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氮掺杂MnCo2O4/N-KB的制备及氧还原催化性能
冯艳, 吴剑波, 张晓玲, 彭超群, 王日初
2019, 35(4): 569-579  doi: 10.11862/CJIC.2019.071
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摘要:
以Mn(Ac)2和Co(Ac)2作为前驱体,导电碳Ketjenblack(KB)作为负载碳源,采用水解-水热法制备氮掺杂的MnCo2O4/N-KB催化剂材料,对其结构特征和碱性溶液中氧还原反应的催化性能进行表征,并进一步分析其氧还原反应活性。结果表明:MnCo2O4/N-KB催化剂的形态是KB骨架上生长纳米级MnCo2O4,并且在N-KB和MnCo2O4之间形成化学耦合,产生协同作用,有效提高了MnCo2O4/N-KB催化剂的氧还原活性。MnCo2O4与N-KB的质量比为1:9时,MnCo2O4/N-KB催化剂在O2饱和0.1 mol·L-1 KOH溶液中对氧还原反应的电催化性能最佳,反应的极限电流密度为5.7 mA·cm-2,半波电位接近0.81 V,电子转移数为4。在相同负载量下,MnCo2O4/N-KB催化剂相比商用Pt/C(电流密度5.2 mA·cm-2,半波电位0.83 V)有着更高的极限电流密度和耐久性。
Cd掺杂δ-Bi2O3纳米片的制备及其光催化固氮性能
高晓明, 尚艳岩, 刘利波, 高凯龙
2019, 35(4): 580-588  doi: 10.11862/CJIC.2019.092
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采用一步醇热法制备了Cd掺杂δ-Bi2O3,并用X射线衍射(XRD)、透射电子显微镜(TEM)等手段对其微观结构、表面元素、能带结构、光电化学性质等进行表征。结果表明Cd掺杂δ-Bi2O3是由二维纳米片组装而成的微球,Cd以Cd2+形式掺杂在δ-Bi2O3晶格间隙。由于Cd的掺杂,δ-Bi2O3禁带宽减小,光响应范围扩大,光生载流子的传递与分离效率提高。在常温常压下,考察了Cd-δ-Bi2O3可见光催化固氮效果,结果表明,光照3 h时,6% Cd-δ-Bi2O3的光催化固氮速率为1.6 mmol·g-1·h-1·L-1,是δ-Bi2O3的10.67倍。Cd的掺杂点会成为光生电子的陷阱,延缓光生电子的表面传递,增强目标分子的化学吸附。
中温固体氧化物燃料电池复合阴极材料LaBiMn2O6-Sm0.2Ce0.8O1.9的制备与电化学性质
于亚泽, 孙丽萍, 赵辉, 霍丽华
2019, 35(4): 589-597  doi: 10.11862/CJIC.2019.081
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采用甘氨酸燃烧法合成了LaBiMn2O6粉体,并与Sm0.2Ce0.8O1.9均匀混合制备了LaBiMn2O6-Sm0.2Ce0.8O1.9(LBM-SDC)复合阴极材料。利用X射线衍射(XRD)和扫描电子显微镜(SEM)对材料的物相及微观形貌进行分析,结果表明LBM与SDC在1 000℃下有良好的化学稳定性。SDC的复合增加了氧离子传导路径,进而使氧还原反应(ORR)速度加快。电化学阻抗谱(EIS)测试结果表明,复合阴极极化电阻(Rp)随SDC复合量的增加呈现先降低后升高的趋势,当复合量为30%(w/w)时,阴极材料的性能最优。在700℃空气气氛下的极化电阻为0.186 Ω·cm2,相对LBM(0.717 Ω·cm2)减少74%。氧分压测试结果表明阴极反应的速率控制步骤为氧分子的吸附-解离过程。以复合阴极构筑的电解质支撑单电池Ni-SDC/SDC/LBM-30% SDC在700℃的最大输出功率密度为234 mW·cm-2,连续测试90 h输出功率衰减约4%。
两个有机锡羟基苯甲酸酯配合物的合成、结构及抗癌活性
张复兴, 何唐锋, 姚淑芬, 朱小明, 盛良兵, 邝代治, 冯泳兰, 庾江喜, 蒋伍玖
2019, 35(4): 598-604  doi: 10.11862/CJIC.2019.083
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合成了2个有机锡羟基苯甲酸酯配合物:梯形结构的二(对氯苄基)锡邻羟基苯甲酸酯[(μ3-O)(μ2-OH)(p-Cl-C6H4CH2Sn)2(O2CC6H4-OH-o)]21)和三苯基锡二(对羟基苯甲酸)酯(2)。通过元素分析、红外光谱、差热分析、X射线单晶衍射等方法对配合物进行了结构表征,并对其进行了量子化学从头计算和体外抗癌活性研究。结果显示:配合物1为具有Sn2O2构筑的3个平面四元环组成的梯形骨架结构,配合物2为单锡核结构,锡原子均为五配位的畸变三角双锥构型;配合物对人结肠癌细胞(HT-29)、肝癌细胞(HepG2)、乳腺癌细胞(MCF-7)、宫颈癌细胞(Hela)和肺癌细胞(A549)均显示出比临床使用的顺铂更强的抗癌活性。
以吡啶-2, 5-二羧酸或噻吩-2, 5-二羧酸为配体的过渡金属配合物的合成、晶体结构及性质
韩佳星, 刘峥, 梁楚欣, 唐群, 李庆伟, 张淑芬
2019, 35(4): 605-612  doi: 10.11862/CJIC.2019.069
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以吡啶-2,5-二羧酸(2,5-pyridinedicarboxylic acid,H2L1)、噻吩-2,5-二羧酸(Thiophene 2,5-dicarboxylic acid,H2L2)为主要配体,4,4'-联吡啶(4,4'-bipy)、菲咯啉(phen)为辅助配体,采用溶剂热法成功合成了3个过渡金属配合物:[Co2(L12(bipy)(H2O)6]·bipy·H2O(1)、[Cu(L22(bipy)2]n2)、[Ni2(L2)(phen)2(H2O)4](3),并利用X射线单晶衍射法、红外光谱(IR)、荧光光谱(FL)和热重分析(TG/DTG)等测试手段对其进行了表征。单晶结构分析表明:配合物1、配合物2P1空间群,配合物3P2/n空间群;配合物1和配合物3为零维双核小分子结构,配合物2为二维层状结构。
多孔硅/TiO2纳米线光阳极的制备及其光电催化性能
赵一铭, 杨继凯, 马福哲, 陈张笑雄, 魏子娟, 张宇飞, 成明, 杨雪, 肖楠, 王国政, 王新, 黄科科
2019, 35(4): 613-620  doi: 10.11862/CJIC.2019.088
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使用金属辅助化学刻蚀(MACE)法与水热法, 改变贵金属粒子的刻蚀时间, 制备不同n型多孔硅/TiO2纳米线光阳极。通过扫描电镜(SEM)和X射线衍射仪(XRD)对光阳极样品进行表征, 结果显示多孔硅宏孔的尺寸会随着刻蚀时间延长而增大, 由0.1 μm变化到0.4 μm, 多孔硅表面长有TiO2纳米线为金红石相及少量锐钛矿相。测试结果显示刻蚀35 min的多孔硅/TiO2样品具有最高的减反射率, 在模拟太阳光下具有较高的光电流(光电流密度)活性, 且在1.5 V外加偏压下具有最高的光电催化活性。这是由于刻蚀35 min的多孔硅基底具有优异的减反射性能, 同时多孔硅与TiO2纳米线复合形成光阳极之后具有异质结效应和窗口效应, 使得多孔硅/TiO2纳米线光阳极具有优异光电化学性能。
硅藻土原位负载网状纳米结构硅酸镁及其对Cr(Ⅵ)吸附性能
靳翠鑫, 杜玉成, 吴俊书, 牛炎, 王学凯, 李杨
2019, 35(4): 621-628  doi: 10.11862/CJIC.2019.076
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采用MgCl2·6H2O作为镁源, NH3·H2O作为沉淀剂, 十六烷基三甲基溴化铵(CTAB)作为模板剂, 以水热法在硅藻土表面原位生长纳米花状Mg(OH)2, 随反应时间增加, 转变成单斜晶系网状结构Mg3Si4O10(OH)2纳米花。采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)、氮气吸附-脱附测试、傅里叶红外光谱(FT-IR)、X射线光电子能谱(XPS)等测试手段对样品进行了表征, 结果显示:反应时间为0.5~2.0 h时硅藻土表面以生长Mg(OH)2为主, 样品的比表面积为180 m2·g-1; 反应时间至3 h时, 硅藻土表面Mg(OH)2转化成网状结构Mg3Si4O10(OH)2, 样品比表面积增大到350 m2·g-1, 此复合结构对Cr(Ⅵ)最大吸附量可达570 mg·g-1
球形TiSAPO-34分子筛的合成、表征及其对亚甲基蓝的吸附性能
罗五魁, 陈峰, 颜桂炀, 白云山
2019, 35(4): 629-634  doi: 10.11862/CJIC.2019.080
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利用水热法合成了TiSAPO-34分子筛, 通过扫描电子显微镜(SEM)、X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、N2吸附-脱附、紫外-可见漫反射吸收光谱(UV-Vis DRS)、热重(TG)等方法对其形貌、物相组成、孔径等进行表征。以亚甲基蓝的水溶液模拟污染物评价TiSAPO-34分子筛吸附性能, 考察了钛的掺杂量及样品再生后对亚甲基蓝吸附性能的影响。结果表明:样品形貌为球形, 是一种微孔分子筛, 具有较好的热稳定性。样品中部分Ti原子成功进入骨架, 仍保持了SAPO-34分子筛的骨架结构。在190℃晶化24 h得到的样品吸附性能较好, 0.3 g样品吸附1 h对0.01 g·L-1亚甲基蓝的水溶液模拟污染物吸附率达到80%。
MIL-125(Ti)及其氨基功能化材料修饰石英晶体微天平的湿敏性能
武月桃, 樊煜, 刘艳丽, 徐甲强
2019, 35(4): 635-642  doi: 10.11862/CJIC.2019.079
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采用简单的溶剂热法制备金属有机框架化合物MIL-125(Ti)和NH2-MIL-125(Ti)材料, 并通过X射线衍射仪、扫描电子显微镜、傅氏转换红外线光谱分析仪和比表面积测试仪对所得样品进行表征。将2种材料修饰构建为石英晶体微天平传感器, 测试其在11%~97% RH相对湿度范围内的湿度感测性能。实验结果表明, 基于MIL-125(Ti)和NH2-MIL-125(Ti)构建的传感器对湿度具有灵敏度高、重复性好、响应/恢复快等特点。相对于没有氨基修饰的MIL-125(Ti), NH2-MIL-125(Ti)材料修饰的传感器对湿度表现出更高的响应性能。在环境湿度约52%时, NH2-MIL-125(Ti)传感器对11% RH湿度响应值比MIL-125(Ti)湿度传感器的大57 Hz, 说明氨基功能化对MIL-125(Ti)的湿敏性能有显著的增强作用。此外, 通过Materials Studio模拟计算获得了水分子与MIL-125(Ti)及NH2-MIL-125(Ti)作用的吸附焓, 也证明氨基功能化对MIL-125(Ti)的湿度敏感性能具有增强作用。
HA/Ag纳米复合材料的制备与性能
翁仪瑾, 张霞, 周韬, 蒋浩, 张垒, 刘肖
2019, 35(4): 643-648  doi: 10.11862/CJIC.2019.072
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采用一锅热熔胶法制备出多孔花状羟基磷灰石/银(HA/Ag)纳米复合材料。通过检测罗丹明B揭示了HA/Ag作为SERS活性底物的独特拉曼增强效应,其检测极限为10-8 mol·L-1。在检测中,改变拉曼激光强度,取点位置等手段能有效提高检测的灵敏度。此外,所制备的多孔纳米复合材料HA/Ag作为对硝基苯酚(4-NP)还原为对氨基苯酚(4-AP)反应的催化剂,可以大大缩短反应时间40 min。
一种“裸眼”可视化检测溶液的pH值及细胞中铁离子的BODIPY类探针
渠星宇, 边永军, 白杨, 沈珍
2019, 35(4): 649-657  doi: 10.11862/CJIC.2019.089
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以吡啶-2-甲酸(4-甲酰基苯酚)酯代替对羟基苯甲醛,将对羟基苯基引入到BODIPY染料的3-位,以高产率得到一个BODIPY类探针2。探针2易溶解到各种有机溶剂中,在甲醇溶液中的最大吸收和发射波长分别为570和585 nm,荧光量子产率达到0.9。当溶液的pH值从酸性过渡到碱性时,对羟基苯乙烯基团会慢慢失去质子,其溶液最大吸收波长发生红移,荧光发生淬灭,而且溶液颜色也发生明显的变化。因此,探针2可作为一种"裸眼"可视化的pH探针。此外,探针2对Fe3+也有明显的响应,在溶液中加入Fe3+,探针2分子结构中乙烯基团发生断裂,其溶液最大吸收波长和最大发射峰均发生蓝移。因此,探针2也可以作为Fe3+的比率型探针。同时探针2毒性较低、渗透性好、对Fe3+选择性高,可以应用到细胞中检测Fe3+的含量。
Fe3O4/GO/PPy复合材料的制备及其对2-硝基-1, 3-苯二酚的吸附性能
雷李玲, 杨清香, 赵俊红, 张琰, 贾朝阳, 路冉, 聂李敏, 陈志军
2019, 35(4): 658-666  doi: 10.11862/CJIC.2019.078
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采用改进的Hummers法制备了氧化石墨烯,用水热法首次制备了Fe3O4/GO/PPy(聚吡咯)三元复合粒子用于处理含2-硝基-1,3-苯二酚(NRC)的废水,研究了其对水中NRC的吸附性能。采用紫外-可见吸收光谱(UV-Vis)、透射电子显微镜(TEM)、傅里叶变换红外光谱(FT-IR)、X射线衍射(XRD)、振动样品磁强计及ζ电位等对所制备复合粒子的结构进行了表征;研究了溶液pH值、吸附剂用量、NRC的初始浓度、吸附时间和温度对吸附NRC的吸附性能的影响,并对吸附过程进行了吸附动力学模拟。结果表明:制备的Fe3O4/GO/PPy复合材料为层状分散结构,PPy及Fe3O4颗粒无规则地镶嵌在石墨烯片层之间。Fe3O4颗粒为多面体晶体结构,尺寸为100~300 nm。Fe3O4/GO/PPy具有超顺磁性,40 s可以磁分离,NRC移除率达91.6%;在NRC浓度为200 mg·L-1、pH=5±0.05、温度T=318 K、吸附剂用量10 mg·L-1和吸附时间6 h的条件下Fe3O4/GO/PPy对NRC的吸附量最大,达到163.3 mg·g-1。NRC吸附动力学符合二级动力学模型,吸附等温线符合Langmuir模型。循环使用5次后,NRC的移除率由最初的91.6%下降至77.6%,说明Fe3O4/GO/Ppy磁性复合物的结构具有较好的稳定性,且可以再重复利用。
LiNi0.8Co0.15Al0.05O2制备过程中聚乙烯吡咯烷酮的加入对其电化学性能的影响
彭俊棋, 高艺珂, 李欢, 胡爱琳, 卢晓英, 江奇
2019, 35(4): 667-673  doi: 10.11862/CJIC.2019.082
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为提高LiNi0.8Co0.15Al0.05O2(NCA)材料的电化学性能,在NCA材料的制备过程中加入聚乙烯吡咯烷酮(PVP),通过调控所得NCA材料的形貌来提高其电化学性能。所得材料采用X射线衍射仪和扫描电子显微镜进行形貌结构表征,电化学性能经组装成纽扣电池,用电池程控测试仪和电化学工作站进行测试。研究结果表明:由于PVP的空间效应和静电作用,PVP改性的NCA材料拥有更完整的棒状结构、发育出更好的层状结构,电化学储能性能得到较大的提升。在0.1C下,材料的首次放电比容量和充放电效率分别从143.36 mAh·g-1、78.25%提高到了170.24 mAh·g-1、89.20%;在0.2C的实验室条件下循环50次后,容量保持率为94.28%。
Articles
Honeycomb-like Carbon Materials Derived from Pomelo Peels for the Simultaneous Detection of Heavy Metal Ions
Ting ZHANG, Shi-Jie MA, Yi PAN, Ji-Biao GUAN, Ming ZHANG, Han ZHU, Ming-Liang DU
2019, 35(4): 674-686  doi: 10.11862/CJIC.2019.077
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The metal-free carbon materials were obtained by a facile KOH activation and pyrolysis process from inexpensive and readily available pomelo peels, and possessed honeycomb-like nanostructures with a high specific surface area of 1 055 m2·g-1 and a high graphitization degree. A porous activated carbon (PAC) material modified electrode was utilized as the working electrode for the simultaneous detection of Cd2+, Pb2+, and Cu2+ using square-wave anodic stripping voltammetry (SWASV) and exhibited high sensitivity, repeatability, stability and a low detection limit. The interconnected micropores and mesopores act as efficient ion-transfer channels and provid active surface areas with high accessibility, which serve as transport highways to accelerate mass diffusion and significantly promote exchange efficiency. High graphitization degree increases the electrical conductivity of the material and accelerates electron transport.
Pb(Ⅱ) Coordination Complexes Based on 5-Methyl-1H-pyrazole-3-carboxylic Acid: Syntheses, Structures and Luminescent Properties
2019, 35(4): 687-694  doi: 10.11862/CJIC.2019.084
[摘要]  (13) [HTML全文] (13) [PDF 2000KB] (0)
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In the presence of different N ancillary ligands, treatment of H2MPCA with corresponding Pb(Ⅱ) salts afforded two complexes, [Pb(HMPCA)2(H2O)2]·H2O (1) and[Pb(HMPCA)2(phen)]·H2O (2) (H2MPCA=5-methyl-1H-pyrazole-3-carboxylic acid, phen=1, 10-phenanthroline). In dinuclear complex 1, the[Pb(μ2-HMPCA))]2 units are extended into a 1D chain structure by a pair of Pb…O secondary bonds. Then, these 1D chains are further assembled to a 2D supramolecular structure through intermolecular hydrogen bonds. While complex 2 displays a mononuclear structure, the Pb…O secondary bonds emerged in the Pb2O2 rhomb, which are further packed into a 3D supramolecular framework though ππ interactions and hydrogen bonds. The thermal and luminescent properties of complexes 1 and 2 have also been investigated.
Efficient F-Doped BiVO4 Photocatalyst Synthesized by One-Step Alcohol-Hydrothermal Method
Hai-Yan JIANG, Fan ZHANG, Shu-Guang YU, Yu-Zhen LI
2019, 35(4): 695-702  doi: 10.11862/CJIC.2019.074
[摘要]  (12) [HTML全文] (12) [PDF 3522KB] (0)
摘要:
F-doped BiVO4 photocatalysts were fabricated by using a simple one-step alcohol-hydrothermal method with NH4F as the precursor of the dopant. The physicochemical properties of the photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis), and photoluminescence spectra (PL). Their photocatalytic activities were determined through the degradation of phenol in the presence of a small amount of H2O2 under visible-light illumination. It is found that compared to the un-doped BiVO4 sample, the F-doped BiVO4 samples retained the monoclinic structure and had higher crystallinity, surface oxygen vacancy densities and separation efficiency of photogenerated charge carriers, stronger optical absorbance performances, and lower bandgap energies. Among these F-doped BiVO4 samples, the F-doped BiVO4 sample (nominal nF/nBi=1.0, bandgap energy=2.43 eV) exhibited the best photocatalytic performance (the conversion of phenol up to 95% in 90 min), due to the highest crystallinity, surface oxygen vacancy density, and separation efficiency of photogenerated charge carriers, the strongest optical absorbance performance, and the lowest bandgap energy.
Syntheses, Crystal Structures and Properties of Zn(Ⅱ), Mn(Ⅱ) Complexes Based on 5-Amino-1H-1, 2, 4-triazole-3- carboxylic Acid
Kang YANG, Yu-Hui TAN, Bin WANG, Hai-Tao ZHOU, Chao LI, Chang-Shang YANG, Yi LIU, Ji-Xing GAO, Yun-Zhi TANG
2019, 35(4): 703-710  doi: 10.11862/CJIC.2019.075
[摘要]  (13) [HTML全文] (13) [PDF 3226KB] (0)
摘要:
Two coordination polymers[Zn(Athy)Br]n (1, HAthy=5-amino-1H-1, 2, 4-triazol-3-ol) and[Mn(Atca)2(H2O)2] (2, HAtca=5-amino-1H-1, 2, 4-triazole-3-carboxylic acid) were separately synthesized by hydrothermal method and solution diffusion method using HAtca, ZnBr2 and MnCl2, respectively. X-ray single crystal diffraction analyses indicate both 1 and 2 have different crystal structures. Complex 1 crystallizes in the orthorhombic system, space group Pbca. Complex 2 crystallizes in the monoclinic system, space group P21/c. Complex 1 is a 2D grid structure without any hydrogen bonds, but complex 2 has a 3D grid structure constructed by highly stable hydrogen bonds. Moreover, 1 and 2 show strong fluorescence emission at 360, 462 nm and 382, 402 nm at room temperature, respectively.
Preparation of PbF2:Er3+, Yb3+ Phosphors and Multi-Wavelength Sensitive Bidirectional Conversion Luminescence Mechanism
Xiao-Yi MA, Biao LI, Yi-Fan WANG, Pan HU, Tong-Ting YAN, Zhao-Hui BAI
2019, 35(4): 711-719  doi: 10.11862/CJIC.2019.070
[摘要]  (13) [HTML全文] (13) [PDF 5172KB] (0)
摘要:
PbF2:Er3+, Yb3+ bidirectional conversion phosphors were successful prepared by the high temperature solid-state reaction method. The samples were characterized by X-ray powder diffraction (XRD), general structure analysis system structure refinement, the intensity-power test and fluorescence spectrum method. XRD and Rietveld refinement were performed to analyze the phase composition and the changes of cell parameters. The fluorescence spectra analysis showed the samples exhibited the intense green emissions in the range of 540~550 nm and weak red emission in the range of 650~660 nm when excited at ultraviolet (378 nm) and different infrared wavelengths (808, 980, 1 064 and 1 550 nm). Finally, luminescence mechanisms excited at different infrared wavelengths were discussed by means of the intensity-power test, and the down-conversion (DC) luminescence mechanism excited at 378 nm was analyzed.
Syntheses, Structural Characterizations and Spectroscopic Properties of Two Copper(Ⅰ) Complexes Based on Diphosphine Ligands and[2, 3-f]pyrazino[1, 10]phenanthroline
Yan-Lei LU, Ning ZHU, Yu-Meng ZHAO, Sen LIN, Xiao-Nan KUANG, Zhong-Feng LI, Xiu-Lan XIN, Yu-Ping YANG, Qiong-Hua JIN, Jiang-Wei ZHANG
2019, 35(4): 720-728  doi: 10.11862/CJIC.2019.059
[摘要]  (37) [HTML全文] (37) [PDF 1687KB] (0)
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Two novel copper(Ⅰ) complexes[Cu(dppBz)(dpq)]ClO4 (1) and[Cu(dppe)(dpq)]ClO4 (2) (dppBz=1, 2-bis(diphenylphosphino)benzene, dppe=1, 2-bis(diphenylphosphino)ethene, dpq=[2, 3-f]pyrazino[1, 10]phenanthroline) have been synthesized and characterized by X-ray diffraction, elemental analysis, infrared spectroscopy, absorption spectra, luminescent spectra, 1H NMR, 31P NMR spectroscopy and terahertz (THz) time-domain absorption spectroscopy. The central Cu(Ⅰ) ion is chelated by a diimine ligand and a diphosphine ligand forming a distorted tetrahedron configuration for 1, and the configuration of 2 is similar to 1. The luminescent spectra of 2 indicated that the emission has metal-to-ligand charge transfer (MLCT) characteristics. The terahertz time-domain absorption spectroscopy analysis in a range of 0.2~2.8 THz showed that the absorption peaks at 0.40~0.90 THz are related to the coordination of the central Cu(Ⅰ).
Electrochemical Sensor Based on Ni12P5 Nanoparticles for Sensitive Determination of Glucose
Wen XU, Xun ZHOU, Jin-Ming XU, Han XU, Fei-Fei TAO
2019, 35(4): 729-736  doi: 10.11862/CJIC.2019.073
[摘要]  (16) [HTML全文] (16) [PDF 3041KB] (0)
摘要:
A non-enzymatic glucose biosensor was designed for the first time based on the employment of monodisperse Ni12P5 nanoparticles (NPs), which were fabricated by a modified one-pot hot-solution colloidal preparation method. The crystal structure, chemical composition and morphology of the Ni12P5 NPs was determined by using power X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectra, X-ray energy dispersive spectrometer. The developed sensor has presented excellent performance which involved a quick response time less than 3 s, a broad detection ranging from 0.002 to 4.2 mmol·L-1, a high sensitivity up to 1 572 mA·L·mol-1·cm-2, and a detection limit as low as 0.8 μmol·L-1. Additionally, it can be used to detect the glucose in the human blood serum with satisfactory result.
High Sensitivity and Selectivity of Aminoantipyrine Schiff Base for the Recognition of Fe2+
Sheng-Tian CHEN, Yu ZHANG, Jian-Ying ZHAO, Kui-Rong MA, Rong-Qing LI, Guo-Dong TANG
2019, 35(4): 737-744  doi: 10.11862/CJIC.2019.091
[摘要]  (18) [HTML全文] (18) [PDF 2921KB] (0)
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An aminoantipyrine based chemosensor, (E)-1, 5-dimethyl-4-((2-(4-methylpyridin-2-yl)pyridin-4-yl)methyleneamino)-2-phenyl-1, 2-dihydropyrazol-3-one(L), derived from 4-aminoantipyrine and 2-(4-methylpyridin-2-yl) isonicotinaldehyde, was synthesized and the optical and metal sensing properties were investigated. The chemosensor L showed a selective colorimetric sensing ability for Fe2+ by changing colors from pale yellow to deep red in water-ethanol (9:1, V/V) medium, which facilitates the 'naked-eye' recognition of Fe2+ from other examined metal ions. The complex stoichiometry of Fe2+ to L(1:3, [FeL3]2+) was obtained by Job's method. The association constant was determined to be 3.70×1021 L3·mol-3. The present results indicate that the chemosensor L could be used as a selective, sensitive colorimetric sensor for Fe2+.
Ga(Ⅲ) and In(Ⅲ) Complexes with 3-Ethyl- 2-acetylpyrazine N(4)-(p-Tolyl) thiosemicarbazone:Synthesis, Crystal Structure and DNA-Binding Activity
Wen-Zhao XUE, Xiao-Lei ZHAO, Xue-Xue YAN, Xue-Jie ZHANG, Wei-Na WU, Yuan WANG, Zhong CHEN
2019, 35(4): 745-751  doi: 10.11862/CJIC.2019.085
[摘要]  (43) [HTML全文] (43) [PDF 2875KB] (0)
摘要:
Two novel complexes, [Ga(L)2]NO3·4CH3OH (1) and[In(L)2]NO3·1.75CH3OH (2) based on HL (HL=3-ethyl-2-acetylpyrazine N(4)-(p-tolyl)thiosemicarbazone) were synthesized and characterized by X-ray diffraction analyses. Complexes 1 and 2 are isostructural and crystallize in the monoclinic system, space group P21/c with different crystal methanol molecules. The metal center in each complex is surrounded by two monoanionic L- with[N2S] donor set, thus giving a distorted octahedral coordination geometry. In addition, the fluorescence spectra indicate that the interactions of complexes with DNA are stronger than that of ligand HL.
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论文
SAPO-18分子筛晶化机理及其甲醇制烯烃性能
郭云鸦, 梁光华, 张燕挺, 何祖光, 梁亚凝, 李宁, 李晓峰, 窦涛
2019, 35(2): 185-193  doi: 10.11862/CJIC.2019.044
[摘要]  (102) [HTML全文] (102) [PDF 6444KB] (102)
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分别以拟薄水铝石、硅溶胶、磷酸为铝源、硅源、磷源,NN-二异丙基乙胺为模板,采用水热法制备出不同晶化时间下的SAPO-18分子筛。采用X射线衍射(XRD)、电子扫描显微镜(SEM)、氨气程序升温脱附(NH3-TPD)、固体核磁共振(29Si MAS NMR,27Al MAS NMR)、傅里叶红外(FT-IR)等对不同晶化时间下的产物进行表征以及甲醇制烯烃(MTO)催化性能检测。表征结果结合MTO催化反应性能表明:水热体系下SAPO-18分子筛生长过程可分为3个阶段:晶化初期(≤ 2 h),快速生长期(6~12 h),生长稳定期(1~3 d)。其中,在晶化初期只有极少量的硅进入Al(PO)4类中间体;此后为快速生长期,硅原子进入Al(PO)4类中间体及SAPO-18晶体取代磷、铝原子,以SMⅡ机制为主,SMⅢ机制为辅;在生长稳定期2种取代机制主次发生了变化。
以[Eu(PBrBA)3phen]和[Eu(PCBA)3phen]为探针的温敏漆制备及其性能对比
毕冠, 孙晶, 周晨, 于文生, 王媛, 唐娟
2019, 35(2): 203-208  doi: 10.11862/CJIC.2019.029
[摘要]  (85) [HTML全文] (85) [PDF 2498KB] (85)
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以氧化铕(Eu2O3)、对氯苯甲酸(PCBA)、对溴苯甲酸(PBrBA)和菲咯啉(phen)为原料制备了菲咯啉对氯苯甲酸铕[Eu(PCBA)3 phen]、菲咯啉对溴苯甲酸铕[Eu(PBrBA)3phen]两种探针分子,并将这2种探针分子掺杂在甲基丙烯酸甲酯(MMA)中,以过氧化苯甲酰(BPO)为引发剂,制得Eu(PCBA)3phen/PMMA和Eu(PBrBA)3phen/PMMA温敏漆样品。利用红外光谱仪、扫描电子显微镜、紫外-可见分度光度计和荧光光谱仪对探针分子的组成结构、发光性能、形貌和温敏漆的温度敏感性进行了测试分析,研究了不同配体对探针分子发光性能和温敏漆性能的影响。结果表明,Eu3+分别与对氯苯甲酸(PCBA)和对溴苯甲酸(PBrBA)2种主配体配位,并且第二配体菲咯啉(phen)均参与了配位,成功合成了2种配合物。2种配合物均发出Eu3+的特征荧光,其中以PBrBA为主配体的菲咯啉铕三元配合物具有更好的发光性能。此外,基于这2种探针分子制备的温敏漆在50~90℃范围内均具有温度猝灭性能,以Eu(PCBA)3phen为探针制成的温敏漆温度敏感性更强。
磷灰石结构荧光粉Ba10(PO4)6F2:Ce3+, Tb3+的合成、发光和能量传递
程少文, 张娜, 卓宁泽, 朱月华, 陈永浩, 蒋鹏, 杜文慧, 叶恩淦, 王海波
2019, 35(2): 209-216  doi: 10.11862/CJIC.2019.038
[摘要]  (98) [HTML全文] (98) [PDF 4371KB] (98)
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采用高温固相法合成了系列Ce3+和Ce3+/Tb3+激活的具有磷灰石结构荧光粉Ba10(PO46F2。用X射线衍射(XRD)、扫描电镜(SEM)、激发和发射(PLE和PL)光谱对样品进行了表征分析。研究结果表明:所合成的荧光粉Ba10(PO46F2:Ce3+,Tb3+具有氟磷灰石结构,样品微观呈现不规则形貌。荧光粉Ba10-x(PO46F2xCe3+的相对发射强度随着x增加而增强,当x=0.09时,荧光强度达到最大。荧光粉Ba10(PO46F2:Ce3+,Tb3+的激发光谱为240~330 nm的宽带,发射光谱呈现出Ce3+的5d→4f跃迁紫外光(335和358 nm)发射和Tb3+的4f→4f跃迁绿光(542 nm)发射。光谱特性表明,发光过程中存在Ce3+→Tb3+能量传递,能量传递效率可以达到60%。计算Ce3+和Tb3+的临界距离为0.79 nm,能量传递机理是偶极-偶极交互作用。此外,详细论述了Ce3+和Tb3+之间的能量传递和发光的过程。通过调节Tb3+的掺杂浓度,对荧光粉发光色坐标与Tb3+的掺杂浓度之间的关系也进行了研究,随着Tb3+的掺杂量从0增加0.52,荧光粉Ba10(PO46F2:Ce3+,Tb3+的发射光谱色坐标可以从(0.149 4,0.045 1)蓝色区变化到(0.280 1,0.585 3)绿色区。
碳纳米管改性g-C3N4提升可见光催化降解性能
王鹏, 李昭, 周颖梅, 徐艳, 朱捷, 王士凡, 蔡可迎, 李靖, 堵锡华, 杨朋举
2019, 35(2): 217-224  doi: 10.11862/CJIC.2019.022
[摘要]  (87) [HTML全文] (87) [PDF 5404KB] (87)
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以尿素为原料,引入少量的多壁碳纳米管(CNT)改性,采用简便方法制备CNT/g-C3N4催化剂。利用扫描电镜(SEM)、透射电镜(TEM)、傅里叶红外光谱仪(FT-IR)、X射线衍射(XRD)、X射线光电子能谱(XPS)、紫外-可见-近红外分光光度计(UV-Vis-NIR Spectrophotometer)、荧光光谱(PL)等手段对CNT/g-C3N4催化剂进行表征。结果表明,g-C3N4与CNT之间的协同作用,影响了g-C3N4的能带结构,增强了其对可见光的吸收,改善了光生载流子的分布,提高了电子-空穴对的分离效率。并以罗丹明B(RhB)水溶液模拟废水,在可见光下考察催化剂的光催化降解性能,发现当CNT掺杂量为0.1%(w/w)时效果最佳,降解速率常数是体相g-C3N4的3.1倍,且研究发现超氧自由基是该体系下的主要活性物种。
系列Ag-Ln配位聚合物的合成、结构及发光性能
王岩, 陈飞霏, 胡晓双, 赵然, 迟玉贤, 金晶
2019, 35(2): 225-235  doi: 10.11862/CJIC.2019.014
[摘要]  (89) [HTML全文] (89) [PDF 5076KB] (89)
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采用水热合成法,以吡嗪-2-羧酸(2-Hpzc)、3,5-吡啶二羧酸(3,5-H2PDA)和草酸(H2ox)为配体,合成9种Ag-Ln配位聚合物:{[LnAg(2-pzc)2(ox)]·H2O}n(Ln=Pr(1),Nd(2),Sm(3),Eu(4)),[LnAg(3,5-PDA)(ox)(H2O)]n(Ln=Pr(5),Nd(6)),[LnAg(3,5-PDA)(3,5-HPDA)(ox)0.5(H2O)2]n(Ln=Sm(7),Dy(8),Ho(9))。配位聚合物1~4是同构的,由2-pzc-和ox2-连接,而配位聚合物5~9是以3,5-PDA2-和ox2-为桥联配体,均呈现3D网状结构。光物理性能研究表明配位聚合物均表现出Ln(Ⅲ)的特征发射,这可归因于Ag-配体部分(d-block)的敏化作用。另外,在晶体场和Ag(Ⅰ)离子4d轨道的共同作用下,Ln(Ⅲ)离子的4f轨道被调谐,使部分能级发生明显的位移,表现为相应NIR发射带的位移,在其UV-Vis-NIR吸收光谱中可以得到佐证。
凹凸棒石/g-C3N4-AgFeO2复合材料制备及其光催化性能
谢登裕, 蒋亿, 纪媛媛, 殷明慧, 盛振环, 赵伟, 殷竟洲, 李乔琦, 仲慧, 张莉莉
2019, 35(2): 236-244  doi: 10.11862/CJIC.2019.040
[摘要]  (106) [HTML全文] (106) [PDF 6432KB] (106)
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以凹凸棒石(简称凹土,ATP)为基体,通过原位化学法一步直接合成g-C3N4薄层材料,并将其有效固载于凹土表面(ATP/g-C3N4),再通过原位沉淀法引入不同比例AgFeO2纳米颗粒,构筑系列兼具磁分离特性和高效光催化活性的ATP/g-C3N4-AgFeO2-Y复合光催化剂(Y=wATP/g-C3N4/(wATP/g-C3N4+wAgFO2)×100%,表示ATP/g-C3N4在ATP/g-C3N4-AgFeO2复合材料中所占的质量百分数)。采用XRD、SEM、BET、UV-Vis、PL和ICP表征其结构和物化性能,以酸性红G(ARG)为目标降解物,研究其光催化性能。研究发现:通过形成Si-O-C键,g-C3N4薄层被均匀固定在凹土表面;AgFeO2纳米颗粒均匀沉积于ATP/g-C3N4表面并形成Z型异质结,ATP/g-C3N4-AgFeO2-Y具有比ATP/g-C3N4和AgFeO2更优异的可见光光催化性能,且随着ATP/g-C3N4含量的增大呈先升高而后下降的趋势;当Y=57%时复合材料的性能最佳,ATP/g-C3N4-AgFeO2-57%对20 mg·L-1酸性红G的降解率可达97.4%,循环4次使用后,降解率仍保持94.2%。通过自由基捕获实验研究了光催化反应机理,发现·O2-是光催化过程的主要活性物种。
Pr1-xSrCo0.5Ni0.5O4+δ阴极材料的合成及电化学性质
刘建伟, 孙丽萍, 赵辉, 霍丽华
2019, 35(2): 245-253  doi: 10.11862/CJIC.2019.030
[摘要]  (115) [HTML全文] (115) [PDF 4338KB] (115)
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采用固相法合成中温固体氧化物燃料电池(IT-SOFC)阴极材料Pr1-xSrCo0.5Ni0.5O4+δ(P1-xSCN,x=0.00,0.05,0.10,0.15,0.20),并对材料的物相、热膨胀系数(TEC)、电导率、电极的微观形貌以及电化学性质进行表征。XRD结果表明,该材料形成单一的K2NiF4结构,空间群为I4/mmm,并与电解质材料Ce0.9Gd0.1O1.95(CGO)具有良好的高温化学相容性。碘量法分析表明随着Pr离子缺位浓度增加,P1-xSCN中Co/Ni离子平均化合价随着x的增加而升高,至x=0.10后逐渐降低,而氧空位含量逐渐升高。引入Pr离子缺位使材料的电导率明显提高,其中P0.90SCN在700℃空气中电导率值为309 S·cm-1。TEC测试结果显示,随着Pr缺位的增加,热膨胀系数逐渐增大,最大值为1.51×10-5 K-1。交流阻抗谱(EIS)测试结果表明,Pr缺位明显降低了电极的极化阻抗值,P0.90SCN阴极在700℃空气中的极化阻抗值为0.21 Ω·cm2。电解质支撑NiO-CGO/CGO/P0.90SCN单电池在700℃最大输出功率密度为197.8 mW·cm-2
g-C3N4/双钙钛矿复合材料的制备及氧催化性能
王成, 黄红霞, 肖阳, 梁大铭
2019, 35(2): 254-262  doi: 10.11862/CJIC.2019.033
[摘要]  (115) [HTML全文] (115) [PDF 3404KB] (115)
摘要:
通过溶胶-凝胶法制备出不同Ni掺杂比例的双钙钛矿Sr2NixCo2-xO6x=0.2,0.4,0.6,0.8),通过热分解法制备出具有层状结构的纳米颗粒g-C3N4,并制备其复合物催化剂。将双钙钛矿和g-C3N4分别制备成双功能电极片,用于测试其对氧还原(ORR)和氧析出(OER)的催化活性,然后选取具有最佳氧催化活性的Ni掺杂比例x=0.4的双钙钛矿与一定重量比例的g-C3N4进行复合,测试复合催化剂的氧催化活性。结果表明,复合后的催化剂催化效果明显优于单一催化剂,当g-C3N4添加量占双钙钛矿的30%(w/w)时复合催化剂催化氧还原反应的最大电流密度为395.7 mA·cm-2(-0.6 V vs Hg/HgO),氧析出反应的最大电流密度为372.0 mA·cm-2(1 V vs Hg/HgO),这表明g-C3N4与Sr2Ni0.4Co1.6O6复合后协同催化能够提高双钙钛矿的氧催化活性。
Bi/BiVO4&Bi4V2O11复合催化剂的制备及其光催化性能
梁梦君, 邓楠, 向心怡, 梅英, 杨志远, 杨赟, 杨水金
2019, 35(2): 263-270  doi: 10.11862/CJIC.2019.028
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摘要:
经由溶剂热反应、光辅助还原过程制备Bi/BiVO4&Bi4V2O11纳米复合光催化材料。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、高分辨率透射电子显微镜(HRTEM)、X射线光电子能谱(XPS)、紫外-可见漫反射光谱(UV-Vis DRS)、N2吸附-脱附等温线和光致发光(PL)等手段对该复合物进行表征。实验结果表明当金属Bi与BiVO4&Bi4V2O11的质量比值为0.8,可见光照射30 min时,Bi/BiVO4&Bi4V2O11复合催化剂对罗丹明B(RhB)的降解率可达95.6%。此外,Bi/BiVO4&Bi4V2O11对四环素(TC)的降解也表现出增强的光催化性能。Bi/BiVO4&Bi4V2O11复合材料提升的光催化性能可能归因于金属Bi的表面等离子体共振(SPR)效应、拓宽的可见光吸收范围和增大的比表面积。此外,提出了复合光催化剂可能的光催化机理。
Bi5O7I/聚苯胺复合光催化剂的制备及光催化活性
王璐, 李曦, 唐子聪, 周楠, 俞峥松, 董永志, 李小争, 魏登贵, 董玉林, 李全华, 刘鹏
2019, 35(2): 271-276  doi: 10.11862/CJIC.2019.047
[摘要]  (93) [HTML全文] (93) [PDF 3322KB] (93)
摘要:
首先采用化学氧化聚合法合成聚苯胺(PANI),再采用溶剂热法制备了Bi5O7I/PANI复合材料,并采用X射线衍射、傅里叶变换红外光谱、场发射扫描电镜、紫外-可见漫反射光谱和荧光光谱等对所制备材料进行了表征,考察了复合材料在可见光光照条件下降解罗丹明B(RhB)的催化性能。结果表明当负载PANI后,Bi5O7I/PANI的复合材料都表现出优异的光催化性能。当PANI负载量在5%(w/w)时,催化效率最佳。在60 min内,其降解RhB的速率常数为Bi5O7I的3.9倍。捕获实验表明超氧自由基和空穴是该过程的主要活性物种。Bi5O7I/PANI具有优异光催化性能的原因主要在于,负载的PANI扩展了可见光吸收范围并增强了可见光吸收强度,而且PANI和Bi5O7I匹配的能级结构抑制了光生电子-空穴的复合效率。
氰基合钴(Ⅲ)氢键型笼状超分子晶体的合成、结构及介电性质
郑晓媛, 刘洋, 秦刘磊, 俞非凡, 朱春立, 刘尊奇
2019, 35(2): 277-284  doi: 10.11862/CJIC.2019.036
[摘要]  (106) [HTML全文] (106) [PDF 3137KB] (106)
摘要:
以2-氯苯胺(o-chloroaniline,o-CA)、18-冠醚-6(18-crown-6)和钴氰酸为原料,在甲醇和水的混合溶液内通过蒸发法合成氰基合钴配合物氢键笼状超分子晶体材料(H)0.5o-CAH)[Co(CN)6]0.5·(18-crown-6)0.5·H2O(1)。并通过单晶X射线衍射、红外光谱、粉末X射线衍射、元素分析、热重分析(TG)和介电常数测试等对超分子晶体进行了结构及电性能表征。测试结果表明,该晶体在低温下属于三斜晶系,空间群为P1,晶胞参数为a=0.869 22(1)nm,b=0.964 09(12)nm,c=1.129 93(14)nm,α=77.894 0(10)°,β=78.877 0(10)°,γ=88.684 0(10)°。结构显示氰基合钴配合物、超分子阳离子和水分子通过氢键相互作用在空间内形成三维笼状。笼状顶点的钴原子随着温度的变化其间距发生明显的伸缩,导致晶体在260 K附近观察到明显的介电异常现象。
原位制备的铁配合物催化烯烃选择性环氧化
宋虹瑾, 李璐, 张妮, 王斐, 吕婧, 孟祥光
2019, 35(2): 285-292  doi: 10.11862/CJIC.2019.046
[摘要]  (115) [HTML全文] (115) [PDF 2296KB] (115)
摘要:
制备了配体2-(2-吡啶基)-噁唑啉。该含氮配体能够在乙腈溶液中与三氟甲磺酸亚铁和其它辅助配体原位形成具有催化活性的六配位金属亚铁配合物。量子化学计算表明配体上的氮原子而非氧原子与铁配位。研究表明,以H2O2为氧化剂,该金属配合物能够在乙腈溶液中高活性地催化末端芳香烯烃和脂肪烯烃的环氧化反应;该反应条件温和、迅速、选择性好并且适用底物范围宽泛。辅助配体、溶剂和氧化剂等因素对反应的活性和选择性影响很敏感,文中对这些影响进行了较详细的研究。
作为Be2+磷光探针的含9-冠-3的铱配合物
潘淼, 胡媛媛, 赵卓, 姚永林, 周会东, 童碧海, 张千峰
2019, 35(2): 293-299  doi: 10.11862/CJIC.2019.049
[摘要]  (94) [HTML全文] (94) [PDF 3014KB] (94)
摘要:
以4'-(2-苯并噻唑基)苯并-9-冠-3(BTZ9C3)为主配体,用2,2'-联吡啶(bpy)及3-三氟甲基-5-(2'-吡啶基)-1,2-二唑(Hfppz)辅助配体分别合成了离子型铱配合物[Ir(BTZ9C3)2(bpy)]PF61)和中性铱配合物[Ir(BTZ9C3)2(fppz)](2)。配合物的结构通过核磁、高分辨质谱进行了表征,并测定了配合物1的单晶结构。对它们光物理性能的研究表明,2种配合物掺杂在PMMA中的发光为黄绿光发射,配合物1的发光波长为535 nm,配合物2的发光波长为541 nm,发光量子效率分别为10.8%,45.0%,发光寿命分别为3.01和2.58 μs,为典型的磷光发射。通过循环伏安法测得配合物12的HOMO能级分别为-5.60和-5.35 eV。2种配合物对Be2+都有发光增强的选择性识别效果,化学计量比为1:2,最低检测限低至6.0 μmol·L-1。抗干扰能力方面,离子型配合物1的抗干扰能力较好,而中性配合物2受Al3+的干扰较大。
三乙醇胺改性Cu/Zn/Al类水滑石衍生氧化物催化合成气制备低碳醇
程淑艳, 郝艳红, 寇佳伟, 高阳艳
2019, 35(2): 300-306  doi: 10.11862/CJIC.2019.041
[摘要]  (91) [HTML全文] (91) [PDF 876KB] (91)
摘要:
采用共沉淀法制备Cu/Zn/Al类水滑石前驱体,并用配体三乙醇胺(TEA)对其进行改性。前驱体经焙烧后成功获得TEA改性的Cu/Zn/Al催化剂。借助XRD、FTIR、H2-TPR、CO-TPD及SEM等方法对催化剂进行表征,并将其应用于合成气制备异丁醇的活性评价反应中。结果表明,TEA的加入能够改变催化剂形貌,使催化剂表面呈松散絮状结构。TEA可使类水滑石前驱体的结构发生膨胀,其焙烧获得的催化剂中有明显的晶格扭曲和晶格缺陷。TEA对催化剂结构的改变有利于Cu/Zn/Al催化剂中CuO组分的氢还原和CO在催化剂表面的化学吸附,从而促进异丁醇的合成。当TEA的添加比例为nTEA/nZn=0.5时,TEA改性的Cu/Zn/Al催化剂的催化效果达到最佳。
具有聚集荧光增强性质的双(4-二乙氨基水杨醛)缩偶氮二甲酰肼二丁基锡的合成和晶体结构
冯泳兰, 邝代治, 张复兴, 庾江喜, 蒋伍玖, 朱小明
2019, 35(2): 307-313  doi: 10.11862/CJIC.2019.043
[摘要]  (105) [HTML全文] (105) [PDF 3776KB] (105)
摘要:
在甲醇溶液中,卡巴肼、(4-二乙氨基)水杨醛和二乙酸二丁基锡"一锅法"反应,合成了一个新颖的基于双(4-二乙氨基水杨醛)缩偶氮二甲酰肼(L)的七配位有机锡配合物[Sn(L)(n-butyl)2]nT)。经元素分析、IR、(1H,119Sn,13C)NMR和X射线衍射晶体结构表征,T的晶体属单斜晶系C2/c空间群,中心锡周围由双(4-二乙氨基水杨醛)缩偶氮二甲酰肼的O,N配位原子占据赤道位置和2个丁基占据顶端位置形成畸变五角双锥构型。通过烯醇式氧原子的桥联配位作用,T向一维带状无限扩展产生"竹筏状"超分子结构。配合物T在二甲基甲酰胺、四氢呋喃、乙醇、甲醇和甲苯有机溶剂及其有机溶剂-水混合物中具有强荧光发射峰,当含水量的体积分数在0~10%(V/V)时具有良好的聚集荧光增强效应,含水量大于10%(V/V)时发生荧光淬灭。
Articles
One-Pot Synthesis of Rose-like Ce-Doped SnS2 with Enhanced Visible-Light Photocatalytic Property for Reduction of Cr(Ⅵ)
Guo-Hui LI, Yuan-Yuan SUN, Hua-Long XING, Jian-Cong ZHENG, Chen-Chen LIN, Zhen-Fan SUN
2019, 35(2): 194-202  doi: 10.11862/CJIC.2019.006
[摘要]  (136) [HTML全文] (136) [PDF 5293KB] (136)
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The Ce-doped SnS2 samples were prepared successfully through a one-pot hydrothermal method under mild conditions. The as-prepared SnS2 samples were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) equipped with Energy dispersive X-ray Spectroscopy (EDS) which confirmed the doping of Ce. The results indicated the spiral growth mode and rose-like morphology of the samples. The effects of Ce doping on the photoabsorption, band gap, the potential of conduction band and the separation efficiency of photo-induced carriers were checked by diffuse reflectance spectrum (DRS) and electrochemical examinations. The reductive abilities of the samples were evaluated by the reduction of Cr(Ⅵ) chosen as a model pollutant. The results reveal that photocatalytic properties of Ce/SnS2 were strongly dependent on the proportion of Ce ions and the optimum doping amount of Ce is 5% (n/n).
Synthesis, Growth Mechanism and Application in Anticancer of CuS Hollow Spheres
Qing-Li HUANG, Li-Li WANG, Ting LI, Yong-Ping WU
2019, 35(2): 314-322  doi: 10.11862/CJIC.2019.032
[摘要]  (70) [HTML全文] (70) [PDF 3007KB] (70)
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Cage-like hollow morphologies of copper sulfide nanostructures have been selectively synthesized using cupric nitrate trihydrate (Cu(NO3)2·3H2O), oxalic acid (H2C2O4) and sodium sulphide nonahydrate (Na2S·9H2O) as starting materials in water solution by a self sacrificing templates hydrothermal method. X-ray diffraction (XRD), field scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) were used to characterize the products. The possible formation mechanism of CuS hollow spheres was proposed. The photo-thermal conversion experiments were also done. The results showed that hollow CuS exhibited high photo-thermal efficiency and high anticancer activity under NIR irradiation.
Syntheses, Structures and Magnetic Properties of Two Binuclear Lanthanide Complexes Bridged by Nitronyl Nitroxide Radical Ligands
Xue-Lan MEI, Min-Jie DU, Peng HU, Zong-Qun LI
2019, 35(2): 323-328  doi: 10.11862/CJIC.2019.034
[摘要]  (97) [HTML全文] (97) [PDF 792KB] (97)
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The reaction of Ln(acac)3·3H2O with NIT-PhOH radical yielded two new Ln-radical complexes[Ln2(acac)4(NIT-PhO)2] (Ln=Tb (1), Y (2); acac=acetylacetonato, NIT-PhOH=2-(2'-hydroxyphenyl)-4, 4, 5, 5-tetramethylimidazo-line-1-oxyl-3-oxide). Two complexes are isostructural and have binuclear structure in which two lanthanide ions are bridged by two radical ligands through their phenoxo-O atoms. DC magnetic susceptibility studies indicated that there exists weak antiferromagnetic interaction in complex 2.
Syntheses, Crystal Structures, and Luminescent Properties of Three Cobalt(Ⅱ), Lead(Ⅱ) and Zinc(Ⅱ) Complexes Constructed from Mixed Biphenyl Tricarboxylic Acid and N-Donor Ligands
Yu LI, Xun-Zhong ZOU, Wen-Da QIU, Wen-Liu ZHUANG, Na ZHAO, Xiao-Ling CHENG
2019, 35(2): 329-336  doi: 10.11862/CJIC.2019.002
[摘要]  (65) [HTML全文] (65) [PDF 2326KB] (65)
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Zero-dimensional mononuclear cobalt(Ⅱ) complex, 1D lead(Ⅱ) and 1D zinc(Ⅱ) coordination polymers, namely[Co(Hbtc)(phen)2(H2O)]·3H2O (1), [Pb(μ3-Hbtc)(2, 2'-bipy)]n (2) and {[Zn3(μ2-btc)2(μ2-H2O)(2, 2'-bipy)3(H2O)5]·8H2O}n (3), have been constructed hydrothermally using H3btc (H3btc=biphenyl-2, 4, 4'-tricarboxylic acid), phen (phen=1, 10-phenanthroline), 2, 2'-bipy (2, 2'-bipy=2, 2'-bipyridine), and cobalt, lead or zinc chlorides. Single-crystal X-ray diffraction analyses revealed that three complexes crystallize in the orthorhombic or triclinic systems, space groups Pna21 or P1. Complex 1 has a discrete monomeric structure, which is assembled to a 3D supramolecular framework through O-H…O hydrogen bond. Complexes 2 and 3 show a 1D chain based on binuclear units. Luminescent properties of all complexes have been studied.
Influences of cis-, trans-1, 2-Cyclohexanediamine Configurations on Iodoantimonate Organic-Inorganic Hybrid Isomers
Zhi-Wen LIANG, Xiao-Rou CHEN, Hui YU, Zhen-Hong WEI, Xiu-Xiu ZHANG, Hu CAI
2019, 35(2): 337-343  doi: 10.11862/CJIC.2019.027
[摘要]  (99) [HTML全文] (99) [PDF 2535KB] (99)
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Reactions of cis-and trans-1, 2-cyclohexanediamine (DAC) with antimony iodide in concentrated HI aqueous solution afforded two organic-inorganic hybrid isomers (cis-1, 2-DACH2)[SbI5]·H2O (1) and {(trans-1, 2-DACH2)[SbI5]·H2O}n (2), respectively. The single-crystal X-ray diffraction revealed that the inorganic component in compound 1 is a dimer[Sb2I10] built up from two[SbI6] octahedra by sharing I-I edge, and that in compound 2 is a zigzag chain constructed with corner-sharing octahedral[SbI6] units. In addition, both compounds have been investigated and compared by UV-Vis, fluorescent spectra, and DFT calculation.
X-ray Crystallography, Spectral Characterization and Computational Studies of Mercury(Ⅱ) Complex with 1-(p-Tolyl)-2-(tri-p-tolyl-λ5-phosphanylidene)ethan-1-one
Pourmirza Mahsa, Ebrahimnezhad Shahla, Ramazani Ali, Bahrami Aidin, Alaei Sholeh., Reza Dadrass Ali.
2019, 35(2): 344-350  doi: 10.11862/CJIC.2019.031
[摘要]  (75) [HTML全文] (75) [PDF 1308KB] (75)
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The α-phosphorus ligand 1-(p-tolyl)-2-(tri-p-tolyl-λ5-phosphanylidene)ethan-1-one(L) was prepared by the reaction of 2-bromo-1-(p-tolyl)ethan-1-one with tri(p-tolyl) phosphine. The reactions of L with cadmium chloride and mercury bromide resulted in[Cd(L)Cl2]2 (C1) and[Hg(L)(μ2-Br)Br]2 (C2), respectively. The complexes were characterized by IR and NMR (1H, 13C, 31P). The structure of C2 was detected by single crystal X-ray diffraction and its DFT computational studies at B3LYP/6-31G* level were also performed to reveal the interaction between the reaction site of complex C2 and nucleophilic groups such as Schiff base.
A Layered Cd(Ⅱ)-Organic Coordination Polymer Exhibiting Dual-Responsive Sensing Towards 2, 4, 6-Trinitrophenol and Fe3+
Jing-Jing SHI, Shan XU, Na LI, Xiu-Guang WANG, Xiao-Jun ZHAO, En-Cui YANG
2019, 35(2): 351-360  doi: 10.11862/CJIC.2019.045
[摘要]  (245) [HTML全文] (245) [PDF 4607KB] (245)
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A layered coordination polymer[Cd(QDA)]n (1) with distorted Cd2+ octahedron extended by three-connected 2, 3-quinoline dicarboxylate linkers was hydrothermally synthesized, exhibiting intense blue fluorescence and highly thermal and chemical stability. More interestingly, the complex dispersed in ethanol can quickly probe the trace amounts of 2, 4, 6-trinitrophenol (Ksv=6.61×104 L·mol-1, LOD=0.83 μmol·L-1) and Fe3+ (Ksv=1.74×104 L·mol-1, LOD=2.70 μmol·L-1) through fluorescence quenching with high quenching constants (Ksv) and low limits of detection (LOD).
Syntheses, Spectroscopic Properties and THz Time Domain Spectroscopy of Two Copper(Ⅰ) Complexes Based on N-Donor and P-Donor Ligands
Xun PAN, Xiao-Nan KUANG, Ning ZHU, Zhi-Gang REN, Yu-Ping YANG, Xiu-Lan XIN, Zhong-Feng LI, Hong-Liang HAN, Qiong-Hua JIN
2019, 35(2): 361-368  doi: 10.11862/CJIC.2019.026
[摘要]  (118) [HTML全文] (118) [PDF 838KB] (118)
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Two novel copper(Ⅰ) complexes[Cu(bdppmapy)(2, 2'-bipy)]BF4 (1) and[Cu(bdppmapy)(2, 2'-bipy)]I (2) (2, 2'-bipy=2, 2'-bipyridine, bdppmapy=N, N-bis((diphenylphosphino)methyl)-2-pyridinamine) have been synthesized in mixed solvents of CH3OH and CH2Cl2 (1:1, V/V) and characterized by single-crystal X-ray diffraction, elemental analysis, IR, 1H NMR and 31P NMR spectroscopy, fluorescence spectra and THz time domain spectroscopy (THz-TDS). Complex 1, a mononuclear complex, was generated by the reaction of[Cu(CH3CN)4]BF4 and bdppmapy with 2, 2'-bipy in 1:1:1 molar ratio. In complex 1, the central Cu(Ⅰ) forms a distorted tetrahedral geometry by coordinating with the diphosphine ligand (bdppmapy) and chelating N-donor ligand (2, 2'-bipy). Like 1, 2 was obtained by the reaction of CuI and bdppmapy with 2, 2'-bipy in 1:1:1 molar ratio. In the asymmetric unit of 2, the bdppmapy and 2, 2'-bipy ligands chelate central Cu(Ⅰ), respectively. The luminescent spectra show that the emission mechanism is metal-to-ligand charge transfer (MLCT). The application of terahertz time-domain spectroscopy also provides useful information for the research of complexes.