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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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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。
2025, 41(8): 1465-1482
doi: 10.11862/CJIC.20240430
摘要:
2D过渡金属碳/氮化物或碳氮化物(MXenes)因其独特的物理和化学性质，在电学、光学、催化和环境等多个领域展现出了广泛的应用潜力。这些独特的性质为MXenes材料在各个领域的创新应用奠定了坚实的基础。近年来，2D MXenes纳米材料的界面调控策略受到了广泛关注。研究者通过不同的方法，如表面基团控制、表面吸附、表面复合和交联等，对MXenes进行了深入的改性研究。本文综述了MXenes的界面调控策略及其功能化材料在能量存储、催化、光电探测、电磁屏蔽、污染物吸附和生物医药领域的研究进展。
2D过渡金属碳/氮化物或碳氮化物(MXenes)因其独特的物理和化学性质，在电学、光学、催化和环境等多个领域展现出了广泛的应用潜力。这些独特的性质为MXenes材料在各个领域的创新应用奠定了坚实的基础。近年来，2D MXenes纳米材料的界面调控策略受到了广泛关注。研究者通过不同的方法，如表面基团控制、表面吸附、表面复合和交联等，对MXenes进行了深入的改性研究。本文综述了MXenes的界面调控策略及其功能化材料在能量存储、催化、光电探测、电磁屏蔽、污染物吸附和生物医药领域的研究进展。
2025, 41(8): 1483-1494
doi: 10.11862/CJIC.20250031
摘要:
将天然产物脱氢松香酸(DHA)引入环金属铱中，成功合成了一种新型环金属铱配合物CycIr-DHA，并通过 1H NMR对配体及配合物进行表征。该配合物在多种肿瘤细胞株中表现出显著的抗肿瘤活性，尤其是对人乳腺癌细胞(MCF-7)的抑制效果最为明显，其半数抑制浓度(IC50)仅为2.5 μmol·L-1，优于传统化疗药物顺铂。实验结果显示，CycIr-DHA主要在MCF-7的线粒体中富集，能够显著提高细胞内活性氧水平，导致线粒体功能障碍。此外，该配合物还能调节凋亡相关蛋白(Bax和Bcl-2)的表达，促进细胞凋亡，并上调LC3-Ⅱ蛋白，诱导细胞自噬。在3D细胞球模型中，CycIr-DHA显著抑制了细胞球的生长。
将天然产物脱氢松香酸(DHA)引入环金属铱中，成功合成了一种新型环金属铱配合物CycIr-DHA，并通过 1H NMR对配体及配合物进行表征。该配合物在多种肿瘤细胞株中表现出显著的抗肿瘤活性，尤其是对人乳腺癌细胞(MCF-7)的抑制效果最为明显，其半数抑制浓度(IC50)仅为2.5 μmol·L-1，优于传统化疗药物顺铂。实验结果显示，CycIr-DHA主要在MCF-7的线粒体中富集，能够显著提高细胞内活性氧水平，导致线粒体功能障碍。此外，该配合物还能调节凋亡相关蛋白(Bax和Bcl-2)的表达，促进细胞凋亡，并上调LC3-Ⅱ蛋白，诱导细胞自噬。在3D细胞球模型中，CycIr-DHA显著抑制了细胞球的生长。
2025, 41(8): 1495-1504
doi: 10.11862/CJIC.20250144
摘要:
本文报道了一种基于二茂铁与苯并硒二唑(SeNBD)偶联物的前药FcNH-SeNBD，用于肿瘤细胞化学动力学治疗(CDT)与荧光成像。FcNH-SeNBD利用肿瘤细胞中过表达的过氧化氢(H2O2)氧化二茂铁发生芬顿反应，高效生成羟基自由基(·OH)，诱导肿瘤细胞凋亡。与此同时，二茂铁的氧化阻断了其与苯并硒二唑之间的光致电子转移(PET)效应，使得原本被猝灭的SeNBD荧光得以恢复，实现了荧光信号“Off-On”的转变，用于实时监测前药在肿瘤细胞中的活化与富集，便于治疗效果的预测与评估。体外实验表明 FcNH-SeNBD对肝癌细胞HepG2[IC50=(7.95±0.98) μg·mL-1]和结直肠癌细胞HCT116[IC50=(15.74±1.5) μg· mL-1]具有显著的选择性杀伤作用，而对正常结肠上皮细胞NCM-460无显著毒性(IC50>100 μg·mL-1)。机制研究证实，FcNH-SeNBD通过激活caspase-3依赖性凋亡通路发挥对肿瘤细胞的杀伤作用。细胞成像实验表明 FcNH-SeNBD可在肿瘤细胞中富集并产生强烈的红色荧光。
本文报道了一种基于二茂铁与苯并硒二唑(SeNBD)偶联物的前药FcNH-SeNBD，用于肿瘤细胞化学动力学治疗(CDT)与荧光成像。FcNH-SeNBD利用肿瘤细胞中过表达的过氧化氢(H2O2)氧化二茂铁发生芬顿反应，高效生成羟基自由基(·OH)，诱导肿瘤细胞凋亡。与此同时，二茂铁的氧化阻断了其与苯并硒二唑之间的光致电子转移(PET)效应，使得原本被猝灭的SeNBD荧光得以恢复，实现了荧光信号“Off-On”的转变，用于实时监测前药在肿瘤细胞中的活化与富集，便于治疗效果的预测与评估。体外实验表明 FcNH-SeNBD对肝癌细胞HepG2[IC50=(7.95±0.98) μg·mL-1]和结直肠癌细胞HCT116[IC50=(15.74±1.5) μg· mL-1]具有显著的选择性杀伤作用，而对正常结肠上皮细胞NCM-460无显著毒性(IC50>100 μg·mL-1)。机制研究证实，FcNH-SeNBD通过激活caspase-3依赖性凋亡通路发挥对肿瘤细胞的杀伤作用。细胞成像实验表明 FcNH-SeNBD可在肿瘤细胞中富集并产生强烈的红色荧光。
2025, 41(8): 1505-1512
doi: 10.11862/CJIC.20250125
摘要:
将[Ag9(Tab)8(MeCN)8]2(PF6)18·4MeCN(Tab=4-(三甲基铵)苯硫酚盐，MeCN=乙腈)与三苯基膦(L1)和二苯基-2-吡啶膦(L2)分别进行固相研磨反应，得到的固体粉末经溶剂溶解、离心分离后，通过溶剂扩散法结晶得到了2个膦配体保护的银硫醇团簇[Ag7(Tab)6(L1)6Cl](PF6)6·8DMF (1)和[Ag17(Tab)20(L2)2](PF6)17·32DMF (2)。对2个簇合物分别进行了单晶X射线衍射、粉末X射线衍射、红外、紫外可见、热重和元素分析表征。单晶X射线衍射分析表明，2个簇合物均由有机磷配体和Tab配体共同保护，且簇合物2结构表面的二苯基-2-吡啶膦配体的P和N原子同时参与了配位。Z扫描技术测试结果表明2个簇合物在溶液中具有一定的三阶非线性光学响应。
将[Ag9(Tab)8(MeCN)8]2(PF6)18·4MeCN(Tab=4-(三甲基铵)苯硫酚盐，MeCN=乙腈)与三苯基膦(L1)和二苯基-2-吡啶膦(L2)分别进行固相研磨反应，得到的固体粉末经溶剂溶解、离心分离后，通过溶剂扩散法结晶得到了2个膦配体保护的银硫醇团簇[Ag7(Tab)6(L1)6Cl](PF6)6·8DMF (1)和[Ag17(Tab)20(L2)2](PF6)17·32DMF (2)。对2个簇合物分别进行了单晶X射线衍射、粉末X射线衍射、红外、紫外可见、热重和元素分析表征。单晶X射线衍射分析表明，2个簇合物均由有机磷配体和Tab配体共同保护，且簇合物2结构表面的二苯基-2-吡啶膦配体的P和N原子同时参与了配位。Z扫描技术测试结果表明2个簇合物在溶液中具有一定的三阶非线性光学响应。
2025, 41(8): 1513-1522
doi: 10.11862/CJIC.20250113
摘要:
合成了膦蒽配体1, 8-双(二苯基磷)蒽(Hbdpa)及其配合物[Au(Hbdpa)2]PF6 (1)和[Ir(tpy)(bdpa)](PF6)2 (2)，其中tpy=2，2′∶6′，2″-三联吡啶。在光照作用下，这些化合物发生光化学反应，生成Hbdpa-2O、[Au(Hbdpa-O)2]PF6 (1-O)和[Ir(tpy)(bdpa-OH)](PF6)2 (2-OH)。通过核磁、质谱和单晶X射线衍射表征了这些化合物的结构。讨论了化合物Hbdpa及其配合物1和2的光化学反应特性以及相关的发光行为调控。研究结果表明，Au(Ⅰ)和Ir(Ⅲ)的配位显著提高了配体Hbdpa的光反应活性。化合物2是首例能发生蒽基去芳构化反应的铱配合物。
合成了膦蒽配体1, 8-双(二苯基磷)蒽(Hbdpa)及其配合物[Au(Hbdpa)2]PF6 (1)和[Ir(tpy)(bdpa)](PF6)2 (2)，其中tpy=2，2′∶6′，2″-三联吡啶。在光照作用下，这些化合物发生光化学反应，生成Hbdpa-2O、[Au(Hbdpa-O)2]PF6 (1-O)和[Ir(tpy)(bdpa-OH)](PF6)2 (2-OH)。通过核磁、质谱和单晶X射线衍射表征了这些化合物的结构。讨论了化合物Hbdpa及其配合物1和2的光化学反应特性以及相关的发光行为调控。研究结果表明，Au(Ⅰ)和Ir(Ⅲ)的配位显著提高了配体Hbdpa的光反应活性。化合物2是首例能发生蒽基去芳构化反应的铱配合物。
2025, 41(8): 1523-1532
doi: 10.11862/CJIC.20250073
摘要:
用N′-[(1E)-吡啶-2-亚甲基]吡啶-4-碳酰肼(HL)配体与铟离子/镝离子合成了2种金属配合物[In(HL)(NO3)3] (1)和[Dy(L)(CH3OH)0.89(H2O)1.11(NO3)2]·0.11H2O (2)。单晶X射线衍射表明，配合物1和2均具有由1个配体连接1个金属离子形成的零维单核结构。体外抗增殖活性研究表明，配合物1对人肝癌细胞SMMC-7721、人乳腺癌细胞MDA-MB-231及人非小细胞肺癌细胞A549的抗肿瘤活性均优于顺铂；配合物2对SMMC-7721及A549的抗肿瘤活性也优于顺铂。伤口愈合实验显示配合物1和2可以抑制A549细胞迁移能力，且呈浓度依赖性。此外，配合物2对大肠杆菌具有显著的抑菌效果，抑菌圈直径达到22 mm。
用N′-[(1E)-吡啶-2-亚甲基]吡啶-4-碳酰肼(HL)配体与铟离子/镝离子合成了2种金属配合物[In(HL)(NO3)3] (1)和[Dy(L)(CH3OH)0.89(H2O)1.11(NO3)2]·0.11H2O (2)。单晶X射线衍射表明，配合物1和2均具有由1个配体连接1个金属离子形成的零维单核结构。体外抗增殖活性研究表明，配合物1对人肝癌细胞SMMC-7721、人乳腺癌细胞MDA-MB-231及人非小细胞肺癌细胞A549的抗肿瘤活性均优于顺铂；配合物2对SMMC-7721及A549的抗肿瘤活性也优于顺铂。伤口愈合实验显示配合物1和2可以抑制A549细胞迁移能力，且呈浓度依赖性。此外，配合物2对大肠杆菌具有显著的抑菌效果，抑菌圈直径达到22 mm。
2025, 41(8): 1533-1544
doi: 10.11862/CJIC.20250063
摘要:
采用固相烧结法制备了Li4GeO4、Li6Ge2O7、Li2GeO3和Li2Ge2O5四种Li2O-GeO2二元系晶体，并通过原位高温拉曼光谱技术结合理论计算的方法对晶态到熔态的结构演变过程以及熔体微结构进行定性和定量分析。研究表明：Li4GeO4、Li6Ge2O7和Li2GeO3熔体分别由[GeO4]4-、[Ge2O7]6-、[GeO3]2-和Li+构成，而Li2Ge2O5晶体在升温至熔融状态过程中由[GeO4]4-四面体形成的三维网络结构逐渐向更小的[Ge3O9]6-三元环递变。另外，通过量子化学从头计算法对团簇结构单元进行了设计、优化和计算，并将理论计算模拟与实验相结合，提出了一种校正熔体实验拉曼光谱的新方法。我们通过引入精细结构概念并利用高斯函数对拉曼光谱中[GeO4]4-四面体非桥氧的伸缩振动包络峰进行了分峰解谱，得到了这4种晶体在熔融状态下的不同结构(Qi，i表示每个[GeO4]4-四面体中桥氧的个数，i=0~4)单元含量的定量分布。
采用固相烧结法制备了Li4GeO4、Li6Ge2O7、Li2GeO3和Li2Ge2O5四种Li2O-GeO2二元系晶体，并通过原位高温拉曼光谱技术结合理论计算的方法对晶态到熔态的结构演变过程以及熔体微结构进行定性和定量分析。研究表明：Li4GeO4、Li6Ge2O7和Li2GeO3熔体分别由[GeO4]4-、[Ge2O7]6-、[GeO3]2-和Li+构成，而Li2Ge2O5晶体在升温至熔融状态过程中由[GeO4]4-四面体形成的三维网络结构逐渐向更小的[Ge3O9]6-三元环递变。另外，通过量子化学从头计算法对团簇结构单元进行了设计、优化和计算，并将理论计算模拟与实验相结合，提出了一种校正熔体实验拉曼光谱的新方法。我们通过引入精细结构概念并利用高斯函数对拉曼光谱中[GeO4]4-四面体非桥氧的伸缩振动包络峰进行了分峰解谱，得到了这4种晶体在熔融状态下的不同结构(Qi，i表示每个[GeO4]4-四面体中桥氧的个数，i=0~4)单元含量的定量分布。
2025, 41(8): 1545-1554
doi: 10.11862/CJIC.20250046
摘要:
为开发在温和条件下高效、高选择性氧化5-羟甲基糠醛(HMF)的多功能催化材料和反应体系，构筑了双金属有机框架(BMOF)材料及其衍生材料，用于低电压下的HMF电催化氧化。采用溶剂热法合成了双金属CoNi-MOF-74，并采用2种方式制备相应的催化材料。其一，对CoNi-MOF-74进行热解处理，制得石墨碳层包覆、碳基体稳定的CoNi合金(CoNi@C)纳米颗粒；其二，在电催化过程中，CoNi-MOF-74发生原位水解反应，生成相应的氢氧化物(CoNi(OH)2)，进而将其作为电极材料使用。研究发现，当Co、Ni的物质的量之比设定为1∶3时，所制备的Co1Ni3-MOF-74材料在800 ℃进行热解处理后，生成的Co1Ni3@C在低电位下对HMF电催化氧化表现出优异的催化活性和高的2, 5-呋喃二甲酸(FDCA)选择性(87.26%)。而Co1Ni1-MOF-74(Co、Ni物质的量之比为1∶1)电解时原位生成的Co0.5Ni0.5(OH)2对中间产物5-(羟甲基)呋喃-2-羧酸(HMFCA)具有很高的选择性(88.59%)和高转化率。这主要得益于衍生材料较好的孔隙结构、Co和Ni双金属之间的协同作用和石墨碳的良好导电性。
为开发在温和条件下高效、高选择性氧化5-羟甲基糠醛(HMF)的多功能催化材料和反应体系，构筑了双金属有机框架(BMOF)材料及其衍生材料，用于低电压下的HMF电催化氧化。采用溶剂热法合成了双金属CoNi-MOF-74，并采用2种方式制备相应的催化材料。其一，对CoNi-MOF-74进行热解处理，制得石墨碳层包覆、碳基体稳定的CoNi合金(CoNi@C)纳米颗粒；其二，在电催化过程中，CoNi-MOF-74发生原位水解反应，生成相应的氢氧化物(CoNi(OH)2)，进而将其作为电极材料使用。研究发现，当Co、Ni的物质的量之比设定为1∶3时，所制备的Co1Ni3-MOF-74材料在800 ℃进行热解处理后，生成的Co1Ni3@C在低电位下对HMF电催化氧化表现出优异的催化活性和高的2, 5-呋喃二甲酸(FDCA)选择性(87.26%)。而Co1Ni1-MOF-74(Co、Ni物质的量之比为1∶1)电解时原位生成的Co0.5Ni0.5(OH)2对中间产物5-(羟甲基)呋喃-2-羧酸(HMFCA)具有很高的选择性(88.59%)和高转化率。这主要得益于衍生材料较好的孔隙结构、Co和Ni双金属之间的协同作用和石墨碳的良好导电性。
2025, 41(8): 1555-1564
doi: 10.11862/CJIC.20250040
摘要:
以废旧棉织物为原料，氯化锌为活化剂，采用一步活化-炭化法制备具有丰富孔隙结构的废旧棉织物基炭吸波材料(CCF)，并探讨了不同氯化锌质量分数对CCF吸波性能的影响。结果表明：氯化锌能够有效丰富CCF的孔隙结构，提高其吸波效果。在炭化温度为700 ℃(N2气氛下)、氯化锌质量分数为10%时制备的CCF-10的比表面积高达1 310 m2·g-1，其在厚度为2.0mm时的最小反射损耗达-35.02 dB，有效吸收带宽为5.6 GHz。
以废旧棉织物为原料，氯化锌为活化剂，采用一步活化-炭化法制备具有丰富孔隙结构的废旧棉织物基炭吸波材料(CCF)，并探讨了不同氯化锌质量分数对CCF吸波性能的影响。结果表明：氯化锌能够有效丰富CCF的孔隙结构，提高其吸波效果。在炭化温度为700 ℃(N2气氛下)、氯化锌质量分数为10%时制备的CCF-10的比表面积高达1 310 m2·g-1，其在厚度为2.0mm时的最小反射损耗达-35.02 dB，有效吸收带宽为5.6 GHz。
2025, 41(8): 1565-1573
doi: 10.11862/CJIC.20250054
摘要:
将MoO3纳米片与2，2，6，6-四甲基哌啶氧化物(TEMPO)氧化的纤维素纳米纤维(TEMPO-CNF)复合，并经过高温碳化工艺制备了MoO3/T-CNF碳化复合气凝胶材料，其中T-CNF指TEMPO-CNT碳化后得到的多孔碳。MoO3/T-CNF具有高导电性、发达的孔隙结构和大的比表面积等特性，将其作为锂硫电池阴极时，能够有效吸附多硫化物，抑制穿梭效应，并缓解充放电过程中的体积膨胀。其中，最佳样品MoO3/T-CNF-3在0.1C倍率下的最高放电比容量达到1 721.8 mAh·g-1，且在200次循环后仍能保持84.8%的容量保持率和99.6%的库仑效率。
将MoO3纳米片与2，2，6，6-四甲基哌啶氧化物(TEMPO)氧化的纤维素纳米纤维(TEMPO-CNF)复合，并经过高温碳化工艺制备了MoO3/T-CNF碳化复合气凝胶材料，其中T-CNF指TEMPO-CNT碳化后得到的多孔碳。MoO3/T-CNF具有高导电性、发达的孔隙结构和大的比表面积等特性，将其作为锂硫电池阴极时，能够有效吸附多硫化物，抑制穿梭效应，并缓解充放电过程中的体积膨胀。其中，最佳样品MoO3/T-CNF-3在0.1C倍率下的最高放电比容量达到1 721.8 mAh·g-1，且在200次循环后仍能保持84.8%的容量保持率和99.6%的库仑效率。
2025, 41(8): 1574-1588
doi: 10.11862/CJIC.20250032
摘要:
在研究沼渣生物炭吸附氨氮(NH4+)的特性及机理的基础上，我们重点探讨了饱和沼渣生物炭的热再生性能，并研究了热再生参数(再生温度、再生时间、升温速率、保护气以及气体流速)对生物炭吸附性能的影响机制。沼渣生物炭对NH4+的吸附量可达19.12 mg·g-1，符合Langmuir模型，吸附机理主要是表面配位和离子交换反应。最佳热再生参数如下：温度为200 ℃，保护气为N2，流速为0.5 L·min-1，以5 ℃·min-1的升温速率再生1 h。饱和生物炭首次吸附再生率为99.59%，经10次吸附-再生循环后，吸附再生率仍达89.55%，失重率小于5%。通过热重-红外联用仪(TG?IR)、傅里叶变换红外光谱(FTIR)、X射线光电子能谱(XPS)、比表面及孔隙度分析和扫描电子显微镜(SEM)等多种手段进行表征，结果表明，多次循环热再生可破坏饱和生物炭表面的C=O、—OH和—COOH等含氧官能团，同时部分吸附位点被永久占用，导致吸附再生率逐渐下降。热再生可实现饱和生物炭中绝大部分氨氮的热解脱附，有效恢复生物炭孔隙结构和表面含氧官能团的吸附位点。
在研究沼渣生物炭吸附氨氮(NH4+)的特性及机理的基础上，我们重点探讨了饱和沼渣生物炭的热再生性能，并研究了热再生参数(再生温度、再生时间、升温速率、保护气以及气体流速)对生物炭吸附性能的影响机制。沼渣生物炭对NH4+的吸附量可达19.12 mg·g-1，符合Langmuir模型，吸附机理主要是表面配位和离子交换反应。最佳热再生参数如下：温度为200 ℃，保护气为N2，流速为0.5 L·min-1，以5 ℃·min-1的升温速率再生1 h。饱和生物炭首次吸附再生率为99.59%，经10次吸附-再生循环后，吸附再生率仍达89.55%，失重率小于5%。通过热重-红外联用仪(TG?IR)、傅里叶变换红外光谱(FTIR)、X射线光电子能谱(XPS)、比表面及孔隙度分析和扫描电子显微镜(SEM)等多种手段进行表征，结果表明，多次循环热再生可破坏饱和生物炭表面的C=O、—OH和—COOH等含氧官能团，同时部分吸附位点被永久占用，导致吸附再生率逐渐下降。热再生可实现饱和生物炭中绝大部分氨氮的热解脱附，有效恢复生物炭孔隙结构和表面含氧官能团的吸附位点。
2025, 41(8): 1589-1600
doi: 10.11862/CJIC.20250011
摘要:
首先通过水热法合成了Fe掺杂ZnO(ZnFeO)花状微球，然后采用物理沉积法将Mn掺杂碳量子点(Mn?CQDs)均匀负载于ZnFeO表面，成功构筑了Mn?CQDs/ZnFeO异质结复合材料。结合粉末X射线衍射、扫描电子显微镜、透射电子显微镜、X射线光电子能谱、紫外可见漫反射光谱和N2脱附-吸附分析，探究了该材料结构与光催化性能的关系。结果表明，Mn掺杂显著提升了CQDs的光吸收范围和荧光稳定性；Mn和Fe双掺杂协同拓展了Mn?CQDs/ZnFeO的可见光吸收边，提高了吸收强度，促进了界面光生电子-空穴对的分离，改善了光催化性能。氙灯光照80 min时，复合材料对甲基橙(MO)的降解率达到91.4%，经过4次循环实验后，降解率仍保持在80.7%。自由基捕获实验证实，光生空穴(h+)和超氧自由基(·O2-)是MO光降解过程中的主要活性物种。
首先通过水热法合成了Fe掺杂ZnO(ZnFeO)花状微球，然后采用物理沉积法将Mn掺杂碳量子点(Mn?CQDs)均匀负载于ZnFeO表面，成功构筑了Mn?CQDs/ZnFeO异质结复合材料。结合粉末X射线衍射、扫描电子显微镜、透射电子显微镜、X射线光电子能谱、紫外可见漫反射光谱和N2脱附-吸附分析，探究了该材料结构与光催化性能的关系。结果表明，Mn掺杂显著提升了CQDs的光吸收范围和荧光稳定性；Mn和Fe双掺杂协同拓展了Mn?CQDs/ZnFeO的可见光吸收边，提高了吸收强度，促进了界面光生电子-空穴对的分离，改善了光催化性能。氙灯光照80 min时，复合材料对甲基橙(MO)的降解率达到91.4%，经过4次循环实验后，降解率仍保持在80.7%。自由基捕获实验证实，光生空穴(h+)和超氧自由基(·O2-)是MO光降解过程中的主要活性物种。
2025, 41(8): 1601-1609
doi: 10.11862/CJIC.20250012
摘要:
合成了二(邻氟苄基)锡-2，2′-联吡啶-6，6′-二甲酸(H2bpdc)配合物[Sn(o-F-C6H4CH2)2(bpdc)(H2O)]2·H2O (1)和二正丁基锡-2，2′-联吡啶-6，6′-二甲酸配合物[Sn(n-C4H9)2(bpdc)(H2O)]·H2O (2)。通过元素分析、红外光谱、核磁共振谱(1H、13C和119Sn)、差热分析进行了表征；用单晶X射线衍射方法测定了配合物的晶体结构，对其结构进行量子化学计算，测定了配合物对人胃腺癌细胞(AGS)、人急性淋巴母细胞白血病细胞(MOLT4)和人乳腺癌细胞(MDA-MB-231)的体外抑制活性。结果显示: 配合物均为单核分子，中心锡原子均为七配位的畸变五角双锥构型；除配合物2对MDA-MB-231的抑制活性相对较弱外，配合物对其它细胞均显示了较强的抑制活性。
合成了二(邻氟苄基)锡-2，2′-联吡啶-6，6′-二甲酸(H2bpdc)配合物[Sn(o-F-C6H4CH2)2(bpdc)(H2O)]2·H2O (1)和二正丁基锡-2，2′-联吡啶-6，6′-二甲酸配合物[Sn(n-C4H9)2(bpdc)(H2O)]·H2O (2)。通过元素分析、红外光谱、核磁共振谱(1H、13C和119Sn)、差热分析进行了表征；用单晶X射线衍射方法测定了配合物的晶体结构，对其结构进行量子化学计算，测定了配合物对人胃腺癌细胞(AGS)、人急性淋巴母细胞白血病细胞(MOLT4)和人乳腺癌细胞(MDA-MB-231)的体外抑制活性。结果显示: 配合物均为单核分子，中心锡原子均为七配位的畸变五角双锥构型；除配合物2对MDA-MB-231的抑制活性相对较弱外，配合物对其它细胞均显示了较强的抑制活性。
2025, 41(8): 1610-1616
doi: 10.11862/CJIC.20240444
摘要:
首先采用水热法在碳布(CC)上生长了Ni掺杂WO3纳米线(Ni-WO3 NWs/CC)，然后利用高真空固相磷化法将其磷化，得到CC表面生长Ni掺杂WP2纳米线复合材料(Ni-WP2 NWs/CC)。研究其电催化析氢性能发现，Ni掺杂能够有效降低电催化析氢反应中的过电位。其中，当Ni、W物质的量之比为10%时制备得到的10%Ni-WP2 NWs/CC表现出最佳的催化性能。在碱性条件下，当电流密度为10和100 mA·cm-2时，10%Ni-WP2 NWs/CC所需的过电位分别为115和190 mV。经过Ni掺杂后，10%Ni-WP2 NWs/CC的电化学活性表面积明显增加。此外，在长时间的电催化条件下，该催化剂依然能保持良好的工作稳定性。
首先采用水热法在碳布(CC)上生长了Ni掺杂WO3纳米线(Ni-WO3 NWs/CC)，然后利用高真空固相磷化法将其磷化，得到CC表面生长Ni掺杂WP2纳米线复合材料(Ni-WP2 NWs/CC)。研究其电催化析氢性能发现，Ni掺杂能够有效降低电催化析氢反应中的过电位。其中，当Ni、W物质的量之比为10%时制备得到的10%Ni-WP2 NWs/CC表现出最佳的催化性能。在碱性条件下，当电流密度为10和100 mA·cm-2时，10%Ni-WP2 NWs/CC所需的过电位分别为115和190 mV。经过Ni掺杂后，10%Ni-WP2 NWs/CC的电化学活性表面积明显增加。此外，在长时间的电催化条件下，该催化剂依然能保持良好的工作稳定性。
2025, 41(8): 1617-1631
doi: 10.11862/CJIC.20240420
摘要:
以六水合硝酸铈(Ce(NO3)3·6H2O)和可溶性淀粉(ST)为原料，通过生物模板法制备了CeO2非均相光芬顿催化剂(ST-CeO2)。采用X射线粉末衍射(XRD)、傅里叶变换红外光谱(FTIR)、拉曼光谱、固体紫外可见漫反射光谱(UV-Vis DRS)和X射线光电子能谱(XPS)对催化剂进行表征。FTIR和Raman光谱证实了Ce—O键及氧空位的存在。UV-Vis DRS显示其在紫外和可见光区域有强吸收，XPS光谱分析表明催化剂表面存在Ce3+和Ce4+的混合价态，这可有效促进光生电荷的分离和H2O2的活化。甲基橙(MO)降解结果表明，ST-CeO2在紫外光下照射60 min时对MO染料的降解率可达82.8%;加入H2O2后，其在60 min时对MO染料的降解率可达99.7%，而且重复回收利用5次后仍然保持优良的催化性能。自由基捕获实验证明空穴(h+)和羟基自由基(·OH)是在MO染料降解反应中起主导作用的活性物质，而超氧自由基(·O2-)起次要作用。此外还详细探讨了ST-CeO2光芬顿降解MO染料的机理。
以六水合硝酸铈(Ce(NO3)3·6H2O)和可溶性淀粉(ST)为原料，通过生物模板法制备了CeO2非均相光芬顿催化剂(ST-CeO2)。采用X射线粉末衍射(XRD)、傅里叶变换红外光谱(FTIR)、拉曼光谱、固体紫外可见漫反射光谱(UV-Vis DRS)和X射线光电子能谱(XPS)对催化剂进行表征。FTIR和Raman光谱证实了Ce—O键及氧空位的存在。UV-Vis DRS显示其在紫外和可见光区域有强吸收，XPS光谱分析表明催化剂表面存在Ce3+和Ce4+的混合价态，这可有效促进光生电荷的分离和H2O2的活化。甲基橙(MO)降解结果表明，ST-CeO2在紫外光下照射60 min时对MO染料的降解率可达82.8%;加入H2O2后，其在60 min时对MO染料的降解率可达99.7%，而且重复回收利用5次后仍然保持优良的催化性能。自由基捕获实验证明空穴(h+)和羟基自由基(·OH)是在MO染料降解反应中起主导作用的活性物质，而超氧自由基(·O2-)起次要作用。此外还详细探讨了ST-CeO2光芬顿降解MO染料的机理。
2025, 41(8): 1632-1640
doi: 10.11862/CJIC.20240398
摘要:
以ZIF-8作为牺牲模板剂，利用其固有的多面体空间结构特征来抑制纳米颗粒催化剂的聚积行为，同时通过进一步引入过渡金属镍(Ni)元素对二氧化钌(RuO2)进行掺杂，以达到优化材料电子结构，提高活性位点的本征活性的目的，从而制备出粒径为8~10 nm的高性能析氧电催化剂(Ni-RuO2)。结果表明，Ni-RuO2具有优异的析氧反应(OER)催化性能，超越了商业RuO2。在碱性条件下，Ni-RuO2在电流密度为10 mA·cm-2时所需的过电位仅为257 mV，且具有较高的电化学活性面积、较快的电荷转移能力和良好的循环稳定性，优于商业RuO2和未进行Ni掺杂的RuO2。将Ni-RuO2作为阳极进行全解水测试时，其获得10 mA·cm-2的电流密度时仅需要1.476 V的分解电压。
以ZIF-8作为牺牲模板剂，利用其固有的多面体空间结构特征来抑制纳米颗粒催化剂的聚积行为，同时通过进一步引入过渡金属镍(Ni)元素对二氧化钌(RuO2)进行掺杂，以达到优化材料电子结构，提高活性位点的本征活性的目的，从而制备出粒径为8~10 nm的高性能析氧电催化剂(Ni-RuO2)。结果表明，Ni-RuO2具有优异的析氧反应(OER)催化性能，超越了商业RuO2。在碱性条件下，Ni-RuO2在电流密度为10 mA·cm-2时所需的过电位仅为257 mV，且具有较高的电化学活性面积、较快的电荷转移能力和良好的循环稳定性，优于商业RuO2和未进行Ni掺杂的RuO2。将Ni-RuO2作为阳极进行全解水测试时，其获得10 mA·cm-2的电流密度时仅需要1.476 V的分解电压。
2025, 41(8): 1641-1649
doi: 10.11862/CJIC.20250152
摘要:
A novel 3D metal-organic framework (MOF) [Pr2(L)3(H2O)5·H2O]n (Pr-1), (H2L=4, 4′-oxybis(benzoic acid)) with a rare structure of broken layer net, was constructed under the condition of solvothermal synthesis. The structure and crystal net were analyzed and characterized. This rod net of Pr-1 is new to both RCSR and ToposPro databases, and is named as rn-12 as suggested. Due to the luminescent properties of H2L and Pr(Ⅲ), the solid-state fluorescence property and sensing performance (solvents and metal ions) of Pr-1 were investigated. The sensing experiments indicated that Pr-1 could act as a fluorescence sensor to detect Cd2+ ions with good sensitivity. In addition, antibacterial activities show that Pr-1 exhibited stronger antibacterial activity against Escherichia coli (E. coli), Staphylococcus aureus (S. aureus), and Bacillus subtilis (B. subtilis) compared to synthetic materials.
A novel 3D metal-organic framework (MOF) [Pr2(L)3(H2O)5·H2O]n (Pr-1), (H2L=4, 4′-oxybis(benzoic acid)) with a rare structure of broken layer net, was constructed under the condition of solvothermal synthesis. The structure and crystal net were analyzed and characterized. This rod net of Pr-1 is new to both RCSR and ToposPro databases, and is named as rn-12 as suggested. Due to the luminescent properties of H2L and Pr(Ⅲ), the solid-state fluorescence property and sensing performance (solvents and metal ions) of Pr-1 were investigated. The sensing experiments indicated that Pr-1 could act as a fluorescence sensor to detect Cd2+ ions with good sensitivity. In addition, antibacterial activities show that Pr-1 exhibited stronger antibacterial activity against Escherichia coli (E. coli), Staphylococcus aureus (S. aureus), and Bacillus subtilis (B. subtilis) compared to synthetic materials.
2025, 41(8): 1650-1660
doi: 10.11862/CJIC.20250143
摘要:
Two metal-organic frameworks (MOFs), trans-[Co(L)(μ2-H2O)(H2O)2]·2H2O (1) and cis-[Mn(L)(Bipy)] (2) (H2L=2, 2′-dimethyl-4, 4′-biphenyldicarboxylic acid, Bipy=4, 4′-bipyridine), have been synthesized and characterized by FTIR, thermogravimetric analysis (TGA), powder and single crystal X-ray diffraction. MOF 1 crystallizes in the triclinic system with a P1 space group and contains two crystallographically different Co(Ⅱ) ions. Each trans-[CoO6] octahedron is connected by μ2-H2O and L2- ligand with a bis(unidentate) coordination mode to produce a 2D sql topological network. MOF 2 crystallizes in the monoclinic system with a C2/c space group. The Mn(Ⅱ) cation adopts a cis-[MnO4N2] octahedron as a 6-connected node and is linked by L2- ligand as a 4-connected node to generate a binodal (4, 6)-connected 3D fsc framework. The intermolecular interactions in 1 and 2 have been investigated by 3D Hirshfeld surface analyses and 2D fingerprint plots to reveal that the main interactions are H…H and O…H/H…O contacts in 1, and H…H and C…H/H…C contacts in 2. The TGA indicated that 1 and 2 were stable below 390 and 370 ℃, respectively.
Two metal-organic frameworks (MOFs), trans-[Co(L)(μ2-H2O)(H2O)2]·2H2O (1) and cis-[Mn(L)(Bipy)] (2) (H2L=2, 2′-dimethyl-4, 4′-biphenyldicarboxylic acid, Bipy=4, 4′-bipyridine), have been synthesized and characterized by FTIR, thermogravimetric analysis (TGA), powder and single crystal X-ray diffraction. MOF 1 crystallizes in the triclinic system with a P1 space group and contains two crystallographically different Co(Ⅱ) ions. Each trans-[CoO6] octahedron is connected by μ2-H2O and L2- ligand with a bis(unidentate) coordination mode to produce a 2D sql topological network. MOF 2 crystallizes in the monoclinic system with a C2/c space group. The Mn(Ⅱ) cation adopts a cis-[MnO4N2] octahedron as a 6-connected node and is linked by L2- ligand as a 4-connected node to generate a binodal (4, 6)-connected 3D fsc framework. The intermolecular interactions in 1 and 2 have been investigated by 3D Hirshfeld surface analyses and 2D fingerprint plots to reveal that the main interactions are H…H and O…H/H…O contacts in 1, and H…H and C…H/H…C contacts in 2. The TGA indicated that 1 and 2 were stable below 390 and 370 ℃, respectively.
2025, 41(8): 1661-1671
doi: 10.11862/CJIC.20250075
摘要:
A functional interlayer based on two-dimensional (2D) porous modified vermiculite nanosheets (PVS) was obtained by acid-etching vermiculite nanosheets. The as-obtained 2D porous nanosheets exhibited a high specific surface area of 427 m2•g-1 and rich surface active sites, which help restrain polysulfides (LiPSs) through good physical and chemical adsorption, while simultaneously accelerating the nucleation and dissolution kinetics of Li2S, effectively suppressing the shuttle effect. The assembled lithium-sulfur batteries (LSBs) employing the PVS-based interlayer delivered a high initial discharge capacity of 1 386 mAh•g-1 at 0.1C (167.5 mAh•g-1), long-term cycling stability, and good rate property.
A functional interlayer based on two-dimensional (2D) porous modified vermiculite nanosheets (PVS) was obtained by acid-etching vermiculite nanosheets. The as-obtained 2D porous nanosheets exhibited a high specific surface area of 427 m2•g-1 and rich surface active sites, which help restrain polysulfides (LiPSs) through good physical and chemical adsorption, while simultaneously accelerating the nucleation and dissolution kinetics of Li2S, effectively suppressing the shuttle effect. The assembled lithium-sulfur batteries (LSBs) employing the PVS-based interlayer delivered a high initial discharge capacity of 1 386 mAh•g-1 at 0.1C (167.5 mAh•g-1), long-term cycling stability, and good rate property.
2025, 41(8): 1672-1680
doi: 10.11862/CJIC.20250013
摘要:
One Yb(Ⅲ)-based coordination polymer, {[Yb(H2dhtp)1.5(H2O)4]·3H2O}n (1) (H4dhtp=2, 5-dihydroxyterephthalic acid), was fabricated and structurally characterized by single-crystal X-ray diffraction, IR, powder X-ray diffraction, X-ray diffraction, and elemental analysis. Complex 1 displays a 1D chain structure, and belongs to P1 group. The solid-state luminescent spectrum of 1 showed an emission band with the maximum at 508 nm (λex=408 nm). It exhibited the emission characteristic of the H4dhtp ligand. The fluorescence of 1 in water displayed the strongest intensity. In detecting various metal ions, adding Zr4+ led to a blue shift in fluorescence, accompanied by an increase in intensity, whereas the presence of Fe3+ resulted in a decrease in luminescence. The changes observed in the IR spectrum indicate an interaction between Fe3+/Zr4+ and complex 1, resulting in the variation of luminescence properties.
One Yb(Ⅲ)-based coordination polymer, {[Yb(H2dhtp)1.5(H2O)4]·3H2O}n (1) (H4dhtp=2, 5-dihydroxyterephthalic acid), was fabricated and structurally characterized by single-crystal X-ray diffraction, IR, powder X-ray diffraction, X-ray diffraction, and elemental analysis. Complex 1 displays a 1D chain structure, and belongs to P1 group. The solid-state luminescent spectrum of 1 showed an emission band with the maximum at 508 nm (λex=408 nm). It exhibited the emission characteristic of the H4dhtp ligand. The fluorescence of 1 in water displayed the strongest intensity. In detecting various metal ions, adding Zr4+ led to a blue shift in fluorescence, accompanied by an increase in intensity, whereas the presence of Fe3+ resulted in a decrease in luminescence. The changes observed in the IR spectrum indicate an interaction between Fe3+/Zr4+ and complex 1, resulting in the variation of luminescence properties.
2025, 41(8): 1681-1688
doi: 10.11862/CJIC.20250004
摘要:
Six coordination polymers based on 9, 10-di(pyridine-4-yl)-anthracene (DPA) and 1, 6-di(1H-imidazol-1-yl)pyrene (DIP) were obtained by solvothermal reactions. {[Zn(DPA)Cl2]·DMF·2H2O}n (1) and {[Zn1.5(DPA)1.5Cl3]·5H2O}n (2) are framework isomers, which both contain zigzag chains formed by DPA, Zn2+, and Cl-. The zigzag chains in 1 are further assembled by C—H…Cl interactions into layers, and these layers exhibit two different orientations, displaying a rare 2D to 3D interpenetration mode. The zigzag chains in 2 are parallelly arranged. {[Zn3(DPA)3Br6]·2DMF·1.5H2O}n (3) is isostructural to 2. 3 was obtained using ZnBr2 instead of ZnCl2.[M(DPA) (formate)2(H2O)2]n[M=Co (4), Cu (5)] are isostructural, contain chain structures formed by DPA, Cu2+/Co2+, and formate ions, which were formed in situ in the solvothermal reaction. {[Zn(DIP)2Cl]ClO4}n (6) contains a layer structure formed by DIP and Zn2+. Free DPA and DIP ligands exhibited high fluorescence at room temperature, and coordination polymers 3 and 6 displayed enhanced fluorescent emissions.
Six coordination polymers based on 9, 10-di(pyridine-4-yl)-anthracene (DPA) and 1, 6-di(1H-imidazol-1-yl)pyrene (DIP) were obtained by solvothermal reactions. {[Zn(DPA)Cl2]·DMF·2H2O}n (1) and {[Zn1.5(DPA)1.5Cl3]·5H2O}n (2) are framework isomers, which both contain zigzag chains formed by DPA, Zn2+, and Cl-. The zigzag chains in 1 are further assembled by C—H…Cl interactions into layers, and these layers exhibit two different orientations, displaying a rare 2D to 3D interpenetration mode. The zigzag chains in 2 are parallelly arranged. {[Zn3(DPA)3Br6]·2DMF·1.5H2O}n (3) is isostructural to 2. 3 was obtained using ZnBr2 instead of ZnCl2.[M(DPA) (formate)2(H2O)2]n[M=Co (4), Cu (5)] are isostructural, contain chain structures formed by DPA, Cu2+/Co2+, and formate ions, which were formed in situ in the solvothermal reaction. {[Zn(DIP)2Cl]ClO4}n (6) contains a layer structure formed by DIP and Zn2+. Free DPA and DIP ligands exhibited high fluorescence at room temperature, and coordination polymers 3 and 6 displayed enhanced fluorescent emissions.
