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2020 Volume 36 Issue 10
2020, 36(10): 1805-1821
doi: 10.11862/CJIC.2020.212
Abstract:
Metal-organic frameworks (MOFs) are porous crystalline materials build up of metal ions/clusters and multidentate organic ligands via coordination bonding interactions. Due to their unique characteristics like high porosity, high specific surface area, adjustable pore size, easy modification structure and diversified functions, MOFs were widely used in many fields including but not limited to gas adsorption/separation and catalysis. Up to now, among several common preparation methods of MOFs and their composites, mechanochemistry (reactions performed by grinding solid reactants in the absence of solvents or very small amounts of solvents) as clean, green and efficient synthesis method has attracted increasing attentions. This review aims to provide a general and easily understood overview of the mechanochemical synthesis for MOFs and their composites, in which the typical progresses of mechanochemical synthsis of MOFs and MOFs composites in recent years are summeried. At present, the research trends have affirmed that the mechanochemical method is a practical and environmentally friendly way to achieve the low-cost and high-throughput production of MOFs and their composites.
Metal-organic frameworks (MOFs) are porous crystalline materials build up of metal ions/clusters and multidentate organic ligands via coordination bonding interactions. Due to their unique characteristics like high porosity, high specific surface area, adjustable pore size, easy modification structure and diversified functions, MOFs were widely used in many fields including but not limited to gas adsorption/separation and catalysis. Up to now, among several common preparation methods of MOFs and their composites, mechanochemistry (reactions performed by grinding solid reactants in the absence of solvents or very small amounts of solvents) as clean, green and efficient synthesis method has attracted increasing attentions. This review aims to provide a general and easily understood overview of the mechanochemical synthesis for MOFs and their composites, in which the typical progresses of mechanochemical synthsis of MOFs and MOFs composites in recent years are summeried. At present, the research trends have affirmed that the mechanochemical method is a practical and environmentally friendly way to achieve the low-cost and high-throughput production of MOFs and their composites.
2020, 36(10): 1822-1830
doi: 10.11862/CJIC.2020.200
Abstract:
This study based on ZIF-67, which was grown on the surface of GO to make GO/ZIF-67 as a template. After etching by nickel nitrate, carbonizing and treating by hydrothermal with sodium sulfide, the final product of rGO/NiCo2S4 composite was obtained. X-ray diffraction (XRD), scanning electron microscope (SEM), and X-ray photoelectron spectroscopy (XPS) were used to characterize the structure and morphology of the composite which confirmed the expected product was obtained. Subsequently, the rGO/NiCo2S4 composite material was made into a positive electrode material and tested the electrochemical performance. The test results show that the rGO/NiCo2S4-1.5 h electrode material has a specific capacitance of 1 577 F·g-1 at current density of 1 A·g-1. When the current density reached 10 A·g-1, the rate performance was 86.4%. After 2 000 cycles at a current density of 10 A·g-1, the capacitance retention rate of rGO/NiCo2S4-1.5 h was 76.9%. In addition, an asymmetric capacitor of AC//rGO/NiCo2S4-1.5 h was assembled in a 6 mol·L-1 KOH electrolyte. It delivered an energy density of 33 Wh·kg-1 at a power density of 723 W·kg-1, and it remained as high as 23 Wh·kg-1 even at 7 277 W·kg-1.
This study based on ZIF-67, which was grown on the surface of GO to make GO/ZIF-67 as a template. After etching by nickel nitrate, carbonizing and treating by hydrothermal with sodium sulfide, the final product of rGO/NiCo2S4 composite was obtained. X-ray diffraction (XRD), scanning electron microscope (SEM), and X-ray photoelectron spectroscopy (XPS) were used to characterize the structure and morphology of the composite which confirmed the expected product was obtained. Subsequently, the rGO/NiCo2S4 composite material was made into a positive electrode material and tested the electrochemical performance. The test results show that the rGO/NiCo2S4-1.5 h electrode material has a specific capacitance of 1 577 F·g-1 at current density of 1 A·g-1. When the current density reached 10 A·g-1, the rate performance was 86.4%. After 2 000 cycles at a current density of 10 A·g-1, the capacitance retention rate of rGO/NiCo2S4-1.5 h was 76.9%. In addition, an asymmetric capacitor of AC//rGO/NiCo2S4-1.5 h was assembled in a 6 mol·L-1 KOH electrolyte. It delivered an energy density of 33 Wh·kg-1 at a power density of 723 W·kg-1, and it remained as high as 23 Wh·kg-1 even at 7 277 W·kg-1.
2020, 36(10): 1845-1852
doi: 10.11862/CJIC.2020.202
Abstract:
A fluorescent probe L was synthesized using 9-anthracene aldehyde as fluorescent group with pyrazoline and morpholine as recognition group, and its structure was characterized by 1H NMR and 13C NMR. The ion recognition performance of probe L was investigated by fluorescence emission spectra and ultraviolet absorption spectra. The results show that L has strong selective recognition performance for Fe3+ and Cu2+ with the fluorescence quantum yield decreasing from 0.47 to 0.21 and 0.14, respectively. The selective recognition for L to Fe3+ and Cu2+ was distinguished by naked eye along with color change from pale yellow to brown and blue, respectively. In addition, a three-input"NOR"logic gate circuit was constructed at the molecular level by the quantum yield of L for Fe3+, Cu2+ and H+ in different combinations.
A fluorescent probe L was synthesized using 9-anthracene aldehyde as fluorescent group with pyrazoline and morpholine as recognition group, and its structure was characterized by 1H NMR and 13C NMR. The ion recognition performance of probe L was investigated by fluorescence emission spectra and ultraviolet absorption spectra. The results show that L has strong selective recognition performance for Fe3+ and Cu2+ with the fluorescence quantum yield decreasing from 0.47 to 0.21 and 0.14, respectively. The selective recognition for L to Fe3+ and Cu2+ was distinguished by naked eye along with color change from pale yellow to brown and blue, respectively. In addition, a three-input"NOR"logic gate circuit was constructed at the molecular level by the quantum yield of L for Fe3+, Cu2+ and H+ in different combinations.
2020, 36(10): 1853-1864
doi: 10.11862/CJIC.2020.214
Abstract:
We synthesized two novel mononuclear ruthenium complexes, [Ru(cym)(L)Cl]Cl (Ru-1) and[Ru(bpy)2(L)] Cl2 (Ru-2) (cym=cymene, bpy=2, 2'-bipyridine, L=(E)-3-(4-hydroxy-3-methoxyphenyl)-N-((4'-methyl-(2, 2'-bipyridin)4-yl)methyl)acrylamide), with the modified natural product trans-ferulic acid. Their structures were determined by 1H NMR, 13C NMR and ESI-MS techniques. Optical properties and lipophilicity of complexes were characterized by using the fluorescence and UV-visible spectra. The results suggested that both complexes exhibited high water solubility. Ru-2 showed good fluorescence performance with the maximum emission wavelength at 631 nm in the near infrared area and had pH responsive ability (pH=8~10). Additionally, Ru-2 exhibited high singlet oxygen quantum yield (Φ=0.70), which might be expected to become an efficient photosensitizer. Both of the complexes binded to CT -DNA through intercalation mode (Kb:1.210×104 L·mol-1 for Ru-1; 1.233×103 L·mol-1 for Ru-2) and interacted with BSA with one site, causing static quenching of their fluorescence (Ka:1.94×104 for Ru-1; 2.45×104 for Ru-2).
We synthesized two novel mononuclear ruthenium complexes, [Ru(cym)(L)Cl]Cl (Ru-1) and[Ru(bpy)2(L)] Cl2 (Ru-2) (cym=cymene, bpy=2, 2'-bipyridine, L=(E)-3-(4-hydroxy-3-methoxyphenyl)-N-((4'-methyl-(2, 2'-bipyridin)4-yl)methyl)acrylamide), with the modified natural product trans-ferulic acid. Their structures were determined by 1H NMR, 13C NMR and ESI-MS techniques. Optical properties and lipophilicity of complexes were characterized by using the fluorescence and UV-visible spectra. The results suggested that both complexes exhibited high water solubility. Ru-2 showed good fluorescence performance with the maximum emission wavelength at 631 nm in the near infrared area and had pH responsive ability (pH=8~10). Additionally, Ru-2 exhibited high singlet oxygen quantum yield (Φ=0.70), which might be expected to become an efficient photosensitizer. Both of the complexes binded to CT -DNA through intercalation mode (Kb:1.210×104 L·mol-1 for Ru-1; 1.233×103 L·mol-1 for Ru-2) and interacted with BSA with one site, causing static quenching of their fluorescence (Ka:1.94×104 for Ru-1; 2.45×104 for Ru-2).
2020, 36(10): 1865-1872
doi: 10.11862/CJIC.2020.220
Abstract:
A series of complexes of surfactant@polyoxoanions were prepared by water/chloroform two-phase electrostatic encapsulating technology, employing polyoxoanion CeW10O369- with high photocatalytic activity and cationic surfactants in different structure as building blocks. The composition and structure of the complexes were analyzed by Fourier infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). The effects of various surfactants, catalyst dosage, concentration of methyl orange, and organic dyes on the photocatalytic degradation rate were investigated, in which methyl orange and surfactant@polyoxoanions complexes were used as photodegradation substrate molecule and photocatalyst, respectively. The photodegradation activities for different composite catalysts of surfac-tant@polyoxoanions are in the order of DTAB (dodecyltrimethylammonium bromide)@CeW10 > TTAB (tetradecyltrimethylammonium bromide)@CeW10 > CTAB (cetyltrimethylammonium bromide)@CeW10 > OTAB (octadecyl trimethyl ammonium bromide)@CeW10 > DODA (dioctadecyl dimethyl ammonium bromide)@CeW10.
A series of complexes of surfactant@polyoxoanions were prepared by water/chloroform two-phase electrostatic encapsulating technology, employing polyoxoanion CeW10O369- with high photocatalytic activity and cationic surfactants in different structure as building blocks. The composition and structure of the complexes were analyzed by Fourier infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). The effects of various surfactants, catalyst dosage, concentration of methyl orange, and organic dyes on the photocatalytic degradation rate were investigated, in which methyl orange and surfactant@polyoxoanions complexes were used as photodegradation substrate molecule and photocatalyst, respectively. The photodegradation activities for different composite catalysts of surfac-tant@polyoxoanions are in the order of DTAB (dodecyltrimethylammonium bromide)@CeW10 > TTAB (tetradecyltrimethylammonium bromide)@CeW10 > CTAB (cetyltrimethylammonium bromide)@CeW10 > OTAB (octadecyl trimethyl ammonium bromide)@CeW10 > DODA (dioctadecyl dimethyl ammonium bromide)@CeW10.
2020, 36(10): 1873-1880
doi: 10.11862/CJIC.2020.222
Abstract:
Herein, we report the preparation of amorphous cobalt sulfide electrode materials using MOF as template and its application in electrocatalytic decomposition of water. Firstly, a new cobalt-based metal-organic framework was prepared by using nitrogen -containing system. Then, a series of amorphous cobalt sulfide samples were prepared by changing curing time, temperature and sulfur sources, such as sodium sulfide and thioacetamide. The materials were characterized by powder X-ray diffraction, scanning electron microscope, X-ray photoelectron spectroscopy and infrared spectra, and their structural characteristics were explained. The electrolysis performance of each sample was characterized in detail, and the structure-activity relationship of each system was established. Combined with various structural characterization and electrochemical performance tests, it was found that when the sulfuration temperature and sulfuration time were controlled to 60℃ and 6 h, respectively, the related samples exhibited the hydrogen evolution reaction and oxygen evolution reaction potential of 178 and 246 mV when the current density was 10 mA·cm-2 in 1.0 mol·L-1 KOH solution, along with the excellent durability. CCDC:2010582.
Herein, we report the preparation of amorphous cobalt sulfide electrode materials using MOF as template and its application in electrocatalytic decomposition of water. Firstly, a new cobalt-based metal-organic framework was prepared by using nitrogen -containing system. Then, a series of amorphous cobalt sulfide samples were prepared by changing curing time, temperature and sulfur sources, such as sodium sulfide and thioacetamide. The materials were characterized by powder X-ray diffraction, scanning electron microscope, X-ray photoelectron spectroscopy and infrared spectra, and their structural characteristics were explained. The electrolysis performance of each sample was characterized in detail, and the structure-activity relationship of each system was established. Combined with various structural characterization and electrochemical performance tests, it was found that when the sulfuration temperature and sulfuration time were controlled to 60℃ and 6 h, respectively, the related samples exhibited the hydrogen evolution reaction and oxygen evolution reaction potential of 178 and 246 mV when the current density was 10 mA·cm-2 in 1.0 mol·L-1 KOH solution, along with the excellent durability. CCDC:2010582.
2020, 36(10): 1881-1890
doi: 10.11862/CJIC.2020.216
Abstract:
NaCaGd(WO4)3:Eu3+ red phosphors with controllable morphology were synthesized via the hydrothermal method. The influences of pH value, reaction temperature and Eu3+ concentration on the crystal structure, morphology and photoluminescence properties of NaCaGd(WO4)3:Eu3+ phosphors were investigated in detail. The results show that the pure tetragonal sheelite structure NaCaGd(WO4)3 with uniform tetragonal plate-like nanocrystallines was obtained when pH value was 9 and reaction temperature of 180℃. Under the excitation of 394 nm, the phosphors displayed a bright red emission corresponding to the characteristic 4f-4f transitions of Eu3+, and the intensity of emission peak mainly depends on the pH value, the reaction temperature and Eu3+ doped concentration. The optimum photoluminescence performance is achieved for NaCaEu(WO4)3 (x=1.0) phosphors synthesized at pH=9 under the reaction temperature 180℃. In addition, the thermal stability of the phosphors was analyzed under different ambient temperatures between 303 and 513 K. The result exhibits that the emission intensity of phosphor decreases with the increase of ambient temperature. Finally, the corresponding chromaticity coordinate and color purity were calculated to (0.658, 0.341) and 96.1%, which is close to the standard CIE chromaticity coordiante values for red light (0.673, 0.327).
NaCaGd(WO4)3:Eu3+ red phosphors with controllable morphology were synthesized via the hydrothermal method. The influences of pH value, reaction temperature and Eu3+ concentration on the crystal structure, morphology and photoluminescence properties of NaCaGd(WO4)3:Eu3+ phosphors were investigated in detail. The results show that the pure tetragonal sheelite structure NaCaGd(WO4)3 with uniform tetragonal plate-like nanocrystallines was obtained when pH value was 9 and reaction temperature of 180℃. Under the excitation of 394 nm, the phosphors displayed a bright red emission corresponding to the characteristic 4f-4f transitions of Eu3+, and the intensity of emission peak mainly depends on the pH value, the reaction temperature and Eu3+ doped concentration. The optimum photoluminescence performance is achieved for NaCaEu(WO4)3 (x=1.0) phosphors synthesized at pH=9 under the reaction temperature 180℃. In addition, the thermal stability of the phosphors was analyzed under different ambient temperatures between 303 and 513 K. The result exhibits that the emission intensity of phosphor decreases with the increase of ambient temperature. Finally, the corresponding chromaticity coordinate and color purity were calculated to (0.658, 0.341) and 96.1%, which is close to the standard CIE chromaticity coordiante values for red light (0.673, 0.327).
2020, 36(10): 1891-1898
doi: 10.11862/CJIC.2020.217
Abstract:
Two transition metal coordination polymer materials {[Cu2(L1)2(L2)(H2O)2(DMF)]·3H2O}n (1) (DMF=N, N-dimethylformamide) and {[Zn(L1)(L3)(H2O)2]·H2O}n (2), were successfully synthesized by solvothermal method with 3, 4-ethylenedioxythiophene-2, 5-dicarboxylic acid (H2L1), 2, 2'-bipyidine (L2), and 4, 4'-bipyidine (L3). The complexes were characterized by X-ray single crystal diffraction, infrared spectroscopy (IR), UV spectrum, fluorescence spectroscopy (FL) and thermogravimetric analysis (TG/DTG). The single crystal structure analysis shows that complex 1 is a two-dimensional (2D) layered structure formed by L12- ligands bridging Cu2+ ions, and a three-dimensional (3D) network structure is further formed by hydrogen bonding interaction of L2 ligands. Complex 2 forms one-dimensional (1D) chain by L12- ligands connecting Zn2+ ions, and further bridging L3 ligand to form 1D band structure, which is stacked to from 3D structure by the hydrogen-bonding and π-π stacking interaction between coordination water molecules and ligand oxygen atom. The FL and TG/DTG results indicate that complexes 1 and 2 have good thermal stability and fluorescence properties. The maximum emission peaks of complexes 1 and 2 are 364 and 365 nm, respectively. CCDC:1946117, 1; 1946113, 2.
Two transition metal coordination polymer materials {[Cu2(L1)2(L2)(H2O)2(DMF)]·3H2O}n (1) (DMF=N, N-dimethylformamide) and {[Zn(L1)(L3)(H2O)2]·H2O}n (2), were successfully synthesized by solvothermal method with 3, 4-ethylenedioxythiophene-2, 5-dicarboxylic acid (H2L1), 2, 2'-bipyidine (L2), and 4, 4'-bipyidine (L3). The complexes were characterized by X-ray single crystal diffraction, infrared spectroscopy (IR), UV spectrum, fluorescence spectroscopy (FL) and thermogravimetric analysis (TG/DTG). The single crystal structure analysis shows that complex 1 is a two-dimensional (2D) layered structure formed by L12- ligands bridging Cu2+ ions, and a three-dimensional (3D) network structure is further formed by hydrogen bonding interaction of L2 ligands. Complex 2 forms one-dimensional (1D) chain by L12- ligands connecting Zn2+ ions, and further bridging L3 ligand to form 1D band structure, which is stacked to from 3D structure by the hydrogen-bonding and π-π stacking interaction between coordination water molecules and ligand oxygen atom. The FL and TG/DTG results indicate that complexes 1 and 2 have good thermal stability and fluorescence properties. The maximum emission peaks of complexes 1 and 2 are 364 and 365 nm, respectively. CCDC:1946117, 1; 1946113, 2.
2020, 36(10): 1899-1905
doi: 10.11862/CJIC.2020.188
Abstract:
In this paper, we report the rational design and preparation of a new type of high-performance oxygen evolution electrocatalyst, namely 3D heterostructured Co3O4@NiMn-LDH (layered double metal hydroxide) arrays supported on Ni foam (Co3O4@NiMn-LDH/NF). It was prepared via facile two-step hydrothermal reactions. Compared with Co3O4, NiMn-LDH and traditional RuO2 electrocatalysts, the as-prepared Co3O4@NiMn-LDH/NF presents better electrocatalytic oxygen evolution performance, achieving a low overpotential of 282 mV at 50 mA·cm-2 with a Tafel slope of 64 mV·dec-1 in 1 mol·L-1 KOH solution. Through designing effective interface engineering, the Co3O4@NiMn-LDH/NF combines synergistically the excellent electrocatalytic activity of Co3O4 and NiMn-LDH. The Co3O4 nanowire array based on Ni foam as a core structure with abundant void spaces not only exposes more active sites, but also ensures easy diffusion of electrolyte and fast release of gas products. And the NiMn-LDH nanosheets on the Co3O4 nanowire array provide rich hydrophilic groups and active sites for easy access of water molecules, thus facilitating efficient oxygen evolution reaction.
In this paper, we report the rational design and preparation of a new type of high-performance oxygen evolution electrocatalyst, namely 3D heterostructured Co3O4@NiMn-LDH (layered double metal hydroxide) arrays supported on Ni foam (Co3O4@NiMn-LDH/NF). It was prepared via facile two-step hydrothermal reactions. Compared with Co3O4, NiMn-LDH and traditional RuO2 electrocatalysts, the as-prepared Co3O4@NiMn-LDH/NF presents better electrocatalytic oxygen evolution performance, achieving a low overpotential of 282 mV at 50 mA·cm-2 with a Tafel slope of 64 mV·dec-1 in 1 mol·L-1 KOH solution. Through designing effective interface engineering, the Co3O4@NiMn-LDH/NF combines synergistically the excellent electrocatalytic activity of Co3O4 and NiMn-LDH. The Co3O4 nanowire array based on Ni foam as a core structure with abundant void spaces not only exposes more active sites, but also ensures easy diffusion of electrolyte and fast release of gas products. And the NiMn-LDH nanosheets on the Co3O4 nanowire array provide rich hydrophilic groups and active sites for easy access of water molecules, thus facilitating efficient oxygen evolution reaction.
2020, 36(10): 1906-1916
doi: 10.11862/CJIC.2020.198
Abstract:
One-step synthesis of NiCoAl-layered double hydroxide (NiCoAl LDH) with different ratios of nickel and cobalt by hydrothermal method, and the electrochemical performance of NiCoAl LDH with different contents of Ni in nickel and cobalt metal elements were investigated. Ni0.3CoAl LDH materials have the best electrochemical performance when the molar ratio of Ni to Co was 3:7. Part of Ni element in the lattice was replaced by Co element, which is helpful to reduce the oxidation potential and improve the chemical reversibility of the material. Then the CNT/Ni0.3CoAl LDH composite was synthesized by hydrothermal method, and the carbon nanotubes improved the conductivity of the material. At a current density of 1 A·g-1, the specific capacitance of CNT/Ni0.3CoAl LDH was as high as 1 332 F·g-1. When the current density was increased to 10 A·g-1, the capacity retention can reach 60.4%, and the CNT/Ni0.3CoAl LDH electrode still exhibited an cycling stability with 87.6% retention at a current density of 5 A·g-1 for 3 000 cycles.
One-step synthesis of NiCoAl-layered double hydroxide (NiCoAl LDH) with different ratios of nickel and cobalt by hydrothermal method, and the electrochemical performance of NiCoAl LDH with different contents of Ni in nickel and cobalt metal elements were investigated. Ni0.3CoAl LDH materials have the best electrochemical performance when the molar ratio of Ni to Co was 3:7. Part of Ni element in the lattice was replaced by Co element, which is helpful to reduce the oxidation potential and improve the chemical reversibility of the material. Then the CNT/Ni0.3CoAl LDH composite was synthesized by hydrothermal method, and the carbon nanotubes improved the conductivity of the material. At a current density of 1 A·g-1, the specific capacitance of CNT/Ni0.3CoAl LDH was as high as 1 332 F·g-1. When the current density was increased to 10 A·g-1, the capacity retention can reach 60.4%, and the CNT/Ni0.3CoAl LDH electrode still exhibited an cycling stability with 87.6% retention at a current density of 5 A·g-1 for 3 000 cycles.
2020, 36(10): 1917-1924
doi: 10.11862/CJIC.2020.219
Abstract:
The effect of the nonionic surfactant primary alcobol ethoxylate (AEO-3) as an additive on the crystallization of β zeolites was investigated by adding it into the conventional hydrothermal synthesis system of the β zeolites with a formula of nAl2O3:nSiO2:nNa2O:nTEAOH:nH2O:nAEO-3:nC2H5OH=(0.28~1):40:1.55:10:640:(0.45~7.69):11.37. It was indicated that the addition of AEO-3 could promote the formation of aluminosilicate sol and increase the degree of its homogenization, as well as the yield of the product. The as-synthesized samples were characterized by X-ray diffraction, N2 and Ar adsorption-desorption, scanning electron microscope, NMR and n-decane adsorption. The results showed that the nano particles of β zeolites were more complete and uniform, the crystallinity and micropore volume increased by the addition of surfactant AEO-3, and the yield of product, Si/Al ratio and acid strength increased as well. In addition, the addition of AEO-3 increased the proportion of chiral polymorph A in the structure of β zeolites.
The effect of the nonionic surfactant primary alcobol ethoxylate (AEO-3) as an additive on the crystallization of β zeolites was investigated by adding it into the conventional hydrothermal synthesis system of the β zeolites with a formula of nAl2O3:nSiO2:nNa2O:nTEAOH:nH2O:nAEO-3:nC2H5OH=(0.28~1):40:1.55:10:640:(0.45~7.69):11.37. It was indicated that the addition of AEO-3 could promote the formation of aluminosilicate sol and increase the degree of its homogenization, as well as the yield of the product. The as-synthesized samples were characterized by X-ray diffraction, N2 and Ar adsorption-desorption, scanning electron microscope, NMR and n-decane adsorption. The results showed that the nano particles of β zeolites were more complete and uniform, the crystallinity and micropore volume increased by the addition of surfactant AEO-3, and the yield of product, Si/Al ratio and acid strength increased as well. In addition, the addition of AEO-3 increased the proportion of chiral polymorph A in the structure of β zeolites.
2020, 36(10): 1925-1933
doi: 10.11862/CJIC.2020.197
Abstract:
Using Cerium (Ⅲ) nitrate hexahydrate as Ce source, LiCexEu1-xTiO4 was synthesized by sol-gel and ion exchange method. The structural, morphological and electrochemical properties of LiCexEu1-xTiO4 were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), cyclic voltammogram (CV), and charge-discharge cycling tests. The results show that the introduction of Ce3+ into the lattice can significantly improve the dynamic properties of the material, which is probably related to Ce-Eu-Ti synergistic effect. This synergistic effect appears as the complicated modulations in terms of lattice parameters and resulted in Ti and Ce in mixed valences. LiEu0.995Ce0.005TiO4 shows the best electrochemical performances.
Using Cerium (Ⅲ) nitrate hexahydrate as Ce source, LiCexEu1-xTiO4 was synthesized by sol-gel and ion exchange method. The structural, morphological and electrochemical properties of LiCexEu1-xTiO4 were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), cyclic voltammogram (CV), and charge-discharge cycling tests. The results show that the introduction of Ce3+ into the lattice can significantly improve the dynamic properties of the material, which is probably related to Ce-Eu-Ti synergistic effect. This synergistic effect appears as the complicated modulations in terms of lattice parameters and resulted in Ti and Ce in mixed valences. LiEu0.995Ce0.005TiO4 shows the best electrochemical performances.
2020, 36(10): 1934-1940
doi: 10.11862/CJIC.2020.211
Abstract:
To solve the problem that it is difficult to immobilize triple-triplet annihilation based upconversion (TTAUC) for biological application, water soluble nanocapsules with n-hexadecane core containing a TTA-UC system were synthesized by a one-step miniemulsion polymerization. In the TTA-UC system, silicon phthalocyanine excited by red light source as sensitizer and rubrene with high efficiency as receptor were introduced into n-hexadecane to endow the nanocapsules with upconversion emission. The TTA-UC nanocapsules (TT-UCNP) have a typical coreshell structure with a uniform size of 190 nm. To eliminate the quenching effect of molecular oxygen on upconversion luminescence, D-limonene and polyisobutylene were selected as anti-oxidant, and the TTA-UCNP showed bright upconversion emission. The TTA-UCNP have been successfully applied in in vivo imaging of sentinel lymph node (SLN) with high signal-to-noise ratio and long-term tracing.
To solve the problem that it is difficult to immobilize triple-triplet annihilation based upconversion (TTAUC) for biological application, water soluble nanocapsules with n-hexadecane core containing a TTA-UC system were synthesized by a one-step miniemulsion polymerization. In the TTA-UC system, silicon phthalocyanine excited by red light source as sensitizer and rubrene with high efficiency as receptor were introduced into n-hexadecane to endow the nanocapsules with upconversion emission. The TTA-UC nanocapsules (TT-UCNP) have a typical coreshell structure with a uniform size of 190 nm. To eliminate the quenching effect of molecular oxygen on upconversion luminescence, D-limonene and polyisobutylene were selected as anti-oxidant, and the TTA-UCNP showed bright upconversion emission. The TTA-UCNP have been successfully applied in in vivo imaging of sentinel lymph node (SLN) with high signal-to-noise ratio and long-term tracing.
2020, 36(10): 1831-1844
doi: 10.11862/CJIC.2020.218
Abstract:
By using a flexible S-containing ligand 4-(2-thiophen-2-yl-ethyl)-4H-[1, 2, 4]triazole (L), four Kegginbased compounds, namely[Cu3ⅠL3(PMo12O40)] (1), [Cu4ⅠL6(SiW12O40)] (2), [Cu4ⅠL6(SiMo12O40)] (3) and[Zn4L6 (SiW12O40)] (4), were successfully synthesized by controlling the reaction parameters and well characterized by single -crystal X-ray diffraction, elemental analyses, and IR spectra. In compound 1, three Cu+ ions are fused by three L ligands inducing a cyclic tri-nuclear Cu+ cluster. The Keggin anions link the tri-nuclear clusters to construct a 2D layer. Compounds 2, 3 and 4 are isostructural, including a tetra-nuclear[M4L6]4+ cluster with six L ligands connected by four M ions (M=Cu in 2 and 3, Zn in 4). The Keggin anion offers two O atoms to link two[Cu4L6]4+ clusters and a 1D chain is formed. The title compounds exhibited good selective degradation of cationic methylene blue (MB) dye in wastewater. Additionally, the 2-CPE (carbon paste electrodes) could act as an amperometric sensor for detection of hydrogen peroxide and nitrite. Compounds 1, 2 and 4 also showed Hg2+ recognition properties.
By using a flexible S-containing ligand 4-(2-thiophen-2-yl-ethyl)-4H-[1, 2, 4]triazole (L), four Kegginbased compounds, namely[Cu3ⅠL3(PMo12O40)] (1), [Cu4ⅠL6(SiW12O40)] (2), [Cu4ⅠL6(SiMo12O40)] (3) and[Zn4L6 (SiW12O40)] (4), were successfully synthesized by controlling the reaction parameters and well characterized by single -crystal X-ray diffraction, elemental analyses, and IR spectra. In compound 1, three Cu+ ions are fused by three L ligands inducing a cyclic tri-nuclear Cu+ cluster. The Keggin anions link the tri-nuclear clusters to construct a 2D layer. Compounds 2, 3 and 4 are isostructural, including a tetra-nuclear[M4L6]4+ cluster with six L ligands connected by four M ions (M=Cu in 2 and 3, Zn in 4). The Keggin anion offers two O atoms to link two[Cu4L6]4+ clusters and a 1D chain is formed. The title compounds exhibited good selective degradation of cationic methylene blue (MB) dye in wastewater. Additionally, the 2-CPE (carbon paste electrodes) could act as an amperometric sensor for detection of hydrogen peroxide and nitrite. Compounds 1, 2 and 4 also showed Hg2+ recognition properties.
2020, 36(10): 1941-1947
doi: 10.11862/CJIC.2020.224
Abstract:
A new three-dimensional Zn2+-based metal-organic framework (MOF), {[Zn2(tyia)2(H2O)2] ·H2O}n (1), where H 2tyia is 5-(1H-1, 2, 4-triazol-1-yl) isophthalic acid, was synthesized under solvothermal conditions. The structure of compound 1 was analyzed by X-ray single crystal diffraction, and characterized by elemental analysis, powder X-ray diffraction, thermogravimetric analysis and solid fluorescence analysis. The fluorescence characteristics of the interaction between compound 1 and small organic molecules were studied. The results show that 1 can response quickly to low concentration of styrene, and the minimum identification concentration is 1.06 mmol·L-1. Furthermore, a possible sensing mechanism was investigated.
A new three-dimensional Zn2+-based metal-organic framework (MOF), {[Zn2(tyia)2(H2O)2] ·H2O}n (1), where H 2tyia is 5-(1H-1, 2, 4-triazol-1-yl) isophthalic acid, was synthesized under solvothermal conditions. The structure of compound 1 was analyzed by X-ray single crystal diffraction, and characterized by elemental analysis, powder X-ray diffraction, thermogravimetric analysis and solid fluorescence analysis. The fluorescence characteristics of the interaction between compound 1 and small organic molecules were studied. The results show that 1 can response quickly to low concentration of styrene, and the minimum identification concentration is 1.06 mmol·L-1. Furthermore, a possible sensing mechanism was investigated.
2020, 36(10): 1948-1958
doi: 10.11862/CJIC.2020.223
Abstract:
A multichip leaf-like MoO3 nanostructure assembled from one-dimensional nanowires has been synthesized by a simple solvothermal method using bis(acetylacetonato) dioxomolybdenum (Ⅵ) in a component solvent of acetic acid and deionized water at relatively lower temperature of 150℃. The field emission scanning electron microscopic (FESEM) and transmission electron microscopy (TEM) observations indicate that the multichip MoO3 nanostructures are composed of a plurality of fine nanowires with rough surface. The X-ray powder diffraction (XRD), high-resolution transmission electron microscope (HRTEM) results signified that the MoO3 nanoleaves with the orthorhombic system, a distorted octahedral structure. And, the dominant exposed crystal plane of the leaf-like MoO3 was (021). In addition, the leaf-like MoO3 possessed distinctive selectivity, ultrahigh sensitivity and response time (~5 s) towards 2.25 g·m-3 triethylamine (TEA) at the operating temperature of 300℃, even attained 12.4 at the low detection level (4.5 mg·m-3). Based on the analysis results, the growth and formation of crystalline phase was deemed to follow the oriented attachment mechanism. Accordingly, the enhanced sensing ability could be mainly ascribed to its unique nanostructure, linear combination of large density, and high specific surface area, which promote the substantial free diffusion of TEA gases into the blade hole, showing excellent response recovery.
A multichip leaf-like MoO3 nanostructure assembled from one-dimensional nanowires has been synthesized by a simple solvothermal method using bis(acetylacetonato) dioxomolybdenum (Ⅵ) in a component solvent of acetic acid and deionized water at relatively lower temperature of 150℃. The field emission scanning electron microscopic (FESEM) and transmission electron microscopy (TEM) observations indicate that the multichip MoO3 nanostructures are composed of a plurality of fine nanowires with rough surface. The X-ray powder diffraction (XRD), high-resolution transmission electron microscope (HRTEM) results signified that the MoO3 nanoleaves with the orthorhombic system, a distorted octahedral structure. And, the dominant exposed crystal plane of the leaf-like MoO3 was (021). In addition, the leaf-like MoO3 possessed distinctive selectivity, ultrahigh sensitivity and response time (~5 s) towards 2.25 g·m-3 triethylamine (TEA) at the operating temperature of 300℃, even attained 12.4 at the low detection level (4.5 mg·m-3). Based on the analysis results, the growth and formation of crystalline phase was deemed to follow the oriented attachment mechanism. Accordingly, the enhanced sensing ability could be mainly ascribed to its unique nanostructure, linear combination of large density, and high specific surface area, which promote the substantial free diffusion of TEA gases into the blade hole, showing excellent response recovery.
2020, 36(10): 1959-1966
doi: 10.11862/CJIC.2020.213
Abstract:
Two polymeric cadmium (Ⅱ) complexes derived from 2-methyl-5-(2-pyridyl)-1, 3, 4-oxadiazole (L), [Cd2(L)2(μ-SCN)4]n (1) and[Cd2(L)2(μ-Cl)4]n (2), were synthesized and characterized by single crystal X-ray diffraction, UV-visible spectra, fluorescence and thermogravimetric analysis (TGA). Complexes 1 and 2 crystallize in triclinic and monoclinic system, respectively. The space groups of complexes 1 and 2 are P\begin{document}$\bar 1$\end{document}
Two polymeric cadmium (Ⅱ) complexes derived from 2-methyl-5-(2-pyridyl)-1, 3, 4-oxadiazole (L), [Cd2(L)2(μ-SCN)4]n (1) and[Cd2(L)2(μ-Cl)4]n (2), were synthesized and characterized by single crystal X-ray diffraction, UV-visible spectra, fluorescence and thermogravimetric analysis (TGA). Complexes 1 and 2 crystallize in triclinic and monoclinic system, respectively. The space groups of complexes 1 and 2 are P
2020, 36(10): 1967-1976
doi: 10.11862/CJIC.2020.215
Abstract:
Two newly designed tetra-nuclear transition metal(Ⅱ) complexes, [Ni2(L)(μ-OAc)(CH3OH)]2·4CH3OH (1) and[Zn2(L)(μ-OAc)(CH3CH2OH)]2 (2), derived from an unsymmetrical salamo-like donors-N2O4 ligand (H3L=6-hydroxy-6'-methoxy-2, 2'-(ethylenediyldioxybis(nitrilomethylidyne))diphenol) were synthesized and characterized by elemental analyses, infrared spectra, ultraviolet-visible spectra, fluorescence spectra, Hirshfeld surfaces analyses, and single crystal X-ray crystallography. X-ray crystallographic analyses show that complexes 1 and 2 are all symmetrical four-nuclear complexes. All hexa-coordinated nickel(Ⅱ) ions in complex 1 form distorted octahedral geometries, while all penta-coordinated zinc(Ⅱ) ions in complex 2 form twisted quadrangular pyramid and triangular biconical geometries.
Two newly designed tetra-nuclear transition metal(Ⅱ) complexes, [Ni2(L)(μ-OAc)(CH3OH)]2·4CH3OH (1) and[Zn2(L)(μ-OAc)(CH3CH2OH)]2 (2), derived from an unsymmetrical salamo-like donors-N2O4 ligand (H3L=6-hydroxy-6'-methoxy-2, 2'-(ethylenediyldioxybis(nitrilomethylidyne))diphenol) were synthesized and characterized by elemental analyses, infrared spectra, ultraviolet-visible spectra, fluorescence spectra, Hirshfeld surfaces analyses, and single crystal X-ray crystallography. X-ray crystallographic analyses show that complexes 1 and 2 are all symmetrical four-nuclear complexes. All hexa-coordinated nickel(Ⅱ) ions in complex 1 form distorted octahedral geometries, while all penta-coordinated zinc(Ⅱ) ions in complex 2 form twisted quadrangular pyramid and triangular biconical geometries.
2020, 36(10): 1977-1987
doi: 10.11862/CJIC.2020.221
Abstract:
Herein, by using sequentially electrostatic layer-by-layer (LBL) deposition method, the artificialdesigned hybrid films were fabricated through the alternatively assemble of negatively charged layered titanium oxide (LTO) nanosheets and DNA molecules with positively charged layered double hydroxide (LDH) nanosheets. The infrared emissivity values at the wavelength of 8~14 μm of the as-synthesized samples were investigated. The X-ray diffraction (XRD) results demonstrate that the (LDH/DNA/LDH/LTO)n hybrid films were orderly stacked on the substrate in the normal direction, in which the DNA molecules and LTO nanosheets were accommodated as monolayer between the LDH nanosheets layers, respectively. It can be seen from the scanning electron microscope (SEM) and atomic force microscope (AFM) images that the surface morphology of the film was uniform and continuous. The energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) analysis verify the composition, the homogenous element distribution, and the well-ordered structure in the multilayer films. This multilayered hybrid film with tetra-layer units possessed a low infrared emissivity value of 0.419 based on the synergistic effect of its multi-components, the interfacial interaction between different layers and the uniform and smooth surface. These results clearly demonstrate that the ordered LBL assembly of the artificial designed hybrid film is quite effective in decreasing the infrared emissivity value.
Herein, by using sequentially electrostatic layer-by-layer (LBL) deposition method, the artificialdesigned hybrid films were fabricated through the alternatively assemble of negatively charged layered titanium oxide (LTO) nanosheets and DNA molecules with positively charged layered double hydroxide (LDH) nanosheets. The infrared emissivity values at the wavelength of 8~14 μm of the as-synthesized samples were investigated. The X-ray diffraction (XRD) results demonstrate that the (LDH/DNA/LDH/LTO)n hybrid films were orderly stacked on the substrate in the normal direction, in which the DNA molecules and LTO nanosheets were accommodated as monolayer between the LDH nanosheets layers, respectively. It can be seen from the scanning electron microscope (SEM) and atomic force microscope (AFM) images that the surface morphology of the film was uniform and continuous. The energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) analysis verify the composition, the homogenous element distribution, and the well-ordered structure in the multilayer films. This multilayered hybrid film with tetra-layer units possessed a low infrared emissivity value of 0.419 based on the synergistic effect of its multi-components, the interfacial interaction between different layers and the uniform and smooth surface. These results clearly demonstrate that the ordered LBL assembly of the artificial designed hybrid film is quite effective in decreasing the infrared emissivity value.
2020, 36(10): 1988-1996
doi: 10.11862/CJIC.2020.206
Abstract:
A cobalt based metal-organic[3+3] self-assembly macrocycle was constructed by tridentate Schiff base ligand L1 with N, O and P atoms (L1=1, 1'-biphenyl-4, 4'-di-carbohydrazide-bis-(2-diphenyphosphinobenzaldehyde)). The functionalized metal-organic triangle with amino groups was connected to photoactive fluorescein isothiocyanate (FITC) via post-assembly modification reaction. This modified complex Co-L3 was used as photocatalyst for hydrogen evolution from water splitting. It was a two-component system for hydrogen production without extra photosensitizer. Besides, compared with the three-component system, the metallosupramolecular catalyst Co-L3 underwent post-assembly modification reactions exhibited higher photocatalytic activity at the same metal catalyst and photosensitizer concentration with a turnover number (TON) of 80, which was approximately 30 times the photocatalytic efficiency of complex Co-L1.
A cobalt based metal-organic[3+3] self-assembly macrocycle was constructed by tridentate Schiff base ligand L1 with N, O and P atoms (L1=1, 1'-biphenyl-4, 4'-di-carbohydrazide-bis-(2-diphenyphosphinobenzaldehyde)). The functionalized metal-organic triangle with amino groups was connected to photoactive fluorescein isothiocyanate (FITC) via post-assembly modification reaction. This modified complex Co-L3 was used as photocatalyst for hydrogen evolution from water splitting. It was a two-component system for hydrogen production without extra photosensitizer. Besides, compared with the three-component system, the metallosupramolecular catalyst Co-L3 underwent post-assembly modification reactions exhibited higher photocatalytic activity at the same metal catalyst and photosensitizer concentration with a turnover number (TON) of 80, which was approximately 30 times the photocatalytic efficiency of complex Co-L1.
2020, 36(10): 1997-2004
doi: 10.11862/CJIC.2020.192
Abstract:
To investigate the performance of Cu-chabazite for selective catalytic reduction of NO with propylene (C3H6-SCR), a series of Cu-SAPO-34 catalysts with varied Cu/Al ratio have been synthesized by the one-pot hydrothermal method. These catalysts were characterized using N2 adsorption-desorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction by H2 (H2-TPR), and in-situ diffuse reflectance infrared Fourier transform spectroscopy (in-situ DRIFTS) techniques. The effect of Cu component on physicochemical properties and C3H6-SCR activity were investigated. Cu-SAPO-34 catalysts with Cu loading (22.76%~ 4.12%(w/w)) exhibited attractive activities, with nearly 100% NOx conversion and 100% N2 selectivity at the temperatures (300~400℃) in the excess of oxygen. Based on in situ DRIFT studies, the formation of NO2-/NO3- intermediates requires the presence of isolated Cu2+ ions in Cu-SAPO-34, which undergo a periodic Cu2+/Cu+ redox cycle during C3H6-SCR.
To investigate the performance of Cu-chabazite for selective catalytic reduction of NO with propylene (C3H6-SCR), a series of Cu-SAPO-34 catalysts with varied Cu/Al ratio have been synthesized by the one-pot hydrothermal method. These catalysts were characterized using N2 adsorption-desorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction by H2 (H2-TPR), and in-situ diffuse reflectance infrared Fourier transform spectroscopy (in-situ DRIFTS) techniques. The effect of Cu component on physicochemical properties and C3H6-SCR activity were investigated. Cu-SAPO-34 catalysts with Cu loading (22.76%~ 4.12%(w/w)) exhibited attractive activities, with nearly 100% NOx conversion and 100% N2 selectivity at the temperatures (300~400℃) in the excess of oxygen. Based on in situ DRIFT studies, the formation of NO2-/NO3- intermediates requires the presence of isolated Cu2+ ions in Cu-SAPO-34, which undergo a periodic Cu2+/Cu+ redox cycle during C3H6-SCR.
