溶液中,(Ni,Co)Se2/NCF达到10 mA·cm-2电流密度所需的析氢过电位为95.5 mV,塔菲尔斜率为115.2 mV·dec-1,表现出优异的电催化析氢性能。
光还原法合成Pt/Fe2O3/氮掺杂还原氧化石墨烯催化剂及其抗烧结性能
李志慧, 王云鹏, 符婉琳, 朱明芸, 柴蕴玲, 吴敏, 孙岳明, 代云茜
2022, 38(1): 73-83  doi: 10.11862/CJIC.2022.001
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摘要:
采用静电纺丝法获得的多孔Fe2O3纳米棒与氮掺杂还原氧化石墨烯(N-RGO)的复合材料作为载体,通过光还原法成功制备清洁、高活性的Pt/Fe2O3/N-RGO催化剂,并进一步研究其中的光还原反应机理和催化剂的抗烧结性能。研究结果表明,在可见光照射下,Fe2O3对光的强吸收作用促使光生电子和空穴的产生,N-RGO有效延长光生载流子的寿命,使得电子从O2-转移到Fe3+。Fe2O3/N-RGO中部分还原的Fe2+具有较强的还原能力,可使PtCl62-在Fe2O3表面还原并迅速成核,生长为粒径约2.13 nm的Pt纳米颗粒。此外,甲醇作为空穴清除剂可以快速有效地消耗掉扩散到载体表面的光生空穴,使导带中积累的电子与PtCl62-发生还原反应,从而提高Pt纳米颗粒的光还原速率。电纺Fe2O3纳米棒独特的粗糙表面为Pt纳米颗粒异相成核提供了大量活性位点。富含点缺陷的N-RGO片层能缩短Fe2O3的光生载流子扩散路径,提高光沉积的效率;同时,其特征褶皱结构可以作为物理屏障,防止Pt纳米颗粒聚集。得益于金属与载体间的强相互作用,在500℃高温老化后,Pt纳米颗粒仍能维持较小的尺寸(2.67 nm),表现出优良的抗烧结性能。在对硝基苯酚加氢反应中,Pt/Fe2O3/N-RGO在400℃老化后仍具有高达22.2 L·g-1·s-1的反应速率常数,约为老化前的1.6倍。
ZnS/SiO2协同包覆光阳极制备高效率Zn-Cu-In-Se量子点敏化太阳能电池
李健豪, 宋含, 张争艳, 潘振晓, 钟新华
2022, 38(1): 84-92  doi: 10.11862/CJIC.2022.025
[摘要]  (244) [HTML全文] (244) [PDF 10025KB] (244)
摘要:
通过光阳极协同包覆的策略抑制Zn-Cu-In-Se(ZCISe)量子点敏化太阳能电池(QDSC)中光阳极/电解液界面上的电荷复合过程,提高电荷收集效率和电池光伏性能。采用溶液法在ZCISe量子点敏化的光阳极表面依次沉积包覆ZnS和SiO2双钝化层,实现较单一ZnS包覆层更有效的界面电荷复合抑制作用,从而提高QDSC的性能。在包覆ZnS/SiO2双钝化层后,所组装的ZCISe QDSC光电转换效率由传统单一ZnS包覆的12.17%提高到13.23%,这归因于双钝化层对光阳极/电解液界面电荷复合过程的有效抑制,电荷收集效率得到相应提升。
pH调控Y型分子筛负载阿霉素纳米药物制备及与MM-231细胞的作用
任晶, 闫锦慧, 张安懿, 闫宇星, 王存存, 李林
2022, 38(1): 93-102  doi: 10.11862/CJIC.2022.019
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针对抗肿瘤小分子药物靶向性差、疗效低和毒副性大等缺陷,我们以Y型分子筛(YMS)为基体、阿霉素(DOX)为药物模型,通过pH调控,借助氢键和范德华力等物理作用力制备得到高负载Y型分子筛纳米药物体系(YMS-DOX)。采用UV-Vis、FT-IR、粒径和电位测试及荧光光谱证实YMS-DOX成功制备,且DOX的负载率可高达99.61%。体外药物释放测试发现YMS-DOX具有pH响应释放特性,在肿瘤环境中(pH=4.5)的药物释放量为正常生理环境(pH=7.4)中的3.8倍,表明其具有良好的药物输送特性。此外,利用流式细胞术和MTT测试法探究了YMS-DOX对乳腺癌细胞(MM-231)和树突细胞(DC)的细胞凋亡和毒性,结果表明YMS-DOX可以诱导肿瘤细胞凋亡,且可降低对正常细胞的毒副作用。
双(3-乙氧基水杨醛)缩间苯二甲酰腙四丁(苯)基二锡的合成、结构和荧光性质
冯泳兰, 王莹, 蒋伍玖, 庾江喜, 张复兴, 邝代治
2022, 38(1): 103-110  doi: 10.11862/CJIC.2022.026
[摘要]  (259) [HTML全文] (259) [PDF 4126KB] (259)
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在乙醇溶液中以3-乙氧基水杨醛和间苯二甲酰肼反应,制备双(3-乙氧基水杨醛)缩间苯二甲酰腙(H4L)配体。用H4L分别与二丁基氧化锡和三苯基氢氧化锡甲醇溶剂热反应,合成了双(3-乙氧基水杨醛)缩间苯二甲酰腙四丁(苯)基二锡配合物:Bu4Sn2L(T1)和Ph4Sn2L(T2)。用元素分析、红外光谱、紫外可见光谱、核磁共振谱以及单晶X射线衍射表征了H4L和配合物的结构。H4L的分子式为C26H26N4O6,晶体属单斜晶系C2/c空间群,2个甲酰肼缩(3-乙氧基)水杨醛呈顺式对称构型。T1的分子式为C42H58N4O6Sn2,晶体属正交晶系Pbcn空间群,H4L的2个甲酰肼缩(3-乙氧基)水杨醛链向内翻转180°,配位原子与锡配位构成畸形三角双锥构型,分子结构关于C2…C4轴对称。T2的分子式为C50H42N4O6Sn2,晶体属三斜晶系P1空间群,配体的一个甲酰肼缩(3-乙氧基)水杨醛保持原构型,另一个甲酰肼缩(3-乙氧基)水杨醛向内翻转180°,形成2个不同构型取向的配位链,分别与二苯基锡配位形成反式双核不对称畸形三角双锥构型的配合物。H4L、T1T2的氯仿溶液(50 μmol·L-1)的荧光光谱表明:H4L在520 nm有弱荧光,T1T2在518 nm具有比配体强14~15倍的荧光发射峰。
铁铁基普鲁士蓝钠离子电池正极材料的共沉淀反应控制
阳澜, 夏鑫, 汪东煌, 周爱军
2022, 38(1): 111-118  doi: 10.11862/CJIC.2022.020
[摘要]  (395) [HTML全文] (395) [PDF 34420KB] (395)
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铁铁基普鲁士蓝(NaFeHCF)是一种较为理想的钠离子电池(SIBs)正极材料。但是,如何有效控制合成反应参数来提升NaFeHCF电极材料的循环稳定性仍然是当前需要解决的问题。采用简单的共沉淀法,探索了合成过程中配位剂添加与否和反应温度(0~80℃)的变化对NaFeHCF沉淀产物的形貌结构和电化学性能的协同影响。结果表明,在添加柠檬酸钠配位剂且合成温度为40℃时所得到的NaFeHCF正极材料在形貌、晶粒尺寸、结晶性等多方面具有综合优势,表现出最佳的循环稳定性,在120 mA·g-1的电流密度下循环1 500圈后仍然具有83.5 mAh·g-1的放电比容量,容量保持率为79.4%。
Ba0.6Sr0.4TiO3/聚偏氟乙烯-聚甲基丙烯酸甲酯复合材料的制备及其介电性能
吴思晨, 郭艺婷, 刘书航, 刘振楠, 史芳军, 李宁, 许杰, 高峰
2022, 38(1): 119-126  doi: 10.11862/CJIC.2022.012
[摘要]  (326) [HTML全文] (326) [PDF 9696KB] (326)
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采用流延热压工艺制备Ba0.6Sr0.4TiO3(BST)/聚偏氟乙烯(PVDF)-聚甲基丙烯酸甲酯(PMMA)复合薄膜,研究了PMMA含量对复合材料微观组织结构和介电性能的影响规律。结果表明,BST相能够均匀分散在聚合物基体中,归因于PMMA与PVDF良好的相容性,2种聚合物之间的界面不分明;随着PMMA含量的增加,复合材料的介电常数先降低后升高,耐击穿强度和介电可调性先增加后减少。PMMA含量(体积分数)为15%的BST/PVDF-PMMA15复合材料的综合性能最佳:介电常数为23.2,介电损耗为0.07,耐击穿强度为1 412 kV·cm-1,在550 kV·cm-1偏压场下,介电可调性为26.2%。
Articles
Constructing and Photocatalytic Performance of Flower-like CeO2/TiO2 Heterostructures
Hong-Xia WANG, Xin-Xing LI, Yu ZHOU
2022, 38(1): 127-136  doi: 10.11862/CJIC.2022.010
[摘要]  (350) [HTML全文] (350) [PDF 19341KB] (350)
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A kind of three-dimensional flower-like CeO2/TiO2 heterojunction as photocatalysts was designed by the solvothermal method. The photocatalytic activity was evaluated by the decomposition of methyl orange (MO) under xenon lamp irradiation. The results showed that the flower-like structure was composed of thin nanosheets, on which many CeO2 particles were uniformly attached. The molar ratio of Ce to Ti (nCe/nTi) and the solvothermal time influenced on the photocatalytic performance. When nCe/nTi=0.1 and the solvothermal time was 6 h, the photocatalytic activity of CeO2/TiO2 reached the best, and the degradation rate reached 95% under xenon lamp irradiation for 50 min. The results suggested that the photocatalytic activity of CeO2/TiO2 heterojunction was greatly improved, compared to TiO2, which was mainly the function of heterojunction formed by CeO2 and TiO2, and was conducive to the separation of photogenerated electrons and holes.
Synthesis of a Water-Stable Zn(Ⅱ)-Based Metal-Organic Framework for Luminescence Detecting Fe3+ and 2, 6-Dichloro-4-nitroaniline
Xiao-Qing WANG, Xue-Hui MA, Dou-Dou FENG, Jing TANG, Dan WU
2022, 38(1): 137-144  doi: 10.11862/CJIC.2022.015
[摘要]  (242) [HTML全文] (242) [PDF 14664KB] (242)
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A novel thermal-stable and water-stable Zn(Ⅱ)-based metal-organic framework (MOF), [Zn2(bcpp)2(1, 4bib)2]·1.5H2O (1) was synthesized by solvothermal method based on 3, 5-bis(4-carboxylphenoxy)pyridine (H2bcpp) and 1, 4 - bis(1 - imidazoly)benzene (1, 4 - bib). Complex 1 belongs to the monoclinic system with space group I2/a, which exhibits a 1D tubular structure. The adjacent 1D tubular structures are interpenetrated with each other to obtain a 3D supramolecular structure. Moreover, complex 1 exhibits excellent photoluminescence property, which can be applied as a"turn-off"fluorescence probe to detect Fe3+ ion and pesticide 2, 6-dichloro-4-nitroaniline in an aqueous solution with high selectivity and sensitivity.
Crystal Structures and Magnetic Properties of Ln2 Complexes Based on a Polydentate Schiff Base Ligand
Xiao-Li GAO, Wen-Ting LEI, Qing-Fang ZHANG, Yu ZHOU, Xiao-Min KANG
2022, 38(1): 145-152  doi: 10.11862/CJIC.2022.002
[摘要]  (296) [HTML全文] (296) [PDF 3513KB] (296)
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Three new Ln2 complexes based on a polydentate Schiff base ligand, namely [Ln2(L)2(acac)2(CH3OH)2]·2CH3OH (Ln=Sm (1), Gd (2), Ho (3), H2L=pyridine-2-carboxylic acid (1-methyl-3-oxo-butylidene)-hydrazide, Hacac =acetylacetone), have been synthesized by using solvothermal method. The crystal structures and magnetic properties of these complexes have been systematically studied. The crystal structures measurement results reveal that complexes 1-3 are isostructural and each eight-coordinated Ln (Ⅲ) ion possesses a square antiprism geometry; the adjacent central rare earth Ln(Ⅲ) ions are connected by two μ2-O to form a parallelogram [Ln2O2] core. The magnetic study showed that complex 2 displayed significant magnetic refrigeration property with a larger magnetic entropy (-ΔSmax) of 31.9 J·K-1·kg-1 at ΔH=70 kOe and T=2.0 K; while complex 3 shows slow magnetic relaxation behavior.
Mn-MOF Derived Mn2O3 Micromotors Applied to Removal of Methyl Blue in Water
Jing HUANG, Xin-Yu TIAN, Lan YANG, Xiao-Miao FENG
2022, 38(1): 153-160  doi: 10.11862/CJIC.2022.008
[摘要]  (275) [HTML全文] (275) [PDF 4524KB] (275)
摘要:
A Mn-based metal-organic framework (Mn-MOF) was selected as the precursors to prepare the Mn-MOF derivative (Mn2O3) microspheres. The Mn2O3 microspheres had a homogenous size of ca. 4 μm, with perfect sphere morphology, rough surface, good crystallinity and high yield. At the same time, the movement behavior of Mn2O3 micromotors under different conditions and the degradation properties of methyl blue (MB) were studied. As-prepared Mn2O3 micromotors had excellent autonomous movement ability, and their moving speed can reach 81.32 μm·s-1 in 10% H2O2 solution. Experimental results show that with the addition of H2O2, the Mn2O3 micromotors can effectively remove MB through degradation within 5 min.
Synthesis, Structures and Catalytic Activity in Knoevenagel Condensation Reaction of Two Diphenyl Ether Tetracarboxylic Acid-Co(Ⅱ) Coordination Polymers
Su-Qin ZHAO, Jin-Zhong GU
2022, 38(1): 161-170  doi: 10.11862/CJIC.2022.004
[摘要]  (281) [HTML全文] (281) [PDF 3963KB] (281)
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Two cobalt(Ⅱ) coordination polymers, namely [Co2(μ3-deta)(H2biim)3(H2O)2]n (1) and {[Co2((μ6-deta)(phen)2]·H2O}n (2), have been constructed hydrothermally using H4deta (2, 3, 3', 4' - diphenyl ether tetracarboxylic acid), H2biim (2, 2'-biimidazole), phen (1, 10-phenanthroline), and cobalt chloride at 160 ℃. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses, and single-crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that compounds 1 and 2 crystallize in the triclinic and monoclinic systems, space groups P1 and P21/c, respectively. Compound 1 discloses a 1D chain structure, and compound 2 features a 2D network. The catalytic activities in Knoevenagel condensation reaction of the compounds were investigated. Compound 1 exhibited excellent catalytic activity in Knoevenagel condensation reaction at room temperature.
Replacement of Carboxylate Ligand Substituent on Modulation of Structures and Magnetic Properties in Salen-Type Dinuclear Dy(Ⅲ) Complexes
Min LI, Hai-Peng WU, Sheng ZHANG, Yu-Fang LIU, Yong-Qiang CHEN, San-Ping CHEN
2022, 38(1): 171-180  doi: 10.11862/CJIC.2022.017
[摘要]  (279) [HTML全文] (279) [PDF 5222KB] (279)
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Three salen - type centrosymmetric dinuclear Dy (Ⅲ) complexes, [Dy2(Hhms)2(C(CH3)3COO)2(H2O)4](NO3)2 (1), [Dy2(Hhms)2(C14H9COO)2(C2H5OH)2(CH3OH)2][ZnCl4] (2), and [Dy2(Hhms)2(C6H3(NH2)2COO)2Cl2]·2CH3CN (3) (H2hms=(2-hydroxy-3-methoxybenzylidene)-semicarbazide), were isolated with different substituted carboxylic acid ligand, and were characterized structurally and magnetically. Structural analyses illustrate that the Dy (Ⅲ) ions in complexes 1 and 2 maintain similar monocapped square-antiprism geometries, but the coordination mode of carboxylate in 1 is different from that in 2; complexes 2 and 3 possess similar phenoxy oxygen and carboxylate bridged structure whereas the coordination geometries around the Dy(Ⅲ) ions are different between 3 and 2 due to the difference of coordinated small molecules. Magnetic characterizations reveal that significant single - molecule magnet (SMM) behavior was observed under zero dc field for complex 3, with an effective energy barrier to the reversal of magnetization of 96 K. Conversely, complex 1 only showed fast quantum tunneling relaxation even 2 was SMM-silent. Furthermore, the magneto-structural correlations in these Dy2 complexes were discussed. The results indicate that utility of carboxylate ligand substituent can give rise to good modulation in the molecular anisotropy and symmetry, hence the enhanced magnetic relaxation.