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2018 Volume 34 Issue 4
2018, 34(4): 615-626
doi: 10.11862/CJIC.2018.100
Abstract:
Dye-sensitized solar cells with p-type photoelectrode is a new type of solar cell. According to the different structure of the device, it can be divided into p-type and p-n tandem dye-sensitized solar cells. The theoretical photoelectric efficiency of the p-n tandem dye-sensitized solar cell can reach 43%, which is higher than that of the traditional dye-sensitized solar cell based on n-type TiO2 photoanode (30%), and has gained great concern of the scientific community. We summarizes the research progress of dye-sensitized solar cells based on p-type photoelectrode (eg. p-type and p-n tandem devices), focuse on the research of electrode materials, dyes and electrolytes for these kinds of devices; and summarize the existed problems and the approaches to further improve the efficiency of the device in this paper.
Dye-sensitized solar cells with p-type photoelectrode is a new type of solar cell. According to the different structure of the device, it can be divided into p-type and p-n tandem dye-sensitized solar cells. The theoretical photoelectric efficiency of the p-n tandem dye-sensitized solar cell can reach 43%, which is higher than that of the traditional dye-sensitized solar cell based on n-type TiO2 photoanode (30%), and has gained great concern of the scientific community. We summarizes the research progress of dye-sensitized solar cells based on p-type photoelectrode (eg. p-type and p-n tandem devices), focuse on the research of electrode materials, dyes and electrolytes for these kinds of devices; and summarize the existed problems and the approaches to further improve the efficiency of the device in this paper.
2018, 34(4): 627-632
doi: 10.11862/CJIC.2018.081
Abstract:
Two new cyclometalated iridium(Ⅲ) complex (dpci)2Ir(paz) and (dpci)2Ir(taz) (dpci=3, 4-diphenylcinnoline, pazH=5-(2-pyridyl)-3-trifuoromethylpyrazole, tazH=5-trifuoromethyl-3-(pyridin-2-yl)-1H-1, 2, 4-triazole), were succ-essfully synthesized and characterized by NMR spectroscopy and high resolution mass spectrometry. The photo-luminescence spectra of (dpci)2Ir(paz) and (dpci)2Ir(taz) in PMMA (1%, w/w) show emission maximum at 616 and 612 nm, which are blue shifted compared to that of reference complex (dpci)2Ir(pic) (pic=picolinate, 625 nm). The quantum yields of (dpci)2Ir(paz) and (dpci)2Ir(taz) are 51.9% and 32.5%, which are higher than that of (dpci)2Ir(pic) (16.1%). After modification, the thermal stability of complexes are enhanced, and they can be used to prepare organic electroluminescent devices by evaporation method. OLED device using (dpci)2Ir(paz) as dopant exhibited intense saturated red emission with CIE coordinates of (0.66, 0.34). The device has the best performance with a maximum external quantum efficiency of 2.7% and luminance efficiency of 8.5 cd·A-1. The maximum luminance was 2 484 cd·m-2. The device based on I(dpci)2Ir(taz) exhibits the best efficiency. Its maximum external quantum efficiency is 5.5% and the corresponding efficiency is 14.5 cd·A-1. The maximum luminance is 2 931 cd·m-2.
Two new cyclometalated iridium(Ⅲ) complex (dpci)2Ir(paz) and (dpci)2Ir(taz) (dpci=3, 4-diphenylcinnoline, pazH=5-(2-pyridyl)-3-trifuoromethylpyrazole, tazH=5-trifuoromethyl-3-(pyridin-2-yl)-1H-1, 2, 4-triazole), were succ-essfully synthesized and characterized by NMR spectroscopy and high resolution mass spectrometry. The photo-luminescence spectra of (dpci)2Ir(paz) and (dpci)2Ir(taz) in PMMA (1%, w/w) show emission maximum at 616 and 612 nm, which are blue shifted compared to that of reference complex (dpci)2Ir(pic) (pic=picolinate, 625 nm). The quantum yields of (dpci)2Ir(paz) and (dpci)2Ir(taz) are 51.9% and 32.5%, which are higher than that of (dpci)2Ir(pic) (16.1%). After modification, the thermal stability of complexes are enhanced, and they can be used to prepare organic electroluminescent devices by evaporation method. OLED device using (dpci)2Ir(paz) as dopant exhibited intense saturated red emission with CIE coordinates of (0.66, 0.34). The device has the best performance with a maximum external quantum efficiency of 2.7% and luminance efficiency of 8.5 cd·A-1. The maximum luminance was 2 484 cd·m-2. The device based on I(dpci)2Ir(taz) exhibits the best efficiency. Its maximum external quantum efficiency is 5.5% and the corresponding efficiency is 14.5 cd·A-1. The maximum luminance is 2 931 cd·m-2.
2018, 34(4): 633-638
doi: 10.11862/CJIC.2018.090
Abstract:
Four mercury(Ⅱ) complexes, namely[Hg2(L1)Cl4]n (1), {[Hg2(L2)Cl4]·L2}n (2), [Hg2(L1)I4]n (3) and[Hg2(L2)I4]n (4), have been obtained by the reaction of mercury salts with two bis(β-diketone) Schiff bases (L1=trans-bis(acetylacetone)-1, 4-diaminocyclohexane, and L2=trans-bis(benzoylacetone)-1, 4-diaminocyclohexane) in the ethanol solution. The structures of these complexes were characterized by elemental analysis, infrared spectroscopy, powder X-ray diffraction and X-ray single-crystal diffraction. In the solid state, the center Hg(Ⅱ) ions connect with γ-C atoms and three Cl-ions to form a one-dimensional chain in complexes 1, 2. In complex 3 the center Hg(Ⅱ) ions connect with O atoms and three I- ions to form a two-dimensional net structure, while in complex 4 the center Hg(Ⅱ) ions connect with O atoms and three I-ions to form a one-dimensional chain.
Four mercury(Ⅱ) complexes, namely[Hg2(L1)Cl4]n (1), {[Hg2(L2)Cl4]·L2}n (2), [Hg2(L1)I4]n (3) and[Hg2(L2)I4]n (4), have been obtained by the reaction of mercury salts with two bis(β-diketone) Schiff bases (L1=trans-bis(acetylacetone)-1, 4-diaminocyclohexane, and L2=trans-bis(benzoylacetone)-1, 4-diaminocyclohexane) in the ethanol solution. The structures of these complexes were characterized by elemental analysis, infrared spectroscopy, powder X-ray diffraction and X-ray single-crystal diffraction. In the solid state, the center Hg(Ⅱ) ions connect with γ-C atoms and three Cl-ions to form a one-dimensional chain in complexes 1, 2. In complex 3 the center Hg(Ⅱ) ions connect with O atoms and three I- ions to form a two-dimensional net structure, while in complex 4 the center Hg(Ⅱ) ions connect with O atoms and three I-ions to form a one-dimensional chain.
Syntheses, Structures and Antibacterial Activity of Lead Complexes with Nitrogen Heterocyclic Ligand
2018, 34(4): 639-646
doi: 10.11862/CJIC.2018.095
Abstract:
Two lead complexes, [Pb(phen)(NO3)(H2O)]NO3 (1) and[Pb(phen)2(NO3)]NO3 (2) (phen=1, 10-phenanthro-line) were synthesized via a solution synthesis method at room temperature. They were characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. In complex 1, the central metal Pb(Ⅱ) is tetra-coordinated to form a distorted tetrahedral geometry. In complex 2, the central metal Pb(Ⅱ) is hexa-coordinated to form a distorted octahedral geometry. By extensive intermolecular hydrogen bonds, complex 1 is connected into 1D chain supramolecular structure, while complex 2 is assembled into 3D supramolecular network. Complexes 1 and 2 have a strong inhibitory effect on Escherichia coli and Golden staph. The higher the concentration, the stronger the inhibitory effect. And the activity of complex 2 is superior to that of complex 1.
Two lead complexes, [Pb(phen)(NO3)(H2O)]NO3 (1) and[Pb(phen)2(NO3)]NO3 (2) (phen=1, 10-phenanthro-line) were synthesized via a solution synthesis method at room temperature. They were characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. In complex 1, the central metal Pb(Ⅱ) is tetra-coordinated to form a distorted tetrahedral geometry. In complex 2, the central metal Pb(Ⅱ) is hexa-coordinated to form a distorted octahedral geometry. By extensive intermolecular hydrogen bonds, complex 1 is connected into 1D chain supramolecular structure, while complex 2 is assembled into 3D supramolecular network. Complexes 1 and 2 have a strong inhibitory effect on Escherichia coli and Golden staph. The higher the concentration, the stronger the inhibitory effect. And the activity of complex 2 is superior to that of complex 1.
2018, 34(4): 647-654
doi: 10.11862/CJIC.2018.091
Abstract:
Spherical precursor Ni0.9Co0.05Al0.03Zr0.02(OH)2 was obtained by controlled crystallization method. A uniform mixture of Ni0.9Co0.05Al0.03Zr0.02(OH)2 and LiOH·H2O was sintered under 750℃ in O2 atmosphere to synthesize layered Li(Ni0.9Co0.05Al0.03Zr0.02)O2 cathode material. SEM images show that the precursor and cathode material have well morphology. XRD patterns show that the product possesse a well-layered α-NaFeO2 structure. EDXS images show the Zr element in the material is distributed evenly. The cells with the material as cathode display excellent electrochemical performance:an initial discharge capacity of 221.5 mAh·g-1 at 0.2C between 2.8 and 4.3 V with an initial coulombic efficiency of 90.3%, a discharge capacity of 192.7 mAh·g-1 at 2C and a capacity retention rate of 92.2% after 100 cycles at 25℃. As the temperature raised to 55℃, the discharge capacity was 236.2 mAh·g-1 at 0.2C in 2.8~4.3 V, and retained a capacity retention rate of 85.1% after 100 cycles at 2C.
Spherical precursor Ni0.9Co0.05Al0.03Zr0.02(OH)2 was obtained by controlled crystallization method. A uniform mixture of Ni0.9Co0.05Al0.03Zr0.02(OH)2 and LiOH·H2O was sintered under 750℃ in O2 atmosphere to synthesize layered Li(Ni0.9Co0.05Al0.03Zr0.02)O2 cathode material. SEM images show that the precursor and cathode material have well morphology. XRD patterns show that the product possesse a well-layered α-NaFeO2 structure. EDXS images show the Zr element in the material is distributed evenly. The cells with the material as cathode display excellent electrochemical performance:an initial discharge capacity of 221.5 mAh·g-1 at 0.2C between 2.8 and 4.3 V with an initial coulombic efficiency of 90.3%, a discharge capacity of 192.7 mAh·g-1 at 2C and a capacity retention rate of 92.2% after 100 cycles at 25℃. As the temperature raised to 55℃, the discharge capacity was 236.2 mAh·g-1 at 0.2C in 2.8~4.3 V, and retained a capacity retention rate of 85.1% after 100 cycles at 2C.
2018, 34(4): 655-661
doi: 10.11862/CJIC.2018.103
Abstract:
Three coordination polymers with the molecular formula[LnSrK(ptc)2(H2O)]n (Ln=Sm (1), Dy (2), Gd (3), H3ptc=2, 4, 6-pyridinetricarboxylic acid) were synthesized by hydrothermal reaction of the solutions of Ln(ClO4)3, SrCO3, K2CO3 and H3ptc at 180℃. The structures of three complexes were determined by X-ray single crystal diffraction and the results showed they are isomorphic compounds and crystallize in triclinic system, P1 space group. The ptc ligands bonded with three metal ions Ln (Sm (1), Dy (2) and Gd (3)), Sr, K with two types of coor-dination modes:connecting seven metal ions and connecting eight metal ions. Ln(Ⅲ) is eight-coordinated by six oxygen atoms from carboxyl groups and two nitrogen atoms from two pyridyl rings. Sr(Ⅱ) ion is also eight-coordinated but the coordination atoms are all oxygen atoms. K(Ⅰ) is coordinated by five oxygen atoms. The emission spectra show Sm(Ⅲ)-Sr(Ⅱ)-K(Ⅰ) and Dy(Ⅲ)-Sr(Ⅱ)-K(Ⅰ) complexes both emit the characteristic fluorescence of Sm(Ⅲ) and Dy(Ⅲ). The Gd(Ⅲ)-Sr(Ⅱ)-K(Ⅰ) complex emits green fluorescence but it is resulted from the charge transfer transitions between the ligands and Gd(Ⅲ).
Three coordination polymers with the molecular formula[LnSrK(ptc)2(H2O)]n (Ln=Sm (1), Dy (2), Gd (3), H3ptc=2, 4, 6-pyridinetricarboxylic acid) were synthesized by hydrothermal reaction of the solutions of Ln(ClO4)3, SrCO3, K2CO3 and H3ptc at 180℃. The structures of three complexes were determined by X-ray single crystal diffraction and the results showed they are isomorphic compounds and crystallize in triclinic system, P1 space group. The ptc ligands bonded with three metal ions Ln (Sm (1), Dy (2) and Gd (3)), Sr, K with two types of coor-dination modes:connecting seven metal ions and connecting eight metal ions. Ln(Ⅲ) is eight-coordinated by six oxygen atoms from carboxyl groups and two nitrogen atoms from two pyridyl rings. Sr(Ⅱ) ion is also eight-coordinated but the coordination atoms are all oxygen atoms. K(Ⅰ) is coordinated by five oxygen atoms. The emission spectra show Sm(Ⅲ)-Sr(Ⅱ)-K(Ⅰ) and Dy(Ⅲ)-Sr(Ⅱ)-K(Ⅰ) complexes both emit the characteristic fluorescence of Sm(Ⅲ) and Dy(Ⅲ). The Gd(Ⅲ)-Sr(Ⅱ)-K(Ⅰ) complex emits green fluorescence but it is resulted from the charge transfer transitions between the ligands and Gd(Ⅲ).
2018, 34(4): 662-668
doi: 10.11862/CJIC.2018.079
Abstract:
Anodic oxidation and hydrothermal method were jointly used to prepare CuO/TiO2 negative material which was synthesized from ethylene glycol, ammonium fluoride, hydrochloric acid, cupric chloride and sodium nitrate. Morphology, element distribution, valence state, microcosmic phase composition of the samples were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD). Furthermore, the electrochemical lithium insertion properties of CuO/TiO2 were tested by the use of battery charge and discharge testing system and electrochemical workstation. The results show that there are particulates arrange the surface of the anatase TiO2 nanotube. The nanometer size was 4 nm×10 nm. The as prepared CuO/TiO2 displays plummy electric properties of initial discharge and charge capacities of 550 and 490 mAh·g-1 at the rate of 0.3C. respectively. After 50 cycles the reserve capacities is 320 mAh·g-1.
Anodic oxidation and hydrothermal method were jointly used to prepare CuO/TiO2 negative material which was synthesized from ethylene glycol, ammonium fluoride, hydrochloric acid, cupric chloride and sodium nitrate. Morphology, element distribution, valence state, microcosmic phase composition of the samples were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD). Furthermore, the electrochemical lithium insertion properties of CuO/TiO2 were tested by the use of battery charge and discharge testing system and electrochemical workstation. The results show that there are particulates arrange the surface of the anatase TiO2 nanotube. The nanometer size was 4 nm×10 nm. The as prepared CuO/TiO2 displays plummy electric properties of initial discharge and charge capacities of 550 and 490 mAh·g-1 at the rate of 0.3C. respectively. After 50 cycles the reserve capacities is 320 mAh·g-1.
2018, 34(4): 669-675
doi: 10.11862/CJIC.2018.089
Abstract:
Three-dimensional dendritic C/PbWO4 composite photocatalyst with different C content (Mass fraction=0.13%, 0.26%, 0.52%, 0.78%) was synthesized by a hydrothermal method. The photocatalysts were characterized by X-ray diffraction, N2 sorption measurements, scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, ultraviolet-visible diffuse reflectance spectroscopies, photoluminescence, and photoelectrochemical measurement. The results showed that the dendritic C/PbWO4 composite photocatalyst with 0.52% C exhibits the best photocatalytic performance in degrading orange Ⅱ, methyl orange and rhodamine B. Under the light irradiation for 100 min, the degradation rate of the acid orange Ⅱ (20 mg·L-1) over 0.52% C/PbWO4 reached 97% which was about 2.48 times as that of bare PbWO4. The main reason for the increase of activity is that carbon attached to the surface of the catalyst becomes the electron trapping center, and it can effectively capture the photogenerated electrons. Therefore, the photo-generated electron-hole pairs were effectively separated to produce more active species (·OH, h+) to participate in the degradation of organic dye molecules.
Three-dimensional dendritic C/PbWO4 composite photocatalyst with different C content (Mass fraction=0.13%, 0.26%, 0.52%, 0.78%) was synthesized by a hydrothermal method. The photocatalysts were characterized by X-ray diffraction, N2 sorption measurements, scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, ultraviolet-visible diffuse reflectance spectroscopies, photoluminescence, and photoelectrochemical measurement. The results showed that the dendritic C/PbWO4 composite photocatalyst with 0.52% C exhibits the best photocatalytic performance in degrading orange Ⅱ, methyl orange and rhodamine B. Under the light irradiation for 100 min, the degradation rate of the acid orange Ⅱ (20 mg·L-1) over 0.52% C/PbWO4 reached 97% which was about 2.48 times as that of bare PbWO4. The main reason for the increase of activity is that carbon attached to the surface of the catalyst becomes the electron trapping center, and it can effectively capture the photogenerated electrons. Therefore, the photo-generated electron-hole pairs were effectively separated to produce more active species (·OH, h+) to participate in the degradation of organic dye molecules.
2018, 34(4): 676-682
doi: 10.11862/CJIC.2018.084
Abstract:
AlF3 coated Natural graphite composite (AF/NG) was synthesized by high speed mechanical dispersion and spray drying with the natural graphite as raw material. On the one hand, a more stable SEI film can be formed with the help of AlF3, which promoting the cycle performance. on the other hand, the AlF3 can promote the diffusion of lithium ions between the particles, which is benefit to the rate capability. AF/NG delivered a reversible capacity more than 278 mAh·g-1 at 0.5C, with a capacity of 78 mAh·g-1 higher than the uncoated sample (NG). The synthetic process is easy to control which is suitable for large-scale commercial production.
AlF3 coated Natural graphite composite (AF/NG) was synthesized by high speed mechanical dispersion and spray drying with the natural graphite as raw material. On the one hand, a more stable SEI film can be formed with the help of AlF3, which promoting the cycle performance. on the other hand, the AlF3 can promote the diffusion of lithium ions between the particles, which is benefit to the rate capability. AF/NG delivered a reversible capacity more than 278 mAh·g-1 at 0.5C, with a capacity of 78 mAh·g-1 higher than the uncoated sample (NG). The synthetic process is easy to control which is suitable for large-scale commercial production.
2018, 34(4): 683-688
doi: 10.11862/CJIC.2018.083
Abstract:
Probe Eu(DBM)3 Bipy was prepared by europium oxide (Eu2O3), dibenzoylmethane (DBM) and 2-2'-dipyridyl(Bipy). The temperature sensitive paint (TSP) was compounded by the polymerization of the probe molecule, methyl methacrylate (MMA) and the initiator of benzoyl peroxide (BPO). The structure, morphology, luminescence property of probe molecule and the temperature quenching property of the temperature sensitive paint (TSP) was characterized by infrared spectrometer, UV-Vis spectrometer, scanning electron microscopy and fluorescence spectrometer. The results of infrared and UV absorption spectrum analysis showed that the rare earth ion Eu3+ coordinates to ligands and Eu(DBM)3 Bipy probe molecule was successfully synthesized. Scanning electron microscopy spectrum and energy spectrum analysis showed that Eu(DBM)3 Bipy probe molecule is fragmented, and the size is about 150 nm, which is mainly composed of four elements, C, N, O and Eu. The fluorescence spectra showed that the optimum emission wavelength is 612 nm under 367 nm excitation, and Bipy as second ligand has a gain effect on Eu(DBM)3. Temperature sensitive paint fluorescence emission characteristics test under different temperature conditions, found that the temperature sensitive paint Eu(DBM)3 Bipy/PMMA has good characteristics of fluorescence quenching of temperature in 40~90℃, and the temperature range of the highest temperature sensitivity at 40~60℃.
Probe Eu(DBM)3 Bipy was prepared by europium oxide (Eu2O3), dibenzoylmethane (DBM) and 2-2'-dipyridyl(Bipy). The temperature sensitive paint (TSP) was compounded by the polymerization of the probe molecule, methyl methacrylate (MMA) and the initiator of benzoyl peroxide (BPO). The structure, morphology, luminescence property of probe molecule and the temperature quenching property of the temperature sensitive paint (TSP) was characterized by infrared spectrometer, UV-Vis spectrometer, scanning electron microscopy and fluorescence spectrometer. The results of infrared and UV absorption spectrum analysis showed that the rare earth ion Eu3+ coordinates to ligands and Eu(DBM)3 Bipy probe molecule was successfully synthesized. Scanning electron microscopy spectrum and energy spectrum analysis showed that Eu(DBM)3 Bipy probe molecule is fragmented, and the size is about 150 nm, which is mainly composed of four elements, C, N, O and Eu. The fluorescence spectra showed that the optimum emission wavelength is 612 nm under 367 nm excitation, and Bipy as second ligand has a gain effect on Eu(DBM)3. Temperature sensitive paint fluorescence emission characteristics test under different temperature conditions, found that the temperature sensitive paint Eu(DBM)3 Bipy/PMMA has good characteristics of fluorescence quenching of temperature in 40~90℃, and the temperature range of the highest temperature sensitivity at 40~60℃.
2018, 34(4): 689-696
doi: 10.11862/CJIC.2018.082
Abstract:
By employing electrospun TiO2 nanofiber as substrate, rare earth Ce doped Bi2MoO6/TiO2 composite nanofibers were prepared via solvothermal method. The composition, morphology and optical properties were characterized by XRD, SEM, XPS, TEM, UV-Vis DRS and PL analysis. The photocatalytic properties were tested by degradation of rhodamine B under visible light. The results show that Ce3+ ion can be a substitute for Bi3+ in the crystal lattice of Bi2MoO6, resulting in an expansion, distortion of lattice cell and hence defects. Photocatalytic test shows that the activity of TiO2 nanofibers under visible light can be enhanced. For example, the degradation percentage of RhB can be as high as 95.1%, which is believed to benefit from the effective charge generation, transfer and separation at the interface of Ce-doped Bi2MoO6/TiO2 heterojunction. Moreover, the Ce-doped Bi2MoO6/TiO2 composite nanofibers are of good stability, whose activity is hardly decreased after cycling 5 times.
By employing electrospun TiO2 nanofiber as substrate, rare earth Ce doped Bi2MoO6/TiO2 composite nanofibers were prepared via solvothermal method. The composition, morphology and optical properties were characterized by XRD, SEM, XPS, TEM, UV-Vis DRS and PL analysis. The photocatalytic properties were tested by degradation of rhodamine B under visible light. The results show that Ce3+ ion can be a substitute for Bi3+ in the crystal lattice of Bi2MoO6, resulting in an expansion, distortion of lattice cell and hence defects. Photocatalytic test shows that the activity of TiO2 nanofibers under visible light can be enhanced. For example, the degradation percentage of RhB can be as high as 95.1%, which is believed to benefit from the effective charge generation, transfer and separation at the interface of Ce-doped Bi2MoO6/TiO2 heterojunction. Moreover, the Ce-doped Bi2MoO6/TiO2 composite nanofibers are of good stability, whose activity is hardly decreased after cycling 5 times.
2018, 34(4): 697-702
doi: 10.11862/CJIC.2018.094
Abstract:
The Gd2O3:Yb3+, Nd3+, Tm3+/SiO2/Ag nanocomposite was synthesized by multi-step chemical methods. XRD, TEM, EDS, XPS and CLSM were used to characterize the prepared samples. The results indicate that the upconversion intensity reach to maximum when the doping concentration of Nd3+ and Tm3+ ions reach to 1.0% and 0.5% (n/n) in Gd2O3 matrix with low phonon energy and good chemistry stability, respectively. Moreover, the blue region intensity is enhanced 1.70 times obviously due to the surface plasmon resonance effect by absorbed Ag nanoparticles.
The Gd2O3:Yb3+, Nd3+, Tm3+/SiO2/Ag nanocomposite was synthesized by multi-step chemical methods. XRD, TEM, EDS, XPS and CLSM were used to characterize the prepared samples. The results indicate that the upconversion intensity reach to maximum when the doping concentration of Nd3+ and Tm3+ ions reach to 1.0% and 0.5% (n/n) in Gd2O3 matrix with low phonon energy and good chemistry stability, respectively. Moreover, the blue region intensity is enhanced 1.70 times obviously due to the surface plasmon resonance effect by absorbed Ag nanoparticles.
2018, 34(4): 703-711
doi: 10.11862/CJIC.2018.093
Abstract:
The Li1.2Mn0.6Ni0.2O2 cathode was prepared by five synthesis routes:sol-gel, high temperature solid, coprecipitation, hydrothermal and solvothermal method. The analysis of Raman spectrum shows that the co-precipitation sample is solid solution structure, while the other four samples are composite structures formed at different scales. The results of electrochemical tests for as-prepared samples show obviously different performance, especially the capacity from the activation of Li2MnO3 during the first charging process (> 4.5 V). The co-precipitation sample with solid solution structure shows the highest capacity from the activation of Li2MnO3. Therefore, we can establish the connection between electrochemical performance and two-phase integration modes. Different integration modes affect the activation capacity of Li2MnO3, leading to different electrochemical properties.
The Li1.2Mn0.6Ni0.2O2 cathode was prepared by five synthesis routes:sol-gel, high temperature solid, coprecipitation, hydrothermal and solvothermal method. The analysis of Raman spectrum shows that the co-precipitation sample is solid solution structure, while the other four samples are composite structures formed at different scales. The results of electrochemical tests for as-prepared samples show obviously different performance, especially the capacity from the activation of Li2MnO3 during the first charging process (> 4.5 V). The co-precipitation sample with solid solution structure shows the highest capacity from the activation of Li2MnO3. Therefore, we can establish the connection between electrochemical performance and two-phase integration modes. Different integration modes affect the activation capacity of Li2MnO3, leading to different electrochemical properties.
2018, 34(4): 712-718
doi: 10.11862/CJIC.2018.012
Abstract:
Au@Ag core-shell nanoparticles were prepared by seed-mediated growth method. The plasmon resonance properties of the core-shell nanoparticles are highly dependent on the size and shape of the core and thickness of the shell, which could be simply adjusted by varying the concentration of HAuCl4 and the volume of AgNO3. The prepared core-shell nanoparticles exhibit excellent SERS performance as substrate to detect rhodamine 6G (R6G). In addition, the precise control of core-shell morphologies (core size and shape, the thickness of the shell) is of significant importance as it strongly determines the overall SERS performance in micro chemical detection.
Au@Ag core-shell nanoparticles were prepared by seed-mediated growth method. The plasmon resonance properties of the core-shell nanoparticles are highly dependent on the size and shape of the core and thickness of the shell, which could be simply adjusted by varying the concentration of HAuCl4 and the volume of AgNO3. The prepared core-shell nanoparticles exhibit excellent SERS performance as substrate to detect rhodamine 6G (R6G). In addition, the precise control of core-shell morphologies (core size and shape, the thickness of the shell) is of significant importance as it strongly determines the overall SERS performance in micro chemical detection.
2018, 34(4): 719-727
doi: 10.11862/CJIC.2018.086
Abstract:
Two coordination polymers, [Zn(CH3COO)2(INH)]n (INH=isonicotinic acid hydrazid; isoniazid) (1) and[Zn(CH3COO)2(2-APy)]n (2-APy=2-aminopyridine) (2) have been synthesized in DMF solution and structurally characterized by elemental analysis, IR spectra, single-crystal and powder X-ray diffractions. Structural analyses reveal that polymer 1 exhibits a 2-dimensional (2D) infinite layer framework, and the resulting 2D structure is interconnected by hydrogen-bond interactions to lead to a 3D supramolecular architecture. It crystallizes in the monoclinic system, space group P21/c, with cell parameters a=0.914 44(17) nm, b=0.161 86(3) nm, c=0.871 75(16) nm, β=96.181(3)°, V=1.282 8(4) nm3, Z=4. Polymer 2 is an infinite 1D zig-zag chain. Polymer 2 crystallizes in the triclinic system, space group P1, with cell parameters a=0.747 0(4) nm, b=0.814 5(5) nm, c=1.895 7(11) nm, α=88.276(8)°, β=86.202(8)°, γ=84.334(8)°, V=1.144 9(11) nm3, Z=2. The solid-state luminescent properties of two polymers have also been investigated at room temperature.
Two coordination polymers, [Zn(CH3COO)2(INH)]n (INH=isonicotinic acid hydrazid; isoniazid) (1) and[Zn(CH3COO)2(2-APy)]n (2-APy=2-aminopyridine) (2) have been synthesized in DMF solution and structurally characterized by elemental analysis, IR spectra, single-crystal and powder X-ray diffractions. Structural analyses reveal that polymer 1 exhibits a 2-dimensional (2D) infinite layer framework, and the resulting 2D structure is interconnected by hydrogen-bond interactions to lead to a 3D supramolecular architecture. It crystallizes in the monoclinic system, space group P21/c, with cell parameters a=0.914 44(17) nm, b=0.161 86(3) nm, c=0.871 75(16) nm, β=96.181(3)°, V=1.282 8(4) nm3, Z=4. Polymer 2 is an infinite 1D zig-zag chain. Polymer 2 crystallizes in the triclinic system, space group P1, with cell parameters a=0.747 0(4) nm, b=0.814 5(5) nm, c=1.895 7(11) nm, α=88.276(8)°, β=86.202(8)°, γ=84.334(8)°, V=1.144 9(11) nm3, Z=2. The solid-state luminescent properties of two polymers have also been investigated at room temperature.
2018, 34(4): 728-732
doi: 10.11862/CJIC.2018.096
Abstract:
A complex of (BenzMeIm)2[PtCl4] was prepared by the reaction of 1-benzyl-3-methylimidazolium chloride (BenzMeIm-Cl) with PtCl2. The structure of the complex was characterized by single crystal X-ray analysis, and it crystallizes in the monoclinic P21/c space group, with a=0.981 80(5) nm, b=0.861 47(3) nm, c=0.144 332(7) nm, β=92.480(2)°, V=121.96(1) nm3, R1=0.014 4, wR2=0.038 8.
A complex of (BenzMeIm)2[PtCl4] was prepared by the reaction of 1-benzyl-3-methylimidazolium chloride (BenzMeIm-Cl) with PtCl2. The structure of the complex was characterized by single crystal X-ray analysis, and it crystallizes in the monoclinic P21/c space group, with a=0.981 80(5) nm, b=0.861 47(3) nm, c=0.144 332(7) nm, β=92.480(2)°, V=121.96(1) nm3, R1=0.014 4, wR2=0.038 8.
2018, 34(4): 733-738
doi: 10.11862/CJIC.2018.102
Abstract:
Three lanthanide-based coordination polymers, namely {[La(OH)(SO4)]}n (1), {[La2(TDC)2(SUC)]}n (2) and {[Gd2(TDC)2(ox)(H2O)4]·2H2O}n (3) (H2TDC=2, 5-thiophenedi-carboxylic acid, SUC=succinate, ox=oxalate), were synthesized through hydrothermal reaction of H2TDC and Ln(NO3)3 (Ln=La, Gd). Investigation on the crystal structure indicates that complex 2 and 3 feature 3D frameworks. Crystal data are orthorhombic, space group Pbca, a=1.372 8(4) nm, b=0.704 0(2) nm, c=2.136 2(6) nm, Z=8 for 2; and monoclinic, space group, C2/c, a=1.934 3(4) nm, b=0.990 5(2) nm, c=1.252 8(3) nm, β=107.463(4)°, Z=4 for 3.
Three lanthanide-based coordination polymers, namely {[La(OH)(SO4)]}n (1), {[La2(TDC)2(SUC)]}n (2) and {[Gd2(TDC)2(ox)(H2O)4]·2H2O}n (3) (H2TDC=2, 5-thiophenedi-carboxylic acid, SUC=succinate, ox=oxalate), were synthesized through hydrothermal reaction of H2TDC and Ln(NO3)3 (Ln=La, Gd). Investigation on the crystal structure indicates that complex 2 and 3 feature 3D frameworks. Crystal data are orthorhombic, space group Pbca, a=1.372 8(4) nm, b=0.704 0(2) nm, c=2.136 2(6) nm, Z=8 for 2; and monoclinic, space group, C2/c, a=1.934 3(4) nm, b=0.990 5(2) nm, c=1.252 8(3) nm, β=107.463(4)°, Z=4 for 3.
2018, 34(4): 739-749
doi: 10.11862/CJIC.2018.070
Abstract:
Two newly designed tetranuclear complexes, {Cu(L)(OAc)Cu(H2O)}2 (1) and {Zn(L)(OAc)Zn(H2O)}2 (2) derived from an Salamo-type N2O3 donor ligand (H3L) were synthesized and characterized by elemental analyses, IR and UV-Vis spectra, fluorescence spectra and X-ray crystallography. Complex 1 is made up of four Cu(Ⅱ) ions, two deprotonated L3- moieties, two coordinated water molecules and two μ2-acetate ions. All of the Cu(Ⅱ) ions in 1 are penta-coordinated with slightly distorted tetragonal pyramidal and trigonal bipyramidal symmetries. Complex 1 forms an infinite 1D chain supramolecular structure via C-H…π interactions. Complex 2 reveals an asymmetrical tetranuclear structure, and consists of four Zn(Ⅱ) ions, two completely deprotonated L3- units, two μ2-acetate ions and two coordinated water molecules, which possesses an infinite 3D supramolecular structure. The fluorescent properties of H3L and complexes 1 and 2 have also been discussed.
Two newly designed tetranuclear complexes, {Cu(L)(OAc)Cu(H2O)}2 (1) and {Zn(L)(OAc)Zn(H2O)}2 (2) derived from an Salamo-type N2O3 donor ligand (H3L) were synthesized and characterized by elemental analyses, IR and UV-Vis spectra, fluorescence spectra and X-ray crystallography. Complex 1 is made up of four Cu(Ⅱ) ions, two deprotonated L3- moieties, two coordinated water molecules and two μ2-acetate ions. All of the Cu(Ⅱ) ions in 1 are penta-coordinated with slightly distorted tetragonal pyramidal and trigonal bipyramidal symmetries. Complex 1 forms an infinite 1D chain supramolecular structure via C-H…π interactions. Complex 2 reveals an asymmetrical tetranuclear structure, and consists of four Zn(Ⅱ) ions, two completely deprotonated L3- units, two μ2-acetate ions and two coordinated water molecules, which possesses an infinite 3D supramolecular structure. The fluorescent properties of H3L and complexes 1 and 2 have also been discussed.
2018, 34(4): 750-756
doi: 10.11862/CJIC.2018.074
Abstract:
NaNi1/3Co1/3Mn1/3O2 material was synthesized by a facile method, and the suitable working voltages (3.75 V, 4 V) are investigated afterwards. The mechanisms of capacity fading when charging to 4 V are studied by ex-situ XRD and EIS measurements, which revealed a collective effect between the thicker of the SEI layer and the irreversible variation of the material structure.
NaNi1/3Co1/3Mn1/3O2 material was synthesized by a facile method, and the suitable working voltages (3.75 V, 4 V) are investigated afterwards. The mechanisms of capacity fading when charging to 4 V are studied by ex-situ XRD and EIS measurements, which revealed a collective effect between the thicker of the SEI layer and the irreversible variation of the material structure.
2018, 34(4): 757-766
doi: 10.11862/CJIC.2018.104
Abstract:
Three novel complexes, namely {[Zn3(L)2(SO4)2(H2O)4]·H2O}n (1), {[Cd2(L)2(SO4)(H2O)]·H2O}n (2) and {[Cd(L)I]·CH3OH}n (3).(HL=N'-nicotinoylpyrazine-2-carbohydrazonamide), have been synthesized and character-ized by elemental analyses, infrared spectra and single-crystal X-ray diffraction analyze.In complex 1, Zn(Ⅱ) ions are connected by μ3, η1η1η1-SO42- anions to form a inorganic layer motif in bc plane, and the L- ligands are decorated on both sides of the layer.Adjacent layers are connected by hydrogen-bonding interactions giving rise to 3D supramolecular network.The 2D complex 2 is formed by the[(Cd2)2(μ2-SO4)2] units and Cd1 ions which are connected by the ligands.Adjacent layers of 2 are extended into 3D supramolecular network by π…π interactions.Zigzag 1D chains of complex 3 are connected by intermolecular hydrogen bonds into extended plane structure.The photocatalytic degradation of methylene blue (MB) results indicate that complexes 1~3 are excellent candidates as photocatalysts in decomposing MB with the presence of H2O2.In addition, the luminescent properties of these three complexes have been studied in the solid-state.
Three novel complexes, namely {[Zn3(L)2(SO4)2(H2O)4]·H2O}n (1), {[Cd2(L)2(SO4)(H2O)]·H2O}n (2) and {[Cd(L)I]·CH3OH}n (3).(HL=N'-nicotinoylpyrazine-2-carbohydrazonamide), have been synthesized and character-ized by elemental analyses, infrared spectra and single-crystal X-ray diffraction analyze.In complex 1, Zn(Ⅱ) ions are connected by μ3, η1η1η1-SO42- anions to form a inorganic layer motif in bc plane, and the L- ligands are decorated on both sides of the layer.Adjacent layers are connected by hydrogen-bonding interactions giving rise to 3D supramolecular network.The 2D complex 2 is formed by the[(Cd2)2(μ2-SO4)2] units and Cd1 ions which are connected by the ligands.Adjacent layers of 2 are extended into 3D supramolecular network by π…π interactions.Zigzag 1D chains of complex 3 are connected by intermolecular hydrogen bonds into extended plane structure.The photocatalytic degradation of methylene blue (MB) results indicate that complexes 1~3 are excellent candidates as photocatalysts in decomposing MB with the presence of H2O2.In addition, the luminescent properties of these three complexes have been studied in the solid-state.
2018, 34(4): 767-776
doi: 10.11862/CJIC.2018.077
Abstract:
Graphene/CdTe quantum dots composites had been successfully synthesized, which was characterized by using transmission electron microscope, absorbance spectrum, fluorescence emission spectrum, fluorescence decay curve and X-ray photoelectron spectroscopy. Transmission electron microscope results indicate that CdTe quantum dots have successfully decorated on the surface of graphene. X-ray photoelectron spectroscopy results indicate that graphene has been reduced and have carboxyl and hydroxyl groups on its surface. Fluorescence emission spectrum indicate that the fluorescence property of CdTe quantum dots has been significantly improved after decorating CdTe quantum dots on the surface of graphene. Furthermore graphene/CdTe quantum dots composites were used to quantitative analysis clenbuterol base on the formation of hydrogen bond between clenbuterol and graphene/CdTe quantum dots composites. The fluorescence of graphene/CdTe quantum dots composites can be efficiently quenched by clenbuterol, and there is a good line relationship between the fluorescence intensity decreasing (F0/F) and the concentration of clenbuterol in the range from 7.22~108.30 μmol·L-1 with the detection limit of 4 μmol·L-1.
Graphene/CdTe quantum dots composites had been successfully synthesized, which was characterized by using transmission electron microscope, absorbance spectrum, fluorescence emission spectrum, fluorescence decay curve and X-ray photoelectron spectroscopy. Transmission electron microscope results indicate that CdTe quantum dots have successfully decorated on the surface of graphene. X-ray photoelectron spectroscopy results indicate that graphene has been reduced and have carboxyl and hydroxyl groups on its surface. Fluorescence emission spectrum indicate that the fluorescence property of CdTe quantum dots has been significantly improved after decorating CdTe quantum dots on the surface of graphene. Furthermore graphene/CdTe quantum dots composites were used to quantitative analysis clenbuterol base on the formation of hydrogen bond between clenbuterol and graphene/CdTe quantum dots composites. The fluorescence of graphene/CdTe quantum dots composites can be efficiently quenched by clenbuterol, and there is a good line relationship between the fluorescence intensity decreasing (F0/F) and the concentration of clenbuterol in the range from 7.22~108.30 μmol·L-1 with the detection limit of 4 μmol·L-1.
2018, 34(4): 777-783
doi: 10.11862/CJIC.2018.098
Abstract:
Using palladium nitrate and silver nitrate as the metal precursor, ethanol and sodium citrate tribasic dehydrate as reducing agents and poly(vinyl pyrrolidone) (PVP) as a stabilizer and guiding agent, Pd-Ag alloy nanowires were synthesized via visible-light-assisted solution approach with a commercial incandescent lamp as light source. The morphologies, crystal structure and optical properties were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), power X-ray diffraction (PXRD), and UV-visible spectroscopy, respectively. The electrocatalytic properties of the Pd-Ag alloy nanowires modified glassy carbon electrode for ethanol oxidation were investigated by cyclic voltammetry and chronoamperometry. The Pd-Ag alloy nanowires exhibited much better electrocatalytic performance than Pd nanoparticles toward ethanol oxidation reaction in alkaline media in terms of the electrocatalytic activity, anti-poisoning ability and stability.
Using palladium nitrate and silver nitrate as the metal precursor, ethanol and sodium citrate tribasic dehydrate as reducing agents and poly(vinyl pyrrolidone) (PVP) as a stabilizer and guiding agent, Pd-Ag alloy nanowires were synthesized via visible-light-assisted solution approach with a commercial incandescent lamp as light source. The morphologies, crystal structure and optical properties were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), power X-ray diffraction (PXRD), and UV-visible spectroscopy, respectively. The electrocatalytic properties of the Pd-Ag alloy nanowires modified glassy carbon electrode for ethanol oxidation were investigated by cyclic voltammetry and chronoamperometry. The Pd-Ag alloy nanowires exhibited much better electrocatalytic performance than Pd nanoparticles toward ethanol oxidation reaction in alkaline media in terms of the electrocatalytic activity, anti-poisoning ability and stability.
2018, 34(4): 784-790
doi: 10.11862/CJIC.2018.099
Abstract:
Amorphous La0.75Sr0.25MnO3(a-LSMO) was deposited by pulsed laser deposition (PLD) as an interlayer of a resistive-switching device (Ag/a-LSMO/ITO) with good non-volatile and bipolar resistance switching behaviour.Bottom ITO substrate and ultra-thin a-LSMO layer allow semi-transparent device fabrication.The formation of Ag filament connected from Ag electrode to ITO electrode is directly observed in the cross-sectional image by the high-resolution transmission electron microscope (HRTEM).The resistive switching in the device is attributed to the growth and dissolution of Ag filament in the amorphous LSMO layer.
Amorphous La0.75Sr0.25MnO3(a-LSMO) was deposited by pulsed laser deposition (PLD) as an interlayer of a resistive-switching device (Ag/a-LSMO/ITO) with good non-volatile and bipolar resistance switching behaviour.Bottom ITO substrate and ultra-thin a-LSMO layer allow semi-transparent device fabrication.The formation of Ag filament connected from Ag electrode to ITO electrode is directly observed in the cross-sectional image by the high-resolution transmission electron microscope (HRTEM).The resistive switching in the device is attributed to the growth and dissolution of Ag filament in the amorphous LSMO layer.
2018, 34(4): 791-799
doi: 10.11862/CJIC.2018.097
Abstract:
Under hydrothermal conditions, two novel polyoxometalate (POM)-based CuⅡ and CuⅠ hybrid materials, namely[Cu2(4-NH2-trz)4(Mo8O26)(H2O)4]·5H2O (1) and[Cu4(4-NH2-trz)4Mo8O26] (2) (4-NH2-trz=4-amino-1, 2, 4-triazole) have been designed and synthesized. Their crystal structures have been determined by single crystal X-ray diffraction, FT-IR infrared spectra and powder X-ray diffraction analysis. In 1, bi-dentate 4-NH2-trz ligands bridge two neighboring CuⅡ centers forming dinuclear structural units, which are further linked by Mo8O264- ions and arranged into a one-dimensional (1D) hybrid coordination framework. In 2, bidentate 4-NH2-trz ligands also link neighboring CuⅠ centers to generate unique 1D[Cu4(4-NH2-trz)4]n helical chains. Further these infinite right-hand and left-hand helical chains are linked by (β-Mo8O26)4- anions to form a 2D hybrid framework. Photocatalytic activities for decomposition of different organic dyes (methylene blue (MB), rhodamine B (RhB) and methyl orange (MO)) have been investigated for 1 and 2, indicating that 1 and 2 are good candidates for the photocatalytic degradation of these organic dyes.
Under hydrothermal conditions, two novel polyoxometalate (POM)-based CuⅡ and CuⅠ hybrid materials, namely[Cu2(4-NH2-trz)4(Mo8O26)(H2O)4]·5H2O (1) and[Cu4(4-NH2-trz)4Mo8O26] (2) (4-NH2-trz=4-amino-1, 2, 4-triazole) have been designed and synthesized. Their crystal structures have been determined by single crystal X-ray diffraction, FT-IR infrared spectra and powder X-ray diffraction analysis. In 1, bi-dentate 4-NH2-trz ligands bridge two neighboring CuⅡ centers forming dinuclear structural units, which are further linked by Mo8O264- ions and arranged into a one-dimensional (1D) hybrid coordination framework. In 2, bidentate 4-NH2-trz ligands also link neighboring CuⅠ centers to generate unique 1D[Cu4(4-NH2-trz)4]n helical chains. Further these infinite right-hand and left-hand helical chains are linked by (β-Mo8O26)4- anions to form a 2D hybrid framework. Photocatalytic activities for decomposition of different organic dyes (methylene blue (MB), rhodamine B (RhB) and methyl orange (MO)) have been investigated for 1 and 2, indicating that 1 and 2 are good candidates for the photocatalytic degradation of these organic dyes.
2018, 34(4): 800-806
doi: 10.11862/CJIC.2018.088
Abstract:
The ZrO2-Al2O3 composite oxides with different mass ratio of ZrO2 to Al2O3 were prepared by co-precipitation method. 1.5%Pt/ZrO2-Al2O3 (w/w) serial catalysts were prepared by isovolume impregnation method. The catalytic performance for C3H6 and CO oxidation show that Pt/Zr(0.4)-Al catalyst owns the most excellent catalytic activity. The temperature of light-off (T50) and the complete conversion temperature (T90) were less than 125 and 150℃ respectively. The effects of catalyst phase structure, specific surface area and particle size on the catalytic activity were investigated by XRD, N2 adsorption-desorption, H2-TPR and CO pulse adsorption. It is found that ZrO2-Al2O3 composite oxides have the mesoporous texture, large specific surface area, and a new phase of AlxZr1-xOy solid solution was also produced. The mass ratio of ZrO2 to Al2O3 is the key to improving the interaction between Pt and ZrO2-Al2O3, promoting the dispersion of Pt and enhancing the low temperature oxidation activity of Pt/ZrO2-Al2O3 catalyst.
The ZrO2-Al2O3 composite oxides with different mass ratio of ZrO2 to Al2O3 were prepared by co-precipitation method. 1.5%Pt/ZrO2-Al2O3 (w/w) serial catalysts were prepared by isovolume impregnation method. The catalytic performance for C3H6 and CO oxidation show that Pt/Zr(0.4)-Al catalyst owns the most excellent catalytic activity. The temperature of light-off (T50) and the complete conversion temperature (T90) were less than 125 and 150℃ respectively. The effects of catalyst phase structure, specific surface area and particle size on the catalytic activity were investigated by XRD, N2 adsorption-desorption, H2-TPR and CO pulse adsorption. It is found that ZrO2-Al2O3 composite oxides have the mesoporous texture, large specific surface area, and a new phase of AlxZr1-xOy solid solution was also produced. The mass ratio of ZrO2 to Al2O3 is the key to improving the interaction between Pt and ZrO2-Al2O3, promoting the dispersion of Pt and enhancing the low temperature oxidation activity of Pt/ZrO2-Al2O3 catalyst.
