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2022 Volume 38 Issue 2
2022, 38(2): 185-197
doi: 10.11862/CJIC.2022.031
Abstract:
Aqueous zinc-ion batteries have advantages in terms of being environmentally friendly and safe with zinc metal anode, which is considered a promising rechargeable battery for large-scale storage energy systems. Zinc metal is more abundant than lithium and easier to be mined and purified. Meanwhile, it shows a low redox potential (-0.76V vs SHE), high theoretical specific capacity (820 mAh·g-1), and high theoretical volumetric capacity (5 854 mAh·cm-3). However, the problems of zinc dendrites and irreversible by-products (such as H2, ZnO, Zn4(OH)6SO4) on the surface of Zn metal during the charging and discharging processes lead to the low coulombic efficiency of the zinc anode, which seriously shorten the cycle life of the zinc-ion battery and limit its practical application. Herein, the difficulties and bottlenecks encountered in the practical application of zinc anode are sorted out, in addition, dynamics and thermodynamic mechanisms are tried to analyze from the microscopic level. Subsequently, various strategies are introduced to improve the performance of zinc anode from the aspects of the surface modification technology of the zinc electrode, the optimization of the zinc internal structure, electrolyte modification, and novel functional separator. The preparation methods, modification mechanism as well as final improvement effect on the battery performance are analyzed, which provide new insights into the practical and efficient zinc anode protection method. Finally, the opportunities and challenges faced by zinc anode in the process of commercialization are discussed, and the future research prospects and hot spots are prospected.
Aqueous zinc-ion batteries have advantages in terms of being environmentally friendly and safe with zinc metal anode, which is considered a promising rechargeable battery for large-scale storage energy systems. Zinc metal is more abundant than lithium and easier to be mined and purified. Meanwhile, it shows a low redox potential (-0.76V vs SHE), high theoretical specific capacity (820 mAh·g-1), and high theoretical volumetric capacity (5 854 mAh·cm-3). However, the problems of zinc dendrites and irreversible by-products (such as H2, ZnO, Zn4(OH)6SO4) on the surface of Zn metal during the charging and discharging processes lead to the low coulombic efficiency of the zinc anode, which seriously shorten the cycle life of the zinc-ion battery and limit its practical application. Herein, the difficulties and bottlenecks encountered in the practical application of zinc anode are sorted out, in addition, dynamics and thermodynamic mechanisms are tried to analyze from the microscopic level. Subsequently, various strategies are introduced to improve the performance of zinc anode from the aspects of the surface modification technology of the zinc electrode, the optimization of the zinc internal structure, electrolyte modification, and novel functional separator. The preparation methods, modification mechanism as well as final improvement effect on the battery performance are analyzed, which provide new insights into the practical and efficient zinc anode protection method. Finally, the opportunities and challenges faced by zinc anode in the process of commercialization are discussed, and the future research prospects and hot spots are prospected.
2022, 38(2): 198-210
doi: 10.11862/CJIC.2022.033
Abstract:
Three 2-TPT-based complexes composed of donor-acceptor units, [Zn(2-TPT)(2, 5-FCA)] (1), [Cd(2-TPT) (2, 5-FCA)]·1.5H2O (2), and[Mn(2-TPT)(2, 5-FCA)] (3), have been synthesized by the combination of 2, 4, 6-tri(2-pyridyl)-1, 3, 5-triazine (2-TPT) and 2, 5-furandicarboxylic acid (2, 5-H2FCA) with different types of metallic nitrates (Zn, Cd, and Mn), respectively. The structures and photochromic properties of 1-3 have been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, FT-IR, UV-Vis, thermogravimetry-differential thermal analysis, electron paramagnetic resonance and X-ray photoelectron spectroscopy. The usage of different metals leads to a 1D single-strand chain for 1 and a double-strand chain for 2 and 3, which are further aggregated into distinct supramolecular frameworks (three-dimensional supramolecular network for 1, two-dimensional supramolecular layer for 2, and discrete chain for 3) through weak interactions. Complexes 1-3 exhibited significantly different photoinduced intermolecular electron transfer (PIET) and photochromic properties, which were mainly reflect in photoresponsive rate and coloration contrast. Thereinto, the photochromic performance of 1 was obviously better than that of 2, while 3 was non-photochromic. These obviously discriminative photochromic behaviors are largely attributed to the different packing modes of crystal structures and the discriminative relative position of electron donors/acceptors caused by different types and coordination patterns of the metal centers, which exhibit the modulating effect of metal centers on the photochromic properties.
Three 2-TPT-based complexes composed of donor-acceptor units, [Zn(2-TPT)(2, 5-FCA)] (1), [Cd(2-TPT) (2, 5-FCA)]·1.5H2O (2), and[Mn(2-TPT)(2, 5-FCA)] (3), have been synthesized by the combination of 2, 4, 6-tri(2-pyridyl)-1, 3, 5-triazine (2-TPT) and 2, 5-furandicarboxylic acid (2, 5-H2FCA) with different types of metallic nitrates (Zn, Cd, and Mn), respectively. The structures and photochromic properties of 1-3 have been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, FT-IR, UV-Vis, thermogravimetry-differential thermal analysis, electron paramagnetic resonance and X-ray photoelectron spectroscopy. The usage of different metals leads to a 1D single-strand chain for 1 and a double-strand chain for 2 and 3, which are further aggregated into distinct supramolecular frameworks (three-dimensional supramolecular network for 1, two-dimensional supramolecular layer for 2, and discrete chain for 3) through weak interactions. Complexes 1-3 exhibited significantly different photoinduced intermolecular electron transfer (PIET) and photochromic properties, which were mainly reflect in photoresponsive rate and coloration contrast. Thereinto, the photochromic performance of 1 was obviously better than that of 2, while 3 was non-photochromic. These obviously discriminative photochromic behaviors are largely attributed to the different packing modes of crystal structures and the discriminative relative position of electron donors/acceptors caused by different types and coordination patterns of the metal centers, which exhibit the modulating effect of metal centers on the photochromic properties.
2022, 38(2): 211-219
doi: 10.11862/CJIC.2022.029
Abstract:
BiOBr/ZnO three-dimensional flower-like nanocomposite with enhanced photocatalytic ability were prepared by simple solvothermal method applying Bi(NO3)3·5H2O, Zn(CH3COO)2·2H2O and NaBr as precursors. The physical and chemical attributes were characterized by various analytical techniques such as X-ray diffraction, scanning electron microscope, X-ray photon spectroscopy, N2 adsorption-desorption, UV-Vis diffusion reflectance spectroscopy, photoluminescence and electron paramagnetic resonance (EPR). The main crystalline structure of BiOBr is not destroyed after doping, but growth of BiOBr crystals is lightly inhibited by doping ZnO. The trapping agent experiment and EPR spectra show that ·O2- and ·OH are the main active species in the process of photocatalytic degradation. The photocatalytic activities of the composite were evaluated by the degradation of rhodamine B (RhB) under visible light. The results showed that BiOBr/ZnO with 5% ZnO had the best photocatalytic activity, and the degradation rate of RhB reached 98.3% after 50 min of irradiation. Its degradation rate constant was 6.3 times and 3.4 times higher than those of pure ZnO and BiOBr, respectively. The introduction of ZnO enhances the absorption of visible light and the charge separation efficiency of photogenerated carriers.
BiOBr/ZnO three-dimensional flower-like nanocomposite with enhanced photocatalytic ability were prepared by simple solvothermal method applying Bi(NO3)3·5H2O, Zn(CH3COO)2·2H2O and NaBr as precursors. The physical and chemical attributes were characterized by various analytical techniques such as X-ray diffraction, scanning electron microscope, X-ray photon spectroscopy, N2 adsorption-desorption, UV-Vis diffusion reflectance spectroscopy, photoluminescence and electron paramagnetic resonance (EPR). The main crystalline structure of BiOBr is not destroyed after doping, but growth of BiOBr crystals is lightly inhibited by doping ZnO. The trapping agent experiment and EPR spectra show that ·O2- and ·OH are the main active species in the process of photocatalytic degradation. The photocatalytic activities of the composite were evaluated by the degradation of rhodamine B (RhB) under visible light. The results showed that BiOBr/ZnO with 5% ZnO had the best photocatalytic activity, and the degradation rate of RhB reached 98.3% after 50 min of irradiation. Its degradation rate constant was 6.3 times and 3.4 times higher than those of pure ZnO and BiOBr, respectively. The introduction of ZnO enhances the absorption of visible light and the charge separation efficiency of photogenerated carriers.
2022, 38(2): 220-226
doi: 10.11862/CJIC.2022.036
Abstract:
A new cyclometalated ruthenium complex[Ru(L)(bpy)2]+ (1) was synthesized by using 3-ethyl-1-(thiophen-2-yl)imidazolium (L) and 2, 2'-bipyridine (bpy), which has been characterized by NMR and HRMS. The interactions between complex 1 and common metal ions were investigated by UV-Vis absorption spectra. Only upon the addition of Hg2+, the absorption was blue-shifted from 548 to 448 nm companied with the solution color varying from red to yellow. By analyzing absorption and MS spectra, the mechanism of complex 1 sensing to Hg2+ could be attributed to the possible conversion of coordination mode from Ru—C to Ru—S resulting from the interaction between Hg2+ and S.
A new cyclometalated ruthenium complex[Ru(L)(bpy)2]+ (1) was synthesized by using 3-ethyl-1-(thiophen-2-yl)imidazolium (L) and 2, 2'-bipyridine (bpy), which has been characterized by NMR and HRMS. The interactions between complex 1 and common metal ions were investigated by UV-Vis absorption spectra. Only upon the addition of Hg2+, the absorption was blue-shifted from 548 to 448 nm companied with the solution color varying from red to yellow. By analyzing absorption and MS spectra, the mechanism of complex 1 sensing to Hg2+ could be attributed to the possible conversion of coordination mode from Ru—C to Ru—S resulting from the interaction between Hg2+ and S.
2022, 38(2): 227-236
doi: 10.11862/CJIC.2022.034
Abstract:
Here, Pt modified anatase-type titanium dioxide (TiO2) nanotube arrays were prepared by electroplating method for a low-platinum Pt/TiO2 nanotubes electrode (Pt/TiO2-NTs). By contrast, we fixed Pt on TiO2 dense film by the same procedure as a control sample (Pt/TiO2-F). The scanning electron microscopy and transmission electron microscopy observation showed that Pt nanoparticles were distributed uniformly in nanotube arrays, and Pt/TiO2-NTs showed a higher efficiency in electrocatalytic hydrogen evolution compared with Pt/TiO2-F and commercial Pt/C catalyst, in which the overpotential of Pt/TiO2-NTs was 0.079 V, the Tafel slope was 42.7 mV·dec-1 at 10 mA·cm-2. The catalytic activity of 3 000 cycles duration stability test results showed that Pt/TiO2-NTs exhibited excellent stability compared with the above contrast electrodes.
Here, Pt modified anatase-type titanium dioxide (TiO2) nanotube arrays were prepared by electroplating method for a low-platinum Pt/TiO2 nanotubes electrode (Pt/TiO2-NTs). By contrast, we fixed Pt on TiO2 dense film by the same procedure as a control sample (Pt/TiO2-F). The scanning electron microscopy and transmission electron microscopy observation showed that Pt nanoparticles were distributed uniformly in nanotube arrays, and Pt/TiO2-NTs showed a higher efficiency in electrocatalytic hydrogen evolution compared with Pt/TiO2-F and commercial Pt/C catalyst, in which the overpotential of Pt/TiO2-NTs was 0.079 V, the Tafel slope was 42.7 mV·dec-1 at 10 mA·cm-2. The catalytic activity of 3 000 cycles duration stability test results showed that Pt/TiO2-NTs exhibited excellent stability compared with the above contrast electrodes.
2022, 38(2): 237-243
doi: 10.11862/CJIC.2022.013
Abstract:
A new fluorescent probe L containing heterocrown ether group was designed and synthesized from t-butyl bis(2-chloroethyl)carbamate, 2, 2'-(ethane-1, 2-diylbis(oxy))diethanethiol, and N-ethyl carbazole. The structure of L was characterized by 1H NMR, 13C NMR, and high-resolution mass spectrometry. The selectivity of probe L with Ag+ was investigated by fluorescence spectroscopy in water/ethanol solvent (4:1, V/V). All the results showed that the binding ratio for probe L to Ag+ was 1:1. The binding constant Ka was calculated to be 2.01×105 L·mol-1 and the detection limit was 4.13 μmol·L-1. The results also showed that probe L could be used to detection of Ag+ in the river and other environmental water samples.
A new fluorescent probe L containing heterocrown ether group was designed and synthesized from t-butyl bis(2-chloroethyl)carbamate, 2, 2'-(ethane-1, 2-diylbis(oxy))diethanethiol, and N-ethyl carbazole. The structure of L was characterized by 1H NMR, 13C NMR, and high-resolution mass spectrometry. The selectivity of probe L with Ag+ was investigated by fluorescence spectroscopy in water/ethanol solvent (4:1, V/V). All the results showed that the binding ratio for probe L to Ag+ was 1:1. The binding constant Ka was calculated to be 2.01×105 L·mol-1 and the detection limit was 4.13 μmol·L-1. The results also showed that probe L could be used to detection of Ag+ in the river and other environmental water samples.
2022, 38(2): 244-252
doi: 10.11862/CJIC.2022.041
Abstract:
Traditional phosphor-converted white light-emitting diode (WLED), which is constructed either by using a blue-chip to pump yellow phosphors or a near-ultraviolet (NUV) chip to excite trichromatic phosphors, suffers from an evident cavity in the cyan region, resulting in the unsatisfied color quality of the white light. Thereby, Eu3+-doped Ca2KZn2 (VO4)3 yellow-emitting phosphors with the emission in a range of 400-750 nm were prepared to cover this spectral gap to obtain the full-spectrum white light. Excited by 378 nm, both the emissions arising from VO43- group and Eu3+ were seen in the prepared samples. The optimal doping content (molar fraction) for Eu3+ ions in the Ca2KZn2(VO4)3 host was 0.05 and energy transfer efficiency from VO43- group to Eu3+ was calculated to be around 64.9%. The thermal quenching performances of the final compounds were investigated via the use of the temperature-dependent emission spectra and the activation energies of the VO43- group and Eu3+ were 0.538 and 0.510 eV, respectively. In addition, a WLED device using the prepared yellow-emitting phosphors, commercial blue phosphors, and NUV chip exhibited well-distributed warm white light with low color correlated temperature of 3 843 K and high color rendering index of 85.8.
Traditional phosphor-converted white light-emitting diode (WLED), which is constructed either by using a blue-chip to pump yellow phosphors or a near-ultraviolet (NUV) chip to excite trichromatic phosphors, suffers from an evident cavity in the cyan region, resulting in the unsatisfied color quality of the white light. Thereby, Eu3+-doped Ca2KZn2 (VO4)3 yellow-emitting phosphors with the emission in a range of 400-750 nm were prepared to cover this spectral gap to obtain the full-spectrum white light. Excited by 378 nm, both the emissions arising from VO43- group and Eu3+ were seen in the prepared samples. The optimal doping content (molar fraction) for Eu3+ ions in the Ca2KZn2(VO4)3 host was 0.05 and energy transfer efficiency from VO43- group to Eu3+ was calculated to be around 64.9%. The thermal quenching performances of the final compounds were investigated via the use of the temperature-dependent emission spectra and the activation energies of the VO43- group and Eu3+ were 0.538 and 0.510 eV, respectively. In addition, a WLED device using the prepared yellow-emitting phosphors, commercial blue phosphors, and NUV chip exhibited well-distributed warm white light with low color correlated temperature of 3 843 K and high color rendering index of 85.8.
2022, 38(2): 253-260
doi: 10.11862/CJIC.2022.011
Abstract:
Graphitic carbon nitride (g-C3N4), an n-type semiconductor with a narrow bandgap of 2.7 eV, has been widely studied as a visible light-driven photocatalyst for organic pollutant degradation, while attapulgite exhibits strong surface activity and adsorption capacity and can be used as support for catalysts. Herein, the hybrid material of graphite phase carbon nitride and attapulgite (ATP/g-C3N4) were chosen as the basis of polyaniline (PANI), and ATP/g-C3N4-Pt/PANI was successfully prepared by depositing Pt nanoparticles onto the surface of ATP/g-C3N4 via a simple reduction reaction, followed by the polymerization of aniline on the surface or into the channels of ATP/g-C3N4-Pt using Pt nanoparticles as a catalyst in acid solution. Methyl orange (MO), a kind of anionic dye, was used as the model system to investigate the visible light photocatalytic activity of the obtained products. The results showed that conjugated structures of PANI and g-C3N4 were well maintained in the hybrid, implying good compatibility. The photocatalyst showed remarkable visible-light photoactivity because of the synergistic effect between multicomponent materials. The degradation rate of 20 mg·L-1 MO solution was achieved to 96.3% within 80 min by using ATP/g-C3N4-Pt/PANI as the photocatalyst, and it remained at 93.5% after five cycles.
Graphitic carbon nitride (g-C3N4), an n-type semiconductor with a narrow bandgap of 2.7 eV, has been widely studied as a visible light-driven photocatalyst for organic pollutant degradation, while attapulgite exhibits strong surface activity and adsorption capacity and can be used as support for catalysts. Herein, the hybrid material of graphite phase carbon nitride and attapulgite (ATP/g-C3N4) were chosen as the basis of polyaniline (PANI), and ATP/g-C3N4-Pt/PANI was successfully prepared by depositing Pt nanoparticles onto the surface of ATP/g-C3N4 via a simple reduction reaction, followed by the polymerization of aniline on the surface or into the channels of ATP/g-C3N4-Pt using Pt nanoparticles as a catalyst in acid solution. Methyl orange (MO), a kind of anionic dye, was used as the model system to investigate the visible light photocatalytic activity of the obtained products. The results showed that conjugated structures of PANI and g-C3N4 were well maintained in the hybrid, implying good compatibility. The photocatalyst showed remarkable visible-light photoactivity because of the synergistic effect between multicomponent materials. The degradation rate of 20 mg·L-1 MO solution was achieved to 96.3% within 80 min by using ATP/g-C3N4-Pt/PANI as the photocatalyst, and it remained at 93.5% after five cycles.
2022, 38(2): 261-273
doi: 10.11862/CJIC.2022.022
Abstract:
The amphiphilic calixarene, namely propyl resorcinol calix[4]arene (PRCA), hexyl resorcinol calix[4] arene (HRCA), and nonyl resorcinol calix[4]arene (NRCA), was used to induce the preparation of ZnO micro-nano structure under the refluxing condition seperately. The composition, morphology, and microstructure of the samples were analyzed by X-ray diffraction, scanning electron microscope, FT-IR, UV-Vis diffuse reflectance spectroscopy, and X-ray photoelectron spectroscopy. Rhodamine B was used as a simulated pollutant to investigate the photocatalytic performance of the ZnO micro-nano structure protected by the resorcinol calix[4]arene. The characterization results showed that the size and morphology of ZnO particles could be controlled by the amphiphilic calixarenes which contained more carbon atoms in the linear alkyl chain connecting to the lower edge (HRCA and NRCA). However, the ability to control the morphology of ZnO was weak when without a protective agent and the resorcinol calix[4]arene with a short linear alkyl chain at the lower edge (PRCA). Under simulated sunlight, the photocatalytic efficiency of HRCA-ZnO and NRCA-ZnO was similar and higher than those of ZnO prepared without a protective agent and PRCA-ZnO.
The amphiphilic calixarene, namely propyl resorcinol calix[4]arene (PRCA), hexyl resorcinol calix[4] arene (HRCA), and nonyl resorcinol calix[4]arene (NRCA), was used to induce the preparation of ZnO micro-nano structure under the refluxing condition seperately. The composition, morphology, and microstructure of the samples were analyzed by X-ray diffraction, scanning electron microscope, FT-IR, UV-Vis diffuse reflectance spectroscopy, and X-ray photoelectron spectroscopy. Rhodamine B was used as a simulated pollutant to investigate the photocatalytic performance of the ZnO micro-nano structure protected by the resorcinol calix[4]arene. The characterization results showed that the size and morphology of ZnO particles could be controlled by the amphiphilic calixarenes which contained more carbon atoms in the linear alkyl chain connecting to the lower edge (HRCA and NRCA). However, the ability to control the morphology of ZnO was weak when without a protective agent and the resorcinol calix[4]arene with a short linear alkyl chain at the lower edge (PRCA). Under simulated sunlight, the photocatalytic efficiency of HRCA-ZnO and NRCA-ZnO was similar and higher than those of ZnO prepared without a protective agent and PRCA-ZnO.
2022, 38(2): 274-284
doi: 10.11862/CJIC.2022.007
Abstract:
Herein, Cu, C co-loaded ZnO photocatalyst was synthesized to promote its photocatalytic nitrogen fixation properties and overcome its disadvantages of high photoelectron-hole recombination rate, poor response to visible light and photocorrosion. The results indicated that CuCZ-3% (the weight of Cu loaded was 3% of the weight of ZnO) photocatalyst achieved the highest nitrogen fixation rate (4.96 mmol·gcat-1·h-1), which was 8.10 times higher than that of ZnO (0.612 mmol·gcat-1·h-1) and 1.65 times higher than that of CZnO (C-loaded ZnO, 3.00 mmol·gcat-1·h-1). To explore possible mechanism for the promoted nitrogen fixation efficiency of CuCZ photocatalyst, X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), photoluminescence spectroscopy (PL), and electrochemical impedance spectroscopy (EIS) were applied. The results indicated that the interfacial charge transfer mechanism induced by the transition metal Cu and the electronic bridging function of C enhanced nitrogen fixation efficiency and inhibited photoelectron-hole recombination of ZnO photocatalyst. CuCZ-3% photocatalyst exhibited excellent stability with the nitrogen fixation rate ranged between 4.61 and 4.96 mmol·gcat-1·h-1 in four cycles. The main reason is that the coating effect of C weakens the photocorrosion of CuCZ photocatalyst.
Herein, Cu, C co-loaded ZnO photocatalyst was synthesized to promote its photocatalytic nitrogen fixation properties and overcome its disadvantages of high photoelectron-hole recombination rate, poor response to visible light and photocorrosion. The results indicated that CuCZ-3% (the weight of Cu loaded was 3% of the weight of ZnO) photocatalyst achieved the highest nitrogen fixation rate (4.96 mmol·gcat-1·h-1), which was 8.10 times higher than that of ZnO (0.612 mmol·gcat-1·h-1) and 1.65 times higher than that of CZnO (C-loaded ZnO, 3.00 mmol·gcat-1·h-1). To explore possible mechanism for the promoted nitrogen fixation efficiency of CuCZ photocatalyst, X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), photoluminescence spectroscopy (PL), and electrochemical impedance spectroscopy (EIS) were applied. The results indicated that the interfacial charge transfer mechanism induced by the transition metal Cu and the electronic bridging function of C enhanced nitrogen fixation efficiency and inhibited photoelectron-hole recombination of ZnO photocatalyst. CuCZ-3% photocatalyst exhibited excellent stability with the nitrogen fixation rate ranged between 4.61 and 4.96 mmol·gcat-1·h-1 in four cycles. The main reason is that the coating effect of C weakens the photocorrosion of CuCZ photocatalyst.
2022, 38(2): 285-294
doi: 10.11862/CJIC.2022.038
Abstract:
Coordination polymer[Mn3(L)6(H2O)4]n (1) was prepared by the reaction of manganese chloride (MnCl2·4H2O) and 4-methyl-1, 2, 3-thiadiazole-5-carboxylic acid (HL) by conventional solution method, and complex[Mn2(phen)4(H2O)2Cl2](L)2·3H2O (2) was synthesized after adding the ligand 1, 10-phenanthroline (phen). The complexes were characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, and singlecrystal X-ray diffraction. The single-crystal structure analysis shows that complex 1 belongs to the monoclinic system, P21/c space group. The three manganese ions are bridged in bidentate fashion by the oxygen atoms in the six thiadiazole formate groups to form a linear trinuclear molecule cluster compound. The cluster unit is connected by the coordination of nitrogen atom from one of the thiadiazole rings and the manganese atom of the other cluster unit to form a layered structure. Complex 2 belongs to the triclinic crystal system, P1 space group. The central metal manganese ion coordinated with four nitrogen atoms from two phen molecules, one chloride anion, and one oxygen atom of coordination water molecule respectively, forming a six-coordinated twisted octahedral structure cation. The thiadiazole formate anion plays the role of charge balance. Ethidium bromide fluorescence spectrometry was used to determine the interaction between HL and complexes with DNA, respectively. The results showed that the interaction between the complexes and DNA was stronger than that of HL, and complex 2 with a planar ligand had a stronger effect than that of complex 1.
Coordination polymer[Mn3(L)6(H2O)4]n (1) was prepared by the reaction of manganese chloride (MnCl2·4H2O) and 4-methyl-1, 2, 3-thiadiazole-5-carboxylic acid (HL) by conventional solution method, and complex[Mn2(phen)4(H2O)2Cl2](L)2·3H2O (2) was synthesized after adding the ligand 1, 10-phenanthroline (phen). The complexes were characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, and singlecrystal X-ray diffraction. The single-crystal structure analysis shows that complex 1 belongs to the monoclinic system, P21/c space group. The three manganese ions are bridged in bidentate fashion by the oxygen atoms in the six thiadiazole formate groups to form a linear trinuclear molecule cluster compound. The cluster unit is connected by the coordination of nitrogen atom from one of the thiadiazole rings and the manganese atom of the other cluster unit to form a layered structure. Complex 2 belongs to the triclinic crystal system, P1 space group. The central metal manganese ion coordinated with four nitrogen atoms from two phen molecules, one chloride anion, and one oxygen atom of coordination water molecule respectively, forming a six-coordinated twisted octahedral structure cation. The thiadiazole formate anion plays the role of charge balance. Ethidium bromide fluorescence spectrometry was used to determine the interaction between HL and complexes with DNA, respectively. The results showed that the interaction between the complexes and DNA was stronger than that of HL, and complex 2 with a planar ligand had a stronger effect than that of complex 1.
2022, 38(2): 295-303
doi: 10.11862/CJIC.2022.018
Abstract:
To explore the regulation of photoelectric properties of zinc porphyrin dyes with heterocyclopentadiene as π-bridge, six new zinc porphyrin dyes were designed by introducing heterocyclopentadiene with different heteroatoms as the π-bridge based on the reference dye YD2-o-C8. The frontier molecular orbital energy levels, absorption spectra, and the hole-electron separation characteristics of the designed dyes were investigated using the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods. The results show that compared with the reference dye YD2-o-C8, the introduction of heterocyclopentadiene in π-bridge can improve the photoelectric performance of dyes. The photoelectric properties of porphyrin dyes can be regulated by changing heteroatoms. Further analysis on the relationship between the properties of heterocyclopentadienes and the photoelectric performance of the porphyrin dyes shows that the lowest unoccupied molecular orbital energy level of heterocyclopentadienes has a good linear relationship with the photoelectric properties of the designed porphyrin dyes. The stronger electron receiving ability of heterocyclopentadiene can lead to the better performance of the porphyrin dye. The silicon-heterocyclopentadiene is of the strongest electron receiving ability, and the corresponding porphyrin dye has the widest absorption spectra and the strongest intramolecular charge transfer ability.
To explore the regulation of photoelectric properties of zinc porphyrin dyes with heterocyclopentadiene as π-bridge, six new zinc porphyrin dyes were designed by introducing heterocyclopentadiene with different heteroatoms as the π-bridge based on the reference dye YD2-o-C8. The frontier molecular orbital energy levels, absorption spectra, and the hole-electron separation characteristics of the designed dyes were investigated using the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods. The results show that compared with the reference dye YD2-o-C8, the introduction of heterocyclopentadiene in π-bridge can improve the photoelectric performance of dyes. The photoelectric properties of porphyrin dyes can be regulated by changing heteroatoms. Further analysis on the relationship between the properties of heterocyclopentadienes and the photoelectric performance of the porphyrin dyes shows that the lowest unoccupied molecular orbital energy level of heterocyclopentadienes has a good linear relationship with the photoelectric properties of the designed porphyrin dyes. The stronger electron receiving ability of heterocyclopentadiene can lead to the better performance of the porphyrin dye. The silicon-heterocyclopentadiene is of the strongest electron receiving ability, and the corresponding porphyrin dye has the widest absorption spectra and the strongest intramolecular charge transfer ability.
2022, 38(2): 304-312
doi: 10.11862/CJIC.2022.037
Abstract:
Keggin-type mesoporous Cs3PMo12O40 (m-Cs3PMo) has been prepared by using H3PMo12O40 and CsCl as starting materials and amphiphilic triblock copolymer F127 as a template. The composition, structure, and morphology were characterized by powder X-ray diffraction (XRD), FT-IR, field emission scanning electron microscopy (FESEM), transmission electron microscope (TEM), N2 adsorption-desorption test, and small-angle X-ray scattering (SAXS). The results show that m-Cs3 PMo belongs to the cubic lattice system and owns 2.5 and 6.0 nm wormlike mesoporous pores. The catalytic activity of m-Cs3PMo in aqueous epimerization of D-glucose, D-xylose, and L-arabinose was investigated. The effects of temperature, time, and catalyst amount on the D-glucose epimerization reaction and the recycling performance of the catalyst were also studied. During the recycling process, the catalyst activity and product selectivity did not decrease significantly, which showed good stability of m-Cs3PMo.
Keggin-type mesoporous Cs3PMo12O40 (m-Cs3PMo) has been prepared by using H3PMo12O40 and CsCl as starting materials and amphiphilic triblock copolymer F127 as a template. The composition, structure, and morphology were characterized by powder X-ray diffraction (XRD), FT-IR, field emission scanning electron microscopy (FESEM), transmission electron microscope (TEM), N2 adsorption-desorption test, and small-angle X-ray scattering (SAXS). The results show that m-Cs3 PMo belongs to the cubic lattice system and owns 2.5 and 6.0 nm wormlike mesoporous pores. The catalytic activity of m-Cs3PMo in aqueous epimerization of D-glucose, D-xylose, and L-arabinose was investigated. The effects of temperature, time, and catalyst amount on the D-glucose epimerization reaction and the recycling performance of the catalyst were also studied. During the recycling process, the catalyst activity and product selectivity did not decrease significantly, which showed good stability of m-Cs3PMo.
2022, 38(2): 313-320
doi: 10.11862/CJIC.2022.040
Abstract:
In this work, the well-monodispersed SiO2 nanoparticles (about 130 nm) were used as the filler while the polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) was used as the polymer matrix. The monodisperse SiO2 composite gel polymer electrolytes (MCGPEs) were prepared by a simple method and applied to lithium batteries. SiO2 has better dispersion and uniformity in the polymer matrix. Compared with the conventional composite gel polymer electrolytes (GPEs) and commercial SiO2 composite gel polymer electrolytes (CGPEs), MCGPEs exhibited the more excellent ability of liquid absorption and better lithium-ion migration ability. Moreover, the cells which used MCGPEs as electrolytes maintained a high specific capacity of 121.1 mAh·g-1 after 300 cycles at 1.0C, showing a satisfactory cycle performance. Meanwhile, the rate performance of MCGPEs was also excellent. The cells using MCGPEs owned the specific capacity of 135 mAh·g-1 at 10C which was higher than GPEs cells (76.2 mAh·g-1).
In this work, the well-monodispersed SiO2 nanoparticles (about 130 nm) were used as the filler while the polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) was used as the polymer matrix. The monodisperse SiO2 composite gel polymer electrolytes (MCGPEs) were prepared by a simple method and applied to lithium batteries. SiO2 has better dispersion and uniformity in the polymer matrix. Compared with the conventional composite gel polymer electrolytes (GPEs) and commercial SiO2 composite gel polymer electrolytes (CGPEs), MCGPEs exhibited the more excellent ability of liquid absorption and better lithium-ion migration ability. Moreover, the cells which used MCGPEs as electrolytes maintained a high specific capacity of 121.1 mAh·g-1 after 300 cycles at 1.0C, showing a satisfactory cycle performance. Meanwhile, the rate performance of MCGPEs was also excellent. The cells using MCGPEs owned the specific capacity of 135 mAh·g-1 at 10C which was higher than GPEs cells (76.2 mAh·g-1).
2022, 38(2): 321-332
doi: 10.11862/CJIC.2022.028
Abstract:
A three-dimensional flower-like Bi2WO6/BiOBr heterojunction was successfully prepared by a hydrothermal approach using didodecyldimethylammonium bromide (DDAB) and cetyltrimethylammonium bromide (CTAB) as structure-directing agents and Br sources. The as-prepared photocatalysts were characterized by X-ray diffraction, scanning electron microscope, transmission electron microscopy, UV-visible diffuse reflection spectroscopy, transient photocurrent, Nyquist plots, and electron paramagnetic resonance to investigate the structure, morphology, composition, and photoelectrochemical properties. The results showed that 20-30 nm BiOBr nanoparticles were uniformly attached to Bi2WO6 sheet to form a three-dimensional flower shape structure. Compared with pure Bi2WO6, Bi2WO6/BiOBr showed a wide visible response range and effective separation efficiency of photogenerated electrons and holes. The optimum photocatalytic performance of Bi2WO6/BiOBr when wDDAB/wCTAB=2.6 was verified by photodegradation experiments. Under the irradiation of a 300 W Xe lamp with 420 nm filter, it showed the highest reaction rate constant (0.099 7 min-1) in the degradation of rhodamine B, which was about 2.7 times and 1.9 times of Bi2WO6 (0.037 6 min-1) and BT-4 (0.052 3 min-1, wDDAB/wCTAB=3.9), respectively, and the activity was no significant decrease after 6 cycles. Bi2WO6/BiOBr heterojunction can also non-selectively degrade other types of organic dyes, such as methylene blue, malachite green, and methyl orange. Finally, the photodegradation mechanism of Bi2WO6/BiOBr heterojunctions was proposed by the active species capture experiment and Mulliken theoretical calculation of atomic electronegativity.
A three-dimensional flower-like Bi2WO6/BiOBr heterojunction was successfully prepared by a hydrothermal approach using didodecyldimethylammonium bromide (DDAB) and cetyltrimethylammonium bromide (CTAB) as structure-directing agents and Br sources. The as-prepared photocatalysts were characterized by X-ray diffraction, scanning electron microscope, transmission electron microscopy, UV-visible diffuse reflection spectroscopy, transient photocurrent, Nyquist plots, and electron paramagnetic resonance to investigate the structure, morphology, composition, and photoelectrochemical properties. The results showed that 20-30 nm BiOBr nanoparticles were uniformly attached to Bi2WO6 sheet to form a three-dimensional flower shape structure. Compared with pure Bi2WO6, Bi2WO6/BiOBr showed a wide visible response range and effective separation efficiency of photogenerated electrons and holes. The optimum photocatalytic performance of Bi2WO6/BiOBr when wDDAB/wCTAB=2.6 was verified by photodegradation experiments. Under the irradiation of a 300 W Xe lamp with 420 nm filter, it showed the highest reaction rate constant (0.099 7 min-1) in the degradation of rhodamine B, which was about 2.7 times and 1.9 times of Bi2WO6 (0.037 6 min-1) and BT-4 (0.052 3 min-1, wDDAB/wCTAB=3.9), respectively, and the activity was no significant decrease after 6 cycles. Bi2WO6/BiOBr heterojunction can also non-selectively degrade other types of organic dyes, such as methylene blue, malachite green, and methyl orange. Finally, the photodegradation mechanism of Bi2WO6/BiOBr heterojunctions was proposed by the active species capture experiment and Mulliken theoretical calculation of atomic electronegativity.
2022, 38(2): 333-343
doi: 10.11862/CJIC.2022.030
Abstract:
Two kinds of MnO2 nanoarrays, including α-MnO2 nanowires and δ-MnO2 nanosheets, were synthesized on carbon fiber paper (CFP) via the one-step hydrothermal method by changing the temperature and the addition of sulfuric acid, respectively. Moreover, the oxygen evolution reaction (OER) properties for the MnO2 nanoarrays were studied. The results showed that the performance of α-MnO2 nanowires outperformed δ-MnO2 nanosheets in alkaline medium and the overpotential of α-MnO2 was 444 mV under 10 mA·cm-2 current density (the overpotential of δ-MnO2 was 522 mV). According to the analysis of X-ray photoelectron spectroscopy, the higher content of Mn3+ and more abundant oxygen vacancies on the surface are the reasons for the higher catalytic activity of α-MnO2 nanowires.
Two kinds of MnO2 nanoarrays, including α-MnO2 nanowires and δ-MnO2 nanosheets, were synthesized on carbon fiber paper (CFP) via the one-step hydrothermal method by changing the temperature and the addition of sulfuric acid, respectively. Moreover, the oxygen evolution reaction (OER) properties for the MnO2 nanoarrays were studied. The results showed that the performance of α-MnO2 nanowires outperformed δ-MnO2 nanosheets in alkaline medium and the overpotential of α-MnO2 was 444 mV under 10 mA·cm-2 current density (the overpotential of δ-MnO2 was 522 mV). According to the analysis of X-ray photoelectron spectroscopy, the higher content of Mn3+ and more abundant oxygen vacancies on the surface are the reasons for the higher catalytic activity of α-MnO2 nanowires.
2022, 38(2): 344-352
doi: 10.11862/CJIC.2022.035
Abstract:
Three new coordination polymers, {[Zn(4-Nbdc) (btx)]·2H2O}n (1·2H2O), [Zn(btx)1.5(1, 3-bdac)]n (2) and {[Zn(mbtx) (1, 3-bdc) (H2O)2]·H2O}n (3) (btx=1, 4-bis(4H-1, 2, 4-triazole)benzene, mbtx=1, 3-bis(4H-1, 2, 4-triazole) benzene, 4-Nbdc=4-nitrophthalate, 1, 3-bdac=1, 3-phenylenediacetate, 1, 3-bdc=1, 3-benzenedicarboxylate), were synthesized under room temperature condition and characterized by single-crystal X-ray diffraction, elemental analyses, powder X-ray diffraction. Sing-crystal X-ray structural analysis show that complex 1 is 2D waved (4, 4) network. 2 and 3 exhibit 1D chain, and the 1D chains are connected into a 3D network by π-π interaction in 2. The adjacent 1D chains are connected into a 2D network by intermolecular hydrogen bond in 3. Two sets of equivalent 2D networks catenate with each other to give a 2D+2D → 2D network through intermolecular hydrogen bond. Luminescence and thermogravimetric analysis of the three complexes were discussed.
Three new coordination polymers, {[Zn(4-Nbdc) (btx)]·2H2O}n (1·2H2O), [Zn(btx)1.5(1, 3-bdac)]n (2) and {[Zn(mbtx) (1, 3-bdc) (H2O)2]·H2O}n (3) (btx=1, 4-bis(4H-1, 2, 4-triazole)benzene, mbtx=1, 3-bis(4H-1, 2, 4-triazole) benzene, 4-Nbdc=4-nitrophthalate, 1, 3-bdac=1, 3-phenylenediacetate, 1, 3-bdc=1, 3-benzenedicarboxylate), were synthesized under room temperature condition and characterized by single-crystal X-ray diffraction, elemental analyses, powder X-ray diffraction. Sing-crystal X-ray structural analysis show that complex 1 is 2D waved (4, 4) network. 2 and 3 exhibit 1D chain, and the 1D chains are connected into a 3D network by π-π interaction in 2. The adjacent 1D chains are connected into a 2D network by intermolecular hydrogen bond in 3. Two sets of equivalent 2D networks catenate with each other to give a 2D+2D → 2D network through intermolecular hydrogen bond. Luminescence and thermogravimetric analysis of the three complexes were discussed.
2022, 38(2): 353-360
doi: 10.11862/CJIC.2022.032
Abstract:
By virtue of Schiff base ligands bis(2-(methyliminomethyl)-4-nitro-phenol) dianion (L1)/2-((3-aminopropylimino)-methyl)-4-nitro-phenol monoanion (L2) that derived from photochromic molecule 2-(3', 3'-dimethyl-6-nitrospiro(chromene-2, 2'-indolin)-1'-yl)ethanol, two metal-organic complexes[Cu(L1)] (1) and[Cu(L2)(1, 3-DAP)]NO3 (2) have been successfully fabricated through in situ ligand reaction in the presence of Cu2+. These complexes were characterized by IR, single-crystal X-ray diffraction, and powder X-ray diffraction. Additionally, certain photocatalytic properties of the two complexes for the degradation of organic dye molecules have been observed.
By virtue of Schiff base ligands bis(2-(methyliminomethyl)-4-nitro-phenol) dianion (L1)/2-((3-aminopropylimino)-methyl)-4-nitro-phenol monoanion (L2) that derived from photochromic molecule 2-(3', 3'-dimethyl-6-nitrospiro(chromene-2, 2'-indolin)-1'-yl)ethanol, two metal-organic complexes[Cu(L1)] (1) and[Cu(L2)(1, 3-DAP)]NO3 (2) have been successfully fabricated through in situ ligand reaction in the presence of Cu2+. These complexes were characterized by IR, single-crystal X-ray diffraction, and powder X-ray diffraction. Additionally, certain photocatalytic properties of the two complexes for the degradation of organic dye molecules have been observed.
2022, 38(2): 361-367
doi: 10.11862/CJIC.2022.003
Abstract:
We report a one-pot method to directly synthesize highly luminescent Cu-n-Zn-S (CIZS) quantum dots (QDs) in aqueous media by using bio-compatible glutathione (GSH) as capping ligand and stabilizer. The influences of various experimental variables, including reaction time, pH value, and precursor ratio, have been systematically investigated. The optical features and structure of the obtained CIZS QDs have been characterized by UV-Vis and fluorescence spectroscopy, transmission electron microscope, powder X-ray diffraction, and FT-IR. As a result, the stable GSH capped CIZS QDs exhibited excellent photoluminescence emission properties, narrow size distribution and excellent biocompatibility under optimum experimental conditions. In addition, as-prepared CIZS QDs were successfully used for fluorescence imaging of MDA-MB-231 cells and emitted bright red fluorescence.
We report a one-pot method to directly synthesize highly luminescent Cu-n-Zn-S (CIZS) quantum dots (QDs) in aqueous media by using bio-compatible glutathione (GSH) as capping ligand and stabilizer. The influences of various experimental variables, including reaction time, pH value, and precursor ratio, have been systematically investigated. The optical features and structure of the obtained CIZS QDs have been characterized by UV-Vis and fluorescence spectroscopy, transmission electron microscope, powder X-ray diffraction, and FT-IR. As a result, the stable GSH capped CIZS QDs exhibited excellent photoluminescence emission properties, narrow size distribution and excellent biocompatibility under optimum experimental conditions. In addition, as-prepared CIZS QDs were successfully used for fluorescence imaging of MDA-MB-231 cells and emitted bright red fluorescence.
2022, 38(2): 368-376
doi: 10.11862/CJIC.2022.039
Abstract:
Coumarin-derived fluorescence sensor was designed and synthesized to selectively recognize Zn2+ ions. The structure and fluorescence properties of the sensor were investigated by NMR, MS, fluorescence spectroscopy, and other technical methods. Sensor CANQ exhibited conspicuous fluorescent enhancement response to Zn2+ ion and had the characteristic of fast response, high selectivity, and good biocompatibility. It has been applied to the imaging of Zn2+ ions in MCF-7 cells.
Coumarin-derived fluorescence sensor was designed and synthesized to selectively recognize Zn2+ ions. The structure and fluorescence properties of the sensor were investigated by NMR, MS, fluorescence spectroscopy, and other technical methods. Sensor CANQ exhibited conspicuous fluorescent enhancement response to Zn2+ ion and had the characteristic of fast response, high selectivity, and good biocompatibility. It has been applied to the imaging of Zn2+ ions in MCF-7 cells.
