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2018 Volume 34 Issue 12
2018, 34(12): 2127-2134
doi: 10.11862/CJIC.2018.277
Abstract:
Inorganic chemistry method is an important approach for the restoration and protection of cultural relics. This paper discussesd the application of inorganic chemistry knowledge in the restoration and protection of cultural relics. The inorganic chemistry principles and methods in the study of preservation and protection of cultural relics were introduced in details, concerning the cleaning, restoration and protection of cultural relics.
Inorganic chemistry method is an important approach for the restoration and protection of cultural relics. This paper discussesd the application of inorganic chemistry knowledge in the restoration and protection of cultural relics. The inorganic chemistry principles and methods in the study of preservation and protection of cultural relics were introduced in details, concerning the cleaning, restoration and protection of cultural relics.
2018, 34(12): 2135-2142
doi: 10.11862/CJIC.2018.276
Abstract:
Different Cu-SSZ-13 catalysts are prepared by one-pot synthesis by changing the crystallization time during the reaction and characterized using various analytical techniques, including H2-temperature program reduction (H2-TPR), X-ray diffraction (XRD), electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS). The result demonstrated that the crystallization time had an important impact on the content and distribution of active copper species. The catalysts with proper crystallization time showed excellent activity and hydrothermal stability for the NH3 selective catalytic reduction (NH3-SCR) reaction and the best crystallization time was about 4 d. In the zeolite, the unstable CuA2+ species may be converted to stable CuB2+ species and the Cu2+ species agglomerated together under high-temperature hydrothermal conditions. In conclusion, the collapse of the zeolite structure and the agglomeration of active Cu2+ species were the main reason for the deterioration of the hydrothermal stability.
Different Cu-SSZ-13 catalysts are prepared by one-pot synthesis by changing the crystallization time during the reaction and characterized using various analytical techniques, including H2-temperature program reduction (H2-TPR), X-ray diffraction (XRD), electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS). The result demonstrated that the crystallization time had an important impact on the content and distribution of active copper species. The catalysts with proper crystallization time showed excellent activity and hydrothermal stability for the NH3 selective catalytic reduction (NH3-SCR) reaction and the best crystallization time was about 4 d. In the zeolite, the unstable CuA2+ species may be converted to stable CuB2+ species and the Cu2+ species agglomerated together under high-temperature hydrothermal conditions. In conclusion, the collapse of the zeolite structure and the agglomeration of active Cu2+ species were the main reason for the deterioration of the hydrothermal stability.
2018, 34(12): 2143-2152
doi: 10.11862/CJIC.2018.243
Abstract:
Pure-phase low-silica chabazite zeolites were rapidly synthesized by the addition of heterogenous seeds (zeolite T) without organic structural directing agents (OSDAs). Structural properties and morphology characteristics of the products were characterized using XRD, SEM, TEM, 27Al MAS NMR and UV Raman spectroscopy. Crystallization process of chabazite and the various parameters such as seed content, nAl2O3/nSiO2, nH2O/nSiO2 and alkalinity on the crystallization of crystals were investigated in detail. The formation mechanism of chabazite zeolite induced by zeolite T seed was also discussed. Only zeolite L was formed in the in-situ synthesis system while pure chabazite zeolite was fast obtained by adding a certain amount of zeolite T into the gel. The six-membered (6R) and four-membered rings (4R) released from the dissolved zeolite T under certain hydrothermal conditions rapidly formed the characteristic unit of chabazite zeolite (CHA cage), which inhibited the formation of the characteristic unit and characteristic cage of zeolite L (the CAN cage without four-membered ring).
Pure-phase low-silica chabazite zeolites were rapidly synthesized by the addition of heterogenous seeds (zeolite T) without organic structural directing agents (OSDAs). Structural properties and morphology characteristics of the products were characterized using XRD, SEM, TEM, 27Al MAS NMR and UV Raman spectroscopy. Crystallization process of chabazite and the various parameters such as seed content, nAl2O3/nSiO2, nH2O/nSiO2 and alkalinity on the crystallization of crystals were investigated in detail. The formation mechanism of chabazite zeolite induced by zeolite T seed was also discussed. Only zeolite L was formed in the in-situ synthesis system while pure chabazite zeolite was fast obtained by adding a certain amount of zeolite T into the gel. The six-membered (6R) and four-membered rings (4R) released from the dissolved zeolite T under certain hydrothermal conditions rapidly formed the characteristic unit of chabazite zeolite (CHA cage), which inhibited the formation of the characteristic unit and characteristic cage of zeolite L (the CAN cage without four-membered ring).
2018, 34(12): 2153-2160
doi: 10.11862/CJIC.2018.267
Abstract:
Mesoporous titanium dioxide (m-TiO2) was synthesized by using Titanium tetraisopropanolate (TTIP) as the raw material and cetyltrimethyl ammonium bromide (CTAB) as the template via sol-gel method. The effects of the synthesis temperature, the amount of H2O and template in the initial gel, as well as the calcination temperature on the photocatalytic hydrogen production activity of m-TiO2 were investigated. The results show that the structure of the m-TiO2 sample transferred from amorphous to anatase phase after calcined under 350℃ for 3 h. The crystallinity of the anatase phase increased with calcination temperature increasing and most of the anatase phase transferred to rutile phase after calcined above 550℃. The sample which synthesized at 30℃, with nCTAB/nTiO2=0.2 and nH2O/nTiO2=100, then calcined at 450℃ showed excellent photocatalytic activity of splitting water under UV irradiation. When the amount of catalyst was 0.4 g·L-1 and the methanol concentration was 20%(V/V), the hydrogen production rate of m-TiO2 reached as high as 170 mmol·g-1·h-1. A series of rGO/m-TiO2 samples with different amount of rGO were synthesized by using hydrothermal method. When wGO/wTiO2 was 0.01, the hydrogen production rate of the sample was 241 mmol·g-1·h-1 under UV light irradiation, and the energy conversion efficiency reached 7.4%, 42.3% higher than that of m-TiO2. Under visible light irradiation, its hydrogen production rate reached 9 mmmol·g-1·h-1.
Mesoporous titanium dioxide (m-TiO2) was synthesized by using Titanium tetraisopropanolate (TTIP) as the raw material and cetyltrimethyl ammonium bromide (CTAB) as the template via sol-gel method. The effects of the synthesis temperature, the amount of H2O and template in the initial gel, as well as the calcination temperature on the photocatalytic hydrogen production activity of m-TiO2 were investigated. The results show that the structure of the m-TiO2 sample transferred from amorphous to anatase phase after calcined under 350℃ for 3 h. The crystallinity of the anatase phase increased with calcination temperature increasing and most of the anatase phase transferred to rutile phase after calcined above 550℃. The sample which synthesized at 30℃, with nCTAB/nTiO2=0.2 and nH2O/nTiO2=100, then calcined at 450℃ showed excellent photocatalytic activity of splitting water under UV irradiation. When the amount of catalyst was 0.4 g·L-1 and the methanol concentration was 20%(V/V), the hydrogen production rate of m-TiO2 reached as high as 170 mmol·g-1·h-1. A series of rGO/m-TiO2 samples with different amount of rGO were synthesized by using hydrothermal method. When wGO/wTiO2 was 0.01, the hydrogen production rate of the sample was 241 mmol·g-1·h-1 under UV light irradiation, and the energy conversion efficiency reached 7.4%, 42.3% higher than that of m-TiO2. Under visible light irradiation, its hydrogen production rate reached 9 mmmol·g-1·h-1.
2018, 34(12): 2161-2171
doi: 10.11862/CJIC.2018.279
Abstract:
The solvation effects of meso-tetrakis(p-methylphenyl) porphyrin (TMPP) and meso-tetrakis(p-methylphenyl) porphyrin cobalt (TMPP-Co), and the luminescence mechanism in aqueous systems have been studied in detail. It was found that the luminescence intensity of TMPP after the complexation of cobalt ions decreased significantly; the solvation effect of TMPP-Co was not only related to the polarity of the solvent but also related to the axial coordination of Co ions. The luminous intensities of TMPP and TMPP-Co showed a trend of increase and then decrease both in aqueous phase and in glycerol. In addition, TMPP-Co has a strong ability to generate singlet oxygen; the preparation of TMPP-TAT-NPs nanoparticles successfully stained cells and localized to the cell lysosomes.
The solvation effects of meso-tetrakis(p-methylphenyl) porphyrin (TMPP) and meso-tetrakis(p-methylphenyl) porphyrin cobalt (TMPP-Co), and the luminescence mechanism in aqueous systems have been studied in detail. It was found that the luminescence intensity of TMPP after the complexation of cobalt ions decreased significantly; the solvation effect of TMPP-Co was not only related to the polarity of the solvent but also related to the axial coordination of Co ions. The luminous intensities of TMPP and TMPP-Co showed a trend of increase and then decrease both in aqueous phase and in glycerol. In addition, TMPP-Co has a strong ability to generate singlet oxygen; the preparation of TMPP-TAT-NPs nanoparticles successfully stained cells and localized to the cell lysosomes.
2018, 34(12): 2172-2178
doi: 10.11862/CJIC.2018.278
Abstract:
Two new mononuclear complexes, [Ni(cepha)2]·6H2O (1) and[Zn(cepha)2]·6H2O (2) (cepha=cephalo-sporoate) have been synthesized and characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis and X-ray powder diffraction analysis. The structures of complexes have also been determined by X-ray single crystal diffraction analysis, and the results show that the complexes 1 and 2 are both in orthorhombic system with space group P22121. The cephalexin hydrolyzes during the coordination process to produce cephalosporin intermediate, cephalosporoate (cepha), which participates in coordination. Metal ion acts as six-coordinated center forming a distorted octahedral geometry, and the complexes are further extended to a three-dimensional network via intermolecular hydrogen bonds. The antitumor activity in vitro of cephalexin, metal acetate and complexes were carried out by MTT assay. The results reveal that complexes 1 and 2 have a certain inhibiting activity against MCF-7 and HepG-2 cell lines.
Two new mononuclear complexes, [Ni(cepha)2]·6H2O (1) and[Zn(cepha)2]·6H2O (2) (cepha=cephalo-sporoate) have been synthesized and characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis and X-ray powder diffraction analysis. The structures of complexes have also been determined by X-ray single crystal diffraction analysis, and the results show that the complexes 1 and 2 are both in orthorhombic system with space group P22121. The cephalexin hydrolyzes during the coordination process to produce cephalosporin intermediate, cephalosporoate (cepha), which participates in coordination. Metal ion acts as six-coordinated center forming a distorted octahedral geometry, and the complexes are further extended to a three-dimensional network via intermolecular hydrogen bonds. The antitumor activity in vitro of cephalexin, metal acetate and complexes were carried out by MTT assay. The results reveal that complexes 1 and 2 have a certain inhibiting activity against MCF-7 and HepG-2 cell lines.
2018, 34(12): 2179-2187
doi: 10.11862/CJIC.2018.272
Abstract:
A series of vanadium-substituted ternary heteropoly acids with Keggin structure were synthesized by acidification-ether extraction method. Furthermore, the heteropolyanion-based ionic liquids with functional sulfonic acid group, [PyPs]3+nPW12-nVnO40 (n=1, 2, 3), were synthesized by an ion exchange method. The products were characterized by nuclear magnetic resonance spectroscopy (NMR), element analysis, Fourier transform infrared spectrophotometry (FT-IR), UV-Vis spectrophotometry, X-ray diffraction (XRD), thermogravimetry-differential scanning calorimetry (TG-DSC) and potentiometric titration measurements. The catalytic ability and reusability of the ionic liquid catalysts were evaluated in esterification reaction of chloroacetic acid with n-pentyl alcohol. The results show that the ionic liquid catalyst was an amorphous structural compound with temperature responsive characteristics, in which Keggin structure and high acid strength of ionic liquid catalyst remain. The catalyst formed a homogeneous mixture with the reactants at the reaction temperature, but precipitated with biphase separation when the reaction ends and reaction temperature was lowered, and so could be easily separated from the products by a simple filtration. Sulfonic acid functionalized heteropolyanion-based ionic liquids exhibited higher ester catalytic activity than heteropoly acids and unsulfonated heteropolyanion-based ionic liquids. Under the optimized reaction conditions, the conversion rate of[PyPS]4PW11VO40 (PyPS is 1-(3-sulfonate) propyl pyridine) to chloroacetic acid could reach 97.6%, and the conversion rate was 91.9% after repeated reaction four times, but the structure of the catalyst had no change significantly.
A series of vanadium-substituted ternary heteropoly acids with Keggin structure were synthesized by acidification-ether extraction method. Furthermore, the heteropolyanion-based ionic liquids with functional sulfonic acid group, [PyPs]3+nPW12-nVnO40 (n=1, 2, 3), were synthesized by an ion exchange method. The products were characterized by nuclear magnetic resonance spectroscopy (NMR), element analysis, Fourier transform infrared spectrophotometry (FT-IR), UV-Vis spectrophotometry, X-ray diffraction (XRD), thermogravimetry-differential scanning calorimetry (TG-DSC) and potentiometric titration measurements. The catalytic ability and reusability of the ionic liquid catalysts were evaluated in esterification reaction of chloroacetic acid with n-pentyl alcohol. The results show that the ionic liquid catalyst was an amorphous structural compound with temperature responsive characteristics, in which Keggin structure and high acid strength of ionic liquid catalyst remain. The catalyst formed a homogeneous mixture with the reactants at the reaction temperature, but precipitated with biphase separation when the reaction ends and reaction temperature was lowered, and so could be easily separated from the products by a simple filtration. Sulfonic acid functionalized heteropolyanion-based ionic liquids exhibited higher ester catalytic activity than heteropoly acids and unsulfonated heteropolyanion-based ionic liquids. Under the optimized reaction conditions, the conversion rate of[PyPS]4PW11VO40 (PyPS is 1-(3-sulfonate) propyl pyridine) to chloroacetic acid could reach 97.6%, and the conversion rate was 91.9% after repeated reaction four times, but the structure of the catalyst had no change significantly.
2018, 34(12): 2188-2196
doi: 10.11862/CJIC.2018.268
Abstract:
Nano porous Ni, Ni-Mo and their oxides electrode materials were prepared by rapid solidification and de-alloying. The phase, morphology and pore size distribution of porous electrode materials were characterized by XRD, SEM, TEM and N2 absorption-desorption test, and the electro-catalytic hydrogen evolution of porous electrode was tested by linear scanning voltammetry, Tafel slope and chronopotentiometry. The results show that the hydrogen evolution activity of Ni-Mo alloy was the strongest and the process of hydrogen evolution is controlled by Volmer-Heyrovsky step. Its apparent exchange current density (j0) was 0.25 mA·cm-2. After electrolyzing 10 000 seconds at constant current density (100 mA·cm-2), hydrogen evolution over-potential increased only by 39 mV, showing excellent hydrogen evolution stability. The improvement of specific surface area and intrinsic catalytic activity of Ni-Mo alloy electrode resulted in lower hydrogen evolution over-potential.
Nano porous Ni, Ni-Mo and their oxides electrode materials were prepared by rapid solidification and de-alloying. The phase, morphology and pore size distribution of porous electrode materials were characterized by XRD, SEM, TEM and N2 absorption-desorption test, and the electro-catalytic hydrogen evolution of porous electrode was tested by linear scanning voltammetry, Tafel slope and chronopotentiometry. The results show that the hydrogen evolution activity of Ni-Mo alloy was the strongest and the process of hydrogen evolution is controlled by Volmer-Heyrovsky step. Its apparent exchange current density (j0) was 0.25 mA·cm-2. After electrolyzing 10 000 seconds at constant current density (100 mA·cm-2), hydrogen evolution over-potential increased only by 39 mV, showing excellent hydrogen evolution stability. The improvement of specific surface area and intrinsic catalytic activity of Ni-Mo alloy electrode resulted in lower hydrogen evolution over-potential.
2018, 34(12): 2197-2204
doi: 10.11862/CJIC.2018.275
Abstract:
Novel silicate nanotubes supported amorphous Co-B (Co-B/MgSNTs) were synthesized via a hydrothermal method followed by impregnation-chemical reduction processes. The catalysts were characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectrometer (XPS), atomic emission spectrometer (ICP) and brunauer-Emmett-Tellerv (BET) surface-area analyzers. The catalytic activity and recyclability of catalysts for hydroformylation of cyclohexene were evaluated. The conversion of cyclohexene over the catalysts is 75.8% and selectivity for aldehyde is 65.8%. The results indicate that Co-B nanoparticles were deposited on the inner and outer surface of MgSNTs, which had large specific surface area and high stability. Furthermore, the tubular structure of nanotubes could prevent nanoparticle from agglomeration. The catalyst used for 3 recycles shows good catalytic activity.
Novel silicate nanotubes supported amorphous Co-B (Co-B/MgSNTs) were synthesized via a hydrothermal method followed by impregnation-chemical reduction processes. The catalysts were characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectrometer (XPS), atomic emission spectrometer (ICP) and brunauer-Emmett-Tellerv (BET) surface-area analyzers. The catalytic activity and recyclability of catalysts for hydroformylation of cyclohexene were evaluated. The conversion of cyclohexene over the catalysts is 75.8% and selectivity for aldehyde is 65.8%. The results indicate that Co-B nanoparticles were deposited on the inner and outer surface of MgSNTs, which had large specific surface area and high stability. Furthermore, the tubular structure of nanotubes could prevent nanoparticle from agglomeration. The catalyst used for 3 recycles shows good catalytic activity.
2018, 34(12): 2205-2210
doi: 10.11862/CJIC.2018.269
Abstract:
Mo-doped Ce/GE catalysts with different loading amounts were prepared by impregnation method, which were examined as catalysts in the selective catalytic reduction of NOx by NH3(NH3-SCR). Furthermore, the intrinsic mechanism of Mo-doped Ce/GE catalysts for enhancing SCR activity was preliminarily investigated. It was found that the addition of Mo can increase the ratio of nCe3+/(nCe3++nCe4+), the oxygen content on the surface and the acid sites of the catalyst, thus enhancing SCR activity. Compared with 5Ce/GE and 5Mo/GE, 5Ce-5Mo/GE catalyst showed more outstanding catalytic activity. In addition, the catalyst exhibited the best activity and almost 99% conversion of NOx at 250℃, when the loading amount is 5%. 5Ce-5Mo/GE catalyst exhibited good sulfur resistance performance.
Mo-doped Ce/GE catalysts with different loading amounts were prepared by impregnation method, which were examined as catalysts in the selective catalytic reduction of NOx by NH3(NH3-SCR). Furthermore, the intrinsic mechanism of Mo-doped Ce/GE catalysts for enhancing SCR activity was preliminarily investigated. It was found that the addition of Mo can increase the ratio of nCe3+/(nCe3++nCe4+), the oxygen content on the surface and the acid sites of the catalyst, thus enhancing SCR activity. Compared with 5Ce/GE and 5Mo/GE, 5Ce-5Mo/GE catalyst showed more outstanding catalytic activity. In addition, the catalyst exhibited the best activity and almost 99% conversion of NOx at 250℃, when the loading amount is 5%. 5Ce-5Mo/GE catalyst exhibited good sulfur resistance performance.
2018, 34(12): 2211-2218
doi: 10.11862/CJIC.2018.238
Abstract:
A novel iridium(Ⅲ) cyclometalated complex Ir(tfmpiq)2(tfmtpip) with 1-(4-(trifluoromethyl) phenyl) isoquinoline(tfmpiq) as main ligand and tetra-(4-trifluoromethylpheny) limidodiphosphinate (tfmtpip) as ancillary ligands have been synthesized. The complex Ir(tfmpiq)2(tfmtpip) is thermally stable up to 373℃ indicating good thermal stability. For the emission spectra in toluene, the maximum peak located at 613 nm with quantum efficiency of 3.7%. The HOMO and LUMO levels are calculated as -5.62 and -3.54 eV, respectively. The devices R1~R4 with the structure of ITO/TAPC(40 nm)/Ir(tfmpiq)2(tfmtpip)(x%):mCP (20 nm)/TmPyPB(40 nm)/LiF(1 nm)/Al(100 nm) were fabricated. The device R3 with a 4%(w/w) doped concentration exhibited a luminance of 10 542 cd·m-2 at a driving voltage of 12.8 V with a maximum power efficiency (ηp) of 5.73 lm·W-1 and a maximum current efficiency (ηc) of 7.13 cd·A-1.
A novel iridium(Ⅲ) cyclometalated complex Ir(tfmpiq)2(tfmtpip) with 1-(4-(trifluoromethyl) phenyl) isoquinoline(tfmpiq) as main ligand and tetra-(4-trifluoromethylpheny) limidodiphosphinate (tfmtpip) as ancillary ligands have been synthesized. The complex Ir(tfmpiq)2(tfmtpip) is thermally stable up to 373℃ indicating good thermal stability. For the emission spectra in toluene, the maximum peak located at 613 nm with quantum efficiency of 3.7%. The HOMO and LUMO levels are calculated as -5.62 and -3.54 eV, respectively. The devices R1~R4 with the structure of ITO/TAPC(40 nm)/Ir(tfmpiq)2(tfmtpip)(x%):mCP (20 nm)/TmPyPB(40 nm)/LiF(1 nm)/Al(100 nm) were fabricated. The device R3 with a 4%(w/w) doped concentration exhibited a luminance of 10 542 cd·m-2 at a driving voltage of 12.8 V with a maximum power efficiency (ηp) of 5.73 lm·W-1 and a maximum current efficiency (ηc) of 7.13 cd·A-1.
2018, 34(12): 2219-2226
doi: 10.11862/CJIC.2018.265
Abstract:
Using fumed silica (FS) as Si precursor, the structure NPs-Si@SiOx@C nanocomposite was prepared by magnesiothermic reduction reaction and coating the obtained NPs-Si with SiOx and C, which was used as the lithium battery negative and tested for electrochemical performance. The results show that the magnesiothermic reduction reaction process was carried out in two steps. Firstly, SiO2 reacted with Mg to form Mg2Si intermediate phase, and then Mg2Si continued to react with SiO2 to form Si. And a high Si yield of magnesiothermic reduction reaction of fumed silica reached 87.9% according to the rule. The NPs-Si@SiOx@C anode had a capacity platform of 1 300 mAh·g-1 at a current density of 2.0 A·g-1 in the electrochemical performance test. And the specific capacity is 964.2 mAh·g-1 after 1 000 cycles with a capacity retention rate of 75%.
Using fumed silica (FS) as Si precursor, the structure NPs-Si@SiOx@C nanocomposite was prepared by magnesiothermic reduction reaction and coating the obtained NPs-Si with SiOx and C, which was used as the lithium battery negative and tested for electrochemical performance. The results show that the magnesiothermic reduction reaction process was carried out in two steps. Firstly, SiO2 reacted with Mg to form Mg2Si intermediate phase, and then Mg2Si continued to react with SiO2 to form Si. And a high Si yield of magnesiothermic reduction reaction of fumed silica reached 87.9% according to the rule. The NPs-Si@SiOx@C anode had a capacity platform of 1 300 mAh·g-1 at a current density of 2.0 A·g-1 in the electrochemical performance test. And the specific capacity is 964.2 mAh·g-1 after 1 000 cycles with a capacity retention rate of 75%.
2018, 34(12): 2227-2237
doi: 10.11862/CJIC.2018.271
Abstract:
Three novel transition metal complexes[Co(MTZA)2(H2O)2]·3H2O (1), [Cu(MTZA)2(H2O)]·2H2O (2) and[Zn(MTZA)2(H2O)2]·3H2O (3) have been synthesized by using 2-methyl-4-thiazolecarboxylic acid (HMTZA, C5H5NO2S), structurally confirmed by single crystal X-ray diffraction method, and characterized by elemental analysis, IR analysis and TG. The single crystal X-ray diffraction reveals that complex 1 crystallizes in monoclinic system with space group P21/n. Central Co2+ is six-coordinated to constitute a slightly distorted octahedral structure. Complex 2 crystallizes in triclinic system with space group P1, and its coordination number is five, forming a slightly distorted pentahedral coordination geometry. Complex 3 crystallizes in monoclinic system with space group P21/n. Each Zn2+ is six-coordinated to constitute a distorted octahedral geometry. In addition, DNA-binding of the ligand and complexes were also studied by EtBr fluorescence probe. The interactions of complexes with DNA were stronger than the ligand.
Three novel transition metal complexes[Co(MTZA)2(H2O)2]·3H2O (1), [Cu(MTZA)2(H2O)]·2H2O (2) and[Zn(MTZA)2(H2O)2]·3H2O (3) have been synthesized by using 2-methyl-4-thiazolecarboxylic acid (HMTZA, C5H5NO2S), structurally confirmed by single crystal X-ray diffraction method, and characterized by elemental analysis, IR analysis and TG. The single crystal X-ray diffraction reveals that complex 1 crystallizes in monoclinic system with space group P21/n. Central Co2+ is six-coordinated to constitute a slightly distorted octahedral structure. Complex 2 crystallizes in triclinic system with space group P1, and its coordination number is five, forming a slightly distorted pentahedral coordination geometry. Complex 3 crystallizes in monoclinic system with space group P21/n. Each Zn2+ is six-coordinated to constitute a distorted octahedral geometry. In addition, DNA-binding of the ligand and complexes were also studied by EtBr fluorescence probe. The interactions of complexes with DNA were stronger than the ligand.
2018, 34(12): 2238-2244
doi: 10.11862/CJIC.2018.270
Abstract:
A new Cd(Ⅱ) coordination polymer {[Cd(BDC)(L)]·1.5H2O}n (1)[L=N, N'-bis (4-pyridin-3-yl)-5-hydroxyi-sophthalamide, H2BDC=1, 4-benzenedicarboxylic acid) has been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction analysis. Complex 1 crystalizes in monoclinic, space group C2/c:a=2.171 45(8), b=1.605 34(6), c=1.678 04(6) nm, Z=8, V=5.116 8(3>) nm3, Dc=1.65 6 g·cm-3, F(000)=2 568, μ=0.914 mm-1, the final R=0.026 5 and wR=0.067 6. The crystal structure analysis indicates that the Cd(Ⅱ) cation is six-coordinated by two pyridyl N atoms from two L ligands, four O atoms from two BDC anions. The BDC anions connects adjacent Cd(Ⅱ) ions to form 1D chain, which is linked by pairs of L to generate two-dimensional 63 connected layer with a 2-fold parallel-interpenetrated structure. The phase purity, thermal stability, fluorescent property of 1 and fluorescence sensing properties of 1 for Fe3+ and dichloromethane have been studied investigated.
A new Cd(Ⅱ) coordination polymer {[Cd(BDC)(L)]·1.5H2O}n (1)[L=N, N'-bis (4-pyridin-3-yl)-5-hydroxyi-sophthalamide, H2BDC=1, 4-benzenedicarboxylic acid) has been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction analysis. Complex 1 crystalizes in monoclinic, space group C2/c:a=2.171 45(8), b=1.605 34(6), c=1.678 04(6) nm, Z=8, V=5.116 8(3>) nm3, Dc=1.65 6 g·cm-3, F(000)=2 568, μ=0.914 mm-1, the final R=0.026 5 and wR=0.067 6. The crystal structure analysis indicates that the Cd(Ⅱ) cation is six-coordinated by two pyridyl N atoms from two L ligands, four O atoms from two BDC anions. The BDC anions connects adjacent Cd(Ⅱ) ions to form 1D chain, which is linked by pairs of L to generate two-dimensional 63 connected layer with a 2-fold parallel-interpenetrated structure. The phase purity, thermal stability, fluorescent property of 1 and fluorescence sensing properties of 1 for Fe3+ and dichloromethane have been studied investigated.
2018, 34(12): 2245-2253
doi: 10.11862/CJIC.2018.280
Abstract:
Three new coordination polymers, {[Zn(μ2-btre)(μ2-adc)]·H2O}n (1·H2O), [Zn2(μ2-btre)(μ2-1, 4-bdc)2(H2O)2]n (2) and[Zn(μ2-btre)(μ2-1, 2-bdc)]n (3) were synthesized at room temperature condition and characterized by IR spectra, elemental analyses, single-crystal and powder X-ray diffractions (btre=1, 2-bis(1, 2, 4-triazol-4-yl) ethane, adc=1, 3-adamantanedicarboxylate, 1, 4-bdc=1, 4-benzenedicarboxylate, 1, 2-bdc=1, 2-benzenedicarboxylate). Structural analyses reveal that complex 1 exhibits a 2D (4, 4) network, and the adjacent 2D (4, 4) networks are connected into 3D network by strong π-π interactions. The structure of 2 and 3 are 3D and 2D (4, 4) network, respectively. Thermal stabilities and the solid-state luminescence at room temperature of 1, 2 and 3 were investigated.
Three new coordination polymers, {[Zn(μ2-btre)(μ2-adc)]·H2O}n (1·H2O), [Zn2(μ2-btre)(μ2-1, 4-bdc)2(H2O)2]n (2) and[Zn(μ2-btre)(μ2-1, 2-bdc)]n (3) were synthesized at room temperature condition and characterized by IR spectra, elemental analyses, single-crystal and powder X-ray diffractions (btre=1, 2-bis(1, 2, 4-triazol-4-yl) ethane, adc=1, 3-adamantanedicarboxylate, 1, 4-bdc=1, 4-benzenedicarboxylate, 1, 2-bdc=1, 2-benzenedicarboxylate). Structural analyses reveal that complex 1 exhibits a 2D (4, 4) network, and the adjacent 2D (4, 4) networks are connected into 3D network by strong π-π interactions. The structure of 2 and 3 are 3D and 2D (4, 4) network, respectively. Thermal stabilities and the solid-state luminescence at room temperature of 1, 2 and 3 were investigated.
2018, 34(12): 2254-2260
doi: 10.11862/CJIC.2018.246
Abstract:
A three-dimensional (3D) porous Zn(Ⅱ)-based framework, {[Zn4(O-BTC)2(H2O)5]·2DMF·0.5H2O}n (1), which is constructed from a multifunctional tricarboxylate ligand, 2-hydroxyl-1, 3, 5-benzenetricarboxylic acid (HO-H3BTC) and Zn(Ⅱ) salts was prepared. Complex 1 has been characterized by X-ray single-crystal diffraction, PXRD, elemental analysis, infrared spectroscopy, thermogravimetric analysis, and solid-state UV-Vis absorption spectra. Complex 1 exhibits a three-dimensional (3D) framework structure based on the rod-shaped Zn-carboxylate/hydroxyl secondary building unit (SBU). Solid-state luminescence studies showed that 1 exhibits intense blue emission at room temperature. Interestingly, 1 could exhibit afterglow property only under low temperature (10 K) condition.
A three-dimensional (3D) porous Zn(Ⅱ)-based framework, {[Zn4(O-BTC)2(H2O)5]·2DMF·0.5H2O}n (1), which is constructed from a multifunctional tricarboxylate ligand, 2-hydroxyl-1, 3, 5-benzenetricarboxylic acid (HO-H3BTC) and Zn(Ⅱ) salts was prepared. Complex 1 has been characterized by X-ray single-crystal diffraction, PXRD, elemental analysis, infrared spectroscopy, thermogravimetric analysis, and solid-state UV-Vis absorption spectra. Complex 1 exhibits a three-dimensional (3D) framework structure based on the rod-shaped Zn-carboxylate/hydroxyl secondary building unit (SBU). Solid-state luminescence studies showed that 1 exhibits intense blue emission at room temperature. Interestingly, 1 could exhibit afterglow property only under low temperature (10 K) condition.
2018, 34(12): 2261-2270
doi: 10.11862/CJIC.2018.261
Abstract:
Two Cu(Ⅱ) and Ni(Ⅱ) complexes, [Cu(L1)2]·(1, 4-dioxane) (1) (HL1=8-(((4-(1-((benzyloxy) imino) ethyl) phenyl) imino) methyl)-7-hydroxy-4-methyl-2H-chromen-2-one) and[Ni(L2)2] (2) (HLL2=1-(4-(((2-hydroxynaphthalen-1-yl) methylene) amino) phenyl) ethanone O-benzyloxime), have been synthesized and characterized by elemental analyses, IR spectra, UV-Vis spectra, fluorescence spectra and X-ray single crystal diffraction method. X-ray crystallographic analysis shows that the Cu(Ⅱ) and Ni(Ⅱ) ions are all four-coordinated in a trans-N2O2 slightly distorted square-planar geometry by two hydroxy O and two imine N atoms from two N, O-bidentate Schiff base ligands. Moreover, complex 1 links some other molecules into an infinite 3D supramolecular structure by intermolecular hydrogen bonds and π…π stacking interactions, while complex 2 forms 1D infinite chain via intermolecular π…π stacking interactions. Furthermore, the fluorescence property of HL1, HLL2 and their metal complexes 1 and 2 are discussed.
Two Cu(Ⅱ) and Ni(Ⅱ) complexes, [Cu(L1)2]·(1, 4-dioxane) (1) (HL1=8-(((4-(1-((benzyloxy) imino) ethyl) phenyl) imino) methyl)-7-hydroxy-4-methyl-2H-chromen-2-one) and[Ni(L2)2] (2) (HLL2=1-(4-(((2-hydroxynaphthalen-1-yl) methylene) amino) phenyl) ethanone O-benzyloxime), have been synthesized and characterized by elemental analyses, IR spectra, UV-Vis spectra, fluorescence spectra and X-ray single crystal diffraction method. X-ray crystallographic analysis shows that the Cu(Ⅱ) and Ni(Ⅱ) ions are all four-coordinated in a trans-N2O2 slightly distorted square-planar geometry by two hydroxy O and two imine N atoms from two N, O-bidentate Schiff base ligands. Moreover, complex 1 links some other molecules into an infinite 3D supramolecular structure by intermolecular hydrogen bonds and π…π stacking interactions, while complex 2 forms 1D infinite chain via intermolecular π…π stacking interactions. Furthermore, the fluorescence property of HL1, HLL2 and their metal complexes 1 and 2 are discussed.
2018, 34(12): 2271-2279
doi: 10.11862/CJIC.2018.259
Abstract:
The rare earth-Mg-Ni (RE-Mg-Ni) based hydrogen storage alloy was treated in the same concentration of 6 mol·L-1 LiOH, NaOH, and KOH aqueous solutions. The effects of different alkaline solutions and the treating times on the morphologies and compositions of the alloy surfaces and the electrochemical characters of the alloy electrodes have been investigated. The alloy electrode treated in 6 mol·L-1 NaOH for 10 min shows the best electrochemical properties. LiOH solution could remove Mg element and diminish the oxygen species on the alloy surface effectively. The alloy surface layer formed in LiOH solution was more unfavorable for H adsorption and desorption but had good resistance for further corrosion. The alloy electrode treated with 6 mol·L-1 LiOH had the best cyclic durability. With the increase of the treating time, the reduction of the discharge capacity was the largest for the alloy electrode treated with 6 mol·L-1 NaOH solution because of the dissolution of a large amount of rare earth (RE) and Al elements, and the loose surface layer containing mainly rare earth hydroxides.
The rare earth-Mg-Ni (RE-Mg-Ni) based hydrogen storage alloy was treated in the same concentration of 6 mol·L-1 LiOH, NaOH, and KOH aqueous solutions. The effects of different alkaline solutions and the treating times on the morphologies and compositions of the alloy surfaces and the electrochemical characters of the alloy electrodes have been investigated. The alloy electrode treated in 6 mol·L-1 NaOH for 10 min shows the best electrochemical properties. LiOH solution could remove Mg element and diminish the oxygen species on the alloy surface effectively. The alloy surface layer formed in LiOH solution was more unfavorable for H adsorption and desorption but had good resistance for further corrosion. The alloy electrode treated with 6 mol·L-1 LiOH had the best cyclic durability. With the increase of the treating time, the reduction of the discharge capacity was the largest for the alloy electrode treated with 6 mol·L-1 NaOH solution because of the dissolution of a large amount of rare earth (RE) and Al elements, and the loose surface layer containing mainly rare earth hydroxides.
2018, 34(12): 2280-2290
doi: 10.11862/CJIC.2018.274
Abstract:
Three novel polyoxometalate (POM)-based Cu(Ⅱ) and Cu(Ⅰ) hybrid materials with multi-dentate mono-and bis-triazole derivatives, namely {[Cu(L1)2(Mo4O13)]·2H2O}n (1), {[Cu1.5(L2)(HL2)(H2O)(Mo4O13)]·2H2O}n (2), {[Cu2(L3)1.5(Mo4O13)]·H2O}n (3) (L1=4-pyridine-2-1, 2, 4-triazole, HL2=3-(4H-1, 2, 4-triazol-4-yl) benzoic acid, L3=trans-4, 4'-azo-1, 2, 4-triazole) have been designed and synthesized by hydrothermal method. The structures of 1~3 have been determined by single crystal X-ray diffraction, FT-IR infrared spectra and powder X-ray diffraction analyses. In 1, Mo4O132- anions and Cu(Ⅱ) centers are inter-linked by bidentate L1, which are arranged into 2D POMs-based Cu(Ⅱ) hybrid metal-organic framework. In 2, Mo4O132- anions and Cu(Ⅱ) centers are inter-linked via bridging aqua atoms (O18), bi-dentate HL2 and tri-dentate L2-, which are arranged into 3D POM-based Cu(Ⅱ) micro-porous metal-organic framework. In 3, L3 ligands bridge neighboring Cu(Ⅰ) centers and Mo4O132- anions, which ultimately forms unique two-fold interpenetrating 3D POM-based Cu(Ⅰ) hybrid coordination framework. Photocatalytic activities for decomposition of different organic dyes of rhodamine B (RhB), methylene blue (MB) and methyl orange (MO) have been investigated for 1~3, indicating that 1~3 are good candidates for photocatalytic degradation of the organic dyes.
Three novel polyoxometalate (POM)-based Cu(Ⅱ) and Cu(Ⅰ) hybrid materials with multi-dentate mono-and bis-triazole derivatives, namely {[Cu(L1)2(Mo4O13)]·2H2O}n (1), {[Cu1.5(L2)(HL2)(H2O)(Mo4O13)]·2H2O}n (2), {[Cu2(L3)1.5(Mo4O13)]·H2O}n (3) (L1=4-pyridine-2-1, 2, 4-triazole, HL2=3-(4H-1, 2, 4-triazol-4-yl) benzoic acid, L3=trans-4, 4'-azo-1, 2, 4-triazole) have been designed and synthesized by hydrothermal method. The structures of 1~3 have been determined by single crystal X-ray diffraction, FT-IR infrared spectra and powder X-ray diffraction analyses. In 1, Mo4O132- anions and Cu(Ⅱ) centers are inter-linked by bidentate L1, which are arranged into 2D POMs-based Cu(Ⅱ) hybrid metal-organic framework. In 2, Mo4O132- anions and Cu(Ⅱ) centers are inter-linked via bridging aqua atoms (O18), bi-dentate HL2 and tri-dentate L2-, which are arranged into 3D POM-based Cu(Ⅱ) micro-porous metal-organic framework. In 3, L3 ligands bridge neighboring Cu(Ⅰ) centers and Mo4O132- anions, which ultimately forms unique two-fold interpenetrating 3D POM-based Cu(Ⅰ) hybrid coordination framework. Photocatalytic activities for decomposition of different organic dyes of rhodamine B (RhB), methylene blue (MB) and methyl orange (MO) have been investigated for 1~3, indicating that 1~3 are good candidates for photocatalytic degradation of the organic dyes.
2018, 34(12): 2291-2297
doi: 10.11862/CJIC.2018.273
Abstract:
Five triorganotin 5-methyl-1H-tetrazolyl-1-acetates and 5-amino-1H-tetrazolyl-1-acetates have been synthesized by the reaction of (R3Sn)2O (R=Ph or n-Bu) or Cy3SnOH (Cy=cyclohexyl) with 5-methyl-1H-tetrazolyl-1-acetic acid or 5-amino-1H-tetrazolyl-1-acetic acid. All the complexes were characterized by elemental analysis, IR and multinuclear NMR (1H, 13C and 119Sn). Their structures have been confirmed by the X-ray single crystal diffraction analysis, suggesting that they form linkage coordination polymers through the intermolecular Sn…N interactions. The cytotoxic activity of the complexes for Hela and A549 cells was tested, showing that most of them displayed good cytotoxicities for these two cells in vitro.
Five triorganotin 5-methyl-1H-tetrazolyl-1-acetates and 5-amino-1H-tetrazolyl-1-acetates have been synthesized by the reaction of (R3Sn)2O (R=Ph or n-Bu) or Cy3SnOH (Cy=cyclohexyl) with 5-methyl-1H-tetrazolyl-1-acetic acid or 5-amino-1H-tetrazolyl-1-acetic acid. All the complexes were characterized by elemental analysis, IR and multinuclear NMR (1H, 13C and 119Sn). Their structures have been confirmed by the X-ray single crystal diffraction analysis, suggesting that they form linkage coordination polymers through the intermolecular Sn…N interactions. The cytotoxic activity of the complexes for Hela and A549 cells was tested, showing that most of them displayed good cytotoxicities for these two cells in vitro.
2018, 34(12): 2298-2306
doi: 10.11862/CJIC.2018.266
Abstract:
Three transition metal complexes based on H4ddb ligand, namely[Co2(ddb)(phen)2(H2O)6]·3H2O (1), [Co(ddb)0.5(bpy)0.5(H2O)3]n (2) and {[Ag(dpe)]·0.5(H2ddb)·H2O}n (3). (H4ddb=3, 3', 4, 4'-tetracarboxyazobenzene, bpy=4, 4'-pyridine, dpe=1, 2-di(4-pyridyl) ethylene) have been synthesized and structurally characterized by elemental anal-yses, IR spectroscopy, powder X-ray diffraction and single-crystal X-ray diffraction analyses. Complex 1 is binuclear structure, which is linked into 3D supramolecular network through rich hydrogen bonding interactions. Complex 2 shows 2D network constructed from Co2+ ion cross-linked by ddb4- ligands via μ4:η1, η1, η1, η1 coordina-tion mode. Complex 3 is linear chain structure based on Ag(Ⅰ) ion and dpe ligands. Interestingly, the guest molecule H2ddb2- extends a 3D supramolecular structure of 3 through intermolecular hydrogen bonding interactions. In addition, the thermal stabilities and luminescence properties of 1~3 were also studied.
Three transition metal complexes based on H4ddb ligand, namely[Co2(ddb)(phen)2(H2O)6]·3H2O (1), [Co(ddb)0.5(bpy)0.5(H2O)3]n (2) and {[Ag(dpe)]·0.5(H2ddb)·H2O}n (3). (H4ddb=3, 3', 4, 4'-tetracarboxyazobenzene, bpy=4, 4'-pyridine, dpe=1, 2-di(4-pyridyl) ethylene) have been synthesized and structurally characterized by elemental anal-yses, IR spectroscopy, powder X-ray diffraction and single-crystal X-ray diffraction analyses. Complex 1 is binuclear structure, which is linked into 3D supramolecular network through rich hydrogen bonding interactions. Complex 2 shows 2D network constructed from Co2+ ion cross-linked by ddb4- ligands via μ4:η1, η1, η1, η1 coordina-tion mode. Complex 3 is linear chain structure based on Ag(Ⅰ) ion and dpe ligands. Interestingly, the guest molecule H2ddb2- extends a 3D supramolecular structure of 3 through intermolecular hydrogen bonding interactions. In addition, the thermal stabilities and luminescence properties of 1~3 were also studied.
2018, 34(12): 2307-2315
doi: 10.11862/CJIC.2018.281
Abstract:
Two novel metal-organic frameworks {[Zn3(TCPB)2(4, 4'-BPY)]·DMF·3H2O}n (1) with trinuclear zinc cluster units and {[Co1.5(TCPB)(DMF)(H2O)]·DMF}n (2) with trinuclear cobalt cluster SBUs, have been prepared under solvothermal conditions based on flexible 1, 3, 5-tri(4-carboxyphenoxy) benzene ligand (H3TCPB) with the help of ancillary bridging N-donor pyridyl linker 4, 4'-bipyridine (4, 4'-BPY), and characterized by single crystal X-ray diffraction, IR spectra, elemental analyses, thermogravimetric analyses (TGA) and powder X-ray diffraction (PXRD). The single crystal X-ray diffraction analysis reveals that complex 1 crystallizes in triclinic space group P1 and exhibits three-dimensional (3D) (3, 8)-connected network with Schläfli symbol of {43}2·{46·618·84}·{6}, complex 2 also belongs to the triclinic system with space group of P1 and shows two-dimensional (2D) (3, 6)-connected net-like layered framework with Schläfli symbol of {43}4·{46·618·84}. In addition, the study of the solid state photoluminescent property of complex 1 indicates that it emits light blue fluorescence arising from TCPB3- and 4, 4'-BPY ligands at room temperature, while complex 2 is non-emissive under similar conditions.
Two novel metal-organic frameworks {[Zn3(TCPB)2(4, 4'-BPY)]·DMF·3H2O}n (1) with trinuclear zinc cluster units and {[Co1.5(TCPB)(DMF)(H2O)]·DMF}n (2) with trinuclear cobalt cluster SBUs, have been prepared under solvothermal conditions based on flexible 1, 3, 5-tri(4-carboxyphenoxy) benzene ligand (H3TCPB) with the help of ancillary bridging N-donor pyridyl linker 4, 4'-bipyridine (4, 4'-BPY), and characterized by single crystal X-ray diffraction, IR spectra, elemental analyses, thermogravimetric analyses (TGA) and powder X-ray diffraction (PXRD). The single crystal X-ray diffraction analysis reveals that complex 1 crystallizes in triclinic space group P1 and exhibits three-dimensional (3D) (3, 8)-connected network with Schläfli symbol of {43}2·{46·618·84}·{6}, complex 2 also belongs to the triclinic system with space group of P1 and shows two-dimensional (2D) (3, 6)-connected net-like layered framework with Schläfli symbol of {43}4·{46·618·84}. In addition, the study of the solid state photoluminescent property of complex 1 indicates that it emits light blue fluorescence arising from TCPB3- and 4, 4'-BPY ligands at room temperature, while complex 2 is non-emissive under similar conditions.
