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2019 Volume 35 Issue 10
2019, 35(10): 1713-1727
doi: 10.11862/CJIC.2019.211
Abstract:
The cell surface shellization is a kind of technology that mainly modifying cell surface to form a complete and uniform organic, inorganic, metal nanoparticles or composite shell structure with physical, chemical and other technical methods. So the cells, which cannot be shellized themselves, can form a protective shell outside and even gain new features, leading to form a multi-functional cell. In recent years, this technology has been widely used in cell storage, cell transportation, cell sensors, cell chips, and cell therapy, and has developed rapidly. This paper synthesizes the current research, and introduces in detail the cell types that can be used for cell surface shellization, the methods of bio-surface shellization, and the application of engineering techniques of artificial cell shells in biomedical and energy environments.
The cell surface shellization is a kind of technology that mainly modifying cell surface to form a complete and uniform organic, inorganic, metal nanoparticles or composite shell structure with physical, chemical and other technical methods. So the cells, which cannot be shellized themselves, can form a protective shell outside and even gain new features, leading to form a multi-functional cell. In recent years, this technology has been widely used in cell storage, cell transportation, cell sensors, cell chips, and cell therapy, and has developed rapidly. This paper synthesizes the current research, and introduces in detail the cell types that can be used for cell surface shellization, the methods of bio-surface shellization, and the application of engineering techniques of artificial cell shells in biomedical and energy environments.
2019, 35(10): 1728-1736
doi: 10.11862/CJIC.2019.170
Abstract:
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.
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.
2019, 35(10): 1791-1804
doi: 10.11862/CJIC.2019.212
Abstract:
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 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.
2019, 35(10): 1805-1812
doi: 10.11862/CJIC.2019.208
Abstract:
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.
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.
2019, 35(10): 1813-1820
doi: 10.11862/CJIC.2019.214
Abstract:
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.
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.
2019, 35(10): 1821-1833
doi: 10.11862/CJIC.2019.209
Abstract:
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.
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.
2019, 35(10): 1834-1842
doi: 10.11862/CJIC.2019.182
Abstract:
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.
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.
2019, 35(10): 1843-1852
doi: 10.11862/CJIC.2019.204
Abstract:
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.
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.
2019, 35(10): 1853-1860
doi: 10.11862/CJIC.2019.206
Abstract:
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.
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.
2019, 35(10): 1861-1868
doi: 10.11862/CJIC.2019.221
Abstract:
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%.
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
2019, 35(10): 1869-1876
doi: 10.11862/CJIC.2019.207
Abstract:
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.
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.
2019, 35(10): 1877-1884
doi: 10.11862/CJIC.2019.217
Abstract:
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.
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.
2019, 35(10): 1885-1895
doi: 10.11862/CJIC.2019.216
Abstract:
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.
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.
2019, 35(10): 1896-1902
doi: 10.11862/CJIC.2019.210
Abstract:
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.
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.
2019, 35(10): 1737-1745
doi: 10.11862/CJIC.2019.205
Abstract:
The 1, 5-disubstituted carbohydrazide and thiocarbohydrazide ligands were prepared by condensation of carbohydrazide, thiocarbohydrazide with 5-methylsalicylaldehyde, 4-diethylaminosalicylaldehyde, respectively. Their benzyltin complexes, T1~T4 were obtained by microwave-assisted solvothermal reaction of dibenzyltind-ichloride precursor with the ligands in methanol environments. However, the structure of T4 is different from those of T1~T3, which is a benzyltin complex bridged by N, N'-bis(4-diethylaminosalicylaldehyde) azine and methoxy group. Also, T4 can be synthesized by the "one pot" method of carbohydrazide, 4-diethylaminosalicylal-dehyde and dibenzyltindichloride. Their structures are characterized by elemental analysis, IR, 1H/13C NMR spectra, and the molecular structure of complex T4 was confirmed by X-ray diffraction. The crystal of T4 belongs to monoclinic system, space group P21/c. The Sn atom is six-coordinated with distorted octahedral geometry formed by O, N atoms from the carbohydrazide ligand, C atom of butyl and two Cl atoms. The complex T4 has strong fluorescence emission in DMF and mixed solvents of DMF-water. When the volume fraction of water is 0~30% (V/V), the aggregation fluorescence enhancement effect is good, and fluorescence quenching occurs when the water content is more than 30% (V/V). The complexes have good growth inhibition on Portulaca oleracea L., and T1 and T3 have selective growth inhibition on Cassia tora L., T2 on Amaranthus tricolor L., T4 on Brassica campestris L. ssp. chinensis var. utilis Tsen et Lee. They can be used as candidate herbicides for further study.
The 1, 5-disubstituted carbohydrazide and thiocarbohydrazide ligands were prepared by condensation of carbohydrazide, thiocarbohydrazide with 5-methylsalicylaldehyde, 4-diethylaminosalicylaldehyde, respectively. Their benzyltin complexes, T1~T4 were obtained by microwave-assisted solvothermal reaction of dibenzyltind-ichloride precursor with the ligands in methanol environments. However, the structure of T4 is different from those of T1~T3, which is a benzyltin complex bridged by N, N'-bis(4-diethylaminosalicylaldehyde) azine and methoxy group. Also, T4 can be synthesized by the "one pot" method of carbohydrazide, 4-diethylaminosalicylal-dehyde and dibenzyltindichloride. Their structures are characterized by elemental analysis, IR, 1H/13C NMR spectra, and the molecular structure of complex T4 was confirmed by X-ray diffraction. The crystal of T4 belongs to monoclinic system, space group P21/c. The Sn atom is six-coordinated with distorted octahedral geometry formed by O, N atoms from the carbohydrazide ligand, C atom of butyl and two Cl atoms. The complex T4 has strong fluorescence emission in DMF and mixed solvents of DMF-water. When the volume fraction of water is 0~30% (V/V), the aggregation fluorescence enhancement effect is good, and fluorescence quenching occurs when the water content is more than 30% (V/V). The complexes have good growth inhibition on Portulaca oleracea L., and T1 and T3 have selective growth inhibition on Cassia tora L., T2 on Amaranthus tricolor L., T4 on Brassica campestris L. ssp. chinensis var. utilis Tsen et Lee. They can be used as candidate herbicides for further study.
2019, 35(10): 1746-1754
doi: 10.11862/CJIC.2019.215
Abstract:
Ni-Co-Al alloys with different Co contents were prepared by vacuum smelting and rapid solidification. XRD, SEM, TEM and N2 adsorption-desorption were used on the structure characterization of nanoporous Ni-Co, and the hydrogen evolution performance of nanoporous Ni-Co/GCE electrode was tested by linear sweep voltammetry (LSV) and ac impedance(IMP). The results showed that there were smaller pores (5~10 nm) on the surface of the nanoporous Ni-Co alloy skeleton, and the catalytic performance of hydrogen evolution was better when the Co content was 40%~60% (w/w). Among them, the pores of Ni2.5Co2.5 and Ni3Co2 are almost uniform, and they have smaller mesoporous pores than others, which is beneficial to the infiltration of electrolyte and increase the surface area of the electrode.Therefore, Ni2.5Co2.5/GCE and Ni3Co2/GCE have high hydrogen evolution performance. When the current density was -0.005 A·cm-2, the hydrogen evolution potential of the two electrodes were almost the same as 380 mV.
Ni-Co-Al alloys with different Co contents were prepared by vacuum smelting and rapid solidification. XRD, SEM, TEM and N2 adsorption-desorption were used on the structure characterization of nanoporous Ni-Co, and the hydrogen evolution performance of nanoporous Ni-Co/GCE electrode was tested by linear sweep voltammetry (LSV) and ac impedance(IMP). The results showed that there were smaller pores (5~10 nm) on the surface of the nanoporous Ni-Co alloy skeleton, and the catalytic performance of hydrogen evolution was better when the Co content was 40%~60% (w/w). Among them, the pores of Ni2.5Co2.5 and Ni3Co2 are almost uniform, and they have smaller mesoporous pores than others, which is beneficial to the infiltration of electrolyte and increase the surface area of the electrode.Therefore, Ni2.5Co2.5/GCE and Ni3Co2/GCE have high hydrogen evolution performance. When the current density was -0.005 A·cm-2, the hydrogen evolution potential of the two electrodes were almost the same as 380 mV.
2019, 35(10): 1755-1766
doi: 10.11862/CJIC.2019.213
Abstract:
We used surface imprinting polymerization to prepare the sensing material HNTs@ⅡPs modified by hyperbranched imprinting polymers (HNTs=halloysite nanotubes). Fourier transform infrared spectroscopy (FTIR), XRD, SEM, nuclear magnetic and thermogravimetry proved that HNTs@ⅡPs was successfully synthesized. Then, we used cyclic voltammetry, differential pulse voltammetry and electrochemical impedance spectroscopy to investigate the electrochemical properties and specific sensing properties to cadmium ion of HNTs@ⅡPs. The results showed that when cCd2+≤ 0.125 μmol·L-1, the peak current of the sensing material had a good quantitative relationship with cCd2+, and the detection limit is 0.026 μmol·L-1. The imprinting factor was 5.97 and the selective factor was 4.97, which indicates that the HNTs@ⅡPs have specificity and strong selective adsorption to Cd2+. It suggests that HNTs@ⅡPs can be used to detect the concentration of Cd2+. The equivalent electrical circuit model of the sensor was obtained by fitting the results of impedance spectrum analysis and the sensing mechanism was analyzed and illustrated.
We used surface imprinting polymerization to prepare the sensing material HNTs@ⅡPs modified by hyperbranched imprinting polymers (HNTs=halloysite nanotubes). Fourier transform infrared spectroscopy (FTIR), XRD, SEM, nuclear magnetic and thermogravimetry proved that HNTs@ⅡPs was successfully synthesized. Then, we used cyclic voltammetry, differential pulse voltammetry and electrochemical impedance spectroscopy to investigate the electrochemical properties and specific sensing properties to cadmium ion of HNTs@ⅡPs. The results showed that when cCd2+≤ 0.125 μmol·L-1, the peak current of the sensing material had a good quantitative relationship with cCd2+, and the detection limit is 0.026 μmol·L-1. The imprinting factor was 5.97 and the selective factor was 4.97, which indicates that the HNTs@ⅡPs have specificity and strong selective adsorption to Cd2+. It suggests that HNTs@ⅡPs can be used to detect the concentration of Cd2+. The equivalent electrical circuit model of the sensor was obtained by fitting the results of impedance spectrum analysis and the sensing mechanism was analyzed and illustrated.
2019, 35(10): 1767-1772
doi: 10.11862/CJIC.2019.219
Abstract:
Nitrogen doped graphene (N/GN) and nitrogen doped graphene/copper-based catalyst (Cu-N/GN) were fabricated by hydrothermal treatment and ultrasonic-assisted equal volume impregnation method, respectively. The microstructure, morphology and elemental composition of Cu-N/GN catalyst were respectively characterized by XRD, SEM, TEM, N2 adsorption-desorption, XPS and XAES. The catalytic performance of Cu-N/GN toward acetylene hydrochlorination was investigated. The results shown that the size of Cu particles is small and Cu species uniform distribution loading N/GN sheets with relatively low amount of Cu (3.6%) in the catalyst. The Cu-N/GN catalyst exhibits good catalytic activity for the acetylene hydrochlorination, and its acetylene conversion and vinyl chloride selectivity are about 68% and 99%, respectively.
Nitrogen doped graphene (N/GN) and nitrogen doped graphene/copper-based catalyst (Cu-N/GN) were fabricated by hydrothermal treatment and ultrasonic-assisted equal volume impregnation method, respectively. The microstructure, morphology and elemental composition of Cu-N/GN catalyst were respectively characterized by XRD, SEM, TEM, N2 adsorption-desorption, XPS and XAES. The catalytic performance of Cu-N/GN toward acetylene hydrochlorination was investigated. The results shown that the size of Cu particles is small and Cu species uniform distribution loading N/GN sheets with relatively low amount of Cu (3.6%) in the catalyst. The Cu-N/GN catalyst exhibits good catalytic activity for the acetylene hydrochlorination, and its acetylene conversion and vinyl chloride selectivity are about 68% and 99%, respectively.
2019, 35(10): 1773-1780
doi: 10.11862/CJIC.2019.218
Abstract:
Bismuth vanadate (BiVO4) is one of the most promising photoanode materials for converting solar energy into hydrogen energy (STH). However, the practical application of BiVO4 is severely hindered by the intrinsically severe electron-hole recombination. Here, we reported bismuth vanadate (BiVO4) photoanode decorated with binary zinc-cobalt LDHs (ZnCo-LDH) co-catalyst by one-step electrodeposition method, which greatly enhances light absorption capacities of bismuth vanadate (BiVO4), accelerates water oxidation kinetics, facilitates efficient hole transfer to the surface and reduces the surface charge recombination. The hybrid photoanode exhibited a high photocurrent density of 2.85 mA·cm-2 at 1.23 V(vs RHE), which corresponds to a 259% increase compared to that of the pristine BiVO4 photoanode. Furthermore, the onset potential (Von) has greatly decreased from 930 to 270 mV, which displays that OER kinetics is improved upon the deposition of ZnCo-LDH. In addition, the BiVO4/ZnCo-LDH composite photoanode showed a high surface charge separation efficiency of 65%, which is 2.17 times that of BiVO4.
Bismuth vanadate (BiVO4) is one of the most promising photoanode materials for converting solar energy into hydrogen energy (STH). However, the practical application of BiVO4 is severely hindered by the intrinsically severe electron-hole recombination. Here, we reported bismuth vanadate (BiVO4) photoanode decorated with binary zinc-cobalt LDHs (ZnCo-LDH) co-catalyst by one-step electrodeposition method, which greatly enhances light absorption capacities of bismuth vanadate (BiVO4), accelerates water oxidation kinetics, facilitates efficient hole transfer to the surface and reduces the surface charge recombination. The hybrid photoanode exhibited a high photocurrent density of 2.85 mA·cm-2 at 1.23 V(vs RHE), which corresponds to a 259% increase compared to that of the pristine BiVO4 photoanode. Furthermore, the onset potential (Von) has greatly decreased from 930 to 270 mV, which displays that OER kinetics is improved upon the deposition of ZnCo-LDH. In addition, the BiVO4/ZnCo-LDH composite photoanode showed a high surface charge separation efficiency of 65%, which is 2.17 times that of BiVO4.
2019, 35(10): 1781-1790
doi: 10.11862/CJIC.2019.222
Abstract:
N-doped carbons with high surface areas were prepared through one-step chemical activation by using polyurethane foam as carbon and nitrogen source and KOH as activation agent. The morphology, elemental content, surface area and the pore structure of the resulting carbon-based products were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen adsorption-desorption, X-ray diffraction (XRD), Raman and X-ray photoelectron spectroscopy (XPS). The carbon-based product obtained at 700℃ (FC700) possesses the largest surface area and pore volume, contributing by the interaction between KOH and the polyurethane foam. In three-electrode system, the capacitance can reach up to 452 F·g-1 at a current density of 0.5 A·g-1 in 6.0 mol·L-1 KOH solution. In a symmetric supercapacitor, the capacitance can reach 344 F·g-1 and the energy density is 11.9 Wh·kg-1 at the power density of 247 W·kg-1. And the capacitance can maintain 98.03% of the initial capacitance, demonstrating the excellent stability. The excellent electrochemical performance of FC700 can be ascribed to the high surface area, large pore volume and nitrogen doping.
N-doped carbons with high surface areas were prepared through one-step chemical activation by using polyurethane foam as carbon and nitrogen source and KOH as activation agent. The morphology, elemental content, surface area and the pore structure of the resulting carbon-based products were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen adsorption-desorption, X-ray diffraction (XRD), Raman and X-ray photoelectron spectroscopy (XPS). The carbon-based product obtained at 700℃ (FC700) possesses the largest surface area and pore volume, contributing by the interaction between KOH and the polyurethane foam. In three-electrode system, the capacitance can reach up to 452 F·g-1 at a current density of 0.5 A·g-1 in 6.0 mol·L-1 KOH solution. In a symmetric supercapacitor, the capacitance can reach 344 F·g-1 and the energy density is 11.9 Wh·kg-1 at the power density of 247 W·kg-1. And the capacitance can maintain 98.03% of the initial capacitance, demonstrating the excellent stability. The excellent electrochemical performance of FC700 can be ascribed to the high surface area, large pore volume and nitrogen doping.
