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2025 Volume 41 Issue 11
2025, 41(11): 2187-2200
doi: 10.11862/CJIC.20250192
Abstract:
Carboranes, as unique polyhedral boron cluster compounds, exhibit broad application prospects in numerous fields due to their three-dimensional aromatic structures and multicenter, multielectron bonding. However, the B—H bonds in carboranes are inert and pose challenges in regioselectivity, thus making their functionalization a great challenge in synthesis. In recent years, researchers have achieved carborane functionalization by employing light-induced strategies. These studies not only open new avenues for carborane functionalization but also yield a series of functionalized molecules containing carboranyl units, thereby laying a solid foundation for the further advancement of carborane chemistry.
Carboranes, as unique polyhedral boron cluster compounds, exhibit broad application prospects in numerous fields due to their three-dimensional aromatic structures and multicenter, multielectron bonding. However, the B—H bonds in carboranes are inert and pose challenges in regioselectivity, thus making their functionalization a great challenge in synthesis. In recent years, researchers have achieved carborane functionalization by employing light-induced strategies. These studies not only open new avenues for carborane functionalization but also yield a series of functionalized molecules containing carboranyl units, thereby laying a solid foundation for the further advancement of carborane chemistry.
2025, 41(11): 2201-2217
doi: 10.11862/CJIC.20250056
Abstract:
Organic-inorganic hybrid metal halides (OIHMHs) have garnered extensive attention from researchers due to their tunable optoelectronic properties, high fluorescence quantum yield, narrow emission spectra, and ease of fabrication. Various OIHMHs with diverse structures, dimensions, and excellent performance can be synthesized by selecting different organic cation templates. In recent years, significant progress has been made, particularly in the study of low-dimensional OIHMHs optoelectronic materials. Here, we try to provide an in-depth analysis of the crystal structures and synthesis methods of these materials, summarize their optical properties and mechanisms, and review their applications in white-light emitting diodes (WLEDs), X-ray detectors, sensors, and solar cells. Finally, we discuss the current challenges and offer prospects for the future development of these materials, aiming to provide a valuable reference for advancing research and innovation in low-dimensional OIHMHs.
Organic-inorganic hybrid metal halides (OIHMHs) have garnered extensive attention from researchers due to their tunable optoelectronic properties, high fluorescence quantum yield, narrow emission spectra, and ease of fabrication. Various OIHMHs with diverse structures, dimensions, and excellent performance can be synthesized by selecting different organic cation templates. In recent years, significant progress has been made, particularly in the study of low-dimensional OIHMHs optoelectronic materials. Here, we try to provide an in-depth analysis of the crystal structures and synthesis methods of these materials, summarize their optical properties and mechanisms, and review their applications in white-light emitting diodes (WLEDs), X-ray detectors, sensors, and solar cells. Finally, we discuss the current challenges and offer prospects for the future development of these materials, aiming to provide a valuable reference for advancing research and innovation in low-dimensional OIHMHs.
2025, 41(11): 2218-2228
doi: 10.11862/CJIC.20250202
Abstract:
A series of NiAlCex (x=0.1, 0.2, 0.4, 0.6, x was the ratio of the amount of substance of Ni to that of Al and Ce combined) catalysts was prepared with the co-precipitation method and applied for the CO2 methanation. The low-temperature catalytic activity of NiAl catalysts for CO2 methanation improved significantly with the introduction of an appropriate amount of Ce. The CO2 conversion reached 80.6% as x=0.2 under the conditions of 220 ℃, 100 kPa, and weight hourly space velocity of 24 000 mL·g-1·h-1. The incorporation of Ce weakened the Ni-Al interaction, suppressed the formation of NiAl2O4 spinel, and promoted the reduction of NiO species in the catalyst. Furthermore, it increased the specific surface area of metallic Ni, thereby facilitating H2 adsorption and activation, while also enhancing the number of basic sites on the catalyst surface to promote CO2 adsorption and activation. Stability tests demonstrated that the presence of Ce hindered the sintering and agglomeration of Ni species, thereby enhancing the catalyst stability. In‑situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) results revealed that the reaction over NiAl catalyst followed the CO intermediate route, and after introducing Ce into the NiAl catalyst, a dual pathway involving both formate and CO intermediates was observed.
A series of NiAlCex (x=0.1, 0.2, 0.4, 0.6, x was the ratio of the amount of substance of Ni to that of Al and Ce combined) catalysts was prepared with the co-precipitation method and applied for the CO2 methanation. The low-temperature catalytic activity of NiAl catalysts for CO2 methanation improved significantly with the introduction of an appropriate amount of Ce. The CO2 conversion reached 80.6% as x=0.2 under the conditions of 220 ℃, 100 kPa, and weight hourly space velocity of 24 000 mL·g-1·h-1. The incorporation of Ce weakened the Ni-Al interaction, suppressed the formation of NiAl2O4 spinel, and promoted the reduction of NiO species in the catalyst. Furthermore, it increased the specific surface area of metallic Ni, thereby facilitating H2 adsorption and activation, while also enhancing the number of basic sites on the catalyst surface to promote CO2 adsorption and activation. Stability tests demonstrated that the presence of Ce hindered the sintering and agglomeration of Ni species, thereby enhancing the catalyst stability. In‑situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) results revealed that the reaction over NiAl catalyst followed the CO intermediate route, and after introducing Ce into the NiAl catalyst, a dual pathway involving both formate and CO intermediates was observed.
2025, 41(11): 2229-2236
doi: 10.11862/CJIC.20250223
Abstract:
Uniform nanowire-assembled CeVO4 hollow microspheres were fabricated by a simple ethylene glycol (EG)-assisted solvothermal route, in which L-aspartic acid (L-Asp) was adopted as a functional agent and structure director. The as-prepared CeVO4 sample was evaluated as an adsorbent for the removal of organic dyes from aqueous solutions, especially exhibiting excellent removal rate towards the Congo red (CR) dye. The kinetics and thermodynamic data confirmed that the adsorption of CR onto CeVO4 microspheres was well fitted to the pseudo-second- order kinetics and Langmuir isotherm models. Moreover, a removal rate of 78.03% was maintained after four cycles, indicating good chemical stability and durability of the CeVO4 adsorbent. The results suggest that the adsorption of CR molecules on CeVO4 is a result of the synergistic effects of physical adsorption and hydrogen bonding.
Uniform nanowire-assembled CeVO4 hollow microspheres were fabricated by a simple ethylene glycol (EG)-assisted solvothermal route, in which L-aspartic acid (L-Asp) was adopted as a functional agent and structure director. The as-prepared CeVO4 sample was evaluated as an adsorbent for the removal of organic dyes from aqueous solutions, especially exhibiting excellent removal rate towards the Congo red (CR) dye. The kinetics and thermodynamic data confirmed that the adsorption of CR onto CeVO4 microspheres was well fitted to the pseudo-second- order kinetics and Langmuir isotherm models. Moreover, a removal rate of 78.03% was maintained after four cycles, indicating good chemical stability and durability of the CeVO4 adsorbent. The results suggest that the adsorption of CR molecules on CeVO4 is a result of the synergistic effects of physical adsorption and hydrogen bonding.
2025, 41(11): 2237-2250
doi: 10.11862/CJIC.20250137
Abstract:
A series of Tb3+-Eu3+ doped glass-ceramics containing Na8.12Y1.293Si6O18 were prepared. The influence of heat-treatment conditions on the microstructure and luminescent properties was systematically investigated using various characterization techniques, and the optimal heat-treatment condition for luminescence was determined to be 670 ℃ for 90 min. The optimal doping concentration (molar fraction) of Tb3+ was 0.5%, beyond which concentration quenching occurs primarily due to quadrupole-quadrupole interactions. The energy transfer from Tb3+ to Eu3+ was observed in co-doped glass-ceramics. Within the temperature range of 293-493 K, co-doped glass-ceramic exhibited good fluorescence thermal stability with a thermal quenching activation energy of 0.24 eV and a chromaticity shift of 2.1×10-2. Furthermore, this material demonstrated promising temperature sensing capabilities, with a maximum sensitivity of 5.7×10-3 K-1 and a thermal repeatability ratio of 96.6%.
A series of Tb3+-Eu3+ doped glass-ceramics containing Na8.12Y1.293Si6O18 were prepared. The influence of heat-treatment conditions on the microstructure and luminescent properties was systematically investigated using various characterization techniques, and the optimal heat-treatment condition for luminescence was determined to be 670 ℃ for 90 min. The optimal doping concentration (molar fraction) of Tb3+ was 0.5%, beyond which concentration quenching occurs primarily due to quadrupole-quadrupole interactions. The energy transfer from Tb3+ to Eu3+ was observed in co-doped glass-ceramics. Within the temperature range of 293-493 K, co-doped glass-ceramic exhibited good fluorescence thermal stability with a thermal quenching activation energy of 0.24 eV and a chromaticity shift of 2.1×10-2. Furthermore, this material demonstrated promising temperature sensing capabilities, with a maximum sensitivity of 5.7×10-3 K-1 and a thermal repeatability ratio of 96.6%.
2025, 41(11): 2251-2260
doi: 10.11862/CJIC.20250133
Abstract:
Using ZIF-67 as the precursor, nitrogen doped carbon coated Co3O4 nanomaterials were first obtained through high-temperature carbonization and low-temperature air oxidation. Then, by introducing oxygen vacancies (Ov) and phosphorus doping, a dual functional electrocatalyst (Ov-Co3O4/NC-P) with high performance and stability was prepared. Electrochemical test results showed that the prepared Ov-Co3O4/NC-P-50 catalyst had an oxygen evolution overpotential of only 281 mV at a current density of 10 mA·cm-2, and the structure of the material remained relatively intact after the stability test, indicating good stability. The half-wave potential in the oxygen reduction reaction process was 0.813 V, and the assembled Ov-Co3O4/NC-P-50 rechargeable zinc-air battery also had a high-power density (155.02 mW·cm-2), and it could cycle 2 880 times (480 h) during the long-term charge- discharge test.
Using ZIF-67 as the precursor, nitrogen doped carbon coated Co3O4 nanomaterials were first obtained through high-temperature carbonization and low-temperature air oxidation. Then, by introducing oxygen vacancies (Ov) and phosphorus doping, a dual functional electrocatalyst (Ov-Co3O4/NC-P) with high performance and stability was prepared. Electrochemical test results showed that the prepared Ov-Co3O4/NC-P-50 catalyst had an oxygen evolution overpotential of only 281 mV at a current density of 10 mA·cm-2, and the structure of the material remained relatively intact after the stability test, indicating good stability. The half-wave potential in the oxygen reduction reaction process was 0.813 V, and the assembled Ov-Co3O4/NC-P-50 rechargeable zinc-air battery also had a high-power density (155.02 mW·cm-2), and it could cycle 2 880 times (480 h) during the long-term charge- discharge test.
2025, 41(11): 2261-2271
doi: 10.11862/CJIC.20250130
Abstract:
Based on the aggregation-induced self-assembly strategy, the ratiometric red fluorescent silver nanoclusters (PEI/PVP-AgNCs) were developed by employing a one-pot low-heat reaction with silver nitrate (AgNO3), which used the complex as ligands that formed by hydrogen-binding between polyethyleneimine (PEI) and polyethylpyrrolidone (PVP) with abundant amine group and carbonyl group, and 2-mercaptobenzothiazole (MBT) as the aggregation inductive agent. The optical properties and structural morphology of PEI/PVP-AgNCs were characterized. It was found that upon the excitation at 365 nm, PEI/PVP-AgNCs exhibits two fluorescence emission peaks centered at 435 and 610 nm, respectively. Besides, it revealed that the morphology of PEI/PVP-AgNCs was quasi-spherical with an average diameter of 2.0 nm. Interestingly, the fluorescence at 610 nm of PEI/PVP-AgNCs could be effectively quenched with the addition of S2-, owing to the formation of Ag2S between the soft base S2- and the soft acid Ag+ based on the "soft affinity soft" binding principle of the hard-soft-acid-base theory, while no significant change at 435 nm due to the PEI/PVP complex does not react with S2-, thus the fluorescence at 610 nm (F610) can be used as a response signal and the fluorescence at 435 nm (F435) as a reference signal. Based on the above response signal and reference signal, the high selectivity and sensitivity detection of S2- can be achieved by utilizing the fluorescence intensity ratio (F435/F610) of PEI/PVP-AgNCs, which expanded the detection range from 50-350 nmol·L-1 and 720-920 nmol·L-1 with a sensitive detection limit of 1.1 nmol·L-1. From this, PEI/PVP-AgNCs was designed as a paper-based sensor, and it was found that the fluorescence color changed from red to blue under ultraviolet lamp after the S2- interacted with PEI/PVP-AgNCs test strips through the analysis of photos taken with a smartphone, thus the visual colorimetric fluorescence detection of S2- can be realized. Based on the established method, the PEI/PVP-AgNCs were successfully applied to the quantification of S2- content in actual water samples with the recoveries of 98.91%-102.24% and obtained satisfying results. The results show that the ratiometric fluorescent silver nanosensor can be applied to assess environmental water contamination.
Based on the aggregation-induced self-assembly strategy, the ratiometric red fluorescent silver nanoclusters (PEI/PVP-AgNCs) were developed by employing a one-pot low-heat reaction with silver nitrate (AgNO3), which used the complex as ligands that formed by hydrogen-binding between polyethyleneimine (PEI) and polyethylpyrrolidone (PVP) with abundant amine group and carbonyl group, and 2-mercaptobenzothiazole (MBT) as the aggregation inductive agent. The optical properties and structural morphology of PEI/PVP-AgNCs were characterized. It was found that upon the excitation at 365 nm, PEI/PVP-AgNCs exhibits two fluorescence emission peaks centered at 435 and 610 nm, respectively. Besides, it revealed that the morphology of PEI/PVP-AgNCs was quasi-spherical with an average diameter of 2.0 nm. Interestingly, the fluorescence at 610 nm of PEI/PVP-AgNCs could be effectively quenched with the addition of S2-, owing to the formation of Ag2S between the soft base S2- and the soft acid Ag+ based on the "soft affinity soft" binding principle of the hard-soft-acid-base theory, while no significant change at 435 nm due to the PEI/PVP complex does not react with S2-, thus the fluorescence at 610 nm (F610) can be used as a response signal and the fluorescence at 435 nm (F435) as a reference signal. Based on the above response signal and reference signal, the high selectivity and sensitivity detection of S2- can be achieved by utilizing the fluorescence intensity ratio (F435/F610) of PEI/PVP-AgNCs, which expanded the detection range from 50-350 nmol·L-1 and 720-920 nmol·L-1 with a sensitive detection limit of 1.1 nmol·L-1. From this, PEI/PVP-AgNCs was designed as a paper-based sensor, and it was found that the fluorescence color changed from red to blue under ultraviolet lamp after the S2- interacted with PEI/PVP-AgNCs test strips through the analysis of photos taken with a smartphone, thus the visual colorimetric fluorescence detection of S2- can be realized. Based on the established method, the PEI/PVP-AgNCs were successfully applied to the quantification of S2- content in actual water samples with the recoveries of 98.91%-102.24% and obtained satisfying results. The results show that the ratiometric fluorescent silver nanosensor can be applied to assess environmental water contamination.
2025, 41(11): 2272-2282
doi: 10.11862/CJIC.20250117
Abstract:
Herein, we engineered a multifunctional nanoplatform DOX-AuNR@ZnO@SiO2 (DOX=doxorubicin, AuNR=gold nanorod) by integrating photothermal therapy, reactive oxygen species (ROS)-mediated oxidative damage, and chemotherapy. The system was constructed by sequentially decorating AuNR with a ZnO layer for ROS generation and a mesoporous silica (mSiO2) shell for biocompatibility enhancement and DOX loading. The nanocomposite exhibited a well-defined core-shell structure with uniform size, excellent colloidal stability, and favorable bio-compatibility. Under near-infrared (NIR) irradiation, the AuNR core demonstrated remarkable photothermal conversion efficiency (20.85%) and photostability over multiple cycles. NIR-triggered thermal expansion can enhance the release of DOX from mesoporous SiO2. Simultaneously, ZnO-mediated cytotoxic ROS were generated to synergize with photothermal ablation and chemotherapy. In vitro evaluations using HeLa cells revealed triple-modal therapeutic efficacy with superior tumor suppression. The rationally designed nanoplatform successfully integrates chemotherapy, photothermal therapy, and ROS-mediated therapy.
Herein, we engineered a multifunctional nanoplatform DOX-AuNR@ZnO@SiO2 (DOX=doxorubicin, AuNR=gold nanorod) by integrating photothermal therapy, reactive oxygen species (ROS)-mediated oxidative damage, and chemotherapy. The system was constructed by sequentially decorating AuNR with a ZnO layer for ROS generation and a mesoporous silica (mSiO2) shell for biocompatibility enhancement and DOX loading. The nanocomposite exhibited a well-defined core-shell structure with uniform size, excellent colloidal stability, and favorable bio-compatibility. Under near-infrared (NIR) irradiation, the AuNR core demonstrated remarkable photothermal conversion efficiency (20.85%) and photostability over multiple cycles. NIR-triggered thermal expansion can enhance the release of DOX from mesoporous SiO2. Simultaneously, ZnO-mediated cytotoxic ROS were generated to synergize with photothermal ablation and chemotherapy. In vitro evaluations using HeLa cells revealed triple-modal therapeutic efficacy with superior tumor suppression. The rationally designed nanoplatform successfully integrates chemotherapy, photothermal therapy, and ROS-mediated therapy.
2025, 41(11): 2283-2298
doi: 10.11862/CJIC.20250109
Abstract:
The multi-component nitrogen vacancy g-C3N4 (NVCN)/Bi/BiOBr/BiOI heterojunction photocatalytic material was prepared by an in-situ solvothermal method. The composition, morphology, specific surface area, pore structure, defect, and elemental chemical state, as well as the optical and photoelectrochemical properties of the prepared catalyst, were characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N2 adsorption-desorption tests, X-ray photoelectron spectroscopy, photoluminescence spectroscopy, and photoelectrochemical measurements. The absorption ability of the heterojunction for visible and near-infrared light was significantly enhanced owing to the localized surface plasmon resonance effect of the defect and metallic Bi. 90.7% and 78.5% of ciprofloxacin could be decomposed by NVCN/Bi/BiOBr/BiOI within 60 min and 6 h of visible and near-infrared light irradiation, and the corresponding mineralization efficiencies were about 73.1% and 62.1%, respectively. Based on the results of photoelectrochemical measurements and free radical capture experiments, it could be inferred that the boosted full-spectrum catalytic performance of NVCN/Bi/BiOBr/BiOI heterojunction is attributed to the enhanced light absorption, improved separation efficiency, and prolonged lifetime of photogenerated charge carriers, as well as the formation of a double S-scheme charge transfer mechanism.
The multi-component nitrogen vacancy g-C3N4 (NVCN)/Bi/BiOBr/BiOI heterojunction photocatalytic material was prepared by an in-situ solvothermal method. The composition, morphology, specific surface area, pore structure, defect, and elemental chemical state, as well as the optical and photoelectrochemical properties of the prepared catalyst, were characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N2 adsorption-desorption tests, X-ray photoelectron spectroscopy, photoluminescence spectroscopy, and photoelectrochemical measurements. The absorption ability of the heterojunction for visible and near-infrared light was significantly enhanced owing to the localized surface plasmon resonance effect of the defect and metallic Bi. 90.7% and 78.5% of ciprofloxacin could be decomposed by NVCN/Bi/BiOBr/BiOI within 60 min and 6 h of visible and near-infrared light irradiation, and the corresponding mineralization efficiencies were about 73.1% and 62.1%, respectively. Based on the results of photoelectrochemical measurements and free radical capture experiments, it could be inferred that the boosted full-spectrum catalytic performance of NVCN/Bi/BiOBr/BiOI heterojunction is attributed to the enhanced light absorption, improved separation efficiency, and prolonged lifetime of photogenerated charge carriers, as well as the formation of a double S-scheme charge transfer mechanism.
2025, 41(11): 2299-2306
doi: 10.11862/CJIC.20250074
Abstract:
In this paper, Ba3P4O13: Eu2+ was selected as the research object. By substituting Ba2+ with Ca2+, we investigated the effect of Ca2+ doping on the crystalline phase of Ba3P4O13 and further explored its impact on the luminescent properties of the Ba2.991P4O13: 0.009Eu2+ phosphor. Fixing Eu2+ concentration (mass fraction) at 0.3%, we further prepared Ba2.991-3xP4O13: 0.009Eu2+, 3xCa2+ phosphors with different Ca2+ concentrations at 850 ℃. By altering the doping concentration of Ca2+ in the Ba2.991P4O13: 0.009Eu2+ phosphor, we examined its effect on the crystal phase transition of the Ba2.991P4O13: 0.009Eu2+ phosphor, as well as investigated changes in its luminescent properties and thermal stability through room-temperature spectroscopy and variable-temperature spectroscopy tests.
In this paper, Ba3P4O13: Eu2+ was selected as the research object. By substituting Ba2+ with Ca2+, we investigated the effect of Ca2+ doping on the crystalline phase of Ba3P4O13 and further explored its impact on the luminescent properties of the Ba2.991P4O13: 0.009Eu2+ phosphor. Fixing Eu2+ concentration (mass fraction) at 0.3%, we further prepared Ba2.991-3xP4O13: 0.009Eu2+, 3xCa2+ phosphors with different Ca2+ concentrations at 850 ℃. By altering the doping concentration of Ca2+ in the Ba2.991P4O13: 0.009Eu2+ phosphor, we examined its effect on the crystal phase transition of the Ba2.991P4O13: 0.009Eu2+ phosphor, as well as investigated changes in its luminescent properties and thermal stability through room-temperature spectroscopy and variable-temperature spectroscopy tests.
2025, 41(11): 2307-2316
doi: 10.11862/CJIC.20250055
Abstract:
TiO2 was incorporated into the preparation process of the rare-earth long-afterglow luminescent material SrAl2O4: Eu2+, Dy3+, yielding the SrTiO3: Eu3+/SrAl2O4: Eu2+, Dy3+ composite luminescent material co-doped with Eu3+ and Eu2+. The effects of raw material ratios on the material's micromorphology, phase composition, and luminescent properties were investigated. The results indicated that the composite material exhibited an irregular morphology, a porous structure, and agglomeration. With the increase of TiO2 addition amount, the luminescent brightness and afterglow duration of the material were significantly improved. When the TiO2 addition amount was 1 mol, the material showed the optimal red emission at 618 nm, with a brightness of 0.217 cd·m-2 and an afterglow duration of 1 000 s. Doping with Eu2O3 made the luminescent properties first enhance and then tend to stabilize: the emission intensity reached the maximum when the amount of Eu2O3 was 0.015 0 mol, while the afterglow performance was optimal when the amount of Eu2O3 was 0.012 5 mol. The introduction of carbon powder obviously enhanced the emission intensity at 618 nm, with the optimal condition at the amount of 0.001 25 mol, and the afterglow brightness reached 0.011 cd·m-2.
TiO2 was incorporated into the preparation process of the rare-earth long-afterglow luminescent material SrAl2O4: Eu2+, Dy3+, yielding the SrTiO3: Eu3+/SrAl2O4: Eu2+, Dy3+ composite luminescent material co-doped with Eu3+ and Eu2+. The effects of raw material ratios on the material's micromorphology, phase composition, and luminescent properties were investigated. The results indicated that the composite material exhibited an irregular morphology, a porous structure, and agglomeration. With the increase of TiO2 addition amount, the luminescent brightness and afterglow duration of the material were significantly improved. When the TiO2 addition amount was 1 mol, the material showed the optimal red emission at 618 nm, with a brightness of 0.217 cd·m-2 and an afterglow duration of 1 000 s. Doping with Eu2O3 made the luminescent properties first enhance and then tend to stabilize: the emission intensity reached the maximum when the amount of Eu2O3 was 0.015 0 mol, while the afterglow performance was optimal when the amount of Eu2O3 was 0.012 5 mol. The introduction of carbon powder obviously enhanced the emission intensity at 618 nm, with the optimal condition at the amount of 0.001 25 mol, and the afterglow brightness reached 0.011 cd·m-2.
2025, 41(11): 2317-2326
doi: 10.11862/CJIC.20250053
Abstract:
In this study, a nickel foam (NF) was treated by cyclic voltammetry (CV) to obtain nickel oxyhydroxide (NiOOH), which was used as the precursor to construct a gold nanoaggregate/foam nickel composite catalyst (Au/RF100-NF, RF represents the surface roughness of NF after CV treatment). The formation of the NiOOH precursors and Au nanoaggregates synergistically enhances the electrochemical active surface area (ECSA) of the Au/RF100-NF while significantly improving the interfacial charge transfer kinetics, thereby contributing to the boosted glycerol oxidation reaction (GOR) performance. Moreover, the formation of Au nanoaggregates promotes the C—C cleavages during GOR, significantly reducing the Faraday efficiency (FE) for lactate (C3 product) and markedly increasing the FE for C2 and C1 products, such as glycolate and formate, over the Au/RF100-NF catalyst. Finally, pulse electrolysis conditions were applied to inhibit the further conversion of glycolate toward formate. As a result, the Au/RF100-NF catalyst achieved highly selectivity to glycolate with a FE up to ca. 49.1%, which was 1.67 times higher than that of the Au/NF catalyst, where Au nanoparticles were directly deposited onto the NF without the formation of NiOOH.
In this study, a nickel foam (NF) was treated by cyclic voltammetry (CV) to obtain nickel oxyhydroxide (NiOOH), which was used as the precursor to construct a gold nanoaggregate/foam nickel composite catalyst (Au/RF100-NF, RF represents the surface roughness of NF after CV treatment). The formation of the NiOOH precursors and Au nanoaggregates synergistically enhances the electrochemical active surface area (ECSA) of the Au/RF100-NF while significantly improving the interfacial charge transfer kinetics, thereby contributing to the boosted glycerol oxidation reaction (GOR) performance. Moreover, the formation of Au nanoaggregates promotes the C—C cleavages during GOR, significantly reducing the Faraday efficiency (FE) for lactate (C3 product) and markedly increasing the FE for C2 and C1 products, such as glycolate and formate, over the Au/RF100-NF catalyst. Finally, pulse electrolysis conditions were applied to inhibit the further conversion of glycolate toward formate. As a result, the Au/RF100-NF catalyst achieved highly selectivity to glycolate with a FE up to ca. 49.1%, which was 1.67 times higher than that of the Au/NF catalyst, where Au nanoparticles were directly deposited onto the NF without the formation of NiOOH.
2025, 41(11): 2327-2336
doi: 10.11862/CJIC.20250021
Abstract:
Using common inexpensive industrial graphene oxide (GO) as a raw material, N/P co-doped reduced graphene oxide (N/P/rGO) was prepared by pyrolysis of urea and NaH2PO4 at high temperature. The N/P co-doping optimized the electronic structure of rGO and created more active sites. Furthermore, the graphene aerogel with a three-dimensional network structure was constructed by the hydrothermal reduction method, and low-content ruthenium nanoparticles were loaded at the same time, so as to achieve efficient hydrogen evolution catalytic reaction. Benefiting from N/P codoping, three-dimensional graphene aerogel structure, and low content of hyperdispersed ruthenium nanoparticles, Ru/N/P/rGO showed excellent HER catalytic reaction performance and had good pH adaptability. In alkaline conditions, the overpotential of Ru/N/P/rGO at 10 mA·cm-2 was only 9 mV, and the Tafel slope was as low as 42 mV·dec-1, greatly surpassing the performance of commercial Pt/C (30 mV, 10 mA·cm-2). Under acidic conditions, the overpotential of Ru/N/P/rGO at 10 mA·cm-2 was 57 mV, and the Tafel slope was 47 mV·dec-1. It also had a high electrochemically active area and low charge transfer impedance, and its performance was almost identical to that of commercial Pt/C.
Using common inexpensive industrial graphene oxide (GO) as a raw material, N/P co-doped reduced graphene oxide (N/P/rGO) was prepared by pyrolysis of urea and NaH2PO4 at high temperature. The N/P co-doping optimized the electronic structure of rGO and created more active sites. Furthermore, the graphene aerogel with a three-dimensional network structure was constructed by the hydrothermal reduction method, and low-content ruthenium nanoparticles were loaded at the same time, so as to achieve efficient hydrogen evolution catalytic reaction. Benefiting from N/P codoping, three-dimensional graphene aerogel structure, and low content of hyperdispersed ruthenium nanoparticles, Ru/N/P/rGO showed excellent HER catalytic reaction performance and had good pH adaptability. In alkaline conditions, the overpotential of Ru/N/P/rGO at 10 mA·cm-2 was only 9 mV, and the Tafel slope was as low as 42 mV·dec-1, greatly surpassing the performance of commercial Pt/C (30 mV, 10 mA·cm-2). Under acidic conditions, the overpotential of Ru/N/P/rGO at 10 mA·cm-2 was 57 mV, and the Tafel slope was 47 mV·dec-1. It also had a high electrochemically active area and low charge transfer impedance, and its performance was almost identical to that of commercial Pt/C.
2025, 41(11): 2337-2344
doi: 10.11862/CJIC.20250003
Abstract:
Employing the first-principles density functional theory (DFT), an in-depth investigation was conducted into the structure, electronic properties, and CO activity of hydroxylated SiO2(001) surface-supported Con (where n is the number of cobalt atoms, n=1-6) materials [Con/SiO2(001)]. Here, n=1 represents a single Co atom, while n=2-6 denotes Con clusters composed of n Co atoms. The findings revealed that the binding energy (Eb-Co5/SiO2(001)) of Co5/SiO2(001) was the highest at 1.88 eV, suggesting that the Co5 cluster exhibits the greatest stability when interfaced with the SiO2(001). A direct linear correlation (y=0.11x-0.23) was observed in the connection between Eb-Con/SiO2(001) and the average Bader charge (Qave-Bader) of the Con/SiO2(001). The greater Qave-Bader value transferred between the Con clusters and the SiO2 support, the stronger the binding and the higher the structural stability. As the Con cluster size increased, the d band center gradually moved away from the Fermi level, with the d band center energy for the Co5/SiO2(001) being the lowest at -0.96 eV. The most favorable reaction pathway for CO activation on the Co3/SiO2(001) is CO*+H*→CHO*→CH*+O*, with an effective energy barrier of 2.39 eV, whereas for Co5/SiO2(001), the optimal path is CO*→C*+O*, with an effective energy barrier of 1.19 eV, and Co5 cluster, the optimal path is CO*+H*→CHO*→CH*+O*, with an effective energy barrier of 2.72 eV. Notably, the introduction of Co5 clusters onto the hydroxylated SiO2 surface proves to be more conducive to the activation of CO. By employing differential charge analysis and crystal orbital hamilton population (COHP) calculations, it was discernible that in the Co3/SiO2(001)-CO, Co5/SiO2(001)-CO and Co5-CO, the transfer of electrons from Co to C amounted to 0.20, 0.15, and 0.24, respectively, the integrated COHP (ICOHP) values for the Co—C bond were -1.46, -0.91, and -1.70 eV, respectively, which are indicated a more robust interaction between C and Co in Co5-CO and Co3/SiO2(001)-CO compared to Co5/SiO2(001)-CO. Notably, the intense interaction between CO and Co in the latter hinders the activation of CO.
Employing the first-principles density functional theory (DFT), an in-depth investigation was conducted into the structure, electronic properties, and CO activity of hydroxylated SiO2(001) surface-supported Con (where n is the number of cobalt atoms, n=1-6) materials [Con/SiO2(001)]. Here, n=1 represents a single Co atom, while n=2-6 denotes Con clusters composed of n Co atoms. The findings revealed that the binding energy (Eb-Co5/SiO2(001)) of Co5/SiO2(001) was the highest at 1.88 eV, suggesting that the Co5 cluster exhibits the greatest stability when interfaced with the SiO2(001). A direct linear correlation (y=0.11x-0.23) was observed in the connection between Eb-Con/SiO2(001) and the average Bader charge (Qave-Bader) of the Con/SiO2(001). The greater Qave-Bader value transferred between the Con clusters and the SiO2 support, the stronger the binding and the higher the structural stability. As the Con cluster size increased, the d band center gradually moved away from the Fermi level, with the d band center energy for the Co5/SiO2(001) being the lowest at -0.96 eV. The most favorable reaction pathway for CO activation on the Co3/SiO2(001) is CO*+H*→CHO*→CH*+O*, with an effective energy barrier of 2.39 eV, whereas for Co5/SiO2(001), the optimal path is CO*→C*+O*, with an effective energy barrier of 1.19 eV, and Co5 cluster, the optimal path is CO*+H*→CHO*→CH*+O*, with an effective energy barrier of 2.72 eV. Notably, the introduction of Co5 clusters onto the hydroxylated SiO2 surface proves to be more conducive to the activation of CO. By employing differential charge analysis and crystal orbital hamilton population (COHP) calculations, it was discernible that in the Co3/SiO2(001)-CO, Co5/SiO2(001)-CO and Co5-CO, the transfer of electrons from Co to C amounted to 0.20, 0.15, and 0.24, respectively, the integrated COHP (ICOHP) values for the Co—C bond were -1.46, -0.91, and -1.70 eV, respectively, which are indicated a more robust interaction between C and Co in Co5-CO and Co3/SiO2(001)-CO compared to Co5/SiO2(001)-CO. Notably, the intense interaction between CO and Co in the latter hinders the activation of CO.
2025, 41(11): 2345-2357
doi: 10.11862/CJIC.20240435
Abstract:
To investigate the photothermal toxicity of Prussian blue nanoparticles (PB NPs) on cervical cancer cells (HeLa cells) and their underlying mechanisms, uniformly sized and well-dispersed PB NPs were synthesized. Using HeLa cells as the experimental model, techniques such as MTT assay, confocal microscopy, and flow cytometry were employed to evaluate the effects of PB NPs on cell viability, membrane permeability, apoptosis, cell cycle arrest, and reactive oxygen species (ROS) generation. The MTT assay revealed that PB NPs inhibited HeLa cell proliferation in a concentration and laser power-dependent manner. At a mass concentration of 50 μg·mL-1 and an 808 nm laser irradiation with a power density of 0.2 W·cm-2, PB NPs reduced HeLa cell viability to 24.2%. Trypan blue staining and Calcein-AM/PI double-staining confocal microscopy demonstrated that the photothermal cytotoxicity of PB NPs primarily manifests as increased cell membrane permeability. Annexin V-FITC flow cytometry indicated that PB NPs induce apoptosis in HeLa cells. Furthermore, DCFH-DA fluorescence assays and flow cytometry showed that 20 μg·mL-1 PB NPs under 808 nm laser irradiation (0.3 W·cm-2) elevated intracellular ROS levels by 11.5-fold and induced cell cycle arrest at the G2/M phase. The above results suggest that the photothermal toxicity effect of PB NPs on HeLa cells is achieved by increasing cell membrane permeability, inducing cell cycle arrest, elevating ROS generation, and triggering apoptosis.
To investigate the photothermal toxicity of Prussian blue nanoparticles (PB NPs) on cervical cancer cells (HeLa cells) and their underlying mechanisms, uniformly sized and well-dispersed PB NPs were synthesized. Using HeLa cells as the experimental model, techniques such as MTT assay, confocal microscopy, and flow cytometry were employed to evaluate the effects of PB NPs on cell viability, membrane permeability, apoptosis, cell cycle arrest, and reactive oxygen species (ROS) generation. The MTT assay revealed that PB NPs inhibited HeLa cell proliferation in a concentration and laser power-dependent manner. At a mass concentration of 50 μg·mL-1 and an 808 nm laser irradiation with a power density of 0.2 W·cm-2, PB NPs reduced HeLa cell viability to 24.2%. Trypan blue staining and Calcein-AM/PI double-staining confocal microscopy demonstrated that the photothermal cytotoxicity of PB NPs primarily manifests as increased cell membrane permeability. Annexin V-FITC flow cytometry indicated that PB NPs induce apoptosis in HeLa cells. Furthermore, DCFH-DA fluorescence assays and flow cytometry showed that 20 μg·mL-1 PB NPs under 808 nm laser irradiation (0.3 W·cm-2) elevated intracellular ROS levels by 11.5-fold and induced cell cycle arrest at the G2/M phase. The above results suggest that the photothermal toxicity effect of PB NPs on HeLa cells is achieved by increasing cell membrane permeability, inducing cell cycle arrest, elevating ROS generation, and triggering apoptosis.
2025, 41(11): 2358-2370
doi: 10.11862/CJIC.20250150
Abstract:
Five novel complexes [Co2(BCTA)(H2O)4]n (1), [Co2(BCTA)(Phen)2(H2O)2] (2), [Co2(BCTA)(Bipy)2(H2O)2] (3), [Cu2(BCTA)(Bipy)2(H2O)2]n (4), and [Cd2(BCTA)(Bipy)2(H2O)2]n (5) (H4BCTA=2,5-bis(carboxymethoxy)terephthalic acid, Phen=1, 10-phenanthroline, Bipy=2, 2′-bipyridine) were synthesized by solvothermal condition. All complexes were structurally characterized by infrared spectroscopy, elemental analysis, thermogravimetric analysis, and single-crystal X-ray diffraction. Complexes 2 and 3 have zero-dimensional structures, complex 5 has a 1D banded structure, and complexes 1 and 4 have 2D network structures. Hirshfeld surface analysis of complexes 1-5 was performed, and antifungal activities of the complexes were investigated. Complex 5 exhibited super-strong antifungal activity against seven pathogenic fungi, with all inhibitory rates reaching 100%.
Five novel complexes [Co2(BCTA)(H2O)4]n (1), [Co2(BCTA)(Phen)2(H2O)2] (2), [Co2(BCTA)(Bipy)2(H2O)2] (3), [Cu2(BCTA)(Bipy)2(H2O)2]n (4), and [Cd2(BCTA)(Bipy)2(H2O)2]n (5) (H4BCTA=2,5-bis(carboxymethoxy)terephthalic acid, Phen=1, 10-phenanthroline, Bipy=2, 2′-bipyridine) were synthesized by solvothermal condition. All complexes were structurally characterized by infrared spectroscopy, elemental analysis, thermogravimetric analysis, and single-crystal X-ray diffraction. Complexes 2 and 3 have zero-dimensional structures, complex 5 has a 1D banded structure, and complexes 1 and 4 have 2D network structures. Hirshfeld surface analysis of complexes 1-5 was performed, and antifungal activities of the complexes were investigated. Complex 5 exhibited super-strong antifungal activity against seven pathogenic fungi, with all inhibitory rates reaching 100%.
2025, 41(11): 2371-2384
doi: 10.11862/CJIC.20250227
Abstract:
A N, O dual-doped honeycomb-like porous carbon (DHPC) was designed and prepared as an efficient selenium host material for lithium-selenium (Li-Se) and sodium-selenium (Na-Se) batteries. The DHPC possessed a hierarchical porous structure that effectively encapsulates Se and suppresses the shuttle effect of polyselenides. Combined with theoretical calculations, it is confirmed that the N, O dual-doping enhances the chemical adsorption of polyselenides. The Se@DHPC cathode delivered a high initial charging capacity of 675 mAh·g-1 and excellent cycling stability (with a capacity decay rate of only 0.14% per cycle) in Li-Se batteries. Moreover, it exhibited a high capacity of 688 mAh·g-1 and a remarkable capacity retention rate after 300 cycles in Na-Se batteries.
A N, O dual-doped honeycomb-like porous carbon (DHPC) was designed and prepared as an efficient selenium host material for lithium-selenium (Li-Se) and sodium-selenium (Na-Se) batteries. The DHPC possessed a hierarchical porous structure that effectively encapsulates Se and suppresses the shuttle effect of polyselenides. Combined with theoretical calculations, it is confirmed that the N, O dual-doping enhances the chemical adsorption of polyselenides. The Se@DHPC cathode delivered a high initial charging capacity of 675 mAh·g-1 and excellent cycling stability (with a capacity decay rate of only 0.14% per cycle) in Li-Se batteries. Moreover, it exhibited a high capacity of 688 mAh·g-1 and a remarkable capacity retention rate after 300 cycles in Na-Se batteries.
2025, 41(11): 2385-2398
doi: 10.11862/CJIC.20250159
Abstract:
The CdS/Ti3AlC2 heterojunction photocatalyst was synthesized by the hydrothermal method, and its structure and performance were systematically analyzed through various characterization methods, including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), and photoluminescence (PL) spectroscopy, etc. The results confirmed the successful construction of the composite material and its excellent charge separation ability. Under ultraviolet light irradiation, the photocatalytic degradation performance of tetracycline was studied, and its degradation mechanism was clarified, among which the superoxide radical (·O2-) was the main active species. Under the conditions of pH=7 and catalyst dosage of 0.1 g·L-1, CdS/Ti3AlC2 exhibited excellent photocatalytic performance, with a TC degradation efficiency as high as 96.3%.
The CdS/Ti3AlC2 heterojunction photocatalyst was synthesized by the hydrothermal method, and its structure and performance were systematically analyzed through various characterization methods, including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), and photoluminescence (PL) spectroscopy, etc. The results confirmed the successful construction of the composite material and its excellent charge separation ability. Under ultraviolet light irradiation, the photocatalytic degradation performance of tetracycline was studied, and its degradation mechanism was clarified, among which the superoxide radical (·O2-) was the main active species. Under the conditions of pH=7 and catalyst dosage of 0.1 g·L-1, CdS/Ti3AlC2 exhibited excellent photocatalytic performance, with a TC degradation efficiency as high as 96.3%.
Co(Ⅱ) coordination polymers: Structural characterization and fluorescence sensing of Al3+ in aqueous
2025, 41(11): 2399-2408
doi: 10.11862/CJIC.20250114
Abstract:
Complexes [Co(hfacac)2(L1)]n (1) and [Co(hfacac)(L2)]n (2) (Hhfacac=hexafluoroacetylacetonate) were synthesized by coordinating Co(hfacac)2 with ligands 3, 6-di(pyridin-4-yl)-9H-carbazole (L1) and 9-methyl-3, 6-di(pyridin-4-yl)-9H-carbazole (L2), respectively. The complexes were characterized by infrared spectrometry, UV-Vis spectrometry, electrospray ionization mass spectrometry, and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analysis revealed that complex 2 crystallizes in a triclinic crystal system with the space group P1, and the unit cell volume is 1.928 7(2) nm3. The Co(Ⅱ) centers exhibit distorted octahedral coordination. One-dimensional chain structures of 2 are stabilized by hydrogen bonding and π-π stacking interactions. Fluorescence studies showed that complex 1 could be highly selective in Al3+ detection with a limit of detection of 51.3 nmol·L-1 and had a significant turn-on response to Al3+, which is attributed to the chelation-enhanced fluorescence (CHEF) mechanism. Furthermore, fluorescent test strips were developed for rapid in situ detection of Al3+.
Complexes [Co(hfacac)2(L1)]n (1) and [Co(hfacac)(L2)]n (2) (Hhfacac=hexafluoroacetylacetonate) were synthesized by coordinating Co(hfacac)2 with ligands 3, 6-di(pyridin-4-yl)-9H-carbazole (L1) and 9-methyl-3, 6-di(pyridin-4-yl)-9H-carbazole (L2), respectively. The complexes were characterized by infrared spectrometry, UV-Vis spectrometry, electrospray ionization mass spectrometry, and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analysis revealed that complex 2 crystallizes in a triclinic crystal system with the space group P1, and the unit cell volume is 1.928 7(2) nm3. The Co(Ⅱ) centers exhibit distorted octahedral coordination. One-dimensional chain structures of 2 are stabilized by hydrogen bonding and π-π stacking interactions. Fluorescence studies showed that complex 1 could be highly selective in Al3+ detection with a limit of detection of 51.3 nmol·L-1 and had a significant turn-on response to Al3+, which is attributed to the chelation-enhanced fluorescence (CHEF) mechanism. Furthermore, fluorescent test strips were developed for rapid in situ detection of Al3+.
