Login In
2025 Volume 41 Issue 12
2025, 41(12): 2411-2428
doi: 10.11862/CJIC.20250142
Abstract:
Layered oxides have received extensive attention in the field of sodium-ion battery (SIB) due to their high theoretical capacity and ease of synthesis. However, the complex phase transitions caused by interlayer slip in layered oxides result in poor cycling stability, which limits their further application. The high-entropy strategy, which provides stable local structures, robust framework structures, and multifunctionality, is regarded as an effective means to modify sodium-ion layered cathode materials. This paper, by combining the research of our group in recent years and important domestic and international literature, reviews the latest research achievements of sodium-ion high-entropy layered oxide cathode materials from two aspects: synthesis methods and structure design. It deeply discusses the effects of synthesis methods (solid-phase method, sol-gel method, hydrothermal method, and coprecipitation method) and structure design (P2, O3, P2/O3, P2/P3, and P3/O3 types) on the structure and sodium storage performance of sodium-ion high-entropy layered oxides. Finally, the development of sodium-ion high-entropy layered oxides in the SIB field is prospectively discussed.
Layered oxides have received extensive attention in the field of sodium-ion battery (SIB) due to their high theoretical capacity and ease of synthesis. However, the complex phase transitions caused by interlayer slip in layered oxides result in poor cycling stability, which limits their further application. The high-entropy strategy, which provides stable local structures, robust framework structures, and multifunctionality, is regarded as an effective means to modify sodium-ion layered cathode materials. This paper, by combining the research of our group in recent years and important domestic and international literature, reviews the latest research achievements of sodium-ion high-entropy layered oxide cathode materials from two aspects: synthesis methods and structure design. It deeply discusses the effects of synthesis methods (solid-phase method, sol-gel method, hydrothermal method, and coprecipitation method) and structure design (P2, O3, P2/O3, P2/P3, and P3/O3 types) on the structure and sodium storage performance of sodium-ion high-entropy layered oxides. Finally, the development of sodium-ion high-entropy layered oxides in the SIB field is prospectively discussed.
2025, 41(12): 2429-2440
doi: 10.11862/CJIC.20250242
Abstract:
Photocatalytic CO2 cycloaddition reaction presents a promising CO2 conversion strategy to establish carbon neutrality. Among emerging catalysts, metal-organic frameworks (MOFs) have been regarded as paradigm-shifting photocatalysts for their atomic precision in active site engineering, controllable porosity, and exceptional photochemical stability under ambient conditions. However, inherent limitations persist in conventional MOFs, including restricted solar spectrum utilization, inefficient charge carrier separation, and inadequate epoxide activation ability. Recent breakthroughs address these challenges through multiple strategies: ligand engineering, dopant incorporation, and composite construction. This review systematically maps the evolutionary trajectory of MOF-based photocatalysts, providing mechanistic insights into structure-activity relationships and providing insights and directions for the design of high-performance MOF-based photocatalysts.
Photocatalytic CO2 cycloaddition reaction presents a promising CO2 conversion strategy to establish carbon neutrality. Among emerging catalysts, metal-organic frameworks (MOFs) have been regarded as paradigm-shifting photocatalysts for their atomic precision in active site engineering, controllable porosity, and exceptional photochemical stability under ambient conditions. However, inherent limitations persist in conventional MOFs, including restricted solar spectrum utilization, inefficient charge carrier separation, and inadequate epoxide activation ability. Recent breakthroughs address these challenges through multiple strategies: ligand engineering, dopant incorporation, and composite construction. This review systematically maps the evolutionary trajectory of MOF-based photocatalysts, providing mechanistic insights into structure-activity relationships and providing insights and directions for the design of high-performance MOF-based photocatalysts.
2025, 41(12): 2441-2454
doi: 10.11862/CJIC.20250264
Abstract:
A novel composite material, ALBC@nZVI, was synthesized by loading nano zero-valent iron (nZVI) onto activated luffa-derived biochar (ALBC) via in-situ liquid-phase reduction. The ALBC was prepared through pyrolysis of natural porous luffa sponge at 600 ℃, followed by KOH activation at 800 ℃. The composite was characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), and Fourier transform infrared (FTIR) spectrometer, confirming the porous structure of ALBC and uniform dispersion of nZVI on its surface. The Cr(Ⅵ) removal performance was systematically investigated under varying pH values (2-8), adsorbent dosage (0.25-2.0 g·L-1), and reaction time (0-360 min). Results showed that ALBC@nZVI achieved a maximum adsorption capacity of 95.27 mg·g-1 and a removal efficiency of 95% at a pH of 2, with an adsorbent dosage of 1.00 g·L-1 and an initial Cr(Ⅵ) mass concentration of 100 mg·L-1. The adsorption process followed the Langmuir isotherm and pseudo-second-order kinetics, indicating monolayer chemisorption. X-ray photoelectron spectrometer (XPS) analysis reveals that the removal of Cr(Ⅵ) is synergistically driven by multidimensional mechanisms, including electrostatic attraction, redox reactions, and surface complexation-coprecipitation. The ALBC@nZVI exhibits the advantages of high adsorption performance, strong reducibility, and rapid magnetic separability (The specific saturation magnetization was 23.4 emu·g-1).
A novel composite material, ALBC@nZVI, was synthesized by loading nano zero-valent iron (nZVI) onto activated luffa-derived biochar (ALBC) via in-situ liquid-phase reduction. The ALBC was prepared through pyrolysis of natural porous luffa sponge at 600 ℃, followed by KOH activation at 800 ℃. The composite was characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), and Fourier transform infrared (FTIR) spectrometer, confirming the porous structure of ALBC and uniform dispersion of nZVI on its surface. The Cr(Ⅵ) removal performance was systematically investigated under varying pH values (2-8), adsorbent dosage (0.25-2.0 g·L-1), and reaction time (0-360 min). Results showed that ALBC@nZVI achieved a maximum adsorption capacity of 95.27 mg·g-1 and a removal efficiency of 95% at a pH of 2, with an adsorbent dosage of 1.00 g·L-1 and an initial Cr(Ⅵ) mass concentration of 100 mg·L-1. The adsorption process followed the Langmuir isotherm and pseudo-second-order kinetics, indicating monolayer chemisorption. X-ray photoelectron spectrometer (XPS) analysis reveals that the removal of Cr(Ⅵ) is synergistically driven by multidimensional mechanisms, including electrostatic attraction, redox reactions, and surface complexation-coprecipitation. The ALBC@nZVI exhibits the advantages of high adsorption performance, strong reducibility, and rapid magnetic separability (The specific saturation magnetization was 23.4 emu·g-1).
2025, 41(12): 2455-2463
doi: 10.11862/CJIC.20250220
Abstract:
Under solvothermal synthetic conditions, this study employed the organic carboxylic acid ligand containing amino groups, 4, 4′-diamino-[1, 1′-biphenyl]-3, 3′, 5, 5′-tetracarboxylic acid (H4L), to react with Mg2+ ions, resulting in the preparation of a novel three-dimensional metal-organic framework: {[Mg2(L)(DMA)(H2O)2]·2DMA·H2O}n (Mg-MOF, DMA=N, N-dimethyl acetamide). The structure and stability of Mg-MOF were determined by single-crystal X-ray diffraction, elemental analysis, thermogravimetric analysis, and so on, and the CO2 adsorption and catalytic conversion properties were also deeply investigated. The results indicate that Mg-MOF crystallizes in the monoclinic system with space group P21/n, unit cell parameters a=1.399 88(15) nm, b=1.400 49(15) nm, c=1.768 57(19) nm, β=94.307(2)°. Mg-MOF shows a 4-connected (42·84)-ant topological net, possessing one-dimensional channels decorated with amino groups. It reveals excellent adsorption selectivity for CO2 over CH4 and CO (18.7-19.9 and 8.9-9.5, respectively), as well as highly efficient catalytic performance for the conversion of CO2 and epoxides into cyclic carbonates at the condition of 298 K and 100 kPa.
Under solvothermal synthetic conditions, this study employed the organic carboxylic acid ligand containing amino groups, 4, 4′-diamino-[1, 1′-biphenyl]-3, 3′, 5, 5′-tetracarboxylic acid (H4L), to react with Mg2+ ions, resulting in the preparation of a novel three-dimensional metal-organic framework: {[Mg2(L)(DMA)(H2O)2]·2DMA·H2O}n (Mg-MOF, DMA=N, N-dimethyl acetamide). The structure and stability of Mg-MOF were determined by single-crystal X-ray diffraction, elemental analysis, thermogravimetric analysis, and so on, and the CO2 adsorption and catalytic conversion properties were also deeply investigated. The results indicate that Mg-MOF crystallizes in the monoclinic system with space group P21/n, unit cell parameters a=1.399 88(15) nm, b=1.400 49(15) nm, c=1.768 57(19) nm, β=94.307(2)°. Mg-MOF shows a 4-connected (42·84)-ant topological net, possessing one-dimensional channels decorated with amino groups. It reveals excellent adsorption selectivity for CO2 over CH4 and CO (18.7-19.9 and 8.9-9.5, respectively), as well as highly efficient catalytic performance for the conversion of CO2 and epoxides into cyclic carbonates at the condition of 298 K and 100 kPa.
2025, 41(12): 2464-2478
doi: 10.11862/CJIC.20250191
Abstract:
Polyvinylidene fluoride (PVDF) was used as the burial interface between the electron transport layer (ETL) and CsPbBr3. Due to the interaction between F contained in PVDF and Pb2+ in CsPbBr3, the interaction between the two provides enough nucleation sites for the growth of PbBr2 crystals, which can improve the morphology of PbBr2 films and promote the reaction between PbBr2 and CsBr, providing a framework for the growth of perovskite films, and ultimately obtain high-quality CsPbBr3 perovskite films. As a result, the device with 1 mg·mL-1 PVDF for buried interface modification could achieve the best champion performance among the CsPbBr3 perovskite solar cells (PSCs). The maximum open-circuit voltage (VOC) reached 1.59 V, the short circuit current density (JSC) was 7.43 mA·cm-2, the fill factor (FF) was 79.69% and the power conversion efficiency (PCE) reached 9.41%. After being exposed to the atmospheric environment for 30 d, the PCE of the device still maintained at 99.4% of the initial value.
Polyvinylidene fluoride (PVDF) was used as the burial interface between the electron transport layer (ETL) and CsPbBr3. Due to the interaction between F contained in PVDF and Pb2+ in CsPbBr3, the interaction between the two provides enough nucleation sites for the growth of PbBr2 crystals, which can improve the morphology of PbBr2 films and promote the reaction between PbBr2 and CsBr, providing a framework for the growth of perovskite films, and ultimately obtain high-quality CsPbBr3 perovskite films. As a result, the device with 1 mg·mL-1 PVDF for buried interface modification could achieve the best champion performance among the CsPbBr3 perovskite solar cells (PSCs). The maximum open-circuit voltage (VOC) reached 1.59 V, the short circuit current density (JSC) was 7.43 mA·cm-2, the fill factor (FF) was 79.69% and the power conversion efficiency (PCE) reached 9.41%. After being exposed to the atmospheric environment for 30 d, the PCE of the device still maintained at 99.4% of the initial value.
2025, 41(12): 2479-2490
doi: 10.11862/CJIC.20250181
Abstract:
Leveraging the synergistic effects of atomically dispersed metallic active sites and N, O co-doped carbon substrate, an atomically dispersed heteronuclear bimetallic single-atom electrocatalyst (Co/Ni-SACs) was designed and synthesized for highly selective electrocatalytic two-electron oxygen reduction reaction (ORR) to produce H2O2. Compared to monometallic single-atom catalysts, Co/Ni-SACs exhibited significantly enhanced electrocatalytic ORR activity and selectivity to two-electron ORR. The H2O2 selectivity of Co/Ni-SACs reached approximately 80% within the potential range of 0-0.6 V (vs RHE). At the optimal potential of 0.4 V (vs RHE), the H2O2 yield achieved a maximum of ca. 1.88 mol·L-1·gcat-1·cm-2 over 4.5 h of electrolysis, along with stable current response, selectivity, and recyclability. Furthermore, a dual-cathode electro-Fenton system was constructed using Co/Ni-SACs and stainless-steel mesh (SSM) without additional reagents, enabling efficient activation of in-situ-generated H2O2 to produce highly oxidative hydroxyl radicals (·OH). This system achieved effective degradation of various organic pollutants (e.g., dyes, antibiotics) and detoxification of heavy metal Cr(Ⅵ).
Leveraging the synergistic effects of atomically dispersed metallic active sites and N, O co-doped carbon substrate, an atomically dispersed heteronuclear bimetallic single-atom electrocatalyst (Co/Ni-SACs) was designed and synthesized for highly selective electrocatalytic two-electron oxygen reduction reaction (ORR) to produce H2O2. Compared to monometallic single-atom catalysts, Co/Ni-SACs exhibited significantly enhanced electrocatalytic ORR activity and selectivity to two-electron ORR. The H2O2 selectivity of Co/Ni-SACs reached approximately 80% within the potential range of 0-0.6 V (vs RHE). At the optimal potential of 0.4 V (vs RHE), the H2O2 yield achieved a maximum of ca. 1.88 mol·L-1·gcat-1·cm-2 over 4.5 h of electrolysis, along with stable current response, selectivity, and recyclability. Furthermore, a dual-cathode electro-Fenton system was constructed using Co/Ni-SACs and stainless-steel mesh (SSM) without additional reagents, enabling efficient activation of in-situ-generated H2O2 to produce highly oxidative hydroxyl radicals (·OH). This system achieved effective degradation of various organic pollutants (e.g., dyes, antibiotics) and detoxification of heavy metal Cr(Ⅵ).
2025, 41(12): 2491-2502
doi: 10.11862/CJIC.20250176
Abstract:
Conductive polypyrrole (PPy) with a lithiophilic site was confined to Co-MOF-74 pores by in situ polymerization strategy to prepare PPy@Co-MOF-74 (PPM), which was used for Cu electrode modification. This architecture achieves dual synergy. PPy effectively suppresses lithium dendrite growth via reduced lithium nucleation overpotential. Meanwhile, the 3D porous framework of Co-MOF-74 provides spatial buffering for lithium deposition to significantly alleviate volume expansion. Electrochemical test results demonstrated remarkable performance enhancements, with the modified PPM@Cu electrode achieving 250 stable cycles at 1 mA·cm-2 and 1 mAh·cm-2 in half-cell configuration. When it was paired with LiFePO4 (LFP) cathodes in full-cell tests, the system maintained 89% capacity retention after 350 cycles.
Conductive polypyrrole (PPy) with a lithiophilic site was confined to Co-MOF-74 pores by in situ polymerization strategy to prepare PPy@Co-MOF-74 (PPM), which was used for Cu electrode modification. This architecture achieves dual synergy. PPy effectively suppresses lithium dendrite growth via reduced lithium nucleation overpotential. Meanwhile, the 3D porous framework of Co-MOF-74 provides spatial buffering for lithium deposition to significantly alleviate volume expansion. Electrochemical test results demonstrated remarkable performance enhancements, with the modified PPM@Cu electrode achieving 250 stable cycles at 1 mA·cm-2 and 1 mAh·cm-2 in half-cell configuration. When it was paired with LiFePO4 (LFP) cathodes in full-cell tests, the system maintained 89% capacity retention after 350 cycles.
2025, 41(12): 2503-2513
doi: 10.11862/CJIC.20250169
Abstract:
A core-shell structured Fe3O4@MIL-100(Fe) composite was synthesized via a solid-phase conversion method, in which the surface of Fe3O4 nanoparticles was partially transformed into the photocatalytically active iron-based metal-organic framework MIL-100(Fe). The photoinduced electrons from MIL-100(Fe) promote the rapid conversion of Fe3+ to Fe2+ in Fe3O4, while the high specific surface area of MIL-100(Fe) enhances the adsorption capacity of the composite toward antibiotic molecules. By controlling the extent of conversion from Fe3O4 to MIL-100(Fe), the synergistic effect between the two was optimized, leading to enhanced performance in the photocatalytic activation of persulfate for antibiotic degradation. The optimal Fe3O4@MIL-100(Fe) composite exhibited a high specific surface area of 406 m2·g-1, achieved a degradation efficiency of 83.0% within 50 min under photocatalytic conditions, and demonstrated high stability over five consecutive recycling tests.
A core-shell structured Fe3O4@MIL-100(Fe) composite was synthesized via a solid-phase conversion method, in which the surface of Fe3O4 nanoparticles was partially transformed into the photocatalytically active iron-based metal-organic framework MIL-100(Fe). The photoinduced electrons from MIL-100(Fe) promote the rapid conversion of Fe3+ to Fe2+ in Fe3O4, while the high specific surface area of MIL-100(Fe) enhances the adsorption capacity of the composite toward antibiotic molecules. By controlling the extent of conversion from Fe3O4 to MIL-100(Fe), the synergistic effect between the two was optimized, leading to enhanced performance in the photocatalytic activation of persulfate for antibiotic degradation. The optimal Fe3O4@MIL-100(Fe) composite exhibited a high specific surface area of 406 m2·g-1, achieved a degradation efficiency of 83.0% within 50 min under photocatalytic conditions, and demonstrated high stability over five consecutive recycling tests.
2025, 41(12): 2514-2526
doi: 10.11862/CJIC.20250163
Abstract:
MnO2 powders doped with different ratios of Ce ions are synthesized by hydrothermal method. X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption-desorption, cyclic voltammetry, constant-current charge/discharge, and electrochemical impedance spectroscopy tests were used to analyze the structural, morphological, and electrochemical properties. The results showed that after doping with Ce ions, the specific surface area of MnO2 increased, the number of oxygen vacancies rose, and the structure became more stable; therefore, the electrode demonstrated more excellent electrochemical performance. The specific capacitance of the optimal sample C6M (the molar ratio of the introduced Ce to the theoretical generation MnO2 was 6%) could reach 192.6 F·g-1 at 1 A·g-1. When the current density increased from 1 to 10 A·g-1, the retention rate of the specific capacitance was 86.4%. After 5 000 cycles at 10 A·g-1, the retention rate of specific capacitance was 83.3%.
MnO2 powders doped with different ratios of Ce ions are synthesized by hydrothermal method. X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption-desorption, cyclic voltammetry, constant-current charge/discharge, and electrochemical impedance spectroscopy tests were used to analyze the structural, morphological, and electrochemical properties. The results showed that after doping with Ce ions, the specific surface area of MnO2 increased, the number of oxygen vacancies rose, and the structure became more stable; therefore, the electrode demonstrated more excellent electrochemical performance. The specific capacitance of the optimal sample C6M (the molar ratio of the introduced Ce to the theoretical generation MnO2 was 6%) could reach 192.6 F·g-1 at 1 A·g-1. When the current density increased from 1 to 10 A·g-1, the retention rate of the specific capacitance was 86.4%. After 5 000 cycles at 10 A·g-1, the retention rate of specific capacitance was 83.3%.
2025, 41(12): 2527-2535
doi: 10.11862/CJIC.20250151
Abstract:
A heterometallic polynuclear complex, [NdCo6(py)6(aib)6(μ3-O)3(NO3)3]·H2O (NdCo6-py), was synthesized through a layered diffusion method utilizing 2-aminoisobutyric acid (Haib) and pyridine (py) as coordinating ligands. Single-crystal X-ray diffraction reveals its unique architecture featuring a trigonal prismatic [NdCo6] core, where the central Nd3⁺ ion is encapsulated between two parallel, nearly equilateral Co3 triangles. This cage-like structure stabilizes the Nd3⁺ center while exposing multiple metal sites at the periphery. Electrocatalytic studies demonstrate that NdCo6-py exhibits remarkable catalytic activity towards the oxygen evolution reaction (OER), achieving a high turnover frequency (TOF) of 279 s⁻1 and Faradaic efficiency of 92.6% at 1.60 V (vs NHE). This exceptional electrocatalytic performance is attributed to the readily accessible bimetallic synergistic active sites within the cluster framework. These sites facilitate the O—O bond formation step through a cooperative mechanism, effectively mitigating the formation of high-valent metal intermediates and consequently lowering the reaction overpotential. These findings provide compelling evidence for the efficacy of the polymetallic synergistic catalysis strategy in modulating the O—O bond formation pathway.
A heterometallic polynuclear complex, [NdCo6(py)6(aib)6(μ3-O)3(NO3)3]·H2O (NdCo6-py), was synthesized through a layered diffusion method utilizing 2-aminoisobutyric acid (Haib) and pyridine (py) as coordinating ligands. Single-crystal X-ray diffraction reveals its unique architecture featuring a trigonal prismatic [NdCo6] core, where the central Nd3⁺ ion is encapsulated between two parallel, nearly equilateral Co3 triangles. This cage-like structure stabilizes the Nd3⁺ center while exposing multiple metal sites at the periphery. Electrocatalytic studies demonstrate that NdCo6-py exhibits remarkable catalytic activity towards the oxygen evolution reaction (OER), achieving a high turnover frequency (TOF) of 279 s⁻1 and Faradaic efficiency of 92.6% at 1.60 V (vs NHE). This exceptional electrocatalytic performance is attributed to the readily accessible bimetallic synergistic active sites within the cluster framework. These sites facilitate the O—O bond formation step through a cooperative mechanism, effectively mitigating the formation of high-valent metal intermediates and consequently lowering the reaction overpotential. These findings provide compelling evidence for the efficacy of the polymetallic synergistic catalysis strategy in modulating the O—O bond formation pathway.
2025, 41(12): 2536-2548
doi: 10.11862/CJIC.20250138
Abstract:
Based on the hydrogen bonding self-assembly strategy, a sodium acetate (NaAc) regulated high loading carrier-free nanodrug (MIT-DOX/NaAc, MIDA) was fabricated by employing a nano-coprecipitation method, which used mitoxantrone (MIT) and doxorubicin (DOX) as antitumor drug models. MIDA successfully formed with a maximum loading efficiency (95%), and the in vitro drug release showed that MIDA is pH-responsive. Excitingly, cytotoxicity and scratch migration assessments demonstrated that MIDA could target tumor cells through the enhanced permeability and retention effect (EPR), subsequently inhibiting the migration and proliferation of human breast carcinoma cells (MCF-7). The efficacy was higher than that of free DOX, MIT, and DOX/NaAc. Examination by fluorescence microscopy and flow cytometry showed that the uptake of MIDA by MCF-7 was time-dependent. In addition, MIDA could enter MCF-7 via both the clathrin and caveolae co-mediated endocytosis pathways, and then the dissociated MIT and DOX migrated into the nucleus to induce MCF-7 late apoptosis.
Based on the hydrogen bonding self-assembly strategy, a sodium acetate (NaAc) regulated high loading carrier-free nanodrug (MIT-DOX/NaAc, MIDA) was fabricated by employing a nano-coprecipitation method, which used mitoxantrone (MIT) and doxorubicin (DOX) as antitumor drug models. MIDA successfully formed with a maximum loading efficiency (95%), and the in vitro drug release showed that MIDA is pH-responsive. Excitingly, cytotoxicity and scratch migration assessments demonstrated that MIDA could target tumor cells through the enhanced permeability and retention effect (EPR), subsequently inhibiting the migration and proliferation of human breast carcinoma cells (MCF-7). The efficacy was higher than that of free DOX, MIT, and DOX/NaAc. Examination by fluorescence microscopy and flow cytometry showed that the uptake of MIDA by MCF-7 was time-dependent. In addition, MIDA could enter MCF-7 via both the clathrin and caveolae co-mediated endocytosis pathways, and then the dissociated MIT and DOX migrated into the nucleus to induce MCF-7 late apoptosis.
2025, 41(12): 2549-2560
doi: 10.11862/CJIC.20250120
Abstract:
N and Mn modified semi-cake activated carbon (SC) catalysts (NxMny-SC, x∶y was the mass ratio of N and Mn) were synthesized via an impregnation method and applied in the catalytic ozonation of tetracycline hydrochloride (TC) in aqueous solution. The results demonstrated that the manganese loading amount was positively correlated with both surface Mn content and structural disorder. The catalyst N1Mn3-SC prepared with an N and Mn mass ratio of 1∶3 exhibited the optimal catalytic performance. The effects of reaction conditions on degradation efficiency were systematically investigated. Increasing catalyst dosage, ozone (O3) flow rate, and reaction temperature promoted TC degradation, whereas a high initial TC concentration inhibited the process. The influence of solution pH showed a promoting-inhibiting transition with increasing pH values, with the best performance achieved at pH 7. Under the optimal conditions (catalyst: 200 mg·L-1, TC: 30 mg·L-1, pH: 7, temperature: 25 ℃, O3 flow rate: 30 mL·min-1), N1Mn3-SC achieved 93.46% degradation rate of TC within 20 min, with a pseudo-first-order reaction rate constant of 0.138 2 min-1, significantly higher than that of pristine semi-coke (0.080 1 min-1). The presence of humic acid, HCO3-, and Cl- slightly suppressed degradation due to competitive consumption of hydroxyl radical (·OH). After five consecutive reaction cycles, the degradation efficiency remained at 84.13%, although the specific surface area decreased to 21 m2·g-1. A reduction in surface Mn, N, and oxygen-containing functional groups was observed, along with a decrease in the intensity ratio (ID/IG) of defect to graphitized Raman peaks intensity to 0.983, indicating increased structural ordering. Radical quenching experiments confirmed the involvement of ·OH, superoxide radical (·O2-), and singlet state oxygen (1O2) in the catalytic process. Intermediate analysis suggested that TC degradation primarily proceeded via dealkylation and deamidation pathways, leading to eventual mineralization into CO2 and H2O.
N and Mn modified semi-cake activated carbon (SC) catalysts (NxMny-SC, x∶y was the mass ratio of N and Mn) were synthesized via an impregnation method and applied in the catalytic ozonation of tetracycline hydrochloride (TC) in aqueous solution. The results demonstrated that the manganese loading amount was positively correlated with both surface Mn content and structural disorder. The catalyst N1Mn3-SC prepared with an N and Mn mass ratio of 1∶3 exhibited the optimal catalytic performance. The effects of reaction conditions on degradation efficiency were systematically investigated. Increasing catalyst dosage, ozone (O3) flow rate, and reaction temperature promoted TC degradation, whereas a high initial TC concentration inhibited the process. The influence of solution pH showed a promoting-inhibiting transition with increasing pH values, with the best performance achieved at pH 7. Under the optimal conditions (catalyst: 200 mg·L-1, TC: 30 mg·L-1, pH: 7, temperature: 25 ℃, O3 flow rate: 30 mL·min-1), N1Mn3-SC achieved 93.46% degradation rate of TC within 20 min, with a pseudo-first-order reaction rate constant of 0.138 2 min-1, significantly higher than that of pristine semi-coke (0.080 1 min-1). The presence of humic acid, HCO3-, and Cl- slightly suppressed degradation due to competitive consumption of hydroxyl radical (·OH). After five consecutive reaction cycles, the degradation efficiency remained at 84.13%, although the specific surface area decreased to 21 m2·g-1. A reduction in surface Mn, N, and oxygen-containing functional groups was observed, along with a decrease in the intensity ratio (ID/IG) of defect to graphitized Raman peaks intensity to 0.983, indicating increased structural ordering. Radical quenching experiments confirmed the involvement of ·OH, superoxide radical (·O2-), and singlet state oxygen (1O2) in the catalytic process. Intermediate analysis suggested that TC degradation primarily proceeded via dealkylation and deamidation pathways, leading to eventual mineralization into CO2 and H2O.
2025, 41(12): 2561-2574
doi: 10.11862/CJIC.20250104
Abstract:
This study presents an integrated optimization strategy that synergistically combines response surface method(RSM) with orthogonal experimental design to achieve efficient performance enhancement of photocatalytic materials. The development of a carbon-doped bismuth vanadate (C-BiVO4) photocatalytic system was employed in this strategy. Orthogonal experiments identified glucose addition as the most significant influencing factor (P is used to determine the significance of factors, P=0.016 1). RSM was used to establish a quantitative relationship between process parameters and photocatalytic performance. The experimental results revealed that 0.9%C-BiVO4-10, prepared under the conditions of a reaction time of 12 h, temperature of 100 ℃, a volume ratio of HNO3 to H2O of 1.25∶1, and glucose addition of 0.01 g, achieved a tetracycline (TC) degradation efficiency of 80.07% under visible light irradiation. X-ray diffraction (XRD), Raman spectrum, and scanning electron microscopy (SEM) analyses demonstrated that carbon doping promotes the phase transition from tetragonal to monoclinic structures and facilitates the formation of regular sheet-like morphologies, thereby increasing active sites. Photoelectrochemical tests further confirmed that doping broadened the light absorption range, reduced carrier recombination rates, and decreased interfacial charge transfer resistance, significantly improving the photocatalytic performance of BiVO4.
This study presents an integrated optimization strategy that synergistically combines response surface method(RSM) with orthogonal experimental design to achieve efficient performance enhancement of photocatalytic materials. The development of a carbon-doped bismuth vanadate (C-BiVO4) photocatalytic system was employed in this strategy. Orthogonal experiments identified glucose addition as the most significant influencing factor (P is used to determine the significance of factors, P=0.016 1). RSM was used to establish a quantitative relationship between process parameters and photocatalytic performance. The experimental results revealed that 0.9%C-BiVO4-10, prepared under the conditions of a reaction time of 12 h, temperature of 100 ℃, a volume ratio of HNO3 to H2O of 1.25∶1, and glucose addition of 0.01 g, achieved a tetracycline (TC) degradation efficiency of 80.07% under visible light irradiation. X-ray diffraction (XRD), Raman spectrum, and scanning electron microscopy (SEM) analyses demonstrated that carbon doping promotes the phase transition from tetragonal to monoclinic structures and facilitates the formation of regular sheet-like morphologies, thereby increasing active sites. Photoelectrochemical tests further confirmed that doping broadened the light absorption range, reduced carrier recombination rates, and decreased interfacial charge transfer resistance, significantly improving the photocatalytic performance of BiVO4.
2025, 41(12): 2575-2583
doi: 10.11862/CJIC.20250132
Abstract:
In this work, three manganese carbonyl complexes [Mn(CO)3(quino(CH=N)phX)Br] [X=Cl (1), Br (2), I (3)] were synthesized by a one-pot method using quinoline-2-carbaldehyde, halogenated aniline, and manganese pentacarbonyl bromide as starting materials. The structures of these complexes were characterized by NMR spectroscopy, single-crystal X-ray diffraction, infrared spectroscopy, and UV-Vis spectroscopy. Furthermore, the decomposition of these complexes under low-energy LED red light (λ=622-770 nm) was investigated by infrared spectroscopy and ultraviolet spectroscopy. The results indicate that these complexes exhibit excellent stability under dark conditions, while rapidly decomposing with carbon monoxide release (CO) upon irradiation of LED red light. Kinetic analysis revealed that the CO-releasing processes follow a first-order kinetic model, with the electronic effects of halogen substituents (Cl/Br/I) exerting significant influence on reaction rates. That is, the stronger the electron donor ability of the complex, the faster the reaction rate. Furthermore, the energy of the light source also plays a crucial role in the decomposition reaction of these complexes. Under certain conditions, the higher the light energy, the faster the decomposition rate of the complexes. Myoglobin assays further confirmed the generation of CO gas from complex 3 under light irradiation. Biocompatibility studies demonstrated significant cytotoxic effects of these complexes against cancer cells (RT112, IC50=2-13 μmol·L-1).
In this work, three manganese carbonyl complexes [Mn(CO)3(quino(CH=N)phX)Br] [X=Cl (1), Br (2), I (3)] were synthesized by a one-pot method using quinoline-2-carbaldehyde, halogenated aniline, and manganese pentacarbonyl bromide as starting materials. The structures of these complexes were characterized by NMR spectroscopy, single-crystal X-ray diffraction, infrared spectroscopy, and UV-Vis spectroscopy. Furthermore, the decomposition of these complexes under low-energy LED red light (λ=622-770 nm) was investigated by infrared spectroscopy and ultraviolet spectroscopy. The results indicate that these complexes exhibit excellent stability under dark conditions, while rapidly decomposing with carbon monoxide release (CO) upon irradiation of LED red light. Kinetic analysis revealed that the CO-releasing processes follow a first-order kinetic model, with the electronic effects of halogen substituents (Cl/Br/I) exerting significant influence on reaction rates. That is, the stronger the electron donor ability of the complex, the faster the reaction rate. Furthermore, the energy of the light source also plays a crucial role in the decomposition reaction of these complexes. Under certain conditions, the higher the light energy, the faster the decomposition rate of the complexes. Myoglobin assays further confirmed the generation of CO gas from complex 3 under light irradiation. Biocompatibility studies demonstrated significant cytotoxic effects of these complexes against cancer cells (RT112, IC50=2-13 μmol·L-1).
2025, 41(12): 2584-2590
doi: 10.11862/CJIC.20250200
Abstract:
A compound containing [FeFe]-hydrogenase, [Fe2((SCH2)2R)(CO)6] (1) (R=4-{(1H-benzo[d]imidazol-1-yl)methyl}-anilino), was prepared and thoroughly characterized by infrared spectroscopy, single-crystal X-ray diffraction, and density functional theory calculations. Its performance as a photocatalyst for hydrogen production via water splitting was evaluated under simulated sunlight. Within 3 h, the amount of H2 produced was 386.5 μmol, achieving a catalytic efficiency of 25.26 μmol·mg-1·h-1 and a turnover number (TON) of 0.45.
A compound containing [FeFe]-hydrogenase, [Fe2((SCH2)2R)(CO)6] (1) (R=4-{(1H-benzo[d]imidazol-1-yl)methyl}-anilino), was prepared and thoroughly characterized by infrared spectroscopy, single-crystal X-ray diffraction, and density functional theory calculations. Its performance as a photocatalyst for hydrogen production via water splitting was evaluated under simulated sunlight. Within 3 h, the amount of H2 produced was 386.5 μmol, achieving a catalytic efficiency of 25.26 μmol·mg-1·h-1 and a turnover number (TON) of 0.45.
2025, 41(12): 2591-2600
doi: 10.11862/CJIC.20250282
Abstract:
Ni2CoS4 was prepared by the liquid-phase method and applied to the benzyl alcohol electro-oxidation reaction (BAOR), demonstrating excellent catalytic activity [with a current density of 271 mA·cm-2 at 1.40 V (vs RHE)] and long-term stability. The S-anion effect can regulate the charge distribution on the catalyst surface, thereby enhancing the additional adsorption capacity of OH- at the Co sites. By combining material characterization and theoretical calculations, it can be observed that this process can increase the concentration of the OH* intermediate, accelerate the activation process of the Ni site, and ultimately achieve an improvement in overall activity and stability.
Ni2CoS4 was prepared by the liquid-phase method and applied to the benzyl alcohol electro-oxidation reaction (BAOR), demonstrating excellent catalytic activity [with a current density of 271 mA·cm-2 at 1.40 V (vs RHE)] and long-term stability. The S-anion effect can regulate the charge distribution on the catalyst surface, thereby enhancing the additional adsorption capacity of OH- at the Co sites. By combining material characterization and theoretical calculations, it can be observed that this process can increase the concentration of the OH* intermediate, accelerate the activation process of the Ni site, and ultimately achieve an improvement in overall activity and stability.
2025, 41(12): 2601-2608
doi: 10.11862/CJIC.20250184
Abstract:
The residues of Al3+, Ga3+, and In3+ in the environment pose an increasingly serious threat to human health and ecosystems. However, their specific and rapid detection remains challenging. In this study, we present a water-stable cadmium metal-organic framework (Cd-MOF) based luminescence probe, which can detect Al3+, Ga3+, and In3+ ions in aqueous solutions via a luminescence "turn-on" mode. The corresponding detection limits for the Al3+, Ga3+, and In3+ ions were 2.31, 3.06, and 2.78 μmol·L-1, respectively. This probe operated effectively within a pH range of 3-10 in an all-aqueous environment. Investigations into the detection mechanism revealed that this "turn-on" recognition is attributed to the formation of new structures upon ion interaction.
The residues of Al3+, Ga3+, and In3+ in the environment pose an increasingly serious threat to human health and ecosystems. However, their specific and rapid detection remains challenging. In this study, we present a water-stable cadmium metal-organic framework (Cd-MOF) based luminescence probe, which can detect Al3+, Ga3+, and In3+ ions in aqueous solutions via a luminescence "turn-on" mode. The corresponding detection limits for the Al3+, Ga3+, and In3+ ions were 2.31, 3.06, and 2.78 μmol·L-1, respectively. This probe operated effectively within a pH range of 3-10 in an all-aqueous environment. Investigations into the detection mechanism revealed that this "turn-on" recognition is attributed to the formation of new structures upon ion interaction.
2025, 41(12): 2609-2620
doi: 10.11862/CJIC.20250170
Abstract:
To achieve efficient catalytic hydrogenation of CO₂ to formate, we employed a transmetallation strategy to develop three novel iridium(Ⅰ) complexes, which feature N-heterocyclic carbene-nitrogen-phosphine ligands (CNP) and a 1, 5-cyclooctadiene (cod) molecule: [Ir(cod)(κ3-CNimP)]Cl (1-Cl), [Ir(cod)(κ3-CNimP)]PF6 (1-PF6), and [Ir(cod)(κ3-CNHP)]Cl (2). The 1H NMR spectra, 31P NMR spectra, and high-resolution mass spectra verify the successful synthesis of these three Ir(Ⅰ)-CNP complexes. Furthermore, single-crystal X-ray diffraction analysis confirms the coordination geometry of 1-PF6. The strong Ir—C(NHC) bond suggests that the carbene carbon plays an enhanced anchoring role to iridium due to its strong σ-donating ability, which helps stabilize the active metal species during CO2 hydrogenation. As a result, the Ir(Ⅰ)-CNP complex exhibits remarkable activity and long catalytic lifetime for the hydrogenation of CO2 to formate, reaching a turnover number (TON) of 1.16×106 after 150 h at a high temperature of 170 ℃, which was a relatively high value among all the Ir complexes.
To achieve efficient catalytic hydrogenation of CO₂ to formate, we employed a transmetallation strategy to develop three novel iridium(Ⅰ) complexes, which feature N-heterocyclic carbene-nitrogen-phosphine ligands (CNP) and a 1, 5-cyclooctadiene (cod) molecule: [Ir(cod)(κ3-CNimP)]Cl (1-Cl), [Ir(cod)(κ3-CNimP)]PF6 (1-PF6), and [Ir(cod)(κ3-CNHP)]Cl (2). The 1H NMR spectra, 31P NMR spectra, and high-resolution mass spectra verify the successful synthesis of these three Ir(Ⅰ)-CNP complexes. Furthermore, single-crystal X-ray diffraction analysis confirms the coordination geometry of 1-PF6. The strong Ir—C(NHC) bond suggests that the carbene carbon plays an enhanced anchoring role to iridium due to its strong σ-donating ability, which helps stabilize the active metal species during CO2 hydrogenation. As a result, the Ir(Ⅰ)-CNP complex exhibits remarkable activity and long catalytic lifetime for the hydrogenation of CO2 to formate, reaching a turnover number (TON) of 1.16×106 after 150 h at a high temperature of 170 ℃, which was a relatively high value among all the Ir complexes.
