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2025 Volume 41 Issue 7
2025, 41(7): 1257-1275
doi: 10.11862/CJIC.20240454
Abstract:
Water splitting is suffering from low energy transformation efficiency due to the slow kinetics of the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), posing a significant barrier to the broad application of green hydrogen. Developing catalysts with excellent catalytic performance and low cost is crucial for overcoming the energy transformation issue. Recently, high-entropy materials have attracted considerable attention in various fields owing to their superior physical and chemical properties. High mixing entropy not only introduces significant lattice distortion in metals and ceramics but also provides them with sluggish diffusion and "cocktail effects", enabling the development of novel catalysts with outstanding catalytic performance. High-entropy materials thereby become one of the ideal catalysts for water splitting to lower the energy consumption on both the HER and OER electrodes. This article reviews the recent development of high-entropy alloys (HEAs) and high-entropy ceramics (HECs) in the field of water splitting. We first introduce the composition and structure design strategies for HEA and HEC catalysts based on the mechanism of water splitting, and then summarize the main HEA and HEC systems that display improved catalytic performance towards HER and OER. The synthesis methods for HEA and HEC catalysts are also introduced, and their advantages and disadvantages are evaluated. Finally, we provide an outlook on the challenges and prospects of the future development and application of HEAs and HECs for water splitting.
Water splitting is suffering from low energy transformation efficiency due to the slow kinetics of the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), posing a significant barrier to the broad application of green hydrogen. Developing catalysts with excellent catalytic performance and low cost is crucial for overcoming the energy transformation issue. Recently, high-entropy materials have attracted considerable attention in various fields owing to their superior physical and chemical properties. High mixing entropy not only introduces significant lattice distortion in metals and ceramics but also provides them with sluggish diffusion and "cocktail effects", enabling the development of novel catalysts with outstanding catalytic performance. High-entropy materials thereby become one of the ideal catalysts for water splitting to lower the energy consumption on both the HER and OER electrodes. This article reviews the recent development of high-entropy alloys (HEAs) and high-entropy ceramics (HECs) in the field of water splitting. We first introduce the composition and structure design strategies for HEA and HEC catalysts based on the mechanism of water splitting, and then summarize the main HEA and HEC systems that display improved catalytic performance towards HER and OER. The synthesis methods for HEA and HEC catalysts are also introduced, and their advantages and disadvantages are evaluated. Finally, we provide an outlook on the challenges and prospects of the future development and application of HEAs and HECs for water splitting.
2025, 41(7): 1276-1284
doi: 10.11862/CJIC.20240424
Abstract:
Converting CO2 into cyclic carbonates, a process with 100% atom efficiency, offers a promising route for carbon utilization, yet it is hindered by harsh reaction conditions (high temperature/pressure). To provide a cost- effective, high-efficiency catalyst design strategy for sustainable CO2 conversion, oxygen-vacancy-rich defective tungsten oxide (W18O49)/reduced graphene oxide (rGO) composites were constructed via an in-situ solvothermal method. Comprehensive characterization confirmed its structural integrity and defect-rich nature. The W18O49/rGO composite exhibited exceptional photothermal catalytic activity for CO2 cycloaddition under ambient conditions, achieving a 95% styrene carbonate yield (173 mmol·g-1·h-1) with excellent cycling stability. The integration of rGO enhances the CO2 adsorption, broadens the light absorption, and facilitates charge transfer efficiency. The coupling effect of photocatalysis and thermal catalysis significantly improves the catalytic performance.
Converting CO2 into cyclic carbonates, a process with 100% atom efficiency, offers a promising route for carbon utilization, yet it is hindered by harsh reaction conditions (high temperature/pressure). To provide a cost- effective, high-efficiency catalyst design strategy for sustainable CO2 conversion, oxygen-vacancy-rich defective tungsten oxide (W18O49)/reduced graphene oxide (rGO) composites were constructed via an in-situ solvothermal method. Comprehensive characterization confirmed its structural integrity and defect-rich nature. The W18O49/rGO composite exhibited exceptional photothermal catalytic activity for CO2 cycloaddition under ambient conditions, achieving a 95% styrene carbonate yield (173 mmol·g-1·h-1) with excellent cycling stability. The integration of rGO enhances the CO2 adsorption, broadens the light absorption, and facilitates charge transfer efficiency. The coupling effect of photocatalysis and thermal catalysis significantly improves the catalytic performance.
2025, 41(7): 1285-1293
doi: 10.11862/CJIC.20250095
Abstract:
The ultra-bulky and stable monodentate amino groups can provide effective kinetic protection during the preparation of low-coordinate transition metal complexes, thereby preventing oligomerization. In this work, the ultra-bulky sodium hexa-isopropyl disilylamide (2) was synthesized for the first time by the reaction of silylamine and sodium amide, and the crystal structures of 2-THF and 2-Tol, which are complexes of 2 coordinated by tetrahydrofuran (THF) or toluene (Tol), respectively, were characterized. Then, the diamino iron [Fe(Ⅱ)(N(SiⅰPr3)2)2] (3) and diamino dichloro-bis-chromium [Cr(Ⅱ)(N(SiiPr3)2)Cl]2 (4) were synthesized through the salt metathesis reaction of 2 with the corresponding transition metal halides FeCl2 and CrCl2. Due to the steric hindrance of the ultra-bulky amino groups, complex 3 presents a nearly linear geometry, with the N—Fe—N bond angle of 178.10°. Complex 4 is a dimer of monoamino chromium(Ⅱ) chloride; the three-coordinate Cr(Ⅱ) ions form a {Cr2Cl2} rhombic core via two Cl-bridges. The improved iCAS method (imposed automatic selection and localization of complete active spaces) was used to calculate the molecular orbitals of 3 and 4 to logically describe the strongly correlated systems of electrons of the low-coordinate sphere of transition metals. The calculation shows that the bonding contribution of 3 mainly consists of the two Fe—N σ bonds, and the charge of Fe (+1.03) and N (-1.21) confirms a strong ionic coordination environment. The Fe—N π-bonding is not evident. The quintuplet high-spin Fe has one doubly occupied orbital and four singly occupied orbitals, originating from the 3d orbitals of Fe. The six fully occupied molecular orbitals of 4 correspond to two Cr—N σ bonds, two p-type lone pairs on Cl atoms, and two p-type lone pairs on N atoms. Two Cr atoms have eight high-energy d electrons, each in a singly occupied active orbital, and one of them exhibits Cr…Cr interaction.
The ultra-bulky and stable monodentate amino groups can provide effective kinetic protection during the preparation of low-coordinate transition metal complexes, thereby preventing oligomerization. In this work, the ultra-bulky sodium hexa-isopropyl disilylamide (2) was synthesized for the first time by the reaction of silylamine and sodium amide, and the crystal structures of 2-THF and 2-Tol, which are complexes of 2 coordinated by tetrahydrofuran (THF) or toluene (Tol), respectively, were characterized. Then, the diamino iron [Fe(Ⅱ)(N(SiⅰPr3)2)2] (3) and diamino dichloro-bis-chromium [Cr(Ⅱ)(N(SiiPr3)2)Cl]2 (4) were synthesized through the salt metathesis reaction of 2 with the corresponding transition metal halides FeCl2 and CrCl2. Due to the steric hindrance of the ultra-bulky amino groups, complex 3 presents a nearly linear geometry, with the N—Fe—N bond angle of 178.10°. Complex 4 is a dimer of monoamino chromium(Ⅱ) chloride; the three-coordinate Cr(Ⅱ) ions form a {Cr2Cl2} rhombic core via two Cl-bridges. The improved iCAS method (imposed automatic selection and localization of complete active spaces) was used to calculate the molecular orbitals of 3 and 4 to logically describe the strongly correlated systems of electrons of the low-coordinate sphere of transition metals. The calculation shows that the bonding contribution of 3 mainly consists of the two Fe—N σ bonds, and the charge of Fe (+1.03) and N (-1.21) confirms a strong ionic coordination environment. The Fe—N π-bonding is not evident. The quintuplet high-spin Fe has one doubly occupied orbital and four singly occupied orbitals, originating from the 3d orbitals of Fe. The six fully occupied molecular orbitals of 4 correspond to two Cr—N σ bonds, two p-type lone pairs on Cl atoms, and two p-type lone pairs on N atoms. Two Cr atoms have eight high-energy d electrons, each in a singly occupied active orbital, and one of them exhibits Cr…Cr interaction.
2025, 41(7): 1294-1300
doi: 10.11862/CJIC.20250080
Abstract:
The crystalline material (MV)2[HPWⅤ2WⅥ10O40]·2H2O achieved from 1, 1′-dimethyl 4, 4′-bipyridine (methyl viologen, MV) dichloride and Keggin-type polyoxometalate unit, was used as a highly efficient catalyst for the synthesis of β-amino alcohols under organic solvent-free and room temperature conditions. Experimental results showed that the catalyst could efficiently accelerate the synthesis of β-amino alcohols while maintaining its stability. It could be reused six times and there was no significant decrease in its catalytic activity, indicating its certain recyclability. Compared with traditional synthetic methods, this system demonstrated its advantages in organic solvent-free, mild experimental conditions, simple procedures, and environmentally friendly conditions.
The crystalline material (MV)2[HPWⅤ2WⅥ10O40]·2H2O achieved from 1, 1′-dimethyl 4, 4′-bipyridine (methyl viologen, MV) dichloride and Keggin-type polyoxometalate unit, was used as a highly efficient catalyst for the synthesis of β-amino alcohols under organic solvent-free and room temperature conditions. Experimental results showed that the catalyst could efficiently accelerate the synthesis of β-amino alcohols while maintaining its stability. It could be reused six times and there was no significant decrease in its catalytic activity, indicating its certain recyclability. Compared with traditional synthetic methods, this system demonstrated its advantages in organic solvent-free, mild experimental conditions, simple procedures, and environmentally friendly conditions.
2025, 41(7): 1301-1308
doi: 10.11862/CJIC.20250064
Abstract:
A fluorescence quenching probe (THI) for visually detecting hydrazine (N2H4) was synthesized and characterized by Knoevenagel condensation reaction using pyrazole derivatives as fluorescent groups. Spectroscopic studies revealed that, under optimal excitation and emission wavelengths, the THI exhibited high selectivity and sensitivity toward N2H4, maintaining excellent anti-interference performance even in the presence of various analytes. Additionally, the THI demonstrated ultrafast response time (18 s), attributed to the efficient nucleophilic addition reaction between its optimized molecular recognition site and N2H4. The detection limit for N2H4 was determined to be 0.141 μmol·L-1, meeting the requirements for trace-level analysis. The detection mechanism, verified by mass spectrometry and density functional theory calculations, is ascribed to N2H4-induced intramolecular charge transfer (ICT), leading to fluorescence quenching. Furthermore, THI was successfully fabricated into test strips for the quantitative detection of N2H4 and applied for fluorescence imaging of N2H4 in HeLa cells.
A fluorescence quenching probe (THI) for visually detecting hydrazine (N2H4) was synthesized and characterized by Knoevenagel condensation reaction using pyrazole derivatives as fluorescent groups. Spectroscopic studies revealed that, under optimal excitation and emission wavelengths, the THI exhibited high selectivity and sensitivity toward N2H4, maintaining excellent anti-interference performance even in the presence of various analytes. Additionally, the THI demonstrated ultrafast response time (18 s), attributed to the efficient nucleophilic addition reaction between its optimized molecular recognition site and N2H4. The detection limit for N2H4 was determined to be 0.141 μmol·L-1, meeting the requirements for trace-level analysis. The detection mechanism, verified by mass spectrometry and density functional theory calculations, is ascribed to N2H4-induced intramolecular charge transfer (ICT), leading to fluorescence quenching. Furthermore, THI was successfully fabricated into test strips for the quantitative detection of N2H4 and applied for fluorescence imaging of N2H4 in HeLa cells.
2025, 41(7): 1309-1317
doi: 10.11862/CJIC.20250043
Abstract:
A two-dimensional copper tetrakis(4-carboxyphenyl)porphyrin (Cu-TCPP, H2TCPP=tetra(4-carboxyphenyl)porphyrin) nanosheet was synthesized via a one-step hydrothermal method, and a Cu-TCPP/AgNWs composite electrode was constructed through a spray coating process. The combination of Cu-TCPP and AgNWs facilitated rapid electron transfer, enhancing the electrochemical performance of flexible transparent supercapacitors (FTSCs). Experimental results showed that the Cu-TCPP/AgNWs-based FTSCs achieved a specific areal capacitance of 5.96 mF·cm-2 with a transmittance of 58.6%. Furthermore, after 180° bending and folding, the capacitance retention remained as high as 87%, demonstrating excellent mechanical flexibility.
A two-dimensional copper tetrakis(4-carboxyphenyl)porphyrin (Cu-TCPP, H2TCPP=tetra(4-carboxyphenyl)porphyrin) nanosheet was synthesized via a one-step hydrothermal method, and a Cu-TCPP/AgNWs composite electrode was constructed through a spray coating process. The combination of Cu-TCPP and AgNWs facilitated rapid electron transfer, enhancing the electrochemical performance of flexible transparent supercapacitors (FTSCs). Experimental results showed that the Cu-TCPP/AgNWs-based FTSCs achieved a specific areal capacitance of 5.96 mF·cm-2 with a transmittance of 58.6%. Furthermore, after 180° bending and folding, the capacitance retention remained as high as 87%, demonstrating excellent mechanical flexibility.
2025, 41(7): 1318-1330
doi: 10.11862/CJIC.20250001
Abstract:
A direct Z-scheme 3D Bi2MoO6/Bi2S3 heterojunction with excellent photocatalytic performance for hydrogen (H2) production from water splitting was successfully fabricated by a simple hydrothermal ion exchange method. The composition, morphology, and microstructure were systematically characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), and N2 adsorption-desorption test. The results showed that the small solubility product of Bi2S3 is conducive to the in-situ conversion of Bi2MoO6 to Bi2S3, and the porous microsphere structure of Bi2MoO6 is conducive to ion transport, so it is easy to form multi-site heterojunctions. UV-Vis-NIR diffuse reflectance spectra (DRS) indicates that the composite harvests a wide range of solar spectrum up to 1 800 nm. Photoluminescence, transient photocurrent response, and electrochemical impedance spectra confirm an accelerated charge generation and migration. The heterojunction overcame the low conduction band potential of bare Bi2MoO6 and the optimal photocatalytic H2 production rate reached 109.0 μmol·g-1·h-1 without using any noble metal cocatalyst. Based on DRS and Mott-Schottky measurements, it can be reasonably deduced that a Z-scheme heterojunction was constructed between Bi2MoO6 and Bi2S3.
A direct Z-scheme 3D Bi2MoO6/Bi2S3 heterojunction with excellent photocatalytic performance for hydrogen (H2) production from water splitting was successfully fabricated by a simple hydrothermal ion exchange method. The composition, morphology, and microstructure were systematically characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), and N2 adsorption-desorption test. The results showed that the small solubility product of Bi2S3 is conducive to the in-situ conversion of Bi2MoO6 to Bi2S3, and the porous microsphere structure of Bi2MoO6 is conducive to ion transport, so it is easy to form multi-site heterojunctions. UV-Vis-NIR diffuse reflectance spectra (DRS) indicates that the composite harvests a wide range of solar spectrum up to 1 800 nm. Photoluminescence, transient photocurrent response, and electrochemical impedance spectra confirm an accelerated charge generation and migration. The heterojunction overcame the low conduction band potential of bare Bi2MoO6 and the optimal photocatalytic H2 production rate reached 109.0 μmol·g-1·h-1 without using any noble metal cocatalyst. Based on DRS and Mott-Schottky measurements, it can be reasonably deduced that a Z-scheme heterojunction was constructed between Bi2MoO6 and Bi2S3.
2025, 41(7): 1331-1337
doi: 10.11862/CJIC.20240461
Abstract:
In this study, a fluorescent probe, CDAS, was synthesized to detect reduced glutathione (GSH). CDAS was designed by incorporating triphenylamine as an electron-donating group and a 2, 4-dinitrobenzenesulfonyl moiety as an electron-withdrawing group, with the response mechanism based on intramolecular charge transfer (ICT). These components were linked through Knoevenagel condensation. The probe exhibited no fluorescence; however, upon interaction with GSH, a nucleophilic substitution reaction occurred between GSH and probe CDAS, significantly enhancing fluorescent intensity at 561 nm. In a mixture of phosphate-buffered saline (PBS) and acetonitrile (1∶1, V/V, 10 mmol·L-1, pH=7.4), CDAS demonstrated a low detection limit of 7.70 μmol·L-1, high selectivity for GSH, and a large Stokes shift of 179 nm. Notably, CDAS can be effectively utilized to detect GSH in human cervical cancer cells (HeLa cells) via fluorescent cell imaging.
In this study, a fluorescent probe, CDAS, was synthesized to detect reduced glutathione (GSH). CDAS was designed by incorporating triphenylamine as an electron-donating group and a 2, 4-dinitrobenzenesulfonyl moiety as an electron-withdrawing group, with the response mechanism based on intramolecular charge transfer (ICT). These components were linked through Knoevenagel condensation. The probe exhibited no fluorescence; however, upon interaction with GSH, a nucleophilic substitution reaction occurred between GSH and probe CDAS, significantly enhancing fluorescent intensity at 561 nm. In a mixture of phosphate-buffered saline (PBS) and acetonitrile (1∶1, V/V, 10 mmol·L-1, pH=7.4), CDAS demonstrated a low detection limit of 7.70 μmol·L-1, high selectivity for GSH, and a large Stokes shift of 179 nm. Notably, CDAS can be effectively utilized to detect GSH in human cervical cancer cells (HeLa cells) via fluorescent cell imaging.
2025, 41(7): 1338-1350
doi: 10.11862/CJIC.20240428
Abstract:
The dyshomeostasis of metal ions is one of the pathogeneses of Alzheimer′s disease (AD), and metal chelation therapy is a promising approach for the treatment of AD. In this work, three glucose-modified bis-Schiff bases were designed and synthesized. Their biological activities in treating AD in vitro were measured by turbidity assay, HRP/Amplex Red assay, fluorescent probe of DCFH-DA, NBT analysis, and MTT assay. The results were compared with cliquinol (CQ) and non-glucose-modified analogues. It was found that the glucose modified bis-Schiff bases had more efficient bio-activities in inhibiting metal ions (Cu2+, Zn2+) induced Aβ1-40 aggregation, decreasing the level of reactive oxygen species (ROS) in Cu2+-Aβ treated PC 12 cells, increasing the activity of superoxide dismutase in Cu2+-Aβ treated PC 12 cells and attenuating the cytotoxicity mediated by metal ions induced Aβ aggregation than CQ. The toxicity of glucose-modified bis-Schiff bases was lower than that of non-glucose functionalized analogues. The bio-activities of glucose-modified bis-Schiff bases on anti-oxidative and improving the survival rate of PC12 cells treated with Aβ and metal ions, were superior to those of non-glucose-modified analogues.
The dyshomeostasis of metal ions is one of the pathogeneses of Alzheimer′s disease (AD), and metal chelation therapy is a promising approach for the treatment of AD. In this work, three glucose-modified bis-Schiff bases were designed and synthesized. Their biological activities in treating AD in vitro were measured by turbidity assay, HRP/Amplex Red assay, fluorescent probe of DCFH-DA, NBT analysis, and MTT assay. The results were compared with cliquinol (CQ) and non-glucose-modified analogues. It was found that the glucose modified bis-Schiff bases had more efficient bio-activities in inhibiting metal ions (Cu2+, Zn2+) induced Aβ1-40 aggregation, decreasing the level of reactive oxygen species (ROS) in Cu2+-Aβ treated PC 12 cells, increasing the activity of superoxide dismutase in Cu2+-Aβ treated PC 12 cells and attenuating the cytotoxicity mediated by metal ions induced Aβ aggregation than CQ. The toxicity of glucose-modified bis-Schiff bases was lower than that of non-glucose functionalized analogues. The bio-activities of glucose-modified bis-Schiff bases on anti-oxidative and improving the survival rate of PC12 cells treated with Aβ and metal ions, were superior to those of non-glucose-modified analogues.
2025, 41(7): 1351-1360
doi: 10.11862/CJIC.20240427
Abstract:
To accurately detect epinephrine (EP), in this work, three lanthanide terbium complexes (α-Tb-CCP, β-Tb-CCP, and γ-Tb-CCP) as cathode electrochemiluminescence (ECL) luminophores were synthesized via a simple hydrothermal synthesis method, and the β-Tb-CCP with the highest ECL intensity was chosen. The highest ECL signal of β-Tb-CCP is mainly attributed to its small size and surface aperture. Finally, a sensitive ECL sensor for EP detection was constructed with β-Tb-CCP as the luminophore, EP as the signal quencher, and flower-shaped zinc oxide as the ECL signal stabilizer and co-reaction accelerator. In a range of 0.1 pmol·L-1 to 10 mmol·L-1, the ECL intensity difference ΔI (ΔI=I0-I, where I0 and I correspond to the blank ECL intensity without EP and with EP, respectively) showed a good quantitative linear relationship with the logarithm of EP concentration (lg c). The linear equation was ΔI=684.3lg c+9 443.0 (R2=0.9978), and the detection limit was 18.2 fmol·L-1 (S/N=3). In addition, the detection results of EP hydrochloride injection were 0.954 mg: 1 mL and 4.883 mg: 5 mL, which were close to the declared EP contents in the injection.
To accurately detect epinephrine (EP), in this work, three lanthanide terbium complexes (α-Tb-CCP, β-Tb-CCP, and γ-Tb-CCP) as cathode electrochemiluminescence (ECL) luminophores were synthesized via a simple hydrothermal synthesis method, and the β-Tb-CCP with the highest ECL intensity was chosen. The highest ECL signal of β-Tb-CCP is mainly attributed to its small size and surface aperture. Finally, a sensitive ECL sensor for EP detection was constructed with β-Tb-CCP as the luminophore, EP as the signal quencher, and flower-shaped zinc oxide as the ECL signal stabilizer and co-reaction accelerator. In a range of 0.1 pmol·L-1 to 10 mmol·L-1, the ECL intensity difference ΔI (ΔI=I0-I, where I0 and I correspond to the blank ECL intensity without EP and with EP, respectively) showed a good quantitative linear relationship with the logarithm of EP concentration (lg c). The linear equation was ΔI=684.3lg c+9 443.0 (R2=0.9978), and the detection limit was 18.2 fmol·L-1 (S/N=3). In addition, the detection results of EP hydrochloride injection were 0.954 mg: 1 mL and 4.883 mg: 5 mL, which were close to the declared EP contents in the injection.
2025, 41(7): 1361-1370
doi: 10.11862/CJIC.20240415
Abstract:
In this study, boric and benzoic acid (BZA) were used as precursors to synthesize boron- doped room-temperature phosphorescent carbon quantum dots (B - CQDs - BZA) through a one-step pyrolysis process. The morphology, structure, and luminescent properties of B-CQDs-BZA were characterized using transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), ultraviolet-visible (UV-Vis) spectroscopy absorption, fluorescence, and phosphorescence spectroscopy. The results demonstrated that the synthesized B-CQDs-BZA primarily consisted of amorphous carbon, with a particle size ranging from 2.0 to 4.5 nm. Upon irradiation with ultraviolet light at 254 or 302 nm, B-CQDs-BZA exhibited a blue phosphorescence signal that persisted for up to 20 s, with a measured lifetime as long as 2.09 s. This method is simple, rapid, and universally applicable, enabling the synthesis of room - temperature phosphorescent CQDs from diverse precursor materials. Leveraging the exceptional room-temperature phosphorescence lifetime of B-CQDs-BZA, these materials can be effectively employed in time - resolved anti - counterfeiting and information encryption. Moreover, based on the quenching effect of water on B-CQDs-BZA, these materials can be further utilized for determining environmental humidity.
In this study, boric and benzoic acid (BZA) were used as precursors to synthesize boron- doped room-temperature phosphorescent carbon quantum dots (B - CQDs - BZA) through a one-step pyrolysis process. The morphology, structure, and luminescent properties of B-CQDs-BZA were characterized using transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), ultraviolet-visible (UV-Vis) spectroscopy absorption, fluorescence, and phosphorescence spectroscopy. The results demonstrated that the synthesized B-CQDs-BZA primarily consisted of amorphous carbon, with a particle size ranging from 2.0 to 4.5 nm. Upon irradiation with ultraviolet light at 254 or 302 nm, B-CQDs-BZA exhibited a blue phosphorescence signal that persisted for up to 20 s, with a measured lifetime as long as 2.09 s. This method is simple, rapid, and universally applicable, enabling the synthesis of room - temperature phosphorescent CQDs from diverse precursor materials. Leveraging the exceptional room-temperature phosphorescence lifetime of B-CQDs-BZA, these materials can be effectively employed in time - resolved anti - counterfeiting and information encryption. Moreover, based on the quenching effect of water on B-CQDs-BZA, these materials can be further utilized for determining environmental humidity.
2025, 41(7): 1371-1379
doi: 10.11862/CJIC.20240401
Abstract:
The electronic structure and optical properties of Au and I monodoped and co-doped double perovskite Cs2NaBiCl6 were studied using the first-principles method based on density functional theory. The results showed that when Au was mono-doped with Cs2NaBiCl6 by replacing Na at a ratio of 0.25, the band gap of the doped struc-ture decreased significantly, reaching a minimum of 1.86 eV. The band gap of the single-doped structure decreased with increased doping concentration. Compared to the pre-doping state, the absorption spectra of various concentra- tions of Au and I monodoped structures exhibited a redshift. The co-doping of Au and I resulted in a reduced band gap. Among them, when Au and I were uniformly adjacent to each other in the Cs2NaBiCl6 crystal, the band gap of the co-doped structure was the smallest, the light absorption capacity in the visible light region of 400-700 nm was the strongest, and the utilization rate of visible light was the highest.
The electronic structure and optical properties of Au and I monodoped and co-doped double perovskite Cs2NaBiCl6 were studied using the first-principles method based on density functional theory. The results showed that when Au was mono-doped with Cs2NaBiCl6 by replacing Na at a ratio of 0.25, the band gap of the doped struc-ture decreased significantly, reaching a minimum of 1.86 eV. The band gap of the single-doped structure decreased with increased doping concentration. Compared to the pre-doping state, the absorption spectra of various concentra- tions of Au and I monodoped structures exhibited a redshift. The co-doping of Au and I resulted in a reduced band gap. Among them, when Au and I were uniformly adjacent to each other in the Cs2NaBiCl6 crystal, the band gap of the co-doped structure was the smallest, the light absorption capacity in the visible light region of 400-700 nm was the strongest, and the utilization rate of visible light was the highest.
2025, 41(7): 1380-1386
doi: 10.11862/CJIC.20240378
Abstract:
The nickel foam (NF)-supported MnCoNi layered double hydroxide (LDH) nano-needle array was used as a substrate. Through a three-step wet-chemical route, a Co-Ni-S polymetallic sulfide-supported MnCoNi LDH@Co-Ni-S/NF amorphous hollow-polyhedral nanocomposite was successfully synthesized, demonstrating outstanding electrocatalytic oxygen evolution performance. The results of electrochemical tests showed that the material could output a current density of 50 mA·cm-2 with an overpotential of only 248 mV in a 1.0 mol·L-1 KOH solution. In addition, the constructed MnCoNi LDH@Co-Ni-S hollow polyhedral electrode could operate continuously and stably for at least 20 h under different current densities of 40, 60, and 80 mA·cm-2, fully demonstrating that this electrode had good long-term stability.
The nickel foam (NF)-supported MnCoNi layered double hydroxide (LDH) nano-needle array was used as a substrate. Through a three-step wet-chemical route, a Co-Ni-S polymetallic sulfide-supported MnCoNi LDH@Co-Ni-S/NF amorphous hollow-polyhedral nanocomposite was successfully synthesized, demonstrating outstanding electrocatalytic oxygen evolution performance. The results of electrochemical tests showed that the material could output a current density of 50 mA·cm-2 with an overpotential of only 248 mV in a 1.0 mol·L-1 KOH solution. In addition, the constructed MnCoNi LDH@Co-Ni-S hollow polyhedral electrode could operate continuously and stably for at least 20 h under different current densities of 40, 60, and 80 mA·cm-2, fully demonstrating that this electrode had good long-term stability.
2025, 41(7): 1387-1396
doi: 10.11862/CJIC.20240384
Abstract:
Using ammonium persulfate - initiated in - situ polymerization of pyrrole monomer to form a three- dimensional porous aerogel as the carrier, and ferrocene as the metal precursor, a series of Fe/N/C catalysts with different iron loadings were prepared via high-temperature pyrolysis under argon atmosphere. The results demonstrated that the aerogel-supported catalysts exhibited excellent oxygen reduction reaction (ORR) activity and stabili- ty in acidic media. The optimal catalyst performance was achieved when the ferrocene loading was 12 mg, showing a half-wave potential of 0.691 V (vs RHE) and an average electron transfer number of 3.97, indicating a reaction pathway approaching the ideal four-electron process. Moreover, after 10 000 cycles of cyclic voltammetry testing, the half -wave potential of this catalyst only decayed by 11 mV, highlighting its superior electrochemical durability.
Using ammonium persulfate - initiated in - situ polymerization of pyrrole monomer to form a three- dimensional porous aerogel as the carrier, and ferrocene as the metal precursor, a series of Fe/N/C catalysts with different iron loadings were prepared via high-temperature pyrolysis under argon atmosphere. The results demonstrated that the aerogel-supported catalysts exhibited excellent oxygen reduction reaction (ORR) activity and stabili- ty in acidic media. The optimal catalyst performance was achieved when the ferrocene loading was 12 mg, showing a half-wave potential of 0.691 V (vs RHE) and an average electron transfer number of 3.97, indicating a reaction pathway approaching the ideal four-electron process. Moreover, after 10 000 cycles of cyclic voltammetry testing, the half -wave potential of this catalyst only decayed by 11 mV, highlighting its superior electrochemical durability.
2025, 41(7): 1397-1408
doi: 10.11862/CJIC.20250028
Abstract:
A flower-like BiOBr photocatalyst (CS/BiOBr) was prepared by using the carbon material derived from corn straw (CS) as the carrier. The prepared composites were characterized by X - ray diffraction (XRD), Fourier transform infrared (FIIR) spectra, scanning electron microscope (SEM), X - ray photoelectron spectra (XPS), and UV-Vis diffuse reflectance spectra (UV-Vis DRS). The SEM analyses indicate that the introduction of CS promotes the formation of a unique flower-like structure in BiOBr, which not only optimizes the efficiency of light capture but also increases the specific surface area of BiOBr. The bandgap of the composite was narrower compared with the pure BiOBr. The CS/BiOBr composites exhibited higher photocatalytic activity than pure CS and BiOBr under visible light irradiation, and a higher first-order reaction rate constant (k) of 0.043 7 min-1 than BiOBr (0.014 6 min-1), and exhibited excellent stability and reusability during the cyclic run. The enhanced photocatalytic activity is attributed to the efficient separation of photoinduced electrons and holes. Superoxide radicals and holes were the major active species.
A flower-like BiOBr photocatalyst (CS/BiOBr) was prepared by using the carbon material derived from corn straw (CS) as the carrier. The prepared composites were characterized by X - ray diffraction (XRD), Fourier transform infrared (FIIR) spectra, scanning electron microscope (SEM), X - ray photoelectron spectra (XPS), and UV-Vis diffuse reflectance spectra (UV-Vis DRS). The SEM analyses indicate that the introduction of CS promotes the formation of a unique flower-like structure in BiOBr, which not only optimizes the efficiency of light capture but also increases the specific surface area of BiOBr. The bandgap of the composite was narrower compared with the pure BiOBr. The CS/BiOBr composites exhibited higher photocatalytic activity than pure CS and BiOBr under visible light irradiation, and a higher first-order reaction rate constant (k) of 0.043 7 min-1 than BiOBr (0.014 6 min-1), and exhibited excellent stability and reusability during the cyclic run. The enhanced photocatalytic activity is attributed to the efficient separation of photoinduced electrons and holes. Superoxide radicals and holes were the major active species.
2025, 41(7): 1409-1415
doi: 10.11862/CJIC.20250065
Abstract:
2‐substituted‐1‐amino‐o‐carboranes 2‐R‐1‐NH2‐ o‐C2B10H10 (R=CH3, 1a; R=Ph, 1b) were synthesized and the reactions of these compounds with the yttrium dialkyl complex [Y(L)(CH2SiMe3)2] (L=[2‐(2, 5‐Me2C4H2N)C6H4NC(Ph)=NDipp]-, Dipp=2, 6‐iPr2C6H3) were investigated. The 1H NMR spectroscopy indicate that the reaction of ytrrium dialkyl complex with one equivalent of 2‐R‐1‐NH2‐ o‐C2B10H10 produce the mixture of ytrrium alkyl‐amido complex [Y(L)(2‐R‐1‐NH‐ o‐C2B10H10)(CH2SiMe3)] (R=CH3, 2a; R=Ph, 2b) and bis(amido) complex [Y(L)(2‐R‐1‐NH‐ o‐C2B10H10)2] (R=CH3, 3a; R=Ph, 3b). The yttrium bridging imido complex [Y(L)(2‐CH3‐1‐N‐ o‐C2B10H10)]2 (4a) was obtained by heating the mixture at 55 ℃ for 12 h. Complex 3a was isolated and characterized by treating the yttrium dialkyl complex with two equivalents of 1a. The structures of complexes 3a and 4a were verified by single‐crystal X‐ray diffraction..
2‐substituted‐1‐amino‐o‐carboranes 2‐R‐1‐NH2‐ o‐C2B10H10 (R=CH3, 1a; R=Ph, 1b) were synthesized and the reactions of these compounds with the yttrium dialkyl complex [Y(L)(CH2SiMe3)2] (L=[2‐(2, 5‐Me2C4H2N)C6H4NC(Ph)=NDipp]-, Dipp=2, 6‐iPr2C6H3) were investigated. The 1H NMR spectroscopy indicate that the reaction of ytrrium dialkyl complex with one equivalent of 2‐R‐1‐NH2‐ o‐C2B10H10 produce the mixture of ytrrium alkyl‐amido complex [Y(L)(2‐R‐1‐NH‐ o‐C2B10H10)(CH2SiMe3)] (R=CH3, 2a; R=Ph, 2b) and bis(amido) complex [Y(L)(2‐R‐1‐NH‐ o‐C2B10H10)2] (R=CH3, 3a; R=Ph, 3b). The yttrium bridging imido complex [Y(L)(2‐CH3‐1‐N‐ o‐C2B10H10)]2 (4a) was obtained by heating the mixture at 55 ℃ for 12 h. Complex 3a was isolated and characterized by treating the yttrium dialkyl complex with two equivalents of 1a. The structures of complexes 3a and 4a were verified by single‐crystal X‐ray diffraction..
2025, 41(7): 1416-1426
doi: 10.11862/CJIC.20250018
Abstract:
Four new coordination polymers, {[Cd(mbtx)(4OHphCOO)]NO3}n (1), {[Zn(mbtx)(1, 4‐bdc)0.5(H2O)2]·(1, 4‐bdc)0.5·4H2O}n (2), {[Cd2(mbtx)(5NO2‐bdc)2(H2O)3]·4.5H2O}n (3), and {[Zn(H2O)6][Zn2(mbtx)2(btc)2(H2O)4]·2H2O}n (4) (mbtx=1, 3‐bis(4H‐1, 2, 4‐triazole)benzene, 4OHphCOO-=p‐hydroxybenzoate, 1, 4‐bdc2-=1, 4‐benzenedicarboxylate, 5NO2‐bdc2-=5‐nitro‐isophthalate, btc3-=1, 3, 5‐benzenetricarboxylate), were synthesized under room temperature condition and characterized by single‐crystal X‐ray diffraction, elemental analyses, and powder X‐ray diffraction. Single‐crystal X‐ray structural analysis shows that complexes 1 and 3 are 2D networks. In 1, the adjacent 2D networks are linked to a 3D network by π‐π stacking interaction. 2 and 4 exhibit 1D chains, and the 1D chains are connected into a 3D network by π‐π stacking interaction and intermolecular hydrogen bond. Luminescence and thermogravimetric analysis of the four complexes were discussed.
Four new coordination polymers, {[Cd(mbtx)(4OHphCOO)]NO3}n (1), {[Zn(mbtx)(1, 4‐bdc)0.5(H2O)2]·(1, 4‐bdc)0.5·4H2O}n (2), {[Cd2(mbtx)(5NO2‐bdc)2(H2O)3]·4.5H2O}n (3), and {[Zn(H2O)6][Zn2(mbtx)2(btc)2(H2O)4]·2H2O}n (4) (mbtx=1, 3‐bis(4H‐1, 2, 4‐triazole)benzene, 4OHphCOO-=p‐hydroxybenzoate, 1, 4‐bdc2-=1, 4‐benzenedicarboxylate, 5NO2‐bdc2-=5‐nitro‐isophthalate, btc3-=1, 3, 5‐benzenetricarboxylate), were synthesized under room temperature condition and characterized by single‐crystal X‐ray diffraction, elemental analyses, and powder X‐ray diffraction. Single‐crystal X‐ray structural analysis shows that complexes 1 and 3 are 2D networks. In 1, the adjacent 2D networks are linked to a 3D network by π‐π stacking interaction. 2 and 4 exhibit 1D chains, and the 1D chains are connected into a 3D network by π‐π stacking interaction and intermolecular hydrogen bond. Luminescence and thermogravimetric analysis of the four complexes were discussed.
2025, 41(7): 1427-1438
doi: 10.11862/CJIC.20240431
Abstract:
Hydroxyapatite nanoparticles (HAP NPs) were synthesized by a one‐step hydrothermal method. The surface of HAP NPs was grafted —SH and —COOH chelating groups via in situ surface‐modification with iminodiacetic acid (IDA) and 3‐mercaptopropyl trimethoxysilane (MPS) to afford dual surface‐capped nano‐amendment HAP‐IDA/MPS. The structure of HAP‐IDA/MPS was characterized, and its adsorption performance for Hg2+, Cu2+, Zn2+, Ni2+, Co2+, and Cd2+ was evaluated. The total adsorption capacity of 0.10 g HAP‐IDA/MPS nano‐amendment for Hg2+, Cu2+, Zn2+, Ni2+, Co2+, and Cd2+ with an initial mass concentration of 20 mg·L-1 reached 13.7 mg·g-1, about 4.3 times as much as that of HAP. Notably, HAP‐IDA/MPS nano‐amendment displayed the highest immobilization rate for Hg2+, possibly because of its chemical reaction with —SH to form sulfide, possessing the lowest solubility product constant among a variety of metal sulfides.
Hydroxyapatite nanoparticles (HAP NPs) were synthesized by a one‐step hydrothermal method. The surface of HAP NPs was grafted —SH and —COOH chelating groups via in situ surface‐modification with iminodiacetic acid (IDA) and 3‐mercaptopropyl trimethoxysilane (MPS) to afford dual surface‐capped nano‐amendment HAP‐IDA/MPS. The structure of HAP‐IDA/MPS was characterized, and its adsorption performance for Hg2+, Cu2+, Zn2+, Ni2+, Co2+, and Cd2+ was evaluated. The total adsorption capacity of 0.10 g HAP‐IDA/MPS nano‐amendment for Hg2+, Cu2+, Zn2+, Ni2+, Co2+, and Cd2+ with an initial mass concentration of 20 mg·L-1 reached 13.7 mg·g-1, about 4.3 times as much as that of HAP. Notably, HAP‐IDA/MPS nano‐amendment displayed the highest immobilization rate for Hg2+, possibly because of its chemical reaction with —SH to form sulfide, possessing the lowest solubility product constant among a variety of metal sulfides.
2025, 41(7): 1439-1444
doi: 10.11862/CJIC.20240376
Abstract:
Under the condition of solvothermal synthesis, the viologen ligand 1, 1′‐bis(3‐carboxyphenyl)‐(4, 4′‐bipyri‐ dine) dichloride (H2bcbpy·2Cl) and KI are coordinated with the metal cadmium ions. A case of thermochromic coor‐ dination polymer [Cd(bcbpy)I2] ·2H2O (1) was constructed. Complex 1 displays a 1D chain structure and exhibits thermochromic behavior. Under different temperature stimulation, the complex (ground) slowly changed from green to yellow‐green, and with the increase of temperature, the color of complex 1 gradually deepened, and finally became orange‐yellow. Therefore, complex 1 was prepared as a thermochromic film. In addition, we also performed electrochemical tests on complex 1, which showed that the complex is a semiconductor material.
Under the condition of solvothermal synthesis, the viologen ligand 1, 1′‐bis(3‐carboxyphenyl)‐(4, 4′‐bipyri‐ dine) dichloride (H2bcbpy·2Cl) and KI are coordinated with the metal cadmium ions. A case of thermochromic coor‐ dination polymer [Cd(bcbpy)I2] ·2H2O (1) was constructed. Complex 1 displays a 1D chain structure and exhibits thermochromic behavior. Under different temperature stimulation, the complex (ground) slowly changed from green to yellow‐green, and with the increase of temperature, the color of complex 1 gradually deepened, and finally became orange‐yellow. Therefore, complex 1 was prepared as a thermochromic film. In addition, we also performed electrochemical tests on complex 1, which showed that the complex is a semiconductor material.
2025, 41(7): 1445-1464
doi: 10.11862/CJIC.20240345
Abstract:
CsxWO3/TiO2 composites with full‐spectrum catalytic activity were prepared by solvothermal reaction. The composites were characterized using X‐ray diffraction (XRD) analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), specific surface area testing, X‐ray photoelectron spectroscopy (XPS), and UV‐Vis diffuse reflectance spectra (UV‐Vis DRS). CsxWO3 and TiO2 were uniformly bonded together in the composites. The heterojunction structure was formed. The band gap was reduced from 2.75 to 2.65 eV. The photocatalytic property of CsxWO3/TiO2 was demonstrated by the degradation rates of 20 mg·L-1 methylene blue dye, which were 99.7%, 91.4%, and 70.7% under irradiation from a 300 W high‐pressure mercury lamp, a 500 W xenon lamp, and a 400 W infrared lamp, respectively. After five cycles of photocatalytic degradation, the composite photocatalyst still showed a degradation efficiency of 87.6%. This indicates that CsxWO3/TiO2 has good photocatalytic degradability and cyclic stability. The photocatalytic mechanism of CsxWO3/TiO2 was investigated. The trapping experiments of the active species showed that the main active substances were the empty hole (h+) and hydroxyl radical (·OH).
CsxWO3/TiO2 composites with full‐spectrum catalytic activity were prepared by solvothermal reaction. The composites were characterized using X‐ray diffraction (XRD) analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), specific surface area testing, X‐ray photoelectron spectroscopy (XPS), and UV‐Vis diffuse reflectance spectra (UV‐Vis DRS). CsxWO3 and TiO2 were uniformly bonded together in the composites. The heterojunction structure was formed. The band gap was reduced from 2.75 to 2.65 eV. The photocatalytic property of CsxWO3/TiO2 was demonstrated by the degradation rates of 20 mg·L-1 methylene blue dye, which were 99.7%, 91.4%, and 70.7% under irradiation from a 300 W high‐pressure mercury lamp, a 500 W xenon lamp, and a 400 W infrared lamp, respectively. After five cycles of photocatalytic degradation, the composite photocatalyst still showed a degradation efficiency of 87.6%. This indicates that CsxWO3/TiO2 has good photocatalytic degradability and cyclic stability. The photocatalytic mechanism of CsxWO3/TiO2 was investigated. The trapping experiments of the active species showed that the main active substances were the empty hole (h+) and hydroxyl radical (·OH).
