Login In
2026 Volume 42 Issue 8
2026, 42(8): 1569-1581
doi: 10.11862/CJIC.20260062
Abstract:
Developing rapid, sensitive, and highly selective on-site detection techniques is crucial for ensuring food safety. Metal-organic frameworks (MOFs), with their high specific surface area, tunable structures, and easy functionalization, exhibit great potential in fluorescence sensing. However, conventional MOFs suffer from insufficient water stability and tend to undergo framework hydrolysis and collapse in aqueous food matrices, which severely restricts their practical applications in food detection. This review systematically summarizes the synthesis strategies of highly water-stable MOFs based on "hard-soft acid-base (HSAB)" theory, steric hindrance effects, hydrophobic modification, and framework interlocking. In addition, typical fluorescence sensing mechanisms, including fluorescence quenching, fluorescence turn-on, and ratiometric fluorescence sensing, are discussed in detail. The latest advances of water-stable MOF-based fluorescence sensors in food safety detection are comprehensively reviewed, involving the detection of pesticide residues, antibiotics, heavy metal ions, foodborne pathogens, and food freshness monitoring. Finally, the current challenges and future development trends are prospected. This review aims to provide a theoretical basis and guidance for the design and application of water-stable MOF fluorescence sensors in complex food systems.
Developing rapid, sensitive, and highly selective on-site detection techniques is crucial for ensuring food safety. Metal-organic frameworks (MOFs), with their high specific surface area, tunable structures, and easy functionalization, exhibit great potential in fluorescence sensing. However, conventional MOFs suffer from insufficient water stability and tend to undergo framework hydrolysis and collapse in aqueous food matrices, which severely restricts their practical applications in food detection. This review systematically summarizes the synthesis strategies of highly water-stable MOFs based on "hard-soft acid-base (HSAB)" theory, steric hindrance effects, hydrophobic modification, and framework interlocking. In addition, typical fluorescence sensing mechanisms, including fluorescence quenching, fluorescence turn-on, and ratiometric fluorescence sensing, are discussed in detail. The latest advances of water-stable MOF-based fluorescence sensors in food safety detection are comprehensively reviewed, involving the detection of pesticide residues, antibiotics, heavy metal ions, foodborne pathogens, and food freshness monitoring. Finally, the current challenges and future development trends are prospected. This review aims to provide a theoretical basis and guidance for the design and application of water-stable MOF fluorescence sensors in complex food systems.
2026, 42(8): 1582-1592
doi: 10.11862/CJIC.20260077
Abstract:
A facile electrostatic self-assembly strategy for the construction of a two-dimensional Cu-TCPP/MXene composite (Cu-TCPP=tetracarboxyphenyl porphyrin copper) was proposed, featuring a well-integrated heterogeneous interface with highly conductive networks and porous ion transport channels. This unique architecture effectively accelerates electrolyte ion diffusion and charge transfer. Under optimized ratio, the Cu-TCPP/MXene electrode exhibited high optical transmittance exceeding 60%, and the assembled transparent supercapacitor delivered an outstanding areal capacitance of 7.48 mF·cm-2. Furthermore, an asymmetric zinc-ion hybrid supercapacitor (ZIHSC) was constructed by employing the Cu-TCPP/MXene as the cathode and electrochemically deposited zinc as the anode. The ZIHSC device achieved a wide voltage window of 0-1.2 V, a high transmittance of 58.9%, an outstanding areal capacitance of 10.5 mF·cm-2, and an energy density of 2.1 μWh·cm-2.
A facile electrostatic self-assembly strategy for the construction of a two-dimensional Cu-TCPP/MXene composite (Cu-TCPP=tetracarboxyphenyl porphyrin copper) was proposed, featuring a well-integrated heterogeneous interface with highly conductive networks and porous ion transport channels. This unique architecture effectively accelerates electrolyte ion diffusion and charge transfer. Under optimized ratio, the Cu-TCPP/MXene electrode exhibited high optical transmittance exceeding 60%, and the assembled transparent supercapacitor delivered an outstanding areal capacitance of 7.48 mF·cm-2. Furthermore, an asymmetric zinc-ion hybrid supercapacitor (ZIHSC) was constructed by employing the Cu-TCPP/MXene as the cathode and electrochemically deposited zinc as the anode. The ZIHSC device achieved a wide voltage window of 0-1.2 V, a high transmittance of 58.9%, an outstanding areal capacitance of 10.5 mF·cm-2, and an energy density of 2.1 μWh·cm-2.
2026, 42(8): 1593-1602
doi: 10.11862/CJIC.20260107
Abstract:
A stable and easily synthesized polyoxometalate (POM)-based Cu-MOF hybrid (POM-Cu-MOF) was synthesized and prepared into a carbon paste electrode (CPE), denoted as POM-Cu-MOF-CPE. A conventional three-electrode system was adopted to investigate its electrochemical properties. The cyclic voltammetry curve of POM-Cu-MOF-CPE showed four pairs of reversible oxidation-reduction peaks corresponding to the single electron oxidation-reduction of Cu2+/Cu+ and the three-step double electron and double proton oxidation-reduction process of Mo6+ in molybdenum based POM. Compared with the electrochemical performance of pristine Keggin-type POM in aqueous solution, POM-Cu-MOF-CPE delivered an expanded electrochemical potential window. Electrocatalytic tests toward typical aquatic contaminants including IO3-, NO2-, and Cr2O72- verified that the cathodic peaks derived from the 4e- to 6e- reduction of Mo6+ in POM-Cu-MOF exhibited outstanding electrocatalytic activity for the reductive conversion of the above pollutants, achieving a detection limit satisfying the requirements for trace-level quantification. Moreover, POM-Cu-MOF-CPE maintained stable current responses in the presence of coexisting common interfering species, demonstrating prominent anti-interference capability.
A stable and easily synthesized polyoxometalate (POM)-based Cu-MOF hybrid (POM-Cu-MOF) was synthesized and prepared into a carbon paste electrode (CPE), denoted as POM-Cu-MOF-CPE. A conventional three-electrode system was adopted to investigate its electrochemical properties. The cyclic voltammetry curve of POM-Cu-MOF-CPE showed four pairs of reversible oxidation-reduction peaks corresponding to the single electron oxidation-reduction of Cu2+/Cu+ and the three-step double electron and double proton oxidation-reduction process of Mo6+ in molybdenum based POM. Compared with the electrochemical performance of pristine Keggin-type POM in aqueous solution, POM-Cu-MOF-CPE delivered an expanded electrochemical potential window. Electrocatalytic tests toward typical aquatic contaminants including IO3-, NO2-, and Cr2O72- verified that the cathodic peaks derived from the 4e- to 6e- reduction of Mo6+ in POM-Cu-MOF exhibited outstanding electrocatalytic activity for the reductive conversion of the above pollutants, achieving a detection limit satisfying the requirements for trace-level quantification. Moreover, POM-Cu-MOF-CPE maintained stable current responses in the presence of coexisting common interfering species, demonstrating prominent anti-interference capability.
2026, 42(8): 1603-1612
doi: 10.11862/CJIC.20260089
Abstract:
An acid-base mixed-ligand strategy was employed by combining basic ligand {2,6-bis[4-(1,2,4-triazol-1-yl)styryl]cyclohexanone} (BTBCH) with aromatic dicarboxylic acids such as terephthalic acid (H2BDC), isophthalic acid (IPA), and 5-methylisophthalic acid (MP), achieving three novel coordination polymers [Zn(BTBCH)2(BDC)]n (1), [Zn(BTBCH)2(IPA)]n (2), and [Zn(BTBCH)(MP)]n (3), respectively. Complexes 1 and 2 exhibit one-dimensional chain structural character, while 3 features a neatly packed two-dimensional network structure, forming tunnels. Under mild conditions, those materials exhibited considerable catalytic activity toward the CO2 cycloaddition reaction. Meanwhile, they could efficiently catalyze the photodegradation of organic dyes. Notably, they could be reused for several cycles.
An acid-base mixed-ligand strategy was employed by combining basic ligand {2,6-bis[4-(1,2,4-triazol-1-yl)styryl]cyclohexanone} (BTBCH) with aromatic dicarboxylic acids such as terephthalic acid (H2BDC), isophthalic acid (IPA), and 5-methylisophthalic acid (MP), achieving three novel coordination polymers [Zn(BTBCH)2(BDC)]n (1), [Zn(BTBCH)2(IPA)]n (2), and [Zn(BTBCH)(MP)]n (3), respectively. Complexes 1 and 2 exhibit one-dimensional chain structural character, while 3 features a neatly packed two-dimensional network structure, forming tunnels. Under mild conditions, those materials exhibited considerable catalytic activity toward the CO2 cycloaddition reaction. Meanwhile, they could efficiently catalyze the photodegradation of organic dyes. Notably, they could be reused for several cycles.
2026, 42(8): 1613-1626
doi: 10.11862/CJIC.20260086
Abstract:
A nitrogen vacancy g-C3N4 (NVCN), Ti3C2Tx (TCT), and W18O49 (WO) composite heterojunction material (CN/TCT/WO) was synthesized by in-situ solvothermal method. The phase composition, microstructure, optical and photoelectrochemical properties, and photocatalytic degradation performance were systematically characterized using various advanced techniques. The results showed that the CN/TCT/WO heterojunction exhibited full-solar-spectrum absorption characteristics owing to the defect-induced surface plasmon resonance effect. Furthermore, the formation of multi-level heterogeneous interfaces and defect-induced localized electromagnetic enhancement collectively improved the separation efficiency of photogenerated electron-hole pairs while prolonging their lifetime. The transformation from a type-Ⅱ heterostructure to a Z-scheme mechanism, with Ti3C2Tx as the electron mediator, enhanced the driving force for surface redox reactions. Hence, the ternary heterojunction possessed markedly boosted photocatalytic degradation performance compared with the single-component material and binary heterojunction. Within 40 min of visible light irradiation and 180 min of near-infrared light irradiation, the mineralization efficiencies by the optimal heterojunction material for tetracycline could reach 82.9% and 72.3%, respectively. In addition, ciprofloxacin, ofloxacin, norfloxacin, and metronidazole could also be efficiently decomposed and mineralized. The results of cyclic experiments indicated that the CN/TCT/WO heterojunction material possessed excellent structural stability and reusability.
A nitrogen vacancy g-C3N4 (NVCN), Ti3C2Tx (TCT), and W18O49 (WO) composite heterojunction material (CN/TCT/WO) was synthesized by in-situ solvothermal method. The phase composition, microstructure, optical and photoelectrochemical properties, and photocatalytic degradation performance were systematically characterized using various advanced techniques. The results showed that the CN/TCT/WO heterojunction exhibited full-solar-spectrum absorption characteristics owing to the defect-induced surface plasmon resonance effect. Furthermore, the formation of multi-level heterogeneous interfaces and defect-induced localized electromagnetic enhancement collectively improved the separation efficiency of photogenerated electron-hole pairs while prolonging their lifetime. The transformation from a type-Ⅱ heterostructure to a Z-scheme mechanism, with Ti3C2Tx as the electron mediator, enhanced the driving force for surface redox reactions. Hence, the ternary heterojunction possessed markedly boosted photocatalytic degradation performance compared with the single-component material and binary heterojunction. Within 40 min of visible light irradiation and 180 min of near-infrared light irradiation, the mineralization efficiencies by the optimal heterojunction material for tetracycline could reach 82.9% and 72.3%, respectively. In addition, ciprofloxacin, ofloxacin, norfloxacin, and metronidazole could also be efficiently decomposed and mineralized. The results of cyclic experiments indicated that the CN/TCT/WO heterojunction material possessed excellent structural stability and reusability.
2026, 42(8): 1627-1636
doi: 10.11862/CJIC.20260084
Abstract:
Herein, inspired by the zincophilicity of the multiple hydroxyl groups in inositol, inositol serves as an electrolyte additive for aqueous zinc-ion batteries (AZIBs) to prepare a composite electrolyte composed of ZnSO4 and inositol (denoted as ZSO+inositol) to achieve a highly stable Zn anode. The polar hydroxyl groups of inositol exhibited excellent zincophilicity, enabling it to participate in the regulation and reconstruction of the Zn2+ solvation structure. This regulation optimizes the coordination environment of Zn2+, effectively reduces the water activity on the electrode/electrolyte interface, and suppresses side reactions. Meanwhile, inositol preferentially adsorbs on the Zn anode surface, which improves the electrolyte-electrode wettability and enhances the stability of the electrode/electrolyte interface. Furthermore, inositol provides abundant active sites for Zn2+ migration, significantly enhancing the diffusion kinetics of Zn2+ and effectively increasing the Zn2+ transference number. Consequently, the Zn||Zn symmetric battery assembled with the ZSO+inositol electrolyte achieved stable cycling for up to 2 000 h at 1 mA·cm-2. The Zn||Cu asymmetric battery delivered an average Coulombic efficiency of 99.7% after 1 000 cycles. Additionally, the Zn||ZVO (Zn3V3O8) full battery exhibited excellent electrochemical performance, retaining a capacity of 72.7 mAh·g-1 after 1 000 cycles.
Herein, inspired by the zincophilicity of the multiple hydroxyl groups in inositol, inositol serves as an electrolyte additive for aqueous zinc-ion batteries (AZIBs) to prepare a composite electrolyte composed of ZnSO4 and inositol (denoted as ZSO+inositol) to achieve a highly stable Zn anode. The polar hydroxyl groups of inositol exhibited excellent zincophilicity, enabling it to participate in the regulation and reconstruction of the Zn2+ solvation structure. This regulation optimizes the coordination environment of Zn2+, effectively reduces the water activity on the electrode/electrolyte interface, and suppresses side reactions. Meanwhile, inositol preferentially adsorbs on the Zn anode surface, which improves the electrolyte-electrode wettability and enhances the stability of the electrode/electrolyte interface. Furthermore, inositol provides abundant active sites for Zn2+ migration, significantly enhancing the diffusion kinetics of Zn2+ and effectively increasing the Zn2+ transference number. Consequently, the Zn||Zn symmetric battery assembled with the ZSO+inositol electrolyte achieved stable cycling for up to 2 000 h at 1 mA·cm-2. The Zn||Cu asymmetric battery delivered an average Coulombic efficiency of 99.7% after 1 000 cycles. Additionally, the Zn||ZVO (Zn3V3O8) full battery exhibited excellent electrochemical performance, retaining a capacity of 72.7 mAh·g-1 after 1 000 cycles.
2026, 42(8): 1637-1646
doi: 10.11862/CJIC.20260049
Abstract:
本工作中，通过引入芳香磺酸配体1，5-萘二磺酸(H2NDS)作为结构导向剂，与七元瓜环(Q[7])和过渡金属离子Cu2+和Cd2+在水热条件下反应，成功制备出了2例同构的新型七元瓜环基超分子自组装体：[M(H2O)4(Q[7])](NDS)·xH2O(1：M=Cd，x=14；2：M=Cu，x=15)，并采用单晶X射线衍射、粉末X射线衍射、红外光谱、热重分析和Hirshfeld表面分析等手段对其进行了测试和表征。结果表明，2种自组装体晶体中，Q[7]均是直接与过渡金属离子配位，形成了1∶1型简单配合物Q[7]-M2+，而磺酸配体则是完全去质子化，以阴离子形式NDS2-来保持体系电荷平衡并分布在Q[7]环外侧；二者通过Q[7]外壁上的次甲基和亚甲基与NDS2-的磺酸根之间的C—H…O氢键、萘环之间的C—H…π作用形成双链型一维超分子链，并进一步通过Q[7]分子间的氢键作用形成了最终的三维超分子框架结构。Hirshfeld表面分析进一步证明了自组装体晶体中含有丰富的弱相互作用，其中氢键作用对于最终三维超分子框架结构的形成起到了主要贡献。此外，荧光测试结果还表明，自组装体1可以通过荧光猝灭的方式选择性检测水体系中的Cu2+。
本工作中，通过引入芳香磺酸配体1，5-萘二磺酸(H2NDS)作为结构导向剂，与七元瓜环(Q[7])和过渡金属离子Cu2+和Cd2+在水热条件下反应，成功制备出了2例同构的新型七元瓜环基超分子自组装体：[M(H2O)4(Q[7])](NDS)·xH2O(1：M=Cd，x=14；2：M=Cu，x=15)，并采用单晶X射线衍射、粉末X射线衍射、红外光谱、热重分析和Hirshfeld表面分析等手段对其进行了测试和表征。结果表明，2种自组装体晶体中，Q[7]均是直接与过渡金属离子配位，形成了1∶1型简单配合物Q[7]-M2+，而磺酸配体则是完全去质子化，以阴离子形式NDS2-来保持体系电荷平衡并分布在Q[7]环外侧；二者通过Q[7]外壁上的次甲基和亚甲基与NDS2-的磺酸根之间的C—H…O氢键、萘环之间的C—H…π作用形成双链型一维超分子链，并进一步通过Q[7]分子间的氢键作用形成了最终的三维超分子框架结构。Hirshfeld表面分析进一步证明了自组装体晶体中含有丰富的弱相互作用，其中氢键作用对于最终三维超分子框架结构的形成起到了主要贡献。此外，荧光测试结果还表明，自组装体1可以通过荧光猝灭的方式选择性检测水体系中的Cu2+。
2026, 42(8): 1647-1657
doi: 10.11862/CJIC.20260041
Abstract:
To address the issues of detrimental phase transition of the O3-type Na0.86Ni1/3Fe1/3Mn1/3O2 (NFM) cathode material during cycling, a Ti4+/P5+ dual-site co-doping strategy was employed to enhance its structural stability. Na0.82Ni1/3Fe1/3Mn1/3Ti0.02P0.01O2 (NFMTP) was successfully synthesized via a combined sol-gel and high-temperature solid-state method. Electrochemical tests demonstrated that the NFMTP cathode exhibited a capacity retention of 80.1% after 200 cycles at 1C (160 mA·g-1), significantly higher than that of pristine NFM (45.4%). NFMTP still delivered a reversible capacity of 111.6 mAh·g-1 at 10C. Mechanistic investigations reveal that the synergistic effect of Ti occupying Na sites and P occupying tetrahedral interstitial sites in the transition metal (TM) layer effectively strengthens the TM—O bonds, suppresses harmful phase transitions, and accelerates Na+ diffusion, thereby collectively improving the overall electrochemical performance of the material.
To address the issues of detrimental phase transition of the O3-type Na0.86Ni1/3Fe1/3Mn1/3O2 (NFM) cathode material during cycling, a Ti4+/P5+ dual-site co-doping strategy was employed to enhance its structural stability. Na0.82Ni1/3Fe1/3Mn1/3Ti0.02P0.01O2 (NFMTP) was successfully synthesized via a combined sol-gel and high-temperature solid-state method. Electrochemical tests demonstrated that the NFMTP cathode exhibited a capacity retention of 80.1% after 200 cycles at 1C (160 mA·g-1), significantly higher than that of pristine NFM (45.4%). NFMTP still delivered a reversible capacity of 111.6 mAh·g-1 at 10C. Mechanistic investigations reveal that the synergistic effect of Ti occupying Na sites and P occupying tetrahedral interstitial sites in the transition metal (TM) layer effectively strengthens the TM—O bonds, suppresses harmful phase transitions, and accelerates Na+ diffusion, thereby collectively improving the overall electrochemical performance of the material.
2026, 42(8): 1658-1668
doi: 10.11862/CJIC.20260009
Abstract:
In this work, the electronic structures and optical properties of a series of vanadate crystals, K3RE(VO4)2 (RE=Sc, Y, La, Lu), are systematically investigated using first-principles calculations based on density functional theory (DFT). The generalized gradient approximation (GGA) with the Perdew-Burke-Ernzerhof (PBE) functional and norm-conserving pseudopotentials is employed to guarantee calculation precision. The results indicate that all compounds in this series crystallize in the trigonal system with the P3m1 space group, featuring a distinct layered structure composed of isolated [VO4] tetrahedra and [REO6] octahedra that do not share vertices. Electronic band structure calculations reveal that these materials are indirect band gap semiconductors with wide band gap values ranging from 3.286 to 3.701 eV, ensuring excellent transparency in the ultraviolet to near-infrared region. Quantitative analysis of the density of states (DOS), Mulliken populations, and electron localization functions (ELF) confirms a characteristic structural framework of "strong covalent [VO4]3- groups + weak ionic K/RE framework". Regarding optical properties, the birefringences (Δn) of K3Sc(VO4)2, K3Y(VO4)2, and K3La(VO4)2 are primarily modulated by the cationic size effect, monotonically decreasing as the ionic radius increases. Crucially, K3Lu(VO4)2 counterintuitively breaks this conventional evolutionary trend, exhibiting an exceptionally high birefringence (Δn=0.250 at 1 064 nm). This giant macroscopic enhancement is successfully achieved by the unique lanthanide contraction effect of Lu3+, which imposes rigorous spatial geometric constraints within the compact lattice, thereby optimizing the subtle balance between functional group distortion and spatial orientation. This effect successfully facilitates a "moderately low distortion + high consistency arrangement" of the core optical active units. Furthermore, quantitative regression analysis based on the relative electron density anisotropy (REDA) theory demonstrates a near-perfect linear correlation between the macroscopic Δn and the geometric distortion index (Δd) of [VO4], as well as its REDA, identifying the [VO4] tetrahedra as the absolute dominant source of optical anisotropy.
In this work, the electronic structures and optical properties of a series of vanadate crystals, K3RE(VO4)2 (RE=Sc, Y, La, Lu), are systematically investigated using first-principles calculations based on density functional theory (DFT). The generalized gradient approximation (GGA) with the Perdew-Burke-Ernzerhof (PBE) functional and norm-conserving pseudopotentials is employed to guarantee calculation precision. The results indicate that all compounds in this series crystallize in the trigonal system with the P3m1 space group, featuring a distinct layered structure composed of isolated [VO4] tetrahedra and [REO6] octahedra that do not share vertices. Electronic band structure calculations reveal that these materials are indirect band gap semiconductors with wide band gap values ranging from 3.286 to 3.701 eV, ensuring excellent transparency in the ultraviolet to near-infrared region. Quantitative analysis of the density of states (DOS), Mulliken populations, and electron localization functions (ELF) confirms a characteristic structural framework of "strong covalent [VO4]3- groups + weak ionic K/RE framework". Regarding optical properties, the birefringences (Δn) of K3Sc(VO4)2, K3Y(VO4)2, and K3La(VO4)2 are primarily modulated by the cationic size effect, monotonically decreasing as the ionic radius increases. Crucially, K3Lu(VO4)2 counterintuitively breaks this conventional evolutionary trend, exhibiting an exceptionally high birefringence (Δn=0.250 at 1 064 nm). This giant macroscopic enhancement is successfully achieved by the unique lanthanide contraction effect of Lu3+, which imposes rigorous spatial geometric constraints within the compact lattice, thereby optimizing the subtle balance between functional group distortion and spatial orientation. This effect successfully facilitates a "moderately low distortion + high consistency arrangement" of the core optical active units. Furthermore, quantitative regression analysis based on the relative electron density anisotropy (REDA) theory demonstrates a near-perfect linear correlation between the macroscopic Δn and the geometric distortion index (Δd) of [VO4], as well as its REDA, identifying the [VO4] tetrahedra as the absolute dominant source of optical anisotropy.
2026, 42(8): 1669-1684
doi: 10.11862/CJIC.20260002
Abstract:
Nano lanthanum hydroxide (n-LH) was prepared into SA/n-LH composite microspheres with sodium alginate (SA) as the encapsulation material by microencapsulation technology. The effects of electrospray process parameters, including receiving distance, inner diameter of needle, voltage, injection rate, SA mass concentration, LaCl3 mass concentration, crosslinking time, and the mass ratio of n-LH to SA (rm), on the particle size and morphology of SA/n-LH composite microspheres were studied. The phosphorus adsorption capacity of SA/n-LH composite microspheres and its related mechanisms were further explored. Along with the increase in needle inner diameter, SA concentration and rm, and the decrease in voltage, the particle size of SA/n-LH composite microspheres increased. Especially, at a voltage of 15 kV, microsphere particle size became non-uniform, and excessively high SA concentration and n-LH content might cause the change of microsphere morphology. The phosphorus adsorption capacity of the SA/n-LH composite microspheres reached the maximum at a pH value of 2.0; as the pH increased, the phosphorus adsorption capacity decreased significantly. As the rm increased, the phosphorus adsorption capacity increased significantly. When the pH was 2.0 and the rm was 2.0, the phosphorus adsorption capacity reached 111.05 mg·g-1. The phosphorus adsorption process of SA/n-LH microspheres better conformed to the pseudo-second-order kinetic model and Langmuir isotherm model. Its phosphorus adsorption rate was significantly slower than that of n-LH, indicating a sustained-release effect.
Nano lanthanum hydroxide (n-LH) was prepared into SA/n-LH composite microspheres with sodium alginate (SA) as the encapsulation material by microencapsulation technology. The effects of electrospray process parameters, including receiving distance, inner diameter of needle, voltage, injection rate, SA mass concentration, LaCl3 mass concentration, crosslinking time, and the mass ratio of n-LH to SA (rm), on the particle size and morphology of SA/n-LH composite microspheres were studied. The phosphorus adsorption capacity of SA/n-LH composite microspheres and its related mechanisms were further explored. Along with the increase in needle inner diameter, SA concentration and rm, and the decrease in voltage, the particle size of SA/n-LH composite microspheres increased. Especially, at a voltage of 15 kV, microsphere particle size became non-uniform, and excessively high SA concentration and n-LH content might cause the change of microsphere morphology. The phosphorus adsorption capacity of the SA/n-LH composite microspheres reached the maximum at a pH value of 2.0; as the pH increased, the phosphorus adsorption capacity decreased significantly. As the rm increased, the phosphorus adsorption capacity increased significantly. When the pH was 2.0 and the rm was 2.0, the phosphorus adsorption capacity reached 111.05 mg·g-1. The phosphorus adsorption process of SA/n-LH microspheres better conformed to the pseudo-second-order kinetic model and Langmuir isotherm model. Its phosphorus adsorption rate was significantly slower than that of n-LH, indicating a sustained-release effect.
2026, 42(8): 1685-1698
doi: 10.11862/CJIC.20250343
Abstract:
We proposes a composition-based cascaded machine learning strategy for the simultaneous prediction of the full width at half maximum (FWHM) and thermal stability (TS) of Eu2+-doped whitlockite-type phosphors. Based on 90 samples collected from 60 papers, six algorithms were compared: decision tree regression (DTR), gradient boosting regression tree (GBR), Bagging, random forest regression (RFR), XGBoosting, and adaptive boosting (AdaBoosting). Using grid search and ten-fold cross-validation, the AdaBoosting model exhibited the best performance in cascaded prediction, achieving coefficient of determination (R2) of 0.951 and root mean square error (RMSE) of 157.2 for FWHM, and R2 of 0.852 with RMSE of 0.005 for TS on the test set. To validate the model reliability, Ca9Y(PO4)7∶0.08Eu2+ phosphor was successfully synthesized. The experimentally measured FWHM and TS (emission intensity ratio at 423 K to that at 303 K) were 79 nm and 0.42, respectively, with deviations from the predicted values of only 2.57% and 1.19%. Rietveld refinement and Gaussian fitting revealed that Eu2+ ions occupy four distinct Ca sites (Ca1, Ca2, Ca3, Ca4) with coordination numbers of 8, 7, 7, and 6, respectively, collectively contributing to the cyan emission at 487 nm. Concentration quenching analysis gave a critical distance (Rc) of 2.758 nm, and the quenching mechanism was identified as quadrupole-quadrupole interaction. Energy level analysis, based on the constructed host-referenced binding energy (HRBE) and vacuum-referenced binding energy (VRBE) diagrams, indicated that the thermal stability was primarily limited by the autoionization effect arising from the small energy gap between the 5d level of Eu2+ and the conduction band minimum. Finally, a white light-emitting diode (LED) device fabricated using this cyan-emitting phosphor together with commercial Y3Al5O12∶Ce3+ (YAG∶Ce) yellow phosphor, CaAlSiN3∶Eu2+ red phosphor, and a 365 nm UV chip exhibited excellent performance: a color rendering index (Ra) of 92.6 and a correlated color temperature (CCT) of 4 266 K, confirming its practical application potential.
We proposes a composition-based cascaded machine learning strategy for the simultaneous prediction of the full width at half maximum (FWHM) and thermal stability (TS) of Eu2+-doped whitlockite-type phosphors. Based on 90 samples collected from 60 papers, six algorithms were compared: decision tree regression (DTR), gradient boosting regression tree (GBR), Bagging, random forest regression (RFR), XGBoosting, and adaptive boosting (AdaBoosting). Using grid search and ten-fold cross-validation, the AdaBoosting model exhibited the best performance in cascaded prediction, achieving coefficient of determination (R2) of 0.951 and root mean square error (RMSE) of 157.2 for FWHM, and R2 of 0.852 with RMSE of 0.005 for TS on the test set. To validate the model reliability, Ca9Y(PO4)7∶0.08Eu2+ phosphor was successfully synthesized. The experimentally measured FWHM and TS (emission intensity ratio at 423 K to that at 303 K) were 79 nm and 0.42, respectively, with deviations from the predicted values of only 2.57% and 1.19%. Rietveld refinement and Gaussian fitting revealed that Eu2+ ions occupy four distinct Ca sites (Ca1, Ca2, Ca3, Ca4) with coordination numbers of 8, 7, 7, and 6, respectively, collectively contributing to the cyan emission at 487 nm. Concentration quenching analysis gave a critical distance (Rc) of 2.758 nm, and the quenching mechanism was identified as quadrupole-quadrupole interaction. Energy level analysis, based on the constructed host-referenced binding energy (HRBE) and vacuum-referenced binding energy (VRBE) diagrams, indicated that the thermal stability was primarily limited by the autoionization effect arising from the small energy gap between the 5d level of Eu2+ and the conduction band minimum. Finally, a white light-emitting diode (LED) device fabricated using this cyan-emitting phosphor together with commercial Y3Al5O12∶Ce3+ (YAG∶Ce) yellow phosphor, CaAlSiN3∶Eu2+ red phosphor, and a 365 nm UV chip exhibited excellent performance: a color rendering index (Ra) of 92.6 and a correlated color temperature (CCT) of 4 266 K, confirming its practical application potential.
2026, 42(8): 1699-1711
doi: 10.11862/CJIC.20250284
Abstract:
A type-Ⅱ heterojunction composite catalyst (ZnO/BNC) was designed and constructed based on ZnO and Bi4NbO8Cl (BNC), aiming to effectively promote carrier separation and enhance catalytic activity through heterojunction interface engineering. ZnO/BNC was successfully synthesized via an optimized impregnation-calcination method and systematically characterized using various techniques to determine its crystal structure, band structure, and piezoelectric properties. The results indicate that the Type-Ⅱ band alignment formed between ZnO and BNC, coupled with the synergistic effect of the spontaneously formed built-in electric field at the interface, significantly facilitates the separation and migration of electron-hole pairs under piezoelectric excitation. Under ultrasonic irradiation, the optimized samples ZnO/BNC-2 achieved an 87% degradation rate of methyl orange (MO) within 90 min. Its piezocatalytic degradation rate constant was ca. 7.3 times that of pure BNC and ca. 5.4 times that of pure ZnO, demonstrating excellent piezocatalytic performance.
A type-Ⅱ heterojunction composite catalyst (ZnO/BNC) was designed and constructed based on ZnO and Bi4NbO8Cl (BNC), aiming to effectively promote carrier separation and enhance catalytic activity through heterojunction interface engineering. ZnO/BNC was successfully synthesized via an optimized impregnation-calcination method and systematically characterized using various techniques to determine its crystal structure, band structure, and piezoelectric properties. The results indicate that the Type-Ⅱ band alignment formed between ZnO and BNC, coupled with the synergistic effect of the spontaneously formed built-in electric field at the interface, significantly facilitates the separation and migration of electron-hole pairs under piezoelectric excitation. Under ultrasonic irradiation, the optimized samples ZnO/BNC-2 achieved an 87% degradation rate of methyl orange (MO) within 90 min. Its piezocatalytic degradation rate constant was ca. 7.3 times that of pure BNC and ca. 5.4 times that of pure ZnO, demonstrating excellent piezocatalytic performance.
2026, 42(8): 1712-1722
doi: 10.11862/CJIC.20260136
Abstract:
Three new 3-pyridazinyl-substituted triaryltriazoles, 4-(4-R-phenyl)-3-(2-pyridyl)-5-(3-pyridazinyl)-1,2,4-triazole (L1: R=OCH3; L2: R=H; L3: R=F) and their Cu(Ⅱ) complexes, trans-[Cu(L1)2(NO3)2]·H2O (1), trans-[Cu(L2)2(NO3)2] (2) and trans-[Cu(L3)2(H2O)2](NO3)2 (3), have been synthesized and characterized by FTIR, 1H NMR, elemental analysis and single crystal X-ray crystallography. Crystal structure analyses reveal that the supramolecular trimer (L1)3 and complex 3 crystallize in the triclinic P1 space group, the ligand L2 and complexes 1 and 2 belong to the monoclinic P21/c space group, while the ligand L3 crystallizes in the monoclinic P21/n space group. There is a hydrogen-bonded trimer (L1)3 in the asymmetric unit of the ligand L1. In the complexes 1-3, there is a distorted [CuN4O2] octahedron with two NO3- ions located in the axial positions in 1 and 2, whereas the two water molecules occupy the axial sites in 3. In the equatorial plane of 1-3, each L ligand adopts a chelating bidentate mode to bind the Cu(Ⅱ) ion through the pyridyl N atom and one triazole N atom, leaving the pyridazinyl group uncoordinated. The intermolecular interactions in the free ligands and the complexes have been explored by 3D Hirshfeld surface analyses and 2D fingerprint plots to reveal that the main intermolecular interactions are H…H and C…H/H…C contacts in (L1)3, H…H and N…H/H…N contacts in L2, H…H, N…H/H…N and C…H/H…C in L3, H…H and O…H/H…O contacts in both 1 and 2, H…H, N…H/H…N and O…H/H…O contacts in 3.
Three new 3-pyridazinyl-substituted triaryltriazoles, 4-(4-R-phenyl)-3-(2-pyridyl)-5-(3-pyridazinyl)-1,2,4-triazole (L1: R=OCH3; L2: R=H; L3: R=F) and their Cu(Ⅱ) complexes, trans-[Cu(L1)2(NO3)2]·H2O (1), trans-[Cu(L2)2(NO3)2] (2) and trans-[Cu(L3)2(H2O)2](NO3)2 (3), have been synthesized and characterized by FTIR, 1H NMR, elemental analysis and single crystal X-ray crystallography. Crystal structure analyses reveal that the supramolecular trimer (L1)3 and complex 3 crystallize in the triclinic P1 space group, the ligand L2 and complexes 1 and 2 belong to the monoclinic P21/c space group, while the ligand L3 crystallizes in the monoclinic P21/n space group. There is a hydrogen-bonded trimer (L1)3 in the asymmetric unit of the ligand L1. In the complexes 1-3, there is a distorted [CuN4O2] octahedron with two NO3- ions located in the axial positions in 1 and 2, whereas the two water molecules occupy the axial sites in 3. In the equatorial plane of 1-3, each L ligand adopts a chelating bidentate mode to bind the Cu(Ⅱ) ion through the pyridyl N atom and one triazole N atom, leaving the pyridazinyl group uncoordinated. The intermolecular interactions in the free ligands and the complexes have been explored by 3D Hirshfeld surface analyses and 2D fingerprint plots to reveal that the main intermolecular interactions are H…H and C…H/H…C contacts in (L1)3, H…H and N…H/H…N contacts in L2, H…H, N…H/H…N and C…H/H…C in L3, H…H and O…H/H…O contacts in both 1 and 2, H…H, N…H/H…N and O…H/H…O contacts in 3.
2026, 42(8): 1723-1732
doi: 10.11862/CJIC.20260103
Abstract:
A heterometallic Mn/Ti cluster formulated as [Ti3Mn2(Sal)8(Phen)(CH3CN)(H2O)] (1) was solvothermally synthesized via the reaction of manganese acetate with a titanate precursor, using salicylic acid (H2Sal) and 1, 10-phenanthroline (Phen) as organic ligands. By carefully tuning the reaction parameters and eliminating Phen from the reaction system, a structurally distinct heterometallic Mn/Ti cluster, [Ti4Mn4(Sal)12(CH3CN)2]·(CH3CN)4 (2), was further isolated. The molecular structures of both complexes 1 and 2 were unambiguously established by elemental analysis, Fourier-transform infrared (FTIR) spectra, and single-crystal X-ray diffraction. Spectroscopic measurements demonstrated that both complexes feature prominent light absorption in the visible region, with the calculated optical band gaps of 1.93 eV for complex 1 and 2.15 eV for complex 2, respectively. Photocatalytic investigations revealed that complexes 1 and 2 exhibited efficient catalytic activity toward CO2 reduction, affording CO as the exclusive carbon-containing product, with corresponding CO evolution rates of 7.21 and 14.39 μmol·g-1·h-1, respectively.
A heterometallic Mn/Ti cluster formulated as [Ti3Mn2(Sal)8(Phen)(CH3CN)(H2O)] (1) was solvothermally synthesized via the reaction of manganese acetate with a titanate precursor, using salicylic acid (H2Sal) and 1, 10-phenanthroline (Phen) as organic ligands. By carefully tuning the reaction parameters and eliminating Phen from the reaction system, a structurally distinct heterometallic Mn/Ti cluster, [Ti4Mn4(Sal)12(CH3CN)2]·(CH3CN)4 (2), was further isolated. The molecular structures of both complexes 1 and 2 were unambiguously established by elemental analysis, Fourier-transform infrared (FTIR) spectra, and single-crystal X-ray diffraction. Spectroscopic measurements demonstrated that both complexes feature prominent light absorption in the visible region, with the calculated optical band gaps of 1.93 eV for complex 1 and 2.15 eV for complex 2, respectively. Photocatalytic investigations revealed that complexes 1 and 2 exhibited efficient catalytic activity toward CO2 reduction, affording CO as the exclusive carbon-containing product, with corresponding CO evolution rates of 7.21 and 14.39 μmol·g-1·h-1, respectively.
2026, 42(8): 1733-1750
doi: 10.11862/CJIC.20260055
Abstract:
Aiming at the problem of water pollution, a broad-spectrum response composite material CQDs/PW12/CdS modified by carbon quantum dots (CQDs) was prepared via a microwave-assisted hydrothermal method using glucose as the carbon source, cadmium sulfide (CdS) and phosphotungstic acid (PW12) as precursors. The photocatalytic mechanism of CQDs/PW12/CdS is more inclined towards the Z-scheme heterojunction. The optimized CQDs/PW12/CdS heterojunction composites achieved 93.01% photodegradation efficiency of rhodamine B (RhB) at 120 min of simulated sunlight irradiation, and they also exhibited a favorable degrading effect on common dyes and antibiotics in water. Using lactic acid as the sacrificial reagent, the photocatalytic hydrogen production activity of the developed photocatalyst was evaluated under simulated sunlight irradiation. According to the experimental results, after 8 h of irradiation, the CQDs/PW12/CdS composite material showed the highest H2 production rate (12.34 mmol·g-1), which was six times that of the monomer CdS (2.05 mmol·g-1). The enhancement of photocatalytic activity is attributed to the effective separation of photogenerated charges caused by the anisotropic junctions in the CQDs/PW12/CdS system.
Aiming at the problem of water pollution, a broad-spectrum response composite material CQDs/PW12/CdS modified by carbon quantum dots (CQDs) was prepared via a microwave-assisted hydrothermal method using glucose as the carbon source, cadmium sulfide (CdS) and phosphotungstic acid (PW12) as precursors. The photocatalytic mechanism of CQDs/PW12/CdS is more inclined towards the Z-scheme heterojunction. The optimized CQDs/PW12/CdS heterojunction composites achieved 93.01% photodegradation efficiency of rhodamine B (RhB) at 120 min of simulated sunlight irradiation, and they also exhibited a favorable degrading effect on common dyes and antibiotics in water. Using lactic acid as the sacrificial reagent, the photocatalytic hydrogen production activity of the developed photocatalyst was evaluated under simulated sunlight irradiation. According to the experimental results, after 8 h of irradiation, the CQDs/PW12/CdS composite material showed the highest H2 production rate (12.34 mmol·g-1), which was six times that of the monomer CdS (2.05 mmol·g-1). The enhancement of photocatalytic activity is attributed to the effective separation of photogenerated charges caused by the anisotropic junctions in the CQDs/PW12/CdS system.
2026, 42(8): 1751-1762
doi: 10.11862/CJIC.20260039
Abstract:
A new cadmium-based coordination polymer (CP) with 1D structure, [Cd(4-DTBPT)(DMF)2(H2O)2](C10H4O8)·4-DTBPT·3H2O (Cd-CP), where 4-DTBPT=2,7-di(4H-1,2,4-triazol-4yl)benzo[lmn][3,8]phenanthroline-1,3,6,8-(2H, 7H)-tetraone, DMF=N,N-dimethylformamide, C10H4O82-=2,5-dicarboxyterephthalate, which originates from the decomposition of N,N′-bis(glycinyl)pyromellitic diimide (BGPD), was firstly synthesized via the interaction of 4-DTBPT, BGPD, and Cd(NO3)2·4H2O, and characterized by IR spectrum, thermogravimetric analysis and single-crystal X-ray diffraction. In Cd-CP, 4-DTBPT ligands linked adjacent Cd(Ⅱ) ions to produce a 1D chain structure. The C10H4O82- anion and the free 4-DTBPT ligands are respectively embedded between 1D chains through electrostatic force and hydrogen bonds, forming a 3D network structure. When Cd-CP was employed as the cathode material of lithium-ion batteries (LIBs), it delivered the first discharge specific capacity of 78.3 mAh·g-1 at 0.05 A·g-1 along with the Coulombic efficiency of close to 100%, and a higher cycle stability with the capacity retention of 85.7% after 100 cycles.
A new cadmium-based coordination polymer (CP) with 1D structure, [Cd(4-DTBPT)(DMF)2(H2O)2](C10H4O8)·4-DTBPT·3H2O (Cd-CP), where 4-DTBPT=2,7-di(4H-1,2,4-triazol-4yl)benzo[lmn][3,8]phenanthroline-1,3,6,8-(2H, 7H)-tetraone, DMF=N,N-dimethylformamide, C10H4O82-=2,5-dicarboxyterephthalate, which originates from the decomposition of N,N′-bis(glycinyl)pyromellitic diimide (BGPD), was firstly synthesized via the interaction of 4-DTBPT, BGPD, and Cd(NO3)2·4H2O, and characterized by IR spectrum, thermogravimetric analysis and single-crystal X-ray diffraction. In Cd-CP, 4-DTBPT ligands linked adjacent Cd(Ⅱ) ions to produce a 1D chain structure. The C10H4O82- anion and the free 4-DTBPT ligands are respectively embedded between 1D chains through electrostatic force and hydrogen bonds, forming a 3D network structure. When Cd-CP was employed as the cathode material of lithium-ion batteries (LIBs), it delivered the first discharge specific capacity of 78.3 mAh·g-1 at 0.05 A·g-1 along with the Coulombic efficiency of close to 100%, and a higher cycle stability with the capacity retention of 85.7% after 100 cycles.
2026, 42(8): 1763-1778
doi: 10.11862/CJIC.20250359
Abstract:
Two novel Cd-based metal-organic frameworks (Cd-MOFs), {[Cd2(DCODBC)(phen)2]·3H2O}n (1) and {[Cd5(DCOTBC)5(H2O)8]·2H2O}n (2), were synthesized by solvothermal method, where H4DCODBC=4,4′-oxydibenzene-1,2-dicarboxylic acid, phen=1,10-phenanthroline, and H5DCOTBC=4-[(3,4-dicarboxyphenyl)oxy]benzene-1,2,3-tricarboxylic acid. The structures of compounds 1 and 2 were determined using single-crystal X-ray diffraction, powder X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis. 1 is a 2D planar structure, and 2 is a 3D grid structure. The DCODBC4- ligand adopts the μ6-к2∶к2∶к2∶к2∶к1∶к1 mode in 1 and the DCOTBC5- ligand adopts the μ9-к2∶к2∶к1∶к1∶к1∶к1∶к1∶к1∶к1 mode in 2. To evaluate their optical performance, the photoluminescent properties of 1 and 2 were analyzed. 1 responded well to nitrobenzene [NB, detection limit (LOD)=0.043 8 μmol·L-1], while 2 responded well to 2,4,6-trinitrophenol (TNP, LOD=0.257 μmol·L-1). Interestingly, 1 and 2 responded well to tetracycline (TC) and fluazinam (FLU); the LODs were all in the μmol·L-1 range. The fluorescence quenching mechanisms of 1 and 2 were discussed. To further evaluate the detection capability of 1 and 2 for FLU in real samples, we conducted a spike recovery experiment using apple peels as the matrix. The recovery rate for 1 ranged from 98.78% to 99.75%, and that for 2 ranged from 98.76% to 99.27%.
Two novel Cd-based metal-organic frameworks (Cd-MOFs), {[Cd2(DCODBC)(phen)2]·3H2O}n (1) and {[Cd5(DCOTBC)5(H2O)8]·2H2O}n (2), were synthesized by solvothermal method, where H4DCODBC=4,4′-oxydibenzene-1,2-dicarboxylic acid, phen=1,10-phenanthroline, and H5DCOTBC=4-[(3,4-dicarboxyphenyl)oxy]benzene-1,2,3-tricarboxylic acid. The structures of compounds 1 and 2 were determined using single-crystal X-ray diffraction, powder X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis. 1 is a 2D planar structure, and 2 is a 3D grid structure. The DCODBC4- ligand adopts the μ6-к2∶к2∶к2∶к2∶к1∶к1 mode in 1 and the DCOTBC5- ligand adopts the μ9-к2∶к2∶к1∶к1∶к1∶к1∶к1∶к1∶к1 mode in 2. To evaluate their optical performance, the photoluminescent properties of 1 and 2 were analyzed. 1 responded well to nitrobenzene [NB, detection limit (LOD)=0.043 8 μmol·L-1], while 2 responded well to 2,4,6-trinitrophenol (TNP, LOD=0.257 μmol·L-1). Interestingly, 1 and 2 responded well to tetracycline (TC) and fluazinam (FLU); the LODs were all in the μmol·L-1 range. The fluorescence quenching mechanisms of 1 and 2 were discussed. To further evaluate the detection capability of 1 and 2 for FLU in real samples, we conducted a spike recovery experiment using apple peels as the matrix. The recovery rate for 1 ranged from 98.78% to 99.75%, and that for 2 ranged from 98.76% to 99.27%.
2026, 42(8): 1779-1791
doi: 10.11862/CJIC.20260142
Abstract:
The double perovskite oxide La0.6Sr1.4Ni0.4Co1.6O6 (LSNC) was synthesized using a simple sol-gel method, followed by physical mixing with S/N co-doped graphene (S/NG) to prepare LSNC@S/NG, thereby achieving excellent electrical conductivity and abundant active sites. When the mass fraction of S/NG was 15%, LSNC@S/NG-15% exhibited the largest specific surface area (11 m2·g-1) and electrochemical double-layer capacitance (71.14 mF·cm-2), which were significantly superior to those of the pristine perovskite. In linear sweep voltammetry (LSV) tests, this optimized composite demonstrated the best electrocatalytic activity for both the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), achieving high anodic and cathodic current densities of 356.0 mA·cm-2 (termination potential: 1.97 V) and 300.4 mA·cm-2 (termination potential: 0.37 V), respectively. This remarkable enhancement in performance is attributed to the strong synergistic effect between the catalytically active LSNC particles and the highly conductive, defect-rich S/NG support, which facilitates rapid charge transfer and provides a larger density of accessible active sites.
The double perovskite oxide La0.6Sr1.4Ni0.4Co1.6O6 (LSNC) was synthesized using a simple sol-gel method, followed by physical mixing with S/N co-doped graphene (S/NG) to prepare LSNC@S/NG, thereby achieving excellent electrical conductivity and abundant active sites. When the mass fraction of S/NG was 15%, LSNC@S/NG-15% exhibited the largest specific surface area (11 m2·g-1) and electrochemical double-layer capacitance (71.14 mF·cm-2), which were significantly superior to those of the pristine perovskite. In linear sweep voltammetry (LSV) tests, this optimized composite demonstrated the best electrocatalytic activity for both the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), achieving high anodic and cathodic current densities of 356.0 mA·cm-2 (termination potential: 1.97 V) and 300.4 mA·cm-2 (termination potential: 0.37 V), respectively. This remarkable enhancement in performance is attributed to the strong synergistic effect between the catalytically active LSNC particles and the highly conductive, defect-rich S/NG support, which facilitates rapid charge transfer and provides a larger density of accessible active sites.
