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2019 Volume 35 Issue 1
2019, 35(1): 1-24
doi: 10.11862/CJIC.2019.008
Abstract:
During the course of evolution, organisms have learned to utilize materials to adapt themselves to changes in the environment. In nature, a few organisms can form inorganic nanomaterials through biomineralization, which can provide extensive protection or unique functions. However, some organisms do not have biomineralization ability in nature. Inspired by nanomodification of organisms in nature, scientists have attempted to modify the organisms by artificially introduction of nanomaterials. In this review, modification of organisms by nanomaterials based on bio-material facial composite technology are systematically elaborated from the aspects of regulatory mechanism, modification methods, functions and applications, and the research progress of nanomodification of organisms by biomimetic mineralization is highlighted. The current situation in the field of modification of organisms by biomimetic inorganic nanomaterials is analyzed and summarized, outlook for the future of the field is also prospected.
During the course of evolution, organisms have learned to utilize materials to adapt themselves to changes in the environment. In nature, a few organisms can form inorganic nanomaterials through biomineralization, which can provide extensive protection or unique functions. However, some organisms do not have biomineralization ability in nature. Inspired by nanomodification of organisms in nature, scientists have attempted to modify the organisms by artificially introduction of nanomaterials. In this review, modification of organisms by nanomaterials based on bio-material facial composite technology are systematically elaborated from the aspects of regulatory mechanism, modification methods, functions and applications, and the research progress of nanomodification of organisms by biomimetic mineralization is highlighted. The current situation in the field of modification of organisms by biomimetic inorganic nanomaterials is analyzed and summarized, outlook for the future of the field is also prospected.
2019, 35(1): 25-33
doi: 10.11862/CJIC.2019.003
Abstract:
A series of phosphors Ca0.955-xAl2Si2O8:0.045Eu2+, xMn2+ (x=0, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.325, 0.35, 0.375, 0.40, 0.425) were prepared via solid-state reaction. As Mn2+ was substituted for Ca2+ into the crystal lattice, the effect on its lattice parameters and spectral properties were discussed. The results show that complete solid solutions were formed in the whole range for x while Mn2+ enterers CaAl2Si2O8 lattice and substitutes for Ca2+. The samples belong to triclinic system, and P1 space group. The lattice parameters (a, b, c, γ) and unit cell volume of phosphors Ca0.955-xAl2Si2O8:0.045Eu2+, xMn2+ decreased linearly, and the lattice parameters (α, β) increased linearly as Mn2+ content increased in the phosphors. When Mn2+ substitutes for Ca2+ the most obvious change is in cell parameter a, the second is c, and the minimum is b. When excited by 357 nm, the Ca0.955-xAl2Si2O8:0.045Eu2+, xMn2+ phosphors exhibited two emission peaks centered at 433 and 567 nm, which are ascribed to 5d→4f and 4T1(4G)→6A1(6S) transition of Eu2+ and Mn2+, respectively. The results show that the existence of efficient energy transfer between Eu2+ and Mn2+ in phosphors Ca0.955-xAl2Si2O8:0.045Eu2+, xMn2+, the critical distance is calculated to be 0.947 1 nm. The energy transfer between Eu2+ and Mn2+ was due to the electric dipole-dipole interaction of the resonance transfer. Under the effective excitation of the ultraviolet chip, by changing the amount of Mn2+ doping, the color of the emitted light of the phosphors can be gradually shifted from blue light (0.158 2, 0.086) to near white light (0.295 3, 0.298 9). UV-excited single-phase white light-emitting phosphors for white LEDs were available.
A series of phosphors Ca0.955-xAl2Si2O8:0.045Eu2+, xMn2+ (x=0, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.325, 0.35, 0.375, 0.40, 0.425) were prepared via solid-state reaction. As Mn2+ was substituted for Ca2+ into the crystal lattice, the effect on its lattice parameters and spectral properties were discussed. The results show that complete solid solutions were formed in the whole range for x while Mn2+ enterers CaAl2Si2O8 lattice and substitutes for Ca2+. The samples belong to triclinic system, and P1 space group. The lattice parameters (a, b, c, γ) and unit cell volume of phosphors Ca0.955-xAl2Si2O8:0.045Eu2+, xMn2+ decreased linearly, and the lattice parameters (α, β) increased linearly as Mn2+ content increased in the phosphors. When Mn2+ substitutes for Ca2+ the most obvious change is in cell parameter a, the second is c, and the minimum is b. When excited by 357 nm, the Ca0.955-xAl2Si2O8:0.045Eu2+, xMn2+ phosphors exhibited two emission peaks centered at 433 and 567 nm, which are ascribed to 5d→4f and 4T1(4G)→6A1(6S) transition of Eu2+ and Mn2+, respectively. The results show that the existence of efficient energy transfer between Eu2+ and Mn2+ in phosphors Ca0.955-xAl2Si2O8:0.045Eu2+, xMn2+, the critical distance is calculated to be 0.947 1 nm. The energy transfer between Eu2+ and Mn2+ was due to the electric dipole-dipole interaction of the resonance transfer. Under the effective excitation of the ultraviolet chip, by changing the amount of Mn2+ doping, the color of the emitted light of the phosphors can be gradually shifted from blue light (0.158 2, 0.086) to near white light (0.295 3, 0.298 9). UV-excited single-phase white light-emitting phosphors for white LEDs were available.
2019, 35(1): 34-42
doi: 10.11862/CJIC.2019.004
Abstract:
CoMoSx/γ-Al2O3 catalyst was prepared by using an impregnation method combining with in-situ reduction method. In order to systematically obtain the structure of the CoMoSx/γ-Al2O3 catalyst and study the adsorption-desorption performance and the surface reactions of CO and SO2, the catalyst was characterized using X-ray diffraction (XRD), scanning electron microscope/energy dispersive spectrdmeter (SEM/EDS), X-ray photoelectron spectroscopy (XPS), temperature programmed desorption/programmed temperature reduction/temperature progra-mmed surface reaction-mass spectrometry (TPD/TPR/TPSR-MS). The catalytic performances of the CoMoSx/γ-Al2O3 catalyst were tested in a packed-bed microreactor. The results show that the CoMoSx/γ-Al2O3 catalyst was composed of γ-Al2O3 and highly dispersed Co-Mo-S. During the pre-vulcanization, no sulfides such as CoS2 and Co9S8 were formed. CO was adsorbed on CoMoSx instead of γ-Al2O3. SO2 was weakly adsorbed on γ-Al2O3 but strongly adsorbed on CoMoSx. COS was adsorbed on γ-Al2O3 with a small amount, but not adsorbed on CoMoSx. Furthermore, SO2 adsorbed on CoMoSx was active and reacted with CO adsorbed on CoMoSx, while SO2 adsorbed on γ-Al2O3 did not react. Finally, the conversion of SO2 and the selectivity of sulfur were obtained up to 100% at 400℃.
CoMoSx/γ-Al2O3 catalyst was prepared by using an impregnation method combining with in-situ reduction method. In order to systematically obtain the structure of the CoMoSx/γ-Al2O3 catalyst and study the adsorption-desorption performance and the surface reactions of CO and SO2, the catalyst was characterized using X-ray diffraction (XRD), scanning electron microscope/energy dispersive spectrdmeter (SEM/EDS), X-ray photoelectron spectroscopy (XPS), temperature programmed desorption/programmed temperature reduction/temperature progra-mmed surface reaction-mass spectrometry (TPD/TPR/TPSR-MS). The catalytic performances of the CoMoSx/γ-Al2O3 catalyst were tested in a packed-bed microreactor. The results show that the CoMoSx/γ-Al2O3 catalyst was composed of γ-Al2O3 and highly dispersed Co-Mo-S. During the pre-vulcanization, no sulfides such as CoS2 and Co9S8 were formed. CO was adsorbed on CoMoSx instead of γ-Al2O3. SO2 was weakly adsorbed on γ-Al2O3 but strongly adsorbed on CoMoSx. COS was adsorbed on γ-Al2O3 with a small amount, but not adsorbed on CoMoSx. Furthermore, SO2 adsorbed on CoMoSx was active and reacted with CO adsorbed on CoMoSx, while SO2 adsorbed on γ-Al2O3 did not react. Finally, the conversion of SO2 and the selectivity of sulfur were obtained up to 100% at 400℃.
2019, 35(1): 43-49
doi: 10.11862/CJIC.2019.023
Abstract:
Two one-dimensional chain polyoxometallic cluster compounds connecting poly-acid anions with organic components benzimidazolyl phenol(bidp) or benzimidazole(bid) by hydrogen bond, electrostatic attraction and π-π stacking have been synthesized at room temperature, which are (Hbidp)3(PMo12O40)·bidp (1) and (Hbid)3(PMo12O40)·bid (2), and they have been unequivocally characterized by IR spectroscopy, complete elemental analysis and single crystal X-ray diffraction. The cyclic voltammogran indicted that compounds 1 and 2 have excellent redox properties. The photocatalytic performance of compounds 1 and 2 were investigated with photodegradation of methylene blue (MB) and rhodamine B (RhB) with UV irradiation.
Two one-dimensional chain polyoxometallic cluster compounds connecting poly-acid anions with organic components benzimidazolyl phenol(bidp) or benzimidazole(bid) by hydrogen bond, electrostatic attraction and π-π stacking have been synthesized at room temperature, which are (Hbidp)3(PMo12O40)·bidp (1) and (Hbid)3(PMo12O40)·bid (2), and they have been unequivocally characterized by IR spectroscopy, complete elemental analysis and single crystal X-ray diffraction. The cyclic voltammogran indicted that compounds 1 and 2 have excellent redox properties. The photocatalytic performance of compounds 1 and 2 were investigated with photodegradation of methylene blue (MB) and rhodamine B (RhB) with UV irradiation.
2019, 35(1): 50-58
doi: 10.11862/CJIC.2019.015
Abstract:
Nitrogen-doped carbon/ZnO nanoparticles (ZnO-N-C) have been synthesized via an ordinary one-step calcination of a two-dimensional zinc-based coordination polymer[Zn(tfbdc)(4, 4'-bpy)(H2O)2] (H2tfbdc=tetrafluoro-terephthalic acid, 4, 4'-bpy=4, 4'-bipyridine). As an anode material for lithium-ion batteries, the obtained ZnO-N-C electrode exhibited high reversible capacity, excellent cyclic stability and better rate capability. The reversible capacity of the ZnO-N-C electrode maintains 611 mAh·g-1 after 50 cycles at a current density of 50 mA·g-1.
Nitrogen-doped carbon/ZnO nanoparticles (ZnO-N-C) have been synthesized via an ordinary one-step calcination of a two-dimensional zinc-based coordination polymer[Zn(tfbdc)(4, 4'-bpy)(H2O)2] (H2tfbdc=tetrafluoro-terephthalic acid, 4, 4'-bpy=4, 4'-bipyridine). As an anode material for lithium-ion batteries, the obtained ZnO-N-C electrode exhibited high reversible capacity, excellent cyclic stability and better rate capability. The reversible capacity of the ZnO-N-C electrode maintains 611 mAh·g-1 after 50 cycles at a current density of 50 mA·g-1.
2019, 35(1): 59-64
doi: 10.11862/CJIC.2019.005
Abstract:
CuGa2O4 powders were prepared by co-precipitation method and characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), etc. The effect of heat treatment temperature and pH on the gas sensing properties of CuGa2O4 powders was investigated. The results indicated that CuGa2O4 powders prepared by calcining at 800℃ for 4 h and pH=6.00 exhibited good gas sensing selectivity and high sensitivity to trimethylamine (TMA) at room temperature (18±2)℃. The responses to 1 000 and 1 μL·L-1 TMA reached 310.1 and 1.3, respectively, and the response and recovery times for 1 000 μL·L-1 TMA were 590 and 80 s.
CuGa2O4 powders were prepared by co-precipitation method and characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), etc. The effect of heat treatment temperature and pH on the gas sensing properties of CuGa2O4 powders was investigated. The results indicated that CuGa2O4 powders prepared by calcining at 800℃ for 4 h and pH=6.00 exhibited good gas sensing selectivity and high sensitivity to trimethylamine (TMA) at room temperature (18±2)℃. The responses to 1 000 and 1 μL·L-1 TMA reached 310.1 and 1.3, respectively, and the response and recovery times for 1 000 μL·L-1 TMA were 590 and 80 s.
2019, 35(1): 65-72
doi: 10.11862/CJIC.2019.001
Abstract:
Mesoporous material KIT-6 was prepared using tetraethyl orthosilicate as the silicon source, triblock copolymer P123 as the template. The PEI functionalized PEI/KIT-6 was prepared with two-step post-grafting method, namely, 3-chloropropyltrimethoxysilane was firstly grafted onto KIT-6 and then polyethyleneimine (PEI) was further grafted. The samples were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermal gravimetric analysis (TGA), elemental analysis, N2 adsorption-desorption and scanning electron microscopy (SEM). The Pb2+ adsorption performance was determined by inductively coupled plasma (ICP). The results showed that the average loading of the amino groups was 0.374 mmol·g-1, and the modified KIT-6 remained highly ordered and no pore blockage occurred. With the dosage of 1 g·L-1 PEI/KIT-6, the optimum pH value for adsorption of 100 mg·L-1 Pb2+ was 6.0 at room temperature. The adsorption capacity of PEI/KIT-6 for Pb2+ increased firstly and then decreased with the increase of temperature, and the optimum adsorption temperature was 35℃. The adsorption capacity tends to reach equilibrium after 120 min. The pseudo-second-order kinetic model was found to be suited well for the entire adsorption process. Adsorption equilibrium data could be also described well by Langmuir and Freundlich isotherm models. The adsorption tends to take chemisorption of monolayer.
Mesoporous material KIT-6 was prepared using tetraethyl orthosilicate as the silicon source, triblock copolymer P123 as the template. The PEI functionalized PEI/KIT-6 was prepared with two-step post-grafting method, namely, 3-chloropropyltrimethoxysilane was firstly grafted onto KIT-6 and then polyethyleneimine (PEI) was further grafted. The samples were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermal gravimetric analysis (TGA), elemental analysis, N2 adsorption-desorption and scanning electron microscopy (SEM). The Pb2+ adsorption performance was determined by inductively coupled plasma (ICP). The results showed that the average loading of the amino groups was 0.374 mmol·g-1, and the modified KIT-6 remained highly ordered and no pore blockage occurred. With the dosage of 1 g·L-1 PEI/KIT-6, the optimum pH value for adsorption of 100 mg·L-1 Pb2+ was 6.0 at room temperature. The adsorption capacity of PEI/KIT-6 for Pb2+ increased firstly and then decreased with the increase of temperature, and the optimum adsorption temperature was 35℃. The adsorption capacity tends to reach equilibrium after 120 min. The pseudo-second-order kinetic model was found to be suited well for the entire adsorption process. Adsorption equilibrium data could be also described well by Langmuir and Freundlich isotherm models. The adsorption tends to take chemisorption of monolayer.
2019, 35(1): 73-81
doi: 10.11862/CJIC.2019.024
Abstract:
The reduced graphene oxide/graphitic carbon nitride/molybdenum disulfide composites (RGO/g-C3N4/MoS2) were synthesized via the pyrolysis-hydrothermal two-step method. The structures, morphologies and photocatalytic properties of as-prepared composites were characterized by various analytical characterization methods. With the good interface contact and rapid transfer of charge, the composites could enhance the photoelectron-hole separation. The results show that the GCM composites could degradation 97% methylene blue (MB) in 120 min under the irradiation of visible-light and the highest apparent reaction rate constant (k) value was 0.028 09 min-1. Moreover, the cycle experiments show that the composites had good stability and could maintained 93.2% photocatalytic activity after 5 cycles.
The reduced graphene oxide/graphitic carbon nitride/molybdenum disulfide composites (RGO/g-C3N4/MoS2) were synthesized via the pyrolysis-hydrothermal two-step method. The structures, morphologies and photocatalytic properties of as-prepared composites were characterized by various analytical characterization methods. With the good interface contact and rapid transfer of charge, the composites could enhance the photoelectron-hole separation. The results show that the GCM composites could degradation 97% methylene blue (MB) in 120 min under the irradiation of visible-light and the highest apparent reaction rate constant (k) value was 0.028 09 min-1. Moreover, the cycle experiments show that the composites had good stability and could maintained 93.2% photocatalytic activity after 5 cycles.
2019, 35(1): 82-88
doi: 10.11862/CJIC.2019.011
Abstract:
Gd and N co-doped SrTiO3/TiO2 composite nanofibers were prepared via one step hydrothermal synthesis growth of SrTiO3 nanostructures using electrospun anatase TiO2 nanofibers as both substance and reactant. The phase composition, microstructure, morphology and optical properties of the sample were characterized by X-ray diffraction (XRD), scanning electron mictoscopy (SEM), high-resolution transmission electron microscopy (HRTEM), energy dispersive X-ray spectroscopy (XPS), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS) and photoluminescence spectroscopy (PL). The results indicated that the heterostructure formed by SrTiO3 and TiO2, plays an important role in the suppression of electron-hole recombination and improves the photocatalytic performance of TiO2 nanofibers. The excellent visible light photocatalytic activity of this substance may be due to the generation of a new band gap that enables the catalyst to absorb visible light and results in the lattice defects which acts as a recombination center of photoinduced electrons and holes. The synergistic effect of Gd-N co-doping and heterojunction could effectively improve the visible-light photocatalytic activity of SrTiO3/TiO2 composite nanofibers.
Gd and N co-doped SrTiO3/TiO2 composite nanofibers were prepared via one step hydrothermal synthesis growth of SrTiO3 nanostructures using electrospun anatase TiO2 nanofibers as both substance and reactant. The phase composition, microstructure, morphology and optical properties of the sample were characterized by X-ray diffraction (XRD), scanning electron mictoscopy (SEM), high-resolution transmission electron microscopy (HRTEM), energy dispersive X-ray spectroscopy (XPS), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS) and photoluminescence spectroscopy (PL). The results indicated that the heterostructure formed by SrTiO3 and TiO2, plays an important role in the suppression of electron-hole recombination and improves the photocatalytic performance of TiO2 nanofibers. The excellent visible light photocatalytic activity of this substance may be due to the generation of a new band gap that enables the catalyst to absorb visible light and results in the lattice defects which acts as a recombination center of photoinduced electrons and holes. The synergistic effect of Gd-N co-doping and heterojunction could effectively improve the visible-light photocatalytic activity of SrTiO3/TiO2 composite nanofibers.
2019, 35(1): 89-94
doi: 10.11862/CJIC.2019.012
Abstract:
Open-pore MFI zeolite nanosheets were prepared by removal of organic structure-directing agents (OSDA) from a multilamellar MFI zeolite (ML-MFI) using a mixture of 95%~98%(w/w) H2SO4 and 30%(w/w) H2O2 with VH2SO4:VH2O2=3:1 (known as piranha solution), followed by ultrasonication for exfoliation and sedimentation for purification. The exfoliated MFI zeolite nanosheets were characterized by various techniques, such as X-ray diffraction (XRD), scanning electron microscope (SEM), transmittance electron microscope (TEM), N2 adsorption-desorption, Fourier transform infrared spectrometer (FT-IR) and thermal gravimetric analyzer (TGA), etc., indicating that OSDA was removed after the piranha solution treatment and dispersed, open-pore MFI nanosheets were obtained followed by exfoliation through ultrasonication. Continuous MFI nanosheet membranes were prepared by depositing the open-pore MFI nanosheets on home-made alumina disc supports by a simple vacuum-assisted filtration method. Single gas permeance tests on the MFI zeolite nanosheet membranes indicated that ideal selectivities for n-butane over i-butane of 4.1~5.8 with a permeance of n-butane of 2.2×10-7~4.1×10-7 mol·m-2·s-1·Pa-1 were achieved.
Open-pore MFI zeolite nanosheets were prepared by removal of organic structure-directing agents (OSDA) from a multilamellar MFI zeolite (ML-MFI) using a mixture of 95%~98%(w/w) H2SO4 and 30%(w/w) H2O2 with VH2SO4:VH2O2=3:1 (known as piranha solution), followed by ultrasonication for exfoliation and sedimentation for purification. The exfoliated MFI zeolite nanosheets were characterized by various techniques, such as X-ray diffraction (XRD), scanning electron microscope (SEM), transmittance electron microscope (TEM), N2 adsorption-desorption, Fourier transform infrared spectrometer (FT-IR) and thermal gravimetric analyzer (TGA), etc., indicating that OSDA was removed after the piranha solution treatment and dispersed, open-pore MFI nanosheets were obtained followed by exfoliation through ultrasonication. Continuous MFI nanosheet membranes were prepared by depositing the open-pore MFI nanosheets on home-made alumina disc supports by a simple vacuum-assisted filtration method. Single gas permeance tests on the MFI zeolite nanosheet membranes indicated that ideal selectivities for n-butane over i-butane of 4.1~5.8 with a permeance of n-butane of 2.2×10-7~4.1×10-7 mol·m-2·s-1·Pa-1 were achieved.
2019, 35(1): 95-100
doi: 10.11862/CJIC.2019.007
Abstract:
The Na2O-Y2O3-P2O5-SiO2 precursor glass was prepared by traditional melting method. The transparent phosphate glass-ceramic was successfully synthesized by heat treatment of the precursor glass sample. XRD patterns of glass-ceramics samples were carried out to determine the precipitation of Na3.6Y1.8(PO4)3 crystals in the glass matrix. The effect of heat treatment time on the crystallinity and grain size of glass ceramics were discussed. The heat treatment temperature was 655℃ and the heat treatment time was 2 h. By comparing the up-conversion luminescence intensity of Ho3+ doped glass-ceramics with that of Ho3+-Yb3+ co-doped glass-ceramics, the optimum doping molar ratio of Ho3+ to Yb3+ was determined to be 1:2. At the same time, the energy transfer between Ho3+-Yb3+ was discussed. The up-conversion luminescence quantum efficiency of the samples were measured by integrating sphere.
The Na2O-Y2O3-P2O5-SiO2 precursor glass was prepared by traditional melting method. The transparent phosphate glass-ceramic was successfully synthesized by heat treatment of the precursor glass sample. XRD patterns of glass-ceramics samples were carried out to determine the precipitation of Na3.6Y1.8(PO4)3 crystals in the glass matrix. The effect of heat treatment time on the crystallinity and grain size of glass ceramics were discussed. The heat treatment temperature was 655℃ and the heat treatment time was 2 h. By comparing the up-conversion luminescence intensity of Ho3+ doped glass-ceramics with that of Ho3+-Yb3+ co-doped glass-ceramics, the optimum doping molar ratio of Ho3+ to Yb3+ was determined to be 1:2. At the same time, the energy transfer between Ho3+-Yb3+ was discussed. The up-conversion luminescence quantum efficiency of the samples were measured by integrating sphere.
2019, 35(1): 101-108
doi: 10.11862/CJIC.2019.025
Abstract:
A solid-solution MAX phase (Ti0.5V0.5)3AlC2 was successfully synthesized with a pressureless sintering method, and its catalytic effect on hydrogen storage reaction of MgH2 was systematically investigated. The solid solution MAX phase (Ti0.5V0.5)3AlC2 exhibited superior catalytic activity, thanks to the synergistic catalysis effect of Ti and V. The on-set dehydrogenation temperature of MgH2-10%(Ti0.5V0.5)3AlC2 samples was only 230℃ (mass fraction of (Ti0.5V0.5)3AlC2 was 10%), which was 60℃ lower than that of pristine MgH2. The desorption rate of MgH2-10%(Ti0.5V0.5)3AlC2 sample at 217℃ was calculated to be 0.35%·min-1, which was 4 times faster than that of the pristine sample. At 150℃, the dehydrogenated MgH2-10%(Ti0.5V0.5)3AlC2 sample absorbs 4.7% of H2 within 60 s under 5 MPa H2. The apparent activation energy of the MgH2-10%(Ti0.5V0.5)3AlC2 sample was determined to be 79.6 kJ·mol-1, representing a 48% reduction in the reaction barrier, compared with pristine MgH2 (153.8 kJ·mol-1). This reasonably explains the significant improvement in dehydrogenation performance.
A solid-solution MAX phase (Ti0.5V0.5)3AlC2 was successfully synthesized with a pressureless sintering method, and its catalytic effect on hydrogen storage reaction of MgH2 was systematically investigated. The solid solution MAX phase (Ti0.5V0.5)3AlC2 exhibited superior catalytic activity, thanks to the synergistic catalysis effect of Ti and V. The on-set dehydrogenation temperature of MgH2-10%(Ti0.5V0.5)3AlC2 samples was only 230℃ (mass fraction of (Ti0.5V0.5)3AlC2 was 10%), which was 60℃ lower than that of pristine MgH2. The desorption rate of MgH2-10%(Ti0.5V0.5)3AlC2 sample at 217℃ was calculated to be 0.35%·min-1, which was 4 times faster than that of the pristine sample. At 150℃, the dehydrogenated MgH2-10%(Ti0.5V0.5)3AlC2 sample absorbs 4.7% of H2 within 60 s under 5 MPa H2. The apparent activation energy of the MgH2-10%(Ti0.5V0.5)3AlC2 sample was determined to be 79.6 kJ·mol-1, representing a 48% reduction in the reaction barrier, compared with pristine MgH2 (153.8 kJ·mol-1). This reasonably explains the significant improvement in dehydrogenation performance.
2019, 35(1): 109-115
doi: 10.11862/CJIC.2019.020
Abstract:
Two coordination polymers [Co(L) Cl2]n (1) and [Co(L)2(SCN)2]n (2) were obtained by using 4-methyl-2, 6-bis(pyridin-3-ylethynyl) aniline (L) and Co(Ⅱ) salts in CH2Cl2/MeOH mixed solvent under room temperature. The complexes 1 and 2 were characterized by IR, elemental analysis and X-ray single crystal diffraction. The structural analysis revealed that complex 1 has 1D chain structure and 2 has 2D plane structure. The reason of the structure difference was anion choice because the L in both of the coordination complexes adopts almost same trans-N, N donor configuration. Complex 1 has four-coordinated Co(Ⅱ)) which coordinated to two L molecules, while complex 2 has six-coordinated Co(Ⅱ) which coordinated to four L molecules. The XRD and fluorescence property of two complexes were investigated. Compared to the emission spectrum of L, the emission maximum of the complex 1 was red shift and 2 was blue shift.
Two coordination polymers [Co(L) Cl2]n (1) and [Co(L)2(SCN)2]n (2) were obtained by using 4-methyl-2, 6-bis(pyridin-3-ylethynyl) aniline (L) and Co(Ⅱ) salts in CH2Cl2/MeOH mixed solvent under room temperature. The complexes 1 and 2 were characterized by IR, elemental analysis and X-ray single crystal diffraction. The structural analysis revealed that complex 1 has 1D chain structure and 2 has 2D plane structure. The reason of the structure difference was anion choice because the L in both of the coordination complexes adopts almost same trans-N, N donor configuration. Complex 1 has four-coordinated Co(Ⅱ)) which coordinated to two L molecules, while complex 2 has six-coordinated Co(Ⅱ) which coordinated to four L molecules. The XRD and fluorescence property of two complexes were investigated. Compared to the emission spectrum of L, the emission maximum of the complex 1 was red shift and 2 was blue shift.
2019, 35(1): 116-124
doi: 10.11862/CJIC.2019.019
Abstract:
Nano-structure flake-like CeO2 crystals with an average size of 4.94 μm×0.92 μm (length and width) and the thickness of 0.04~0.08 μm were prepared by simply calcining cerium carbonate precursors (CCPs) at 500℃ for 4 h, in which the flake-like CCPs were firstly prepared by stirring CeCl3 aqueous solution with CO2-storage material (CO2SM) for 0.5 h at room temperature. Interesting, the CO2SM could provide CO32- and act as dispersant and structure-directing agent for the preparation of flake-like CCPs. In the process, the effect of three factors, including CO2SM dosage, Ce3+ concentration and stirring time, on the morphology and size of CCPs were systemically studied, and the optimum preparation conditions of flake-like CCPs were confirmed at 0.1 g CO2SM with 50 mL 0.03 mol·L-1 Ce3+ aqueous solution at 1 000 r·min-1 for 0.5 h at room temperature. After calcining CCPs, the as-prepared flake-like CeO2 crystals presented the CO2 adsorption amount of 0.554 mmol·g-1 at room temperature.
Nano-structure flake-like CeO2 crystals with an average size of 4.94 μm×0.92 μm (length and width) and the thickness of 0.04~0.08 μm were prepared by simply calcining cerium carbonate precursors (CCPs) at 500℃ for 4 h, in which the flake-like CCPs were firstly prepared by stirring CeCl3 aqueous solution with CO2-storage material (CO2SM) for 0.5 h at room temperature. Interesting, the CO2SM could provide CO32- and act as dispersant and structure-directing agent for the preparation of flake-like CCPs. In the process, the effect of three factors, including CO2SM dosage, Ce3+ concentration and stirring time, on the morphology and size of CCPs were systemically studied, and the optimum preparation conditions of flake-like CCPs were confirmed at 0.1 g CO2SM with 50 mL 0.03 mol·L-1 Ce3+ aqueous solution at 1 000 r·min-1 for 0.5 h at room temperature. After calcining CCPs, the as-prepared flake-like CeO2 crystals presented the CO2 adsorption amount of 0.554 mmol·g-1 at room temperature.
2019, 35(1): 125-132
doi: 10.11862/CJIC.2019.013
Abstract:
The first metal complex of the clinical antivirus agent, penciclovir (PCV), was synthesized and structurally characterized by IR, elemental analysis and X-ray single crystal diffraction analysis. In this complex, copper(Ⅱ) was selected as the bioactive metal center, which was coordinated by two PCV molecules to form a new copper(Ⅱ) complex of PCV, [Cu(PCV)2(H2O)3]SO4 (1). The in vitro antitumor activity of complex 1 towards a variety of typical human tumor cell lines has been explored. The results indicated that complex 1 showed enhanced antitumor activity comparing with PCV alone towards all the tested cell lines, in which the human hepatoma cell line BEL-7404 was the most sensitive one to complex 1 (Inhibition ratio (55.83±16.41)%). The inhibitory activity of complex 1 is more than 3 times that of PCV (Inhibition ratio (17.38±5.53)%). Furthermore, the DNA binding mechanism of complex 1 was also studied and discussed by means of UV-Vis absorption and fluorescence emission spectral analyses, as well as the DNA viscosity experiment. The results suggested that DNA, as the primary antitumor target, should be an important binding target of complex 1. And the classic intercalative binding mode might exist between complex 1 and CT-DNA.
The first metal complex of the clinical antivirus agent, penciclovir (PCV), was synthesized and structurally characterized by IR, elemental analysis and X-ray single crystal diffraction analysis. In this complex, copper(Ⅱ) was selected as the bioactive metal center, which was coordinated by two PCV molecules to form a new copper(Ⅱ) complex of PCV, [Cu(PCV)2(H2O)3]SO4 (1). The in vitro antitumor activity of complex 1 towards a variety of typical human tumor cell lines has been explored. The results indicated that complex 1 showed enhanced antitumor activity comparing with PCV alone towards all the tested cell lines, in which the human hepatoma cell line BEL-7404 was the most sensitive one to complex 1 (Inhibition ratio (55.83±16.41)%). The inhibitory activity of complex 1 is more than 3 times that of PCV (Inhibition ratio (17.38±5.53)%). Furthermore, the DNA binding mechanism of complex 1 was also studied and discussed by means of UV-Vis absorption and fluorescence emission spectral analyses, as well as the DNA viscosity experiment. The results suggested that DNA, as the primary antitumor target, should be an important binding target of complex 1. And the classic intercalative binding mode might exist between complex 1 and CT-DNA.
2019, 35(1): 133-140
doi: 10.11862/CJIC.2019.018
Abstract:
Two zinc(Ⅱ) coordination polymers, [Zn(HIMB)2]n (1) and {[Zn(IMB)]·1.5H2O}n (2), (H2IMB=4, 4'-((1H-imidazol-1-yl) methylene) dibenzoic acid), have been synthesized and characterized by IR spectroscopy, elemental analyses, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction. Complex 1 crystallizes in orthorhombic, space group C2221 with a=0.935 2(3) nm, b=2.583 3(8) nm, c=1.396 4(4) nm, V=3.373 6(18) nm3, Mr=707.98, Dc=1.394 g·cm-3, F(000)=1 456, μ=0.786 mm-1 and Z=4. The final R1=0.048 6 and wR2=0.120 1 for 2 794 observed reflections when I>2σ(I). Complex 2 belongs to tetragonal, space group I41/acd with a=1.853 5(2) nm, b=1.853 5(2) nm, c=4.309 7(5) nm, V=14.806 (4) nm3, Mr=412.69, Dc=1.481 g·cm-3, F(000)=6 752, μ=0.136 0 mm-1 and Z=32. The final R1=0.043 7 and wR2=0.117 1 for 3 615 observed reflections when I>2σ(I). Structural analyses reveal that complex 1 shows a 2D→2D polycatenane of 2-fold interpenetrated sql layer, whereas complex 2 possesses a 3D 2-fold interpenetrated (3, 6)-connected net with the point symbol of (611.84)(63)2. The results show that the solvent plays a significant role in the structure of the final products.
Two zinc(Ⅱ) coordination polymers, [Zn(HIMB)2]n (1) and {[Zn(IMB)]·1.5H2O}n (2), (H2IMB=4, 4'-((1H-imidazol-1-yl) methylene) dibenzoic acid), have been synthesized and characterized by IR spectroscopy, elemental analyses, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction. Complex 1 crystallizes in orthorhombic, space group C2221 with a=0.935 2(3) nm, b=2.583 3(8) nm, c=1.396 4(4) nm, V=3.373 6(18) nm3, Mr=707.98, Dc=1.394 g·cm-3, F(000)=1 456, μ=0.786 mm-1 and Z=4. The final R1=0.048 6 and wR2=0.120 1 for 2 794 observed reflections when I>2σ(I). Complex 2 belongs to tetragonal, space group I41/acd with a=1.853 5(2) nm, b=1.853 5(2) nm, c=4.309 7(5) nm, V=14.806 (4) nm3, Mr=412.69, Dc=1.481 g·cm-3, F(000)=6 752, μ=0.136 0 mm-1 and Z=32. The final R1=0.043 7 and wR2=0.117 1 for 3 615 observed reflections when I>2σ(I). Structural analyses reveal that complex 1 shows a 2D→2D polycatenane of 2-fold interpenetrated sql layer, whereas complex 2 possesses a 3D 2-fold interpenetrated (3, 6)-connected net with the point symbol of (611.84)(63)2. The results show that the solvent plays a significant role in the structure of the final products.
2019, 35(1): 141-148
doi: 10.11862/CJIC.2019.017
Abstract:
Amorphous Co nanoparticles formed in-situ displayed high catalytic activity for hydrogen generation from the methanolysis reaction of ammonia borane, among many homogeneous catalysts and heterogeneous catalysts of cobalt. Its turnover number (TON) was up to 6 000 for ten cycles and its turnover frequency (TOF) was up to 515 molH2·molmetal-1·h-1. Moreover, the easily preparation and the great recycling performance made it have good application in future. After the kinetics studies, its catalytic activation energy (Ea) for the methanolysis reaction was measured as 20.00 kJ·mol-1, which was lower than most of the reported values for other nano-sized catalysts. Through the 11B NMR, trimethylborate was the only product. Furthermore, the catalytic reaction mechanism was preliminarily explained and discussed.
Amorphous Co nanoparticles formed in-situ displayed high catalytic activity for hydrogen generation from the methanolysis reaction of ammonia borane, among many homogeneous catalysts and heterogeneous catalysts of cobalt. Its turnover number (TON) was up to 6 000 for ten cycles and its turnover frequency (TOF) was up to 515 molH2·molmetal-1·h-1. Moreover, the easily preparation and the great recycling performance made it have good application in future. After the kinetics studies, its catalytic activation energy (Ea) for the methanolysis reaction was measured as 20.00 kJ·mol-1, which was lower than most of the reported values for other nano-sized catalysts. Through the 11B NMR, trimethylborate was the only product. Furthermore, the catalytic reaction mechanism was preliminarily explained and discussed.
2019, 35(1): 149-154
doi: 10.11862/CJIC.2019.009
Abstract:
Two 1D zinc(Ⅱ) coordination polymers, namely[Zn(μ-Hcpta)(4, 4'-bipy)(H2O)]n (1) and {[Zn3(μ3-dbba)2(phen)3]·6H2O}n (2), have been constructed hydrothermally using two ether-bridged tricarboxylic acids:2-(4-carbo-xylphenoxy) terephthalic acid (H3cpta) and 2-(3, 5-dicarboxylatobenzyloxy) benzoic acid(H3dbba), 4, 4'-bipyridine (4, 4'-bipy), 1, 10-phenanthroline (phen) and zinc chloride. Single-crystal X-ray diffraction analyses revealed that two complexes crystallize in the monoclinic system, space groups P21 or I2. Complexes 1 and 2 show two different 1D chain structures.
Two 1D zinc(Ⅱ) coordination polymers, namely[Zn(μ-Hcpta)(4, 4'-bipy)(H2O)]n (1) and {[Zn3(μ3-dbba)2(phen)3]·6H2O}n (2), have been constructed hydrothermally using two ether-bridged tricarboxylic acids:2-(4-carbo-xylphenoxy) terephthalic acid (H3cpta) and 2-(3, 5-dicarboxylatobenzyloxy) benzoic acid(H3dbba), 4, 4'-bipyridine (4, 4'-bipy), 1, 10-phenanthroline (phen) and zinc chloride. Single-crystal X-ray diffraction analyses revealed that two complexes crystallize in the monoclinic system, space groups P21 or I2. Complexes 1 and 2 show two different 1D chain structures.
2019, 35(1): 155-164
doi: 10.11862/CJIC.2019.010
Abstract:
Complexes of[CuL2Cl]Cl·H2O (1), [NiL2(H2O)2](NO3)2 (2), [CuL2(H2O)2](ClO4)2 (3) and[CdL2(NO3)2]·CH3CN (4) were synthesized by the reactions of 4-methyl-3-phenyl-5-(2-pyridyl)-1, 2, 4-triazole (L) with CuCl2·2H2O, Ni(NO3)2·6H2O, Cu(ClO4)2·6H2O and Cd(NO3)2·4H2O, respectively. Their structures were determined by single crystal X-ray diffraction, and characterized by IR, UV-Vis, fluorescence and TGA. Complex 1 belongs to orthorhombic system with space group Fddd, and the central Cu1(Ⅱ) ion has a distorted tetragonal pyramid geometry[CuN4Cl]. The complexes of 2, 3 and 4 all belong to monoclinic system with space groups P21/n, P21/n and P21/c, respectively. All the central metal ions of 2, 3 and 4 have distorted octahedral configuration[NiN4O2], [CuN4O2], [CdN4O2].
Complexes of[CuL2Cl]Cl·H2O (1), [NiL2(H2O)2](NO3)2 (2), [CuL2(H2O)2](ClO4)2 (3) and[CdL2(NO3)2]·CH3CN (4) were synthesized by the reactions of 4-methyl-3-phenyl-5-(2-pyridyl)-1, 2, 4-triazole (L) with CuCl2·2H2O, Ni(NO3)2·6H2O, Cu(ClO4)2·6H2O and Cd(NO3)2·4H2O, respectively. Their structures were determined by single crystal X-ray diffraction, and characterized by IR, UV-Vis, fluorescence and TGA. Complex 1 belongs to orthorhombic system with space group Fddd, and the central Cu1(Ⅱ) ion has a distorted tetragonal pyramid geometry[CuN4Cl]. The complexes of 2, 3 and 4 all belong to monoclinic system with space groups P21/n, P21/n and P21/c, respectively. All the central metal ions of 2, 3 and 4 have distorted octahedral configuration[NiN4O2], [CuN4O2], [CdN4O2].
2019, 35(1): 165-173
doi: 10.11862/CJIC.2019.021
Abstract:
Two cadmium metal-organic frameworks, {[Cd(L)(fma)]·0.5H2O}n (1) and {[Cd(L)0.5(sdb)]·DMF}n (2) (L=E, E-2, 5-dihexyloxy-1, 4-bis-(2-pyridin-vinyl) benzene, H2fma=fumaric acid, H2sdb=4, 4'-sulfonyldibenzoic acid), have been hydrothermally synthesized. Their applications in luminescence sensing of metal anions and organic molecules were explored. The results show that Fe3+ has a significant quenching influence on the luminescence intensity of MOFs 1 and 2. In addition, MOFs 1 and 2 also show some luminescence quenching ability on salicylaldehyde.
Two cadmium metal-organic frameworks, {[Cd(L)(fma)]·0.5H2O}n (1) and {[Cd(L)0.5(sdb)]·DMF}n (2) (L=E, E-2, 5-dihexyloxy-1, 4-bis-(2-pyridin-vinyl) benzene, H2fma=fumaric acid, H2sdb=4, 4'-sulfonyldibenzoic acid), have been hydrothermally synthesized. Their applications in luminescence sensing of metal anions and organic molecules were explored. The results show that Fe3+ has a significant quenching influence on the luminescence intensity of MOFs 1 and 2. In addition, MOFs 1 and 2 also show some luminescence quenching ability on salicylaldehyde.
2019, 35(1): 174-182
doi: 10.11862/CJIC.2019.016
Abstract:
A novel high luminescent performance of graphene oxide-rare earth hybrid material was prepared using a noncovalent approach. Herein, a heteronuclear rare earth complex were revealed in which the benzoic acid (BA) and 1, 10-phenanthroline hydrate (Phen) coordinated with Sm3+ and Gd3+, which was used to functionalize graphene oxide sheets (GOSs). The as-prepared products were characterized via Fourier-transform infrared spectroscopy, X-ray diffraction, scanning electron microscope, fluorescence spectrometer, decay lifetime and thermogravimetric analysis. The hybrid materials exhibited strong luminescence intensity, long lifetime and good thermal stability. Besides, Gd3+ ions had a strong sensitizing effect on materials and played a significant role in improving the luminescence intensity. The presence of GOSs did not quench the fluorescence performance of hybrid materials. Moreover, their fluorescence properties of Sm3+ and Gd3+ with different molar ratios were also studied.
A novel high luminescent performance of graphene oxide-rare earth hybrid material was prepared using a noncovalent approach. Herein, a heteronuclear rare earth complex were revealed in which the benzoic acid (BA) and 1, 10-phenanthroline hydrate (Phen) coordinated with Sm3+ and Gd3+, which was used to functionalize graphene oxide sheets (GOSs). The as-prepared products were characterized via Fourier-transform infrared spectroscopy, X-ray diffraction, scanning electron microscope, fluorescence spectrometer, decay lifetime and thermogravimetric analysis. The hybrid materials exhibited strong luminescence intensity, long lifetime and good thermal stability. Besides, Gd3+ ions had a strong sensitizing effect on materials and played a significant role in improving the luminescence intensity. The presence of GOSs did not quench the fluorescence performance of hybrid materials. Moreover, their fluorescence properties of Sm3+ and Gd3+ with different molar ratios were also studied.
