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2025 Volume 41 Issue 9
2025, 41(9): 1689-1701
doi: 10.11862/CJIC.20250007
Abstract:
Fluorine-containing perovskites and their derivatives have garnered extensive attention in new energy, optoelectronic devices, catalysis, and magnetic materials due to their excellent physical and chemical properties. The synthesis methods of these materials are one of the core aspects of research, as the choice and optimization of the synthetic pathway directly influence the structure, performance, morphology, and practical application of the materials. Currently, the main synthesis methods for fluorine-containing perovskites and their derivatives include traditional solid-state reactions, precipitation methods, hydrothermal/solvothermal techniques, emerging soft chemical synthesis methods, and deposition techniques. However, a systematic overview of these materials has yet to be provided. This paper reviews the synthesis methods of this class of compounds, summarizes the current challenges, and provides future perspectives, with the hope of promoting deeper and broader research in this field.
Fluorine-containing perovskites and their derivatives have garnered extensive attention in new energy, optoelectronic devices, catalysis, and magnetic materials due to their excellent physical and chemical properties. The synthesis methods of these materials are one of the core aspects of research, as the choice and optimization of the synthetic pathway directly influence the structure, performance, morphology, and practical application of the materials. Currently, the main synthesis methods for fluorine-containing perovskites and their derivatives include traditional solid-state reactions, precipitation methods, hydrothermal/solvothermal techniques, emerging soft chemical synthesis methods, and deposition techniques. However, a systematic overview of these materials has yet to be provided. This paper reviews the synthesis methods of this class of compounds, summarizes the current challenges, and provides future perspectives, with the hope of promoting deeper and broader research in this field.
2025, 41(9): 1719-1730
doi: 10.11862/CJIC.20250124
Abstract:
Solid oxide cells (SOCs), as efficient and clean energy conversion devices, enable reversible transformation between chemical and electrical energy, and hold strategic value in distributed power generation, industrial waste heat recovery, and low-carbon energy systems. However, conventional electrode materials face trade-offs between electrocatalytic activity and structural stability. Elemental segregation and interfacial degradation at high temperatures severely reduce efficiency and lifespan. In recent years, high-entropy engineering has offered new pathways for overcoming performance bottlenecks in electrode materials by leveraging high configurational entropy-induced effects: configurational entropy effect, lattice distortion effect, sluggish diffusion effect, and the cocktail effect. This review summarizes recent progress in high-entropy SOC electrodes and explains how the four major entropy-driven effects improve catalytic activity, ion/electron transport, and long-term structural stability. Building on this foundation, this review identifies multi-principal element design as the key to synchronizing interfacial reaction kinetics and thermo-mechanical durability. This review systematically consolidates recent advances in high-entropy electrode materials for enhancing critical SOC performance, highlighting their potential in improving electrode activity, poisoning resistance, and thermal stability. Core challenges and emerging opportunities for future research are also discussed.
Solid oxide cells (SOCs), as efficient and clean energy conversion devices, enable reversible transformation between chemical and electrical energy, and hold strategic value in distributed power generation, industrial waste heat recovery, and low-carbon energy systems. However, conventional electrode materials face trade-offs between electrocatalytic activity and structural stability. Elemental segregation and interfacial degradation at high temperatures severely reduce efficiency and lifespan. In recent years, high-entropy engineering has offered new pathways for overcoming performance bottlenecks in electrode materials by leveraging high configurational entropy-induced effects: configurational entropy effect, lattice distortion effect, sluggish diffusion effect, and the cocktail effect. This review summarizes recent progress in high-entropy SOC electrodes and explains how the four major entropy-driven effects improve catalytic activity, ion/electron transport, and long-term structural stability. Building on this foundation, this review identifies multi-principal element design as the key to synchronizing interfacial reaction kinetics and thermo-mechanical durability. This review systematically consolidates recent advances in high-entropy electrode materials for enhancing critical SOC performance, highlighting their potential in improving electrode activity, poisoning resistance, and thermal stability. Core challenges and emerging opportunities for future research are also discussed.
2025, 41(9): 1731-1754
doi: 10.11862/CJIC.20240412
Abstract:
Laser technology has become a widely used synthesis technology in recent years, offering certain controllability, reduced contact, and low pollution, with simple and efficient operation. This technology can reduce material waste and energy consumption, thereby minimizing the environmental impact. Electrochemical functional materials with porous structures prepared by laser synthesis technology have a good potential for application in the field of energy storage, such as photoelectric catalysis, batteries, supercapacitors, etc. The application of laser synthesis technology can realize the efficient use of resources and the sustainable development of the environment. In this paper, the principle of laser synthesis technology and its application in energy storage and biosensing are reviewed, and the opportunities and challenges of lasers are discussed. With deepening research on laser-synthesized materials, laser synthesis technology for energy storage will be rapidly developed.
Laser technology has become a widely used synthesis technology in recent years, offering certain controllability, reduced contact, and low pollution, with simple and efficient operation. This technology can reduce material waste and energy consumption, thereby minimizing the environmental impact. Electrochemical functional materials with porous structures prepared by laser synthesis technology have a good potential for application in the field of energy storage, such as photoelectric catalysis, batteries, supercapacitors, etc. The application of laser synthesis technology can realize the efficient use of resources and the sustainable development of the environment. In this paper, the principle of laser synthesis technology and its application in energy storage and biosensing are reviewed, and the opportunities and challenges of lasers are discussed. With deepening research on laser-synthesized materials, laser synthesis technology for energy storage will be rapidly developed.
2025, 41(9): 1702-1718
doi: 10.11862/CJIC.20240387
Abstract:
Malignant tumours always threaten human health. For tumour diagnosis, positron emission tomography (PET) is the most sensitive and advanced imaging technique by radiotracers, such as radioactive 18F, 11C, 64Cu, 68Ga, and 89Zr. Among the radiotracers, the radioactive 18F-labelled chemical agent as PET probes plays a predominant role in monitoring, detecting, treating, and predicting tumours due to its perfect half-life. In this paper, the 18F-labelled chemical materials as PET probes are systematically summarized. First, we introduce various radionuclides of PET and elaborate on the mechanism of PET imaging. It highlights the 18F-labelled chemical agents used as PET probes, including [18F]-2-deoxy-2-[18F]fluoro-D-glucose ([18F]-FDG), 18F-labelled amino acids, 18F-labelled nucleic acids, 18F-labelled receptors, 18F-labelled reporter genes, and 18F-labelled hypoxia agents. In addition, some PET probes with metal as a supplementary element are introduced briefly. Meanwhile, the 18F-labelled nanoparticles for the PET probe and the multi-modality imaging probe are summarized in detail. The approach and strategies for the fabrication of 18F-labelled PET probes are also described briefly. The future development of the PET probe is also prospected. The development and application of 18F-labelled PET probes will expand our knowledge and shed light on the diagnosis and theranostics of tumours.
Malignant tumours always threaten human health. For tumour diagnosis, positron emission tomography (PET) is the most sensitive and advanced imaging technique by radiotracers, such as radioactive 18F, 11C, 64Cu, 68Ga, and 89Zr. Among the radiotracers, the radioactive 18F-labelled chemical agent as PET probes plays a predominant role in monitoring, detecting, treating, and predicting tumours due to its perfect half-life. In this paper, the 18F-labelled chemical materials as PET probes are systematically summarized. First, we introduce various radionuclides of PET and elaborate on the mechanism of PET imaging. It highlights the 18F-labelled chemical agents used as PET probes, including [18F]-2-deoxy-2-[18F]fluoro-D-glucose ([18F]-FDG), 18F-labelled amino acids, 18F-labelled nucleic acids, 18F-labelled receptors, 18F-labelled reporter genes, and 18F-labelled hypoxia agents. In addition, some PET probes with metal as a supplementary element are introduced briefly. Meanwhile, the 18F-labelled nanoparticles for the PET probe and the multi-modality imaging probe are summarized in detail. The approach and strategies for the fabrication of 18F-labelled PET probes are also described briefly. The future development of the PET probe is also prospected. The development and application of 18F-labelled PET probes will expand our knowledge and shed light on the diagnosis and theranostics of tumours.
2025, 41(9): 1755-1764
doi: 10.11862/CJIC.20250198
Abstract:
Cu(In, Ga)S2 semiconductor thin films were fabricated via a blading method using metal salts and thiourea precursor solutions. The influence of the Ga to Ga+In ratio (GGI) on material properties and solar cell performance was systematically investigated. Results demonstrated that the band gap of Cu(In, Ga)S2 progressively widens with increasing GGI. While moderate GGI can enhance grain growth and improve device open-circuit voltage (VOC) and fill factor (FF), excessive Ga incorporation hinders crystallinity and degrades photovoltaic performance. Optimal performance was achieved at GGI of 0.25, yielding a band gap of 1.69 eV, and a record photoelectric conversion efficiency of 9.06% for solution-processed wide-band gap Cu(In, Ga)S2 solar cells, representing a 37.48% improvement over Ga-free reference devices. Further analysis confirms that Ga alloying effectively reduces both bulk and interfacial defect densities, improves heterojunction interface quality, and significantly suppresses carrier recombination.
Cu(In, Ga)S2 semiconductor thin films were fabricated via a blading method using metal salts and thiourea precursor solutions. The influence of the Ga to Ga+In ratio (GGI) on material properties and solar cell performance was systematically investigated. Results demonstrated that the band gap of Cu(In, Ga)S2 progressively widens with increasing GGI. While moderate GGI can enhance grain growth and improve device open-circuit voltage (VOC) and fill factor (FF), excessive Ga incorporation hinders crystallinity and degrades photovoltaic performance. Optimal performance was achieved at GGI of 0.25, yielding a band gap of 1.69 eV, and a record photoelectric conversion efficiency of 9.06% for solution-processed wide-band gap Cu(In, Ga)S2 solar cells, representing a 37.48% improvement over Ga-free reference devices. Further analysis confirms that Ga alloying effectively reduces both bulk and interfacial defect densities, improves heterojunction interface quality, and significantly suppresses carrier recombination.
2025, 41(9): 1765-1775
doi: 10.11862/CJIC.20250103
Abstract:
BiOBr/NH2-MIL-101(Fe) composite photocatalysts were prepared by compositing BiOBr and NH2-MIL-101(Fe) using a solvothermal method and used for the photocatalytic reduction of greenhouse gases CO2. The structure and properties of the composite photocatalysts were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscope spectroscopy-energy dispersive X-ray spectroscopy, UV-Vis diffuse reflectance spectroscopy, photoluminescence spectroscopy, and electrochemical impedance spectroscopy. The photocatalytic CO2 reduction performance study revealed that the activity of BiOBr/NH2-MIL-101(Fe) was significantly superior to that of pure BiOBr. The composite catalyst prepared with the molar ratio of NH2-MIL-101(Fe) to BiOBr of 0.09 showed the best catalytic activity, and the CH3OH yield in the pure aqueous system reached 49.68 μmol·g-1 after reacting under visible light irradiation for 6 h. The BiOBr/NH2-MIL-101(Fe) heterojunction achieved rapid elimination of low-energy streams and effective separation and enrichment of high-energy carriers, which enabled the CH3OH yield photocatalytic produced by BiOBr/NH2-MIL-101(Fe)-0.09 to be 2.94 times that of pure BiOBr. This catalyst demonstrated good recycling performance, with a yield of 84.9% still achievable after the first five cycles.
BiOBr/NH2-MIL-101(Fe) composite photocatalysts were prepared by compositing BiOBr and NH2-MIL-101(Fe) using a solvothermal method and used for the photocatalytic reduction of greenhouse gases CO2. The structure and properties of the composite photocatalysts were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscope spectroscopy-energy dispersive X-ray spectroscopy, UV-Vis diffuse reflectance spectroscopy, photoluminescence spectroscopy, and electrochemical impedance spectroscopy. The photocatalytic CO2 reduction performance study revealed that the activity of BiOBr/NH2-MIL-101(Fe) was significantly superior to that of pure BiOBr. The composite catalyst prepared with the molar ratio of NH2-MIL-101(Fe) to BiOBr of 0.09 showed the best catalytic activity, and the CH3OH yield in the pure aqueous system reached 49.68 μmol·g-1 after reacting under visible light irradiation for 6 h. The BiOBr/NH2-MIL-101(Fe) heterojunction achieved rapid elimination of low-energy streams and effective separation and enrichment of high-energy carriers, which enabled the CH3OH yield photocatalytic produced by BiOBr/NH2-MIL-101(Fe)-0.09 to be 2.94 times that of pure BiOBr. This catalyst demonstrated good recycling performance, with a yield of 84.9% still achievable after the first five cycles.
2025, 41(9): 1776-1788
doi: 10.11862/CJIC.20250102
Abstract:
Different types of nitrogen (pyridine nitrogen, pyrrole nitrogen, graphite nitrogen) were doped and iron single atom was loaded on graphene to construct the Fe-N-C structures, and the coordination number (x=3-6) of pyridine nitrogen and iron single atom was changed to study the reaction mechanism of oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) based on the first-principles method. It is found that nitrogen doping and iron single-atom loading both are beneficial to increase the OER/ORR activity of graphene, but for the iron single atoms, or the nitrogen atoms, or the carbon atoms adjacent to nitrogen atoms, these active sites show different catalytic activity. The carbon atom next to graphite nitrogen in Fe-N-C is the best OER active site, while the iron single atom formed a tetra-coordination structure with pyridine nitrogen is the best ORR active site.
Different types of nitrogen (pyridine nitrogen, pyrrole nitrogen, graphite nitrogen) were doped and iron single atom was loaded on graphene to construct the Fe-N-C structures, and the coordination number (x=3-6) of pyridine nitrogen and iron single atom was changed to study the reaction mechanism of oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) based on the first-principles method. It is found that nitrogen doping and iron single-atom loading both are beneficial to increase the OER/ORR activity of graphene, but for the iron single atoms, or the nitrogen atoms, or the carbon atoms adjacent to nitrogen atoms, these active sites show different catalytic activity. The carbon atom next to graphite nitrogen in Fe-N-C is the best OER active site, while the iron single atom formed a tetra-coordination structure with pyridine nitrogen is the best ORR active site.
2025, 41(9): 1789-1795
doi: 10.11862/CJIC.20250086
Abstract:
A pyridinium-chalcone-based probe (1) was prepared via a two-step reaction, which was characterized through 1H NMR and mass spectra. Probe 1 was weakly emissive in water-sufficient solution, while hypochlorite (ClO-) could remarkably enhance the yellow fluorescence emission of the probe at 550 nm. The detection of probe 1 for ClO- had the advantages of fast response (< 30 s), high sensitivity (a detection limit of 0.4 μmol·L-1), and large Stokes shift (130 nm). The ClO--promoted oxidation-elimination of probe 1 was suggested by mass spectra and theoretical calculation methods. Furthermore, the probe was successfully used to monitor mitochondrial ClO- in living cells and zebrafish.
A pyridinium-chalcone-based probe (1) was prepared via a two-step reaction, which was characterized through 1H NMR and mass spectra. Probe 1 was weakly emissive in water-sufficient solution, while hypochlorite (ClO-) could remarkably enhance the yellow fluorescence emission of the probe at 550 nm. The detection of probe 1 for ClO- had the advantages of fast response (< 30 s), high sensitivity (a detection limit of 0.4 μmol·L-1), and large Stokes shift (130 nm). The ClO--promoted oxidation-elimination of probe 1 was suggested by mass spectra and theoretical calculation methods. Furthermore, the probe was successfully used to monitor mitochondrial ClO- in living cells and zebrafish.
2025, 41(9): 1796-1804
doi: 10.11862/CJIC.20250033
Abstract:
A MOF-74-Mn/g-C3N4 photocatalyst with a Z-scheme heterojunction structure was synthesized via a hydrothermal method. Under visible-light irradiation, the degradation rate of tetracycline reached 95% within 60 min, which was 2.4 times that of the pure MOF-74-Mn and 1.8 times that of the pure g-C3N4. The results indicate that the MOF-74-Mn/g-C3N4 Z-scheme heterojunction can effectively achieve the spatial separation of photogenerated carriers, suppress the recombination of photogenerated electron-hole pairs, and accelerate the carrier, thus enhancing the photocatalytic degradation performance.
A MOF-74-Mn/g-C3N4 photocatalyst with a Z-scheme heterojunction structure was synthesized via a hydrothermal method. Under visible-light irradiation, the degradation rate of tetracycline reached 95% within 60 min, which was 2.4 times that of the pure MOF-74-Mn and 1.8 times that of the pure g-C3N4. The results indicate that the MOF-74-Mn/g-C3N4 Z-scheme heterojunction can effectively achieve the spatial separation of photogenerated carriers, suppress the recombination of photogenerated electron-hole pairs, and accelerate the carrier, thus enhancing the photocatalytic degradation performance.
2025, 41(9): 1805-1816
doi: 10.11862/CJIC.20250066
Abstract:
By introducing methylammonium chloride (MACl) molecules onto the TiO2 electron transport layer, the TiO2/CsPbBr3 interface was modified to passivate the existing interface defects, while improving the crystallinity and grain size of CsPbBr3 films, thereby enhancing the carrier transport efficiency. Experimental results demonstrated that after modification with a 5.0 mg·mL-1 MACl solution, the device achieved a maximum open-circuit voltage (VOC) of 1.58 V, a short-circuit current density (JSC) of 7.89 mA·cm-2, a fill factor (FF) of 81.09%, and an optimal photoelectric conversion efficiency (PCE) of 10.10%.
By introducing methylammonium chloride (MACl) molecules onto the TiO2 electron transport layer, the TiO2/CsPbBr3 interface was modified to passivate the existing interface defects, while improving the crystallinity and grain size of CsPbBr3 films, thereby enhancing the carrier transport efficiency. Experimental results demonstrated that after modification with a 5.0 mg·mL-1 MACl solution, the device achieved a maximum open-circuit voltage (VOC) of 1.58 V, a short-circuit current density (JSC) of 7.89 mA·cm-2, a fill factor (FF) of 81.09%, and an optimal photoelectric conversion efficiency (PCE) of 10.10%.
2025, 41(9): 1817-1826
doi: 10.11862/CJIC.20250058
Abstract:
As a potential biomarker for breast cancer, the highly sensitive detection of lipase is conducive to improving the accuracy of disease diagnosis. Lipase has the property that it can react with the reactant at the contact surface, such as when a solid in solution reacts with lipase. Illuminated by the lipase catalytic property, a lipase-responsive fluorescent probe BTPA with the aggregation-induced emission (AIE) was designed and synthesized. The probe could be hydrolyzed by the lipase enzyme and emit yellow fluorescence, because it self-aggregated into granulums with the external solution, and the granulums provided a surface to activate the activity of the lipase enzyme. The fluorescence emission intensity of BTPA was linearly correlated with the activity of lipase in a range of 5.0×10-5-4.5×10-4 U·mL-1, and the detection limit was 4.94×10-6 U·mL-1. Besides, the probe could be applied in a complex biochemical system investigated by a selectivity and interference experiment. The laser-confocal imaging experiment showed that the fluorescent probe could accurately identify breast cancer cells in situ and emit strong fluorescence.
As a potential biomarker for breast cancer, the highly sensitive detection of lipase is conducive to improving the accuracy of disease diagnosis. Lipase has the property that it can react with the reactant at the contact surface, such as when a solid in solution reacts with lipase. Illuminated by the lipase catalytic property, a lipase-responsive fluorescent probe BTPA with the aggregation-induced emission (AIE) was designed and synthesized. The probe could be hydrolyzed by the lipase enzyme and emit yellow fluorescence, because it self-aggregated into granulums with the external solution, and the granulums provided a surface to activate the activity of the lipase enzyme. The fluorescence emission intensity of BTPA was linearly correlated with the activity of lipase in a range of 5.0×10-5-4.5×10-4 U·mL-1, and the detection limit was 4.94×10-6 U·mL-1. Besides, the probe could be applied in a complex biochemical system investigated by a selectivity and interference experiment. The laser-confocal imaging experiment showed that the fluorescent probe could accurately identify breast cancer cells in situ and emit strong fluorescence.
2025, 41(9): 1827-1839
doi: 10.11862/CJIC.20240460
Abstract:
In this paper, the hydrogen storage properties of C6S6Li6 were studied by two density functional methods. C6S6Li6 was dynamically stable and could adsorb up to 38 H2 molecules with a hydrogen storage density of 20.213%. The average adsorption energy of C6S6Li6(H2)38 was very close to the energy range (0.1-0.8 eV) for reversible hydrogen storage at near ambient conditions. Various wave function analysis methods revealed that the 2s→2p electron transition of Li in C6S6Li6 and the electric field of each charged atom jointly dominated Van der Waals attractions between C6S6Li6 and hydrogen molecules. Thermo-chemistry calculations indicated that 6, 32, and 38 H2 molecules in C6S6Li6(H2)38 could be readily adsorbed at 77 K and desorbed at 298.15 K under 0.1, 2.5, and 5.0 MPa, respectively. This process corresponds to the reversible hydrogen storage densities of 3.846%, 17.582%, and 20.213%. Atom density matrix propagation (ADMP) molecular dynamic simulations indicated that most of the hydrogen molecules in C6S6Li6(H2)38 got efficiently released at room temperature. The (C6S6Li6)2 dimer could also adsorb 53 H2 molecules with a gravimetric density of 15.014%. The average adsorption energy for C12S12Li12(H2)53 could approach the reversible energy range for hydrogen storage.
In this paper, the hydrogen storage properties of C6S6Li6 were studied by two density functional methods. C6S6Li6 was dynamically stable and could adsorb up to 38 H2 molecules with a hydrogen storage density of 20.213%. The average adsorption energy of C6S6Li6(H2)38 was very close to the energy range (0.1-0.8 eV) for reversible hydrogen storage at near ambient conditions. Various wave function analysis methods revealed that the 2s→2p electron transition of Li in C6S6Li6 and the electric field of each charged atom jointly dominated Van der Waals attractions between C6S6Li6 and hydrogen molecules. Thermo-chemistry calculations indicated that 6, 32, and 38 H2 molecules in C6S6Li6(H2)38 could be readily adsorbed at 77 K and desorbed at 298.15 K under 0.1, 2.5, and 5.0 MPa, respectively. This process corresponds to the reversible hydrogen storage densities of 3.846%, 17.582%, and 20.213%. Atom density matrix propagation (ADMP) molecular dynamic simulations indicated that most of the hydrogen molecules in C6S6Li6(H2)38 got efficiently released at room temperature. The (C6S6Li6)2 dimer could also adsorb 53 H2 molecules with a gravimetric density of 15.014%. The average adsorption energy for C12S12Li12(H2)53 could approach the reversible energy range for hydrogen storage.
2025, 41(9): 1840-1850
doi: 10.11862/CJIC.20250136
Abstract:
Reaction of the non-substituted/substituted unsymmetric pinene-derived complex [Pt(N^C^N′)Cl] with the aryl isocyanide 2,6-dimethylphenyl isocyanide (CNXyl) afforded a mixture of two isomeric species: the ionic complex [Pt(κ3-N^C^N′)(CNXyl)]Cl ([A]Cl) and the molecular complex [Pt(κ2-N^C^N′)(CNXyl)Cl] (B). Isomer B was almost the dominating product. The structures of the isomer B derivatives bearing —CF3 and —Cl substituents on the pyridine ring of the pinene moiety (5B and 7B, respectively) have been confirmed by single-crystal X-ray diffraction, revealing a slightly distorted square planar geometry with trans-NN^C^N′, CNR configuration (The terminal N atom of the κ2-N^C^N′ ligand is trans to the isocyanide ligand CNXyl.). Isomer B is thermodynamically more stable, as confirmed by theoretical calculations.
Reaction of the non-substituted/substituted unsymmetric pinene-derived complex [Pt(N^C^N′)Cl] with the aryl isocyanide 2,6-dimethylphenyl isocyanide (CNXyl) afforded a mixture of two isomeric species: the ionic complex [Pt(κ3-N^C^N′)(CNXyl)]Cl ([A]Cl) and the molecular complex [Pt(κ2-N^C^N′)(CNXyl)Cl] (B). Isomer B was almost the dominating product. The structures of the isomer B derivatives bearing —CF3 and —Cl substituents on the pyridine ring of the pinene moiety (5B and 7B, respectively) have been confirmed by single-crystal X-ray diffraction, revealing a slightly distorted square planar geometry with trans-NN^C^N′, CNR configuration (The terminal N atom of the κ2-N^C^N′ ligand is trans to the isocyanide ligand CNXyl.). Isomer B is thermodynamically more stable, as confirmed by theoretical calculations.
2025, 41(9): 1851-1858
doi: 10.11862/CJIC.20250131
Abstract:
To extend a new family of aminophosphine-coordinated [FeFe]-hydrogenase mimics for catalytic hydrogen (H2) evolution, we carried out the ligand substitutions of diiron hexacarbonyl precursors [Fe2(μ-X2pdt)(CO)6] (X2pdt=(SCH2)2CX2, X=Me, H) with aminodiphosphines (Ph2PCH2)2NY(Y=(CH2)2OH, (CH2)3OH) to obtain two new diiron aminophosphine complexes [Fe2(L1)(μ-Me2pdt)(CO)5] (1) and [Fe2(L2)(μ-H2pdt)(CO)5] (2), where L1=3-[(diphenylphosphaneyl)methyl]oxazolidine, L2=3-[(diphenylphosphaneyl)methyl]-1, 3-oxazinane. Moreover, the structures of 1 and 2 have been fully confirmed by elemental analysis, spectroscopic techniques, and single-crystal X-ray diffraction. Using cyclic voltammetry (CV), we investigated the electrochemical redox performance and proton reduction activities of 1 and 2 in acetic acid (HOAc). The CV study indicates that diiron aminophosphine complexes 1 and 2 can be considered to be hydrogenase-inspired diiron molecular electrocatalysts for the reduction of protons into H2 generation in the presence of HOAc.
To extend a new family of aminophosphine-coordinated [FeFe]-hydrogenase mimics for catalytic hydrogen (H2) evolution, we carried out the ligand substitutions of diiron hexacarbonyl precursors [Fe2(μ-X2pdt)(CO)6] (X2pdt=(SCH2)2CX2, X=Me, H) with aminodiphosphines (Ph2PCH2)2NY(Y=(CH2)2OH, (CH2)3OH) to obtain two new diiron aminophosphine complexes [Fe2(L1)(μ-Me2pdt)(CO)5] (1) and [Fe2(L2)(μ-H2pdt)(CO)5] (2), where L1=3-[(diphenylphosphaneyl)methyl]oxazolidine, L2=3-[(diphenylphosphaneyl)methyl]-1, 3-oxazinane. Moreover, the structures of 1 and 2 have been fully confirmed by elemental analysis, spectroscopic techniques, and single-crystal X-ray diffraction. Using cyclic voltammetry (CV), we investigated the electrochemical redox performance and proton reduction activities of 1 and 2 in acetic acid (HOAc). The CV study indicates that diiron aminophosphine complexes 1 and 2 can be considered to be hydrogenase-inspired diiron molecular electrocatalysts for the reduction of protons into H2 generation in the presence of HOAc.
2025, 41(9): 1859-1866
doi: 10.11862/CJIC.20250128
Abstract:
Luminescence thermometry has attracted more and more attention due to its non-contact and noninvasive operation, fast response, high spatial resolution, and so on, for which the luminescent thermometers are the key. Here, a 1D complex [Tb4(HTC4A)(TC4A)(OBBA)2(CH3OH)4(μ4-OH)]n (1) was obtained by solvothermal synthesis, where H4TC4A=p-tert-butylthiacalix[4 ]arene, and H2OBBA=4, 4′-oxybisbenzoic acid. This complex is featured with a chain-like polymer constructed by bridging some sandwich-like Tb4-(TC4A)2 entities through OBBA2- ligands. It exhibited the characteristic emission of the Tb3+ ion. Both fluorescence intensity and lifetime decreased with increasing temperature. The relative sensitivity was up to 8.743%·K-1 at 473 K, indicating it is a good ratiometric luminescent thermometer. This complex had good stability under different pH values and in common solvents.
Luminescence thermometry has attracted more and more attention due to its non-contact and noninvasive operation, fast response, high spatial resolution, and so on, for which the luminescent thermometers are the key. Here, a 1D complex [Tb4(HTC4A)(TC4A)(OBBA)2(CH3OH)4(μ4-OH)]n (1) was obtained by solvothermal synthesis, where H4TC4A=p-tert-butylthiacalix[
2025, 41(9): 1867-1877
doi: 10.11862/CJIC.20250100
Abstract:
Two Gd2 complexes, namely [Gd2(dbm)2(HL1)2(CH3OH)2]·4CH3OH (1) and [Gd2(dbm)2(L2)2(CH3OH)2]·2CH3OH (2), where H3L1=(Z)-N′-[4-(diethylamino)-2-hydroxybenzylidene]-2-hydroxyacetohydrazide, H2L2=(E)-N′- (5-bromo-2-hydroxy-3-methoxybenzylidene)nicotinohydrazide, Hdbm=dibenzoylmethane, have been constructed by adopting the solvothermal method. Structural characterization unveils that both complexes 1 and 2 are constituted by two Gd3+ ions, two dbm- ions, two CH3OH molecules, and two polydentate Schiff-base ligands (HL12- or L22-). In addition, complex 1 contains four free methanol molecules, whereas complex 2 harbors two free methanol molecules. By investigating the interactions between complexes 1 and 2 and four types of bacteria (Bacillus subtilis, Escherichia coli, Staphylococcus aureus, Candida albicans), it was found that both complexes 1 and 2 exhibited potent antibacterial activities. The interaction mechanisms between the ligands H3L1, H2L2, complexes 1 and 2, and calf thymus DNA (CT-DNA) were studied using ultraviolet-visible spectroscopy, fluorescence titration, and cyclic voltammetry. The results demonstrated that both complexes 1 and 2 can intercalate into CT-DNA molecules, thereby inhibiting bacterial proliferation to achieve the antibacterial effects.
Two Gd2 complexes, namely [Gd2(dbm)2(HL1)2(CH3OH)2]·4CH3OH (1) and [Gd2(dbm)2(L2)2(CH3OH)2]·2CH3OH (2), where H3L1=(Z)-N′-[4-(diethylamino)-2-hydroxybenzylidene]-2-hydroxyacetohydrazide, H2L2=(E)-N′- (5-bromo-2-hydroxy-3-methoxybenzylidene)nicotinohydrazide, Hdbm=dibenzoylmethane, have been constructed by adopting the solvothermal method. Structural characterization unveils that both complexes 1 and 2 are constituted by two Gd3+ ions, two dbm- ions, two CH3OH molecules, and two polydentate Schiff-base ligands (HL12- or L22-). In addition, complex 1 contains four free methanol molecules, whereas complex 2 harbors two free methanol molecules. By investigating the interactions between complexes 1 and 2 and four types of bacteria (Bacillus subtilis, Escherichia coli, Staphylococcus aureus, Candida albicans), it was found that both complexes 1 and 2 exhibited potent antibacterial activities. The interaction mechanisms between the ligands H3L1, H2L2, complexes 1 and 2, and calf thymus DNA (CT-DNA) were studied using ultraviolet-visible spectroscopy, fluorescence titration, and cyclic voltammetry. The results demonstrated that both complexes 1 and 2 can intercalate into CT-DNA molecules, thereby inhibiting bacterial proliferation to achieve the antibacterial effects.
2025, 41(9): 1878-1888
doi: 10.11862/CJIC.20250079
Abstract:
A Co3O4/BiOBr heterojunction was synthesized via a facile one-step solvothermal method for highly selective photocatalytic CO2 reduction. The optimized Co3O4/BiOBr-0.8 catalyst exhibited CO and CH4 evolution rates of 112.2 and 5.5 μmol·g-1·h-1, respectively, representing 6.3-fold and 3.9-fold enhancements over pristine BiOBr. The heterojunction demonstrated broadened light absorption, enhanced photoelectrochemical activity, reduced charge-transfer resistance, and improved separation efficiency of photogenerated carriers (e-/h+). These synergistic effects were attributed to the formation of a Z-scheme heterostructure, which facilitated solar energy utilization and electron reduction capacity while suppressing carrier recombination.
A Co3O4/BiOBr heterojunction was synthesized via a facile one-step solvothermal method for highly selective photocatalytic CO2 reduction. The optimized Co3O4/BiOBr-0.8 catalyst exhibited CO and CH4 evolution rates of 112.2 and 5.5 μmol·g-1·h-1, respectively, representing 6.3-fold and 3.9-fold enhancements over pristine BiOBr. The heterojunction demonstrated broadened light absorption, enhanced photoelectrochemical activity, reduced charge-transfer resistance, and improved separation efficiency of photogenerated carriers (e-/h+). These synergistic effects were attributed to the formation of a Z-scheme heterostructure, which facilitated solar energy utilization and electron reduction capacity while suppressing carrier recombination.
2025, 41(9): 1889-1902
doi: 10.11862/CJIC.20250097
Abstract:
A cobalt-based metal-organic framework [Co3(L)2(1, 4-bib)4]·4H2O (Co-MOF) was prepared using 5-[(4-carboxyphenoxy)methyl]isophthalic acid (H3L) and 1, 4-bis(1H-imidazol-1-yl)benzene (1, 4-bib) as ligands. Then, an electrochemical sensor modified with Co-MOF on a glassy carbon electrode (Co-MOF@GCE) was constructed for detecting Cd2+ and Pb2+ in aqueous solutions. The sensor exhibited a linear range of 1.0-16.0 μmol·L-1 with a detection limit (LOD) of 4.609 nmol·L-1 for Cd2+, and 0.5-10.0 μmol·L-1 with an LOD of 1.307 nmol·L-1 for Pb2+. Simultaneous detection of both ions within 0.5-7.0 μmol·L-1 achieved LOD values of 0.47 nmol·L-1 (Cd2+) and 0.008 nmol·L-1 (Pb2+), respectively. Analysis of real water samples (tap water, mineral water, and river water) yielded recoveries of 95%-105%, validating practical applicability. Density functional theory (DFT) calculations reveal that synergistic interactions between cobalt centers and N/O atoms enhance adsorption and electron-transfer efficiency. CCDC: 2160744.
A cobalt-based metal-organic framework [Co3(L)2(1, 4-bib)4]·4H2O (Co-MOF) was prepared using 5-[(4-carboxyphenoxy)methyl]isophthalic acid (H3L) and 1, 4-bis(1H-imidazol-1-yl)benzene (1, 4-bib) as ligands. Then, an electrochemical sensor modified with Co-MOF on a glassy carbon electrode (Co-MOF@GCE) was constructed for detecting Cd2+ and Pb2+ in aqueous solutions. The sensor exhibited a linear range of 1.0-16.0 μmol·L-1 with a detection limit (LOD) of 4.609 nmol·L-1 for Cd2+, and 0.5-10.0 μmol·L-1 with an LOD of 1.307 nmol·L-1 for Pb2+. Simultaneous detection of both ions within 0.5-7.0 μmol·L-1 achieved LOD values of 0.47 nmol·L-1 (Cd2+) and 0.008 nmol·L-1 (Pb2+), respectively. Analysis of real water samples (tap water, mineral water, and river water) yielded recoveries of 95%-105%, validating practical applicability. Density functional theory (DFT) calculations reveal that synergistic interactions between cobalt centers and N/O atoms enhance adsorption and electron-transfer efficiency. CCDC: 2160744.
2025, 41(9): 1903-1915
doi: 10.11862/CJIC.20250026
Abstract:
Herein, copper nanoclusters (Cu NCs) were synthesized in aqueous solution through a chemical reduction method using polyethyleneimine as reducing agent and protective ligand, with Cu(NO3)2 as copper source. Subsequently, composite fluorescent nanoparticles, chitosan-functionalized silica nanoparticles (CSNPs)-coated Cu NCs (Cu NCs/CSNPs), were synthesized via a reverse microemulsion method. Compared with Cu NCs, the composite Cu NCs/CSNPs exhibited an increased quantum yield and enhanced fluorescence sensing performance. Based on the composite Cu NCs/CSNPs, a fluorescence method for the detection of cefixime fluorescence quenching was established. The technique was simple, sensitive, and selective for detecting cefixime. The fluorescence quenching efficiency of Cu NCs/CSNPs was linearly related to the concentration of cefixime in the range of 3.98-38.5 μmol·L-1 (1.81-17.46 mg·L-1), with a limit of detection of 0.045 5 μmol·L-1 (20.6 μg·L-1).
Herein, copper nanoclusters (Cu NCs) were synthesized in aqueous solution through a chemical reduction method using polyethyleneimine as reducing agent and protective ligand, with Cu(NO3)2 as copper source. Subsequently, composite fluorescent nanoparticles, chitosan-functionalized silica nanoparticles (CSNPs)-coated Cu NCs (Cu NCs/CSNPs), were synthesized via a reverse microemulsion method. Compared with Cu NCs, the composite Cu NCs/CSNPs exhibited an increased quantum yield and enhanced fluorescence sensing performance. Based on the composite Cu NCs/CSNPs, a fluorescence method for the detection of cefixime fluorescence quenching was established. The technique was simple, sensitive, and selective for detecting cefixime. The fluorescence quenching efficiency of Cu NCs/CSNPs was linearly related to the concentration of cefixime in the range of 3.98-38.5 μmol·L-1 (1.81-17.46 mg·L-1), with a limit of detection of 0.045 5 μmol·L-1 (20.6 μg·L-1).
2025, 41(9): 1916-1926
doi: 10.11862/CJIC.20240442
Abstract:
Herein, an FMS/CC composite was successfully fabricated by depositing FeMoS4 onto a pristine carbon fiber cloth (CC) substrate via a facile two-step hydrothermal method. The amorphous nature of the FMS/CC composite endows it with abundant catalytically active sites, thereby accelerating the reduction of I3-. More importantly, the dye-sensitized solar cells (DSSCs) prepared by scraping it on flexible titanium mesh with low resistance had low series resistance (Rs). Electrochemical characterizations revealed that the DSSCs employing the FMS/CC counter electrode achieved a power conversion efficiency (PCE) of ca. 9.51% (surpassing the ca. 8.15% efficiency of the Pt counter electrode), open-circuit voltage (Voc) of ca. 0.79 V, short-circuit current density (Jsc) of ca. 18.31 mA·cm-2, and fill factor (FF) of ca. 0.65. Moreover, after 100 times of cyclic voltammetry (CV) test, the CV curve remainedunchanged, indicating the excellent stability of FMS/CC in the electrolyte containing I3-/I-.
Herein, an FMS/CC composite was successfully fabricated by depositing FeMoS4 onto a pristine carbon fiber cloth (CC) substrate via a facile two-step hydrothermal method. The amorphous nature of the FMS/CC composite endows it with abundant catalytically active sites, thereby accelerating the reduction of I3-. More importantly, the dye-sensitized solar cells (DSSCs) prepared by scraping it on flexible titanium mesh with low resistance had low series resistance (Rs). Electrochemical characterizations revealed that the DSSCs employing the FMS/CC counter electrode achieved a power conversion efficiency (PCE) of ca. 9.51% (surpassing the ca. 8.15% efficiency of the Pt counter electrode), open-circuit voltage (Voc) of ca. 0.79 V, short-circuit current density (Jsc) of ca. 18.31 mA·cm-2, and fill factor (FF) of ca. 0.65. Moreover, after 100 times of cyclic voltammetry (CV) test, the CV curve remainedunchanged, indicating the excellent stability of FMS/CC in the electrolyte containing I3-/I-.
