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2023 Volume 39 Issue 4
2023, 39(4): 585-595
doi: 10.11862/CJIC.2023.037
Abstract:
Four new cucurbit[5]uril-based (Q[5]) supramolecular self-assemblies (Q[5]-SA), namely{[M (H2O)4(Q[5])]·(NDA)}·xH2O (M=Co (1), Ni (2), Zn (3)) and{[Cd2Cl2(H2O)4(Q[5])]·(NDA)}·13H2O (4), were synthesized by employing naphthalene-2, 7-disulphonate anion (2, 7-NDA2-) as the structure-directing agent to react with Q[5]and transition metal cations (Co2+, Ni2+, Zn2+, Cd2+) under hydrothermal conditions.Single-crystal X-ray diffraction (SC-XRD) results reveal that self-assemblies 1-3 are isostructural and the metal cations (Co2+, Ni2+, Zn2+) merely coordinate with the carbonyl groups from one portal of Q[5]to form simple coordination compounds, while the Cd2+ cation in selfassembly 4 is bound to both of the two portals of Q[5]to generate 1D coordination chains.In particular, the 2, 7NDA2- ligands in all self-assemblies are deprotonated to form organic anions 2, 7-NDA2-, which balanced the system charge.However, 2, 7-NDA2- fails to coordinate with the metal ions coordinated with Q[5], and these Q[5]-based coordination compounds are assembled into 3D supramolecular architectures through outer surface interactions of Q[5].Furthermore, the fluorescence sensing properties of 1 and 4 were investigated and the results indicated that they could both function as ratiometric fluorescence sensors for norfloxacin (NFX).
Four new cucurbit[5]uril-based (Q[5]) supramolecular self-assemblies (Q[5]-SA), namely{[M (H2O)4(Q[5])]·(NDA)}·xH2O (M=Co (1), Ni (2), Zn (3)) and{[Cd2Cl2(H2O)4(Q[5])]·(NDA)}·13H2O (4), were synthesized by employing naphthalene-2, 7-disulphonate anion (2, 7-NDA2-) as the structure-directing agent to react with Q[5]and transition metal cations (Co2+, Ni2+, Zn2+, Cd2+) under hydrothermal conditions.Single-crystal X-ray diffraction (SC-XRD) results reveal that self-assemblies 1-3 are isostructural and the metal cations (Co2+, Ni2+, Zn2+) merely coordinate with the carbonyl groups from one portal of Q[5]to form simple coordination compounds, while the Cd2+ cation in selfassembly 4 is bound to both of the two portals of Q[5]to generate 1D coordination chains.In particular, the 2, 7NDA2- ligands in all self-assemblies are deprotonated to form organic anions 2, 7-NDA2-, which balanced the system charge.However, 2, 7-NDA2- fails to coordinate with the metal ions coordinated with Q[5], and these Q[5]-based coordination compounds are assembled into 3D supramolecular architectures through outer surface interactions of Q[5].Furthermore, the fluorescence sensing properties of 1 and 4 were investigated and the results indicated that they could both function as ratiometric fluorescence sensors for norfloxacin (NFX).
2023, 39(4): 596-606
doi: 10.11862/CJIC.2023.027
Abstract:
A Co-MOF{[Co3(L)2(H2O)6]·3H2O}n(1) was obtained by hydrothermal reactions of rigid polycarboxylic acid organic ligand H3L (3-(3', 5'-dicarboxyphenyl)-6-carboxypyridine) and transition metal Co (Ⅱ).The IR spectrum and stability of 1 were characterized.The X-ray single crystal structure analyses showed that ligand L3- uses its three carboxylate groups and pyridine nitrogen atoms to connect Co (Ⅱ) cations to form a 3D porous framework with lattice water molecules filled in.The coordinated and lattice water molecules are connected by hydrogen bonds to form a continuous 1D water chain.To study the proton conduction behavior of complex 1, it was doped with Nafion to obtain a 1/Nafion composite membrane.The results of AC impedance analyses showed that the doping of complex 1 can increase the proton conductivity of the composite membrane by 40.3% compared with pure Nafion membrane.The studies of the structure-property relationship showed that the continuous hydrogen bond chains and hydrophilic channels in the crystal structure of 1 are the main reasons for its good proton conductivity.
A Co-MOF{[Co3(L)2(H2O)6]·3H2O}n(1) was obtained by hydrothermal reactions of rigid polycarboxylic acid organic ligand H3L (3-(3', 5'-dicarboxyphenyl)-6-carboxypyridine) and transition metal Co (Ⅱ).The IR spectrum and stability of 1 were characterized.The X-ray single crystal structure analyses showed that ligand L3- uses its three carboxylate groups and pyridine nitrogen atoms to connect Co (Ⅱ) cations to form a 3D porous framework with lattice water molecules filled in.The coordinated and lattice water molecules are connected by hydrogen bonds to form a continuous 1D water chain.To study the proton conduction behavior of complex 1, it was doped with Nafion to obtain a 1/Nafion composite membrane.The results of AC impedance analyses showed that the doping of complex 1 can increase the proton conductivity of the composite membrane by 40.3% compared with pure Nafion membrane.The studies of the structure-property relationship showed that the continuous hydrogen bond chains and hydrophilic channels in the crystal structure of 1 are the main reasons for its good proton conductivity.
2023, 39(4): 607-616
doi: 10.11862/CJIC.2023.036
Abstract:
Using a two-step method, a Co metal-organic framework (Co-MOF) nanosheet array was grown in situ on nickel foam (NF), and then Co-MOF nanosheets were etched with different concentrations of Ni2+ ion solution to obtain NiCo layered double hydroxide (NiCo-LDH). NiCo-LDH/NF inherits the Co-MOF nano-sheet structure to form a primary nano-sheet array and a secondary nano-sheet fold on the surface of the primary nano-sheet. NiCo-LDH/NF obtained by etching in 2 mmol Ni (NO3)2·6H2O solution showed a small number of thin and folded secondary nano-sheets grown on the primary nano-sheet array, exhibited a high capacitance and high rate performance, had a specific capacitance of 7764.5 and 6098.2 mF·cm-2 at a current density of 5 and 20 mA·cm-2, and capacitance retention rate of 78.5%. After 5000 cycles at a current density of 20 A·g-1, the capacitance retention rate was 85.9%. The hybrid capacitor assembled by NiCo-LDH/NF and active carbon achieved an maximum energy density of 38.9 Wh·kg-1 and a maximum power density of 8000.0 W·kg-1.
Using a two-step method, a Co metal-organic framework (Co-MOF) nanosheet array was grown in situ on nickel foam (NF), and then Co-MOF nanosheets were etched with different concentrations of Ni2+ ion solution to obtain NiCo layered double hydroxide (NiCo-LDH). NiCo-LDH/NF inherits the Co-MOF nano-sheet structure to form a primary nano-sheet array and a secondary nano-sheet fold on the surface of the primary nano-sheet. NiCo-LDH/NF obtained by etching in 2 mmol Ni (NO3)2·6H2O solution showed a small number of thin and folded secondary nano-sheets grown on the primary nano-sheet array, exhibited a high capacitance and high rate performance, had a specific capacitance of 7764.5 and 6098.2 mF·cm-2 at a current density of 5 and 20 mA·cm-2, and capacitance retention rate of 78.5%. After 5000 cycles at a current density of 20 A·g-1, the capacitance retention rate was 85.9%. The hybrid capacitor assembled by NiCo-LDH/NF and active carbon achieved an maximum energy density of 38.9 Wh·kg-1 and a maximum power density of 8000.0 W·kg-1.
2023, 39(4): 617-626
doi: 10.11862/CJIC.2023.032
Abstract:
In this work, manganese dioxide nanoparticles (MnO2 NPs) were synthesized through a in situ redox reaction using polyethyleneimine (PEI) as both template and reductant. The morphology, composition, UV-visible absorption, and catalytic oxidation performance of MnO2 NPs were characterized. MnO2 NPs possessed the characteristic of catalytic oxidation of o-phenylenediamine (OPD) to 2, 3-diaminophenazine (DAP), producing the UV-visible absorption at 420 nm and fluorescence emission at 560 nm. Owing to its active sulfhydryl, D-penicillamine (DPA) could decompose MnO2 NPs through a unique redox reaction. Therefore, the catalytic oxidation activity was inhibited that made UV-visible absorption-fluorescence signals decreased and even disappeared. Based on the relationship between spectral variation and DPA concentration, a MnO2 NPs mediated UV-visible absorption-fluorescence dual channel sensing method for DPA was established. Fluorescence channel sensing possessed satisfactory linear range and sensitivity. The linear range was 1-80 μmol·L-1 with a detection limit of 0.54 μmol·L-1. Moreover, MnO2 NPs mediated fluorescence sensing was applied in human urine sample detection and the recovery was in a range of 98.31%-107.76%, which proved the reliability of this method.
In this work, manganese dioxide nanoparticles (MnO2 NPs) were synthesized through a in situ redox reaction using polyethyleneimine (PEI) as both template and reductant. The morphology, composition, UV-visible absorption, and catalytic oxidation performance of MnO2 NPs were characterized. MnO2 NPs possessed the characteristic of catalytic oxidation of o-phenylenediamine (OPD) to 2, 3-diaminophenazine (DAP), producing the UV-visible absorption at 420 nm and fluorescence emission at 560 nm. Owing to its active sulfhydryl, D-penicillamine (DPA) could decompose MnO2 NPs through a unique redox reaction. Therefore, the catalytic oxidation activity was inhibited that made UV-visible absorption-fluorescence signals decreased and even disappeared. Based on the relationship between spectral variation and DPA concentration, a MnO2 NPs mediated UV-visible absorption-fluorescence dual channel sensing method for DPA was established. Fluorescence channel sensing possessed satisfactory linear range and sensitivity. The linear range was 1-80 μmol·L-1 with a detection limit of 0.54 μmol·L-1. Moreover, MnO2 NPs mediated fluorescence sensing was applied in human urine sample detection and the recovery was in a range of 98.31%-107.76%, which proved the reliability of this method.
2023, 39(4): 627-636
doi: 10.11862/CJIC.2023.044
Abstract:
Boron and phosphorus co-doped Fe-Co (Fe-Co-B-P) materials were successfully synthesized by one-step hydrothermal method.The morphology, structure, and composition of the synthesized materials were characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), X-ray photoelectron spectrometer (XPS), and Fourier transform infrared spectroscopy (FT-IR).The electrochemical oxygen evolution reaction (OER) properties of the materials were studied by linear sweep voltammetry (LSV), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) techniques.The results showed that the loose rough surface of as-synthesized Fe-Co-B-P had many voids among particles, which can expose abundant active sites and improve the OER electrocatalytic activity.The overpotential of Fe-Co-B-P was 278 and 309 mV under the current density of 10 and 100 mA·cm-2, respectively.And the Fe-Co-B-P electrocatalyst possessed favorable reaction kinetics with a low Tafel slope of 24 mV·dec-1 and facilitated charge transfer, indicating that Fe-Co-B-P had better OER electrocatalytic performance.Moreover, the potential was basically maintained at 1.55 V (vs RHE) after 10 h chronopotentiometric test, suggesting that the catalyst had good electrochemical stability.This is due to the synergistic effect between Fe-Co bimetal and B-P-nonmetal to promote electron transfer.
Boron and phosphorus co-doped Fe-Co (Fe-Co-B-P) materials were successfully synthesized by one-step hydrothermal method.The morphology, structure, and composition of the synthesized materials were characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), X-ray photoelectron spectrometer (XPS), and Fourier transform infrared spectroscopy (FT-IR).The electrochemical oxygen evolution reaction (OER) properties of the materials were studied by linear sweep voltammetry (LSV), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) techniques.The results showed that the loose rough surface of as-synthesized Fe-Co-B-P had many voids among particles, which can expose abundant active sites and improve the OER electrocatalytic activity.The overpotential of Fe-Co-B-P was 278 and 309 mV under the current density of 10 and 100 mA·cm-2, respectively.And the Fe-Co-B-P electrocatalyst possessed favorable reaction kinetics with a low Tafel slope of 24 mV·dec-1 and facilitated charge transfer, indicating that Fe-Co-B-P had better OER electrocatalytic performance.Moreover, the potential was basically maintained at 1.55 V (vs RHE) after 10 h chronopotentiometric test, suggesting that the catalyst had good electrochemical stability.This is due to the synergistic effect between Fe-Co bimetal and B-P-nonmetal to promote electron transfer.
2023, 39(4): 637-648
doi: 10.11862/CJIC.2023.023
Abstract:
A series of phosphorus-modified Ni-Al-O catalysts (Px-Ni-Al-O) were prepared by the one-pot hydrothermal method.The performance of the oxidative dehydrogenation of ethane to ethylene over series catalysts was evaluated by using O2 as an oxidant.The results showed that the P incorporation can not only reduce the crystallite sizes of NiO, but also affect the interaction between Ni and Al.In the temperature range of 350-475℃, the selectivities towards ethylene over P-modified Ni-Al-O catalysts were higher than those over the unmodified catalyst, and the addition of the appropriate amount of P could also improve the ethane conversion.The selectivity and yield of ethylene over the P0.15-Ni-Al-O catalyst were 61.4% and 31.9% at 475℃, respectively.Moreover, the P-modified catalyst showed a strong resistance to carbon deposition and remained the catalytic performance for 22 h after a continuous reaction.
A series of phosphorus-modified Ni-Al-O catalysts (Px-Ni-Al-O) were prepared by the one-pot hydrothermal method.The performance of the oxidative dehydrogenation of ethane to ethylene over series catalysts was evaluated by using O2 as an oxidant.The results showed that the P incorporation can not only reduce the crystallite sizes of NiO, but also affect the interaction between Ni and Al.In the temperature range of 350-475℃, the selectivities towards ethylene over P-modified Ni-Al-O catalysts were higher than those over the unmodified catalyst, and the addition of the appropriate amount of P could also improve the ethane conversion.The selectivity and yield of ethylene over the P0.15-Ni-Al-O catalyst were 61.4% and 31.9% at 475℃, respectively.Moreover, the P-modified catalyst showed a strong resistance to carbon deposition and remained the catalytic performance for 22 h after a continuous reaction.
2023, 39(4): 649-658
doi: 10.11862/CJIC.2023.031
Abstract:
Two tetranuclear di(n‐butyl)tin aryloyacetates [(o‐R—C6H4—OCH2COOSn(n‐Bu)2)2O]2 (R=H (C1), Cl (C2)) have been synthesized by the reaction of phenoxyacetic acid or o‐chlorophenoxyacetic acid with dibutyltin oxide, respectively. The structures were characterized by elemental analysis, IR, 1H, 13C NMR, and X‐ray crystal diffraction. There is a ladder structure formed by a four‐membered central endocyclic Sn2O2 unit in the independent molecules of complexes C1 and C2, two carboxyl oxygen atoms and an Sn—O—Sn unit constituted the six‐membered ring on both sides of the ladder, which constitutes the Sn4O8 configuration. Thermogravimetric analysis shows that the complexes possess good thermal stability in the air atmosphere. Herbicidal activity results show that complex C1 has good regulative effects on the growth of Cassia tora Linn., and complex C2 has better inhibitory activity against the root and stalk of Amaranthus spinosus at the concentration of 50 mol·L-1.
Two tetranuclear di(n‐butyl)tin aryloyacetates [(o‐R—C6H4—OCH2COOSn(n‐Bu)2)2O]2 (R=H (C1), Cl (C2)) have been synthesized by the reaction of phenoxyacetic acid or o‐chlorophenoxyacetic acid with dibutyltin oxide, respectively. The structures were characterized by elemental analysis, IR, 1H, 13C NMR, and X‐ray crystal diffraction. There is a ladder structure formed by a four‐membered central endocyclic Sn2O2 unit in the independent molecules of complexes C1 and C2, two carboxyl oxygen atoms and an Sn—O—Sn unit constituted the six‐membered ring on both sides of the ladder, which constitutes the Sn4O8 configuration. Thermogravimetric analysis shows that the complexes possess good thermal stability in the air atmosphere. Herbicidal activity results show that complex C1 has good regulative effects on the growth of Cassia tora Linn., and complex C2 has better inhibitory activity against the root and stalk of Amaranthus spinosus at the concentration of 50 mol·L-1.
2023, 39(4): 659-670
doi: 10.11862/CJIC.2023.038
Abstract:
In this study, a series of pure-phase EU-1 zeolites were synthesized by introducing seeds into a series of synthetic gels with different SiO2/Al2O3 ratios (nSiO2/nAl2O3, containing pure silicon gel).The effect of the aluminum source, the amount of template and seed on the crystallinity, and the morphology and size of EU-1 zeolite were investigated.The effects of different SiO2/Al2O3 ratios synthesis systems on the crystallinity, crystal size, acidic property, specific surface area, and pore volume of the samples were emphatically studied.Pure phase EU-1 was synthesized not only in a high-silicon system but also in an aluminum-free system by the seeding method.The results were plotted into a ternary plot of the synthesis conditions of pure phase EU-1 zeolite.It is obvious from the ternary plot that the crystal seed method can significantly expand the synthesis region of pure phase EU1 zeolite.Pt/H-EU-1 was applied to catalyze the n-hexane isomerization reaction.The results showed that the catalyst had excellent n-hexane isomerization activity and stability, and high selectivity to isoparaffins.
In this study, a series of pure-phase EU-1 zeolites were synthesized by introducing seeds into a series of synthetic gels with different SiO2/Al2O3 ratios (nSiO2/nAl2O3, containing pure silicon gel).The effect of the aluminum source, the amount of template and seed on the crystallinity, and the morphology and size of EU-1 zeolite were investigated.The effects of different SiO2/Al2O3 ratios synthesis systems on the crystallinity, crystal size, acidic property, specific surface area, and pore volume of the samples were emphatically studied.Pure phase EU-1 was synthesized not only in a high-silicon system but also in an aluminum-free system by the seeding method.The results were plotted into a ternary plot of the synthesis conditions of pure phase EU-1 zeolite.It is obvious from the ternary plot that the crystal seed method can significantly expand the synthesis region of pure phase EU1 zeolite.Pt/H-EU-1 was applied to catalyze the n-hexane isomerization reaction.The results showed that the catalyst had excellent n-hexane isomerization activity and stability, and high selectivity to isoparaffins.
Synthesis of Fe-doped CuS nanoparticles for the combination of photothermal and chemodynamic therapy
2023, 39(4): 671-679
doi: 10.11862/CJIC.2023.026
Abstract:
Copper sulfide (CuS) nanoparticles with strong absorption in the near-infrared region were synthesized in oleic acid (OA)-oleylamine (OM)-octadecene (ODE) system using copper acetylacetonate and sulfur powder as copper and sulfur sources respectively.By adjusting the activation solvent for the sulfur powder, the absorption peak can be tuned to around 1 064 nm which was beneficial for photothermal therapy.The Fe and Mn elements doped CuS nanoparticles were further prepared by the cation exchange approach, and the absorption peak can be retained after the reaction.Then, these hydrophobic nanoparticles were transferred into an aqueous solution by the microemulsion method, the obtained PEGylated (PEG=poly (ethylene glycol)) nanoparticles exhibited excellent dispersity and colloidal stability.Their photothermal performance and the hydroxyl radical (·OH) production before and after Fe3+ doping were investigated thereafter.The mass extinction coefficient of Fe3+ doped CuS nanoparticles after PEGylation (CuS∶FePEG) at 1064 nm was 37.5 L·g-1·cm-1, with a high photothermal conversion efficiency of around 43.7%.Although these values were slightly decreased compared with undoped CuS-PEG, their ability to produce ·OH was significantly improved.A higher inhibition ratio of cancer cells was observed with CuS∶FePEG nanoparticles under weak acid condition.And under 1 064 nm laser, these nanoparticles can kill cancer cells more effectively.Therefore, the prepared CuS∶Fe-PEG nanoparticles can be used for the combination of photothermal and chemodynamic therapy.
Copper sulfide (CuS) nanoparticles with strong absorption in the near-infrared region were synthesized in oleic acid (OA)-oleylamine (OM)-octadecene (ODE) system using copper acetylacetonate and sulfur powder as copper and sulfur sources respectively.By adjusting the activation solvent for the sulfur powder, the absorption peak can be tuned to around 1 064 nm which was beneficial for photothermal therapy.The Fe and Mn elements doped CuS nanoparticles were further prepared by the cation exchange approach, and the absorption peak can be retained after the reaction.Then, these hydrophobic nanoparticles were transferred into an aqueous solution by the microemulsion method, the obtained PEGylated (PEG=poly (ethylene glycol)) nanoparticles exhibited excellent dispersity and colloidal stability.Their photothermal performance and the hydroxyl radical (·OH) production before and after Fe3+ doping were investigated thereafter.The mass extinction coefficient of Fe3+ doped CuS nanoparticles after PEGylation (CuS∶FePEG) at 1064 nm was 37.5 L·g-1·cm-1, with a high photothermal conversion efficiency of around 43.7%.Although these values were slightly decreased compared with undoped CuS-PEG, their ability to produce ·OH was significantly improved.A higher inhibition ratio of cancer cells was observed with CuS∶FePEG nanoparticles under weak acid condition.And under 1 064 nm laser, these nanoparticles can kill cancer cells more effectively.Therefore, the prepared CuS∶Fe-PEG nanoparticles can be used for the combination of photothermal and chemodynamic therapy.
2023, 39(4): 680-688
doi: 10.11862/CJIC.2023.033
Abstract:
Three manganese carbonyl complexes[Mn (CO)3(py (CH=N) ph X) Br], where X=Cl (1), Br (2), I (3), containing Schiff base ligands were synthesized by a one-step method using manganese pentacarbonyl bromide, 2pyridine formaldehyde, and halogenated aniline.They were characterized by NMR, X-ray single crystal diffraction, IR spectrum, UV-Vis spectrum, and fluorescence spectrum.These complexes were stable under non-illumination, but they could decompose to release CO under visible light (LED blue, green, and red light), which can be used as photo-induced carbon monoxide release molecules (photoCORMs).The CO release rate could be conveniently controlled by selecting different lights.It has been shown that blue light was the most effective light source to promote the decomposition of these complexes to release CO.The differences in the electronic effects of the halogenated ligands in these complexes also contribute to the differences in their reaction rates.In addition, the kinetic analysis of CO release shows that the process conforms to the first-order kinetic model.The carbon monoxide release of complex 3 was also studied by standard myoglobin assay, showing that deoxymyoglobin was able to capture the released CO.Although the cytotoxicity of these complexes itself reached the micromolar level, the cell compatibility under light was significantly improved, rising to nearly 100 micromolar levels.These complexes had fluorescent properties, emitting a certain intensity of fluorescence in a range of 500-700 nm at the excitation wavelength of 450 nm, which can be used as fluorescent markers to monitor the distribution of release agents and CO release in cells or organisms.
Three manganese carbonyl complexes[Mn (CO)3(py (CH=N) ph X) Br], where X=Cl (1), Br (2), I (3), containing Schiff base ligands were synthesized by a one-step method using manganese pentacarbonyl bromide, 2pyridine formaldehyde, and halogenated aniline.They were characterized by NMR, X-ray single crystal diffraction, IR spectrum, UV-Vis spectrum, and fluorescence spectrum.These complexes were stable under non-illumination, but they could decompose to release CO under visible light (LED blue, green, and red light), which can be used as photo-induced carbon monoxide release molecules (photoCORMs).The CO release rate could be conveniently controlled by selecting different lights.It has been shown that blue light was the most effective light source to promote the decomposition of these complexes to release CO.The differences in the electronic effects of the halogenated ligands in these complexes also contribute to the differences in their reaction rates.In addition, the kinetic analysis of CO release shows that the process conforms to the first-order kinetic model.The carbon monoxide release of complex 3 was also studied by standard myoglobin assay, showing that deoxymyoglobin was able to capture the released CO.Although the cytotoxicity of these complexes itself reached the micromolar level, the cell compatibility under light was significantly improved, rising to nearly 100 micromolar levels.These complexes had fluorescent properties, emitting a certain intensity of fluorescence in a range of 500-700 nm at the excitation wavelength of 450 nm, which can be used as fluorescent markers to monitor the distribution of release agents and CO release in cells or organisms.
2023, 39(4): 689-698
doi: 10.11862/CJIC.2023.029
Abstract:
TiO2/g-C3N4(T-CN) composite catalyst was successfully prepared by hydrothermal reaction of hollow tubular g-C3N4 and TiO2 nanosheets.Its morphology, structure, and photophysical properties were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), UV-visible diffuse reflectance spectrum (UV-Vis DRS), and photocurrent response.The effect of different amounts of TiO2 on the photoreduction and fixation of U(Ⅵ) by T-CN was studied.The results showed that when the mass ratio of TiO2 to g-C3N4 was 20%, the removal rate of U(Ⅵ) by T-CN-20 was 85.64% in 60 min, which was 4.0 times of that of pure phase g-C3N4.The removal rate of U(Ⅵ) was still more than 69.8% under the coexistence of 10 times of high concentration cations, and had excellent structural stability.According to the analysis of photocatalytic products, T-CN-20 reduced U(Ⅵ) to insoluble U (Ⅳ)(63.68%) for removal, which can effectively solve the problem of U(Ⅵ) pollution in uranium-containing nuclear wastewater.Based on the analysis of energy band theory, the type-Ⅱ photocatalysis mechanism of composite catalyst heterojunction was proposed.
TiO2/g-C3N4(T-CN) composite catalyst was successfully prepared by hydrothermal reaction of hollow tubular g-C3N4 and TiO2 nanosheets.Its morphology, structure, and photophysical properties were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), UV-visible diffuse reflectance spectrum (UV-Vis DRS), and photocurrent response.The effect of different amounts of TiO2 on the photoreduction and fixation of U(Ⅵ) by T-CN was studied.The results showed that when the mass ratio of TiO2 to g-C3N4 was 20%, the removal rate of U(Ⅵ) by T-CN-20 was 85.64% in 60 min, which was 4.0 times of that of pure phase g-C3N4.The removal rate of U(Ⅵ) was still more than 69.8% under the coexistence of 10 times of high concentration cations, and had excellent structural stability.According to the analysis of photocatalytic products, T-CN-20 reduced U(Ⅵ) to insoluble U (Ⅳ)(63.68%) for removal, which can effectively solve the problem of U(Ⅵ) pollution in uranium-containing nuclear wastewater.Based on the analysis of energy band theory, the type-Ⅱ photocatalysis mechanism of composite catalyst heterojunction was proposed.
2023, 39(4): 699-708
doi: 10.11862/CJIC.2023.030
Abstract:
In this work, we prepared double heterojunction Bi2Ti2O7/TiO2/Bi4Ti3O12 composite nanofibers by employing electrospun TiO2 nanofibers as the substrate, bismuth nitrate as the bismuth source, and potassium hydroxide as the mineralizing agent.Through a series of tests such as X-ray diffraction (XRD), scanning electron microscope (SEM), UV-visible diffuse reflectance spectrum (UV-Vis DRS), the phase composition, micromorphology, and optical properties of the Bi2Ti2O7/TiO2/Bi4Ti3O12 catalyst were analyzed.The results showed that the TiO2 changed type Ⅰ heterojunction into multi-heterojunction integrating two type Ⅱ heterojunctions.Photocatalytic tests demonstrated the activity of as-constructed multi-heterojunction was higher than that of single type Ⅰ or Ⅱ heterojunctions, respectively, where photogenerated electrons were accumulated on the surface of TiO2 and photogenerated holes were accumulated on Bi2Ti2O7 and Bi4Ti3O12, respectively.The synergistic effect of Bi2Ti2O7, Bi4Ti3O12, and TiO2 effectively improves the visible light absorption capacity, changes the transmission path of photo-generated carriers, and reduces the recombination probability of photogenerated electron-hole pairs, thereby obtaining the efficient photocatalytic degradation of CH3CHO.The acetaldehyde degradation rate of Bi2Ti2O7/TiO2/Bi4Ti3O12 reached 87.1% under visible light illumination for 8 h.
In this work, we prepared double heterojunction Bi2Ti2O7/TiO2/Bi4Ti3O12 composite nanofibers by employing electrospun TiO2 nanofibers as the substrate, bismuth nitrate as the bismuth source, and potassium hydroxide as the mineralizing agent.Through a series of tests such as X-ray diffraction (XRD), scanning electron microscope (SEM), UV-visible diffuse reflectance spectrum (UV-Vis DRS), the phase composition, micromorphology, and optical properties of the Bi2Ti2O7/TiO2/Bi4Ti3O12 catalyst were analyzed.The results showed that the TiO2 changed type Ⅰ heterojunction into multi-heterojunction integrating two type Ⅱ heterojunctions.Photocatalytic tests demonstrated the activity of as-constructed multi-heterojunction was higher than that of single type Ⅰ or Ⅱ heterojunctions, respectively, where photogenerated electrons were accumulated on the surface of TiO2 and photogenerated holes were accumulated on Bi2Ti2O7 and Bi4Ti3O12, respectively.The synergistic effect of Bi2Ti2O7, Bi4Ti3O12, and TiO2 effectively improves the visible light absorption capacity, changes the transmission path of photo-generated carriers, and reduces the recombination probability of photogenerated electron-hole pairs, thereby obtaining the efficient photocatalytic degradation of CH3CHO.The acetaldehyde degradation rate of Bi2Ti2O7/TiO2/Bi4Ti3O12 reached 87.1% under visible light illumination for 8 h.
2023, 39(4): 709-715
doi: 10.11862/CJIC.2023.028
Abstract:
In this paper, we report the synthesis, characterization, and molecular structure of the dioxidomolybdenum (Ⅵ) complex[MoO2(H2L)(H2O)].The complex was obtained by reaction of malanoyldihydrazones ligand bis (2 hydroxy-1-naphthaldehyde) malonoyldihydrazone (H4L) with molybdenum bis (acetylacetonato) dioxomolybdenum (Ⅵ) in a 1∶1 molar ratio in methanol.The complex was characterized by using various spectroscopic studies, such as IR, MS, and NMR.The structure of the complex was established by single-crystal X-ray crystallography.The complex crystallizes in the monoclinic space group P21/c.The metal center has distorted octahedral coordination environments, connected to one azomethine nitrogen atom of H4L, two terminal oxido groups, two oxygen atoms of H4L, and one oxygen atom of a coordinated water molecule.
In this paper, we report the synthesis, characterization, and molecular structure of the dioxidomolybdenum (Ⅵ) complex[MoO2(H2L)(H2O)].The complex was obtained by reaction of malanoyldihydrazones ligand bis (2 hydroxy-1-naphthaldehyde) malonoyldihydrazone (H4L) with molybdenum bis (acetylacetonato) dioxomolybdenum (Ⅵ) in a 1∶1 molar ratio in methanol.The complex was characterized by using various spectroscopic studies, such as IR, MS, and NMR.The structure of the complex was established by single-crystal X-ray crystallography.The complex crystallizes in the monoclinic space group P21/c.The metal center has distorted octahedral coordination environments, connected to one azomethine nitrogen atom of H4L, two terminal oxido groups, two oxygen atoms of H4L, and one oxygen atom of a coordinated water molecule.
2023, 39(4): 716-722
doi: 10.11862/CJIC.2023.035
Abstract:
In this work, the (P (VDF-TrFE)(55/45)) was used as polymer matrix and 0.75BiFeO3-0.25BaTiO3(BFO-BTO) nanofiber was used as fillers to enhance the thermal conductivity of the copolymer.The enhanced thermal conductivity was achieved by adding a small amount of BFO-BTO nanofibers to the copolymer.A thermal conductivity of the composite film with 2% nanofibers was 0.21 W·m-1·K-1 at 75℃, which was nearly twice that of the P (VDF-TrFE)(55/45) copolymer film.At the same time, the electrocaloric effect (ECE) of the copolymer almost remained unchanged after the addition of nanofibers.The results suggest that the addition of BFO-BTO nanofibers is effective to improve the thermal conductivity of P (VDF-TrFE)(55/45) copolymer while maintaining high ECE.
In this work, the (P (VDF-TrFE)(55/45)) was used as polymer matrix and 0.75BiFeO3-0.25BaTiO3(BFO-BTO) nanofiber was used as fillers to enhance the thermal conductivity of the copolymer.The enhanced thermal conductivity was achieved by adding a small amount of BFO-BTO nanofibers to the copolymer.A thermal conductivity of the composite film with 2% nanofibers was 0.21 W·m-1·K-1 at 75℃, which was nearly twice that of the P (VDF-TrFE)(55/45) copolymer film.At the same time, the electrocaloric effect (ECE) of the copolymer almost remained unchanged after the addition of nanofibers.The results suggest that the addition of BFO-BTO nanofibers is effective to improve the thermal conductivity of P (VDF-TrFE)(55/45) copolymer while maintaining high ECE.
2023, 39(4): 723-734
doi: 10.11862/CJIC.2023.042
Abstract:
To improve the multiple-dye adsorption performance of the adsorbent and endow it with magnetism, a magnetic composite adsorbent composed of chitosan, magnetite nanoparticles, and graphene oxide (CS/Fe3O4/GO) was prepared by a simple co-precipitation method.Careful structural investigations indicated that magnetite nanoparticles covered by CS were evenly distributed on the surface of graphene oxide.CS, Fe3O4, and GO were chemically bonded together to form a stable composite material.The magnetism of CS/Fe3O4/GO was tested as 42.5 emu·g-1, which is strong enough for efficient solid-liquid separation under an applied magnetic field.CS/Fe3O4/GO was used to adsorb multiple synthetic dyes, including methylene blue (MB), Congo red (CR), and methyl orange (MO), and showed high multi-dye adsorption performance.It is found that the adsorption of MB, MO, and CR under optimal conditions reached 210.6, 258.6, and 308.9 mg·g-1, respectively.The effect of pH, initial concentration, and contact time on the adsorption was investigated.Recycling experiments showed that CS/Fe3O4/GO had excellent
To improve the multiple-dye adsorption performance of the adsorbent and endow it with magnetism, a magnetic composite adsorbent composed of chitosan, magnetite nanoparticles, and graphene oxide (CS/Fe3O4/GO) was prepared by a simple co-precipitation method.Careful structural investigations indicated that magnetite nanoparticles covered by CS were evenly distributed on the surface of graphene oxide.CS, Fe3O4, and GO were chemically bonded together to form a stable composite material.The magnetism of CS/Fe3O4/GO was tested as 42.5 emu·g-1, which is strong enough for efficient solid-liquid separation under an applied magnetic field.CS/Fe3O4/GO was used to adsorb multiple synthetic dyes, including methylene blue (MB), Congo red (CR), and methyl orange (MO), and showed high multi-dye adsorption performance.It is found that the adsorption of MB, MO, and CR under optimal conditions reached 210.6, 258.6, and 308.9 mg·g-1, respectively.The effect of pH, initial concentration, and contact time on the adsorption was investigated.Recycling experiments showed that CS/Fe3O4/GO had excellent
2023, 39(4): 735-745
doi: 10.11862/CJIC.2023.045
Abstract:
Carbon dots (CDs) were synthesized by a facile hydrothermal method using cheap black rice as a carbon source.The synthesized CDs exhibited excellent stability, which was not sensitive to changes in temperature, pH, and solution of NaCl, and were immune to many metal ions.The purified CDs also had low cytotoxicity against human oral keratinocytes (Hok), cancer cells (cervical cancer, Hela), and bone marrow mesenchymal stem (BMSC, MC3T3) cells.Meanwhile, it behaved with excitation-independent behavior in the shorter wavelength range (410-470 nm) and excitation-dependent behavior in the longer wavelength range (470-510 nm).Due to the excellent fluorescence properties and stability, we applied them to the intracellular imaging of Hok, Hela, and MC3T3 cells.
Carbon dots (CDs) were synthesized by a facile hydrothermal method using cheap black rice as a carbon source.The synthesized CDs exhibited excellent stability, which was not sensitive to changes in temperature, pH, and solution of NaCl, and were immune to many metal ions.The purified CDs also had low cytotoxicity against human oral keratinocytes (Hok), cancer cells (cervical cancer, Hela), and bone marrow mesenchymal stem (BMSC, MC3T3) cells.Meanwhile, it behaved with excitation-independent behavior in the shorter wavelength range (410-470 nm) and excitation-dependent behavior in the longer wavelength range (470-510 nm).Due to the excellent fluorescence properties and stability, we applied them to the intracellular imaging of Hok, Hela, and MC3T3 cells.
2023, 39(4): 746-752
doi: 10.11862/CJIC.2023.034
Abstract:
It is still a great challenge to construct heterometallic uranyl phosphonates. In this work, a series of isostructural heterometallic uranyl sulfophosphonates, namely [UO2M(L)2(H2O)4], where M=Mn (1), Co (2), Ni (3), Zn (4), Cd (5) and Et2L=diethyl ((phenylsulfonyl)methyl)phosphonate, have been successfully synthesized and systematically characterized. The sulfonyl group is not involved in coordination with the metal centers, whereas the phosphonate group is fully deprotonated and connects with two uranyl cations and one transition metal ion, affording a 2D layered crystal structure. It was found that the luminescent emission was almost totally quenched in the presence of Mn(Ⅱ), Co(Ⅱ), and Ni(Ⅱ), whereas showed strong emissions in the presence of Zn(Ⅱ) and Cd(Ⅱ).
It is still a great challenge to construct heterometallic uranyl phosphonates. In this work, a series of isostructural heterometallic uranyl sulfophosphonates, namely [UO2M(L)2(H2O)4], where M=Mn (1), Co (2), Ni (3), Zn (4), Cd (5) and Et2L=diethyl ((phenylsulfonyl)methyl)phosphonate, have been successfully synthesized and systematically characterized. The sulfonyl group is not involved in coordination with the metal centers, whereas the phosphonate group is fully deprotonated and connects with two uranyl cations and one transition metal ion, affording a 2D layered crystal structure. It was found that the luminescent emission was almost totally quenched in the presence of Mn(Ⅱ), Co(Ⅱ), and Ni(Ⅱ), whereas showed strong emissions in the presence of Zn(Ⅱ) and Cd(Ⅱ).
2023, 39(4): 753-764
doi: 10.11862/CJIC.2023.018
Abstract:
Herein, we present a novel and simple method to fabricate a large-area ordered Au/Ag nanobowl (Au/AgNB) array based on SiO2 colloidal crystals by wet chemosynthesis. The arrays combine the advantages of gold and silver and have been well recognized as excellent surface-enhanced Raman scattering (SERS) substrates in practical application. First of all, a 3D SiO2 colloidal crystal was arrayed on the glass substrate as a template. Then, a layer of Au nanoshell (AuNS) was deposited on the 3D SiO2 template by in-situ growth method with the help of Au nanoparticle (AuNP) seeds. Afterward, silver nanoshells were further deposited on the surface of AuNS by HCHO-reduced Ag+, then Ag/Au double nanoshell (Ag/AuNS) array was formed. A monolayer-ordered reversed Ag/AuNB array was conveniently obtained by an acrylic ester-modified biaxial-oriented polypropylene (BOPP). The ordered Au/AgNB array with adjustable periodic holes, shapes, and sizes could be obtained when the SiO2 core was etched by HF solution. With prominent stability and reproducibility, the SERS analytical enhancement factor (AEF) of this ordered Au/AgNB array could reach 2.23×107, which shows high SERS-enhancing activity and can be used as a universal SERS substrate.
Herein, we present a novel and simple method to fabricate a large-area ordered Au/Ag nanobowl (Au/AgNB) array based on SiO2 colloidal crystals by wet chemosynthesis. The arrays combine the advantages of gold and silver and have been well recognized as excellent surface-enhanced Raman scattering (SERS) substrates in practical application. First of all, a 3D SiO2 colloidal crystal was arrayed on the glass substrate as a template. Then, a layer of Au nanoshell (AuNS) was deposited on the 3D SiO2 template by in-situ growth method with the help of Au nanoparticle (AuNP) seeds. Afterward, silver nanoshells were further deposited on the surface of AuNS by HCHO-reduced Ag+, then Ag/Au double nanoshell (Ag/AuNS) array was formed. A monolayer-ordered reversed Ag/AuNB array was conveniently obtained by an acrylic ester-modified biaxial-oriented polypropylene (BOPP). The ordered Au/AgNB array with adjustable periodic holes, shapes, and sizes could be obtained when the SiO2 core was etched by HF solution. With prominent stability and reproducibility, the SERS analytical enhancement factor (AEF) of this ordered Au/AgNB array could reach 2.23×107, which shows high SERS-enhancing activity and can be used as a universal SERS substrate.
2023, 39(4): 765-774
doi: 10.11862/CJIC.2023.041
Abstract:
In this work, the dominant structures of Zr(Ⅳ) in zirconium oxychloride octahydrate solution were measured by using small-angle X-ray scattering (SAXS).The results show that the dominant structures of Zr(Ⅳ) are in the form of polymers in the solution, and the degrees of polymerization are susceptible to acidity.The different effects of the concentration, heating treatment, standing time, and HCl concentration of zirconium oxychloride in octahydrate were studied.With 0.0-5.0 mol·L-1 HCl as the solvent, 10-300 g·L-1 zirconium oxychloride solution was prepared, moreover, the solution was heated and placed for a long time respectively.The SAXS tests were carried out for all the solutions, and the Rg experiments of the particles in the solution were calculated using the Guinier equation.Meanwhile, the CYLview program for solving the most minor enclosing cylinder problems was used to simulate the different polymer structures of Zr(Ⅳ) in zirconium oxychloride octahydrate solution and obtain the theoretical Rg values of different structures.By comparing the experimental Rg and the calculated Rg, the dominant structures of Zr(Ⅳ) in solution under different conditions were obtained.The results show that the dominant structures of Zr(Ⅳ) are affected by many factors such as acidity and concentration, especially the concentration of HCl is the key factor affecting the degree of polymerization.When the solvent is deionized water, the polymerization degree of zirconium is relatively high in solutions with low zirconium concentration.
In this work, the dominant structures of Zr(Ⅳ) in zirconium oxychloride octahydrate solution were measured by using small-angle X-ray scattering (SAXS).The results show that the dominant structures of Zr(Ⅳ) are in the form of polymers in the solution, and the degrees of polymerization are susceptible to acidity.The different effects of the concentration, heating treatment, standing time, and HCl concentration of zirconium oxychloride in octahydrate were studied.With 0.0-5.0 mol·L-1 HCl as the solvent, 10-300 g·L-1 zirconium oxychloride solution was prepared, moreover, the solution was heated and placed for a long time respectively.The SAXS tests were carried out for all the solutions, and the Rg experiments of the particles in the solution were calculated using the Guinier equation.Meanwhile, the CYLview program for solving the most minor enclosing cylinder problems was used to simulate the different polymer structures of Zr(Ⅳ) in zirconium oxychloride octahydrate solution and obtain the theoretical Rg values of different structures.By comparing the experimental Rg and the calculated Rg, the dominant structures of Zr(Ⅳ) in solution under different conditions were obtained.The results show that the dominant structures of Zr(Ⅳ) are affected by many factors such as acidity and concentration, especially the concentration of HCl is the key factor affecting the degree of polymerization.When the solvent is deionized water, the polymerization degree of zirconium is relatively high in solutions with low zirconium concentration.
2023, 39(4): 775-784
doi: 10.11862/CJIC.2023.039
Abstract:
Using nitrogen-containing tetra-carboxylate ligands 3, 5-bis (3', 5'-dicarboxyphenyl)-1H-1, 2, 4-triazole (H4BDT), four isostructural lanthanide metal-organic frameworks (Ln-MOFs): {[La3(BDT)2(HCOO)(H2O)5]·0.5H2O· 3DMF}n(1), {[Ce3(BDT)2(HCOO)(H2O)5]·3DMF}n(2), {[Pr3(BDT)2(HCOO)(H2O)5]·3DMF}n(3), and{[Nd3(BDT)2(HCOO)(H2O)5]·3DMF}n(4), have been synthesized by solvothermal method and characterized by single-crystal Xray diffraction, powder X-ray diffraction, elemental analysis, thermogravimetric analysis, FT-IR, adsorption experiment of N2, and luminescence spectra.The results show that all these Ln-MOFs are monoclinic C2/m space group crystals and have 3D mesoporous structures with double cores as inorganic building units.Among them, 2 could selectively fluorescently detect Fe3+ ion and ciprofloxacin hydrochloride drug molecule and the limits of detection were 4.59 and 0.77 μmol·L-1, respectively.
Using nitrogen-containing tetra-carboxylate ligands 3, 5-bis (3', 5'-dicarboxyphenyl)-1H-1, 2, 4-triazole (H4BDT), four isostructural lanthanide metal-organic frameworks (Ln-MOFs): {[La3(BDT)2(HCOO)(H2O)5]·0.5H2O· 3DMF}n(1), {[Ce3(BDT)2(HCOO)(H2O)5]·3DMF}n(2), {[Pr3(BDT)2(HCOO)(H2O)5]·3DMF}n(3), and{[Nd3(BDT)2(HCOO)(H2O)5]·3DMF}n(4), have been synthesized by solvothermal method and characterized by single-crystal Xray diffraction, powder X-ray diffraction, elemental analysis, thermogravimetric analysis, FT-IR, adsorption experiment of N2, and luminescence spectra.The results show that all these Ln-MOFs are monoclinic C2/m space group crystals and have 3D mesoporous structures with double cores as inorganic building units.Among them, 2 could selectively fluorescently detect Fe3+ ion and ciprofloxacin hydrochloride drug molecule and the limits of detection were 4.59 and 0.77 μmol·L-1, respectively.
