Login In
2024 Volume 40 Issue 9
2024, 40(9): 1633-1639
doi: 10.11862/CJIC.20240162
Abstract:
Here, we report a new method for constructing single-atom platinum/CNC(SA-Pt/CNC) nanozyme using the impregnation adsorption method with porous carbon nanocages(CNC) as the carrier. The microstructure of SA-Pt/CNC was thoroughly analyzed using transmission electron microscopy(TEM), high-resolution transmission electron microscopy(HRTEM), and X-ray photoelectron spectroscopy (XPS). Enzyme activity tests showed that SA-Pt/CNC exhibited excellent peroxidase-like activity, efficiently catalyzing the oxidation of various substrate molecules by hydrogen peroxide.
Here, we report a new method for constructing single-atom platinum/CNC(SA-Pt/CNC) nanozyme using the impregnation adsorption method with porous carbon nanocages(CNC) as the carrier. The microstructure of SA-Pt/CNC was thoroughly analyzed using transmission electron microscopy(TEM), high-resolution transmission electron microscopy(HRTEM), and X-ray photoelectron spectroscopy (XPS). Enzyme activity tests showed that SA-Pt/CNC exhibited excellent peroxidase-like activity, efficiently catalyzing the oxidation of various substrate molecules by hydrogen peroxide.
2024, 40(9): 1640-1652
doi: 10.11862/CJIC.20240183
Abstract:
The multi-layer hexagonal hole MXene electrode material was constructed by using the carbon vacancy defect ordering strategy, and the energy density of 235.8 Wh·kg-1 in the soft-pack supercapacitor was realized at the power density of 6 480 W·kg-1. The electrode material has a structure of three-dimensional hexagonal holes, which increases the contact area with the electrolyte and provides more active sites for potassium ion storage. Combined with the pseudo-capacitance effect caused by the change of valency of newly exposed titanium atoms in the inner wall of the hexagonal hole, the internal reason for the increase of specific capacity of multi-layer hexagonal hole MXene water system potassium ion supercapacitor is explained. The adsorption energy of multilayer hexagonal porous MXene for potassium ion was calculated by density functional theory, and the optimal position of potassium ion adsorption was determined by electrochemical potassium storage experiment and kinetic analysis, and the adsorption law of potassium ion was obtained. By a quantitative analysis of the band structure and differential charge density of electrons in multi-layer hexagonal hole MXene, the internal mechanism of high conductivity and good magnification performance of the water system potassium ion supercapacitor is revealed.
The multi-layer hexagonal hole MXene electrode material was constructed by using the carbon vacancy defect ordering strategy, and the energy density of 235.8 Wh·kg-1 in the soft-pack supercapacitor was realized at the power density of 6 480 W·kg-1. The electrode material has a structure of three-dimensional hexagonal holes, which increases the contact area with the electrolyte and provides more active sites for potassium ion storage. Combined with the pseudo-capacitance effect caused by the change of valency of newly exposed titanium atoms in the inner wall of the hexagonal hole, the internal reason for the increase of specific capacity of multi-layer hexagonal hole MXene water system potassium ion supercapacitor is explained. The adsorption energy of multilayer hexagonal porous MXene for potassium ion was calculated by density functional theory, and the optimal position of potassium ion adsorption was determined by electrochemical potassium storage experiment and kinetic analysis, and the adsorption law of potassium ion was obtained. By a quantitative analysis of the band structure and differential charge density of electrons in multi-layer hexagonal hole MXene, the internal mechanism of high conductivity and good magnification performance of the water system potassium ion supercapacitor is revealed.
2024, 40(9): 1653-1660
doi: 10.11862/CJIC.20240154
Abstract:
A simple Schiff base probe, namely 2-(((E)-(3H-benzo[f]chromen-2-yl)methylene)amino)-3-aminomaleonitrile (1), was prepared by the condensation reaction, which was characterized through 1H NMR, 13C NMR, ESI-MS, and single crystal X-ray diffraction. The fluorescence experiments indicated that probe 1 was non-emissive, while hypochlorite (ClO-) could induce a strong emission of the probe at 530 nm. The response of probe 1 toward ClO- was highly sensitive and finished within a few seconds. The ClO--promoted decomposition of probe 1 was suggested by spectral and theoretical methods. Furthermore, the probe was applied to imaging exogenous and endogenous ClO- in living cells, zebrafish, and Arabidopsis thaliana.
A simple Schiff base probe, namely 2-(((E)-(3H-benzo[f]chromen-2-yl)methylene)amino)-3-aminomaleonitrile (1), was prepared by the condensation reaction, which was characterized through 1H NMR, 13C NMR, ESI-MS, and single crystal X-ray diffraction. The fluorescence experiments indicated that probe 1 was non-emissive, while hypochlorite (ClO-) could induce a strong emission of the probe at 530 nm. The response of probe 1 toward ClO- was highly sensitive and finished within a few seconds. The ClO--promoted decomposition of probe 1 was suggested by spectral and theoretical methods. Furthermore, the probe was applied to imaging exogenous and endogenous ClO- in living cells, zebrafish, and Arabidopsis thaliana.
2024, 40(9): 1661-1670
doi: 10.11862/CJIC.20240145
Abstract:
Na(Ⅰ)/Cd(Ⅱ) complexes, [Na(HBBA)]n (1) and [Cd(HBBA)2(4, 4'-Bipy)]n (2), (H2BBA=5-bromo-2-hydroxy-benzoic acid and 4, 4'-Bipy=4, 4'-bipyridine) were synthesized with 5-bromo-2-hydroxybenzoic acid ligands by solvo-thermal condition and structurally characterized by elemental analysis, IR, thermogravimetric analysis, powder X-ray diffraction and single crystal X-ray diffraction. The asymmetric unit of complex 1 consists of one Na(Ⅰ) ion and one HBBA- ligand. Na(Ⅰ) ion is a six-coordinated triangular prism structure. Three oxygen atoms of the HBBAligand coordinate with two Na(Ⅰ) ions, connecting adjacent Na(Ⅰ) ions to form three 1D chain structures, and the HBBA- ligand connects three adjacent 1D chains to form a 2D network structure. Intermolecular hydrogen bonds connect adjacent 2D network structures to form a 3D hydrogen bond network structure. The asymmetric unit of complex 2 consists of one Cd(Ⅱ) ion, two HBBA- ligands, and one 4, 4'-Bipy ligand. Cadmium ion is a six-coordinated twisted octahedron structure, and the 4, 4'-Bipy ligand connects two adjacent cadmium ions to form a 1D chain structure. Intermolecular hydrogen bonds connect adjacent 1D links to form a 3D hydrogen bond network structure. The weak intermolecular interaction in building crystal blocks was analyzed in detail by Hirshfeld surface analysis. The reciprocal Na…O/H…Br/H…H/C…C/C…H/O…O contacts dominate over 87% of total Hirshfeld surface of complex 1, and the reciprocal H…H/H…O/H…Br/C…C/C…H/O…O/C…Br contacts dominate over 86.8% of the total Hirshfeld surface of complex 2. The thermal stability and antifungal activity of complexes 1 and 2 were studied in detail. Complex 2 has a good inhibitory effect on eight pathogenic fungi, among which the antifungal effect on Fusarium oxysporum f. sp. niveum and Rhizoctonia solani AG1 were the best, and the inhibitory rates were as high as 99.94% and 100%.
Na(Ⅰ)/Cd(Ⅱ) complexes, [Na(HBBA)]n (1) and [Cd(HBBA)2(4, 4'-Bipy)]n (2), (H2BBA=5-bromo-2-hydroxy-benzoic acid and 4, 4'-Bipy=4, 4'-bipyridine) were synthesized with 5-bromo-2-hydroxybenzoic acid ligands by solvo-thermal condition and structurally characterized by elemental analysis, IR, thermogravimetric analysis, powder X-ray diffraction and single crystal X-ray diffraction. The asymmetric unit of complex 1 consists of one Na(Ⅰ) ion and one HBBA- ligand. Na(Ⅰ) ion is a six-coordinated triangular prism structure. Three oxygen atoms of the HBBAligand coordinate with two Na(Ⅰ) ions, connecting adjacent Na(Ⅰ) ions to form three 1D chain structures, and the HBBA- ligand connects three adjacent 1D chains to form a 2D network structure. Intermolecular hydrogen bonds connect adjacent 2D network structures to form a 3D hydrogen bond network structure. The asymmetric unit of complex 2 consists of one Cd(Ⅱ) ion, two HBBA- ligands, and one 4, 4'-Bipy ligand. Cadmium ion is a six-coordinated twisted octahedron structure, and the 4, 4'-Bipy ligand connects two adjacent cadmium ions to form a 1D chain structure. Intermolecular hydrogen bonds connect adjacent 1D links to form a 3D hydrogen bond network structure. The weak intermolecular interaction in building crystal blocks was analyzed in detail by Hirshfeld surface analysis. The reciprocal Na…O/H…Br/H…H/C…C/C…H/O…O contacts dominate over 87% of total Hirshfeld surface of complex 1, and the reciprocal H…H/H…O/H…Br/C…C/C…H/O…O/C…Br contacts dominate over 86.8% of the total Hirshfeld surface of complex 2. The thermal stability and antifungal activity of complexes 1 and 2 were studied in detail. Complex 2 has a good inhibitory effect on eight pathogenic fungi, among which the antifungal effect on Fusarium oxysporum f. sp. niveum and Rhizoctonia solani AG1 were the best, and the inhibitory rates were as high as 99.94% and 100%.
2024, 40(9): 1671-1678
doi: 10.11862/CJIC.20240149
Abstract:
Herein, F-doped MnO2 with abundant oxygen vacancy (named F-MnO2) was synthesized by an efficient and simple one-step hydrothermal method. The introduced oxygen vacancy and pre-intercalated F-doping play a vital role in improving the electrical conductivity of F-MnO2 and facilitating ion diffusion, contributing to enhanced rate capability. In addition, the F doping results in the formation of F—Mn bonds, which can effectively inhibit the Jahn-Teller distortion of Mn3+ in the discharge product, thus improving the structural stability. Benefiting from these synergic effects, the assembled Zn||F-MnO2 full battery exhibited a high capacity of 274 mAh·g-1 at 0.5 A·g-1, as well as a long cycle life and superior rate performance. Meanwhile, the energy storage mechanism was proved to be a H+ and Zn2+ co-insertion/extraction process by cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) tests.
Herein, F-doped MnO2 with abundant oxygen vacancy (named F-MnO2) was synthesized by an efficient and simple one-step hydrothermal method. The introduced oxygen vacancy and pre-intercalated F-doping play a vital role in improving the electrical conductivity of F-MnO2 and facilitating ion diffusion, contributing to enhanced rate capability. In addition, the F doping results in the formation of F—Mn bonds, which can effectively inhibit the Jahn-Teller distortion of Mn3+ in the discharge product, thus improving the structural stability. Benefiting from these synergic effects, the assembled Zn||F-MnO2 full battery exhibited a high capacity of 274 mAh·g-1 at 0.5 A·g-1, as well as a long cycle life and superior rate performance. Meanwhile, the energy storage mechanism was proved to be a H+ and Zn2+ co-insertion/extraction process by cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) tests.
2024, 40(9): 1679-1688
doi: 10.11862/CJIC.20240135
Abstract:
Mesoporous nanomaterials showed potential application in drug delivery, but non-specific leakage and multi-drug resistance seriously restricted the efficacy of chemotherapy. Based on the synthesis of mesoporous poly-dopamine (MPDA), pH/photothermal dual-responsive MPDA-DOX@PCM delivery nanosystem was constructed by loading chemotherapy drug doxorubicin (DOX) and coating phase-change material (PCM) 1-tetradecanol, by which the photothermal therapy (PTT) and chemotherapy were achieved towards drug-resistant bladder cancer cell (BIU-87/ADR). The results indicated that the size of MPDA-DOX@PCM was about 179 nm, the max loading rate of DOX was 22%, and the photothermal conversion efficiency was up to 49.1%. Under the conditions of pH=7.4 and 25 ℃, the accumulative release rate of DOX was 4.57%, but can increase to 60.13% with the conditions of pH=5.5 and 45 ℃. Under the irradiation of 808 nm laser, the viability of BIU-87/ADR cells incubated with MPDA-DOX@PCM decreased to 9.5%, demonstrating the excellent combination performance of PTT/chemotherapy.
Mesoporous nanomaterials showed potential application in drug delivery, but non-specific leakage and multi-drug resistance seriously restricted the efficacy of chemotherapy. Based on the synthesis of mesoporous poly-dopamine (MPDA), pH/photothermal dual-responsive MPDA-DOX@PCM delivery nanosystem was constructed by loading chemotherapy drug doxorubicin (DOX) and coating phase-change material (PCM) 1-tetradecanol, by which the photothermal therapy (PTT) and chemotherapy were achieved towards drug-resistant bladder cancer cell (BIU-87/ADR). The results indicated that the size of MPDA-DOX@PCM was about 179 nm, the max loading rate of DOX was 22%, and the photothermal conversion efficiency was up to 49.1%. Under the conditions of pH=7.4 and 25 ℃, the accumulative release rate of DOX was 4.57%, but can increase to 60.13% with the conditions of pH=5.5 and 45 ℃. Under the irradiation of 808 nm laser, the viability of BIU-87/ADR cells incubated with MPDA-DOX@PCM decreased to 9.5%, demonstrating the excellent combination performance of PTT/chemotherapy.
2024, 40(9): 1689-1696
doi: 10.11862/CJIC.20240115
Abstract:
Herein, the structure and electrochemical properties of nano Li2FeSiO4/C cathode materials were optimized through co-doping potassium and chlorine ions. A series of nano Li2-xKxFeSiO4-0.5xClx/C (x=0, 0.01, 0.02) composites were prepared by a solid-state reaction. The microstructure and electrochemical performance of the three kinds of composites were analyzed using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, constant current charge-discharge test, etc. The results showed that nano Li1.99K0.01FeSiO3.995Cl0.01/C cathode material owned the largest interplanar spacing, biggest cell volume, and smallest average particle size among the three materials. The average particle size of nano Li1.99K0.01FeSiO3.995Cl0.01/C cathode material was as small as 32 nm. These particular structures made it exhibit the best electrochemical performance. The initial specific discharge capacity of the nano Li1.99K0.01FeSiO3.995Cl0.01/C cathode material at 0.1C was as high as 203 mAh·g-1. In addition, a capacity retention rate of 97.72% was acquired for the nano Li1.99K0.01FeSiO3.995Cl0.01/C cathode material at 1C after 100 charge-discharge cycles.
Herein, the structure and electrochemical properties of nano Li2FeSiO4/C cathode materials were optimized through co-doping potassium and chlorine ions. A series of nano Li2-xKxFeSiO4-0.5xClx/C (x=0, 0.01, 0.02) composites were prepared by a solid-state reaction. The microstructure and electrochemical performance of the three kinds of composites were analyzed using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, constant current charge-discharge test, etc. The results showed that nano Li1.99K0.01FeSiO3.995Cl0.01/C cathode material owned the largest interplanar spacing, biggest cell volume, and smallest average particle size among the three materials. The average particle size of nano Li1.99K0.01FeSiO3.995Cl0.01/C cathode material was as small as 32 nm. These particular structures made it exhibit the best electrochemical performance. The initial specific discharge capacity of the nano Li1.99K0.01FeSiO3.995Cl0.01/C cathode material at 0.1C was as high as 203 mAh·g-1. In addition, a capacity retention rate of 97.72% was acquired for the nano Li1.99K0.01FeSiO3.995Cl0.01/C cathode material at 1C after 100 charge-discharge cycles.
2024, 40(9): 1697-1707
doi: 10.11862/CJIC.20240108
Abstract:
Co-doped Ni(OH)2 was prepared by a simple co-precipitation method, and the electrochemical performance was improved by the Co/Ni synergistic effect. Co-doping refined the grain size of Ni(OH)2, improved the morphology of the material, exposed more active sites, and improved the electrochemical activity of the material. Meanwhile, the first-principle calculation showed that Co-doping also changed the electron density distribution of Ni, leading to the improvement of the charge transport and ion diffusion properties of the material. Due to the appropriate quantity of Co doping, Ni0.84Co0.16(OH)2 had excellent electrochemical energy storage of 1 589.6 F·g-1 at the current density of 1 A·g-1, far higher than that of Ni(OH)2 (1 191.7 F·g-1). Meanwhile, the assembled asymmetric super-capacitor had an energy density of 8.30 Wh·kg-1 when the power density was 21.33 kW·kg-1, showing a good energy storage performance and cycle performance.
Co-doped Ni(OH)2 was prepared by a simple co-precipitation method, and the electrochemical performance was improved by the Co/Ni synergistic effect. Co-doping refined the grain size of Ni(OH)2, improved the morphology of the material, exposed more active sites, and improved the electrochemical activity of the material. Meanwhile, the first-principle calculation showed that Co-doping also changed the electron density distribution of Ni, leading to the improvement of the charge transport and ion diffusion properties of the material. Due to the appropriate quantity of Co doping, Ni0.84Co0.16(OH)2 had excellent electrochemical energy storage of 1 589.6 F·g-1 at the current density of 1 A·g-1, far higher than that of Ni(OH)2 (1 191.7 F·g-1). Meanwhile, the assembled asymmetric super-capacitor had an energy density of 8.30 Wh·kg-1 when the power density was 21.33 kW·kg-1, showing a good energy storage performance and cycle performance.
2024, 40(9): 1708-1718
doi: 10.11862/CJIC.20240067
Abstract:
CeCO3OH-rGO (reduced graphene oxide) was prepared by a one-step hydrothermal method, and CeO2-rGO composites were prepared by roasting under argon (Ar) atmosphere. The phase composition, microstructure, vacancy defects, and photoelectrochemical properties of the composites were studied by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, UV visible diffuse reflectance spectroscopy (UV-Vis DRS), etc. The photocatalytic performance of the composites with different GO (graphene oxide) and NH4HCO3 addition amounts respectively were comparatively studied. It was found that the CeO2-10rGO-15 with GO and NH4HCO3 addition amounts of 10 mg and 15 mmol respectively had the narrowest band-gap width (3.17 eV), and the photocatalytic degradation ratio of methylene blue (MB) could reach 80.66%. It is beneficial to the formation vacancy defect of CeO2 and the separation of photogenic carriers for rGO loading suitably, thus promoting photocatalytic performance.
CeCO3OH-rGO (reduced graphene oxide) was prepared by a one-step hydrothermal method, and CeO2-rGO composites were prepared by roasting under argon (Ar) atmosphere. The phase composition, microstructure, vacancy defects, and photoelectrochemical properties of the composites were studied by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, UV visible diffuse reflectance spectroscopy (UV-Vis DRS), etc. The photocatalytic performance of the composites with different GO (graphene oxide) and NH4HCO3 addition amounts respectively were comparatively studied. It was found that the CeO2-10rGO-15 with GO and NH4HCO3 addition amounts of 10 mg and 15 mmol respectively had the narrowest band-gap width (3.17 eV), and the photocatalytic degradation ratio of methylene blue (MB) could reach 80.66%. It is beneficial to the formation vacancy defect of CeO2 and the separation of photogenic carriers for rGO loading suitably, thus promoting photocatalytic performance.
2024, 40(9): 1719-1730
doi: 10.11862/CJIC.20240102
Abstract:
A BaTiO3/Pt/NiS double heterojunction photocatalyst with Pt and NiS as co-catalysts was prepared using electrostatic spinning, hydrothermal, and photo-deposition methods. The optimized BaTiO3/Pt/NiS sample showed the highest hydrogen production rate of 489 μmol·h-1·g-1, which is 2.5 times higher than that of pure BaTiO3. Exper-imental results and density functional theory (DFT) calculations have demonstrated the construction of a p-n junction between BaTiO3 and NiS, which efficiently facilitates the transfer of photogenerated holes from BaTiO3 to NiS. Additionally, the Schottky junction formed between BaTiO3 and Pt promotes the migration of photogenerated electrons from BaTiO3 to Pt. The opposite transfer routes of photogenerated electrons and holes naturally inhibit their recombination, resulting in a higher rate of hydrogen evolution. These results were further validated by photoelectro-chemical testing. The highest photocurrent density and smallest electrochemical impedance of the optimized BaTiO3/Pt/NiS sample convincingly proved its fastest separation of photogenerated electrons and holes, thus displaying the highest activity for hydrogen production.
A BaTiO3/Pt/NiS double heterojunction photocatalyst with Pt and NiS as co-catalysts was prepared using electrostatic spinning, hydrothermal, and photo-deposition methods. The optimized BaTiO3/Pt/NiS sample showed the highest hydrogen production rate of 489 μmol·h-1·g-1, which is 2.5 times higher than that of pure BaTiO3. Exper-imental results and density functional theory (DFT) calculations have demonstrated the construction of a p-n junction between BaTiO3 and NiS, which efficiently facilitates the transfer of photogenerated holes from BaTiO3 to NiS. Additionally, the Schottky junction formed between BaTiO3 and Pt promotes the migration of photogenerated electrons from BaTiO3 to Pt. The opposite transfer routes of photogenerated electrons and holes naturally inhibit their recombination, resulting in a higher rate of hydrogen evolution. These results were further validated by photoelectro-chemical testing. The highest photocurrent density and smallest electrochemical impedance of the optimized BaTiO3/Pt/NiS sample convincingly proved its fastest separation of photogenerated electrons and holes, thus displaying the highest activity for hydrogen production.
2024, 40(9): 1731-1742
doi: 10.11862/CJIC.20240077
Abstract:
Magnetically mesoporous carbon (Fe3O4@C)/nano-zerovalent iron (nZVI) composites (Fe3O4@C-nZVI) were successfully prepared by a liquid-phase reduction for the effective removal of Cr(Ⅲ)-EDTA (EDTA: ethylenediaminetetra-acetic acid) in high-salinity wastewater. By characterization and analysis by scanning electron microscope (SEM) and electron microscope (TEM), the nZVI has been successfully loaded into the carbon layer without significant agglomeration and can be magnetically separated and nZVI was stable under the protection of a carbon layer which is favorable for the reuse of materials. The presence of nZVI on the adsorbents greatly improved the adsorption of Cr(Ⅲ)-EDTA and the maximum adsorption capacity of Fe3O4@C-nZVI was 10.24 mg·g-1 at pH=4.0, 25 ℃, which was remarkably higher than that of Fe3O4@C (4.31 mg·g-1). The results showed that the Langmuir model and the pseudo-second-order kinetic model can better describe the adsorption of Cr(Ⅲ)-EDTA by Fe3O4@C-nZVI. The adsorption capacity of Fe3O4@C-nZVI on Cr(Ⅲ)-EDTA increased and then decreased with the increase of solution pH value; low concentrations of complexing agents (EDTA, citric acid) would promote the adsorption of Cr(Ⅲ)-EDTA, whereas an increase in the concentration of the complexing agents showed inhibition; due to the charge shielding effect, high concentrations of cations (Na+, K+, Ca2+) in the solution will promote the adsorption of Cr(Ⅲ)-EDTA. Fe3O4@C-nZVI still showed significant adsorption of Cr(Ⅲ)-EDTA in a salt and complexant environment. The adsorption saturated Fe3O4@C-nZVI was regenerated by 0.1 mol·L-1 HCl solution, the adsorption of Cr(Ⅲ)-EDTA by Fe3O4@CnZVI reached 6.90 mg·g-1 after three regeneration cycles. X -ray photoelectron spectrum analysis of Fe3O4@C-nZVI before and after reaction showed that the adsorption mechanism was mainly through complexation between surface FeⅢ and Cr(Ⅲ)-EDTA to form FeⅢ-EDTA-Cr(Ⅲ) complexation products, and subsequently displaces Cr(Ⅲ) due to ionic displacement, and the displaced Cr(Ⅲ) will be removed by co-precipitation with FeⅢ as CrxFe1-x(OH)3 deposited on the nZVI surface.
Magnetically mesoporous carbon (Fe3O4@C)/nano-zerovalent iron (nZVI) composites (Fe3O4@C-nZVI) were successfully prepared by a liquid-phase reduction for the effective removal of Cr(Ⅲ)-EDTA (EDTA: ethylenediaminetetra-acetic acid) in high-salinity wastewater. By characterization and analysis by scanning electron microscope (SEM) and electron microscope (TEM), the nZVI has been successfully loaded into the carbon layer without significant agglomeration and can be magnetically separated and nZVI was stable under the protection of a carbon layer which is favorable for the reuse of materials. The presence of nZVI on the adsorbents greatly improved the adsorption of Cr(Ⅲ)-EDTA and the maximum adsorption capacity of Fe3O4@C-nZVI was 10.24 mg·g-1 at pH=4.0, 25 ℃, which was remarkably higher than that of Fe3O4@C (4.31 mg·g-1). The results showed that the Langmuir model and the pseudo-second-order kinetic model can better describe the adsorption of Cr(Ⅲ)-EDTA by Fe3O4@C-nZVI. The adsorption capacity of Fe3O4@C-nZVI on Cr(Ⅲ)-EDTA increased and then decreased with the increase of solution pH value; low concentrations of complexing agents (EDTA, citric acid) would promote the adsorption of Cr(Ⅲ)-EDTA, whereas an increase in the concentration of the complexing agents showed inhibition; due to the charge shielding effect, high concentrations of cations (Na+, K+, Ca2+) in the solution will promote the adsorption of Cr(Ⅲ)-EDTA. Fe3O4@C-nZVI still showed significant adsorption of Cr(Ⅲ)-EDTA in a salt and complexant environment. The adsorption saturated Fe3O4@C-nZVI was regenerated by 0.1 mol·L-1 HCl solution, the adsorption of Cr(Ⅲ)-EDTA by Fe3O4@CnZVI reached 6.90 mg·g-1 after three regeneration cycles. X -ray photoelectron spectrum analysis of Fe3O4@C-nZVI before and after reaction showed that the adsorption mechanism was mainly through complexation between surface FeⅢ and Cr(Ⅲ)-EDTA to form FeⅢ-EDTA-Cr(Ⅲ) complexation products, and subsequently displaces Cr(Ⅲ) due to ionic displacement, and the displaced Cr(Ⅲ) will be removed by co-precipitation with FeⅢ as CrxFe1-x(OH)3 deposited on the nZVI surface.
2024, 40(9): 1743-1754
doi: 10.11862/CJIC.20240075
Abstract:
Ordered single-layer polystyrene (PS) microsphere arrays were fabricated by using the gas/liquid interface self-assembly method, and then employed as a template, single-layer hexagonal nonclose packed Au nanoparticle arrays were prepared by combining magnetron sputtering deposition method as well as heat treatment technology. Sub-sequently, highly ordered ZIF-8/Au composite nanostructure arrays were successfully obtained by using the hydrothermal method. The growth mechanism of composite nanostructure arrays and the effects of reaction temperature as well as time on the microstructure and optical properties were explored. Moreover, the sensitivity and uniformity of surface-enhanced Raman scattering (SERS) signals obtained from Ag film-decorated nanostructure arrays were further investigated. The results indicated that when the hydrothermal reaction temperature increased from 25 to 100 ℃, the number and size of ZIF-8 nanoparticles gradually increased, and the surface plasmon resonance (SPR) and diffraction peaks both red-shifted. When the hydrothermal reaction time increased from 10 to 60 min, ZIF-8 nanoparticles appeared from selective growth around Au nanoparticles to spread throughout the material surface. After depositing a specific thickness of Ag film onto the obtained array surface, the detection limits of Raman sig-nals from both 4-aminothiophenol (4-ATP) and rhodamine 6G (R6G) probe molecules were 10-11 mol·L-1. The SERS peak intensity located at 1 430 cm-1 (4-ATP) and 1 355 cm-1 (R6G) showed a linear relationship with the concentra-tion of each molecular solution, and the correlation coefficients R2 were 0.980 1 and 0.984 4, respectively. The rela-tive standard deviation (RSD) was 8.86% by comparison to the peak intensity located at 1 430 cm-1 obtained from 4-ATP molecules (10-5 mol·L-1) measured at 10 randomly selected positions on the arrays. It indicated that ordered ZIF-8/Au composite nanostructure arrays as SERS enhanced substrate exhibited good stability and uniformity.
Ordered single-layer polystyrene (PS) microsphere arrays were fabricated by using the gas/liquid interface self-assembly method, and then employed as a template, single-layer hexagonal nonclose packed Au nanoparticle arrays were prepared by combining magnetron sputtering deposition method as well as heat treatment technology. Sub-sequently, highly ordered ZIF-8/Au composite nanostructure arrays were successfully obtained by using the hydrothermal method. The growth mechanism of composite nanostructure arrays and the effects of reaction temperature as well as time on the microstructure and optical properties were explored. Moreover, the sensitivity and uniformity of surface-enhanced Raman scattering (SERS) signals obtained from Ag film-decorated nanostructure arrays were further investigated. The results indicated that when the hydrothermal reaction temperature increased from 25 to 100 ℃, the number and size of ZIF-8 nanoparticles gradually increased, and the surface plasmon resonance (SPR) and diffraction peaks both red-shifted. When the hydrothermal reaction time increased from 10 to 60 min, ZIF-8 nanoparticles appeared from selective growth around Au nanoparticles to spread throughout the material surface. After depositing a specific thickness of Ag film onto the obtained array surface, the detection limits of Raman sig-nals from both 4-aminothiophenol (4-ATP) and rhodamine 6G (R6G) probe molecules were 10-11 mol·L-1. The SERS peak intensity located at 1 430 cm-1 (4-ATP) and 1 355 cm-1 (R6G) showed a linear relationship with the concentra-tion of each molecular solution, and the correlation coefficients R2 were 0.980 1 and 0.984 4, respectively. The rela-tive standard deviation (RSD) was 8.86% by comparison to the peak intensity located at 1 430 cm-1 obtained from 4-ATP molecules (10-5 mol·L-1) measured at 10 randomly selected positions on the arrays. It indicated that ordered ZIF-8/Au composite nanostructure arrays as SERS enhanced substrate exhibited good stability and uniformity.
2024, 40(9): 1755-1762
doi: 10.11862/CJIC.20240061
Abstract:
Solvothermal reactions of a tetradentate imidazole-containing ligand, 3, 3', 5, 5'-tetraimidazolyl biphenyl (L), combined with Zn(Ⅱ) salt in the presence of varied auxiliary dicarboxylic acids yield two new metal-organic frameworks (MOFs) with (4, 4) topologies, namely [Zn2(L) (BPDC)2]·H2O (1) and [Zn2(L) (OBA)2] ·6H2O (2), where H2BPDC=4, 4'-biphenyldicarboxylic acid, H2OBA=4, 4'-oxydibenzoic acid. Single crystal X-ray diffraction analysis has shown that complex 1 consists of 1D chains interconnected by Zn—N bonds, forming a layer structure, which can be further linked by BPDC2- ligands, resulting in the formation of a 3D framework, while complex 2 consists of 2D layers with different 46-membered macrocycles, which are further connected by carboxylates to bring about 3D frameworks. Furthermore, activated complex 2(2') possesses remarkable selective adsorption characteristics for H2O and EtOH. The photoluminescence properties of these MOFs were also thoroughly examined.
Solvothermal reactions of a tetradentate imidazole-containing ligand, 3, 3', 5, 5'-tetraimidazolyl biphenyl (L), combined with Zn(Ⅱ) salt in the presence of varied auxiliary dicarboxylic acids yield two new metal-organic frameworks (MOFs) with (4, 4) topologies, namely [Zn2(L) (BPDC)2]·H2O (1) and [Zn2(L) (OBA)2] ·6H2O (2), where H2BPDC=4, 4'-biphenyldicarboxylic acid, H2OBA=4, 4'-oxydibenzoic acid. Single crystal X-ray diffraction analysis has shown that complex 1 consists of 1D chains interconnected by Zn—N bonds, forming a layer structure, which can be further linked by BPDC2- ligands, resulting in the formation of a 3D framework, while complex 2 consists of 2D layers with different 46-membered macrocycles, which are further connected by carboxylates to bring about 3D frameworks. Furthermore, activated complex 2(2') possesses remarkable selective adsorption characteristics for H2O and EtOH. The photoluminescence properties of these MOFs were also thoroughly examined.
2024, 40(9): 1763-1774
doi: 10.11862/CJIC.20240060
Abstract:
To improve the adsorption performance of nano-hydroxyapatite (HAP) as a heavy metal ion adsorbent, the polymer-induced liquid-like precursor mineralization process in the human body was simulated. A stable suspended nano HAP system was prepared by hydrothermal method using polyacrylic acid (PAA) as a regulator. The effects of R (the ratio of the amount of substance of COOH in PAA to Ca), reaction pH, and hydrothermal temperature on the prepared nano HAP were investigated. The optimized synthesis conditions for nano HAP were R=1, pH=9.00, 180 ℃, which is a spindle-shaped structure composed of small particles and stably suspended while maintaining several tens of nanoparticle sizes. Subsequently, the effects of adsorption time, initial metal ion concentration, pH of adsorption environment, and suspension on the Co2+ adsorption performance of nano HAP were investigated. The adsorption results indicate that the adsorption kinetics follow a pseudo-second-order kinetic model, and the adsorption process includes surface adsorption and intra-particle diffusion. The linear equation fitting results of the Freun-dlich and Langmuir models had a high degree of agreement with the experimental results. The adsorption belongs to the chemical adsorption of nonuniform adsorbents, and the linear fitting result of the Langmuir model corresponding to the maximum adsorption amount was 229.358 mg·g-1. The removal rate of Co2+ increased with the increase of adsorption environment pH (6.48-9.00), and the main adsorption mechanism was surface coordination reaction. The adsorption capacity of the prepared nano HAP suspension was significantly better than that of the non-suspended control nano HAP. The addition of PAA enhances the adsorption capacity of nano HAP.
To improve the adsorption performance of nano-hydroxyapatite (HAP) as a heavy metal ion adsorbent, the polymer-induced liquid-like precursor mineralization process in the human body was simulated. A stable suspended nano HAP system was prepared by hydrothermal method using polyacrylic acid (PAA) as a regulator. The effects of R (the ratio of the amount of substance of COOH in PAA to Ca), reaction pH, and hydrothermal temperature on the prepared nano HAP were investigated. The optimized synthesis conditions for nano HAP were R=1, pH=9.00, 180 ℃, which is a spindle-shaped structure composed of small particles and stably suspended while maintaining several tens of nanoparticle sizes. Subsequently, the effects of adsorption time, initial metal ion concentration, pH of adsorption environment, and suspension on the Co2+ adsorption performance of nano HAP were investigated. The adsorption results indicate that the adsorption kinetics follow a pseudo-second-order kinetic model, and the adsorption process includes surface adsorption and intra-particle diffusion. The linear equation fitting results of the Freun-dlich and Langmuir models had a high degree of agreement with the experimental results. The adsorption belongs to the chemical adsorption of nonuniform adsorbents, and the linear fitting result of the Langmuir model corresponding to the maximum adsorption amount was 229.358 mg·g-1. The removal rate of Co2+ increased with the increase of adsorption environment pH (6.48-9.00), and the main adsorption mechanism was surface coordination reaction. The adsorption capacity of the prepared nano HAP suspension was significantly better than that of the non-suspended control nano HAP. The addition of PAA enhances the adsorption capacity of nano HAP.
2024, 40(9): 1775-1783
doi: 10.11862/CJIC.20240043
Abstract:
A high electroactive hybrid film of CoNi-layered double hydroxide grown on graphene (CoNi-LDH/G) with a three-dimensional (3D) flower-like structure was successfully prepared by using two-step coating and electro-deposition method, and applied to separate and recover low concentrated phosphate anions from wastewater via electrically switched ion exchange. The morphology, composition, and structure of the CoNi-LDH/G hybrid film were demonstrated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscope (TEM). The effect of absorption potentials, initial phosphate concentrations, co-existing anions, and pH on the phosphate electrochemistry adsorption performance of the hybrid film was also investigated. The experimental results indicated that the hybrid film had a high adsorption performance by adjusting the redox potential, even at low concentrations. In addition, it can be used in a wide pH range (4-10), and its adsorption capacity for PO43- was little affected by coexisting ions and their variations in concentration. Further-more, the adsorption capacity of G and CoNi-LDH for PO43- was 1.10 and 11.74 mg·g-1, respectively. Moreover, the sum of these two was also lower than that of the CoNi-LDH/G hybrid film (16.25 mg·g-1). Combined with O1s XPS analysis, it was found that PO43- adsorption on CoNi-LDH/G hybrid film aside from interlayer ion exchange, complexation ligand exchange between PO43- and layer-plate metal ions, the synergistic effects between G and CoNiLDH also existed.
A high electroactive hybrid film of CoNi-layered double hydroxide grown on graphene (CoNi-LDH/G) with a three-dimensional (3D) flower-like structure was successfully prepared by using two-step coating and electro-deposition method, and applied to separate and recover low concentrated phosphate anions from wastewater via electrically switched ion exchange. The morphology, composition, and structure of the CoNi-LDH/G hybrid film were demonstrated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscope (TEM). The effect of absorption potentials, initial phosphate concentrations, co-existing anions, and pH on the phosphate electrochemistry adsorption performance of the hybrid film was also investigated. The experimental results indicated that the hybrid film had a high adsorption performance by adjusting the redox potential, even at low concentrations. In addition, it can be used in a wide pH range (4-10), and its adsorption capacity for PO43- was little affected by coexisting ions and their variations in concentration. Further-more, the adsorption capacity of G and CoNi-LDH for PO43- was 1.10 and 11.74 mg·g-1, respectively. Moreover, the sum of these two was also lower than that of the CoNi-LDH/G hybrid film (16.25 mg·g-1). Combined with O1s XPS analysis, it was found that PO43- adsorption on CoNi-LDH/G hybrid film aside from interlayer ion exchange, complexation ligand exchange between PO43- and layer-plate metal ions, the synergistic effects between G and CoNiLDH also existed.
2024, 40(9): 1784-1794
doi: 10.11862/CJIC.20240146
Abstract:
Crystalline@amorphous NiCo2S4@MoS2 (v-NCS@MS) nanostructures were designed and constructed via an ethylene glycol-induced strategy with hydrothermal synthesis and solvothermal method, which simultaneously realized the defect regulation of crystal NiCo2S4 in the core. Taking advantage of the flexible protection of an amor-phous shell and the high capacity of a conductive core with defects, the v-NCS@MS electrode exhibited high specific capacity (1 034 mAh·g-1 at 1 A·g-1) and outstanding rate capability. Moreover, a hybrid supercapacitor was assembled with v-NCS@MS as cathode and activated carbon (AC) as anode, which can achieve remarkably high specific energy of 111 Wh·kg-1 at a specific power of 219 W·kg-1 and outstanding capacity retention of 80.5% after 15 000 cycling at different current densities.
Crystalline@amorphous NiCo2S4@MoS2 (v-NCS@MS) nanostructures were designed and constructed via an ethylene glycol-induced strategy with hydrothermal synthesis and solvothermal method, which simultaneously realized the defect regulation of crystal NiCo2S4 in the core. Taking advantage of the flexible protection of an amor-phous shell and the high capacity of a conductive core with defects, the v-NCS@MS electrode exhibited high specific capacity (1 034 mAh·g-1 at 1 A·g-1) and outstanding rate capability. Moreover, a hybrid supercapacitor was assembled with v-NCS@MS as cathode and activated carbon (AC) as anode, which can achieve remarkably high specific energy of 111 Wh·kg-1 at a specific power of 219 W·kg-1 and outstanding capacity retention of 80.5% after 15 000 cycling at different current densities.
2024, 40(9): 1795-1802
doi: 10.11862/CJIC.20240081
Abstract:
Three zinc(Ⅱ) and cobalt(Ⅱ) coordination polymers, namely {[Zn2(μ6-adip)(phen)2]·4H2O}n (1), {[Co2(μ6-adip)(bipy)2]·4H2O}n (2), and [Co2(μ4-adip)(μ-bpa)2]n (3) have been constructed hydrothermally using H4adip (H4adip= 5, 5'-azanediyldiisophthalic acid), phen (phen=1, 10-phenanthroline), bipy (bipy=2, 2'-bipyridine), bpa (bpa=bis(4-pyridyl)amine), and zinc and cobalt chlorides at 160 ℃. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses, and single-crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the orthorhombic system Pnna (1 and 2) or P21212 (3) space groups. All compounds exhibit 3D frameworks. The catalytic perfor-mances in the Henry reaction of these compounds were investigated. Compound 3 exhibited an effective catalytic activity in the Henry reaction at 70 ℃.
Three zinc(Ⅱ) and cobalt(Ⅱ) coordination polymers, namely {[Zn2(μ6-adip)(phen)2]·4H2O}n (1), {[Co2(μ6-adip)(bipy)2]·4H2O}n (2), and [Co2(μ4-adip)(μ-bpa)2]n (3) have been constructed hydrothermally using H4adip (H4adip= 5, 5'-azanediyldiisophthalic acid), phen (phen=1, 10-phenanthroline), bipy (bipy=2, 2'-bipyridine), bpa (bpa=bis(4-pyridyl)amine), and zinc and cobalt chlorides at 160 ℃. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses, and single-crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the orthorhombic system Pnna (1 and 2) or P21212 (3) space groups. All compounds exhibit 3D frameworks. The catalytic perfor-mances in the Henry reaction of these compounds were investigated. Compound 3 exhibited an effective catalytic activity in the Henry reaction at 70 ℃.
2024, 40(9): 1803-1810
doi: 10.11862/CJIC.20240068
Abstract:
Three zinc(Ⅱ), cobalt(Ⅱ), and nickel(Ⅱ) coordination polymers, namely [Zn(μ3-cpna)(μ-dpea)0.5]n (1), [Co(μ3-cpna)(μ-dpey)0.5]n (2), and [Ni(μ3-cpna)(μ-dpey)0.5(H2O)]n (3), have been constructed hydrothermally using H2cpna (5-(4-carboxyphenoxy)nicotinic acid), dpea (1, 2-di(4-pyridyl)ethane), dpey (1, 2-di(4-pyridyl)ethylene), and zinc, cobalt, and nickel chlorides at 160 ℃. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses, and single-crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the triclinic system, space group P1. Compounds 1-3 show 2D layer structures. The catalytic activities in the Knoevenagel condensation reaction of these compounds were investigated. Compounds 1 and 2 exhibit effective catalytic activities in the Knoevenagel condensation reaction at room temperature. For this reaction, various parameters were optimized, followed by the investigation of the substrate scope.
Three zinc(Ⅱ), cobalt(Ⅱ), and nickel(Ⅱ) coordination polymers, namely [Zn(μ3-cpna)(μ-dpea)0.5]n (1), [Co(μ3-cpna)(μ-dpey)0.5]n (2), and [Ni(μ3-cpna)(μ-dpey)0.5(H2O)]n (3), have been constructed hydrothermally using H2cpna (5-(4-carboxyphenoxy)nicotinic acid), dpea (1, 2-di(4-pyridyl)ethane), dpey (1, 2-di(4-pyridyl)ethylene), and zinc, cobalt, and nickel chlorides at 160 ℃. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses, and single-crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the triclinic system, space group P1. Compounds 1-3 show 2D layer structures. The catalytic activities in the Knoevenagel condensation reaction of these compounds were investigated. Compounds 1 and 2 exhibit effective catalytic activities in the Knoevenagel condensation reaction at room temperature. For this reaction, various parameters were optimized, followed by the investigation of the substrate scope.
2024, 40(9): 1811-1824
doi: 10.11862/CJIC.20240054
Abstract:
MoS2/CuS composite catalysts were successfully synthesized using a one-step hydrothermal method with sodium molybdate dihydrate, thiourea, oxalic acid, and copper nitrate trihydrate as raw materials. The hydrogen production performance of MoS2/CuS prepared with different molar ratios of Mo to Cu precursors (nMo∶nCu) as cathodic catalysts was investigated in the two-chamber microbial electrolytic cell (MEC). X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscope (TEM), linear scanning voltammetry (LSV), electrochemical impedance analysis (EIS), and cyclic voltammetry (CV) were used to characterize the synthesized catalysts for testing and analyzing the hydrogen-producing performance. The results showed that the hydrogen evolution performance of MoS2/CuS-20% (nMo∶nCu=5∶1) was better than that of platinum (Pt) mesh, and the hydrogen production rate of MoS2/CuS-20% as a cathode in MEC was (0.203 1±0.023 7) mH23·m-3·d-1 for 72 h at an applied voltage of 0.8 V, which was slightly higher than that of Pt mesh of (0.188 6±0.013 4) mH23·m-3·d-1. The addition of a certain amount of CuS not only regulates the electron transfer ability of MoS2 but also increases the density of active sites.
MoS2/CuS composite catalysts were successfully synthesized using a one-step hydrothermal method with sodium molybdate dihydrate, thiourea, oxalic acid, and copper nitrate trihydrate as raw materials. The hydrogen production performance of MoS2/CuS prepared with different molar ratios of Mo to Cu precursors (nMo∶nCu) as cathodic catalysts was investigated in the two-chamber microbial electrolytic cell (MEC). X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscope (TEM), linear scanning voltammetry (LSV), electrochemical impedance analysis (EIS), and cyclic voltammetry (CV) were used to characterize the synthesized catalysts for testing and analyzing the hydrogen-producing performance. The results showed that the hydrogen evolution performance of MoS2/CuS-20% (nMo∶nCu=5∶1) was better than that of platinum (Pt) mesh, and the hydrogen production rate of MoS2/CuS-20% as a cathode in MEC was (0.203 1±0.023 7) mH23·m-3·d-1 for 72 h at an applied voltage of 0.8 V, which was slightly higher than that of Pt mesh of (0.188 6±0.013 4) mH23·m-3·d-1. The addition of a certain amount of CuS not only regulates the electron transfer ability of MoS2 but also increases the density of active sites.
