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锆基金属有机骨架材料用于四甲基硅烷/异戊烷分离
王月, 李咸贞, 来雨洁, 牛政
2023, 39(10): 1841-1847  doi: 10.11862/CJIC.2023.163
[摘要]  (121) [HTML华泰娱乐地址] (121) [PDF 3742KB] (5)
摘要:
在半导体工业中,从四甲基硅烷(TMS)/异戊烷混合物中高效捕获异戊烷从而获得超高纯度的TMS是非常重要的。在本工作中,我们选择了具有笼结构的MOF-801,通过其对TMS和异戊烷吸附能力的差异,实现了TMS与异戊烷的分离。气体吸附测试结果表明,在298 K和60 kPa时,MOF-801对异戊烷吸附量为2.56 mmol·g-1,而其对TMS的吸附量为1.20 mmol·g-1。理想吸附溶液理论(IAST)计算结果表明,MOF-801对TMS/异戊烷(95∶5,体积比)混合物的分离选择性达到105.8。而之后的液相吸附分离实验进一步验证了MOF-801的分离效果,最终可以得到体积分数大于99.98%的TMS。
微波原位合成Ag NPs/MoS2复合材料及其电化学性能
杨松松, 韩璐, 蔡和庆, 胡堃, 刘儒平, 孙志成, 危岩
2023, 39(10): 1848-1856  doi: 10.11862/CJIC.2023.155
[摘要]  (134) [HTML华泰娱乐地址] (134) [PDF 16056KB] (1)
摘要:
二硫化钼纳米片(MoS2)受到带电杂质、结构缺陷和易聚集等因素的影响,导致其电子转移性能下降,使其应用受限。将银纳米颗粒(Ag NPs)与少层MoS2纳米片复合,可提升MoS2纳米片的电化学性能。本研究创新性地采用微波还原法,使Ag NPs原位沉积于MoS2,得到Ag NPs/MoS2复合材料。结果表明,将Ag NPs/MoS2复合材料修饰于丝网印刷电极(screen printed electrodes,SPE)后,测得的循环伏安(cyclic voltammetry,CV)曲线峰电流值为同浓度单一MoS2修饰电极的1.8倍,方波伏安(squarewave voltammetry,SWV)曲线峰电流值为单一MoS2修饰电极的3.4倍,电化学阻抗谱(electrochemical impedance spectroscopy,EIS)的电子转移阻抗值(R et)仅为167 Ω,相比MoS2/SPE的R et (320 Ω)显著减小,说明Ag NPs与MoS2复合可显著增强单一MoS2的电化学性能。此外,还推测了高导电性Ag NPs/MoS2复合材料的导电机理。最后,基于Ag NPs/MoS2复合材料构建了电化学传感器并对前列腺特异性抗原(PSA)进行检测。结果表明,该传感器针对PSA的检测限为0.009 ng·mL-1,线性检测范围为0.1~1 000 ng·mL-1,灵敏度为0.011 μA·mL·ng-1
5年被点名7次,广电总局发文禁止宣传槟榔及其制品
朱羽科, 蒋孝佳, 陈嘉奕, 付小航, 吴礼光, 王挺
2023, 39(10): 1857-1868  doi: 10.11862/CJIC.2023.164
[摘要]  (115) [HTML华泰娱乐地址] (115) [PDF 17598KB] (6)
摘要:
为了提升微污染水体中抗生素的降解效率,利用过硫酸钠(PDS)激活协同手性介孔TiO2可见光催化(PDS/vis-TiO2)对四环素(TC)进行降解。详细对比研究了以手性TiO2作为催化剂的PDS激活(PDS/TiO2)、可见光催化(vis-TiO2)和PDS/vis-TiO2三种体系中,降解污染物的活性物种和污染物降解路径等的差异。结果表明,不对称的螺旋堆积结构在手性介孔TiO2中引入了丰富的Ti3+,不仅提升了其可见光响应,同时能够激活PDS生成自由基。PDS/vis-TiO2体系中光生空穴h+和·OH等多种自由基可以同时参与TC的降解,5 h内其对TC去除率可达到95%以上,远超PDS/TiO2体系(TC去除率为48.9%)和vis-TiO2体系(TC去除率为71.1%)。PDS加入到光催化体系中,会受到光生电子的激活而产生自由基,从而消耗光生电子,提升光生空穴和电子的分离率,达到协同增强污染物的降解能力。另外PDS激活后产生自由基也会大大增加体系对TC的降解性能。密度泛函理论计算和中间产物分析结果表明,TC在PDS/vis-TiO2体系中的降解路径包含了光生空穴h+攻击TC的降解路径,同时也包括自由基攻击TC的降解路径。
芳基四硫富瓦烯与碘电荷转移复合物的合成及其晶体结构
左琦, 马龙飞
2023, 39(10): 1869-1876  doi: 10.11862/CJIC.2023.156
[摘要]  (93) [HTML华泰娱乐地址] (93) [PDF 11512KB] (5)
摘要:
采用缓慢挥发溶剂的方法合成了硫原子桥联芳基取代四硫富瓦烯(Ar-S-TTF)与碘的3种电荷转移复合物(1 )(I3)·I2、(2 )(I5)·I2和(3 2+)(I3)2,采用单晶X射线衍射、紫外可见光谱、循环伏安对其进行了表征。复合物(1 )(I3)·I2C2/c空间群,1 呈椅式构型。化合物1与碘之间在溶液中和复合物中电荷转移一致。复合物(2 )(I5)·I2P 1空间群,2 呈椅式构型。复合物(3 2+)(I3)2Pbca空间群,3 2+呈独特的平面构型。化合物23与碘之间在溶液中和复合物中呈现不同的电荷转移。复合物中聚碘阴离子呈现不同的堆积结构:由I3 -或I5 -/I2组成的一维链状和I3 -/I2组成的二维网格状。
水热老化对Cu改性的W/CeTi催化剂NH3-SCR性能的影响
高文翔, 文婕, 邓杰, 徐海迪, 陈永东
2023, 39(10): 1877-1886  doi: 10.11862/CJIC.2023.153
[摘要]  (72) [HTML华泰娱乐地址] (72) [PDF 32244KB] (2)
摘要:
采用浸渍法制备了CuW/CeTi和W/CuCeTi催化剂,考察了催化剂中Cu的不同作用方式对氨气选择性催化还原NO x (NH3-SCR)反应脱硝性能的影响。新鲜的CuW/CeTi和W/CuCeTi在低温下显示出优异的活性。经过800℃、10 h水热老化后,W/CuCeTi表现出比CuW/CeTi更优异的脱硝性能,证明W/CuCeTi具有更高的水热稳定性。通过透射电子显微镜(TEM)、X射线衍射(XRD)、拉曼光谱(Raman)、N2物理吸附-脱附、X射线光电子能谱(XPS)、氨气程序升温脱附(NH3-TPD)和氢气程序升温还原(H2-TPR)表征,发现Cu的掺杂形成的Cu-O-Ce结构能够提高CeTi的抗烧结能力,同时削弱W-CeO2相互作用,抑制老化过程中Ce2(WO4)3物质的形成,使W/CuCeTi表现出更优异的水热稳定性。
双核芳基Os(Ⅱ)配合物的合成及诱导肿瘤铁死亡机制
郭冰莲, 李季, 吕梦迪, 薛旭玲, 刘红科
2023, 39(10): 1887-1897  doi: 10.11862/CJIC.2023.160
[摘要]  (82) [HTML华泰娱乐地址] (82) [PDF 19078KB] (0)
摘要:
本文报道了一种双核锇Os(Ⅱ)配合物[Os (η 6-bip)(1,3-bib) Cl]2Cl2(bib-Os),其中η 6-bip=η 6-联苯,1,3-bib=1,3-二(1H-咪唑-1-基)苯。并通过1H NMR和ESI-MS进行基础表征。配合物bib-Os具有良好的脂溶性,易在细胞中积累。配合物bib-Os对人卵巢癌A2780细胞表现出高效的抗增殖活性,可产生活性氧(ROS)并诱导线粒体损伤。脂质过氧化物(LPO)积累、谷胱甘肽(GSH)消耗和谷胱甘肽过氧化物酶4(GPX4)下调表明,配合物bib-Os诱导A2780细胞死亡的主要机制是铁死亡,bib-Os是第一例诱导肿瘤细胞铁死亡的Os金属配合物。
La3+掺杂CaFe2O4材料的制备及室温检测超低浓度甲醛
白玉莹, 王春水, 李佳豪, 刘醒醒, 储向峰, 梁士明
2023, 39(10): 1898-1904  doi: 10.11862/CJIC.2023.165
[摘要]  (83) [HTML华泰娱乐地址] (83) [PDF 7270KB] (1)
摘要:
采用静电纺丝法成功制备了La3+掺杂CaFe2O4材料。通过X射线衍射、扫描电子显微镜和X射线光电子能谱对La3+掺杂CaFe2O4材料的结构和形貌进行了表征。随后,研究了La3+的掺杂量(质量分数)对CaFe2O4气敏性能的影响。研究表明,3% La3+掺杂CaFe2O4材料在室温下对100 μL·L-1甲醛的响应最高(R a/R g=14.1)。更为重要的是,对甲醛的最低检测限低至0.1 nL·L-1,并且响应/恢复时间仅为4.3 s/8.4 s。
NiFe水滑石纳米片阵列负载Ru用于提升碱性电催化析氢和析氧性能
李英杰, 王鑫, 周昱成
2023, 39(10): 1905-1913  doi: 10.11862/CJIC.2023.150
[摘要]  (133) [HTML华泰娱乐地址] (133) [PDF 22442KB] (0)
摘要:
通过离子交换的方式将Ru负载到NiFe水滑石(LDH)纳米阵列表面得到(Ru/NiFe LDH),Ru的引入显著提升了NiFe LDH的活性比表面积,暴露了更多的活性位点,同时调控了其电子结构,大大提升了其本征催化活性。在碱性条件下,催化析氢反应时仅需50 mV的过电位即可达到10 mA·cm-2的电流密度,Tafel斜率为52.3 mV·dec-1。而相同条件下原始NiFe LDH达到10mA·cm-2的电流密度则需要226 mV的过电位,Tafel斜率为157.5 mV·dec-1。同时制备的Ru/NiFe LDH也展现出了良好的析氧催化活性,在50 mA·cm-2的电流密度下,过电位仅为231 mV,而NiFe LDH则需237 mV。Ru/NiFe LDH在长时间的电催化条件下依然能保持良好的工作稳定性。
基于席夫碱的四种Zn2+荧光探针的合成及其性能
何薇, 龚兰, 邓绍文, 李中燕, 袁霖
2023, 39(10): 1914-1922  doi: 10.11862/CJIC.2023.152
[摘要]  (69) [HTML华泰娱乐地址] (69) [PDF 4155KB] (2)
摘要:
以乙二胺与水杨醛及其衍生物为原料,构建了4种席夫碱Zn2+荧光探针,其结构均由1H NMR、13C NMR和IR进行了表征。光谱分析实验结果表明,相比于其他探针,探针L2对Zn2+具有更好的选择性和灵敏度,检出限为92.15 nmol·L-1。在0~30μmol·L-1的浓度范围内,探针L2的荧光强度与Zn2+浓度可呈良好的线性关系,在紫外灯下可用肉眼观察到明显颜色变化。通过Job曲线、核磁滴定实验、密度泛函理论计算和L2-Zn2+配合物单晶结构对识别机理进行了研究,结果表明探针L2与Zn2+以物质的量之比1∶1配位。此外,探针L2还可用于检测实际水样中的Zn2+
低温烧结NaBi(WO4)2陶瓷的介电性能
张甦, 杨秋红, 李启笛
2023, 39(10): 1923-1930  doi: 10.11862/CJIC.2023.149
[摘要]  (66) [HTML华泰娱乐地址] (66) [PDF 13311KB] (1)
摘要:
采用固相合成法制备了NaBi (WO4)2(NBW)陶瓷,研究了NBW陶瓷的相结构、形貌、烧结特性和微波介电性能。NBW陶瓷在625~800℃烧结1~4 h能够致密化。X射线衍射表明在625~800℃烧结2 h的NBW陶瓷均为四方晶系白钨矿结构的单相陶瓷。随着烧结温度的提高,NBW陶瓷的介电常数、品质因数(Qf值)先增加后降低,谐振频率温度系数逐渐降低。经650℃烧结2 h获得的NBW陶瓷的介电常数为14.36,Qf值为16 503 GHz,谐振频率温度系数为-1.055×10-5-1。NBW陶瓷与银共烧反应生成Ag2W2O7相,而与Au、Al共烧具备化学兼容性。
基于铈配合物信号探针的凝血酶电化学适体传感器
王存, 邹晓川, 黄远波, 胡静, 邓明川, 冯霞
2023, 39(10): 1931-1940  doi: 10.11862/CJIC.2023.162
[摘要]  (54) [HTML华泰娱乐地址] (54) [PDF 19246KB] (0)
摘要:
以Ce3+为中心离子,NN-二甲基甲酰胺(DMF)为有机配体,通过温度调节,合成系列形貌和电化学信号不同的铈配合物(Ce-COPs)。筛选出电化学信号最强的多面体状Ce-COP为信号探针。通过凝血酶(TB)与TB适体链之间的特异性识别作用,设计了一种简单通用的TB适体传感器。最优实验条件下,该传感器对TB的线性响应范围为1.0 fmol·L-1~1.0 nmol·L-1,检测限为0.94 fmol·L-1。此外,本方案方法与商品人凝血酶(TM) ELISA试剂盒检测结果相近。结果表明,我们构建的TB适体传感器具有良好的灵敏度、特异性、选择性和稳定性。
ZnFe2O4/Ag/TiO2复合材料的制备及其光催化性能
范顶, 王黎明, 刘峰强, 徐丽慧, 潘虹
2023, 39(10): 1941-1949  doi: 10.11862/CJIC.2023.159
[摘要]  (69) [HTML华泰娱乐地址] (69) [PDF 26076KB] (8)
摘要:
以硝酸银、钛酸四丁酯、无水氯化锌、六水氯化铁为原料,采用溶胶-凝胶法与溶剂热相结合的方法制备了ZnFe2O4/Ag/TiO2复合材料,通过扫描电子显微镜、能谱分析仪、X射线粉末衍射仪、X射线光电子能谱仪、振动样品磁强计、紫外可见分光光度计对样品进行表征及测试。结果表明:ZnFe2O4/Ag/TiO2-10具有最佳的光催化效果,在紫外和可见光下对染料的降解率都能达到90%以上,具有优异的紫外可见光光催化活性。ZnFe2O4/Ag/TiO2具有独特的磁性,能在外部磁场作用下进行回收利用,这使其在实际应用中成为可能。通过磁分离技术重复回收利用5次后仍然保持优良的光催化性能,说明ZnFe2O4/Ag/TiO2-10具有优异的磁性及较高的光催化循环稳定性。
Articles
Synthesis, structures, and luminescent properties of a series of lanthanide carboxylate-phosphonates
Yan XU, Su-Zhi LI, Xin-Xing LI
2023, 39(10): 1950-1958  doi: 10.11862/CJIC.2023.167
[摘要]  (61) [HTML华泰娱乐地址] (61) [PDF 5935KB] (3)
摘要:
Three lanthanide carboxylate-phosphonates based on lanthanide nitrate hexahydrate and (5-carboxynaph-thalen-1-yl)phosphonic acid (5-pncH3) formulated as [Pr(5-pnc)(H2O)]·2H2O (1), [Sm(5-pnc)(H2O)]·H2O (2), and [Eu(5-pnc)(H2O)]·H2O (3) has been obtained as single phases under solvothermal conditions. Complexes 1-3 were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, IR spectra, thermo-gravimetric analysis, and fluorescence spectra. Crystal structures reveal that each lanthanide ion is seven-coordinated by six O atoms from five phosphonate ligands and one O atom from one water molecule. The building blocks [LnO7] of complexes 1-3 are linked into a 1D double metal chain structure by the O—C—O, O—P—O, or —O— units. The 1D double metal chain is fused into a 3D open-framework structure by 5-pnc3-. Complex 3 exhibited very strong characteristic emission bands for the Eu (Ⅲ) ion in the visible region under 330 nm excitation. Complexes 1 and 2 displayed very broad ligand -centered emission bands in the blue light region.
Preparation of zeolitic imidazolate frameworks-8/modified polyacrylonitrile electrospun nanofibers for efficient removal of malachite green from water
Peng XU, Wei DAI, Wei-Shan SHI, Gang XING, Zhao-Gui WANG, Sha-Sha WANG, Qun LI, Chao-Qun YOU, De-Jun HAO
2023, 39(10): 1959-1968  doi: 10.11862/CJIC.2023.154
[摘要]  (76) [HTML华泰娱乐地址] (76) [PDF 11342KB] (0)
摘要:
A simple in-situ growth method was presented to synthesize zeolitic imidazolate framework-8 (ZIF-8), one of the most common metal-organic frameworks (MOFs) crystals, onto a carboxymethylated polyacrylonitrile electrospun nanofibers (PAN-COOH NFs). The synthesized ZIF-8/PAN-COOH NFs were characterized by field-emission scanning electron microscope (SEM), energy dispersive spectroscopy (EDS), X-ray powder diffraction (XRD), and Fourier-transform infrared (FTIR) spectroscopy. The characterization results confirmed that the ZIF-8 particles were successfully loaded on the surface of the PAN-COOH NFs. The ability of ZIF-8/PAN-COOH NFs to remove malachite green (MG), a model organic dye, from wastewater was evaluated to examine the potential of this novel material as an adsorbent. The adsorption to MG was consistent with the pseudo -second -order kinetic equation, and the adsorption process was expressed by the Langmuir isotherm model. The maximum adsorption capacity for MG was examined as 3 604 mg·g-1. It is noteworthy that the ZIF-8/PAN-COOH NFs could be easily separated from the dye solution and regenerated through a simple washing process for recycling.
Structure and magnetism of cyanide-bridged [FeCo]-based chain-like complexes
Yan-Rui LEI, Hai-Lang ZHU, Jie HUANG, Ren-He ZHOU, Tao LIU
2023, 39(10): 1969-1979  doi: 10.11862/CJIC.2023.147
[摘要]  (51) [HTML华泰娱乐地址] (51) [PDF 12594KB] (1)
摘要:
We report two cyanide-bridged mixed-valence chain-like coordination polymers by the self-assembly reaction of tricyanoferrate(Ⅲ) building blocks (Bu4N)[Fe(PzTp)(CN)3] (PzTp=tetrakis(pyrazolyl)borate) and Co(Ⅱ) ions in the presence of monodentate ligand (E)-1-styryl-1H-imidazole (Bzi). X-ray diffraction analysis indicated that complex [Fe(PzTp)(CN)3]2[Co(Bzi)4]2(ClO4)2·H2O (1) adopts a square-wave type chain structure, while complex [Fe(PzTp) (CN)3]2[Co(Bzi)2]·CH3OH (2) forms double zigzag chains that contain methanol solvent molecules. Magnetic studies revealed that complex 1 displayed a thermally induced spin transition at around 360 K, while complex 2 exhibited a solvent-induced two-step spin transition at approximately 200 K. Variable-temperature infrared spectra confirmed the thermally induced intermetallic charge transfer behavior. Additionally, photomagnetic experiments revealed that complex 1 displayed reversible light-induced charge transfer behavior when alternately irradiated with 808 and 532 nm light, while the charge transfer behavior of complex 2 could be induced by 808 nm irradiation. The magneto-structural relationship analysis indicates that the different hydrogen bonding interactions and local coordination environments of the cobalt sites in complexes 1 and 2 are the main factors contributing to their distinct charge transfer and light-responsive properties.
Schottky barrier of blue phosphorus/graphene heterostructure regulated by the adsorption of oxygen atoms
Wang-Yang DUAN, Yue-Huan CHENG, Ji-Song HU, Xin-Guo MA, Ling PEI
2023, 39(10): 1980-1990  doi: 10.11862/CJIC.2023.161
[摘要]  (62) [HTML华泰娱乐地址] (62) [PDF 11215KB] (0)
摘要:
Controlling the p-type transmission operation of nanoelectronics remains a major challenge in lowering the Schottky barrier. To solve this problem, we systematically investigated the effects of O atoms adsorption doped on the interlayer interactions and electronic properties of the BP/graphene (BP=blue phosphorus) heterostructures by first-principles calculations incorporating a semiempirical dispersion-correction scheme. The results show that the interfacial binding can be enhanced by O atom adsorption doped inside the interface. The height of the Schottky barrier can be adjusted by changing the concentration of O atom adsorption doped inside the interface. It is further found that by increasing the concentration of O atoms inside the interface, a low p - type Schottky barrier can be obtained, thereby achieving efficient charge transfer. Finally, it is confirmed that the redistribution of the interfacial charge leads to the movement of the Fermi level, which determines the height of the Schottky barrier.
Adsorption, photocatalytic degradation, and their mechanisms of methylene blue on three-dimensional Cu-MOF
Xue-Ying LU, Mei-Li ZHANG, Yi-Xia REN, Ji-Jiang WANG, Xiao-Gang YANG
2023, 39(10): 1991-2002  doi: 10.11862/CJIC.2023.158
[摘要]  (60) [HTML华泰娱乐地址] (60) [PDF 12572KB] (3)
摘要:
Herein, we report the synthesis, structure, adsorption and photocatalytic degradation properties of a novel metal-organic framework [Cu3(ppda)3(tib)2(H2O)4]·6H2O (Cu-MOF) by the selection of the flexible 1,4-phenylenedi-acetic acid (H2ppda) and the rigid 1,3,5-tris(1-imidazolyl) benzene (tib). In Cu-MOF, ppda2- and tib ligands alternately link Cu ions to form 2D polymeric layers, the layer and layer interpenetrate each other by trans-ppda2- to form a stable 3D structure. Cu-MOF has excellent thermal stability and semiconductor properties, so it can be used as a catalyst. Cu-MOF had the best catalytic effect on methylene blue (MB), with a catalytic efficiency of up to 97% and the highest reaction rate constant of 0.019 7 min-1. The main photocatalytic degradation mechanism is the separation of the photogenerated electron and hole pair of the catalyst under the light excitation, and the redox reaction occurs to produce the active species to degrade the dye and eventually decompose into carbon dioxide and water. Cu - MOF exhibited high adsorption capacity after adding NaCl (200 g·L-1) to MB solution (87.23 mg·g-1). The adsorption process is a spontaneous monolayer chemisorption process illustrated by the pseudo-second-order kinetic and Langmuir isotherm models and thermodynamic studies.
A mononuclear Co-nitronyl nitroxide hetero-spin complex with single-molecule magnet behavior
Bao-Yi LI, Xiao-Ting HAO, Hong-Dao LI
2023, 39(10): 2003-2008  doi: 10.11862/CJIC.2023.151
[摘要]  (64) [HTML华泰娱乐地址] (64) [PDF 3938KB] (1)
摘要:
A 2p-3d hetero-spin complex, namely [Co(hfac)2(NIT-PyzMe-PhCHO)] (1), where hfac=hexafluoroacetyl-acetone, NIT-PyzMe-PhCHO=2-(3-(1H-imidazol-1-ylmethyl)benzaldehyde)-4, 4, 5, 5-tetramethylimidazoline-1-oxyl-3-oxide, has been successfully isolated and characterized. Complex 1 displays a mononuclear structure. Strong antifer-romagnetic interaction was detected between the Co ion and the directly coordinated nitroxide group. Moreover, the frequency-dependent out-of-phase signals related to the slow relaxation of magnetization verify the typical single-molecule magnet behavior of the system.
Preparation and characterization of 2D nickel coordination polymer (Ni-CP) and Ag@Ni-CP Schottky junctions for photocatalytic degradation of cationic dyes
Zhi-Hu MA, Yi-Xia REN, Zhi-Xiang WANG, Mei-Li ZHANG, Ji-Jiang WANG
2023, 39(10): 2009-2019  doi: 10.11862/CJIC.2023.148
[摘要]  (56) [HTML华泰娱乐地址] (56) [PDF 11800KB] (3)
摘要:
A new 2D nickel (Ⅱ) coordination polymer (Ni - CP) has been synthesized hydrothermally, named as [Ni(DDB)0.5(2, 2'-bipy)(H2O)]·H2O (H4DDB=1, 4-di(3, 5-dicarboylphenoxy) benzene, 2, 2'-bipy=2, 2'-bipyridine), and characterized by element analysis, thermogravimetric analysis, powder X-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy. Single-crystal structural analysis shows that the coordination polymer possesses a 2D waved network through DDB4- ligand in μ4 fashion. Ag-loaded products (Ag@Ni-CP) with Schottky junction were prepared by the photoreduction method. Photocatalytic degradation performance of Ni-CP and Ag@ Ni-CP were investigated, and the latter exhibited excellent degradation effect, especially for rhodamine B and methylene blue with a high degradation rate of 99% rapidly in 60 min. Ag@Ni-CP exhibited higher and faster degradation performance than the reported MOF catalyst materials. The photocatalytic mechanism was investigated by free radical trapping experiments.
Peanut shell-based porous carbon supported Pd-Co catalyst for electrooxidation of methanol in alkaline media
Zhao-Hui HUO, Xue-Rong WEI, Yong HUANG, Ze-Yu CHEN, Wei-Bing CHEN, Qi-Tong ZHANG, Gang ZHANG, Geng-Long WEN, Jun-Jie SHI
2023, 39(10): 2020-2032  doi: 10.11862/CJIC.2023.157
[摘要]  (66) [HTML华泰娱乐地址] (66) [PDF 24312KB] (0)
摘要:
Peanut shells were used as raw materials and activated to peanut shell-based porous carbon (HC) by KOH. Nitrogen adsorption-desorption studies showed that the obtained porous carbon featured a total surface area as high as 1 645 m2·g-1. Pd-Co/HC catalyst was prepared by the impregnation reduction method, in which HC was the carrier. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analysis demonstrated that Co in the catalyst was mainly in the form of Co and CoO, and Co was entered into the crystal lattice of Pd and formed a Pd-Co alloy. The TEM image of Pd-Co/HC0.5-700 showed that numerous Pd-Co nanoparticles were successfully dispersed in the prepared porous carbon with a small particle size (ca. 4 nm). Pd-Co/HC0.5-700 exhibited apparent electrocatalytic activity, CO tolerance, and stability towards methanol electrooxidation in alkaline media. This remarkable high performance can be attributed to the large surface area of the biomass carrier and the doping of Co into Pd.
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论文
基于席夫碱配体构筑的Ln 2配合物的结构、荧光性质及生物活性
辛晓艳, 陈凤姣, 李文钰, 王捷, 杨晨, 李敏, 石瑛, 王文敏
2023, 39(1): 1-12  doi: 10.11862/CJIC.2022.268
[摘要]  (694) [HTML华泰娱乐地址] (694) [PDF 9948KB] (694)
摘要:
以多齿席夫碱配体H2L (H2L=(E)-N'-(3-乙氧基-2-羟基亚苄基)-3-羟基吡啶甲酰肼)为配体,与Ln (acac)3·2H2O (Ln=Tb、Ho、Er;acac-=乙酰丙酮根)反应,通过溶剂热法,成功得到了3例新的双核稀土配合物[Ln2(acac)2(L)2(C2H5OH)2](Ln=Tb (1)、Ho (2)、Er (3))。单晶X射线衍射分析表明:配合物1~3的结构主要由2个Ln离子、2个乙酰丙酮根(acac-)、2个L2-及2个C2H5OH组成,中心Ln离子通过2个μ 2-O原子相互连接,形成一个平行四边形的Ln2O2核心。固体荧光实验测试结果表明:配合物1在室温下表现出Tb离子的荧光特征发射峰。此外,生物活性研究表明,与配体H2L和稀土离子相比较,配合物1~3具有更强的抗菌活性。采用紫外光谱法、循环伏安法、凝胶电泳法和荧光光谱法研究了配合物1~3与小牛胸腺DNA之间的相互作用,结果表明配合物主要以插入作用的方式与小牛胸腺DNA结合。
SiC表面Ni沉积超疏水膜层的形成机理
宿辉, 栾柏瑞, 李春彦
2023, 39(1): 13-22  doi: 10.11862/CJIC.2022.259
[摘要]  (1945) [HTML华泰娱乐地址] (1945) [PDF 30828KB] (1945)
摘要:
前期采用环境友好方法制备的改性碳化硅颗粒,经较长时间放置,发现其由亲水性转变为超疏水性,接触角为156°。为解释这一新的现象,采用扫描电子显微镜、能谱、(高分辨)透射电子显微镜、X射线光电子能谱(XPS)对原粉碳化硅、改性后碳化硅及久置碳化硅进行了测试与分析。结果显示:改性后碳化硅经较长时间放置,表面胞状颗粒增大并出现凸起物,粗糙度增加,存在类似于荷叶的微纳米结构。改性后颗粒的主要成分为Ni、Si、O,其中凸起处Ni、O元素的含量明显高于凹陷处。Ni颗粒表面出现清晰的膜层,膜层厚度为2~3 nm,但结晶度偏低。XPS测试结果显示金属镍的特征峰正向移动近4 eV,与镍的氧化态特征峰相一致,从而解释了颗粒表面形态发生细小改变,自发形成超疏水膜层的机理。
BiVO4/ZnFe2O4同型异质结光阳极的构筑及其光电催化分解水性能
樊萌萌, 文晓江, 陶紫阳, 赵强, 李晋平, 刘光
2023, 39(1): 23-31  doi: 10.11862/CJIC.2022.257
[摘要]  (832) [HTML华泰娱乐地址] (832) [PDF 7434KB] (832)
摘要:
光生电子-空穴对的复合被认为是限制BiVO4材料光电催化转换效率的重要原因之一。基于此,通过简单的水热-煅烧方法构筑了BiVO4/ZnFe2O4同型异质结光阳极,BiVO4/ZnFe2O4复合光阳极在1.23 V (vs RHE)下的光电流密度为3.33 mA·cm-2,较纯BiVO4提升了2倍(1.20 mA·cm-2)。相关的结构及性能测试表明,BiVO4和ZnFe2O4形成了带隙错开的n-n异质结,使得光生载流子得到有效分离,更有效地参与水氧化过程,进而提高了BiVO4的光电催化水分解性能。
N缺陷g-C3N5修饰S掺杂苝酰亚胺增强可见光自芬顿苯酚氧化耦合Cr(Ⅵ)还原
徐凯旋, 亢玉龙, 贺红斌, 高晓明, 赵晨宇, 任瑞阳
2023, 39(1): 32-44  doi: 10.11862/CJIC.2022.264
[摘要]  (512) [HTML华泰娱乐地址] (512) [PDF 17627KB] (512)
摘要:
通过静电自组装制备有机复合半导体N缺陷g-C3N5(NVs)修饰S掺杂苝酰亚胺(S-PDI)。NVs具有丰富的活性位点,而具有氨基基团的酰胺增强了S-PDI与NVs的分子间作用力。NVs质量分数30%的30% NVs/S-PDI对Cr(Ⅵ)的还原率为79.96%,对苯酚的降解率为74.40%;30% NVs/S-PDI协同氧化苯酚与还原Cr(Ⅵ)过程中,Cr(Ⅵ)的还原率为92.83%,苯酚的降解率为93.89%,即苯酚的氧化降解促进了Cr(Ⅵ)的还原,Cr(Ⅵ)的还原增强了苯酚的氧化降解。NVs/S-PDI充分利用导带的还原性能和价带的氧化性能,实现电子空穴的空间分离,协同强化光催化过程中的氧化半反应和还原半反应,同步提升光催化氧化还原性能。同时,光照产生的电子、H2O2与Cr(Ⅵ)形成一个光自芬顿反应过程,进一步促进了苯酚的氧化降解与Cr(Ⅵ)的还原去除。
共轭微孔聚合物热解制备氮、硫杂原子硬炭及其储锂性能
张庆堂, 许宗强, 舒琦琪, 连斐
2023, 39(1): 45-54  doi: 10.11862/CJIC.2022.263
[摘要]  (497) [HTML华泰娱乐地址] (497) [PDF 18988KB] (497)
摘要:
选取溴代噻唑和三乙炔基苯为单体,利用聚合反应自下而上构建含噻唑共轭微孔聚合物(NSCMP),通过热解和KOH活化热解NSCMP制备了氮、硫杂原子硬炭(NSHC)和活化NSHC (KNSHC)。利用扫描电子显微镜、能量色散谱、氮气吸附-脱附和恒流充放电等表征2个样品的结构与电化学性能。研究表明KNSHC中N和S的质量分数分别为10.42%和2.23%,KNSHC比表面积高达2 140 m2·g-1。在0.2 A·g-1电流密度下循环500次后KNSHC和NSHC的可逆比容量分别为946.2和493.7 mAh·g-1。KNSHC的优异电化学性能归因于其独特的孔结构和氮、硫杂原子的协同作用。
锰源对尖晶石LiMn2O4高温性能的影响
刘培松, 宋利君, 黄朝连, 胡磊, 卢晓英, 江奇
2023, 39(1): 55-62  doi: 10.11862/CJIC.2022.258
[摘要]  (592) [HTML华泰娱乐地址] (592) [PDF 9945KB] (592)
摘要:
为考察不同锰源对所制备尖晶石LiMn2O4(LMO)电化学性能的影响(特别是高温性能),采用沉淀法制备前驱体,通过不同煅烧温度制备得到最常用的锰氧化物(MnO2、Mn2O3和Mn3O4)为锰源,经相同条件制备得到LMO正极材料,通过考察所得LMO形貌及电化学性能来研究锰源与LMO电化学性能的关系。研究结果表明,相同的前驱体在不同煅烧温度下可以得到不同的锰氧化物,且各自具有不同的形貌结构。由这些锰氧化物都可以得到高纯度的LMO,但产物形貌结构以及材料中的八面体晶体含量和尺寸不同。由Mn2O3制备得到的LMO材料中的八面体晶体含量最多,且尺寸最均匀,在3种LMO中容量性能、倍率性能和循环性能最好:0.2C (1C=148 mA·g-1)下首次放电比容量为131.8 mAh·g-1;3C下还有100.4 mAh·g-1的放电比容量。其对应半电池在0.5C下循环100次后,放电比容量还有116.0 mAh·g-1,容量保持率为93.9%,电化学储能性能远远优于其他2种LMO。即使是在高温55℃下,由Mn2O3得到的LMO也表现出明显优于其他2种材料的高倍率性能和抗衰减性能。
Eu2+掺杂MgY2Al3Si2O11N青光荧光粉的制备和发光性能
李莉宇, 时秋峰, 郭海洁, 崔彩娥, 黄平, 王磊
2023, 39(1): 63-70  doi: 10.11862/CJIC.2022.271
[摘要]  (439) [HTML华泰娱乐地址] (439) [PDF 4249KB] (439)
摘要:
采用高温固相法合成了一系列Eu2+掺杂的MgY2Al3Si2O11N (MYASON)青光荧光粉。详细探讨了不同制备方法对荧光粉的物相结构和发光强度的影响,利用X射线衍射精修和X射线光电子能谱实验证明Si4+-N3-离子对成功掺入石榴石晶格中。通过荧光光谱、寿命衰减曲线和变温光谱研究了发光性能,研究结果表明,用365 nm紫外光激发MYASON∶Eu2+荧光粉时,在青光区域呈现不对称宽带发射,峰值为490 nm,可以为紫外芯片激发的白光发光二极管有效提供青光成分。
胺醇修饰的β-二酮铕配合物对有机小分子胺的高灵敏检测
李静雅, 黄文儒, 王峰, 周妍妍
2023, 39(1): 71-79  doi: 10.11862/CJIC.2022.265
[摘要]  (447) [HTML华泰娱乐地址] (447) [PDF 6380KB] (447)
摘要:
稀土发光传感器可用于有害的有机小分子胺的检测,然而稀土离子较大的离子半径和不稳定的配位构型,使其在固态下对有机小分子胺实现高灵敏性的发光检测具有一定的挑战。通过在单β-二酮配体上引入胺醇识别基团,使其与稀土铕离子通过配位成功构筑了具有可调控配体内电荷转移(ILCT)性质的单核稀土配合物[Eu(L)3(H2O)2](HL=(2Z)-1-(4-(双(2-羟基乙基)氨基)苯基)-4,4,4-三氟-3-羟基丁-2-烯-1-酮)。配合物的传感研究表明,[Eu(L)3(H2O)2]在弱的亲核作用下对三丙胺等有机小分子胺表现出明显的发光增强响应。
MoO2@氮掺杂碳复合物的制备及其降解有机污染物
曹诗雨, 陈斌杰, 郁非繁, 徐象威, 姚玉元
2023, 39(1): 80-90  doi: 10.11862/CJIC.2022.255
[摘要]  (603) [HTML华泰娱乐地址] (603) [PDF 23258KB] (603)
摘要:
以多巴胺、钼酸铵、碳酸氢铵为原料,通过一步煅烧法合成一种MoO2@氮掺杂碳复合物(MoO2@CN),并利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)、拉曼光谱(Raman)等对其进行表征。以卡马西平(CBZ)为目标污染物,以过一硫酸氢钾(PMS)为氧化剂,在温度为25℃、pH为6.5的条件下,MoO2@CN/PMS在12 min内对CBZ的去除率达99.2%,与商用MoO2相比,其表观速率常数k obs(0.393 min-1)是商用MoO2(0.016 4 min-1)的24.0倍,这主要是由于制备的MoO2@CN比商用MoO2具有更好的电子传输能力以及更大的比表面积。MoO2@CN在pH为2.5~10.5时均能有效降解CBZ,而且对大多数染料、酚类化合物、抗生素等多种污染物均具有良好的降解性能。此外,MoO2@CN/PMS在60 min内对CBZ的总有机碳(TOC)去除率高达74.0%。电子顺磁共振波谱(EPR)和自由基猝灭实验显示MoO2@CN/PMS体系中主要起作用是硫酸根自由基(SO4 ·-)和羟基自由基(·OH)。更有意思的是,在Fe2+/PMS体系加入MoO2@CN后,其催化降解CBZ的性能显著增强,k obs(1.25 min-1)是单独Fe2+/PMS体系(0.079 7 min-1)的15.7倍,这主要归因于MoO2@CN的引入加快了Fe3+到Fe2+的转变,导致更多·OH的生成。
两步变温晶种法制备丝光沸石膜及其渗透汽化乙酸脱水性能
王佳轩, 李良清, 马磊, 吕金印, 杨建华, 鲁金明
2023, 39(1): 91-97  doi: 10.11862/CJIC.2022.270
[摘要]  (393) [HTML华泰娱乐地址] (393) [PDF 11451KB] (393)
摘要:
在水热晶种法基础上采用两步变温晶化以高水硅比(n H2O/n SiO2 )稀溶液配方为合成液,研制用于渗透汽化(PV)乙酸脱水的丝光沸石膜(MOR膜),考察了变温晶化各段时间、水硅比与氟离子对MOR膜的形貌与分离性能的影响规律。结果表明:高温段晶化时间、水硅比与氟离子对MOR膜的形貌、结晶度和膜层厚度产生显著影响,并影响MOR膜渗透气化分离性能;在高温段(150℃)和低温段(120℃)的晶化时间分别为18和6 h,在水硅比为60且含氟离子体系中所制备的MOR膜的性能最佳,其对质量分数50%的乙酸水溶液的渗透通量和分离系数分别为1.45 kg·m-2·h-1和1 008。
PO4 3-掺杂Bi2O2CO3/Bi0的制备及其可见光催化性能
马珑珑, 秦立波, 田亚洋, 秦鹂, 杨志, 杨超
2023, 39(1): 98-108  doi: 10.11862/CJIC.2022.281
[摘要]  (438) [HTML华泰娱乐地址] (438) [PDF 71380KB] (438)
摘要:
构建氧空位以及附着金属单质Bi (Bi0)是增强半导体材料光吸收性能、促进半导体光生载流子分离的有效方法。通过简单的共沉淀法及氢气热还原成功制备了PO4 3-掺杂Bi2O2CO3附着Bi0(Bi-P-BOC)的可见光催化剂,并对其在可见光下催化降解氧氟沙星(OFX)的性能及机理进行了研究。材料表征结果表明BOC随着PO4 3-的均匀掺杂,可见光吸收能力增强,表面缺陷增多,比表面积增大。而随着氢气热还原,BOC表面形成Bi0的同时也原位构建了大量的氧空位。可见光催化性能测试表明,Bi-P-BOC可以在180 min内降解约85%的OFX,降解速率为0.013 0 min-1,是BOC降解速率的8倍。Bi-P-BOC光催化降解机理表明其具有更好的可见光吸收能力,Bi0以及氧空位的存在促进了光生载流子的分离,h+是其光催化降解过程中的主要的活性氧物种(ROS),此外,1O2和·O2 -也对降解有一定贡献。
Se掺杂WO3·0.5H2O/g-C3N4光电催化剂的析氢反应性能
崔慧娜, 董文斌, 廖港丽, 赵震, 姚垚
2023, 39(1): 109-116  doi: 10.11862/CJIC.2022.261
[摘要]  (451) [HTML华泰娱乐地址] (451) [PDF 15123KB] (451)
摘要:
以二氰二胺、硒粉和钨酸钠为前驱体,采用一锅法成功制备出Se掺杂WO3·0.5H2O/g-C3N4(Se/WCN)催化剂。并采用X射线衍射仪(XRD)、场发射扫描电子显微镜(FE-SEM)和X射线光电子能谱(XPS)对样品的物相结构、形貌及化学组成进行表征。与原始的WO3和g-C3N4相比,Se/WCN催化剂的起始电位降到了-0.75 V (vs RHE),电流密度高达70 mA·cm-2,表现出更高的电催化活性。而光照后,Se/WCN的催化性能进一步提升,起始电位从-0.75 V (vs RHE)降至-0.65 V (vs RHE),电荷转移电阻由371.4 Ω减小到310.0 Ω。
菲咯啉与1-萘甲酸配体共同构筑的多核Ca(Ⅱ)、双核Mn(Ⅱ)配合物的合成、结构及性质
杨婷英, 郭丹, 胡宇琼, 易思佳, 谷淑琪, 贺霞, 朱小明, 张复兴
2023, 39(1): 117-126  doi: 10.11862/CJIC.2022.282
[摘要]  (533) [HTML华泰娱乐地址] (533) [PDF 5128KB] (533)
摘要:
设计、合成了2种配合物:[Ca (Phen)(Nap)2] n (1)和[Mn2(Phen)2(Nap)4(H2O)](2)(Phen=菲咯啉,HNap=1-萘甲酸)。通过红外光谱、元素分析、X射线单晶衍射和热重对其进行了结构表征。测定了配合物的激发光谱、发射光谱,以及配合物对人肺癌细胞(NCI-H460)、人乳腺癌细胞(MCF-7)、人肝癌细胞(HepG2)的体外抑制活性;利用紫外吸收光谱、荧光分光光度法研究了配合物与小牛胸腺DNA的相互作用。结果表明:配合物12的激发光谱和发射光谱具有很好的镜像关系,且配合物2的斯托克斯位移大于配合物1;配合物对3种癌细胞都有较好的抑制作用,但是2更优于1;配合物12与小牛胸腺DNA以静电作用发生沟面结合,结合常数分别为5.83×103和6.46×103 L·mol-1
无模板电化学沉积法制备多孔WO3·2H2O薄膜及其电致变色性能
宋艳玲, 张启源, 姚爱华
2023, 39(1): 127-134  doi: 10.11862/CJIC.2022.260
[摘要]  (620) [HTML华泰娱乐地址] (620) [PDF 16344KB] (620)
摘要:
二水合氧化钨(WO3·2H2O)因其独特的层状结构且富含层间结构水,与无水WO3相比显示出更加优异的电致变色性能。我们采用简单、无模板的阴极电化学沉积方法,成功在氧化铟锡(ITO)导电玻璃基底上制备了WO3·2H2O薄膜。通过改变电沉积液中过氧化氢(H2O2)的加入量优化沉积液的成分,获得了具有纳米多孔结构的薄膜。由此制备的WO3·2H2O薄膜显示出大的光学对比度(633 nm处的光学对比度大于90%)、快速的响应速度(着色、褪色时间均小于10 s),以及良好的循环稳定性(经10 000次循环后,光学对比度仍保持在90%左右)。
Articles
Ternary lanthanide complexes of 3-((4, 6-dimethyl-2-pyrimidinyl)thio)-propanoic acid and 1, 10-phenanthroline: Crystal structure and photoluminescent property
Shuai LAN, Yu ZHANG, Jie REN, Si-Bo SHEN, Lei CAO, Dan-Dan JIA, Dong-Jun WANG
2023, 39(1): 135-140  doi: 10.11862/CJIC.2022.276
[摘要]  (404) [HTML华泰娱乐地址] (404) [PDF 1631KB] (404)
摘要:
Two ternary lanthanide complexes, [Eu(L)3(Phen)]2·2H2O (1) and [Tb(L)3(Phen)]2·2H2O (2), based on 3-((4, 6-dimethyl-2-pyrimidinyl)thio)-propanoic acid (HL) and 1, 10-phenanthroline (Phen) were prepared and structurally characterized. Single-crystal X-ray diffraction analyses reveal that they are isostructural. Two lanthanide ions (Ln) are bridged by four carboxylate ligands. The rest two carboxylate ligands and Phen coordinate with Ln with bidentate chelating mode, forming the dimeric arrangement. The coordination number of Ln is nine with a distorted mono-capped square antiprismatic coordination polyhedron. The solid-state photoluminescent measurements suggest that both complexes showcase the characteristic emission bands of the metal center.
Synthesis, crystal structure, and anticancer activity of a polypyridyl binuclear monofunctional platinum(Ⅱ) complex
Xun-Yi LI, Yu-Jing WANG, Zi-Mo ZHOU, Xiao FANG, Qing-Qing WANG, Mei-Chun HU, Xiao-Song YANG, Xiao-Bo WANG
2023, 39(1): 141-149  doi: 10.11862/CJIC.2022.272
[摘要]  (474) [HTML华泰娱乐地址] (474) [PDF 3440KB] (474)
摘要:
A binuclear monofunctional platinum(Ⅱ) complex, [Pt2(BPA-TPA)Cl2]Cl2 (Pt2-BPA-TPA), containing polypyridyl ligand 2, 6-bis((bis(pyridin-2-ylmethyl)amino)methyl)pyridine was synthesized and characterized by nuclear magnetic resonance and high-resolution mass spectroscopy. In addition, the structure of Pt2-BPA-TPA was determined by X-ray single-crystal diffraction. Agarose gel electrophoresis experiments were used to demonstrate the efficient pBR322 DNA-cleaving activity of Pt2-BPA-TPA at a low concentration of 10 μmol·L-1. In CCK-8 (cell counting kit-8) cytotoxicity studies using the A549 human lung cancer cell line, Pt2-BPA-TPA demonstrated enhanced anticancer activity compared with cisplatin. Mechanistic studies provided evidence that Pt2-BPA-TPA induces apoptosis via triggering DNA damage and upregulating downstream cellular signaling cascades of p21 and cleaved-caspase-3.
First-principles study on electronic structure and optical properties of Lu-doped AlNLu
Rui-Liang ZHANG, Sheng-Shang LU, Qing-Quan XIAO, Quan XIE
2023, 39(1): 150-158  doi: 10.11862/CJIC.2022.280
[摘要]  (446) [HTML华泰娱乐地址] (446) [PDF 6188KB] (446)
摘要:
To explore the potential applications of AlN in optoelectronic devices, the electronic structure and optical properties of AlN with different Lu doping concentrations (denoted as Al1-x Lu x N, where x is the atomic fraction of Lu) were calculated by first-principles. The results show that the supercell volume of Al1-x Lu x N increases with the increase of Lu doping concentration, while the bandgap does the opposite. The static dielectric constant of Al1-x Lu x N increases in the low-energy region with the increase of Lu doping concentration. As Lu doping concentration increases, the peak intensity of reflectivity, refractive index, and absorption coefficient decrease, and the peaks shift to lower energy. The energy-loss spectra of Al1-x Lu x N exhibit obvious plasma oscillation features, and the peaks are lower than that of the intrinsic AlN. The photoconductivity of Al1-x Lu x N increases sharply in the low-energy region with the increase of energy.
Synthesis, crystal structure, and properties of manganese/cobalt complexes based on 2,5-dibromoterephthalic acid ligands
Rui-Qin HUANG, Zheng LIU, Sheng WANG, Cai-Li YU, Run-Zhi WEI, Qun TANG
2023, 39(1): 159-167  doi: 10.11862/CJIC.2022.277
[摘要]  (410) [HTML华泰娱乐地址] (410) [PDF 10749KB] (410)
摘要:
The organic substance 2,5-dibromoterephthalic acid (H2L1) was used as the primary ligand and 2,2'-bipyridine (L2) and 1,10-phenanthroline (L3) as the secondary ligands, respectively, and reacted with manganese sulphate monohydrate and cobalt nitrate hexahydrate by the solvothermal method to give complexes [Mn2(L1)2(L2)2 (H2O)2] n (1) and [Co2(L1)2(L3)2(H2O)2] n (2). The two complexes were investigated analytically by such as single-crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis, etc. The results show that complex 1 is composed of Mn2+ coordination linking L1 2- and L2 to form an infinitely extended 2D network-like structure, with the layers forming a 3D network-like structure under intermolecular hydrogen bonding and π-π stacking. Complex 2 consists of Co2+ ligated to L1 2- and L3 to form an infinitely extended 2D network, with the layers stacked in a 3D network by intermolecular hydrogen bonding and π -π stacking. Both complexes had good fluorescence property and thermal stability, and the maximum emission wavelengths of complexes 1 and 2 were 355 and 365 nm, respectively.
Two cadmium-based coordination polymers with tripodal carboxylate and imidazolyl ligands: Syntheses, structures, and fluorescent properties
Long TANG, Lu-Yuan CHEN, Xiang-Yang HOU, Xiao WANG, Ji-Jiang WANG
2023, 39(1): 168-180  doi: 10.11862/CJIC.2022.273
[摘要]  (590) [HTML华泰娱乐地址] (590) [PDF 17875KB] (590)
摘要:
Two cadmium-based coordination polymers [Cd(Htatb) (1,4-bimb)] ·H2O (1) and [Cd(Htatb) (1,4-bib) (H2O)]·DMF (2) (H3tatb=4, 4', 4″-s-triazine-2,4,6-tribenzoic acid, 1,4-bimb=1,4-bis(imidazole-1-ylmethyl) benzene, 1,4-bib=1,4-bis(1-imidazoly) benzene) were synthesized by hydrothermal reactions and characterized by single-crystal X-ray diffraction, thermogravimetric analyses, IR spectroscopy, elemental analysis, etc. 1 displays a 2D layer structure, further these layers are joined by O—H⋯O hydrogen bonding to generate a four-fold interpenetrating 3D architecture. 2 shows a 2D layer structure, further joined through O—H⋯O hydrogen bonding to produce a two-fold interpenetrating 3D architecture. Complexes 1 and 2 had fluorescent properties. 1 was highly selective and sensitive towards nitrobenzene and Fe3+ ion through different detection mechanisms, while CP 2 was highly selective and sensitive towards 2,4,6-trinitrophenol and CrO4 2- ion.
Syntheses of two Mg-based metal-organic frameworks by a coordination competitive strategy and the selective CO2 capture
Yu-Ao DONG, Zhe FENG, Dun-Ru ZHU
2023, 39(1): 181-190  doi: 10.11862/CJIC.2022.278
[摘要]  (450) [HTML华泰娱乐地址] (450) [PDF 13012KB] (450)
摘要:
Two Mg-based metal-organic frameworks (MOFs) were prepared using a coordination competition strategy. Under acidic conditions, the reaction of Mg(Ⅱ) ions with formic acid generated from the thermal decomposition of N, N-dimethylformamide (DMF) formed a 3D formate Mg-MOF: [Mg3(HCO2)6]·DMF (1). However, under the same conditions but with a competing ligand 1,1'∶3',1″-terphenyl-3,3″,5, 5″-tetracarboxylic acid (H4L), formic acid was no longer involved in the coordination, resulting in a new 3D Mg-MOF: [Mg2(L) (H2O)3]·2H2O·2CH3CN·DMF (2). Single-crystal X-ray analysis revealed that 1 possesses [Mg4@Mg2] tetrahedral building units that form a dia topological network with a 1D channel size of 0.44 nm. In contrast, 2 has a unique [Mg2] binuclear cluster to build a sra topology network after bridging the 4-connected L4- linker. Interestingly, a dumbbell-shaped pore with a length of 1.42 nm is observed along the a-axis in 2. Gas adsorption studies reveal that 1 had a significantly accessible inner surface with a surface area of 342 m2·g-1. However, after solvent removal, 2 could not retain the original porous character. Featuring good water stability, 1 exhibited a type-Ⅰ CO2 adsorption isotherm with quick uptake at low pressure, and up to 14.5% of the sample weight at 298 K and 2 000 kPa. Ideal adsorption solution theory (IAST) and adsorption heat calculations show that 1 has a good ability for selective CO2 capture from CH4 contained mixture.