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无机化学学报
Chinese Journal of Inorganic Chemistry
主管 : 中国科学技术协会
刊期 : 月刊主编 : 游效曾
语种 : 中文主办 : 中国化学会
ISSN : 1001-4861 CN : 32-1185/O6展开 >《无机化学学报》由中国化学会主办，是展示我国无机化学研究成果的学术性期刊，月刊。1985年由化学前辈戴安邦院士（发起）创刊，现任主编游效曾院士。编辑部设在南京大学化学化工学院化学楼。报道我国无机化学领域的基础研究和应用基础研究的创新成果，内容涉及固体无机化学、配位化学、无机材料化学、生物无机化学、有机金属化学、理论无机化学、超分子化学和应用无机化学、催化等，着重报道新的和已知化合物的合成、热力学、动力学性质、谱学、结构和成键等。设有综述、研究快报及论文等栏目。
本刊所刊论文均为美国《科学引文索引》（SCI）网络版、美国《化学文摘》(CA)、《中国学术期刊文摘》（中、英文版）、《中国科技论文与引文数据库（CSTPCD）》、《中国科学引文数据库》、《中文科技期刊数据库》、《中国期刊全文数据库》、《中国核心期刊（遴选）数据库》、中国台湾华艺《中文电子期刊服务》等国内外多种著名检索刊物和文献数据库摘引和收录。
《无机化学学报》2011年每期200页，定价28.00元、全年定价336.00元。本刊由各地邮局征订，邮发代号28-133。也可直接向编辑部订阅。
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期刊内热点文章
2026, 42(2): 217-226
doi: 10.11862/CJIC.20250219
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
采用六氟磷酸铵(NH4PF6)短链配体对CsPbI2Br钙钛矿量子点进行表面修饰，在钙钛矿吸光层与碳电极之间构建多功能界面层。该方法有效钝化了钙钛矿层的表面缺陷，协同优化了界面形貌。基于该策略的碳基全无机钙钛矿太阳能电池实现了缺陷密度的降低与非辐射复合的抑制，光电转换效率从11.55%显著提升至13.23%，并且未封装器件在低湿环境中储存600 h后仍保持82%的初始效率。
采用六氟磷酸铵(NH4PF6)短链配体对CsPbI2Br钙钛矿量子点进行表面修饰，在钙钛矿吸光层与碳电极之间构建多功能界面层。该方法有效钝化了钙钛矿层的表面缺陷，协同优化了界面形貌。基于该策略的碳基全无机钙钛矿太阳能电池实现了缺陷密度的降低与非辐射复合的抑制，光电转换效率从11.55%显著提升至13.23%，并且未封装器件在低湿环境中储存600 h后仍保持82%的初始效率。
2026, 42(2): 237-246
doi: 10.11862/CJIC.20250257
摘要:
采用水热法耦合气相沉积磷化法，在泡沫镍(NF)上负载NiFeP/NiFcDCA(FcDCA=1，1′-二茂铁二羧酸)异质结催化剂。受益于层状堆叠的非均相纳米结构、丰富的活性位点和高效的电荷转移速率，磷化温度为350 ℃时制备的NiFeP/NiFcDCA@NF-350在1 mol·L-1 KOH+0.33 mol·L-1尿素溶液中表现出优异的尿素氧化反应(UOR)活性，其仅需1.332和1.368 V(vs RHE)的超低电位即可分别达到100和500 mA·cm-2的电流密度；其在50 mA·cm-2的电流密度下经50 h稳定性测试后性能衰减仅为0.54%，表现出优异的催化选择性和良好的稳定性。
采用水热法耦合气相沉积磷化法，在泡沫镍(NF)上负载NiFeP/NiFcDCA(FcDCA=1，1′-二茂铁二羧酸)异质结催化剂。受益于层状堆叠的非均相纳米结构、丰富的活性位点和高效的电荷转移速率，磷化温度为350 ℃时制备的NiFeP/NiFcDCA@NF-350在1 mol·L-1 KOH+0.33 mol·L-1尿素溶液中表现出优异的尿素氧化反应(UOR)活性，其仅需1.332和1.368 V(vs RHE)的超低电位即可分别达到100和500 mA·cm-2的电流密度；其在50 mA·cm-2的电流密度下经50 h稳定性测试后性能衰减仅为0.54%，表现出优异的催化选择性和良好的稳定性。
2026, 42(2): 247-262
doi: 10.11862/CJIC.20250255
摘要:
采用水热法成功将镁(Mg)引入ZSM-5分子筛骨架结构中，系统考察了Mg含量对分子筛孔的结构、酸性质、骨架铝(framework aluminum，AlF)分布及催化生物乙醇制丙烯(bioethanol to propylene，ETP)反应性能的影响。结果表明，随着Mg含量的增加，分子筛介孔体积显著增大，结晶度略有下降。氨气程序升温脱附(NH3-TPD)和吡啶红外(Py-IR)分析结果显示，Mg的引入有效降低了分子筛总酸量和强酸强度，同时提高了Brønsted酸的比例。固体核磁共振(27Al MAS NMR)和紫外可见漫反射光谱(UV-Vis DRS)表明，Mg的引入促使AlF从通道交叉处向正弦或直通道迁移，并减少了铝对(aluminum pair，Alpair)的形成。催化反应评价结果显示，适量Mg改性的分子筛(2-MgHZ5)表现出最优的ETP性能，丙烯选择性从改性前的ZSM-5(HZ5)的26.8%提高至29.5%，丙烯选择性维持在不低于10%的时间更是从HZ5的15 h显著延长至30 h，这归因于其适中的酸强度、丰富的介孔结构以及Al分布的优化有效抑制了芳烃循环和积碳生成，促进了烯烃-环戊二烯循环路径。
采用水热法成功将镁(Mg)引入ZSM-5分子筛骨架结构中，系统考察了Mg含量对分子筛孔的结构、酸性质、骨架铝(framework aluminum，AlF)分布及催化生物乙醇制丙烯(bioethanol to propylene，ETP)反应性能的影响。结果表明，随着Mg含量的增加，分子筛介孔体积显著增大，结晶度略有下降。氨气程序升温脱附(NH3-TPD)和吡啶红外(Py-IR)分析结果显示，Mg的引入有效降低了分子筛总酸量和强酸强度，同时提高了Brønsted酸的比例。固体核磁共振(27Al MAS NMR)和紫外可见漫反射光谱(UV-Vis DRS)表明，Mg的引入促使AlF从通道交叉处向正弦或直通道迁移，并减少了铝对(aluminum pair，Alpair)的形成。催化反应评价结果显示，适量Mg改性的分子筛(2-MgHZ5)表现出最优的ETP性能，丙烯选择性从改性前的ZSM-5(HZ5)的26.8%提高至29.5%，丙烯选择性维持在不低于10%的时间更是从HZ5的15 h显著延长至30 h，这归因于其适中的酸强度、丰富的介孔结构以及Al分布的优化有效抑制了芳烃循环和积碳生成，促进了烯烃-环戊二烯循环路径。
2026, 42(2): 263-270
doi: 10.11862/CJIC.20250236
摘要:
采用溶胶-凝胶法成功合成La2(1-x)MgZrO6:2xSm3+(x=0.01~0.11)双钙钛矿结构橙红色荧光粉。X射线衍射(XRD)和扫描电子显微镜(SEM)分析表明，所制备的样品为双钙钛矿结构，Sm3+离子均匀分布于La2MgZrO6基质中，未观察到杂质相。在405 nm近紫外光激发下，样品展现出典型的Sm3+离子特征发射光谱。当Sm3+掺杂浓度为0.03时，荧光强度达到最大值，随后出现明显的浓度猝灭现象。最佳组分样品的CIE色坐标为(0.536 1，0.452 6)，相对色温为2 177 K。此外，该荧光粉表现出良好的热稳定性：在473 K高温下，其发光强度仍可保持室温强度的81%，其热猝灭活化能为0.156 5 eV，进一步证实了其优异的热稳定性。
采用溶胶-凝胶法成功合成La2(1-x)MgZrO6:2xSm3+(x=0.01~0.11)双钙钛矿结构橙红色荧光粉。X射线衍射(XRD)和扫描电子显微镜(SEM)分析表明，所制备的样品为双钙钛矿结构，Sm3+离子均匀分布于La2MgZrO6基质中，未观察到杂质相。在405 nm近紫外光激发下，样品展现出典型的Sm3+离子特征发射光谱。当Sm3+掺杂浓度为0.03时，荧光强度达到最大值，随后出现明显的浓度猝灭现象。最佳组分样品的CIE色坐标为(0.536 1，0.452 6)，相对色温为2 177 K。此外，该荧光粉表现出良好的热稳定性：在473 K高温下，其发光强度仍可保持室温强度的81%，其热猝灭活化能为0.156 5 eV，进一步证实了其优异的热稳定性。
2026, 42(2): 271-283
doi: 10.11862/CJIC.20250230
摘要:
开发具有肿瘤选择性的金属药物，在发挥抗增殖活性的同时，规避生理毒副作用成为白血病治疗的重要难题。本研究通过钌/铱金属前体和二氢乳清脱氢酶(DHODH)抑制剂CS2进行酰胺化连接，开发了2种用于诱导铁死亡和加强细胞对铁死亡敏感性的新型配合物CS2-Ru和CS2-Ir。CS2-Ru、CS2-Ir通过诱导人急性早幼粒白血病细胞(NB-4细胞)内活性氧(ROS)水平升高和线粒体膜电位去极化，破坏细胞内氧化还原平衡。此外，基于配体CS2的特性，配合物仅对NB-4细胞表现出优异的选择性，通过GPX4/DHODH(GPX4=谷胱甘肽过氧化物酶4)双通路抑制，诱导NB-4细胞内脂质过氧化物异常积累至致死阈值，以及增加NB-4细胞对铁死亡的敏感性。
开发具有肿瘤选择性的金属药物，在发挥抗增殖活性的同时，规避生理毒副作用成为白血病治疗的重要难题。本研究通过钌/铱金属前体和二氢乳清脱氢酶(DHODH)抑制剂CS2进行酰胺化连接，开发了2种用于诱导铁死亡和加强细胞对铁死亡敏感性的新型配合物CS2-Ru和CS2-Ir。CS2-Ru、CS2-Ir通过诱导人急性早幼粒白血病细胞(NB-4细胞)内活性氧(ROS)水平升高和线粒体膜电位去极化，破坏细胞内氧化还原平衡。此外，基于配体CS2的特性，配合物仅对NB-4细胞表现出优异的选择性，通过GPX4/DHODH(GPX4=谷胱甘肽过氧化物酶4)双通路抑制，诱导NB-4细胞内脂质过氧化物异常积累至致死阈值，以及增加NB-4细胞对铁死亡的敏感性。
2026, 42(2): 284-296
doi: 10.11862/CJIC.20250171
摘要:
通过高温固相法成功合成了一系列Pr3+掺杂的Cd3Al2Ge3O12橙色荧光粉，并引入碱金属离子(Li+、Na+、K+)进行电荷补偿。利用X射线衍射(XRD)和荧光光谱仪等表征手段，分别对样品的晶体结构、发光性能及热稳定性进行研究。结果表明，Pr3+的掺杂没有改变基质的晶体结构，碱金属的掺杂也未引起杂相。样品在450 nm激发光作用下，发射光谱主峰位于613 nm处。比较不同掺杂浓度Cd3-xAl2Ge3O12: xPr3+(x=0.01~0.09)的荧光发射谱，发现Pr3+的最佳掺杂浓度为0.03。碱金属离子掺杂策略有效改善了材料的发光性能，其中Li+、Na+、K+掺杂系列荧光粉的荧光强度和寿命均得到有效提升，均优于未掺杂样品，且不同碱金属离子掺杂的增强效果大小依次为Li+、Na+、K+。Li+掺杂样品的发光强度最佳，是未掺杂体系的1.58倍。此外，探究了电荷补偿后的热稳定性，在393 K时，Li+补偿后的Cd2.94Al2Ge3O12: 0.03Pr3+，0.03Li+样品的发光强度为293 K时的72.70%。CIE色坐标确认了该荧光粉的发射均位于橙光区域。进一步利用最佳样品制作了白光发光二极管，其CIE色坐标为(0.368 2，0.300 1)，位于白光圈内。
通过高温固相法成功合成了一系列Pr3+掺杂的Cd3Al2Ge3O12橙色荧光粉，并引入碱金属离子(Li+、Na+、K+)进行电荷补偿。利用X射线衍射(XRD)和荧光光谱仪等表征手段，分别对样品的晶体结构、发光性能及热稳定性进行研究。结果表明，Pr3+的掺杂没有改变基质的晶体结构，碱金属的掺杂也未引起杂相。样品在450 nm激发光作用下，发射光谱主峰位于613 nm处。比较不同掺杂浓度Cd3-xAl2Ge3O12: xPr3+(x=0.01~0.09)的荧光发射谱，发现Pr3+的最佳掺杂浓度为0.03。碱金属离子掺杂策略有效改善了材料的发光性能，其中Li+、Na+、K+掺杂系列荧光粉的荧光强度和寿命均得到有效提升，均优于未掺杂样品，且不同碱金属离子掺杂的增强效果大小依次为Li+、Na+、K+。Li+掺杂样品的发光强度最佳，是未掺杂体系的1.58倍。此外，探究了电荷补偿后的热稳定性，在393 K时，Li+补偿后的Cd2.94Al2Ge3O12: 0.03Pr3+，0.03Li+样品的发光强度为293 K时的72.70%。CIE色坐标确认了该荧光粉的发射均位于橙光区域。进一步利用最佳样品制作了白光发光二极管，其CIE色坐标为(0.368 2，0.300 1)，位于白光圈内。
2026, 42(2): 297-308
doi: 10.11862/CJIC.20250214
摘要:
设计并合成了一种基于脲基配位作用和Si—O键断裂的新型双功能荧光探针1-甲基-2，4-双[2-(叔丁基二甲硅烷氧基)乙基脲基]苯(T1)，用于高选择性检测环境及生物样品中的Cr(Ⅵ)和F-。实验结果表明，T1在二甲基亚砜/水(DMSO/H2O，1∶1，V/V)溶剂体系中表现出优异的识别性能。基于脲基的配位作用，该探针对Cr(Ⅵ)的检测在395 nm处呈现荧光猝灭效应，检测限达4.70×10-7 mol·L-1，不受其他金属离子干扰；对F-的识别依赖于Si—O键的断裂机制，在320 nm处表现出显著荧光增强，检测限低至7.07×10-8 mol·L-1，在多种阴离子共存条件下也能保持高选择性。光谱分析表明，T1与Cr(Ⅵ)以1∶2的物质的量之比结合(结合常数Ka=2.62×104 L·mol-1)，与F-通过Si—O键断裂以1∶2的物质的量之比定量反应。该探针在0~20.00 μmol·L-1范围内呈现良好的线性响应。
设计并合成了一种基于脲基配位作用和Si—O键断裂的新型双功能荧光探针1-甲基-2，4-双[2-(叔丁基二甲硅烷氧基)乙基脲基]苯(T1)，用于高选择性检测环境及生物样品中的Cr(Ⅵ)和F-。实验结果表明，T1在二甲基亚砜/水(DMSO/H2O，1∶1，V/V)溶剂体系中表现出优异的识别性能。基于脲基的配位作用，该探针对Cr(Ⅵ)的检测在395 nm处呈现荧光猝灭效应，检测限达4.70×10-7 mol·L-1，不受其他金属离子干扰；对F-的识别依赖于Si—O键的断裂机制，在320 nm处表现出显著荧光增强，检测限低至7.07×10-8 mol·L-1，在多种阴离子共存条件下也能保持高选择性。光谱分析表明，T1与Cr(Ⅵ)以1∶2的物质的量之比结合(结合常数Ka=2.62×104 L·mol-1)，与F-通过Si—O键断裂以1∶2的物质的量之比定量反应。该探针在0~20.00 μmol·L-1范围内呈现良好的线性响应。
2026, 42(2): 309-316
doi: 10.11862/CJIC.20250212
摘要:
以2，5-二溴噻吩-3，4-二羧酸(H2L)、4，4′-联吡啶(4，4′-bipy)为配体，分别与六水合硝酸钴、四水合乙酸锰通过溶剂热合成法制备了2种过渡金属有机骨架：{[Co2(L)2(4，4′-bipy)2(H2O)4]·H2O}n (Co-MOF)和{[Mn(L)(4，4′-bipy)0.5(H2O)2]·H2O}n (Mn-MOF)。通过单晶X射线衍射、粉末X射线衍射、元素分析、红外光谱、紫外可见光谱、荧光光谱、热重分析方法表征其结构及谱学性质。结果表明，Co-MOF的Co(Ⅱ)间以4，4′-bipy桥联，经氢键相连延展成二维层状结构，最后以层间氢键堆叠成三维结构。Mn-MOF的Mn(Ⅱ)与4，4′-bipy及L2-配体配位，以配位键延伸形成蜂窝状的三维结构。
以2，5-二溴噻吩-3，4-二羧酸(H2L)、4，4′-联吡啶(4，4′-bipy)为配体，分别与六水合硝酸钴、四水合乙酸锰通过溶剂热合成法制备了2种过渡金属有机骨架：{[Co2(L)2(4，4′-bipy)2(H2O)4]·H2O}n (Co-MOF)和{[Mn(L)(4，4′-bipy)0.5(H2O)2]·H2O}n (Mn-MOF)。通过单晶X射线衍射、粉末X射线衍射、元素分析、红外光谱、紫外可见光谱、荧光光谱、热重分析方法表征其结构及谱学性质。结果表明，Co-MOF的Co(Ⅱ)间以4，4′-bipy桥联，经氢键相连延展成二维层状结构，最后以层间氢键堆叠成三维结构。Mn-MOF的Mn(Ⅱ)与4，4′-bipy及L2-配体配位，以配位键延伸形成蜂窝状的三维结构。
2026, 42(2): 317-330
doi: 10.11862/CJIC.20250199
摘要:
为提升氯氧铋/硅藻土(BiOCl/D)的可见光催化性能，引入了碳量子点(CQDs)，以温和水解法成功构建了CQDs/BiOCl/D三元复合体系，并研究了其在可见光下对水中抗生素环丙沙星(CIP)的光降解性能。结果表明，当CQDs加入量为催化剂总质量的3%时，所制备的3%CQDs/BiOCl/D在90 min可见光照射后，对CIP的降解率为90.1%，同时发现在80 min照射后，CIP的抑菌活性可消除。捕获剂实验和电子顺磁共振(EPR)结果证实，3%CQDs/BiOCl/D光降解反应中主要活性物种为空穴(h+)、羟基自由基(·OH)和超氧自由基(·O2-)。通过超高效液相色谱-质谱联用(UPLC-MS/MS)数据确认了CIP降解过程的中间产物并推测其降解路径。CQDs的上转换荧光性能、催化剂的稳态和瞬态荧光光谱及其相应的光电化学测试证明，3%CQDs/BiOCl/D光催化性能提升归功于CQDs的上转换作用、电子接收性能、转移性能和光热效应以及CQDs、硅藻土与BiOCl之间的协同作用。
为提升氯氧铋/硅藻土(BiOCl/D)的可见光催化性能，引入了碳量子点(CQDs)，以温和水解法成功构建了CQDs/BiOCl/D三元复合体系，并研究了其在可见光下对水中抗生素环丙沙星(CIP)的光降解性能。结果表明，当CQDs加入量为催化剂总质量的3%时，所制备的3%CQDs/BiOCl/D在90 min可见光照射后，对CIP的降解率为90.1%，同时发现在80 min照射后，CIP的抑菌活性可消除。捕获剂实验和电子顺磁共振(EPR)结果证实，3%CQDs/BiOCl/D光降解反应中主要活性物种为空穴(h+)、羟基自由基(·OH)和超氧自由基(·O2-)。通过超高效液相色谱-质谱联用(UPLC-MS/MS)数据确认了CIP降解过程的中间产物并推测其降解路径。CQDs的上转换荧光性能、催化剂的稳态和瞬态荧光光谱及其相应的光电化学测试证明，3%CQDs/BiOCl/D光催化性能提升归功于CQDs的上转换作用、电子接收性能、转移性能和光热效应以及CQDs、硅藻土与BiOCl之间的协同作用。
2026, 42(1): 1-22
doi: 10.11862/CJIC.20250197
摘要:
CO2 reduction technology can promote the resource utilization of carbon and help alleviate global warming and energy supply pressure. It is an effective way to achieve energy conversion and utilization. Covalent organic frameworks (COFs) are porous crystalline materials formed by connecting organic monomers through covalent bonds. They have the characteristics of functional diversity and rich chemical properties. Their advantages, such as high porosity, a wide range of visible light absorption, and excellent charge separation efficiency, give them good potential in CO2 capture, separation, and conversion. Currently, Cu is a key metal in the catalytic CO2 reduction reaction (CO2RR) for the preparation of high-value-added chemicals. The preparation of highly stable and large-pore Cu-based COFs using COFs as an ideal sacrificial template for loading Cu can be used to develop high-performance electrocatalysts and photocatalysts. In this review, we discuss the latest advancements in this field, including the development of various Cu-based COFs and their applications as catalysts for CO2RR. Here, we mainly introduce the synthesis strategies, some important characterization information, and the applications of electrocatalytic and photocatalytic CO2 conversion using these previously reported Cu-based COFs.
CO2 reduction technology can promote the resource utilization of carbon and help alleviate global warming and energy supply pressure. It is an effective way to achieve energy conversion and utilization. Covalent organic frameworks (COFs) are porous crystalline materials formed by connecting organic monomers through covalent bonds. They have the characteristics of functional diversity and rich chemical properties. Their advantages, such as high porosity, a wide range of visible light absorption, and excellent charge separation efficiency, give them good potential in CO2 capture, separation, and conversion. Currently, Cu is a key metal in the catalytic CO2 reduction reaction (CO2RR) for the preparation of high-value-added chemicals. The preparation of highly stable and large-pore Cu-based COFs using COFs as an ideal sacrificial template for loading Cu can be used to develop high-performance electrocatalysts and photocatalysts. In this review, we discuss the latest advancements in this field, including the development of various Cu-based COFs and their applications as catalysts for CO2RR. Here, we mainly introduce the synthesis strategies, some important characterization information, and the applications of electrocatalytic and photocatalytic CO2 conversion using these previously reported Cu-based COFs.
2026, 42(1): 23-44
doi: 10.11862/CJIC.20250188
摘要:
钌合金催化剂是一类重要的催化材料，得益于其独特的电子结构和表面特性，在多相催化、电催化、光催化等众多领域备受关注。通过与其他金属元素的高效结合，可显著改善钌基催化剂的催化性能，拓宽其应用范围。尤其是在析氢反应(HER)中，钌合金催化剂凭借催化活性高、成本效益低、稳定性和耐久性好等突出优势，成为驱动绿色氢能高效转化的研究焦点，其优异性能为可持续能源技术的突破带来了新的可能。本文围绕HER钌合金催化剂，着重从制备方法、组分设计、改性手段及性能研究4个核心维度切入，深入探讨了近年来有关HER钌合金催化剂的最新进展。同时，结合行业发展趋势对未来研究方向进行前瞻性展望，旨在为高性能HER钌合金催化剂的创新设计与工程化开发提供理论支撑与参考，助力推动该领域技术的快速发展。
钌合金催化剂是一类重要的催化材料，得益于其独特的电子结构和表面特性，在多相催化、电催化、光催化等众多领域备受关注。通过与其他金属元素的高效结合，可显著改善钌基催化剂的催化性能，拓宽其应用范围。尤其是在析氢反应(HER)中，钌合金催化剂凭借催化活性高、成本效益低、稳定性和耐久性好等突出优势，成为驱动绿色氢能高效转化的研究焦点，其优异性能为可持续能源技术的突破带来了新的可能。本文围绕HER钌合金催化剂，着重从制备方法、组分设计、改性手段及性能研究4个核心维度切入，深入探讨了近年来有关HER钌合金催化剂的最新进展。同时，结合行业发展趋势对未来研究方向进行前瞻性展望，旨在为高性能HER钌合金催化剂的创新设计与工程化开发提供理论支撑与参考，助力推动该领域技术的快速发展。
2026, 42(1): 45-54
doi: 10.11862/CJIC.20250196
摘要:
Under hydrothermal and solvothermal conditions, two novel cobalt-based complexes, {[Co2(CIA)(OH)(1, 4-dtb)]·2H2O}n (HU23) and {[Co2(CIA)(OH)(1, 4-dib)]·3.5H2O·DMF}n (HU24), were successfully constructed by coordinatively assembling the semi-rigid multidentate ligand 5-(1-carboxyethoxy)isophthalic acid (H3CIA) with the N-heterocyclic ligands 1, 4-di(4H-1, 2, 4-triazol-4-yl)benzene (1, 4-dtb) and 1, 4-di(1H-imidazol-1-yl)benzene (1, 4-dib), respectively, around Co2+ ions. Single-crystal X-ray diffraction analysis revealed that in both complexes HU23 and HU24, the CIA3- anions adopt a κ7-coordination mode, bridging six Co2+ ions via their five carboxylate oxygen atoms and one ether oxygen atom. This linkage forms tetranuclear [Co4(μ3-OH)2]6+ units. These Co-oxo cluster units were interconnected by CIA3- anions to assemble into 2D kgd-type structures featuring a 3, 6-connected topology. The 2D layers were further connected by 1, 4-dtb and 1, 4-dib, resulting in 3D pillar-layered frameworks for HU23 and HU24. Notably, despite the similar configurations of 1, 4-dtb and 1, 4-dib, differences in their coordination spatial orientations lead to topological divergence in the 3D frameworks of HU23 and HU24. Topological analysis indicates that the frameworks of HU23 and HU24 can be simplified into a 3, 10-connected net (point symbol: (410.63.82)(43)2) and a 3, 8-connected tfz-d net (point symbol: (43)2(46.618.84)), respectively. This structural differentiation confirms the precise regulatory role of ligands on the topology of metal-organic frameworks. Moreover, the ultraviolet-visible absorption spectra confirmed that HU23 and HU24 have strong absorption capabilities for ultraviolet and visible light. According to the Kubelka-Munk method, their bandwidths were 2.15 and 2.08 eV, respectively, which are consistent with those of typical semiconductor materials. Variable-temperature magnetic susceptibility measurements (2-300 K) revealed significant antiferromagnetic coupling in both complexes, with their effective magnetic moments decreasing markedly as the temperature lowered.
Under hydrothermal and solvothermal conditions, two novel cobalt-based complexes, {[Co2(CIA)(OH)(1, 4-dtb)]·2H2O}n (HU23) and {[Co2(CIA)(OH)(1, 4-dib)]·3.5H2O·DMF}n (HU24), were successfully constructed by coordinatively assembling the semi-rigid multidentate ligand 5-(1-carboxyethoxy)isophthalic acid (H3CIA) with the N-heterocyclic ligands 1, 4-di(4H-1, 2, 4-triazol-4-yl)benzene (1, 4-dtb) and 1, 4-di(1H-imidazol-1-yl)benzene (1, 4-dib), respectively, around Co2+ ions. Single-crystal X-ray diffraction analysis revealed that in both complexes HU23 and HU24, the CIA3- anions adopt a κ7-coordination mode, bridging six Co2+ ions via their five carboxylate oxygen atoms and one ether oxygen atom. This linkage forms tetranuclear [Co4(μ3-OH)2]6+ units. These Co-oxo cluster units were interconnected by CIA3- anions to assemble into 2D kgd-type structures featuring a 3, 6-connected topology. The 2D layers were further connected by 1, 4-dtb and 1, 4-dib, resulting in 3D pillar-layered frameworks for HU23 and HU24. Notably, despite the similar configurations of 1, 4-dtb and 1, 4-dib, differences in their coordination spatial orientations lead to topological divergence in the 3D frameworks of HU23 and HU24. Topological analysis indicates that the frameworks of HU23 and HU24 can be simplified into a 3, 10-connected net (point symbol: (410.63.82)(43)2) and a 3, 8-connected tfz-d net (point symbol: (43)2(46.618.84)), respectively. This structural differentiation confirms the precise regulatory role of ligands on the topology of metal-organic frameworks. Moreover, the ultraviolet-visible absorption spectra confirmed that HU23 and HU24 have strong absorption capabilities for ultraviolet and visible light. According to the Kubelka-Munk method, their bandwidths were 2.15 and 2.08 eV, respectively, which are consistent with those of typical semiconductor materials. Variable-temperature magnetic susceptibility measurements (2-300 K) revealed significant antiferromagnetic coupling in both complexes, with their effective magnetic moments decreasing markedly as the temperature lowered.
2026, 42(1): 152-160
doi: 10.11862/CJIC.20250204
摘要:
Three copper(Ⅱ), nickel and cadmium(Ⅱ) complexes, namely [Cu2(μ-H2dbda)2(phen)2]·2H2O (1), [Ni(μ-H2dbda)(μ-bpb)(H2O)2]n (2), and [Cd(μ-H2dbda)(μ-bpa)]n (3), have been constructed hydrothermally using H4dbda (4,4′-dihydroxy-[1,1′-biphenyl]-3,3′-dicarboxylic acid), phen (1,10-phenanthroline), bpb (1,4-bis(pyrid-4-yl)benzene), bpa (bis(4-pyridyl)amine), and copper, nickel and cadmium chlorides at 160 ℃. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses, and single-crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that three complexes crystallize in the monoclinic P21/n, tetragonal I42d, and orthorhombic P21212 space groups. The complexes exhibit molecular dimers (1) or 2D metal-organic networks (2 and 3). The catalytic performances in the Knoevenagel reaction of these complexes were investigated. Complex 1 exhibits an effective catalytic activity and excellent reusability as a heterogeneous catalyst in the Knoevenagel reaction at room temperature.
Three copper(Ⅱ), nickel and cadmium(Ⅱ) complexes, namely [Cu2(μ-H2dbda)2(phen)2]·2H2O (1), [Ni(μ-H2dbda)(μ-bpb)(H2O)2]n (2), and [Cd(μ-H2dbda)(μ-bpa)]n (3), have been constructed hydrothermally using H4dbda (4,4′-dihydroxy-[1,1′-biphenyl]-3,3′-dicarboxylic acid), phen (1,10-phenanthroline), bpb (1,4-bis(pyrid-4-yl)benzene), bpa (bis(4-pyridyl)amine), and copper, nickel and cadmium chlorides at 160 ℃. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses, and single-crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that three complexes crystallize in the monoclinic P21/n, tetragonal I42d, and orthorhombic P21212 space groups. The complexes exhibit molecular dimers (1) or 2D metal-organic networks (2 and 3). The catalytic performances in the Knoevenagel reaction of these complexes were investigated. Complex 1 exhibits an effective catalytic activity and excellent reusability as a heterogeneous catalyst in the Knoevenagel reaction at room temperature.
2026, 42(1): 161-169
doi: 10.11862/CJIC.20250195
摘要:
The complexes 1-4 of cyclobutanocucurbit[5]uril (CyB5Q[5]) with Na+/K+ have been synthesized and characterized by single-crystal X-ray diffraction. The results show that although the inorganic salts are used when the cations are the same and the anions are different, in complex 1, Na+ closes one port of CyB5Q[5] through Na—O seven coordination bonds to form a molecular bowl; in complex 3, Na+ completely closes the two ports of CyB5Q[5] to form a molecular capsule with six Na—O coordination bonds; in complexes 2 and 4, the two ports of CyB5Q[5] are completely closed to form K—O coordinated molecular capsules, but the K+ of complex 2 is six-coordinated and that of complex 4 is eight-/nine-coordinated. and complex 4 are connected by three oxygen bridges to form a 1D molecular chain.
The complexes 1-4 of cyclobutanocucurbit[5]uril (CyB5Q[5]) with Na+/K+ have been synthesized and characterized by single-crystal X-ray diffraction. The results show that although the inorganic salts are used when the cations are the same and the anions are different, in complex 1, Na+ closes one port of CyB5Q[5] through Na—O seven coordination bonds to form a molecular bowl; in complex 3, Na+ completely closes the two ports of CyB5Q[5] to form a molecular capsule with six Na—O coordination bonds; in complexes 2 and 4, the two ports of CyB5Q[5] are completely closed to form K—O coordinated molecular capsules, but the K+ of complex 2 is six-coordinated and that of complex 4 is eight-/nine-coordinated. and complex 4 are connected by three oxygen bridges to form a 1D molecular chain.
2026, 42(1): 170-180
doi: 10.11862/CJIC.20250161
摘要:
Three zinc(Ⅱ), nickel(Ⅱ), and cadmium(Ⅱ) complexes, namely [Zn(μ-Htpta)(py)2]n (1), [Ni(H2biim)2(H2O)2][Ni(tpta)(H2biim)2(H2O)]2·3H2O (2), and [Cd3(μ4-tpta)2(μ-dpe)3]n (3), have been constructed hydrothermally at 160 ℃ using H3tpta ([1, 1′: 3′, 1″-terphenyl]-4, 4′, 5′-tricarboxylic acid), py (pyridine), H2biim (2, 2′-biimidazole), dpe (1, 2-di (4-pyridyl)ethylene), and zinc, nickel and cadmium chlorides, resulting in the formation of stable crystalline solids which were subsequently analyzed using infrared spectroscopy, element analysis, thermogravimetric analysis, as well as structural analyses conducted via single-crystal X-ray diffraction. The findings from these single-crystal X-ray diffraction studies indicate that complexes 1-3 form crystals within the monoclinic system P21/c space group (1) or triclinic system P1 space group (2 and 3), and possess 1D, 0D, and 3D structures, respectively. Complex 1 demonstrated substantial catalytic efficiency and excellent reusability as a heterogeneous catalyst in the reaction of Knoevenagel condensation under ambient temperature conditions. In addition, complex 1 also showcased notable anti-wear performance when used in polyalphaolefin synthetic lubricants.
Three zinc(Ⅱ), nickel(Ⅱ), and cadmium(Ⅱ) complexes, namely [Zn(μ-Htpta)(py)2]n (1), [Ni(H2biim)2(H2O)2][Ni(tpta)(H2biim)2(H2O)]2·3H2O (2), and [Cd3(μ4-tpta)2(μ-dpe)3]n (3), have been constructed hydrothermally at 160 ℃ using H3tpta ([1, 1′: 3′, 1″-terphenyl]-4, 4′, 5′-tricarboxylic acid), py (pyridine), H2biim (2, 2′-biimidazole), dpe (1, 2-di (4-pyridyl)ethylene), and zinc, nickel and cadmium chlorides, resulting in the formation of stable crystalline solids which were subsequently analyzed using infrared spectroscopy, element analysis, thermogravimetric analysis, as well as structural analyses conducted via single-crystal X-ray diffraction. The findings from these single-crystal X-ray diffraction studies indicate that complexes 1-3 form crystals within the monoclinic system P21/c space group (1) or triclinic system P1 space group (2 and 3), and possess 1D, 0D, and 3D structures, respectively. Complex 1 demonstrated substantial catalytic efficiency and excellent reusability as a heterogeneous catalyst in the reaction of Knoevenagel condensation under ambient temperature conditions. In addition, complex 1 also showcased notable anti-wear performance when used in polyalphaolefin synthetic lubricants.
2026, 42(1): 181-192
doi: 10.11862/CJIC.20250126
摘要:
Six new lanthanide complexes: [Ln(3,4-DEOBA)3(4,4′-DM-2,2′-bipy)]2·2C2H5OH, [Ln=Dy (1), Eu (2), Tb (3), Sm (4), Ho (5), Gd (6); 3,4-DEOBA-=3,4-diethoxybenzoate, 4,4′-DM-2,2′-bipy=4,4′-dimethyl-2,2′-bipyridine] were successfully synthesized by the volatilization of the solution at room temperature. The crystal structures of six complexes were determined by single-crystal X-ray diffraction technology. The results showed that the complexes all have a binuclear structure, and the structures contain free ethanol molecules. Moreover, the coordination number of the central metal of each structural unit is eight. Adjacent structural units interact with each other through hydrogen bonds and further expand to form 1D chain-like and 2D planar structures. After conducting a systematic study on the luminescence properties of complexes 1-4, their emission and excitation spectra were obtained. Experimental results indicated that the fluorescence lifetimes of complexes 2 and 3 were 0.807 and 0.845 ms, respectively. The emission spectral data of complexes 1-4 were imported into the CIE chromaticity coordinate system, and their corresponding luminescent regions cover the yellow light, red light, green light, and orange-red light bands, respectively. Within the temperature range of 299.15-1 300 K, the thermal decomposition processes of the six complexes were comprehensively analyzed by using TG-DSC/FTIR/MS technology. The hypothesis of the gradual loss of ligand groups during the decomposition process was verified by detecting the escaped gas, 3D infrared spectroscopy, and ion fragment information detected by mass spectrometry. The specific decomposition path is as follows: firstly, free ethanol molecules and neutral ligands are removed, and finally, acidic ligands are released; the final product is the corresponding metal oxide.
Six new lanthanide complexes: [Ln(3,4-DEOBA)3(4,4′-DM-2,2′-bipy)]2·2C2H5OH, [Ln=Dy (1), Eu (2), Tb (3), Sm (4), Ho (5), Gd (6); 3,4-DEOBA-=3,4-diethoxybenzoate, 4,4′-DM-2,2′-bipy=4,4′-dimethyl-2,2′-bipyridine] were successfully synthesized by the volatilization of the solution at room temperature. The crystal structures of six complexes were determined by single-crystal X-ray diffraction technology. The results showed that the complexes all have a binuclear structure, and the structures contain free ethanol molecules. Moreover, the coordination number of the central metal of each structural unit is eight. Adjacent structural units interact with each other through hydrogen bonds and further expand to form 1D chain-like and 2D planar structures. After conducting a systematic study on the luminescence properties of complexes 1-4, their emission and excitation spectra were obtained. Experimental results indicated that the fluorescence lifetimes of complexes 2 and 3 were 0.807 and 0.845 ms, respectively. The emission spectral data of complexes 1-4 were imported into the CIE chromaticity coordinate system, and their corresponding luminescent regions cover the yellow light, red light, green light, and orange-red light bands, respectively. Within the temperature range of 299.15-1 300 K, the thermal decomposition processes of the six complexes were comprehensively analyzed by using TG-DSC/FTIR/MS technology. The hypothesis of the gradual loss of ligand groups during the decomposition process was verified by detecting the escaped gas, 3D infrared spectroscopy, and ion fragment information detected by mass spectrometry. The specific decomposition path is as follows: firstly, free ethanol molecules and neutral ligands are removed, and finally, acidic ligands are released; the final product is the corresponding metal oxide.
2026, 42(1): 193-202
doi: 10.11862/CJIC.20250029
摘要:
The poor electrical conductivity of metal-organic frameworks (MOFs) limits their electrocatalytic performance in the oxygen evolution reaction (OER). In this study, a Py@Co-MOF composite material based on pyrene (Py) molecules and {[Co2(BINDI)(DMA)2]·DMA}n (Co-MOF, H4BINDI=N,N′-bis(5-isophthalic acid)naphthalenediimide, DMA=N,N-dimethylacetamide) was synthesized via a one-pot method, leveraging π-π interactions between pyrene and Co-MOF to modulate electrical conductivity. Results demonstrate that the Py@Co-MOF catalyst exhibited significantly enhanced OER performance compared to pure Co-MOF or pyrene-based electrodes, achieving an overpotential of 246 mV at a current density of 10 mA·cm-2 along with excellent stability. Density functional theory (DFT) calculations reveal that the formation of O* in the second step is the rate-determining step (RDS) during the OER process on Co-MOF, with an energy barrier of 0.85 eV due to the weak adsorption affinity of the OH* intermediate for Co sites.
The poor electrical conductivity of metal-organic frameworks (MOFs) limits their electrocatalytic performance in the oxygen evolution reaction (OER). In this study, a Py@Co-MOF composite material based on pyrene (Py) molecules and {[Co2(BINDI)(DMA)2]·DMA}n (Co-MOF, H4BINDI=N,N′-bis(5-isophthalic acid)naphthalenediimide, DMA=N,N-dimethylacetamide) was synthesized via a one-pot method, leveraging π-π interactions between pyrene and Co-MOF to modulate electrical conductivity. Results demonstrate that the Py@Co-MOF catalyst exhibited significantly enhanced OER performance compared to pure Co-MOF or pyrene-based electrodes, achieving an overpotential of 246 mV at a current density of 10 mA·cm-2 along with excellent stability. Density functional theory (DFT) calculations reveal that the formation of O* in the second step is the rate-determining step (RDS) during the OER process on Co-MOF, with an energy barrier of 0.85 eV due to the weak adsorption affinity of the OH* intermediate for Co sites.
CoMoNiO-S/nickel foam heterostructure composite for efficient oxygen evolution catalysis performance
2026, 42(1): 203-215
doi: 10.11862/CJIC.20250041
摘要:
A composite electrocatalyst, CoMoNiO-S/NF-110 (NF is nickel foam), was synthesized through electrodeposition, followed by pyrolysis and then the vulcanization process. CoMoNiO-S/NF-110 exhibited a structure where Ni3S2 and Mo2S3 nanoparticles were integrated at the edges of Co3O4 nanosheets, creating a rich, heterogeneous interface that enhances the synergistic effects of each component. In an alkaline electrolyte, the synthesized CoMoNiO-S/NF-110 exhibited superior electrocatalytic performance for oxygen evolution reaction (OER), achieving current densities of 100 and 200 mA·cm-2 with low overpotentials of 199.4 and 224.4 mV, respectively, outperforming RuO2 and several high-performance Mo and Ni-based catalysts. This excellent performance is attributed to the rich interface formed between the components and active sites exposed by the defect structure.
A composite electrocatalyst, CoMoNiO-S/NF-110 (NF is nickel foam), was synthesized through electrodeposition, followed by pyrolysis and then the vulcanization process. CoMoNiO-S/NF-110 exhibited a structure where Ni3S2 and Mo2S3 nanoparticles were integrated at the edges of Co3O4 nanosheets, creating a rich, heterogeneous interface that enhances the synergistic effects of each component. In an alkaline electrolyte, the synthesized CoMoNiO-S/NF-110 exhibited superior electrocatalytic performance for oxygen evolution reaction (OER), achieving current densities of 100 and 200 mA·cm-2 with low overpotentials of 199.4 and 224.4 mV, respectively, outperforming RuO2 and several high-performance Mo and Ni-based catalysts. This excellent performance is attributed to the rich interface formed between the components and active sites exposed by the defect structure.
2026, 42(1): 55-64
doi: 10.11862/CJIC.20250178
摘要:
使用不同金属盐(高氯酸锌、高氯酸镍)与配体2，7-萘二羧酸(H2NDA)、1，4-二(1H-咪唑-1-基)苯(1，4-DMB)反应，在溶剂热条件下成功构筑出2例具有不同性质的配位聚合物：{[Zn(NDA)(1，4-DMB)0.5(H2O)]}n (Zn-CP)和{[Ni(NDA)(1，4-DMB)(H2O)3]}n (Ni-CP)，并采取单晶X射线衍射、Hirshfeld表面分析、热重分析等手段进一步探究二者的结构、晶体内相互作用、相纯度及热稳定性。研究结果表明：2个配位聚合物均为一维链状结构，并最终都通过丰富的分子间氢键和π…π堆积相互作用形成了3D超分子结构。值得注意的是，2个配合物合成时，除金属阳离子不同外，阴离子及其余试剂和条件方法均相同，但在Zn-CP中Zn2+处于四配位的变形四面体中心，NDA2-配体中的羧基均参与配位，为一双齿桥联配体，配位聚合物最终结构为一维梯子形链；而Ni-CP中，Ni2+处于六配位的变形八面体中心，但NDA2-配体中只有一个羧基参与配位，为一单齿端基配体，因此配位聚合物仅为一维扭曲梯形链。此外，固体荧光和电催化硝酸根还原制氨性能测试结果显示，Zn-CP具有较好的荧光性质，而Ni-CP具备一定的电催化硝酸根还原制氨能力。
使用不同金属盐(高氯酸锌、高氯酸镍)与配体2，7-萘二羧酸(H2NDA)、1，4-二(1H-咪唑-1-基)苯(1，4-DMB)反应，在溶剂热条件下成功构筑出2例具有不同性质的配位聚合物：{[Zn(NDA)(1，4-DMB)0.5(H2O)]}n (Zn-CP)和{[Ni(NDA)(1，4-DMB)(H2O)3]}n (Ni-CP)，并采取单晶X射线衍射、Hirshfeld表面分析、热重分析等手段进一步探究二者的结构、晶体内相互作用、相纯度及热稳定性。研究结果表明：2个配位聚合物均为一维链状结构，并最终都通过丰富的分子间氢键和π…π堆积相互作用形成了3D超分子结构。值得注意的是，2个配合物合成时，除金属阳离子不同外，阴离子及其余试剂和条件方法均相同，但在Zn-CP中Zn2+处于四配位的变形四面体中心，NDA2-配体中的羧基均参与配位，为一双齿桥联配体，配位聚合物最终结构为一维梯子形链；而Ni-CP中，Ni2+处于六配位的变形八面体中心，但NDA2-配体中只有一个羧基参与配位，为一单齿端基配体，因此配位聚合物仅为一维扭曲梯形链。此外，固体荧光和电催化硝酸根还原制氨性能测试结果显示，Zn-CP具有较好的荧光性质，而Ni-CP具备一定的电催化硝酸根还原制氨能力。
2026, 42(1): 65-77
doi: 10.11862/CJIC.20250172
摘要:
为改善光催化剂的载流子复合效率高、光响应能力差的问题，利用碱性KOH的“剪切效应”原位合成了具有可见光响应能力的Bi12TiO20/BaTiO3复合压电-光催化剂，通过BaTiO3持有的内置电场调制Bi12TiO20的光生载流子运输行为，提升其分离效率。采用X射线衍射、傅里叶变换红外光谱、紫外可见吸收光谱、X射线光电子能谱、扫描电子显微镜对合成粉体的物相、形貌进行表征、分析，获得了Bi12TiO20/BaTiO3的时间演化过程。Bi12TiO20/BaTiO3对染料的压电-光催化降解反应速率常数为9.76×10-2 min-1，优于压电催化(2.39×10-2 min-1)和光催化(8.17×10-2 min-1)；此外，结合自由基捕获实验、电子自旋共振(ESR)技术与Bi12TiO20/BaTiO3异质结能带结构揭示了压电-光催化增强机制。
为改善光催化剂的载流子复合效率高、光响应能力差的问题，利用碱性KOH的“剪切效应”原位合成了具有可见光响应能力的Bi12TiO20/BaTiO3复合压电-光催化剂，通过BaTiO3持有的内置电场调制Bi12TiO20的光生载流子运输行为，提升其分离效率。采用X射线衍射、傅里叶变换红外光谱、紫外可见吸收光谱、X射线光电子能谱、扫描电子显微镜对合成粉体的物相、形貌进行表征、分析，获得了Bi12TiO20/BaTiO3的时间演化过程。Bi12TiO20/BaTiO3对染料的压电-光催化降解反应速率常数为9.76×10-2 min-1，优于压电催化(2.39×10-2 min-1)和光催化(8.17×10-2 min-1)；此外，结合自由基捕获实验、电子自旋共振(ESR)技术与Bi12TiO20/BaTiO3异质结能带结构揭示了压电-光催化增强机制。
2026, 42(1): 78-86
doi: 10.11862/CJIC.20250141
摘要:
通过原位反应，设计合成了2例配合物[Ni(HL1)2]·CH3CN·CH3OH (1)和[Ni(L2)2] (2)，其中H2L1=2-羟基苯甲酸(6-甲氧基-吡啶-2-基亚甲基)-肼，HL2=4-溴-2-[(6-甲氧基吡啶-2-基亚甲基)-氨基]-苯酚。单晶X射线衍射分析表明：配合物1和2均具有以二价镍离子为中心的单核零维结构。打孔抑菌圈实验数据表明，与单纯的过渡金属镍离子相比，配合物1和2表现出更强的抑菌活性。采用紫外可见光谱法、循环伏安法和荧光光谱法研究了配合物1和2与小牛胸腺DNA(CTDNA)之间的相互作用，结果表明2个配合物均通过插入作用模式与CTDNA结合。
通过原位反应，设计合成了2例配合物[Ni(HL1)2]·CH3CN·CH3OH (1)和[Ni(L2)2] (2)，其中H2L1=2-羟基苯甲酸(6-甲氧基-吡啶-2-基亚甲基)-肼，HL2=4-溴-2-[(6-甲氧基吡啶-2-基亚甲基)-氨基]-苯酚。单晶X射线衍射分析表明：配合物1和2均具有以二价镍离子为中心的单核零维结构。打孔抑菌圈实验数据表明，与单纯的过渡金属镍离子相比，配合物1和2表现出更强的抑菌活性。采用紫外可见光谱法、循环伏安法和荧光光谱法研究了配合物1和2与小牛胸腺DNA(CTDNA)之间的相互作用，结果表明2个配合物均通过插入作用模式与CTDNA结合。
2026, 42(1): 87-96
doi: 10.11862/CJIC.20250127
摘要:
选用食醋为碳源，通过直接透析法得到荧光碳量子点(vCDs)，并对其形貌、组成、结构、光谱性能进行了表征和测试。结果表明，食醋提取的vCDs溶液的质量浓度为0.006 2 g·mL-1。所制备的vCDs表现出均一的尺寸分布，平均粒径为4.05 nm。vCDs的最佳荧光发射波长为460 nm，具有良好的抗光漂白性和抗盐性。由于表面质子化引发的电子能级变化，以及vCDs对Fe3+具有高选择性荧光猝灭，使得vCDs针对pH和Fe3+表现出特异的荧光分析传感特性。此外，将vCDs与聚乙烯醇丁醛(PVB)相融合，制备出荧光薄膜。
选用食醋为碳源，通过直接透析法得到荧光碳量子点(vCDs)，并对其形貌、组成、结构、光谱性能进行了表征和测试。结果表明，食醋提取的vCDs溶液的质量浓度为0.006 2 g·mL-1。所制备的vCDs表现出均一的尺寸分布，平均粒径为4.05 nm。vCDs的最佳荧光发射波长为460 nm，具有良好的抗光漂白性和抗盐性。由于表面质子化引发的电子能级变化，以及vCDs对Fe3+具有高选择性荧光猝灭，使得vCDs针对pH和Fe3+表现出特异的荧光分析传感特性。此外，将vCDs与聚乙烯醇丁醛(PVB)相融合，制备出荧光薄膜。
2026, 42(1): 97-110
doi: 10.11862/CJIC.20250116
摘要:
采用液相还原法首先合成纳米Cu2O，再通过煅烧的方式成功制备出系列价态可调的Cu2O/CuO复合结构，并测试其在黑暗条件下的普通催化性能以及光辅助催化氨硼烷水解制氢的性能。通过X射线衍射、傅里叶红外光谱、扫描电子显微镜、透射电子显微镜、X射线光电子能谱和紫外可见分光光度计对催化剂进行系统表征。结果表明，Cu2O/CuO复合结构为类树莓状纳米空心球，其中CuO的含量随煅烧时长增加而升高，并且相较于单相Cu2O增强了对可见光的吸收与利用。复合结构在可见光辅助条件下，催化水解制氢速率最高可达150.09 mL·g-1·min-1，且反应所需活化能仅为37.1 kJ·mol-1，明显优于黑暗条件。Cu2O/CuO催化剂在催化氨硼烷水解过程中发生表面重构形成Cu/Cu2O/CuO，金属与氧化物的复合结构在可见光下提供了更加高效的活性氢产生过程，进而增强了催化活性。
采用液相还原法首先合成纳米Cu2O，再通过煅烧的方式成功制备出系列价态可调的Cu2O/CuO复合结构，并测试其在黑暗条件下的普通催化性能以及光辅助催化氨硼烷水解制氢的性能。通过X射线衍射、傅里叶红外光谱、扫描电子显微镜、透射电子显微镜、X射线光电子能谱和紫外可见分光光度计对催化剂进行系统表征。结果表明，Cu2O/CuO复合结构为类树莓状纳米空心球，其中CuO的含量随煅烧时长增加而升高，并且相较于单相Cu2O增强了对可见光的吸收与利用。复合结构在可见光辅助条件下，催化水解制氢速率最高可达150.09 mL·g-1·min-1，且反应所需活化能仅为37.1 kJ·mol-1，明显优于黑暗条件。Cu2O/CuO催化剂在催化氨硼烷水解过程中发生表面重构形成Cu/Cu2O/CuO，金属与氧化物的复合结构在可见光下提供了更加高效的活性氢产生过程，进而增强了催化活性。
2026, 42(1): 111-119
doi: 10.11862/CJIC.20250121
摘要:
以低毒的乙酸乙酯为溶剂，合成了一种含溴离子的乙烯基咪唑-三联吡啶离子液体单体(TerVi[Br])，经聚合后再通过离子交换法引入双三氟甲烷磺酰亚胺阴离子(Tf2N-)，制得疏水型的聚离子液体(PTerVi[Tf2N])。该结构中三联吡啶基团不仅可有效配位稀土Eu3+离子，还可作为“天线”基团敏化其发光，从而构建高性能稀土发光材料。系统研究聚合与离子交换顺序对发光材料结构与性能的影响发现，“先聚合后离子交换”路径所得产物(PTerVi[Tf2N]-Eu)的发光性能显著优于“先离子交换后聚合”产物(P(TerVi[Tf2N])-Eu)。结果表明，PTerVi[Tf2N]-Eu的量子产率达20.52%，高于P(TerVi[Tf2N])-Eu的15.70%，同时其Eu3+的5D0能级荧光寿命也更长。
以低毒的乙酸乙酯为溶剂，合成了一种含溴离子的乙烯基咪唑-三联吡啶离子液体单体(TerVi[Br])，经聚合后再通过离子交换法引入双三氟甲烷磺酰亚胺阴离子(Tf2N-)，制得疏水型的聚离子液体(PTerVi[Tf2N])。该结构中三联吡啶基团不仅可有效配位稀土Eu3+离子，还可作为“天线”基团敏化其发光，从而构建高性能稀土发光材料。系统研究聚合与离子交换顺序对发光材料结构与性能的影响发现，“先聚合后离子交换”路径所得产物(PTerVi[Tf2N]-Eu)的发光性能显著优于“先离子交换后聚合”产物(P(TerVi[Tf2N])-Eu)。结果表明，PTerVi[Tf2N]-Eu的量子产率达20.52%，高于P(TerVi[Tf2N])-Eu的15.70%，同时其Eu3+的5D0能级荧光寿命也更长。
2026, 42(1): 120-128
doi: 10.11862/CJIC.20250091
摘要:
采用静电吸附层层组装技术，在氨基修饰的硅片上构建了不同组装层数(n)的氧化石墨烯(GO)与金纳米棒(AuNR)复合组装体(GO/AuNR)n。系统研究了该复合组装体在催化还原4-硝基苯酚(4-NP)和光催化降解罗丹明B(RhB)反应中的性能，并评估了其作为表面增强拉曼散射(SERS)基底在检测多种污染物(如4-NP、RhB、吡啶和4-氨基苯硫酚)以及实时原位监测上述催化反应过程中的应用。结果表明，(GO/AuNR)n复合组装体相较于单一AuNR表现出更优异的催化活性和SERS增强性能，且随着组装层数的增加，其催化与SERS性能均显著提升。
采用静电吸附层层组装技术，在氨基修饰的硅片上构建了不同组装层数(n)的氧化石墨烯(GO)与金纳米棒(AuNR)复合组装体(GO/AuNR)n。系统研究了该复合组装体在催化还原4-硝基苯酚(4-NP)和光催化降解罗丹明B(RhB)反应中的性能，并评估了其作为表面增强拉曼散射(SERS)基底在检测多种污染物(如4-NP、RhB、吡啶和4-氨基苯硫酚)以及实时原位监测上述催化反应过程中的应用。结果表明，(GO/AuNR)n复合组装体相较于单一AuNR表现出更优异的催化活性和SERS增强性能，且随着组装层数的增加，其催化与SERS性能均显著提升。
2026, 42(1): 129-140
doi: 10.11862/CJIC.20250069
摘要:
基于A位点阳离子替代策略，采用高温固相反应法制备了系列Li0.5La0.5MgSrWO6∶xMn4+(LLMSW∶xMn4+)荧光粉，并对其结构和发光性能进行了系统的研究。实验结果表明，LLMSW∶xMn4+荧光粉为八面体结构，Mn4+占据八面体中心。Li+与La3+结合，形成阳离子对，平衡了格位取代时的多余电荷，实现了有效的电荷补偿，也导致了Mn4+周围局域环境发生变化，打破了发光中心的反演对称性，有利于实现2Eg→4A2g发光增强。LLMSW∶xMn4+荧光粉激发波段为270~600 nm，其激发峰分别归属于Mn→O电荷转移带(318 nm)、4A2g→4T1g(342 nm)、4A2g→2T2g(361 nm)和4A2g→4T2g(484 nm)。在332 nm紫外光激发下，其发射光谱位于650~800 nm(2Eg→4A2g)，呈深红色，峰值波长为708 nm。Mn4+最佳掺杂浓度为0.012，对应LLMSW∶0.012Mn4+荧光粉的荧光寿命为1.528 ms，内量子效率为65.74%，温度升高至423 K时，荧光强度降为室温下的53.1%，激活能为0.32 eV。采用365 nm紫外芯片封装的LED在40 mA电流激发下的光谱呈深红色，色坐标位于(0.724 0，0.269 6)，色纯度为98.1%。且其光谱与植物光敏色素(Pfr)具有很好的匹配性。
基于A位点阳离子替代策略，采用高温固相反应法制备了系列Li0.5La0.5MgSrWO6∶xMn4+(LLMSW∶xMn4+)荧光粉，并对其结构和发光性能进行了系统的研究。实验结果表明，LLMSW∶xMn4+荧光粉为八面体结构，Mn4+占据八面体中心。Li+与La3+结合，形成阳离子对，平衡了格位取代时的多余电荷，实现了有效的电荷补偿，也导致了Mn4+周围局域环境发生变化，打破了发光中心的反演对称性，有利于实现2Eg→4A2g发光增强。LLMSW∶xMn4+荧光粉激发波段为270~600 nm，其激发峰分别归属于Mn→O电荷转移带(318 nm)、4A2g→4T1g(342 nm)、4A2g→2T2g(361 nm)和4A2g→4T2g(484 nm)。在332 nm紫外光激发下，其发射光谱位于650~800 nm(2Eg→4A2g)，呈深红色，峰值波长为708 nm。Mn4+最佳掺杂浓度为0.012，对应LLMSW∶0.012Mn4+荧光粉的荧光寿命为1.528 ms，内量子效率为65.74%，温度升高至423 K时，荧光强度降为室温下的53.1%，激活能为0.32 eV。采用365 nm紫外芯片封装的LED在40 mA电流激发下的光谱呈深红色，色坐标位于(0.724 0，0.269 6)，色纯度为98.1%。且其光谱与植物光敏色素(Pfr)具有很好的匹配性。
2026, 42(1): 141-151
doi: 10.11862/CJIC.20250049
摘要:
采用硫酸铝(Al2(SO4)3)来强化硫酸(H2SO4)对混合稀土精矿中氟碳铈矿的浸取，使用三异辛胺和N1923对浸出液中的余酸和稀土元素进行分步萃取，并获得硫酸钙、冰晶石副产品及独居石精矿。结果表明，铝与氟的强配位作用不仅强化了浸取，还消除了HF的产生，有利于稀土与氟铝的分离及氟铝的综合回收利用，消除了对环境的影响。在液固比(矿浆中液体体积与固体的质量之比)为32 mL·g-1的条件下，100目的稀土混合精矿与3.0 mol·L-1 H2SO4和0.3 mol·L-1 Al2(SO4)3的混合溶液在135 ℃和200 r·min-1的搅拌条件下反应2 h时，精矿和稀土浸出率分别达到68.00%和66.91%，氟离子浸出率和萤石的分解率分别为94.42%和99.30%。采用三异辛胺萃取浸出液中的大部分余酸后，直接用N1923萃取稀土，萃取率为97.38%；用HCl反萃负载有机相中的稀土，反萃率为98.05%，反萃液中铝与稀土的质量比仅为0.008 0。萃余水相中的氟铝配合物与外加氟源反应生成冰晶石，实现了氟铝资源的回收。
采用硫酸铝(Al2(SO4)3)来强化硫酸(H2SO4)对混合稀土精矿中氟碳铈矿的浸取，使用三异辛胺和N1923对浸出液中的余酸和稀土元素进行分步萃取，并获得硫酸钙、冰晶石副产品及独居石精矿。结果表明，铝与氟的强配位作用不仅强化了浸取，还消除了HF的产生，有利于稀土与氟铝的分离及氟铝的综合回收利用，消除了对环境的影响。在液固比(矿浆中液体体积与固体的质量之比)为32 mL·g-1的条件下，100目的稀土混合精矿与3.0 mol·L-1 H2SO4和0.3 mol·L-1 Al2(SO4)3的混合溶液在135 ℃和200 r·min-1的搅拌条件下反应2 h时，精矿和稀土浸出率分别达到68.00%和66.91%，氟离子浸出率和萤石的分解率分别为94.42%和99.30%。采用三异辛胺萃取浸出液中的大部分余酸后，直接用N1923萃取稀土，萃取率为97.38%；用HCl反萃负载有机相中的稀土，反萃率为98.05%，反萃液中铝与稀土的质量比仅为0.008 0。萃余水相中的氟铝配合物与外加氟源反应生成冰晶石，实现了氟铝资源的回收。
