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2025 Volume 41 Issue 3
2025, 41(3): 425-439
doi: 10.11862/CJIC.20240201
Abstract:
Electrocatalytic carbon dioxide reduction technology can effectively convert CO2 into valuable chemicals to reduce CO2 emissions, providing a solution for CO2 management and helping China to achieve the carbon emission target of"carbon peak and carbon neutrality". Currently, the commonly used monometallic nanocatalysts have the shortcomings of a single catalytic site and difficult regulation of the adsorption energy between products and intermediates, and face problems such as poor catalyst selectivity, activity, and stability. In contrast, bimetallic nanocatalysts have been widely studied due to the existence of two atomic coordinations, which can adjust the electronic structure of the catalyst, finely regulate the binding energy of the intermediates, and bring abundant and flexible active sites. This paper reviews the latest research progress of bimetallic nanocatalysts, mainly focusing on the fine regulation of bimetallic nanocatalysts, such as doping control, heterogeneous structure control, alloying control, and geometric structure control, and the catalytic mechanism of bimetal nanocatalysts such as synergistic effect, stress effect, and electronic effect. Moreover, the current shortcomings and future research of bimetallic nanocatalysts are discussed.
Electrocatalytic carbon dioxide reduction technology can effectively convert CO2 into valuable chemicals to reduce CO2 emissions, providing a solution for CO2 management and helping China to achieve the carbon emission target of"carbon peak and carbon neutrality". Currently, the commonly used monometallic nanocatalysts have the shortcomings of a single catalytic site and difficult regulation of the adsorption energy between products and intermediates, and face problems such as poor catalyst selectivity, activity, and stability. In contrast, bimetallic nanocatalysts have been widely studied due to the existence of two atomic coordinations, which can adjust the electronic structure of the catalyst, finely regulate the binding energy of the intermediates, and bring abundant and flexible active sites. This paper reviews the latest research progress of bimetallic nanocatalysts, mainly focusing on the fine regulation of bimetallic nanocatalysts, such as doping control, heterogeneous structure control, alloying control, and geometric structure control, and the catalytic mechanism of bimetal nanocatalysts such as synergistic effect, stress effect, and electronic effect. Moreover, the current shortcomings and future research of bimetallic nanocatalysts are discussed.
2025, 41(3): 440-452
doi: 10.11862/CJIC.20240371
Abstract:
Al-doped SrTiO3 (Al-SrTiO3) was prepared by the molten salt method, and then the Ni3N cocatalyst was loaded closely on the Al-SrTiO3 to obtain Ni3N /Al-SrTiO3 material by hydrothermal and gas phase nitrization method. Through fluorescence, impedance, surface photovoltage testing as well as density functional theory calculations, it is found that the photogenerated electrons on Al-SrTiO3 can quickly transfer to Ni3N under the effect of Fermi energy difference, effectively promoting the separation of photogenerated carriers on Al-SrTiO3 and improving the performance hydrogen evolution from water splitting. The photocatalytic hydrogen evolution test results showed that 7%Ni3N /Al-SrTiO3 with a loading amount (a mass ratio of Ni to Al-SrTiO3) of 7% had the highest hydrogen evolution rate, which was 82 times higher than that of Al-SrTiO3.
Al-doped SrTiO3 (Al-SrTiO3) was prepared by the molten salt method, and then the Ni3N cocatalyst was loaded closely on the Al-SrTiO3 to obtain Ni3N /Al-SrTiO3 material by hydrothermal and gas phase nitrization method. Through fluorescence, impedance, surface photovoltage testing as well as density functional theory calculations, it is found that the photogenerated electrons on Al-SrTiO3 can quickly transfer to Ni3N under the effect of Fermi energy difference, effectively promoting the separation of photogenerated carriers on Al-SrTiO3 and improving the performance hydrogen evolution from water splitting. The photocatalytic hydrogen evolution test results showed that 7%Ni3N /Al-SrTiO3 with a loading amount (a mass ratio of Ni to Al-SrTiO3) of 7% had the highest hydrogen evolution rate, which was 82 times higher than that of Al-SrTiO3.
2025, 41(3): 453-460
doi: 10.11862/CJIC.20240326
Abstract:
V-doped MnO2 (VMO) was prepared as the aqueous zinc ion battery (ZIB) cathode by a simple hydrothermal method and its electrochemical performance was tested. The material characterization and electrochemical performance test indicated that the bismuth was evenly incorporated into MnO2. V doping expanded the interlayer spacing of MnO2, increased the specific surface area, and improved its internal ionic conductivity. The initial discharge capacity of the assembled ZIB reached 362 mAh·g-1 at a current density of 0.1 A·g-1. The doping of V made the lattice structure of MnO2 more stable, weakened the Jahn-Teller distortion effect, and improved the structural stability of the electrode material. The specific capacity remained 87% of the initial stage after 300 cycles at a 1 A·g-1 current density.
V-doped MnO2 (VMO) was prepared as the aqueous zinc ion battery (ZIB) cathode by a simple hydrothermal method and its electrochemical performance was tested. The material characterization and electrochemical performance test indicated that the bismuth was evenly incorporated into MnO2. V doping expanded the interlayer spacing of MnO2, increased the specific surface area, and improved its internal ionic conductivity. The initial discharge capacity of the assembled ZIB reached 362 mAh·g-1 at a current density of 0.1 A·g-1. The doping of V made the lattice structure of MnO2 more stable, weakened the Jahn-Teller distortion effect, and improved the structural stability of the electrode material. The specific capacity remained 87% of the initial stage after 300 cycles at a 1 A·g-1 current density.
2025, 41(3): 461-468
doi: 10.11862/CJIC.20240316
Abstract:
A series of red-emitting phosphors, specifically Eu3+-doped Sc2W3O12, were synthesized using the sol-gel method. Furthermore, the symmetry of the Sc2W3O12 matrix crystal structure was diminished through Gd3+ doping, thereby enhancing the luminescence intensity of the phosphor. The findings indicate that incorporating Gd3+ did not alter the intrinsic crystal structure of Sc2W3O12. As the doping concentration of Gd3+ increased, the lattice distortion became more pronounced, resulting in a significant enhancement of the luminescence intensity corresponding to the 5D0→7F2 transition (612 nm) from Eu3+. The optimal doping concentration of Gd3+ was determined to be 0.25, yielding a luminescence intensity that was 1.95 times greater than that of solely Eu3+-doped samples. Additionally, the color coordinates (0.613 4, 0.350 3) were near the standard red color coordinates (0.670, 0.330). Furthermore, the fluorescent powder exhibited notable thermal stability; specifically, when the temperature reached 498 K, the fluorescence intensity of the sample with a Gd3+ ion concentration of 0.25 was enhanced compared to that of undoped Gd3+ ions, achieving 53% of its value at room temperature. Additionally, its activation energy was measured at 0.104 1 eV.
A series of red-emitting phosphors, specifically Eu3+-doped Sc2W3O12, were synthesized using the sol-gel method. Furthermore, the symmetry of the Sc2W3O12 matrix crystal structure was diminished through Gd3+ doping, thereby enhancing the luminescence intensity of the phosphor. The findings indicate that incorporating Gd3+ did not alter the intrinsic crystal structure of Sc2W3O12. As the doping concentration of Gd3+ increased, the lattice distortion became more pronounced, resulting in a significant enhancement of the luminescence intensity corresponding to the 5D0→7F2 transition (612 nm) from Eu3+. The optimal doping concentration of Gd3+ was determined to be 0.25, yielding a luminescence intensity that was 1.95 times greater than that of solely Eu3+-doped samples. Additionally, the color coordinates (0.613 4, 0.350 3) were near the standard red color coordinates (0.670, 0.330). Furthermore, the fluorescent powder exhibited notable thermal stability; specifically, when the temperature reached 498 K, the fluorescence intensity of the sample with a Gd3+ ion concentration of 0.25 was enhanced compared to that of undoped Gd3+ ions, achieving 53% of its value at room temperature. Additionally, its activation energy was measured at 0.104 1 eV.
2025, 41(3): 469-479
doi: 10.11862/CJIC.20240309
Abstract:
To address the issue of charge carrier non-radiative recombination in CsPbBr3 perovskite solar cells, which limits the improvement of their photoelectric conversion efficiency, we propose a method of spin-coating a 1.5 mg·mL-1 SnCl2 solution onto the TiO2 surface to effectively enhance the crystallinity and surface morphology of the perovskite film, thereby reducing non-radiative recombination of photogenerated carriers and improving carrier extraction and transport capabilities. Experimental results showed that modifying the TiO2 surface with SnCl2 increased the device′s maximum open-circuit voltage (VOC) to 1.59 V, short-circuit current density (JSC) to 7.62 mA·cm-2, and fill factor (FF) of 81.35%. At the same time, the photoelectric conversion efficiency (PCE) improved from 8.01% to 9.92%.
To address the issue of charge carrier non-radiative recombination in CsPbBr3 perovskite solar cells, which limits the improvement of their photoelectric conversion efficiency, we propose a method of spin-coating a 1.5 mg·mL-1 SnCl2 solution onto the TiO2 surface to effectively enhance the crystallinity and surface morphology of the perovskite film, thereby reducing non-radiative recombination of photogenerated carriers and improving carrier extraction and transport capabilities. Experimental results showed that modifying the TiO2 surface with SnCl2 increased the device′s maximum open-circuit voltage (VOC) to 1.59 V, short-circuit current density (JSC) to 7.62 mA·cm-2, and fill factor (FF) of 81.35%. At the same time, the photoelectric conversion efficiency (PCE) improved from 8.01% to 9.92%.
2025, 41(3): 480-490
doi: 10.11862/CJIC.20240259
Abstract:
Lanthanum cobaltate (LaCoO3, LCO) was first prepared by the citric acid-assisted sol-gel method, and the hydrothermal method prepared LaCoO3/g-C3N4 (LCO/CN) p-n heterojunction composite photocatalysts. The LCO/CN was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), and photoluminescence (PL) spectroscopy. Its photocatalytic degradation of tetracycline hydrochloride (TC) was evaluated, and the reactive groups that play a role in the photocatalytic reaction were verified using free radical trappers and the reaction mechanism was hypothesized. The results showed that the composite of LCO and CN significantly enhanced the photocatalytic activity of CN, and the 10%LCO/CN prepared with a mass ratio of 10% of LCO to CN exhibited the best photocatalytic performance, with a high degradation rate of 96.2% of 10 mg·L-1 TC in 120 min, and a reaction rate constant of 0.018 93 min-1, 3.04-fold and 1.93-fold higher than that of CN and LCO, respectively. The results of three recycling experiments showed that the degradation rate of TC by 10%LCO/CN decreased less, indicating that the catalyst had good stability and practicability.
Lanthanum cobaltate (LaCoO3, LCO) was first prepared by the citric acid-assisted sol-gel method, and the hydrothermal method prepared LaCoO3/g-C3N4 (LCO/CN) p-n heterojunction composite photocatalysts. The LCO/CN was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), and photoluminescence (PL) spectroscopy. Its photocatalytic degradation of tetracycline hydrochloride (TC) was evaluated, and the reactive groups that play a role in the photocatalytic reaction were verified using free radical trappers and the reaction mechanism was hypothesized. The results showed that the composite of LCO and CN significantly enhanced the photocatalytic activity of CN, and the 10%LCO/CN prepared with a mass ratio of 10% of LCO to CN exhibited the best photocatalytic performance, with a high degradation rate of 96.2% of 10 mg·L-1 TC in 120 min, and a reaction rate constant of 0.018 93 min-1, 3.04-fold and 1.93-fold higher than that of CN and LCO, respectively. The results of three recycling experiments showed that the degradation rate of TC by 10%LCO/CN decreased less, indicating that the catalyst had good stability and practicability.
2025, 41(3): 491-498
doi: 10.11862/CJIC.20240271
Abstract:
To explore the effects of ligands on the structure, properties, and applications of cerium oxo clusters, we synthesized the first cerium oxo cluster using furoate (FA) as ligands. The crystal NH4[Ce6O4(OH)4(FA)12(NO3)(H2O)]·5CH3CN·12H2O (1) of this cluster were thoroughly characterized using techniques such as single-crystal X-ray diffraction, powder X-ray diffraction, X-ray photoelectron spectroscopy, elemental analysis, thermogravimetry, and spectroscopy. Single-crystal X-ray diffraction analysis revealed that compound 1 exhibits a hexanuclear cluster structure with a [Ce6O4(OH)4]12+ core. As confirmed by the Raman spectrum, the Ce—O—Ce bond in this core suggests its formation via the hydrolysis reaction of Ce(Ⅳ) ions. This core is further stabilized by one water, one nitrate, and twelve FA groups to form the entire cluster structure. These results reveal that the hydrolysis and condensation reactions of Ce(Ⅳ) ions and their complex reaction with FA result in the formation of the cluster. The Fenton reaction was used to generate hydroxyl radicals, and methyl violet was utilized as an indicator to explore the free radical scavenging ability of compound 1. The UV-visible spectra indicated that the solution of compound 1 effectively scavenges hydroxyl radicals. As the volume of the compound 1 solution gradually increased from 50 to 2 000 μL, the scavenging efficiency rose from 8.32% to 91.06%.
To explore the effects of ligands on the structure, properties, and applications of cerium oxo clusters, we synthesized the first cerium oxo cluster using furoate (FA) as ligands. The crystal NH4[Ce6O4(OH)4(FA)12(NO3)(H2O)]·5CH3CN·12H2O (1) of this cluster were thoroughly characterized using techniques such as single-crystal X-ray diffraction, powder X-ray diffraction, X-ray photoelectron spectroscopy, elemental analysis, thermogravimetry, and spectroscopy. Single-crystal X-ray diffraction analysis revealed that compound 1 exhibits a hexanuclear cluster structure with a [Ce6O4(OH)4]12+ core. As confirmed by the Raman spectrum, the Ce—O—Ce bond in this core suggests its formation via the hydrolysis reaction of Ce(Ⅳ) ions. This core is further stabilized by one water, one nitrate, and twelve FA groups to form the entire cluster structure. These results reveal that the hydrolysis and condensation reactions of Ce(Ⅳ) ions and their complex reaction with FA result in the formation of the cluster. The Fenton reaction was used to generate hydroxyl radicals, and methyl violet was utilized as an indicator to explore the free radical scavenging ability of compound 1. The UV-visible spectra indicated that the solution of compound 1 effectively scavenges hydroxyl radicals. As the volume of the compound 1 solution gradually increased from 50 to 2 000 μL, the scavenging efficiency rose from 8.32% to 91.06%.
2025, 41(3): 499-508
doi: 10.11862/CJIC.20240238
Abstract:
Here, we have prepared a kind of anode current collector based on Li6.4La3Zr1.4Ta0.6O12 (LLZTO) solid electrolyte and copper composite layer with 3D porous structure by phase-transformation co-banding casting method, and the addition of LLZTO provides abundant ion transport channels and nucleation sites for lithium ions, while the copper with 3D porous structure provides enlarged specific surface area and can accommodate a large amount of dead lithium and other by-products generated in electrochemical process, and at the same time, the phase-transformation co-banding casting method is easy to operate and suitable for anode interface impedance increase. The prepared Cu-LLZTO@Li symmetric cell achieved a long cycle life of 280 h at a current density of 4 mA·cm-2 with an ultra-low voltage hysteresis of 25 mV, which was 4 times and 3 times higher than that of Cu foil and 3D-Cu, respectively. Thanks to the constructed stable solid electrolyte interphase (SEI) film and no lithium dendrite generation, the Cu-LLZTO@Li symmetric cell exhibited the lowest ohmic resistance (2.749 Ω·cm-2) and interface resistance (0.544 Ω·cm-2) compared to Cu foil@Li and 3D-Cu@Li. In the half-cell, Cu-LLZTO did not produce a soft short circuit and maintained 98.4% Coulombic efficiency over 70 cycles, and the charging and discharging voltage plateau was consistently maintained at a low level of 0.15 V during the cycle.
Here, we have prepared a kind of anode current collector based on Li6.4La3Zr1.4Ta0.6O12 (LLZTO) solid electrolyte and copper composite layer with 3D porous structure by phase-transformation co-banding casting method, and the addition of LLZTO provides abundant ion transport channels and nucleation sites for lithium ions, while the copper with 3D porous structure provides enlarged specific surface area and can accommodate a large amount of dead lithium and other by-products generated in electrochemical process, and at the same time, the phase-transformation co-banding casting method is easy to operate and suitable for anode interface impedance increase. The prepared Cu-LLZTO@Li symmetric cell achieved a long cycle life of 280 h at a current density of 4 mA·cm-2 with an ultra-low voltage hysteresis of 25 mV, which was 4 times and 3 times higher than that of Cu foil and 3D-Cu, respectively. Thanks to the constructed stable solid electrolyte interphase (SEI) film and no lithium dendrite generation, the Cu-LLZTO@Li symmetric cell exhibited the lowest ohmic resistance (2.749 Ω·cm-2) and interface resistance (0.544 Ω·cm-2) compared to Cu foil@Li and 3D-Cu@Li. In the half-cell, Cu-LLZTO did not produce a soft short circuit and maintained 98.4% Coulombic efficiency over 70 cycles, and the charging and discharging voltage plateau was consistently maintained at a low level of 0.15 V during the cycle.
2025, 41(3): 509-520
doi: 10.11862/CJIC.20240270
Abstract:
A bimetallic (Co, Fe) and nitrogen-doped porous carbon/sulfur composite material (e-CF@NPC/S, CF represents CoFe alloy, NPC represents nitrogen-doped porous carbon) was prepared by hydro-thermal reaction, carbonization, acid etching, and S loading. Then a series of composite materials with different nuclear shell ratios were obtained by changing the ratio of raw materials. The structural analysis and electrochemical properties test results of these composite materials show that core-shell structure porous carbon composite had a rich surface area and space to serve active substance loading and volume changes. The spatial domain restriction of the shell can be helpful to anchor sulfur and polysulfide (LiPSs) inside the structure, however, the shell can also block ion diffusion. The catalytic and absorptive capability of Co-Fe alloy depends on the quantities of active sites. Cathodes of e-CF@NPC-3/S show the best electrochemistry performance with a capacity retention rate of 92.35% at 0.2C after 100 cycles (initial capacity was 996.9 mAh·g-1). After 300 cycles at 1C, it can achieve a capacity decay rate of 0.049% per cycle (initial capacity was 684.5 mAh·g-1).
A bimetallic (Co, Fe) and nitrogen-doped porous carbon/sulfur composite material (e-CF@NPC/S, CF represents CoFe alloy, NPC represents nitrogen-doped porous carbon) was prepared by hydro-thermal reaction, carbonization, acid etching, and S loading. Then a series of composite materials with different nuclear shell ratios were obtained by changing the ratio of raw materials. The structural analysis and electrochemical properties test results of these composite materials show that core-shell structure porous carbon composite had a rich surface area and space to serve active substance loading and volume changes. The spatial domain restriction of the shell can be helpful to anchor sulfur and polysulfide (LiPSs) inside the structure, however, the shell can also block ion diffusion. The catalytic and absorptive capability of Co-Fe alloy depends on the quantities of active sites. Cathodes of e-CF@NPC-3/S show the best electrochemistry performance with a capacity retention rate of 92.35% at 0.2C after 100 cycles (initial capacity was 996.9 mAh·g-1). After 300 cycles at 1C, it can achieve a capacity decay rate of 0.049% per cycle (initial capacity was 684.5 mAh·g-1).
2025, 41(3): 521-530
doi: 10.11862/CJIC.20240221
Abstract:
Amorphous activated carbon (AC) material was obtained by carbonizing rice husk at low temperatures and activated by KOH at high temperatures. A series of MgO-loaded AC materials (MgO/AC) were prepared by in-situ loading of magnesium chloride. The surface morphology and elemental composition of MgO/AC materials were studied using X-ray diffraction (XRD), laser co-polymerization Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy-energy dispersive spectrometer (SEM-EDS), and nitrogen adsorption-desorption test. The possible relationship between pore structure and electrochemical performance was analyzed in detail. The test results indicated that 2.0MgO/AC electrodes were assembled into a symmetric supercapacitor, and the gravimetric capacitance was 211.9 F·g-1 at 0.5 A·g-1. It had an energy density of 18.30 Wh·kg-1 at a power density of 0.41 kW·kg-1 and the retention rate was 86.8% after 5 000 cycles.
Amorphous activated carbon (AC) material was obtained by carbonizing rice husk at low temperatures and activated by KOH at high temperatures. A series of MgO-loaded AC materials (MgO/AC) were prepared by in-situ loading of magnesium chloride. The surface morphology and elemental composition of MgO/AC materials were studied using X-ray diffraction (XRD), laser co-polymerization Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy-energy dispersive spectrometer (SEM-EDS), and nitrogen adsorption-desorption test. The possible relationship between pore structure and electrochemical performance was analyzed in detail. The test results indicated that 2.0MgO/AC electrodes were assembled into a symmetric supercapacitor, and the gravimetric capacitance was 211.9 F·g-1 at 0.5 A·g-1. It had an energy density of 18.30 Wh·kg-1 at a power density of 0.41 kW·kg-1 and the retention rate was 86.8% after 5 000 cycles.
2025, 41(3): 531-539
doi: 10.11862/CJIC.20240256
Abstract:
Employing an exfoliation-reassembly route, β-Bi2O3 pillared CoAl layered double hydroxide (CoAl-LDH) nanohybrid (β-Bi2O3/CoAl-LDH) was successfully fabricated using the delaminated CoAl-LDH nanosheets as the host and the β-Bi2O3 nanosol as the guest. The as-prepared catalyst morphology, structure, and photoelectrochemical behaviors were characterized by X-ray diffraction, transmission electron microscopy, UV-Vis absorption spectroscopy, X-ray photoelectron spectroscopy, etc. The pillared nanohybrid β-Bi2O3/CoAl-LDH shows a pillared interlayer region with a spacing of 2.1 nm, an expanded specific surface area of 62 m2·g-1, and superior visible-light response-ability. Under visible light radiation, the photocatalytic properties were investigated by tetracycline (TC) degradation. β-Bi2O3/CoAl-LDH exhibits a high degradation efficiency and 91.3% of TC was degraded within 90 min, much higher than its parents β-Bi2O3 and CoAl-LDH. The radial capture and electron paramagnetic resonance experiments reveal that oxygen radical ·O2- and hydroxyl radical ·OH were the predominant radicals in the photocatalytic system, which is attributed to the synergistic effect between β-Bi2O3 and CoAl-LDH. Their electronic coupling interactions lead to the formation of Z-scheme heterojunction in the pillared nanohybrid. The separation efficiency of the photogenerated electron-hole pairs is improved and the photocatalytic activity is enhanced significantly.
Employing an exfoliation-reassembly route, β-Bi2O3 pillared CoAl layered double hydroxide (CoAl-LDH) nanohybrid (β-Bi2O3/CoAl-LDH) was successfully fabricated using the delaminated CoAl-LDH nanosheets as the host and the β-Bi2O3 nanosol as the guest. The as-prepared catalyst morphology, structure, and photoelectrochemical behaviors were characterized by X-ray diffraction, transmission electron microscopy, UV-Vis absorption spectroscopy, X-ray photoelectron spectroscopy, etc. The pillared nanohybrid β-Bi2O3/CoAl-LDH shows a pillared interlayer region with a spacing of 2.1 nm, an expanded specific surface area of 62 m2·g-1, and superior visible-light response-ability. Under visible light radiation, the photocatalytic properties were investigated by tetracycline (TC) degradation. β-Bi2O3/CoAl-LDH exhibits a high degradation efficiency and 91.3% of TC was degraded within 90 min, much higher than its parents β-Bi2O3 and CoAl-LDH. The radial capture and electron paramagnetic resonance experiments reveal that oxygen radical ·O2- and hydroxyl radical ·OH were the predominant radicals in the photocatalytic system, which is attributed to the synergistic effect between β-Bi2O3 and CoAl-LDH. Their electronic coupling interactions lead to the formation of Z-scheme heterojunction in the pillared nanohybrid. The separation efficiency of the photogenerated electron-hole pairs is improved and the photocatalytic activity is enhanced significantly.
2025, 41(3): 540-548
doi: 10.11862/CJIC.20240405
Abstract:
Using 2-dicyanomethylene-3-cyano-4, 5, 5-trimethyl-2, 5-dihydrofuran (TCF) as a near-infrared fluorescent chromophore, we designed and synthesized a TCF-based fluorescent probe TCF-NS by introducing 2, 4-dinitrophenyl ether as the recognized site for H2S. The probe TCF-NS displayed a rapid-response fluorescent against H2S with high sensitivity and selection but had no significant fluorescence response to other biothiols. Furthermore, TCF-NS was applied to sense H2S in living cells successfully with minimized cytotoxicity and a large Stokes shift.
Using 2-dicyanomethylene-3-cyano-4, 5, 5-trimethyl-2, 5-dihydrofuran (TCF) as a near-infrared fluorescent chromophore, we designed and synthesized a TCF-based fluorescent probe TCF-NS by introducing 2, 4-dinitrophenyl ether as the recognized site for H2S. The probe TCF-NS displayed a rapid-response fluorescent against H2S with high sensitivity and selection but had no significant fluorescence response to other biothiols. Furthermore, TCF-NS was applied to sense H2S in living cells successfully with minimized cytotoxicity and a large Stokes shift.
2025, 41(3): 549-560
doi: 10.11862/CJIC.20240348
Abstract:
(2E, 6E)-4-methyl-2, 6-bis(pyridin-3-ylmethylene)cyclohexan-1-one (L1) and 4-methyl-2, 6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one (L2) were synthesized and combined with isophthalic acid (H2IP), then under solvothermal conditions, to react with transition metals achieving four novel metal organic frameworks (MOFs): [Zn(IP)(L1)]n (1), {[Cd(IP)(L1)]·H2O}n (2), {[Co(IP)(L1)]·H2O}n (3), and [Zn(IP)(L2)(H2O)]n (4). MOFs 1-4 have been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetry, and elemental analysis. Single-crystal X-ray diffraction shows that MOF 1 crystallizes in the monoclinic crystal system with space group P21/n, and MOFs 2-4 belong to the triclinic system with the P1 space group. 1-3 are 2D sheet structures, 2 and 3 have similar structural characters, whereas 4 is a 1D chain structure. Furthermore, 1-3 exhibited certain photocatalytic capability in the degradation of rhodamine B (RhB) and pararosaniline hydrochloride (PH). 4 could be used as a heterogeneous catalyst for the Knoevenagel reaction starting with benzaldehyde derivative and malononitrile. 4 could promote the reaction to achieve corresponding products in moderate yields within 3 h. Moreover, the catalyst exhibited recyclability for up to three cycles without significantly dropping its activity. A mechanism for MOF 4 catalyzed Knoevenagel condensation reaction of aromatic aldehyde and malononitrile has been initially proposed.
(2E, 6E)-4-methyl-2, 6-bis(pyridin-3-ylmethylene)cyclohexan-1-one (L1) and 4-methyl-2, 6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one (L2) were synthesized and combined with isophthalic acid (H2IP), then under solvothermal conditions, to react with transition metals achieving four novel metal organic frameworks (MOFs): [Zn(IP)(L1)]n (1), {[Cd(IP)(L1)]·H2O}n (2), {[Co(IP)(L1)]·H2O}n (3), and [Zn(IP)(L2)(H2O)]n (4). MOFs 1-4 have been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetry, and elemental analysis. Single-crystal X-ray diffraction shows that MOF 1 crystallizes in the monoclinic crystal system with space group P21/n, and MOFs 2-4 belong to the triclinic system with the P1 space group. 1-3 are 2D sheet structures, 2 and 3 have similar structural characters, whereas 4 is a 1D chain structure. Furthermore, 1-3 exhibited certain photocatalytic capability in the degradation of rhodamine B (RhB) and pararosaniline hydrochloride (PH). 4 could be used as a heterogeneous catalyst for the Knoevenagel reaction starting with benzaldehyde derivative and malononitrile. 4 could promote the reaction to achieve corresponding products in moderate yields within 3 h. Moreover, the catalyst exhibited recyclability for up to three cycles without significantly dropping its activity. A mechanism for MOF 4 catalyzed Knoevenagel condensation reaction of aromatic aldehyde and malononitrile has been initially proposed.
2025, 41(3): 561-573
doi: 10.11862/CJIC.20240294
Abstract:
We used the natural product chamomile as a carbon source to synthesize praseodymium(Pr) and nitrogen (N) co-doped biomass carbon dots (Pr/N-BCDs) with remarkable luminescence properties by one-step hydrothermal method. Compared with single N doped BCDs (N BCDs) and Prdoped BCDs (PrBCDs), Pr/N BCDs not only showed better fluorescence properties and stability but also achieved a significant increase in quantum yield of 12%. More importantly, under certain conditions, Pr/N-BCDs and 2, 4-dinitrophenylhydrazide (2, 4-DNPH) had significant fluorescence internal filtration effect (IFE) and dynamic quenching effect, and in the concentration range of 0.50-20 μmol·L-1, the concentration of 2, 4-DNPH had a good linear relationship with the fluorescence quenching signal, and the detection limit was as low as 2.1 nmol·L-1.
We used the natural product chamomile as a carbon source to synthesize praseodymium(Pr) and nitrogen (N) co-doped biomass carbon dots (Pr/N-BCDs) with remarkable luminescence properties by one-step hydrothermal method. Compared with single N doped BCDs (N BCDs) and Prdoped BCDs (PrBCDs), Pr/N BCDs not only showed better fluorescence properties and stability but also achieved a significant increase in quantum yield of 12%. More importantly, under certain conditions, Pr/N-BCDs and 2, 4-dinitrophenylhydrazide (2, 4-DNPH) had significant fluorescence internal filtration effect (IFE) and dynamic quenching effect, and in the concentration range of 0.50-20 μmol·L-1, the concentration of 2, 4-DNPH had a good linear relationship with the fluorescence quenching signal, and the detection limit was as low as 2.1 nmol·L-1.
2025, 41(3): 574-586
doi: 10.11862/CJIC.20240287
Abstract:
A coordination polymer {[Cd(H2dpa)(bpy)]·3H2O}n (Cd-CP) was designed and hydrothermal synthesized based on 4-(2, 4-dicarboxyphenoxy) phthalic acid (H4dpa), 2, 2′-bipyridine (bpy) and Cd(NO3)2·4H2O. The structure was characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, and infrared spectroscopy. Cd-CP belongs to the monoclinic crystal system with the P21/c space group and performs in a 1D double-chain structure. The adjacent double chains further form a 3D supramolecular network structure through hydrogen bonding. Thermogravimetric analysis shows that Cd-CP has good thermal stability. Fluorescence analysis showed that Cd-CP had good choosing selectively and was sensitive to metal ions (Fe3+ and Zn2+), 2, 4, 6-trinitrophenylhydrazine (TRI), and pyrimethanil (Pth). Interestingly, when Cd-CP was used for fluorescence detection of metal ions, it was found to have a fluorescence quenching effect on Fe3+ but had an obvious enhancement effect on Zn2+. Therefore, we designed an "on-off-on" logic gate. In addition, the mechanism of fluorescence sensing has been deeply explored.
A coordination polymer {[Cd(H2dpa)(bpy)]·3H2O}n (Cd-CP) was designed and hydrothermal synthesized based on 4-(2, 4-dicarboxyphenoxy) phthalic acid (H4dpa), 2, 2′-bipyridine (bpy) and Cd(NO3)2·4H2O. The structure was characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, and infrared spectroscopy. Cd-CP belongs to the monoclinic crystal system with the P21/c space group and performs in a 1D double-chain structure. The adjacent double chains further form a 3D supramolecular network structure through hydrogen bonding. Thermogravimetric analysis shows that Cd-CP has good thermal stability. Fluorescence analysis showed that Cd-CP had good choosing selectively and was sensitive to metal ions (Fe3+ and Zn2+), 2, 4, 6-trinitrophenylhydrazine (TRI), and pyrimethanil (Pth). Interestingly, when Cd-CP was used for fluorescence detection of metal ions, it was found to have a fluorescence quenching effect on Fe3+ but had an obvious enhancement effect on Zn2+. Therefore, we designed an "on-off-on" logic gate. In addition, the mechanism of fluorescence sensing has been deeply explored.
2025, 41(3): 587-596
doi: 10.11862/CJIC.20240269
Abstract:
Two new Mn(Ⅱ) coordination polymers, namely {[Mn2(HL)(phen)3(H2O)2]·7.5H2O}n (1) and [Mn4(HL)2(1, 4-bib)3(H2O)2]n (2), were synthesized under hydrothermal conditions by using Mn(Ⅱ) ions and 6-(3′, 4′-dicarboxylphenoxy)-1, 2, 4-benzenetricarboxylic acid (H5L) in the presence of N-auxiliary ligands 1, 10-phenanthroline (phen) and 1, 4-bis(1H-imidazol-1-yl)benzene (1, 4-bib). The structures of coordination polymers 1 and 2 were characterized by infrared spectroscopy, single-crystal X-ray diffraction, thermogravimetric analysis, and powder X-ray diffraction. Single-crystal X-ray diffraction reveals that 1 has a 1D chain structure based on binuclear Mn(Ⅱ) units, while 2 features a (3, 8)-connected 3D network structure based on tetranuclear Mn(Ⅱ) units. Magnetic studies show that 1 and 2 exhibit antiferromagnetic interactions between manganese ions. 2 shows stronger antiferromagnetic interactions due to the shorter Mn…Mn distances within the tetranuclear manganese units.
Two new Mn(Ⅱ) coordination polymers, namely {[Mn2(HL)(phen)3(H2O)2]·7.5H2O}n (1) and [Mn4(HL)2(1, 4-bib)3(H2O)2]n (2), were synthesized under hydrothermal conditions by using Mn(Ⅱ) ions and 6-(3′, 4′-dicarboxylphenoxy)-1, 2, 4-benzenetricarboxylic acid (H5L) in the presence of N-auxiliary ligands 1, 10-phenanthroline (phen) and 1, 4-bis(1H-imidazol-1-yl)benzene (1, 4-bib). The structures of coordination polymers 1 and 2 were characterized by infrared spectroscopy, single-crystal X-ray diffraction, thermogravimetric analysis, and powder X-ray diffraction. Single-crystal X-ray diffraction reveals that 1 has a 1D chain structure based on binuclear Mn(Ⅱ) units, while 2 features a (3, 8)-connected 3D network structure based on tetranuclear Mn(Ⅱ) units. Magnetic studies show that 1 and 2 exhibit antiferromagnetic interactions between manganese ions. 2 shows stronger antiferromagnetic interactions due to the shorter Mn…Mn distances within the tetranuclear manganese units.
2025, 41(3): 597-604
doi: 10.11862/CJIC.20240268
Abstract:
A trinuclear copper complex [Cu3(L2)2(SO4)2(H2O)7)]·8H2O (1) (HL2=1-hydroxy-3-(pyrazin-2-yl)-N- (pyrazin-2-ylmethyl)imidazo[1, 5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1, 5-a]pyrazine scaffold was serendipitously prepared from the reaction of the pro-ligand of H2L1 (N, N′-bis(pyrazin-2-ylmethyl)pyrazine-2, 3-dicarboxamide) with CuSO4·5H2O in aqueous solution at room temperature. Complex 1 was characterized by IR, single-crystal X-ray analysis, and magnetic susceptibility measurements. Single-crystal X-ray analysis reveals that the complex consists of three Cu(Ⅱ) ions, two in situ transformed L2- ligands, two coordinated sulfates, seven coordinated water molecules, and eight uncoordinated water molecules. Magnetic susceptibility measurement indicates that there are obvious ferromagnetic coupling interactions between the adjacent Cu(Ⅱ) ions in 1.
A trinuclear copper complex [Cu3(L2)2(SO4)2(H2O)7)]·8H2O (1) (HL2=1-hydroxy-3-(pyrazin-2-yl)-N- (pyrazin-2-ylmethyl)imidazo[1, 5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1, 5-a]pyrazine scaffold was serendipitously prepared from the reaction of the pro-ligand of H2L1 (N, N′-bis(pyrazin-2-ylmethyl)pyrazine-2, 3-dicarboxamide) with CuSO4·5H2O in aqueous solution at room temperature. Complex 1 was characterized by IR, single-crystal X-ray analysis, and magnetic susceptibility measurements. Single-crystal X-ray analysis reveals that the complex consists of three Cu(Ⅱ) ions, two in situ transformed L2- ligands, two coordinated sulfates, seven coordinated water molecules, and eight uncoordinated water molecules. Magnetic susceptibility measurement indicates that there are obvious ferromagnetic coupling interactions between the adjacent Cu(Ⅱ) ions in 1.
2025, 41(3): 605-612
doi: 10.11862/CJIC.20240251
Abstract:
A tetranuclear Ln(Ⅲ)-based complex: [Dy4(dbm)4(L)6(μ3-OH)2]·CH3CN (1) (HL=5-[(4-methylbenzylidene)amino]quinolin-8-ol, Hdbm=dibenzoylmethane) was manufactured and its structure was characterized in detail. X-ray diffraction analysis shows that complex 1 belongs to the monoclinic crystal system and its space group is P21/n, which contains a rhombic Dy4 core. Magnetic measurements of 1 suggest it possesses extraordinary single-molecule magnet (SMM) behavior. Its energy barrier Ueff/kB was 116.7 K, and the pre-exponential coefficient τ0=1.05×10-8 s.
A tetranuclear Ln(Ⅲ)-based complex: [Dy4(dbm)4(L)6(μ3-OH)2]·CH3CN (1) (HL=5-[(4-methylbenzylidene)amino]quinolin-8-ol, Hdbm=dibenzoylmethane) was manufactured and its structure was characterized in detail. X-ray diffraction analysis shows that complex 1 belongs to the monoclinic crystal system and its space group is P21/n, which contains a rhombic Dy4 core. Magnetic measurements of 1 suggest it possesses extraordinary single-molecule magnet (SMM) behavior. Its energy barrier Ueff/kB was 116.7 K, and the pre-exponential coefficient τ0=1.05×10-8 s.
2025, 41(3): 613-623
doi: 10.11862/CJIC.20240273
Abstract:
Two new transition-metal coordination polymers, {[Cd(oba)(L)2]·H2O}n (1) and [Cd(4-nph)(L)2]n (2) (H2oba=4, 4′-oxydibenzoic acid, 4-H2nph=4-nitrophthalic acid, L=2, 2′-biimidazole), were successfully synthesized under hydrothermal conditions and characterized structurally by IR spectroscopy, elemental analyses, single-crystal X-ray diffraction, powder X-ray diffraction, and thermogravimetric analysis. The results of single-crystal X-ray diffraction show that complex 1 presents a 1D zigzag chain structure and further extends to a 2D network through N—H…O hydrogen bonds and π-π stacking interactions. Meanwhile, complex 2 has a zero-dimensional structure and also extends to form a 2D network through N—H…O hydrogen bonds and π-π stacking interactions. In addition, both 1 and 2 exhibited luminescent properties in the solid state. Furthermore, quantum chemical calculations were carried out on the "molecular fragments" extracted from the crystal structures of 1 and 2 using the PBE0/LANL2DZ method constructed by the Gaussian16 program. The calculated values signify a significant covalent interaction between the coordination atoms and the Cd(Ⅱ) ions.
Two new transition-metal coordination polymers, {[Cd(oba)(L)2]·H2O}n (1) and [Cd(4-nph)(L)2]n (2) (H2oba=4, 4′-oxydibenzoic acid, 4-H2nph=4-nitrophthalic acid, L=2, 2′-biimidazole), were successfully synthesized under hydrothermal conditions and characterized structurally by IR spectroscopy, elemental analyses, single-crystal X-ray diffraction, powder X-ray diffraction, and thermogravimetric analysis. The results of single-crystal X-ray diffraction show that complex 1 presents a 1D zigzag chain structure and further extends to a 2D network through N—H…O hydrogen bonds and π-π stacking interactions. Meanwhile, complex 2 has a zero-dimensional structure and also extends to form a 2D network through N—H…O hydrogen bonds and π-π stacking interactions. In addition, both 1 and 2 exhibited luminescent properties in the solid state. Furthermore, quantum chemical calculations were carried out on the "molecular fragments" extracted from the crystal structures of 1 and 2 using the PBE0/LANL2DZ method constructed by the Gaussian16 program. The calculated values signify a significant covalent interaction between the coordination atoms and the Cd(Ⅱ) ions.
