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2022 Volume 38 Issue 9
2022, 38(9): 1673-1689
doi: 10.11862/CJIC.2022.179
Abstract:
At present, the capacity of commercial graphite anode materials for lithium-ion batteries is close to the theoretical value, which limits the development of power batteries. Therefore, it is particularly important to develop anode materials with high capacity, good stability, long cycle life, and excellent rate performance. Co-based oxide materials are one of the ideal anode materials for lithium-ion batteries due to their high specific capacity. In this review, the influence of the increase of active sites of Co-based oxides to promote lithium storage performance is reviewed from the structural design including the construction of one-dimensional structures, two-dimensional structures, three-dimensional structures, hollow structures, carbon material support structures, and heterostructures. The control of intrinsic activity includes the introduction of amorphous structure, non-metallic heteroatom doping, metal heteroatom doping, and the construction of high-entropy oxides. Finally, the future development of Co-based oxides in the field of lithium-ion batteries is prospected.
At present, the capacity of commercial graphite anode materials for lithium-ion batteries is close to the theoretical value, which limits the development of power batteries. Therefore, it is particularly important to develop anode materials with high capacity, good stability, long cycle life, and excellent rate performance. Co-based oxide materials are one of the ideal anode materials for lithium-ion batteries due to their high specific capacity. In this review, the influence of the increase of active sites of Co-based oxides to promote lithium storage performance is reviewed from the structural design including the construction of one-dimensional structures, two-dimensional structures, three-dimensional structures, hollow structures, carbon material support structures, and heterostructures. The control of intrinsic activity includes the introduction of amorphous structure, non-metallic heteroatom doping, metal heteroatom doping, and the construction of high-entropy oxides. Finally, the future development of Co-based oxides in the field of lithium-ion batteries is prospected.
2022, 38(9): 1690-1706
doi: 10.11862/CJIC.2022.182
Abstract:
Electrochromism is a phenomenon exhibiting color changes under an external electrical stimulus. Electrochromic materials can switch reversibly between different redox and/or oxidation states, resulting in new absorption bands in the visible or near?infrared region. So far, electrochromic materials mainly included transition metal oxides, transition metal coordination polymers, viologens, organic conjugated polymers, and so on. Transition metal coordination polymers-based electrochromic materials possessed the combined advantages of both inorganic materials and organic materials and showed a wide application prospect. Ferric coordination polymers were excellent electrochromic materials with good redox properties and abundant electronic transitions. In this paper, the research progress of electrochromic materials of ferric coordination polymers is reviewed, mainly from the aspects of arm shape, type, and spacer group of organic ligands.
Electrochromism is a phenomenon exhibiting color changes under an external electrical stimulus. Electrochromic materials can switch reversibly between different redox and/or oxidation states, resulting in new absorption bands in the visible or near?infrared region. So far, electrochromic materials mainly included transition metal oxides, transition metal coordination polymers, viologens, organic conjugated polymers, and so on. Transition metal coordination polymers-based electrochromic materials possessed the combined advantages of both inorganic materials and organic materials and showed a wide application prospect. Ferric coordination polymers were excellent electrochromic materials with good redox properties and abundant electronic transitions. In this paper, the research progress of electrochromic materials of ferric coordination polymers is reviewed, mainly from the aspects of arm shape, type, and spacer group of organic ligands.
2022, 38(9): 1707-1715
doi: 10.11862/CJIC.2022.178
Abstract:
The restacking of MXene nanosheets resulted in poor ion accessibility to absorption sites, preventing MXene from high energy density and power density. Herein, 0D/2D composite Ti3C 2Tx MXene was prepared by hydrothermal method to alleviate the restacking problem. The quantum dot-interspersed Ti3C2Tx nanosheets (QDT) structure was confirmed by X - ray diffraction, dynamic light scattering, and fluorescence spectroscopy. The free - standing film electrodes assembled by QDT showed prominently improved electrochemical properties compared to the pristine Ti3C2Tx nanosheets. In three-electrode system, the mass specific capacitance reached 338 F·g-1 under a scan rate of 5 mV·s-1. The capacitance retention reached 46% as the scan rate was 2 000 mV·s-1. In two-electrode system, the assembled symmetric supercapacitor delivered a discharge capacitance of 216 F·g-1 at a current density of 0.5 A·g-1. The capacitance retention rate was 87% after 10 000 cycles. The above electrochemical properties of QDT film electrodes were ascribed to the increased ion absorption sites from quantum dots and shortened ion path-way resulted from reduced nanosheet sizes.
The restacking of MXene nanosheets resulted in poor ion accessibility to absorption sites, preventing MXene from high energy density and power density. Herein, 0D/2D composite Ti3C 2Tx MXene was prepared by hydrothermal method to alleviate the restacking problem. The quantum dot-interspersed Ti3C2Tx nanosheets (QDT) structure was confirmed by X - ray diffraction, dynamic light scattering, and fluorescence spectroscopy. The free - standing film electrodes assembled by QDT showed prominently improved electrochemical properties compared to the pristine Ti3C2Tx nanosheets. In three-electrode system, the mass specific capacitance reached 338 F·g-1 under a scan rate of 5 mV·s-1. The capacitance retention reached 46% as the scan rate was 2 000 mV·s-1. In two-electrode system, the assembled symmetric supercapacitor delivered a discharge capacitance of 216 F·g-1 at a current density of 0.5 A·g-1. The capacitance retention rate was 87% after 10 000 cycles. The above electrochemical properties of QDT film electrodes were ascribed to the increased ion absorption sites from quantum dots and shortened ion path-way resulted from reduced nanosheet sizes.
2022, 38(9): 1716-1728
doi: 10.11862/CJIC.2022.177
Abstract:
Bismuth nitrate pentahydrate and sodium tungstate dihydrate were used as raw materials, and cetyltrimethylammonium bromide (CTAB) was used as bromine source to achieve Br-doped Bi2WO 6. By adjusting the content of CTAB, Bi2WO6 catalysts with different Br doping amounts were prepared by hydrothermal method. The antibiotics ciprofloxacin and norfloxacin were used as pollutants to test the photocatalytic performance of the Br - doped Bi2WO6 catalyst. The results showed that the 2% (molar fraction) doped Bi2WO6 had the best photocatalytic degradation performance compared to pure Bi2WO6. In addition, through a series of tests such as X-ray powder diffraction, Fourier transform infrared spectra, scanning electron microscope, photoluminescence spectra, UV-Vis diffuse reflection spectra, Raman, and X-ray photoelectron spectra, the phase composition, micro morphology, photo-generated charge separation rate, and optical properties of the Br-doped catalyst were analyzed. The free radical capture experiments were carried out and the possible photocatalytic mechanisms were proposed.
Bismuth nitrate pentahydrate and sodium tungstate dihydrate were used as raw materials, and cetyltrimethylammonium bromide (CTAB) was used as bromine source to achieve Br-doped Bi2WO 6. By adjusting the content of CTAB, Bi2WO6 catalysts with different Br doping amounts were prepared by hydrothermal method. The antibiotics ciprofloxacin and norfloxacin were used as pollutants to test the photocatalytic performance of the Br - doped Bi2WO6 catalyst. The results showed that the 2% (molar fraction) doped Bi2WO6 had the best photocatalytic degradation performance compared to pure Bi2WO6. In addition, through a series of tests such as X-ray powder diffraction, Fourier transform infrared spectra, scanning electron microscope, photoluminescence spectra, UV-Vis diffuse reflection spectra, Raman, and X-ray photoelectron spectra, the phase composition, micro morphology, photo-generated charge separation rate, and optical properties of the Br-doped catalyst were analyzed. The free radical capture experiments were carried out and the possible photocatalytic mechanisms were proposed.
2022, 38(9): 1729-1738
doi: 10.11862/CJIC.2022.172
Abstract:
Herein, the nickel molybdate nanorods arrays supported on Ni foam (NMO/NF) precursor were firstly fabricated by hydrothermal method. Then the surface sulfidation and phosphating for NMO/NF were conducted in turn, to obtain a three-dimensional self-supported electrode (PS-NMO/NF). The sulfidation induces the formation of amorphous sulfides with significantly enhanced electrochemical active area on the surface of nickel molybdate (S- NMO/ NF), as well as a coral-like sphere structure. Phosphates were induced on the surface of sulfides by subsequent phosphating. The formed sulfides/phosphates heterogeneous interfaces can promote the electron transfer and improve the hydrogen evolution reaction (HER) performance of NMO. In 1 mol·L-1 KOH electrolyte, when the current density was 10 and 100 mA·cm-2, the corresponding HER overpotential of PS-NMO/NF was 93 and 180 mV, respectively. The Tafel slope of PS-NMO/NF was 67 mV·dec-1, and it had good stability within 20 h of running.
Herein, the nickel molybdate nanorods arrays supported on Ni foam (NMO/NF) precursor were firstly fabricated by hydrothermal method. Then the surface sulfidation and phosphating for NMO/NF were conducted in turn, to obtain a three-dimensional self-supported electrode (PS-NMO/NF). The sulfidation induces the formation of amorphous sulfides with significantly enhanced electrochemical active area on the surface of nickel molybdate (S- NMO/ NF), as well as a coral-like sphere structure. Phosphates were induced on the surface of sulfides by subsequent phosphating. The formed sulfides/phosphates heterogeneous interfaces can promote the electron transfer and improve the hydrogen evolution reaction (HER) performance of NMO. In 1 mol·L-1 KOH electrolyte, when the current density was 10 and 100 mA·cm-2, the corresponding HER overpotential of PS-NMO/NF was 93 and 180 mV, respectively. The Tafel slope of PS-NMO/NF was 67 mV·dec-1, and it had good stability within 20 h of running.
2022, 38(9): 1739-1751
doi: 10.11862/CJIC.2022.195
Abstract:
In this paper, molybdenum dioxide (MoO2) nanoparticles were prepared by hydrothermal synthesis method using molybdenum pentachloride (MoCl5) as molybdenum source and polyvinylpyrrolidone (PVP) as a structural guiding agent as well as reducing agent. The results from X - ray powder diffraction (XRD), transmission electron microscopy (TEM), UV-Vis-near-infrared (UV-Vis-NIR) absorption spectroscopy, X-ray photoelectron spectroscopy (XPS), and electron spin resonance spectroscopy (EPR) illustrated that the diameter of the prepared MoO2 nanoparticles were about 18 nm. The particle size was uniform with abundant oxygen defects, and had good light absorption ability in the near-infrared region of 650-1 100 nm. The photothermal test demonstrated that the 100 μg·mL-1 aqueous solution of the material heated up 31.5 ℃ within 10 min, the photothermal conversion rate was up to 67.9% with excellent photothermal stability. Cytotoxicity test showed that the nanomaterial had no toxicity to cells, meanwhile possessing an obvious photothermal killing effect on hepatoma cells.
In this paper, molybdenum dioxide (MoO2) nanoparticles were prepared by hydrothermal synthesis method using molybdenum pentachloride (MoCl5) as molybdenum source and polyvinylpyrrolidone (PVP) as a structural guiding agent as well as reducing agent. The results from X - ray powder diffraction (XRD), transmission electron microscopy (TEM), UV-Vis-near-infrared (UV-Vis-NIR) absorption spectroscopy, X-ray photoelectron spectroscopy (XPS), and electron spin resonance spectroscopy (EPR) illustrated that the diameter of the prepared MoO2 nanoparticles were about 18 nm. The particle size was uniform with abundant oxygen defects, and had good light absorption ability in the near-infrared region of 650-1 100 nm. The photothermal test demonstrated that the 100 μg·mL-1 aqueous solution of the material heated up 31.5 ℃ within 10 min, the photothermal conversion rate was up to 67.9% with excellent photothermal stability. Cytotoxicity test showed that the nanomaterial had no toxicity to cells, meanwhile possessing an obvious photothermal killing effect on hepatoma cells.
2022, 38(9): 1752-1758
doi: 10.11862/CJIC.2022.198
Abstract:
To develop novel metal-organic framework-based derivatives with excellent electrochemical properties, a bimetal-organic framework (Fe-Cr-MOF) was synthesized by microwave method using terephthalic acid, and chromium trichloride, and ferric nitrate nonahydrate as raw materials. Under nitrogen protection, Fe -Cr -MOF was selenized at high temperatures to obtain nanoparticulate Fe - CrSe/C composites, which were used as anode materials for lithium -ion batteries. The results showed that the reversible specific capacity of the Fe -CrSe/C electrode reached 958.4 mAh·g-1 in the first cycle, and the specific capacity can maintain 891.6 mAh·g-1 after 150 cycles at the current density of 100 mA·g-1.
To develop novel metal-organic framework-based derivatives with excellent electrochemical properties, a bimetal-organic framework (Fe-Cr-MOF) was synthesized by microwave method using terephthalic acid, and chromium trichloride, and ferric nitrate nonahydrate as raw materials. Under nitrogen protection, Fe -Cr -MOF was selenized at high temperatures to obtain nanoparticulate Fe - CrSe/C composites, which were used as anode materials for lithium -ion batteries. The results showed that the reversible specific capacity of the Fe -CrSe/C electrode reached 958.4 mAh·g-1 in the first cycle, and the specific capacity can maintain 891.6 mAh·g-1 after 150 cycles at the current density of 100 mA·g-1.
2022, 38(9): 1759-1770
doi: 10.11862/CJIC.2022.171
Abstract:
Based on low-cost, non-toxic, and strong light absorption ferric oxide (Fe3O4) and layered double hydrox-ides (LDHs) with large specific surface and high stability, Fe3O4@MAl -LDHs (M=Zn, Co, Ni) composites were pre-pared and used for photocatalytic degradation of methylene blue. The composition and structure of the composites were characterized by X-ray powder diffraction (XRD), UV-Vis absorption spectroscopy, scanning electron microsco-py (SEM), transmission electron microscopy (TEM), and N2 adsorption-desorption test. The optimum conditions were as follows: the amount of catalyst was 50 mg, the light intensity was 500 W, the pH value was 9, and the reaction temperature was 40 ℃. The degradation rate of methylene blue increased significantly from 23.2% of LDHs to 87.0% of Fe 3O4@MAl- LDHs. The degradation of methylene blue by LDHs mainly comes from ·OH, while the photo-degradation activity of Fe3O4@MAl-LDHs is mainly contributed by both ·OH and holes. In addition, there were also great differences in the electrochemical properties of LDHs and Fe3O4@MAl-LDHs.
Based on low-cost, non-toxic, and strong light absorption ferric oxide (Fe3O4) and layered double hydrox-ides (LDHs) with large specific surface and high stability, Fe3O4@MAl -LDHs (M=Zn, Co, Ni) composites were pre-pared and used for photocatalytic degradation of methylene blue. The composition and structure of the composites were characterized by X-ray powder diffraction (XRD), UV-Vis absorption spectroscopy, scanning electron microsco-py (SEM), transmission electron microscopy (TEM), and N2 adsorption-desorption test. The optimum conditions were as follows: the amount of catalyst was 50 mg, the light intensity was 500 W, the pH value was 9, and the reaction temperature was 40 ℃. The degradation rate of methylene blue increased significantly from 23.2% of LDHs to 87.0% of Fe 3O4@MAl- LDHs. The degradation of methylene blue by LDHs mainly comes from ·OH, while the photo-degradation activity of Fe3O4@MAl-LDHs is mainly contributed by both ·OH and holes. In addition, there were also great differences in the electrochemical properties of LDHs and Fe3O4@MAl-LDHs.
2022, 38(9): 1771-1780
doi: 10.11862/CJIC.2022.197
Abstract:
Solvothermal reactions of the conjugated triene pyridine ligand 1, 6-bis(4-pyridyl)-l, 3, 5-hexatriene (bphte) and Cd salts in the presence of auxiliary carboxylic acid ligands (2, 5-furandicarboxylic acid (2, 5-H2FDC) and 1, 3, 5-trimesic acid (1, 3, 5-H3BTC)) gave rise to two coordination polymers [Cd(2, 5-FDC)(bphte)(H2O)]n (1) and [Cd(1, 3, 5-HBTC)(bphte)]n (2), respectively. Both complexes were characterized by elemental analysis, IR, single-crystal X-ray diffraction, powder X - ray diffraction, and thermogravimetric analysis. Complex 1 has a 3D framework with an spl topological structure, while complex 2 holds another 3D architecture formed by bridging 1D [Cd2(1, 3, 5-HBTC)2]n chains via bphte ligands. Both complexes exhibited luminescence emission in the solid state. Complex 2 showed an emission quenching phenomenon in Fe3+ aqueous solution, and thus was used as an excellent fluorescence probe to selectively detect Fe3+ in water with a low detection limit of 0.013 μmol·L-1. The above emission quenching mecha-nism is likely due to the overlap between the absorption band of the Fe3+ ion and the excitation band of 2.
Solvothermal reactions of the conjugated triene pyridine ligand 1, 6-bis(4-pyridyl)-l, 3, 5-hexatriene (bphte) and Cd salts in the presence of auxiliary carboxylic acid ligands (2, 5-furandicarboxylic acid (2, 5-H2FDC) and 1, 3, 5-trimesic acid (1, 3, 5-H3BTC)) gave rise to two coordination polymers [Cd(2, 5-FDC)(bphte)(H2O)]n (1) and [Cd(1, 3, 5-HBTC)(bphte)]n (2), respectively. Both complexes were characterized by elemental analysis, IR, single-crystal X-ray diffraction, powder X - ray diffraction, and thermogravimetric analysis. Complex 1 has a 3D framework with an spl topological structure, while complex 2 holds another 3D architecture formed by bridging 1D [Cd2(1, 3, 5-HBTC)2]n chains via bphte ligands. Both complexes exhibited luminescence emission in the solid state. Complex 2 showed an emission quenching phenomenon in Fe3+ aqueous solution, and thus was used as an excellent fluorescence probe to selectively detect Fe3+ in water with a low detection limit of 0.013 μmol·L-1. The above emission quenching mecha-nism is likely due to the overlap between the absorption band of the Fe3+ ion and the excitation band of 2.
2022, 38(9): 1781-1789
doi: 10.11862/CJIC.2022.159
Abstract:
Herein, the bottom - up method was utilized for the synthesis of MFI nanosheet with a high aspect ratio and crystallinity by using homemade dC5 (bis-1, 5(tripropyl ammonium). b-Oriented MFI nanosheets seed layer was coated on glass supports by slip coating method with an average thickness of about 100 nm. The SDA (structure - directing agent) free secondary growth of the MFI nanosheet layer was conducted to effectively seal the interlayer and nanoscale gap among the nanosheet layer. The SDA-free secondary growth effectively preserves the b- orientation of the MFI film while maintaining the minimal thickness. A continuous and dense b-oriented MFI zeolite film with a thickness of about 200 nm was prepared under nSiO2∶nNa2O∶nC2H5OH∶nH2O=1∶0.03∶1.3∶0.89 with a crystallization time and temperature of 48 h and 180 ℃, respectively. A significant decrease was observed in the thickness (approxi-mately 90%) of the synthesized film by the SDA-free secondary growth method as compared to MFI zeolite film pre-pared by the conventional secondary growth method containing tetrapropylammonium hydroxide (TPAOH) as SDA that fails to preserve the desired b-orientation of the film.
Herein, the bottom - up method was utilized for the synthesis of MFI nanosheet with a high aspect ratio and crystallinity by using homemade dC5 (bis-1, 5(tripropyl ammonium). b-Oriented MFI nanosheets seed layer was coated on glass supports by slip coating method with an average thickness of about 100 nm. The SDA (structure - directing agent) free secondary growth of the MFI nanosheet layer was conducted to effectively seal the interlayer and nanoscale gap among the nanosheet layer. The SDA-free secondary growth effectively preserves the b- orientation of the MFI film while maintaining the minimal thickness. A continuous and dense b-oriented MFI zeolite film with a thickness of about 200 nm was prepared under nSiO2∶nNa2O∶nC2H5OH∶nH2O=1∶0.03∶1.3∶0.89 with a crystallization time and temperature of 48 h and 180 ℃, respectively. A significant decrease was observed in the thickness (approxi-mately 90%) of the synthesized film by the SDA-free secondary growth method as compared to MFI zeolite film pre-pared by the conventional secondary growth method containing tetrapropylammonium hydroxide (TPAOH) as SDA that fails to preserve the desired b-orientation of the film.
2022, 38(9): 1790-1798
doi: 10.11862/CJIC.2022.176
Abstract:
Two complexes [Cd2(L)2(NO3)2] (1) and [Fe(L)2]NO3·3CH3OH (2), as well as (H2L)NO3 (HL=4-fluorophenyl-N-(quinolin-2-ylmethylene)thiosemicarbazide) have been synthesized and structurally determined by single-crystal X-ray diffraction, elemental analysis, and IR. The results show that 1 is a centrosymmetry binuclear complex, in which each central Cd(Ⅱ) ion is coordinated by one independent anionic ligand L- with a [N2S] donor set, one bidentate nitrate anion, and another μ2-bridged S atom from the adjacent thiosemicarbazone, thus providing a distorted octahedron geometry. The Fe(Ⅲ) ion in complex 2 displays the same coordination geometry as the Cd(Ⅱ) ion in 1, while is surrounded by two tridentate L- ligands. The fluorescence spectra, the absorption spectra, and the viscosity measurements indicate that complex 2 could effectively bind with ct-DNA through intercalation mode, while HL and complex 1 might interact with ct-DNA by outside groove binding mode, and the binding affinity of complex 2 with ct-DNA was stronger than those of HL and complex 1. In addition, the results of cytotoxicity experiments showed that complex 2 had the strongest ability to inhibit the proliferation of HeLa tumor cells among the three compounds.
Two complexes [Cd2(L)2(NO3)2] (1) and [Fe(L)2]NO3·3CH3OH (2), as well as (H2L)NO3 (HL=4-fluorophenyl-N-(quinolin-2-ylmethylene)thiosemicarbazide) have been synthesized and structurally determined by single-crystal X-ray diffraction, elemental analysis, and IR. The results show that 1 is a centrosymmetry binuclear complex, in which each central Cd(Ⅱ) ion is coordinated by one independent anionic ligand L- with a [N2S] donor set, one bidentate nitrate anion, and another μ2-bridged S atom from the adjacent thiosemicarbazone, thus providing a distorted octahedron geometry. The Fe(Ⅲ) ion in complex 2 displays the same coordination geometry as the Cd(Ⅱ) ion in 1, while is surrounded by two tridentate L- ligands. The fluorescence spectra, the absorption spectra, and the viscosity measurements indicate that complex 2 could effectively bind with ct-DNA through intercalation mode, while HL and complex 1 might interact with ct-DNA by outside groove binding mode, and the binding affinity of complex 2 with ct-DNA was stronger than those of HL and complex 1. In addition, the results of cytotoxicity experiments showed that complex 2 had the strongest ability to inhibit the proliferation of HeLa tumor cells among the three compounds.
2022, 38(9): 1799-1807
doi: 10.11862/CJIC.2022.175
Abstract:
Two complexes {[Ni(HIPA) (2, 5-DPBI)1.5(H2O)]·2.25H2O}n (1) and [Ni(HIPA) (2, 5-DPBMI) (H2O)]n (2) (H2HIPA=5-(hydroxymethyl) isophthalic acid, 2, 5-DPBI=1, 1'-(2, 5-dimethyl-1, 4-phenylene)bis(1H-imidazole), 2, 5-DPBMI=1, 1'-(2, 5-dimethyl-1, 4 -phenylene)bis(4-methyl-1H-imidazole)) were synthesized via hydrothermal method. Structural analysis reveals that Ni(Ⅱ) centers have different coordination environments in the existence of different imidazole ligands. As a result, complex 1 possesses a 5-connected framework with the topological symbol of (42.66.82), while complex 2 shows a 4-connected framework with dia net. The powder X -ray diffraction further firms that complexes 1 and 2 are very stable not only in a normal organic solvent but also in water under UV light. Moreover, the UV-Vis spectra, Mott-Schottky measurements, and electrochemical impedance spectroscopy (EIS) demonstrate that complex 1 and 2 are typical n-type semiconductors with low resistance in charge transportation. Finally, photocatalytic tests confirm that complexes 1 and 2 have catalytic activity for the degradation of methylene blue.
Two complexes {[Ni(HIPA) (2, 5-DPBI)1.5(H2O)]·2.25H2O}n (1) and [Ni(HIPA) (2, 5-DPBMI) (H2O)]n (2) (H2HIPA=5-(hydroxymethyl) isophthalic acid, 2, 5-DPBI=1, 1'-(2, 5-dimethyl-1, 4-phenylene)bis(1H-imidazole), 2, 5-DPBMI=1, 1'-(2, 5-dimethyl-1, 4 -phenylene)bis(4-methyl-1H-imidazole)) were synthesized via hydrothermal method. Structural analysis reveals that Ni(Ⅱ) centers have different coordination environments in the existence of different imidazole ligands. As a result, complex 1 possesses a 5-connected framework with the topological symbol of (42.66.82), while complex 2 shows a 4-connected framework with dia net. The powder X -ray diffraction further firms that complexes 1 and 2 are very stable not only in a normal organic solvent but also in water under UV light. Moreover, the UV-Vis spectra, Mott-Schottky measurements, and electrochemical impedance spectroscopy (EIS) demonstrate that complex 1 and 2 are typical n-type semiconductors with low resistance in charge transportation. Finally, photocatalytic tests confirm that complexes 1 and 2 have catalytic activity for the degradation of methylene blue.
2022, 38(9): 1808-1816
doi: 10.11862/CJIC.2022.193
Abstract:
Triazole -derived energetic complexes have paid significant attention in the field of energetic materials. An energetic complex [Cd(Hatzc)2(H2O)] (LH1) (H2atzc=3-carboxyl-5-amino-1, 2, 4-triazole) was synthesized and fully characterized by single crystal X-ray diffraction, elemental analysis, infrared spectral analysis, and thermogravimetric analysis. LH1 belongs to the monoclinic system, space group P21/n. The structural analyses illustrate that LH1 exhibits a 1D chain, which is linked by hydrogen-bonding interactions to give a 3D supramolecular architecture. Complex LH1 had high detonation velocity (D=10.4 km·s-1), detonation pressure (p =55.2 GPa), energy of detonation (16.51 kJ·g-1), and density (2.363 g·cm-3), which were superior to most of the energetic compounds. The impact sensitivity (> 40 J) and friction sensitivity (> 360 N) reveal that LH1 is less sensitive to impact and friction. The results of the catalytic thermal decomposition of ammonium perchlorate (AP) show that LH1 decreased the higher thermal decomposition temperature of AP by 38 ℃ and increased the exothermic quantity of decomposition by 0.46 kJ·g-1 in a short time, which showed a good catalytic effect on the thermal decomposition of AP.
Triazole -derived energetic complexes have paid significant attention in the field of energetic materials. An energetic complex [Cd(Hatzc)2(H2O)] (LH1) (H2atzc=3-carboxyl-5-amino-1, 2, 4-triazole) was synthesized and fully characterized by single crystal X-ray diffraction, elemental analysis, infrared spectral analysis, and thermogravimetric analysis. LH1 belongs to the monoclinic system, space group P21/n. The structural analyses illustrate that LH1 exhibits a 1D chain, which is linked by hydrogen-bonding interactions to give a 3D supramolecular architecture. Complex LH1 had high detonation velocity (D=10.4 km·s-1), detonation pressure (p =55.2 GPa), energy of detonation (16.51 kJ·g-1), and density (2.363 g·cm-3), which were superior to most of the energetic compounds. The impact sensitivity (> 40 J) and friction sensitivity (> 360 N) reveal that LH1 is less sensitive to impact and friction. The results of the catalytic thermal decomposition of ammonium perchlorate (AP) show that LH1 decreased the higher thermal decomposition temperature of AP by 38 ℃ and increased the exothermic quantity of decomposition by 0.46 kJ·g-1 in a short time, which showed a good catalytic effect on the thermal decomposition of AP.
2022, 38(9): 1817-1824
doi: 10.11862/CJIC.2022.174
Abstract:
As an emerging type of porous material, metal-organic frameworks (MOFs) have been developed as sensors for monitoring environmental pollutants in water. It is of high significance to develop fluorescent MOFs with simple precursors for selective detection of toxic Fe3+ ions. In this work, we present a water-stable two-fold interpenetrated indium-based metal-organic framework (NH2Me2)[In(fdc)2]·2H2O named BUT-205 (BUT stands for Beijing University of Technology, H2fdc=furan -2, 5-dicarboxylic acid) constructed from a biomass-derived ligand. BUT-205 has been structurally characterized by single-crystal X-ray diffraction. BUT-205 was an efficient sensor for Fe3+ ions in water with high sensitivity and selectivity. The limit of detection (LOD) was calculated to be 1.3 μmol·L-1 being lower than the US-EPA (U. S. Environmental Protection Agency) standard (15.7 μmol·L-1) in drinking water. Furthermore, BUT-205 could be recycled and used for at least four cycles.
As an emerging type of porous material, metal-organic frameworks (MOFs) have been developed as sensors for monitoring environmental pollutants in water. It is of high significance to develop fluorescent MOFs with simple precursors for selective detection of toxic Fe3+ ions. In this work, we present a water-stable two-fold interpenetrated indium-based metal-organic framework (NH2Me2)[In(fdc)2]·2H2O named BUT-205 (BUT stands for Beijing University of Technology, H2fdc=furan -2, 5-dicarboxylic acid) constructed from a biomass-derived ligand. BUT-205 has been structurally characterized by single-crystal X-ray diffraction. BUT-205 was an efficient sensor for Fe3+ ions in water with high sensitivity and selectivity. The limit of detection (LOD) was calculated to be 1.3 μmol·L-1 being lower than the US-EPA (U. S. Environmental Protection Agency) standard (15.7 μmol·L-1) in drinking water. Furthermore, BUT-205 could be recycled and used for at least four cycles.
2022, 38(9): 1825-1833
doi: 10.11862/CJIC.2022.184
Abstract:
A carboxybenzyl viologen ligand 1, 1'-bis(4-carboxybenzyl)-4, 4'-bipyridinium dichloride ((H2Bpybc)Cl2) was used as the functional ligand, and the auxiliary ligand 1, 3, 5-benzene tricarboxylic acid (H3BTC) was introduced to self-assemble with different metal ions to synthesize three complexes: {[Cd(Bpybc)0.5(HBTC)(H2O)]·0.6H2O}n (1), [Ni(Bpybc)0.5(HBTC)(H2O)4] (2), and [Co(Bpybc)0.5(HBTC)(H2O)4] (3). The three complexes display different structural features, including a 2D structure of 1 and 0D structures of 2 and 3. Furthermore, these three complexes displayed different chromic properties. Complex 1 was photochromic only due to the generation of viologen radicals, while complexes 2 and 3 were photochromic originating from the photo-induced formation of viologen radicals accompanying the redox activity of metal ions. In addition, complex 2 showed thermochromic behavior, which is associated with the radical formation through electron transfer, while complex 3 exhibited a color change accompanying a reversible structural transformation due to dehydration and rehydration. These results suggest that metal ions play a significant role in regulating the structure and chromic behavior of viologen complexes.
A carboxybenzyl viologen ligand 1, 1'-bis(4-carboxybenzyl)-4, 4'-bipyridinium dichloride ((H2Bpybc)Cl2) was used as the functional ligand, and the auxiliary ligand 1, 3, 5-benzene tricarboxylic acid (H3BTC) was introduced to self-assemble with different metal ions to synthesize three complexes: {[Cd(Bpybc)0.5(HBTC)(H2O)]·0.6H2O}n (1), [Ni(Bpybc)0.5(HBTC)(H2O)4] (2), and [Co(Bpybc)0.5(HBTC)(H2O)4] (3). The three complexes display different structural features, including a 2D structure of 1 and 0D structures of 2 and 3. Furthermore, these three complexes displayed different chromic properties. Complex 1 was photochromic only due to the generation of viologen radicals, while complexes 2 and 3 were photochromic originating from the photo-induced formation of viologen radicals accompanying the redox activity of metal ions. In addition, complex 2 showed thermochromic behavior, which is associated with the radical formation through electron transfer, while complex 3 exhibited a color change accompanying a reversible structural transformation due to dehydration and rehydration. These results suggest that metal ions play a significant role in regulating the structure and chromic behavior of viologen complexes.
2022, 38(9): 1834-1842
doi: 10.11862/CJIC.2022.183
Abstract:
A preparation procedure for the title compound (C7H11N2)2[CdCl4]·0.5H2O (C7H11N2=4-(dimethylamino) pyridinium) was developed and gave good yields and purity. The Cd(Ⅱ) ion is coordinated in a slightly distorted tetrahedral environment by four chlorides. The crystal arrangement shows a layered structure with alternating organic and inorganic layers parallel to the (001) plane and located at x=n+1/2 (n ∈ Z). In the crystal, the organic and inorganic layers are linked by C—H…Cl, C—H…O, N—H…Cl and N —H…O hydrogen bonding interactions. Hirshfeld surface analysis and fingerprint plots of the structure reveal that molecular packing is governed by hydrogen bonds and π-stacking. The UV-Vis diffuse reflectance spectrum allowed us to determine a direct band gap of 3.596 eV with a semiconducting character, using the Tauc-extrapolation method. The observed photoluminescence band with a maximum at 562 nm is assigned to excited π-π* states in the 4-(dimethylamino)pyridinium cation.
A preparation procedure for the title compound (C7H11N2)2[CdCl4]·0.5H2O (C7H11N2=4-(dimethylamino) pyridinium) was developed and gave good yields and purity. The Cd(Ⅱ) ion is coordinated in a slightly distorted tetrahedral environment by four chlorides. The crystal arrangement shows a layered structure with alternating organic and inorganic layers parallel to the (001) plane and located at x=n+1/2 (n ∈ Z). In the crystal, the organic and inorganic layers are linked by C—H…Cl, C—H…O, N—H…Cl and N —H…O hydrogen bonding interactions. Hirshfeld surface analysis and fingerprint plots of the structure reveal that molecular packing is governed by hydrogen bonds and π-stacking. The UV-Vis diffuse reflectance spectrum allowed us to determine a direct band gap of 3.596 eV with a semiconducting character, using the Tauc-extrapolation method. The observed photoluminescence band with a maximum at 562 nm is assigned to excited π-π* states in the 4-(dimethylamino)pyridinium cation.
2022, 38(9): 1843-1852
doi: 10.11862/CJIC.2022.196
Abstract:
A novel coordination polymer, {[Eu(L)2(H2O) 4]Cl3·2H2O}n (1) (L=1, 1'-((2, 3, 5, 6-tetramethyl-1, 4-phenylene) bis(methylene))bis(pyridin-1-ium-4-carboxylate)), was synthesized under hydrothermal conditions by a zwitterionic organic ligand and characterized by single crystal X-ray diffraction. Powder X-ray diffraction, IR, thermogravimetry, and luminescence properties of 1 were also determined. The solid-state luminescence properties of 1 were investigated, realizing the zwitterionic ligand is an excellent antenna chromophore for sensitizing Eu3+ ions. In addition, this water-stable 1 was utilized as a chemosensor to detect various common antibiotics to find that this one can exhibit high selectivity, sensitivity, and recyclability in the detection of furacilin molecules in aqueous phases.
A novel coordination polymer, {[Eu(L)2(H2O) 4]Cl3·2H2O}n (1) (L=1, 1'-((2, 3, 5, 6-tetramethyl-1, 4-phenylene) bis(methylene))bis(pyridin-1-ium-4-carboxylate)), was synthesized under hydrothermal conditions by a zwitterionic organic ligand and characterized by single crystal X-ray diffraction. Powder X-ray diffraction, IR, thermogravimetry, and luminescence properties of 1 were also determined. The solid-state luminescence properties of 1 were investigated, realizing the zwitterionic ligand is an excellent antenna chromophore for sensitizing Eu3+ ions. In addition, this water-stable 1 was utilized as a chemosensor to detect various common antibiotics to find that this one can exhibit high selectivity, sensitivity, and recyclability in the detection of furacilin molecules in aqueous phases.
2022, 38(9): 1853-1861
doi: 10.11862/CJIC.2022.199
Abstract:
A bis-pyridine pendant-armed macrocyclic heterobinuclear Zn(Ⅱ)-Ni(Ⅱ) complex [ZnNi(L)](ClO4)2·H2O (H2L=3, 3'-((ethane-1, 2-diylbis((pyridin-2-ylmethyl)azanediyl))bis(methylene)) bis(2-hydroxy-5-methylbenzaldehyde)) has been obtained and characterized by spectroscopy, elemental analysis and single-crystal X-ray diffraction. The coordination environment of Zn(Ⅱ) and Ni(Ⅱ) can be described as approximately distorted triangular prism and square pyramid, respectively. The Zn—Ni distance bridged by two phenoxide groups is 0.303 63(6) nm. The interaction between the complex and calf thymus DNA (CT-DNA) has been further confirmed by UV-Vis spectrophotometry, viscosity, and cyclic voltammetry study. The complex showed a good binding property to CT-DNA with a binding constant of 1.05×105 L·mol-1. The DNA cleavage activity has also been investigated using agarose gel electrophoresis.
A bis-pyridine pendant-armed macrocyclic heterobinuclear Zn(Ⅱ)-Ni(Ⅱ) complex [ZnNi(L)](ClO4)2·H2O (H2L=3, 3'-((ethane-1, 2-diylbis((pyridin-2-ylmethyl)azanediyl))bis(methylene)) bis(2-hydroxy-5-methylbenzaldehyde)) has been obtained and characterized by spectroscopy, elemental analysis and single-crystal X-ray diffraction. The coordination environment of Zn(Ⅱ) and Ni(Ⅱ) can be described as approximately distorted triangular prism and square pyramid, respectively. The Zn—Ni distance bridged by two phenoxide groups is 0.303 63(6) nm. The interaction between the complex and calf thymus DNA (CT-DNA) has been further confirmed by UV-Vis spectrophotometry, viscosity, and cyclic voltammetry study. The complex showed a good binding property to CT-DNA with a binding constant of 1.05×105 L·mol-1. The DNA cleavage activity has also been investigated using agarose gel electrophoresis.
2022, 38(9): 1862-1870
doi: 10.11862/CJIC.2022.173
Abstract:
For the first time, Fe2O3/Fe2TiO5 heterojunction materials have been fabricated by a facile one-pot solvothermal method. After the construction of the S-scheme heterojunction, compared to pure Fe2O3 and Fe2TiO5, the photocatalytic degradation rate and efficiency of Fe2O3/Fe2TiO5 were significantly improved. After being illuminated for 2.5 h, nearly 100% of methylene blue (MB) has been degraded by Fe2O3/Fe2TiO5. In Fe2O3/Fe2TiO5 composite material, a built-in field is formed between Fe2O3 and Fe2TiO5, thus promoting the separation of photogenerated electron-hole pairs. Therefore, electrons in the conduction band (CB) of Fe2TiO5 and holes in the valence band (VB) of Fe2O3 with higher energy, which show high reduction and oxidation capacity, respectively, can retain and transfer to the surface to participate in the degradation reaction. Moreover, Fe2O3/Fe2TiO5 composite showed good photocatalytic stability.
For the first time, Fe2O3/Fe2TiO5 heterojunction materials have been fabricated by a facile one-pot solvothermal method. After the construction of the S-scheme heterojunction, compared to pure Fe2O3 and Fe2TiO5, the photocatalytic degradation rate and efficiency of Fe2O3/Fe2TiO5 were significantly improved. After being illuminated for 2.5 h, nearly 100% of methylene blue (MB) has been degraded by Fe2O3/Fe2TiO5. In Fe2O3/Fe2TiO5 composite material, a built-in field is formed between Fe2O3 and Fe2TiO5, thus promoting the separation of photogenerated electron-hole pairs. Therefore, electrons in the conduction band (CB) of Fe2TiO5 and holes in the valence band (VB) of Fe2O3 with higher energy, which show high reduction and oxidation capacity, respectively, can retain and transfer to the surface to participate in the degradation reaction. Moreover, Fe2O3/Fe2TiO5 composite showed good photocatalytic stability.
2022, 38(9): 1871-1877
doi: 10.11862/CJIC.2022.181
Abstract:
A 2D layered metal-organic framework [Cd(L) (H2O)]·H2O (1) was synthesized from 5-((naphthalen-1-ylmethyl)amino)isophthalic acid (H2L) and Cd2+ by a solvothermal method. Structural analysis reveals that the adjacent layers are connected by π-π stacking and C—H⋯π interactions to form a 3D supramolecular structure. Notably, the luminescence of 1 was significantly enhanced under acidic conditions, which can be used for selective and sensitive detection of acidic amino acids. The limits of detection of 1 for aspartic acid and glutamic acid were 3.88 and 5.43 μmol·L-1, respectively.
A 2D layered metal-organic framework [Cd(L) (H2O)]·H2O (1) was synthesized from 5-((naphthalen-1-ylmethyl)amino)isophthalic acid (H2L) and Cd2+ by a solvothermal method. Structural analysis reveals that the adjacent layers are connected by π-π stacking and C—H⋯π interactions to form a 3D supramolecular structure. Notably, the luminescence of 1 was significantly enhanced under acidic conditions, which can be used for selective and sensitive detection of acidic amino acids. The limits of detection of 1 for aspartic acid and glutamic acid were 3.88 and 5.43 μmol·L-1, respectively.
2022, 38(9): 1878-1886
doi: 10.11862/CJIC.2022.194
Abstract:
Complexes [Zn(2-pyterpy)2](ClO4)2·0.25H2O (1) and [Cd(2-pyterpy)2]2(ClO4)4·2.33H2O·CH3OH(2)(2-pyterpy=4'-(2-pyridyl)-2, 2'∶6', 2″-terpyridine) were synthesized under solvothermal conditions, and structurally characterized by elemental analysis, FT-IR spectra, X-ray single crystal diffraction and powder X-ray diffraction. X-ray single crystal diffraction results show that they crystallize in the triclinic system with the P1 space group. In solidstate, complexes 1 and 2 showed the maxima emission band approximately at 539 and 547 nm upon excitation at 405 nm, respectively. In methanol solution, complexes 1 and 2 exhibited emissions at 408 and 371 nm upon excitation at 357 and 352 nm, respectively. The metastable-state photoacid mPAH1 showed fluorescence at 556 nm upon excitation at 467 nm. When complex 1 was titrated with mPAH1, the fluorescence of complex 1 at 408 nm was quenched by mPAH1 with a quenching constant KSV of 2.961×104 L·mol-1, but the fluorescence lifetime of complex 1 remained nearly unchanged, which is attributed to the inner filter effect. Conversely, titration of mPAH1 with complex 1 resulted in enhanced fluorescence of the mixed solution at 556 nm, which is attributed to partial protonation of complex 1 by mPAH1.
Complexes [Zn(2-pyterpy)2](ClO4)2·0.25H2O (1) and [Cd(2-pyterpy)2]2(ClO4)4·2.33H2O·CH3OH(2)(2-pyterpy=4'-(2-pyridyl)-2, 2'∶6', 2″-terpyridine) were synthesized under solvothermal conditions, and structurally characterized by elemental analysis, FT-IR spectra, X-ray single crystal diffraction and powder X-ray diffraction. X-ray single crystal diffraction results show that they crystallize in the triclinic system with the P1 space group. In solidstate, complexes 1 and 2 showed the maxima emission band approximately at 539 and 547 nm upon excitation at 405 nm, respectively. In methanol solution, complexes 1 and 2 exhibited emissions at 408 and 371 nm upon excitation at 357 and 352 nm, respectively. The metastable-state photoacid mPAH1 showed fluorescence at 556 nm upon excitation at 467 nm. When complex 1 was titrated with mPAH1, the fluorescence of complex 1 at 408 nm was quenched by mPAH1 with a quenching constant KSV of 2.961×104 L·mol-1, but the fluorescence lifetime of complex 1 remained nearly unchanged, which is attributed to the inner filter effect. Conversely, titration of mPAH1 with complex 1 resulted in enhanced fluorescence of the mixed solution at 556 nm, which is attributed to partial protonation of complex 1 by mPAH1.
