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2024 Volume 40 Issue 10
2024, 40(10): 1825-1839
doi: 10.11862/CJIC.20240225
Abstract:
Bimetallic organic frameworks (BMOFs) are a new type of hybrid materials connected by coordination bonds between two metal ions as nodes and organic ligands. BMOFs have been widely used in catalysis, biomedicine, luminescence sensing, and other fields because of their large surface area, high load capacity, adjustable composition, and aperture. Besides, BMOFs can be used as precursors for synthesizing functional nanomaterials with controlled size, composition, and structure and have exposed active sites, good stability, and electrical conductivity. This review summarizes the latest research progress of BMOFs in tumor monotherapy, combination therapy, and magnetic resonance imaging. Finally, the challenges and future trends of BMOFs in tumor diagnosis and treatment are discussed.
Bimetallic organic frameworks (BMOFs) are a new type of hybrid materials connected by coordination bonds between two metal ions as nodes and organic ligands. BMOFs have been widely used in catalysis, biomedicine, luminescence sensing, and other fields because of their large surface area, high load capacity, adjustable composition, and aperture. Besides, BMOFs can be used as precursors for synthesizing functional nanomaterials with controlled size, composition, and structure and have exposed active sites, good stability, and electrical conductivity. This review summarizes the latest research progress of BMOFs in tumor monotherapy, combination therapy, and magnetic resonance imaging. Finally, the challenges and future trends of BMOFs in tumor diagnosis and treatment are discussed.
2024, 40(10): 1840-1849
doi: 10.11862/CJIC.20240216
Abstract:
A 3D nitrogen-doped graphene/multi-walled carbon nanotube (CS-GO-NCNT) crosslinked network material was successfully synthesized utilizing chitosan and melamine as carbon and nitrogen sources, concomitant with the incorporation of multi-wall carbon nanotubes and employing freeze drying technology. The material amalgamates the merits of 1D/2D hybrid carbon materials, wherein 1D carbon nanotubes confer robustness and expedited electron transport pathways, while 2D graphene sheets facilitate rapid ion migration. Furthermore, the introduction of nitrogen heteroatoms serves to furnish additional active sites for lithium storage. When served as an anode material for lithium-ion batteries, the CS-GO-NCNT electrode delivered a reversible capacity surpassing 500 mAh·g-1, markedly outperforming commercial graphite anodes. Even after 300 cycles at a high current density of 1 A·g-1, it remained a reversible capacity of up to 268 mAh·g-1.
A 3D nitrogen-doped graphene/multi-walled carbon nanotube (CS-GO-NCNT) crosslinked network material was successfully synthesized utilizing chitosan and melamine as carbon and nitrogen sources, concomitant with the incorporation of multi-wall carbon nanotubes and employing freeze drying technology. The material amalgamates the merits of 1D/2D hybrid carbon materials, wherein 1D carbon nanotubes confer robustness and expedited electron transport pathways, while 2D graphene sheets facilitate rapid ion migration. Furthermore, the introduction of nitrogen heteroatoms serves to furnish additional active sites for lithium storage. When served as an anode material for lithium-ion batteries, the CS-GO-NCNT electrode delivered a reversible capacity surpassing 500 mAh·g-1, markedly outperforming commercial graphite anodes. Even after 300 cycles at a high current density of 1 A·g-1, it remained a reversible capacity of up to 268 mAh·g-1.
2024, 40(10): 1975-1985
doi: 10.11862/CJIC.20240180
Abstract:
Three coordination polymers [Mn(epda)(2,2′-bipy)(H2O)] (1), [Mn(epda)(phen)] (2), and [Co2(epda)2(bpe)2(H2O)4]·5H2O (3) (H2epda=5-ethyl-pyridine-2,3-dicarboxylic acid, 2,2′-bipy=2,2′-bipyridine, phen=phenanthroline, bpe=1,2-bis(4-pyridyl) ethylene) were synthesized by solvothermal reactions and characterized by single-crystal X-ray diffraction, thermogravimetric analyses, IR spectroscopy and elemental analysis. 1 displays a 1D chain structure, and these chains are joined by O—H…O hydrogen bonding and π-π stacking interactions to generate a 2D layer structure. 2 displays a 2D layer structure, and adjacent layers are generated 3D architecture through π-π stacking interactions. 3 displays a 1D chain structure, and adjacent chains are generated double layer structure through O—H…O hydrogen bonding. The fluorescent properties of 1 and 3 indicate that they can potentially be used as a luminescent sensor. 1 was highly selective and sensitive towards o-nitrophenol through different detection mechanisms, however, 3 was highly selective and sensitive towards 2,4,6-trinitrophenol. In addition, the magnetic behavior of 2 has also been investigated.
Three coordination polymers [Mn(epda)(2,2′-bipy)(H2O)] (1), [Mn(epda)(phen)] (2), and [Co2(epda)2(bpe)2(H2O)4]·5H2O (3) (H2epda=5-ethyl-pyridine-2,3-dicarboxylic acid, 2,2′-bipy=2,2′-bipyridine, phen=phenanthroline, bpe=1,2-bis(4-pyridyl) ethylene) were synthesized by solvothermal reactions and characterized by single-crystal X-ray diffraction, thermogravimetric analyses, IR spectroscopy and elemental analysis. 1 displays a 1D chain structure, and these chains are joined by O—H…O hydrogen bonding and π-π stacking interactions to generate a 2D layer structure. 2 displays a 2D layer structure, and adjacent layers are generated 3D architecture through π-π stacking interactions. 3 displays a 1D chain structure, and adjacent chains are generated double layer structure through O—H…O hydrogen bonding. The fluorescent properties of 1 and 3 indicate that they can potentially be used as a luminescent sensor. 1 was highly selective and sensitive towards o-nitrophenol through different detection mechanisms, however, 3 was highly selective and sensitive towards 2,4,6-trinitrophenol. In addition, the magnetic behavior of 2 has also been investigated.
2024, 40(10): 1986-1994
doi: 10.11862/CJIC.20240153
Abstract:
A novel compound (H2L)SCN (5-methyl-3-phenyl-2H-pyrazol-1-ium thiocyanate) has been obtained by the reaction of thiosemicarbazide with benzoylacetone in ethanol. Two zinc(Ⅱ) complexes [Zn(HL)2(NCS)(CH3COO)] (1) and [Zn2(L)2(HL)2(NCS)2]2·2CH3OH (2) have been synthesized by the coordination reactions of Zn(OAc)2·2H2O or ZnCl2 with (H2L)SCN under reflux conditions. Elemental analyses and single-crystal X-ray diffraction have confirmed the structures of the synthesized compounds. The (H2L)SCN ligand and complex 1 pertain to the triclinic system with space group P1, while complex 2 belongs to the monoclinic system with space group P21/n. Additionally, the antibacterial activities of the compounds were evaluated in vitro using the agar diffusion method against the bacterial strains (Candida albicans, Staphylococcus aureus, and Escherichia coli). The results showed that the ligand exhibited relatively good antibacterial activities against the bacteria, and the complexes possessed stronger antibacterial activities against the same bacteria than the free ligand.
A novel compound (H2L)SCN (5-methyl-3-phenyl-2H-pyrazol-1-ium thiocyanate) has been obtained by the reaction of thiosemicarbazide with benzoylacetone in ethanol. Two zinc(Ⅱ) complexes [Zn(HL)2(NCS)(CH3COO)] (1) and [Zn2(L)2(HL)2(NCS)2]2·2CH3OH (2) have been synthesized by the coordination reactions of Zn(OAc)2·2H2O or ZnCl2 with (H2L)SCN under reflux conditions. Elemental analyses and single-crystal X-ray diffraction have confirmed the structures of the synthesized compounds. The (H2L)SCN ligand and complex 1 pertain to the triclinic system with space group P1, while complex 2 belongs to the monoclinic system with space group P21/n. Additionally, the antibacterial activities of the compounds were evaluated in vitro using the agar diffusion method against the bacterial strains (Candida albicans, Staphylococcus aureus, and Escherichia coli). The results showed that the ligand exhibited relatively good antibacterial activities against the bacteria, and the complexes possessed stronger antibacterial activities against the same bacteria than the free ligand.
2024, 40(10): 1995-2008
doi: 10.11862/CJIC.20240164
Abstract:
This work adopts a multi-step etching-heat treatment strategy to prepare porous silicon microsphere composite with Sb-Sn surface modification and carbon coating (pSi/Sb-Sn@C), using industrial grade SiAl alloy micro-spheres as a precursor. pSi/Sb-Sn@C had a 3D structure with bimetallic (Sb-Sn) modified porous silicon micro-spheres (pSi/Sb-Sn) as the core and carbon coating as the shell. Carbon shells can improve the electronic conductivity and mechanical stability of porous silicon microspheres, which is beneficial for obtaining a stable solid electrolyte interface (SEI) film. The 3D porous core promotes the diffusion of lithium ions, increases the intercalation/delithiation active sites, and buffers the volume expansion during the intercalation process. The introduction of active metals (Sb-Sn) can improve the conductivity of the composite and contribute to a certain amount of lithium storage capacity. Due to its unique composition and microstructure, pSi/Sb-Sn@C showed a reversible capacity of 1 247.4 mAh·g-1 after 300 charge/discharge cycles at a current density of 1.0 A·g-1, demonstrating excellent rate lithium storage performance and enhanced electrochemical cycling stability.
This work adopts a multi-step etching-heat treatment strategy to prepare porous silicon microsphere composite with Sb-Sn surface modification and carbon coating (pSi/Sb-Sn@C), using industrial grade SiAl alloy micro-spheres as a precursor. pSi/Sb-Sn@C had a 3D structure with bimetallic (Sb-Sn) modified porous silicon micro-spheres (pSi/Sb-Sn) as the core and carbon coating as the shell. Carbon shells can improve the electronic conductivity and mechanical stability of porous silicon microspheres, which is beneficial for obtaining a stable solid electrolyte interface (SEI) film. The 3D porous core promotes the diffusion of lithium ions, increases the intercalation/delithiation active sites, and buffers the volume expansion during the intercalation process. The introduction of active metals (Sb-Sn) can improve the conductivity of the composite and contribute to a certain amount of lithium storage capacity. Due to its unique composition and microstructure, pSi/Sb-Sn@C showed a reversible capacity of 1 247.4 mAh·g-1 after 300 charge/discharge cycles at a current density of 1.0 A·g-1, demonstrating excellent rate lithium storage performance and enhanced electrochemical cycling stability.
2024, 40(10): 2009-2020
doi: 10.11862/CJIC.20240120
Abstract:
In this work, p-phenylenediamine and L-cysteine were used as raw materials, and water-soluble N, S co-doped carbon dots (N, S-CDs) with excellent performance were prepared through a one-step solvothermal method. The morphology and structure of N, S-CDs were characterized by transmission electron microscope, X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy, and the basic photophysical properties were investigated via UV-Vis absorption spectra and fluorescence spectra. Meanwhile, the N, S-CDs have excellent luminescence stability with pH, ionic strength, radiation time, and storage time. Experimental results illustrated the present sensor platform exhibited high sensitivity and selectivity in response to baicalein with a detection limit of 85 nmol·L-1. The quenching mechanism is proved to be the inner filter effect. In addition, this sensor can also detect baicalein in biofluids (serum and urine) with good accuracy and reproducibility.
In this work, p-phenylenediamine and L-cysteine were used as raw materials, and water-soluble N, S co-doped carbon dots (N, S-CDs) with excellent performance were prepared through a one-step solvothermal method. The morphology and structure of N, S-CDs were characterized by transmission electron microscope, X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy, and the basic photophysical properties were investigated via UV-Vis absorption spectra and fluorescence spectra. Meanwhile, the N, S-CDs have excellent luminescence stability with pH, ionic strength, radiation time, and storage time. Experimental results illustrated the present sensor platform exhibited high sensitivity and selectivity in response to baicalein with a detection limit of 85 nmol·L-1. The quenching mechanism is proved to be the inner filter effect. In addition, this sensor can also detect baicalein in biofluids (serum and urine) with good accuracy and reproducibility.
Green synthesis of MIL-101/Au composite particles and their sensitivity to Raman detection of thiram
2024, 40(10): 2021-2030
doi: 10.11862/CJIC.20240059
Abstract:
Metal-organic framework (MOF) MIL-101 and surface plasmon polariton (SPP) supported gold nanoparticles (Au NPs) hybrid systems were developed as a highly sensitive and reproducible surface-enhanced Raman scattering (SERS) detection platform, in which a green electrostatic self-assembly technology was adopted to construct the substrate. In an aqueous solution, the electronegativity of the particles can be used to prepare the composite substrate without any surface modifier. Due to the enrichment capacity of MIL-101 and the electromagnetic enhancement from Au NPs, the well-designed MIL-101/Au composites possessed ultrahigh sensitivity with the detection limit of Rhodamine 6G (R6G) as low as 10-10 mol·L-1. Meanwhile, the substrate exhibits high stability, excellent reproducibility, and recyclability. Additionally, the novel substrate can be explored for direct capture, and sensitively detect pesticide residues such as thiram.
Metal-organic framework (MOF) MIL-101 and surface plasmon polariton (SPP) supported gold nanoparticles (Au NPs) hybrid systems were developed as a highly sensitive and reproducible surface-enhanced Raman scattering (SERS) detection platform, in which a green electrostatic self-assembly technology was adopted to construct the substrate. In an aqueous solution, the electronegativity of the particles can be used to prepare the composite substrate without any surface modifier. Due to the enrichment capacity of MIL-101 and the electromagnetic enhancement from Au NPs, the well-designed MIL-101/Au composites possessed ultrahigh sensitivity with the detection limit of Rhodamine 6G (R6G) as low as 10-10 mol·L-1. Meanwhile, the substrate exhibits high stability, excellent reproducibility, and recyclability. Additionally, the novel substrate can be explored for direct capture, and sensitively detect pesticide residues such as thiram.
2024, 40(10): 2031-2039
doi: 10.11862/CJIC.20240109
Abstract:
Two new coordination polymers, [Ni(Hpdc)(bib)(H2O)]n (1) and {[Ni(bib)3](ClO4)2}n (2), were prepared by mixing Ni2+, 3, 5-pyrazoledicarboxylic acid (H3pdc)/p-nitrobenzoic acid and 1, 4-bis(imidazol-1-ylmethyl) butane (bib) by a hydrothermal method, respectively. X-ray crystallography reveals a 2D network constructed by six-coordinated Ni (Ⅱ) centers, bib, and Hpdc2- ligands in complex 1, while a 2D network is built by Ni (Ⅱ) and bib ligands in 2. Furthermore, the quantum-chemical calculations have been performed on'molecular fragments'extracted from the crystal structure of 1 using the PBE0/LANL2DZ method in Gaussian 16 and the VASP program.
Two new coordination polymers, [Ni(Hpdc)(bib)(H2O)]n (1) and {[Ni(bib)3](ClO4)2}n (2), were prepared by mixing Ni2+, 3, 5-pyrazoledicarboxylic acid (H3pdc)/p-nitrobenzoic acid and 1, 4-bis(imidazol-1-ylmethyl) butane (bib) by a hydrothermal method, respectively. X-ray crystallography reveals a 2D network constructed by six-coordinated Ni (Ⅱ) centers, bib, and Hpdc2- ligands in complex 1, while a 2D network is built by Ni (Ⅱ) and bib ligands in 2. Furthermore, the quantum-chemical calculations have been performed on'molecular fragments'extracted from the crystal structure of 1 using the PBE0/LANL2DZ method in Gaussian 16 and the VASP program.
2024, 40(10): 1850-1860
doi: 10.11862/CJIC.20240173
Abstract:
A novel metal coordination polymer {[Zn2(L)(H2O)(DMA)] ·DMA·2.3H2O}n (1) has been isolated under solvothermal method, where L4- is the four-deprotonated N, N'-bis(4-carboxybenzyl)-5-aminoisophthalic acid and DMA is N, N-dimethylacetamide. Single crystal X-ray diffraction results showed that the complex belongs to the triclinic crystal system with the space group of P1, a=0.989 6(5) nm, b=1.370 5(5) nm, c=1.382 1(5) nm, α = 80.067(5)°, β =76.729(5)°, γ =76.611(5)° and the structure of complex 1 is a 3D supramolecular framework that expanded by 2D metal-organic layers through π…π interactions. Interestingly, a"bowl"shaped structure exists in the 2D layer, and the center of the"bowl"is a cavity with a size of about 1.493 nm×1.503 nm, which can be used to load a certain volume of guest molecules. Infrared spectroscopy verified the successful coordination of zinc ions with the L4- ligand. Powder X-ray diffraction (PXRD) experiments confirmed that complex 1 had high purity. Thermo-gravimetric analysis showed that complex 1 had good thermal stability in a range from room temperature to 416.9 ℃. Under the excitation light of 273 nm, complex 1 exhibited strong fluorescence emission at 437 nm in an ethanol solution, which could quickly detect the anthrax biomarker of pyridine-2, 6-dicarboxylic acid (DPA) through fluorescence quenching within 30 s. The results of concentration-dependent experiments showed that there was a good linear relationship between the concentration of DPA and the fluorescence intensity of complex 1, with R2=0.996 51 and a quenching constant value of 4.052×104 L·mol-1. The calculated limit of detection was approximately 15 μmol·L-1, which was significantly lower than the infection dose of anthrax spores (60 μmol·L-1). After adding various inter-ferents to the solution of complex 1, the change in fluorescence intensity of complex 1 was negligible. However, when DPA was added, the fluorescence intensity decreased significantly, indicating that complex 1 had a high selectivity for DPA. The detection mechanism was revealed by combining PXRD patterns and UV-Vis absorption spectra, which is fluorescence quenching induced by the collapse of the crystal framework.
A novel metal coordination polymer {[Zn2(L)(H2O)(DMA)] ·DMA·2.3H2O}n (1) has been isolated under solvothermal method, where L4- is the four-deprotonated N, N'-bis(4-carboxybenzyl)-5-aminoisophthalic acid and DMA is N, N-dimethylacetamide. Single crystal X-ray diffraction results showed that the complex belongs to the triclinic crystal system with the space group of P1, a=0.989 6(5) nm, b=1.370 5(5) nm, c=1.382 1(5) nm, α = 80.067(5)°, β =76.729(5)°, γ =76.611(5)° and the structure of complex 1 is a 3D supramolecular framework that expanded by 2D metal-organic layers through π…π interactions. Interestingly, a"bowl"shaped structure exists in the 2D layer, and the center of the"bowl"is a cavity with a size of about 1.493 nm×1.503 nm, which can be used to load a certain volume of guest molecules. Infrared spectroscopy verified the successful coordination of zinc ions with the L4- ligand. Powder X-ray diffraction (PXRD) experiments confirmed that complex 1 had high purity. Thermo-gravimetric analysis showed that complex 1 had good thermal stability in a range from room temperature to 416.9 ℃. Under the excitation light of 273 nm, complex 1 exhibited strong fluorescence emission at 437 nm in an ethanol solution, which could quickly detect the anthrax biomarker of pyridine-2, 6-dicarboxylic acid (DPA) through fluorescence quenching within 30 s. The results of concentration-dependent experiments showed that there was a good linear relationship between the concentration of DPA and the fluorescence intensity of complex 1, with R2=0.996 51 and a quenching constant value of 4.052×104 L·mol-1. The calculated limit of detection was approximately 15 μmol·L-1, which was significantly lower than the infection dose of anthrax spores (60 μmol·L-1). After adding various inter-ferents to the solution of complex 1, the change in fluorescence intensity of complex 1 was negligible. However, when DPA was added, the fluorescence intensity decreased significantly, indicating that complex 1 had a high selectivity for DPA. The detection mechanism was revealed by combining PXRD patterns and UV-Vis absorption spectra, which is fluorescence quenching induced by the collapse of the crystal framework.
2024, 40(10): 1861-1868
doi: 10.11862/CJIC.20240242
Abstract:
A series of Eu3+-doped CaLaGaO4 red-emitting phosphors with different concentrations were prepared via the high-temperature solid phase method. The results indicate that the obtained phosphors can be effectively pumped by a 392 nm near-ultraviolet light. The Eu3+-doped CaLaGaO4 phosphor displayed the characteristic transitions of Eu3+ with the strongest emission at 609 nm, originating from 5D0→7F2 transition and the luminescence intensity reached its maximum when the concentration of Eu3+ reached 0.3. In addition, the phosphor demonstrated a remarkable color purity value of 96.3% with CIE coordinates (0.613, 0.359) lying closer to the ideal red color CIE coordinates (0.670, 0.330). Furthermore, the photoluminescence emission intensity maintained 75% at 498 K compared to 298 K due to the thermal quenching effect, showcasing excellent thermal stability with an activation energy of 0.151 3 eV.
A series of Eu3+-doped CaLaGaO4 red-emitting phosphors with different concentrations were prepared via the high-temperature solid phase method. The results indicate that the obtained phosphors can be effectively pumped by a 392 nm near-ultraviolet light. The Eu3+-doped CaLaGaO4 phosphor displayed the characteristic transitions of Eu3+ with the strongest emission at 609 nm, originating from 5D0→7F2 transition and the luminescence intensity reached its maximum when the concentration of Eu3+ reached 0.3. In addition, the phosphor demonstrated a remarkable color purity value of 96.3% with CIE coordinates (0.613, 0.359) lying closer to the ideal red color CIE coordinates (0.670, 0.330). Furthermore, the photoluminescence emission intensity maintained 75% at 498 K compared to 298 K due to the thermal quenching effect, showcasing excellent thermal stability with an activation energy of 0.151 3 eV.
2024, 40(10): 1869-1880
doi: 10.11862/CJIC.20240187
Abstract:
The magnetic catalyst MnFe2O4@AC (MFA) was synthesized using a water bath-inverse co-precipitation method and was systematically characterized to assess its structural and magnetic properties. The results indicated that MnFe 2O4 nanoparticles were successfully encapsulated on the surface of activated carbon (AC), resulting in a multistage pore structure. Although the specific surface area of MFA decreased compared to that of the AC base material, it remained high at 176 m2·g-1, with an average pore size of 8.49 nm. The specific magnetization intensity of MFA reached 38.92 emu·g-1, enabling high-efficiency solid-liquid separation when subjected to an external magnetic field. Tetracycline hydrochloride (TC) was degraded using activated peroxymonosulfate (PMS) with UV-assisted activation, employing MFA as a catalyst. The degradation rate of TC in the MFA/PMS system under UV irradiation achieved 97.70%, which was 1.2 times that of the system without UV irradiation. The presence of coexisting anions, the pharmaceutical matrix, and the initial mass concentration of TC significantly influenced the catalytic performance of the system. Notably, the degradation rate remained at 82.76% after five cycles. Free radical burst experiments revealed that superoxide radicals (·O2-) and monoclinic oxygen (1O2) were the primary reactive oxygen species in the UV-assisted MFA/PMS advanced oxidation system. Mechanistic analysis indicated that the high adsor p-tion capacity of MFA provided a solid foundation for catalytic degradation, and the synergistic effect of UV irradiation with the MFA/PMS advanced oxidation system significantly enhanced the generation efficiency of reactive species, thereby facilitating the degradation of organic molecules.
The magnetic catalyst MnFe2O4@AC (MFA) was synthesized using a water bath-inverse co-precipitation method and was systematically characterized to assess its structural and magnetic properties. The results indicated that MnFe 2O4 nanoparticles were successfully encapsulated on the surface of activated carbon (AC), resulting in a multistage pore structure. Although the specific surface area of MFA decreased compared to that of the AC base material, it remained high at 176 m2·g-1, with an average pore size of 8.49 nm. The specific magnetization intensity of MFA reached 38.92 emu·g-1, enabling high-efficiency solid-liquid separation when subjected to an external magnetic field. Tetracycline hydrochloride (TC) was degraded using activated peroxymonosulfate (PMS) with UV-assisted activation, employing MFA as a catalyst. The degradation rate of TC in the MFA/PMS system under UV irradiation achieved 97.70%, which was 1.2 times that of the system without UV irradiation. The presence of coexisting anions, the pharmaceutical matrix, and the initial mass concentration of TC significantly influenced the catalytic performance of the system. Notably, the degradation rate remained at 82.76% after five cycles. Free radical burst experiments revealed that superoxide radicals (·O2-) and monoclinic oxygen (1O2) were the primary reactive oxygen species in the UV-assisted MFA/PMS advanced oxidation system. Mechanistic analysis indicated that the high adsor p-tion capacity of MFA provided a solid foundation for catalytic degradation, and the synergistic effect of UV irradiation with the MFA/PMS advanced oxidation system significantly enhanced the generation efficiency of reactive species, thereby facilitating the degradation of organic molecules.
2024, 40(10): 1881-1891
doi: 10.11862/CJIC.20240170
Abstract:
Using ultra-long MnO2 nanowires as templates and ZIF-67 as precursors, hollow bead string structured MnO2/CoNi2S4 was prepared via a simple room temperature stirring method and one-step vulcanization. In the unique structure, the ultra-long MnO2 nanowires provide a direct pathway for electron transfer, and their largeaspect ratio is conducive to the formation of self-supporting three-dimensional conductive network structure; the hollow and porous CoNi2S4 provides richer active sites and mitigates the charging and discharging process of the volume change during charging and discharging. Thanks to the above advantages, MnO2/CoNi2S4 had a specific capacitance value of 1 531.1 F·g-1 at 1 A·g-1 and a capacitance retention rate of 86.9% at 10 A·g-1. Using MnO2/CoNi2S4 as the positive electrode and activated carbon (AC) as the negative electrode, the assembled MnO2/CoNi2S4||AC devices achieved high energy density (40 Wh·kg-1 at 800 W·kg-1) and excellent cycling stability (64.8% retention after 5 000 cycles).
Using ultra-long MnO2 nanowires as templates and ZIF-67 as precursors, hollow bead string structured MnO2/CoNi2S4 was prepared via a simple room temperature stirring method and one-step vulcanization. In the unique structure, the ultra-long MnO2 nanowires provide a direct pathway for electron transfer, and their largeaspect ratio is conducive to the formation of self-supporting three-dimensional conductive network structure; the hollow and porous CoNi2S4 provides richer active sites and mitigates the charging and discharging process of the volume change during charging and discharging. Thanks to the above advantages, MnO2/CoNi2S4 had a specific capacitance value of 1 531.1 F·g-1 at 1 A·g-1 and a capacitance retention rate of 86.9% at 10 A·g-1. Using MnO2/CoNi2S4 as the positive electrode and activated carbon (AC) as the negative electrode, the assembled MnO2/CoNi2S4||AC devices achieved high energy density (40 Wh·kg-1 at 800 W·kg-1) and excellent cycling stability (64.8% retention after 5 000 cycles).
2024, 40(10): 1892-1902
doi: 10.11862/CJIC.20240139
Abstract:
Lanthanide-organic complex scintillators, known for their structural flexibility and optical tunability, have shown great promise as X-ray scintillators. Herein, four lanthanide-organic complex scintillators, named [Tb (DFBA)3(terpy)(H2O)] (1), [Eu(DFBA)3(terpy)(H2O)] (2), [Tb(DFBA)3(phen)] (3), and [Eu(DFBA)3(phen)] (4), were successfully synthesized by solvent volatilization using 2, 5-difluoro benzoic acid (HDFBA) as the first ligand, 2, 2'∶6', 2″-terpy (terpy) and 1, 10-phenanthroline (phen) as the second ligands. The incorporation of phen in these complexes enhanced their molecular structural rigidity and coordination field stability, reduced non-radiative transitions, and resulted in excellent luminescent properties. The fluorine-substituted organic ligands minimized non-radiative O—H vibrations, thereby improving luminescence efficiency. As a result, the lanthanide-organic complex-based scintillators exhibited high radiation responsiveness and excellent X-ray absorption capability, and achieved a high steady-state X-ray excited relative light yield of (25 100±2 000) photons·MeV-1. Additionally, scintillators with multi-color luminescence ranging from green to red were fabricated by manipulating the molar ratio of Eu3+ to Tb3+ ions. Finally, when incorporated into a polyvinyl alcohol (PVA) matrix, a uniform, flexible scintillator film with high-resolution X-ray imaging (11.2 lp·mm-1) was obtained. These findings demonstrate that the introduction of a second ligand and appropriate hydrophobic groups (such as fluorine substitution) hold significant potential for designing high-performance lanthanide-organic complex scintillators for high-resolution X-ray imaging.
Lanthanide-organic complex scintillators, known for their structural flexibility and optical tunability, have shown great promise as X-ray scintillators. Herein, four lanthanide-organic complex scintillators, named [Tb (DFBA)3(terpy)(H2O)] (1), [Eu(DFBA)3(terpy)(H2O)] (2), [Tb(DFBA)3(phen)] (3), and [Eu(DFBA)3(phen)] (4), were successfully synthesized by solvent volatilization using 2, 5-difluoro benzoic acid (HDFBA) as the first ligand, 2, 2'∶6', 2″-terpy (terpy) and 1, 10-phenanthroline (phen) as the second ligands. The incorporation of phen in these complexes enhanced their molecular structural rigidity and coordination field stability, reduced non-radiative transitions, and resulted in excellent luminescent properties. The fluorine-substituted organic ligands minimized non-radiative O—H vibrations, thereby improving luminescence efficiency. As a result, the lanthanide-organic complex-based scintillators exhibited high radiation responsiveness and excellent X-ray absorption capability, and achieved a high steady-state X-ray excited relative light yield of (25 100±2 000) photons·MeV-1. Additionally, scintillators with multi-color luminescence ranging from green to red were fabricated by manipulating the molar ratio of Eu3+ to Tb3+ ions. Finally, when incorporated into a polyvinyl alcohol (PVA) matrix, a uniform, flexible scintillator film with high-resolution X-ray imaging (11.2 lp·mm-1) was obtained. These findings demonstrate that the introduction of a second ligand and appropriate hydrophobic groups (such as fluorine substitution) hold significant potential for designing high-performance lanthanide-organic complex scintillators for high-resolution X-ray imaging.
2024, 40(10): 1903-1910
doi: 10.11862/CJIC.20240155
Abstract:
Hollow copper sulfide (H-Cu2-xS) nanoparticles were developed and multifunctional nanoagent (PpIX@H-Cu2-xS) was obtained by loading sonosensitizers protoporphyrin (PpIX) in their cavity structures. H-Cu2-xS had a good photothermal conversion effect under near-infrared (NIR) light irradiation conditions and had a large specific surface area (68 m2·g-1), which could realize efficient loading of sonosensitizers PpIX. Under ultrasonic (US) excitation conditions (10 min), it was found that 46.1% of 1, 3-diphenylisobenzofuran (DPBF) was oxidized by reactive oxygen species (ROS) produced by PpIX@H-Cu2-xS. In vitro cell experiments, PpIX@H-Cu2-xS had shown good biosafety and could effectively kill tumor cells under NIR/US excitation conditions.
Hollow copper sulfide (H-Cu2-xS) nanoparticles were developed and multifunctional nanoagent (PpIX@H-Cu2-xS) was obtained by loading sonosensitizers protoporphyrin (PpIX) in their cavity structures. H-Cu2-xS had a good photothermal conversion effect under near-infrared (NIR) light irradiation conditions and had a large specific surface area (68 m2·g-1), which could realize efficient loading of sonosensitizers PpIX. Under ultrasonic (US) excitation conditions (10 min), it was found that 46.1% of 1, 3-diphenylisobenzofuran (DPBF) was oxidized by reactive oxygen species (ROS) produced by PpIX@H-Cu2-xS. In vitro cell experiments, PpIX@H-Cu2-xS had shown good biosafety and could effectively kill tumor cells under NIR/US excitation conditions.
2024, 40(10): 1911-1918
doi: 10.11862/CJIC.20240105
Abstract:
The mechanical stripping method prepared the 2H-phase α-In2Se3 (α-In2Se3(2H)) nanosheets. The structure and ferroelectric properties of the nanosheets were characterized by X-ray diffraction (XRD), Raman spectroscopy, spherical aberration electron microscopy, and piezoelectric force microscopy. The nanosheets were identified as α-In2Se3(2H) ferroelectric materials with a special structure. Further, a planar four-terminal device based on α-In2Se3 (2H) ferroelectricity was successfully constructed on the SiO2/Si substrate, and its photoresponse in all directions was investigated in detail. The results show that α-In2Se3(2H) with intrinsic structure has no photoresponse in both mutually perpendicular directions. After applying voltages at each end of the device, the α-In2Se3(2H) device shows obvious photoresponse in the mutually perpendicular directions. In particular, after utilizing a point voltage close to the direction of the easy polarization axis, the α-In2Se3(2H) device shows an anisotropic photoresponse.
The mechanical stripping method prepared the 2H-phase α-In2Se3 (α-In2Se3(2H)) nanosheets. The structure and ferroelectric properties of the nanosheets were characterized by X-ray diffraction (XRD), Raman spectroscopy, spherical aberration electron microscopy, and piezoelectric force microscopy. The nanosheets were identified as α-In2Se3(2H) ferroelectric materials with a special structure. Further, a planar four-terminal device based on α-In2Se3 (2H) ferroelectricity was successfully constructed on the SiO2/Si substrate, and its photoresponse in all directions was investigated in detail. The results show that α-In2Se3(2H) with intrinsic structure has no photoresponse in both mutually perpendicular directions. After applying voltages at each end of the device, the α-In2Se3(2H) device shows obvious photoresponse in the mutually perpendicular directions. In particular, after utilizing a point voltage close to the direction of the easy polarization axis, the α-In2Se3(2H) device shows an anisotropic photoresponse.
2024, 40(10): 1919-1931
doi: 10.11862/CJIC.20240094
Abstract:
A bone repair material of Mn, Bi co-doped sodium niobate with piezoelectricity was prepared using the hydrothermal method. The microscopic morphology, composition, piezoelectricity, sonodynamic and enzyme-like activity of the material was characterized by scanning electron microscope, X-ray diffractometer, X-ray photoelectron spectrometer, piezoelectric force microscope, electrochemical workstation, ultraviolet-visible-near-infrared spectrometer, and electron paramagnetic resonance spectrometer. The results demonstrate that the material possesses both piezoelectric properties and enzyme-like activity; the ultrasound-triggered piezoelectric effect not only promotes cell proliferation but also enhances sonodynamic and enzyme-like activity, which generates reactive oxygen species for synergistic killing of bacteria/removal of biofilm.
A bone repair material of Mn, Bi co-doped sodium niobate with piezoelectricity was prepared using the hydrothermal method. The microscopic morphology, composition, piezoelectricity, sonodynamic and enzyme-like activity of the material was characterized by scanning electron microscope, X-ray diffractometer, X-ray photoelectron spectrometer, piezoelectric force microscope, electrochemical workstation, ultraviolet-visible-near-infrared spectrometer, and electron paramagnetic resonance spectrometer. The results demonstrate that the material possesses both piezoelectric properties and enzyme-like activity; the ultrasound-triggered piezoelectric effect not only promotes cell proliferation but also enhances sonodynamic and enzyme-like activity, which generates reactive oxygen species for synergistic killing of bacteria/removal of biofilm.
2024, 40(10): 1932-1942
doi: 10.11862/CJIC.20240065
Abstract:
Co@C/MoS2 wave-absorbing materials were successfully synthesized by the combination of carbonization techniques and hydrothermal reactions. The results indicate that the carbonization temperature of ZIF-67 and the microstructure of Co@C/MoS2 critically influence the wave absorption properties of the Co@C/MoS2 composite material. The wrinkled structure of Co@C/MoS2 enhances the reflection and scattering of incident waves, thereby optimizing the impedance matching and enhancing the electromagnetic wave (EMW) performance of the material. When the calcination temperature of ZIF-67 was 800 ℃, the minimum reflection loss (RLmin) of -101.84 dB was obtained at the thickness of 1.7 mm, and the corresponding effective absorption bandwidth (EAB) was up to 7.4 GHz.
Co@C/MoS2 wave-absorbing materials were successfully synthesized by the combination of carbonization techniques and hydrothermal reactions. The results indicate that the carbonization temperature of ZIF-67 and the microstructure of Co@C/MoS2 critically influence the wave absorption properties of the Co@C/MoS2 composite material. The wrinkled structure of Co@C/MoS2 enhances the reflection and scattering of incident waves, thereby optimizing the impedance matching and enhancing the electromagnetic wave (EMW) performance of the material. When the calcination temperature of ZIF-67 was 800 ℃, the minimum reflection loss (RLmin) of -101.84 dB was obtained at the thickness of 1.7 mm, and the corresponding effective absorption bandwidth (EAB) was up to 7.4 GHz.
2024, 40(10): 1943-1952
doi: 10.11862/CJIC.20240079
Abstract:
We have successfully synthesized three cadmium(Ⅱ) complexes [Cd(Hppb)2Br2] (1), [Cd2(ppb)2Br2] (2) and [Cd(Hppb)Br2]n (3) in which the bromide ions are involved based on an asymmetric ligand 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)benzoate (Hppb). Employment of different synthetic conditions has resulted in different architectures. In the three complexes, the ratios of Cd(Ⅱ) ions, ligands, and bromide ions were 1∶2∶2, 1∶1∶1, and 1∶1∶2, respectively, resulting in different structures of mononuclear (0D), binuclear (0D), and 1D framework. The Cd(Ⅱ) coordinated environments in 1 are slightly distorted octahedral geometries, but central ions in 2 and 3 display distorted square pyramidal geometries. There are obvious differences in the ligation modes of the ppb- or Hppb ligands for both complexes. In 1, two Hppb ligands display μ1-κN, N′ coordination modes. In 2, two ppb- ligands display μ2-κN, N′∶κO coordination modes. Two ppb- ligands act as two μ1, 1-bridges linking the binuclear Cd(Ⅱ) cations with a distance of 0.409 1(4) nm. In 3, the neutral Hppb ligands exhibit a μ2-κN, N′∶κO coordination mode, and connecting Cd(Ⅱ) ions by μ1, 6-bridges and forming an infinite 1D chain along the b-axis. The complexes were both studied using Hirshfeld surface analyses and 2D fingerprint plots. Moreover, the photoluminescent properties of 1-3 indicate that the coordination anions make a great contribution to the fluorescent emission of Cd(Ⅱ) polymers.
We have successfully synthesized three cadmium(Ⅱ) complexes [Cd(Hppb)2Br2] (1), [Cd2(ppb)2Br2] (2) and [Cd(Hppb)Br2]n (3) in which the bromide ions are involved based on an asymmetric ligand 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)benzoate (Hppb). Employment of different synthetic conditions has resulted in different architectures. In the three complexes, the ratios of Cd(Ⅱ) ions, ligands, and bromide ions were 1∶2∶2, 1∶1∶1, and 1∶1∶2, respectively, resulting in different structures of mononuclear (0D), binuclear (0D), and 1D framework. The Cd(Ⅱ) coordinated environments in 1 are slightly distorted octahedral geometries, but central ions in 2 and 3 display distorted square pyramidal geometries. There are obvious differences in the ligation modes of the ppb- or Hppb ligands for both complexes. In 1, two Hppb ligands display μ1-κN, N′ coordination modes. In 2, two ppb- ligands display μ2-κN, N′∶κO coordination modes. Two ppb- ligands act as two μ1, 1-bridges linking the binuclear Cd(Ⅱ) cations with a distance of 0.409 1(4) nm. In 3, the neutral Hppb ligands exhibit a μ2-κN, N′∶κO coordination mode, and connecting Cd(Ⅱ) ions by μ1, 6-bridges and forming an infinite 1D chain along the b-axis. The complexes were both studied using Hirshfeld surface analyses and 2D fingerprint plots. Moreover, the photoluminescent properties of 1-3 indicate that the coordination anions make a great contribution to the fluorescent emission of Cd(Ⅱ) polymers.
2024, 40(10): 1953-1964
doi: 10.11862/CJIC.20240028
Abstract:
Self-supporting Cu/α-FeOOH/NF catalysts were prepared by in-situ growth of Cu/α-FeOOH nanocomposites on foam nickel (NF) substrate by one-step solvothermal method. Compared with the α-FeOOH/NF catalyst, adding Cu provided more attachment sites for the growth of α-FeOOH, which makes the catalyst surface morphology rougher and increases the contact area between the catalyst and reactants. The assembled heterointerface between crystalline Cu and amorphous α-FeOOH altered the electronic structure of the catalyst. It promoted electron transfer from Ni and Fe to Cu, thus enhancing methanol adsorption and oxidation. The electrochemical tests revealed that the Cu/α-FeOOH/NF catalyst exhibited excellent methanol oxidation reaction (MOR) and hydrogen evolution reaction (HER) performance. In the Cu/α-FeOOH/NF||Cu/α-FeOOH/NF HER-MOR system, the voltage was reduced by 125 mV compared to the overall water splitting system at the geometric current density of 10 mA·cm-2. The catalytic system operated stably for 96 h under high voltage (2.4 V). In addition, the anode MOR produced value-added formate and the calculated Faraday efficiency based on formate was close to 97% under an applied voltage of 1.80 V.
Self-supporting Cu/α-FeOOH/NF catalysts were prepared by in-situ growth of Cu/α-FeOOH nanocomposites on foam nickel (NF) substrate by one-step solvothermal method. Compared with the α-FeOOH/NF catalyst, adding Cu provided more attachment sites for the growth of α-FeOOH, which makes the catalyst surface morphology rougher and increases the contact area between the catalyst and reactants. The assembled heterointerface between crystalline Cu and amorphous α-FeOOH altered the electronic structure of the catalyst. It promoted electron transfer from Ni and Fe to Cu, thus enhancing methanol adsorption and oxidation. The electrochemical tests revealed that the Cu/α-FeOOH/NF catalyst exhibited excellent methanol oxidation reaction (MOR) and hydrogen evolution reaction (HER) performance. In the Cu/α-FeOOH/NF||Cu/α-FeOOH/NF HER-MOR system, the voltage was reduced by 125 mV compared to the overall water splitting system at the geometric current density of 10 mA·cm-2. The catalytic system operated stably for 96 h under high voltage (2.4 V). In addition, the anode MOR produced value-added formate and the calculated Faraday efficiency based on formate was close to 97% under an applied voltage of 1.80 V.
2024, 40(10): 1965-1974
doi: 10.11862/CJIC.20240014
Abstract:
The precursor-calcination approach was employed to fabricate ZnAl@layered double oxides (LDOs) with dual functionality with adsorption and photocatalysis. The effect of bimetallic ratios and calcination temperatures on the adsorption-photocatalytic degradation of tetracycline (TC) was systematically investigated by X-ray powder diffraction (XRD), infrared spectroscopy (FTIR), ultraviolet-visible diffuse reflection spectroscopy (UV-Vis DRS), and scanning electron microscope (SEM). The results indicated that a molar ratio of 2∶1 for Zn to Al and a calcination temperature of 400 ℃ resulted in Zn2Al1@LDO400 with outstanding adsorption-photocatalytic activity. Moreover, adsorption studies revealed that Zn2Al1@LDO400 displayed the chemisorption-limited heterogeneous monolayer adsorption for TC, with higher temperatures promoting the adsorption process. Simultaneously, the collaborative degradation of TC by photogenerated holes (h+), hydroxyl radicals (·OH), and superoxide radicals (·O2-) was confirmed through free radical quenching experiments and electron paramagnetic resonance (EPR) tests.
The precursor-calcination approach was employed to fabricate ZnAl@layered double oxides (LDOs) with dual functionality with adsorption and photocatalysis. The effect of bimetallic ratios and calcination temperatures on the adsorption-photocatalytic degradation of tetracycline (TC) was systematically investigated by X-ray powder diffraction (XRD), infrared spectroscopy (FTIR), ultraviolet-visible diffuse reflection spectroscopy (UV-Vis DRS), and scanning electron microscope (SEM). The results indicated that a molar ratio of 2∶1 for Zn to Al and a calcination temperature of 400 ℃ resulted in Zn2Al1@LDO400 with outstanding adsorption-photocatalytic activity. Moreover, adsorption studies revealed that Zn2Al1@LDO400 displayed the chemisorption-limited heterogeneous monolayer adsorption for TC, with higher temperatures promoting the adsorption process. Simultaneously, the collaborative degradation of TC by photogenerated holes (h+), hydroxyl radicals (·OH), and superoxide radicals (·O2-) was confirmed through free radical quenching experiments and electron paramagnetic resonance (EPR) tests.
