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2026 Volume 42 Issue 6
2026, 42(6): 1121-1130
doi: 10.11862/CJIC.20260115
Abstract:
Two novel Cd(Ⅱ)-based pillared-layer coordination polymers, [Cd2(1,5-bpvn)2(bdc)2]n (CP1) and [Cd(1,5-bpvn)(4,4′-bpdc)]n (CP2), were constructed via a solvothermal strategy using the bis-olefin ligand 1,5-bis[(E)-2-(pyridin-4-yl)vinyl]naphthalene (1,5-bpvn) in combination with auxiliary dicarboxylate ligands of different axial lengths, namely terephthalic acid (H2bdc) and biphenyl-4,4′-dicarboxylic acid (4,4′-H2bpdc). Single-crystal X-ray diffraction analyses reveal that the axial length of the auxiliary ligands plays a crucial role in regulating the framework topology and interpenetration mode. CP1 exhibits a typical two-fold interpenetrated framework with pcu topology, whereas CP2 adopts a rare self-penetrating architecture with the Schläfli symbol {44·610·8}. In CP1, the 1,5-bpvn ligands display both in-phase and out-of-phase packing arrangements, with the distance and orientation between adjacent olefin groups satisfying the geometric criteria for a solid-state [2+2] photocycloaddition reaction. Upon exposure to daylight, CP1 underwent a single-crystal-to-single-crystal transformation, affording the photoproduct [Cd2(tpdnpp)(bdc)2]n (CP1-C), which contains the bis(cyclobutane) dimer tetrakis(pyridin-4-yl)-1,2,11,12-diethano[2.2]naphthalenophane (tpdnpp). In contrast, the 1,5-bpvn ligands in CP2 adopt significantly twisted conformations, resulting in larger C=C separations that are unfavorable for photocycloaddition. In addition, the luminescent properties of CP1 before and after the photocycloaddition reaction were investigated, revealing the influence of the photochemical transformation on the emission behavior.
Two novel Cd(Ⅱ)-based pillared-layer coordination polymers, [Cd2(1,5-bpvn)2(bdc)2]n (CP1) and [Cd(1,5-bpvn)(4,4′-bpdc)]n (CP2), were constructed via a solvothermal strategy using the bis-olefin ligand 1,5-bis[(E)-2-(pyridin-4-yl)vinyl]naphthalene (1,5-bpvn) in combination with auxiliary dicarboxylate ligands of different axial lengths, namely terephthalic acid (H2bdc) and biphenyl-4,4′-dicarboxylic acid (4,4′-H2bpdc). Single-crystal X-ray diffraction analyses reveal that the axial length of the auxiliary ligands plays a crucial role in regulating the framework topology and interpenetration mode. CP1 exhibits a typical two-fold interpenetrated framework with pcu topology, whereas CP2 adopts a rare self-penetrating architecture with the Schläfli symbol {44·610·8}. In CP1, the 1,5-bpvn ligands display both in-phase and out-of-phase packing arrangements, with the distance and orientation between adjacent olefin groups satisfying the geometric criteria for a solid-state [2+2] photocycloaddition reaction. Upon exposure to daylight, CP1 underwent a single-crystal-to-single-crystal transformation, affording the photoproduct [Cd2(tpdnpp)(bdc)2]n (CP1-C), which contains the bis(cyclobutane) dimer tetrakis(pyridin-4-yl)-1,2,11,12-diethano[2.2]naphthalenophane (tpdnpp). In contrast, the 1,5-bpvn ligands in CP2 adopt significantly twisted conformations, resulting in larger C=C separations that are unfavorable for photocycloaddition. In addition, the luminescent properties of CP1 before and after the photocycloaddition reaction were investigated, revealing the influence of the photochemical transformation on the emission behavior.
2026, 42(6): 1131-1145
doi: 10.11862/CJIC.20260063
Abstract:
A series of magnetic porous CaCO3/CaFe2O4 (CCFO-x, x represents the molar ratio of Ca(CH3COO)2·H2O to CaFe2O4 during synthesis) composites were prepared by coating CaCO3 onto porous supports. The porous CaFe2O4 support not only enables the effective dispersion of active CaCO3 and provides more accessible adsorption sites, but also endows the adsorbent with certain magnetism, allowing it to be rapidly separated from the solution. Adsorption tests indicated that the phosphate adsorption capacity by CCFO-x increased with the rise of Ca content in the material. Among them, CCFO-5 showed a maximum phosphate adsorption capacity of 246 mg·g-1, which was much higher than that of the CaFe2O4 support (134 mg·g-1). Kinetic fittings and adsorption isotherms reveal that monolayer chemical adsorption dominates the adsorption between phosphate and CCFO-5. Furthermore, CCFO-5 presented an excellent phosphate adsorption performance under acidic conditions (pH=3.00-7.00, equilibrium adsorption capacity Qe=174-144 mg·g-1) and exhibited good resistance to ionic interference. Mechanism analysis indicates that multiple chemical processes including surface protonation, electrostatic interaction, ligand exchange, and inner-sphere complexation reaction occurred between phosphate and CCFO-5 during the adsorption, resulting in a stable Ca10(PO4)6(OH)2 compound. Recycling tests showed that, at a solid-liquid ratio of 15 g·L-1, the enrichment efficiency of adsorbed phosphorus reached 567.4% when using 1.0 mol·L-1 HCl as the eluent.
A series of magnetic porous CaCO3/CaFe2O4 (CCFO-x, x represents the molar ratio of Ca(CH3COO)2·H2O to CaFe2O4 during synthesis) composites were prepared by coating CaCO3 onto porous supports. The porous CaFe2O4 support not only enables the effective dispersion of active CaCO3 and provides more accessible adsorption sites, but also endows the adsorbent with certain magnetism, allowing it to be rapidly separated from the solution. Adsorption tests indicated that the phosphate adsorption capacity by CCFO-x increased with the rise of Ca content in the material. Among them, CCFO-5 showed a maximum phosphate adsorption capacity of 246 mg·g-1, which was much higher than that of the CaFe2O4 support (134 mg·g-1). Kinetic fittings and adsorption isotherms reveal that monolayer chemical adsorption dominates the adsorption between phosphate and CCFO-5. Furthermore, CCFO-5 presented an excellent phosphate adsorption performance under acidic conditions (pH=3.00-7.00, equilibrium adsorption capacity Qe=174-144 mg·g-1) and exhibited good resistance to ionic interference. Mechanism analysis indicates that multiple chemical processes including surface protonation, electrostatic interaction, ligand exchange, and inner-sphere complexation reaction occurred between phosphate and CCFO-5 during the adsorption, resulting in a stable Ca10(PO4)6(OH)2 compound. Recycling tests showed that, at a solid-liquid ratio of 15 g·L-1, the enrichment efficiency of adsorbed phosphorus reached 567.4% when using 1.0 mol·L-1 HCl as the eluent.
2026, 42(6): 1146-1154
doi: 10.11862/CJIC.20260053
Abstract:
Boron neutron capture therapy (BNCT) enables cell-level precision in cancer ablation through the emission of high-energy particles upon neutron irradiation of boron-containing agents. However, clinically employed boron carriers, including boronophenylalanine (BPA) and sodium mercaptoundecahydro-closo-dodecaborate (BSH), suffer from limited boron loading capacity and lack intrinsic imaging capability, which significantly limits their therapeutic efficacy. In this study, icosahedral carborane was selected as a boron-rich source, while gold nanoclusters (AuNCs) were utilized as a fluorescent scaffold. Through surface functionalization with glucose moieties, a novel boron delivery platform (AuGSCB-Glu) was constructed that integrates tumor targeting, boron enrichment, and fluorescence imaging into a single nanostructure. The resulting probe exhibited highly selective fluorescence imaging toward breast cancer MCF-7 cells and markedly enhanced intracellular boron accumulation, ultimately leading to effective BNCT performance at the cellular level.
Boron neutron capture therapy (BNCT) enables cell-level precision in cancer ablation through the emission of high-energy particles upon neutron irradiation of boron-containing agents. However, clinically employed boron carriers, including boronophenylalanine (BPA) and sodium mercaptoundecahydro-closo-dodecaborate (BSH), suffer from limited boron loading capacity and lack intrinsic imaging capability, which significantly limits their therapeutic efficacy. In this study, icosahedral carborane was selected as a boron-rich source, while gold nanoclusters (AuNCs) were utilized as a fluorescent scaffold. Through surface functionalization with glucose moieties, a novel boron delivery platform (AuGSCB-Glu) was constructed that integrates tumor targeting, boron enrichment, and fluorescence imaging into a single nanostructure. The resulting probe exhibited highly selective fluorescence imaging toward breast cancer MCF-7 cells and markedly enhanced intracellular boron accumulation, ultimately leading to effective BNCT performance at the cellular level.
2026, 42(6): 1155-1163
doi: 10.11862/CJIC.20260018
Abstract:
Based on first-principles calculations, we presented a systematic analysis of the electronic structures, optical properties, intrinsic point defects, and defect passivation effects of nitride perovskites CeBN3 (B=Ta, Nb). The calculation results demonstrate that both CeTaN3 and CeNbN3 are direct-band-gap semiconductors, with band gaps of 1.10 and 0.91 eV, respectively. CeTaN3 exhibits a deep-level defect associated with nitrogen interstitial (Ni), whereas CeNbN3 introduces no deep-level defects. In addition, CeNbN3 features more localized charge distribution near the band edges, along with lower carrier effective masses and higher optical absorption coefficients. These characteristics indicate that CeNbN3 lacks deep-level centers that induce non-radiative carrier recombination, while simultaneously exhibiting superior carrier mobility and stronger light-absorption capacity, thus exhibiting greater application potential in the field of photocatalysis. Furthermore, an alkali metal (Li, Na, K, Rb, Cs) doping strategy is adopted to passivate the Ni defects in CeTaN3. It is found that doping with Li, Na, K, and Rb can reduce the depth of the transition energy level of Ni, among which Rb doping yields the most prominent defect passivation effect. By contrast, Cs doping fails to passivate the transition energy level of Ni.
Based on first-principles calculations, we presented a systematic analysis of the electronic structures, optical properties, intrinsic point defects, and defect passivation effects of nitride perovskites CeBN3 (B=Ta, Nb). The calculation results demonstrate that both CeTaN3 and CeNbN3 are direct-band-gap semiconductors, with band gaps of 1.10 and 0.91 eV, respectively. CeTaN3 exhibits a deep-level defect associated with nitrogen interstitial (Ni), whereas CeNbN3 introduces no deep-level defects. In addition, CeNbN3 features more localized charge distribution near the band edges, along with lower carrier effective masses and higher optical absorption coefficients. These characteristics indicate that CeNbN3 lacks deep-level centers that induce non-radiative carrier recombination, while simultaneously exhibiting superior carrier mobility and stronger light-absorption capacity, thus exhibiting greater application potential in the field of photocatalysis. Furthermore, an alkali metal (Li, Na, K, Rb, Cs) doping strategy is adopted to passivate the Ni defects in CeTaN3. It is found that doping with Li, Na, K, and Rb can reduce the depth of the transition energy level of Ni, among which Rb doping yields the most prominent defect passivation effect. By contrast, Cs doping fails to passivate the transition energy level of Ni.
2026, 42(6): 1164-1174
doi: 10.11862/CJIC.20250378
Abstract:
Aiming to meet the demand for rapid and sensitive detection of organophosphate residues, a high- performance electrochemical sensor, NF/KbE-CS/Au25-xAgx@G/GCE (where NF, KbE, CS, Au25-xAgx, G, and GCE represented Nafion, white kidney bean enzyme, chitosan, Au25-xAgx(PET)18 (PET=2-phenylethanethiol), multilayer graphene, and glassy carbon electrode, respectively), was rationally fabricated based on the enzyme inhibition principle. In the as-constructed sensing interface, Au25-xAgx@G composite acts as an ideal supporting matrix for enzyme immobilization, meanwhile, its outstanding electrical conductivity and distinct bimetallic synergistic effect significantly accelerate interfacial electron transfer efficiency, thus giving rise to obvious amplification of electrochemical detection signals. Furthermore, the synergistic enhancement between Au25-xAgx@G and the white KbE-CS composite enables the sensor to realize highly sensitive determination of profenofos.Under optimal experimental conditions, the developed NF/KbE-CS/Au25-xAgx@G/GCE sensor presented a good linear relationship (R2=0.988 4) between the inhibition rate of KbE activity and the logarithm of profenofos mass concentration ranging from 10 to 2 200 μg·L-1, with a detection limit as low as 0.064 μg·L-1. In addition, the as-fabricated sensor demonstrated satisfactory reproducibility, favorable stability, and strong anti-interference capability, has been successfully applied to the quantitative detection of organophosphate pesticide residues in real samples.
Aiming to meet the demand for rapid and sensitive detection of organophosphate residues, a high- performance electrochemical sensor, NF/KbE-CS/Au25-xAgx@G/GCE (where NF, KbE, CS, Au25-xAgx, G, and GCE represented Nafion, white kidney bean enzyme, chitosan, Au25-xAgx(PET)18 (PET=2-phenylethanethiol), multilayer graphene, and glassy carbon electrode, respectively), was rationally fabricated based on the enzyme inhibition principle. In the as-constructed sensing interface, Au25-xAgx@G composite acts as an ideal supporting matrix for enzyme immobilization, meanwhile, its outstanding electrical conductivity and distinct bimetallic synergistic effect significantly accelerate interfacial electron transfer efficiency, thus giving rise to obvious amplification of electrochemical detection signals. Furthermore, the synergistic enhancement between Au25-xAgx@G and the white KbE-CS composite enables the sensor to realize highly sensitive determination of profenofos.Under optimal experimental conditions, the developed NF/KbE-CS/Au25-xAgx@G/GCE sensor presented a good linear relationship (R2=0.988 4) between the inhibition rate of KbE activity and the logarithm of profenofos mass concentration ranging from 10 to 2 200 μg·L-1, with a detection limit as low as 0.064 μg·L-1. In addition, the as-fabricated sensor demonstrated satisfactory reproducibility, favorable stability, and strong anti-interference capability, has been successfully applied to the quantitative detection of organophosphate pesticide residues in real samples.
2026, 42(6): 1175-1189
doi: 10.11862/CJIC.20250375
Abstract:
A mixed-ligand strategy was employed to construct a novel 3D metal-organic framework (MOF) with rhombic channels, namely [Co4(μ3-OH)2(ABTC)(INA)2(DMF)2]n (SXNU-6-Co, DMF=N, N-dimethylformamide, SXNU=Shanxi Normal University), by the hydrothermal assembly of cobalt nitrate with isonicotinic acid (HINA) and the rigid ligand 3, 3′, 5, 5′-azobenzenetetracarboxylic acid (H4ABTC). The well-defined pore channels of SXNU-6-Co are decorated with abundant azo groups and pyridine nitrogen active sites, while the tetranuclear metal-oxygen clusters provide reversible Co2+/Co3+ redox pairs with different coordination numbers. The synergistic effect of these structural features enables precise regulation of 4-aminophenol (4-AP) adsorption and electrocatalytic performance. An electrochemical sensor was fabricated by modifying a glassy carbon electrode (GCE) with SXNU-6-Co, which exhibited a wide linear response range of 0.2-328 μmol·L-1 towards 4-AP, with a low detection limit of 10.47 nmol·L-1 (S/N=3). Grand canonical Monte Carlo (GCMC) simulations confirm that the strong interactions between 4-AP molecules and the SXNU-6-Co framework are mainly driven by π-π stacking and hydrogen bonding with the nitrogen-containing sites, significantly enhancing substrate affinity. The SXNU-6-Co/GCE sensor was successfully applied to detect 4-AP in real water samples, demonstrating high sensitivity, excellent selectivity, and long-term stability.
A mixed-ligand strategy was employed to construct a novel 3D metal-organic framework (MOF) with rhombic channels, namely [Co4(μ3-OH)2(ABTC)(INA)2(DMF)2]n (SXNU-6-Co, DMF=N, N-dimethylformamide, SXNU=Shanxi Normal University), by the hydrothermal assembly of cobalt nitrate with isonicotinic acid (HINA) and the rigid ligand 3, 3′, 5, 5′-azobenzenetetracarboxylic acid (H4ABTC). The well-defined pore channels of SXNU-6-Co are decorated with abundant azo groups and pyridine nitrogen active sites, while the tetranuclear metal-oxygen clusters provide reversible Co2+/Co3+ redox pairs with different coordination numbers. The synergistic effect of these structural features enables precise regulation of 4-aminophenol (4-AP) adsorption and electrocatalytic performance. An electrochemical sensor was fabricated by modifying a glassy carbon electrode (GCE) with SXNU-6-Co, which exhibited a wide linear response range of 0.2-328 μmol·L-1 towards 4-AP, with a low detection limit of 10.47 nmol·L-1 (S/N=3). Grand canonical Monte Carlo (GCMC) simulations confirm that the strong interactions between 4-AP molecules and the SXNU-6-Co framework are mainly driven by π-π stacking and hydrogen bonding with the nitrogen-containing sites, significantly enhancing substrate affinity. The SXNU-6-Co/GCE sensor was successfully applied to detect 4-AP in real water samples, demonstrating high sensitivity, excellent selectivity, and long-term stability.
2026, 42(6): 1190-1202
doi: 10.11862/CJIC.20250365
Abstract:
Using nickel foam (NF) as both the substrate and nickel source, ammonium molybdate as the molybdenum source, and thiourea as the sulfur source, MoS2/Ni3S2@NF (MNS@NF) composite photothermal materials were in situ grown on the NF skeleton via the hydrothermal method. The structure and morphology of the composite material were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS), and its light-absorption and interfacial-evaporation performance were studied. The results indicated that under simulated solar illumination (light intensity of 1 kW·m-2), the sample MNS@NF-200-24 synthesized at a hydrothermal reaction temperature of 200 ℃ and reaction time of 24 h achieved a light absorption rate of 91.7%, a deionized water interfacial evaporation rate of 2.846 kg·m-2·h-1, and an interfacial evaporation efficiency of 95.6%. Additionally, the interfacial evaporation performance in simulated seawater was tested. After 1 h of evaporation, the rate reached 2.360 kg·m-2·h-1, and after 12 h of continuous interfacial evaporation, it stabilized at 2.000 kg·m-2·h-1, with no crystalline salt precipitating on the macroscopic surface. The water obtained through evaporation and condensation met the drinking water standards set by the World Health Organization (WHO) and the Environmental Protection Agency (EPA).
Using nickel foam (NF) as both the substrate and nickel source, ammonium molybdate as the molybdenum source, and thiourea as the sulfur source, MoS2/Ni3S2@NF (MNS@NF) composite photothermal materials were in situ grown on the NF skeleton via the hydrothermal method. The structure and morphology of the composite material were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS), and its light-absorption and interfacial-evaporation performance were studied. The results indicated that under simulated solar illumination (light intensity of 1 kW·m-2), the sample MNS@NF-200-24 synthesized at a hydrothermal reaction temperature of 200 ℃ and reaction time of 24 h achieved a light absorption rate of 91.7%, a deionized water interfacial evaporation rate of 2.846 kg·m-2·h-1, and an interfacial evaporation efficiency of 95.6%. Additionally, the interfacial evaporation performance in simulated seawater was tested. After 1 h of evaporation, the rate reached 2.360 kg·m-2·h-1, and after 12 h of continuous interfacial evaporation, it stabilized at 2.000 kg·m-2·h-1, with no crystalline salt precipitating on the macroscopic surface. The water obtained through evaporation and condensation met the drinking water standards set by the World Health Organization (WHO) and the Environmental Protection Agency (EPA).
2026, 42(6): 1203-1214
doi: 10.11862/CJIC.20250370
Abstract:
Poplar catkins (PC) were used as raw material, and an ethanol solvothermal method was employed for pretreatment to high-surface-area poplar catkin-derived porous carbon (DPCC). The adsorption performance and kinetics of DPCC towards dye molecules were systematically evaluated. Pretreatment parameters were optimized using single-factor experiments, establishing the optimal conditions: a liquid-to-solid ratio of 17 mL·g-1 and a thermal treatment at 200 ℃ for 2 h. Under these optimized conditions, the specific surface area of DPCC-10 was significantly enhanced to 518 m2·g-1. Comprehensive characterization employing Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscope (SEM), and N2 adsorption-desorption test confirmed that the pretreatment effectively removed lignin components, hemicellulose, etc., and induced the formation of a hierarchical porous structure. Adsorption experiments showed that the optimized DPCC-10 exhibited a maximum adsorption capacity of 385.71 mg·g-1 for methylene blue (MB), surpassing most reported values for biomass-derived adsorbents. The adsorption process of dyes by DPCC-10 follows the pseudo-second-order kinetic equation, indicating that the adsorption is primarily a chemisorption-dominated mechanism. The cyclic stability test indicated that after four adsorption-desorption cycles, the adsorption capacity for MB still remained 92.01% of the initial value, indicating the excellent regenerability of the material.
Poplar catkins (PC) were used as raw material, and an ethanol solvothermal method was employed for pretreatment to high-surface-area poplar catkin-derived porous carbon (DPCC). The adsorption performance and kinetics of DPCC towards dye molecules were systematically evaluated. Pretreatment parameters were optimized using single-factor experiments, establishing the optimal conditions: a liquid-to-solid ratio of 17 mL·g-1 and a thermal treatment at 200 ℃ for 2 h. Under these optimized conditions, the specific surface area of DPCC-10 was significantly enhanced to 518 m2·g-1. Comprehensive characterization employing Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscope (SEM), and N2 adsorption-desorption test confirmed that the pretreatment effectively removed lignin components, hemicellulose, etc., and induced the formation of a hierarchical porous structure. Adsorption experiments showed that the optimized DPCC-10 exhibited a maximum adsorption capacity of 385.71 mg·g-1 for methylene blue (MB), surpassing most reported values for biomass-derived adsorbents. The adsorption process of dyes by DPCC-10 follows the pseudo-second-order kinetic equation, indicating that the adsorption is primarily a chemisorption-dominated mechanism. The cyclic stability test indicated that after four adsorption-desorption cycles, the adsorption capacity for MB still remained 92.01% of the initial value, indicating the excellent regenerability of the material.
2026, 42(6): 1215-1228
doi: 10.11862/CJIC.20250368
Abstract:
A Z-scheme g-C3N4/Bi2WO6 heterojunction photocatalytic material was constructed via high-temperature thermal polymerization combined with an in-situ solvothermal method. The composition, structure, and optical properties of the heterojunction were thoroughly characterized using X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, and ultraviolet-visible-near infrared diffuse reflectance spectroscopy. The results indicate that the presence of oxygen vacancies enhances the absorption capacity of the heterojunction for visible and NIR light. The transformation of the Ⅱ-type structure to the Z-scheme mechanism improves the separation efficiency and redox ability of photogenerated electron-hole pairs. Under visible and NIR light irradiation, the apparent rate constants for the degradation of ofloxacin by the optimal g-C3N4/Bi2WO6 heterojunction reached 0.045 8 and 0.003 8 min-1, respectively, which were significantly higher than those of the individual g-C3N4 and Bi2WO6 components. Moreover, the prepared heterojunction exhibited excellent cycling stability and reusability.
A Z-scheme g-C3N4/Bi2WO6 heterojunction photocatalytic material was constructed via high-temperature thermal polymerization combined with an in-situ solvothermal method. The composition, structure, and optical properties of the heterojunction were thoroughly characterized using X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, and ultraviolet-visible-near infrared diffuse reflectance spectroscopy. The results indicate that the presence of oxygen vacancies enhances the absorption capacity of the heterojunction for visible and NIR light. The transformation of the Ⅱ-type structure to the Z-scheme mechanism improves the separation efficiency and redox ability of photogenerated electron-hole pairs. Under visible and NIR light irradiation, the apparent rate constants for the degradation of ofloxacin by the optimal g-C3N4/Bi2WO6 heterojunction reached 0.045 8 and 0.003 8 min-1, respectively, which were significantly higher than those of the individual g-C3N4 and Bi2WO6 components. Moreover, the prepared heterojunction exhibited excellent cycling stability and reusability.
2026, 42(6): 1229-1236
doi: 10.11862/CJIC.20250355
Abstract:
Three charge-transfer complexes, (T1)[Cu2Br6]·2THF, (T2)[Cu2Br6]·2THF, and (T3)[Cu2Br6], have been prepared via diffusion methods comprising extended tetrathiafulvalene (exTTF) derivatives C14H8(C3S2(S-R)2)2 [R=phenyl (T1), thiophen-2-yl (T2), pyridin-2-yl (T3)] and CuBr2. Crystallographic studies indicate that T12+, T22+, and T32+ present different molecular configurations, while [Cu2Br6]2- anions exhibit two different coordination configurations (planar and octahedral), which further lead to different crystal packing structures of the three complexes. Notably, altering the peripheral aryl groups of exTTF derivatives can effectively regulate the anion configuration, and compounds T1-T3 can flexibly adjust their own configurations to match the anion structure and crystal packing requirements, thereby providing a solid basis for designing tunable supramolecular materials with potential optoelectronic applications.
Three charge-transfer complexes, (T1)[Cu2Br6]·2THF, (T2)[Cu2Br6]·2THF, and (T3)[Cu2Br6], have been prepared via diffusion methods comprising extended tetrathiafulvalene (exTTF) derivatives C14H8(C3S2(S-R)2)2 [R=phenyl (T1), thiophen-2-yl (T2), pyridin-2-yl (T3)] and CuBr2. Crystallographic studies indicate that T12+, T22+, and T32+ present different molecular configurations, while [Cu2Br6]2- anions exhibit two different coordination configurations (planar and octahedral), which further lead to different crystal packing structures of the three complexes. Notably, altering the peripheral aryl groups of exTTF derivatives can effectively regulate the anion configuration, and compounds T1-T3 can flexibly adjust their own configurations to match the anion structure and crystal packing requirements, thereby providing a solid basis for designing tunable supramolecular materials with potential optoelectronic applications.
2026, 42(6): 1237-1246
doi: 10.11862/CJIC.20250322
Abstract:
A strategy of co-doping with Sm3+ and Sb3+ was proposed, achieving effective modulation of the luminescence color from blue to white in Cs2NaGdCl6 phosphors. A series of Cs2NaGd0.985-xCl6∶0.015Sb3+, xSm3+ (x=0-0.130) phosphors were synthesized via the microwave solid-state method. Phase analysis confirms that all samples maintain a pure double perovskite structure, with Sm3+ successfully incorporated into the lattice. Photoluminescence spectrum analysis revealed that under 336 nm excitation, the material simultaneously produced broad blue emission centered at 460 nm originating from self-trapped excitons (STEs) and characteristic emissions (568, 604, 653 nm) from Sm3+. Efficient energy transfer from STEs to Sm3+ was confirmed in this system, with an efficiency of 13.34% (x=0.070). When the Sm3+ doping concentration was 0.070, the phosphor exhibited optimal performance: a photoluminescence quantum yield (PLQY) of 35.49%, good thermal stability (maintaining 68.6% of its room temperature intensity at 423 K), and a thermal activation energy of 163 meV. Furthermore, by adjusting the Sm3+ concentration, a continuously controllable variation of the luminescence color from the blue region to the white region in the CIE chromaticity diagram was achieved.
A strategy of co-doping with Sm3+ and Sb3+ was proposed, achieving effective modulation of the luminescence color from blue to white in Cs2NaGdCl6 phosphors. A series of Cs2NaGd0.985-xCl6∶0.015Sb3+, xSm3+ (x=0-0.130) phosphors were synthesized via the microwave solid-state method. Phase analysis confirms that all samples maintain a pure double perovskite structure, with Sm3+ successfully incorporated into the lattice. Photoluminescence spectrum analysis revealed that under 336 nm excitation, the material simultaneously produced broad blue emission centered at 460 nm originating from self-trapped excitons (STEs) and characteristic emissions (568, 604, 653 nm) from Sm3+. Efficient energy transfer from STEs to Sm3+ was confirmed in this system, with an efficiency of 13.34% (x=0.070). When the Sm3+ doping concentration was 0.070, the phosphor exhibited optimal performance: a photoluminescence quantum yield (PLQY) of 35.49%, good thermal stability (maintaining 68.6% of its room temperature intensity at 423 K), and a thermal activation energy of 163 meV. Furthermore, by adjusting the Sm3+ concentration, a continuously controllable variation of the luminescence color from the blue region to the white region in the CIE chromaticity diagram was achieved.
2026, 42(6): 1247-1260
doi: 10.11862/CJIC.20250299
Abstract:
The chemical structure of palladium precursors and their synergistic interactions with ligands play a decisive role in regulating the configuration of in situ generated Pd(0) active species, thereby governing the efficiency of C—C coupling reactions. So, in this work, 1, 5-cyclooctadiene palladium halides, [Pd(COD)X2] (COD=1, 5-cyclooctadiene, X=Cl, Br), were employed as palladium precursors, and organophosphines (PR3) were introduced as regulatory ligands to systematically investigate their effects on catalytic performance in C—C coupling reactions. The structural characteristics and solvent stability of the Pd(Ⅱ) precursors were elucidated by elemental analysis, infrared spectroscopy, nuclear magnetic resonance spectroscopy, and density functional theory calculations. In combination with single-crystal X-ray diffraction analysis of catalyst-derived species after reaction, the structural evolution of the palladium precursor during catalysis was examined. The results demonstrate that PR3-regulated cis-[Pd(COD)X2]/Pd(0) catalytic systems exhibit significantly higher catalytic efficiency than the commercially available trans-[Pd(PPh3)2Cl2] system. The in situ generated electron-rich cis-(PR3)2Pd(0) species display enhanced nucleophilicity, which facilitates C—X bond activation and accelerates the oxidative addition step. A clear ligand-dependent trend in catalytic activity was observed in the order: cis-[Pd(COD)X2]/Xantphos > cis-[Pd(COD)X2]/PPh3 > trans-[Pd(PPh3)2 Cl2] > [Pd(COD)X2]. Mechanistic studies indicate that coordination of electron-rich phosphine ligands to Pd(0), together with steric hindrance effects, effectively suppresses palladium aggregation and deactivation. Furthermore, ligand-controlled configuration and halogen effects synergistically promote Pd(0) generation. The rigid backbone of Xantphos enforces cis coordination at the palladium center, affording highly active cis-(Xantphos)Pd(0) species with increased exposure of active sites, whereas intermediates derived from PPh3 readily form mixtures of cis and trans isomers. Halogen dependence was also evident (cis-[Pd(COD)Br2] > cis-[Pd(COD)Cl2]): the lower electronegativity of bromide increases electron density at the Pd(0) center, thereby improving resistance to oxidation and stabilizing the active species. In addition, the weaker Pd—Br bond facilitates the faster generation of Pd(0), leading to improved catalytic efficiency and higher product yields.
The chemical structure of palladium precursors and their synergistic interactions with ligands play a decisive role in regulating the configuration of in situ generated Pd(0) active species, thereby governing the efficiency of C—C coupling reactions. So, in this work, 1, 5-cyclooctadiene palladium halides, [Pd(COD)X2] (COD=1, 5-cyclooctadiene, X=Cl, Br), were employed as palladium precursors, and organophosphines (PR3) were introduced as regulatory ligands to systematically investigate their effects on catalytic performance in C—C coupling reactions. The structural characteristics and solvent stability of the Pd(Ⅱ) precursors were elucidated by elemental analysis, infrared spectroscopy, nuclear magnetic resonance spectroscopy, and density functional theory calculations. In combination with single-crystal X-ray diffraction analysis of catalyst-derived species after reaction, the structural evolution of the palladium precursor during catalysis was examined. The results demonstrate that PR3-regulated cis-[Pd(COD)X2]/Pd(0) catalytic systems exhibit significantly higher catalytic efficiency than the commercially available trans-[Pd(PPh3)2Cl2] system. The in situ generated electron-rich cis-(PR3)2Pd(0) species display enhanced nucleophilicity, which facilitates C—X bond activation and accelerates the oxidative addition step. A clear ligand-dependent trend in catalytic activity was observed in the order: cis-[Pd(COD)X2]/Xantphos > cis-[Pd(COD)X2]/PPh3 > trans-[Pd(PPh3)2 Cl2] > [Pd(COD)X2]. Mechanistic studies indicate that coordination of electron-rich phosphine ligands to Pd(0), together with steric hindrance effects, effectively suppresses palladium aggregation and deactivation. Furthermore, ligand-controlled configuration and halogen effects synergistically promote Pd(0) generation. The rigid backbone of Xantphos enforces cis coordination at the palladium center, affording highly active cis-(Xantphos)Pd(0) species with increased exposure of active sites, whereas intermediates derived from PPh3 readily form mixtures of cis and trans isomers. Halogen dependence was also evident (cis-[Pd(COD)Br2] > cis-[Pd(COD)Cl2]): the lower electronegativity of bromide increases electron density at the Pd(0) center, thereby improving resistance to oxidation and stabilizing the active species. In addition, the weaker Pd—Br bond facilitates the faster generation of Pd(0), leading to improved catalytic efficiency and higher product yields.
2026, 42(6): 1261-1275
doi: 10.11862/CJIC.20250329
Abstract:
A series of color-tunable Ca0.993-yScBO4∶0.007Bi3+, yEu3+ (y=0-0.100) phosphors was synthesized using a high-temperature solid-state reaction method. Through the construction of an efficient non-radiative energy transfer channel from Bi3+ to Eu3+ in the CaScBO4 lattice, the emission color was continuously tuned from the blue region [CIE chromaticity coordinate: (0.153, 0.050)] to the orange-red region [CIE chromaticity coordinate: (0.530, 0.270)] under 330 nm excitation. The energy transfer efficiency reached a maximum of 71.2%, and the mechanism was determined to be the electric dipole-dipole interaction with a critical distance of 1.36 nm. As the representative orange-red phosphor, Ca0.893ScBO4∶0.007Bi3+, 0.100Eu3+ demonstrated excellent thermal stability, retaining 77.7% of the initial integrated intensity at 423 K, with a thermal quenching activation energy of 0.417 eV. Compared to the single-doped Ca0.993ScBO4∶0.007Bi3+ blue phosphor, this co-doped system achieves a broad color tuning range from blue to orange-red while maintaining relatively high quantum efficiency and excellent thermal stability.
A series of color-tunable Ca0.993-yScBO4∶0.007Bi3+, yEu3+ (y=0-0.100) phosphors was synthesized using a high-temperature solid-state reaction method. Through the construction of an efficient non-radiative energy transfer channel from Bi3+ to Eu3+ in the CaScBO4 lattice, the emission color was continuously tuned from the blue region [CIE chromaticity coordinate: (0.153, 0.050)] to the orange-red region [CIE chromaticity coordinate: (0.530, 0.270)] under 330 nm excitation. The energy transfer efficiency reached a maximum of 71.2%, and the mechanism was determined to be the electric dipole-dipole interaction with a critical distance of 1.36 nm. As the representative orange-red phosphor, Ca0.893ScBO4∶0.007Bi3+, 0.100Eu3+ demonstrated excellent thermal stability, retaining 77.7% of the initial integrated intensity at 423 K, with a thermal quenching activation energy of 0.417 eV. Compared to the single-doped Ca0.993ScBO4∶0.007Bi3+ blue phosphor, this co-doped system achieves a broad color tuning range from blue to orange-red while maintaining relatively high quantum efficiency and excellent thermal stability.
2026, 42(6): 1276-1288
doi: 10.11862/CJIC.20260011
Abstract:
Using sodium phytate (PA) as a ligand precursor, boron-doped iron-cobalt phytate materials (B-FeCoPA) were synthesized via a one-step hydrothermal method. Boron incorporation into FeCoPA effectively modulates the local bonding environment and electronic structure through synergistic B-Fe-Co interactions, thereby facilitating electron transfer and enhancing the electrocatalytic activity for the oxygen evolution reaction (OER). The optimized B-FeCoPA exhibited an outstanding OER catalytic activity in alkaline electrolyte, achieving low overpotentials of 299 mV at 10 mA·cm-2 and 354 mV at 100 mA·cm-2, a small Tafel slope of 46 mV·dec-1, and a high Faradaic efficiency of 96%. Moreover, B-FeCoPA demonstrated good operational stability, maintaining a stable potential of approximately 1.52 V (vs RHE) at 10 mA·cm-2 over a 10-h continuous test in 1.0 mol·L-1 KOH.
Using sodium phytate (PA) as a ligand precursor, boron-doped iron-cobalt phytate materials (B-FeCoPA) were synthesized via a one-step hydrothermal method. Boron incorporation into FeCoPA effectively modulates the local bonding environment and electronic structure through synergistic B-Fe-Co interactions, thereby facilitating electron transfer and enhancing the electrocatalytic activity for the oxygen evolution reaction (OER). The optimized B-FeCoPA exhibited an outstanding OER catalytic activity in alkaline electrolyte, achieving low overpotentials of 299 mV at 10 mA·cm-2 and 354 mV at 100 mA·cm-2, a small Tafel slope of 46 mV·dec-1, and a high Faradaic efficiency of 96%. Moreover, B-FeCoPA demonstrated good operational stability, maintaining a stable potential of approximately 1.52 V (vs RHE) at 10 mA·cm-2 over a 10-h continuous test in 1.0 mol·L-1 KOH.
2026, 42(6): 1289-1298
doi: 10.11862/CJIC.20250369
Abstract:
A composite catalyst (Ni-NiO@CN) with nickel-nickel oxide (Ni-NiO) loaded on two-dimensional g-C3N4 (CN) was successfully constructed by hydrothermal coupled pyrolysis. The Ni-NiO nanostructure served as the methanol oxidation reaction (MOR) active center, and the N-rich CN matrix promoted electron transfer and effectively protected the active components from shedding through physical isolation. Ni-NiO@CN-500, obtained by calcination at 500 ℃, exhibited the highest activity with the current density of 164 mA·cm-2 at 1.67 V (vs RHE) in the alkaline medium. Furthermore, the current density of Ni-NiO@CN-500 could be maintained at 154.9 mA·cm-2 (94.5% of its initial value) in the CO-saturated alkaline methanol electrolyte, significantly outperforming commercial Pt/C catalysts.
A composite catalyst (Ni-NiO@CN) with nickel-nickel oxide (Ni-NiO) loaded on two-dimensional g-C3N4 (CN) was successfully constructed by hydrothermal coupled pyrolysis. The Ni-NiO nanostructure served as the methanol oxidation reaction (MOR) active center, and the N-rich CN matrix promoted electron transfer and effectively protected the active components from shedding through physical isolation. Ni-NiO@CN-500, obtained by calcination at 500 ℃, exhibited the highest activity with the current density of 164 mA·cm-2 at 1.67 V (vs RHE) in the alkaline medium. Furthermore, the current density of Ni-NiO@CN-500 could be maintained at 154.9 mA·cm-2 (94.5% of its initial value) in the CO-saturated alkaline methanol electrolyte, significantly outperforming commercial Pt/C catalysts.
2026, 42(6): 1299-1311
doi: 10.11862/CJIC.20260362
Abstract:
A highly sensitive surface-enhanced Raman scattering (SERS) substrate was constructed, which was a Cu2O-GO-AuNSts sandwich heterostructure assembled on a filter membrane, with ultrathin graphene oxide (GO) precisely embedded between the thorn-like Cu2O microcrystals and gold nanostars (AuNSts). This heterostructure achieved strong electromagnetic enhancement and rapid photogenerated charge transfer by synergistically coupling broadband light absorption, efficient molecular enrichment, and abundant plasma "hotspots". Using rhodamine 6G (R6G) as probe molecules, the substrate achieved an ultra-low detection limit of 10-13 mol·L-1, demonstrating superior SERS sensitivity. More importantly, the heterostructure concurrently exhibited significant photocatalytic performance, thereby endowing the substrate with self-cleaning functionality. Even for the highly stable and recalcitrant persistent organic pollutant (POP), 2, 2′, 4, 4′-tetrabromodiphenyl ether (BDE-47), the characteristic SERS fingerprint could be clearly identified at a concentration as low as 10-7 mol·L-1. UV-Vis spectroscopy analysis revealed a degradation efficiency of approximately 66% after 20 h of light irradiation. The excellent SERS property of the sandwich structure originates from the synergistic effect of local surface plasmon resonance (LSPR) effect attributed to AuNSts and the molecular enrichment effect of GO lamellae and filter membrane, while the photocatalytic activity originates from the photo-induced charge transfer mechanism within the structure.
A highly sensitive surface-enhanced Raman scattering (SERS) substrate was constructed, which was a Cu2O-GO-AuNSts sandwich heterostructure assembled on a filter membrane, with ultrathin graphene oxide (GO) precisely embedded between the thorn-like Cu2O microcrystals and gold nanostars (AuNSts). This heterostructure achieved strong electromagnetic enhancement and rapid photogenerated charge transfer by synergistically coupling broadband light absorption, efficient molecular enrichment, and abundant plasma "hotspots". Using rhodamine 6G (R6G) as probe molecules, the substrate achieved an ultra-low detection limit of 10-13 mol·L-1, demonstrating superior SERS sensitivity. More importantly, the heterostructure concurrently exhibited significant photocatalytic performance, thereby endowing the substrate with self-cleaning functionality. Even for the highly stable and recalcitrant persistent organic pollutant (POP), 2, 2′, 4, 4′-tetrabromodiphenyl ether (BDE-47), the characteristic SERS fingerprint could be clearly identified at a concentration as low as 10-7 mol·L-1. UV-Vis spectroscopy analysis revealed a degradation efficiency of approximately 66% after 20 h of light irradiation. The excellent SERS property of the sandwich structure originates from the synergistic effect of local surface plasmon resonance (LSPR) effect attributed to AuNSts and the molecular enrichment effect of GO lamellae and filter membrane, while the photocatalytic activity originates from the photo-induced charge transfer mechanism within the structure.
2026, 42(6): 1312-1320
doi: 10.11862/CJIC.20250354
Abstract:
Two isostructural coordination polymers [Zn(L)(HCOO)]n (Zn-LFor) and [Zn(L)Cl]n (Zn-LCl) were synthesized by a hydrothermal method based on HL·NaX (HL=2-{[(pyridin-4-yl)methyl]amino}-3, 3-dimethylbutanoic acid, X-=HCOO-, Cl-). Zn-LFor and Zn-LCl belong to the orthorhombic system with space group P212121, which exhibit distorted square pyramidal structures. Interestingly, the values of the trigonality factor (τ5) are distinctively different. Zn-LCl has a τ5 value of 0.144, while the value of τ5 for Zn-LFor is only 0.089. Zn-LFor displayed an excellent fluorescence property, which can be used as a fluorescence probe to detect Cr2O72- in H2O solution with high selectivity and sensitivity, with a quenching constant (KSV) of 2.23×104 L·mol-1. The detection limit of Cr2O72- was calculated from the experimental data, and the value was 1.03 μmol·L-1.
Two isostructural coordination polymers [Zn(L)(HCOO)]n (Zn-LFor) and [Zn(L)Cl]n (Zn-LCl) were synthesized by a hydrothermal method based on HL·NaX (HL=2-{[(pyridin-4-yl)methyl]amino}-3, 3-dimethylbutanoic acid, X-=HCOO-, Cl-). Zn-LFor and Zn-LCl belong to the orthorhombic system with space group P212121, which exhibit distorted square pyramidal structures. Interestingly, the values of the trigonality factor (τ5) are distinctively different. Zn-LCl has a τ5 value of 0.144, while the value of τ5 for Zn-LFor is only 0.089. Zn-LFor displayed an excellent fluorescence property, which can be used as a fluorescence probe to detect Cr2O72- in H2O solution with high selectivity and sensitivity, with a quenching constant (KSV) of 2.23×104 L·mol-1. The detection limit of Cr2O72- was calculated from the experimental data, and the value was 1.03 μmol·L-1.
2026, 42(6): 1321-1336
doi: 10.11862/CJIC.20250333
Abstract:
Two density functional theory methods were employed to evaluate the H2 storage capabilities of metallo-borospherenes TM8B6 (TM=Ni, Pd). Consequently, the superatoms Ni8B6 and Pd8B6, which accommodate 40 and 32 H2 molecules, respectively, exhibit gravimetric H2 uptake capacities of 13.134% and 6.562%, respectively. The average binding energies of Ni8B6(H2)40 and Pd8B6(H2)32 fall within the optimal range for reversible H2 storage applications. The interactions between H2 molecules and the parent structures were characterized using various wave function analysis methods. Polarization effects, alongside the Kubas mechanism, are pivotal to the adsorption of H2 on TM8B6. Moreover, the investigations examine the effect of temperature on the H2 storage capacity of TM8B6 at atmospheric pressure. Atom-centered density-matrix propagation molecular dynamics simulations confirm the reversibility of H2 adsorption and desorption cycles. The thermodynamic analyses of the desorption behavior of H2 molecules were conducted via a three-dimensional graph, plotted based on the relationship between the number of adsorbed H2 molecules and temperature as well as pressure, revealing that the majority of adsorbed H2 molecules can be released at 0.5 MPa and 358 K. Compared to the respective monomeric counterparts, the H2 storage densities of (TM8B6)2 dimers exhibit a slight reduction.
Two density functional theory methods were employed to evaluate the H2 storage capabilities of metallo-borospherenes TM8B6 (TM=Ni, Pd). Consequently, the superatoms Ni8B6 and Pd8B6, which accommodate 40 and 32 H2 molecules, respectively, exhibit gravimetric H2 uptake capacities of 13.134% and 6.562%, respectively. The average binding energies of Ni8B6(H2)40 and Pd8B6(H2)32 fall within the optimal range for reversible H2 storage applications. The interactions between H2 molecules and the parent structures were characterized using various wave function analysis methods. Polarization effects, alongside the Kubas mechanism, are pivotal to the adsorption of H2 on TM8B6. Moreover, the investigations examine the effect of temperature on the H2 storage capacity of TM8B6 at atmospheric pressure. Atom-centered density-matrix propagation molecular dynamics simulations confirm the reversibility of H2 adsorption and desorption cycles. The thermodynamic analyses of the desorption behavior of H2 molecules were conducted via a three-dimensional graph, plotted based on the relationship between the number of adsorbed H2 molecules and temperature as well as pressure, revealing that the majority of adsorbed H2 molecules can be released at 0.5 MPa and 358 K. Compared to the respective monomeric counterparts, the H2 storage densities of (TM8B6)2 dimers exhibit a slight reduction.
2026, 42(6): 1337-1344
doi: 10.11862/CJIC.20250325
Abstract:
A novel viologen-based photochromic coordination polymer, namely [Zn(CV)0.5(BDC)(H2O)]·2H2O (1), has been successfully constructed via solvothermal self-assembly of Zn2+ ions with the 1, 1′-bis(2-carboxyethyl)-4, 4′-bipyridinium ((H2CV)2+) as a photo-responsive functional unit and terephthalic acid (H2BDC) as an auxiliary bridging ligand. Single-crystal X-ray diffraction analysis reveals that complex 1 features a 1D chain-like framework. Upon light irradiation, complex 1 exhibited a distinct photo-responsive color-changing behavior, transforming from colorless to blue. The blue-colored sample gradually faded and reverted to its original colorless state upon being placed in a dark environment at room temperature, demonstrating excellent reversible photochromic properties. On the basis of its photochromic performance, the application of this complex in ink-free printing has been explored. Furthermore, complex 1 emitted blue light under UV irradiation in a dark environment, revealing favorable photoluminescent characteristics. In addition, complex 1 possessed multiple photoswitchable properties.
A novel viologen-based photochromic coordination polymer, namely [Zn(CV)0.5(BDC)(H2O)]·2H2O (1), has been successfully constructed via solvothermal self-assembly of Zn2+ ions with the 1, 1′-bis(2-carboxyethyl)-4, 4′-bipyridinium ((H2CV)2+) as a photo-responsive functional unit and terephthalic acid (H2BDC) as an auxiliary bridging ligand. Single-crystal X-ray diffraction analysis reveals that complex 1 features a 1D chain-like framework. Upon light irradiation, complex 1 exhibited a distinct photo-responsive color-changing behavior, transforming from colorless to blue. The blue-colored sample gradually faded and reverted to its original colorless state upon being placed in a dark environment at room temperature, demonstrating excellent reversible photochromic properties. On the basis of its photochromic performance, the application of this complex in ink-free printing has been explored. Furthermore, complex 1 emitted blue light under UV irradiation in a dark environment, revealing favorable photoluminescent characteristics. In addition, complex 1 possessed multiple photoswitchable properties.
