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二氧化钛基Z型异质结光催化剂
梅邱峰, 张飞燕, 王宁, 鲁闻生, 宿新泰, 王伟, 武荣兰
2019, 35(8): 1321-1339  doi: 10.11862/CJIC.2019.167
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摘要:
二氧化钛(TiO2)因廉价、无毒、化学性质稳定以及具有较强的光催化氧化还原能力,在光催化领域占据着重要的地位。然而,可见光利用率低以及光生电子-空穴对的快速复合是限制其应用的2个主要因素。二氧化钛基Z型异质结作为一种新型光催化剂,既改善了二氧化钛的2个缺陷,又表现出比TiO2更强的氧化或还原能力。本文概括了TiO2光催化剂、异质结光催化剂和TiO2基Z型光催化剂的能带排列和电子传递原则,探讨了Z型异质结和type-Ⅱ异质结的异同点以及区分方法,并归纳总结了TiO2基Z型异质结在光催化领域中的应用。
Articles
Benzoimidazole-Based Cyclometalated Ir(Ⅲ) Complexes: Syntheses, Structures and Luminescence Modulation/Switching
Kai RUI, Shi-Shan WU, Deng-Ke CAO
2019, 35(8): 1340-1348  doi: 10.11862/CJIC.2019.156
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Two iridium complexes[Ir(ppy)(qbiH)]NO3 (1·NO3) and[Ir(ppy)(qbi)] (2) have been synthesized. Their crystal structures indicate that an[Ir(ppy)2]+ unit is chelated by a neutral benzoimidazole-based ligand qbiH in 1·NO3, while anion ligand qbi- in 2. The different deprotonation degrees of ligands qbiH and qbi- in the two complexes lead to their clear differences in luminescence both in solution and in solid state. Complexes 1·NO3 and 2 in CH2Cl2 show the emissions at 581 and 574 nm, respectively. In solid state, a red emission at 611 nm was observed for 1·NO3, while an orange emission at 598 nm for 2. It is interesting that both 1·NO3 and 2 in solid state exhibited luminescence switching between red emission and orange emission, upon meeting Et3N/TFA vapor. This is due to the acid/base-induced structural interconversion between ligand qbiH and ligand qbi- in complexes 1·NO3 and 2. Moreover, we discuss the relationship between structure and luminescence for 1·NO3 and 2.
Cyclic Regeneration of Potassium-Modified Activated Semi-coke by Impregnation Method for Flue Gas Desulfurization
Hai-Tao WU, Qi-Dong ZHUO, Zi YANG, Jian-Dong SHI, Hong-Jian CHEN, Wen-Yu YIN, Xiao-Yan TANG, Yun-Shen MA, Rong-Xin YUAN
2019, 35(8): 1427-1435  doi: 10.11862/CJIC.2019.175
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The potassium modified Activated Semi-coke (K/ASC) for SO2 removal was prepared using potassium carbonate (K2CO3) by the impregnation method. The ASC modified by 10%(w/w) K2CO3 (K10) exhibited good SO2 removal efficiency at 120℃. From 400 to 700℃, the higher the regeneration temperature is, the better is the desulfurization activity of K10 after regeneration. Cyclic regeneration of K10 (K10-R-600-n) showed that the sample had the best desulfurization performance after four regeneration cycles (K10-R-600-4), and its sulfur capacity was 68.9 mg·g-1, 24.37% higher than that of K10 (55.4 mg·g-1). The desulfurization products are divided into physisorbed SO2, H2SO4 and sulfate. The deposition of sulfate, which does not decompose after regeneration, results in the decrease of the desulfurization activity. The sulfur capacity of the sample after ten regeneration cycles (K10-R-600-10) remained 70% that of the fresh K10.
Syntheses and Crystal Structures of Two Discrete Complexes Generated from 3, 6-Bis(2-(4-oxide-quinoxaline)-yl)-4, 5-diaza-3, 5-octadiene and Ag(Ⅰ) Salt
Xiu-Hui REN, Peng WANG, Jian SU, Jun-Yan CHENG
2019, 35(8): 1436-1444  doi: 10.11862/CJIC.2019.174
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Two novel discrete complexes with Ag(Ⅰ) centers based on the double Schiff-base ligand, 3, 6-bis(2-(4-oxide-quinoxaline)-yl)-4, 5-diaza-3, 5-octadiene (L), have been synthesized. The obtained Ag(Ⅰ) complexes, [Ag8(L)8](BF4)8·CH2Cl2·3CH3OH (1) and[Ag4(L)4](PF6)4·CH2Cl2 (2), were fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. Both complexes exist as dimers. Through hydrogen bonds, uncoordinated counter ions and discrete molecular complex building blocks formed one-dimensional (1D) or two-dimensional (2D) frameworks.
Highly Sensitive Luminescent Sensor for Cr(Ⅲ) Based on a Water Dispersed Nano-sized Amorphous Methyl Salicylate Terbium Complex
Xiao-Jun LIU, Li-Ting SUN, Shu ZHANG, Chen ZHOU, Yan-Zhu LIU, Xue-Zhen ZHOU, Yong-Xiu LI
2019, 35(8): 1445-1454  doi: 10.11862/CJIC.2019.166
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To expand the application fields of rare earth fluorescence complexes, and meet the requirements of high sensitivity and selectivity for the detection of trace chromium in aqueous solution, we prepared a sensitive luminescence sensor for Cr3+ ion based on a water dispersed nano-sized amorphous luminescence terbium complex with methyl salicylate (A-MS-Tb). It was found that the synthesized A-MS-Tb is an amorphous precipitation with particle size ranging from 50 to 100 nm and similar composition to the reported crystalline MS-Tb(C-MS-Tb). A-MS-Tb showed strong green luminescence at 494, 549, 591, 625 nm, which belongs to the energy level transition of 5D47FJ (J=6, 5, 4, 3) of Tb3+, respectively. The difference between A-MS-Tb and the reported C-MS-Tb lies in the stability and dispersion performance towards water which is very important for expanding its application as materials and sensors. In particularly, with the addition of Cr3+ into the water suspension of A-MS-Tb, the coordination between the ligand and Tb3+ is weakened, causing its green fluorescence to be quenched. Therefore, a highly sensitive sensor for detecting Cr3+ was established, and the sensitivity, selectivity and anti-interference ability was evaluated.
Preparation of Metal-Organic Framework-Derived Nano-Scale Nickel Phosphide Catalysts
Dan XU, Liang-Kui ZHU, Dan ZHOU, Yu-Rong FU, Xiao-Wen FU, Rong CHEN, Hai-Xia LI
2019, 35(8): 1455-1462  doi: 10.11862/CJIC.2019.148
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Herein, nickel phosphides nanoparticles with different phases were successfully prepared by multi-step calcination and phosphidation process at low temperature using Ni based MOF (Ni-MOF) as the precursor. The resulting materials were applied to the hydrogen evolution reaction (HER) catalyst, Ni1P1-500 obtained at a mass ratio of Ni@C to red phosphorus of 1:1 and a pyrolysis temperature of 500℃ exhibited a remarkably enhanced electrocatalytic performance with a current density of 10 mA·cm-2 at an overpotential of 178 mV and a superior durability for the HER in acid media. A small Tafel slope of 62 mV·dec-1 revealed a Desorption-Heyrovsky mechanism during the HER. The excellent electrocatalytic performance might be ascribed to the presence of the proton acceptor (P site) and hydride-acceptor (Ni site) centers on the surface of nickel phosphide.
Three Cu(Ⅱ) Complexes with 1-(3-Ethylpyrazin-2-yl)ethylidene)-4-methylthiosemicarbazide: Crystal Structures and DNA-Binding Properties
Mu-Xuan LÜ, Lin-Yan BIAN, Meng-Ru LI, Yi YANG, Wei-Na WU, Yuan WANG, Zhong CHEN
2019, 35(8): 1463-1469  doi: 10.11862/CJIC.2019.169
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Three Cu(Ⅱ) complexes, [Cu(L)Br]·DMF (1), [Cu(L)Cl]·2H2O (2), and [Cu2(L)2(SO4)]·H2O·CH3OH (3) (HL=1-(3-ethylpyrazin-2-yl)ethylidene)-4-methylthiosemicarbazide) have been synthesized and structurally determined by single-crystal X-ray diffraction. The results show that the Cu(Ⅱ) ion in 1 and 2 is surrounded by one anionic thiosemicarbazone ligand with N2S donor set and one halide ion (bromide for 1 and chloride for 2), thus giving a distorted planar square coordination geometry. However, in the dimeric complex 3, two Cu(Ⅱ) ions were doubly bridged by two S atoms of two TSC ligands to form a Cu2S2 core with Cu…Cu distance of 0.318 0 nm. Each of the Cu(Ⅱ) ions is also coordinated by two nitrogen atoms from one TSC ligand and one oxygen atom from the η2-SO42- at the outer axial site, with a distorted square pyramid coordination geometry. Moreover, the fluorescence spectra indicate that the interactions of the complexes with DNA are stronger than that of the thiosemicarbazone ligand.
Preparation of Coral-like Rutile Titania with Enhanced Photocatalytic Activity under UV and Visible Light
Jie ZHU, Feng-Juan GE, Yan CHEN, Yan XU, Xue-Yang ZHANG, Wei-Xin ZOU, Lin DONG
2019, 35(8): 1470-1476  doi: 10.11862/CJIC.2019.162
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Coral-like rutile titania (Rut-dg) was synthesized by solvothermal method in diethylene glycol solution. Scanning electron microscope (SEM) and X-ray diffraction (XRD) indicated the spherical particles were homogeneously dispersed with the diameter about 1 μm, consisting regular arranged branches on the surface with diameter less than 10 nm. The BET surface area was as large as 228 m2·g-1, more than 7 times of commercial rutile titania sample. Given its unique morphology, the Rut-dg showed superior photocatalytic activity with hydrogen evolution 25 000 μmol·g-1·h-1 under ultraviolet irradiation, 50% higher than P25 and 13 times of commercial rutile sample. The hydrogen production under visible light was 270 μmol·g-1·h-1, while P25 and commercial rutile had no obvious activity. Further investigation demonstrated that no organics could be detected on the surface of Rut-dg, indicating the coral-like structures played the key role for the photocatalytic activity. After calcined at 300℃, the coral-like structures were sintered obviously and the surface area decreased by 50%. Meanwhile, the hydrogen production decreased by 15%~25%, also implying that the coral-like structures facilitated the hydrogen production dramatically.
Syntheses, Crystal Structures, Hirshfeld Surface Analysis of Two Salen-Type Halogenated Schiff-Base Ni(Ⅱ) Complexes
Qiong WU, Ya-Fang TANG, Qiao-Li ZI
2019, 35(8): 1477-1484  doi: 10.11862/CJIC.2019.189
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The reaction between nickel nitrate and halogenated salen-type Schiff-base ligand in methanol solution led to the isolation of two new salen nickel(Ⅱ) complexes[Ni(3, 5-Cl-salcy)] (1) and[Ni(3-Cl-salcy)] (2), where 3, 5-Cl-salcyH2=N, N'-(±)-bis(3, 5-dichlorosalicylidene)cyclohexane-1, 2-diamine and 3-Cl-salcyH2=N, N'-(±)-bis(3-chloro-salicylidene)cyclohexane-1, 2-diamine. The crystal structures of complexes 1 and 2 were structurally characterized by single-crystal X-ray diffraction. Structural analysis reveals that the basic units of both complexes all consist of one nickel(Ⅱ) ion in[N2O2] coordination sphere, forming similar square planar geometries. PLATON software analysis indicates that there is not any hydrogen bond exists in the crystal structure of 1, and only unclassical hydrogen bonds exist in 2. However, Hirshfeld surface analysis shows that, although the strength of halogen atoms formed hydrogen bonds are weak, the C-H…X bonds play an important role in stabilization of three-dimensional networks of both complexes. Moreover, by comparison of the two complexes, we found that the difference in the number of halogen atoms in the ligand can have a very important influence on the proportion of weak exchange in the crystal.
Layered Co3O4/Ti Nanosheet Flexible Electrode with Low Transfer Resistance for Supercapacitor
Dan-Dan HAN, Yuan ZHAO, Ye SHEN, Yuan-Sheng DING, Zhen-Yu CHENG, Xiao-Yan JING, Xue-Yi ZHANG
2019, 35(8): 1485-1492  doi: 10.11862/CJIC.2019.165
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The layered Co3O4 nanosheets with porous nature on Ti mesh were adopted to optimize the transfer resistance by a facile hydrothermal method. The synthesized materials were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electrochemical techniques. The results showed that the materials consisted of well-arranged micrometer length rectangular 2D flakes with uniform pore distribution. This unique microstructure obtained the electrode lower transfer resistance, higher structure stability, and better electrochemical performance for supercapacitor. The 2D porous layered Co3O4 nanosheet could achieve a relatively good capacitance retention of 91.8% at a current density of 100 mA·g-1 after 1 000 cycles and a low transfer resistance (Rct) of 0.29 Ω. These remarkable supercapacitive performances are attributed to the rationally 2D layered structure on flexible Ti mesh substrate, high utilization ratio of active materials of the flexible Co3O4/Ti electrode.
Biomass Derived Highly-Ordered Carbon Tube as Cathode Material for High Performance Lithium-Sulfur Batteries
Meng-Yuan ZHANG, Xiao-Long YOU, Li-Jun LIU, Dessie Walle Maru, Ya-Juan LI, You-Nian LIU
2019, 35(8): 1493-1499  doi: 10.11862/CJIC.2019.178
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A novel highly ordered carbon tube (OCT) arrays derived from palm tree fiber by carbonization and activation with KOH was prepared and used as hosts for lithium sulfur battery. The OCT possessed large specific area and pore volume, which could effectively store sulfur. The method was clean, facile and low cost. Moreover, the S@OCT composite exhibited admirable electrochemical performances. The S@OCT with 65%(w/w) sulfur delivered an initial discharge capacity of 1 255.2 mAh·g-1 (1.8 mAh·cm-2) and retained 756.9 mAh·g-1 (1.09 mAh·cm-2) at the current rate of 0.2C after 100 cycles with a high coulomb efficiency. What's more, when tested at 5C, its initial capacity was up to 649.1 mAh·g-1 (0.93 mA h·cm-2) and retained 504.2 mAh·g1 (0.72 mAh·cm-2) after 100 cycles.
DNA Targeting Rigid Dinuclear Ruthenium-Arene Complexes
Ji LI, Yuan-Yuan HAO, Yong QIAN, Xu-Lin XUE, Zhi SU, Hong-Ke LIU
2019, 35(8): 1500-1508  doi: 10.11862/CJIC.2019.184
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Three dinuclear Ru(Ⅱ)-arene complexes[Ru2(η6-p-bip)2(1, 3-bib)2XY]X2 (X=Y=Cl- (1), X=Y=Br- (2), X=I- and Y=Cl- (3); 1, 3-bib=1, 3-di(1H-imidazol-1-yl)benzene, p-bip=biphenyl) were synthesized and fully characterized by 1H NMR and ESI-MS. Single crystal X-ray diffractions studies showed that complex 1 owns a rigid M2L2 bowl-like structure, where one Cl- is trapped inside the cavity to balance the charge. Complex 3 showed the best anticancer activities among complexes 1~3. The IC50 value of 3 towards to human lung cancer cells (A549) reached to 13.9 μmol·L-1, which is comparable to that of cisplatin (IC50=15.2 μmol·L-1). Complexes 1~3 have shown strong interactions with DNA and could induce the unwinding of the DNA superhelix structure.
Hydrogen Production from Formic Acid Decomposition Using AuPd and AgPd Dendritic Nanocatalysts
Jun LIU, Jia-Qi XIE, Xin-Hua WU, Rong LI, Li-Xin LAN
2019, 35(8): 1509-1519  doi: 10.11862/CJIC.2019.172
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Three-dimensional (3D) porous thin films of AuPd and AgPd foams comprised of nanodendrites possess superior catalytic activity for the production of high-quality H2 from formic acid decomposition at room temperature. The high catalytic activity was attributed to the presence of abundant active sites like steps, corners, kinks and edges in the nanodendrites, and to the electronic effect. Besides the high activity, there were some more advantages for the nanodendrtic alloy foam films. For example, the foam films could be quickly electrodeposited in 5 min on a Ti substrate utilizing the template of hydrogen bubbles without needing organic additives, and it could be used directly for the hydrogen production without post-treatments. The hydrogen production was easily controllable, and we could get hydrogen and stop hydrogen production just by immersing the electrodeposited foam film into and pulling it out of the solution of HCOOH+HCOONa. The foam films could also be easily reactivated either by drying after water cleaning or by potential cycling in H2SO4 solution.
论文
磺酸基功能化有机聚苯乙烯/无机磷酸氢锆催化环氧大豆油
邹晓川, 黄林玉, 全纹萱, 王存, 王跃, 赵欣, 谭脂文
2019, 35(8): 1349-1356  doi: 10.11862/CJIC.2019.173
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首先制备了2种磺酸功能化的有机聚苯乙烯/无机磷酸氢锆非均相催化剂,运用傅里叶红外光谱(FT-IR)、N2吸附-脱附测试、X射线衍射(XRD)、扫描电子显微镜(SEM)等测试技术对催化剂进行了表征,提出了催化剂可能的模型。其次,考察了非均相催化剂催化合成环氧化大豆油的催化性能。结果表明:以叔丁基过氧化氢(TBHP)为氧化剂,固体催化剂对大豆油的环氧反应具有良好的催化性能,相比于催化剂1(磺酸化低聚苯乙烯基膦酸-磷酸氢锆),在相同的条件下,催化剂2(磺酸化聚(苯乙烯-苯乙烯膦酸)-磷酸氢锆)表现出更高的催化活性(产率:58.6% vs 53.3%),这主要归因于催化剂2拥有更大的比表面积、孔容以及孔径,为底物和催化剂的接触提供足够的催化场所。催化剂2重复使用7次后,催化活性未见明显降低。第8次反应结束后,将其置于2 mol·L-1稀盐酸中静置过夜后,在进行第9和10次循环时,催化活性又得以恢复。
Li2O-Na2O-B2O3-SiO2烧结助剂对BaAl2Si2O8陶瓷结构与介电性能的影响
严欣堪, 丁士华, 张晓云, 黄龙, 张云
2019, 35(8): 1357-1362  doi: 10.11862/CJIC.2019.152
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采用传统固相反应工艺,按化学计量比合成BaO-Al2O3-SiO2(BAS)-x%(w/w)Li2O-Na2O-B2O3-SiO2(LNBS)(x=0,1,2,3,4)陶瓷。研究不同LNBS烧结助剂添加量对BAS系微波介质陶瓷的结构和介电性能的影响。通过Clausius-Mossotti公式计算讨论了BAS理论与实验介电常数(εr)的差异。研究结果表明:LNBS烧结助剂中Li+进入钡长石Al3+位或单四元环(S4R)间隙,并产生了O2-空位或Ba2+空位,从而促进BAS六方相向单斜相的转变。添加适量的LNBS烧结助剂后,BAS陶瓷的烧结温度从1 400℃降低到1 325℃,同时BAS陶瓷样品密度、品质因数(Qf)值以及频率温度系数(τf)得到改善。当x=1,烧结温度为1 325℃时,可获得综合性能相对较好的BAS陶瓷,其介电性能:Qf=35 199 GHz,εr=6.37,τf=-1.613×10-5-1
ZIF67衍生硫化钴/多孔碳复合催化剂的制备及其电催化性能
李京修, 赵媛, 薛建军, 何娉婷, 王玲
2019, 35(8): 1363-1370  doi: 10.11862/CJIC.2019.163
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采用离子交换法与热处理相结合的方法,以ZIF67为前驱体,硫代乙酰胺为硫源,制备出硫化钴/多孔碳(CoS/C)复合催化材料,并探讨了硫化时间对复合催化剂的形貌、结构及其氧还原(ORR)性能的影响。采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射仪(XRD)、N2吸附-脱附测定仪、X射线光电子能谱分析(XPS)、拉曼光谱仪(Raman)和旋转圆盘电极(RDE)技术表征催化剂的物理特征和电催化性能。研究结果显示,在碱性条件下该复合催化剂具有与20%(w/w)的商业Pt/C催化剂相媲美的ORR活性,其半波电位仅比Pt/C催化剂低31 mV。随着硫化时间的增加,硫化钴颗粒逐渐增大,催化剂中碳材料的无序程度出现先减小后增大的趋势。在硫化时间为10 min时,复合催化剂在0.1 mol·L-1 KOH中表现出良好的电催化活性,且在ORR过程中复合催化剂的平均转移电子数可达到3.72,接近于4,说明氧气在该催化剂表面发生的是四电子转移过程。
Bi@Bi2Sn2O7/TiO2等离子体复合纤维的制备及增强的光催化产氢活性
李跃军, 曹铁平, 赵艳辉, 孙大伟, 王霞
2019, 35(8): 1371-1378  doi: 10.11862/CJIC.2019.187
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以电纺TiO2纳米纤维为基质,采用一步水热法合成了Bi@Bi2Sn2O7/TiO2等离子体复合纤维光催化剂。利用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、高分辨透射电镜(HRTEM)、紫外-可见漫反射(UV-Vis DRS)和光致发光光谱(PL)等分析测试手段对样品的物相、形貌和光电性能等进行表征。以三乙醇胺为电子给体,研究了Bi@Bi2Sn2O7/TiO2复合纤维光催化裂解水制氢的反应过程。结果表明:在水热过程中,Bi2Sn2O7构筑在TiO2纳米纤维表面形成p-n结的同时,部分Bi3+被葡萄糖还原成金属Bi沉积在Bi2Sn2O7上。金属Bi的等离子体共振效应与p-n结的协同作用,有效提高了样品的光催化活性,产氢速率达到7.26 mmol·h-1·g-1
磺化酞菁铝修饰氨基功能化磁性材料及其光敏化降解双酚A
郭冬菁, 胡美琴, 沈昊宇, 张建, 孙洁, 许宜铭
2019, 35(8): 1379-1386  doi: 10.11862/CJIC.2019.168
[摘要]  (18) [HTML全文] (18) [PDF 5897KB] (1)
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采用溶剂热法制备氨基功能化Fe3O4磁性材料(NH2@nFe3O4),通过浸渍法将磺化酞菁铝(AlPcS)负载于NH2@nFe3O4。材料的傅立叶红外、漫反射、X射线衍射、扫描电镜、透射电镜、振动磁强计等表征表明:AlPcS主要通过静电作用与NH2@nFe3O4结合,AlPcS-NH2@nFe3O4平均粒径为127 nm,饱和磁化强度为75.3 emu·g-1。在可见光和空气作用下,该功能化磁性材料对降解弱碱性水溶液中环境内分泌干扰物双酚A(BPA)具有较高的光敏化活性。随着AlPcS负载量的增加活性呈先升高后下降的趋势,负载量为3.4%(质量分数)的复合材料性能最佳,反应60 min后,20.0 mg·L-1 BPA降解率为96%;循环使用10次,BPA降解率仍保持93%以上。通过NaN3猝灭实验探讨了反应机理,证实1O2是光敏化过程中的主要活性物种。
施主掺杂对BaTiO3钙钛矿半导体纳米晶光催化性能的影响
孟国祥, 田晓霞, 张家瑞, 张翔, 韩丰庆, 屈绍波
2019, 35(8): 1387-1395  doi: 10.11862/CJIC.2019.183
[摘要]  (16) [HTML全文] (16) [PDF 4318KB] (1)
摘要:
以沉淀法制备的Cu2O为牺牲模板剂,采用水热法制备La施主掺杂的BaTiO3钙钛矿半导体纳米晶,借助X射线衍射(XRD)、透射电子显微镜(TEM)、高分辨透射电镜(HRTEM)、X射线光电子能谱((XPS)、扫描电子显微镜(SEM)、紫外-可见漫反射光谱(UV-Vis DRS)表征La掺杂的BaTiO3晶的物相、微观形貌及光催化性能。结果表明,La掺杂BaTiO3构建了晶体缺陷,有效提高了BaTiO3的光催化性能。当掺杂量为4%(w/w)时,样品的光催化性能最好,在可见光照射360 min后,对4-硝基苯酚溶液的降解率可达到93.2%。该催化剂5次循环后的活性仍然大于86.7%,表明La施主掺杂的BaTiO3是一种有效的可见光催化剂。
烷基膦酸促进负载磷钨酸催化异丁烷/丁烯烷基化反应
许孟霞, 王怡博, 邓长顺, 丁丽平, 许逸达, 薛念华, 郭学锋, 彭路明, 丁维平
2019, 35(8): 1396-1402  doi: 10.11862/CJIC.2019.145
[摘要]  (17) [HTML全文] (17) [PDF 3651KB] (1)
摘要:
异丁烷/丁烯烷基化是生产高辛烷值汽油的重要反应,目前主要采用液体强酸为催化剂,而固体催化剂用于该反应的性能均不理想。我们设计合成出十六烷基膦酸(HDPA)修饰的氧化硅负载型磷钨酸纳米多级结构催化剂(HDPA-HPW/SiO2),其结构与悬铃木果实相似。通过X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、透射电子显微镜镜(TEM)、氮气吸附-脱附、异丁烷吸附-脱附等对该催化剂进行了表征,并使用固定床微型反应器评价了其对异丁烷/丁烯烷基化反应的催化性能。结果表明,HDPA的外围修饰增强了催化剂对烃类反应物的吸附,减少了烯烃聚合副反应和催化剂表面积碳的产生,提高了高辛烷值产物的选择性,延长了催化剂的寿命。
锌镍单液流电池正极Ni1-xMnx(OH)2倍率性能分析
姚寿广, 窦飞, 邢如月, 程杰, 肖民
2019, 35(8): 1403-1410  doi: 10.11862/CJIC.2019.177
[摘要]  (15) [HTML全文] (15) [PDF 1689KB] (1)
摘要:
采用缓冲溶液法制备Mn掺杂Ni1-xMnx(OH)2x=0.1,0.2,0.3,0.4)。X射线衍射(XRD)测试表明x=0.1和0.2的样品主要是由β相组成;扫描电子显微镜(SEM)和氮气吸附-脱附测试表明掺杂Mn样品比不掺Mn的商用β-Ni(OH)2的颗粒更细小、多孔;恒流充放电测试表明,这种电极具有优良的高倍率性能,当x=0.2,电流密度800 mA·g-1时放电比容量为288.8 mAh·g-1,同等条件测试的商用β-Ni(OH)2放电比容量为198.7 mAh·g-1,循环580圈后仍有276 mAh·g-1的放电比容量,其衰减率为4.1%,而同等测试条件下的其它4种样品衰减率分别为46.1%(商用β-Ni(OH)2)、13.0%(x=0.1)、25.6%(x=0.3)、34.1%(x=0.4),可见这种Mn掺杂电极材料适合大电流密度充放电,能够改善镍电极的循环稳定性,降低镍电极成本。
“自上而下”方法制备少层石墨用作高容量铝离子电池正极
刘东海, 王俊明, 范卫超, 房金刚, 朱晓军, 孟垂舟
2019, 35(8): 1411-1418  doi: 10.11862/CJIC.2019.171
[摘要]  (18) [HTML全文] (18) [PDF 5609KB] (1)
摘要:
采用“自上而下”方法制备了具有少片层、小尺寸特征且晶型结构完美的石墨材料,通过增加离子嵌入位点的方式,突破传统石墨作为正极材料的固有容量限制,提升铝离子电池的电化学储能性能。扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)等测试结果表明,该方法可以在不破坏石墨材料本身结构的前提下,有效实现对石墨片层的剥离,并且可以通过调节球磨时间的方式实现对石墨片层厚度和尺寸的调控。电化学测试结果表明,在3C的大电流密度下,以剥离的石墨材料为正极的铝离子电池放电容量可以达到93 mAh·g-1,在10C的高倍率下,放电容量仍保持在68 mAh·g-1,并显示出优异的循环性能。另外,该方法制备工艺简单、成本低廉,为促进高容量、长寿命铝离子电池的商业化应用打下了良好的基础。
NiCo2S4@碳纳米管构筑柔性薄膜电极的制备及其电化学性能
周阅微, 季昀辉, 谭徜彬, 宋伟杰, 许亮亮, 唐少春
2019, 35(8): 1419-1426  doi: 10.11862/CJIC.2019.185
[摘要]  (28) [HTML全文] (28) [PDF 5758KB] (1)
摘要:
以浮动催化化学气相沉积致密超薄碳纳米管薄膜(CNTF)为基体,通过两步酸处理使薄膜内制备的碳纳米管(CNT)分开并赋予其活性官能团,CNTF由超疏水转变为超亲水性,然后在CNT表面生长均匀的前驱体包覆层,离子进入超亲水薄膜内部确保了高负载量,最后进行液相硫化制得NiCo2S4@碳纳米管构筑柔性薄膜(NiCo2S4@CNTF)电极。利用扫描电子显微镜、X射线衍射等对产物进行了表征,证明优化产物为NiCo2S4均匀包覆多壁CNT构筑而成的三维网状柔性复合薄膜,单根CNT的表面是NiCo2S4纳米粒子构成、厚度约70 nm的粗糙包覆层。该复合薄膜比电容达到270.3 mF·cm-2,即使在高电流密度2.5 mA·cm-2下充放电循环10 000次后仍保持很好的可逆性,电容保持率达93%,库伦效率持续稳定在92%附近;重复大变形(弯曲、折叠、卷曲)后能保持结构完整性和性能稳定性。同时,探讨了电化学性能与结构间的关系,并揭示了性能增强的内在机理。
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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]  (295) [HTML全文] (295) [PDF 6444KB] (295)
摘要:
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]  (221) [HTML全文] (221) [PDF 2498KB] (221)
摘要:
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]  (233) [HTML全文] (233) [PDF 4371KB] (233)
摘要:
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]  (240) [HTML全文] (240) [PDF 5404KB] (240)
摘要:
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]  (201) [HTML全文] (201) [PDF 5076KB] (201)
摘要:
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]  (237) [HTML全文] (237) [PDF 6432KB] (237)
摘要:
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]  (262) [HTML全文] (262) [PDF 4338KB] (262)
摘要:
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]  (279) [HTML全文] (279) [PDF 3404KB] (279)
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
[摘要]  (203) [HTML全文] (203) [PDF 5498KB] (203)
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]  (260) [HTML全文] (260) [PDF 3322KB] (260)
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]  (294) [HTML全文] (294) [PDF 3137KB] (294)
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]  (227) [HTML全文] (227) [PDF 2296KB] (227)
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]  (246) [HTML全文] (246) [PDF 3014KB] (246)
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]  (251) [HTML全文] (251) [PDF 876KB] (251)
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]  (232) [HTML全文] (232) [PDF 3776KB] (232)
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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]  (309) [HTML全文] (309) [PDF 5293KB] (309)
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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]  (183) [HTML全文] (183) [PDF 3007KB] (183)
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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]  (217) [HTML全文] (217) [PDF 792KB] (217)
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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]  (161) [HTML全文] (161) [PDF 2326KB] (161)
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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]  (187) [HTML全文] (187) [PDF 2535KB] (187)
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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]  (190) [HTML全文] (190) [PDF 1308KB] (190)
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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]  (418) [HTML全文] (418) [PDF 4607KB] (418)
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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
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摘要:
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.