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2026 Volume 42 Issue 3
2026, 42(3): 441-452
doi: 10.11862/CJIC.20250303
Abstract:
Tributyl citrate (TBC) is an environmentally friendly plasticizer with low toxicity, good compatibility and degradability. Compared to the traditional catalysts of the concentrated H2SO4 to produce TBC, heteropolyacid (HPA), as solid superacid, are non-volatile and no-corrosive to equipment, but are expensive and difficult to recycle. In order to recycle HPA, supported heteropolyacid catalysts using different carriers exhibit promising potential in the preparation of TBC owing to their large surface area and easy separability. This review summarizes the research progress in preparing TBC using supported HPA catalysts. Those catalysts are loaded on the carriers such metal oxides, carbon materials, molecular sieves, and ionic liquids through surface loading, internal encapsulation and ionic bonding. A key challenge in advancing these materials toward industrial application is strengthening the interaction between the HPAs and their supporting carriers. Polyoxometalate-based metal-organic frameworks (POMOFs) and polyoxometalate-based covalent organic frameworks (POMCOFs), which employ metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) as carriers to support HPAs, effectively reduce the leaching of HPA catalysts through internal encapsulation. The characteristics and limitations of different carrier systems in terms of catalytic activity, structure-activity relationships, and compatibility with novel processes are systematically summarized, which can provide some references to develop efficient, stable, and eco-friendly catalysts for TBC synthesis.
Tributyl citrate (TBC) is an environmentally friendly plasticizer with low toxicity, good compatibility and degradability. Compared to the traditional catalysts of the concentrated H2SO4 to produce TBC, heteropolyacid (HPA), as solid superacid, are non-volatile and no-corrosive to equipment, but are expensive and difficult to recycle. In order to recycle HPA, supported heteropolyacid catalysts using different carriers exhibit promising potential in the preparation of TBC owing to their large surface area and easy separability. This review summarizes the research progress in preparing TBC using supported HPA catalysts. Those catalysts are loaded on the carriers such metal oxides, carbon materials, molecular sieves, and ionic liquids through surface loading, internal encapsulation and ionic bonding. A key challenge in advancing these materials toward industrial application is strengthening the interaction between the HPAs and their supporting carriers. Polyoxometalate-based metal-organic frameworks (POMOFs) and polyoxometalate-based covalent organic frameworks (POMCOFs), which employ metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) as carriers to support HPAs, effectively reduce the leaching of HPA catalysts through internal encapsulation. The characteristics and limitations of different carrier systems in terms of catalytic activity, structure-activity relationships, and compatibility with novel processes are systematically summarized, which can provide some references to develop efficient, stable, and eco-friendly catalysts for TBC synthesis.
2026, 42(3): 453-466
doi: 10.11862/CJIC.20250295
Abstract:
Copper sulfide (CuS), a transition metal chalcogenide, exhibits unique electrical and optical properties, making it a promising candidate as an adsorbent or photocatalyst for pollutant removal from water. However, its high electron-hole pair recombination rate and poor photostability significantly limit its practical applications. To address these challenges, ion doping strategies have been widely employed to enhance the photostability and photocatalytic activity of CuS. This review summarizes the synthesis methods of ion-doped CuS nanomaterials, including the hydrothermal method, annealing method, solution method, solvothermal method, and microwave hydrothermal method, highlighting the efficiency and application advantages of the microwave hydrothermal synthesis method. It also provides an in-depth analysis of the influence mechanisms of ion doping on the energy band structure, defect states, and carrier dynamics. It provides a commentary on the latest progress of ion-doped CuS in the fields of photocatalysis and energy from 2020 to 2025, encompassing photocatalytic degradation of pollutants, photocatalytic hydrogen production, CO2 photocatalytic reduction, supercapacitor electrode materials, and battery materials.
Copper sulfide (CuS), a transition metal chalcogenide, exhibits unique electrical and optical properties, making it a promising candidate as an adsorbent or photocatalyst for pollutant removal from water. However, its high electron-hole pair recombination rate and poor photostability significantly limit its practical applications. To address these challenges, ion doping strategies have been widely employed to enhance the photostability and photocatalytic activity of CuS. This review summarizes the synthesis methods of ion-doped CuS nanomaterials, including the hydrothermal method, annealing method, solution method, solvothermal method, and microwave hydrothermal method, highlighting the efficiency and application advantages of the microwave hydrothermal synthesis method. It also provides an in-depth analysis of the influence mechanisms of ion doping on the energy band structure, defect states, and carrier dynamics. It provides a commentary on the latest progress of ion-doped CuS in the fields of photocatalysis and energy from 2020 to 2025, encompassing photocatalytic degradation of pollutants, photocatalytic hydrogen production, CO2 photocatalytic reduction, supercapacitor electrode materials, and battery materials.
2026, 42(3): 467-478
doi: 10.11862/CJIC.20250347
Abstract:
To address the longstanding challenge in traditional carborane methodology of rapidly and efficiently constructing carboranyl-based polycyclic frameworks, Pd-catalyzed one-pot reactions between pyridyl-substituted nido-carboranes and alkynes directly afford two distinct types of 2D-3D fused carboranyl polycyclic compounds: 3a-3f, 4a-4d. The structures of this series of compounds were characterized by nuclear magnetic resonance spectroscopy, single-crystal X-ray diffraction, and high-resolution mass spectrometry, and a plausible reaction mechanism was proposed. Crystal structures reveal that the multiple rings in such 2D-3D fused carboranyl polycyclic compounds exhibit a certain degree of coplanarity. Furthermore, these compounds exhibited properties distinct from those of conventional 2D polycyclic systems.
To address the longstanding challenge in traditional carborane methodology of rapidly and efficiently constructing carboranyl-based polycyclic frameworks, Pd-catalyzed one-pot reactions between pyridyl-substituted nido-carboranes and alkynes directly afford two distinct types of 2D-3D fused carboranyl polycyclic compounds: 3a-3f, 4a-4d. The structures of this series of compounds were characterized by nuclear magnetic resonance spectroscopy, single-crystal X-ray diffraction, and high-resolution mass spectrometry, and a plausible reaction mechanism was proposed. Crystal structures reveal that the multiple rings in such 2D-3D fused carboranyl polycyclic compounds exhibit a certain degree of coplanarity. Furthermore, these compounds exhibited properties distinct from those of conventional 2D polycyclic systems.
2026, 42(3): 593-605
doi: 10.11862/CJIC.20250278
Abstract:
In this study, a nickel-based MOF {(NH2(CH3)2)2[Ni3(O)(L)3(NH(CH3)2)3]}n (Ni3-MOF), with pore sizes of approximately 1.6 nm×1.6 nm, was synthesized by reacting 4, 4′-biphenyldicarboxylic acid (H2L) with Ni(NO3)2·6H2O in an N, N-dimethylformamide (DMF) solution. The nanoscale adsorbent Ni3-MOF-N with a particle diameter of approximately 200 nm was prepared using Ni3-MOF. It exhibited a maximum equilibrium tetracycline (TC) adsorption capacity of 358.2 mg·g-1 at its isoelectric point (pH=6.50), outperforming most reported MOF-based adsorbents. This exceptional performance is likely attributed to the well-matched pore size of Ni3-MOF-N (1.6 nm×1.6 nm) and the molecular dimensions of TC (0.8 nm×1.2 nm), combined with the presence of partial Ni(Ⅱ) sites on the surface of Ni3-MOF-N. These features collectively facilitate effective TC adsorption through a combination of pore filling, electrostatic attraction, hydrogen bonding, surface complexation, and π-π interactions. Recycling experiments demonstrated that Ni3-MOF-N possesses excellent structural stability and consistent adsorption performance.
In this study, a nickel-based MOF {(NH2(CH3)2)2[Ni3(O)(L)3(NH(CH3)2)3]}n (Ni3-MOF), with pore sizes of approximately 1.6 nm×1.6 nm, was synthesized by reacting 4, 4′-biphenyldicarboxylic acid (H2L) with Ni(NO3)2·6H2O in an N, N-dimethylformamide (DMF) solution. The nanoscale adsorbent Ni3-MOF-N with a particle diameter of approximately 200 nm was prepared using Ni3-MOF. It exhibited a maximum equilibrium tetracycline (TC) adsorption capacity of 358.2 mg·g-1 at its isoelectric point (pH=6.50), outperforming most reported MOF-based adsorbents. This exceptional performance is likely attributed to the well-matched pore size of Ni3-MOF-N (1.6 nm×1.6 nm) and the molecular dimensions of TC (0.8 nm×1.2 nm), combined with the presence of partial Ni(Ⅱ) sites on the surface of Ni3-MOF-N. These features collectively facilitate effective TC adsorption through a combination of pore filling, electrostatic attraction, hydrogen bonding, surface complexation, and π-π interactions. Recycling experiments demonstrated that Ni3-MOF-N possesses excellent structural stability and consistent adsorption performance.
2026, 42(3): 606-616
doi: 10.11862/CJIC.20250277
Abstract:
A collection of ordered-disordered Bi2WO6 homojunction catalysts was prepared in-situ through a facile one-step hydrothermal process, and their photocatalytic nitrogen fixation to synthesize ammonia performance was evaluated. Results showed that ordered-disordered Bi2WO6 (OD-2) obtained by adding 1.5 mL of ethylene glycol during preparation exhibited the optimal nitrogen fixation performance, with a nitrogen fixation rate of 114.92 μmol·g-1·h-1. However, its crystal counterpart, Bi2WO6 (BWO), lacked nitrogen-fixation activity. In-situ diffuse reflectance-Fourier transform infrared technique (DR-FTIR), electrochemical tests, and energy band structure analysis confirmed that the surface disordered structure in OD-2 not only promoted nitrogen activation but also enabled the effective separation of photogenerated electron-hole pairs at the ordered-disordered interface, facilitating the interface electrons transfer to the surface disordered structure of OD-2 and reacting with N2 adsorbed on the disordered structure, thereby promoting the smooth progress of the nitrogen fixation reaction.
A collection of ordered-disordered Bi2WO6 homojunction catalysts was prepared in-situ through a facile one-step hydrothermal process, and their photocatalytic nitrogen fixation to synthesize ammonia performance was evaluated. Results showed that ordered-disordered Bi2WO6 (OD-2) obtained by adding 1.5 mL of ethylene glycol during preparation exhibited the optimal nitrogen fixation performance, with a nitrogen fixation rate of 114.92 μmol·g-1·h-1. However, its crystal counterpart, Bi2WO6 (BWO), lacked nitrogen-fixation activity. In-situ diffuse reflectance-Fourier transform infrared technique (DR-FTIR), electrochemical tests, and energy band structure analysis confirmed that the surface disordered structure in OD-2 not only promoted nitrogen activation but also enabled the effective separation of photogenerated electron-hole pairs at the ordered-disordered interface, facilitating the interface electrons transfer to the surface disordered structure of OD-2 and reacting with N2 adsorbed on the disordered structure, thereby promoting the smooth progress of the nitrogen fixation reaction.
2026, 42(3): 617-631
doi: 10.11862/CJIC.20250265
Abstract:
Two Co(Ⅱ) and Ni(Ⅱ) complexes were synthesized by synergistic coordination of 3,3-diphenylpropionic acid (HDPA) and 2,2′-bipyridylamine (PAm). The structures of complexes [Co(DPA)2(PAm)]·2H2O (1) and [Ni(DPA)2(PAm)]·2H2O (2) were determined by single-crystal X-ray diffraction, IR spectroscopy, and powder X-ray diffraction. Hirshfeld surface analysis provided quantitative insights into the intermolecular interactions within the complexes, while molecular docking studies elucidated their binding modes and affinities toward urease. Furthermore, the biological activities of both complexes were systematically evaluated through a range of assays, including DNA binding, urease inhibition, antibacterial activity, and in vitro cytotoxicity against cancer cells. Both complexes exhibited binding affinity for DNA and displayed notable urease inhibitory activity. Under in vitro conditions, both complexes showed appreciable cytotoxicity toward HepG2 cells with efficacy comparable to clinically used platinum-based anticancer agents.
Two Co(Ⅱ) and Ni(Ⅱ) complexes were synthesized by synergistic coordination of 3,3-diphenylpropionic acid (HDPA) and 2,2′-bipyridylamine (PAm). The structures of complexes [Co(DPA)2(PAm)]·2H2O (1) and [Ni(DPA)2(PAm)]·2H2O (2) were determined by single-crystal X-ray diffraction, IR spectroscopy, and powder X-ray diffraction. Hirshfeld surface analysis provided quantitative insights into the intermolecular interactions within the complexes, while molecular docking studies elucidated their binding modes and affinities toward urease. Furthermore, the biological activities of both complexes were systematically evaluated through a range of assays, including DNA binding, urease inhibition, antibacterial activity, and in vitro cytotoxicity against cancer cells. Both complexes exhibited binding affinity for DNA and displayed notable urease inhibitory activity. Under in vitro conditions, both complexes showed appreciable cytotoxicity toward HepG2 cells with efficacy comparable to clinically used platinum-based anticancer agents.
Synthesis, structure, and properties of hydrated tricyclohexyltin theophylline-7-acetic acid complex
2026, 42(3): 632-640
doi: 10.11862/CJIC.20250244
Abstract:
The hydrated tricyclohexyltin theophylline-7-acetic acid (tpH) complex [Sn(C6H11)3(tp)(H2O)] was synthesized via an ethanol solvothermal method using tricyclohexyltin hydroxide and tpH in a 1∶1 molar ratio. The complex was characterized by IR, 1H (13C) NMR, elemental analysis, and powder X-ray diffraction, and the crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the orthorhombic system with space group Iba2, and the central tin atom is in a five-coordinated trigonal bipyramidal configuration. Quantum chemistry ab initio calculations were performed to investigate the stability, molecular orbital energy, and frontier molecular orbital characteristics of the complex. Additionally, its thermal stability, electrochemical properties, and in vitro anticancer activity were evaluated.
The hydrated tricyclohexyltin theophylline-7-acetic acid (tpH) complex [Sn(C6H11)3(tp)(H2O)] was synthesized via an ethanol solvothermal method using tricyclohexyltin hydroxide and tpH in a 1∶1 molar ratio. The complex was characterized by IR, 1H (13C) NMR, elemental analysis, and powder X-ray diffraction, and the crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the orthorhombic system with space group Iba2, and the central tin atom is in a five-coordinated trigonal bipyramidal configuration. Quantum chemistry ab initio calculations were performed to investigate the stability, molecular orbital energy, and frontier molecular orbital characteristics of the complex. Additionally, its thermal stability, electrochemical properties, and in vitro anticancer activity were evaluated.
2026, 42(3): 641-656
doi: 10.11862/CJIC.20250221
Abstract:
In this study, sawdust served as a carbon source and urea as a nitrogen source to synthesize carbon- supported, nitrogen-doped TiO2 composites via a one-pot solvothermal method. The composites were characterized using FTIR, powder X-ray diffraction, X-ray photoelectron spectroscopy, ultraviolet-visible diffuse reflectance spectroscopy, thermogravimetry-derivative thermogravimetry, scanning electron microscopy-energy dispersive spectroscopy, and transmission electron microscopy. Results indicated that all synthesized composites exhibit the anatase phase, with those calcined at 800 ℃ demonstrating enhanced crystallinity. Nitrogen is incorporated into the TiO2 lattice, while carbon is predominantly located on the surface. Photodegradation experiments showed that 20 mg of composite N-TiO2/C-800 achieved degradation rates of 93.4% for methylene blue (20 mg·L-1, 50 mL) and 99.4% for oxytetracycline (20 mg·L-1, 50 mL) within 30 min. Free radical capture experiments indicated that h+ was the primary active species in the photocatalytic degradation process.
In this study, sawdust served as a carbon source and urea as a nitrogen source to synthesize carbon- supported, nitrogen-doped TiO2 composites via a one-pot solvothermal method. The composites were characterized using FTIR, powder X-ray diffraction, X-ray photoelectron spectroscopy, ultraviolet-visible diffuse reflectance spectroscopy, thermogravimetry-derivative thermogravimetry, scanning electron microscopy-energy dispersive spectroscopy, and transmission electron microscopy. Results indicated that all synthesized composites exhibit the anatase phase, with those calcined at 800 ℃ demonstrating enhanced crystallinity. Nitrogen is incorporated into the TiO2 lattice, while carbon is predominantly located on the surface. Photodegradation experiments showed that 20 mg of composite N-TiO2/C-800 achieved degradation rates of 93.4% for methylene blue (20 mg·L-1, 50 mL) and 99.4% for oxytetracycline (20 mg·L-1, 50 mL) within 30 min. Free radical capture experiments indicated that h+ was the primary active species in the photocatalytic degradation process.
2026, 42(3): 479-487
doi: 10.11862/CJIC.20250292
Abstract:
The α-MnO2 cathode material was prepared using a simple one-step hydrothermal method, and the effect of preparation temperature on its morphology and electrochemical performance was investigated. The experimental results indicated that α-MnO2 synthesized at different temperatures all exhibited a nanowire structure. It was found that the α-MnO2 prepared at 180 ℃ exhibited superior electrochemical performance: at a current density of 0.1 A·g-1, it achieved a discharge specific capacity of 229.2 mAh·g-1, which was higher than those prepared at other temperatures, and after 110 cycles, its capacity remained at 90 mAh·g-1; at a current density of 1 A·g-1, after 1 000 cycles, it still maintained a discharge specific capacity of 38 mAh·g-1. Additionally, its charge transfer resistance was significantly lower than that of samples prepared at other temperatures.
The α-MnO2 cathode material was prepared using a simple one-step hydrothermal method, and the effect of preparation temperature on its morphology and electrochemical performance was investigated. The experimental results indicated that α-MnO2 synthesized at different temperatures all exhibited a nanowire structure. It was found that the α-MnO2 prepared at 180 ℃ exhibited superior electrochemical performance: at a current density of 0.1 A·g-1, it achieved a discharge specific capacity of 229.2 mAh·g-1, which was higher than those prepared at other temperatures, and after 110 cycles, its capacity remained at 90 mAh·g-1; at a current density of 1 A·g-1, after 1 000 cycles, it still maintained a discharge specific capacity of 38 mAh·g-1. Additionally, its charge transfer resistance was significantly lower than that of samples prepared at other temperatures.
2026, 42(3): 488-498
doi: 10.11862/CJIC.20250272
Abstract:
In this work, a 3D hierarchical nitrogen-doped carbon quantum dots/cuprous oxide (N-CDs/Cu2O) nanocomposite was successfully fabricated through an amino acid-mediated self-assembly approach. The Cu2O, formed under the guidance of amino acids with distinct acidities, exhibited varying sizes and crystallinities. The 3D hierarchical structure, formed upon integration with N-CDs, endowed the material with an abundant porous network, thus effectively promoting electrolyte infiltration. Moreover, N-CDs accelerated ion/electron transport through defect engineering and interface optimization. Additionally, the robust heterointerfaces established by N-CDs constrained volume expansion during the charge-discharge process. Notably, the glycine-assisted synthesized N-CDs/Cu2O composite electrode demonstrated an impressive initial discharge capacity of 373 mAh·g-1 at a current density of 0.1 A·g-1, and retained 78% of its capacity after 100 cycles.
In this work, a 3D hierarchical nitrogen-doped carbon quantum dots/cuprous oxide (N-CDs/Cu2O) nanocomposite was successfully fabricated through an amino acid-mediated self-assembly approach. The Cu2O, formed under the guidance of amino acids with distinct acidities, exhibited varying sizes and crystallinities. The 3D hierarchical structure, formed upon integration with N-CDs, endowed the material with an abundant porous network, thus effectively promoting electrolyte infiltration. Moreover, N-CDs accelerated ion/electron transport through defect engineering and interface optimization. Additionally, the robust heterointerfaces established by N-CDs constrained volume expansion during the charge-discharge process. Notably, the glycine-assisted synthesized N-CDs/Cu2O composite electrode demonstrated an impressive initial discharge capacity of 373 mAh·g-1 at a current density of 0.1 A·g-1, and retained 78% of its capacity after 100 cycles.
2026, 42(3): 499-506
doi: 10.11862/CJIC.20250281
Abstract:
The carboxyl-modified UiO-67 nanomaterials (UiO-67-COOH) were synthesized by the solvothermal method, in which 4, 4′-biphenyldicarboxylic acid and 1, 1′-biphenyl-3, 4′, 4-tricarboxylic acid, and ZrCl4 were adopted as ligands and metal salt, respectively. The maximum adsorption capacities of carboxyl-modified UiO-67 were 698.7, 295.9, and 200.8 mg·g-1 for Congo red (CR), methyl orange (MO), and acid orange 7 (AO7), respectively, indicating that they exhibit superior dye removal performance. The removal efficiency of UiO-67-COOH toward CR, MO, and AO7 decreased with the electrostatic interaction, π-π interactions, adsorption space, and steric hindrance effect.
The carboxyl-modified UiO-67 nanomaterials (UiO-67-COOH) were synthesized by the solvothermal method, in which 4, 4′-biphenyldicarboxylic acid and 1, 1′-biphenyl-3, 4′, 4-tricarboxylic acid, and ZrCl4 were adopted as ligands and metal salt, respectively. The maximum adsorption capacities of carboxyl-modified UiO-67 were 698.7, 295.9, and 200.8 mg·g-1 for Congo red (CR), methyl orange (MO), and acid orange 7 (AO7), respectively, indicating that they exhibit superior dye removal performance. The removal efficiency of UiO-67-COOH toward CR, MO, and AO7 decreased with the electrostatic interaction, π-π interactions, adsorption space, and steric hindrance effect.
2026, 42(3): 507-518
doi: 10.11862/CJIC.20250275
Abstract:
To develop an environmentally friendly Ti-based mesoporous catalyst for efficient persulfate activation toward organic pollutant degradation, Co- and Zr-doped mesoporous TiO2 catalysts (Co-TiO2 and Zr-TiO2) were prepared. The mechanisms governing active species generation and tetracycline (TC) degradation performance during sodium persulfate (PDS) activation were investigated. Structural characterization results revealed that both Co and Zr doping significantly enhanced the specific surface area and oxygen vacancy concentration of the catalysts. Specifically, Zr4+ doping induced lattice distortion due to its larger ionic radius compared to Ti4+, while Co doping facilitated electron migration owing to the electronegativity difference between Co and Ti. TC degradation experiments demonstrated that the Co-TiO2/PDS and Zr-TiO2/PDS systems achieved TC degradation rates of 93.1% and 89.6% within 6 h, respectively, significantly outperforming the undoped TiO2/PDS system. Their reaction rate constants were 2.8 times and 2.4 times higher than that of the undoped system. Quenching experiments and electron spin resonance (ESR) analysis confirmed that hydroxyl radicals (·OH) was the primary active species in the Co-TiO2/PDS system, whereas singlet oxygen (1O2) served as the primary active species in the Zr-TiO2/PDS system. Phosphate (PO43-) addition experiments demonstrated that modulating hydroxyl groups on the catalyst surface could optimize the reactant utilization efficiency (ηRU) of the Co-TiO2/PDS system. This study elucidates the discrepancies in the PDS activation process by metal-doped mesoporous TiO2 catalysts and the regulatory mechanisms governing reactive species and contaminant degradation performance.
To develop an environmentally friendly Ti-based mesoporous catalyst for efficient persulfate activation toward organic pollutant degradation, Co- and Zr-doped mesoporous TiO2 catalysts (Co-TiO2 and Zr-TiO2) were prepared. The mechanisms governing active species generation and tetracycline (TC) degradation performance during sodium persulfate (PDS) activation were investigated. Structural characterization results revealed that both Co and Zr doping significantly enhanced the specific surface area and oxygen vacancy concentration of the catalysts. Specifically, Zr4+ doping induced lattice distortion due to its larger ionic radius compared to Ti4+, while Co doping facilitated electron migration owing to the electronegativity difference between Co and Ti. TC degradation experiments demonstrated that the Co-TiO2/PDS and Zr-TiO2/PDS systems achieved TC degradation rates of 93.1% and 89.6% within 6 h, respectively, significantly outperforming the undoped TiO2/PDS system. Their reaction rate constants were 2.8 times and 2.4 times higher than that of the undoped system. Quenching experiments and electron spin resonance (ESR) analysis confirmed that hydroxyl radicals (·OH) was the primary active species in the Co-TiO2/PDS system, whereas singlet oxygen (1O2) served as the primary active species in the Zr-TiO2/PDS system. Phosphate (PO43-) addition experiments demonstrated that modulating hydroxyl groups on the catalyst surface could optimize the reactant utilization efficiency (ηRU) of the Co-TiO2/PDS system. This study elucidates the discrepancies in the PDS activation process by metal-doped mesoporous TiO2 catalysts and the regulatory mechanisms governing reactive species and contaminant degradation performance.
2026, 42(3): 519-530
doi: 10.11862/CJIC.20250274
Abstract:
To simultaneously accelerate ion transport and catalyze polysulfide conversion in lithium-sulfur (Li-S) batteries, a CeO2/g-C3N4 composite with both lithium affinity and catalytic activity was designed. The abundant nitrogen units within the g-C3N4 nanosheets serve as lithium-affinity sites, reducing the lithium-ion (Li+) migration energy barrier and accelerating Li+ transport via Lewis acid-base interactions. Meanwhile, the Ce4+/Ce3+ redox couple is the key catalytically active sites that drive the generation of thiosulfate and establish a reversible thiosulfate-mediated polysulfide conversion pathway. Such a thiosulfate-mediated pathway promotes the bidirectional conversion of polysulfide. Therefore, modifying the commercial PP separator with CeO2/g-C3N4 composites can effectively enhance the kinetics of polysulfide conversion, reduce charge transfer resistance, and significantly improve the rate performance and cycling performance (1 000 cycles at 1.0C, with a capacity decay rate of only 0.049% per cycle).
To simultaneously accelerate ion transport and catalyze polysulfide conversion in lithium-sulfur (Li-S) batteries, a CeO2/g-C3N4 composite with both lithium affinity and catalytic activity was designed. The abundant nitrogen units within the g-C3N4 nanosheets serve as lithium-affinity sites, reducing the lithium-ion (Li+) migration energy barrier and accelerating Li+ transport via Lewis acid-base interactions. Meanwhile, the Ce4+/Ce3+ redox couple is the key catalytically active sites that drive the generation of thiosulfate and establish a reversible thiosulfate-mediated polysulfide conversion pathway. Such a thiosulfate-mediated pathway promotes the bidirectional conversion of polysulfide. Therefore, modifying the commercial PP separator with CeO2/g-C3N4 composites can effectively enhance the kinetics of polysulfide conversion, reduce charge transfer resistance, and significantly improve the rate performance and cycling performance (1 000 cycles at 1.0C, with a capacity decay rate of only 0.049% per cycle).
2026, 42(3): 531-542
doi: 10.11862/CJIC.20250271
Abstract:
The antimicrobial activities of silver(Ⅰ) complexes can be enhanced by increasing the content and release of silver ions, which may also cause potential toxicity. Additionally, the powder form of silver(Ⅰ) complexes is not advantageous for clinical applications. To address the above challenges, an antimicrobial film based on silver(Ⅰ) complex was constructed through the following three design strategies. First, complex 1 was self-assembled using an antimicrobial ligand (indole-3-carboxylic acid) and tert-butylacetylene silver to enhance antimicrobial effects by releasing Ag+ and antimicrobial ligands simultaneously. Then, the third antimicrobial source, i.e., graphene oxide (GO), was introduced to prepare 1@GO composite with GO addition optimized by antimicrobial performance. Finally, 1@GO/PVA film was prepared by selecting polyvinyl alcohol (PVA) as a matrix for potential applications. The structure, photostability, and solution stability of 1 were characterized by IR spectra and powder X-ray diffraction. Ag+ releasing test showed the enhanced pH-responsive Ag+ release of 1. The results of the inhibition zones test showed weak antimicrobial effects of GO (1 000 μg·mL-1) on Escherichia coli (E. coli), Pseudomonas aeruginosa (P. aeruginosa), Staphylococcus aureus (S. aureus), and Candida albicans (C. albicans) with increased inhibition zone diameters of 1.1, 2.5, 3.5, and 1.8 mm, respectively. 1 showed good broad-spectra antimicrobial activities against the four microorganisms, and diameters of inhibitory zones increased by 5.0, 10.5, 5.8, and 5.0 mm, respectively. SEM images of 1@GO (1∶1 of mass concentration ratio) exhibited that 1 was dispersed evenly in GO, exposing a large number of sharp edges. The diameters of inhibition zones for 1@GO(1∶1) against E. coli, S. aureus, and C. albicans increased by 6.2, 10.4, and 9.8 mm, respectively, which are larger than the algebraic sum of respective contributions of 1 and GO to the diameter of inhibition zones (6.1, 9.3, and 6.8 mm). This result indicated clearly the successful realization of synergistic antimicrobial effects of silver complex and GO. Minimum inhibitory concentration (MIC) results exhibited the best inhibitory effect of 1 on P. aeruginosa and S. aureus with low MIC values of 20 and 15 μg·mL-1, respectively. After adding GO, MIC values of 1@GO against E. coli, P. aeruginosa, S. aureus, and C. albicans reduced to 5-10 μg·mL-1, 5-10 μg·mL-1, and 10-15 μg·mL-1, respectively. 1(0.5%)@GO(1∶1)/PVA film displayed good antimicrobial properties for four strains, with the largest diameter of inhibition zones of 18.5 mm against P. aeruginosa.
The antimicrobial activities of silver(Ⅰ) complexes can be enhanced by increasing the content and release of silver ions, which may also cause potential toxicity. Additionally, the powder form of silver(Ⅰ) complexes is not advantageous for clinical applications. To address the above challenges, an antimicrobial film based on silver(Ⅰ) complex was constructed through the following three design strategies. First, complex 1 was self-assembled using an antimicrobial ligand (indole-3-carboxylic acid) and tert-butylacetylene silver to enhance antimicrobial effects by releasing Ag+ and antimicrobial ligands simultaneously. Then, the third antimicrobial source, i.e., graphene oxide (GO), was introduced to prepare 1@GO composite with GO addition optimized by antimicrobial performance. Finally, 1@GO/PVA film was prepared by selecting polyvinyl alcohol (PVA) as a matrix for potential applications. The structure, photostability, and solution stability of 1 were characterized by IR spectra and powder X-ray diffraction. Ag+ releasing test showed the enhanced pH-responsive Ag+ release of 1. The results of the inhibition zones test showed weak antimicrobial effects of GO (1 000 μg·mL-1) on Escherichia coli (E. coli), Pseudomonas aeruginosa (P. aeruginosa), Staphylococcus aureus (S. aureus), and Candida albicans (C. albicans) with increased inhibition zone diameters of 1.1, 2.5, 3.5, and 1.8 mm, respectively. 1 showed good broad-spectra antimicrobial activities against the four microorganisms, and diameters of inhibitory zones increased by 5.0, 10.5, 5.8, and 5.0 mm, respectively. SEM images of 1@GO (1∶1 of mass concentration ratio) exhibited that 1 was dispersed evenly in GO, exposing a large number of sharp edges. The diameters of inhibition zones for 1@GO(1∶1) against E. coli, S. aureus, and C. albicans increased by 6.2, 10.4, and 9.8 mm, respectively, which are larger than the algebraic sum of respective contributions of 1 and GO to the diameter of inhibition zones (6.1, 9.3, and 6.8 mm). This result indicated clearly the successful realization of synergistic antimicrobial effects of silver complex and GO. Minimum inhibitory concentration (MIC) results exhibited the best inhibitory effect of 1 on P. aeruginosa and S. aureus with low MIC values of 20 and 15 μg·mL-1, respectively. After adding GO, MIC values of 1@GO against E. coli, P. aeruginosa, S. aureus, and C. albicans reduced to 5-10 μg·mL-1, 5-10 μg·mL-1, and 10-15 μg·mL-1, respectively. 1(0.5%)@GO(1∶1)/PVA film displayed good antimicrobial properties for four strains, with the largest diameter of inhibition zones of 18.5 mm against P. aeruginosa.
2026, 42(3): 543-550
doi: 10.11862/CJIC.20250270
Abstract:
Under solvothermal synthesis conditions, two pyridylpyrazole ligands with different substituents, 3, 5-dimethyl-4-(4-pyridyl)pyrazole (Hdmppz) and 3, 5-diethyl-4-(4-pyridyl)pyrazole (Hdeppz), were reacted with Cu(Ⅰ) ions to get two planar trinuclear [Cu(pz)]3 complexes containing Cu3N6 nine-membered rings: [Cu(dmppz)]3·H2O (1) and [Cu(deppz)]3 (2). The structures and properties of the ligands and complexes were characterized using elemental analysis, infrared spectroscopy, single-crystal X-ray diffraction, thermogravimetric analysis, and luminescence spectroscopy, exploring the effects of ligand substituents on the structures and properties of the complexes. The results showed that complex 1 belongs to the monoclinic crystal system with the P21/c space group, with lattice parameters a=0.746 65(5) nm, b=2.116 92(12) nm, c=2.004 46(10) nm, and β=107.725(2)°. Complex 2 also belongs to the monoclinic crystal system with the P21/c space group, with lattice parameters a=1.056 74(6) nm, b=2.283 14(13) nm, c=1.535 72(9) nm, and β=103.647 0(10)°. Both complexes exhibit abundant intramolecular and intermolecular Cu…Cu and Cu…π interactions, and the variation between methyl and ethyl substituent groups leads to different structural packing modes. Additionally, complexes 1 and 2 demonstrated high thermal stability (250 and 330 ℃) and strong blue-green and light green luminescence properties with the maximum emission wavelengths of 513 and 550 nm, respectively.
Under solvothermal synthesis conditions, two pyridylpyrazole ligands with different substituents, 3, 5-dimethyl-4-(4-pyridyl)pyrazole (Hdmppz) and 3, 5-diethyl-4-(4-pyridyl)pyrazole (Hdeppz), were reacted with Cu(Ⅰ) ions to get two planar trinuclear [Cu(pz)]3 complexes containing Cu3N6 nine-membered rings: [Cu(dmppz)]3·H2O (1) and [Cu(deppz)]3 (2). The structures and properties of the ligands and complexes were characterized using elemental analysis, infrared spectroscopy, single-crystal X-ray diffraction, thermogravimetric analysis, and luminescence spectroscopy, exploring the effects of ligand substituents on the structures and properties of the complexes. The results showed that complex 1 belongs to the monoclinic crystal system with the P21/c space group, with lattice parameters a=0.746 65(5) nm, b=2.116 92(12) nm, c=2.004 46(10) nm, and β=107.725(2)°. Complex 2 also belongs to the monoclinic crystal system with the P21/c space group, with lattice parameters a=1.056 74(6) nm, b=2.283 14(13) nm, c=1.535 72(9) nm, and β=103.647 0(10)°. Both complexes exhibit abundant intramolecular and intermolecular Cu…Cu and Cu…π interactions, and the variation between methyl and ethyl substituent groups leads to different structural packing modes. Additionally, complexes 1 and 2 demonstrated high thermal stability (250 and 330 ℃) and strong blue-green and light green luminescence properties with the maximum emission wavelengths of 513 and 550 nm, respectively.
2026, 42(3): 551-561
doi: 10.11862/CJIC.20250269
Abstract:
The spherical Bi4Ti3O12 photocatalyst formed by self-assembly of nanosheets was successfully prepared via the hydrothermal method using tetrabutyl titanate (TBOT) and bismuth nitrate pentahydrate (Bi(NO3)3·5H2O) as precursors, assisted by two surfactants, sodium dodecyl sulfate (SDS) or sodium oleate. The structure and properties of the as-prepared materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet-visible absorption spectroscopy (UV-Vis), Fourier transform infrared spectroscopy (FTIR), and electrochemical impedance spectroscopy (EIS). The results indicated that the sample modified with surface surfactants reduced the band gap from 2.72 to 2.46 eV, thereby significantly enhancing light absorption. The photocatalytic performance of the catalysts was evaluated under UV light irradiation for the degradation of methylene blue (MB), rhodamine B (RhB), and methyl orange (MO). The Bi4Ti3O12 (BTO-1) prepared with SDS assistance exhibited the highest degradation rate of 98.9% for MB, while the Bi4Ti3O12 (BTO-2) prepared with sodium oleate assistance achieved the degradation rate of 98.5% for RhB, and kept the degradation rate of over 96% after five cyclic runs. Mechanism studies revealed that surface chemical modification effectively regulated the surface charge and hydrophobicity of the materials, leading to enhanced dye adsorption capacity. A synergistic mechanism of "surface modification-adsorption-photocatalysis" was therefore proposed.
The spherical Bi4Ti3O12 photocatalyst formed by self-assembly of nanosheets was successfully prepared via the hydrothermal method using tetrabutyl titanate (TBOT) and bismuth nitrate pentahydrate (Bi(NO3)3·5H2O) as precursors, assisted by two surfactants, sodium dodecyl sulfate (SDS) or sodium oleate. The structure and properties of the as-prepared materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet-visible absorption spectroscopy (UV-Vis), Fourier transform infrared spectroscopy (FTIR), and electrochemical impedance spectroscopy (EIS). The results indicated that the sample modified with surface surfactants reduced the band gap from 2.72 to 2.46 eV, thereby significantly enhancing light absorption. The photocatalytic performance of the catalysts was evaluated under UV light irradiation for the degradation of methylene blue (MB), rhodamine B (RhB), and methyl orange (MO). The Bi4Ti3O12 (BTO-1) prepared with SDS assistance exhibited the highest degradation rate of 98.9% for MB, while the Bi4Ti3O12 (BTO-2) prepared with sodium oleate assistance achieved the degradation rate of 98.5% for RhB, and kept the degradation rate of over 96% after five cyclic runs. Mechanism studies revealed that surface chemical modification effectively regulated the surface charge and hydrophobicity of the materials, leading to enhanced dye adsorption capacity. A synergistic mechanism of "surface modification-adsorption-photocatalysis" was therefore proposed.
2026, 42(3): 562-570
doi: 10.11862/CJIC.20250267
Abstract:
An in-situ self-assembly approach was employed to fabricate a zinc anode with a protective layer ofhydrated vanadium pentoxide (HVO) through direct growth on the zinc foil surface (named VOZn). The thickness of the protective layer can be precisely controlled by adjusting the self-assembly duration of the HVO suspension. The in-situ formation of the HVO layer ensures strong interfacial adhesion between the protective layer and the Zn substrate, thereby minimizing delamination during repeated charge-discharge cycles. More importantly, the presence of abundant oxygen-containing functional groups in HVO significantly enhances the zincophilicity of the anode surface, promoting uniform Zn2+ ion distribution and facilitating homogeneous nucleation and deposition of metallic zinc. Furthermore, the protective layer serve as an effective physical barrier that limits direct contact between free water molecules in the electrolyte and the zinc anode, thereby suppressing undesirable side reactions. As a result, the resulting composite electrode exhibited a notably low overpotential of 37 mV and long cycling stability of 700 h at 0.5 mA·cm-2. More impressively, the full cells based on the VOZn showed a long cycle life of 1 000 cycles with a high capacity retention of 71%.
An in-situ self-assembly approach was employed to fabricate a zinc anode with a protective layer ofhydrated vanadium pentoxide (HVO) through direct growth on the zinc foil surface (named VOZn). The thickness of the protective layer can be precisely controlled by adjusting the self-assembly duration of the HVO suspension. The in-situ formation of the HVO layer ensures strong interfacial adhesion between the protective layer and the Zn substrate, thereby minimizing delamination during repeated charge-discharge cycles. More importantly, the presence of abundant oxygen-containing functional groups in HVO significantly enhances the zincophilicity of the anode surface, promoting uniform Zn2+ ion distribution and facilitating homogeneous nucleation and deposition of metallic zinc. Furthermore, the protective layer serve as an effective physical barrier that limits direct contact between free water molecules in the electrolyte and the zinc anode, thereby suppressing undesirable side reactions. As a result, the resulting composite electrode exhibited a notably low overpotential of 37 mV and long cycling stability of 700 h at 0.5 mA·cm-2. More impressively, the full cells based on the VOZn showed a long cycle life of 1 000 cycles with a high capacity retention of 71%.
2026, 42(3): 571-583
doi: 10.11862/CJIC.20250263
Abstract:
Polyvinylpyrrolidone (PVP) was added during solvothermal synthesis to regulate the morphology and structure of HKUST-1 crystals, which were then in situ incorporated into a polyimide (PI) matrix to fabricate mixed matrix membranes (MMMs). The morphology and structure of the HKUST-1 crystals were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and nitrogen adsorption-desorption test. On the basis of CO2 adsorption experiments of HKUST-1, gas permeation measurements of the MMMs, and grand canonical Monte Carlo (GCMC) simulations, the effect of HKUST-1 crystal size on the CO2 permeation performance of the MMMs was investigated, and the mechanism by which PVP regulates the CO2 separation performance of MMMs was elucidated. The results showed that, owing to the steric hindrance effect of PVP, the HKUST-1 crystals synthesized with PVP exhibited an average particle size of 1-3 μm and a specific surface area of 731-1 007 m2·g-1. Compared with HKUST-1 crystals synthesized without PVP, their average particle size was significantly reduced with a narrower size distribution and a larger specific surface area, while more Cu2+ metal sites and aromatic ring structures were exposed. This enhances the interfacial compatibility between HKUST-1 and PI, as well as the π-π interactions and Lewis acid interactions between HKUST-1 and CO2. The MMM prepared by in situ incorporation of HKUST-1 (K30), whose synthesis was regulated by K30-type PVP with a dopping amount (mass fraction) of 3%, exhibited a CO2 permeability of 142.81 Barrer [1 Barrer=7.5×10-14 cm3(STP)·cm·cm-2·s-1·Pa-1] and a CO2/N2 selectivity of 25.05, which are 76 times and 18 times those of the pristine PI membrane, respectively. These results demonstrate that tailoring the morphology of HKUST-1 crystals via PVP is an effective approach to enhancing the CO2 separation performance of MMMs.
Polyvinylpyrrolidone (PVP) was added during solvothermal synthesis to regulate the morphology and structure of HKUST-1 crystals, which were then in situ incorporated into a polyimide (PI) matrix to fabricate mixed matrix membranes (MMMs). The morphology and structure of the HKUST-1 crystals were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and nitrogen adsorption-desorption test. On the basis of CO2 adsorption experiments of HKUST-1, gas permeation measurements of the MMMs, and grand canonical Monte Carlo (GCMC) simulations, the effect of HKUST-1 crystal size on the CO2 permeation performance of the MMMs was investigated, and the mechanism by which PVP regulates the CO2 separation performance of MMMs was elucidated. The results showed that, owing to the steric hindrance effect of PVP, the HKUST-1 crystals synthesized with PVP exhibited an average particle size of 1-3 μm and a specific surface area of 731-1 007 m2·g-1. Compared with HKUST-1 crystals synthesized without PVP, their average particle size was significantly reduced with a narrower size distribution and a larger specific surface area, while more Cu2+ metal sites and aromatic ring structures were exposed. This enhances the interfacial compatibility between HKUST-1 and PI, as well as the π-π interactions and Lewis acid interactions between HKUST-1 and CO2. The MMM prepared by in situ incorporation of HKUST-1 (K30), whose synthesis was regulated by K30-type PVP with a dopping amount (mass fraction) of 3%, exhibited a CO2 permeability of 142.81 Barrer [1 Barrer=7.5×10-14 cm3(STP)·cm·cm-2·s-1·Pa-1] and a CO2/N2 selectivity of 25.05, which are 76 times and 18 times those of the pristine PI membrane, respectively. These results demonstrate that tailoring the morphology of HKUST-1 crystals via PVP is an effective approach to enhancing the CO2 separation performance of MMMs.
2026, 42(3): 584-592
doi: 10.11862/CJIC.20250217
Abstract:
Systematic studies were conducted on the Raman spectroscopic properties of Bi2SeO5, revealing that Raman peak intensity increased with nanosheet thickness, exhibiting a distinct thickness dependence. Furthermore, Bi2SeO5 was integrated with typical 2D semiconductors, such as in back-gated field-effect transistors (FETs) with MoS2 as the channel, where Bi2SeO5 achieves efficient gate modulation due to its excellent dielectric properties. The devices demonstrated a high on/off ratio of up to 106 and a low subthreshold swing (SS) of 144 mV·dec-1, highlighting outstanding dielectric modulation capability. Meanwhile, as an encapsulation layer, Bi2SeO5 could effectively protect air-sensitive black phosphorus (BP) and indium selenide (InSe), significantly enhancing their stability in air. These results confirm that Bi2SeO5 can form smooth and dense interfaces with 2D materials, and that it possesses both excellent dielectric properties and efficient protective capabilities.
Systematic studies were conducted on the Raman spectroscopic properties of Bi2SeO5, revealing that Raman peak intensity increased with nanosheet thickness, exhibiting a distinct thickness dependence. Furthermore, Bi2SeO5 was integrated with typical 2D semiconductors, such as in back-gated field-effect transistors (FETs) with MoS2 as the channel, where Bi2SeO5 achieves efficient gate modulation due to its excellent dielectric properties. The devices demonstrated a high on/off ratio of up to 106 and a low subthreshold swing (SS) of 144 mV·dec-1, highlighting outstanding dielectric modulation capability. Meanwhile, as an encapsulation layer, Bi2SeO5 could effectively protect air-sensitive black phosphorus (BP) and indium selenide (InSe), significantly enhancing their stability in air. These results confirm that Bi2SeO5 can form smooth and dense interfaces with 2D materials, and that it possesses both excellent dielectric properties and efficient protective capabilities.
