Login In
2026 Volume 42 Issue 1
2026, 42(1): 1-22
doi: 10.11862/CJIC.20250197
Abstract:
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
Abstract:
Ruthenium alloy catalysts are a class of important catalytic materials, garnering significant attention in various fields such as heterogeneous catalysis, electrocatalysis, and photocatalysis, owing to their unique electronic structure and surface properties. By efficiently combining with other metal elements, the catalytic performance of ruthenium-based catalysts can be significantly improved, expanding their application range. Especially in the hydrogen evolution reaction (HER), ruthenium alloy catalysts have become a research focus for driving efficient conversion of green hydrogen energy due to their outstanding advantages such as high catalytic activity, low cost-effectiveness, good stability and durability. Their excellent performance has brought new possibilities for breakthroughs in sustainable energy technology. This article focuses on HER ruthenium alloy catalysts, with a focus on four core dimensions: preparation methods, component design, modification methods, and performance research. It deeply explores the latest developments in HER ruthenium alloy catalysts in recent years. At the same time, a forward-looking outlook is made on future research directions based on industry development trends, aiming to provide theoretical support and reference for the innovative design and engineering development of high-performance HER ruthenium alloy catalysts, and help promote rapid technological progress in this field.
Ruthenium alloy catalysts are a class of important catalytic materials, garnering significant attention in various fields such as heterogeneous catalysis, electrocatalysis, and photocatalysis, owing to their unique electronic structure and surface properties. By efficiently combining with other metal elements, the catalytic performance of ruthenium-based catalysts can be significantly improved, expanding their application range. Especially in the hydrogen evolution reaction (HER), ruthenium alloy catalysts have become a research focus for driving efficient conversion of green hydrogen energy due to their outstanding advantages such as high catalytic activity, low cost-effectiveness, good stability and durability. Their excellent performance has brought new possibilities for breakthroughs in sustainable energy technology. This article focuses on HER ruthenium alloy catalysts, with a focus on four core dimensions: preparation methods, component design, modification methods, and performance research. It deeply explores the latest developments in HER ruthenium alloy catalysts in recent years. At the same time, a forward-looking outlook is made on future research directions based on industry development trends, aiming to provide theoretical support and reference for the innovative design and engineering development of high-performance HER ruthenium alloy catalysts, and help promote rapid technological progress in this field.
2026, 42(1): 45-54
doi: 10.11862/CJIC.20250196
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
Two coordination polymers with different properties were successfully constructed under solvothermal conditions using zinc perchlorate, nickel perchlorate, and the same mixed ligand composed of 2, 7-naphthalenedicarboxylic acid (H2NDA) and 1, 4-bis(1H-imidazol-1-yl)benzene (1, 4-DMB): {[Zn(NDA)(1, 4-DMB)0.5(H2O)]}n (Zn-CP) and {[Ni(NDA)(1, 4-DMB)(H2O)3]}n (Ni-CP). Single-crystal X-ray diffraction, thermogravimetric analysis, Hirshfeld surface analysis, and other characterization methods further explored the phase purity, thermal stability, and interaction in the crystal of the two complexes. The results show that the two coordination polymers have a 1D chain structure, and both of them are finally separated by abundant intermolecular hydrogen bonds and π…π stacking interactions form a 3D supramolecular structure. However, it is worth noting that when the two complexes are synthesized, except for the metal cations, the anions and other reagents and conditions are the same. Still, in Zn-CP, Zn2+ is in the center of the deformed tetrahedron with four coordinations, and the carboxyl groups in the NDA2- ligands are all involved in the coordination, which is a bidentate bridging ligand. The final structure of the coordination polymer is a 1D ladder-shaped chain. In Ni-CP, Ni2+ is in the center of the deformed octahedron with hexacoordination, but only one carboxyl group is involved in the coordination in the NDA2- ligand, which is a monodentate ligand end-group ligand, so the coordination polymer is only a 1D twisted trapezoidal chain. In addition, the solid-state fluorescence test results under 275 nm excitation showed that Zn-CP exhibited good fluorescence properties at 363 nm. Furthermore, the electrocatalytic performance test for nitrate reduction to ammonia indicated that Ni-CP exhibited a certain degree of electrocatalytic ability for nitrate reduction to ammonia.
Two coordination polymers with different properties were successfully constructed under solvothermal conditions using zinc perchlorate, nickel perchlorate, and the same mixed ligand composed of 2, 7-naphthalenedicarboxylic acid (H2NDA) and 1, 4-bis(1H-imidazol-1-yl)benzene (1, 4-DMB): {[Zn(NDA)(1, 4-DMB)0.5(H2O)]}n (Zn-CP) and {[Ni(NDA)(1, 4-DMB)(H2O)3]}n (Ni-CP). Single-crystal X-ray diffraction, thermogravimetric analysis, Hirshfeld surface analysis, and other characterization methods further explored the phase purity, thermal stability, and interaction in the crystal of the two complexes. The results show that the two coordination polymers have a 1D chain structure, and both of them are finally separated by abundant intermolecular hydrogen bonds and π…π stacking interactions form a 3D supramolecular structure. However, it is worth noting that when the two complexes are synthesized, except for the metal cations, the anions and other reagents and conditions are the same. Still, in Zn-CP, Zn2+ is in the center of the deformed tetrahedron with four coordinations, and the carboxyl groups in the NDA2- ligands are all involved in the coordination, which is a bidentate bridging ligand. The final structure of the coordination polymer is a 1D ladder-shaped chain. In Ni-CP, Ni2+ is in the center of the deformed octahedron with hexacoordination, but only one carboxyl group is involved in the coordination in the NDA2- ligand, which is a monodentate ligand end-group ligand, so the coordination polymer is only a 1D twisted trapezoidal chain. In addition, the solid-state fluorescence test results under 275 nm excitation showed that Zn-CP exhibited good fluorescence properties at 363 nm. Furthermore, the electrocatalytic performance test for nitrate reduction to ammonia indicated that Ni-CP exhibited a certain degree of electrocatalytic ability for nitrate reduction to ammonia.
2026, 42(1): 65-77
doi: 10.11862/CJIC.20250172
Abstract:
To address the issues of high carrier recombination rate and poor photoresponse capability in photocatalysts, a visible-light-responsive Bi12TiO20/BaTiO3 composite piezo-photocatalyst was synthesized in situ by the "shearing effect" of alkaline KOH. The built-in electric field of BaTiO3 was utilized to modulate the photogenerated carrier transport behavior in Bi12TiO20, thereby enhancing charge separation efficiency. The synthesized powders were systematically characterized using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), ultraviolet-visible (UV-Vis) absorption spectroscopy, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM), with particular focus on phase composition and morphological evolution. The time-dependent formation process of Bi12TiO20/BaTiO3 was successfully elucidated. The piezo-photocatalytic degradation reaction rate constant of Bi12TiO20/BaTiO3 for dyes reached 9.76×10-2 min-1, outperforming that of piezocatalysis (2.39×10-2 min-1) and photocatalysis (8.17×10-2 min-1). Furthermore, the enhanced piezo-photocatalytic mechanism was elucidated by combining free radical trapping experiments, electron spin resonance (ESR) spectroscopy, and the band structure of the Bi12TiO20/BaTiO3 heterojunction.
To address the issues of high carrier recombination rate and poor photoresponse capability in photocatalysts, a visible-light-responsive Bi12TiO20/BaTiO3 composite piezo-photocatalyst was synthesized in situ by the "shearing effect" of alkaline KOH. The built-in electric field of BaTiO3 was utilized to modulate the photogenerated carrier transport behavior in Bi12TiO20, thereby enhancing charge separation efficiency. The synthesized powders were systematically characterized using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), ultraviolet-visible (UV-Vis) absorption spectroscopy, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM), with particular focus on phase composition and morphological evolution. The time-dependent formation process of Bi12TiO20/BaTiO3 was successfully elucidated. The piezo-photocatalytic degradation reaction rate constant of Bi12TiO20/BaTiO3 for dyes reached 9.76×10-2 min-1, outperforming that of piezocatalysis (2.39×10-2 min-1) and photocatalysis (8.17×10-2 min-1). Furthermore, the enhanced piezo-photocatalytic mechanism was elucidated by combining free radical trapping experiments, electron spin resonance (ESR) spectroscopy, and the band structure of the Bi12TiO20/BaTiO3 heterojunction.
2026, 42(1): 78-86
doi: 10.11862/CJIC.20250141
Abstract:
Through in situ reaction, two complexes [Ni(HL1)2]·CH3CN·CH3OH (1) and [Ni(L2)2] (2), where H2L1=2-hydroxy-benzoic acid (6-methoxy-pyridin-2-ylmethylene)-hydrazide and HL2=4-bromo-2-[(6-methoxy-pyridin-2-ylmethylene)-amino]-phenol, were designed and synthesized. A comprehensive analysis of the complexes' structures and properties was performed using single-crystal X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and X-ray photoelectron spectroscopy. Single crystal X-ray diffraction results show that both complexes 1 and 2 are centered on Ni2+ ions and form a mononuclear zero-dimensional structure. The antibacterial properties of complexes 1-2 were investigated using the agar well diffusion method, and the results show that both complexes have more potent antibacterial activity compared to a single transition metal nickel ion. The interaction between complexes 1-2 and calf thymus DNA (CTDNA) was studied using UV-Vis spectroscopy, the cyclic voltammetry method, and fluorescence spectroscopy. The results show that the two complexes bind to CTDNA mainly through intercalation.
Through in situ reaction, two complexes [Ni(HL1)2]·CH3CN·CH3OH (1) and [Ni(L2)2] (2), where H2L1=2-hydroxy-benzoic acid (6-methoxy-pyridin-2-ylmethylene)-hydrazide and HL2=4-bromo-2-[(6-methoxy-pyridin-2-ylmethylene)-amino]-phenol, were designed and synthesized. A comprehensive analysis of the complexes' structures and properties was performed using single-crystal X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and X-ray photoelectron spectroscopy. Single crystal X-ray diffraction results show that both complexes 1 and 2 are centered on Ni2+ ions and form a mononuclear zero-dimensional structure. The antibacterial properties of complexes 1-2 were investigated using the agar well diffusion method, and the results show that both complexes have more potent antibacterial activity compared to a single transition metal nickel ion. The interaction between complexes 1-2 and calf thymus DNA (CTDNA) was studied using UV-Vis spectroscopy, the cyclic voltammetry method, and fluorescence spectroscopy. The results show that the two complexes bind to CTDNA mainly through intercalation.
2026, 42(1): 87-96
doi: 10.11862/CJIC.20250127
Abstract:
This study developed a facile and green method using vinegar as the carbon source to prepare fluorescent carbon quantum dots (vCDs) via direct dialysis. The synthesized vCDs were characterized by morphology, composition, and fluorescent properties. The results showed that the vCDs had a mass concentration of 0.006 2 g·mL-1. The vCDs showed the uniform particle distribution with an average size of 4.05 nm and displayed optimal fluorescence emission at 460 nm. Notably, the vCDs showed excellent photostability and salt resistance. Furthermore, the fluorescence of vCDs was highly sensitive to pH due to the surface protonation effects and Fe3+ via selective fluorescence quenching, which endowed the potential capacity in pH and Fe3+ sensing. Besides, vCDs were incorporated into polyvinyl butyral (PVB) to fabricate the fluorescent films.
This study developed a facile and green method using vinegar as the carbon source to prepare fluorescent carbon quantum dots (vCDs) via direct dialysis. The synthesized vCDs were characterized by morphology, composition, and fluorescent properties. The results showed that the vCDs had a mass concentration of 0.006 2 g·mL-1. The vCDs showed the uniform particle distribution with an average size of 4.05 nm and displayed optimal fluorescence emission at 460 nm. Notably, the vCDs showed excellent photostability and salt resistance. Furthermore, the fluorescence of vCDs was highly sensitive to pH due to the surface protonation effects and Fe3+ via selective fluorescence quenching, which endowed the potential capacity in pH and Fe3+ sensing. Besides, vCDs were incorporated into polyvinyl butyral (PVB) to fabricate the fluorescent films.
2026, 42(1): 97-110
doi: 10.11862/CJIC.20250116
Abstract:
A series of Cu2O/CuO composite structures with adjustable valence states was successfully prepared by calcining nano-Cu2O prepared by the liquid phase reduction method. The composite conventional catalytic performances under dark conditions and photo-assisted catalytic performances for hydrogen production by hydrolysis of ammonia borane were tested, respectively. The catalysts were systematically characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and a UV-visible spectrophotometer. The results show that the Cu2O/CuO composite formed a raspberry-like nano-hollow sphere, in which the CuO content increases with increasing calcination time, and the absorption and utilization of visible light were enhanced compared to single-phase Cu2O. Under visible light-assisted conditions, the rate of hydrogen production by catalytic hydrolysis of the composite structure could reach up to 150.09 mL·g-1·min-1, and the activation energy required for the reaction was only 37.1 kJ·mol-1, which was significantly better than that under dark conditions. The Cu2O/CuO catalyst underwent surface reconstruction to form Cu/Cu2O/CuO during the catalytic hydrolysis of ammonia borane. The composite structure of metal and oxide provides a more efficient active hydrogen production process under visible light, thereby enhancing the catalytic activity.
A series of Cu2O/CuO composite structures with adjustable valence states was successfully prepared by calcining nano-Cu2O prepared by the liquid phase reduction method. The composite conventional catalytic performances under dark conditions and photo-assisted catalytic performances for hydrogen production by hydrolysis of ammonia borane were tested, respectively. The catalysts were systematically characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and a UV-visible spectrophotometer. The results show that the Cu2O/CuO composite formed a raspberry-like nano-hollow sphere, in which the CuO content increases with increasing calcination time, and the absorption and utilization of visible light were enhanced compared to single-phase Cu2O. Under visible light-assisted conditions, the rate of hydrogen production by catalytic hydrolysis of the composite structure could reach up to 150.09 mL·g-1·min-1, and the activation energy required for the reaction was only 37.1 kJ·mol-1, which was significantly better than that under dark conditions. The Cu2O/CuO catalyst underwent surface reconstruction to form Cu/Cu2O/CuO during the catalytic hydrolysis of ammonia borane. The composite structure of metal and oxide provides a more efficient active hydrogen production process under visible light, thereby enhancing the catalytic activity.
2026, 42(1): 111-119
doi: 10.11862/CJIC.20250121
Abstract:
A vinylimidazole-terpyridine ionic liquid monomer containing bromide ions (TerVi[Br]) was synthesized using low-toxicity ethyl acetate as the solvent. After polymerization, a hydrophobic polymeric ionic liquid (PTerVi[Tf2N]) was subsequently obtained by introducing the bis(trifluoromethanesulfonyl)imide anion (Tf2N-) via ion exchange. The terpyridine group in the structure not only effectively coordinates with the rare-earth Eu3+ ion but also acts as an "antenna" to sensitize its luminescence, enabling the construction of high-performance rare-earth luminescent materials. The influence of the sequence of polymerization and ion exchange on the structure and properties of the materials was systematically investigated. It was found that the product obtained via the "polymerization first, then ion exchange" route (PTerVi[Tf2N]-Eu) exhibited significantly better luminescence performance than that prepared by the "ion exchange first, then polymerization" route (P(TerVi[Tf2N])-Eu). Specifically, PTerVi[Tf2N]-Eu achieved a quantum yield of 20.52%, higher than the 15.70% of P(TerVi[Tf2N])-Eu, along with a longer fluorescence lifetime of the 5D0 energy level of Eu3+.
A vinylimidazole-terpyridine ionic liquid monomer containing bromide ions (TerVi[Br]) was synthesized using low-toxicity ethyl acetate as the solvent. After polymerization, a hydrophobic polymeric ionic liquid (PTerVi[Tf2N]) was subsequently obtained by introducing the bis(trifluoromethanesulfonyl)imide anion (Tf2N-) via ion exchange. The terpyridine group in the structure not only effectively coordinates with the rare-earth Eu3+ ion but also acts as an "antenna" to sensitize its luminescence, enabling the construction of high-performance rare-earth luminescent materials. The influence of the sequence of polymerization and ion exchange on the structure and properties of the materials was systematically investigated. It was found that the product obtained via the "polymerization first, then ion exchange" route (PTerVi[Tf2N]-Eu) exhibited significantly better luminescence performance than that prepared by the "ion exchange first, then polymerization" route (P(TerVi[Tf2N])-Eu). Specifically, PTerVi[Tf2N]-Eu achieved a quantum yield of 20.52%, higher than the 15.70% of P(TerVi[Tf2N])-Eu, along with a longer fluorescence lifetime of the 5D0 energy level of Eu3+.
2026, 42(1): 120-128
doi: 10.11862/CJIC.20250091
Abstract:
Graphene oxide (GO)/gold nanorod (AuNR) composite (GO/AuNR)n assemblies with different numbers of assembly layers were constructed on amino-modified silicon wafers using an electrostatic adsorption layer-by-layer assembly technique. The performance of these composite assemblies in the catalytic reduction of 4-nitrophenol (4-NP) and the photocatalytic degradation of rhodamine B (RhB) was systematically investigated. Furthermore, their application as surface-enhanced Raman scattering (SERS) substrates for detecting various pollutants (such as 4-NP, RhB, pyridine, and 4-aminothiophenol) and for real-time in situ monitoring of the aforementioned catalytic reaction processes was evaluated. The results indicated that the (GO/AuNR)n composite assemblies exhibited superior catalytic activity and SERS enhancement performance compared to AuNR alone. Moreover, both the catalytic and SERS performances were significantly enhanced with an increasing number of assembly layers.
Graphene oxide (GO)/gold nanorod (AuNR) composite (GO/AuNR)n assemblies with different numbers of assembly layers were constructed on amino-modified silicon wafers using an electrostatic adsorption layer-by-layer assembly technique. The performance of these composite assemblies in the catalytic reduction of 4-nitrophenol (4-NP) and the photocatalytic degradation of rhodamine B (RhB) was systematically investigated. Furthermore, their application as surface-enhanced Raman scattering (SERS) substrates for detecting various pollutants (such as 4-NP, RhB, pyridine, and 4-aminothiophenol) and for real-time in situ monitoring of the aforementioned catalytic reaction processes was evaluated. The results indicated that the (GO/AuNR)n composite assemblies exhibited superior catalytic activity and SERS enhancement performance compared to AuNR alone. Moreover, both the catalytic and SERS performances were significantly enhanced with an increasing number of assembly layers.
2026, 42(1): 129-140
doi: 10.11862/CJIC.20250069
Abstract:
A series of Mn4+ doped Li0.5La0.5MgSrWO6∶xMn4+ (LLMSW∶xMn4+) phosphors based on the A-site cation substitution strategy were synthesized by the high-temperature solid-state reaction method, and their structure and properties were investigated systematically. The results showed that the prepared LLSMW∶xMn4+ phosphors had an octahedral structure. In this structure, Mn4+ occupied the center of the octahedron. And the co-doped Li+ coupled with La3+ formed a cation-pair, which not only balances charges but also changes the local symmetry of the Mn4+ site. Meanwhile, the introduction of cation pairs may break the reversal symmetry of the luminescence center and facilitate the luminescence enhancement of the 2Eg→4A2g transition. The LLSMW∶xMn4+ phosphors had a broad excitation band in the range of 270-600 nm, attributed to the Mn→O charge transfer band (318 nm), 4A2g→4T1g (342 nm), 4A2g→2T2g (361 nm), and 4A2g→4T2g (484 nm) spin-allowed transitions of Mn4+ ions, respectively. Excited by 332 nm light, the photoluminescence (PL) spectrum with the peak at 708 nm had a broad band between 650 and 800 nm due to the 2Eg→4A2g transition of Mn4+. The optimal doping concentration of Mn4+ was 0.012, with a 1.528 ms decay lifetime, and its quantum yield was 65.74%. When the temperature rose to 423 K, the fluorescence intensity decreased to 53.1% of that at room temperature, and the activation energy was 0.32 eV. A deep red-emitting LED device with a 365 nm near ultraviolet (NUV) chip was fabricated. The color coordinates of the LED were located at (0.724 0, 0.269 6), and the color purity was determined to be 98.1% under excitation at a current of 40 mA. Furthermore, its electroluminescence (EL) spectrum could effectively match the absorption spectrum of phytochrome (Pfr).
A series of Mn4+ doped Li0.5La0.5MgSrWO6∶xMn4+ (LLMSW∶xMn4+) phosphors based on the A-site cation substitution strategy were synthesized by the high-temperature solid-state reaction method, and their structure and properties were investigated systematically. The results showed that the prepared LLSMW∶xMn4+ phosphors had an octahedral structure. In this structure, Mn4+ occupied the center of the octahedron. And the co-doped Li+ coupled with La3+ formed a cation-pair, which not only balances charges but also changes the local symmetry of the Mn4+ site. Meanwhile, the introduction of cation pairs may break the reversal symmetry of the luminescence center and facilitate the luminescence enhancement of the 2Eg→4A2g transition. The LLSMW∶xMn4+ phosphors had a broad excitation band in the range of 270-600 nm, attributed to the Mn→O charge transfer band (318 nm), 4A2g→4T1g (342 nm), 4A2g→2T2g (361 nm), and 4A2g→4T2g (484 nm) spin-allowed transitions of Mn4+ ions, respectively. Excited by 332 nm light, the photoluminescence (PL) spectrum with the peak at 708 nm had a broad band between 650 and 800 nm due to the 2Eg→4A2g transition of Mn4+. The optimal doping concentration of Mn4+ was 0.012, with a 1.528 ms decay lifetime, and its quantum yield was 65.74%. When the temperature rose to 423 K, the fluorescence intensity decreased to 53.1% of that at room temperature, and the activation energy was 0.32 eV. A deep red-emitting LED device with a 365 nm near ultraviolet (NUV) chip was fabricated. The color coordinates of the LED were located at (0.724 0, 0.269 6), and the color purity was determined to be 98.1% under excitation at a current of 40 mA. Furthermore, its electroluminescence (EL) spectrum could effectively match the absorption spectrum of phytochrome (Pfr).
2026, 42(1): 141-151
doi: 10.11862/CJIC.20250049
Abstract:
In this study, aluminum sulfate was used to enhance the leaching of bastnasite in mixed rare earth concentrate (MREC) by sulfuric acid, then triethyloctamine and N1923 were used to extract residual acid and rare earth elements in the leaching solution, sequentially to produce calcium sulfate and cryolite by-products and monazite concentrate. The results show that the strong coordination of Al with F not only strengthens the leaching but also eliminates the generation of HF, which is convenient for the separation and comprehensive recycling of rare earth (RE), F, and Al, and eliminates the environmental impact. For the 100 mesh MREC, the concentrate and RE leaching rates by a mix solution of 3.0 mol·L-1 H2SO4 and 0.3 mol·L-1 Al2(SO4)3 with a liquid-solid ratio (the ratio of the volume of liquid to the mass of solid in mineral fluid) of 32 mL·g-1 and a reaction of 135 ℃ and 200 r·min-1 for 2 h reached 68.00% and 66.91%, respectively. The leaching rate of F- and the decomposition rate of CaF2 are 94.42% and 99.3%, respectively. After triethyloctanamine extracted most of the residual acid in the leaching solution, the RE was directly extracted with N1923, and the extraction rate was 97.38%. The RE in the organic phase was stripped by HCl with a stripping rate of 98.05%, and the ratio of Al to RE in the stripping solution was only 0.008 0. The F-Al complex in raffinate was transferred to cryolite by adding an external fluorine source to realize the recovery of F-Al resources.
In this study, aluminum sulfate was used to enhance the leaching of bastnasite in mixed rare earth concentrate (MREC) by sulfuric acid, then triethyloctamine and N1923 were used to extract residual acid and rare earth elements in the leaching solution, sequentially to produce calcium sulfate and cryolite by-products and monazite concentrate. The results show that the strong coordination of Al with F not only strengthens the leaching but also eliminates the generation of HF, which is convenient for the separation and comprehensive recycling of rare earth (RE), F, and Al, and eliminates the environmental impact. For the 100 mesh MREC, the concentrate and RE leaching rates by a mix solution of 3.0 mol·L-1 H2SO4 and 0.3 mol·L-1 Al2(SO4)3 with a liquid-solid ratio (the ratio of the volume of liquid to the mass of solid in mineral fluid) of 32 mL·g-1 and a reaction of 135 ℃ and 200 r·min-1 for 2 h reached 68.00% and 66.91%, respectively. The leaching rate of F- and the decomposition rate of CaF2 are 94.42% and 99.3%, respectively. After triethyloctanamine extracted most of the residual acid in the leaching solution, the RE was directly extracted with N1923, and the extraction rate was 97.38%. The RE in the organic phase was stripped by HCl with a stripping rate of 98.05%, and the ratio of Al to RE in the stripping solution was only 0.008 0. The F-Al complex in raffinate was transferred to cryolite by adding an external fluorine source to realize the recovery of F-Al resources.
