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2024 Volume 40 Issue 7
2024, 40(7): 1233-1242
doi: 10.11862/CJIC.20240057
Abstract:
In this study, parallelogram-like macrocyclic supramolecular metallacycles [Pd6(bpy)6(L1)4](PF6)8 (1a) and [Pd6(bpy)6(L2)4](PF6)8 (2a), where HL1=1-(1H-pyrazole-4-yl)-4-(4-pyridyl)benzene, HL2=9-(1H-pyrazole-4-yl)-10-(4-pyridyl)anthracene, and bpy=2, 2'-bipyridine, are synthesized by reacting aryl pyrazole pyridine ligands with dipalla-dium corners in aqueous solutions via metal-directed hierarchical self-assembly. The structures of the supramolecular Pd parallelograms are confirmed through single-crystal X-ray diffraction. Notably, the two parallelogram metallacycles can be used as"turn-on"fluorescence sensors to detect HSO3- through a disassembly mechanism. In addition, the 1a-based sensor shows selective detection of HSO3- without interference from other anions. The detection limit was as low as 0.131 μmol·L-1. Furthermore, complex 1a presented the semiquantitative visual detection ability for HSO3- in the test trip mode via fluorescence changes.
In this study, parallelogram-like macrocyclic supramolecular metallacycles [Pd6(bpy)6(L1)4](PF6)8 (1a) and [Pd6(bpy)6(L2)4](PF6)8 (2a), where HL1=1-(1H-pyrazole-4-yl)-4-(4-pyridyl)benzene, HL2=9-(1H-pyrazole-4-yl)-10-(4-pyridyl)anthracene, and bpy=2, 2'-bipyridine, are synthesized by reacting aryl pyrazole pyridine ligands with dipalla-dium corners in aqueous solutions via metal-directed hierarchical self-assembly. The structures of the supramolecular Pd parallelograms are confirmed through single-crystal X-ray diffraction. Notably, the two parallelogram metallacycles can be used as"turn-on"fluorescence sensors to detect HSO3- through a disassembly mechanism. In addition, the 1a-based sensor shows selective detection of HSO3- without interference from other anions. The detection limit was as low as 0.131 μmol·L-1. Furthermore, complex 1a presented the semiquantitative visual detection ability for HSO3- in the test trip mode via fluorescence changes.
2024, 40(7): 1368-1376
doi: 10.11862/CJIC.20240066
Abstract:
Two new viologen-polyoxometalate hybrid crystalline materials: (MV)2[HPW2ⅤW10ⅥO40] ·2H2O (1) and (EV)2[Mo8O26] (2) have been synthesized by using the cations of 1, 1'-dimethyl-4, 4'-bipyridinium dichloride (methyl viologen, MV) and 1, 1'-diethyl-4, 4'-bipyridinium dibromide (ethyl viologen, EV) as the electron acceptors, and the electron-rich polyoxometalate anions as the electron donors. The structures of compounds 1 and 2 have been determined by single-crystal X-ray crystallography. Hydrogen bond interactions exist between the cations and the anions in 1 and 2. Interestingly, 2 has a photochromic performance with a light response time within 1 min. The photochromic mechanism of compound 2 has been investigated by solid-state diffuse reflection, electron paramagnetic resonance and theoretical calculation. 1 and 2 show good catalytic performance in the photocatalytic degradation of several organic dyes (methylene blue, pararosaniline hydrochloride and rhodamine 6G).
Two new viologen-polyoxometalate hybrid crystalline materials: (MV)2[HPW2ⅤW10ⅥO40] ·2H2O (1) and (EV)2[Mo8O26] (2) have been synthesized by using the cations of 1, 1'-dimethyl-4, 4'-bipyridinium dichloride (methyl viologen, MV) and 1, 1'-diethyl-4, 4'-bipyridinium dibromide (ethyl viologen, EV) as the electron acceptors, and the electron-rich polyoxometalate anions as the electron donors. The structures of compounds 1 and 2 have been determined by single-crystal X-ray crystallography. Hydrogen bond interactions exist between the cations and the anions in 1 and 2. Interestingly, 2 has a photochromic performance with a light response time within 1 min. The photochromic mechanism of compound 2 has been investigated by solid-state diffuse reflection, electron paramagnetic resonance and theoretical calculation. 1 and 2 show good catalytic performance in the photocatalytic degradation of several organic dyes (methylene blue, pararosaniline hydrochloride and rhodamine 6G).
2024, 40(7): 1377-1386
doi: 10.11862/CJIC.20230415
Abstract:
Two metal-organic frameworks (MOFs) containing rigid bis(triazole) ligand, namely {[Zn2(L)(TP)2(H2O)·H2O]}n (1) and [Zn(L)(HTMA)]n (2), where L=4, 4'-(3, 3'-dimethyl-(1, 1'-biphenyl)-4, 4'-diyl)bis(4H-1, 2, 4-triazole), H2TP=terephthalic acid, H3TMA=1, 3, 5-benzenetricarboxylic acid, were synthesized by using acid-base mixed ligands strategy and structurally characterized by X-ray single-crystal diffraction. Structural analysis reveals that MOF 1 displays a 3, 6-connected 2D structure with a new topological point symbol of (42·6)2(48·66·8), while MOF 2 presents a 2D sql topology structure. The catalytic studies reveal that 2 exhibits excellent catalytic activity for the cycloaddition reaction of CO2 with epoxides under mild conditions. Furthermore, 2 can be reused at least three times while maintaining its catalytic ability.
Two metal-organic frameworks (MOFs) containing rigid bis(triazole) ligand, namely {[Zn2(L)(TP)2(H2O)·H2O]}n (1) and [Zn(L)(HTMA)]n (2), where L=4, 4'-(3, 3'-dimethyl-(1, 1'-biphenyl)-4, 4'-diyl)bis(4H-1, 2, 4-triazole), H2TP=terephthalic acid, H3TMA=1, 3, 5-benzenetricarboxylic acid, were synthesized by using acid-base mixed ligands strategy and structurally characterized by X-ray single-crystal diffraction. Structural analysis reveals that MOF 1 displays a 3, 6-connected 2D structure with a new topological point symbol of (42·6)2(48·66·8), while MOF 2 presents a 2D sql topology structure. The catalytic studies reveal that 2 exhibits excellent catalytic activity for the cycloaddition reaction of CO2 with epoxides under mild conditions. Furthermore, 2 can be reused at least three times while maintaining its catalytic ability.
2024, 40(7): 1387-1396
doi: 10.11862/CJIC.20240045
Abstract:
Two alkali-metal sulfamates nonlinear optical (NLO) crystals, Li(NH2SO3) and Na(NH2SO3), have been obtained through the facile evaporation method. Li(NH2SO3) crystallizes in the polar space group Pca21 (No.29). The structure of Li(NH2SO3) can be described as a 3D network formed by [LiO4]7- polyhedral connecting with NH2SO3- tetrahedra through corner-sharing. Na(NH2SO3) crystallizes in the polar space group P212121 (No.19). The structure of Na(NH2SO3) can be described as a 3D network formed by distorted [NaO6]11- octahedral connecting with NH2SO3- tetrahedra through corner-sharing. The UV-Vis-near-infrared spectra demonstrate that Li(NH2SO3) and Na(NH2SO3) possessed large optical band gaps of 5.25 and 4.81 eV, respectively. Powder second-harmonic generation (SHG) measurements demonstrate that the SHG intensity of Li(NH2SO3) and Na(NH2SO3) were 0.32 times and 0.31 times that of KH2PO4, respectively. First-principles calculations confirm the nonlinear optical performance mainly derived from the synergistic effect of amino sulfonate anions and alkali metal oxide anionic polyhedra.
Two alkali-metal sulfamates nonlinear optical (NLO) crystals, Li(NH2SO3) and Na(NH2SO3), have been obtained through the facile evaporation method. Li(NH2SO3) crystallizes in the polar space group Pca21 (No.29). The structure of Li(NH2SO3) can be described as a 3D network formed by [LiO4]7- polyhedral connecting with NH2SO3- tetrahedra through corner-sharing. Na(NH2SO3) crystallizes in the polar space group P212121 (No.19). The structure of Na(NH2SO3) can be described as a 3D network formed by distorted [NaO6]11- octahedral connecting with NH2SO3- tetrahedra through corner-sharing. The UV-Vis-near-infrared spectra demonstrate that Li(NH2SO3) and Na(NH2SO3) possessed large optical band gaps of 5.25 and 4.81 eV, respectively. Powder second-harmonic generation (SHG) measurements demonstrate that the SHG intensity of Li(NH2SO3) and Na(NH2SO3) were 0.32 times and 0.31 times that of KH2PO4, respectively. First-principles calculations confirm the nonlinear optical performance mainly derived from the synergistic effect of amino sulfonate anions and alkali metal oxide anionic polyhedra.
2024, 40(7): 1397-1408
doi: 10.11862/CJIC.20240009
Abstract:
5-(dimethylamino) isophthalic acid (H2dia) and 1H-imidazole (mdz) were used as ligands to react with Zn(Ⅱ) or Cu(Ⅱ) metal salts to generate three new transition metal complexes [Zn(dia)(mdz)2]·2H2O (1), [Cu(dia)(mdz)2 (DMF)] (2) and [Cu(dia)(mdz)2]·H2O (3). Their structures were characterized by single-crystal X-ray diffraction, elemental analysis, IR, thermogravimetric analyses, and Hirshfeld surface analyses. The results revealed that complexes 1 and 2 possess 1D linear chains, each four-coordinated Zn(Ⅱ) of 1 is located in the geometric center of the distorted tetrahedron, but the Cu(Ⅱ) metal center of 2 is five-coordinated and holds a triangular bipyramidal geometry. The zigzag 1D chain of complex 3 was obtained by changing the solvent in the synthesis, and the four-coordinated Cu(Ⅱ) ion is in the centre of the square planar. Results indicate that the geometries of metal centers and synthetic solvents have important effects on the structures of complexes. Abundant intermolecular hydrogen bonding plays an important role in the stability of their 3D supramolecular structures. Thermogravimetric analyses revealed that the complexes have good thermal stabilities. Solid fluorescence analyses showed that complex 1 had excellent fluorescence, but the fluorescence intensities of complexes 2 and 3 were much lower than those of ligands.
5-(dimethylamino) isophthalic acid (H2dia) and 1H-imidazole (mdz) were used as ligands to react with Zn(Ⅱ) or Cu(Ⅱ) metal salts to generate three new transition metal complexes [Zn(dia)(mdz)2]·2H2O (1), [Cu(dia)(mdz)2 (DMF)] (2) and [Cu(dia)(mdz)2]·H2O (3). Their structures were characterized by single-crystal X-ray diffraction, elemental analysis, IR, thermogravimetric analyses, and Hirshfeld surface analyses. The results revealed that complexes 1 and 2 possess 1D linear chains, each four-coordinated Zn(Ⅱ) of 1 is located in the geometric center of the distorted tetrahedron, but the Cu(Ⅱ) metal center of 2 is five-coordinated and holds a triangular bipyramidal geometry. The zigzag 1D chain of complex 3 was obtained by changing the solvent in the synthesis, and the four-coordinated Cu(Ⅱ) ion is in the centre of the square planar. Results indicate that the geometries of metal centers and synthetic solvents have important effects on the structures of complexes. Abundant intermolecular hydrogen bonding plays an important role in the stability of their 3D supramolecular structures. Thermogravimetric analyses revealed that the complexes have good thermal stabilities. Solid fluorescence analyses showed that complex 1 had excellent fluorescence, but the fluorescence intensities of complexes 2 and 3 were much lower than those of ligands.
2024, 40(7): 1409-1422
doi: 10.11862/CJIC.20240007
Abstract:
Three new copper(Ⅱ) complexes 1-3 of Schiff base ligands HL1 (2-hydroxybenzaldehyde2-(2-oxo-1, 2-diphenylethylidene)hydrazone), HL2 (4-hydroxybenzaldehyde2-(2-oxo-1, 2-diphenylethylidene)hydrazone) and L3 (2-methoxybenzaldehyde2-(2-oxo-1, 2-diphenylethylidene)hydrazone) were synthesized from methanolic medium. The complexes were characterized by elemental analyses, spectroscopic methods, magnetic susceptibility measurements, and density functional theory (DFT) studies. The synthesized ligands were characterized structurally by single-crystal X-ray diffraction studies. The optimized structure of the complexes was ascertained by DFT studies. The DNA binding ability of the complexes with calf thymus DNA (CT-DNA) was studied by UV-Vis absorption and fluorescence emission spectral studies. Absorption spectral studies revealed a hyperchromic effect and suggested the possible mode of interaction with CT-DNA. The competitive binding studies using ethidium bromide (EB) show that the complexes can replace DNA from DNA-EB adduct and suggests that the complexes probably bind to CT-DNA in intercalative mode. In vitro antibacterial activity of the complexes against Gram-negative bacteria Klebsiella pneumoniae (K. pneumoniae), Escherichia coli(E. coli), and Shigella boydii (S. boydii), and gram-positive bacteria Staphylococcus aureus (S. aureus) exhibited an appreciable antibacterial activity of complex 2 against K. pneumoniae and S. boydii, but complexes 1 and 3 did not show any significant antibacterial activity.
Three new copper(Ⅱ) complexes 1-3 of Schiff base ligands HL1 (2-hydroxybenzaldehyde2-(2-oxo-1, 2-diphenylethylidene)hydrazone), HL2 (4-hydroxybenzaldehyde2-(2-oxo-1, 2-diphenylethylidene)hydrazone) and L3 (2-methoxybenzaldehyde2-(2-oxo-1, 2-diphenylethylidene)hydrazone) were synthesized from methanolic medium. The complexes were characterized by elemental analyses, spectroscopic methods, magnetic susceptibility measurements, and density functional theory (DFT) studies. The synthesized ligands were characterized structurally by single-crystal X-ray diffraction studies. The optimized structure of the complexes was ascertained by DFT studies. The DNA binding ability of the complexes with calf thymus DNA (CT-DNA) was studied by UV-Vis absorption and fluorescence emission spectral studies. Absorption spectral studies revealed a hyperchromic effect and suggested the possible mode of interaction with CT-DNA. The competitive binding studies using ethidium bromide (EB) show that the complexes can replace DNA from DNA-EB adduct and suggests that the complexes probably bind to CT-DNA in intercalative mode. In vitro antibacterial activity of the complexes against Gram-negative bacteria Klebsiella pneumoniae (K. pneumoniae), Escherichia coli(E. coli), and Shigella boydii (S. boydii), and gram-positive bacteria Staphylococcus aureus (S. aureus) exhibited an appreciable antibacterial activity of complex 2 against K. pneumoniae and S. boydii, but complexes 1 and 3 did not show any significant antibacterial activity.
2024, 40(7): 1243-1253
doi: 10.11862/CJIC.20240110
Abstract:
Herein, a dense and hydrophobic Cu metal protective layer was constructed in-situ on the Zn electrode (Cu@Zn) through a displacement reaction in an organic solvent. Specifically, CuI powder was dissolved in N-methyl-2-pyrrolidone (NMP) and stirred for 12 h to obtain a uniform solution. Subsequently, the bare Zn was immersed in the solution at 80 ℃ for 6 h, and then washed with absolute ethanol three times to achieve the Cu@Zn electrode. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) analyses confirm a dense Cu protective layer on the surface of the Cu@Zn electrode. Additionally, the better hydrophobicity of the Cu@Zn electrode was demonstrated through contact angle measurements with a 2 mol·L-1 ZnSO4 electrolyte. The dense and hydrophobic Cu metal protective layer can effectively isolate the direct contact between the Zn electrode and electrolyte, suppressing side reactions such as hydrogen evolution and corrosion at the electrode/electrolyte interface. Furthermore, the Cu layer possesses zincophilicity, reduced interfacial resistance, and a lower nucleation energy barrier, thereby promoting uniform Zn deposition and effectively inhibiting dendritic growth. As a result, Cu@Zn symmetric cells exhibited continuous stable performance for 1 700 and 1 330 h at 1 mA·cm-2, 1 mAh·cm-2 and 3 mA·cm-2, 1 mAh·cm-2, respectively, which were higher than those of bare Zn symmetric cells (204 and 120 h). Furthermore, the Cu@Zn||MnO2 full cell delivered a specific capacity of 168.5 mAh·g-1 at 1 A·g-1 respectively, maintaining stability for over 2 000 cycles.
Herein, a dense and hydrophobic Cu metal protective layer was constructed in-situ on the Zn electrode (Cu@Zn) through a displacement reaction in an organic solvent. Specifically, CuI powder was dissolved in N-methyl-2-pyrrolidone (NMP) and stirred for 12 h to obtain a uniform solution. Subsequently, the bare Zn was immersed in the solution at 80 ℃ for 6 h, and then washed with absolute ethanol three times to achieve the Cu@Zn electrode. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) analyses confirm a dense Cu protective layer on the surface of the Cu@Zn electrode. Additionally, the better hydrophobicity of the Cu@Zn electrode was demonstrated through contact angle measurements with a 2 mol·L-1 ZnSO4 electrolyte. The dense and hydrophobic Cu metal protective layer can effectively isolate the direct contact between the Zn electrode and electrolyte, suppressing side reactions such as hydrogen evolution and corrosion at the electrode/electrolyte interface. Furthermore, the Cu layer possesses zincophilicity, reduced interfacial resistance, and a lower nucleation energy barrier, thereby promoting uniform Zn deposition and effectively inhibiting dendritic growth. As a result, Cu@Zn symmetric cells exhibited continuous stable performance for 1 700 and 1 330 h at 1 mA·cm-2, 1 mAh·cm-2 and 3 mA·cm-2, 1 mAh·cm-2, respectively, which were higher than those of bare Zn symmetric cells (204 and 120 h). Furthermore, the Cu@Zn||MnO2 full cell delivered a specific capacity of 168.5 mAh·g-1 at 1 A·g-1 respectively, maintaining stability for over 2 000 cycles.
2024, 40(7): 1254-1260
doi: 10.11862/CJIC.20240047
Abstract:
An alloy nanocluster of Au11-xCux(dppf)4Cl2 (x=1, 2; dppf=1, 1'-bis(diphenylphosphine) ferrocene) was synthesized via a one -pot reduction method. X-ray crystallography shows that this nanocluster has a defective icosahedral core, which is analog to that of Au11(dppf)4Cl2. The difference lies in that Cu atoms replace the inner shell Au atoms that are coordinated with the Cl atom. Therefore, Au11-xCux(dppf)4Cl2 can be regarded as Cu-doped Au11(dppf)4Cl2. The introduction of Cu atoms exerts an influence on the electronic property of the template nanocluster with the structural framework maintained, further resulting in a red shift of the optical absorption.
An alloy nanocluster of Au11-xCux(dppf)4Cl2 (x=1, 2; dppf=1, 1'-bis(diphenylphosphine) ferrocene) was synthesized via a one -pot reduction method. X-ray crystallography shows that this nanocluster has a defective icosahedral core, which is analog to that of Au11(dppf)4Cl2. The difference lies in that Cu atoms replace the inner shell Au atoms that are coordinated with the Cl atom. Therefore, Au11-xCux(dppf)4Cl2 can be regarded as Cu-doped Au11(dppf)4Cl2. The introduction of Cu atoms exerts an influence on the electronic property of the template nanocluster with the structural framework maintained, further resulting in a red shift of the optical absorption.
2024, 40(7): 1270-1278
doi: 10.11862/CJIC.20240037
Abstract:
BiOBr-Pt catalysts with hierarchical hollow structures were synthesized by a one-step solvothermal method using ethylene glycol as solvent and polyvinylpyrrolidone as surfactant. The synthesized hierarchical hollow structure BiOBr-2h catalyst had a specific surface area of 28 m2·g-1, twice as large as the comparison sample BiOBr-1h. This structure provides more reactive sites for the catalytic reaction. Meanwhile, introducing Pt into the catalyst can enhance the carrier conduction rate of BiOBr. Moreover, it can act as an electron trap to capture many surrounding electrons and inhibit the complexation of photogenerated carriers, thus improving the catalytic activity of CO2 reduction. The main product of BiOBr-Pt was CO with 99% product selectivity and its CO yield was 20.8 μmol·h-1· g-1. Its performance was 2.1 times that of primitive BiOBr. This Pt loading with a hierarchical hollow structure can effectively convert CO2.
BiOBr-Pt catalysts with hierarchical hollow structures were synthesized by a one-step solvothermal method using ethylene glycol as solvent and polyvinylpyrrolidone as surfactant. The synthesized hierarchical hollow structure BiOBr-2h catalyst had a specific surface area of 28 m2·g-1, twice as large as the comparison sample BiOBr-1h. This structure provides more reactive sites for the catalytic reaction. Meanwhile, introducing Pt into the catalyst can enhance the carrier conduction rate of BiOBr. Moreover, it can act as an electron trap to capture many surrounding electrons and inhibit the complexation of photogenerated carriers, thus improving the catalytic activity of CO2 reduction. The main product of BiOBr-Pt was CO with 99% product selectivity and its CO yield was 20.8 μmol·h-1· g-1. Its performance was 2.1 times that of primitive BiOBr. This Pt loading with a hierarchical hollow structure can effectively convert CO2.
2024, 40(7): 1279-1289
doi: 10.11862/CJIC.20240026
Abstract:
Combined strategy of alkali treatment and chromium modification was used to synergistically regulate the pore structure and acidic property of the high-silica ZSM-5 zeolite. During the alkaline treatment, the abundant intergrowth boundaries constructed by adjusting the composition of the synthesis gel induced the formation of meso-pores. Thereby, the limitation of the conventional alkali treatment method coming from the framework Si/Al ratio of parent zeolite was circumvented. In the process of chromium modification, the unique hierarchical pore structure promoted the dispersion of chromium species in the catalyst. Thus, a deep modification of the acidic property was realized. As a result, a high-silica hierarchical zeolite catalyst with suitable acidities was obtained. During the catalytic conversion of methanol to propylene, the variation of the pore structure and acidic property caused obvious changes in the coke deposition behavior of the catalyst and the mass transfer of products. Consequently, the prepared catalyst exhibited excellent catalytic stability and a high selectivity towards propylene and total light olefins.
Combined strategy of alkali treatment and chromium modification was used to synergistically regulate the pore structure and acidic property of the high-silica ZSM-5 zeolite. During the alkaline treatment, the abundant intergrowth boundaries constructed by adjusting the composition of the synthesis gel induced the formation of meso-pores. Thereby, the limitation of the conventional alkali treatment method coming from the framework Si/Al ratio of parent zeolite was circumvented. In the process of chromium modification, the unique hierarchical pore structure promoted the dispersion of chromium species in the catalyst. Thus, a deep modification of the acidic property was realized. As a result, a high-silica hierarchical zeolite catalyst with suitable acidities was obtained. During the catalytic conversion of methanol to propylene, the variation of the pore structure and acidic property caused obvious changes in the coke deposition behavior of the catalyst and the mass transfer of products. Consequently, the prepared catalyst exhibited excellent catalytic stability and a high selectivity towards propylene and total light olefins.
2024, 40(7): 1290-1300
doi: 10.11862/CJIC.20240021
Abstract:
The CsPbBr3 absorber layer made from CsBr aqueous solution was modified by spin-coating I2 isopropa- nol solution, which the surface defects of the CsPbBr3 layer were passivated, and the CsPbBr3 film with better mor- phology was obtained. The solar cells were optimized by exploring different spin-coating concentrations of CsBr methanol solution, and when 5 mg·mL-1 I2 isopropanol solution was used for interface modification, the perovskite film was significantly improved in morphology from the result of X-ray diffraction, scanning electron microscope and had the best optoelectronic performance. As a consequence, CsPbBr3-based perovskite solar cells (PSCs) with 5 mg· mL-1I2 isopropanol solution can reach the best open-circuit voltage (VOC), short circuit current density (JSC), fill factor (FF) of 1.55 V, 7.45 mA·cm-2, 85.54%, respectively, and the ultimate photoelectric conversion efficiency (PCE) attained 9.88%.
The CsPbBr3 absorber layer made from CsBr aqueous solution was modified by spin-coating I2 isopropa- nol solution, which the surface defects of the CsPbBr3 layer were passivated, and the CsPbBr3 film with better mor- phology was obtained. The solar cells were optimized by exploring different spin-coating concentrations of CsBr methanol solution, and when 5 mg·mL-1 I2 isopropanol solution was used for interface modification, the perovskite film was significantly improved in morphology from the result of X-ray diffraction, scanning electron microscope and had the best optoelectronic performance. As a consequence, CsPbBr3-based perovskite solar cells (PSCs) with 5 mg· mL-1I2 isopropanol solution can reach the best open-circuit voltage (VOC), short circuit current density (JSC), fill factor (FF) of 1.55 V, 7.45 mA·cm-2, 85.54%, respectively, and the ultimate photoelectric conversion efficiency (PCE) attained 9.88%.
2024, 40(7): 1301-1308
doi: 10.11862/CJIC.20240003
Abstract:
Two dimethylglyoxime organotin compounds, bis(tri(2-methyl-2-phenylpropyl)tin) dimethylglyoxime complex (C6H5C(CH3)2CH2)3Sn(ON=C(CH3)C(CH3) =NO)Sn(CH2C(CH3)2C6H5)3 (1) and di(benzyl)tin oxide, chlorine, butanedione oxime multinuclear complex [μ3-O-((C6H5CH2)2Sn)2(ON=C(CH3)C(CH3)=NOH)(O)Cl]2 (2), were synthesized. The compounds were characterized by elemental analysis, IR spectroscopy, NMR (1H, 13C, and 119Sn), thermogravimetric analysis, and single-crystal X-ray diffraction, and quantum chemical ab initio calculation was performed for their structure and in vitro anticancer activity were studied for the compounds. The results showed that complex 1 is a central symmetric molecule with double tin nuclei bridged by the ligand dimethylglyoxime, and the tin atoms are distorted tetrahedral configurations with four coordination. Complex 2 is a central symmetric polycyclic polymerization structure of tetratin nuclei bridged by oxygen atoms and dimethylglyoxime, and the tin atoms are five-coordinated distorted triangular bipyramidal configuration and six-coordinated distorted octahedral configuration, respectively. In addition, the complexes have stronger inhibitory activity on human liver cancer cells(HUH7), human lung cancer cells (A549), human epidermal cancer cells (A431), human colon cancer cells (HCT-116), and breast cancer cells (MDA-MB-231).
Two dimethylglyoxime organotin compounds, bis(tri(2-methyl-2-phenylpropyl)tin) dimethylglyoxime complex (C6H5C(CH3)2CH2)3Sn(ON=C(CH3)C(CH3) =NO)Sn(CH2C(CH3)2C6H5)3 (1) and di(benzyl)tin oxide, chlorine, butanedione oxime multinuclear complex [μ3-O-((C6H5CH2)2Sn)2(ON=C(CH3)C(CH3)=NOH)(O)Cl]2 (2), were synthesized. The compounds were characterized by elemental analysis, IR spectroscopy, NMR (1H, 13C, and 119Sn), thermogravimetric analysis, and single-crystal X-ray diffraction, and quantum chemical ab initio calculation was performed for their structure and in vitro anticancer activity were studied for the compounds. The results showed that complex 1 is a central symmetric molecule with double tin nuclei bridged by the ligand dimethylglyoxime, and the tin atoms are distorted tetrahedral configurations with four coordination. Complex 2 is a central symmetric polycyclic polymerization structure of tetratin nuclei bridged by oxygen atoms and dimethylglyoxime, and the tin atoms are five-coordinated distorted triangular bipyramidal configuration and six-coordinated distorted octahedral configuration, respectively. In addition, the complexes have stronger inhibitory activity on human liver cancer cells(HUH7), human lung cancer cells (A549), human epidermal cancer cells (A431), human colon cancer cells (HCT-116), and breast cancer cells (MDA-MB-231).
2024, 40(7): 1309-1319
doi: 10.11862/CJIC.20240001
Abstract:
A Cu2O/Cu-vertical graphene microelectrode was prepared by combining Cu(Ⅱ) ion impregnation adsorption and direct current (DC) arc plasma jet chemical vapor deposition methods for dual functions including electro-chemical detection of uric acid and recording electroencephalogram (EEG) signals. The morphology, microstructure, and crystal composition of the microelectrode were characterized using scanning electron microscopy, transmission electron microscopy, and X-ray diffraction, and the electrochemical and EEG recording capabilities were evaluated. The microelectrode was composed of vertically grown graphene nanosheets embedded with Cu2O/Cu nanoparticles, with a diameter of approximately 200 μm. Because these nanosheets are arranged into a three-dimensional porous structure, the microelectrode has a short ion diffusion path and a long conductive network, which promotes high elec-trocatalytic activity and electrical performance. The scalp-contact resistance of the microelectrode with physiological saline was as low as 7.05 kΩ. The signal-to-noise ratios of electromyography (EMG), electrooculogram (EOG), and EEG of the microelectrode were close to or exceeded those of a commercial wet electrode coated with conductive gel. In addition, the microelectrode also electrochemically responded to uric acid, with a wide concentration range of 0.5-500 μmol·L-1 and a low detection limit of 0.024 μmol·L-1, as well as excellent anti-interference and long-term stability.
A Cu2O/Cu-vertical graphene microelectrode was prepared by combining Cu(Ⅱ) ion impregnation adsorption and direct current (DC) arc plasma jet chemical vapor deposition methods for dual functions including electro-chemical detection of uric acid and recording electroencephalogram (EEG) signals. The morphology, microstructure, and crystal composition of the microelectrode were characterized using scanning electron microscopy, transmission electron microscopy, and X-ray diffraction, and the electrochemical and EEG recording capabilities were evaluated. The microelectrode was composed of vertically grown graphene nanosheets embedded with Cu2O/Cu nanoparticles, with a diameter of approximately 200 μm. Because these nanosheets are arranged into a three-dimensional porous structure, the microelectrode has a short ion diffusion path and a long conductive network, which promotes high elec-trocatalytic activity and electrical performance. The scalp-contact resistance of the microelectrode with physiological saline was as low as 7.05 kΩ. The signal-to-noise ratios of electromyography (EMG), electrooculogram (EOG), and EEG of the microelectrode were close to or exceeded those of a commercial wet electrode coated with conductive gel. In addition, the microelectrode also electrochemically responded to uric acid, with a wide concentration range of 0.5-500 μmol·L-1 and a low detection limit of 0.024 μmol·L-1, as well as excellent anti-interference and long-term stability.
2024, 40(7): 1320-1328
doi: 10.11862/CJIC.20230480
Abstract:
Aiming at the difficulty that the alkaline substances left on the surface of Li[Ni0.8Co0.15Al0.05]O2 (NCA) precursor preparation and lithium preparation sintering process can seriously affect its cycling stability performance, a proposal was made to employ Y(PO3)3 for surface coating modification. This modification involves utilizing Y(PO3)3 to react with the surface residual LiOH to eliminate surface residual alkali and investigate the impact mechanism of coating modification on the overall performance of NCA. The thickness of the cladding layer was not affected by the residual alkali content on the surface. Test analysis results demonstrate that during low-temperature calcination, a uniform and dense coating layer of Y(PO3)3 and LiPO3 formed on the precursor's surface. LiPO3 exhibited higher ionic conductivity, and the dual coating layer can prevent harmful side reactions between the active material and the electrolyte during the electrochemical cycling process, enhancing the cycling stability of the electrode material. Specifically, for samples with a mass fraction of 1% Y(PO3)3 coating, at 0.1C, the initial Coulombic efficiency increased from 78.65% for unmodified samples to 88.50%. After 150 cycles at 1C, the capacity retention rate increased from 59.38% to 85.33%. Compared to unmodified samples, it showed higher initial Coulombic efficiency and superior cycling performance.
Aiming at the difficulty that the alkaline substances left on the surface of Li[Ni0.8Co0.15Al0.05]O2 (NCA) precursor preparation and lithium preparation sintering process can seriously affect its cycling stability performance, a proposal was made to employ Y(PO3)3 for surface coating modification. This modification involves utilizing Y(PO3)3 to react with the surface residual LiOH to eliminate surface residual alkali and investigate the impact mechanism of coating modification on the overall performance of NCA. The thickness of the cladding layer was not affected by the residual alkali content on the surface. Test analysis results demonstrate that during low-temperature calcination, a uniform and dense coating layer of Y(PO3)3 and LiPO3 formed on the precursor's surface. LiPO3 exhibited higher ionic conductivity, and the dual coating layer can prevent harmful side reactions between the active material and the electrolyte during the electrochemical cycling process, enhancing the cycling stability of the electrode material. Specifically, for samples with a mass fraction of 1% Y(PO3)3 coating, at 0.1C, the initial Coulombic efficiency increased from 78.65% for unmodified samples to 88.50%. After 150 cycles at 1C, the capacity retention rate increased from 59.38% to 85.33%. Compared to unmodified samples, it showed higher initial Coulombic efficiency and superior cycling performance.
2024, 40(7): 1329-1336
doi: 10.11862/CJIC.20230447
Abstract:
Reduced graphene oxide/ZnS (rGO/ZnS) composites were successfully prepared by hydrothermal method using graphene oxide (GO), zinc acetate (Zn(CH3COO)2), and thiourea as raw materials. The microstructure and morphology of the sample were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM), etc. The material was used as anodes for lithium-ion batteries, and electrochemical test results demonstrated that the asprepared rGO/ZnS composite exhibited significantly enhanced electrochemical lithium storage performance in comparison to rGO. The highly conductive rGO can provide an efficient path for the transport of lithium ions and electrons, and ZnS can provide a high theoretical specific capacity. The rGO/ZnS composites exhibited good lithium intercalation capacity and cycling performance under the synergistic effect of rGO and nanoscale highly dispersed spherical ZnS particles. When the GO mass concentration was 2 mg·mL-1, the rGO/ZnS composites had the best rate performance and the best cycling stability.
Reduced graphene oxide/ZnS (rGO/ZnS) composites were successfully prepared by hydrothermal method using graphene oxide (GO), zinc acetate (Zn(CH3COO)2), and thiourea as raw materials. The microstructure and morphology of the sample were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM), etc. The material was used as anodes for lithium-ion batteries, and electrochemical test results demonstrated that the asprepared rGO/ZnS composite exhibited significantly enhanced electrochemical lithium storage performance in comparison to rGO. The highly conductive rGO can provide an efficient path for the transport of lithium ions and electrons, and ZnS can provide a high theoretical specific capacity. The rGO/ZnS composites exhibited good lithium intercalation capacity and cycling performance under the synergistic effect of rGO and nanoscale highly dispersed spherical ZnS particles. When the GO mass concentration was 2 mg·mL-1, the rGO/ZnS composites had the best rate performance and the best cycling stability.
2024, 40(7): 1337-1346
doi: 10.11862/CJIC.20230414
Abstract:
To design a highly stable and sensitive metal-organic framework (MOF) electrochemical sensor for detecting dopamine (DA), we selected indium-based MOF [In(2-NH3-BDC)(2-NH2-BDC)]·1.5H2O (RSMOF-1, RSMOF=resistance switchable metal-organic framework, 2-NH2-H2BDC=2-amino terephthalic acid) to modify the glassy carbon electrode (RSMOF-1/GCE). The DPV test results of the prepared electrode RSMOF-1/GCE showed a linear range of 0.990-663 μmol·L-1 and a detection limit of 0.770 μmol·L-1. In the presence of various interfering substances (uric acid, urea, glucose, acetaminophen), RSMOF-1/GCE still exhibited high selectivity towards DA. The theoretical simulation results demonstrated that the —NH2 on the inner wall of the RSMOF-1 pore can enhance interaction with DA molecules through hydrogen bonding, indicating its sensitive electrochemical sensing performance for DA.
To design a highly stable and sensitive metal-organic framework (MOF) electrochemical sensor for detecting dopamine (DA), we selected indium-based MOF [In(2-NH3-BDC)(2-NH2-BDC)]·1.5H2O (RSMOF-1, RSMOF=resistance switchable metal-organic framework, 2-NH2-H2BDC=2-amino terephthalic acid) to modify the glassy carbon electrode (RSMOF-1/GCE). The DPV test results of the prepared electrode RSMOF-1/GCE showed a linear range of 0.990-663 μmol·L-1 and a detection limit of 0.770 μmol·L-1. In the presence of various interfering substances (uric acid, urea, glucose, acetaminophen), RSMOF-1/GCE still exhibited high selectivity towards DA. The theoretical simulation results demonstrated that the —NH2 on the inner wall of the RSMOF-1 pore can enhance interaction with DA molecules through hydrogen bonding, indicating its sensitive electrochemical sensing performance for DA.
2024, 40(7): 1347-1356
doi: 10.11862/CJIC.20230357
Abstract:
A new lanthanide binuclear Tb(Ⅲ)-based complex with the formula [Tb2(L)(H2L)]·2CH3OH·CH3CN (1) have been synthesized via the solvothermal method by using a polydentate Schiff base ligand (H4L=N', N″-((1E, 1'E)-(1, 10 -phenanthroline-2, 9-diyl) bis (methaneylylidene)) bis (2-hydroxybenzohydrazide)) reacting with Tb(acac)3·2H2O (acac-=acetylacetonate). It was characterized by IR, elemental analysis, single-crystal and powder X-ray diffraction. Single-crystal X-ray structure analysis reveals that complex 1 belongs to the triclinic system with $P \overline{1}$ space group, and the asymmetric unit mainly includes two TbⅢ ions and two different deprotonated ligands (L4- and H2L2-). Both centre Tb1 and Tb2 ions are nine-coordinated with a [N4O5] coordination environment. The coordination geometry is shown as a distorted hula-hoop. In addition, the biological activity study shows that the complex has stronger antibacterial activity than H4L and Tb(acac)3·2H2O. The interaction between 1 and DNA was studied by UV-Vis spectroscopy, cyclic voltammetry, gel electrophoresis, and fluorescence spectroscopy. The results reveal that 1 could bind to calf thymus DNA mainly by intercalation. Ethidium bromide (EB) displacement experiments indicated that Stern-Volmer quenching constants of complexes 1 and H4L were 1.04 and 0.30, respectively.
A new lanthanide binuclear Tb(Ⅲ)-based complex with the formula [Tb2(L)(H2L)]·2CH3OH·CH3CN (1) have been synthesized via the solvothermal method by using a polydentate Schiff base ligand (H4L=N', N″-((1E, 1'E)-(1, 10 -phenanthroline-2, 9-diyl) bis (methaneylylidene)) bis (2-hydroxybenzohydrazide)) reacting with Tb(acac)3·2H2O (acac-=acetylacetonate). It was characterized by IR, elemental analysis, single-crystal and powder X-ray diffraction. Single-crystal X-ray structure analysis reveals that complex 1 belongs to the triclinic system with $P \overline{1}$ space group, and the asymmetric unit mainly includes two TbⅢ ions and two different deprotonated ligands (L4- and H2L2-). Both centre Tb1 and Tb2 ions are nine-coordinated with a [N4O5] coordination environment. The coordination geometry is shown as a distorted hula-hoop. In addition, the biological activity study shows that the complex has stronger antibacterial activity than H4L and Tb(acac)3·2H2O. The interaction between 1 and DNA was studied by UV-Vis spectroscopy, cyclic voltammetry, gel electrophoresis, and fluorescence spectroscopy. The results reveal that 1 could bind to calf thymus DNA mainly by intercalation. Ethidium bromide (EB) displacement experiments indicated that Stern-Volmer quenching constants of complexes 1 and H4L were 1.04 and 0.30, respectively.
2024, 40(7): 1357-1367
doi: 10.11862/CJIC.20230350
Abstract:
Melamine, RuCl3, and carbon black were dispersed in ethanol with a certain proportion, and a nitrogen-doped carbon (NC)-supported Ru catalyst (Ru/NC) was synthesized by spin evaporation drying and high-temperature thermal treatment. The PtRu/NC catalysts with different Pt and Ru contents were synthesized by sodium borohydride liquid phase chemical reduction, which was used for electrocatalytic methanol oxidation reaction (MOR) and hydrogen evolution reaction (HER) by water electrolysis. The results showed that Pt1Ru/NC (mass fraction: 1.14% for Pt, 0.54% for Ru) had the best MOR performance among as-synthesized catalysts, with a mass activity of 4.96 A·mgPtRu-1, and it maintained 91.1% of the initial mass activity after 10 000 s stability test. In addition, when the current density was 100 mA·cm-2, Pt1Ru/NC exhibited the lowest overpotential (103 mV) and the smallest Tafel slope (15.29 mV·dec-1) for HER. The characterization techniques of X-ray diffractometer (XRD), X -ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), inductively coupled plasma-optical emission spectroscopy (ICP-OES), and STEM-energy-dispersive X-ray spectroscopy (STEM-EDS) were used to analyze the reasons for excellent catalytic performance of Pt1Ru/NC, as follows: firstly, the PtRu bimetallic nanoparticles are highly dispersed on NC; secondly, Pt is loaded on Ru with nanoclusters or single atoms, forming Pt-Ru phase segregation; thirdly, there is a synergistic effect between Pt, Ru, and N.
Melamine, RuCl3, and carbon black were dispersed in ethanol with a certain proportion, and a nitrogen-doped carbon (NC)-supported Ru catalyst (Ru/NC) was synthesized by spin evaporation drying and high-temperature thermal treatment. The PtRu/NC catalysts with different Pt and Ru contents were synthesized by sodium borohydride liquid phase chemical reduction, which was used for electrocatalytic methanol oxidation reaction (MOR) and hydrogen evolution reaction (HER) by water electrolysis. The results showed that Pt1Ru/NC (mass fraction: 1.14% for Pt, 0.54% for Ru) had the best MOR performance among as-synthesized catalysts, with a mass activity of 4.96 A·mgPtRu-1, and it maintained 91.1% of the initial mass activity after 10 000 s stability test. In addition, when the current density was 100 mA·cm-2, Pt1Ru/NC exhibited the lowest overpotential (103 mV) and the smallest Tafel slope (15.29 mV·dec-1) for HER. The characterization techniques of X-ray diffractometer (XRD), X -ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), inductively coupled plasma-optical emission spectroscopy (ICP-OES), and STEM-energy-dispersive X-ray spectroscopy (STEM-EDS) were used to analyze the reasons for excellent catalytic performance of Pt1Ru/NC, as follows: firstly, the PtRu bimetallic nanoparticles are highly dispersed on NC; secondly, Pt is loaded on Ru with nanoclusters or single atoms, forming Pt-Ru phase segregation; thirdly, there is a synergistic effect between Pt, Ru, and N.
