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综述
锂离子电池用钴基氧化物的结构设计及本征活性调控的研究进展
王雄, 王睿, 康巧玲, 李冬云, 徐扬, 葛洪良, 高峰, 陆轻铱
2022, 38(9): 1673-1689  doi: 10.11862/CJIC.2022.179
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摘要:
锂离子电池的商业石墨负极材料的容量已经接近理论值,限制了动力电池的发展,开发容量高、稳定性好、循环寿命长和倍率性能优良的新型负极材料显得尤为重要。钴基氧化物材料由于其具有较高的比容量,是锂离子电池的理想负极材料之一。本文分别从结构设计和化学成分调控2个方面,结合本课题组近年来的研究及国内外重要文献综述了钴基氧化物作为锂离子电池负极材料的研究进展。在结构设计方面,通过构建一维结构、二维结构、三维结构、空心结构、碳材料支撑结构以及异质结构来增加钴基氧化物的反应活性位点数量;而在化学成分调控方面则通过引入无定型结构、非金属杂原子掺杂、金属杂原子掺杂、构筑高熵氧化物来提高钴基氧化物的本征活性,从而提高钴基氧化物的锂离子电池性能。最后,对钴基氧化物在锂离子电池领域未来的发展进行了展望。
铁(Ⅱ)配位聚合物电致变色材料研究进展
束敏, 刘海涛, 彭胜, 武志荣, 张蕤, 李峰, 刘建
2022, 38(9): 1690-1706  doi: 10.11862/CJIC.2022.182
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电致变色是一种响应外部电刺激而发生颜色变化的现象,材料可以在不同的氧化还原状态之间进行可逆切换,从而在可见光或近红外区域产生新的吸收带。迄今为止,电致变色材料主要包括过渡金属氧化物、过渡金属配位聚合物、紫罗精、有机共轭聚合物等。过渡金属配位聚合物类电致变色材料兼具无机材料和有机材料的优点,具有广泛的应用前景。铁配位聚合物具有良好的氧化还原性质和丰富的电子跃迁,是一类性能优异的电致变色材料。本文综述了铁金属配位聚合物类电致变色材料的研究进展,主要从有机配体的臂形、种类和间隔基团等方面进行分类阐述。
论文
零维/二维MXene复合膜的制备及其超级电容器性能
王晨, 刘启航, 戚晨阳, 王琮钰, 赵晓莉, 杨晓伟
2022, 38(9): 1707-1715  doi: 10.11862/CJIC.2022.178
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采用水热法制备了0D/2D复合Ti3C2Tx MXene,利用X射线衍射、动态光散射和荧光光谱表征了其结构与形貌,结果表明形成了量子点吸附于纳米片的Ti3C2Tx复合结构(QDT)。相比未引入量子点的Ti3C2Tx,由QDT组装得到的自支撑膜电极的电化学性能有了显著提高:在三电极体系中,扫速为5 mV·s-1时,比电容为338 F·g-1,当扫速达到2 000 mV·s-1,电容保持率达到46%;在两电极体系中,0.5 A·g-1时的比电容达到216 F·g-1,10 000次循环后电容保持率为87%。以上性能可归结于:量子点提供了更多的离子吸附位点,且纳米片尺寸减小,缩短了离子传输路径。
Br掺杂Bi2WO6微球的制备及其光催化性能
周鑫, 张志, 陈飘, 杨水金, 杨赟
2022, 38(9): 1716-1728  doi: 10.11862/CJIC.2022.177
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以五水合硝酸铋和二水合钨酸钠为原料,以十六烷基三甲基溴化铵(CTAB)为溴源,制备Br掺杂Bi2WO6,通过调节CTAB的含量,利用水热法制备了Br掺杂量不同的Bi2WO6催化剂。以抗生素环丙沙星、诺氟沙星作为污染物,测试Br掺杂Bi2WO6催化剂的光催化性能。结果表明,2% 掺杂量(物质的量分数)的Bi2WO6相比于Bi2WO6的光催化降解性能最好。此外,通过X射线粉末衍射、红外光谱、扫描电镜、荧光光谱、X射线光电子能谱和拉曼光谱等一系列表征,对Br掺杂后催化剂的物相组成、微观形貌、光生电荷分离率和光学性质等进行分析。最后进行了自由基捕获实验并提出了可能的光催化机理。
表面硫化和磷化提升钼酸镍的析氢性能
姜仁政, 常峻华, 高颖, 张金凤, 李孟江, 谢英鹏
2022, 38(9): 1729-1738  doi: 10.11862/CJIC.2022.172
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首先通过水热过程在泡沫镍(NF)上生长出钼酸镍纳米棒阵列(NMO/NF),再依次利用水热硫化和气相磷化法改性钼酸镍纳米棒阵列获得三维自支撑析氢电催化剂(PS-NMO/NF)。研究表明,硫化作用诱导钼酸镍纳米棒阵列向类珊瑚球结构转变并形成具有高电化学活性表面积的无定形硫化物壳层,显著提高钼酸镍析氢反应(HER)活性。进一步磷化处理,表面形成的无定形磷酸盐与硫化物形成丰富的异质界面,促进了电子转移,进一步提升了电极的HER性能。在1 mol·L-1 KOH电解液中,电流密度为10 mA·cm-2时,PS-NMO/NF所对应的析氢过电势为93 mV;100 mA·cm-2的电流密度所对应的析氢过电势仅为180 mV,Tafel斜率为67 mV·dec-1,而且在20 h内可稳定运行,无明显衰减。
近红外光热转换剂氧缺陷二氧化钼的制备及其在光热治疗中的应用
王曾学, 刘艳, 赵盼, 张训迪, 阳一鸣, 孙鹏, 张秀云, 冯玉, 郑婷婷, 陈辰, 李伟
2022, 38(9): 1739-1751  doi: 10.11862/CJIC.2022.195
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通过水热合成法,以五氯化钼(MoCl5)为钼源,聚乙烯吡咯烷酮(PVP)为结构导向剂和还原剂,制备了二氧化钼(MoO2)纳米颗粒,对纳米材料进行X射线粉末衍射(XRD)、透射电镜(TEM)、紫外可见近红外(UV-Vis-NIR)吸收光谱、X射线光电子能谱(XPS)、电子自旋共振谱(EPR)等表征,结果表明制备的MoO2纳米颗粒粒度约18 nm,粒度均匀,具有丰富的氧缺陷,在650~1 100 nm的近红外区具有良好的光吸收能力。光热测试表明该材料100 μg·mL-1的水溶液10 min内升温达31.5 ℃,光热转换率高达67.9%,并且具有优异的光热稳定性。细胞毒性实验表明低剂量的该纳米材料对细胞几乎没有毒性,且对肝癌细胞的光热杀伤效果明显。
双金属有机骨架衍生的Fe-CrSe/C负极材料制备及储锂性能
陈修栋, 简佳琴, 严平, 刘培芳, 曹小华, 刘金杭
2022, 38(9): 1752-1758  doi: 10.11862/CJIC.2022.198
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为了开发电化学性能优异的新型金属有机骨架基衍生材料,以对苯二甲酸、三氯化铬和九水合硝酸铁作为原料,通过微波法合成了双金属有机骨架材料(Fe-Cr-MOF)。在氮气保护下,对Fe-Cr-MOF进行高温硒化得到纳米颗粒状Fe-CrSe/C复合材料,用作锂离子电池负极。结果表明,在100 mA·g-1的电流密度下,Fe-CrSe/C电极的首圈可逆比容量达到958.4 mAh·g-1,循环150圈后比容量还能维持891.6 mAh·g-1
Fe3O4/MAl水滑石(M=Zn、Co、Ni)复合物光催化降解亚甲基蓝的性能、动力学与机理
倪梯铜, 孟跃, 青木功荘, 姚屹洋, 唐浩东, 陈爱民, 夏盛杰
2022, 38(9): 1759-1770  doi: 10.11862/CJIC.2022.171
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基于低成本、无毒害、光吸收性强的四氧化三铁(Fe3O4)和大比表面、高稳定性的水滑石(LDHs),制备了Fe3O4@MAl-LDHs (M=Zn、Co、Ni)复合物并用于典型偶氮染料亚甲基蓝的光催化降解。通过X射线粉末衍射(XRD)、紫外可见(UV-Vis)吸收光谱、扫描电子显微镜(SEM)、透射电子显微镜(TEM)以及N2吸附-脱附测试表征了复合材料的组成与结构。光催化实验表明,最佳反应条件为催化剂用量50 mg、光照强度500 W、pH=9、反应温度40 ℃,此时,Fe3O4@MAl-LDHs复合材料对亚甲基蓝的降解率从LDHs的23.2% 大幅提升到87.0%。LDHs对亚甲基蓝的降解主要来自·OH,而Fe3O4@CoAl-LDHs光降解活性的贡献主要由·OH和空穴提供。此外,LDHs和Fe3O4@CoAl-LDHs的电化学性质也存在较大差异。
含共轭三烯吡啶配体的配位聚合物的合成、结构及荧光性质
王鑫, 王梦凡, 张敏杰, 曹晨, 牛政, 郎建平
2022, 38(9): 1771-1780  doi: 10.11862/CJIC.2022.197
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将1,6-双(4-吡啶基)-1,3,5-己三烯(bphte)和镉盐分别与2种羧酸配体(2,5-二呋喃二甲酸(2,5-H2FDC)及1,3,5-均苯三甲酸(1,3,5-H3BTC))进行溶剂热反应,得到2个配位聚合物:[Cd(2,5-FDC)(bphte)(H2O)]n (1)和[Cd(1,3,5-HBTC)(bphte)]n (2)。对配合物12分别进行了元素分析、红外光谱、单晶X射线衍射、粉末X射线衍射和热重分析表征。配位聚合物1具有spl拓扑结构的三维互穿超分子框架,而配合物2是由bphte配体交叉连接一维链[Cd2(1,3,5-HBTC)2]n形成的三维结构。配合物12在固态时表现出不同的荧光性质。配合物2遇到水溶液中Fe3+会发生荧光猝灭,因此以其作为荧光探针对水溶液中Fe3+进行了选择性荧光检测,它对Fe3+的检测限可达到0.013 μmol·L-1。这种荧光猝灭过程可归因于Fe3+离子的吸收带与配合物2的激发带之间存在部分重叠。
MFI沸石纳米片及b轴取向MFI沸石薄膜的制备
宋文森, HammadSaulat, 颜韬, 吕金印, 杨建华, 鲁金明, 张艳
2022, 38(9): 1781-1789  doi: 10.11862/CJIC.2022.159
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我们通过自下而上(bottom-up)的方法制备了高宽深比、高结晶度的b轴方向上超薄的MFI沸石纳米片,为制备b轴取向MFI沸石薄膜提供了基础。采用滑动涂覆法(slip coating method)在玻璃片载体上制备了厚度约为100 nm的b轴取向MFI纳米片晶种层。采用无模板剂二次生长法,抑制晶种层面外孪晶生长,实现了晶种层的面内外延生长。在合成体系的nSiO2nNa2OnC2H5OHnH2O=1∶0.03∶1.3∶0.89、晶化时间48 h、晶化温度180 ℃时,制备了厚度约为200 nm的连续致密的b轴取向MFI沸石膜,与基于四丙基氢氧化铵(TPAOH)的常规合成溶液水热二次生长制备的MFI沸石膜相比,厚度降低了90%,并且保持了晶种层的b轴取向性。
Articles
Synthesis, Crystal Structures, and DNA-Binding Properties of Cd(Ⅱ)/Fe(Ⅲ) Complexes with 4-Fluorophenyl-N-(quinolin-2-ylmethylene)thiosemicarbazide
Xiao-Hong LI, Xian-Wei WU, Yuan WANG, Wei-Na WU
2022, 38(9): 1790-1798  doi: 10.11862/CJIC.2022.176
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Two complexes [Cd2(L)2(NO3)2] (1) and [Fe(L)2]NO3·3CH3OH (2), as well as (H2L)NO3 (HL=4-fluorophenyl-N-(quinolin-2-ylmethylene)thiosemicarbazide) have been synthesized and structurally determined by single-crystal X-ray diffraction, elemental analysis, and IR. The results show that 1 is a centrosymmetry binuclear complex, in which each central Cd(Ⅱ) ion is coordinated by one independent anionic ligand L- with a [N2S] donor set, one bidentate nitrate anion, and another μ2-bridged S atom from the adjacent thiosemicarbazone, thus providing a distorted octahedron geometry. The Fe(Ⅲ) ion in complex 2 displays the same coordination geometry as the Cd(Ⅱ) ion in 1, while is surrounded by two tridentate L- ligands. The fluorescence spectra, the absorption spectra, and the viscosity measurements indicate that complex 2 could effectively bind with ct-DNA through intercalation mode, while HL and complex 1 might interact with ct-DNA by outside groove binding mode, and the binding affinity of complex 2 with ct-DNA was stronger than those of HL and complex 1. In addition, the results of cytotoxicity experiments showed that complex 2 had the strongest ability to inhibit the proliferation of HeLa tumor cells among the three compounds.
Semiconductive Ni-MOFs Based on 5-(Hydroxymethyl) Isophthalic Acid and Imidazole Derivatives: Synthesis, Crystal Structures, and Photocatalytic Properties
Zhong-Xuan XU, Ming-Feng SHI, Xu-Ling BAI, Ting-Ting YUAN
2022, 38(9): 1799-1807  doi: 10.11862/CJIC.2022.175
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Two complexes {[Ni(HIPA) (2, 5-DPBI)1.5(H2O)]·2.25H2O}n (1) and [Ni(HIPA) (2, 5-DPBMI) (H2O)]n (2) (H2HIPA=5-(hydroxymethyl) isophthalic acid, 2, 5-DPBI=1, 1'-(2, 5-dimethyl-1, 4-phenylene)bis(1H-imidazole), 2, 5-DPBMI=1, 1'-(2, 5-dimethyl-1, 4 -phenylene)bis(4-methyl-1H-imidazole)) were synthesized via hydrothermal method. Structural analysis reveals that Ni(Ⅱ) centers have different coordination environments in the existence of different imidazole ligands. As a result, complex 1 possesses a 5-connected framework with the topological symbol of (42.66.82), while complex 2 shows a 4-connected framework with dia net. The powder X -ray diffraction further firms that complexes 1 and 2 are very stable not only in a normal organic solvent but also in water under UV light. Moreover, the UV-Vis spectra, Mott-Schottky measurements, and electrochemical impedance spectroscopy (EIS) demonstrate that complex 1 and 2 are typical n-type semiconductors with low resistance in charge transportation. Finally, photocatalytic tests confirm that complexes 1 and 2 have catalytic activity for the degradation of methylene blue.
Synthesis, Crystal Structure, and Catalytic Performance of a Cd(Ⅱ) Complex Based on 3-Carboxyl-5-ammino-1, 2, 4-triazole
Xue-Zhi GAO, Huan SONG, Bing LI, Rui WANG, Xiao-Shuang ZHU, Xiao-Yan TIAN
2022, 38(9): 1808-1816  doi: 10.11862/CJIC.2022.193
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Triazole -derived energetic complexes have paid significant attention in the field of energetic materials. An energetic complex [Cd(Hatzc)2(H2O)] (LH1) (H2atzc=3-carboxyl-5-amino-1, 2, 4-triazole) was synthesized and fully characterized by single crystal X-ray diffraction, elemental analysis, infrared spectral analysis, and thermogravimetric analysis. LH1 belongs to the monoclinic system, space group P21/n. The structural analyses illustrate that LH1 exhibits a 1D chain, which is linked by hydrogen-bonding interactions to give a 3D supramolecular architecture. Complex LH1 had high detonation velocity (D=10.4 km·s-1), detonation pressure (p =55.2 GPa), energy of detonation (16.51 kJ·g-1), and density (2.363 g·cm-3), which were superior to most of the energetic compounds. The impact sensitivity (> 40 J) and friction sensitivity (> 360 N) reveal that LH1 is less sensitive to impact and friction. The results of the catalytic thermal decomposition of ammonium perchlorate (AP) show that LH1 decreased the higher thermal decomposition temperature of AP by 38 ℃ and increased the exothermic quantity of decomposition by 0.46 kJ·g-1 in a short time, which showed a good catalytic effect on the thermal decomposition of AP.
An Interpenetrated Anionic In(Ⅲ) Metal-Organic Framework for Selective Sensing of Fe3+ in Water
Alamgir, Yan-Long ZHAO, Talha Khalid, Ya-Bo XIE, Lu WANG, Lin-Hua XIE, Xin ZHANG, Jian-Rong LI
2022, 38(9): 1817-1824  doi: 10.11862/CJIC.2022.174
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As an emerging type of porous material, metal-organic frameworks (MOFs) have been developed as sensors for monitoring environmental pollutants in water. It is of high significance to develop fluorescent MOFs with simple precursors for selective detection of toxic Fe3+ ions. In this work, we present a water-stable two-fold interpenetrated indium-based metal-organic framework (NH2Me2)[In(fdc)2]·2H2O named BUT-205 (BUT stands for Beijing University of Technology, H2fdc=furan -2, 5-dicarboxylic acid) constructed from a biomass-derived ligand. BUT-205 has been structurally characterized by single-crystal X-ray diffraction. BUT-205 was an efficient sensor for Fe3+ ions in water with high sensitivity and selectivity. The limit of detection (LOD) was calculated to be 1.3 μmol·L-1 being lower than the US-EPA (U. S. Environmental Protection Agency) standard (15.7 μmol·L-1) in drinking water. Furthermore, BUT-205 could be recycled and used for at least four cycles.
Three Multiple-Responsive Complexes Based on a Carboxybenzyl Viologen Ligand
Jin-Jian IU, Na LIU, Yi-Wei LU
2022, 38(9): 1825-1833  doi: 10.11862/CJIC.2022.184
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A carboxybenzyl viologen ligand 1, 1'-bis(4-carboxybenzyl)-4, 4'-bipyridinium dichloride ((H2Bpybc)Cl2) was used as the functional ligand, and the auxiliary ligand 1, 3, 5-benzene tricarboxylic acid (H3BTC) was introduced to self-assemble with different metal ions to synthesize three complexes: {[Cd(Bpybc)0.5(HBTC)(H2O)]·0.6H2O}n (1), [Ni(Bpybc)0.5(HBTC)(H2O)4] (2), and [Co(Bpybc)0.5(HBTC)(H2O)4] (3). The three complexes display different structural features, including a 2D structure of 1 and 0D structures of 2 and 3. Furthermore, these three complexes displayed different chromic properties. Complex 1 was photochromic only due to the generation of viologen radicals, while complexes 2 and 3 were photochromic originating from the photo-induced formation of viologen radicals accompanying the redox activity of metal ions. In addition, complex 2 showed thermochromic behavior, which is associated with the radical formation through electron transfer, while complex 3 exhibited a color change accompanying a reversible structural transformation due to dehydration and rehydration. These results suggest that metal ions play a significant role in regulating the structure and chromic behavior of viologen complexes.
Crystal Structure, Spectroscopic Characterization, and Optical Properties of the Hybrid Compound (C7H11N2)2[CdCl4]·0.5H2O
Garci Fatma, Klein Axel, Chebbi Hammouda, Faouzi Zid Mohamed
2022, 38(9): 1834-1842  doi: 10.11862/CJIC.2022.183
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摘要:
A preparation procedure for the title compound (C7H11N2)2[CdCl4]·0.5H2O (C7H11N2=4-(dimethylamino) pyridinium) was developed and gave good yields and purity. The Cd(Ⅱ) ion is coordinated in a slightly distorted tetrahedral environment by four chlorides. The crystal arrangement shows a layered structure with alternating organic and inorganic layers parallel to the (001) plane and located at x=n+1/2 (nZ). In the crystal, the organic and inorganic layers are linked by C—H…Cl, C—H…O, N—H…Cl and N —H…O hydrogen bonding interactions. Hirshfeld surface analysis and fingerprint plots of the structure reveal that molecular packing is governed by hydrogen bonds and π-stacking. The UV-Vis diffuse reflectance spectrum allowed us to determine a direct band gap of 3.596 eV with a semiconducting character, using the Tauc-extrapolation method. The observed photoluminescence band with a maximum at 562 nm is assigned to excited π-π* states in the 4-(dimethylamino)pyridinium cation.
Crystal Structure of Eu(Ⅲ) Coordination Polymer Based on Zwitterionic Ligand and Detection of Furacilin
Kai-Min WANG, Li-Feng LI, Ming-Feng SHI, Yan-Qing YE, Yu-Na WANG, Jin-Rong GUO, Huai-Jun TANG, Yu-Lu MA
2022, 38(9): 1843-1852  doi: 10.11862/CJIC.2022.196
[摘要]  (27) [HTML全文] (27) [PDF 5026KB] (0)
摘要:
A novel coordination polymer, {[Eu(L)2(H2O) 4]Cl3·2H2O}n (1) (L=1, 1'-((2, 3, 5, 6-tetramethyl-1, 4-phenylene) bis(methylene))bis(pyridin-1-ium-4-carboxylate)), was synthesized under hydrothermal conditions by a zwitterionic organic ligand and characterized by single crystal X-ray diffraction. Powder X-ray diffraction, IR, thermogravimetry, and luminescence properties of 1 were also determined. The solid-state luminescence properties of 1 were investigated, realizing the zwitterionic ligand is an excellent antenna chromophore for sensitizing Eu3+ ions. In addition, this water-stable 1 was utilized as a chemosensor to detect various common antibiotics to find that this one can exhibit high selectivity, sensitivity, and recyclability in the detection of furacilin molecules in aqueous phases.
Synthesis, Crystal Structure, and DNA Binding/Cleavage Properties of a Macrocyclic Heterobinuclear Zn(Ⅱ)-Ni(Ⅱ) Complex with Pyridylmethyl Pendant-Arms
Pei-Pei DING, Ming LI, Yu WU, Jun-Tao YAN, Chun-Lei WANG, Yang WANG, Jia-Wei MAO
2022, 38(9): 1853-1861  doi: 10.11862/CJIC.2022.199
[摘要]  (31) [HTML全文] (31) [PDF 1697KB] (0)
摘要:
A bis-pyridine pendant-armed macrocyclic heterobinuclear Zn(Ⅱ)-Ni(Ⅱ) complex [ZnNi(L)](ClO4)2·H2O (H2L=3, 3'-((ethane-1, 2-diylbis((pyridin-2-ylmethyl)azanediyl))bis(methylene)) bis(2-hydroxy-5-methylbenzaldehyde)) has been obtained and characterized by spectroscopy, elemental analysis and single-crystal X-ray diffraction. The coordination environment of Zn(Ⅱ) and Ni(Ⅱ) can be described as approximately distorted triangular prism and square pyramid, respectively. The Zn—Ni distance bridged by two phenoxide groups is 0.303 63(6) nm. The interaction between the complex and calf thymus DNA (CT-DNA) has been further confirmed by UV-Vis spectrophotometry, viscosity, and cyclic voltammetry study. The complex showed a good binding property to CT-DNA with a binding constant of 1.05×105 L·mol-1. The DNA cleavage activity has also been investigated using agarose gel electrophoresis.
One-Pot Preparation of Fe2O3/Fe2TiO5 S-Scheme Heterojunction Photocatalyst for Highly Efficient Degradation of Organic Pollution
Fang CHANG, Ying-Jie ZHAO, You-Ping SHOU, Lu ZHANG, Jiang-Nan WANG, Ting-Ting SHI
2022, 38(9): 1862-1870  doi: 10.11862/CJIC.2022.173
[摘要]  (27) [HTML全文] (27) [PDF 4950KB] (0)
摘要:
For the first time, Fe2O3/Fe2TiO5 heterojunction materials have been fabricated by a facile one-pot solvothermal method. After the construction of the S-scheme heterojunction, compared to pure Fe2O3 and Fe2TiO5, the photocatalytic degradation rate and efficiency of Fe2O3/Fe2TiO5 were significantly improved. After being illuminated for 2.5 h, nearly 100% of methylene blue (MB) has been degraded by Fe2O3/Fe2TiO5. In Fe2O3/Fe2TiO5 composite material, a built-in field is formed between Fe2O3 and Fe2TiO5, thus promoting the separation of photogenerated electron-hole pairs. Therefore, electrons in the conduction band (CB) of Fe2TiO5 and holes in the valence band (VB) of Fe2O3 with higher energy, which show high reduction and oxidation capacity, respectively, can retain and transfer to the surface to participate in the degradation reaction. Moreover, Fe2O3/Fe2TiO5 composite showed good photocatalytic stability.
Synthesis, Crystal Structure, and Detection of Acidic Amino Acids of a Cd(Ⅱ) Metal-Organic Framework Based on 5-((Naphthalen-1-ylmethyl)amino)isophthalic Acid
Ling-Wen ZHANG, Shu-Qin LIU, Pei-Pei ZHANG, Ai-Yun NI, Jian-Jun ZHANG
2022, 38(9): 1871-1877  doi: 10.11862/CJIC.2022.181
[摘要]  (33) [HTML全文] (33) [PDF 2357KB] (2)
摘要:
A 2D layered metal-organic framework [Cd(L) (H2O)]·H2O (1) was synthesized from 5-((naphthalen-1-ylmethyl)amino)isophthalic acid (H2L) and Cd2+ by a solvothermal method. Structural analysis reveals that the adjacent layers are connected by π-π stacking and C—H⋯π interactions to form a 3D supramolecular structure. Notably, the luminescence of 1 was significantly enhanced under acidic conditions, which can be used for selective and sensitive detection of acidic amino acids. The limits of detection of 1 for aspartic acid and glutamic acid were 3.88 and 5.43 μmol·L-1, respectively.
Zinc(Ⅱ) and Cadmium(Ⅲ) Complexes Derived from 4′-(2-Pyridyl)-2, 2′: 6′, 2″-terpyridine: Crystal Structures and Fluorescence Property
Ya-Nan YUAN, Zi-Xuan WANG, Zhao-Yang WANG, Yao-Yao SONG, Qing-Lun WANG, Chun YANG
2022, 38(9): 1878-1886  doi: 10.11862/CJIC.2022.194
[摘要]  (30) [HTML全文] (30) [PDF 2989KB] (0)
摘要:
Complexes [Zn(2-pyterpy)2](ClO4)2·0.25H2O (1) and [Cd(2-pyterpy)2]2(ClO4)4·2.33H2O·CH3OH(2)(2-pyterpy=4'-(2-pyridyl)-2, 2'∶6', 2″-terpyridine) were synthesized under solvothermal conditions, and structurally characterized by elemental analysis, FT-IR spectra, X-ray single crystal diffraction and powder X-ray diffraction. X-ray single crystal diffraction results show that they crystallize in the triclinic system with the P1 space group. In solidstate, complexes 1 and 2 showed the maxima emission band approximately at 539 and 547 nm upon excitation at 405 nm, respectively. In methanol solution, complexes 1 and 2 exhibited emissions at 408 and 371 nm upon excitation at 357 and 352 nm, respectively. The metastable-state photoacid mPAH1 showed fluorescence at 556 nm upon excitation at 467 nm. When complex 1 was titrated with mPAH1, the fluorescence of complex 1 at 408 nm was quenched by mPAH1 with a quenching constant KSV of 2.961×104 L·mol-1, but the fluorescence lifetime of complex 1 remained nearly unchanged, which is attributed to the inner filter effect. Conversely, titration of mPAH1 with complex 1 resulted in enhanced fluorescence of the mixed solution at 556 nm, which is attributed to partial protonation of complex 1 by mPAH1.

  

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]  (826) [HTML全文] (826) [PDF 34796KB] (826)
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]  (445) [HTML全文] (445) [PDF 12447KB] (445)
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]  (440) [HTML全文] (440) [PDF 13364KB] (440)
摘要:
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
[摘要]  (451) [HTML全文] (451) [PDF 4242KB] (451)
摘要:
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
[摘要]  (442) [HTML全文] (442) [PDF 2424KB] (442)
摘要:
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]  (347) [HTML全文] (347) [PDF 5369KB] (347)
摘要:
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]  (450) [HTML全文] (450) [PDF 28404KB] (450)
摘要:
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]  (384) [HTML全文] (384) [PDF 15848KB] (384)
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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
[摘要]  (456) [HTML全文] (456) [PDF 14635KB] (456)
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]  (341) [HTML全文] (341) [PDF 10025KB] (341)
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
[摘要]  (480) [HTML全文] (480) [PDF 13947KB] (480)
摘要:
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]  (366) [HTML全文] (366) [PDF 4126KB] (366)
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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]  (593) [HTML全文] (593) [PDF 34420KB] (593)
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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]  (515) [HTML全文] (515) [PDF 9696KB] (515)
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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]  (496) [HTML全文] (496) [PDF 19341KB] (496)
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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]  (346) [HTML全文] (346) [PDF 14664KB] (346)
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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]  (392) [HTML全文] (392) [PDF 3513KB] (392)
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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]  (370) [HTML全文] (370) [PDF 4524KB] (370)
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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]  (392) [HTML全文] (392) [PDF 3963KB] (392)
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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]  (376) [HTML全文] (376) [PDF 5222KB] (376)
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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.