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2026 Volume 42 Issue 4
2026, 42(4): 657-667
doi: 10.11862/CJIC.20250250
Abstract:
Metal-organic frameworks (MOFs) are a class of crystalline porous materials composed of organic ligands and metal ions/metal clusters. Due to their unique physical, chemical, and biological characteristics, they have become excellent platforms for drug delivery and play a significant role in the treatment of glioma. This article reviews the latest progress in MOFs for glioma treatment, including research advancements in drug penetration through the blood-brain barrier (BBB), targeted delivery of anti-glioma drugs, controlled drug release, and multiple-drug combination therapy. The aim is to provide a reference basis for the application and promotion of MOFs in glioma treatment.
Metal-organic frameworks (MOFs) are a class of crystalline porous materials composed of organic ligands and metal ions/metal clusters. Due to their unique physical, chemical, and biological characteristics, they have become excellent platforms for drug delivery and play a significant role in the treatment of glioma. This article reviews the latest progress in MOFs for glioma treatment, including research advancements in drug penetration through the blood-brain barrier (BBB), targeted delivery of anti-glioma drugs, controlled drug release, and multiple-drug combination therapy. The aim is to provide a reference basis for the application and promotion of MOFs in glioma treatment.
2026, 42(4): 668-692
doi: 10.11862/CJIC.20250319
Abstract:
With the rapid development of new energy vehicles and electronic products, energy storage devices are placing higher demands on the energy density of battery cathode materials. Lithium-rich manganese-based cathode materials (xLi2MnO3·(1-x)LiTMO2, TM=Ni, Co, Mn) have attracted significant attention due to their unique anionic redox characteristics and the high specific capacity and low cost resulting from their high manganese content. They have become one of the preferred cathode materials for developing high-energy-density batteries. However, the phase transformation processes and valence changes of elements during their synthesis are not yet fully understood. Furthermore, there is a lack of systematic research on how the synthesis process affects electrochemical performance, such as initial Coulombic efficiency, rate capability, and voltage decay. To achieve the controllable preparation of lithium-rich manganese-based cathode materials, this paper systematically reviews common synthesis methods—including solid-state synthesis, coprecipitation, sol-gel, hydrothermal, and spray pyrolysis—along with their characteristics, based on the materials′ unique structures and reaction mechanisms. It systematically elaborates on the relationships between different reactants and reaction conditions, precursor types, and Li sources, the ratio of transition metals to Li sources, sintering oxygen partial pressure, and sintering processes (high-temperature sintering, pre-sintering combined with high-temperature sintering, annealing, and non-isothermal sintering) on material properties. It also comprehensively analyzes the lithium evolution mechanism during material formation (mechanism of interaction between Li source and precursor), phase transformations (Fd3m→R3m→C2/m), elemental oxidation state changes, and defects (oxygen vacancies) on their physicochemical and electrochemical properties. By controlling the reaction conditions during synthesis, the Li2MnO3 domains within the material can be dispersed to mitigate capacity loss caused by lattice oxygen release, reduce defects generated during synthesis, ensure structural stability, and widen lithium-ion diffusion channels. Finally, the research on the synthesis process of lithium-rich manganese-based cathode materials is summarized, and prospects are discussed.
With the rapid development of new energy vehicles and electronic products, energy storage devices are placing higher demands on the energy density of battery cathode materials. Lithium-rich manganese-based cathode materials (xLi2MnO3·(1-x)LiTMO2, TM=Ni, Co, Mn) have attracted significant attention due to their unique anionic redox characteristics and the high specific capacity and low cost resulting from their high manganese content. They have become one of the preferred cathode materials for developing high-energy-density batteries. However, the phase transformation processes and valence changes of elements during their synthesis are not yet fully understood. Furthermore, there is a lack of systematic research on how the synthesis process affects electrochemical performance, such as initial Coulombic efficiency, rate capability, and voltage decay. To achieve the controllable preparation of lithium-rich manganese-based cathode materials, this paper systematically reviews common synthesis methods—including solid-state synthesis, coprecipitation, sol-gel, hydrothermal, and spray pyrolysis—along with their characteristics, based on the materials′ unique structures and reaction mechanisms. It systematically elaborates on the relationships between different reactants and reaction conditions, precursor types, and Li sources, the ratio of transition metals to Li sources, sintering oxygen partial pressure, and sintering processes (high-temperature sintering, pre-sintering combined with high-temperature sintering, annealing, and non-isothermal sintering) on material properties. It also comprehensively analyzes the lithium evolution mechanism during material formation (mechanism of interaction between Li source and precursor), phase transformations (Fd3m→R3m→C2/m), elemental oxidation state changes, and defects (oxygen vacancies) on their physicochemical and electrochemical properties. By controlling the reaction conditions during synthesis, the Li2MnO3 domains within the material can be dispersed to mitigate capacity loss caused by lattice oxygen release, reduce defects generated during synthesis, ensure structural stability, and widen lithium-ion diffusion channels. Finally, the research on the synthesis process of lithium-rich manganese-based cathode materials is summarized, and prospects are discussed.
2026, 42(4): 693-702
doi: 10.11862/CJIC.20250350
Abstract:
To address the pressing demand for proton-conducting materials with enhanced environmental adaptability and long-term stability, an ionic hydrogen-bonded organic framework (iHOF 1) was successfully constructed via a solvothermal method using 2, 5-dibromoterephthalic acid (H2BDC-Br2) as the building block. Its crystal structure, stability profiles, proton transport behavior, and photoluminescent properties were systematically investigated by a combination of characterization techniques, including single-crystal X-ray diffraction, powder X-ray diffraction, electrochemical impedance spectroscopy, solid-state fluorescence spectroscopy, etc. Structural analysis reveals that iHOF 1 crystallizes in the monoclinic space group C2/c, with its 3D framework stabilized by robust intermolecular H-bonds and electrostatic interactions between HBDC-Br2- anions and (Me2NH2)+ cations. Proton conductivity measurements demonstrate a distinct dependence on both temperature and relative humidity (RH), reaching a maximum value of 1.72×10-3 S·cm-1 at 100 ℃ and 98% of RH. Activation energy calculations yield values of 0.44 eV (at 68% of RH) and 0.41 eV (at 98% of RH), confirming that proton transport within the framework follows the Grotthuss hopping mechanism. This efficient proton conduction is facilitated by a contiguous H-bonded network formed by hydrophilic carboxyl groups, bromine atoms, and (Me2NH2)+ cations in the framework. Stability assessments indicated that iHOF 1 possessed excellent thermal stability (decomposition temperature: 230 ℃) and chemical stability, as evidenced by the retention of structural integrity after water immersion and prolonged electrochemical testing. Furthermore, upon excitation at 324 nm, the material exhibited a strong and monochromatic blue emission peak at 432 nm, which originates from the π→π* transition of the aromatic moieties and is significantly enhanced by the confinement effect of the rigid framework.
To address the pressing demand for proton-conducting materials with enhanced environmental adaptability and long-term stability, an ionic hydrogen-bonded organic framework (iHOF 1) was successfully constructed via a solvothermal method using 2, 5-dibromoterephthalic acid (H2BDC-Br2) as the building block. Its crystal structure, stability profiles, proton transport behavior, and photoluminescent properties were systematically investigated by a combination of characterization techniques, including single-crystal X-ray diffraction, powder X-ray diffraction, electrochemical impedance spectroscopy, solid-state fluorescence spectroscopy, etc. Structural analysis reveals that iHOF 1 crystallizes in the monoclinic space group C2/c, with its 3D framework stabilized by robust intermolecular H-bonds and electrostatic interactions between HBDC-Br2- anions and (Me2NH2)+ cations. Proton conductivity measurements demonstrate a distinct dependence on both temperature and relative humidity (RH), reaching a maximum value of 1.72×10-3 S·cm-1 at 100 ℃ and 98% of RH. Activation energy calculations yield values of 0.44 eV (at 68% of RH) and 0.41 eV (at 98% of RH), confirming that proton transport within the framework follows the Grotthuss hopping mechanism. This efficient proton conduction is facilitated by a contiguous H-bonded network formed by hydrophilic carboxyl groups, bromine atoms, and (Me2NH2)+ cations in the framework. Stability assessments indicated that iHOF 1 possessed excellent thermal stability (decomposition temperature: 230 ℃) and chemical stability, as evidenced by the retention of structural integrity after water immersion and prolonged electrochemical testing. Furthermore, upon excitation at 324 nm, the material exhibited a strong and monochromatic blue emission peak at 432 nm, which originates from the π→π* transition of the aromatic moieties and is significantly enhanced by the confinement effect of the rigid framework.
Mixed-size MXene for the application of high-performance transparent zinc-ion hybrid supercapacitors
2026, 42(4): 703-712
doi: 10.11862/CJIC.20250331
Abstract:
Large-sized Ti3C2Tx MXene nanosheets (L-MXene, the average lateral dimension was ca. 3.5 μm) were prepared via in-situ etching and mechanical exfoliation, and smaller-sized MXene nanosheets (S-MXene, the average lateral dimension was ca. 0.2 μm) were further fabricated under ultrasonic condition. By controlling the ratio of different sized MXene, a new type of L-MXene/S-MXene was constructed, so as to optimize the stacking structure of MXene layers and shorten the ion transport path. Based on the L-MXene/S-MXene transparent electrode, the assembled flexible transparent zinc-ion hybrid supercapacitors (ZHSCs) achieved large areal capacitance of 8.34 mF·cm-2, high optical transparency of 64.7% and good capacity retention of 93.9% even under 180° bending state.
Large-sized Ti3C2Tx MXene nanosheets (L-MXene, the average lateral dimension was ca. 3.5 μm) were prepared via in-situ etching and mechanical exfoliation, and smaller-sized MXene nanosheets (S-MXene, the average lateral dimension was ca. 0.2 μm) were further fabricated under ultrasonic condition. By controlling the ratio of different sized MXene, a new type of L-MXene/S-MXene was constructed, so as to optimize the stacking structure of MXene layers and shorten the ion transport path. Based on the L-MXene/S-MXene transparent electrode, the assembled flexible transparent zinc-ion hybrid supercapacitors (ZHSCs) achieved large areal capacitance of 8.34 mF·cm-2, high optical transparency of 64.7% and good capacity retention of 93.9% even under 180° bending state.
2026, 42(4): 713-721
doi: 10.11862/CJIC.20250318
Abstract:
To passivate defects in 2D perovskite crystals and improve crystal quality, chlorobenzene was incorporated into the (PMA)2PbBr4 perovskite precursor (PMA+=C6H5CH2NH3+), yielding large, high-quality perovskite single crystals via a cooling-controlled crystallization method. To systematically study the effect of chlorobenzene passivation, (PMA)2PbBr4 crystals were synthesized by cool-controlled crystallization at different concentrations (0.19, 0.38, and 0.47 mol·L-1). The structural, morphological, and optical properties of the perovskite crystals were systematically characterized by using powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and steady-state/time-resolved photoluminescence spectroscopy. The results demonstrate that the addition of chlorobenzene at a concentration of 0.38 mol·L-1 effectively modulates the crystal growth rate, enhances crystallographic orientation, and passivates surface and interface defects, thereby significantly suppressing non-radiative recombination of photogenerated carriers. It effectively passivates surface and interfacial defects, leading to remarkably improved crystal morphology with reduced cracks and enhanced smoothness, as directly observed in SEM and cross-sectional analyses. Furthermore, the chlorobenzene additive can regulate the cationic stacking effect, inducing changes in the microscopic strain of the crystals, which in turn affects electron-phonon coupling and improves the optoelectronic properties. The optimized crystals exhibited a significant increase in the intensities of the dual photoluminescence peaks. Specifically, the low-energy emission peak of the 0.38 mol·L-1 chlorobenzene-passivated crystal showed a red shift and a reduced full width at half maximum, indicating that the chlorobenzene additive effectively alleviates lattice distortion stress both on the surface and within the crystal.
To passivate defects in 2D perovskite crystals and improve crystal quality, chlorobenzene was incorporated into the (PMA)2PbBr4 perovskite precursor (PMA+=C6H5CH2NH3+), yielding large, high-quality perovskite single crystals via a cooling-controlled crystallization method. To systematically study the effect of chlorobenzene passivation, (PMA)2PbBr4 crystals were synthesized by cool-controlled crystallization at different concentrations (0.19, 0.38, and 0.47 mol·L-1). The structural, morphological, and optical properties of the perovskite crystals were systematically characterized by using powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and steady-state/time-resolved photoluminescence spectroscopy. The results demonstrate that the addition of chlorobenzene at a concentration of 0.38 mol·L-1 effectively modulates the crystal growth rate, enhances crystallographic orientation, and passivates surface and interface defects, thereby significantly suppressing non-radiative recombination of photogenerated carriers. It effectively passivates surface and interfacial defects, leading to remarkably improved crystal morphology with reduced cracks and enhanced smoothness, as directly observed in SEM and cross-sectional analyses. Furthermore, the chlorobenzene additive can regulate the cationic stacking effect, inducing changes in the microscopic strain of the crystals, which in turn affects electron-phonon coupling and improves the optoelectronic properties. The optimized crystals exhibited a significant increase in the intensities of the dual photoluminescence peaks. Specifically, the low-energy emission peak of the 0.38 mol·L-1 chlorobenzene-passivated crystal showed a red shift and a reduced full width at half maximum, indicating that the chlorobenzene additive effectively alleviates lattice distortion stress both on the surface and within the crystal.
2026, 42(4): 722-736
doi: 10.11862/CJIC.20250312
Abstract:
A series of porphyrin-based ionic polymeric materials, IP1, IP2, and IP1-M (M=Zn, Mg, Ni), were synthesized via olefin polymerization and thoroughly characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), specific surface area and porosity analyses, and X-ray photoelectron spectroscopy (XPS). These materials all exhibited excellent catalytic performance in the cycloaddition reaction of CO2 with epoxides under mild conditions of low temperature and atmospheric pressure. Among them, IP1-Zn, with Zn2+ coordinated to the porphyrin ring, demonstrated the highest catalytic activity. Under solvent-free conditions at 80 ℃ for 5 h under 101 kPa CO2, it catalyzed the conversion of epichlorohydrin to the corresponding cyclic carbonate with a yield of 94.1%, along with a certain degree of substrate generality. Furthermore, IP1-Zn showed remarkable stability and reusability, maintaining a catalytic yield above 90% even after eight consecutive cycles, indicating promising potential for industrial applications.
A series of porphyrin-based ionic polymeric materials, IP1, IP2, and IP1-M (M=Zn, Mg, Ni), were synthesized via olefin polymerization and thoroughly characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), specific surface area and porosity analyses, and X-ray photoelectron spectroscopy (XPS). These materials all exhibited excellent catalytic performance in the cycloaddition reaction of CO2 with epoxides under mild conditions of low temperature and atmospheric pressure. Among them, IP1-Zn, with Zn2+ coordinated to the porphyrin ring, demonstrated the highest catalytic activity. Under solvent-free conditions at 80 ℃ for 5 h under 101 kPa CO2, it catalyzed the conversion of epichlorohydrin to the corresponding cyclic carbonate with a yield of 94.1%, along with a certain degree of substrate generality. Furthermore, IP1-Zn showed remarkable stability and reusability, maintaining a catalytic yield above 90% even after eight consecutive cycles, indicating promising potential for industrial applications.
2026, 42(4): 737-746
doi: 10.11862/CJIC.20250305
Abstract:
Iron-nitrogen co-doped carbon-based catalyst (180FeNC-2) was prepared using sodium carboxymethyl cellulose (CMC) as a precursor. The results indicate that pre-deoxygenation treatment of CMC induces cleavage of glycosidic bonds, which facilitates a higher nitrogen doping level in the catalyst obtained from co-carbonization with a nitrogen precursor. This process also promotes the formation of well-defined thin carbon sheets, constructing a hierarchical mesoporous structure that enhances mass transport and exposure of active sites during the catalytic reaction. The resulting catalyst (180FeNC-2) exhibited an oxygen reduction reaction half-wave potential of 0.887 V (vs RHE), an electrochemical active surface area of 11.26 mF·cm-2, and a charge transfer resistance of 81 Ω in an alkaline electrolyte. Its catalytic performance surpasses that of the catalyst (0FeNC-2) derived from untreated CMC and was comparable to the standard Pt/C catalyst, while also demonstrating excellent stability and methanol tolerance. A zinc-air battery assembled based on 180FeNC-2 delivered an open-circuit voltage of 1.478 V, a maximum power density of 162 mW·cm-2, and could stable discharge at 1.25 V under a current density of 10 mA·cm-2.
Iron-nitrogen co-doped carbon-based catalyst (180FeNC-2) was prepared using sodium carboxymethyl cellulose (CMC) as a precursor. The results indicate that pre-deoxygenation treatment of CMC induces cleavage of glycosidic bonds, which facilitates a higher nitrogen doping level in the catalyst obtained from co-carbonization with a nitrogen precursor. This process also promotes the formation of well-defined thin carbon sheets, constructing a hierarchical mesoporous structure that enhances mass transport and exposure of active sites during the catalytic reaction. The resulting catalyst (180FeNC-2) exhibited an oxygen reduction reaction half-wave potential of 0.887 V (vs RHE), an electrochemical active surface area of 11.26 mF·cm-2, and a charge transfer resistance of 81 Ω in an alkaline electrolyte. Its catalytic performance surpasses that of the catalyst (0FeNC-2) derived from untreated CMC and was comparable to the standard Pt/C catalyst, while also demonstrating excellent stability and methanol tolerance. A zinc-air battery assembled based on 180FeNC-2 delivered an open-circuit voltage of 1.478 V, a maximum power density of 162 mW·cm-2, and could stable discharge at 1.25 V under a current density of 10 mA·cm-2.
2026, 42(4): 747-759
doi: 10.11862/CJIC.20250286
Abstract:
To address the issue of low interfacial charge transfer efficiency in heterojunction photocatalysts, an S-scheme heterojunction photocatalyst based on polydopamine (PDA) electron bridges was constructed. A powdered S-scheme heterojunction photocatalyst, designated as g-C3N4@PDA-Bi4Ti3O12 (CN@PDA-BTO), was fabricated via electrostatic assembly of Bi4Ti3O12 onto PDA-modified graphitic carbon nitride (g-C3N4). Photocatalytic degradation experiments, photoluminescence spectroscopy, and electrochemical measurements revealed that PDA serves as an electron transport "bridge", significantly enhancing the interfacial contact and charge separation between g-C3N4 and Bi4Ti3O12. The optimized sample CN@PDA-BTO-20 achieved degradation rates of 98.2% for methylene blue (MB) within 60 min and 81.1% for tetracycline hydrochloride (TCH) within 90 min under visible light irradiation, with reaction rate constants markedly higher than those of the single-component and binary composites. Furthermore, to overcome the difficulty of recycling powdered catalysts, the optimal CN@PDA-BTO powder was immobilized within a polyvinyl alcohol (PVA) hydrogel network, resulting in a flexible film designated as CN@PDA-BTO-PVA. The composite film maintained the degradation rates of 77.5% for MB and 71.6% for TCH after five consecutive cycles, demonstrating significantly improved stability and recyclability.
To address the issue of low interfacial charge transfer efficiency in heterojunction photocatalysts, an S-scheme heterojunction photocatalyst based on polydopamine (PDA) electron bridges was constructed. A powdered S-scheme heterojunction photocatalyst, designated as g-C3N4@PDA-Bi4Ti3O12 (CN@PDA-BTO), was fabricated via electrostatic assembly of Bi4Ti3O12 onto PDA-modified graphitic carbon nitride (g-C3N4). Photocatalytic degradation experiments, photoluminescence spectroscopy, and electrochemical measurements revealed that PDA serves as an electron transport "bridge", significantly enhancing the interfacial contact and charge separation between g-C3N4 and Bi4Ti3O12. The optimized sample CN@PDA-BTO-20 achieved degradation rates of 98.2% for methylene blue (MB) within 60 min and 81.1% for tetracycline hydrochloride (TCH) within 90 min under visible light irradiation, with reaction rate constants markedly higher than those of the single-component and binary composites. Furthermore, to overcome the difficulty of recycling powdered catalysts, the optimal CN@PDA-BTO powder was immobilized within a polyvinyl alcohol (PVA) hydrogel network, resulting in a flexible film designated as CN@PDA-BTO-PVA. The composite film maintained the degradation rates of 77.5% for MB and 71.6% for TCH after five consecutive cycles, demonstrating significantly improved stability and recyclability.
2026, 42(4): 760-772
doi: 10.11862/CJIC.20250273
Abstract:
MXene Ti3C2Tx/ hollow ZIF-67 (HMZ) host capable of loading the cathode active material sulfur in lithium-sulfur batteries was constructed by in-situ electrostatic self-assembly method and etching with tannic acid solution. Hollow ZIF-67 can effectively mitigate the irreversible stacking trend of MXene Ti3C2Tx, and suppress the shuttle effect through the joint chemical adsorption of lithium polysulfides by Ti and Co elements. while also physically confining lithium polysulfides and alleviating the volume expansion. HMZ-5 formed by etching with tannic acid solution for 5 min could provide a specific capacity of 615.1 mAh·g-1 at 1C after being loaded with sulfur, with a low capacity decay rate of 0.055% per cycle after 700 cycles.
MXene Ti3C2Tx/ hollow ZIF-67 (HMZ) host capable of loading the cathode active material sulfur in lithium-sulfur batteries was constructed by in-situ electrostatic self-assembly method and etching with tannic acid solution. Hollow ZIF-67 can effectively mitigate the irreversible stacking trend of MXene Ti3C2Tx, and suppress the shuttle effect through the joint chemical adsorption of lithium polysulfides by Ti and Co elements. while also physically confining lithium polysulfides and alleviating the volume expansion. HMZ-5 formed by etching with tannic acid solution for 5 min could provide a specific capacity of 615.1 mAh·g-1 at 1C after being loaded with sulfur, with a low capacity decay rate of 0.055% per cycle after 700 cycles.
2026, 42(4): 773-788
doi: 10.11862/CJIC.20250251
Abstract:
This study systematically investigates the influence of Ba/Bi stoichiometric ratios on the crystal structure, morphological evolution, and catalytic properties of Bi12TiO20/BaTiO3 composites. A series of characterization techniques, including powder X-ray diffraction, Fourier-transform infrared spectroscopy, ultraviolet-visible absorption spectroscopy, and scanning electron microscopy, was employed to track the phase transformation and structural development of the materials. The synthesis process, particularly under “shearing effect” in alkaline conditions, promoted a multi-stage evolution pathway: chemical bond reorganization, crystal nucleation, oriented growth, and Ostwald ripening. The catalytic performance was evaluated through dye degradation experiments under different energy excitation conditions. The results revealed reaction rate constants (k) of 2.05×10-2 min-1 (ultrasonic vibration), 1.06×10-1 min-1 (light irradiation), and 1.47×10-1 min-1 (coupled ultrasonic-light irradiation), indicating a significant synergistic piezo-photocatalytic effect. This enhanced activity is mainly ascribed to two factors: the established Bi12TiO20/BaTiO3 heterojunction facilitates efficient transport of photogenerated charge carriers, while the intrinsic built-in electric field of BaTiO3 promotes effective carrier separation.
This study systematically investigates the influence of Ba/Bi stoichiometric ratios on the crystal structure, morphological evolution, and catalytic properties of Bi12TiO20/BaTiO3 composites. A series of characterization techniques, including powder X-ray diffraction, Fourier-transform infrared spectroscopy, ultraviolet-visible absorption spectroscopy, and scanning electron microscopy, was employed to track the phase transformation and structural development of the materials. The synthesis process, particularly under “shearing effect” in alkaline conditions, promoted a multi-stage evolution pathway: chemical bond reorganization, crystal nucleation, oriented growth, and Ostwald ripening. The catalytic performance was evaluated through dye degradation experiments under different energy excitation conditions. The results revealed reaction rate constants (k) of 2.05×10-2 min-1 (ultrasonic vibration), 1.06×10-1 min-1 (light irradiation), and 1.47×10-1 min-1 (coupled ultrasonic-light irradiation), indicating a significant synergistic piezo-photocatalytic effect. This enhanced activity is mainly ascribed to two factors: the established Bi12TiO20/BaTiO3 heterojunction facilitates efficient transport of photogenerated charge carriers, while the intrinsic built-in electric field of BaTiO3 promotes effective carrier separation.
2026, 42(4): 789-807
doi: 10.11862/CJIC.20250208
Abstract:
This study fabricated an amphiphilic magnetic composite Fe3O4/rGO/PDA (polydopamine)/SDBS/HSB, denoted as FGPSH, via a one-step solvothermal method followed by multi-surface modification. The composite was constructed using Fe3O4 and reduced graphene oxide (rGO) as core materials, grafted with dopamine hydrochloride (DA), sodium dodecylbenzenesulfonate (SDBS), and hexadecyl dimethyl hydroxypropyl sulfonated betaine (HSB1618). Its adsorption behavior toward polyvinyl chloride (PVC) and polyethylene terephthalate (PET) microplastics (MPs) in aqueous solutions was systematically investigated. Results showed that FGPSH exhibited a nanoporous spherical structure with an average particle size of 426.15 nm and an average pore size of 33.02 nm. It displayed excellent superparamagnetism, with a saturation magnetization of 44.15 emu·g-1, enabling efficient magnetic separation. The multilayer surface modification imparts both hydrophilic and hydrophobic properties, allowing high dispersibility in water while offering matched adsorption sites for MPs of different polarities, thereby achieving broad-spectrum and selective adsorption. Under optimized conditions (initial MPs mass concentration: 25 mg·L-1 for both PVC and PET; solution pH: 9.0; FGPSH dosage: 0.50 g·L-1 for PVC and 0.40 g·L-1 for PET; adsorption time: 30 min for PVC and 80 min for PET), the adsorption rates for PVC and PET reached 97.58% and 95.30%, respectively, with equilibrium capacities of 48.75 and 60.33 mg·g-1. After five adsorption-desorption cycles, the material maintained an adsorption efficiency exceeding 85%. Thermodynamic studies indicated that the adsorption of hydrophilic PVC followed pseudo-second-order kinetics and the Freundlich model, whereas the adsorption of hydrophobic PET conformed to the Langmuir model, reflecting distinct adsorption mechanisms based on MPs polarity.
This study fabricated an amphiphilic magnetic composite Fe3O4/rGO/PDA (polydopamine)/SDBS/HSB, denoted as FGPSH, via a one-step solvothermal method followed by multi-surface modification. The composite was constructed using Fe3O4 and reduced graphene oxide (rGO) as core materials, grafted with dopamine hydrochloride (DA), sodium dodecylbenzenesulfonate (SDBS), and hexadecyl dimethyl hydroxypropyl sulfonated betaine (HSB1618). Its adsorption behavior toward polyvinyl chloride (PVC) and polyethylene terephthalate (PET) microplastics (MPs) in aqueous solutions was systematically investigated. Results showed that FGPSH exhibited a nanoporous spherical structure with an average particle size of 426.15 nm and an average pore size of 33.02 nm. It displayed excellent superparamagnetism, with a saturation magnetization of 44.15 emu·g-1, enabling efficient magnetic separation. The multilayer surface modification imparts both hydrophilic and hydrophobic properties, allowing high dispersibility in water while offering matched adsorption sites for MPs of different polarities, thereby achieving broad-spectrum and selective adsorption. Under optimized conditions (initial MPs mass concentration: 25 mg·L-1 for both PVC and PET; solution pH: 9.0; FGPSH dosage: 0.50 g·L-1 for PVC and 0.40 g·L-1 for PET; adsorption time: 30 min for PVC and 80 min for PET), the adsorption rates for PVC and PET reached 97.58% and 95.30%, respectively, with equilibrium capacities of 48.75 and 60.33 mg·g-1. After five adsorption-desorption cycles, the material maintained an adsorption efficiency exceeding 85%. Thermodynamic studies indicated that the adsorption of hydrophilic PVC followed pseudo-second-order kinetics and the Freundlich model, whereas the adsorption of hydrophobic PET conformed to the Langmuir model, reflecting distinct adsorption mechanisms based on MPs polarity.
2026, 42(4): 808-816
doi: 10.11862/CJIC.20260012
Abstract:
5, 5′-dithiobis(2-nitrobenzoic acid) (H2DTNB) was employed as the second ligand to react with cucurbit[6]uril (Q[6]) and Cd(NO3)2, and it was deprotonated or transformed into HDTNB-, TNB2- and NSB2- (H2TNB=5, 5′-thiobis(2-nitrobenzoic acid), H2NSB=2-nitro-5-sulfobenzoic acid) under different conditions to afford three novel supramolecular assemblies with the formulas of [Cd(H2O)4(Q[6])](HDTNB)2·3H2O (1), [Cd(H2O)6]2(TNB)2·Q[6]·4H2O (2) and [Cd(H2O)5(NSB)]2·Q[6] (3). Singe-crystal diffraction (SC-XRD) analysis revealed that assembly 1 is constructed from 2D [Cd(H2O)4(Q[6])]2+ supramolecular layers and HDTNB- supra molecular layers, the structure of assembly 2 is comprised of the 2D {[Cd(H2O)6]2·Q[6]}4+ supramolecular layers and 1D TNB2- supramolecular chains, while assembly 3 is built from the 3D Q[6] frameworks with [Cd(H2O)5(NSB)] supramolecular chains filled in the pores. Meanwhile, the noncovalent interactions between the ligands HDTNB-/TNB2-/NSB2- and the outer-surface of Q[6] molecules contributed greatly to the formation of the supramolecular architecture of assemblies 1-3.
5, 5′-dithiobis(2-nitrobenzoic acid) (H2DTNB) was employed as the second ligand to react with cucurbit[6]uril (Q[6]) and Cd(NO3)2, and it was deprotonated or transformed into HDTNB-, TNB2- and NSB2- (H2TNB=5, 5′-thiobis(2-nitrobenzoic acid), H2NSB=2-nitro-5-sulfobenzoic acid) under different conditions to afford three novel supramolecular assemblies with the formulas of [Cd(H2O)4(Q[6])](HDTNB)2·3H2O (1), [Cd(H2O)6]2(TNB)2·Q[6]·4H2O (2) and [Cd(H2O)5(NSB)]2·Q[6] (3). Singe-crystal diffraction (SC-XRD) analysis revealed that assembly 1 is constructed from 2D [Cd(H2O)4(Q[6])]2+ supramolecular layers and HDTNB- supra molecular layers, the structure of assembly 2 is comprised of the 2D {[Cd(H2O)6]2·Q[6]}4+ supramolecular layers and 1D TNB2- supramolecular chains, while assembly 3 is built from the 3D Q[6] frameworks with [Cd(H2O)5(NSB)] supramolecular chains filled in the pores. Meanwhile, the noncovalent interactions between the ligands HDTNB-/TNB2-/NSB2- and the outer-surface of Q[6] molecules contributed greatly to the formation of the supramolecular architecture of assemblies 1-3.
2026, 42(4): 817-825
doi: 10.11862/CJIC.20250376
Abstract:
Two [FeFe]-hydrogenase compounds with 2-cyanobenzyl groups, {Fe2[(SCH2CH3)(SR)](CO)6} (1 or 1′, which are the crystalline states from petroleum ether and dichloromethane solution, respectively) and {Fe2[(SCH2CH3)(SR)](CO)5(PPh3)} (2) (R=2-cyanobenzyl), were synthesized and characterized by infrared spectroscopy, UV-Vis spectroscopy, single-crystal diffraction, powder X-ray diffraction, etc. Their performances as photocatalysts for H2 production through water splitting were evaluated. The results showed that 316.8 μmol of H2 was produced on compound 1 after 3 h of illumination, with a catalytic efficiency of 25.1 μmol·mg-1·h-1 and a turnover number (TON) of 36.8. The replacement of carbonyl with PPh3 could significantly improve the catalytic performance of the complex, and 705.0 μmol of H2 was produced on 2 after 3 h of illumination, with a catalytic efficiency of 37.9 μmol·mg-1·h-1 and a TON of 81.8.
Two [FeFe]-hydrogenase compounds with 2-cyanobenzyl groups, {Fe2[(SCH2CH3)(SR)](CO)6} (1 or 1′, which are the crystalline states from petroleum ether and dichloromethane solution, respectively) and {Fe2[(SCH2CH3)(SR)](CO)5(PPh3)} (2) (R=2-cyanobenzyl), were synthesized and characterized by infrared spectroscopy, UV-Vis spectroscopy, single-crystal diffraction, powder X-ray diffraction, etc. Their performances as photocatalysts for H2 production through water splitting were evaluated. The results showed that 316.8 μmol of H2 was produced on compound 1 after 3 h of illumination, with a catalytic efficiency of 25.1 μmol·mg-1·h-1 and a turnover number (TON) of 36.8. The replacement of carbonyl with PPh3 could significantly improve the catalytic performance of the complex, and 705.0 μmol of H2 was produced on 2 after 3 h of illumination, with a catalytic efficiency of 37.9 μmol·mg-1·h-1 and a TON of 81.8.
2026, 42(4): 826-842
doi: 10.11862/CJIC.20250332
Abstract:
A metal-organic framework/inorganic composite (ZIF-8@AMP) was synthesized by the in situ introduction of the active component ammonium phosphomolybdate (AMP) during the ambient solution-phase synthesis of the metal-organic framework (ZIF-8). The structure and properties of the composite were characterized using scanning electron microscopy (SEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and Fourier transform infrared spectroscopy (FTIR). Its adsorption performance for Rb+ and Cs+ in water was investigated. Results indicate that ZIF-8@AMP exhibited adsorption efficiencies of 93.5% and 95.6% for Rb+ and Cs+ within 30 min, with maximum adsorption capacities of 92.7 and 104.5 mg·g-1, respectively. After five adsorption-desorption cycles, it maintained high adsorption capacity and achieved over 84.9% adsorption efficiency for Rb+ and Cs+ in actual brine samples. The adsorption of ZIF-8@AMP for Rb+ and Cs+ follows pseudo-second-order kinetics and the Langmuir adsorption isotherm, indicating an endothermic, entropy-increasing, and spontaneous process. The adsorption mechanism involves electrostatic attraction and ion exchange between ZIF-8@AMP and Rb+ and Cs+.
A metal-organic framework/inorganic composite (ZIF-8@AMP) was synthesized by the in situ introduction of the active component ammonium phosphomolybdate (AMP) during the ambient solution-phase synthesis of the metal-organic framework (ZIF-8). The structure and properties of the composite were characterized using scanning electron microscopy (SEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and Fourier transform infrared spectroscopy (FTIR). Its adsorption performance for Rb+ and Cs+ in water was investigated. Results indicate that ZIF-8@AMP exhibited adsorption efficiencies of 93.5% and 95.6% for Rb+ and Cs+ within 30 min, with maximum adsorption capacities of 92.7 and 104.5 mg·g-1, respectively. After five adsorption-desorption cycles, it maintained high adsorption capacity and achieved over 84.9% adsorption efficiency for Rb+ and Cs+ in actual brine samples. The adsorption of ZIF-8@AMP for Rb+ and Cs+ follows pseudo-second-order kinetics and the Langmuir adsorption isotherm, indicating an endothermic, entropy-increasing, and spontaneous process. The adsorption mechanism involves electrostatic attraction and ion exchange between ZIF-8@AMP and Rb+ and Cs+.
2026, 42(4): 843-860
doi: 10.11862/CJIC.20250301
Abstract:
To overcome the limitations of traditional photocatalysts, such as inefficient separation of charge carriers and poor visible-light absorption, S-scheme g-C3N4/TiO2 heterojunction photocatalysts were synthesized via a combined method of thermal polymerization, hydrothermal synthesis, and calcination. The crystal structures, morphological features, and optical properties of the composites were systematically characterized, and their photocatalytic performance was evaluated through tetracycline (TC) degradation and hydrogen evolution experiments. Trapping experiments and electron paramagnetic resonance (EPR) measurements were conducted to elucidate the reaction mechanisms. The results demonstrate that the S-scheme heterojunction effectively extends the visible-light absorption range and facilitates the efficient separation of photogenerated electron-hole pairs. Under optimal conditions, the composite achieved a TC degradation rate of 94.5% and a hydrogen evolution rate of 329.1 μmol·h-1·g-1 after 8 h of irradiation, both values being significantly higher than those of pristine g-C3N4 or TiO2. Moreover, the S-scheme g-C3N4/TiO2 heterojunction retained high photocatalytic activity over five consecutive cycles, confirming its excellent stability. Mechanistic investigations revealed that the S-scheme heterojunction maintained strong redox capacities, with superoxide radicals (·O2-), hydroxyl radicals (·OH), electrons (e-), and holes (h+) serving as the primary active species responsible for TC degradation and H2 production.
To overcome the limitations of traditional photocatalysts, such as inefficient separation of charge carriers and poor visible-light absorption, S-scheme g-C3N4/TiO2 heterojunction photocatalysts were synthesized via a combined method of thermal polymerization, hydrothermal synthesis, and calcination. The crystal structures, morphological features, and optical properties of the composites were systematically characterized, and their photocatalytic performance was evaluated through tetracycline (TC) degradation and hydrogen evolution experiments. Trapping experiments and electron paramagnetic resonance (EPR) measurements were conducted to elucidate the reaction mechanisms. The results demonstrate that the S-scheme heterojunction effectively extends the visible-light absorption range and facilitates the efficient separation of photogenerated electron-hole pairs. Under optimal conditions, the composite achieved a TC degradation rate of 94.5% and a hydrogen evolution rate of 329.1 μmol·h-1·g-1 after 8 h of irradiation, both values being significantly higher than those of pristine g-C3N4 or TiO2. Moreover, the S-scheme g-C3N4/TiO2 heterojunction retained high photocatalytic activity over five consecutive cycles, confirming its excellent stability. Mechanistic investigations revealed that the S-scheme heterojunction maintained strong redox capacities, with superoxide radicals (·O2-), hydroxyl radicals (·OH), electrons (e-), and holes (h+) serving as the primary active species responsible for TC degradation and H2 production.
2026, 42(4): 861-871
doi: 10.11862/CJIC.20250294
Abstract:
A metal-organic framework {[Zn(L)0.5(1,2,4,5-tpb)0.5]·DMF·3H2O}n (1) was synthesized by solvothermal reaction, where H4L=5,5′-(ethane-1,2-diyl)diisophthalic acid, and 1,2,4,5-tpb=1,2,4,5-tetra(pyridin-4-yl)benzene. The analysis of the single crystal structure indicates that L4- and 1,2,4,5-tpb are connected with Zn(Ⅱ) to form a 2D layered structure, and the layers are linked by 1,2,4,5-tpb to form a 3D structure. 1 can be used as a highly selective fluorescent probe for the detection of 2,4-dinitrophenylhydrazine (DNP) and tetracycline (TET), and the detection limits were 0.013 and 0.31 μmol·L-1, respectively. 1 was applied successfully to the determination of TET content in the Yanhe River water sample.
A metal-organic framework {[Zn(L)0.5(1,2,4,5-tpb)0.5]·DMF·3H2O}n (1) was synthesized by solvothermal reaction, where H4L=5,5′-(ethane-1,2-diyl)diisophthalic acid, and 1,2,4,5-tpb=1,2,4,5-tetra(pyridin-4-yl)benzene. The analysis of the single crystal structure indicates that L4- and 1,2,4,5-tpb are connected with Zn(Ⅱ) to form a 2D layered structure, and the layers are linked by 1,2,4,5-tpb to form a 3D structure. 1 can be used as a highly selective fluorescent probe for the detection of 2,4-dinitrophenylhydrazine (DNP) and tetracycline (TET), and the detection limits were 0.013 and 0.31 μmol·L-1, respectively. 1 was applied successfully to the determination of TET content in the Yanhe River water sample.
2026, 42(4): 872-882
doi: 10.11862/CJIC.20250287
Abstract:
Based on 4′-(1H-tetrazol-5-yl)-[1, 1′-biphenyl]-2, 4, 6-tricarboxylic acid (H4bta) ligand, zinc metal-organic framework (Zn-MOF): {[Zn2(bta)(bpy)2(H2O)]·1.5H2O}n (bpy=2, 2′-bipyridine) was designed and synthesized by hydrothermal method. Its structure was characterized by elemental analysis, IR spectra, X-ray single crystal diffraction, etc. The asymmetric unit of Zn-MOF contains two crystallographically independent Zn2+ ions. Through the connection of Zn2+ ions via H4bta, a 1D double-layer network structure is formed. Adjacent double-layer networks further form a 2D supramolecular network through hydrogen bonding. Notably, Zn-MOF exhibited excellent fluorescence properties and could efficiently and sensitively detect various water pollutants: 4-nitrophenol (4-NP), Cu2+, and pyrimethanil (Pth). Additionally, the mechanism of fluorescence sensing was investigated.
Based on 4′-(1H-tetrazol-5-yl)-[1, 1′-biphenyl]-2, 4, 6-tricarboxylic acid (H4bta) ligand, zinc metal-organic framework (Zn-MOF): {[Zn2(bta)(bpy)2(H2O)]·1.5H2O}n (bpy=2, 2′-bipyridine) was designed and synthesized by hydrothermal method. Its structure was characterized by elemental analysis, IR spectra, X-ray single crystal diffraction, etc. The asymmetric unit of Zn-MOF contains two crystallographically independent Zn2+ ions. Through the connection of Zn2+ ions via H4bta, a 1D double-layer network structure is formed. Adjacent double-layer networks further form a 2D supramolecular network through hydrogen bonding. Notably, Zn-MOF exhibited excellent fluorescence properties and could efficiently and sensitively detect various water pollutants: 4-nitrophenol (4-NP), Cu2+, and pyrimethanil (Pth). Additionally, the mechanism of fluorescence sensing was investigated.
2026, 42(4): 883-896
doi: 10.11862/CJIC.20250248
Abstract:
The ionothermal reaction between CuCl2, 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene (BBTZ), and (NH4)6Mo7O24 in 1-ethyl-3-methylimidazolium bromide ((Emim)Br) led to a new octamolybdate-based coordination polymer (Emim)2[Cu(BBTZ)2(β-Mo8O26)] (Mo8-CP). Mo8-CP was characterized by elemental analysis, thermogravimetry, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. In Mo8-CP, structural analysis reveals that Cu coordinates with BBTZ ligands to form an interlocked 1D chain. These chains are further bridged by (β-Mo8O26)4- to construct a 3D coordination polymer. Notably, (Emim)+ acts as a structure-directing agent, occupying the channels of the 3D coordination polymer. Based on this unique structure, the ion exchange properties of Mo8-CP toward rare-earth ions were investigated. It has been found that the luminescent color of the material can be successfully regulated by introducing Eu3+ or Tb3+ through ion exchange.
The ionothermal reaction between CuCl2, 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene (BBTZ), and (NH4)6Mo7O24 in 1-ethyl-3-methylimidazolium bromide ((Emim)Br) led to a new octamolybdate-based coordination polymer (Emim)2[Cu(BBTZ)2(β-Mo8O26)] (Mo8-CP). Mo8-CP was characterized by elemental analysis, thermogravimetry, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. In Mo8-CP, structural analysis reveals that Cu coordinates with BBTZ ligands to form an interlocked 1D chain. These chains are further bridged by (β-Mo8O26)4- to construct a 3D coordination polymer. Notably, (Emim)+ acts as a structure-directing agent, occupying the channels of the 3D coordination polymer. Based on this unique structure, the ion exchange properties of Mo8-CP toward rare-earth ions were investigated. It has been found that the luminescent color of the material can be successfully regulated by introducing Eu3+ or Tb3+ through ion exchange.
