Login In
2026 Volume 42 Issue 10
2026, 42(10): 2051-2062
doi: 10.11862/CJIC.20260204
Abstract:
Urea is an important agricultural fertilizer and chemical feedstock; however, its conventional production is plagued by high energy consumption and substantial carbon emissions. Electrocatalytic urea synthesis offers a green alternative that facilitates both carbon reduction and nitrogen resource recycling. Nevertheless, this route is currently hindered by key scientific bottlenecks, including the difficulty of activating reactants and low C-N coupling efficiency. Metal-organic frameworks (MOFs), featuring tunable active sites, porous architectures conducive to mass transfer, and functionalizable ligands, represent an ideal material platform to overcome these limitations. This review systematically summarizes recent advances in single-metal MOFs, multi-metal MOFs, and MOF-based composites for electrocatalytic urea production, with a focus on structural design strategies, catalytic mechanisms, and performance enhancement approaches. Furthermore, we critically analyze the persistent challenges regarding C-N coupling efficiency and reaction selectivity, and discuss the prospects for large-scale applications. This review aims to offer guidance for the rational design and development of high-performance electrocatalysts for urea synthesis.
Urea is an important agricultural fertilizer and chemical feedstock; however, its conventional production is plagued by high energy consumption and substantial carbon emissions. Electrocatalytic urea synthesis offers a green alternative that facilitates both carbon reduction and nitrogen resource recycling. Nevertheless, this route is currently hindered by key scientific bottlenecks, including the difficulty of activating reactants and low C-N coupling efficiency. Metal-organic frameworks (MOFs), featuring tunable active sites, porous architectures conducive to mass transfer, and functionalizable ligands, represent an ideal material platform to overcome these limitations. This review systematically summarizes recent advances in single-metal MOFs, multi-metal MOFs, and MOF-based composites for electrocatalytic urea production, with a focus on structural design strategies, catalytic mechanisms, and performance enhancement approaches. Furthermore, we critically analyze the persistent challenges regarding C-N coupling efficiency and reaction selectivity, and discuss the prospects for large-scale applications. This review aims to offer guidance for the rational design and development of high-performance electrocatalysts for urea synthesis.
2026, 42(10): 2063-2076
doi: 10.11862/CJIC.20260194
Abstract:
Aqueous zinc-ion batteries have attracted increasing attention for large-scale energy storage because of their intrinsic safety, low cost, high ionic conductivity, and environmental friendliness. However, the practical application of aqueous zinc-ion batteries is still limited by unstable Zn anodes and complex electrode/electrolyte interfacial reactions, including dendrite growth, hydrogen evolution, corrosion, interfacial by-product accumulation, and cathode dissolution. Electrolyte additives provide an efficient and readily implementable strategy to regulate these issues at the molecular and interfacial levels. In this review, recent progress in electrolyte additives for aqueous zinc-ion batteries is summarized with emphasis on their roles in modulating Zn2+ solvation structures, reconstructing the electric double layer and electrode/electrolyte interface, regulating Zn deposition texture, suppressing cathode dissolution and buffering interfacial pH fluctuations. The structure-function relationships of representative additives are discussed, and the remaining challenges associated with mechanistic understanding, additive consumption, long-term stability, multicomponent synergy, harsh-condition adaptability, and practical engineering are further highlighted. This review aims to provide guidance for the rational design of electrolyte additives toward highly reversible, durable, and scalable aqueous zinc-ion batteries.
Aqueous zinc-ion batteries have attracted increasing attention for large-scale energy storage because of their intrinsic safety, low cost, high ionic conductivity, and environmental friendliness. However, the practical application of aqueous zinc-ion batteries is still limited by unstable Zn anodes and complex electrode/electrolyte interfacial reactions, including dendrite growth, hydrogen evolution, corrosion, interfacial by-product accumulation, and cathode dissolution. Electrolyte additives provide an efficient and readily implementable strategy to regulate these issues at the molecular and interfacial levels. In this review, recent progress in electrolyte additives for aqueous zinc-ion batteries is summarized with emphasis on their roles in modulating Zn2+ solvation structures, reconstructing the electric double layer and electrode/electrolyte interface, regulating Zn deposition texture, suppressing cathode dissolution and buffering interfacial pH fluctuations. The structure-function relationships of representative additives are discussed, and the remaining challenges associated with mechanistic understanding, additive consumption, long-term stability, multicomponent synergy, harsh-condition adaptability, and practical engineering are further highlighted. This review aims to provide guidance for the rational design of electrolyte additives toward highly reversible, durable, and scalable aqueous zinc-ion batteries.
2026, 42(10): 2077-2091
doi: 10.11862/CJIC.20260220
Abstract:
Using Keggin-type phosphomolybdic acid (H3PMo12O40) as the template and tetraisopropyl ethylenediphosphonate (L) as the neutral bidentate chelating ligand, four rare-earth complexes [Ln(L)3(H2O)2](PMo12O40)·4CH3CN (Ln=Pr, Tb, Dy, Er) were synthesized via a water-bath reflux method. The complexes were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, and solid-state UV-Vis diffuse reflectance spectroscopy. Single-crystal structure determination revealed that the four complexes are isostructural and crystallize in the triclinic space group P1. Each central Ln3+ ion adopts an eight-coordinate distorted square-antiprism geometry, coordinated by three bidentate chelating L ligands and two water molecules. The polyoxometalate anions serve as counterions and are held in the lattice via hydrogen bonds. Thermogravimetric analysis recorded three-stage mass-loss processes for all complexes. The optical band gaps, calculated from solid-state UV-Vis diffuse reflectance spectra, were 2.56-2.57 eV. Photocatalytic degradation experiments of the complexes on rhodamine B showed degradation rates of 95.21%-97.53% within 90 min of UV irradiation. Radical trapping experiments identified ·OH, ·O2- and h+ as the reactive species participating in the photocatalytic process. Terahertz time-domain spectroscopy (0.4-2.4 THz) recorded characteristic absorption peaks arising from ligand skeleton vibrations and intermolecular weak interactions, with spectral profiles remaining largely unchanged across the four lanthanide centers.
Using Keggin-type phosphomolybdic acid (H3PMo12O40) as the template and tetraisopropyl ethylenediphosphonate (L) as the neutral bidentate chelating ligand, four rare-earth complexes [Ln(L)3(H2O)2](PMo12O40)·4CH3CN (Ln=Pr, Tb, Dy, Er) were synthesized via a water-bath reflux method. The complexes were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, and solid-state UV-Vis diffuse reflectance spectroscopy. Single-crystal structure determination revealed that the four complexes are isostructural and crystallize in the triclinic space group P1. Each central Ln3+ ion adopts an eight-coordinate distorted square-antiprism geometry, coordinated by three bidentate chelating L ligands and two water molecules. The polyoxometalate anions serve as counterions and are held in the lattice via hydrogen bonds. Thermogravimetric analysis recorded three-stage mass-loss processes for all complexes. The optical band gaps, calculated from solid-state UV-Vis diffuse reflectance spectra, were 2.56-2.57 eV. Photocatalytic degradation experiments of the complexes on rhodamine B showed degradation rates of 95.21%-97.53% within 90 min of UV irradiation. Radical trapping experiments identified ·OH, ·O2- and h+ as the reactive species participating in the photocatalytic process. Terahertz time-domain spectroscopy (0.4-2.4 THz) recorded characteristic absorption peaks arising from ligand skeleton vibrations and intermolecular weak interactions, with spectral profiles remaining largely unchanged across the four lanthanide centers.
2026, 42(10): 2092-2098
doi: 10.11862/CJIC.20260157
Abstract:
Glutathione (GSH)-responsive nano-sized metal-organic framework (nMOF) materials, namely Cu-TCPP-nMOF, with tetrakis(4-carboxyphenyl)porphyrin (TCPP) as the ligand, were successfully synthesized based on the hydrothermal reaction method. Due to the presence of variable valence metals, this nanomaterial exhibited strong peroxidase-like activity. In the presence of H2O2, it could catalyze the reaction of the enzyme substrate 3, 3′, 5, 5′-tetramethylbenzidine (TMB), causing the color of the reaction system to change from colorless to blue. In addition, this nanomaterial can serve as a GSH-responsive colorimetric nanoprobes for highly sensitive detection of GSH. Cu-TCPP-nMOF could react with GSH, and the color of TMB+H2O2 system gradually faded with the gradual addition of GSH. The linear range of GSH detection was 10-60 μmol·L-1, and the detection limit reached 1.20 μmol·L-1.
Glutathione (GSH)-responsive nano-sized metal-organic framework (nMOF) materials, namely Cu-TCPP-nMOF, with tetrakis(4-carboxyphenyl)porphyrin (TCPP) as the ligand, were successfully synthesized based on the hydrothermal reaction method. Due to the presence of variable valence metals, this nanomaterial exhibited strong peroxidase-like activity. In the presence of H2O2, it could catalyze the reaction of the enzyme substrate 3, 3′, 5, 5′-tetramethylbenzidine (TMB), causing the color of the reaction system to change from colorless to blue. In addition, this nanomaterial can serve as a GSH-responsive colorimetric nanoprobes for highly sensitive detection of GSH. Cu-TCPP-nMOF could react with GSH, and the color of TMB+H2O2 system gradually faded with the gradual addition of GSH. The linear range of GSH detection was 10-60 μmol·L-1, and the detection limit reached 1.20 μmol·L-1.
2026, 42(10): 2099-2108
doi: 10.11862/CJIC.20260150
Abstract:
A nano-sized copper coordination polymer, {[Cu(4, 4′-bipy)(H2O)3(SO4)]·2H2O}n (Cu-CP), was successfully synthesized via a room-temperature solid-state reaction method using CuSO4·5H2O and 4, 4′-bipyridine (4, 4′-bipy) as the starting materials. Scanning electron microscopy (SEM) characterization revealed that the as-prepared Cu-CP exhibited a uniform particle morphology, with particle sizes predominantly distributed in the range of 100-300 nm. The adsorption performance of Cu-CP toward various organic dyes in aqueous solutions was systematically investigated. Impressively, Cu-CP demonstrated excellent removal efficiency toward Congo red (CR) dye, achieving an adsorption capacity as high as 5 486 mg·g-1 and a removal rate of 99.50% in 30 min. Kinetic studies demonstrated that the adsorption process follows the pseudo-second-order kinetic model, while thermodynamic analysis further confirmed that the adsorption is spontaneous, exothermic, and proceeds predominantly via monolayer chemisorption. More importantly, the ball-milling-assisted room-temperature solid-state synthetic route adopted offers multiple advantages, including straightforward operation, solvent-free conditions, facile scalability, and high product yield.
A nano-sized copper coordination polymer, {[Cu(4, 4′-bipy)(H2O)3(SO4)]·2H2O}n (Cu-CP), was successfully synthesized via a room-temperature solid-state reaction method using CuSO4·5H2O and 4, 4′-bipyridine (4, 4′-bipy) as the starting materials. Scanning electron microscopy (SEM) characterization revealed that the as-prepared Cu-CP exhibited a uniform particle morphology, with particle sizes predominantly distributed in the range of 100-300 nm. The adsorption performance of Cu-CP toward various organic dyes in aqueous solutions was systematically investigated. Impressively, Cu-CP demonstrated excellent removal efficiency toward Congo red (CR) dye, achieving an adsorption capacity as high as 5 486 mg·g-1 and a removal rate of 99.50% in 30 min. Kinetic studies demonstrated that the adsorption process follows the pseudo-second-order kinetic model, while thermodynamic analysis further confirmed that the adsorption is spontaneous, exothermic, and proceeds predominantly via monolayer chemisorption. More importantly, the ball-milling-assisted room-temperature solid-state synthetic route adopted offers multiple advantages, including straightforward operation, solvent-free conditions, facile scalability, and high product yield.
2026, 42(10): 2109-2118
doi: 10.11862/CJIC.20260145
Abstract:
Based on the modification of polydopamine (PDA), the catechol functional groups, which can adsorb cations, were in situ formed on the surface of carbon nanotubes (CNTs). With the incipient wetness impregnation method of manganese acetate, the MnOx was generated in situ on the surface of CNTs, and the MnOx/PDA@CNTs catalysts were prepared. The N2 adsorption-desorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), and denitration performance were applied to characterize the microstructure and properties. The interaction effects between loading and Brunauer-Emmett-Teller (BET) surface area were analysed using response surface methodology (RSM) based on the central composite design (CCD), and the loading of the denitration catalyst with the optimal denitration efficiency and BET surface area could be obtained through optimization. The results indicated that after loading the active components, the resultant catalysts showed a larger BET surface. Meanwhile, the active components of MnO2, Mn2O3, and MnO were formed on the surface of CNTs. Among the prepared catalysts, the 1.40%MnOx/PDA@CNTs catalyst exhibited the best selective catalytic reduction (SCR) activity at 180 ℃, and the denitration efficiency could reach 86.2%. The results of response surface optimization revealed that the 1.44%MnOx/PDA@CNTs catalyst obtained optimal denitration efficiency (85.1%) and BET surface area (88 m2·g-1). Again, the results of three validation experiments indicated that the denitration efficiencies of 1.44%MnOx/PDA@CNTs were 84.6%, 87.9%, and 86.5%, respectively. Meanwhile, the BET surface areas were 86, 87, and 89 m2·g-1, respectively. The above results suggested that the denitration efficiencies and BET surface areas of the 1.44%MnOx/PDA@CNTs catalyst from the response surface optimization were almost the same as those of the 1.40%MnOx/PDA@CNTs catalyst originating from the optimal experiment, revealing the good predictive ability of the CCD model.
Based on the modification of polydopamine (PDA), the catechol functional groups, which can adsorb cations, were in situ formed on the surface of carbon nanotubes (CNTs). With the incipient wetness impregnation method of manganese acetate, the MnOx was generated in situ on the surface of CNTs, and the MnOx/PDA@CNTs catalysts were prepared. The N2 adsorption-desorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), and denitration performance were applied to characterize the microstructure and properties. The interaction effects between loading and Brunauer-Emmett-Teller (BET) surface area were analysed using response surface methodology (RSM) based on the central composite design (CCD), and the loading of the denitration catalyst with the optimal denitration efficiency and BET surface area could be obtained through optimization. The results indicated that after loading the active components, the resultant catalysts showed a larger BET surface. Meanwhile, the active components of MnO2, Mn2O3, and MnO were formed on the surface of CNTs. Among the prepared catalysts, the 1.40%MnOx/PDA@CNTs catalyst exhibited the best selective catalytic reduction (SCR) activity at 180 ℃, and the denitration efficiency could reach 86.2%. The results of response surface optimization revealed that the 1.44%MnOx/PDA@CNTs catalyst obtained optimal denitration efficiency (85.1%) and BET surface area (88 m2·g-1). Again, the results of three validation experiments indicated that the denitration efficiencies of 1.44%MnOx/PDA@CNTs were 84.6%, 87.9%, and 86.5%, respectively. Meanwhile, the BET surface areas were 86, 87, and 89 m2·g-1, respectively. The above results suggested that the denitration efficiencies and BET surface areas of the 1.44%MnOx/PDA@CNTs catalyst from the response surface optimization were almost the same as those of the 1.40%MnOx/PDA@CNTs catalyst originating from the optimal experiment, revealing the good predictive ability of the CCD model.
2026, 42(10): 2119-2126
doi: 10.11862/CJIC.20260140
Abstract:
Solvothermal reactions of 2, 7-bis(4-pyridylvinyl)pyrene (2, 7-bpep) with Zn(Ⅱ) salt and terephthalic acid (H2PTA) and pimelic acid (H2GDA) afforded two photoreactive metal-organic frameworks (MOFs), {[Zn2(2, 7-bpep)2(PTA)2]·2DMA}n (MOF1) and [Zn(2, 7-bpep)(GDA)]n (MOF2) (DMA=N, N-dimethylacetamide). Single-crystal X-ray diffraction analysis reveals that the 2, 7-bpep ligands adopt a face-to-face arrangement with olefinic double bonds positioned at distances consistent with Schmidt's criteria, thereby enabling solid-state [2+2] photocycloaddition. Upon irradiation with 420 nm visible light, both MOFs undergo quantitative [2+2] cycloaddition to yield the corresponding cyclobutane-linked frameworks (MOF1C and MOF2C), while MOF1C retains crystallinity. Photophysical studies show that these transformations cause pronounced blue shifts in emission relative to the parent frameworks, attributable to disrupted π-conjugation upon cyclobutane formation. These findings demonstrate that rational preorganization of photoactive ligands within MOFs provides an effective strategy for controlling solid-state photoreactivity and tuning luminescence properties, offering insights into the design of photoresponsive functional materials.
Solvothermal reactions of 2, 7-bis(4-pyridylvinyl)pyrene (2, 7-bpep) with Zn(Ⅱ) salt and terephthalic acid (H2PTA) and pimelic acid (H2GDA) afforded two photoreactive metal-organic frameworks (MOFs), {[Zn2(2, 7-bpep)2(PTA)2]·2DMA}n (MOF1) and [Zn(2, 7-bpep)(GDA)]n (MOF2) (DMA=N, N-dimethylacetamide). Single-crystal X-ray diffraction analysis reveals that the 2, 7-bpep ligands adopt a face-to-face arrangement with olefinic double bonds positioned at distances consistent with Schmidt's criteria, thereby enabling solid-state [2+2] photocycloaddition. Upon irradiation with 420 nm visible light, both MOFs undergo quantitative [2+2] cycloaddition to yield the corresponding cyclobutane-linked frameworks (MOF1C and MOF2C), while MOF1C retains crystallinity. Photophysical studies show that these transformations cause pronounced blue shifts in emission relative to the parent frameworks, attributable to disrupted π-conjugation upon cyclobutane formation. These findings demonstrate that rational preorganization of photoactive ligands within MOFs provides an effective strategy for controlling solid-state photoreactivity and tuning luminescence properties, offering insights into the design of photoresponsive functional materials.
2026, 42(10): 2127-2137
doi: 10.11862/CJIC.20260127
Abstract:
Using Ni-Mo bimetallic-oxygen clusters as precursors, a mesoporous carbon-coated high-activity NiMoS hydrodesulfurization catalyst (NiMoS/C-FD) was constructed through an in-situ synthesis strategy. By combining the introduction of the precursor and the preparation of the support, the spatial encapsulation and uniform dispersion of metal active components in the mesoporous carbon support were achieved. The as-prepared catalyst was analyzed using various techniques such as X-ray diffraction, N2 adsorption-desorption, scanning electron microscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, etc. Compared with the reference catalyst (NiMoS/C-IM) prepared by the traditional impregnation method, the MoS2 particles of the as-prepared catalyst (NiMoS/C-FD) had a smaller size, higher dispersion, more sulfurization, and formed more highly active NiMoS phases. In the hydrodesulfurization evaluation, the catalyst showed excellent catalytic performance, with a conversion rate of 93.2%. The reaction rate constant and turnover frequency reached 1.6×10-6 mol·g-1·s-1 and 3.3×10-3 s-1, respectively, which were significantly higher than NiMoS/C-IM.
Using Ni-Mo bimetallic-oxygen clusters as precursors, a mesoporous carbon-coated high-activity NiMoS hydrodesulfurization catalyst (NiMoS/C-FD) was constructed through an in-situ synthesis strategy. By combining the introduction of the precursor and the preparation of the support, the spatial encapsulation and uniform dispersion of metal active components in the mesoporous carbon support were achieved. The as-prepared catalyst was analyzed using various techniques such as X-ray diffraction, N2 adsorption-desorption, scanning electron microscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, etc. Compared with the reference catalyst (NiMoS/C-IM) prepared by the traditional impregnation method, the MoS2 particles of the as-prepared catalyst (NiMoS/C-FD) had a smaller size, higher dispersion, more sulfurization, and formed more highly active NiMoS phases. In the hydrodesulfurization evaluation, the catalyst showed excellent catalytic performance, with a conversion rate of 93.2%. The reaction rate constant and turnover frequency reached 1.6×10-6 mol·g-1·s-1 and 3.3×10-3 s-1, respectively, which were significantly higher than NiMoS/C-IM.
Hydrogen evolution performance of light-assisted defect-rich MoS2 nanoflowers for water electrolysis
2026, 42(10): 2138-2152
doi: 10.11862/CJIC.20260117
Abstract:
A MoS2 nanoflower catalyst containing a large amount of low-coordination Mo atoms, unsaturated S sites, and oxygen-rich doping was prepared using a simple one-step hydrothermal method, and it was applied in electrocatalytic hydrogen evolution reaction. Meanwhile, the effects of temperature and raw material ratio on the activity of MoS2 catalysts were studied. The experimental results showed that the MoS2 nanoflower catalyst prepared under hydrothermal conditions at 200 ℃ and with a mass ratio of S to Mo (mS/mMo) of 2.0 exhibited excellent electrocatalytic activity for hydrogen evolution reaction in 0.5 mol·L-1 H2SO4 electrolyte. This catalyst had a high specific surface area, excellent intrinsic conductivity, and good long-term operational stability; at a current density of 10 mA·cm-2, its overpotential was 258.98 mV and the Tafel slope was 68.26 mV·dec-1, indicating its rapid kinetic response capability. The improvement in performance can be attributed to the synergistic effect of two aspects: on the one hand, the in-situ doping of oxygen atoms effectively regulated the electronic structure of MoS2, increased the carrier concentration and mobility, thereby optimizing the intrinsic conductivity. On the other hand, the rich defect structure (including a large number of low-coordination Mo atoms and unsaturated S sites) significantly activated the originally inert MoS2 basal plane, significantly increasing the density of accessible catalytic active sites, achieving multi-directional coordinated regulation of nanoflower morphology, defect configuration, and electronic state. With the assistance of light, the interface electron transmission dynamics can be significantly accelerated, and the hydrogen evolution reaction performance is further improved. At 10 mA·cm-2, the overpotential was reduced to 228 mV.
A MoS2 nanoflower catalyst containing a large amount of low-coordination Mo atoms, unsaturated S sites, and oxygen-rich doping was prepared using a simple one-step hydrothermal method, and it was applied in electrocatalytic hydrogen evolution reaction. Meanwhile, the effects of temperature and raw material ratio on the activity of MoS2 catalysts were studied. The experimental results showed that the MoS2 nanoflower catalyst prepared under hydrothermal conditions at 200 ℃ and with a mass ratio of S to Mo (mS/mMo) of 2.0 exhibited excellent electrocatalytic activity for hydrogen evolution reaction in 0.5 mol·L-1 H2SO4 electrolyte. This catalyst had a high specific surface area, excellent intrinsic conductivity, and good long-term operational stability; at a current density of 10 mA·cm-2, its overpotential was 258.98 mV and the Tafel slope was 68.26 mV·dec-1, indicating its rapid kinetic response capability. The improvement in performance can be attributed to the synergistic effect of two aspects: on the one hand, the in-situ doping of oxygen atoms effectively regulated the electronic structure of MoS2, increased the carrier concentration and mobility, thereby optimizing the intrinsic conductivity. On the other hand, the rich defect structure (including a large number of low-coordination Mo atoms and unsaturated S sites) significantly activated the originally inert MoS2 basal plane, significantly increasing the density of accessible catalytic active sites, achieving multi-directional coordinated regulation of nanoflower morphology, defect configuration, and electronic state. With the assistance of light, the interface electron transmission dynamics can be significantly accelerated, and the hydrogen evolution reaction performance is further improved. At 10 mA·cm-2, the overpotential was reduced to 228 mV.
2026, 42(10): 2153-2161
doi: 10.11862/CJIC.20260082
Abstract:
A ratiometric fluorescent probe TCM was designed and synthesized based on carbazole and pyrazole fluorophores to detect trace hydrazine sensitively. Spectroscopic studies revealed that TCM exhibits an exceptionally large Stokes shift (241 nm) and a single-excitation, dual-emission characteristic. After reacting with hydrazine, TCM showed reduced orange-yellow fluorescence at 601 nm and enhanced blue fluorescence at 411 nm, with the fluorescence intensity ratio (F601/F411) decreasing by 97%. The fluorescence recognition mechanism and ratiometric response mode of the probe based on intramolecular charge transfer (ICT) were verified by mass spectrometry and density functional theory (DFT) calculations. In addition, TCM exhibited excellent selectivity, strong anti-interference performance, short response time (20 min), and a low detection limit (0.15 μmol·L-1). TCM has been successfully used to detect hydrazine in real water samples and soil, and has been fabricated into fluorescent filter paper strips for qualitative hydrazine analysis.
A ratiometric fluorescent probe TCM was designed and synthesized based on carbazole and pyrazole fluorophores to detect trace hydrazine sensitively. Spectroscopic studies revealed that TCM exhibits an exceptionally large Stokes shift (241 nm) and a single-excitation, dual-emission characteristic. After reacting with hydrazine, TCM showed reduced orange-yellow fluorescence at 601 nm and enhanced blue fluorescence at 411 nm, with the fluorescence intensity ratio (F601/F411) decreasing by 97%. The fluorescence recognition mechanism and ratiometric response mode of the probe based on intramolecular charge transfer (ICT) were verified by mass spectrometry and density functional theory (DFT) calculations. In addition, TCM exhibited excellent selectivity, strong anti-interference performance, short response time (20 min), and a low detection limit (0.15 μmol·L-1). TCM has been successfully used to detect hydrazine in real water samples and soil, and has been fabricated into fluorescent filter paper strips for qualitative hydrazine analysis.
2026, 42(10): 2162-2168
doi: 10.11862/CJIC.20260071
Abstract:
A high-performance Ta-based halide electrolyte material (denoted Cs-LTOC) and an efficient preparation method were developed. Structural analysis revealed that the Cs-LTOC electrolyte primarily comprises three crystalline phases: LiTaCl6, LiTaOCl4, and Ta2O5. After process optimization, the as-prepared electrolyte material achieved a high ionic conductivity of 9.02 mS·cm-1 by simply co-sintering at 250 ℃ for 3 h. All-solid-state batteries assembled with this electrolyte and the high-nickel cathode material LiNi0.83Co0.12Mn0.05O2 (NCM83) exhibited excellent electrochemical performance. Specifically, at charge/discharge rates of 0.1C (1.0C=200 mA·g-1), 0.3C, 0.5C, 1.0C, 2.0C, 3.0C, and 5.0C, the NCM83 cathode delivered specific discharge capacities of 221.7, 212.1, 205.9, 195.2, 183.1, 174.8, and 160.8 mAh·g-1, respectively. Furthermore, it maintained an 81.2% capacity retention after 1 900 cycles at 5.0C.
A high-performance Ta-based halide electrolyte material (denoted Cs-LTOC) and an efficient preparation method were developed. Structural analysis revealed that the Cs-LTOC electrolyte primarily comprises three crystalline phases: LiTaCl6, LiTaOCl4, and Ta2O5. After process optimization, the as-prepared electrolyte material achieved a high ionic conductivity of 9.02 mS·cm-1 by simply co-sintering at 250 ℃ for 3 h. All-solid-state batteries assembled with this electrolyte and the high-nickel cathode material LiNi0.83Co0.12Mn0.05O2 (NCM83) exhibited excellent electrochemical performance. Specifically, at charge/discharge rates of 0.1C (1.0C=200 mA·g-1), 0.3C, 0.5C, 1.0C, 2.0C, 3.0C, and 5.0C, the NCM83 cathode delivered specific discharge capacities of 221.7, 212.1, 205.9, 195.2, 183.1, 174.8, and 160.8 mAh·g-1, respectively. Furthermore, it maintained an 81.2% capacity retention after 1 900 cycles at 5.0C.
2026, 42(10): 2169-2178
doi: 10.11862/CJIC.20260046
Abstract:
Bulky hexacoordinate anions, with main-group heavy elements as central atoms and fused-ring diphenols as ligands, can act as weakly coordinating ligands for the construction of novel functional coordination complexes with metals. In this work, reactions of 9, 10-phenanthrenequinone (C14H8O2, 1) and sodium 9, 10-phenanthrenediolate (C14H8O2Na2, 2) with SiCl4, GeCl4, SnCl2, and SbCl3 were carried out, leading to the first isolation of compounds of octahedral weakly coordinating anions of Si, Ge, Sn, and Sb chelated by three phenanthrenediolate ligands, namely [Na(THF)3]2[Si(C14H8O2)3] (3), [Na(THF)3]2[Ge(C14H8O2)3] (4), [Na(THF)3]2[Sn(C14H8O2)3] (5), and Na[Sb(C14H8O2)3] (6). Further cation-exchange reactions of 6 yielded tris(9, 10-phenanthrenediolato)antimonate(Ⅴ) salts (7 and 8), with [Li(THF)4]+ and Et3NH+ as counterions, respectively. All products were characterized by 1H and 13C NMR spectroscopy for composition and purity, and the structures of 3-5, 7, and 8 were determined by single-crystal X-ray diffraction. Structural analyses indicated that the core [EO6] units (E=Si, Ge, Sn) in 3-5 have strong internal bonding but weak interactions with peripheral Na+ cations, showing pronounced outward weak coordination. In 7 and 8, non-coordinating cation-anion contacts yield an ideal symmetric [SbO6] core, endowing the antimonate anion with greater resistance to cation perturbation.
Bulky hexacoordinate anions, with main-group heavy elements as central atoms and fused-ring diphenols as ligands, can act as weakly coordinating ligands for the construction of novel functional coordination complexes with metals. In this work, reactions of 9, 10-phenanthrenequinone (C14H8O2, 1) and sodium 9, 10-phenanthrenediolate (C14H8O2Na2, 2) with SiCl4, GeCl4, SnCl2, and SbCl3 were carried out, leading to the first isolation of compounds of octahedral weakly coordinating anions of Si, Ge, Sn, and Sb chelated by three phenanthrenediolate ligands, namely [Na(THF)3]2[Si(C14H8O2)3] (3), [Na(THF)3]2[Ge(C14H8O2)3] (4), [Na(THF)3]2[Sn(C14H8O2)3] (5), and Na[Sb(C14H8O2)3] (6). Further cation-exchange reactions of 6 yielded tris(9, 10-phenanthrenediolato)antimonate(Ⅴ) salts (7 and 8), with [Li(THF)4]+ and Et3NH+ as counterions, respectively. All products were characterized by 1H and 13C NMR spectroscopy for composition and purity, and the structures of 3-5, 7, and 8 were determined by single-crystal X-ray diffraction. Structural analyses indicated that the core [EO6] units (E=Si, Ge, Sn) in 3-5 have strong internal bonding but weak interactions with peripheral Na+ cations, showing pronounced outward weak coordination. In 7 and 8, non-coordinating cation-anion contacts yield an ideal symmetric [SbO6] core, endowing the antimonate anion with greater resistance to cation perturbation.
2026, 42(10): 2179-2185
doi: 10.11862/CJIC.20260068
Abstract:
Cs2PdBr6 microcrystals with a uniform grain size of approximately 1.3 μm were successfully prepared via a solvothermal route. Femtosecond transient absorption spectroscopy was utilized to clarify the ultrafast carrier relaxation behavior and dynamic mechanism of the obtained Cs2PdBr6 photocatalyst. The transient kinetic curves can be well fitted with three characteristic decay components. The ultrafast component (2.1 ps) is assigned to carrier trapping, which is primarily associated with abundant surface defect states. The intermediate component (853.8 ps) is attributed to the intrinsic radiative recombination of photogenerated electron-hole pairs. The slow component (4.1 ns) is ascribed to defect-mediated carrier relaxation, which prolongs the carrier lifetime by effectively suppressing radiative recombination. These results demonstrate the critical role of defect states in regulating carrier dynamics and promoting charge separation in Cs2PdBr6. Benefiting from the optimized carrier dynamics, the Cs2PdBr6 microcrystals exhibited excellent photocatalytic CO2 reduction performance, achieving CO and CH4 evolution rates of 14.4 and 1.5 μmol·g-1·h-1, respectively.
Cs2PdBr6 microcrystals with a uniform grain size of approximately 1.3 μm were successfully prepared via a solvothermal route. Femtosecond transient absorption spectroscopy was utilized to clarify the ultrafast carrier relaxation behavior and dynamic mechanism of the obtained Cs2PdBr6 photocatalyst. The transient kinetic curves can be well fitted with three characteristic decay components. The ultrafast component (2.1 ps) is assigned to carrier trapping, which is primarily associated with abundant surface defect states. The intermediate component (853.8 ps) is attributed to the intrinsic radiative recombination of photogenerated electron-hole pairs. The slow component (4.1 ns) is ascribed to defect-mediated carrier relaxation, which prolongs the carrier lifetime by effectively suppressing radiative recombination. These results demonstrate the critical role of defect states in regulating carrier dynamics and promoting charge separation in Cs2PdBr6. Benefiting from the optimized carrier dynamics, the Cs2PdBr6 microcrystals exhibited excellent photocatalytic CO2 reduction performance, achieving CO and CH4 evolution rates of 14.4 and 1.5 μmol·g-1·h-1, respectively.
2026, 42(10): 2186-2192
doi: 10.11862/CJIC.20260058
Abstract:
A microporous acs-metal-organic framework (MOF) is reported as [Fe2.9Mn0.1(μ3-OH)(L)3·xGuest] (NJTU-Bai88, NJTU-Bai=Nanjing Tech University Bai′s group; H2L=bicyclo[2.2.2]octane-1, 4-dicarboxylic acid), in which potential open metal sites (OMSs) are occupied by solvent molecules with the pore size adjusted (approximately 0.47 nm by Horváth-Kawazoe model) to be close to the kinetic diameter of C3H4 (0.476 nm) and the strong adsorption sites reduced. Interestingly, NJTU-Bai88 showed a high C3H4 adsorption uptake (27.5 cm3·g-1 at 298 K and 1 kPa) and moderate adsorption enthalpy (-58.8 kJ·mol-1).
A microporous acs-metal-organic framework (MOF) is reported as [Fe2.9Mn0.1(μ3-OH)(L)3·xGuest] (NJTU-Bai88, NJTU-Bai=Nanjing Tech University Bai′s group; H2L=bicyclo[2.2.2]octane-1, 4-dicarboxylic acid), in which potential open metal sites (OMSs) are occupied by solvent molecules with the pore size adjusted (approximately 0.47 nm by Horváth-Kawazoe model) to be close to the kinetic diameter of C3H4 (0.476 nm) and the strong adsorption sites reduced. Interestingly, NJTU-Bai88 showed a high C3H4 adsorption uptake (27.5 cm3·g-1 at 298 K and 1 kPa) and moderate adsorption enthalpy (-58.8 kJ·mol-1).
2026, 42(10): 2193-2202
doi: 10.11862/CJIC.20260156
Abstract:
A binder-free self-supported Mo-Ni alloy electrode was in-situ fabricated on a metallic Ti substrate through a facile one-step electrochemical deposition strategy. The microscopic morphology, crystal phase structure, and surface chemical valence state of the synthesized electrode were systematically characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), confirming the successful formation of well-integrated Mo-Ni alloy active sites on the conductive substrate. Electrochemical tests demonstrated that the optimized Mo-Ni alloy electrode delivered prominent alkaline hydrogen evolution reaction (HER) activity, with a low overpotential of 107 mV at 10 mA·cm-2. Notably, it achieved a further reduced overpotential of 95 mV in simulated seawater electrolyte. Moreover, the electrode exhibited remarkable long-term durability and robust catalytic stability under varied current density conditions.
A binder-free self-supported Mo-Ni alloy electrode was in-situ fabricated on a metallic Ti substrate through a facile one-step electrochemical deposition strategy. The microscopic morphology, crystal phase structure, and surface chemical valence state of the synthesized electrode were systematically characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), confirming the successful formation of well-integrated Mo-Ni alloy active sites on the conductive substrate. Electrochemical tests demonstrated that the optimized Mo-Ni alloy electrode delivered prominent alkaline hydrogen evolution reaction (HER) activity, with a low overpotential of 107 mV at 10 mA·cm-2. Notably, it achieved a further reduced overpotential of 95 mV in simulated seawater electrolyte. Moreover, the electrode exhibited remarkable long-term durability and robust catalytic stability under varied current density conditions.
2026, 42(10): 2203-2216
doi: 10.11862/CJIC.20260108
Abstract:
PtCu 3D nanoporous conductive networks (3D NCNs) with highly interconnected and interwoven structures were synthesized via a one-pot, surfactant-free, inorganic-salt-mediated self-assembly method. The role of inorganic salt ions in the formation mechanism of 3D NCNs and their effects on the structural characteristics and catalytic properties were investigated. The obtained best Pt3Cu1/C (using carbon as the carrier) NCNs possessed a large specific surface area, abundant low-coordinated edge and corner atoms, and enhanced oxygen reduction reaction (ORR) performance due to the synergistic effect of Pt-Cu alloying. The ORR mass activity (MA) of Pt3Cu1/C was approximately 2.6 times higher than that of commercial Pt/C catalysts. Furthermore, the Pt-rich shell formed during the dealloying process contributes to the improved stability of the catalyst. After 30 000 accelerated durability test cycles, Pt3Cu1/C retained 75% of its initial electrochemical surface area (ECSA), compared with 59% for the commercial Pt/C catalyst.
PtCu 3D nanoporous conductive networks (3D NCNs) with highly interconnected and interwoven structures were synthesized via a one-pot, surfactant-free, inorganic-salt-mediated self-assembly method. The role of inorganic salt ions in the formation mechanism of 3D NCNs and their effects on the structural characteristics and catalytic properties were investigated. The obtained best Pt3Cu1/C (using carbon as the carrier) NCNs possessed a large specific surface area, abundant low-coordinated edge and corner atoms, and enhanced oxygen reduction reaction (ORR) performance due to the synergistic effect of Pt-Cu alloying. The ORR mass activity (MA) of Pt3Cu1/C was approximately 2.6 times higher than that of commercial Pt/C catalysts. Furthermore, the Pt-rich shell formed during the dealloying process contributes to the improved stability of the catalyst. After 30 000 accelerated durability test cycles, Pt3Cu1/C retained 75% of its initial electrochemical surface area (ECSA), compared with 59% for the commercial Pt/C catalyst.
2026, 42(10): 2217-2231
doi: 10.11862/CJIC.20260056
Abstract:
The rare-earth (La3+, Gd3+, or Er3+)-doped NiCo2O4 catalysts were supported on nickel foam to optimize charge rearrangement and structural reconstruction, thereby improving oxygen evolution reaction (OER) performance. Notably, the incorporation of La3+ collectively modulates the electronic configuration of Ni2+ and Co3+ through lattice distortion. It strengthens metal-oxygen bonding, thereby constructing the La—O—Ni/Co structural unit, which promotes charge transfer during the OER process and enhances catalytic activity. As a result, the ultrafine seagrass-shaped La-NiCo2O4-1 exhibited excellent OER activity. In a 1 mol·L-1 KOH electrolyte, the prepared 0.25 mmol La3+ doped NiCo2O4 exhibited high OER activity with a low overpotential of 283 mV at 10 mA·cm-2, along with outstanding stability for over 75 h at the multi-step chronoamperometry curve of 50→100→150→100→50 mA·cm-2.
The rare-earth (La3+, Gd3+, or Er3+)-doped NiCo2O4 catalysts were supported on nickel foam to optimize charge rearrangement and structural reconstruction, thereby improving oxygen evolution reaction (OER) performance. Notably, the incorporation of La3+ collectively modulates the electronic configuration of Ni2+ and Co3+ through lattice distortion. It strengthens metal-oxygen bonding, thereby constructing the La—O—Ni/Co structural unit, which promotes charge transfer during the OER process and enhances catalytic activity. As a result, the ultrafine seagrass-shaped La-NiCo2O4-1 exhibited excellent OER activity. In a 1 mol·L-1 KOH electrolyte, the prepared 0.25 mmol La3+ doped NiCo2O4 exhibited high OER activity with a low overpotential of 283 mV at 10 mA·cm-2, along with outstanding stability for over 75 h at the multi-step chronoamperometry curve of 50→100→150→100→50 mA·cm-2.
2026, 42(10): 2232-2244
doi: 10.11862/CJIC.20260054
Abstract:
In response to the relative scarcity of microscopic mechanism studies on electrically switched ion exchange materials in the field of ion removal, a theoretical investigation based on density functional theory was conducted to explore the adsorption and migration mechanisms of lead ions (Pb2+) at the α-Zirconium phosphate (α-ZrP)/polypyrrole (PPy) composite from an atomic scale perspective. It is found that the introduction of PPy not only enhances the structural stability of α-ZrP through a physical support effect, but more importantly, the formation of interfacial chemical bonds and the accompanying electron transfer induce the generation of an internal electric field, which confers exceptional electrochemical properties to the composite. The mechanistic analysis indicates that, within the coupled interfacial region, the synergistic interplay between multi-site “cooperative anchoring” and interfacial electronic structure regulation collectively enables the highly stable coordination of Pb2+, with an adsorption energy as high as -4.64 eV. Meanwhile, the kinetic results confirm that the pronounced electron-ion coupled transport effect in the interface effectively reduces the migration energy barrier, resulting in significantly enhanced interfacial diffusion kinetics of Pb2+ of the composite compared with those of the individual components.
In response to the relative scarcity of microscopic mechanism studies on electrically switched ion exchange materials in the field of ion removal, a theoretical investigation based on density functional theory was conducted to explore the adsorption and migration mechanisms of lead ions (Pb2+) at the α-Zirconium phosphate (α-ZrP)/polypyrrole (PPy) composite from an atomic scale perspective. It is found that the introduction of PPy not only enhances the structural stability of α-ZrP through a physical support effect, but more importantly, the formation of interfacial chemical bonds and the accompanying electron transfer induce the generation of an internal electric field, which confers exceptional electrochemical properties to the composite. The mechanistic analysis indicates that, within the coupled interfacial region, the synergistic interplay between multi-site “cooperative anchoring” and interfacial electronic structure regulation collectively enables the highly stable coordination of Pb2+, with an adsorption energy as high as -4.64 eV. Meanwhile, the kinetic results confirm that the pronounced electron-ion coupled transport effect in the interface effectively reduces the migration energy barrier, resulting in significantly enhanced interfacial diffusion kinetics of Pb2+ of the composite compared with those of the individual components.
2026, 42(10): 2245-2258
doi: 10.11862/CJIC.20260042
Abstract:
Two p-sulfosulfonylcalix[4 ]arene supramolecular coordination complexes, namely, {[(CH3)4N]4[Co3(μ3-O)(H4TC4AS-SO2)]2(TDC)2·2H2O·67CH3OH}n (LLU-101) and {[(CH3)4N]2[Co3(μ4-O)(H4TC4AS-SO2)0.5(TDC)2]·32DMF}n (LLU-102) were obtained via solvothermal reactions involving a mixture of cobalt salt, p-sulfosulfonylcalix[4 ]arene (H8TC4AS-SO2) and thiophene-2,5-dicarboxylic acid (H2TDC) ligands under methanol or DMF solvents, respectively. Structural analysis revealed that solvent regulation has a significant impact on the formation of the structure. Complex LLU-101 exhibits a 2D layered structure, which can be viewed as a structure composed of trinuclear shuttlecock-like secondary building units (SBUs), {Co3-H4TC4AS-SO2}, connected by the TDC2- ligand via a single coordination mode. In this architecture, both the upper and lower rims of the main ligand coordinate to Co2+ centers. In sharp contrast, LLU-102 displays a 3D network architecture, which can be conceptualized as a structure formed by tetranuclear shuttlecock-like {Co4-H4TC4AS-SO2} SBUs, which are connected through two different coordination modes of TDC2- ligands. Within the LLU-102 framework, the main ligand exhibits two distinct coordination patterns: one involving only the lower rim attached to Co2+ ions, and the other engaging both the upper and lower rims simultaneously in coordination. Magnetic studies reveal that all the cobalt centers in both complexes exhibit antiferromagnetic interactions.
Two p-sulfosulfonylcalix[
