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2019 Volume 35 Issue 2
Crystallization Mechanism and Performance in Methanol to Olefins Reaction of SAPO-18 Molecular Sieve
2019, 35(2): 185-193
doi: 10.11862/CJIC.2019.044
Abstract:
SAPO-18 molecular sieves with the different crystallization times were prepared by hydrothermal method, which respectively taking the pseudo-boehmite, silica sol and phosphoric acid as the aluminum source, silicon source, phosphorus source, and N, N-diisopropylethylamine as the template. The samples at different crystallization times and its MTO (methanol to olefins) catalytic performance were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), NH3-TPD, 29Si MAS NMR, 27Al MAS NMR, FT-IR and other methods. The characterization results combined with the catalytic performance of MTO indicated that the growth process of SAPO-18 molecular sieve in the hydrothermal system could be divided into three stages:initial crystallization (≤ 2 h), rapid growth (6~12 h) and stable growth (1~3 d). In the early stage of crystallization, only a small amount of silicon enter the Al(PO)4 intermediates. The silicon atoms then enter the Al(PO)4 intermediates and SAPO-18 crystal, and replace phosphorus and aluminum atoms. SMⅡ mechanism is as the priority and SMⅢ mechanism is as the auxiliary pole in the fast growing period. The two substitution mechanisms of growth stabilization are in the opposite order.
SAPO-18 molecular sieves with the different crystallization times were prepared by hydrothermal method, which respectively taking the pseudo-boehmite, silica sol and phosphoric acid as the aluminum source, silicon source, phosphorus source, and N, N-diisopropylethylamine as the template. The samples at different crystallization times and its MTO (methanol to olefins) catalytic performance were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), NH3-TPD, 29Si MAS NMR, 27Al MAS NMR, FT-IR and other methods. The characterization results combined with the catalytic performance of MTO indicated that the growth process of SAPO-18 molecular sieve in the hydrothermal system could be divided into three stages:initial crystallization (≤ 2 h), rapid growth (6~12 h) and stable growth (1~3 d). In the early stage of crystallization, only a small amount of silicon enter the Al(PO)4 intermediates. The silicon atoms then enter the Al(PO)4 intermediates and SAPO-18 crystal, and replace phosphorus and aluminum atoms. SMⅡ mechanism is as the priority and SMⅢ mechanism is as the auxiliary pole in the fast growing period. The two substitution mechanisms of growth stabilization are in the opposite order.
2019, 35(2): 203-208
doi: 10.11862/CJIC.2019.029
Abstract:
Europiumsesquioxide (Eu2O3), parachlorobenzoic-acid (PCBA), parabromobenzoic acid (PBrBA) and o-phenanthroline (phen) were used as raw materials to synthesize two kinds of probe molecules Eu(PCBA)3phen and Eu(PBrBA)3phen. And these two probe molecules were doped in the substrate of polymethyl methacrylate (MMA), benzoyl (BPO) peroxide as initiator, to prepare two kinds of temperature sensitive paints. The infrared spectrometer, ultraviolet spectrometer, scanning electron microscope and fluorescence spectrometer were utilized to analyze the structure, fluorescence properties, morphology and temperature sensitivity of the probes, respectively. Meanwhile the effects of different ligands on the fluorescence properties of the probe molecules and the relevant temperature sensitive paints were studied. The results showed that Eu3+ was coordinated with the main ligand of PCBA and PBrBA, respectively, and the second ligand phen was involved in the coordination, which confirms that two new complexes were synthesized. Both complexes emit characteristic fluorescence of Eu3+, and the ternary complex of phenanthroline europium with PBrBA as the main ligand has better fluorescent properties. Furthermore, the temperature sensitive paints based on these two probes both had temperature-quenching performance in a range of 50~90℃, and the temperature sensitive paint doped with Eu(PCBA)3phen had better temperature sensitivity.
Europiumsesquioxide (Eu2O3), parachlorobenzoic-acid (PCBA), parabromobenzoic acid (PBrBA) and o-phenanthroline (phen) were used as raw materials to synthesize two kinds of probe molecules Eu(PCBA)3phen and Eu(PBrBA)3phen. And these two probe molecules were doped in the substrate of polymethyl methacrylate (MMA), benzoyl (BPO) peroxide as initiator, to prepare two kinds of temperature sensitive paints. The infrared spectrometer, ultraviolet spectrometer, scanning electron microscope and fluorescence spectrometer were utilized to analyze the structure, fluorescence properties, morphology and temperature sensitivity of the probes, respectively. Meanwhile the effects of different ligands on the fluorescence properties of the probe molecules and the relevant temperature sensitive paints were studied. The results showed that Eu3+ was coordinated with the main ligand of PCBA and PBrBA, respectively, and the second ligand phen was involved in the coordination, which confirms that two new complexes were synthesized. Both complexes emit characteristic fluorescence of Eu3+, and the ternary complex of phenanthroline europium with PBrBA as the main ligand has better fluorescent properties. Furthermore, the temperature sensitive paints based on these two probes both had temperature-quenching performance in a range of 50~90℃, and the temperature sensitive paint doped with Eu(PCBA)3phen had better temperature sensitivity.
2019, 35(2): 209-216
doi: 10.11862/CJIC.2019.038
Abstract:
A series of Ce3+-and Ce3+/Tb3+-activated Ba10(PO4)6F2 phosphors with apatite structure have been synthesized via high temperature solid-state reaction. X-ray diffraction (XRD), scanning electron microscopy (SEM), the photoluminenscence excitation (PLE) spectra and photoluminescence (PL) spectra were used to characterize samples. The results revealed that the fluorapatite structured Ba10(PO4)6F2:Ce3+, Tb3+ phosphor particles with irregular morphology have been obtained. The relative intensities of PL spectra of Ba10-x(PO4)6F2:xCe3+ phosphors increased with increasing x values, and reached the maximum at x=0.09. The as-prepared phosphors Ba10(PO4)6F2:Ce3+, Tb3+ phosphors exhibited broad excitation band ranging from 240 to 330 nm. The emission spectra of Ba10(PO4)6F2:Ce3+, Tb3+ phosphor showed the violet-emitting band centered at 335 and 358 nm and green light-emitting band centered at 542 nm, which originate from the 5d→4f transitions of Ce3+ and 4f→4f transitions of Tb3+, respectively. The spectral characteristics showed that the energy transfer occurs from Ce3+ to Tb3+ in Ba10(PO4)6F2:Ce3+, Tb3+ phosphors, and the energy transfer efficiency between Ce3+ and Tb3+ could reach up to 60%. The critical distance of Ce3+ and Tb3+ was calculated to be 0.79 nm, and the mechanism of energy transfer from Ce3+ to Tb3+ is dipole-dipole interaction. In addition, the energy transfer behavior and luminescence process were discussed in detail. By adjusting the concentration of Tb3+, the relationship between chromatic coordinate and the doping concentration of Tb3+ was studied. The Ba10(PO4)6F2:Ce3+, Tb3+ phosphors emission color could adjust from blue to green, and the chromatic coordinate tuned from (0.149 4, 0.045 1) to (0.280 1, 0.585 3) with increasing the concentration of Tb3+ from 0 to 0.52.
A series of Ce3+-and Ce3+/Tb3+-activated Ba10(PO4)6F2 phosphors with apatite structure have been synthesized via high temperature solid-state reaction. X-ray diffraction (XRD), scanning electron microscopy (SEM), the photoluminenscence excitation (PLE) spectra and photoluminescence (PL) spectra were used to characterize samples. The results revealed that the fluorapatite structured Ba10(PO4)6F2:Ce3+, Tb3+ phosphor particles with irregular morphology have been obtained. The relative intensities of PL spectra of Ba10-x(PO4)6F2:xCe3+ phosphors increased with increasing x values, and reached the maximum at x=0.09. The as-prepared phosphors Ba10(PO4)6F2:Ce3+, Tb3+ phosphors exhibited broad excitation band ranging from 240 to 330 nm. The emission spectra of Ba10(PO4)6F2:Ce3+, Tb3+ phosphor showed the violet-emitting band centered at 335 and 358 nm and green light-emitting band centered at 542 nm, which originate from the 5d→4f transitions of Ce3+ and 4f→4f transitions of Tb3+, respectively. The spectral characteristics showed that the energy transfer occurs from Ce3+ to Tb3+ in Ba10(PO4)6F2:Ce3+, Tb3+ phosphors, and the energy transfer efficiency between Ce3+ and Tb3+ could reach up to 60%. The critical distance of Ce3+ and Tb3+ was calculated to be 0.79 nm, and the mechanism of energy transfer from Ce3+ to Tb3+ is dipole-dipole interaction. In addition, the energy transfer behavior and luminescence process were discussed in detail. By adjusting the concentration of Tb3+, the relationship between chromatic coordinate and the doping concentration of Tb3+ was studied. The Ba10(PO4)6F2:Ce3+, Tb3+ phosphors emission color could adjust from blue to green, and the chromatic coordinate tuned from (0.149 4, 0.045 1) to (0.280 1, 0.585 3) with increasing the concentration of Tb3+ from 0 to 0.52.
2019, 35(2): 217-224
doi: 10.11862/CJIC.2019.022
Abstract:
Graphitic carbon nitride hybridized with a small number of carbon nanotubes (CNT) was synthesized using urea as precursor. The resulting CNT/g-C3N4 composite photocatalysts were characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), Fourier infrared spectrometer (FT-IR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible-near infrared Reflection Spectrophotometer (UV-Vis-NIR Spectrophotometer) and photoluminescence spectroscopy (PL). Results indicate that the synergistic interaction between CNT and g-C3N4 changed the optical properties of bulk g-C3N4, affected the energy band structure, enhanced the absorption of visible light, optimized the distribution of the photogenerated carrier and improved the electron-hole separation rate. The photocatalytic degradation of rhodamine B solution (RhB) was performed under visible light irradiation. The photocatalytic activity of CNT/g-C3N4 composite was the highest when 0.1%(w/w) CNT was loaded on the substrate, the rate constant for the photocatalyst was 3.1 times as high as that of pure g-C3N4. It was also found that the superoxide radical was the main active species for catalytic degradation in this system.
Graphitic carbon nitride hybridized with a small number of carbon nanotubes (CNT) was synthesized using urea as precursor. The resulting CNT/g-C3N4 composite photocatalysts were characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), Fourier infrared spectrometer (FT-IR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible-near infrared Reflection Spectrophotometer (UV-Vis-NIR Spectrophotometer) and photoluminescence spectroscopy (PL). Results indicate that the synergistic interaction between CNT and g-C3N4 changed the optical properties of bulk g-C3N4, affected the energy band structure, enhanced the absorption of visible light, optimized the distribution of the photogenerated carrier and improved the electron-hole separation rate. The photocatalytic degradation of rhodamine B solution (RhB) was performed under visible light irradiation. The photocatalytic activity of CNT/g-C3N4 composite was the highest when 0.1%(w/w) CNT was loaded on the substrate, the rate constant for the photocatalyst was 3.1 times as high as that of pure g-C3N4. It was also found that the superoxide radical was the main active species for catalytic degradation in this system.
2019, 35(2): 225-235
doi: 10.11862/CJIC.2019.014
Abstract:
Using pyrazine-2-carboxylic acid (2-Hpzc), 3, 5-pyridinedicarboxylic acid (3, 5-H2PDA) and oxalic acid (H2ox) as ligands, nine Ag-Ln coordination polymers are synthesized by hydrothermal methods:{[LnAg(2-pzc)2(ox)]·H2O}n (Ln=Pr (1), Nd (2), Sm (3), Eu (4)), [LnAg(3, 5-PDA)(ox)(H2O)]n (Ln=Pr (5), Nd (6)), [LnAg(3, 5-PDA)(3, 5-HPDA)(ox)0.5(H2O)2]n (Ln=Sm (7), Dy (8), Ho (9)). All of them possess the 3D network structure, i.e., coordination polymers 1~4 are isomorphic and connected by 2-pzc- and ox2-, while coordination polymers 5~9 use 3, 5-PDA2- and ox2- as bridging ligands. Photophysical properties of these coordination polymers are studied, and they show characteristic emissions of corresponding Ln(Ⅲ) ions which should be attributed to the sensitization of the Ag-ligand section (d-block). In addition, under the co-action of crystal field and 4d orbits of Ag(Ⅰ) ion, the 4f orbits of Ln(Ⅲ) ions are tuned and cause obvious shift of partial energy levels, which present shifts of the corresponding NIR emission bands and can be corroborated in their UV-Vis-NIR absorption spectra.
Using pyrazine-2-carboxylic acid (2-Hpzc), 3, 5-pyridinedicarboxylic acid (3, 5-H2PDA) and oxalic acid (H2ox) as ligands, nine Ag-Ln coordination polymers are synthesized by hydrothermal methods:{[LnAg(2-pzc)2(ox)]·H2O}n (Ln=Pr (1), Nd (2), Sm (3), Eu (4)), [LnAg(3, 5-PDA)(ox)(H2O)]n (Ln=Pr (5), Nd (6)), [LnAg(3, 5-PDA)(3, 5-HPDA)(ox)0.5(H2O)2]n (Ln=Sm (7), Dy (8), Ho (9)). All of them possess the 3D network structure, i.e., coordination polymers 1~4 are isomorphic and connected by 2-pzc- and ox2-, while coordination polymers 5~9 use 3, 5-PDA2- and ox2- as bridging ligands. Photophysical properties of these coordination polymers are studied, and they show characteristic emissions of corresponding Ln(Ⅲ) ions which should be attributed to the sensitization of the Ag-ligand section (d-block). In addition, under the co-action of crystal field and 4d orbits of Ag(Ⅰ) ion, the 4f orbits of Ln(Ⅲ) ions are tuned and cause obvious shift of partial energy levels, which present shifts of the corresponding NIR emission bands and can be corroborated in their UV-Vis-NIR absorption spectra.
2019, 35(2): 236-244
doi: 10.11862/CJIC.2019.040
Abstract:
Attapulgite (ATP) was chosen as the matrix of g-C3N4 thin layer and AgFeO2 nanoparticles to fabricate a series of ATP/g-C3N4-AgFeO2-Y composites presenting both magnetic separation and high photocatalytic activity by in-situ chemical method, where Y stands for the mass percentage of ATP/g-C3N4 in the composite (Y=wATP/g-C3N4/(wATP/g-C3N4+wAgFO2)×100%). XRD, SEM, BET, UV-Vis, PL and ICP were used to characterize the structure and physicochemical properties of the products. Photodegradation of acid red G (ARG) was chosen as target to investigate the photocatalytic property of all the products. It was found that g-C3N4 thin layer was uniformly fixed on the surface of the ATP by forming a Si-O-C bond, while the AgFeO2 nanoparticles were deposited on the surface of ATP/g-C3N4 uniformly to form a type Z heterojunction structure. ATP/g-C3N4-AgFeO2-Y presented higher visible light photocatalytic performance than that of ATP/g-C3N4 and AgFeO2. The photocatalytic activity of ATP/g-C3N4-AgFeO2-Y changed with the content of ATP/g-C3N4, and when Y=57%, ATP/g-C3N4-AgFeO2-57% shows the best photocatalytic activity. The degradation rate of 20 mg·L-1 acid red G was up to 97.4%, and it remained at 94.2% after 4 cycles when catalyzed by ATP/g-C3N4-AgFeO2-57%. The photocatalytic mechanism was studied by free radical trapping experiments. It was found that·O2- is the main active species in the photocatalytic process.
Attapulgite (ATP) was chosen as the matrix of g-C3N4 thin layer and AgFeO2 nanoparticles to fabricate a series of ATP/g-C3N4-AgFeO2-Y composites presenting both magnetic separation and high photocatalytic activity by in-situ chemical method, where Y stands for the mass percentage of ATP/g-C3N4 in the composite (Y=wATP/g-C3N4/(wATP/g-C3N4+wAgFO2)×100%). XRD, SEM, BET, UV-Vis, PL and ICP were used to characterize the structure and physicochemical properties of the products. Photodegradation of acid red G (ARG) was chosen as target to investigate the photocatalytic property of all the products. It was found that g-C3N4 thin layer was uniformly fixed on the surface of the ATP by forming a Si-O-C bond, while the AgFeO2 nanoparticles were deposited on the surface of ATP/g-C3N4 uniformly to form a type Z heterojunction structure. ATP/g-C3N4-AgFeO2-Y presented higher visible light photocatalytic performance than that of ATP/g-C3N4 and AgFeO2. The photocatalytic activity of ATP/g-C3N4-AgFeO2-Y changed with the content of ATP/g-C3N4, and when Y=57%, ATP/g-C3N4-AgFeO2-57% shows the best photocatalytic activity. The degradation rate of 20 mg·L-1 acid red G was up to 97.4%, and it remained at 94.2% after 4 cycles when catalyzed by ATP/g-C3N4-AgFeO2-57%. The photocatalytic mechanism was studied by free radical trapping experiments. It was found that·O2- is the main active species in the photocatalytic process.
2019, 35(2): 245-253
doi: 10.11862/CJIC.2019.030
Abstract:
Intermediate temperature solid oxide fuel cells (IT-SOFCs) cathode materials Pr1-xSrCo0.5Ni0.5O4+δ (P1-xSCN, x=0.0, 0.05, 0.10, 0.15, 0.20) are synthesized by solid-state reaction method. The phase, thermal expansion coefficient (TEC), conductivity, electrode morphology and electrochemical properties are characterized. XRD results show that the oxides crystallize in a single K2NiF4 structure with a space group of I4/mmm. The cathode materials exhibited good high temperature chemical compatibility with electrolyte Ce0.9Gd0.1O1.95 (CGO). Iodometry analysis shows that with the increase of Pr3+ vacancy concentration, the average valence of Co/Ni ions in oxides increased stepwise with the increase of x and then decreased after x=0.10, while the content of oxygen vacancy increased gradually. Introducing Pr3+ vacancy significantly improved the conductivity of the material. The highest conductivity of 309 S·cm-1 was found in P0.90SCN at 700℃ in air. The thermal expansion measurement results show that TEC increased with the increase of Pr3+ deficiency, and the maximum value is 1.51×10-5 K-1. Electrochemical impedance spectroscopy (EIS) measurements show that Pr vacancy significantly reduced the polarization resistance of the electrode, and the smallest polarization resistance of 0.21 Ω·cm2 was obtained on P0.90SCN cathode at 700℃ in air. The maximum output power density of electrolyte supported single cell NiO-CGO/CGO/P0.90SCN was 197.8 mW·cm-2 at 700℃.
Intermediate temperature solid oxide fuel cells (IT-SOFCs) cathode materials Pr1-xSrCo0.5Ni0.5O4+δ (P1-xSCN, x=0.0, 0.05, 0.10, 0.15, 0.20) are synthesized by solid-state reaction method. The phase, thermal expansion coefficient (TEC), conductivity, electrode morphology and electrochemical properties are characterized. XRD results show that the oxides crystallize in a single K2NiF4 structure with a space group of I4/mmm. The cathode materials exhibited good high temperature chemical compatibility with electrolyte Ce0.9Gd0.1O1.95 (CGO). Iodometry analysis shows that with the increase of Pr3+ vacancy concentration, the average valence of Co/Ni ions in oxides increased stepwise with the increase of x and then decreased after x=0.10, while the content of oxygen vacancy increased gradually. Introducing Pr3+ vacancy significantly improved the conductivity of the material. The highest conductivity of 309 S·cm-1 was found in P0.90SCN at 700℃ in air. The thermal expansion measurement results show that TEC increased with the increase of Pr3+ deficiency, and the maximum value is 1.51×10-5 K-1. Electrochemical impedance spectroscopy (EIS) measurements show that Pr vacancy significantly reduced the polarization resistance of the electrode, and the smallest polarization resistance of 0.21 Ω·cm2 was obtained on P0.90SCN cathode at 700℃ in air. The maximum output power density of electrolyte supported single cell NiO-CGO/CGO/P0.90SCN was 197.8 mW·cm-2 at 700℃.
2019, 35(2): 254-262
doi: 10.11862/CJIC.2019.033
Abstract:
Double perovskite Sr2NixCo2-xO6 (x=0.2, 0.4, 0.6, 0.8) with different Ni doping ratios were prepared by sol-gel method, and nanoparticles g-C3N4 with layered structure was prepared by thermal decomposition. Synthesis of double perovskite and g-C3N4 composite that were used as bifunctional catalysts, which were prepared into bifunctional electrodes, and used to test its catalytic activity for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Then, the doping ratio (x=0.4) of Ni in double perovskite with the best oxygen catalytic activity was selected to be composited with a certain weight ratio of g-C3N4, testing the catalytic activity of the composite catalysts. The results show that the composite catalysts were obviously better than the single catalysts. When the amount of g-C3N4 added was 30% of the mass of the double perovskite, the maximum current densities of the catalytic ORR was 395.7 mA·cm-2 (-0.6 V vs Hg/HgO), the catalytic OER was 372.0 mA·cm-2 (1 V vs Hg/HgO). This indicates that the synergistic catalysis of g-C3N4 and Sr2Ni0.4Co1.6O6 could improve the catalytic activity of the double perovskite.
Double perovskite Sr2NixCo2-xO6 (x=0.2, 0.4, 0.6, 0.8) with different Ni doping ratios were prepared by sol-gel method, and nanoparticles g-C3N4 with layered structure was prepared by thermal decomposition. Synthesis of double perovskite and g-C3N4 composite that were used as bifunctional catalysts, which were prepared into bifunctional electrodes, and used to test its catalytic activity for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Then, the doping ratio (x=0.4) of Ni in double perovskite with the best oxygen catalytic activity was selected to be composited with a certain weight ratio of g-C3N4, testing the catalytic activity of the composite catalysts. The results show that the composite catalysts were obviously better than the single catalysts. When the amount of g-C3N4 added was 30% of the mass of the double perovskite, the maximum current densities of the catalytic ORR was 395.7 mA·cm-2 (-0.6 V vs Hg/HgO), the catalytic OER was 372.0 mA·cm-2 (1 V vs Hg/HgO). This indicates that the synergistic catalysis of g-C3N4 and Sr2Ni0.4Co1.6O6 could improve the catalytic activity of the double perovskite.
2019, 35(2): 263-270
doi: 10.11862/CJIC.2019.028
Abstract:
The Bi/BiVO4&Bi4V2O11 nanocomposite photocatalytic material was prepared by solvothermal reaction and photo-assisted reduction process. The composites were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), high resolution transmission electron microscope (HRTEM), X-ray photo-electron spectroscopy (XPS), ultraviolet visible diffuse reflection spectra (UV-Vis DRS), nitrogen absorption-desorption isotherms and photoluminescence (PL) methods. The experimental results show that when the mass ratio of metal Bi to BiVO4&Bi4V2O11 is 0.8 and the visible light was irradiated for 30 min, the degradation rate of rhodamine B (RhB) could reach 95.6% over Bi/BiVO4&Bi4V2O11 composite catalysts. Besides, Bi/BiVO4& Bi4V2O11 also exhibited enhanced photocatalytic properties for the degradation of tetracycline (TC). The enhanced photocatalytic performance of Bi/BiVO4&Bi4V2O11 might be attributed to the surface plasmonic resonance (SPR) effect of metal Bi, the widened visible light absorption range and the increased specific surface area. In addition, the possible photocatalytic mechanism for composite photocatalysts was proposed.
The Bi/BiVO4&Bi4V2O11 nanocomposite photocatalytic material was prepared by solvothermal reaction and photo-assisted reduction process. The composites were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), high resolution transmission electron microscope (HRTEM), X-ray photo-electron spectroscopy (XPS), ultraviolet visible diffuse reflection spectra (UV-Vis DRS), nitrogen absorption-desorption isotherms and photoluminescence (PL) methods. The experimental results show that when the mass ratio of metal Bi to BiVO4&Bi4V2O11 is 0.8 and the visible light was irradiated for 30 min, the degradation rate of rhodamine B (RhB) could reach 95.6% over Bi/BiVO4&Bi4V2O11 composite catalysts. Besides, Bi/BiVO4& Bi4V2O11 also exhibited enhanced photocatalytic properties for the degradation of tetracycline (TC). The enhanced photocatalytic performance of Bi/BiVO4&Bi4V2O11 might be attributed to the surface plasmonic resonance (SPR) effect of metal Bi, the widened visible light absorption range and the increased specific surface area. In addition, the possible photocatalytic mechanism for composite photocatalysts was proposed.
2019, 35(2): 271-276
doi: 10.11862/CJIC.2019.047
Abstract:
Polyaniline (PANI) was prepared by chemical oxidative polymerization and Bi5O7I/PANI composites were prepared by the hydrothermal method. The prepared samples were characterized by X-ray diffraction, Fourier-transform infrared spectroscopy, field emission scanning electron microscopy, UV-Vis diffuse reflectance spectroscopy and photoluminescence spectroscopy. The photocatalytic performance of Bi5O7I/PANI composites were evaluated by the degradation of RhB under the visible light irradiation. The experiment results showed that all the composites exhibited the higher degradation efficiency than Bi5O7I. When the loading of PANI was 5%(w/w), the catalytic efficiency was the best. The reaction rate constant was about 3.9 times higher than that of Bi5O7I within 60 min. The results of trapping experiments indicated that superoxide radical and holes are the main active species in the photodegradation process. The loading of PANI could expand the visible light range and enhance the light absorption. Moreover, the suitable energy structure could inhibit the recombination efficiency of photo-generated electron-hole.
Polyaniline (PANI) was prepared by chemical oxidative polymerization and Bi5O7I/PANI composites were prepared by the hydrothermal method. The prepared samples were characterized by X-ray diffraction, Fourier-transform infrared spectroscopy, field emission scanning electron microscopy, UV-Vis diffuse reflectance spectroscopy and photoluminescence spectroscopy. The photocatalytic performance of Bi5O7I/PANI composites were evaluated by the degradation of RhB under the visible light irradiation. The experiment results showed that all the composites exhibited the higher degradation efficiency than Bi5O7I. When the loading of PANI was 5%(w/w), the catalytic efficiency was the best. The reaction rate constant was about 3.9 times higher than that of Bi5O7I within 60 min. The results of trapping experiments indicated that superoxide radical and holes are the main active species in the photodegradation process. The loading of PANI could expand the visible light range and enhance the light absorption. Moreover, the suitable energy structure could inhibit the recombination efficiency of photo-generated electron-hole.
2019, 35(2): 277-284
doi: 10.11862/CJIC.2019.036
Abstract:
Using o-chloroaniline(o-CA), 18-crown-6 and cobalt cyanide as reactant, a small-molecule metal complex (H)0.5(o-CAH)[Co(CN)6]0.5·(18-crown-6)0.5·H2O (1) was synthesized by evaporation in the mixed solution of methanol and water. The structure and electrical properties of 1 were characterized by single crystal X-ray diffraction, infrared spectroscopy, thermogravimetric analysis (TG) and dielectric measurements. The results showed that 1 crystalizes in the triclinic system with the space group P1 at low-temperature (100 K). The cell parameters are as follows:a=0.869 22(1) nm, b=0.964 09(12) nm, c=1.129 93(14) nm, α=77.894 0(10)°, β=78.877 0(10)°, γ=88.684 0(10)°. Single crystal X-ray diffraction show a three-dimensional cage-like structure through hydrogen bonds of cyanide cobalt, supramolecular cations and water molecules. When the temperature changed, the space between the cobalt atoms of the cage-like vertex showed significant stretching deformation, which resulted in the distinct dielectric anomaly observed around 260 K.
Using o-chloroaniline(o-CA), 18-crown-6 and cobalt cyanide as reactant, a small-molecule metal complex (H)0.5(o-CAH)[Co(CN)6]0.5·(18-crown-6)0.5·H2O (1) was synthesized by evaporation in the mixed solution of methanol and water. The structure and electrical properties of 1 were characterized by single crystal X-ray diffraction, infrared spectroscopy, thermogravimetric analysis (TG) and dielectric measurements. The results showed that 1 crystalizes in the triclinic system with the space group P1 at low-temperature (100 K). The cell parameters are as follows:a=0.869 22(1) nm, b=0.964 09(12) nm, c=1.129 93(14) nm, α=77.894 0(10)°, β=78.877 0(10)°, γ=88.684 0(10)°. Single crystal X-ray diffraction show a three-dimensional cage-like structure through hydrogen bonds of cyanide cobalt, supramolecular cations and water molecules. When the temperature changed, the space between the cobalt atoms of the cage-like vertex showed significant stretching deformation, which resulted in the distinct dielectric anomaly observed around 260 K.
2019, 35(2): 285-292
doi: 10.11862/CJIC.2019.046
Abstract:
A ligand of 2-(2-pyridyl)-oxazoline(Pyrox) was prepared. The complex of containing Iron(Ⅱ) trifluome-thanesulfonate, Pyrox and another auxiliary ligand can be in situ formed in acetonitrile solution. Quantum chemistry calculations showed that the nitrogen rather than oxygen atom on the Pyrox coordinates with Iron. It was found the terminal aromatic and aliphatic olefins could be efficiently epoxidized with H2O2 catalyzed by this Iron complex in acetonitrile at room temperature. The reaction with good selectivity was rapid, mild and in an wide range of substrates. The influences of axial ligands, solvents and oxidants are sensitive to the activity and selectivity of the reaction, and the effects have been investigated in detail.
A ligand of 2-(2-pyridyl)-oxazoline(Pyrox) was prepared. The complex of containing Iron(Ⅱ) trifluome-thanesulfonate, Pyrox and another auxiliary ligand can be in situ formed in acetonitrile solution. Quantum chemistry calculations showed that the nitrogen rather than oxygen atom on the Pyrox coordinates with Iron. It was found the terminal aromatic and aliphatic olefins could be efficiently epoxidized with H2O2 catalyzed by this Iron complex in acetonitrile at room temperature. The reaction with good selectivity was rapid, mild and in an wide range of substrates. The influences of axial ligands, solvents and oxidants are sensitive to the activity and selectivity of the reaction, and the effects have been investigated in detail.
2019, 35(2): 293-299
doi: 10.11862/CJIC.2019.049
Abstract:
Ionic iridium complex[Ir(BTZ9C3)2(bpy)]PF6 (1) and neutral iridium complex[Ir(BTZ9C3)2(fppz)] (2) were synthesized with 4'-(2-benzothiazolyl)benzo-9-crown-3 ether(BTZ9C3) primary ligand and different ancillary ligands:2, 2'-bipyridine(bpy) and 3-trifluoromethyl-5-(2'-pyridyl)-1, 2-diazole(Hfppz). The structures of the complexes were characterized by NMR, high resolution mass spectrometry, and the single crystal structure of 1 was determined by X-ray structural analysis. All these complexes showed a strong Kelly phosphorescent emission. The photoluminescence spectra of complexes 1 and 2 in PMMA (1%(w/w)) showed emission maximum at 535 and 541 nm, respectively. Their quantum efficiencies were 10.8% and 45.0% and the luminescence lifetimes were 3.01 and 2.58 μs. By means of the cyclic voltammogram, the HOMO levels of complexes 1 and 2 were calculated to be -5.60 and -5.35 eV. Both complexes displayed a high selectivity for Be2+ among relevant metal ions, and exhibited luminescence enhancement effect in the presence of Be2+. The stoichiometric ratio of iridium complexes responding to Be2+ was determined to be 1:2, and the detection limit is down to 6.0 μmol·L-1. The ionic iridium complex 1 has good anti-disturbance, however the neutral iridium complex 2 is greatly interfered by Al3+.
Ionic iridium complex[Ir(BTZ9C3)2(bpy)]PF6 (1) and neutral iridium complex[Ir(BTZ9C3)2(fppz)] (2) were synthesized with 4'-(2-benzothiazolyl)benzo-9-crown-3 ether(BTZ9C3) primary ligand and different ancillary ligands:2, 2'-bipyridine(bpy) and 3-trifluoromethyl-5-(2'-pyridyl)-1, 2-diazole(Hfppz). The structures of the complexes were characterized by NMR, high resolution mass spectrometry, and the single crystal structure of 1 was determined by X-ray structural analysis. All these complexes showed a strong Kelly phosphorescent emission. The photoluminescence spectra of complexes 1 and 2 in PMMA (1%(w/w)) showed emission maximum at 535 and 541 nm, respectively. Their quantum efficiencies were 10.8% and 45.0% and the luminescence lifetimes were 3.01 and 2.58 μs. By means of the cyclic voltammogram, the HOMO levels of complexes 1 and 2 were calculated to be -5.60 and -5.35 eV. Both complexes displayed a high selectivity for Be2+ among relevant metal ions, and exhibited luminescence enhancement effect in the presence of Be2+. The stoichiometric ratio of iridium complexes responding to Be2+ was determined to be 1:2, and the detection limit is down to 6.0 μmol·L-1. The ionic iridium complex 1 has good anti-disturbance, however the neutral iridium complex 2 is greatly interfered by Al3+.
2019, 35(2): 300-306
doi: 10.11862/CJIC.2019.041
Abstract:
The Cu/Zn/Al hydrotalcite-like precursor was prepared by co-precipitation method and modified by triethanolamine (TEA), and then the precursor was calcined to obtain TEA-modified Cu/Zn/Al catalysts. The catalysts were characterized by XRD, FTIR, H2-TPR, CO-TPD and SEM techniques, and their catalytic activities for isobutanol synthesis were evaluated. The results revealed that TEA can change morphology of the catalysts and form flocculent structure on the surface of the catalysts. In addition, TEA can result in structural expansion of hydrotalcite-like precursor and thus lead to structural changes in the Cu/Zn/Al catalysts, which facilitate hydrogen reduction of CuO components and CO chemisorption on the surface of the catalysts. These changes promote isobutanol synthesis. The catalytic performance of the TEA-modified Cu/Zn/Al catalysts was optimal when addition ratio of TEA reached to nTEA/nZn=0.5.
The Cu/Zn/Al hydrotalcite-like precursor was prepared by co-precipitation method and modified by triethanolamine (TEA), and then the precursor was calcined to obtain TEA-modified Cu/Zn/Al catalysts. The catalysts were characterized by XRD, FTIR, H2-TPR, CO-TPD and SEM techniques, and their catalytic activities for isobutanol synthesis were evaluated. The results revealed that TEA can change morphology of the catalysts and form flocculent structure on the surface of the catalysts. In addition, TEA can result in structural expansion of hydrotalcite-like precursor and thus lead to structural changes in the Cu/Zn/Al catalysts, which facilitate hydrogen reduction of CuO components and CO chemisorption on the surface of the catalysts. These changes promote isobutanol synthesis. The catalytic performance of the TEA-modified Cu/Zn/Al catalysts was optimal when addition ratio of TEA reached to nTEA/nZn=0.5.
2019, 35(2): 307-313
doi: 10.11862/CJIC.2019.043
Abstract:
A novel seven-coordinated organotin complex[Sn(L)(n-butyl)2]n (T) based on bis(4-(diethylamino)salicylaldehyde) azodicarbonhydrazide(L) has been prepared by a one-pot reaction of carbohydrazide, 4-(diethylamino) salicylaldehyde and dibutyltin diacetate in methanol environments. The complex has been structurally characterized by elemental analysis, IR, (1H, 13C, 119Sn) NMR spectra. The crystal of T belongs to monoclinic system and C2/c space group. The coordination around tin is distorted pentagonal bipyramid configuration by O, N atoms of L in the equatorial positions and the two butyl at the apices. A supramolecular structure of one-dimensional bands with a bamboo-row-like framework is formed by the bridging coordination of enol oxygen atoms. The complex had strong fluorescence emission in organic solvents, dimethyl formamide, tetrahydrofuran, ethanol, methanol and toluene, and in mixed solvents of organic solvent and water. When the volume fraction of water content is between 0 and 10%(V/V), the aggregation induced enhancement effect (AIEE) was good, and fluorescence quenching occured when the water content was more than 10%(V/V).
A novel seven-coordinated organotin complex[Sn(L)(n-butyl)2]n (T) based on bis(4-(diethylamino)salicylaldehyde) azodicarbonhydrazide(L) has been prepared by a one-pot reaction of carbohydrazide, 4-(diethylamino) salicylaldehyde and dibutyltin diacetate in methanol environments. The complex has been structurally characterized by elemental analysis, IR, (1H, 13C, 119Sn) NMR spectra. The crystal of T belongs to monoclinic system and C2/c space group. The coordination around tin is distorted pentagonal bipyramid configuration by O, N atoms of L in the equatorial positions and the two butyl at the apices. A supramolecular structure of one-dimensional bands with a bamboo-row-like framework is formed by the bridging coordination of enol oxygen atoms. The complex had strong fluorescence emission in organic solvents, dimethyl formamide, tetrahydrofuran, ethanol, methanol and toluene, and in mixed solvents of organic solvent and water. When the volume fraction of water content is between 0 and 10%(V/V), the aggregation induced enhancement effect (AIEE) was good, and fluorescence quenching occured when the water content was more than 10%(V/V).
2019, 35(2): 194-202
doi: 10.11862/CJIC.2019.006
Abstract:
The Ce-doped SnS2 samples were prepared successfully through a one-pot hydrothermal method under mild conditions. The as-prepared SnS2 samples were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) equipped with Energy dispersive X-ray Spectroscopy (EDS) which confirmed the doping of Ce. The results indicated the spiral growth mode and rose-like morphology of the samples. The effects of Ce doping on the photoabsorption, band gap, the potential of conduction band and the separation efficiency of photo-induced carriers were checked by diffuse reflectance spectrum (DRS) and electrochemical examinations. The reductive abilities of the samples were evaluated by the reduction of Cr(Ⅵ) chosen as a model pollutant. The results reveal that photocatalytic properties of Ce/SnS2 were strongly dependent on the proportion of Ce ions and the optimum doping amount of Ce is 5% (n/n).
The Ce-doped SnS2 samples were prepared successfully through a one-pot hydrothermal method under mild conditions. The as-prepared SnS2 samples were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) equipped with Energy dispersive X-ray Spectroscopy (EDS) which confirmed the doping of Ce. The results indicated the spiral growth mode and rose-like morphology of the samples. The effects of Ce doping on the photoabsorption, band gap, the potential of conduction band and the separation efficiency of photo-induced carriers were checked by diffuse reflectance spectrum (DRS) and electrochemical examinations. The reductive abilities of the samples were evaluated by the reduction of Cr(Ⅵ) chosen as a model pollutant. The results reveal that photocatalytic properties of Ce/SnS2 were strongly dependent on the proportion of Ce ions and the optimum doping amount of Ce is 5% (n/n).
2019, 35(2): 314-322
doi: 10.11862/CJIC.2019.032
Abstract:
Cage-like hollow morphologies of copper sulfide nanostructures have been selectively synthesized using cupric nitrate trihydrate (Cu(NO3)2·3H2O), oxalic acid (H2C2O4) and sodium sulphide nonahydrate (Na2S·9H2O) as starting materials in water solution by a self sacrificing templates hydrothermal method. X-ray diffraction (XRD), field scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) were used to characterize the products. The possible formation mechanism of CuS hollow spheres was proposed. The photo-thermal conversion experiments were also done. The results showed that hollow CuS exhibited high photo-thermal efficiency and high anticancer activity under NIR irradiation.
Cage-like hollow morphologies of copper sulfide nanostructures have been selectively synthesized using cupric nitrate trihydrate (Cu(NO3)2·3H2O), oxalic acid (H2C2O4) and sodium sulphide nonahydrate (Na2S·9H2O) as starting materials in water solution by a self sacrificing templates hydrothermal method. X-ray diffraction (XRD), field scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) were used to characterize the products. The possible formation mechanism of CuS hollow spheres was proposed. The photo-thermal conversion experiments were also done. The results showed that hollow CuS exhibited high photo-thermal efficiency and high anticancer activity under NIR irradiation.
2019, 35(2): 323-328
doi: 10.11862/CJIC.2019.034
Abstract:
The reaction of Ln(acac)3·3H2O with NIT-PhOH radical yielded two new Ln-radical complexes[Ln2(acac)4(NIT-PhO)2] (Ln=Tb (1), Y (2); acac=acetylacetonato, NIT-PhOH=2-(2'-hydroxyphenyl)-4, 4, 5, 5-tetramethylimidazo-line-1-oxyl-3-oxide). Two complexes are isostructural and have binuclear structure in which two lanthanide ions are bridged by two radical ligands through their phenoxo-O atoms. DC magnetic susceptibility studies indicated that there exists weak antiferromagnetic interaction in complex 2.
The reaction of Ln(acac)3·3H2O with NIT-PhOH radical yielded two new Ln-radical complexes[Ln2(acac)4(NIT-PhO)2] (Ln=Tb (1), Y (2); acac=acetylacetonato, NIT-PhOH=2-(2'-hydroxyphenyl)-4, 4, 5, 5-tetramethylimidazo-line-1-oxyl-3-oxide). Two complexes are isostructural and have binuclear structure in which two lanthanide ions are bridged by two radical ligands through their phenoxo-O atoms. DC magnetic susceptibility studies indicated that there exists weak antiferromagnetic interaction in complex 2.
2019, 35(2): 329-336
doi: 10.11862/CJIC.2019.002
Abstract:
Zero-dimensional mononuclear cobalt(Ⅱ) complex, 1D lead(Ⅱ) and 1D zinc(Ⅱ) coordination polymers, namely[Co(Hbtc)(phen)2(H2O)]·3H2O (1), [Pb(μ3-Hbtc)(2, 2'-bipy)]n (2) and {[Zn3(μ2-btc)2(μ2-H2O)(2, 2'-bipy)3(H2O)5]·8H2O}n (3), have been constructed hydrothermally using H3btc (H3btc=biphenyl-2, 4, 4'-tricarboxylic acid), phen (phen=1, 10-phenanthroline), 2, 2'-bipy (2, 2'-bipy=2, 2'-bipyridine), and cobalt, lead or zinc chlorides. Single-crystal X-ray diffraction analyses revealed that three complexes crystallize in the orthorhombic or triclinic systems, space groups Pna21 or P1. Complex 1 has a discrete monomeric structure, which is assembled to a 3D supramolecular framework through O-H…O hydrogen bond. Complexes 2 and 3 show a 1D chain based on binuclear units. Luminescent properties of all complexes have been studied.
Zero-dimensional mononuclear cobalt(Ⅱ) complex, 1D lead(Ⅱ) and 1D zinc(Ⅱ) coordination polymers, namely[Co(Hbtc)(phen)2(H2O)]·3H2O (1), [Pb(μ3-Hbtc)(2, 2'-bipy)]n (2) and {[Zn3(μ2-btc)2(μ2-H2O)(2, 2'-bipy)3(H2O)5]·8H2O}n (3), have been constructed hydrothermally using H3btc (H3btc=biphenyl-2, 4, 4'-tricarboxylic acid), phen (phen=1, 10-phenanthroline), 2, 2'-bipy (2, 2'-bipy=2, 2'-bipyridine), and cobalt, lead or zinc chlorides. Single-crystal X-ray diffraction analyses revealed that three complexes crystallize in the orthorhombic or triclinic systems, space groups Pna21 or P1. Complex 1 has a discrete monomeric structure, which is assembled to a 3D supramolecular framework through O-H…O hydrogen bond. Complexes 2 and 3 show a 1D chain based on binuclear units. Luminescent properties of all complexes have been studied.
2019, 35(2): 337-343
doi: 10.11862/CJIC.2019.027
Abstract:
Reactions of cis-and trans-1, 2-cyclohexanediamine (DAC) with antimony iodide in concentrated HI aqueous solution afforded two organic-inorganic hybrid isomers (cis-1, 2-DACH2)[SbI5]·H2O (1) and {(trans-1, 2-DACH2)[SbI5]·H2O}n (2), respectively. The single-crystal X-ray diffraction revealed that the inorganic component in compound 1 is a dimer[Sb2I10] built up from two[SbI6] octahedra by sharing I-I edge, and that in compound 2 is a zigzag chain constructed with corner-sharing octahedral[SbI6] units. In addition, both compounds have been investigated and compared by UV-Vis, fluorescent spectra, and DFT calculation.
Reactions of cis-and trans-1, 2-cyclohexanediamine (DAC) with antimony iodide in concentrated HI aqueous solution afforded two organic-inorganic hybrid isomers (cis-1, 2-DACH2)[SbI5]·H2O (1) and {(trans-1, 2-DACH2)[SbI5]·H2O}n (2), respectively. The single-crystal X-ray diffraction revealed that the inorganic component in compound 1 is a dimer[Sb2I10] built up from two[SbI6] octahedra by sharing I-I edge, and that in compound 2 is a zigzag chain constructed with corner-sharing octahedral[SbI6] units. In addition, both compounds have been investigated and compared by UV-Vis, fluorescent spectra, and DFT calculation.
2019, 35(2): 344-350
doi: 10.11862/CJIC.2019.031
Abstract:
The α-phosphorus ligand 1-(p-tolyl)-2-(tri-p-tolyl-λ5-phosphanylidene)ethan-1-one(L) was prepared by the reaction of 2-bromo-1-(p-tolyl)ethan-1-one with tri(p-tolyl) phosphine. The reactions of L with cadmium chloride and mercury bromide resulted in[Cd(L)Cl2]2 (C1) and[Hg(L)(μ2-Br)Br]2 (C2), respectively. The complexes were characterized by IR and NMR (1H, 13C, 31P). The structure of C2 was detected by single crystal X-ray diffraction and its DFT computational studies at B3LYP/6-31G* level were also performed to reveal the interaction between the reaction site of complex C2 and nucleophilic groups such as Schiff base.
The α-phosphorus ligand 1-(p-tolyl)-2-(tri-p-tolyl-λ5-phosphanylidene)ethan-1-one(L) was prepared by the reaction of 2-bromo-1-(p-tolyl)ethan-1-one with tri(p-tolyl) phosphine. The reactions of L with cadmium chloride and mercury bromide resulted in[Cd(L)Cl2]2 (C1) and[Hg(L)(μ2-Br)Br]2 (C2), respectively. The complexes were characterized by IR and NMR (1H, 13C, 31P). The structure of C2 was detected by single crystal X-ray diffraction and its DFT computational studies at B3LYP/6-31G* level were also performed to reveal the interaction between the reaction site of complex C2 and nucleophilic groups such as Schiff base.
2019, 35(2): 351-360
doi: 10.11862/CJIC.2019.045
Abstract:
A layered coordination polymer[Cd(QDA)]n (1) with distorted Cd2+ octahedron extended by three-connected 2, 3-quinoline dicarboxylate linkers was hydrothermally synthesized, exhibiting intense blue fluorescence and highly thermal and chemical stability. More interestingly, the complex dispersed in ethanol can quickly probe the trace amounts of 2, 4, 6-trinitrophenol (Ksv=6.61×104 L·mol-1, LOD=0.83 μmol·L-1) and Fe3+ (Ksv=1.74×104 L·mol-1, LOD=2.70 μmol·L-1) through fluorescence quenching with high quenching constants (Ksv) and low limits of detection (LOD).
A layered coordination polymer[Cd(QDA)]n (1) with distorted Cd2+ octahedron extended by three-connected 2, 3-quinoline dicarboxylate linkers was hydrothermally synthesized, exhibiting intense blue fluorescence and highly thermal and chemical stability. More interestingly, the complex dispersed in ethanol can quickly probe the trace amounts of 2, 4, 6-trinitrophenol (Ksv=6.61×104 L·mol-1, LOD=0.83 μmol·L-1) and Fe3+ (Ksv=1.74×104 L·mol-1, LOD=2.70 μmol·L-1) through fluorescence quenching with high quenching constants (Ksv) and low limits of detection (LOD).
2019, 35(2): 361-368
doi: 10.11862/CJIC.2019.026
Abstract:
Two novel copper(Ⅰ) complexes[Cu(bdppmapy)(2, 2'-bipy)]BF4 (1) and[Cu(bdppmapy)(2, 2'-bipy)]I (2) (2, 2'-bipy=2, 2'-bipyridine, bdppmapy=N, N-bis((diphenylphosphino)methyl)-2-pyridinamine) have been synthesized in mixed solvents of CH3OH and CH2Cl2 (1:1, V/V) and characterized by single-crystal X-ray diffraction, elemental analysis, IR, 1H NMR and 31P NMR spectroscopy, fluorescence spectra and THz time domain spectroscopy (THz-TDS). Complex 1, a mononuclear complex, was generated by the reaction of[Cu(CH3CN)4]BF4 and bdppmapy with 2, 2'-bipy in 1:1:1 molar ratio. In complex 1, the central Cu(Ⅰ) forms a distorted tetrahedral geometry by coordinating with the diphosphine ligand (bdppmapy) and chelating N-donor ligand (2, 2'-bipy). Like 1, 2 was obtained by the reaction of CuI and bdppmapy with 2, 2'-bipy in 1:1:1 molar ratio. In the asymmetric unit of 2, the bdppmapy and 2, 2'-bipy ligands chelate central Cu(Ⅰ), respectively. The luminescent spectra show that the emission mechanism is metal-to-ligand charge transfer (MLCT). The application of terahertz time-domain spectroscopy also provides useful information for the research of complexes.
Two novel copper(Ⅰ) complexes[Cu(bdppmapy)(2, 2'-bipy)]BF4 (1) and[Cu(bdppmapy)(2, 2'-bipy)]I (2) (2, 2'-bipy=2, 2'-bipyridine, bdppmapy=N, N-bis((diphenylphosphino)methyl)-2-pyridinamine) have been synthesized in mixed solvents of CH3OH and CH2Cl2 (1:1, V/V) and characterized by single-crystal X-ray diffraction, elemental analysis, IR, 1H NMR and 31P NMR spectroscopy, fluorescence spectra and THz time domain spectroscopy (THz-TDS). Complex 1, a mononuclear complex, was generated by the reaction of[Cu(CH3CN)4]BF4 and bdppmapy with 2, 2'-bipy in 1:1:1 molar ratio. In complex 1, the central Cu(Ⅰ) forms a distorted tetrahedral geometry by coordinating with the diphosphine ligand (bdppmapy) and chelating N-donor ligand (2, 2'-bipy). Like 1, 2 was obtained by the reaction of CuI and bdppmapy with 2, 2'-bipy in 1:1:1 molar ratio. In the asymmetric unit of 2, the bdppmapy and 2, 2'-bipy ligands chelate central Cu(Ⅰ), respectively. The luminescent spectra show that the emission mechanism is metal-to-ligand charge transfer (MLCT). The application of terahertz time-domain spectroscopy also provides useful information for the research of complexes.
