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2021 Volume 37 Issue 7
2021, 37(7): 1153-1176
doi: 10.11862/CJIC.2021.121
Abstract:
Carbon dioxide (CO2), as a major greenhouse gas, causes global warming and ocean acidification, and is also an important C1 resource at the same time. It is of great significance for high efficiently and selectively conversion of CO2 into high value-added chemicals using desired catalysts under mild conditions to mitigate the negative impact of CO2 on climate change and reduce the dependence on fossil energy. Metal-organic frameworks (MOFs), as a new kind of porous crystalline materials, are attractive heterogeneous catalysts due to their reusability of heterogenous as well as high selectivity and acitivity of homogenous catalysts. This review mainly focuses on the up-to-date developments of functional MOFs catalysts with emphasis on their architecture characteristics and applications in catalytic conversion of CO2. Recent research progress together with the prospect and outlook of MOFs in this field will be introduced.
Carbon dioxide (CO2), as a major greenhouse gas, causes global warming and ocean acidification, and is also an important C1 resource at the same time. It is of great significance for high efficiently and selectively conversion of CO2 into high value-added chemicals using desired catalysts under mild conditions to mitigate the negative impact of CO2 on climate change and reduce the dependence on fossil energy. Metal-organic frameworks (MOFs), as a new kind of porous crystalline materials, are attractive heterogeneous catalysts due to their reusability of heterogenous as well as high selectivity and acitivity of homogenous catalysts. This review mainly focuses on the up-to-date developments of functional MOFs catalysts with emphasis on their architecture characteristics and applications in catalytic conversion of CO2. Recent research progress together with the prospect and outlook of MOFs in this field will be introduced.
2021, 37(7): 1177-1183
doi: 10.11862/CJIC.2021.154
Abstract:
Using 6-chloro-2-hydropyridine (Hcp) as ligand and pivalic acid (Hpiv) as the auxiliary ligand, five heterometallic complexes {Ln2ⅢCo6Ⅱ} (Ln=Sm (1), Eu (2), Tb (3), Er (4), Tm (5)) were synthesized. Single-crystal X-ray diffraction analyses reveal that complexes 1~5 are isostructural and belong to triclinic system space group P1. Magnetic susceptibilities revealed antiferromagnetic coupling within complexes 1~5, and complex 1 displayed slow relaxation of magnetization. Medium diffusion method was used to determine the antibacterial activity of complexes 1~5 and their isomorphisms {Ln2ⅢCo6Ⅱ} (Ln=Dy (6), Ho (7), Gd (8), Y (9)). All complexes possessed antibacterial activity on both escherichia coli (E. coli) and staphylococcus aureus (S. aureus). Thereinto, complex 5 displayed best antibacterial effect on E. coli, while complex 9 exhibited effective antibacterial activities against S. aureus. CCDC: 2022664, 1; 2022665, 2; 2022666, 3;2022667, 4; 2022668, 5.
Using 6-chloro-2-hydropyridine (Hcp) as ligand and pivalic acid (Hpiv) as the auxiliary ligand, five heterometallic complexes {Ln2ⅢCo6Ⅱ} (Ln=Sm (1), Eu (2), Tb (3), Er (4), Tm (5)) were synthesized. Single-crystal X-ray diffraction analyses reveal that complexes 1~5 are isostructural and belong to triclinic system space group P1. Magnetic susceptibilities revealed antiferromagnetic coupling within complexes 1~5, and complex 1 displayed slow relaxation of magnetization. Medium diffusion method was used to determine the antibacterial activity of complexes 1~5 and their isomorphisms {Ln2ⅢCo6Ⅱ} (Ln=Dy (6), Ho (7), Gd (8), Y (9)). All complexes possessed antibacterial activity on both escherichia coli (E. coli) and staphylococcus aureus (S. aureus). Thereinto, complex 5 displayed best antibacterial effect on E. coli, while complex 9 exhibited effective antibacterial activities against S. aureus. CCDC: 2022664, 1; 2022665, 2; 2022666, 3;2022667, 4; 2022668, 5.
2021, 37(7): 1184-1190
doi: 10.11862/CJIC.2021.150
Abstract:
Multi-walled carbon nanotube/vanadium nitride composite (MWCNT-VN) was used as the positive elec- trode carrier material of lithium - sulfur battery, and sulfur was stored through the hollow structure of vanadium nitride, and it can also effectively limit the shuttle effect of polysulfide. In addition, carbon nanotubes can form a conductive network, which further improves the conductive performance. The initial capacities were 702.2 and 809.3 mAh·g-1 for VN/S and MWCNT - VN/S cathode at a current density of 1C, respectively. After 350 charge- discharge cycles, the capacity attenuation was about 0.1% per cycle. Compared with pure VN/S, the electrochemical performance of the obtained MWCNT - VN/S was improved, such as high lithium ion mobility, stable rate perfor- mance and excellent long-cycle stability.
Multi-walled carbon nanotube/vanadium nitride composite (MWCNT-VN) was used as the positive elec- trode carrier material of lithium - sulfur battery, and sulfur was stored through the hollow structure of vanadium nitride, and it can also effectively limit the shuttle effect of polysulfide. In addition, carbon nanotubes can form a conductive network, which further improves the conductive performance. The initial capacities were 702.2 and 809.3 mAh·g-1 for VN/S and MWCNT - VN/S cathode at a current density of 1C, respectively. After 350 charge- discharge cycles, the capacity attenuation was about 0.1% per cycle. Compared with pure VN/S, the electrochemical performance of the obtained MWCNT - VN/S was improved, such as high lithium ion mobility, stable rate perfor- mance and excellent long-cycle stability.
2021, 37(7): 1191-1196
doi: 10.11862/CJIC.2021.143
Abstract:
The enantiomers of complex 1 (1Δ and 1Λ), [Zn(MPA)(2, 5-DIP)]·1.4H2O (H2MPA=2-methoxyterephthalic acid, 2, 5-DIP=2, 5-di(1H-imidazol-1-yl)pyridine) were obtained by spontaneous resolution upon crystallization in the absence of any enantiopure reagents under hydrothermal condition. X-ray crystallography reveals that complexes 1Δ and 1Λ crystallize in chiral space groups P41 and P43 with near-zero Flack parameters, respectively. In complexes 1Δ and 1Λ, three types of helical chains are constructed by Zn2+ ions, MPA2- and/or 2, 5-DIP ligands along c axis. Although these helical chains contain different components and show different structures, they still have same righthanded helical configuration in 1Δ and left-handed helical configuration in 1Λ, respectively. For the width of channels based on helical chains are up to 1.1 nm×1.1 nm, 1.1 nm×0.8 nm and 0.8 nm×0.8 nm, respectively, and such empty structures result in 5-fold-interpenetrating 3D frameworks with 4-connected dia net in complexes 1Δ and 1Λ. Furthermore, UV-Vis spectra measurement for 1 showed a strong absorption band in ultraviolet region, while solid fluorescence curve revealed blue fluorescence property with emission peak at about 435 nm in complex 1. CCDC: 2049948, 1Δ; 2049947, 1Λ.
The enantiomers of complex 1 (1Δ and 1Λ), [Zn(MPA)(2, 5-DIP)]·1.4H2O (H2MPA=2-methoxyterephthalic acid, 2, 5-DIP=2, 5-di(1H-imidazol-1-yl)pyridine) were obtained by spontaneous resolution upon crystallization in the absence of any enantiopure reagents under hydrothermal condition. X-ray crystallography reveals that complexes 1Δ and 1Λ crystallize in chiral space groups P41 and P43 with near-zero Flack parameters, respectively. In complexes 1Δ and 1Λ, three types of helical chains are constructed by Zn2+ ions, MPA2- and/or 2, 5-DIP ligands along c axis. Although these helical chains contain different components and show different structures, they still have same righthanded helical configuration in 1Δ and left-handed helical configuration in 1Λ, respectively. For the width of channels based on helical chains are up to 1.1 nm×1.1 nm, 1.1 nm×0.8 nm and 0.8 nm×0.8 nm, respectively, and such empty structures result in 5-fold-interpenetrating 3D frameworks with 4-connected dia net in complexes 1Δ and 1Λ. Furthermore, UV-Vis spectra measurement for 1 showed a strong absorption band in ultraviolet region, while solid fluorescence curve revealed blue fluorescence property with emission peak at about 435 nm in complex 1. CCDC: 2049948, 1Δ; 2049947, 1Λ.
2021, 37(7): 1197-1203
doi: 10.11862/CJIC.2021.153
Abstract:
Two Zn(Ⅱ)/Cd(Ⅱ) complexes, [Zn(CMOPAA)(Phen)(H2O)]n (1) and [Cd(CMOPAA)(Phen)]n (2), (H2CMOPAA =4-carboxymethoxy-3-phenylpropenoate and Phen=1, 10-phenanthroline) were synthesized with H2CMOPAA ligand by solvothermal condition and structurally characterized by element analysis, IR, TGA (thermogravimetric analysis) and single crystal X-ray diffraction. Complex 1 crystalizes in the monoclinic system, space group P21/n with a= 0.698 84(8) nm, b=1.751 16(19) nm, c=1.655 49(18) nm, β=95.165(10)°, V=2.017 7(4) nm3. The asymmetric unit of complex 1 consists of one Zn(Ⅱ) ion, one CMOPAA2- ligand, one Phen ligand and one coordinated H2O. Zn(Ⅱ) ion is a six-coordinated distorted octahedral configuration. The carboxyl group of CMOPAA2- ligand connects the adjacent zinc ions to form a helical one-dimensional chain. Hydrogen bonds link the adjacent one-dimensional chains to form a two-dimensional network. Complex 2 crystalizes in the triclinic system, space group P1 with a=0.988 28(16) nm, b =1.040 08(17) nm, c=1.096 15(18) nm, α=72.213(2)°, β=74.439(2)°, γ=71.265(2)°, V=0.997 8(3) nm3. The asymmetric unit of complex 2 consists of one Cd(Ⅱ) ion, one CMOPAA2- ligand and one Phen ligand. Cd(Ⅱ) ion is a seven-coordinated twisted single-cap triangular prism configuration. The carboxyl group of CMOPAA2- ligand connects the adjacent cadmium ions to form a parallelogram 26-membered large ring structure. The 26-membered large rings are linked to a one-dimensional band-like structure. The thermal stabilities and antibacterial activities of complexes 1 and 2 were studied. CCDC: 2054460, 1; 2068057, 2
Two Zn(Ⅱ)/Cd(Ⅱ) complexes, [Zn(CMOPAA)(Phen)(H2O)]n (1) and [Cd(CMOPAA)(Phen)]n (2), (H2CMOPAA =4-carboxymethoxy-3-phenylpropenoate and Phen=1, 10-phenanthroline) were synthesized with H2CMOPAA ligand by solvothermal condition and structurally characterized by element analysis, IR, TGA (thermogravimetric analysis) and single crystal X-ray diffraction. Complex 1 crystalizes in the monoclinic system, space group P21/n with a= 0.698 84(8) nm, b=1.751 16(19) nm, c=1.655 49(18) nm, β=95.165(10)°, V=2.017 7(4) nm3. The asymmetric unit of complex 1 consists of one Zn(Ⅱ) ion, one CMOPAA2- ligand, one Phen ligand and one coordinated H2O. Zn(Ⅱ) ion is a six-coordinated distorted octahedral configuration. The carboxyl group of CMOPAA2- ligand connects the adjacent zinc ions to form a helical one-dimensional chain. Hydrogen bonds link the adjacent one-dimensional chains to form a two-dimensional network. Complex 2 crystalizes in the triclinic system, space group P1 with a=0.988 28(16) nm, b =1.040 08(17) nm, c=1.096 15(18) nm, α=72.213(2)°, β=74.439(2)°, γ=71.265(2)°, V=0.997 8(3) nm3. The asymmetric unit of complex 2 consists of one Cd(Ⅱ) ion, one CMOPAA2- ligand and one Phen ligand. Cd(Ⅱ) ion is a seven-coordinated twisted single-cap triangular prism configuration. The carboxyl group of CMOPAA2- ligand connects the adjacent cadmium ions to form a parallelogram 26-membered large ring structure. The 26-membered large rings are linked to a one-dimensional band-like structure. The thermal stabilities and antibacterial activities of complexes 1 and 2 were studied. CCDC: 2054460, 1; 2068057, 2
2021, 37(7): 1204-1210
doi: 10.11862/CJIC.2021.141
Abstract:
Na3V2(PO4)2O2F (NVPOF) sodium ion battery cathode materials were prepared by hydrothermal method, and the morphology, structure and electrochemical properties were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and galvanostatic charge/discharge (GCD). The results showed that as-prepared pure phase NVPOF had regular tetraprisms morphology, which was 1~3 μm in length, 300 nm~1 μm in width, and the ratio of length to width was 2~3. NVPOF showed two pairs of stable charging and discharging platforms, the discharge specific capacities of NVPOF were 124.2 and 70.5 mAh·g-1 at 0.2C and 2C at room temperature, and decreased to 105.8 and 59.6 mAh·g-1 after 100 cycles, the capacity retention rate were about 85.2% and 84.5% while the Coulombic efficiency was more than 97%. In addition, NVPOF also had good electrochemical performance at low temperature (0 ℃). By coating reduced graphene oxide (rGO) to increase the electrical conductivity, NVPOF@rGO presented high specific discharge capacities of 124.4 and 88.4 mAh·g-1 at 0.2C and 2C at room temperature. The specific capacity was still 78.7 mAh·g-1 after 200 cycles at 2C, and the capacity retention rate was as high as 89% while the Coulomb efficiency was always about 99%, showing excellent rate and cycling performance.
Na3V2(PO4)2O2F (NVPOF) sodium ion battery cathode materials were prepared by hydrothermal method, and the morphology, structure and electrochemical properties were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and galvanostatic charge/discharge (GCD). The results showed that as-prepared pure phase NVPOF had regular tetraprisms morphology, which was 1~3 μm in length, 300 nm~1 μm in width, and the ratio of length to width was 2~3. NVPOF showed two pairs of stable charging and discharging platforms, the discharge specific capacities of NVPOF were 124.2 and 70.5 mAh·g-1 at 0.2C and 2C at room temperature, and decreased to 105.8 and 59.6 mAh·g-1 after 100 cycles, the capacity retention rate were about 85.2% and 84.5% while the Coulombic efficiency was more than 97%. In addition, NVPOF also had good electrochemical performance at low temperature (0 ℃). By coating reduced graphene oxide (rGO) to increase the electrical conductivity, NVPOF@rGO presented high specific discharge capacities of 124.4 and 88.4 mAh·g-1 at 0.2C and 2C at room temperature. The specific capacity was still 78.7 mAh·g-1 after 200 cycles at 2C, and the capacity retention rate was as high as 89% while the Coulomb efficiency was always about 99%, showing excellent rate and cycling performance.
2021, 37(7): 1211-1217
doi: 10.11862/CJIC.2021.145
Abstract:
Mo doped NiS (Mo-NiS) hierarchical nanoflowers were prepared on porous nickel foam substrates by hydrothermal method for high-efficient electrocatalytic nitrogen fixation. Within 2 h, the optimized Mo-NiS sample 0.83 Mo-NiS (the ratio of the amount of molybdenum and nickel during preparation was 0.83) exhibited a remarkable average NH3 formation rate of 4.21 μg·cm-2·h-1 and an average Faraday efficiency of 18% at -0.7 V (vs RHE). XPS and DFT analysis revealed that Mo doping NiS nanoflower increased the electron cloud density of Ni atom, and reduced the energy barrier from *NNH2 to *N in the rate-determining step for nitrogen fixation.
Mo doped NiS (Mo-NiS) hierarchical nanoflowers were prepared on porous nickel foam substrates by hydrothermal method for high-efficient electrocatalytic nitrogen fixation. Within 2 h, the optimized Mo-NiS sample 0.83 Mo-NiS (the ratio of the amount of molybdenum and nickel during preparation was 0.83) exhibited a remarkable average NH3 formation rate of 4.21 μg·cm-2·h-1 and an average Faraday efficiency of 18% at -0.7 V (vs RHE). XPS and DFT analysis revealed that Mo doping NiS nanoflower increased the electron cloud density of Ni atom, and reduced the energy barrier from *NNH2 to *N in the rate-determining step for nitrogen fixation.
2021, 37(7): 1218-1226
doi: 10.11862/CJIC.2021.126
Abstract:
Based on the nanoscale lamellar porous MgO as template, a facile method of petroleum pitch via in-situ KOH activation was designed to obtain multi-stage pore carbon material with large spacing or carbon layers. Meanwhile, the effect of the amount of template on the physicochemical and chemical properties of porous carbon materials, such as pore distribution, carbon layer spacing and electrochemical properties were investigated. The results showed that the specific surface area and pore volume of the carbon material were 2 634 m2·g-1, 1.12 cm3·g-1 respectively. What's more, the spacing of carbon layers was 0.374 nm, when the dosage of template was 25% of the quality of asphalt. As electrodes for supercapacitors, 338 F·g-1 at 1 A·g-1, 277 F·g-1 at 20 A·g-1, and superior cycle stability with 93.5% capacitance retention at 1 A·g-1 after 10 000 cycles in 6 mol·L-1 KOH electrolyte, demonstrating excellent electrochemical performance.
Based on the nanoscale lamellar porous MgO as template, a facile method of petroleum pitch via in-situ KOH activation was designed to obtain multi-stage pore carbon material with large spacing or carbon layers. Meanwhile, the effect of the amount of template on the physicochemical and chemical properties of porous carbon materials, such as pore distribution, carbon layer spacing and electrochemical properties were investigated. The results showed that the specific surface area and pore volume of the carbon material were 2 634 m2·g-1, 1.12 cm3·g-1 respectively. What's more, the spacing of carbon layers was 0.374 nm, when the dosage of template was 25% of the quality of asphalt. As electrodes for supercapacitors, 338 F·g-1 at 1 A·g-1, 277 F·g-1 at 20 A·g-1, and superior cycle stability with 93.5% capacitance retention at 1 A·g-1 after 10 000 cycles in 6 mol·L-1 KOH electrolyte, demonstrating excellent electrochemical performance.
2021, 37(7): 1227-1236
doi: 10.11862/CJIC.2021.135
Abstract:
The flower-like Sn3O4 and x%Ti-SnO2/Sn3O4 (x% was the molar ratio of Ti to Sn) microspheres stacked by the layered nanosheets were prepared by the hydrothermal method. The synthesized samples were analyzed by physical and chemical methods, e. g., X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, ultraviolet-visible diffuse reflectance spectroscopy, infrared spectroscopy, and photocurrent response. The results show that because ion radius of Ti4+ is similar to Sn4+, it can enter the Sn3O4 lattice instead of Sn4+ to form alternative dopants. At the same time, the doping of Ti4+ makes a part of Sn4+ directly combine with oxygen to form nano-spherical SnO2 dispersed over the surface of Sn3O4, forming a SnO2/Sn3O4 heterojunction. The photocatalytic activity test shows that x%Ti-SnO2/Sn3O4 not only has the ability to reduce Cr6+, but also has the ability to degrade methyl orange and acid orange Ⅱ. The enhanced catalytic activity is attributed to the surface area and light absorption of x%Ti-SnO2/Sn3O4. Moreover, the produced SnO2/Sn3O4 heterojunction can effectively promote the separation efficiency of photo-generated electrons and holes.
The flower-like Sn3O4 and x%Ti-SnO2/Sn3O4 (x% was the molar ratio of Ti to Sn) microspheres stacked by the layered nanosheets were prepared by the hydrothermal method. The synthesized samples were analyzed by physical and chemical methods, e. g., X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, ultraviolet-visible diffuse reflectance spectroscopy, infrared spectroscopy, and photocurrent response. The results show that because ion radius of Ti4+ is similar to Sn4+, it can enter the Sn3O4 lattice instead of Sn4+ to form alternative dopants. At the same time, the doping of Ti4+ makes a part of Sn4+ directly combine with oxygen to form nano-spherical SnO2 dispersed over the surface of Sn3O4, forming a SnO2/Sn3O4 heterojunction. The photocatalytic activity test shows that x%Ti-SnO2/Sn3O4 not only has the ability to reduce Cr6+, but also has the ability to degrade methyl orange and acid orange Ⅱ. The enhanced catalytic activity is attributed to the surface area and light absorption of x%Ti-SnO2/Sn3O4. Moreover, the produced SnO2/Sn3O4 heterojunction can effectively promote the separation efficiency of photo-generated electrons and holes.
2021, 37(7): 1237-1244
doi: 10.11862/CJIC.2021.147
Abstract:
In this study, a series of broadband emitting yellow phosphors Sr8MgAl(PO4)7: xEu2+ (SMAP: xEu2+) were synthesized by high temperature solid-state reaction; and the structure, luminescent properties and potential application in white light-emitting diode (WLED) were investigated. The X-ray diffraction (XRD) results showed that the SMAP: xEu2+ phosphors had monoclinic system and C2/m space group; and the activator Eu2+ ions can enter into the SMAP matrix and occupy the lattice site of Sr2+ ions. Diffuse reflectance spectroscopy showed that SMAP host was a wide band-gap material with a band gap of 3.60 eV. In addition, SMAP: xEu2+ had a broad excitation range (280~ 500 nm), corresponding to the 4f7→4f65d1 transition of Eu2+ ions. Under the excitation of 380 nm near-ultraviolet light, there was an asymmetric yellow emission at the wavelength of 450~800 nm from multiple emission centers; and the emission peak was located at 590 nm. Based on Gaussian multi-peak fitting results, three emission centers were located at 528, 600 and 680 nm, respectively. Finally, the as-prepared yellow phosphor SMAP: 0.05Eu2+ and commercial blue phosphor BaMgAl10O17: Eu2+ were mixed and coated on the surface of 400 nm chip to fabricate WLED with good color temperature (3 344 K) and high color rendering index (90.1).
In this study, a series of broadband emitting yellow phosphors Sr8MgAl(PO4)7: xEu2+ (SMAP: xEu2+) were synthesized by high temperature solid-state reaction; and the structure, luminescent properties and potential application in white light-emitting diode (WLED) were investigated. The X-ray diffraction (XRD) results showed that the SMAP: xEu2+ phosphors had monoclinic system and C2/m space group; and the activator Eu2+ ions can enter into the SMAP matrix and occupy the lattice site of Sr2+ ions. Diffuse reflectance spectroscopy showed that SMAP host was a wide band-gap material with a band gap of 3.60 eV. In addition, SMAP: xEu2+ had a broad excitation range (280~ 500 nm), corresponding to the 4f7→4f65d1 transition of Eu2+ ions. Under the excitation of 380 nm near-ultraviolet light, there was an asymmetric yellow emission at the wavelength of 450~800 nm from multiple emission centers; and the emission peak was located at 590 nm. Based on Gaussian multi-peak fitting results, three emission centers were located at 528, 600 and 680 nm, respectively. Finally, the as-prepared yellow phosphor SMAP: 0.05Eu2+ and commercial blue phosphor BaMgAl10O17: Eu2+ were mixed and coated on the surface of 400 nm chip to fabricate WLED with good color temperature (3 344 K) and high color rendering index (90.1).
2021, 37(7): 1245-1250
doi: 10.11862/CJIC.2021.161
Abstract:
To develop a method with high selectivity and sensitivity to detect thiophenol, based on the excellent optical properties and good membrane permeability of dicyanoisophorone dyes, we chose dicyanoisophorone derivatives as fluorophores and introduced a strong electron-withdrawing 2, 4-dinitrobenzene synthetic fluorescent probe (YC1) for the specific recognition of thiophenol. The probe showed obvious red fluorescence on thiophenol (emission wavelength: 594 nm, excitation wavelength: 420 nm) and had a fluorescence-enhanced (turn-on) property for the recognition of thiophenol. The probe had a good selectivity for the recognition of thiophenol and the detection limit of the probe was 0.65 μmol·L-1 in PBS/DMSO system (PBS=phosphate buffer saline, DMSO=dimethyl sulfoxide). In addition, the probe has been successfully applied to the fluorescence imaging of 4-methylthiophenol in HeLa cells.
To develop a method with high selectivity and sensitivity to detect thiophenol, based on the excellent optical properties and good membrane permeability of dicyanoisophorone dyes, we chose dicyanoisophorone derivatives as fluorophores and introduced a strong electron-withdrawing 2, 4-dinitrobenzene synthetic fluorescent probe (YC1) for the specific recognition of thiophenol. The probe showed obvious red fluorescence on thiophenol (emission wavelength: 594 nm, excitation wavelength: 420 nm) and had a fluorescence-enhanced (turn-on) property for the recognition of thiophenol. The probe had a good selectivity for the recognition of thiophenol and the detection limit of the probe was 0.65 μmol·L-1 in PBS/DMSO system (PBS=phosphate buffer saline, DMSO=dimethyl sulfoxide). In addition, the probe has been successfully applied to the fluorescence imaging of 4-methylthiophenol in HeLa cells.
2021, 37(7): 1251-1257
doi: 10.11862/CJIC.2021.152
Abstract:
In this paper, a series of Ba5-2x-yTbxNax(PO4)3Cl: yEu2+ phosphor powder was prepared via [Na+, Tb3+] ion pairs substituting [Ba2+, Ba2+] ion pairs. The structure, morphology, composition and luminescence properties were studied through X-ray powder diffraction, scanning electron microscope, photoexcitation and emission spectroscopy. Under excitation at 354 nm, the emission spectra of Ba3.97Tb0.50Na0.50(PO4)3Cl: 0.03Eu2+ sample was composed of the characteristic broad peak of Eu2+ at about 450 nm and the four characteristic sharp peaks of Tb3+ at 490, 545, 583 and 622 nm. Due to Eu2+→Tb3+ energy transfer, the luminescence intensity of Tb3+ in Ba3.97Tb0.50Na0.50(PO4)3Cl: 0.03Eu2+ was significantly increased compared with that of Tb3+ in Ba4.00Tb0.50Na0.50(PO4)3Cl sample. By changing the concentration of [Na+, Tb3+] ion pairs, the spectral control of Ba5-2x-yTbxNax(PO4)3Cl: yEu2+ phosphor was achieved. When x=0.50, the luminescence intensity of Tb3+ in Ba4.97-2xTbxNax(PO4)3Cl: 0.03Eu2+ reached the maximum.
In this paper, a series of Ba5-2x-yTbxNax(PO4)3Cl: yEu2+ phosphor powder was prepared via [Na+, Tb3+] ion pairs substituting [Ba2+, Ba2+] ion pairs. The structure, morphology, composition and luminescence properties were studied through X-ray powder diffraction, scanning electron microscope, photoexcitation and emission spectroscopy. Under excitation at 354 nm, the emission spectra of Ba3.97Tb0.50Na0.50(PO4)3Cl: 0.03Eu2+ sample was composed of the characteristic broad peak of Eu2+ at about 450 nm and the four characteristic sharp peaks of Tb3+ at 490, 545, 583 and 622 nm. Due to Eu2+→Tb3+ energy transfer, the luminescence intensity of Tb3+ in Ba3.97Tb0.50Na0.50(PO4)3Cl: 0.03Eu2+ was significantly increased compared with that of Tb3+ in Ba4.00Tb0.50Na0.50(PO4)3Cl sample. By changing the concentration of [Na+, Tb3+] ion pairs, the spectral control of Ba5-2x-yTbxNax(PO4)3Cl: yEu2+ phosphor was achieved. When x=0.50, the luminescence intensity of Tb3+ in Ba4.97-2xTbxNax(PO4)3Cl: 0.03Eu2+ reached the maximum.
2021, 37(7): 1258-1268
doi: 10.11862/CJIC.2021.149
Abstract:
Herein, finely dispersed silver decorated TiO2 microspheres have been synthesized by one-pot solvothermal method using tetrabutyl titanate and vitamin C in ethanol. The structure of TiO2 microsphere and high dispersion of nano silver were regulated by the alcoholysis of tetrabutyl titanate and reducibility of enol in vitamin C. The one-pot method was beneficial to reduce the complex procedures and obtain uniform spherical particles with a diameter of 250 nm. The silver lattice stripes integrated into the surface of microsperes show crystal plane (111) characteristics. The composite electrode exhibited excellent electrocatalytic activity of H2O2. The developed sensor allowed the detection of H2O2 with the linear range of 0.1~102 μmol·L-1, sensitivity of 3.13×10-3 μA·L·μmol-1·cm-2 and detection limit of 0.04 μmol·L-1. The resulting device also had longterm stability, reproducibility and repeatability. The performance could be maintained at 82.1% after a month.
Herein, finely dispersed silver decorated TiO2 microspheres have been synthesized by one-pot solvothermal method using tetrabutyl titanate and vitamin C in ethanol. The structure of TiO2 microsphere and high dispersion of nano silver were regulated by the alcoholysis of tetrabutyl titanate and reducibility of enol in vitamin C. The one-pot method was beneficial to reduce the complex procedures and obtain uniform spherical particles with a diameter of 250 nm. The silver lattice stripes integrated into the surface of microsperes show crystal plane (111) characteristics. The composite electrode exhibited excellent electrocatalytic activity of H2O2. The developed sensor allowed the detection of H2O2 with the linear range of 0.1~102 μmol·L-1, sensitivity of 3.13×10-3 μA·L·μmol-1·cm-2 and detection limit of 0.04 μmol·L-1. The resulting device also had longterm stability, reproducibility and repeatability. The performance could be maintained at 82.1% after a month.
2021, 37(7): 1269-1276
doi: 10.11862/CJIC.2021.139
Abstract:
A novel Pr(Ⅲ)-based co-crystal complex, (H2pipz)1.5[Pr(pdc)3]·7H2O (1, pdc2-=pyridine-2,6-dicarboxylate and pipz=piperazine) has been synthesized under hydrothermal condition. Infrared (IR) spectroscopy, elemental analysis, and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure of complex 1. To deeply reveal the electronic structure of complex 1, density functional theory (DFT) calculations were employed to investigate the electrostatic potential (ESP) and frontier molecular orbitals (FMO) of the structural unit [Pr(pdc)3]3-. More importantly, the antitumor test showed that complex 1 exhibited good cytotoxic activity against K562 (IC50=(61.3±10.2) μg·mL-1) and OE-19 cells (IC50=(15.9±3.2) μg·mL-1), especially more effective against OE-19 cells. CCDC: 1834053.
A novel Pr(Ⅲ)-based co-crystal complex, (H2pipz)1.5[Pr(pdc)3]·7H2O (1, pdc2-=pyridine-2,6-dicarboxylate and pipz=piperazine) has been synthesized under hydrothermal condition. Infrared (IR) spectroscopy, elemental analysis, and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure of complex 1. To deeply reveal the electronic structure of complex 1, density functional theory (DFT) calculations were employed to investigate the electrostatic potential (ESP) and frontier molecular orbitals (FMO) of the structural unit [Pr(pdc)3]3-. More importantly, the antitumor test showed that complex 1 exhibited good cytotoxic activity against K562 (IC50=(61.3±10.2) μg·mL-1) and OE-19 cells (IC50=(15.9±3.2) μg·mL-1), especially more effective against OE-19 cells. CCDC: 1834053.
2021, 37(7): 1277-1283
doi: 10.11862/CJIC.2021.151
Abstract:
To develop a novel antitumor Ru agent, [Ru(L)(DMSO)2Cl2] (1) (DMSO=dimethyl sulfoxide) was synthesized by employing a Schiff base ligand 3-methyl-2-thiophenecarboxaldehyde-4-hydroxybenzhydrazide (L). The single crystal X-ray crystallographic study was carried out to determine the crystallographic structure of 1. The structure of complex 1 is composed of a central Ru(Ⅱ) ion, two DMSO molecules, two chloride ions, and a ligand L. In addition, 1 possessed strong antitumor activity against T24 cells by MTT analysis. Furthermore, the potential antitumor mechanism of 1 was investigated by comet assays, western-blotting assays, and DNA agarose gel electrophoresis. These results indicate that 1 can effectively bind to DNA and induce DNA damage, and eventually kill the tumor cells. DNA damage may be caused by the production of reactive oxygen species.CCDC: 2080249.
To develop a novel antitumor Ru agent, [Ru(L)(DMSO)2Cl2] (1) (DMSO=dimethyl sulfoxide) was synthesized by employing a Schiff base ligand 3-methyl-2-thiophenecarboxaldehyde-4-hydroxybenzhydrazide (L). The single crystal X-ray crystallographic study was carried out to determine the crystallographic structure of 1. The structure of complex 1 is composed of a central Ru(Ⅱ) ion, two DMSO molecules, two chloride ions, and a ligand L. In addition, 1 possessed strong antitumor activity against T24 cells by MTT analysis. Furthermore, the potential antitumor mechanism of 1 was investigated by comet assays, western-blotting assays, and DNA agarose gel electrophoresis. These results indicate that 1 can effectively bind to DNA and induce DNA damage, and eventually kill the tumor cells. DNA damage may be caused by the production of reactive oxygen species.CCDC: 2080249.
2021, 37(7): 1284-1294
doi: 10.11862/CJIC.2021.136
Abstract:
In this work, the Li-ion batteries (LIB) made with 3D network structure anodes were fabricated through incorporating ultrathin δ-MnO2 nanoparticles (NPs) into a reduced graphene oxide aerogel (RGOA), while KMnO4 was employed as a raw for preparing δ-MnO2. The influence of MnO2 adding amounts on the electrochemical performance of the obtained RGOA/δ-MnO2 composite electrode was investigated. As the MnO2 adding amount increased, the electrochemical performance of RGOA/δ-MnO2 was increased firstly and then decreased, reaching a maximum reversible capacity of 1 701.9 mA·g-1 at a suitable loading amount of MnO2, which is significantly higher than the theoretical capacity of δ-MnO2 (1 230 mAh·g-1). Besides, for the LIBs containing RGOA/δ-MnO2 anodes, a high capacity of 210.5 mA·g-1 remained even after 600 discharge-charge cycles at 5 A·g-1. The excellent performance of RGOA/δ-MnO2-160 mg can be attributed to the synergistic effect from large specific area and high conductivity of RGOA, as well as high theoretical capacity and small particle size of δ-MnO2. Furthermore, the 3D framework porous structure provided by RGOA makes it possible to wrap δ-MnO2 NPs, avoiding the volume expansion of δ-MnO2 and suppressing the thickening of solid electrolyte interphase (SEI) layer. By calculating the contributions from pseudocapacitance and diffusion-controlled process, it was demonstrated that the charge/discharge mechanism of the RGOA/δ-MnO2-160 mg anode was dominated by the pseudocapacitance process, which also facilitated achieving good rate performance and cyclic stability.
In this work, the Li-ion batteries (LIB) made with 3D network structure anodes were fabricated through incorporating ultrathin δ-MnO2 nanoparticles (NPs) into a reduced graphene oxide aerogel (RGOA), while KMnO4 was employed as a raw for preparing δ-MnO2. The influence of MnO2 adding amounts on the electrochemical performance of the obtained RGOA/δ-MnO2 composite electrode was investigated. As the MnO2 adding amount increased, the electrochemical performance of RGOA/δ-MnO2 was increased firstly and then decreased, reaching a maximum reversible capacity of 1 701.9 mA·g-1 at a suitable loading amount of MnO2, which is significantly higher than the theoretical capacity of δ-MnO2 (1 230 mAh·g-1). Besides, for the LIBs containing RGOA/δ-MnO2 anodes, a high capacity of 210.5 mA·g-1 remained even after 600 discharge-charge cycles at 5 A·g-1. The excellent performance of RGOA/δ-MnO2-160 mg can be attributed to the synergistic effect from large specific area and high conductivity of RGOA, as well as high theoretical capacity and small particle size of δ-MnO2. Furthermore, the 3D framework porous structure provided by RGOA makes it possible to wrap δ-MnO2 NPs, avoiding the volume expansion of δ-MnO2 and suppressing the thickening of solid electrolyte interphase (SEI) layer. By calculating the contributions from pseudocapacitance and diffusion-controlled process, it was demonstrated that the charge/discharge mechanism of the RGOA/δ-MnO2-160 mg anode was dominated by the pseudocapacitance process, which also facilitated achieving good rate performance and cyclic stability.
2021, 37(7): 1295-1300
doi: 10.11862/CJIC.2021.140
Abstract:
Flower-like silver particles with tunable size and shape had been synthesized in one-step by reducing silver nitrate (AgNO3) with ascorbic acid as reducing agent and citric acid as structure directing agent. The size of nanoparticles could be adjusted from 600 to 1 200 nm, and the surface protrusion could reach 10~25 nm. The chemical nature of citric acid played a vital role in the process of assembling silver nanoparticles into flower-like hierarchical structure. The anisotropic morphologies of as-synthesized silver structures could be readily tuned by varying the dosage of citric acid or ascorbic acid solution. The textured flower-like Ag particles were tested as substrates for the surface enhanced Raman scattering (SERS) and showed high sensitivity for detecting rhodamine 6G (R6G) at a concentration as low as 10-10 mol·L-1.
Flower-like silver particles with tunable size and shape had been synthesized in one-step by reducing silver nitrate (AgNO3) with ascorbic acid as reducing agent and citric acid as structure directing agent. The size of nanoparticles could be adjusted from 600 to 1 200 nm, and the surface protrusion could reach 10~25 nm. The chemical nature of citric acid played a vital role in the process of assembling silver nanoparticles into flower-like hierarchical structure. The anisotropic morphologies of as-synthesized silver structures could be readily tuned by varying the dosage of citric acid or ascorbic acid solution. The textured flower-like Ag particles were tested as substrates for the surface enhanced Raman scattering (SERS) and showed high sensitivity for detecting rhodamine 6G (R6G) at a concentration as low as 10-10 mol·L-1.
2021, 37(7): 1301-1306
doi: 10.11862/CJIC.2021.119
Abstract:
Herein, the NASICON-type Na4FeV(PO4)3 single crystal was successfully synthesized by high temperature molten salt method. The analysis of single crystal X-ray diffraction data shows that Na4FeV(PO4)3 crystallizes in hexagonal R3c space group with a=b=0.878 17(4) nm, c=2.17 01(2) nm, Z=6 and V=1.449 31(18) nm3. The crystal structure of this phosphate belongs to the typical NASICON structure, which is built up from corner-sharing PO4 tetrahedra and Fe/VO6 octahedra, providing a three-dimensional Na+ transmission channel with two different types of Na+ located in the gap of the frame. Additionally, the electrochemical tests of the as-synthesized Na4FeV(PO4)3/C as cathode material of sodium-ion battery showed a high capacity. CCDC: 2048805.
Herein, the NASICON-type Na4FeV(PO4)3 single crystal was successfully synthesized by high temperature molten salt method. The analysis of single crystal X-ray diffraction data shows that Na4FeV(PO4)3 crystallizes in hexagonal R3c space group with a=b=0.878 17(4) nm, c=2.17 01(2) nm, Z=6 and V=1.449 31(18) nm3. The crystal structure of this phosphate belongs to the typical NASICON structure, which is built up from corner-sharing PO4 tetrahedra and Fe/VO6 octahedra, providing a three-dimensional Na+ transmission channel with two different types of Na+ located in the gap of the frame. Additionally, the electrochemical tests of the as-synthesized Na4FeV(PO4)3/C as cathode material of sodium-ion battery showed a high capacity. CCDC: 2048805.
2021, 37(7): 1307-1314
doi: 10.11862/CJIC.2021.137
Abstract:
Singlet oxygen (1O2) is an efficient and convenient oxidant for the selective oxidation of sulfides to sulfoxides. It is critical to develop efficient photosensitizers with the high 1O2 quantum yield. Herein, we describe the fabrication and characterization of ultrathin two-dimensional covalent organic frameworks (COFs) nanosheets (NSs), COF-367 NSs. In particular, the good dispersibility in various organic solvent and high efficiency in light harvesting of COF-367 NS endow the remarkable performance towards 1O2 generation upon irradiation with visible light, much better than the bulk COF-367. We also demonstrate that COF-367 NSs are an excellent heterogeneous catalyst in photocatalytic oxidation of sulfides to sulfoxides with high yield and selectivity as well as good recycling stability.
Singlet oxygen (1O2) is an efficient and convenient oxidant for the selective oxidation of sulfides to sulfoxides. It is critical to develop efficient photosensitizers with the high 1O2 quantum yield. Herein, we describe the fabrication and characterization of ultrathin two-dimensional covalent organic frameworks (COFs) nanosheets (NSs), COF-367 NSs. In particular, the good dispersibility in various organic solvent and high efficiency in light harvesting of COF-367 NS endow the remarkable performance towards 1O2 generation upon irradiation with visible light, much better than the bulk COF-367. We also demonstrate that COF-367 NSs are an excellent heterogeneous catalyst in photocatalytic oxidation of sulfides to sulfoxides with high yield and selectivity as well as good recycling stability.
2021, 37(7): 1315-1321
doi: 10.11862/CJIC.2021.158
Abstract:
A monolayer close-packed Au nanorods (GNRs) film has been prepared by an easy seed-growth approach, followed by self-assembling method with the surfactants and subsequent calcination treatment. During the calcination process, the surfactants were decomposed and eliminated completely, resulting in a clean surface of GNRs. Resultantly, these monolayer GNRs films explored as a SERS (surface-enhanced Raman spectroscopy) substrate have good uniformity and high sensibility for detecting probe molecules. Subsequently, the prepared SERS substrate was used to detect ultra-low concentration (10-9 mol·L-1) of pesticide molecules.
A monolayer close-packed Au nanorods (GNRs) film has been prepared by an easy seed-growth approach, followed by self-assembling method with the surfactants and subsequent calcination treatment. During the calcination process, the surfactants were decomposed and eliminated completely, resulting in a clean surface of GNRs. Resultantly, these monolayer GNRs films explored as a SERS (surface-enhanced Raman spectroscopy) substrate have good uniformity and high sensibility for detecting probe molecules. Subsequently, the prepared SERS substrate was used to detect ultra-low concentration (10-9 mol·L-1) of pesticide molecules.
2021, 37(7): 1322-1336
doi: 10.11862/CJIC.2021.146
Abstract:
A series of dual copper-cobalt oxides-containing mesoporous molecular sieve catalysts xCuyCo/NS-MS-s were successfully fabricated by an improved micelle-assisted synthetic method. Taking gaseous toluene as the representative pollutant of VOCs, the removal effect of toluene by the catalysts was investigated. The physicochemical properties including structure, the morphology of catalysts, and the chemical status of Cu-Co bimetallic species were detailedly identified through various characterizations. The results showed that when the ratio of bimetal was controlled as nCu: nCo=1:3, the catalyst had the best catalytic combustion activity of toluene (T50=232 ℃, T99=239 ℃, where T50 is the reaction temperature when the toluene conversion is 50%, and T99 is the reaction temperature when the toluene conversion is 99%) and good stability.
A series of dual copper-cobalt oxides-containing mesoporous molecular sieve catalysts xCuyCo/NS-MS-s were successfully fabricated by an improved micelle-assisted synthetic method. Taking gaseous toluene as the representative pollutant of VOCs, the removal effect of toluene by the catalysts was investigated. The physicochemical properties including structure, the morphology of catalysts, and the chemical status of Cu-Co bimetallic species were detailedly identified through various characterizations. The results showed that when the ratio of bimetal was controlled as nCu: nCo=1:3, the catalyst had the best catalytic combustion activity of toluene (T50=232 ℃, T99=239 ℃, where T50 is the reaction temperature when the toluene conversion is 50%, and T99 is the reaction temperature when the toluene conversion is 99%) and good stability.
2021, 37(7): 1337-1344
doi: 10.11862/CJIC.2021.157
Abstract:
A series of Co3O4/CeO2 heterojunctions were prepared by a facile two-step method. Their structure and morphology were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM) measurements, respectively. In alkaline media, electrocatalytic oxygen evolution performance test showed that the performance changed with the ratio of Co3O4/CeO2, and there was an optimal value. When the mass ratio of Co3O4 and CeO2 was 58.5%, its overpotential was 347 mV which was lower than that of Co3O4 (440 mV), commercial RuO2 (359 mV) and CeO2 (570 mV), with Tafel slope of 72.7 mV·dec-1, and the good stability in 1.0 mol·L-1 KOH solution at current density of 10 mA·cm-2. X-ray photoelectronic energy spectra (XPS) confirmed that some of Co3O4 electrons transferred to CeO2, which resulted in increase of the conductivity of the composite materials, the surface oxygen vacancy concentration, and active oxygen species of CeO2.
A series of Co3O4/CeO2 heterojunctions were prepared by a facile two-step method. Their structure and morphology were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM) measurements, respectively. In alkaline media, electrocatalytic oxygen evolution performance test showed that the performance changed with the ratio of Co3O4/CeO2, and there was an optimal value. When the mass ratio of Co3O4 and CeO2 was 58.5%, its overpotential was 347 mV which was lower than that of Co3O4 (440 mV), commercial RuO2 (359 mV) and CeO2 (570 mV), with Tafel slope of 72.7 mV·dec-1, and the good stability in 1.0 mol·L-1 KOH solution at current density of 10 mA·cm-2. X-ray photoelectronic energy spectra (XPS) confirmed that some of Co3O4 electrons transferred to CeO2, which resulted in increase of the conductivity of the composite materials, the surface oxygen vacancy concentration, and active oxygen species of CeO2.
