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2025 Volume 41 Issue 5
2025, 41(5): 833-846
doi: 10.11862/CJIC.20240308
Abstract:
Compared with traditional room temperature phosphorescent (RTP) materials, room temperature phosphorescent carbon dots (RTP-CDs) have the advantages of good biocompatibility, low toxicity, and stable performance, and have been favored by researchers in recent years. However, its phosphorescent lifetime is usually short, in the millisecond range, limiting its application. Therefore, promoting the intersystem crossing of carbon dots and stabilizing the excited triplet state of carbon dots is the key to realizing the emission and application of ultralong room temperature phosphorescent (URTP). Based on the latest research progress of ultralong room temperature phosphorescent carbon dots (URTP-CDs) in recent years, this paper summarizes its construction strategies and its applications in anti-counterfeiting and information encryption, sensing, biological imaging, and light-emitting diode, and looks forward to its development prospects.
Compared with traditional room temperature phosphorescent (RTP) materials, room temperature phosphorescent carbon dots (RTP-CDs) have the advantages of good biocompatibility, low toxicity, and stable performance, and have been favored by researchers in recent years. However, its phosphorescent lifetime is usually short, in the millisecond range, limiting its application. Therefore, promoting the intersystem crossing of carbon dots and stabilizing the excited triplet state of carbon dots is the key to realizing the emission and application of ultralong room temperature phosphorescent (URTP). Based on the latest research progress of ultralong room temperature phosphorescent carbon dots (URTP-CDs) in recent years, this paper summarizes its construction strategies and its applications in anti-counterfeiting and information encryption, sensing, biological imaging, and light-emitting diode, and looks forward to its development prospects.
2025, 41(5): 847-854
doi: 10.11862/CJIC.20240367
Abstract:
We report five coordination polymers (CPs) based on fluorescent ligands [1, 6-di(1H-imidazol-1-yl)pyrene (dip), 9, 10-di(1H-imidazol-1-yl)anthracene (dia)] and anionic ligands [cyclohexane-1, 4-dicarboxylic acid (H2cda), camphoric acid (H2cpa)]. In [Cd(dip)(cda)]·4H2O}n (1), the Cd2+ ions, acting as tetrahedral nodes, are linked by dip and cda2- ligands with four Cd2+ ions into five-fold interpenetrating network array of topology of dia. In {[Cd(dip) (cpa)]·4H2O}n (2), the Cd2+ ions, acting as a 4-connector, are linked by cpa2- and dip ligands into a 3D framework of cds topology. In {[Ni(dia)2Cl2]·DMF}n (3), the Ni2+ ion is linked by four dia ligands into a layer structure, and 1D channels of a cross-section of 1.35 nm×0.96 nm are formed. In {[Cd(dia)2(H2O)2](NO3)2·2DMSO}n (4), the dia ligands connected Cd2+ ions into a 2D layer, and 1D channels are formed between adjacent layers with a cross-section of 0.87 nm×0.43 nm. In [Zn(dip)Cl2]n (5), the Zn2+ ion is linked by dip ligands into an infinite 1D chain. The infrared, thermal gravimetric, and fluorescent emission data were collected and analyzed for these coordination polymers.
We report five coordination polymers (CPs) based on fluorescent ligands [1, 6-di(1H-imidazol-1-yl)pyrene (dip), 9, 10-di(1H-imidazol-1-yl)anthracene (dia)] and anionic ligands [cyclohexane-1, 4-dicarboxylic acid (H2cda), camphoric acid (H2cpa)]. In [Cd(dip)(cda)]·4H2O}n (1), the Cd2+ ions, acting as tetrahedral nodes, are linked by dip and cda2- ligands with four Cd2+ ions into five-fold interpenetrating network array of topology of dia. In {[Cd(dip) (cpa)]·4H2O}n (2), the Cd2+ ions, acting as a 4-connector, are linked by cpa2- and dip ligands into a 3D framework of cds topology. In {[Ni(dia)2Cl2]·DMF}n (3), the Ni2+ ion is linked by four dia ligands into a layer structure, and 1D channels of a cross-section of 1.35 nm×0.96 nm are formed. In {[Cd(dia)2(H2O)2](NO3)2·2DMSO}n (4), the dia ligands connected Cd2+ ions into a 2D layer, and 1D channels are formed between adjacent layers with a cross-section of 0.87 nm×0.43 nm. In [Zn(dip)Cl2]n (5), the Zn2+ ion is linked by dip ligands into an infinite 1D chain. The infrared, thermal gravimetric, and fluorescent emission data were collected and analyzed for these coordination polymers.
2025, 41(5): 983-993
doi: 10.11862/CJIC.20240394
Abstract:
Herein, a one-pot chemical reduction method was reported to prepare folic acid (FA)-stabilized silver nanoclusters (FA@Ag NCs), in which FA, hydrazine hydrate, and silver nitrate were used as capping agent, reducing agent, and precursor, respectively. Several technologies were employed to investigate the structures and optical properties of FA@Ag NCs, including transmission electron microscopy (TEM), X ray photoelectron spectrometer (XPS), Fourier transform infrared spectrometer (FTIR), X-ray diffractometer (XRD), fluorescence spectrometer, and ultraviolet visible absorption spectrometer. FA@Ag NCs were suggested to be highly dispersed and spherical with a size of around 2.8 nm. Moreover, the maximum excitation and emission wavelengths of FA@Ag NCs were 370 and 447 nm, respectively. Under the optimal detection conditions, FA@Ag NCs could be used to effectively detect malachite green with the linear detection range of 0.5-200 μmol·L-1. The detection limit was 0.084 μmol·L-1. The fluorescence-quenching mechanism was ascribed to the static quenching. The detection system based on FA@Ag NCs was successfully used for the detection of malachite green in actual samples with good accuracy and reproducibility.
Herein, a one-pot chemical reduction method was reported to prepare folic acid (FA)-stabilized silver nanoclusters (FA@Ag NCs), in which FA, hydrazine hydrate, and silver nitrate were used as capping agent, reducing agent, and precursor, respectively. Several technologies were employed to investigate the structures and optical properties of FA@Ag NCs, including transmission electron microscopy (TEM), X ray photoelectron spectrometer (XPS), Fourier transform infrared spectrometer (FTIR), X-ray diffractometer (XRD), fluorescence spectrometer, and ultraviolet visible absorption spectrometer. FA@Ag NCs were suggested to be highly dispersed and spherical with a size of around 2.8 nm. Moreover, the maximum excitation and emission wavelengths of FA@Ag NCs were 370 and 447 nm, respectively. Under the optimal detection conditions, FA@Ag NCs could be used to effectively detect malachite green with the linear detection range of 0.5-200 μmol·L-1. The detection limit was 0.084 μmol·L-1. The fluorescence-quenching mechanism was ascribed to the static quenching. The detection system based on FA@Ag NCs was successfully used for the detection of malachite green in actual samples with good accuracy and reproducibility.
2025, 41(5): 994-1006
doi: 10.11862/CJIC.20240392
Abstract:
AgVO3/ZIF 8 composites with enhanced photocatalytic effect were prepared by the combination of AgVO3 and ZIF-8. X-ray diffraction (XRD), scanning electron microscopy (SEM), high-power transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), photoluminescence (PL) spectroscopy, electron spin resonance (ESR) spectroscopy, transient photocurrent and electrochemical impedance spectroscopy (EIS) were used to characterize binary composites. Tetracycline (TC) was used as a substrate to study the performance efficiency of the degradation of photocatalysts under light conditions, and the degradation effect of TC was also evaluated under different mass concentrations and ionic contents. In addition, we further investigated the photocatalytic mechanism of the binary composite material AgVO3/ZIF-8 and identified the key active components responsible for the catalytic degradation of this new photocatalyst. The experimental results show that the degradation efficiency of 10% AZ, prepared with a molar ratio of 10% AgVO3 and ZIF-8 to TC, was 75.0%. This indicates that the photocatalytic activity can be maintained even under a certain ionic content, making it a suitable photocatalyst for optimal use. In addition, the photocatalytic mechanism of binary composites was further studied by the active species trapping experiment.
AgVO3/ZIF 8 composites with enhanced photocatalytic effect were prepared by the combination of AgVO3 and ZIF-8. X-ray diffraction (XRD), scanning electron microscopy (SEM), high-power transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), photoluminescence (PL) spectroscopy, electron spin resonance (ESR) spectroscopy, transient photocurrent and electrochemical impedance spectroscopy (EIS) were used to characterize binary composites. Tetracycline (TC) was used as a substrate to study the performance efficiency of the degradation of photocatalysts under light conditions, and the degradation effect of TC was also evaluated under different mass concentrations and ionic contents. In addition, we further investigated the photocatalytic mechanism of the binary composite material AgVO3/ZIF-8 and identified the key active components responsible for the catalytic degradation of this new photocatalyst. The experimental results show that the degradation efficiency of 10% AZ, prepared with a molar ratio of 10% AgVO3 and ZIF-8 to TC, was 75.0%. This indicates that the photocatalytic activity can be maintained even under a certain ionic content, making it a suitable photocatalyst for optimal use. In addition, the photocatalytic mechanism of binary composites was further studied by the active species trapping experiment.
2025, 41(5): 1007-1019
doi: 10.11862/CJIC.20240390
Abstract:
This paper delves into the theoretical mechanisms of the electronic structure and optical properties of aluminum-based semiconductors (AlX, X=N, P, As, Sb) and indium-based semiconductors (InX, X=N, P, As, Sb) as potential materials for optical devices. Band structure calculations reveal that, except for InSb, all other compounds are direct bandgap semiconductors, with AlN exhibiting a bandgap of 3.245 eV. The valence band maximum of these eight compounds primarily stems from the p-orbitals of Al/In and X. In contrast, the conduction band minimum is influenced by all orbitals, with a predominant contribution from the p-orbitals. The static dielectric constant increased with the expansion of the unit cell volume. Compared to AlX and InX with larger X atoms, AlN and InN showed broader absorption spectra in the near-ultraviolet region and higher photoelectric conductance. Regarding mechanical properties, AlN and InN displayed greater shear and bulk modulus than the other compounds. Moreover, among these eight crystal types, a higher modulus was associated with a lower light loss function value, indicating that AlN and InN have superior transmission efficiency and a wider spectral range in optoelectronic material applications.
This paper delves into the theoretical mechanisms of the electronic structure and optical properties of aluminum-based semiconductors (AlX, X=N, P, As, Sb) and indium-based semiconductors (InX, X=N, P, As, Sb) as potential materials for optical devices. Band structure calculations reveal that, except for InSb, all other compounds are direct bandgap semiconductors, with AlN exhibiting a bandgap of 3.245 eV. The valence band maximum of these eight compounds primarily stems from the p-orbitals of Al/In and X. In contrast, the conduction band minimum is influenced by all orbitals, with a predominant contribution from the p-orbitals. The static dielectric constant increased with the expansion of the unit cell volume. Compared to AlX and InX with larger X atoms, AlN and InN showed broader absorption spectra in the near-ultraviolet region and higher photoelectric conductance. Regarding mechanical properties, AlN and InN displayed greater shear and bulk modulus than the other compounds. Moreover, among these eight crystal types, a higher modulus was associated with a lower light loss function value, indicating that AlN and InN have superior transmission efficiency and a wider spectral range in optoelectronic material applications.
2025, 41(5): 1020-1036
doi: 10.11862/CJIC.20240317
Abstract:
Three efficient methods for the synthesis of a series of Cu(Ⅱ) and Cu(Ⅰ) complexes based on imidazo[1,5-a] pyridine derivatives were developed. These methods include the following: (ⅰ) Cu(Ⅱ) salts were used as metal sources and N, N-dimethylformamide was employed as a solvent as well as a reductant to produce Cu(Ⅰ) complexes. (ⅱ) An iodidecontaining compound was utilized as a ligand and iodide source to prepare complexes. An in situ metalligand reaction occurred and an iodide-bridged copper complex was generated. (ⅲ) A series of aldehydes were added to the reaction systems to induce in situ metal-ligand reactions between the aldehydes and the imidazo[1,5-a]pyridine derivatives, producing polydentate ligand scaffolds. Eight complexes were prepared and characterized. The catalytic activities of these complexes toward the ketalization of ketones by ethylene glycol were investigated. With the exception of complex 4, the remaining seven complexes all showed high catalytic activity. The lower activity of 4 may be due to the larger radius of bridging iodide ions and the shorter Cu(Ⅰ)…Cu(Ⅰ) distance.
Three efficient methods for the synthesis of a series of Cu(Ⅱ) and Cu(Ⅰ) complexes based on imidazo[1,5-a] pyridine derivatives were developed. These methods include the following: (ⅰ) Cu(Ⅱ) salts were used as metal sources and N, N-dimethylformamide was employed as a solvent as well as a reductant to produce Cu(Ⅰ) complexes. (ⅱ) An iodidecontaining compound was utilized as a ligand and iodide source to prepare complexes. An in situ metalligand reaction occurred and an iodide-bridged copper complex was generated. (ⅲ) A series of aldehydes were added to the reaction systems to induce in situ metal-ligand reactions between the aldehydes and the imidazo[1,5-a]pyridine derivatives, producing polydentate ligand scaffolds. Eight complexes were prepared and characterized. The catalytic activities of these complexes toward the ketalization of ketones by ethylene glycol were investigated. With the exception of complex 4, the remaining seven complexes all showed high catalytic activity. The lower activity of 4 may be due to the larger radius of bridging iodide ions and the shorter Cu(Ⅰ)…Cu(Ⅰ) distance.
2025, 41(5): 1037-1048
doi: 10.11862/CJIC.20240320
Abstract:
Sulfur-doped iron-cobalt tannate nanorods (S-FeCoTA) derived from metal-organic frameworks (MOFs) as electrocatalysts were synthesized via a one-step hydrothermal method. The optimized S-FeCoTA was interlaced by loose nanorods, which had many voids. The S-FeCoTA catalysts exhibited excellent electrochemical oxygen evolution reaction (OER) performance with a low overpotential of 273 mV at 10 mA·cm-2 and a small Tafel slope of 36 mV·dec-1 in 1 mol·L-1 KOH. The potential remained at 1.48 V (vs RHE) at 10 mA·cm-2 under continuous testing for 15 h, implying that S-FeCoTA had good stability. The Faraday efficiency of S-FeCoTA was 94%. The outstanding OER activity of S-FeCoTA is attributed to the synergistic effects among S, Fe, and Co, thus promoting electron transfer, reducing the reaction kinetic barrier, and enhancing the OER performance.
Sulfur-doped iron-cobalt tannate nanorods (S-FeCoTA) derived from metal-organic frameworks (MOFs) as electrocatalysts were synthesized via a one-step hydrothermal method. The optimized S-FeCoTA was interlaced by loose nanorods, which had many voids. The S-FeCoTA catalysts exhibited excellent electrochemical oxygen evolution reaction (OER) performance with a low overpotential of 273 mV at 10 mA·cm-2 and a small Tafel slope of 36 mV·dec-1 in 1 mol·L-1 KOH. The potential remained at 1.48 V (vs RHE) at 10 mA·cm-2 under continuous testing for 15 h, implying that S-FeCoTA had good stability. The Faraday efficiency of S-FeCoTA was 94%. The outstanding OER activity of S-FeCoTA is attributed to the synergistic effects among S, Fe, and Co, thus promoting electron transfer, reducing the reaction kinetic barrier, and enhancing the OER performance.
2025, 41(5): 855-863
doi: 10.11862/CJIC.20250009
Abstract:
Two novel pyridyl ligands, 4-[4-(9, 9-dimethyl-9H-fluoren-2-yl)phenyl]pyridine (dmfpp) and 9-[4-(pyridin-4-yl)phenyl]-9H-carbazole (ppcbz), were successfully synthesized and structurally characterized by 1H NMR and 13C NMR. Two dinuclear Cu(Ⅰ) complexes, [Cu2(dmfpp)2(PPh3)2I2]·2CH2Cl2 (1) and [Cu2(ppcbz)2(PPh3)2I2] (2), have been synthesized by reacting two pyridyl ligands with [Cu4I4(PPh3)4], in a stoichiometric ratio. The complexes have been characterized by elemental analysis, fluorescence spectrum, thermogravimetric analysis (TGA), and single-crystal and powder X-ray diffraction. Complex 1 crystallizes in monoclinic system, space group P21/c with a=1.853 43(3) nm, b=1.266 34(2) nm, c=1.833 48(3) nm, β=106.319 3(18)°, V=4.082 24(12) nm3. Complex 2 crystallizes in mono-clinic system, space group $P \overline{1}$ with a=0.941 07(4) nm, b=1.128 86(4) nm, c=1.697 77(6) nm, α=87.775(3)°, β=79.622(3)°, γ=71.418(3)°, V=1.681 26(11) nm3. Both complexes feature a [Cu2I2] core with tetrahedrally coordinated Cu(Ⅰ) centers. TGA results demonstrated their good thermal stability, with structural decomposition initiating above 220 ℃. Fluorescence studies under 370 nm excitation revealed green emission for both complexes. Complex 2 exhibited an outstanding photoluminescence quantum yield (PLQY) of 0.79, significantly higher than that of complex 1 (PLQY: 0.02).
Two novel pyridyl ligands, 4-[4-(9, 9-dimethyl-9H-fluoren-2-yl)phenyl]pyridine (dmfpp) and 9-[4-(pyridin-4-yl)phenyl]-9H-carbazole (ppcbz), were successfully synthesized and structurally characterized by 1H NMR and 13C NMR. Two dinuclear Cu(Ⅰ) complexes, [Cu2(dmfpp)2(PPh3)2I2]·2CH2Cl2 (1) and [Cu2(ppcbz)2(PPh3)2I2] (2), have been synthesized by reacting two pyridyl ligands with [Cu4I4(PPh3)4], in a stoichiometric ratio. The complexes have been characterized by elemental analysis, fluorescence spectrum, thermogravimetric analysis (TGA), and single-crystal and powder X-ray diffraction. Complex 1 crystallizes in monoclinic system, space group P21/c with a=1.853 43(3) nm, b=1.266 34(2) nm, c=1.833 48(3) nm, β=106.319 3(18)°, V=4.082 24(12) nm3. Complex 2 crystallizes in mono-clinic system, space group $P \overline{1}$ with a=0.941 07(4) nm, b=1.128 86(4) nm, c=1.697 77(6) nm, α=87.775(3)°, β=79.622(3)°, γ=71.418(3)°, V=1.681 26(11) nm3. Both complexes feature a [Cu2I2] core with tetrahedrally coordinated Cu(Ⅰ) centers. TGA results demonstrated their good thermal stability, with structural decomposition initiating above 220 ℃. Fluorescence studies under 370 nm excitation revealed green emission for both complexes. Complex 2 exhibited an outstanding photoluminescence quantum yield (PLQY) of 0.79, significantly higher than that of complex 1 (PLQY: 0.02).
2025, 41(5): 864-876
doi: 10.11862/CJIC.20240438
Abstract:
Particulate matters collected from subway tunnels, were identified as predominant zero-valent iron (ZVI) via powder X ray diffraction and X ray photoelectron spectroscopy, which was innovatively adopted to activate peroxodisulfate (PDS) for degrading organic dye pollutants. The as-obtained ZVI exhibited exceptional catalytic performance under diverse light sources, including low-power LED ultraviolet light (UVL), visible light (VL), and real solar light (SL), achieving complete rhodamine B (RhB, 10.0 mg·L-1) degradation within 2.0 min. Radical quenching experiments confirmed the synergistic roles of sulfate radicals (SO4·-), hydroxyl radicals (·OH), superoxide radicals (·O2-), and holes (h+). Systematic parametric studies revealed that boosted RhB removal efficiencies were accomplished across a wide pH range (2.0-10.0), in the presence of common interfering ions (Cl-, SO42-, HCO3-, H 2PO4-, and NO3-), humic acid, and real water matrices, demonstrating remarkable environmental adaptability. Notably, ZVI maintained high catalytic activity even under complicated aqueous conditions, underscoring its resistance to matrix influence. The magnetic properties of ZVI enabled its facile recovery and reuse for multiple cycles without significant performance loss, aligning with sustainable resource utilization principles. This study not only presents a cost-effective strategy for valorizing urban particulate waste but also advances solar-driven advanced oxidation processes (AOPs) for practical water treatment applications.
Particulate matters collected from subway tunnels, were identified as predominant zero-valent iron (ZVI) via powder X ray diffraction and X ray photoelectron spectroscopy, which was innovatively adopted to activate peroxodisulfate (PDS) for degrading organic dye pollutants. The as-obtained ZVI exhibited exceptional catalytic performance under diverse light sources, including low-power LED ultraviolet light (UVL), visible light (VL), and real solar light (SL), achieving complete rhodamine B (RhB, 10.0 mg·L-1) degradation within 2.0 min. Radical quenching experiments confirmed the synergistic roles of sulfate radicals (SO4·-), hydroxyl radicals (·OH), superoxide radicals (·O2-), and holes (h+). Systematic parametric studies revealed that boosted RhB removal efficiencies were accomplished across a wide pH range (2.0-10.0), in the presence of common interfering ions (Cl-, SO42-, HCO3-, H 2PO4-, and NO3-), humic acid, and real water matrices, demonstrating remarkable environmental adaptability. Notably, ZVI maintained high catalytic activity even under complicated aqueous conditions, underscoring its resistance to matrix influence. The magnetic properties of ZVI enabled its facile recovery and reuse for multiple cycles without significant performance loss, aligning with sustainable resource utilization principles. This study not only presents a cost-effective strategy for valorizing urban particulate waste but also advances solar-driven advanced oxidation processes (AOPs) for practical water treatment applications.
Three-dimensional homochiral Eu(Ⅲ) coordination polymer and its amino acid configuration recognition
2025, 41(5): 877-884
doi: 10.11862/CJIC.20250052
Abstract:
Solvothermal reaction of a designed enantiomerically pure chiral ligand S-4'-[(2-carboxy-5-oxopyrrolidin1-yl)methyl]-(1, 1'-biphenyl)-3, 5-dicarboxylic acid (H3L) with Eu(Ⅲ) salt produced a new homochiral coordination polymer {[Eu(L)]·0.5CH3CN}n (1). Single crystal X-ray diffraction analysis has displayed that 1 belongs to the tetragonal I4 1 chiral space group. In 1, anionic ligands L3- acted as μ7-bridges and connected Eu(Ⅲ) ions to form a 3D helical structure with 7-connected topology. Ligand H3L not only transfers chirality to the resulting metal-organic framework but also induces helical chirality generation. Complex 1 exhibited excellent ligandsensitized emission and thermal stability. Using complex 1 as a fluorescent probe, its configuration recognition performance on common amino acids was investigated. Our results showed that the different enantiomers of aspartic acid, alanine, lysine, leucine, tyrosine, and valine had various impacts on the fluorescence intensity of 1, indicating that 1 can detect their configurations of the six amino acids mentioned above.
Solvothermal reaction of a designed enantiomerically pure chiral ligand S-4'-[(2-carboxy-5-oxopyrrolidin1-yl)methyl]-(1, 1'-biphenyl)-3, 5-dicarboxylic acid (H3L) with Eu(Ⅲ) salt produced a new homochiral coordination polymer {[Eu(L)]·0.5CH3CN}n (1). Single crystal X-ray diffraction analysis has displayed that 1 belongs to the tetragonal I4 1 chiral space group. In 1, anionic ligands L3- acted as μ7-bridges and connected Eu(Ⅲ) ions to form a 3D helical structure with 7-connected topology. Ligand H3L not only transfers chirality to the resulting metal-organic framework but also induces helical chirality generation. Complex 1 exhibited excellent ligandsensitized emission and thermal stability. Using complex 1 as a fluorescent probe, its configuration recognition performance on common amino acids was investigated. Our results showed that the different enantiomers of aspartic acid, alanine, lysine, leucine, tyrosine, and valine had various impacts on the fluorescence intensity of 1, indicating that 1 can detect their configurations of the six amino acids mentioned above.
2025, 41(5): 885-892
doi: 10.11862/CJIC.20240402
Abstract:
Under hydrothermal conditions, a manganese complex [Mn(na)2(Dmbpy)(H2O)]·Hna (1) was synthesized by using manganese sulfate, 1-naphthoic acid (Hna), and 4,4'-dimethyl-2, 2'-bipyridine (Dmbpy), and characterized by elemental analysis, single crystal X ray diffraction, powder X ray diffraction, infrared spectrum, Hirshfeld surface analysis, and thermogravimetric analysis. The single-crystal X-ray diffraction result shows that 1 belongs to the triclinic crystal system, $P \overline{1}$ space group, and the central metal Mn(Ⅱ) is located in a six-coordinated, distorted trigonal prism configuration. The 2D supramolecular network structure is formed by intermolecular C/O—H···O, C—H···π, and π···π interactions. CrystalExplorer was used to analyze the Hirshfeld surface of 1. The 2D fingerprint of 1 shows that the H···H interaction plays a significant role in maintaining structural stability. Powder X-ray diffraction analysis shows that the synthesized 1 is in pure phase. Thermogravimetric analysis shows that 1 has good thermal stability. The solid-state fluorescence spectrum showed that 1 had a maximum emission wavelength of 423 nm at an excitation wavelength of 347 nm. In the fluorescence sensing experiment, 1 showed selective recognition ability to Fe3+ with a detection limit of 0.52 μmol·L-1. In addition, the mechanism analysis shows that the fluorescence quenching of 1 may be due to the energy-competitive absorption between Fe3+ and 1.
Under hydrothermal conditions, a manganese complex [Mn(na)2(Dmbpy)(H2O)]·Hna (1) was synthesized by using manganese sulfate, 1-naphthoic acid (Hna), and 4,4'-dimethyl-2, 2'-bipyridine (Dmbpy), and characterized by elemental analysis, single crystal X ray diffraction, powder X ray diffraction, infrared spectrum, Hirshfeld surface analysis, and thermogravimetric analysis. The single-crystal X-ray diffraction result shows that 1 belongs to the triclinic crystal system, $P \overline{1}$ space group, and the central metal Mn(Ⅱ) is located in a six-coordinated, distorted trigonal prism configuration. The 2D supramolecular network structure is formed by intermolecular C/O—H···O, C—H···π, and π···π interactions. CrystalExplorer was used to analyze the Hirshfeld surface of 1. The 2D fingerprint of 1 shows that the H···H interaction plays a significant role in maintaining structural stability. Powder X-ray diffraction analysis shows that the synthesized 1 is in pure phase. Thermogravimetric analysis shows that 1 has good thermal stability. The solid-state fluorescence spectrum showed that 1 had a maximum emission wavelength of 423 nm at an excitation wavelength of 347 nm. In the fluorescence sensing experiment, 1 showed selective recognition ability to Fe3+ with a detection limit of 0.52 μmol·L-1. In addition, the mechanism analysis shows that the fluorescence quenching of 1 may be due to the energy-competitive absorption between Fe3+ and 1.
2025, 41(5): 893-902
doi: 10.11862/CJIC.20240368
Abstract:
By adding polyaniline (PANI) to improve the conductivity of poly(vinyl alcohol) (PVA) hydrogel electrolyte and introducing nano-SiO2 to form hydrogen bond interaction with the hydroxyl group in PVA, the mechanical properties, ion transport capacity, and structural stability of the electrolyte were improved. The prepared PVA/PANI/ SiO2 conductive hydrogel electrolytes showed high tensile stress (15.45 MPa), strain (516.09%), high ion mobility (0.56), ionic conductivity (0.992 mS·cm-1), and wide electrochemical window (2.56 V). A symmetrical battery using this electrolyte could achieve a stable cycle of more than 1 200 h with uniform deposition of zinc. The modified electrolyte significantly improves both the electrochemical and mechanical properties, while enhancing cycle stability and electrochemical reversibility.
By adding polyaniline (PANI) to improve the conductivity of poly(vinyl alcohol) (PVA) hydrogel electrolyte and introducing nano-SiO2 to form hydrogen bond interaction with the hydroxyl group in PVA, the mechanical properties, ion transport capacity, and structural stability of the electrolyte were improved. The prepared PVA/PANI/ SiO2 conductive hydrogel electrolytes showed high tensile stress (15.45 MPa), strain (516.09%), high ion mobility (0.56), ionic conductivity (0.992 mS·cm-1), and wide electrochemical window (2.56 V). A symmetrical battery using this electrolyte could achieve a stable cycle of more than 1 200 h with uniform deposition of zinc. The modified electrolyte significantly improves both the electrochemical and mechanical properties, while enhancing cycle stability and electrochemical reversibility.
2025, 41(5): 903-912
doi: 10.11862/CJIC.20240366
Abstract:
A novel Bi/Bi2S3/TiO2 composite fibers photocatalytic materials were constructed by in-situ hydrothermal method using TiO2 nanofibers prepared by electrospinning technology serve as the matrix, bismuth nitrate as the bismuth source and ethylene glycol as the reducing agent. The morphology, structure, and optoelectronic properties of the composite fibers material were analyzed by powder X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscope, ultraviolet-visible absorption spectroscopy, photocurrent response, electrochemical impedance spectroscopy, and fluorescence emission spectroscopy. The photocatalytic CO2 reduction performance of Bi/Bi2S3/TiO2 composite fibers under a gas-solid reaction system was investigated. The results show that metal Bi nanoparticles and scaly Bi2S3 are orderly constructed on the surface of TiO2 nanofibers. The surface plasmon resonance (SPR) effect of metal Bi has a synergistic effect with the Bi2S3/TiO2 S-scheme heterojunction, which enables the efficient spatial separation and transfer of photogenerated carriers and effectively enhances the photocatalytic activity of Bi/Bi2S3/TiO2. In-depth research found that the S-scheme heterojunction possesses a unique mechanism of carrier movement, resulting in a robust redox capacity and strong driving force. The main products of the photocatalytic CO2 reduction were CH4 and CH3OH, with yields of 4.21 and 9.86 μmol·h-1·g-1, respectively, about three times that of Bi2S3/TiO2.
A novel Bi/Bi2S3/TiO2 composite fibers photocatalytic materials were constructed by in-situ hydrothermal method using TiO2 nanofibers prepared by electrospinning technology serve as the matrix, bismuth nitrate as the bismuth source and ethylene glycol as the reducing agent. The morphology, structure, and optoelectronic properties of the composite fibers material were analyzed by powder X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscope, ultraviolet-visible absorption spectroscopy, photocurrent response, electrochemical impedance spectroscopy, and fluorescence emission spectroscopy. The photocatalytic CO2 reduction performance of Bi/Bi2S3/TiO2 composite fibers under a gas-solid reaction system was investigated. The results show that metal Bi nanoparticles and scaly Bi2S3 are orderly constructed on the surface of TiO2 nanofibers. The surface plasmon resonance (SPR) effect of metal Bi has a synergistic effect with the Bi2S3/TiO2 S-scheme heterojunction, which enables the efficient spatial separation and transfer of photogenerated carriers and effectively enhances the photocatalytic activity of Bi/Bi2S3/TiO2. In-depth research found that the S-scheme heterojunction possesses a unique mechanism of carrier movement, resulting in a robust redox capacity and strong driving force. The main products of the photocatalytic CO2 reduction were CH4 and CH3OH, with yields of 4.21 and 9.86 μmol·h-1·g-1, respectively, about three times that of Bi2S3/TiO2.
2025, 41(5): 913-922
doi: 10.11862/CJIC.20240255
Abstract:
The catalysts of bismuth oxychloride (BiOCl) and polyaniline (PANI) were prepared by in-situ polymerization, resulting in the formation of a type Ⅱ heterojunction photocatalyst (BiOCl/PANI). The catalysts were characterized using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), as well as nitrogen adsorption and desorption techniques. The experimental results show that the BiOCl/PANI catalyst has higher photocatalytic activity than both PANI and BiOCl. Under the conditions of RhB mass concentration 50 mg· L-1, the molar ratio of PANI to BiOCl substance was 0.02∶1, and 50 mg·L-1 catalyst, after 150 min photocatalysis, 98.8% of RhB was degraded by BiOCl/PANI, and the rate constant was 0.031 min-1. After four cycles, the degradation rate of RhB decreased from 98.8% to 98.4%, showing good stability and reusability. The photocatalyst BiOCl/ PANI realizes the rapid separation of electrons and holes, reduces the recombination rate of the two in the catalyst, and improves the photocatalytic performance.
The catalysts of bismuth oxychloride (BiOCl) and polyaniline (PANI) were prepared by in-situ polymerization, resulting in the formation of a type Ⅱ heterojunction photocatalyst (BiOCl/PANI). The catalysts were characterized using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), as well as nitrogen adsorption and desorption techniques. The experimental results show that the BiOCl/PANI catalyst has higher photocatalytic activity than both PANI and BiOCl. Under the conditions of RhB mass concentration 50 mg· L-1, the molar ratio of PANI to BiOCl substance was 0.02∶1, and 50 mg·L-1 catalyst, after 150 min photocatalysis, 98.8% of RhB was degraded by BiOCl/PANI, and the rate constant was 0.031 min-1. After four cycles, the degradation rate of RhB decreased from 98.8% to 98.4%, showing good stability and reusability. The photocatalyst BiOCl/ PANI realizes the rapid separation of electrons and holes, reduces the recombination rate of the two in the catalyst, and improves the photocatalytic performance.
2025, 41(5): 923-938
doi: 10.11862/CJIC.20240243
Abstract:
This paper aims to improve hydrogen production through photolysis water performance of GaN/ZnO heterojunction by doping Li and Au. First principles methods were used to investigate the electronic structures, optical properties, and photocatalytic performance of Li and Au doping GaN/ZnO heterojunction. The electronic structure calculation shows that the GaN/ZnO heterojunction is a direct band-gap semiconductor, and the heterojunction type is a Z-type heterojunction with a band gap of 1.41 eV, which can effectively promote carrier separation. The structures doped with Li and Au are magnetic except for the Li substitution Zn structure. The results of optical property analysis show that the doping of Li and Au can improve the absorption coefficient of the system, and the heterojunction after Li substitution Zn has a large optical absorption coefficient, a large work function (7.37 eV), and an interface potential difference (2.55 V), indicating that the visible light utilization rate is high, the interface structure is stable and has a large built-in electric field, which can more effectively promote the migration of electrons and holes and reduce the binding of electron-hole pairs. The Bader charge analysis shows that the doped elements Li and Au lose electrons. The electrons are transferred from the GaN layer to the ZnO layer, forming an effective internal electric field at the interface. More electrons are transferred between the two structural layers of Ga and Zn, which are substituted by Li and Au, indicating that the interfacial potential difference is large and has a high migration rate of photogenerated carriers. The analysis of the performance of photolysis of water to hydrogen production shows that the four systems of ZnO film, GaN/ZnO heterojunction, Li substitution Ga, and Ga and Zn with simultaneous displacement of Li meet the conditions for hydrogen production by photolysis at pH=0. The GaN film, ZnO film, and Ga and Zn systems with a simultaneous displacement of Li meet the conditions for hydrogen production by photolysis of water at pH=7.
This paper aims to improve hydrogen production through photolysis water performance of GaN/ZnO heterojunction by doping Li and Au. First principles methods were used to investigate the electronic structures, optical properties, and photocatalytic performance of Li and Au doping GaN/ZnO heterojunction. The electronic structure calculation shows that the GaN/ZnO heterojunction is a direct band-gap semiconductor, and the heterojunction type is a Z-type heterojunction with a band gap of 1.41 eV, which can effectively promote carrier separation. The structures doped with Li and Au are magnetic except for the Li substitution Zn structure. The results of optical property analysis show that the doping of Li and Au can improve the absorption coefficient of the system, and the heterojunction after Li substitution Zn has a large optical absorption coefficient, a large work function (7.37 eV), and an interface potential difference (2.55 V), indicating that the visible light utilization rate is high, the interface structure is stable and has a large built-in electric field, which can more effectively promote the migration of electrons and holes and reduce the binding of electron-hole pairs. The Bader charge analysis shows that the doped elements Li and Au lose electrons. The electrons are transferred from the GaN layer to the ZnO layer, forming an effective internal electric field at the interface. More electrons are transferred between the two structural layers of Ga and Zn, which are substituted by Li and Au, indicating that the interfacial potential difference is large and has a high migration rate of photogenerated carriers. The analysis of the performance of photolysis of water to hydrogen production shows that the four systems of ZnO film, GaN/ZnO heterojunction, Li substitution Ga, and Ga and Zn with simultaneous displacement of Li meet the conditions for hydrogen production by photolysis at pH=0. The GaN film, ZnO film, and Ga and Zn systems with a simultaneous displacement of Li meet the conditions for hydrogen production by photolysis of water at pH=7.
2025, 41(5): 939-947
doi: 10.11862/CJIC.20240416
Abstract:
To explore new biomimics for the [FeFe]-hydrogenases active site, two di-iron complexes containing a phosphine ligand with a pendant amine were synthesized and characterized. Reaction of complex [Fe2(CO)6(μ-pdt)] (1), where pdt=SCH2CH2CH2S, with a diphosphine ligand (Ph2PCH2)2NC10H15 (dppad) and Me3NO·2H2O gave a major product [Fe2(CO)5(mpad)(μ-pdt)] (2) in 60% yield together with a minor product [Fe2(CO)4(κ2-dppad)(μ-pdt)] (3) in 6% yield, where mpad=Ph2PCH2NHC10H15. Complexes 2 and 3 were identified by elemental analysis, IR, 1H NMR, 31P NMR, and single-crystal X-ray diffraction analysis. The crystal structure of complex 2 contains an apicallycoordinated phosphine ligand mpad whereas complex 3·0.5CH2Cl2 contains a chelated diphosphine ligand dppad in an apical-basal position. The Fe-Fe bond length in complex 2 [0.251 66(6) nm] is notably shorter than that in complex 3·0.5CH2Cl2 [0.255 88(6) nm]. Furthermore, the electrochemical properties of complexes 2 and 3 were investigated by cyclic voltammetry (CV), revealing that their CV curves contained two reduction peaks and one oxidation peak within the solvent window. The electrocatalytic properties of both complexes showed that they can catalyze the reduction of protons to H2 with HOAc as a proton source. For comparison, the catalytic efficiency (turnover frequency) of 3 was slightly better than that of 2.
To explore new biomimics for the [FeFe]-hydrogenases active site, two di-iron complexes containing a phosphine ligand with a pendant amine were synthesized and characterized. Reaction of complex [Fe2(CO)6(μ-pdt)] (1), where pdt=SCH2CH2CH2S, with a diphosphine ligand (Ph2PCH2)2NC10H15 (dppad) and Me3NO·2H2O gave a major product [Fe2(CO)5(mpad)(μ-pdt)] (2) in 60% yield together with a minor product [Fe2(CO)4(κ2-dppad)(μ-pdt)] (3) in 6% yield, where mpad=Ph2PCH2NHC10H15. Complexes 2 and 3 were identified by elemental analysis, IR, 1H NMR, 31P NMR, and single-crystal X-ray diffraction analysis. The crystal structure of complex 2 contains an apicallycoordinated phosphine ligand mpad whereas complex 3·0.5CH2Cl2 contains a chelated diphosphine ligand dppad in an apical-basal position. The Fe-Fe bond length in complex 2 [0.251 66(6) nm] is notably shorter than that in complex 3·0.5CH2Cl2 [0.255 88(6) nm]. Furthermore, the electrochemical properties of complexes 2 and 3 were investigated by cyclic voltammetry (CV), revealing that their CV curves contained two reduction peaks and one oxidation peak within the solvent window. The electrocatalytic properties of both complexes showed that they can catalyze the reduction of protons to H2 with HOAc as a proton source. For comparison, the catalytic efficiency (turnover frequency) of 3 was slightly better than that of 2.
2025, 41(5): 948-958
doi: 10.11862/CJIC.20240400
Abstract:
LiNi0.5Mn1.5O4 (LNMO) was prepared by a high-temperature solid phase method, and then AlPO4 (AP) was coated on the polyhedral LNMO surface by the wet chemical method. The experimental results showed that the LNMO-1%AP|Li cell prepared with a 1% mass ratio of AlPO4 and LNMO had better electrochemical performance; after 450 cycles at 1C, its discharge specific capacity maintained 108.78 mAh·g-1, while that of the LNMO|Li cell was only 86.04 mAh·g-1. Especially at the high rates of 5C and 10C, the electrochemical properties of the former were far superior to the latter. This was attributed to the fact that the AP coating made the surface of LNMO in con- tact with the electrolyte more stable, effectively promoted the Li+ transport, and reduced the polarization voltage of the electrode.
LiNi0.5Mn1.5O4 (LNMO) was prepared by a high-temperature solid phase method, and then AlPO4 (AP) was coated on the polyhedral LNMO surface by the wet chemical method. The experimental results showed that the LNMO-1%AP|Li cell prepared with a 1% mass ratio of AlPO4 and LNMO had better electrochemical performance; after 450 cycles at 1C, its discharge specific capacity maintained 108.78 mAh·g-1, while that of the LNMO|Li cell was only 86.04 mAh·g-1. Especially at the high rates of 5C and 10C, the electrochemical properties of the former were far superior to the latter. This was attributed to the fact that the AP coating made the surface of LNMO in con- tact with the electrolyte more stable, effectively promoted the Li+ transport, and reduced the polarization voltage of the electrode.
2025, 41(5): 959-968
doi: 10.11862/CJIC.20240411
Abstract:
A zinc sulfate open framework matrix, [Zn(SO4)(DMSO)] (1), was synthesized by solvothermal evaporation using dimethyl sulfoxide (DMSO) as the solvent. A composite P@1, which exhibits fluorescence and room temperature phosphorescence (RTP) properties, was prepared by doping 2, 6-naphthalic acid (P) into matrix 1 at a low concentration. P@1 emitted a green RTP that was visible to the naked eye and lasted for approximately 2 s. P@1 exhibited selective phosphorescence enhancement response towards Pb2+, with a detection limit of 2.52 μmol·L-1. The main detection mechanism is the Pb—O coordination-induced phosphorescence enhancement in the system. Interestingly, P@1 also functioned as a dualchannel probe for the rapid detection of Fe3+ ions through fluorescence quenching with a detection limit of 0.038 μmol·L-1. The recognition mechanism may be attributed to the competitive energy absorption between P@1 and Fe3+ ions.
A zinc sulfate open framework matrix, [Zn(SO4)(DMSO)] (1), was synthesized by solvothermal evaporation using dimethyl sulfoxide (DMSO) as the solvent. A composite P@1, which exhibits fluorescence and room temperature phosphorescence (RTP) properties, was prepared by doping 2, 6-naphthalic acid (P) into matrix 1 at a low concentration. P@1 emitted a green RTP that was visible to the naked eye and lasted for approximately 2 s. P@1 exhibited selective phosphorescence enhancement response towards Pb2+, with a detection limit of 2.52 μmol·L-1. The main detection mechanism is the Pb—O coordination-induced phosphorescence enhancement in the system. Interestingly, P@1 also functioned as a dualchannel probe for the rapid detection of Fe3+ ions through fluorescence quenching with a detection limit of 0.038 μmol·L-1. The recognition mechanism may be attributed to the competitive energy absorption between P@1 and Fe3+ ions.
2025, 41(5): 969-982
doi: 10.11862/CJIC.20240395
Abstract:
Two novel lanthanide complexes, [Sm2(BA)6(4-OH-terpy)2]·2H2O·2EtOH (1) and [Pr2(BA)6(4-OH-terpy)2 (H2O)2]·HBA·H2O (2), where HBA=benzoic acid, 4-OH-terpy=4-hydroxy-2, 2'∶6', 2″-terpyridine, were successfully synthesized using ultrasonic dissolution and the conventional solution method with two mixed ligands HBA and 4OH-terpy. During the synthesis, 4-OH-terpy was involved in the reaction as a neutral ligand, while HBA, in its deprotonated form (BA-), coordinated with the lanthanide ions as an acidic ligand. The crystal structures of these two complexes were precisely determined by single crystal X ray diffraction. Elemental analysis, infrared and Raman spectroscopy, and powder X-ray diffraction techniques were also employed to further explore the physicochemical properties of the two complexes. The single-crystal X-ray diffraction data indicate that, despite their structural differences, both complexes belong to the triclinic crystal system $P \overline{1}$ space group. The central lanthanide ions have the same coordination number but exhibit different coordination environments. To comprehensively evaluate the thermal stability of these two complexes, comprehensive tests including thermogravimetric analysis, differential thermogravimetric analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy, and mass spectrometry were conducted. Meanwhile, an in depth investigation was conducted into the 3D infrared stacked images and mass spectra of the gases emitted from the complexes. In addition, studies of the fluorescence properties of complex 1 showed that it exhibited fluorescence emission matching the Sm3+ characteristic transition.
Two novel lanthanide complexes, [Sm2(BA)6(4-OH-terpy)2]·2H2O·2EtOH (1) and [Pr2(BA)6(4-OH-terpy)2 (H2O)2]·HBA·H2O (2), where HBA=benzoic acid, 4-OH-terpy=4-hydroxy-2, 2'∶6', 2″-terpyridine, were successfully synthesized using ultrasonic dissolution and the conventional solution method with two mixed ligands HBA and 4OH-terpy. During the synthesis, 4-OH-terpy was involved in the reaction as a neutral ligand, while HBA, in its deprotonated form (BA-), coordinated with the lanthanide ions as an acidic ligand. The crystal structures of these two complexes were precisely determined by single crystal X ray diffraction. Elemental analysis, infrared and Raman spectroscopy, and powder X-ray diffraction techniques were also employed to further explore the physicochemical properties of the two complexes. The single-crystal X-ray diffraction data indicate that, despite their structural differences, both complexes belong to the triclinic crystal system $P \overline{1}$ space group. The central lanthanide ions have the same coordination number but exhibit different coordination environments. To comprehensively evaluate the thermal stability of these two complexes, comprehensive tests including thermogravimetric analysis, differential thermogravimetric analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy, and mass spectrometry were conducted. Meanwhile, an in depth investigation was conducted into the 3D infrared stacked images and mass spectra of the gases emitted from the complexes. In addition, studies of the fluorescence properties of complex 1 showed that it exhibited fluorescence emission matching the Sm3+ characteristic transition.
