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2018 Volume 34 Issue 9
2018, 34(9): 1591-1599
doi: 10.11862/CJIC.2018.198
Abstract:
Ta3N5@Ta2O5 nano-photocatalysts with shell-core heterojunction structure were successfully synthesized by a high-temperature ammonolysis of Ta2O5 nano-powders prepared by a hydrothermal method. Effects of nitridation temperature and nitridation time on surface composition, crystal plane structure, energy band structure, and carrier separation efficiency of the samples were investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), N2 adsorption-desorption test, UV-Vis diffused reflectance spectroscopy (DRS), and electrochemical measurements. Under the condition of ammonia flowing rate of 50 mL·min-1 and nitriding temperature of 750℃, the bandgap structure of Ta2O5 samples could be controlled effectively between 3.86~2.08 eV, through transforming the phases from Ta2O5 to TaON@Ta2O5, and to Ta3N5@Ta2O5. When the nitriding temperature was elevated from 750 to 900℃, the bandgap energy of Ta3N5@Ta2O5 was further narrowed to be about 2.04 eV by 3 h nitridation. When the nitridation time was prolonged to 12 h, Ta2O5 was completely transformed into Ta3N5, of which the bandgap energy was further narrowed to 2.02 eV, by nitriding at 850℃. After nitriding at 850℃ for 3 h, the crystal plane of Ta3N5 shell gradually changed to the (110), and the sample possessed the highest carrier separation efficiency, on which optical H2 evolution rate reaches 21.75 μmol·g-1·h-1 under visible light (λ>420 nm) irradiation.
Ta3N5@Ta2O5 nano-photocatalysts with shell-core heterojunction structure were successfully synthesized by a high-temperature ammonolysis of Ta2O5 nano-powders prepared by a hydrothermal method. Effects of nitridation temperature and nitridation time on surface composition, crystal plane structure, energy band structure, and carrier separation efficiency of the samples were investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), N2 adsorption-desorption test, UV-Vis diffused reflectance spectroscopy (DRS), and electrochemical measurements. Under the condition of ammonia flowing rate of 50 mL·min-1 and nitriding temperature of 750℃, the bandgap structure of Ta2O5 samples could be controlled effectively between 3.86~2.08 eV, through transforming the phases from Ta2O5 to TaON@Ta2O5, and to Ta3N5@Ta2O5. When the nitriding temperature was elevated from 750 to 900℃, the bandgap energy of Ta3N5@Ta2O5 was further narrowed to be about 2.04 eV by 3 h nitridation. When the nitridation time was prolonged to 12 h, Ta2O5 was completely transformed into Ta3N5, of which the bandgap energy was further narrowed to 2.02 eV, by nitriding at 850℃. After nitriding at 850℃ for 3 h, the crystal plane of Ta3N5 shell gradually changed to the (110), and the sample possessed the highest carrier separation efficiency, on which optical H2 evolution rate reaches 21.75 μmol·g-1·h-1 under visible light (λ>420 nm) irradiation.
2018, 34(9): 1610-1614
doi: 10.11862/CJIC.2018.189
Abstract:
Gold nanospheres in size of 5 nm were prepared by chloroauric acid (HAuCl4) as raw material, polyvi-nylpyrrolidone K30 (PVP) as a stabilizer and sodium borohydride (NaBH4) as reducing agent. Seed growth method was used to prepare gold nanorods in aspect ratio R ranged from 2.5 to 4, by cationic surfactant cetyltrimethyla-mmonium bromide (CTAB) as template and sodium oleate (NaOL) as stabilizer. Temperature of gold nanospheres solution in concentration of 0.4 mg·mL-1 rises 10.2℃ and the solution catalyzes the release of NO from nitrosothiols in the blood under irradiation of 2 W·cm-2 NIR laser (808 nm) for 10 min, with the maximum release is up to 1.42 nmol·L-1. Under the same photothermal and catalytic conditions, temperature of gold nanorods (R=3.01) solution in concentration of 0.4 mg·mL-1 rises 41.3℃ and the solution catalyzes the release of NO from nitrosothiols in the blood with the maximum release is up to 1.89 nmol·L-1. Photothermal effect and the catalytic performance of both nanospheres and nanorods increase with the increase of the concentration, and the catalytic effect and photothermal conversion performance of gold nanorods are superior to those of gold nanospheres.
Gold nanospheres in size of 5 nm were prepared by chloroauric acid (HAuCl4) as raw material, polyvi-nylpyrrolidone K30 (PVP) as a stabilizer and sodium borohydride (NaBH4) as reducing agent. Seed growth method was used to prepare gold nanorods in aspect ratio R ranged from 2.5 to 4, by cationic surfactant cetyltrimethyla-mmonium bromide (CTAB) as template and sodium oleate (NaOL) as stabilizer. Temperature of gold nanospheres solution in concentration of 0.4 mg·mL-1 rises 10.2℃ and the solution catalyzes the release of NO from nitrosothiols in the blood under irradiation of 2 W·cm-2 NIR laser (808 nm) for 10 min, with the maximum release is up to 1.42 nmol·L-1. Under the same photothermal and catalytic conditions, temperature of gold nanorods (R=3.01) solution in concentration of 0.4 mg·mL-1 rises 41.3℃ and the solution catalyzes the release of NO from nitrosothiols in the blood with the maximum release is up to 1.89 nmol·L-1. Photothermal effect and the catalytic performance of both nanospheres and nanorods increase with the increase of the concentration, and the catalytic effect and photothermal conversion performance of gold nanorods are superior to those of gold nanospheres.
2018, 34(9): 1615-1624
doi: 10.11862/CJIC.2018.201
Abstract:
The Inner Mongolia lignite was used to prepare hyper-coal(HPC) at different temperatures by N-methylpyrolidone during KOH extraction. To explore the effect of extraction temperatures on activated carbons(ACs), the activation was operated at the same condition, mKOH:mcoal=3:1 and activated at 650℃ for 2 hours. The results show that the extraction temperature of HPC has great effect on the electrochemical properties of HPC-based ACs. Comparing the ash contents, surface oxo-functional groups, the specific surface areas, pore structures and electrochemical performances of the corresponding ACs with the lignite, the HPC prepared at 330℃ is in possession of the most suitable reactivity and its specific surface area of corresponding ACs could reach 1 252 m2·g-1 with appropriate amount of surface oxo-function groups. Besides, the specific capacitor could still retain almost 90% in 3 mol·L-1 KOH electrolyte at 50 mA·g-1 reaching 322 F·g-1, and a capacity retention as high as near 90% was achieved at 2 000 mA·g-1.
The Inner Mongolia lignite was used to prepare hyper-coal(HPC) at different temperatures by N-methylpyrolidone during KOH extraction. To explore the effect of extraction temperatures on activated carbons(ACs), the activation was operated at the same condition, mKOH:mcoal=3:1 and activated at 650℃ for 2 hours. The results show that the extraction temperature of HPC has great effect on the electrochemical properties of HPC-based ACs. Comparing the ash contents, surface oxo-functional groups, the specific surface areas, pore structures and electrochemical performances of the corresponding ACs with the lignite, the HPC prepared at 330℃ is in possession of the most suitable reactivity and its specific surface area of corresponding ACs could reach 1 252 m2·g-1 with appropriate amount of surface oxo-function groups. Besides, the specific capacitor could still retain almost 90% in 3 mol·L-1 KOH electrolyte at 50 mA·g-1 reaching 322 F·g-1, and a capacity retention as high as near 90% was achieved at 2 000 mA·g-1.
2018, 34(9): 1625-1631
doi: 10.11862/CJIC.2018.203
Abstract:
The ZnO powders doped by different ratios of Co2+ ions were synthesized via solid-state reaction. The effects of Co2+ doping ratio on microstructure and morphology, and thus on thermochromic and variable emissivity properties of ZnO were studied in detail. The results show that Co2+ ions would substitute for part of the Zn2+ ions in ZnO, and it does not change wurtzite(hexagonal) zincite crystal structure of the ZnO. While when doping ratio reaches 7.5% and 10%, impurity phase Co3O4 would form in the samples. The crystal quality and forbidden bandwidth of ZnO decreases gradually while morphology and grain size of ZnO barely change with doping ratio of Co2+ ions increasing. The Co2+ doped ZnO powders are green at room temperature, which gets deep initially and then becomes shallow with Co2+ content increasing. When the testing temperature improves from room temperature to 700℃, all the samples could turn into tawny color and the emissivity increases simultaneously. And the color change is more obvious and the change value in emissivity increases with enhancement of Co2+ doping ratio.
The ZnO powders doped by different ratios of Co2+ ions were synthesized via solid-state reaction. The effects of Co2+ doping ratio on microstructure and morphology, and thus on thermochromic and variable emissivity properties of ZnO were studied in detail. The results show that Co2+ ions would substitute for part of the Zn2+ ions in ZnO, and it does not change wurtzite(hexagonal) zincite crystal structure of the ZnO. While when doping ratio reaches 7.5% and 10%, impurity phase Co3O4 would form in the samples. The crystal quality and forbidden bandwidth of ZnO decreases gradually while morphology and grain size of ZnO barely change with doping ratio of Co2+ ions increasing. The Co2+ doped ZnO powders are green at room temperature, which gets deep initially and then becomes shallow with Co2+ content increasing. When the testing temperature improves from room temperature to 700℃, all the samples could turn into tawny color and the emissivity increases simultaneously. And the color change is more obvious and the change value in emissivity increases with enhancement of Co2+ doping ratio.
2018, 34(9): 1632-1640
doi: 10.11862/CJIC.2018.208
Abstract:
Novel complexes of Copper(Ⅱ) with Schiff-base intercalated zinc-chromium layered double hydroxides (ZnCr-SBCu-LDHs) were successfully prepared via coprecipitation. Zn-Cr-Cu composite metal oxides (ZnCr-SBCu-LDO) as an original photocatalytic material was derived from ZnCr-SBCu-LDHs after calcination at 500℃. The structure and properties of the photocatalytic materials were thoroughly characterized by powder X-ray diffraction (XRD), ultraviolet visible diffuse reflectance spectroscopy (UV-Vis DRS), scanning electron microscopy (SEM) and inductively coupled plasma-atomic emission spectrometry (ICP-AES). The activities of the photocata-lytic materials were investigated by photodegradation of cationic dye rhodamin B (RhB) which was hard to adsorb by LDHs. The effects of initial photocatalyst amount, initial pH, temperature of RhB solution and initial concentration of H2O2 on the photocatalytic efficiency were discussed. The results show that ZnCr-SBCu-LDO display higher photocatalytic activity for RhB degradation. The degradation efficiency of RhB solution (5 mg·L-1) with ZnCr-SBCu-LDO (1 g·L-1) reached 98.68% after 4 h irradiation, when the temperature was 25℃, the initial pH value was 7.40 and the initial concentration of H2O2 was 10 mmol·L-1. In addition, the regeneration of the catalyst was studied and the mechanism of photocatalysis was preliminarily discussed.
Novel complexes of Copper(Ⅱ) with Schiff-base intercalated zinc-chromium layered double hydroxides (ZnCr-SBCu-LDHs) were successfully prepared via coprecipitation. Zn-Cr-Cu composite metal oxides (ZnCr-SBCu-LDO) as an original photocatalytic material was derived from ZnCr-SBCu-LDHs after calcination at 500℃. The structure and properties of the photocatalytic materials were thoroughly characterized by powder X-ray diffraction (XRD), ultraviolet visible diffuse reflectance spectroscopy (UV-Vis DRS), scanning electron microscopy (SEM) and inductively coupled plasma-atomic emission spectrometry (ICP-AES). The activities of the photocata-lytic materials were investigated by photodegradation of cationic dye rhodamin B (RhB) which was hard to adsorb by LDHs. The effects of initial photocatalyst amount, initial pH, temperature of RhB solution and initial concentration of H2O2 on the photocatalytic efficiency were discussed. The results show that ZnCr-SBCu-LDO display higher photocatalytic activity for RhB degradation. The degradation efficiency of RhB solution (5 mg·L-1) with ZnCr-SBCu-LDO (1 g·L-1) reached 98.68% after 4 h irradiation, when the temperature was 25℃, the initial pH value was 7.40 and the initial concentration of H2O2 was 10 mmol·L-1. In addition, the regeneration of the catalyst was studied and the mechanism of photocatalysis was preliminarily discussed.
2018, 34(9): 1641-1648
doi: 10.11862/CJIC.2018.204
Abstract:
A simple hydrothermal preparation method was developed to prepare sodium fluoride phosphate vanadium oxide (Na3V2(PO4)2O2F, abbreviated as NVPOF) material, regulating the morphology and size of the NVPOF by adjusting the key parameters including the pH value and hydrothermal temperature. The optimized NVPOF material exhibits the highest particle-size uniformity and thereby the best electrochemical properties. The pH value is 7.00±0.05 and the hydrothermal temperature is 170℃, which is the optimized parameters for the NVPOF preparation. The NVPOF material prepared at this condition delivers the specific capacity of 123.2 mAh·g-1 at 0.1C (1C=130 mAh·g-1) and 85.9 mAh·g-1 at a high rate of 20C. The capacity retention is 96.2% after 200 cycles at 1C. All of the results indicate its high capacity, excellent rate and long cycle stability for Na storage. This is mainly attributed to the nanometer size and high uniformity of the NVPOF particles, which can provide the short Na+ transport path and hence shorten the time. Combining with the high stability of crystal structure, the optimized NVPOF material exhibits excellent performance as practical cathode for SIBs.
A simple hydrothermal preparation method was developed to prepare sodium fluoride phosphate vanadium oxide (Na3V2(PO4)2O2F, abbreviated as NVPOF) material, regulating the morphology and size of the NVPOF by adjusting the key parameters including the pH value and hydrothermal temperature. The optimized NVPOF material exhibits the highest particle-size uniformity and thereby the best electrochemical properties. The pH value is 7.00±0.05 and the hydrothermal temperature is 170℃, which is the optimized parameters for the NVPOF preparation. The NVPOF material prepared at this condition delivers the specific capacity of 123.2 mAh·g-1 at 0.1C (1C=130 mAh·g-1) and 85.9 mAh·g-1 at a high rate of 20C. The capacity retention is 96.2% after 200 cycles at 1C. All of the results indicate its high capacity, excellent rate and long cycle stability for Na storage. This is mainly attributed to the nanometer size and high uniformity of the NVPOF particles, which can provide the short Na+ transport path and hence shorten the time. Combining with the high stability of crystal structure, the optimized NVPOF material exhibits excellent performance as practical cathode for SIBs.
2018, 34(9): 1649-1654
doi: 10.11862/CJIC.2018.211
Abstract:
CPL-1501 and CPL-1504, two platinum(Ⅳ) prodrugs with dihydrogen phosphate as one axial ligand, were synthesized from cisplatin and oxaliplatin, respectively, as the starting material, and characterized by elemental analysis, IR as well as 13C and 31P NMR. Their reduction potential was measured via the cyclic voltammetry. The standard MTT was used to evaluate anticancer activity of the two prodrugs against several human cancer cell lines. CPL-1501 has a good water-solubility (10 mg·mL-1) and water-stability. With the favorable Ep values, it can be readily reduced to an active prototype cisplatin in the oxygen-deprived micro-environment of cancer cells. The biological tests reveal that CPL-1501 is able to inhibit the growth of cancer cells and its anticancer activity is comparable to that of cisplatin but much greater than that of carboplatin, whereas CPL-1504 does not show significant activity, probably due to its lower Ep values.
CPL-1501 and CPL-1504, two platinum(Ⅳ) prodrugs with dihydrogen phosphate as one axial ligand, were synthesized from cisplatin and oxaliplatin, respectively, as the starting material, and characterized by elemental analysis, IR as well as 13C and 31P NMR. Their reduction potential was measured via the cyclic voltammetry. The standard MTT was used to evaluate anticancer activity of the two prodrugs against several human cancer cell lines. CPL-1501 has a good water-solubility (10 mg·mL-1) and water-stability. With the favorable Ep values, it can be readily reduced to an active prototype cisplatin in the oxygen-deprived micro-environment of cancer cells. The biological tests reveal that CPL-1501 is able to inhibit the growth of cancer cells and its anticancer activity is comparable to that of cisplatin but much greater than that of carboplatin, whereas CPL-1504 does not show significant activity, probably due to its lower Ep values.
2018, 34(9): 1655-1662
doi: 10.11862/CJIC.2018.210
Abstract:
Vertically aligned ZnO nanorod arrays have been extensively applied to the fabrication of various optoelectronic devices owing to their versatile properties. However, to control and investigate the morphology of nanorods is directly related to device performances. A seeded substrate is favourable for the hydrothermal synthesis of nanorods by lowering the nucleation barrier and restricting the migration of the disordered nucleation. Therefore, varying the seed layer properties is a feasible and effective way to control the nanorod growth. In this paper, three different methods sol-gel, spray pyrolysis and pulse laser deposition (PLD) were employed to the ZnO seed layer preparation. For each preparation method, the crystal structure, morphologies, surface roughness and properties of ZnO seed layers were characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM), respectively. ZnO nanorod arrays with different structures and morphological properties were synthesised on the prepared seed layers by hydrothermal treatment. The ZnO nanorods exhibit strong substrate-dependent properties. Combined with the characteristics of ZnO seed layers, the difference of growth mechanisms for each method is proposed by analyzing the nanorod properties on the seed layers.
Vertically aligned ZnO nanorod arrays have been extensively applied to the fabrication of various optoelectronic devices owing to their versatile properties. However, to control and investigate the morphology of nanorods is directly related to device performances. A seeded substrate is favourable for the hydrothermal synthesis of nanorods by lowering the nucleation barrier and restricting the migration of the disordered nucleation. Therefore, varying the seed layer properties is a feasible and effective way to control the nanorod growth. In this paper, three different methods sol-gel, spray pyrolysis and pulse laser deposition (PLD) were employed to the ZnO seed layer preparation. For each preparation method, the crystal structure, morphologies, surface roughness and properties of ZnO seed layers were characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM), respectively. ZnO nanorod arrays with different structures and morphological properties were synthesised on the prepared seed layers by hydrothermal treatment. The ZnO nanorods exhibit strong substrate-dependent properties. Combined with the characteristics of ZnO seed layers, the difference of growth mechanisms for each method is proposed by analyzing the nanorod properties on the seed layers.
2018, 34(9): 1663-1669
doi: 10.11862/CJIC.2018.176
Abstract:
Metal-organic framework@mesoporous composites were obtained via introducing H2BDC into the composite materials Al2O3@SBA-15, which was synthesized through vapor-induced internal hydrolysis (VIH) method. The structure of MIL-53@SBA-15 composites was confirmed by combination of different characterization techniques, such as powder X-ray diffraction (PXRD), N2 adsorption-desorption isotherm test, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Through dye adsorption experiment, MIL-53@SBA-15 compound demonstrated the best adsorptivity performance of butyl rhodamine B dye compared to SBA-15, MIL-53, and physical mixed samples.
Metal-organic framework@mesoporous composites were obtained via introducing H2BDC into the composite materials Al2O3@SBA-15, which was synthesized through vapor-induced internal hydrolysis (VIH) method. The structure of MIL-53@SBA-15 composites was confirmed by combination of different characterization techniques, such as powder X-ray diffraction (PXRD), N2 adsorption-desorption isotherm test, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Through dye adsorption experiment, MIL-53@SBA-15 compound demonstrated the best adsorptivity performance of butyl rhodamine B dye compared to SBA-15, MIL-53, and physical mixed samples.
2018, 34(9): 1670-1676
doi: 10.11862/CJIC.2018.221
Abstract:
A highly ordered mesoporous α-Fe2O3 nanoparticle has been synthesized by using SBA-15 as hard template and iron nitrate as iron precursor. α-Fe2O3 was employed as an anode material for both lithium and sodium ion batteries. The ordered mesoporous structure of α-Fe2O3 alleviated the volume change during the discharge/charge process and improved the wettability of the electrolyte. α-Fe2O3 anode delivered high initial discharge capacity of 983.9 and 687.7 mAh·g-1 with good cycle performance for 100 and 50 cycles in lithium and sodium ion batteries, respectively.
A highly ordered mesoporous α-Fe2O3 nanoparticle has been synthesized by using SBA-15 as hard template and iron nitrate as iron precursor. α-Fe2O3 was employed as an anode material for both lithium and sodium ion batteries. The ordered mesoporous structure of α-Fe2O3 alleviated the volume change during the discharge/charge process and improved the wettability of the electrolyte. α-Fe2O3 anode delivered high initial discharge capacity of 983.9 and 687.7 mAh·g-1 with good cycle performance for 100 and 50 cycles in lithium and sodium ion batteries, respectively.
2018, 34(9): 1600-1609
doi: 10.11862/CJIC.2018.194
Abstract:
A series of Ni(Ⅱ)-Ln(Ⅲ) heterometallic isomers[Ln2Ni(tia)4(H2O)4]n (Ln=La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8) and Dy (9)), and {[Yb2Ni(tia)4(H2O)2]·2H2O}n (10) (tia=5-(1H-1, 2, 3-triazol-1-yl)isophthalate) have been constructed from the tritopic 1, 2, 3-trazol-based aromatic heterocyclic carboxylic ligand H3ctia (H3ctia=5-(4-carboxyl-1H-1, 2, 3-triazol-1-yl) isophthalic acid). The results of single crystal X-ray diffraction show that all of these complexes possess 3D microporous frameworks. Complexes 1~9 are isomorphic. The chemical composition of complex 10 is the same as those of 1~9, but the crystallographic structure is totally different from 1~9. In the visible region, complexes 5, 6, 8 and 9 exhibit the characteristic luminescent emissions of Sm(Ⅲ), Eu(Ⅲ), Tb(Ⅲ) and Dy(Ⅲ) with the long luminescent lifetime (234 μs for 6, 598 μs for 8 and 2.96 μs for 9). Complexes 4, 9 and 10 show characteristic emissions of Nd(Ⅲ), Dy(Ⅲ), and Yb(Ⅲ) in the near infrared region with the average lifetime of 4.25, 3.42 and 5.66 μs, respectively.
A series of Ni(Ⅱ)-Ln(Ⅲ) heterometallic isomers[Ln2Ni(tia)4(H2O)4]n (Ln=La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8) and Dy (9)), and {[Yb2Ni(tia)4(H2O)2]·2H2O}n (10) (tia=5-(1H-1, 2, 3-triazol-1-yl)isophthalate) have been constructed from the tritopic 1, 2, 3-trazol-based aromatic heterocyclic carboxylic ligand H3ctia (H3ctia=5-(4-carboxyl-1H-1, 2, 3-triazol-1-yl) isophthalic acid). The results of single crystal X-ray diffraction show that all of these complexes possess 3D microporous frameworks. Complexes 1~9 are isomorphic. The chemical composition of complex 10 is the same as those of 1~9, but the crystallographic structure is totally different from 1~9. In the visible region, complexes 5, 6, 8 and 9 exhibit the characteristic luminescent emissions of Sm(Ⅲ), Eu(Ⅲ), Tb(Ⅲ) and Dy(Ⅲ) with the long luminescent lifetime (234 μs for 6, 598 μs for 8 and 2.96 μs for 9). Complexes 4, 9 and 10 show characteristic emissions of Nd(Ⅲ), Dy(Ⅲ), and Yb(Ⅲ) in the near infrared region with the average lifetime of 4.25, 3.42 and 5.66 μs, respectively.
2018, 34(9): 1677-1687
doi: 10.11862/CJIC.2018.206
Abstract:
A novel catalyst was synthesized using CNx nanotube (CNxNT) converted from polypyrrole nanotube as support and CeOx as co-catalyst. The as-prepared Pt-CeOx/CNxNT catalyst showed superior ORR activity compared to Pt/CNxNT and commercial Pt/C catalyst, which is attributed to the existence of CeOx, pyridine-like nitrogenin support and the unique hollow tube nanostructure of CNxNT support. Moreover, the presence of CeOx can significantly enhance the durability for both Pt nanoparticles and support.
A novel catalyst was synthesized using CNx nanotube (CNxNT) converted from polypyrrole nanotube as support and CeOx as co-catalyst. The as-prepared Pt-CeOx/CNxNT catalyst showed superior ORR activity compared to Pt/CNxNT and commercial Pt/C catalyst, which is attributed to the existence of CeOx, pyridine-like nitrogenin support and the unique hollow tube nanostructure of CNxNT support. Moreover, the presence of CeOx can significantly enhance the durability for both Pt nanoparticles and support.
2018, 34(9): 1688-1700
doi: 10.11862/CJIC.2018.220
Abstract:
Mono-shelled hollow sphere CaCO3 microspheres were prepared in the presence of L-methionine (L-Met) via a CO2 bubbling method; after that, the effects of L-Met adding amount, CO2 flow rate, and temperature on morphology, size, and phase composition of CaCO3 have been systemically explored. As a potential guest molecule carrier, the as-synthesized hollow sphere CaCO3 microspheres could load with rhodamine B (RhB) to prepare a novel luminescent composite material (RhB@hollow-CaCO3). This luminescent composite material not only presented good biocompatibility to the A-549 lung cancer cells (A-549 LCCs) and HO8910 ovarian cancer cells (HO8910 OCCs), but also had the ability of luminescence in above cells.
Mono-shelled hollow sphere CaCO3 microspheres were prepared in the presence of L-methionine (L-Met) via a CO2 bubbling method; after that, the effects of L-Met adding amount, CO2 flow rate, and temperature on morphology, size, and phase composition of CaCO3 have been systemically explored. As a potential guest molecule carrier, the as-synthesized hollow sphere CaCO3 microspheres could load with rhodamine B (RhB) to prepare a novel luminescent composite material (RhB@hollow-CaCO3). This luminescent composite material not only presented good biocompatibility to the A-549 lung cancer cells (A-549 LCCs) and HO8910 ovarian cancer cells (HO8910 OCCs), but also had the ability of luminescence in above cells.
2018, 34(9): 1701-1709
doi: 10.11862/CJIC.2018.205
Abstract:
Small-sized amorphous TiO2 nanoparticles were prepared and deposited on mesoporous SiO2 support via sol-gel method at room temperature. This structure greatly increases the surface areas of the amorphous TiO2 particles, which facilitates the enhancement of photocatalytic activity and preserved the optical performance of the films in the same time. The resultant SiO2&amorphous-TiO2 films afford glasses a maximum transmittance of 99.97% and show a much higher photocatalytic activity than the monolayer amorphous TiO2 film. Surprisingly, the SiO2&amorphous-TiO2 even shows a higher photocatalytic activity than the counterparts with anatase phase. This higher photocatalytic activity is attributed to abundant surface hydroxyl groups and relative loose structure of the amorphous TiO2 nanoparticles, which can help enhance photocatalytic activity through reducing recombination of electron-hole pairs and increase the migration rates of the photoexcited electrons and holes, respectively. And these characteristics may be preferable to crystal structure for enhancing photocatalytic activity. Meanwhile, the coating process is very simple, low cost and conducted at room temperature, which is feasible for polymer substrates.
Small-sized amorphous TiO2 nanoparticles were prepared and deposited on mesoporous SiO2 support via sol-gel method at room temperature. This structure greatly increases the surface areas of the amorphous TiO2 particles, which facilitates the enhancement of photocatalytic activity and preserved the optical performance of the films in the same time. The resultant SiO2&amorphous-TiO2 films afford glasses a maximum transmittance of 99.97% and show a much higher photocatalytic activity than the monolayer amorphous TiO2 film. Surprisingly, the SiO2&amorphous-TiO2 even shows a higher photocatalytic activity than the counterparts with anatase phase. This higher photocatalytic activity is attributed to abundant surface hydroxyl groups and relative loose structure of the amorphous TiO2 nanoparticles, which can help enhance photocatalytic activity through reducing recombination of electron-hole pairs and increase the migration rates of the photoexcited electrons and holes, respectively. And these characteristics may be preferable to crystal structure for enhancing photocatalytic activity. Meanwhile, the coating process is very simple, low cost and conducted at room temperature, which is feasible for polymer substrates.
2018, 34(9): 1710-1718
doi: 10.11862/CJIC.2018.200
Abstract:
The grain boundaries defect is solved by titanium ion (Ti4+) doping. Ti4+ has small radius which is proved to form at the grain boundary of polycrystalline perovskite. By control doping of titanium ion, grain size become more uniform, which leads to more continuous perovskite thin film. Studies suggest that the defects in grain boundary of polycrystalline perovskite are passivated by doping Ti4+, which results in the trap states concentration greatly decrease. And experimental test clearly exhibits more excellent performance of short-circuit current density (JSC=22.3 mA·cm-2), open-circuit voltage (VOC=1.10 V), fill factor (FF=72.4%) and photovoltaic conversion efficiency (PCE=17.4%) with low amount Ti4+ doping compared with pure planar heterojunction perovskite solar cells (AM1.5).
The grain boundaries defect is solved by titanium ion (Ti4+) doping. Ti4+ has small radius which is proved to form at the grain boundary of polycrystalline perovskite. By control doping of titanium ion, grain size become more uniform, which leads to more continuous perovskite thin film. Studies suggest that the defects in grain boundary of polycrystalline perovskite are passivated by doping Ti4+, which results in the trap states concentration greatly decrease. And experimental test clearly exhibits more excellent performance of short-circuit current density (JSC=22.3 mA·cm-2), open-circuit voltage (VOC=1.10 V), fill factor (FF=72.4%) and photovoltaic conversion efficiency (PCE=17.4%) with low amount Ti4+ doping compared with pure planar heterojunction perovskite solar cells (AM1.5).
2018, 34(9): 1719-1724
doi: 10.11862/CJIC.2018.188
Abstract:
Two new Cu(Ⅰ)Fe(Ⅱ) heterobimetallic complexes, [Cu(mbpy)(dppf)]ClO4·CH2Cl2 (1) and[Cu(mmbpy)(dppf)]ClO4 (2), were synthesized by using[Cu(CH3CN)4]ClO4, 6-methoxycarbonyl-2, 2'-bipyridine (mbpy), 6-metho-xycarbonyl-4, 4'-dimethyl-2, 2'-bipyridine (mmbpy), and 1, 1'-bis(diphenylphosphino)ferrocene (dppf) as the starting materials. As revealed by single-crystal X-ray diffraction analysis, complexes 1 and 2 are all Cu(Ⅰ)Fe(Ⅱ) heterobimetallic species and exhibit tetra-coordinated and distorted tetrahedral configuration. Complexes 1 and 2 all show a weak low-energy broad absorption in the wavelength range of 330～520 nm, which is mainly assigned to metal-to-ligand charge-transfer (MLCT) transition. No emission is detected in solution and solid states at room temperature for 1 and 2, due to the introduction of 1, 1'-bis(diphenylphosphino)ferrocene.
Two new Cu(Ⅰ)Fe(Ⅱ) heterobimetallic complexes, [Cu(mbpy)(dppf)]ClO4·CH2Cl2 (1) and[Cu(mmbpy)(dppf)]ClO4 (2), were synthesized by using[Cu(CH3CN)4]ClO4, 6-methoxycarbonyl-2, 2'-bipyridine (mbpy), 6-metho-xycarbonyl-4, 4'-dimethyl-2, 2'-bipyridine (mmbpy), and 1, 1'-bis(diphenylphosphino)ferrocene (dppf) as the starting materials. As revealed by single-crystal X-ray diffraction analysis, complexes 1 and 2 are all Cu(Ⅰ)Fe(Ⅱ) heterobimetallic species and exhibit tetra-coordinated and distorted tetrahedral configuration. Complexes 1 and 2 all show a weak low-energy broad absorption in the wavelength range of 330～520 nm, which is mainly assigned to metal-to-ligand charge-transfer (MLCT) transition. No emission is detected in solution and solid states at room temperature for 1 and 2, due to the introduction of 1, 1'-bis(diphenylphosphino)ferrocene.
2018, 34(9): 1725-1732
doi: 10.11862/CJIC.2018.218
Abstract:
Two binuclear copper(Ⅱ) complexes of the reduced Schiff base, namely, HL=2-(((2-(2-benzimidazyl) ethyl)aimino)methyl)phenol (HL) have been synthesized and characterized by C, H and N microanalyses, spectroscopic (FT-IR, UV-Vis) as well as electrochemical techniques and single-crystal X-ray diffraction. The crystal structures of[CuL(CH3OH)]2(BF4)2 (1) and[CuL(NO3)2]2 (2) show that the Cu(Ⅱ) atoms are bridged by two phenolato oxygen atoms in the dimers. The geometries around Cu(Ⅱ) atoms are distorted square pyramid with the Addison parameters (τ) of 0.31 and 0.35 for 1 and 2, respectively. Furthermore, the complex units in 1 and 2 are linked into 1D and 3D supramolecular networks by H-bonding in the solid state, respectively. The electrochemical studies of 1 and 2 show two quasi-reversible one electron reduction processes.
Two binuclear copper(Ⅱ) complexes of the reduced Schiff base, namely, HL=2-(((2-(2-benzimidazyl) ethyl)aimino)methyl)phenol (HL) have been synthesized and characterized by C, H and N microanalyses, spectroscopic (FT-IR, UV-Vis) as well as electrochemical techniques and single-crystal X-ray diffraction. The crystal structures of[CuL(CH3OH)]2(BF4)2 (1) and[CuL(NO3)2]2 (2) show that the Cu(Ⅱ) atoms are bridged by two phenolato oxygen atoms in the dimers. The geometries around Cu(Ⅱ) atoms are distorted square pyramid with the Addison parameters (τ) of 0.31 and 0.35 for 1 and 2, respectively. Furthermore, the complex units in 1 and 2 are linked into 1D and 3D supramolecular networks by H-bonding in the solid state, respectively. The electrochemical studies of 1 and 2 show two quasi-reversible one electron reduction processes.
2018, 34(9): 1733-1738
doi: 10.11862/CJIC.2018.193
Abstract:
Two novel silver(Ⅰ) complexes, [Ag2(dppp)2(phen)2](CF3SO3)2 (1) and[Ag2(dppm)2(dpq)2](CF3SO3)2·3CH3OH (2) (dppp=bis(diphenylphosphino)propane, dppm=bis(diphenylphosphino)methane, phen=1, 10-phenan-throline, dpq=pyrazino[2, 3-f][1, 10]phenanthroline), have been synthesized in mixed solvent CH3OH and CH2Cl2 and characterized by IR, single-crystal X-ray diffraction, 1H NMR spectroscopy, fluorescence spectra and THz time domain spectroscopy (THz-TDS). Complex 1 is of a binuclear complex, which was generated by the reaction of AgCF3SO3 and dppp with phen in 1:1:1 molar ratio. In complex 1, the central Ag(Ⅰ) ion forms a ring by the bridging bisphosphine ligand (dppp) and chelating N-donor ligand (phen). Like 1, 2 is of a binuclear complex, which was obtained by the reaction of AgCF3SO3 and dppm with dpq in 1:1:1 molar ratio. The luminescent spectra show that all these emissions are assigned to ligand centered π-π* transition.
Two novel silver(Ⅰ) complexes, [Ag2(dppp)2(phen)2](CF3SO3)2 (1) and[Ag2(dppm)2(dpq)2](CF3SO3)2·3CH3OH (2) (dppp=bis(diphenylphosphino)propane, dppm=bis(diphenylphosphino)methane, phen=1, 10-phenan-throline, dpq=pyrazino[2, 3-f][1, 10]phenanthroline), have been synthesized in mixed solvent CH3OH and CH2Cl2 and characterized by IR, single-crystal X-ray diffraction, 1H NMR spectroscopy, fluorescence spectra and THz time domain spectroscopy (THz-TDS). Complex 1 is of a binuclear complex, which was generated by the reaction of AgCF3SO3 and dppp with phen in 1:1:1 molar ratio. In complex 1, the central Ag(Ⅰ) ion forms a ring by the bridging bisphosphine ligand (dppp) and chelating N-donor ligand (phen). Like 1, 2 is of a binuclear complex, which was obtained by the reaction of AgCF3SO3 and dppm with dpq in 1:1:1 molar ratio. The luminescent spectra show that all these emissions are assigned to ligand centered π-π* transition.
2018, 34(9): 1739-1746
doi: 10.11862/CJIC.2018.219
Abstract:
Two 4-(1, 2, 4-triazol-1-yl)phenol (hptrz)-based transition metal complexes, {[Ni(H2O)2(hptrz)2(tp)]·2DMF}n (1) and[Cu(hptrz)2(SCN)2]·2H2O (2) (H2tp=terephthalic acid), have been prepared and characterized by single-crystal and powder X-ray diffractions, elemental analysis, FT-IR spectra, thermogravimertric and luminescence spectra. X-ray diffraction analysis revealed that 1 is a one-dimensional linear chain with octahedral Ni(Ⅱ) ions extended by bis-unidentate tp2- anions; whereas 2 exhibits a centrosymmetric mononuclear entity. The neutral hptrz ligand in the both complexes serves as terminal ligands to complete the metal coordination sphere and to help to assemble the low-dimensional aggregates into a high-dimensional supramolecular architecture by O-H…O hydrogen-bonding interactions. Additionally, the complexes display strong emissions in UV region originated from intraligand electronic transfer.
Two 4-(1, 2, 4-triazol-1-yl)phenol (hptrz)-based transition metal complexes, {[Ni(H2O)2(hptrz)2(tp)]·2DMF}n (1) and[Cu(hptrz)2(SCN)2]·2H2O (2) (H2tp=terephthalic acid), have been prepared and characterized by single-crystal and powder X-ray diffractions, elemental analysis, FT-IR spectra, thermogravimertric and luminescence spectra. X-ray diffraction analysis revealed that 1 is a one-dimensional linear chain with octahedral Ni(Ⅱ) ions extended by bis-unidentate tp2- anions; whereas 2 exhibits a centrosymmetric mononuclear entity. The neutral hptrz ligand in the both complexes serves as terminal ligands to complete the metal coordination sphere and to help to assemble the low-dimensional aggregates into a high-dimensional supramolecular architecture by O-H…O hydrogen-bonding interactions. Additionally, the complexes display strong emissions in UV region originated from intraligand electronic transfer.
2018, 34(9): 1747-1752
doi: 10.11862/CJIC.2018.207
Abstract:
The hydrothermal reaction of cobalt(Ⅱ) salts with 2-hydroxyl-1, 3, 5-benzenetricarboxylic acid (OH-H3BTC) in the presence of sodium hydroxide afforded a cobalt(Ⅱ) coordination polymer, namely[Co2(O-BTC)(H2O)5]n (1), which has been characterized by powder and single-crystal X-ray diffraction, infrared spectroscopy, elemental analysis, and thermogravimetric analysis. Compound 1 contains a linear tetranuclear unit[Co4O7] through the carboxylate oxygen and hydroxyl atoms, which are further linked to form a two-dimensional (2D) layered structure in the ab plane by the O-BTC4- organic ligands. Adjacent layers are packed along the c-axis with the hydrogen bond interactions dominating between the layers to form a three-dimensional (3D) supramolecular structure. Thermal analysis reveals that 1 begins to lose weight at ca. 100℃. Magnetic studies reveal that dominant antiferromagnetic interactions are dominated between the magnetic centers in 1.
The hydrothermal reaction of cobalt(Ⅱ) salts with 2-hydroxyl-1, 3, 5-benzenetricarboxylic acid (OH-H3BTC) in the presence of sodium hydroxide afforded a cobalt(Ⅱ) coordination polymer, namely[Co2(O-BTC)(H2O)5]n (1), which has been characterized by powder and single-crystal X-ray diffraction, infrared spectroscopy, elemental analysis, and thermogravimetric analysis. Compound 1 contains a linear tetranuclear unit[Co4O7] through the carboxylate oxygen and hydroxyl atoms, which are further linked to form a two-dimensional (2D) layered structure in the ab plane by the O-BTC4- organic ligands. Adjacent layers are packed along the c-axis with the hydrogen bond interactions dominating between the layers to form a three-dimensional (3D) supramolecular structure. Thermal analysis reveals that 1 begins to lose weight at ca. 100℃. Magnetic studies reveal that dominant antiferromagnetic interactions are dominated between the magnetic centers in 1.
2018, 34(9): 1753-1760
doi: 10.11862/CJIC.2018.209
Abstract:
The magnetic Y-MOF@SiO2@Fe3O4 catalysts with different Y-MOF contents were synthesized by encapsulating magnetic SiO2@Fe3O4 nanospheres into Y-MOF through an in-situ method. The structure of the catalyst was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), infrared spectroscopy (FT-IR), vibration sample magnetometer (VSM) and the N2 adsorption-desorption test. The performance of the catalyst for Aza-Micheal addition reaction with aniline and methyl acrylate was evaluated. The results showed that Y-MOF was uniformly coated on the surface of the SiO2@Fe3O4 nanospheres to form a core-shell magnetic Y-MOF@SiO2@Fe3O4 catalyst. The catalysts exhibited good superparamagnetism. When Y-MOF content was 43.3% (w/w), the Y-MOF@SiO2@Fe3O4 catalyst had better catalytic performance for the Aza-Micheal addition reaction. The conversion of methyl acrylate was 88.3% and the selectivity of N-(β-methoxycarbonylethyl) aniline was 99.8%. After reaction, the catalyst was recovered by magnetic recovery. It was reused five times, and still has high conversion and selectivity.
The magnetic Y-MOF@SiO2@Fe3O4 catalysts with different Y-MOF contents were synthesized by encapsulating magnetic SiO2@Fe3O4 nanospheres into Y-MOF through an in-situ method. The structure of the catalyst was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), infrared spectroscopy (FT-IR), vibration sample magnetometer (VSM) and the N2 adsorption-desorption test. The performance of the catalyst for Aza-Micheal addition reaction with aniline and methyl acrylate was evaluated. The results showed that Y-MOF was uniformly coated on the surface of the SiO2@Fe3O4 nanospheres to form a core-shell magnetic Y-MOF@SiO2@Fe3O4 catalyst. The catalysts exhibited good superparamagnetism. When Y-MOF content was 43.3% (w/w), the Y-MOF@SiO2@Fe3O4 catalyst had better catalytic performance for the Aza-Micheal addition reaction. The conversion of methyl acrylate was 88.3% and the selectivity of N-(β-methoxycarbonylethyl) aniline was 99.8%. After reaction, the catalyst was recovered by magnetic recovery. It was reused five times, and still has high conversion and selectivity.
2018, 34(9): 1761-1767
doi: 10.11862/CJIC.2018.202
Abstract:
A mononuclear dysprosium(Ⅲ) complex, namely (Tmim)[Dy(thd)4] (1), was synthesized by the combination of 2, 2, 6, 6-tetramethylheptanedione (thd-) anion ligand and a 1, 3, 4, 5-tetramethylimidazolium (Tmim+) cation balancing the charge. Complex 1 was structurally and magnetically characterized. The coordination geometry of Dy(Ⅲ) ion is ascribed to approximately square antiprismatic (D4d) symmetry with the SAPR-8 parameter of 0.316. In the solid state, every mononuclear[Dy(thd)4]- anion is separated by Tmim+ cations regularly and the shortest Dy…Dy distance is 1.229 8 nm. Magnetic studies suggest that complex 1 behaves as a single-ion magnet under 500 Oe dc-applied field with a high effective energy of 30.9 K.
A mononuclear dysprosium(Ⅲ) complex, namely (Tmim)[Dy(thd)4] (1), was synthesized by the combination of 2, 2, 6, 6-tetramethylheptanedione (thd-) anion ligand and a 1, 3, 4, 5-tetramethylimidazolium (Tmim+) cation balancing the charge. Complex 1 was structurally and magnetically characterized. The coordination geometry of Dy(Ⅲ) ion is ascribed to approximately square antiprismatic (D4d) symmetry with the SAPR-8 parameter of 0.316. In the solid state, every mononuclear[Dy(thd)4]- anion is separated by Tmim+ cations regularly and the shortest Dy…Dy distance is 1.229 8 nm. Magnetic studies suggest that complex 1 behaves as a single-ion magnet under 500 Oe dc-applied field with a high effective energy of 30.9 K.
2018, 34(9): 1768-1774
doi: 10.11862/CJIC.2018.213
Abstract:
Three novel d10 complexes[M2(HL)3] NO3·H2O (M=Cd (1), Zn (2, 3), H2L=7, 7'-(ethane-1, 1-diyl)diquinolin-8-ol) have been synthesized under solvothermal conditions. Single crystal X-ray diffraction analysis reveals that the complexes have the same coordination positive charged unit, [M2(HL)3]+, but different lattice structures due to the different places of the guest molecules. Complexes 1 and 3 crystallize in hexagonal system (P63/m) and complex 2 crystallizes in trigonal system (R3). The metal ions are six-coordinated with three oxygen atoms and three nitrogen atoms of three HL- ligands, presenting a slightly distorted octahedron geometry. There are abundant weak interactions between HL- ligands and guest molecule (NO3- and H2O), which play a vital role in the form of the crystal packing. These complexes show good thermal stabilities and exhibit green fluorescence. Further, the fluorescence of ligand H2L extracted from the complex 1 has also been studied firstly and blue light emission of it was observed.
Three novel d10 complexes[M2(HL)3] NO3·H2O (M=Cd (1), Zn (2, 3), H2L=7, 7'-(ethane-1, 1-diyl)diquinolin-8-ol) have been synthesized under solvothermal conditions. Single crystal X-ray diffraction analysis reveals that the complexes have the same coordination positive charged unit, [M2(HL)3]+, but different lattice structures due to the different places of the guest molecules. Complexes 1 and 3 crystallize in hexagonal system (P63/m) and complex 2 crystallizes in trigonal system (R3). The metal ions are six-coordinated with three oxygen atoms and three nitrogen atoms of three HL- ligands, presenting a slightly distorted octahedron geometry. There are abundant weak interactions between HL- ligands and guest molecule (NO3- and H2O), which play a vital role in the form of the crystal packing. These complexes show good thermal stabilities and exhibit green fluorescence. Further, the fluorescence of ligand H2L extracted from the complex 1 has also been studied firstly and blue light emission of it was observed.
