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2020 Volume 36 Issue 1
2020, 36(1): 1-10
doi: 10.11862/CJIC.2019.262
Abstract:
In order to shorten the migration pathway of e- and h+ and improve the defect of recombination of photo-generated carriers in g-C3N4, this study used different molar concentrations of HNO3 to activate melamine precursor, and formed a series of x-HNO3-g-C3N4 (x=1, 2, 3, 4, 5 mol·L-1) photocatalyst by forming a protonated amino group. In order to investigate the effect of the structure of the catalyst on its photocatalytic properties, all these above obtained photocatalysts were characterized by nitrogen gas adsorption-desorption isotherms, X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), photoluminescence (PL), ultraviolet-visible diffuse reflection (UV-Vis DRS), transient photocurrent spectroscopy (TCS), electrochemical impedance spectroscopy (EIS), etc. The difference of visible light catalytic degradation activity of x-HNO3-g-C3N4 and g-C3N4 obtained by direct calcination of melamine was studied with the using of rhodamine B (RhB) as a simulated dye contaminant. The resuts of experimental showed that the photocatalytic activity of 3 mol·L-1-HNO3-g-C3N4 was the highest. Compared with g-C3N4 obtained by directly calcining melamine, the degradation rate of RhB increased from 38% to 99% within 60 minutes. The 3 mol·L-1-HNO3-g-C3N4 catalyst was recycled 4 times, and the catalytic effect was still 99%. The high catalytic activity and stability of x-HNO3-g-C3N4 can be explained as follows:after activation of HNO3, the melamine precursor can make the g-C3N4 product prepared by thermal polymerization have a higher degree of polymerization, thereby a multi-layer g-C3N4 with large specific surface area was obtained. The PL results showed that the fluorescence intensity was significantly reduced, and the carrier lifetime was significantly improved. The EIS results showed that the carrier transport capacity was significantly enhanced, which improved the photocatalytic activity of g-C3N4.
In order to shorten the migration pathway of e- and h+ and improve the defect of recombination of photo-generated carriers in g-C3N4, this study used different molar concentrations of HNO3 to activate melamine precursor, and formed a series of x-HNO3-g-C3N4 (x=1, 2, 3, 4, 5 mol·L-1) photocatalyst by forming a protonated amino group. In order to investigate the effect of the structure of the catalyst on its photocatalytic properties, all these above obtained photocatalysts were characterized by nitrogen gas adsorption-desorption isotherms, X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), photoluminescence (PL), ultraviolet-visible diffuse reflection (UV-Vis DRS), transient photocurrent spectroscopy (TCS), electrochemical impedance spectroscopy (EIS), etc. The difference of visible light catalytic degradation activity of x-HNO3-g-C3N4 and g-C3N4 obtained by direct calcination of melamine was studied with the using of rhodamine B (RhB) as a simulated dye contaminant. The resuts of experimental showed that the photocatalytic activity of 3 mol·L-1-HNO3-g-C3N4 was the highest. Compared with g-C3N4 obtained by directly calcining melamine, the degradation rate of RhB increased from 38% to 99% within 60 minutes. The 3 mol·L-1-HNO3-g-C3N4 catalyst was recycled 4 times, and the catalytic effect was still 99%. The high catalytic activity and stability of x-HNO3-g-C3N4 can be explained as follows:after activation of HNO3, the melamine precursor can make the g-C3N4 product prepared by thermal polymerization have a higher degree of polymerization, thereby a multi-layer g-C3N4 with large specific surface area was obtained. The PL results showed that the fluorescence intensity was significantly reduced, and the carrier lifetime was significantly improved. The EIS results showed that the carrier transport capacity was significantly enhanced, which improved the photocatalytic activity of g-C3N4.
2020, 36(1): 11-20
doi: 10.11862/CJIC.2020.023
Abstract:
The Z-scheme CdS/Au/Bi2MoO6 heterostructure have been successfully synthesized by CdS and Au co-modification via a facile chemical reduction deposition and secondary hydrothermal method. X-ray diffraction (XRD), X-ray photo-electron spectroscopy (XPS), transmission electron microscope (TEM), scanning electron microscopy (SEM) and other testing techniques were employed to systematically characterize its composition, morphology, optical absorption characteristics and photoelectrochemical properties. The experimental results showed that CdS/Au/Bi2MoO6-2 composite showed the best degradation efficiency under visible light irradiation, and the degradation rate of RhB was about 8.8 and 20 times that of Bi2MoO6 and CdS, respectively. As a solid electronic medium, Au NPs provides a channel for the transmission and transfer of photogenerated electrons. Meanwhile, the response range of the catalytic system to visible light was significantly broadened through Au NPs surface plasmon resonance (SPR) effect and CdS nanoparticles. Besides, the energy band structure of CdS/Au/BMO was determined through the characterizations of the composition, photoelectrochemical properties and valance band-XPS results of the as-prepared photocatalyst. Moreover, the mechanism for the enhancement of the photocatalytic activity of CdS/Au/BMO was also discussed by comparison of their photoluminescence spectra and electron spin resonance spectroscopy (ESR) spectra.
The Z-scheme CdS/Au/Bi2MoO6 heterostructure have been successfully synthesized by CdS and Au co-modification via a facile chemical reduction deposition and secondary hydrothermal method. X-ray diffraction (XRD), X-ray photo-electron spectroscopy (XPS), transmission electron microscope (TEM), scanning electron microscopy (SEM) and other testing techniques were employed to systematically characterize its composition, morphology, optical absorption characteristics and photoelectrochemical properties. The experimental results showed that CdS/Au/Bi2MoO6-2 composite showed the best degradation efficiency under visible light irradiation, and the degradation rate of RhB was about 8.8 and 20 times that of Bi2MoO6 and CdS, respectively. As a solid electronic medium, Au NPs provides a channel for the transmission and transfer of photogenerated electrons. Meanwhile, the response range of the catalytic system to visible light was significantly broadened through Au NPs surface plasmon resonance (SPR) effect and CdS nanoparticles. Besides, the energy band structure of CdS/Au/BMO was determined through the characterizations of the composition, photoelectrochemical properties and valance band-XPS results of the as-prepared photocatalyst. Moreover, the mechanism for the enhancement of the photocatalytic activity of CdS/Au/BMO was also discussed by comparison of their photoluminescence spectra and electron spin resonance spectroscopy (ESR) spectra.
Effect of Heat Treatment on Structure and Lithium Ion Storage Properties of N-Rich Carbon Nanofibers
2020, 36(1): 31-39
doi: 10.11862/CJIC.2020.026
Abstract:
Carbon nanofibers (CNFs) were prepared from polyacrylonitrile (PAN) via electrospinning followed by stabilization and carbonization. The morphology and structure of the carbon nanofibers were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), and X-ray photo-electron spectroscopy (XPS). The electrochemical properties were investigated as anode material in lithium ion batteries (LIBs). A systematic study was made to confirm the effect of the nitrogen species on the performance of lithium ion storage and the capacities of anodes in LIBs. It is noticed that the structure change has a great influence on the storage position of lithium ion in CNFs electrode. The results showed that lithium ions can be stored not only between the graphitized carbon layers, but also in the defects caused by the functionalization of nitrogen, the latter was mainly because the improvement of the electrochemical performance of LIBs due to the N-doping of carbon materials. There is a strong correlation between the atomic structure, with lithium ion storage behavior and electrochemical properties of anode materials. It is revealed that thermal annealing had an important effect on the atomic structure and morphology of CNFs. A high temperature treatment promoted graphitization and improved electrical conductivity through the growth of aromatic groups. During the transition from amorphous carbon to graphite structure at high temperature, defects and heteroatoms were removed with the decrease of nitrogen contents. Therefore, CNFs obtained at high carbonization temperature may have high lithium ion storage capacity between graphene layers, but it failed to provide attractive capacity due to low nitrogen content. An optimized carbonization temperature of 600℃ was identified, the electrode gave rise to a sufficiently high nitrogen content and thus a high capacity about 560 mAh·g-1 after 200 cycles at the current density of 0.1 A·g-1, the specific capacity at the high current density of 1 A·g-1 even still remained 200 mAh·g-1 after 1 000 cycles.
Carbon nanofibers (CNFs) were prepared from polyacrylonitrile (PAN) via electrospinning followed by stabilization and carbonization. The morphology and structure of the carbon nanofibers were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), and X-ray photo-electron spectroscopy (XPS). The electrochemical properties were investigated as anode material in lithium ion batteries (LIBs). A systematic study was made to confirm the effect of the nitrogen species on the performance of lithium ion storage and the capacities of anodes in LIBs. It is noticed that the structure change has a great influence on the storage position of lithium ion in CNFs electrode. The results showed that lithium ions can be stored not only between the graphitized carbon layers, but also in the defects caused by the functionalization of nitrogen, the latter was mainly because the improvement of the electrochemical performance of LIBs due to the N-doping of carbon materials. There is a strong correlation between the atomic structure, with lithium ion storage behavior and electrochemical properties of anode materials. It is revealed that thermal annealing had an important effect on the atomic structure and morphology of CNFs. A high temperature treatment promoted graphitization and improved electrical conductivity through the growth of aromatic groups. During the transition from amorphous carbon to graphite structure at high temperature, defects and heteroatoms were removed with the decrease of nitrogen contents. Therefore, CNFs obtained at high carbonization temperature may have high lithium ion storage capacity between graphene layers, but it failed to provide attractive capacity due to low nitrogen content. An optimized carbonization temperature of 600℃ was identified, the electrode gave rise to a sufficiently high nitrogen content and thus a high capacity about 560 mAh·g-1 after 200 cycles at the current density of 0.1 A·g-1, the specific capacity at the high current density of 1 A·g-1 even still remained 200 mAh·g-1 after 1 000 cycles.
2020, 36(1): 40-52
doi: 10.11862/CJIC.2020.006
Abstract:
A series of nano-ZnO doped with different amounts of cerium were prepared by co-precipitation method with Zn(NO3)2·6H2O and Ce(NO3)3·6H2O as raw materials. The as-made samples were characterized by powder X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscope (SEM), energy dispersive spectrometer (EDS) and UV-visible diffuse reflectance spectroscopy (UV-Vis DRS). Some samples were further characterized by X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL). Photocatalytic activity of these materials toward photodegradation of methylene blue (MB) was evaluated under UV and sunlight irradiation, respectively. It was found that the sample with 3% Ce3+ doped ZnO, named as ZnO-3% Ce, exhibited highest photocatalytic activity among the prepared samples and its MB-degradation efficiency was over 98%. Then, the sample of ZnO-3% Ce was selected to further evaluate its photocatalytic activity toward photodegradation of rhodamine B (RhB) and methyl orange (MO) under both UV and sunlight irradiation. The results showed that the sample of ZnO-3% Ce presented good photodegradation activity under both UV and sunlight condition. The order of photodegradation efficiency under sunlight irradiation was as follows:MB > RhB > MO, while the photocatalytic activity under UV irradiation was increased by the following order RhB > MB > MO. The stability of ZnO-3%Ce catalyst was studied by cyclic experiments. The results showed that the photodegradation efficiency still retained more than 97% after three cycles, suggesting that the catalyst maintained its structure and component and presented good stability and application prospect.
A series of nano-ZnO doped with different amounts of cerium were prepared by co-precipitation method with Zn(NO3)2·6H2O and Ce(NO3)3·6H2O as raw materials. The as-made samples were characterized by powder X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscope (SEM), energy dispersive spectrometer (EDS) and UV-visible diffuse reflectance spectroscopy (UV-Vis DRS). Some samples were further characterized by X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL). Photocatalytic activity of these materials toward photodegradation of methylene blue (MB) was evaluated under UV and sunlight irradiation, respectively. It was found that the sample with 3% Ce3+ doped ZnO, named as ZnO-3% Ce, exhibited highest photocatalytic activity among the prepared samples and its MB-degradation efficiency was over 98%. Then, the sample of ZnO-3% Ce was selected to further evaluate its photocatalytic activity toward photodegradation of rhodamine B (RhB) and methyl orange (MO) under both UV and sunlight irradiation. The results showed that the sample of ZnO-3% Ce presented good photodegradation activity under both UV and sunlight condition. The order of photodegradation efficiency under sunlight irradiation was as follows:MB > RhB > MO, while the photocatalytic activity under UV irradiation was increased by the following order RhB > MB > MO. The stability of ZnO-3%Ce catalyst was studied by cyclic experiments. The results showed that the photodegradation efficiency still retained more than 97% after three cycles, suggesting that the catalyst maintained its structure and component and presented good stability and application prospect.
2020, 36(1): 62-68
doi: 10.11862/CJIC.2020.010
Abstract:
We demonstrated the preparation of graphene oxide (GO) decorated Co3V2O8 to form (Co3V2O8/rGO) composite through a facile approach combining hydrothermal synthesis with thermal reduction. The XRD, Raman, XPS, SEM, (HR-)TEM, and electrochemical performance tests were used to study the relationship between the physical character and the electrochemical properties of the electrode material. As the anode material, the Co3V2O8/rGO delivered excellent lithium storage properties, stable cycle performance, and high rate capability (1 208 mAh·g-1 at 200 mA·g-1 after 100 cycles). It is demonstrated that an enhanced cycle performance can be acquired because graphene can accelerate the electron diffusion among the Co3V2O8 active particles, prevent the aggregation of Co3V2O8 particles, and effectively accommodate the volume variation during the discharge/charge process and offer short pathways for the ions as well as electrons. Meanwhile, the incorporation of the Co3V2O8 particles suppress the stack of graphene layer.
We demonstrated the preparation of graphene oxide (GO) decorated Co3V2O8 to form (Co3V2O8/rGO) composite through a facile approach combining hydrothermal synthesis with thermal reduction. The XRD, Raman, XPS, SEM, (HR-)TEM, and electrochemical performance tests were used to study the relationship between the physical character and the electrochemical properties of the electrode material. As the anode material, the Co3V2O8/rGO delivered excellent lithium storage properties, stable cycle performance, and high rate capability (1 208 mAh·g-1 at 200 mA·g-1 after 100 cycles). It is demonstrated that an enhanced cycle performance can be acquired because graphene can accelerate the electron diffusion among the Co3V2O8 active particles, prevent the aggregation of Co3V2O8 particles, and effectively accommodate the volume variation during the discharge/charge process and offer short pathways for the ions as well as electrons. Meanwhile, the incorporation of the Co3V2O8 particles suppress the stack of graphene layer.
2020, 36(1): 69-78
doi: 10.11862/CJIC.2020.024
Abstract:
Water-soluble AgInS2/ZnS (AIS/ZnS) core/shell quantum dots (QDs) were synthesized by hydrothermal method using thiourea (TU) as sulfur source, glutathione (GSH) and sodium citrate (SC) as ligands. The effects of reaction temperature and addition amount of ligands on the synthesis and fluorescence properties of AIS/ZnS QDs were systematically studied by XRD, TEM, UV-Vis absorption spectra and PL spectra, respectively, and their stability was also investigated. The results show that the emissive intensity of AIS/ZnS core/shell QDs is significantly improved by increasing the reaction temperature from 70 to 90℃. The increase of temperature promotes the growth of ZnS shell, on which the surface defects is effectively passivated. Meanwhile, the emissive peak showed a blue-shift from 600 nm to 580 nm. Furthermore, the ligands could balance the chemical reactivity of Zn2+, slow the growth rate of ZnS shell, inhibit the interface defects formation and eliminate the surface states. The AIS/ZnS core/shell QDs showed the strongest emission with nGSH/nZn2+ of 2.0 and nSC/nZn2+ of 2.5. Importantly, the obtained AIS/ZnS core/shell QDs exhibited excellent optical stability.
Water-soluble AgInS2/ZnS (AIS/ZnS) core/shell quantum dots (QDs) were synthesized by hydrothermal method using thiourea (TU) as sulfur source, glutathione (GSH) and sodium citrate (SC) as ligands. The effects of reaction temperature and addition amount of ligands on the synthesis and fluorescence properties of AIS/ZnS QDs were systematically studied by XRD, TEM, UV-Vis absorption spectra and PL spectra, respectively, and their stability was also investigated. The results show that the emissive intensity of AIS/ZnS core/shell QDs is significantly improved by increasing the reaction temperature from 70 to 90℃. The increase of temperature promotes the growth of ZnS shell, on which the surface defects is effectively passivated. Meanwhile, the emissive peak showed a blue-shift from 600 nm to 580 nm. Furthermore, the ligands could balance the chemical reactivity of Zn2+, slow the growth rate of ZnS shell, inhibit the interface defects formation and eliminate the surface states. The AIS/ZnS core/shell QDs showed the strongest emission with nGSH/nZn2+ of 2.0 and nSC/nZn2+ of 2.5. Importantly, the obtained AIS/ZnS core/shell QDs exhibited excellent optical stability.
2020, 36(1): 79-86
doi: 10.11862/CJIC.2020.011
Abstract:
The nickel-rich and cobalt-free binary cathode materials were prepared, and the effects of lithium content, calcination temperature and coating modification on the properties of samples were studied. X-ray diffraction (XRD) analyses and electrochemical properties such as first charge-discharge performance, rate performance and cycling performance of different samples and modified materials were investigated. Among them, the material with excess lithium content of 5%(w/w) and calcination temperature of 820℃ had excellent performance. Its first discharge specific capacity was 171.6 mAh·g-1, and the discharge specific capacities of 1C and 3C were 147.8 and 129.8 mAh·g-1, respectively. After coating the material with 1.0%(w/w) manganese compound, the residual alkali content of the material decreased obviously. The processing performance was excellent, the rate performance was improved obviously, and the discharge specific capacities of 1C and 3C were increased to 156.5, 141.8 mAh·g-1, respectively. The capacity retention rate of 2Ah soft-packed battery was 80% after 830 cycles at room temperature and 80% after 345 cycles at high temperature.
The nickel-rich and cobalt-free binary cathode materials were prepared, and the effects of lithium content, calcination temperature and coating modification on the properties of samples were studied. X-ray diffraction (XRD) analyses and electrochemical properties such as first charge-discharge performance, rate performance and cycling performance of different samples and modified materials were investigated. Among them, the material with excess lithium content of 5%(w/w) and calcination temperature of 820℃ had excellent performance. Its first discharge specific capacity was 171.6 mAh·g-1, and the discharge specific capacities of 1C and 3C were 147.8 and 129.8 mAh·g-1, respectively. After coating the material with 1.0%(w/w) manganese compound, the residual alkali content of the material decreased obviously. The processing performance was excellent, the rate performance was improved obviously, and the discharge specific capacities of 1C and 3C were increased to 156.5, 141.8 mAh·g-1, respectively. The capacity retention rate of 2Ah soft-packed battery was 80% after 830 cycles at room temperature and 80% after 345 cycles at high temperature.
2020, 36(1): 87-96
doi: 10.11862/CJIC.2020.031
Abstract:
A series of perovskite-type La1-xSrxCo1-yFeyO3 catalysts were successfully prepared by the citric acid-EDTA complexation. The catalysts exhibited excellent catalytic oxidation soot activity and sulfur resistance. The characterization of X-ray diffraction (XRD), fourier transform infrared spectra (FT-IR), scanning electron microscope (SEM), H2-temperature-programmed reduction (H2-TPR), X-ray photoelectron spectroscopy (XPS) and SO2-temperature programmed desorption (SO2-TPD) were used to reveal the effect of Sr and Fe doping on the physicochemical properties and sulfur tolerance of La1-xSrxCo1-yFeyO3 catalysts. Experimental results demonstrated that when the Sr doped with LaCoO3, it was beneficial for the catalyst to form more surface adsorption oxygen (O2- or O-) and oxygen vacancies, thereby improving both the low-temperature redox ability and catalytic oxidation soot activity of catalyst. Ti (ignition temperature of soot) and Tm (complete conversion temperature of soot) are only 284 and 347℃. Furthermore, with the doping of Fe, the low-temperature redox performance of catalyst was further improved, because the high-valent ions (Fe4+) were formed in the surface of catalyst, the Fe4+ ion could enhance the oxidation soot activity of catalyst. Moreover, the poisoning of SO2 was mainly attributed to the sulfation (SO32-, SO42-) of Co2+/Co3+ and surface adsorbed oxygen, leading to deactivating the active site (O2- or O- and Fe4+) of catalyst. Simultaneous doping of Sr and Fe can form a strong interaction, which can effectively inhibit the deposition of sulfur species on the catalyst surface and reduce the poisoning of SO2 into the catalyst. Both XPS and SO2-TPD characterizations showed that the sulfur resistance of catalyst was mainly attributed the competitive adsorption of metal ions (Fe3+) on SO2, which could effectively reduce the poisoning of SO2 on the surface adsorption oxygen and Fe4+. TPO (temperature programmed oxidation) activity characterization showed that LaSrCoFeO3-S still maintained good catalytic oxidation soot activity. Ti and Tm were 320 and 361℃, respectively, indicating that the simultaneous doping of Sr and Fe has excellent low-temperature catalytic soot activity and good sulfur poisoning ability.
A series of perovskite-type La1-xSrxCo1-yFeyO3 catalysts were successfully prepared by the citric acid-EDTA complexation. The catalysts exhibited excellent catalytic oxidation soot activity and sulfur resistance. The characterization of X-ray diffraction (XRD), fourier transform infrared spectra (FT-IR), scanning electron microscope (SEM), H2-temperature-programmed reduction (H2-TPR), X-ray photoelectron spectroscopy (XPS) and SO2-temperature programmed desorption (SO2-TPD) were used to reveal the effect of Sr and Fe doping on the physicochemical properties and sulfur tolerance of La1-xSrxCo1-yFeyO3 catalysts. Experimental results demonstrated that when the Sr doped with LaCoO3, it was beneficial for the catalyst to form more surface adsorption oxygen (O2- or O-) and oxygen vacancies, thereby improving both the low-temperature redox ability and catalytic oxidation soot activity of catalyst. Ti (ignition temperature of soot) and Tm (complete conversion temperature of soot) are only 284 and 347℃. Furthermore, with the doping of Fe, the low-temperature redox performance of catalyst was further improved, because the high-valent ions (Fe4+) were formed in the surface of catalyst, the Fe4+ ion could enhance the oxidation soot activity of catalyst. Moreover, the poisoning of SO2 was mainly attributed to the sulfation (SO32-, SO42-) of Co2+/Co3+ and surface adsorbed oxygen, leading to deactivating the active site (O2- or O- and Fe4+) of catalyst. Simultaneous doping of Sr and Fe can form a strong interaction, which can effectively inhibit the deposition of sulfur species on the catalyst surface and reduce the poisoning of SO2 into the catalyst. Both XPS and SO2-TPD characterizations showed that the sulfur resistance of catalyst was mainly attributed the competitive adsorption of metal ions (Fe3+) on SO2, which could effectively reduce the poisoning of SO2 on the surface adsorption oxygen and Fe4+. TPO (temperature programmed oxidation) activity characterization showed that LaSrCoFeO3-S still maintained good catalytic oxidation soot activity. Ti and Tm were 320 and 361℃, respectively, indicating that the simultaneous doping of Sr and Fe has excellent low-temperature catalytic soot activity and good sulfur poisoning ability.
2020, 36(1): 97-105
doi: 10.11862/CJIC.2020.009
Abstract:
The emission spectra of 2-PBI (2-(2'-pyridyl) benzimidazole) show a red shift at a specific wavelength in both aqueous and acetonitrile solutions. However, 2-PBI cannot be used as ratiometric fluorescent probe for Zn2+ because of its low binding ability and variable coordination ratio to Zn2+. In this study, in order to add coordination atoms and promote the ICT effect of the probe by introducing N, N-dimethyl group at its 5-position of 2-PBI, design and synthesize a new ratiometric Zn2+ fluorescent probe DBITA. The results show that, besides large Stokes shift of 172 nm, DBITA exhibits the specific Zn2+-induced emission red-shift from 534 nm to 609 nm. DBITA combines with Zn2+ as 1:1 binding ratio. Moreover, DBITA displays the extremely high affinity toward Zn2+ of 0.16 pmol·L-1. In HeLa cells, DBITA can be used to quantitatively detect intracellular Zn2+.
The emission spectra of 2-PBI (2-(2'-pyridyl) benzimidazole) show a red shift at a specific wavelength in both aqueous and acetonitrile solutions. However, 2-PBI cannot be used as ratiometric fluorescent probe for Zn2+ because of its low binding ability and variable coordination ratio to Zn2+. In this study, in order to add coordination atoms and promote the ICT effect of the probe by introducing N, N-dimethyl group at its 5-position of 2-PBI, design and synthesize a new ratiometric Zn2+ fluorescent probe DBITA. The results show that, besides large Stokes shift of 172 nm, DBITA exhibits the specific Zn2+-induced emission red-shift from 534 nm to 609 nm. DBITA combines with Zn2+ as 1:1 binding ratio. Moreover, DBITA displays the extremely high affinity toward Zn2+ of 0.16 pmol·L-1. In HeLa cells, DBITA can be used to quantitatively detect intracellular Zn2+.
2020, 36(1): 106-112
doi: 10.11862/CJIC.2020.008
Abstract:
Na-doped K-based Prussian blue (NKPB) material (K1.9Na0.1Mn[Fe(CN)6]·0.4H2O) was prepared by ion-exchange method using KCl and Na-based Prussian blue (NPB) material(Na2-xMn[Fe(CN)6]z·yH2O) as the precursors. The electrochemical tests reveal that compared with the K-based Prussian blue (KPB) material K1.85Mn[Fe(CN)6]0.98□0.02·0.7H2O (□ is the[Fe(CN)6] vacancy) prepared by a conversional coprecipitation route, the NKPB prepared by ion-exchange method shows higher capacity (the initial discharge capacity at 0.1C reached 136.3 mAh·g-1), longer cycle life (the capacity retention after 100 cycles at 0.5C was 96.1%), and better rate capability (the capacities at 5C and 10C were 87.6 and 68.4 mAh·g-1, respectively). The outstanding electrochemical performance of the NKPB material is ascribed to its high K content, good crystal integrity, Na-ion doping, nanosized particles and the unique open framework structure.
Na-doped K-based Prussian blue (NKPB) material (K1.9Na0.1Mn[Fe(CN)6]·0.4H2O) was prepared by ion-exchange method using KCl and Na-based Prussian blue (NPB) material(Na2-xMn[Fe(CN)6]z·yH2O) as the precursors. The electrochemical tests reveal that compared with the K-based Prussian blue (KPB) material K1.85Mn[Fe(CN)6]0.98□0.02·0.7H2O (□ is the[Fe(CN)6] vacancy) prepared by a conversional coprecipitation route, the NKPB prepared by ion-exchange method shows higher capacity (the initial discharge capacity at 0.1C reached 136.3 mAh·g-1), longer cycle life (the capacity retention after 100 cycles at 0.5C was 96.1%), and better rate capability (the capacities at 5C and 10C were 87.6 and 68.4 mAh·g-1, respectively). The outstanding electrochemical performance of the NKPB material is ascribed to its high K content, good crystal integrity, Na-ion doping, nanosized particles and the unique open framework structure.
2020, 36(1): 113-122
doi: 10.11862/CJIC.2020.004
Abstract:
In order to improve the application efficiency of vermiculite and broaden its application field, high expansion rate expanded vermiculite (HEV) was prepared by chemical-microwave method based on the excellent thermal expansion and cation exchange properties of industrial vermiculite and the adsorption properties of methylene blue (MB) were studied by comparative analysis. The experimental results showed that the HEV has a high expansion rate (K=60 times), large specific surface area (80 m2·g-1), and the pore diameter was mainly distributed between 2 and 5 nm. The crystalline formof vermiculite, hydrophlogopite and phlogopite were still maintained, and the cation exchange capacity increased to 1.005 mmol·g-1 from the original 0.835 mmol·g-1. The adsorption capacity of HEV was influenced by the initial concentration of MB, adsorption time, solution pH and adsorption temperature. When the initial concentration of MB solution was 300 mg·L-1, the adsorption time was 240 min, the pH value was 9, the adsorption temperature was 298 K, and the adsorption capacity was 419.87 mg·g-1, much higher than the original vermiculite ore. The adsorption process conforms to the Langmuir model and the pseudo-second order kinetic model, and is a spontaneous and disordered endothermic reaction process with single molecular layer adsorption and low adsorption barrier. Removal of HEV effect on MB has surpassed that of some natural minerals as well as commercial-grade activated carbon, indicating that HEV is an efficient, low-cost cationic dye waste water adsorbent.
In order to improve the application efficiency of vermiculite and broaden its application field, high expansion rate expanded vermiculite (HEV) was prepared by chemical-microwave method based on the excellent thermal expansion and cation exchange properties of industrial vermiculite and the adsorption properties of methylene blue (MB) were studied by comparative analysis. The experimental results showed that the HEV has a high expansion rate (K=60 times), large specific surface area (80 m2·g-1), and the pore diameter was mainly distributed between 2 and 5 nm. The crystalline formof vermiculite, hydrophlogopite and phlogopite were still maintained, and the cation exchange capacity increased to 1.005 mmol·g-1 from the original 0.835 mmol·g-1. The adsorption capacity of HEV was influenced by the initial concentration of MB, adsorption time, solution pH and adsorption temperature. When the initial concentration of MB solution was 300 mg·L-1, the adsorption time was 240 min, the pH value was 9, the adsorption temperature was 298 K, and the adsorption capacity was 419.87 mg·g-1, much higher than the original vermiculite ore. The adsorption process conforms to the Langmuir model and the pseudo-second order kinetic model, and is a spontaneous and disordered endothermic reaction process with single molecular layer adsorption and low adsorption barrier. Removal of HEV effect on MB has surpassed that of some natural minerals as well as commercial-grade activated carbon, indicating that HEV is an efficient, low-cost cationic dye waste water adsorbent.
2020, 36(1): 123-131
doi: 10.11862/CJIC.2020.014
Abstract:
Using the porphyrin molecule H2-pTCPP as a basic dye, we modified antenna molecule S3 into dye structure by coordination self-assembly method. The results show that the overall performance of the device has been greatly improved after the modification of antenna molecule. The antenna effect effectively improves the light-harvesting ability and the photocurrent of the device, in addition, the charge recombination is obviously reduced. The device based on H2-pTCPP showed a PCE of 1.18%, and the device based on Mn-pTCPP+S3 showed a PCE of 2.64%. So, the overall performance of the device is increased by 1.2 times.
Using the porphyrin molecule H2-pTCPP as a basic dye, we modified antenna molecule S3 into dye structure by coordination self-assembly method. The results show that the overall performance of the device has been greatly improved after the modification of antenna molecule. The antenna effect effectively improves the light-harvesting ability and the photocurrent of the device, in addition, the charge recombination is obviously reduced. The device based on H2-pTCPP showed a PCE of 1.18%, and the device based on Mn-pTCPP+S3 showed a PCE of 2.64%. So, the overall performance of the device is increased by 1.2 times.
2020, 36(1): 132-138
doi: 10.11862/CJIC.2020.030
Abstract:
Reaction of (1R, 2R)-diaminocyclohexane with 2-hydroxy-1-naphthaldehyde and 3, 5-di-tert-butyl sali-cylaldehyde gave an asymmetric salen ligand H2L. Then H2L conducted the coordination reaction with Ni(OAc)2·4H2O, Cu(OAc)2·H2O and Mn(OAc)2·4H2O, and three mononuclear complex of[Ni(L)]·CH2Cl2 (1), [Cu(L)] (2) and[Mn(L)(Cl)]·CH2Cl2 (3) were obtained. The compounds were characterized by 1H NMR, FT-IR and elemental analysis respectively and the crystal structure of ligand and three complexes were measured through X-ray single crystal diffraction technology. The ligand H2L belongs to the orthorhombic system, P212121 space group. Complex 1 belongs to the monoclinic system, P21/c space group, and the structures of complex 2 and 1 are similar. Complex 3 belongs to the triclinic system, P1 space group.
Reaction of (1R, 2R)-diaminocyclohexane with 2-hydroxy-1-naphthaldehyde and 3, 5-di-tert-butyl sali-cylaldehyde gave an asymmetric salen ligand H2L. Then H2L conducted the coordination reaction with Ni(OAc)2·4H2O, Cu(OAc)2·H2O and Mn(OAc)2·4H2O, and three mononuclear complex of[Ni(L)]·CH2Cl2 (1), [Cu(L)] (2) and[Mn(L)(Cl)]·CH2Cl2 (3) were obtained. The compounds were characterized by 1H NMR, FT-IR and elemental analysis respectively and the crystal structure of ligand and three complexes were measured through X-ray single crystal diffraction technology. The ligand H2L belongs to the orthorhombic system, P212121 space group. Complex 1 belongs to the monoclinic system, P21/c space group, and the structures of complex 2 and 1 are similar. Complex 3 belongs to the triclinic system, P1 space group.
Preparation and High Electrocatalytic Activity for the Oxidation of Ethanol of PdAu Alloy Foam Films
2020, 36(1): 21-30
doi: 10.11862/CJIC.2019.195
Abstract:
Three-dimensional (3D) porous Au-doped PdAu alloy foam films were obtained by using a hydrogen bubble dynamic template electrodeposition method. The morphology and structure features of 3D porous Au-doped Pd alloy foam films were characterized by field-emission scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Due to the special porous structures and the electronic effects, the Au-doped PdAu alloy foam films showed high electrocatalytic activity toward the electrooxidation of ethanol in alkaline media as compared to pure porous Pd film.
Three-dimensional (3D) porous Au-doped PdAu alloy foam films were obtained by using a hydrogen bubble dynamic template electrodeposition method. The morphology and structure features of 3D porous Au-doped Pd alloy foam films were characterized by field-emission scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Due to the special porous structures and the electronic effects, the Au-doped PdAu alloy foam films showed high electrocatalytic activity toward the electrooxidation of ethanol in alkaline media as compared to pure porous Pd film.
2020, 36(1): 53-61
doi: 10.11862/CJIC.2020.022
Abstract:
In this work, atomically precise[Pd3Cl(PPh2)2(PPh3)3]+ (denoted as Pd3Cl) nanoclusters with high monodispersity were supported on the rod-like mesoporous SBA-15 by electrostatic attraction strategy. The well-defined Pd3Cl/SBA-15 catalysts exhibited good catalytic performance and recyclability for Sonogashira C-C coupling reaction under mild condition with environment-friendly water as solvent. Importantly, we investigated the relationship between structures and properties of Pd3Cl, which demonstrated that the synergistic effect between Pdδ+ (0 < δ < 2) and the ligand was the key to the catalytic reaction.
In this work, atomically precise[Pd3Cl(PPh2)2(PPh3)3]+ (denoted as Pd3Cl) nanoclusters with high monodispersity were supported on the rod-like mesoporous SBA-15 by electrostatic attraction strategy. The well-defined Pd3Cl/SBA-15 catalysts exhibited good catalytic performance and recyclability for Sonogashira C-C coupling reaction under mild condition with environment-friendly water as solvent. Importantly, we investigated the relationship between structures and properties of Pd3Cl, which demonstrated that the synergistic effect between Pdδ+ (0 < δ < 2) and the ligand was the key to the catalytic reaction.
2020, 36(1): 139-147
doi: 10.11862/CJIC.2019.273
Abstract:
The chiral metal-organic framework, HMOF-Zn, with a large one-dimensional chiral channel and acetylene black (AB) were chosen as electrode materials to modify glassy carbon electrode (GCE) via a simple electrochemical method, denoted as HMOF-Zn@AB-Nafion-GCE. The HMOF-Zn@AB-Nafion-GCE sensor was used for simultaneous detection of dopamine (DA) and uric acid (UA). The experimental results showed that the HMOF-Zn@AB-Nafion-GCE sensor had high sensitivity and selectivity for UA and DA. And it was found that it exhibited higher sensitivity for DA than for UA on HMOF-Zn@AB-Nafion-GCE sensor. The high sensitivity and good selectivity of HMOF-Zn@AB-Nafion-GCE sensor for DA and UA are attributed to the synergistic effect of the large surface of HMOF-Zn, the bonding interaction between the analytes (DA or UA) and HMOF-Zn as well as the high conductivity of AB. At the same time, the proposed sensor exhibited excellent linear responses to DA and UA under optimized conditions. The detection ranges were 0.15~2.5 μmol·L-1 for DA and 0.2~4 μmol·L-1 for UA, with the detection limits of 0.003 and 0.02 μmol·L-1, respectively. Moreover, the high reproducibility of the sensor was obtained in all the experiments. The sensor was also successfully applied to the determination of DA in dopamine hydrochloride injection and UA in human urine sample.
The chiral metal-organic framework, HMOF-Zn, with a large one-dimensional chiral channel and acetylene black (AB) were chosen as electrode materials to modify glassy carbon electrode (GCE) via a simple electrochemical method, denoted as HMOF-Zn@AB-Nafion-GCE. The HMOF-Zn@AB-Nafion-GCE sensor was used for simultaneous detection of dopamine (DA) and uric acid (UA). The experimental results showed that the HMOF-Zn@AB-Nafion-GCE sensor had high sensitivity and selectivity for UA and DA. And it was found that it exhibited higher sensitivity for DA than for UA on HMOF-Zn@AB-Nafion-GCE sensor. The high sensitivity and good selectivity of HMOF-Zn@AB-Nafion-GCE sensor for DA and UA are attributed to the synergistic effect of the large surface of HMOF-Zn, the bonding interaction between the analytes (DA or UA) and HMOF-Zn as well as the high conductivity of AB. At the same time, the proposed sensor exhibited excellent linear responses to DA and UA under optimized conditions. The detection ranges were 0.15~2.5 μmol·L-1 for DA and 0.2~4 μmol·L-1 for UA, with the detection limits of 0.003 and 0.02 μmol·L-1, respectively. Moreover, the high reproducibility of the sensor was obtained in all the experiments. The sensor was also successfully applied to the determination of DA in dopamine hydrochloride injection and UA in human urine sample.
2020, 36(1): 148-158
doi: 10.11862/CJIC.2020.005
Abstract:
CFx-Ru cathode materials for lithium primary batteries were synthesized by a simple in-situ chemical modification for the first time. Compared with pristine commercial CFx, CFx-Ru exhibited an improved capacity of 605 mAh·g-1 and a maximum power density of 8 727 W·kg-1 with a plateau of 2 V at 5C, which shows a promising application in the market. The structure, chemical environment and morphology were investigated by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and transmission electron microscopy. It is found that the ratio of F to C (nF/nC) and the peak area ratio of the C-F2 bond to the C-F covalent bond in CFx-Ru were both lowered, which is supposed to come from the reaction of RuO2 with CF2 inert group of CFx materials in situ synthesis. This in-situ chemical reaction consumed inactive CF2, produced conductive elemental ruthenium, and increased specific surface area due to gas phase product evolution. These features contribute to the excellent electrochemical performance of the modified material. The improved conductivity and larger specific surface area were further comfirmed by the results of electrochemical impedance spectroscopy and N2 adorption-desorption measurements.
CFx-Ru cathode materials for lithium primary batteries were synthesized by a simple in-situ chemical modification for the first time. Compared with pristine commercial CFx, CFx-Ru exhibited an improved capacity of 605 mAh·g-1 and a maximum power density of 8 727 W·kg-1 with a plateau of 2 V at 5C, which shows a promising application in the market. The structure, chemical environment and morphology were investigated by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and transmission electron microscopy. It is found that the ratio of F to C (nF/nC) and the peak area ratio of the C-F2 bond to the C-F covalent bond in CFx-Ru were both lowered, which is supposed to come from the reaction of RuO2 with CF2 inert group of CFx materials in situ synthesis. This in-situ chemical reaction consumed inactive CF2, produced conductive elemental ruthenium, and increased specific surface area due to gas phase product evolution. These features contribute to the excellent electrochemical performance of the modified material. The improved conductivity and larger specific surface area were further comfirmed by the results of electrochemical impedance spectroscopy and N2 adorption-desorption measurements.
2020, 36(1): 159-164
doi: 10.11862/CJIC.2020.003
Abstract:
Reactions of ligands 1, 3-di(1H-imidazol-4-yl)benzene (L) and with corresponding metal salts under hydrothermal conditions gave rise to two new metal-organic frameworks (MOFs), namely[Cd(L)(SO4)]n (1) and {[Ni(L)(SO4)]·H2O}n (2). All of MOFs have been structurally characterized by single-crystal X-ray diffraction analyses and characterized by elemental analysis, infrared spectra (IR), powder X-ray diffraction (PXRD) and thermo-gravimetric analysis (TGA). 1 belongs to orthorhombic system, space group Pnma, with a=0.707 28(5) nm, b=1.343 81(9) nm, c=1.407 31(9) nm, V=1.337 58(16) nm3, Dc=2.079 g·cm-3, Z=4, F(000)=824, GOF=1.072, R1=0.019 0, wR2=0.050 6. 2 belongs to triclinic system, space group P1, with a=0.986 65(18) nm, b=1.145 7(2) nm, c=1.302 5(2) nm, α=65.029(3)°, β=83.497(3)°, γ=86.423(4)°, V=1.326 0(4) nm3, Dc=1.441 g·cm-3, Z=2, F(000)=592, GOF=1.016, R1=0.043 4, wR2=0.077 1. All the MOFs have two-dimensional (2D) layer structures. Furthermore, the thermal stability and photoluminescence property of the MOFs were investigated.
Reactions of ligands 1, 3-di(1H-imidazol-4-yl)benzene (L) and with corresponding metal salts under hydrothermal conditions gave rise to two new metal-organic frameworks (MOFs), namely[Cd(L)(SO4)]n (1) and {[Ni(L)(SO4)]·H2O}n (2). All of MOFs have been structurally characterized by single-crystal X-ray diffraction analyses and characterized by elemental analysis, infrared spectra (IR), powder X-ray diffraction (PXRD) and thermo-gravimetric analysis (TGA). 1 belongs to orthorhombic system, space group Pnma, with a=0.707 28(5) nm, b=1.343 81(9) nm, c=1.407 31(9) nm, V=1.337 58(16) nm3, Dc=2.079 g·cm-3, Z=4, F(000)=824, GOF=1.072, R1=0.019 0, wR2=0.050 6. 2 belongs to triclinic system, space group P1, with a=0.986 65(18) nm, b=1.145 7(2) nm, c=1.302 5(2) nm, α=65.029(3)°, β=83.497(3)°, γ=86.423(4)°, V=1.326 0(4) nm3, Dc=1.441 g·cm-3, Z=2, F(000)=592, GOF=1.016, R1=0.043 4, wR2=0.077 1. All the MOFs have two-dimensional (2D) layer structures. Furthermore, the thermal stability and photoluminescence property of the MOFs were investigated.
2020, 36(1): 165-172
doi: 10.11862/CJIC.2020.029
Abstract:
Two homochiral coordination polymers[Cd3((R)-CIA)2(bipy)2.5(H2O)2]·xGuest (1) and[Zn3((R)-CIA)(bmib)2(H2O)2Cl]·H2O·xGuest (2) ((R)-H3CIA=(R)-5-(1-carboxyethoxy) isophthalic acid, bipy=4, 4'-bipyridine, bmib=1, 4-bis(2-methyl-1H-imidazol-1-yl)benzene) were obtained under solvothermal reaction conditions. X-ray single crystal structure analysis reveals that complexes 1 and 2 are all 3D pillar-layered frameworks. From the viewpoint of structural topology, complex 1 possesses a (3, 3, 3, 6, 6)-connected net with a point symbol of (4.52)2(4.82)2(42.68.83. 102)(42.68.83.92)(5.8.9)2, while complex 2 is a (3, 4, 4)-connected net with a point symbol of (6·72)2(6·75)2(62·74). Moreover, thermal stabilities, CD spectra and luminescent properties of these new complexes have been studied.
Two homochiral coordination polymers[Cd3((R)-CIA)2(bipy)2.5(H2O)2]·xGuest (1) and[Zn3((R)-CIA)(bmib)2(H2O)2Cl]·H2O·xGuest (2) ((R)-H3CIA=(R)-5-(1-carboxyethoxy) isophthalic acid, bipy=4, 4'-bipyridine, bmib=1, 4-bis(2-methyl-1H-imidazol-1-yl)benzene) were obtained under solvothermal reaction conditions. X-ray single crystal structure analysis reveals that complexes 1 and 2 are all 3D pillar-layered frameworks. From the viewpoint of structural topology, complex 1 possesses a (3, 3, 3, 6, 6)-connected net with a point symbol of (4.52)2(4.82)2(42.68.83. 102)(42.68.83.92)(5.8.9)2, while complex 2 is a (3, 4, 4)-connected net with a point symbol of (6·72)2(6·75)2(62·74). Moreover, thermal stabilities, CD spectra and luminescent properties of these new complexes have been studied.
2020, 36(1): 173-182
doi: 10.11862/CJIC.2019.257
Abstract:
Two new coordination polymers (CPs) based on H4tptc, namely, {[Zn2(tptc)(1, 4-bimb)2]·H2O}n (1) and {[Ni(tptc)0.5(1, 2-bimb)(H2O)]·H2O}n (2) (H4tptc=p-terphenyl-3, 3", 5, 5"-tetracarboxylic acid, 1, 4-bimb=1, 4-bis (imid-azol-1-ylmethyl) benzene, 1, 2-bimb=1, 2-bis (imidazol-1-ylmethyl) benzene), have been synthesized under solvo-thermal conditions. The structural analyses reveal that complex 1 shows a 3D structure with the symbol of (86), while complex 2 presents a 2D layer network, which is further expanded into a 3D supramolecular structure through H-bonding interactions. Furthermore, the luminescence sensing of 1 for cations, anions as well as magnetic property of 2 have also been studied.
Two new coordination polymers (CPs) based on H4tptc, namely, {[Zn2(tptc)(1, 4-bimb)2]·H2O}n (1) and {[Ni(tptc)0.5(1, 2-bimb)(H2O)]·H2O}n (2) (H4tptc=p-terphenyl-3, 3", 5, 5"-tetracarboxylic acid, 1, 4-bimb=1, 4-bis (imid-azol-1-ylmethyl) benzene, 1, 2-bimb=1, 2-bis (imidazol-1-ylmethyl) benzene), have been synthesized under solvo-thermal conditions. The structural analyses reveal that complex 1 shows a 3D structure with the symbol of (86), while complex 2 presents a 2D layer network, which is further expanded into a 3D supramolecular structure through H-bonding interactions. Furthermore, the luminescence sensing of 1 for cations, anions as well as magnetic property of 2 have also been studied.
2020, 36(1): 183-191
doi: 10.11862/CJIC.2020.015
Abstract:
Herein, two novel copper(Ⅰ) complexes, [Cu(PPh3)2(dppz)]Ⅰ (1) and[Cu2(dppm)2(dppz)2]Cl2 (2) (PPh3=triphenylphosphine, dppz=dipyrido[3, 2-a:2', 3'-c]phenazine, dppm=bis(diphenylphosphino) methane) have been synthesized, and the characterization of the complexes was carried out through single-crystal X-ray diffraction, elemental analysis, IR, 1H/31P NMR spectroscopy, fluorescence spectra and THz time domain spectroscopy (THz-TDS). The results show that 1 is a mononuclear complex. The central Cu(Ⅰ) builds a distorted tetrahedral geometry by coordinating with two phosphine ligands (PPh3) and one chelating N-donor ligand (dppz). Different from 1, 2 exhibits a dinuclear structure which was obtained by the reaction of CuCl and dppm with dppz in 1:1:1 molar ratio, where the diphosphine ligand (dppm) was utilized as a bridging ligand coordinating to two copper(Ⅰ) atoms. The luminescent spectra show that the emission mechanism belongs to metal-to-ligand charge transfer (MLCT). At the same time, the terahertz (THz) time-domain spectroscopy was used to represent these two complexes as well as the corresponding ligands.
Herein, two novel copper(Ⅰ) complexes, [Cu(PPh3)2(dppz)]Ⅰ (1) and[Cu2(dppm)2(dppz)2]Cl2 (2) (PPh3=triphenylphosphine, dppz=dipyrido[3, 2-a:2', 3'-c]phenazine, dppm=bis(diphenylphosphino) methane) have been synthesized, and the characterization of the complexes was carried out through single-crystal X-ray diffraction, elemental analysis, IR, 1H/31P NMR spectroscopy, fluorescence spectra and THz time domain spectroscopy (THz-TDS). The results show that 1 is a mononuclear complex. The central Cu(Ⅰ) builds a distorted tetrahedral geometry by coordinating with two phosphine ligands (PPh3) and one chelating N-donor ligand (dppz). Different from 1, 2 exhibits a dinuclear structure which was obtained by the reaction of CuCl and dppm with dppz in 1:1:1 molar ratio, where the diphosphine ligand (dppm) was utilized as a bridging ligand coordinating to two copper(Ⅰ) atoms. The luminescent spectra show that the emission mechanism belongs to metal-to-ligand charge transfer (MLCT). At the same time, the terahertz (THz) time-domain spectroscopy was used to represent these two complexes as well as the corresponding ligands.
2020, 36(1): 192-206
doi: 10.11862/CJIC.2020.017
Abstract:
Two 1D cadmium(Ⅱ) and nickel(Ⅱ) coordination polymers, namely {[M2(μ3-L)(phen)3]·5H2O}n (M=Cd (1), Ni (2)), were constructed hydrothermally using H4L (H4L=3-(2, 4-dicarboxyphenyl)-2, 6-pyridinedicarboxylic acid), phen (phen=1, 10-phenanthroline), and cadmium or nickel chlorides. Single-crystal X-ray diffraction analyses reveal that both compounds are isostructural and crystallize in the orthorhombic system, space group Pbca. Compound 1 or 2 feature a 1D metal-organic chain, which is assembled to a 2D supramolecular network through O-H…O hydrogen bond. The luminescent and magnetic properties for two compounds were also investigated.
Two 1D cadmium(Ⅱ) and nickel(Ⅱ) coordination polymers, namely {[M2(μ3-L)(phen)3]·5H2O}n (M=Cd (1), Ni (2)), were constructed hydrothermally using H4L (H4L=3-(2, 4-dicarboxyphenyl)-2, 6-pyridinedicarboxylic acid), phen (phen=1, 10-phenanthroline), and cadmium or nickel chlorides. Single-crystal X-ray diffraction analyses reveal that both compounds are isostructural and crystallize in the orthorhombic system, space group Pbca. Compound 1 or 2 feature a 1D metal-organic chain, which is assembled to a 2D supramolecular network through O-H…O hydrogen bond. The luminescent and magnetic properties for two compounds were also investigated.
