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2017 Volume 33 Issue 10
2017, 33(10): 1705-1721
doi: 10.11862/CJIC.2017.223
Abstract:
Four-coordinated organoboron compounds with a π-conjugated N, C-chelate backbone have high thermal stability, intense luminescence, and strong electron affinity, and thereby, are promising candidates as novel optoelectronic materials for applications in organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), organic solar cells and sensors. This article summarized the recent research progress on the synthesis and the application of this important class of optoelectronic materials.
Four-coordinated organoboron compounds with a π-conjugated N, C-chelate backbone have high thermal stability, intense luminescence, and strong electron affinity, and thereby, are promising candidates as novel optoelectronic materials for applications in organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), organic solar cells and sensors. This article summarized the recent research progress on the synthesis and the application of this important class of optoelectronic materials.
2017, 33(10): 1722-1730
doi: 10.11862/CJIC.2017.227
Abstract:
Two fluorescent probes BMO and NBMO were developed for the highly selective detection of Zn2+ based on C=N isomerization and chelation-enhanced fluorescence (CHEF) mechanism. Structure identification of the probes was confirmed by 1H NMR, 13C NMR, 1H-1H COSY, HSQC, IR and HRMS spectroscopy. The results of spectral analysis show that BMO and NBMO are sensitive and highly selective to Zn2+. The detection limit of BMO and NBMO are found to be 30 and 21 nmol·L-1 respectively. There is a good linear relationship between the fluorescence intensity of probes (BMO and NBMO) and the concentration of Zn2+ in the range of 0 to 20 μmol·L-1. The X-ray crystal structure of the NBMO-Zn2+ complex exposes its coordination feature and the Job plots reveal a 1:1 probe-Zn2+ identification. The cell images show that NBMO can be used to detect intracellular Zn2+.
Two fluorescent probes BMO and NBMO were developed for the highly selective detection of Zn2+ based on C=N isomerization and chelation-enhanced fluorescence (CHEF) mechanism. Structure identification of the probes was confirmed by 1H NMR, 13C NMR, 1H-1H COSY, HSQC, IR and HRMS spectroscopy. The results of spectral analysis show that BMO and NBMO are sensitive and highly selective to Zn2+. The detection limit of BMO and NBMO are found to be 30 and 21 nmol·L-1 respectively. There is a good linear relationship between the fluorescence intensity of probes (BMO and NBMO) and the concentration of Zn2+ in the range of 0 to 20 μmol·L-1. The X-ray crystal structure of the NBMO-Zn2+ complex exposes its coordination feature and the Job plots reveal a 1:1 probe-Zn2+ identification. The cell images show that NBMO can be used to detect intracellular Zn2+.
2017, 33(10): 1731-1740
doi: 10.11862/CJIC.2017.236
Abstract:
AgI/h-MoO3 heterojunction photocatalysts were successfully fabricated by a facile deposition method. XRD, SEM, UV-Vis-DRS, EDS, XPS, PL and EIS were employed to characterize the structure, morphology, optical absorption and photo-electrochemical properties of as-synthesized samples. The photocatalytic oxidative desulfurization activity of as-synthesized samples was investigated with thiophene simulated the catalytic cracking (FCC) gasoline as the probe. The results indicate that AgI/h-MoO3-18 heterojunction has the highest photocatalytic activity and its removal efficiency for thiophene can be up to 98% with catalyst dosage (1.5 g·L-1) under irradiation of visible light for 2 h. XRD, XPS and UV-Vis-DRS measurements reveal that a small amount of metallic Ag which facilitates photoinduced electrons transfer is formed on the surface of used AgI/h-MoO3, thus leading to the transformation from AgI/h-MoO3 to AgI/Ag/h-MoO3. The photocatalytic oxidative desulfurization mechanism and stability performance of AgI/Ag/h-MoO3 were also studied by the active species trapping experiment and recycling run experiment. The experimental results have exhibited that the as-prepared AgI/h-MoO3 heterojunctions not only have higher photocatalytic oxidative desulfurization activity for thiophene, but also have good stability.
AgI/h-MoO3 heterojunction photocatalysts were successfully fabricated by a facile deposition method. XRD, SEM, UV-Vis-DRS, EDS, XPS, PL and EIS were employed to characterize the structure, morphology, optical absorption and photo-electrochemical properties of as-synthesized samples. The photocatalytic oxidative desulfurization activity of as-synthesized samples was investigated with thiophene simulated the catalytic cracking (FCC) gasoline as the probe. The results indicate that AgI/h-MoO3-18 heterojunction has the highest photocatalytic activity and its removal efficiency for thiophene can be up to 98% with catalyst dosage (1.5 g·L-1) under irradiation of visible light for 2 h. XRD, XPS and UV-Vis-DRS measurements reveal that a small amount of metallic Ag which facilitates photoinduced electrons transfer is formed on the surface of used AgI/h-MoO3, thus leading to the transformation from AgI/h-MoO3 to AgI/Ag/h-MoO3. The photocatalytic oxidative desulfurization mechanism and stability performance of AgI/Ag/h-MoO3 were also studied by the active species trapping experiment and recycling run experiment. The experimental results have exhibited that the as-prepared AgI/h-MoO3 heterojunctions not only have higher photocatalytic oxidative desulfurization activity for thiophene, but also have good stability.
2017, 33(10): 1741-1747
doi: 10.11862/CJIC.2017.213
Abstract:
CaWO4:xEu3+, ySm3+, zLi+ red phosphors were prepared by the microwave solid state method. The XRD was used to analyze the microstructures of samples. The excitation spectra, emission spectra and luminescence decay curves of the samples were measured. The influences of the concentration of Sm3+, Eu3+, Li+ on the microstructure, luminescence properties, energy transfer, fluorescence decay and energy level lifetime for synthesized samples were researched. The results show that the doping of Eu3+, Sm3+ or Li+ can not cause the change of the crystalline phase of the synthesized powders, which is still single tetragonal structure of CaWO4. For Eu3+ and Sm3+ co-doped samples, when the doping concentration of Sm3+ was 3%, and the energy transfer from Sm3+ to Eu3+ was the most effective. The doped Li+ acted as a flux and sensitizer, which improved the luminescent intensity of the sample. At the excitation wavelength 394 nm, compared with Eu3+ single doped CaWO4, the luminescence of 3%Eu3+, 3%Sm3+ co-doped CaWO4 and 3%Eu3+, 3%Sm3+, 1%Li+ co-doped CaWO4 increased by 2 times and 2.4 times respectively. At the same excitation wavelength, Eu3+ single doped samples had the shortest lifestime. With the increase of Sm3+ concentration, the lifetime of Eu3+, Sm3+ co-doped samples first decreased and then increased. The 5D0 energy level lifetime of the sample doped with Li+ increased compared the sample without Li+.
CaWO4:xEu3+, ySm3+, zLi+ red phosphors were prepared by the microwave solid state method. The XRD was used to analyze the microstructures of samples. The excitation spectra, emission spectra and luminescence decay curves of the samples were measured. The influences of the concentration of Sm3+, Eu3+, Li+ on the microstructure, luminescence properties, energy transfer, fluorescence decay and energy level lifetime for synthesized samples were researched. The results show that the doping of Eu3+, Sm3+ or Li+ can not cause the change of the crystalline phase of the synthesized powders, which is still single tetragonal structure of CaWO4. For Eu3+ and Sm3+ co-doped samples, when the doping concentration of Sm3+ was 3%, and the energy transfer from Sm3+ to Eu3+ was the most effective. The doped Li+ acted as a flux and sensitizer, which improved the luminescent intensity of the sample. At the excitation wavelength 394 nm, compared with Eu3+ single doped CaWO4, the luminescence of 3%Eu3+, 3%Sm3+ co-doped CaWO4 and 3%Eu3+, 3%Sm3+, 1%Li+ co-doped CaWO4 increased by 2 times and 2.4 times respectively. At the same excitation wavelength, Eu3+ single doped samples had the shortest lifestime. With the increase of Sm3+ concentration, the lifetime of Eu3+, Sm3+ co-doped samples first decreased and then increased. The 5D0 energy level lifetime of the sample doped with Li+ increased compared the sample without Li+.
2017, 33(10): 1748-1756
doi: 10.11862/CJIC.2017.232
Abstract:
Zn-Al layered double hydroxides (LDHs) with different Zn/Al molar ratios were prepare by co-preci-pitation method in this work. The structure and composition were investigated using X-ray diffraction (XRD), scanning electron microscope (SEM), thermogravimetric (TG), N2 adsorption-desorption and inductively coupled plasma mass spectrometry (ICP-MS). The adsorption properties of as-prepared Zn/Al hydrotalcites for phthalic acid removal from water were investigated and compared. Results show that the adsorption capacity increased with the increasing of Zn/Al molar ratios at low Zn/Al molar ratios for hydrotalcites. Further increasing the nZn/nAl molar ratios (>6), the adsorption capacity shows little change. Among those hydrotalcites, one sample with the highest adsorption capacity was selected and its adsorption kinetic and isotherm was further investigated. The adsorption equilibrium data were well described by Freundlich isotherm model and the kinetics followed a pseudo-second order kinetic equation/mechanism. In addition, the hydrotalcite can be reused at least 3 cycles without significant loss of adsorption capacity.
Zn-Al layered double hydroxides (LDHs) with different Zn/Al molar ratios were prepare by co-preci-pitation method in this work. The structure and composition were investigated using X-ray diffraction (XRD), scanning electron microscope (SEM), thermogravimetric (TG), N2 adsorption-desorption and inductively coupled plasma mass spectrometry (ICP-MS). The adsorption properties of as-prepared Zn/Al hydrotalcites for phthalic acid removal from water were investigated and compared. Results show that the adsorption capacity increased with the increasing of Zn/Al molar ratios at low Zn/Al molar ratios for hydrotalcites. Further increasing the nZn/nAl molar ratios (>6), the adsorption capacity shows little change. Among those hydrotalcites, one sample with the highest adsorption capacity was selected and its adsorption kinetic and isotherm was further investigated. The adsorption equilibrium data were well described by Freundlich isotherm model and the kinetics followed a pseudo-second order kinetic equation/mechanism. In addition, the hydrotalcite can be reused at least 3 cycles without significant loss of adsorption capacity.
2017, 33(10): 1757-1762
doi: 10.11862/CJIC.2017.235
Abstract:
Zn2GeO4 nanorods were synthesized through a facile hydrothermal method at different pH values, and the morphology and luminescence properties of Zn2GeO4 nanorods were systematically studied. The SEM results indicate that the particle sizes decreased with the increased in pH values from micro-to nano-size, and the length of Zn2GeO4 nanorods (L=200~500 nm) can be controlled through the pH values. Two emission bands centered at 450 and 530 nm were observed which are associated with different native defects in Zn2GeO4 nanocrystals.
Zn2GeO4 nanorods were synthesized through a facile hydrothermal method at different pH values, and the morphology and luminescence properties of Zn2GeO4 nanorods were systematically studied. The SEM results indicate that the particle sizes decreased with the increased in pH values from micro-to nano-size, and the length of Zn2GeO4 nanorods (L=200~500 nm) can be controlled through the pH values. Two emission bands centered at 450 and 530 nm were observed which are associated with different native defects in Zn2GeO4 nanocrystals.
2017, 33(10): 1763-1768
doi: 10.11862/CJIC.2017.226
Abstract:
The Si@void@C composites were prepared by a stober method with Si nanoparticles as the cores. This preparation process involved coating a SiO2 layer through hydrolyzing and self-assembly approach of TEOS, coating a carbon layer through in-situ polymerization and high temperature carbonization of dopamine, and etching SiO2 by HF. Crystalline structure, morphology and electrochemical performances of the composites were characterized by X-ray diffraction, scanning electron microscope, TEM and charge-discharge tests. The results indicate that the Si@void@C anode material retains a charge capacity of 1 319.5 mAh·g-1 at current density of 0.1 A·g-1 along with the capacity retention of 78.4% after 100 cycles, and shows an excellent electrochemical performance.
The Si@void@C composites were prepared by a stober method with Si nanoparticles as the cores. This preparation process involved coating a SiO2 layer through hydrolyzing and self-assembly approach of TEOS, coating a carbon layer through in-situ polymerization and high temperature carbonization of dopamine, and etching SiO2 by HF. Crystalline structure, morphology and electrochemical performances of the composites were characterized by X-ray diffraction, scanning electron microscope, TEM and charge-discharge tests. The results indicate that the Si@void@C anode material retains a charge capacity of 1 319.5 mAh·g-1 at current density of 0.1 A·g-1 along with the capacity retention of 78.4% after 100 cycles, and shows an excellent electrochemical performance.
2017, 33(10): 1769-1774
doi: 10.11862/CJIC.2017.224
Abstract:
Using ethylene glycol, ethanol as mixed solvents, cubic shape ITO powders were synthesized. The effect of reaction time, the concentration of NaOH on the phase and the morphology of ITO powders was investigated, and their influence on the electric conductivity and the mechanisms of ITO powders were also discussed. The results show that using the ethylene glycol and ethanol as mixed solvents, VEG:VEtOH=4:1, the cubic shape ITO powders with good dispersancy are prepared, the average particle size is 10.7 nm, and the XRD diffraction intensity ratio I400/I222 gets up to 0.380. when the ethylene glycol and ethanol act as mixed solvents, VEG:VEtOH=4:1, and the concentration of NaOH is 0.275 mol·L-1, the electric conductivity of the powder gets up to the maximum 46.75 mS·cm-1.
Using ethylene glycol, ethanol as mixed solvents, cubic shape ITO powders were synthesized. The effect of reaction time, the concentration of NaOH on the phase and the morphology of ITO powders was investigated, and their influence on the electric conductivity and the mechanisms of ITO powders were also discussed. The results show that using the ethylene glycol and ethanol as mixed solvents, VEG:VEtOH=4:1, the cubic shape ITO powders with good dispersancy are prepared, the average particle size is 10.7 nm, and the XRD diffraction intensity ratio I400/I222 gets up to 0.380. when the ethylene glycol and ethanol act as mixed solvents, VEG:VEtOH=4:1, and the concentration of NaOH is 0.275 mol·L-1, the electric conductivity of the powder gets up to the maximum 46.75 mS·cm-1.
2017, 33(10): 1775-1781
doi: 10.11862/CJIC.2017.217
Abstract:
ZrO2-coated H1.6Mn1.6O4 was synthesized from Li1.6Mn1.6O4 precursor prepared by a hydrothermal method. The liquid precipitation process followed by acid washing was utilized to coat ZrO2 on the precursor. The structure, morphology and composition of the ZrO2-coated precursor were investigated by SEM, XRD, EDS and HRTEM analysis. The influences of coating content and roasting temperature on Mn dissolution loss ratio and Li adsorption capacity were discussed. The results indicate that a layer of ZrO2 with 15 nm in thickness is coated on the precursor when ZrO2 content is 3% and roasting temperature is 450℃. The Mn dissolution loss ratio decreases from 3.14% to 2.65% and Li adsorption capacity of the resulting ion sieve in the salt lake brine maintains 29.4 mg·g-1. After 10 cycles of adsorption and desorption, the corresponding Mn dissolution loss ratio and Li adsorption capacity is 0.34% and 24.4 mg·g-1, respectively. The adsorption capacity is higher than the bare lithium ion-sieve (22.9 mg·g-1). The results suggest that the structure and cycle stability of H1.6Mn1.6O4 are improved by a ZrO2 coating layer.
ZrO2-coated H1.6Mn1.6O4 was synthesized from Li1.6Mn1.6O4 precursor prepared by a hydrothermal method. The liquid precipitation process followed by acid washing was utilized to coat ZrO2 on the precursor. The structure, morphology and composition of the ZrO2-coated precursor were investigated by SEM, XRD, EDS and HRTEM analysis. The influences of coating content and roasting temperature on Mn dissolution loss ratio and Li adsorption capacity were discussed. The results indicate that a layer of ZrO2 with 15 nm in thickness is coated on the precursor when ZrO2 content is 3% and roasting temperature is 450℃. The Mn dissolution loss ratio decreases from 3.14% to 2.65% and Li adsorption capacity of the resulting ion sieve in the salt lake brine maintains 29.4 mg·g-1. After 10 cycles of adsorption and desorption, the corresponding Mn dissolution loss ratio and Li adsorption capacity is 0.34% and 24.4 mg·g-1, respectively. The adsorption capacity is higher than the bare lithium ion-sieve (22.9 mg·g-1). The results suggest that the structure and cycle stability of H1.6Mn1.6O4 are improved by a ZrO2 coating layer.
2017, 33(10): 1782-1788
doi: 10.11862/CJIC.2017.212
Abstract:
The Ag3PO4/MoS2 nanosheets composite photocatalyst was successfully prepared via a mechanical milling method. The structure of composite photocatalyst was characterized by using X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), UV-Vis diffuse reflectance spectroscopy (DRS) and photoluminescence spectroscopy (PL). The results indicate that Ag3PO4 nanoparticles are successfully coupled into the surface of MoS2 nanosheets. The photocatalytic activity of composite photocatalyst was evaluated by the degradation of organic methylene blue (MB) under visible light irradiation. The obtained Ag3PO4/1%MoS2 nanosheets composite photocatalyst exhibite the optimal photocatalytic performance, which can degrade almost all MB under visible-light irradiation within 30 min. The kinetic constant of MB degradation with Ag3PO4/1%MoS2 nanosheets composite photocatalyst is about 2 times as high as that of the pure Ag3PO4. The enhanced photocatalytic activity is mainly attributed to the efficient separation and transport of photo-induced electron-hole pairs in the heterojunction structure. The recycling experiment shows that the photocatalytic activity of Ag3PO4/1%MoS2 nanosheets composite photocatalyst is maintained at about 84% after 5 cycles, while the photocatalytic activity of the pure Ag3PO4 decreases to 35%. The high photocatalytic stability is due to the successful inhibition of the photo-corrosion of Ag3PO4 by transferring the photo-generated electrons of Ag3PO4 to MoS2 nanosheets.
The Ag3PO4/MoS2 nanosheets composite photocatalyst was successfully prepared via a mechanical milling method. The structure of composite photocatalyst was characterized by using X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), UV-Vis diffuse reflectance spectroscopy (DRS) and photoluminescence spectroscopy (PL). The results indicate that Ag3PO4 nanoparticles are successfully coupled into the surface of MoS2 nanosheets. The photocatalytic activity of composite photocatalyst was evaluated by the degradation of organic methylene blue (MB) under visible light irradiation. The obtained Ag3PO4/1%MoS2 nanosheets composite photocatalyst exhibite the optimal photocatalytic performance, which can degrade almost all MB under visible-light irradiation within 30 min. The kinetic constant of MB degradation with Ag3PO4/1%MoS2 nanosheets composite photocatalyst is about 2 times as high as that of the pure Ag3PO4. The enhanced photocatalytic activity is mainly attributed to the efficient separation and transport of photo-induced electron-hole pairs in the heterojunction structure. The recycling experiment shows that the photocatalytic activity of Ag3PO4/1%MoS2 nanosheets composite photocatalyst is maintained at about 84% after 5 cycles, while the photocatalytic activity of the pure Ag3PO4 decreases to 35%. The high photocatalytic stability is due to the successful inhibition of the photo-corrosion of Ag3PO4 by transferring the photo-generated electrons of Ag3PO4 to MoS2 nanosheets.
2017, 33(10): 1789-1796
doi: 10.11862/CJIC.2017.219
Abstract:
The TiO2/schorl(3%) were prepared by a hydrothermal method in order to solve the defects easy agglo-meration and wide band gap of TiO2. The influences of the hydrothermal time (2~10 h) and the hydrothermal temperature (120~200℃) on photocatalytic activity of TiO2/schorl(3%) were studied. It was found that the degra-dation efficiency to rhodamine B improved from 60% (TiO2) to 99.4% by composited with schorl. The schorl shows spontaneous polarization electric field, which can effectively reduce the recombination rate of photogenerated electrons and holes of TiO2. The sample TiO2/schorl(3%) synthesized at 160℃ for 4 h shows the highest photo-catalytic performance. These results indicate that the material with spontaneous polarization can effectively improve the photocatalytic properties of TiO2.
The TiO2/schorl(3%) were prepared by a hydrothermal method in order to solve the defects easy agglo-meration and wide band gap of TiO2. The influences of the hydrothermal time (2~10 h) and the hydrothermal temperature (120~200℃) on photocatalytic activity of TiO2/schorl(3%) were studied. It was found that the degra-dation efficiency to rhodamine B improved from 60% (TiO2) to 99.4% by composited with schorl. The schorl shows spontaneous polarization electric field, which can effectively reduce the recombination rate of photogenerated electrons and holes of TiO2. The sample TiO2/schorl(3%) synthesized at 160℃ for 4 h shows the highest photo-catalytic performance. These results indicate that the material with spontaneous polarization can effectively improve the photocatalytic properties of TiO2.
2017, 33(10): 1797-1804
doi: 10.11862/CJIC.2017.197
Abstract:
The iron oxide coating Fenton-like catalyst on Ti alloy was successfully prepared in silicate electrolyte via micro-arc oxidation. The surface morphology, crystal structure and phase composition were studied by SEM, XRD and XPS. The results indicated that the as-prepared coating included the rutile TiO2 (R-TiO2), and amorphous Fe3O4 which was analyzed by XPS. The SEM images suggested that after the addition of K3[Fe(CN)6] in the electrolyte, the surface roughness and average pore size of the as-prepared coating were increased. The Fenton-like catalytic activity of as-prepared coating was investigated by degradation of phenol. What's more, the influences of K3[Fe(CN)6] content, phenol concentration, H2O2 dosage and pH value on phenol degradation were also studied and finally the optimal degradation condition was confirmed. Under pH 3.0, 30℃, H2O2 6.0 mmol·L-1, phenol 35 mg·L-1 and K3[Fe(CN)6] 10 g·L-1, 90% phenol could be removed. The effect of degradation temperature on degradation efficiency was also evaluated and the reaction kinetics under different temperature were also studied. The activation energy of Fenton-like degradation of phenol through Arrhenius equation is 96.9 kJ·mol-1. Finally, the stability was studied and the stability degradation was also analyzed.
The iron oxide coating Fenton-like catalyst on Ti alloy was successfully prepared in silicate electrolyte via micro-arc oxidation. The surface morphology, crystal structure and phase composition were studied by SEM, XRD and XPS. The results indicated that the as-prepared coating included the rutile TiO2 (R-TiO2), and amorphous Fe3O4 which was analyzed by XPS. The SEM images suggested that after the addition of K3[Fe(CN)6] in the electrolyte, the surface roughness and average pore size of the as-prepared coating were increased. The Fenton-like catalytic activity of as-prepared coating was investigated by degradation of phenol. What's more, the influences of K3[Fe(CN)6] content, phenol concentration, H2O2 dosage and pH value on phenol degradation were also studied and finally the optimal degradation condition was confirmed. Under pH 3.0, 30℃, H2O2 6.0 mmol·L-1, phenol 35 mg·L-1 and K3[Fe(CN)6] 10 g·L-1, 90% phenol could be removed. The effect of degradation temperature on degradation efficiency was also evaluated and the reaction kinetics under different temperature were also studied. The activation energy of Fenton-like degradation of phenol through Arrhenius equation is 96.9 kJ·mol-1. Finally, the stability was studied and the stability degradation was also analyzed.
2017, 33(10): 1805-1809
doi: 10.11862/CJIC.2017.205
Abstract:
Nitrogen-doped carbon nanotubes (NCNT) with N-content of 3%~5%(w/w) and specific surface area of 235 m2·g-1 were used as support for the immobilization of Pt nanoparticles. Pt nanoparticles were highly dispersed on NCNT without needing pre-modification of the support by taking advantage of the inherent chemical activity of NCNT arising from the N-incorporation. A series of Pt/NCNT catalysts with the loadings of 18.2%~58.7%(w/w, the same below) were conveniently prepared via the microwave-assisted polyol reduction. With increasing Pt loading, the average sizes of Pt nanoparticles increase slightly from 2.2 to 3.7 nm. The mass activity for MOR first increases and reaches the maximum at Pt loading of 47.8%, then decreases dramatically, while the activity based on the Pt mass presents a high-value platform in the Pt-loading range of 27.6%~47.8%. Such a changing tendency is well correlated with the remarkable difference of MOR activity for Pt nanoparticles with the sizes smaller and larger than 3 nm, respectively. The dramatic activity deterioration for the catalyst with high Pt-loading of 58.7% comes from the serious agglomeration of Pt nanoparticles, leading to poor Pt utilization.
Nitrogen-doped carbon nanotubes (NCNT) with N-content of 3%~5%(w/w) and specific surface area of 235 m2·g-1 were used as support for the immobilization of Pt nanoparticles. Pt nanoparticles were highly dispersed on NCNT without needing pre-modification of the support by taking advantage of the inherent chemical activity of NCNT arising from the N-incorporation. A series of Pt/NCNT catalysts with the loadings of 18.2%~58.7%(w/w, the same below) were conveniently prepared via the microwave-assisted polyol reduction. With increasing Pt loading, the average sizes of Pt nanoparticles increase slightly from 2.2 to 3.7 nm. The mass activity for MOR first increases and reaches the maximum at Pt loading of 47.8%, then decreases dramatically, while the activity based on the Pt mass presents a high-value platform in the Pt-loading range of 27.6%~47.8%. Such a changing tendency is well correlated with the remarkable difference of MOR activity for Pt nanoparticles with the sizes smaller and larger than 3 nm, respectively. The dramatic activity deterioration for the catalyst with high Pt-loading of 58.7% comes from the serious agglomeration of Pt nanoparticles, leading to poor Pt utilization.
2017, 33(10): 1810-1816
doi: 10.11862/CJIC.2017.234
Abstract:
Two new mononuclear copper(Ⅰ) diphosphine complexes based on 6-methoxycarbonyl-4, 4'-dimethyl-2, 2'-bipyridine (mmbpy), [Cu(mmbpy)(dppp)]ClO4 (1) and [Cu(mmbpy)(dppb)]ClO4 (2), have been synthesized and characterized. It is revealed that Cu(Ⅰ) complexes 1 and 2 all exhibit distorted N2P2 tetrahedral geometries with varied P-Cu-P angles regulated by auxiliary diphosphine ligands. The two Cu(Ⅰ) complexes are all emissive in the solid state at ambient temperature, and their photophysical properties are more markedly influenced by the P-Cu-P angle than the methylene chain length of diphosphine. It is also demonstrated that the introduction of two methyl substituents into the 2, 2'-bipyridyl ring is effective for improving luminescence properties of Cu(Ⅰ) complexes.
Two new mononuclear copper(Ⅰ) diphosphine complexes based on 6-methoxycarbonyl-4, 4'-dimethyl-2, 2'-bipyridine (mmbpy), [Cu(mmbpy)(dppp)]ClO4 (1) and [Cu(mmbpy)(dppb)]ClO4 (2), have been synthesized and characterized. It is revealed that Cu(Ⅰ) complexes 1 and 2 all exhibit distorted N2P2 tetrahedral geometries with varied P-Cu-P angles regulated by auxiliary diphosphine ligands. The two Cu(Ⅰ) complexes are all emissive in the solid state at ambient temperature, and their photophysical properties are more markedly influenced by the P-Cu-P angle than the methylene chain length of diphosphine. It is also demonstrated that the introduction of two methyl substituents into the 2, 2'-bipyridyl ring is effective for improving luminescence properties of Cu(Ⅰ) complexes.
2017, 33(10): 1817-1824
doi: 10.11862/CJIC.2017.233
Abstract:
Two coordination polymers, [Cd2(L)(DMF)1.5(H2O)2]n (1) and {[Cd(L)0.5(4, 4'-bpy)(H2O)]·2H2O}n (2), have been designed and synthesized by solvothermal or hydrothermal reactions of 5, 5'-(hexane-1, 6-diyl)-bis(oxy)diisophthalic acid ligand (H4L) with Cd(Ⅱ) metal ions in the presence/absence of N-donor ligands. The structures of 1~2 have been determined by single-crystal X-ray diffraction analyses and further characterized via infrared spectra (IR), powder X-ray diffraction (PXRD), elemental analyses and thermogravimetric (TG) analyses. Complex 1 features a (4, 4)-connected sql topology net with point symbol of {44·62}2. Complex 2 presents a trinodal (4, 4, 4)-connected 3D 3-fold interpenetrating bbf network with a Schläfli symbol of (66)(64·82). Additionally, complexes 1 and 2 present better thermal stabilities, and show different photoluminescence behaviors in the solid state.
Two coordination polymers, [Cd2(L)(DMF)1.5(H2O)2]n (1) and {[Cd(L)0.5(4, 4'-bpy)(H2O)]·2H2O}n (2), have been designed and synthesized by solvothermal or hydrothermal reactions of 5, 5'-(hexane-1, 6-diyl)-bis(oxy)diisophthalic acid ligand (H4L) with Cd(Ⅱ) metal ions in the presence/absence of N-donor ligands. The structures of 1~2 have been determined by single-crystal X-ray diffraction analyses and further characterized via infrared spectra (IR), powder X-ray diffraction (PXRD), elemental analyses and thermogravimetric (TG) analyses. Complex 1 features a (4, 4)-connected sql topology net with point symbol of {44·62}2. Complex 2 presents a trinodal (4, 4, 4)-connected 3D 3-fold interpenetrating bbf network with a Schläfli symbol of (66)(64·82). Additionally, complexes 1 and 2 present better thermal stabilities, and show different photoluminescence behaviors in the solid state.
2017, 33(10): 1825-1834
doi: 10.11862/CJIC.2017.237
Abstract:
K2FeO4 was synthesized by wet chemical method with calcium hypochlorite and iron nitrate nonahydrate as raw material. The contrative analysis from X ray diffraction(XRD), scanning electron microscope(SEM), infrared absorption spectrometer(FTIR) and energy dispersive spectrometer(EDS) show that higher purity and more uniform K2FeO4 crystals can be obtained by second recrystallized purification from crude products. Several experiments were performed to investigate the removal properties of K2FeO4 on Cu(Ⅱ) and Cd(Ⅱ) ions in the phenol-aqueous solution, including dosage of K2FeO4, shock time, solution pH, shock temperature, initial concentration and mixed ions. The K2FeO4 can remove Cu(Ⅱ), Cd(Ⅱ) and degrade phenol from phenol-aqueous solution in a single step of treatment. In addition, the removal mechanisms of metal ions including of adsorption, co-precipitate and surface complexation were revealed by scanning electron microscope (SEM), energy dispersive spectrometer (EDS), fourier transform infrared absorption spectrum (FTIR) in detail. The research results can provide a water treatment agent, which may be used to treat wastewater containing heavy metal and organic matter.
K2FeO4 was synthesized by wet chemical method with calcium hypochlorite and iron nitrate nonahydrate as raw material. The contrative analysis from X ray diffraction(XRD), scanning electron microscope(SEM), infrared absorption spectrometer(FTIR) and energy dispersive spectrometer(EDS) show that higher purity and more uniform K2FeO4 crystals can be obtained by second recrystallized purification from crude products. Several experiments were performed to investigate the removal properties of K2FeO4 on Cu(Ⅱ) and Cd(Ⅱ) ions in the phenol-aqueous solution, including dosage of K2FeO4, shock time, solution pH, shock temperature, initial concentration and mixed ions. The K2FeO4 can remove Cu(Ⅱ), Cd(Ⅱ) and degrade phenol from phenol-aqueous solution in a single step of treatment. In addition, the removal mechanisms of metal ions including of adsorption, co-precipitate and surface complexation were revealed by scanning electron microscope (SEM), energy dispersive spectrometer (EDS), fourier transform infrared absorption spectrum (FTIR) in detail. The research results can provide a water treatment agent, which may be used to treat wastewater containing heavy metal and organic matter.
2017, 33(10): 1835-1842
doi: 10.11862/CJIC.2017.193
Abstract:
A morphology-evolution of Pd nanocrystals was successfully triggered by using N, N-dimethyloctade-cylammonium bromide acetate sodium (OTAB-Na) as the capping agent. Uniform and monodisperse dendritic and concave Pd nanocrystals were synthesized by directly changing the pH value of the reaction solution. In the following catalytic test of liquid-phase reduction of 4-nitrophenol (4-NP) by ammonia-borane complex (AB), the as-obtained Pd nanocrystals exhibit a shape-dependent catalytic properties, in which the dendritic nanosphere is the better one.
A morphology-evolution of Pd nanocrystals was successfully triggered by using N, N-dimethyloctade-cylammonium bromide acetate sodium (OTAB-Na) as the capping agent. Uniform and monodisperse dendritic and concave Pd nanocrystals were synthesized by directly changing the pH value of the reaction solution. In the following catalytic test of liquid-phase reduction of 4-nitrophenol (4-NP) by ammonia-borane complex (AB), the as-obtained Pd nanocrystals exhibit a shape-dependent catalytic properties, in which the dendritic nanosphere is the better one.
2017, 33(10): 1843-1848
doi: 10.11862/CJIC.2017.189
Abstract:
The reaction of Co(OAc)2·2H2O, 4, 4'-azopyridine(4, 4'-azpy) with N-(pyridine-3-sulfonyl amino) acetate (H2L) in ethanol and water leads to the formation of one mononuclear cobalt polymer {[Co(L)(4, 4'-azpy)(H2O)]·2H2O}n (1). The structure of 1 was analyzed by elemental analysis, IR, TG and single crystal X-ray diffraction. The results show that complex 1 belongs to monoclinic system and P21/n space groups. The TGA shows that the structure of 1 remains unchanged during the loss of coordination water molecules and free water molecules, and begins to decompose at 238℃, indicating 1 has good stability. The magnetic investigation shows that there is antiferromagnetic interactions between Co(Ⅱ) ions in polymer 1.
The reaction of Co(OAc)2·2H2O, 4, 4'-azopyridine(4, 4'-azpy) with N-(pyridine-3-sulfonyl amino) acetate (H2L) in ethanol and water leads to the formation of one mononuclear cobalt polymer {[Co(L)(4, 4'-azpy)(H2O)]·2H2O}n (1). The structure of 1 was analyzed by elemental analysis, IR, TG and single crystal X-ray diffraction. The results show that complex 1 belongs to monoclinic system and P21/n space groups. The TGA shows that the structure of 1 remains unchanged during the loss of coordination water molecules and free water molecules, and begins to decompose at 238℃, indicating 1 has good stability. The magnetic investigation shows that there is antiferromagnetic interactions between Co(Ⅱ) ions in polymer 1.
2017, 33(10): 1849-1854
doi: 10.11862/CJIC.2017.214
Abstract:
Two complexes, namely[Cu(HL)Cl2]·H2O (1) and[ZnL2] (2) (HL=methyl (1-(3-ethylpyrazin-2-yl)ethylidene) carbazate) have been synthesized and characterized by single-crystal X-ray diffraction, elemental analysis and IR spectroscopy. X-ray diffraction analysis results show that in complex 1, the Cu(Ⅱ) ion with a distorted square pyramid coordination geometry is coordinated with one neutral ligand HL and two chloride anions. However, the central Zn(Ⅱ) ion in complex 2 is surrounded by two independent anionic ligands with N2O donor set, thus possesses a distorted octahedral coordination geometry. The luminescent properties of the complexes were also studied in detail.
Two complexes, namely[Cu(HL)Cl2]·H2O (1) and[ZnL2] (2) (HL=methyl (1-(3-ethylpyrazin-2-yl)ethylidene) carbazate) have been synthesized and characterized by single-crystal X-ray diffraction, elemental analysis and IR spectroscopy. X-ray diffraction analysis results show that in complex 1, the Cu(Ⅱ) ion with a distorted square pyramid coordination geometry is coordinated with one neutral ligand HL and two chloride anions. However, the central Zn(Ⅱ) ion in complex 2 is surrounded by two independent anionic ligands with N2O donor set, thus possesses a distorted octahedral coordination geometry. The luminescent properties of the complexes were also studied in detail.
2017, 33(10): 1855-1860
doi: 10.11862/CJIC.2017.225
Abstract:
Two homogeneous compounds, {(4-CH3-Bz-4-Ph-Py)[PbI3]}n (1) (4-CH3-Bz-4-Ph-Py=4-methylbenzyl-4-phenylpyridinium) and {(4-CF3-Bz-4-Ph-Py)[PbI3]}n (2) (4-CF3-Bz-4-Ph-Py=4-trifluoromethylbenzyl-4-phenylpyri-dinium), have been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. Compound 1 crystallizes in orthorhombic, space group P21212, and compounds 1 and 2 are isostructural. Structure analyses reveal that iodoplumbate ion exhibits octahedron topology in compounds 1 and 2, and all these octahedron topologies form 1D polymeric chain through edge-sharing connecting modes. The organic cation fill in the gap formed by inorganic iodoplumbate polymeric chain.
Two homogeneous compounds, {(4-CH3-Bz-4-Ph-Py)[PbI3]}n (1) (4-CH3-Bz-4-Ph-Py=4-methylbenzyl-4-phenylpyridinium) and {(4-CF3-Bz-4-Ph-Py)[PbI3]}n (2) (4-CF3-Bz-4-Ph-Py=4-trifluoromethylbenzyl-4-phenylpyri-dinium), have been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. Compound 1 crystallizes in orthorhombic, space group P21212, and compounds 1 and 2 are isostructural. Structure analyses reveal that iodoplumbate ion exhibits octahedron topology in compounds 1 and 2, and all these octahedron topologies form 1D polymeric chain through edge-sharing connecting modes. The organic cation fill in the gap formed by inorganic iodoplumbate polymeric chain.
2017, 33(10): 1861-1868
doi: 10.11862/CJIC.2017.220
Abstract:
The title complexes, Ni(L)2 (1) and Cu(L)2 (2) based on HL (HL=N-(3-methylsalicylidene)tryptamine) have been synthesized under solvothermal conditions and characterized structurally by TGA, infrared spectra, elemental analysis and single-crystal X-ray diffraction. Complexes 1 and 2 both crystallize in monoclinic system, and the space groups are P21/n with the unit cell parameters for complex 1:a=1.481 6(7) nm, b=1.310 0(6) nm, c=1.668 7(7) nm, β=111.346(7)°, and for complex 2:a=1.479 7(2) nm, b=1.299 41(19) nm, c=1.667 6(2) nm, β=111.537(3)°. Complexes 1 and 2 possess the similar mononuclear structures, which are further extended into infinite 3D supramolecular frameworks by intramolecular C-H…O hydrogen bonds and intermolecular D-H…π hydrogen bonds, respectively. Furthermore, the complexes and the ligand have been investigated for their preliminary antibacterial activities in detail by agar diffusion method, and the results demonstrate that complexes 1 and 2 display more excellent inhibiting effects than the ligand.
The title complexes, Ni(L)2 (1) and Cu(L)2 (2) based on HL (HL=N-(3-methylsalicylidene)tryptamine) have been synthesized under solvothermal conditions and characterized structurally by TGA, infrared spectra, elemental analysis and single-crystal X-ray diffraction. Complexes 1 and 2 both crystallize in monoclinic system, and the space groups are P21/n with the unit cell parameters for complex 1:a=1.481 6(7) nm, b=1.310 0(6) nm, c=1.668 7(7) nm, β=111.346(7)°, and for complex 2:a=1.479 7(2) nm, b=1.299 41(19) nm, c=1.667 6(2) nm, β=111.537(3)°. Complexes 1 and 2 possess the similar mononuclear structures, which are further extended into infinite 3D supramolecular frameworks by intramolecular C-H…O hydrogen bonds and intermolecular D-H…π hydrogen bonds, respectively. Furthermore, the complexes and the ligand have been investigated for their preliminary antibacterial activities in detail by agar diffusion method, and the results demonstrate that complexes 1 and 2 display more excellent inhibiting effects than the ligand.
2017, 33(10): 1869-1875
doi: 10.11862/CJIC.2017.215
Abstract:
Two novel coordination polymers[Ag4(BPTC)]n (1) and[Cd(PIMPHC)2]n (2) were synthesized under hydrothermal reactions by using biphenyl-2, 4, 4', 6-tetracarboxylic acid (H4BPTC, C16H10O8) and 2-(4-(1H-imidazo-2-[4, 5-f] [1, 10]phenanthrolinyl)phenoxy) acetic acid (HPIMPHC, C21H14N4O3). They were characterized by elemental analysis, IR spectra, TGA, single crystal X-ray diffraction. Complex 1 crystallizes in triclinic system with space group P1, the coordination numbers of Ag(Ⅰ) are four, three and two, forming distorted tetrahedron, flat triangular and V-type coordination geometry. Complex 2 crystallizes in orthorhombic system with space group Pbcn, Each Cd(Ⅱ) is bridged by the PIMPHC- anions, forming a distorted octahedral coordination geometry. The interaction of complexes, ligands and ct-DNA were studied by EtBr fluorescence probe.
Two novel coordination polymers[Ag4(BPTC)]n (1) and[Cd(PIMPHC)2]n (2) were synthesized under hydrothermal reactions by using biphenyl-2, 4, 4', 6-tetracarboxylic acid (H4BPTC, C16H10O8) and 2-(4-(1H-imidazo-2-[4, 5-f] [1, 10]phenanthrolinyl)phenoxy) acetic acid (HPIMPHC, C21H14N4O3). They were characterized by elemental analysis, IR spectra, TGA, single crystal X-ray diffraction. Complex 1 crystallizes in triclinic system with space group P1, the coordination numbers of Ag(Ⅰ) are four, three and two, forming distorted tetrahedron, flat triangular and V-type coordination geometry. Complex 2 crystallizes in orthorhombic system with space group Pbcn, Each Cd(Ⅱ) is bridged by the PIMPHC- anions, forming a distorted octahedral coordination geometry. The interaction of complexes, ligands and ct-DNA were studied by EtBr fluorescence probe.
2017, 33(10): 1876-1880
doi: 10.11862/CJIC.2017.221
Abstract:
The crystalline compound[C4H3N{CH=NCH(Me)C6H5}-2]AlMe2 was synthesized by the reaction of the ligand (d, l)-N-(2-pyrrolylmethylene)-1-phenylethylamine and trimethylaluminum in high yield. And it was well characterized by 1H NMR, 13C NMR spectroscopy, elemental analyses and single crystal X-ray crystallography. Compound[C4H3N{CH=NCH(Me)C6H5}-2]AlMe2 is an active initiator for the polymerization of rac-lactide leading to the isotactic-rich polylactides.
The crystalline compound[C4H3N{CH=NCH(Me)C6H5}-2]AlMe2 was synthesized by the reaction of the ligand (d, l)-N-(2-pyrrolylmethylene)-1-phenylethylamine and trimethylaluminum in high yield. And it was well characterized by 1H NMR, 13C NMR spectroscopy, elemental analyses and single crystal X-ray crystallography. Compound[C4H3N{CH=NCH(Me)C6H5}-2]AlMe2 is an active initiator for the polymerization of rac-lactide leading to the isotactic-rich polylactides.
2017, 33(10): 1881-1888
doi: 10.11862/CJIC.2017.228
Abstract:
Effects of Al content on the comprehensive electrochemical performance of Ce-rich MmNi4-xCo0.7Mn0.3Alx (x=0, 0.1, 0.2, 0.3) hydrogen storage alloys, particularly the low-temperature and high-rate capacity have been systematically investigated. At room temperature, both the discharge capacity and cycling stability of the electrode increase with the Al content increases, but the high-rate dischargeability seriously deteriorates. The discharge capacity still increases with the increase of Al content at -20℃, but gradually deteriorates when the temperature drops down to -40℃. Electrochemical kinetics results demonstrate that the high-rate capacity recession of the high-Al alloy at room temperature is contributed to the deterioration of the charge-transfer process. When the temperature drops down to -40℃, Al deteriorates both the surface catalytic ability and the bulk hydrogen diffusion ability, leading to the severe drop of discharge capacity and potential of the high-Al alloy. Based on the comprehensive electrochemical properties of the electrodes, the optimal composition of MmNi4-xCo0.7Mn0.3Alx is obtained when x=0.2.
Effects of Al content on the comprehensive electrochemical performance of Ce-rich MmNi4-xCo0.7Mn0.3Alx (x=0, 0.1, 0.2, 0.3) hydrogen storage alloys, particularly the low-temperature and high-rate capacity have been systematically investigated. At room temperature, both the discharge capacity and cycling stability of the electrode increase with the Al content increases, but the high-rate dischargeability seriously deteriorates. The discharge capacity still increases with the increase of Al content at -20℃, but gradually deteriorates when the temperature drops down to -40℃. Electrochemical kinetics results demonstrate that the high-rate capacity recession of the high-Al alloy at room temperature is contributed to the deterioration of the charge-transfer process. When the temperature drops down to -40℃, Al deteriorates both the surface catalytic ability and the bulk hydrogen diffusion ability, leading to the severe drop of discharge capacity and potential of the high-Al alloy. Based on the comprehensive electrochemical properties of the electrodes, the optimal composition of MmNi4-xCo0.7Mn0.3Alx is obtained when x=0.2.
2017, 33(10): 1889-1895
doi: 10.11862/CJIC.2017.196
Abstract:
Two new coordination polymers, {[Cd3(SO4)4(TITMB)2(H2O)4] [Cd(H2O)6]·2CH3OH}n (1) and {[Zn(TTTMB) (HCOO)2]·CH3OH}n (2), based on the flexible tripodal ligands 1, 3, 5-tris(imidazol-1-ylmethyl)-2, 4, 6-trimethylbenzene (TITMB) and 1, 3, 5-tris(triazol-1-ylmethyl)-2, 4, 6-trimethylbenzene (TTTMB), have been synthesized and character-ized by single-crystal XRD analyses, IR spectra, solid state photoluminescence studies, thermogravimetric analyses, and elemental analyses. Single-crystal X-ray diffraction reveals that both complexes 1 and 2 are two-dimensional layers, and extended to three-dimensional structure by hydrogen bonds. In complex 1, inorganic chains constructed by SO42- and Cd(Ⅱ) are linked by ligand TITMB to the 2D networks, where the[Cd(H2O)6]2+ units locate in the cavity between two adjacent 2D layers by hydrogen bonds to neutralize the charge. Complex 2 owns typical 63 2D topological networks. The thermal stability and photoluminescence property were also studied. Both complexes show high thermal stabilities and display blue fluorescent emissions in the solid state at room temperature.
Two new coordination polymers, {[Cd3(SO4)4(TITMB)2(H2O)4] [Cd(H2O)6]·2CH3OH}n (1) and {[Zn(TTTMB) (HCOO)2]·CH3OH}n (2), based on the flexible tripodal ligands 1, 3, 5-tris(imidazol-1-ylmethyl)-2, 4, 6-trimethylbenzene (TITMB) and 1, 3, 5-tris(triazol-1-ylmethyl)-2, 4, 6-trimethylbenzene (TTTMB), have been synthesized and character-ized by single-crystal XRD analyses, IR spectra, solid state photoluminescence studies, thermogravimetric analyses, and elemental analyses. Single-crystal X-ray diffraction reveals that both complexes 1 and 2 are two-dimensional layers, and extended to three-dimensional structure by hydrogen bonds. In complex 1, inorganic chains constructed by SO42- and Cd(Ⅱ) are linked by ligand TITMB to the 2D networks, where the[Cd(H2O)6]2+ units locate in the cavity between two adjacent 2D layers by hydrogen bonds to neutralize the charge. Complex 2 owns typical 63 2D topological networks. The thermal stability and photoluminescence property were also studied. Both complexes show high thermal stabilities and display blue fluorescent emissions in the solid state at room temperature.
