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2026 Volume 42 Issue 2
2026, 42(2): 217-226
doi: 10.11862/CJIC.20250219
Abstract:
In this study, using 3, 5-di(3′, 5′-dicarboxylphenyl)-1H-1, 2, 4-triazole (H4L) as ligands, a gadolinia-based organic framework complex {[GdNa(L)(H2O)3]·2H2O}n (Gd-Na-MOF) was successfully designed and synthesized by hydrothermal method. The structure and properties were systematically characterized and tested by techniques such as single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analysis, infrared spectroscopy, and fluorescence spectroscopy. The results indicate that this complex has a unique 3D structure, excellent thermal stability, and outstanding luminescent performance. Based on its luminescent properties, a polymer-embedding method was employed to fabricate the Gd-Na-MOF into a flexible, washable composite fluorescent film, Gd-Na-MOF@PMMA/BMA (PMMA=polymethyl methacrylate, BMA=butyl methacrylate). This fluorescent film exhibited highly sensitive recognition capability for tyramine, with a low detection limit of 1.66 μmol·L-1. It was used for the detection of tyramine in bananas, with a recovery rate of 96.92%-100.26%.
In this study, using 3, 5-di(3′, 5′-dicarboxylphenyl)-1H-1, 2, 4-triazole (H4L) as ligands, a gadolinia-based organic framework complex {[GdNa(L)(H2O)3]·2H2O}n (Gd-Na-MOF) was successfully designed and synthesized by hydrothermal method. The structure and properties were systematically characterized and tested by techniques such as single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analysis, infrared spectroscopy, and fluorescence spectroscopy. The results indicate that this complex has a unique 3D structure, excellent thermal stability, and outstanding luminescent performance. Based on its luminescent properties, a polymer-embedding method was employed to fabricate the Gd-Na-MOF into a flexible, washable composite fluorescent film, Gd-Na-MOF@PMMA/BMA (PMMA=polymethyl methacrylate, BMA=butyl methacrylate). This fluorescent film exhibited highly sensitive recognition capability for tyramine, with a low detection limit of 1.66 μmol·L-1. It was used for the detection of tyramine in bananas, with a recovery rate of 96.92%-100.26%.
2026, 42(2): 331-339
doi: 10.11862/CJIC.20250260
Abstract:
Under solvothermal conditions, 1, 4-naphthalenedicarboxylic acid (H2ndc) and 9, 9′-dihexyl-2, 7-di(pyridin-4-yl)fluorene (hfdp) reacted with Co2+ ions and Cd2+ ions to form two coordination polymers, [Co(hfdp)(ndc)(H2O)]·DMA}n (1) and {[Cd(hfdp)(ndc)(H2O)]·DMA}n (2), respectively (DMA=N, N-dimethylacetamide). Single-crystal X-ray diffraction analyses showed that both complexes 1 and 2 contain similar structures. Topological analysis indicates that complexes 1 and 2 have a {44·62} planar structure. In addition, both complexes reveal good thermal stability and fluorescence sensing performance. They exhibited good sensitivity and selectivity towards 2, 4, 6-trinitrophenol (TNP) by fluorescent quenching. The limits of detection of 1 and 2 for TNP were 0.107 and 0.327 μmol·L-1, respectively.
Under solvothermal conditions, 1, 4-naphthalenedicarboxylic acid (H2ndc) and 9, 9′-dihexyl-2, 7-di(pyridin-4-yl)fluorene (hfdp) reacted with Co2+ ions and Cd2+ ions to form two coordination polymers, [Co(hfdp)(ndc)(H2O)]·DMA}n (1) and {[Cd(hfdp)(ndc)(H2O)]·DMA}n (2), respectively (DMA=N, N-dimethylacetamide). Single-crystal X-ray diffraction analyses showed that both complexes 1 and 2 contain similar structures. Topological analysis indicates that complexes 1 and 2 have a {44·62} planar structure. In addition, both complexes reveal good thermal stability and fluorescence sensing performance. They exhibited good sensitivity and selectivity towards 2, 4, 6-trinitrophenol (TNP) by fluorescent quenching. The limits of detection of 1 and 2 for TNP were 0.107 and 0.327 μmol·L-1, respectively.
2026, 42(2): 340-354
doi: 10.11862/CJIC.20250226
Abstract:
Four distinct coordination polymers (CPs) were successfully synthesized by altering solvent types and adjusting ligand concentrations, and their crystal structures were investigated. [Co(L)(FDCA)(H2O)2]·0.5H2O (1) was synthesized as a 2D structure using Co(Ⅱ) as the metal source, methanol-water (4∶6, V/V) as the solvent, and specific concentrations of 2, 5-furandicarboxylic acid (H2FDCA) and 1, 3, 5-triimidazole benzene (L). Adjusting to pure water and lowering the concentration of L yielded the 1D chain structure of [Co(HL)2(H2O)2](FDCA)2·6H2O (2). Using Cu(Ⅱ) as the metal source, methanol/water (9∶1, V/V) as the solvent, and specific concentrations of L and H2FDCA, the 1D chain structure of [Cu(L)(FDCA)(H2O)]·2H2O (3) was synthesized. Upon increasing the concentrations of L and H2FDCA, and switching the solvent to pure water, the 1D chain structure of [Cu(HL)2(H2O)2](FDCA)2·6H2O (4) was obtained. This shows that changing the solvent and ligand concentrations can affect the structural changes of CPs. In addition, the solid-state photoluminescence of CPs 1-4 at room temperature was studied, and their morphological changes were observed via scanning electron microscopy. Density functional theory calculations revealed that the negative charge concentrates on the O and N atoms of the ligand, facilitating ligand-metal ion coordination.
Four distinct coordination polymers (CPs) were successfully synthesized by altering solvent types and adjusting ligand concentrations, and their crystal structures were investigated. [Co(L)(FDCA)(H2O)2]·0.5H2O (1) was synthesized as a 2D structure using Co(Ⅱ) as the metal source, methanol-water (4∶6, V/V) as the solvent, and specific concentrations of 2, 5-furandicarboxylic acid (H2FDCA) and 1, 3, 5-triimidazole benzene (L). Adjusting to pure water and lowering the concentration of L yielded the 1D chain structure of [Co(HL)2(H2O)2](FDCA)2·6H2O (2). Using Cu(Ⅱ) as the metal source, methanol/water (9∶1, V/V) as the solvent, and specific concentrations of L and H2FDCA, the 1D chain structure of [Cu(L)(FDCA)(H2O)]·2H2O (3) was synthesized. Upon increasing the concentrations of L and H2FDCA, and switching the solvent to pure water, the 1D chain structure of [Cu(HL)2(H2O)2](FDCA)2·6H2O (4) was obtained. This shows that changing the solvent and ligand concentrations can affect the structural changes of CPs. In addition, the solid-state photoluminescence of CPs 1-4 at room temperature was studied, and their morphological changes were observed via scanning electron microscopy. Density functional theory calculations revealed that the negative charge concentrates on the O and N atoms of the ligand, facilitating ligand-metal ion coordination.
2026, 42(2): 355-364
doi: 10.11862/CJIC.20250253
Abstract:
This paper reports the preparation of three di-iron complexes containing a thiazole moiety. Esterification of complex [Fe2(CO)6(μ-SCH2CH(CH2OH)S)] (1) with 4-methylthiazole-5-carboxylic acid gave the corresponding ester [Fe2(CO)6(μ-tedt)] (2), where tedt=SCH2CH(CH2OOC(5-C3HNSCH3))S. Further reactions of complex 2 with tri(p-tolyl)phosphine (tp) or tris(4-fluorophenyl)phosphine (fp) gave the phosphine-substituted derivatives [Fe2(CO)5(tp)(μ-tedt)] (3) and [Fe2(CO)5(fp)(μ-tedt)] (4). The structures of the newly prepared complexes were elucidated by elemental analysis, NMR, IR, and X-ray photoelectron spectroscopy. Moreover, single-crystal X-ray diffraction analysis confirmed their molecular structures, showing that they contain a di-iron core ligated by a bridged dithiolate bearing a thiazole moiety and terminal carbonyls. The electrochemical and electrocatalytic proton reduction were probed by cyclic voltammetry, revealing that three complexes can catalyze the reduction of protons to H2 under the electrochemical conditions. For comparison, complex 4 possessed the best efficiency with a turnover frequency of 23.5 s-1 at 10 mmol·L-1 HOAc concentration. In addition, the fungicidal activity of these complexes was also investigated in this study.
This paper reports the preparation of three di-iron complexes containing a thiazole moiety. Esterification of complex [Fe2(CO)6(μ-SCH2CH(CH2OH)S)] (1) with 4-methylthiazole-5-carboxylic acid gave the corresponding ester [Fe2(CO)6(μ-tedt)] (2), where tedt=SCH2CH(CH2OOC(5-C3HNSCH3))S. Further reactions of complex 2 with tri(p-tolyl)phosphine (tp) or tris(4-fluorophenyl)phosphine (fp) gave the phosphine-substituted derivatives [Fe2(CO)5(tp)(μ-tedt)] (3) and [Fe2(CO)5(fp)(μ-tedt)] (4). The structures of the newly prepared complexes were elucidated by elemental analysis, NMR, IR, and X-ray photoelectron spectroscopy. Moreover, single-crystal X-ray diffraction analysis confirmed their molecular structures, showing that they contain a di-iron core ligated by a bridged dithiolate bearing a thiazole moiety and terminal carbonyls. The electrochemical and electrocatalytic proton reduction were probed by cyclic voltammetry, revealing that three complexes can catalyze the reduction of protons to H2 under the electrochemical conditions. For comparison, complex 4 possessed the best efficiency with a turnover frequency of 23.5 s-1 at 10 mmol·L-1 HOAc concentration. In addition, the fungicidal activity of these complexes was also investigated in this study.
2026, 42(2): 365-374
doi: 10.11862/CJIC.20250222
Abstract:
A series of blue and blue-green Ir(Ⅲ) complexes has been investigated theoretically to explore their electronic structures, photophysical properties, efficiency roll-off effect, and thermal activation delayed fluorescence (TADF) properties. All calculations were performed using density functional theory (DFT) and time-dependent density functional theory (TDDFT). Calculations for electronic structures, frontier molecular orbital characteristics (which determine the efficiency roll-off effect of the complexes), and photophysical properties were conducted using the Gaussian 09 software package. The calculation of spin-orbit coupling matrix elements <T|HSOC|S>, which determine the TADF properties of the complexes, was performed using the ORCA software package. The calculation results show that the auxiliary ligand tetraphenylimidodiphosphinate (tpip), a strong electron-withdrawing group, can mitigate the efficiency roll-off effect of the complex. Furthermore, TADF is observed in one of the designed complexes, (F3Phppy)2Ir(tpip), where F3Phppy=2-[4-(2,4,6-trifluorophenyl)phenyl] pyridine.
A series of blue and blue-green Ir(Ⅲ) complexes has been investigated theoretically to explore their electronic structures, photophysical properties, efficiency roll-off effect, and thermal activation delayed fluorescence (TADF) properties. All calculations were performed using density functional theory (DFT) and time-dependent density functional theory (TDDFT). Calculations for electronic structures, frontier molecular orbital characteristics (which determine the efficiency roll-off effect of the complexes), and photophysical properties were conducted using the Gaussian 09 software package. The calculation of spin-orbit coupling matrix elements <T|HSOC|S>, which determine the TADF properties of the complexes, was performed using the ORCA software package. The calculation results show that the auxiliary ligand tetraphenylimidodiphosphinate (tpip), a strong electron-withdrawing group, can mitigate the efficiency roll-off effect of the complex. Furthermore, TADF is observed in one of the designed complexes, (F3Phppy)2Ir(tpip), where F3Phppy=2-[4-(2,4,6-trifluorophenyl)phenyl] pyridine.
2026, 42(2): 375-386
doi: 10.11862/CJIC.20250213
Abstract:
Herein, 3-aminopropyltriethoxysilane (APTES) was used to modify F-containing silica slag (SS) by simple grafting and served as a multifunctional barrier layer. The amino group (—NH2) in the amino-modified SS (NH2-SS) forms ligand bonds or hydrogen bonds with sulfur ions in lithium polysulfides (LiPSs), thus inhibiting the shuttle effect. Electrochemical analyses demonstrated that lithium-sulfur (Li-S) batteries employing the NH2-SS interlayer exhibited discharge specific capacities of 1 048 and 789 mAh·g-1 at 0.2C and 2C, respectively, and even at 4C, the initial discharge specific capacity remained at 590 mAh·g-1, outperforming the Li-S battery with unmodified SS as the interlayer.
Herein, 3-aminopropyltriethoxysilane (APTES) was used to modify F-containing silica slag (SS) by simple grafting and served as a multifunctional barrier layer. The amino group (—NH2) in the amino-modified SS (NH2-SS) forms ligand bonds or hydrogen bonds with sulfur ions in lithium polysulfides (LiPSs), thus inhibiting the shuttle effect. Electrochemical analyses demonstrated that lithium-sulfur (Li-S) batteries employing the NH2-SS interlayer exhibited discharge specific capacities of 1 048 and 789 mAh·g-1 at 0.2C and 2C, respectively, and even at 4C, the initial discharge specific capacity remained at 590 mAh·g-1, outperforming the Li-S battery with unmodified SS as the interlayer.
2026, 42(2): 387-397
doi: 10.11862/CJIC.20250211
Abstract:
Herein, manganese (Mn)-doped poly(1, 5-diaminonaphthalene) (PN) electrode material (Mn@PN) was synthesized via chemical oxidative polymerization. The material′s distinctive vesicular architecture enables rapid ion transport while maintaining the structural stability of the electrode under continuous charge-discharge cycles. Electrochemical characterization under a three-electrode system revealed exceptional rate capability: Mn@PN delivered an ultrahigh specific capacitance of 10 318 F·g-1 at a low current density of 3 A·g-1 and retained 9 415 F·g-1 (91.2% retention compared to the value at 3 A·g-1) even at an ultrahigh current density of 50 A·g-1. Moreover, the material exhibited 97.4% capacitance retention after 9 000 cycles at 30 A·g-1, corresponding with a low capacitance decay rate of 0.003‰ per cycle, significantly outperforming conventional conductive polymers like polyaniline (PANI). An asymmetric supercapacitor assembled with Mn@PN as the positive electrode (Mn@PN||AC) achieved an energy density of 328 Wh·kg-1 at 15 A·g-1 and retained 80.7% of its initial specific capacitance after 4 000 cycles at 20 A·g-1.
Herein, manganese (Mn)-doped poly(1, 5-diaminonaphthalene) (PN) electrode material (Mn@PN) was synthesized via chemical oxidative polymerization. The material′s distinctive vesicular architecture enables rapid ion transport while maintaining the structural stability of the electrode under continuous charge-discharge cycles. Electrochemical characterization under a three-electrode system revealed exceptional rate capability: Mn@PN delivered an ultrahigh specific capacitance of 10 318 F·g-1 at a low current density of 3 A·g-1 and retained 9 415 F·g-1 (91.2% retention compared to the value at 3 A·g-1) even at an ultrahigh current density of 50 A·g-1. Moreover, the material exhibited 97.4% capacitance retention after 9 000 cycles at 30 A·g-1, corresponding with a low capacitance decay rate of 0.003‰ per cycle, significantly outperforming conventional conductive polymers like polyaniline (PANI). An asymmetric supercapacitor assembled with Mn@PN as the positive electrode (Mn@PN||AC) achieved an energy density of 328 Wh·kg-1 at 15 A·g-1 and retained 80.7% of its initial specific capacitance after 4 000 cycles at 20 A·g-1.
2026, 42(2): 398-412
doi: 10.11862/CJIC.20250207
Abstract:
Herein, antibacterial silver-doped fluorescent carbon dots (Ag-CDs) were synthesized through a stepwise hydrothermal method, with polyethyleneimine (PEI), citric acid (CA), and silver nitrate (AgNO3) serving as precursors. The applicability and antimicrobial efficacy of these nanomaterials were systematically investigated for metal ion sensing. Experimental evidence demonstrated that the Ag-CDs exhibited a pronounced fluorescence quenching response toward ferric ions (Fe3+), enabling their quantitative determination via a linear concentration-dependent relationship. These Ag-CDs exhibited significant inhibitory effects on biofilm growth and disruption for both Escherichia coli and Staphylococcus aureus. Mechanism investigations indicate that Ag-CDs induced the death of Escherichia coli and Pseudomonas aeruginosa by disrupting their bacterial morphology and structure, triggering the generation of intracellular reactive oxygen species (ROS), and impairing their antioxidant defense system.
Herein, antibacterial silver-doped fluorescent carbon dots (Ag-CDs) were synthesized through a stepwise hydrothermal method, with polyethyleneimine (PEI), citric acid (CA), and silver nitrate (AgNO3) serving as precursors. The applicability and antimicrobial efficacy of these nanomaterials were systematically investigated for metal ion sensing. Experimental evidence demonstrated that the Ag-CDs exhibited a pronounced fluorescence quenching response toward ferric ions (Fe3+), enabling their quantitative determination via a linear concentration-dependent relationship. These Ag-CDs exhibited significant inhibitory effects on biofilm growth and disruption for both Escherichia coli and Staphylococcus aureus. Mechanism investigations indicate that Ag-CDs induced the death of Escherichia coli and Pseudomonas aeruginosa by disrupting their bacterial morphology and structure, triggering the generation of intracellular reactive oxygen species (ROS), and impairing their antioxidant defense system.
2026, 42(2): 413-427
doi: 10.11862/CJIC.20250183
Abstract:
An upconversion nanoparticle (NaErF4: Yb/Tm@NaLuF4: Yb@NaLuF4: Nd/Yb@NaLuF4, noted as UC) was designed, emitting strong red light by 808 nm laser. The mesoporous silica (mSiO2) shell co-doped with chlorin e6 (Ce6) and triethoxy(1H, 1H, 2H, 2H-nonafluorohexyl)silane (TFS) was coated on the outer layer of UC, and then a layer of HKUST-1 shell was coated. The obtained nanocomposite UC@Ce6/TFS@mSiO2@HKUST-1 (noted as UCTSH) was used for the synergistic treatment of chemodynamic therapy (CDT) and photodynamic therapy (PDT). Interestingly, the nanostructures can specifically re lease Cu2+ in the acidic tumor microenvironment. Cu2+ reacts with excess hydrogen peroxide (H2O2) in the tumor microenvironment to form cytotoxic hydroxyl radical. Secondly, Ce6, with the action of oxygen-carrying TFS, selectively produces a large amount of singlet oxygen by 808 nm laser irradiation. UCTSH can enhance the anti-tumor effects of PDT and CDT by increasing the production level of reactive oxygen species, without causing damage to normal cells.
An upconversion nanoparticle (NaErF4: Yb/Tm@NaLuF4: Yb@NaLuF4: Nd/Yb@NaLuF4, noted as UC) was designed, emitting strong red light by 808 nm laser. The mesoporous silica (mSiO2) shell co-doped with chlorin e6 (Ce6) and triethoxy(1H, 1H, 2H, 2H-nonafluorohexyl)silane (TFS) was coated on the outer layer of UC, and then a layer of HKUST-1 shell was coated. The obtained nanocomposite UC@Ce6/TFS@mSiO2@HKUST-1 (noted as UCTSH) was used for the synergistic treatment of chemodynamic therapy (CDT) and photodynamic therapy (PDT). Interestingly, the nanostructures can specifically re lease Cu2+ in the acidic tumor microenvironment. Cu2+ reacts with excess hydrogen peroxide (H2O2) in the tumor microenvironment to form cytotoxic hydroxyl radical. Secondly, Ce6, with the action of oxygen-carrying TFS, selectively produces a large amount of singlet oxygen by 808 nm laser irradiation. UCTSH can enhance the anti-tumor effects of PDT and CDT by increasing the production level of reactive oxygen species, without causing damage to normal cells.
2026, 42(2): 428-438
doi: 10.11862/CJIC.20250123
Abstract:
Chitosan (CTS) was grafted onto the surface of amino-functionalized silver chloride silicon dioxide (AgCl@SiO2-NH2) cores to obtain AgCl@SiO2/CTS hybrid nanoparticles. The as-obtained AgCl@SiO2/CTS nanoparticles were chlorinated by NaClO solution to get AgCl@SiO2/CTS-based chloramine nano-hybrid materials, denoted as AgCl@SiO2/CTS-Cl. A transmission electron microscope was used to observe the morphology of the as-prepared samples AgCl@SiO2/CTS and AgCl@SiO2/CTS-Cl. At the same time, an X-ray diffractometer and an infrared spectroscope were utilized to characterize their crystal and chemical structures. Besides, ζ potentials were measured to elucidate the surface modification of AgCl nanoparticles by —NH2, the antibacterial mechanism of AgCl@SiO2/CTS-Cl was investigated by scanning electron microscopy, and Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) were used as the to-be-tested strains to evaluate the antimicrobial activity of samples AgCl@SiO2/CTS and AgCl@SiO2/CTS-Cl. Findings demonstrate that sample AgCl@SiO2/CTS exhibits a chain-like structure ascribed to the interaction between —NH2, and each AgCl@SiO2/CTS hybrid nanoparticle contains several AgCl cores. In the meantime, sample AgCl@SiO2/CTS-Cl exhibits excellent antibacterial activity against E. coli and S. aureus, which is attributed to the synergistic antibacterial effect of Ag+ and Cl-. Sample AgCl@SiO2/CTS-Cl with a dosage of 640.00 μg·mL-1 could completely kill the two kinds of tested bacteria in 12 h of incubation; it retains a high antibacterial efficiency even after 10 cycles of antibacterial tests.
Chitosan (CTS) was grafted onto the surface of amino-functionalized silver chloride silicon dioxide (AgCl@SiO2-NH2) cores to obtain AgCl@SiO2/CTS hybrid nanoparticles. The as-obtained AgCl@SiO2/CTS nanoparticles were chlorinated by NaClO solution to get AgCl@SiO2/CTS-based chloramine nano-hybrid materials, denoted as AgCl@SiO2/CTS-Cl. A transmission electron microscope was used to observe the morphology of the as-prepared samples AgCl@SiO2/CTS and AgCl@SiO2/CTS-Cl. At the same time, an X-ray diffractometer and an infrared spectroscope were utilized to characterize their crystal and chemical structures. Besides, ζ potentials were measured to elucidate the surface modification of AgCl nanoparticles by —NH2, the antibacterial mechanism of AgCl@SiO2/CTS-Cl was investigated by scanning electron microscopy, and Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) were used as the to-be-tested strains to evaluate the antimicrobial activity of samples AgCl@SiO2/CTS and AgCl@SiO2/CTS-Cl. Findings demonstrate that sample AgCl@SiO2/CTS exhibits a chain-like structure ascribed to the interaction between —NH2, and each AgCl@SiO2/CTS hybrid nanoparticle contains several AgCl cores. In the meantime, sample AgCl@SiO2/CTS-Cl exhibits excellent antibacterial activity against E. coli and S. aureus, which is attributed to the synergistic antibacterial effect of Ag+ and Cl-. Sample AgCl@SiO2/CTS-Cl with a dosage of 640.00 μg·mL-1 could completely kill the two kinds of tested bacteria in 12 h of incubation; it retains a high antibacterial efficiency even after 10 cycles of antibacterial tests.
2026, 42(2): 227-236
doi: 10.11862/CJIC.20250279
Abstract:
Short-chain ligand ammonium hexafluorophosphate (NH4PF6) was used to modify the surface of CsPbI2Br perovskite quantum dots, thereby constructing a multifunctional interlayer between the perovskite light-absorbing layer and the carbon electrode. This strategy effectively passivated surface defects in the perovskite layer and synergistically improved the interfacial morphology. As a result, the carbon-based, all-inorganic perovskite solar cells fabricated using this approach exhibited a reduced defect density. They suppressed non-radiative recombination, leading to a notable increase in photoelectric conversion efficiency from 11.55% to 13.23%. Moreover, the unencapsulated device retained 82% of its initial efficiency after being stored for 600 h in a low-humidity environment.
Short-chain ligand ammonium hexafluorophosphate (NH4PF6) was used to modify the surface of CsPbI2Br perovskite quantum dots, thereby constructing a multifunctional interlayer between the perovskite light-absorbing layer and the carbon electrode. This strategy effectively passivated surface defects in the perovskite layer and synergistically improved the interfacial morphology. As a result, the carbon-based, all-inorganic perovskite solar cells fabricated using this approach exhibited a reduced defect density. They suppressed non-radiative recombination, leading to a notable increase in photoelectric conversion efficiency from 11.55% to 13.23%. Moreover, the unencapsulated device retained 82% of its initial efficiency after being stored for 600 h in a low-humidity environment.
2026, 42(2): 237-246
doi: 10.11862/CJIC.20250257
Abstract:
A NiFeP/NiFcDCA (FcDCA=1,1′-ferrocene dicarboxylic acid) heterojunction catalyst was loaded on the nickel foam (NF) using a hydrothermal method coupled with vapor-phase deposition phosphorization. Benefiting from the layered stacked heterogeneous nanostructure, abundant active sites, and efficient charge transfer rate, NiFeP/NiFcDCA@NF-350 prepared at a phosphorization temperature of 350 ℃ exhibited excellent urea oxidation reaction (UOR) activity in 1 mol·L-1 KOH+0.33 mol·L-1 urea solution. It achieved current densities of 100 and 500 mA·cm-2 at ultra-low voltages of 1.332 and 1.368 V (vs RHE), respectively. After a 50-hour stability test at a current density of 50 mA·cm-2, its performance decay was merely 0.54%, demonstrating excellent catalytic selectivity and good stability.
A NiFeP/NiFcDCA (FcDCA=1,1′-ferrocene dicarboxylic acid) heterojunction catalyst was loaded on the nickel foam (NF) using a hydrothermal method coupled with vapor-phase deposition phosphorization. Benefiting from the layered stacked heterogeneous nanostructure, abundant active sites, and efficient charge transfer rate, NiFeP/NiFcDCA@NF-350 prepared at a phosphorization temperature of 350 ℃ exhibited excellent urea oxidation reaction (UOR) activity in 1 mol·L-1 KOH+0.33 mol·L-1 urea solution. It achieved current densities of 100 and 500 mA·cm-2 at ultra-low voltages of 1.332 and 1.368 V (vs RHE), respectively. After a 50-hour stability test at a current density of 50 mA·cm-2, its performance decay was merely 0.54%, demonstrating excellent catalytic selectivity and good stability.
2026, 42(2): 247-262
doi: 10.11862/CJIC.20250255
Abstract:
Magnesium (Mg) was successfully incorporated into the ZSM-5 zeolite framework via hydrothermal synthesis, and its effects on pore structure, acidity, framework aluminum (AlF) distribution, and catalytic performance in bioethanol-to-propylene (ETP) conversion were systematically investigated. It was demonstrated that the mesopore volume was significantly enhanced while the crystallinity was slightly reduced with increasing Mg content. By temperature programmed desorption (NH3-TPD) and pyridine infrared (Py-IR) analyses, it was revealed that the total acid amount and strong acid strength were effectively decreased by Mg incorporation, while the Brønsted-to-Lewis acid ratio was increased. Through solid-state nuclear magnetic resonance (27Al MAS NMR) and UV-visible diffuse reflectance spectra (UV-Vis DRS) characterizations, it was indicated that the migration of AlF from channel intersections to sinusoidal or straight channels was promoted by Mg, and the formation of aluminum pairs (Alpair) was reduced. In the ETP reaction, the 2-MgHZ5 catalyst with moderate Mg modification demonstrated superior performance, exhibiting an enhanced propylene selectivity (29.5%) compared to the unmodified ZSM-5(HZ5) (26.8%), along with a twofold extension in the time during which the propylene selectivity was maintained at no less than 10% (30 vs 15 h for HZ5). This improved catalytic performance was attributed to its moderate acid strength, well-developed mesoporous structure, and optimized aluminum distribution, through which aromatization and coke formation were collectively suppressed while the olefin-cyclopentadiene cycle pathway was promoted.
Magnesium (Mg) was successfully incorporated into the ZSM-5 zeolite framework via hydrothermal synthesis, and its effects on pore structure, acidity, framework aluminum (AlF) distribution, and catalytic performance in bioethanol-to-propylene (ETP) conversion were systematically investigated. It was demonstrated that the mesopore volume was significantly enhanced while the crystallinity was slightly reduced with increasing Mg content. By temperature programmed desorption (NH3-TPD) and pyridine infrared (Py-IR) analyses, it was revealed that the total acid amount and strong acid strength were effectively decreased by Mg incorporation, while the Brønsted-to-Lewis acid ratio was increased. Through solid-state nuclear magnetic resonance (27Al MAS NMR) and UV-visible diffuse reflectance spectra (UV-Vis DRS) characterizations, it was indicated that the migration of AlF from channel intersections to sinusoidal or straight channels was promoted by Mg, and the formation of aluminum pairs (Alpair) was reduced. In the ETP reaction, the 2-MgHZ5 catalyst with moderate Mg modification demonstrated superior performance, exhibiting an enhanced propylene selectivity (29.5%) compared to the unmodified ZSM-5(HZ5) (26.8%), along with a twofold extension in the time during which the propylene selectivity was maintained at no less than 10% (30 vs 15 h for HZ5). This improved catalytic performance was attributed to its moderate acid strength, well-developed mesoporous structure, and optimized aluminum distribution, through which aromatization and coke formation were collectively suppressed while the olefin-cyclopentadiene cycle pathway was promoted.
2026, 42(2): 263-270
doi: 10.11862/CJIC.20250236
Abstract:
A series of orange-red phosphors based on La2(1-x)MgZrO6:2xSm3+ double perovskite (x=0.01-0.11) were successfully synthesized via the sol-gel method. X-ray diffraction (XRD) and scanning electron microscopy (SEM) characterizations confirmed that the as-prepared samples crystallize in a pure double perovskite structure, with Sm3+ ions homogeneously dispersed within the La2MgZrO6 host lattice without detectable impurity phases. Under 405 nm near-ultraviolet excitation, the phosphors exhibited characteristic emission spectra of Sm3+ ions. The optimum photoluminescence intensity was achieved at a Sm3+ doping concentration of 0.03, beyond which significant concentration quenching occurred. The CIE chromaticity coordinates and correlated color temperature for the optimal phosphor were determined to be (0.536 1, 0.452 6) and 2 177 K, respectively. Furthermore, the phosphor demonstrated excellent thermal stability: its emission intensity at 473 K retained 81% of the initial value measured at room temperature. The activation energy for thermal quenching, calculated to be 0.156 5 eV, further corroborated its superior thermal stability.
A series of orange-red phosphors based on La2(1-x)MgZrO6:2xSm3+ double perovskite (x=0.01-0.11) were successfully synthesized via the sol-gel method. X-ray diffraction (XRD) and scanning electron microscopy (SEM) characterizations confirmed that the as-prepared samples crystallize in a pure double perovskite structure, with Sm3+ ions homogeneously dispersed within the La2MgZrO6 host lattice without detectable impurity phases. Under 405 nm near-ultraviolet excitation, the phosphors exhibited characteristic emission spectra of Sm3+ ions. The optimum photoluminescence intensity was achieved at a Sm3+ doping concentration of 0.03, beyond which significant concentration quenching occurred. The CIE chromaticity coordinates and correlated color temperature for the optimal phosphor were determined to be (0.536 1, 0.452 6) and 2 177 K, respectively. Furthermore, the phosphor demonstrated excellent thermal stability: its emission intensity at 473 K retained 81% of the initial value measured at room temperature. The activation energy for thermal quenching, calculated to be 0.156 5 eV, further corroborated its superior thermal stability.
2026, 42(2): 271-283
doi: 10.11862/CJIC.20250230
Abstract:
Developing metal-based drugs that exhibit tumor selectivity, exert anti-proliferative effects, and minimize physiological toxicity remains a major challenge in leukemia therapy. In this study, two novel ruthenium- and iridium-based complexes (CS2-Ru and CS2-Ir) were synthesized by conjugating ruthenium/iridium metal precursors with the DHODH (dihydroorotate dehydrogenase) inhibitor CS2. CS2-Ru and CS2-Ir disrupt the intracellular redox balance in human acute promyelocytic leukemia cells (NB-4 cells) by elevating the levels of reactive oxygen species (ROS) and inducing mitochondrial membrane depolarization. In addition to these effects, the complexes also exert a dual-pathway inhibition (GPX4/DHODH) (GPX4=glutathione peroxidase 4), which leads to the abnormal accumulation of lipid peroxides to a lethal threshold and increases the sensitivity of NB-4 cells to ferroptosis.
Developing metal-based drugs that exhibit tumor selectivity, exert anti-proliferative effects, and minimize physiological toxicity remains a major challenge in leukemia therapy. In this study, two novel ruthenium- and iridium-based complexes (CS2-Ru and CS2-Ir) were synthesized by conjugating ruthenium/iridium metal precursors with the DHODH (dihydroorotate dehydrogenase) inhibitor CS2. CS2-Ru and CS2-Ir disrupt the intracellular redox balance in human acute promyelocytic leukemia cells (NB-4 cells) by elevating the levels of reactive oxygen species (ROS) and inducing mitochondrial membrane depolarization. In addition to these effects, the complexes also exert a dual-pathway inhibition (GPX4/DHODH) (GPX4=glutathione peroxidase 4), which leads to the abnormal accumulation of lipid peroxides to a lethal threshold and increases the sensitivity of NB-4 cells to ferroptosis.
2026, 42(2): 284-296
doi: 10.11862/CJIC.20250171
Abstract:
A series of Pr3+-doped Cd3Al2Ge3O12 orange phosphors was successfully synthesized using a high- temperature solid-state method, and alkali metal ions (Li+, Na+, K+) for charge compensation. Characterization methods, such as X-ray diffraction (XRD) and fluorescence spectroscopy, were used to study the crystal structure, luminescence properties, and thermal stability of the samples, respectively. The results showed that the doping of Pr3+ did not alter the crystal structure of the matrix, and co-doping with alkali metals did not cause phase heterogeneity. Under 450 nm excitation, the main peak of the emission spectrum was located at 613 nm; from the fluorescence emission spectra of Cd3-xAl2Ge3O12: xPr3+ (x=0.01-0.09) with different doping concentrations, it was found that the optimal doping concentration of Pr3+ was 0.03. The strategy of co-doping with alkali metal ions effectively improves the luminescent performance of the materials. Among them, the fluorescence intensity and lifetime of the Li+, Na+, and K+ co-doped phosphor series were significantly enhanced, surpassing the undoped samples. The enhancement effect of different alkali metal ion dopings follows the order of Li+, Na+, and K+, with the Li+ co-doped sample exhibiting the best luminescence intensity, which was 1.58 times that of the undoped system. Additionally, the thermal stability after charge compensation was investigated at 393 K, where the luminous intensity of the Li-compensated Cd2.94Al2Ge3O12: 0.03Pr3+, 0.03Li+ sample was 72.70% of that at 293 K. The CIE color coordinates confirmed that the emission of this phosphor was located in the orange region. Furthermore, the optimal sample was used to fabricate a white light-emitting diode, with CIE color coordinates of (0.368 2, 0.300 1), which lies within the white light circle.
A series of Pr3+-doped Cd3Al2Ge3O12 orange phosphors was successfully synthesized using a high- temperature solid-state method, and alkali metal ions (Li+, Na+, K+) for charge compensation. Characterization methods, such as X-ray diffraction (XRD) and fluorescence spectroscopy, were used to study the crystal structure, luminescence properties, and thermal stability of the samples, respectively. The results showed that the doping of Pr3+ did not alter the crystal structure of the matrix, and co-doping with alkali metals did not cause phase heterogeneity. Under 450 nm excitation, the main peak of the emission spectrum was located at 613 nm; from the fluorescence emission spectra of Cd3-xAl2Ge3O12: xPr3+ (x=0.01-0.09) with different doping concentrations, it was found that the optimal doping concentration of Pr3+ was 0.03. The strategy of co-doping with alkali metal ions effectively improves the luminescent performance of the materials. Among them, the fluorescence intensity and lifetime of the Li+, Na+, and K+ co-doped phosphor series were significantly enhanced, surpassing the undoped samples. The enhancement effect of different alkali metal ion dopings follows the order of Li+, Na+, and K+, with the Li+ co-doped sample exhibiting the best luminescence intensity, which was 1.58 times that of the undoped system. Additionally, the thermal stability after charge compensation was investigated at 393 K, where the luminous intensity of the Li-compensated Cd2.94Al2Ge3O12: 0.03Pr3+, 0.03Li+ sample was 72.70% of that at 293 K. The CIE color coordinates confirmed that the emission of this phosphor was located in the orange region. Furthermore, the optimal sample was used to fabricate a white light-emitting diode, with CIE color coordinates of (0.368 2, 0.300 1), which lies within the white light circle.
2026, 42(2): 297-308
doi: 10.11862/CJIC.20250214
Abstract:
A novel bifunctional fluorescent probe 1-methyl-2, 4-bis[2-(tert-butyldimethylsilyloxy)ethylurea]benzene (T1) based on urea-based coordination and Si—O bond cleavage was designed and synthesized for highly selective detection of Cr(Ⅵ) and F- in environmental and biological samples. The probe exhibited excellent recognition performance in dimethyl sulfoxide/water (DMSO/H2O, 1∶1, V/V) solvent. For Cr(Ⅵ) detection, T1 showed fluorescence quenching at 395 nm based on urea coordination with a detection limit of 4.70×10-7 mol·L-1, without interference from other metal ions. For F- recognition, the probe displayed significant fluorescence enhancement at 320 nm via Si—O bond cleavage mechanism with a detection limit of 7.07×10-8 mol·L-1, maintaining high selectivity in the presence of various anions. Spectroscopic analyses confirmed that T1 binds Cr(Ⅵ) in a 1∶2 stoichiometric ratio (Ka=2.62×104 L·mol-1) and reacts quantitatively with F- through Si—O bond cleavage in a molar ratio of 1∶2. The probe showed good linear response in the 0-20.00 μmol·L-1 range, providing an efficient analytical tool for environmental monitoring and biomedical detection.
A novel bifunctional fluorescent probe 1-methyl-2, 4-bis[2-(tert-butyldimethylsilyloxy)ethylurea]benzene (T1) based on urea-based coordination and Si—O bond cleavage was designed and synthesized for highly selective detection of Cr(Ⅵ) and F- in environmental and biological samples. The probe exhibited excellent recognition performance in dimethyl sulfoxide/water (DMSO/H2O, 1∶1, V/V) solvent. For Cr(Ⅵ) detection, T1 showed fluorescence quenching at 395 nm based on urea coordination with a detection limit of 4.70×10-7 mol·L-1, without interference from other metal ions. For F- recognition, the probe displayed significant fluorescence enhancement at 320 nm via Si—O bond cleavage mechanism with a detection limit of 7.07×10-8 mol·L-1, maintaining high selectivity in the presence of various anions. Spectroscopic analyses confirmed that T1 binds Cr(Ⅵ) in a 1∶2 stoichiometric ratio (Ka=2.62×104 L·mol-1) and reacts quantitatively with F- through Si—O bond cleavage in a molar ratio of 1∶2. The probe showed good linear response in the 0-20.00 μmol·L-1 range, providing an efficient analytical tool for environmental monitoring and biomedical detection.
2026, 42(2): 309-316
doi: 10.11862/CJIC.20250212
Abstract:
Two transition-metal-organic frameworks, {[Co2(L)2(4, 4′-bipy)2(H2O)4]·H2O}n (Co-MOF) and {[Mn(L)(4, 4′-bipy)0.5(H2O)2]·H2O}n (Mn-MOF), were prepared by solvothermal synthesis using 2, 5-dibromothiophene-3, 4- dicarboxylic acid (H2L) and 4, 4′-bipyridine (4, 4′-bipy) as ligands, respectively, with cobalt nitrate hexahydrate and manganese acetate tetrahydrate. Their structures and spectroscopic properties were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, infrared spectroscopy, UV-Vis spectroscopy, fluorescence spectroscopy, and thermogravimetric analysis methods. The results show that the Co(Ⅱ) of Co-MOF has two coordination forms: centrosymmetric and linear binuclear. The Co(Ⅱ) ions are all bridged by 4, 4′-bipy, extended into a 2D layered structure through hydrogen bonds, and finally, a 3D network structure is constructed by the cross- linking effect of interlayer hydrogen bonds. The Mn(Ⅱ) of Mn-MOF is connected into six-membered rings through L2- ligand bridges, with 4, 4′-bipy bridges between each six-membered ring. Additionally, L2- ligands are stacked along the c-axis to form a 3D honeycomb structure with two different 1D channels. These two distinct structural modes stem from the different coordination geometric configurations of the metal center.
Two transition-metal-organic frameworks, {[Co2(L)2(4, 4′-bipy)2(H2O)4]·H2O}n (Co-MOF) and {[Mn(L)(4, 4′-bipy)0.5(H2O)2]·H2O}n (Mn-MOF), were prepared by solvothermal synthesis using 2, 5-dibromothiophene-3, 4- dicarboxylic acid (H2L) and 4, 4′-bipyridine (4, 4′-bipy) as ligands, respectively, with cobalt nitrate hexahydrate and manganese acetate tetrahydrate. Their structures and spectroscopic properties were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, infrared spectroscopy, UV-Vis spectroscopy, fluorescence spectroscopy, and thermogravimetric analysis methods. The results show that the Co(Ⅱ) of Co-MOF has two coordination forms: centrosymmetric and linear binuclear. The Co(Ⅱ) ions are all bridged by 4, 4′-bipy, extended into a 2D layered structure through hydrogen bonds, and finally, a 3D network structure is constructed by the cross- linking effect of interlayer hydrogen bonds. The Mn(Ⅱ) of Mn-MOF is connected into six-membered rings through L2- ligand bridges, with 4, 4′-bipy bridges between each six-membered ring. Additionally, L2- ligands are stacked along the c-axis to form a 3D honeycomb structure with two different 1D channels. These two distinct structural modes stem from the different coordination geometric configurations of the metal center.
2026, 42(2): 317-330
doi: 10.11862/CJIC.20250199
Abstract:
To enhance the visible-light-driven photocatalytic performance of bismuth oxychloride/diatomite (BiOCl/D) composite photocatalysts, carbon quantum dots (CQDs) were introduced, and ternary CQDs/BiOCl/D composites were successfully constructed via a mild hydrolysis method. The CQDs/BiOCl/D composites were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) etc. The visible light photocatalytic performance of catalysts was evaluated using the antibiotic ciprofloxacin (CIP) in water, while the effects of CQDs addition on the photocatalytic performance of composites were also investigated. The results showed that irregular BiOCl microspheres in the CQDs/BiOCl/D composites were constructed through multilayer nanosheets, with a diameter of approximately 1 μm. The predominant exposed facet of BiOCl in CQDs/BiOCl/D composites was the (001) plane, which was dispersed on the surface of diatomite. Due to the relatively low quantity, the CQDs in the CQDs/BiOCl/D composites could not be observed in the SEM and TEM images. When the addition of CQDs accounted for 3% of the total catalyst, the adsorption rate of 3%CQDs/BiOCl/D for CIP was 55.0% after 30 min of dark treatment, and the CIP degradation rate was 90.1% after 90 min of visible light irradiation. At the same time, it was found that the antibacterial activity of CIP could be ignored after 80 min of irradiation. The dominant active species in the photocatalytic reaction of 3%CQDs/BiOCl/D were confirmed to be holes (h+), hydroxyl radicals (·OH), and superoxide radical (·O2-) by trapping agent experiments and electron spin resonance (EPR). The degradation intermediates were identified, and the photodegradation pathways were speculated by ultra-high performance liquid chromatography-mass spectrometry (UPLC-MS/MS). Finally, the photocatalytic degradation mechanism of 3%CQDs/ BiOCl/D was proposed based on the upconversion fluorescence properties of CQDs, as well as the steady-state and time-resolved transient fluorescence spectra and their corresponding photoelectrochemical performance tests of the catalysts. The enhanced photocatalytic performance of 3%CQDs/BiOCl/D was attributed to the upconversion, reception, or transfer of electrons (e-) and the photothermal effect of CQDs, as well as the synergistic effect among CQDs, diatomite, and BiOCl.
To enhance the visible-light-driven photocatalytic performance of bismuth oxychloride/diatomite (BiOCl/D) composite photocatalysts, carbon quantum dots (CQDs) were introduced, and ternary CQDs/BiOCl/D composites were successfully constructed via a mild hydrolysis method. The CQDs/BiOCl/D composites were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) etc. The visible light photocatalytic performance of catalysts was evaluated using the antibiotic ciprofloxacin (CIP) in water, while the effects of CQDs addition on the photocatalytic performance of composites were also investigated. The results showed that irregular BiOCl microspheres in the CQDs/BiOCl/D composites were constructed through multilayer nanosheets, with a diameter of approximately 1 μm. The predominant exposed facet of BiOCl in CQDs/BiOCl/D composites was the (001) plane, which was dispersed on the surface of diatomite. Due to the relatively low quantity, the CQDs in the CQDs/BiOCl/D composites could not be observed in the SEM and TEM images. When the addition of CQDs accounted for 3% of the total catalyst, the adsorption rate of 3%CQDs/BiOCl/D for CIP was 55.0% after 30 min of dark treatment, and the CIP degradation rate was 90.1% after 90 min of visible light irradiation. At the same time, it was found that the antibacterial activity of CIP could be ignored after 80 min of irradiation. The dominant active species in the photocatalytic reaction of 3%CQDs/BiOCl/D were confirmed to be holes (h+), hydroxyl radicals (·OH), and superoxide radical (·O2-) by trapping agent experiments and electron spin resonance (EPR). The degradation intermediates were identified, and the photodegradation pathways were speculated by ultra-high performance liquid chromatography-mass spectrometry (UPLC-MS/MS). Finally, the photocatalytic degradation mechanism of 3%CQDs/ BiOCl/D was proposed based on the upconversion fluorescence properties of CQDs, as well as the steady-state and time-resolved transient fluorescence spectra and their corresponding photoelectrochemical performance tests of the catalysts. The enhanced photocatalytic performance of 3%CQDs/BiOCl/D was attributed to the upconversion, reception, or transfer of electrons (e-) and the photothermal effect of CQDs, as well as the synergistic effect among CQDs, diatomite, and BiOCl.
