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综述
细胞表面壳化的研究进展
苏慧, 许浩, 张利闯, 徐双梦, 魏延, 杜晶晶, 黄棣
2019, 35(10): 1713-1727  doi: 10.11862/CJIC.2019.211
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摘要:
细胞表面壳化主要是通过物理、化学等技术方法对细胞表面进行修饰,形成完整均匀的有机、无机、金属纳米粒子或者复合壳层结构,从而使不能自身壳化的生物细胞表面形成保护壳甚至赋予细胞新的功能,使细胞具备多功能性。近年来,此技术在细胞存储、细胞运输、细胞传感器、细胞芯片以及细胞治疗等方面应用广泛,发展迅速。本文综合目前的研究现状,详细介绍了可进行细胞表面壳化的细胞类型、生物表面壳化的方法以及人造细胞外壳的工程技术在生物医学以及能源环境中的应用等。
Articles
Syntheses, Structures and Properties of Four Transition Metal Complexes with 2, 4-Oxybis(benzoic acid) and N-Donor Ligands
Long TANG, Si-Yu YIN, Ying-Lu WANG, De-Qian SHI, Xiang-Yang HOU, Xiao WANG, Ji-Jiang WANG
2019, 35(10): 1728-1736  doi: 10.11862/CJIC.2019.170
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摘要:
Four transition metal coordination polymers {[Mn(2, 4-Hoba)2(bipy)(H2O)2]·2H2O}n (1), [Mn(2, 4-oba)(phen)]n (2), [Co(2, 4-oba)(bimyb)0.5]n (3) and[Ni(2, 4-oba)(bimyb)0.5]n (4) (2, 4-H2oba=2, 4-oxybis(benzoic acid), bipy=4, 4'-bipyridine, phen=1, 10-phenanthroline, bimyb=1, 4-bis(imidazole-1-ylmethyl) benzene) were synthesized by hydrothermal reactions and characterized by single-crystal X-ray diffraction, thermogravimetric analyses, IR spectroscopy and elemental analysis. Complex 1 is a 1D chain structure, which is extended to a 2D supramolecular architecture by O-H…O hydrogen bonding. Complex 2 shows a 1D wavy chain structure, which is expanded to a 2D wavelike network through aromatic π-π stacking interactions. Complexes 3 and 4 are 2D layer structures produced by ligands bridging binuclear paddle-wheel units. The magnetic properties of 2~4 have also been investigated, and the exchange conpling constants were -0.79, -8.97 and -11.42 cm-1, respectively. According to the crystal structures, the magnetic coupling behavior of complexes 2~4 were studied by using hybrid DFT-BS method, and the result reveals that the calculated exchange coupling constants (J) are in good agreement with the experimental data.
Multihalogen-Substituted Salamo-Type Mn(Ⅱ) Complexes: Syntheses, Crystal Structures, Hirshfeld Analyses and Fluorescence Properties
Lan WANG, Zhi-Li WEI, Meng YU, Ying-Qi PAN, Yang ZHANG, Wen-Kui DONG
2019, 35(10): 1791-1804  doi: 10.11862/CJIC.2019.212
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摘要:
Two manganese(Ⅱ) complexes[Mn(L1)(H2O)2] (1) and[Mn(L2)(H2O)2]·0.37H2O (2) were synthesized by the reactions of halogen-substituted salamo-type bisoxime ligands H2L1, H2L1 with manganese(Ⅱ) acetate tetrahydrate in organic solvents, and the two complexes were characterized by the means of elemental analyses, FT-IR, UV-visible absorption spectra, single-crystal X-ray diffractions, fluorescence spectra and Hirshfeld surfaces analyses. X-ray crystallography results indicated that the manganese(Ⅱ) ions in the two complexes are all six-coordinated, in which the N2O2 of the salamo-type ligand occupied the planar position, and two coordinated water molecules occupied the axial positions, forming distorted octahedral coordination geometries. Due to abundant hydrogen bonding interactions, infinite 1D and 2D supramolecular structures are formed in complexes 1 and 2, respectively.
Two Inorganic-Organic Hybrid Crystals Based on[SMo12O40]2- Polyoxometallates and Supramolecular Cation: Syntheses and Crystal Structures
Jun XIONG, Mao-Kun TAN, Shao-Fang LÜ, Ming LI, Shui-Bin YANG
2019, 35(10): 1805-1812  doi: 10.11862/CJIC.2019.208
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摘要:
Two inorganic-organic hybrids, [(4-I-Anis)([18]crown-6)]2[SMo12O40]·CH3CN (1) and[(3-F-4-Cl-Anis)2(DB[30]crown-10)] [SMo12O40]·2CH3CN (2) (4-I-Anis=4-iodoanilinium; 3-F-4-Cl-Anis=3-fluoro-4-chloroanilinium; DB[30]crown-10=dibenzo[30]crown-10) have been synthesized and characterized by infrared spectrum (IR), elemental analysis (EA), powder XRD, thermogravimetric (TG), solid state diffuse reflectance spectra (DRS) and X-ray diffraction. Crystals 1 and 2 are constructed through noncovalent bonding interaction, and the polyoxo-metalates and supramolecular cation arrange alternately. Supramolecular cation forms through the N-H…O hydrogen bonding interaction between the nitrogen atom of anilinium and oxygen atoms of crown ether derivatives. In crystal 1, each polyoxoanion is surrounded by six monovalent supramolecular cations (4-I-Anis)([18]crown-6) and forms hexagonal arrangement in bc plane. In crystal 2, each polyoxoanion is surrounded by four large supramolecular cations (3-F-4-Cl-Anis)2(DB[30]crown-10) and forms tetragonal arrangement in bc plane. TG measurement indicated that hydrogen bonding interaction plays an important role in maintaining the structural stability of crystals 1 and 2. DRS indicated that there exists charge-transfer interaction between[SMo12O40]2- polyoxoanions and crown ether based supramolecular cations in crystals 1 and 2.
Crystal Structure and Electrochemistry Properties of Three Co(Ⅱ) Complexes Based on Flexible Phenylenediacetate Ligands
Mei-Li ZHANG, Yan-Jin ZHENG, Min LIU, Yi-Xia REN, Ji-Jiang WANG, Hua-Li CUI, Lin LIU
2019, 35(10): 1813-1820  doi: 10.11862/CJIC.2019.214
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Three new coordination complexes, {[Co1.5(opda)1.5(mbib)2(H2O)2]·H2O}n (1), {[Co(mpda)(mbib)]·H2O}n (2) and {[Co(ppda)(mbib)]·H2O}n (3) (H2opda=1, 2-phenylenediacetic acid, H2mpda=1, 3-phenylenediacetic acid, H2ppda=1, 4-phenylenediacetic acid, mbib=1, 3-bis(1-imidazoly)benzene), have been synthesized by using cobalt salt and bis(imidazole) ligand in the presence of different flexible phenylenediacetate blocks under hydrothermal conditions, and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray crystallography. Single-crystal X-ray diffraction analysis revealed that the diverse structures of these complexes are mainly attributed to various coordination geometries of the central cobalt(Ⅱ) cations, coordination modes and conformations of the flexible phenylenediacetic acid and bis(imidazole) ligands. Furthermore, thermal gravimetric analysis (TGA) and the electrochemistry properties of 1~3 are also investigated, and all of them have good cyclic voltammograms.
Crystallization Kinetics of Mg-Borates Precipitating from Diluted Boron-Containing Brine of Da Qaidam Saline Lake
Jiao-Yu PENG, Bo ZHANG, Jing CHEN, Ya-Ping DONG, Wu LI
2019, 35(10): 1821-1833  doi: 10.11862/CJIC.2019.209
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摘要:
The crystallization kinetics of Mg-borates from different diluted brines was investigated by dynamical method. With the aid of simple optimum method and Runge-Kutta digital solution of differential equations, the experimental data was fitted by computer and the optimum kinetic equations of Mg-borates were obtained. Factors such as temperature, mass dilution ratios and boron concentrations during crystallization were tested. The crystallization rate was also calculated based on the kinetic equations. The results show that low temperature, high boron concentration and medium dilution ratio favor the Mg-borates crystallization. The boron yield would be more than 88% in B2O3 under the optimized condition. The kinetic parameters indicate that almost all of the crystallization mechanisms of Mg-borates in diluted brine are polynuclear layer controlled growth. Besides, the crystallization reactions in diluted solutions were also proposed.
Metal-Organic Framework Derived Co3O4/C Composite as High-Performance Anode Material for Lithium-Ion Batteries
Lei GOU, Shao-Pan ZHAO, Peng-Gang LIU, Jiang-Fan YANG, Xiao-Yong FAN, Dong-Lin LI
2019, 35(10): 1834-1842  doi: 10.11862/CJIC.2019.182
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摘要:
In order to overcome the disadvantages of the low electrical conductivity and poor cycling stability of Co3O4 anode material, a Co3O4/C composite was obtained by the judicious selection of Co2(NDC)2DMF2 (NDC=1,4-naphthalene dicarboxylate) as precursor through a two-step calcination process. The sample was characterized by X-ray diffraction (XRD), scanning electronic microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The content of amorphous carbon in Co3O4/C was tested by thermogravimetric analysis (TGA). As anode material for lithium-ion batteries (LIBs), Co3O4/C material showed a high reversible specific capacity, remarkable cycling performance (the specific discharge capacity was stable at 1 000 mAh·g-1 under the current density of 200 mA·g-1 even after 200 cycles) and an excellent rate performance with high average discharge specific capacities of 1 076.3, 976.2, 872.9, 783.6 and 670.1 mAh·g-1 at 100, 200, 500, 1 000 and 2 000 mA·g-1, respectively. The excellent electrochemical performance was attributed to the amorphous carbon derived from the organic ligand, which served as conductive path for easy electric charge transfer and buffer layer to slow down the volumetric stresses.
Two Homologous Metal-Organic Frameworks Based on Zn(Ⅱ) and Cd(Ⅱ): Luminescent Sensors for Nitro Aromatic Compounds in Solution and Vapor Medium
Jiang LI, Sen HAN, Tuan-Jie CHEN, Zhao-Xi GOU, Qi ZHANG, Xiao-Sahuang NIE, Hai-Ru CAO
2019, 35(10): 1843-1852  doi: 10.11862/CJIC.2019.204
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Two homologous luminescent metal-organic frameworks (LMOFs), [Cd2(DDCPB)(DMF)2(H2O)]n (CHD-1) and {[Zn2(DDCPB)(DMA)2]·DMA}n (CHD-2) (H4DDCPB=1, 1':3', 1″-terphenyl-3, 3″, 5, 5″-tetracarboxylic acid), were constructed to explore sensing mechanisms for series of nitro aromatic compounds (NACs). Among various kinds of organic compounds, both CHD-1 and CHD-2 only respond to a series of nitro aromatic compounds through luminescence quenching with distinct analytes concentration in vapor and liquid phase. Quantitative experiments in solution were conducted to confirm the higher dynamic quenching efficiency and to calculate the quenching constants. Meanwhile, both CHD-1 and CHD-2 show high selectivity and excellent sensitivity for NACs with low detection limits in solution. Moreover, the film based on the MOFs sample identifies high sensitivity towards nitrobenzene (NB) and 2-nitrotoluene (o-MNT) vapor. In addition, the relationship between the sensing efficiency and the inherent structure of compounds the sensing mechanisms were discussed in detail.
Syntheses, Crystal Structures, Luminescent and Magnetic Properties of One 0D Zinc(Ⅱ) and Two 1D Manganese(Ⅱ) Coordination Compounds Assembled from Pyridine-Tricarboxylate Blocks
Yu LI, Guang-Min PAN, Xun-Zhong ZOU, An-Sheng FENG, Ao YOU, Wen-Da QIU
2019, 35(10): 1853-1860  doi: 10.11862/CJIC.2019.206
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One 0D zinic(Ⅱ) and two 1D manganese(Ⅱ) coordination compounds, namely[Zn(H2biim)2(H2O)2] [Zn(HL)(Hbiim)(H2O)]2·8H2O (1), [Mn(μ-HL)(phen)(H2O)]n (2) and {[Mn(μ-HL)(2, 2'-bipy)(H2O)]·0.5(2, 2'-bipy)}n (3) have been constructed hydrothermally using H3L (H3L=4-(6-carboxy-pyridin-3-yl)-isophthalic acid), H2biim (H2biim=2, 2'-biimidazole), phen (phen=1, 10-phenanthroline), 2, 2'-bipy (2, 2'-bipy=2, 2'-bipyridine), and zinc or manganese chlorides. Single-crystal X-ray diffraction analyses reveal that three compounds crystallize in the monoclinic system, space groups P21/n or P21/c. Compound 1 shows a 0D structure composed of three monomer Zn(Ⅱ) units, which is arranged into a 3D supramolecular framework through O-H…O/N or N-H…O hydrogen bonds. Compounds 2 and 3 feature a 1D metal-organic chain, which is assembled to a 2D supramolecular network through O-H…O hydrogen bond. The luminescent and magnetic properties for three compounds were also investigated.
Fabrication of Honeycomb-like Ag Nanoparticles Film Used as Surface Enhanced Raman Scattering Substrate
Yuan-Jun LIU, Fen YE, Wei WANG, Jun-Hao ZHANG, Chao YAN, Ai-Hua YUAN
2019, 35(10): 1861-1868  doi: 10.11862/CJIC.2019.221
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Highly ordered polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) honeycomb-patterned film was prepared by a static breath figure method, which was used as a template for the preparation of metal particles array. Honeycomb-like Ag nanoparticles array film was prepared with this polymer pattern through a photochemical reduction route. The SERS performance of this Ag nanoparticle array film was investigated with rhodamine 6G (R6G) as model molecule, which provides enhancement factors (EF) as high as 1.31×109. In addition, the substrate shows a lower limit of detection to 10-10 mol·L-1 for R6G and favorable uniformity through SERS mapping-scan spectra. The SERS signals collected at 120 points over a 30 μm×30 μm area present relative standard deviation of~12%.
Coumarin-Based Turn-on Fluorescent Probe for Copper(Ⅱ) Detection and Its Application in Cell Imaging
Chang-Li ZHANG, Hong ZHANG, Feng-Yun HE, Hui YANG, Shao-Xian LIU, Min-Sheng LIU
2019, 35(10): 1869-1876  doi: 10.11862/CJIC.2019.207
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A new coumarin-based Cu2+ probe (Cou-P) according to the Cu2+-coordination induced hydrolysis mechanism has been developed. Cou-P exhibits a highly selective turn-on response to Cu2+ over other transition metal ions in aqueous media. The recognition mechanism of Cou-P for Cu2+ was comfirmed by UV-Vis, fluorescence and mass spectrometry. The results show that Cou-P first forms Cou-P/Cu2+(1:1) complex, and Cou-P/Cu2+ complex is further catalyzed to 3-(carboxylic acid)-7-(diethylamino)-coumarin (Cou-COOH) by excessive Cu2+. Cou-P has low cytotoxicity and good membrane permeability. It has been successfully used to detect Cu2+ in MCF-7 cells.
Syntheses, Crystal Structures, and Luminescence Sensing of Three Coordination Polymers Based on Bis(benzimidazole) Bridging Linkers
Yu-Lan NIU, Li-Jun ZHAI, Xiao-Yan HAO, Jiao-Jiao JIA, Li-Ming FAN
2019, 35(10): 1877-1884  doi: 10.11862/CJIC.2019.217
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Three 1D coordination polymers (CPs), namely, {[Mn(bbib)(H2O)4](H2BTC)·2H2O}n (1), [Zn(bbib)Cl2]n (2), and[Zn(bbibp)Cl2]n (3), have been assembled from the reaction of bbib (1, 4-bis(2-benzimidazolyl)benzene) or bbibp (4, 4'-bis(2-benzimidazolyl)biphenyl) and transition metal salts. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses (EA), IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Structural analysis reveals that the strong O-H…O hydrogen bonds in 1, and C-H…Cl hydrogen bonds in 2 and 3 play important roles in the formation of those CPs, with the final packing architectures being (4, 6)-connected {42·58·64·7}{42·64} net for 1, 5-connected {43·67} net for 2, and 6-connected (48·67)-msw net for 3. Besides, the luminescent sensing investigation indicates that complexes 2 and 3 exhibit highly sensitivity and selectively sensing of Fe3+ ion in aqueous solutions.
Preparation and Characterization of Mullite Whiskers from Different Silica Sources via Molten Salt Reaction
Xue-Dong MA, Ji-Chang HAN, Wei DU, Wei WANG
2019, 35(10): 1885-1895  doi: 10.11862/CJIC.2019.216
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Mullite whiskers were prepared using molten salt reaction. The resulting whiskers have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TG-DSC) and high resolution transmission electron microscopy (HRTEM). SEM studies showed that diameter of the mullite whiskers was in a range of 200~400 nm and their length was several microns. The analysis of HRTEM data revealed that the interplanar spacing was 0.539 nm, in accordance with the spacing of (110) crystal plane of mullite. As silica species was introduced into starting reactants, the combination reaction of mullite formation took place, γ-Al2O3 was consumed and mullite whiskers grew continuously. The most important factor in controlling mullite formation is the decomposition reaction of aluminum sulfate, and α-Al2O3 is fabricated by thermal pyrolysis of aluminum sulfate at 900℃ in molten sodium sulfate system without silica species participating. According to the thermodynamic calculation, α-Al2O3 is a stable phase as the product of the decomposition of Al2(SO4)3 in comparison to γ-Al2O3, and mullite formation reaction is a spontaneous process in the whole temperature range. The decomposition reaction of aluminum sulfate was investigated by Kissinger-Akahira-Suno method with various heating rates (β=5, 10 and 15 K·min-1), and the apparent activation energy (Ea) of reaction is 257.2 kJ·mol-1.
Syntheses, Crystal Structures and Luminescence Properties of Two Zn(Ⅱ) Coordination Polymers Based on Flexible Bisbenzimidazole Ligand
Hong-Hong LAN, Xiao-Tong LI, Wen-Juan CHU, Chun-Ying XU, Bao-Ming JI
2019, 35(10): 1896-1902  doi: 10.11862/CJIC.2019.210
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Two new coordination polymers, {[Zn(bmb)0.5(btec)0.5(H2O)]·H2O}n (1) and {[Zn2(bmb)2(dcbp)]·5H2O}n (2) were synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffractions, IR spectra, elemental analyses and powder X-ray diffractions (bmb=1, 4-bis(2-methylbenzimidazol-1-ylmethyl) benzene, H4btec=1, 2, 4, 5-benzenetetracarboxylic acid, H4dcbp=4-(3, 4-dicarboxybenzoyl)phthalic acid). Structural analyses reveal that both polymers 1 and 2 exhibit complicated 3D frameworks in which bmb acts as linker with μ2-η1:η1 coordination mode. Thermal stabilities and solid-state luminescence at room temperature of 1 and 2 also were investigated.
论文
双(取代水杨醛)缩卡巴肼及其苄基锡配合物的合成、表征、荧光性质和除草活性
冯泳兰, 杨春林, 张复兴, 邝代治
2019, 35(10): 1737-1745  doi: 10.11862/CJIC.2019.205
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用5-甲基水杨醛、4-二乙氨基水杨醛分别与卡巴肼或硫代卡巴肼缩合,制得1,5-二取代卡巴肼或硫代卡巴肼配体。在微波甲醇溶剂热条件下,二苄基二氯化锡前体与配体反应,合成了双(取代水杨醛)缩(硫代)卡巴肼苄基锡配合物T1~T4,但T4的结构与T1~T3不同,T4NN'-双(4-二乙氨基水杨醛)缩连氮及甲氧基桥联锡组成的苄基锡配合物,T4还可由卡巴肼、4-二乙氨基水杨醛和二苄基二氯化锡“一锅法”合成。T1~T4的结构经元素分析、IR、1H/13C NMR表征,并用X射线衍射法确证配合物T4的晶体分子结构。T4属单斜晶系,P21/c空间群,中心锡原子与氮、氧、苄基碳和氯原子组成六配位变形八面体构型。T4在DMF-H2O溶液中具有良好的荧光性质,当含水量0~30%(V/V)时具有聚集荧光增强效应,含水量大于30%时,随含水体积分数增加荧光强度减弱,以至最后淬灭。配合物对马齿苋具有良好的生长抑制作用,T1T3对决明子、T2对苋菜和T4对四九菜心具有选择性生长抑制作用,可作为除草剂的候选化合物进一步研究。
不同Co含量对纳米多孔Ni-Co结构及析氢催化性能的影响
冯基伟, 周琦
2019, 35(10): 1746-1754  doi: 10.11862/CJIC.2019.215
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摘要:
通过真空熔炼和快速凝固的方法制备了不同Co含量的Ni-Co-Al合金,经脱合金化后得到纳米多孔Ni-Co。采用XRD、SEM、TEM、N2吸附-脱附研究了所得纳米多孔Ni-Co结构特征,以线性扫描伏安法(LSV)、交流阻抗(IMP)等手段对纳米多孔Ni-Co/GCE电极析氢性能进行了测试。结果表明:纳米多孔Ni-Co合金骨架表面存在尺寸更为细小的5~10 nm的小孔,Co含量(质量分数)在40%~60%时,析氢催化性能较好。
埃洛石基离子印迹材料的制备及其镉离子传感性能
胡莹露, 卢闻君, 郭明, 王珏
2019, 35(10): 1755-1766  doi: 10.11862/CJIC.2019.213
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用表面印迹聚合法制备了埃洛石纳米管(HNTs)基超支化镉离子印迹传感材料HNTs@ⅡPs。用傅立叶变换红外光谱(FTIR)、XRD、SEM、核磁及热重等方法表征材料的结构;利用循环伏安法(cyclic voltammetry,CV)、差分脉冲伏安法(differential pulse voltammetry,DPV)及交流阻抗法(electrochemical impedance spectroscopy,EIS)等考察了HNTs@ⅡPs的电化学性能及其对镉离子的特异性传感性能。结果表明成功合成了HNTs@ⅡPs,且在cCd2+≤0.125 μmol·L-1时,感应峰电流与镉离子浓度有良好的定量关系,检出限为0.026 μmol·L-1,印迹因子α为5.97,选择因子β为4.97,表明HNTs@ⅡPs对Cd2+具有专一性和强选择性。对阻抗谱分析结果拟合得到了传感器的电学等效电路模型,并分析阐明了传感机理。
掺氮石墨烯-铜基催化剂的制备及催化性能
唐晓宁, 邵姣婧
2019, 35(10): 1767-1772  doi: 10.11862/CJIC.2019.219
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采用水热法合成掺氮石墨烯(N/GN),通过超声辅助等体积浸渍法制备掺氮石墨烯-铜基催化剂(Cu-N/GN)。通过XRD、SEM、TEM、N2吸附脱附、XPS和XAES对催化剂的微观结构、形貌及元素组成进行表征,并考察Cu-N/GN对乙炔氢氯化反应的催化性能。结果表明:在催化剂中铜颗粒尺寸较小、均匀分布于N/GN片层上,且铜含量较低(3.6%);Cu-N/GN对乙炔氢氯化反应的催化效果良好,乙炔转化率为68%,氯乙烯选择性为99%。
二元ZnCo-LDH助催化剂对BiVO4光电化学性能的促进
李娜, 王慕恒, 赵勇, 姚瑞, 刘光, 李晋平
2019, 35(10): 1773-1780  doi: 10.11862/CJIC.2019.218
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钒酸铋(BiVO4)是最有前景的将太阳能转化为氢能(STH)的光阳极材料之一,但其本身严重的电子-空穴复合严重影响了其实用性。本文中,我们报道了用一步电沉积法将高效的二元ZnCo-LDH助催化剂沉积在钒酸铋(BiVO4)光阳极上,大大提升了钒酸铋(BiVO4)的光吸收能力,并且加速了水氧化反应动力学,显著促进了光生空穴向半导体表面的转移,减轻了表面电荷复合。BiVO4/ZnCo-LDH光阳极在1.23 V(vs RHE)偏压下,0.5 mol·L-1磷酸钾(KPi)电解液中的光电流密度达到2.85 mA·cm-2,是纯BiVO4的2.59倍,且起始电位(Von)从930 mV下降到270 mV。BiVO4/ZnCo-LDH复合光阳极表现出65%的高表面电荷分离效率(1.23 V(vs RHE)),而纯BiVO4的仅为30%。
氮掺杂高比表面多孔碳的一步化学活化法制备及其超电容性能
辛冉冉, 缪杭锦, 姜伟, 胡庚申
2019, 35(10): 1781-1790  doi: 10.11862/CJIC.2019.222
[摘要]  (11) [HTML全文] (11) [PDF 7459KB] (3)
摘要:
以聚氨酯发泡剂为碳源和氮源,以氢氧化钾为活化剂,采用一步化学活化法制备了具有高比表面积的氮掺杂活性炭。采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、N2吸附-脱附、X射线粉末衍射(XRD)、拉曼光谱(Raman)、光电子能谱(XPS)对碳材料的微观形貌、组成、比表面积和孔道结构进行了表征。结果表明,在700℃活化的碳材料FC700具有最高的比表面积(2 740 m2·g-1)和最大的孔容(1.27 cm3·g-1),这归因于KOH与泡沫的充分相互作用。在以6.0 mol·L-1 KOH为电解液的三电极体系中,当电流密度为0.5 A·g-1时,其比电容达到了452 F·g-1。在组装的对称超级电容器中,其比电容达到了344 F·g-1,功率密度为247 W·kg-1时对应的能量密度为11.9 Wh·kg-1。在10 000次循环后电容保持率为98.03%,表现出优异的稳定性。FC700的优异电化学性能可能归因于高的比表面积,大的孔体积和氮原子的掺杂。

  

综述
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
[摘要]  (106) [HTML全文] (106) [PDF 12300KB] (106)
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
[摘要]  (72) [HTML全文] (72) [PDF 2725KB] (72)
摘要:
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
[摘要]  (82) [HTML全文] (82) [PDF 3737KB] (82)
摘要:
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
[摘要]  (72) [HTML全文] (72) [PDF 5617KB] (72)
摘要:
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
[摘要]  (81) [HTML全文] (81) [PDF 5335KB] (81)
摘要:
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
[摘要]  (70) [HTML全文] (70) [PDF 3498KB] (70)
摘要:
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
[摘要]  (82) [HTML全文] (82) [PDF 2680KB] (82)
摘要:
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
[摘要]  (102) [HTML全文] (102) [PDF 3535KB] (102)
摘要:
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
[摘要]  (81) [HTML全文] (81) [PDF 4058KB] (81)
摘要:
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
[摘要]  (88) [HTML全文] (88) [PDF 3433KB] (88)
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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
[摘要]  (79) [HTML全文] (79) [PDF 3754KB] (79)
摘要:
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
[摘要]  (71) [HTML全文] (71) [PDF 2001KB] (71)
摘要:
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
[摘要]  (59) [HTML全文] (59) [PDF 3432KB] (59)
摘要:
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
[摘要]  (85) [HTML全文] (85) [PDF 3287KB] (85)
摘要:
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
[摘要]  (103) [HTML全文] (103) [PDF 2090KB] (103)
摘要:
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
[摘要]  (86) [HTML全文] (86) [PDF 5413KB] (86)
摘要:
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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摘要:
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
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摘要:
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
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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
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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]  (87) [HTML全文] (87) [PDF 1689KB] (87)
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
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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
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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。