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2021 Volume 37 Issue 4
2021, 37(4): 577-591
doi: 10.11862/CJIC.2021.081
Abstract:
With the development of electronic technology, functional electronic devices with characteristics such as transparency and flexibility have received widespread attention. As a novel electronic device, the memristor has broad application prospects in the new generation of information technology including low-power neuromorphic computing, non-volatile logic, data storage, etc., and has become a new type of nanodevice that has attracted much attention in recent years. Indium tin oxide, which is an ideal conductive oxide material for transparent memristor preparation due to its excellent optical transparency, is always used in memristor. This review first briefly introduces the structure of memristors, and then reviews the research and application of memristors based on indium tin oxide materials, including their use as memory, electronic synapses, and nociceptor. Then the resistive switching mechanism of indium tin oxide based memristors, especially the newly discovered indium diffusion mechanism in recent years, is summarized. At last, the development prospect of indium tin oxide memristors is summarized and forecasted.
With the development of electronic technology, functional electronic devices with characteristics such as transparency and flexibility have received widespread attention. As a novel electronic device, the memristor has broad application prospects in the new generation of information technology including low-power neuromorphic computing, non-volatile logic, data storage, etc., and has become a new type of nanodevice that has attracted much attention in recent years. Indium tin oxide, which is an ideal conductive oxide material for transparent memristor preparation due to its excellent optical transparency, is always used in memristor. This review first briefly introduces the structure of memristors, and then reviews the research and application of memristors based on indium tin oxide materials, including their use as memory, electronic synapses, and nociceptor. Then the resistive switching mechanism of indium tin oxide based memristors, especially the newly discovered indium diffusion mechanism in recent years, is summarized. At last, the development prospect of indium tin oxide memristors is summarized and forecasted.
2021, 37(4): 592-600
doi: 10.11862/CJIC.2021.073
Abstract:
The nitronyl nitroxide radicals NIT-5Br-2PhOH(2-(2′-hydroxy-5′-bromophenyl)-4, 4, 5, 5-tetramethylimidazoline-1-oxyl-3-oxide) and NIT-5NO2-2 PhOH(2-(2′-hydroxy-5′-nitrophenyl)-4, 4, 5, 5-tetramethylimidazoline-1-oxyl-3-oxide) were selected as ligands to react with Ln(tfac)3·2H2O(tfac=trifluoroacetylacetonate) to produce three new lanthanide-radical complexes [Ln(tfac)2(NIT-5Br-2PhO)]2(Ln=Gd(1), Dy(2)) and [Dy(tfac)2(NIT-5NO2-2 PhO)]2(3).Single crystal X-ray crystallographic analysis reveals that all three complexes possess binuclear structure in which two lanthanide ions are connected through the hydroxy groups of the radicals. DC magnetic susceptibilities of Gd complex reveal that the antiferromagnetic coupling between the Gd(Ⅲ) centers plays a major role for the magnetic behavior. CCDC: 1981623, 1; 1981622, 2; 2021836, 3.
The nitronyl nitroxide radicals NIT-5Br-2PhOH(2-(2′-hydroxy-5′-bromophenyl)-4, 4, 5, 5-tetramethylimidazoline-1-oxyl-3-oxide) and NIT-5NO2-2 PhOH(2-(2′-hydroxy-5′-nitrophenyl)-4, 4, 5, 5-tetramethylimidazoline-1-oxyl-3-oxide) were selected as ligands to react with Ln(tfac)3·2H2O(tfac=trifluoroacetylacetonate) to produce three new lanthanide-radical complexes [Ln(tfac)2(NIT-5Br-2PhO)]2(Ln=Gd(1), Dy(2)) and [Dy(tfac)2(NIT-5NO2-2 PhO)]2(3).Single crystal X-ray crystallographic analysis reveals that all three complexes possess binuclear structure in which two lanthanide ions are connected through the hydroxy groups of the radicals. DC magnetic susceptibilities of Gd complex reveal that the antiferromagnetic coupling between the Gd(Ⅲ) centers plays a major role for the magnetic behavior. CCDC: 1981623, 1; 1981622, 2; 2021836, 3.
2021, 37(4): 735-743
doi: 10.11862/CJIC.2021.086
Abstract:
Two new Co(Ⅱ) -MOFs based on flexible ligands, namely {[Co(glu)(bimb)]·4H2O}n(1) and [Co(glu)(bix)0.5]n(2)(H2glu=glutaric acid; bimb=1, 4-bis(imidazol-1-yl)-butane; bix=1, 4-bis(imidazol-1-yl-methylene)-benzene), have been hydrothermally synthesized and structurally characterized. Compound 1 displays non-interpenetrated(4, 4)-rhomboid grid layers. A 3D supramolecular framework is invoked through interlayer hydrogen bonding and π…π interactions. Upon dehydration the structure of 1 degraded irreversibly. Compound 2 exhibits a typical pillar-layered 3D framework with 41263 topology, in which the Co(Ⅱ) ion adopts a square pyramidal coordination geometry. Moreover, Compound 1 exhibited significant adsorption activity towards methyl orange in aqueous solution, and 2 showed weak antiferromagnetic behavior. CCDC: 2012753, 1; 2012754, 2.
Two new Co(Ⅱ) -MOFs based on flexible ligands, namely {[Co(glu)(bimb)]·4H2O}n(1) and [Co(glu)(bix)0.5]n(2)(H2glu=glutaric acid; bimb=1, 4-bis(imidazol-1-yl)-butane; bix=1, 4-bis(imidazol-1-yl-methylene)-benzene), have been hydrothermally synthesized and structurally characterized. Compound 1 displays non-interpenetrated(4, 4)-rhomboid grid layers. A 3D supramolecular framework is invoked through interlayer hydrogen bonding and π…π interactions. Upon dehydration the structure of 1 degraded irreversibly. Compound 2 exhibits a typical pillar-layered 3D framework with 41263 topology, in which the Co(Ⅱ) ion adopts a square pyramidal coordination geometry. Moreover, Compound 1 exhibited significant adsorption activity towards methyl orange in aqueous solution, and 2 showed weak antiferromagnetic behavior. CCDC: 2012753, 1; 2012754, 2.
2021, 37(4): 744-750
doi: 10.11862/CJIC.2021.089
Abstract:
A new coordination polymer {[Ni2(L)(bib)1.5(H2O)4]·3H2O}n (1)(H4L=1-(3,5-dicarboxybenzyl)-1H-pyrazole-3,5-dicarboxylic acid, bib=1,4-bis(1-imidazolyl)benzene) was synthesized by hydrothermal method and characterized by single-crystal X-ray diffraction, elemental analyses and thermogravimetric analysis. Complex 1 features a 3D network structure. The variable temperature magnetic susceptibility measurements reveal that there are antiferromagnetic interactions between the Ni(Ⅱ) ions in complex 1. In addition, photocatalytic experiments indicated that complex 1 exhibited high photocatalytic activity up to 82.7% for the degradation of methylene blue pollutant.CCDC: 2030837.
A new coordination polymer {[Ni2(L)(bib)1.5(H2O)4]·3H2O}n (1)(H4L=1-(3,5-dicarboxybenzyl)-1H-pyrazole-3,5-dicarboxylic acid, bib=1,4-bis(1-imidazolyl)benzene) was synthesized by hydrothermal method and characterized by single-crystal X-ray diffraction, elemental analyses and thermogravimetric analysis. Complex 1 features a 3D network structure. The variable temperature magnetic susceptibility measurements reveal that there are antiferromagnetic interactions between the Ni(Ⅱ) ions in complex 1. In addition, photocatalytic experiments indicated that complex 1 exhibited high photocatalytic activity up to 82.7% for the degradation of methylene blue pollutant.CCDC: 2030837.
2021, 37(4): 751-757
doi: 10.11862/CJIC.2021.080
Abstract:
One 2D coordination polymer, namely[Mn(μ3-Hdpna)(2, 2'-bipy)]n (1), has been constructed hydrothermally using Hdbna (Hdbna=5-(2, 3-dicyanobenzoxy)nicotic acid), 2, 2'-bipy (2, 2'-bipy=2, 2'-bipyridine), and manganese chloride at 160 ℃. Interestingly, the H3dpna (H3dpna=5-(2, 3-dicarboxylphenoxy)nicotic acid) ligand was generated by in situ hydrolysis of cyano groups in Hdbna. The product was isolated as stable crystalline solid and was characterized by IR spectrum, elemental analysis, thermogravimetric analysis (TGA), and single-crystal X-ray diffraction analysis. Single-crystal X-ray diffraction analysis reveals that compound 1 crystallizes in the triclinic system, space group P1. Compound 1 discloses a 2D sheet with an hcb topology. Compound 1 was applied as an efficient heterogeneous catalyst for the cyanosilylation.
One 2D coordination polymer, namely[Mn(μ3-Hdpna)(2, 2'-bipy)]n (1), has been constructed hydrothermally using Hdbna (Hdbna=5-(2, 3-dicyanobenzoxy)nicotic acid), 2, 2'-bipy (2, 2'-bipy=2, 2'-bipyridine), and manganese chloride at 160 ℃. Interestingly, the H3dpna (H3dpna=5-(2, 3-dicarboxylphenoxy)nicotic acid) ligand was generated by in situ hydrolysis of cyano groups in Hdbna. The product was isolated as stable crystalline solid and was characterized by IR spectrum, elemental analysis, thermogravimetric analysis (TGA), and single-crystal X-ray diffraction analysis. Single-crystal X-ray diffraction analysis reveals that compound 1 crystallizes in the triclinic system, space group P1. Compound 1 discloses a 2D sheet with an hcb topology. Compound 1 was applied as an efficient heterogeneous catalyst for the cyanosilylation.
2021, 37(4): 758-766
doi: 10.11862/CJIC.2021.087
Abstract:
The quaternary ammonium amphiphile A6 with carboxylic acid group was employed to encapsulate the europium-containing inorganic polyoxometalate Na9[EuW10O36] through ionic self-assembly strategy. The resultant surfactant-encapsulated polyoxometalate complex A6Eu was characterized by FT-IR spectra, thermogravimetric analysis and elemental analysis in detail. The dimerization of the carboxylic acid groups through intermolecular hydrogen bonding gives rise to a branched bola-form structure of the organic moieties, which leads to a lateral attachement of the peripheral mesogen to the inorganic cluster. The thermotropic liquid crystalline properties of polyoxometalate complex were characterized by differential scanning calorimetry, polarized optical microscopy, and temperature-dependent X-ray diffraction. A6Eu exhibited novel lamellar-smectic mesophase in which the mesogen is organized parallel to the layer planes, while the amphiphile A6 alone was found to form simple smectic structures.The lateral attachment of the mesogen was demonstrated to have an important influence on the thermotropic organized structures of the complex. The luminescence of polyoxometalate is well retained in the liquid crystalline mesophase.
The quaternary ammonium amphiphile A6 with carboxylic acid group was employed to encapsulate the europium-containing inorganic polyoxometalate Na9[EuW10O36] through ionic self-assembly strategy. The resultant surfactant-encapsulated polyoxometalate complex A6Eu was characterized by FT-IR spectra, thermogravimetric analysis and elemental analysis in detail. The dimerization of the carboxylic acid groups through intermolecular hydrogen bonding gives rise to a branched bola-form structure of the organic moieties, which leads to a lateral attachement of the peripheral mesogen to the inorganic cluster. The thermotropic liquid crystalline properties of polyoxometalate complex were characterized by differential scanning calorimetry, polarized optical microscopy, and temperature-dependent X-ray diffraction. A6Eu exhibited novel lamellar-smectic mesophase in which the mesogen is organized parallel to the layer planes, while the amphiphile A6 alone was found to form simple smectic structures.The lateral attachment of the mesogen was demonstrated to have an important influence on the thermotropic organized structures of the complex. The luminescence of polyoxometalate is well retained in the liquid crystalline mesophase.
2021, 37(4): 601-607
doi: 10.11862/CJIC.2021.071
Abstract:
ZnO/ZnS/2TiO2: Eu3+ phosphor was prepared by sol-gel-precipitation method. The structure, composition, morphology and luminescent properties were characterized by used X-ray diffraction(XRD), infrared spectroscopy(IR), transmission electron microscope(TEM) and fluorescence spectrum. The mechanism of luminescence was investigated. The results showed that phosphor changed into a stable structure when the temperature was above 600 ℃, and structure of the irregular shape. The phosphor mainly composed of ZnO, TiO2 and ZnS. IR spectra show that the structure of Ti—O—Ti bridge oxygen bond network is conducive to pass energy among the Eu3+. Fluorescence spectra show that the addition of TiO2 can remove the inhibition of Eu3+ spectral melody and improve the luminescence properties of phosphor. And the best luminescence performance was obtained in the phosphor prepared with nZn(NO3)2: nTiO2=1:2. The strongest emission peak was 5D0→7F2 electric dipole transition at 612 nm, and the optimum annealing temperature was 600 ℃.
ZnO/ZnS/2TiO2: Eu3+ phosphor was prepared by sol-gel-precipitation method. The structure, composition, morphology and luminescent properties were characterized by used X-ray diffraction(XRD), infrared spectroscopy(IR), transmission electron microscope(TEM) and fluorescence spectrum. The mechanism of luminescence was investigated. The results showed that phosphor changed into a stable structure when the temperature was above 600 ℃, and structure of the irregular shape. The phosphor mainly composed of ZnO, TiO2 and ZnS. IR spectra show that the structure of Ti—O—Ti bridge oxygen bond network is conducive to pass energy among the Eu3+. Fluorescence spectra show that the addition of TiO2 can remove the inhibition of Eu3+ spectral melody and improve the luminescence properties of phosphor. And the best luminescence performance was obtained in the phosphor prepared with nZn(NO3)2: nTiO2=1:2. The strongest emission peak was 5D0→7F2 electric dipole transition at 612 nm, and the optimum annealing temperature was 600 ℃.
2021, 37(4): 608-614
doi: 10.11862/CJIC.2021.074
Abstract:
A MIL-53(Al)-based carbon composites(C-MIL-53(Al) and C-Co@MIL-53(Al)) with carbon nanotubes(CNTs) grown in-situ on porous carbon was firstly synthesized. Benefiting from the structure of MIL-53(Al) and CNTs, and the formation of CoF2, the C-Co@MIL-53(Al) electrode exhibited a high specific capacitance of 240.1 F·g-1 at 0.5 A·g-1 and a high retention value can be also maintained even after 2 000 cycles.
A MIL-53(Al)-based carbon composites(C-MIL-53(Al) and C-Co@MIL-53(Al)) with carbon nanotubes(CNTs) grown in-situ on porous carbon was firstly synthesized. Benefiting from the structure of MIL-53(Al) and CNTs, and the formation of CoF2, the C-Co@MIL-53(Al) electrode exhibited a high specific capacitance of 240.1 F·g-1 at 0.5 A·g-1 and a high retention value can be also maintained even after 2 000 cycles.
2021, 37(4): 615-622
doi: 10.11862/CJIC.2021.072
Abstract:
Using B3LYP/6-311++G(3df, 2pd) method, the activity difference of three sites of MIL-53(Al) for the preparation of dimethyldichlorosilane was calculated. The change of reaction channels, energy, virtual modes of transition states, intrinsic response coordinates(IRC) and the distance between key atoms were discussed, and the same conclusion was drawn. The activation energy of the rate-determining-step in main reaction were 157.15, 155.31 and 123.44 kJ·mol-1, and those in the side reaction were 206.48, 214.87 and 166.07 kJ·mol-1, respectively. It can be seen that the order of catalytic activity of three sites was 3 > 1 > 2. The catalytic disproportionation activity of MIL-53(Al) is attributed to the Brønsted acid H on its catalytic center(Al—O—H). The difference in activity results from the difference in their coordination environment.
Using B3LYP/6-311++G(3df, 2pd) method, the activity difference of three sites of MIL-53(Al) for the preparation of dimethyldichlorosilane was calculated. The change of reaction channels, energy, virtual modes of transition states, intrinsic response coordinates(IRC) and the distance between key atoms were discussed, and the same conclusion was drawn. The activation energy of the rate-determining-step in main reaction were 157.15, 155.31 and 123.44 kJ·mol-1, and those in the side reaction were 206.48, 214.87 and 166.07 kJ·mol-1, respectively. It can be seen that the order of catalytic activity of three sites was 3 > 1 > 2. The catalytic disproportionation activity of MIL-53(Al) is attributed to the Brønsted acid H on its catalytic center(Al—O—H). The difference in activity results from the difference in their coordination environment.
2021, 37(4): 623-628
doi: 10.11862/CJIC.2021.082
Abstract:
A mononuclear dysprosium complex [Dy(pmbp)3(H2O)2]·CH3CN(1)(Hpmbp=1-phenyl-3-methyl-4-benzoyl-pyrazol-5-one) was synthesized by the slow evaporation method. The complex exhibits a distorted square antiprism geometry around Dy(Ⅲ)ion, which coordinates to three pmbp- and two H2O ligands. The magnetic properties measurements show that 1 can exhibit a slow magnetic relaxation behavior under an applied dc field, and the effective energy barrier was 42 K. The ab intio calculations point out that the magnetic easy axis is along the direction of two pmbp- ligands in trans position, and the gz value of low-lying ground state was 18.818. Magneto-structural correlation studies analyzed the influence of conjugation effect in pmbp- ligand on the magnetic anisotropy of complex 1.CCDC: 2032517.
A mononuclear dysprosium complex [Dy(pmbp)3(H2O)2]·CH3CN(1)(Hpmbp=1-phenyl-3-methyl-4-benzoyl-pyrazol-5-one) was synthesized by the slow evaporation method. The complex exhibits a distorted square antiprism geometry around Dy(Ⅲ)ion, which coordinates to three pmbp- and two H2O ligands. The magnetic properties measurements show that 1 can exhibit a slow magnetic relaxation behavior under an applied dc field, and the effective energy barrier was 42 K. The ab intio calculations point out that the magnetic easy axis is along the direction of two pmbp- ligands in trans position, and the gz value of low-lying ground state was 18.818. Magneto-structural correlation studies analyzed the influence of conjugation effect in pmbp- ligand on the magnetic anisotropy of complex 1.CCDC: 2032517.
2021, 37(4): 629-637
doi: 10.11862/CJIC.2021.069
Abstract:
Flower-like Ni-Co-Mg-Al layered hydrotalcite materials were prepared by a hydrothermal crystallization method. After high-temperature calcination and hydrogen reduction, a series of Ni-Co alloy catalysts supported on MgAl composite oxides were successfully prepared. The physicochemical properties of the catalysts were characterized by scanning electron microscopy, transmission electron microscopy, nitrogen adsorption-desorption test, powder X-ray diffraction and temperature programmed reduction. The catalysts were tested for hydrogen production from steam reforming of n-dodecane. The results show that the precursor of hydrothermal crystallization catalyst was spherical flower-like layered hydrotalcite structure, and the as-calcined catalyst was in the form of composite oxide with abundant mesopores and macropores. The metal-support interaction and particles size of metal can be controlled by adjusting the amount of Co added. After reduction, Ni and Co formed an alloy and distributed uniformly on the lamellar MgAl composite oxide. Compared with the catalyst of single-metal Ni, the activity and hydrogen production rate of Ni-Co alloy catalyst were greatly improved, and the coke resistance was greatly improved. This is due to the synergistic effects of Ni-Co alloy and small metal nanoparticles.
Flower-like Ni-Co-Mg-Al layered hydrotalcite materials were prepared by a hydrothermal crystallization method. After high-temperature calcination and hydrogen reduction, a series of Ni-Co alloy catalysts supported on MgAl composite oxides were successfully prepared. The physicochemical properties of the catalysts were characterized by scanning electron microscopy, transmission electron microscopy, nitrogen adsorption-desorption test, powder X-ray diffraction and temperature programmed reduction. The catalysts were tested for hydrogen production from steam reforming of n-dodecane. The results show that the precursor of hydrothermal crystallization catalyst was spherical flower-like layered hydrotalcite structure, and the as-calcined catalyst was in the form of composite oxide with abundant mesopores and macropores. The metal-support interaction and particles size of metal can be controlled by adjusting the amount of Co added. After reduction, Ni and Co formed an alloy and distributed uniformly on the lamellar MgAl composite oxide. Compared with the catalyst of single-metal Ni, the activity and hydrogen production rate of Ni-Co alloy catalyst were greatly improved, and the coke resistance was greatly improved. This is due to the synergistic effects of Ni-Co alloy and small metal nanoparticles.
2021, 37(4): 638-644
doi: 10.11862/CJIC.2021.070
Abstract:
A novel Gd2O3: Eu@mSiO2 core-shell bifunctional nanorods were prepared by hydrothermal and tetraethyl orthosilicate hydrolysis methods. The morphology and phase structure of the samples were characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray powder diffraction(XRD), infrared spectroscopy(FTIR). The results shows that the core-shell nanomaterial was composed of Gd2O3: Eu nanorods(length ~400 nm, diameter ~100 nm) as the core and mesoporous SiO2 as the shell, and had uniform size and good dispersion. And the core-shell structured nanorod obtained strong red luminescence, giving the function of cell imaging upon incubation with the NCI-H460 lung cancer cells. The drug loading capacity and releasing behavior of the as-prepared Gd2O3: Eu@mSiO2 were studied by using ibuprofen(IBU) as model drug. The results show that the IBU loading capacity of the Gd2O3: Eu@mSiO2 core-shell nanorods could reach 10.25%, and the core-shell nanorods had obvious slow-release effect. Furthermore, IBU-loaded Gd2O3: Eu@mSiO2 core-shell nanorod still showed red luminescence of Eu3+ under UV irradiation, and the emission intensity of Eu3+ in the drug-carrier system varied with the released amount of IBU, so that the drug together with its release situation can be easily tracked and monitored by the change in luminescence intensity.
A novel Gd2O3: Eu@mSiO2 core-shell bifunctional nanorods were prepared by hydrothermal and tetraethyl orthosilicate hydrolysis methods. The morphology and phase structure of the samples were characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray powder diffraction(XRD), infrared spectroscopy(FTIR). The results shows that the core-shell nanomaterial was composed of Gd2O3: Eu nanorods(length ~400 nm, diameter ~100 nm) as the core and mesoporous SiO2 as the shell, and had uniform size and good dispersion. And the core-shell structured nanorod obtained strong red luminescence, giving the function of cell imaging upon incubation with the NCI-H460 lung cancer cells. The drug loading capacity and releasing behavior of the as-prepared Gd2O3: Eu@mSiO2 were studied by using ibuprofen(IBU) as model drug. The results show that the IBU loading capacity of the Gd2O3: Eu@mSiO2 core-shell nanorods could reach 10.25%, and the core-shell nanorods had obvious slow-release effect. Furthermore, IBU-loaded Gd2O3: Eu@mSiO2 core-shell nanorod still showed red luminescence of Eu3+ under UV irradiation, and the emission intensity of Eu3+ in the drug-carrier system varied with the released amount of IBU, so that the drug together with its release situation can be easily tracked and monitored by the change in luminescence intensity.
Synthesis, Structure and Proton Conduction of a Crystalline Ni(Ⅱ)-MOF with Continuous Hydrogen Bonds
2021, 37(4): 645-652
doi: 10.11862/CJIC.2021.088
Abstract:
The flexible multi-carboxylic acid organic ligand and Ni(Ⅱ) cation were selected to construct Ni-MOF[Ni2(L)(Nphen)2(H2O)4]n(1)(H4L=5, 5′-(butane-1, 4-diylbis(oxy)) diisophthalic acid, Nphen=5-nitro-1, 10-phenanthro-line) under hydrothermal condition. X-ray single diffraction studies reveal that there are continuous hydrogen bonds in the crystal structure of complex 1, which would be beneficial to its proton conducting behavior. The IR, powder X-ray diffraction and thermogravimetric analyses suggest that the obtained complex is pure and stable. The electrochemical researches on the composite membrane incorporated by complex 1 and Nafion reveal that doping of complex 1 can significantly improve the proton conduction behavior of Nafion membrane. The proton conductivity of the composite membrane was 24.08% higher than that of pure Nafion membrane. CCDC: 2052757.
The flexible multi-carboxylic acid organic ligand and Ni(Ⅱ) cation were selected to construct Ni-MOF[Ni2(L)(Nphen)2(H2O)4]n(1)(H4L=5, 5′-(butane-1, 4-diylbis(oxy)) diisophthalic acid, Nphen=5-nitro-1, 10-phenanthro-line) under hydrothermal condition. X-ray single diffraction studies reveal that there are continuous hydrogen bonds in the crystal structure of complex 1, which would be beneficial to its proton conducting behavior. The IR, powder X-ray diffraction and thermogravimetric analyses suggest that the obtained complex is pure and stable. The electrochemical researches on the composite membrane incorporated by complex 1 and Nafion reveal that doping of complex 1 can significantly improve the proton conduction behavior of Nafion membrane. The proton conductivity of the composite membrane was 24.08% higher than that of pure Nafion membrane. CCDC: 2052757.
2021, 37(4): 653-660
doi: 10.11862/CJIC.2021.061
Abstract:
Anisotropic SiO2 nanoparticles with dumbbell-like structure were prepared from nano SiO2 hydrosol in aqueous phase by a simple chemical process. Nano SiO2 hydrosol were previously modified with 3-aminopropyl triethoxysilane(APTES) and 3-chloropropyl triethoxysilane(CPTES), respectively. The APTES and CPTES modified SiO2 hydrosol were then mixed with different proportions, the SiO2 nanoparticles coupled to form dumbbell-like particles with a particle size of about 45 nm via the reaction of amine group and chloropropyl groups grafted on the surface of silica. The morphology, structure and chemical performance of SiO2 nanoparticles were systematically characterized by transmission electron microscopy(TEM), Fourier transform infrared(FT-IR), X-ray photoelectron spectroscopy(XPS) and dynamic light scatering(DLS). As a result, the dumbbell-like SiO2 nanoparticles with different hydrophilicity on both sides were successfully prepared, and the particle size was approximately equal to the sum of the particle size of APTES modified SiO2 particles and CPTES modified SiO2 particles.
Anisotropic SiO2 nanoparticles with dumbbell-like structure were prepared from nano SiO2 hydrosol in aqueous phase by a simple chemical process. Nano SiO2 hydrosol were previously modified with 3-aminopropyl triethoxysilane(APTES) and 3-chloropropyl triethoxysilane(CPTES), respectively. The APTES and CPTES modified SiO2 hydrosol were then mixed with different proportions, the SiO2 nanoparticles coupled to form dumbbell-like particles with a particle size of about 45 nm via the reaction of amine group and chloropropyl groups grafted on the surface of silica. The morphology, structure and chemical performance of SiO2 nanoparticles were systematically characterized by transmission electron microscopy(TEM), Fourier transform infrared(FT-IR), X-ray photoelectron spectroscopy(XPS) and dynamic light scatering(DLS). As a result, the dumbbell-like SiO2 nanoparticles with different hydrophilicity on both sides were successfully prepared, and the particle size was approximately equal to the sum of the particle size of APTES modified SiO2 particles and CPTES modified SiO2 particles.
2021, 37(4): 661-667
doi: 10.11862/CJIC.2021.084
Abstract:
In this paper, the electrochemical performance of the composite material with MWCNT content(mass fraction) of 3% at -20 and 60 ℃ was reported, and the results show that the specific capacities were as high as 169 and 303 mAh·g-1, respectively, as well as superior rate performance and cycle stability. Combined with the results of the electrochemical impedance test, it can be concluded that MWCNTs were attached to the surface of the layered particles uniformly, which can reduce the corrosion of the electrode material effectively, hinder the production of the solid electrolyte interface film, and improve the electronic conductivity of the material.
In this paper, the electrochemical performance of the composite material with MWCNT content(mass fraction) of 3% at -20 and 60 ℃ was reported, and the results show that the specific capacities were as high as 169 and 303 mAh·g-1, respectively, as well as superior rate performance and cycle stability. Combined with the results of the electrochemical impedance test, it can be concluded that MWCNTs were attached to the surface of the layered particles uniformly, which can reduce the corrosion of the electrode material effectively, hinder the production of the solid electrolyte interface film, and improve the electronic conductivity of the material.
2021, 37(4): 668-674
doi: 10.11862/CJIC.2021.090
Abstract:
The photocatalytic activity of graphic carbon nitride(g-C3N4) was limited because of poor visible-light utilization and low photogenerated carriers separation. Herein, carbon self-doping g-C3N4(CNNS-x, x mg represents the mass of TAPD in precursor) was simply prepared by one-step thermal co-polymerization of the homogeneous mixture of urea and 2, 4, 6-triaminopyrimidine(TAPD). The as-prepared CNNS-x was carefully characterized by powder X-ray diffraction(XRD), elemental analysis(EA), and X-ray photoelectron spectroscopy(XPS), which indicated that the pyrimidine was incorporated into the π-conjugated graphic carbon nitride. Thus, the CNNS-x was endowed with narrower bandgap, higher electric conductivity, which are favorable for improving the efficiency of visible-light absorption and photogenerated carrier separation. As a consequence, all the CNNS-x show remarkably improved performance in photocatalytic hydrogen evolution activity under visible-light irradiation. The optimum sample(CNNS-30) showed an excellent hydrogen evolution rate(~57 μmol·h-1), which was up to 4 times higher than that of g-C3N4 nanosheets(CNNS).
The photocatalytic activity of graphic carbon nitride(g-C3N4) was limited because of poor visible-light utilization and low photogenerated carriers separation. Herein, carbon self-doping g-C3N4(CNNS-x, x mg represents the mass of TAPD in precursor) was simply prepared by one-step thermal co-polymerization of the homogeneous mixture of urea and 2, 4, 6-triaminopyrimidine(TAPD). The as-prepared CNNS-x was carefully characterized by powder X-ray diffraction(XRD), elemental analysis(EA), and X-ray photoelectron spectroscopy(XPS), which indicated that the pyrimidine was incorporated into the π-conjugated graphic carbon nitride. Thus, the CNNS-x was endowed with narrower bandgap, higher electric conductivity, which are favorable for improving the efficiency of visible-light absorption and photogenerated carrier separation. As a consequence, all the CNNS-x show remarkably improved performance in photocatalytic hydrogen evolution activity under visible-light irradiation. The optimum sample(CNNS-30) showed an excellent hydrogen evolution rate(~57 μmol·h-1), which was up to 4 times higher than that of g-C3N4 nanosheets(CNNS).
2021, 37(4): 675-683
doi: 10.11862/CJIC.2021.062
Abstract:
A series of Nix/MgyAl2Oy+3(x=0.2 or 1, 5≤y≤11.8) bifunctional catalysts were prepared by calcination and hydrogen reduction of Nix/zMgy/zAl2/z(OH)2(CO3)1/z(z=x+y+2, x=0.2 or 1, 5≤y≤11.8) hydrotalcite precursors. The structure and morphology of these catalysts were characterized via X-ray diffraction(XRD), transmission electron microscope(TEM), temperature program reduction(TPR), temperature program desorption(TPD) and other technologies.It was found that Ni/Mg9Al2O12 exhibited excellent activity for the alkylation of butanone(MEK) with methanol. The conversion of butanone reached 61.6%, with the 45.0% and 17.7% selectivity of 3-pentanone(DEK) and 3-methyl-2-butanone(MIPK) under atmospheric pressure, 280 ℃, and liquid hourly space velocity(LHSV) of 6.0 h-1. The characterization results show that the appropriate active metal Ni and MgO contents in the catalyst play an important role on the selectivity of DEK and MIPK. The synergistic effect between Ni and the surface alkalinity may be the main factor affecting the activity and selectivity of the catalyst.
A series of Nix/MgyAl2Oy+3(x=0.2 or 1, 5≤y≤11.8) bifunctional catalysts were prepared by calcination and hydrogen reduction of Nix/zMgy/zAl2/z(OH)2(CO3)1/z(z=x+y+2, x=0.2 or 1, 5≤y≤11.8) hydrotalcite precursors. The structure and morphology of these catalysts were characterized via X-ray diffraction(XRD), transmission electron microscope(TEM), temperature program reduction(TPR), temperature program desorption(TPD) and other technologies.It was found that Ni/Mg9Al2O12 exhibited excellent activity for the alkylation of butanone(MEK) with methanol. The conversion of butanone reached 61.6%, with the 45.0% and 17.7% selectivity of 3-pentanone(DEK) and 3-methyl-2-butanone(MIPK) under atmospheric pressure, 280 ℃, and liquid hourly space velocity(LHSV) of 6.0 h-1. The characterization results show that the appropriate active metal Ni and MgO contents in the catalyst play an important role on the selectivity of DEK and MIPK. The synergistic effect between Ni and the surface alkalinity may be the main factor affecting the activity and selectivity of the catalyst.
2021, 37(4): 684-692
doi: 10.11862/CJIC.2021.083
Abstract:
Two p-chlorobenzyltin complexes have been synthesized via the reaction of p-methyl benzoyl hydrazide-benzoyl formic acid or benzoyl hydrazide-benzoyl formic acid with di-p-chlorobenzyltin dichloride. The complexes C1 and C2 have been characterized by IR, 1H NMR, 13C NMR, 119Sn NMR spectra, elemental analysis and HRMS, and the crystal structures have been determined by X-ray diffraction. The thermogravimetric of the complexes C1 and C2 were analyzed, and in vitro antitumor activities of both complexes were evaluated by MTT(3-(4, 5-dimethyl-thiazole-2)-2, 5-diphenyltetrazolium bromide) against three human cancer cell lines(NCI-H460, Hep G2 and MCF7).It was found that complex C2 showed a good inhibitory effect on cancer cells NCI-H460, HepG2, MCF7. The interaction of complex C2 with DNA was investigated using electronic absorption spectroscopy, fluorescence quench, and viscosity measurement. It was found that the complex could bind to DNA through an intercalation mode. CCDC: 2039991, C1; 2039990, C2.
Two p-chlorobenzyltin complexes have been synthesized via the reaction of p-methyl benzoyl hydrazide-benzoyl formic acid or benzoyl hydrazide-benzoyl formic acid with di-p-chlorobenzyltin dichloride. The complexes C1 and C2 have been characterized by IR, 1H NMR, 13C NMR, 119Sn NMR spectra, elemental analysis and HRMS, and the crystal structures have been determined by X-ray diffraction. The thermogravimetric of the complexes C1 and C2 were analyzed, and in vitro antitumor activities of both complexes were evaluated by MTT(3-(4, 5-dimethyl-thiazole-2)-2, 5-diphenyltetrazolium bromide) against three human cancer cell lines(NCI-H460, Hep G2 and MCF7).It was found that complex C2 showed a good inhibitory effect on cancer cells NCI-H460, HepG2, MCF7. The interaction of complex C2 with DNA was investigated using electronic absorption spectroscopy, fluorescence quench, and viscosity measurement. It was found that the complex could bind to DNA through an intercalation mode. CCDC: 2039991, C1; 2039990, C2.
2021, 37(4): 693-699
doi: 10.11862/CJIC.2021.075
Abstract:
Eu3+-Tb3+ co-doped SiO2-B2O3-Na2O-Y2O3-P2O5 precursor glasses were prepared by high temperature melting method. Differential scanning calorimetry(DSC) analysis of precursor glasses powder was carried out to determine the heat treatment temperature of glass ceramic samples. X-ray diffraction(XRD) and scanning electron microscope(SEM) results showed that Na3.6Y1.8(PO4)3 grains precipitated in the precursor glass after heat treatment. The luminescence properties of glass ceramics were characterized by fluorescence spectra. The fluorescence decay curves of Tb3+ ions were analyzed to determine the luminescence mechanism and energy transfer process of Eu3+ and Tb3+ ions. By collecting the emission spectra of Eu3+-Tb3+ co-doped glass ceramic samples, the chromatic coordinates and correlated color temperatures of glass ceramics samples were obtained by using color coordinate software and color temperature calculation program.
Eu3+-Tb3+ co-doped SiO2-B2O3-Na2O-Y2O3-P2O5 precursor glasses were prepared by high temperature melting method. Differential scanning calorimetry(DSC) analysis of precursor glasses powder was carried out to determine the heat treatment temperature of glass ceramic samples. X-ray diffraction(XRD) and scanning electron microscope(SEM) results showed that Na3.6Y1.8(PO4)3 grains precipitated in the precursor glass after heat treatment. The luminescence properties of glass ceramics were characterized by fluorescence spectra. The fluorescence decay curves of Tb3+ ions were analyzed to determine the luminescence mechanism and energy transfer process of Eu3+ and Tb3+ ions. By collecting the emission spectra of Eu3+-Tb3+ co-doped glass ceramic samples, the chromatic coordinates and correlated color temperatures of glass ceramics samples were obtained by using color coordinate software and color temperature calculation program.
2021, 37(4): 700-708
doi: 10.11862/CJIC.2021.085
Abstract:
Carbon coated CaSnO3 nanofibers(denoted as CaSnO3@C NFs) were prepared via the electrospinning technique combined with in-situ polymerization and carbonization processes. The phase compositions, surface morphology and microstructures of the samples were characterized by means of X-ray diffraction, scanning electron microscope, transmitting electron microscope and X-ray photoelectron spectroscopy. The influences of carbon coating and carbonization temperature on the electrochemical properties of CaSnO3 NFs-based anode materials were investigated using cyclic voltammetry, galvanostatic charge/discharge and AC impedance spectroscopy. The test results show that the electrochemical performance of CaSnO3 NFs was greatly improved after carbon coating, and meanwhile the specific capacity of CaSnO3@C NFs composites first increased and then decreased with increasing carbonization temperature, in which the CaSnO3@C NFs-600 composite obtained by carbonization at 600 ℃ exhibited an optimal electrochemical performance. The CaSnO3@C NFs-600 electrode had a high initial discharge specific capacity of 1 102.2 mAh·g-1 at a current density of 100 mA·g-1, and delivered a reversible specific capacity of 548.8 mAh·g-1 after 100 charge/discharge cycles. Moreover, it also showed a superior rate performance and retained a specific capacity of 333.5 mAh·g-1 even at 2 A·g-1.
Carbon coated CaSnO3 nanofibers(denoted as CaSnO3@C NFs) were prepared via the electrospinning technique combined with in-situ polymerization and carbonization processes. The phase compositions, surface morphology and microstructures of the samples were characterized by means of X-ray diffraction, scanning electron microscope, transmitting electron microscope and X-ray photoelectron spectroscopy. The influences of carbon coating and carbonization temperature on the electrochemical properties of CaSnO3 NFs-based anode materials were investigated using cyclic voltammetry, galvanostatic charge/discharge and AC impedance spectroscopy. The test results show that the electrochemical performance of CaSnO3 NFs was greatly improved after carbon coating, and meanwhile the specific capacity of CaSnO3@C NFs composites first increased and then decreased with increasing carbonization temperature, in which the CaSnO3@C NFs-600 composite obtained by carbonization at 600 ℃ exhibited an optimal electrochemical performance. The CaSnO3@C NFs-600 electrode had a high initial discharge specific capacity of 1 102.2 mAh·g-1 at a current density of 100 mA·g-1, and delivered a reversible specific capacity of 548.8 mAh·g-1 after 100 charge/discharge cycles. Moreover, it also showed a superior rate performance and retained a specific capacity of 333.5 mAh·g-1 even at 2 A·g-1.
2021, 37(4): 709-716
doi: 10.11862/CJIC.2021.056
Abstract:
The Cu3P nanoflake array was uniformly coated onto the commercial Cu foam skeleton(NF-Cu3P@Cu)through an in-situ growth method, and then used as a highly efficient 3D host for stable lithium metal anodes. The Cu3P nanoflake array with high lithiophilicity could provide abundant and homogenous active-sites for Li nucleation, leading to the fast nucleation and homogenous deposition of Li metal into the NF-Cu3P@Cu. Furthermore, during the electrochemical deposition process of Li metal, the Cu3P nanoflake array could be lithiated to form the fastion conductor Li3P, which ensures fast and uniform diffusion of Li+ in the NF-Cu3P@Cu, thus resulting in the effective suppression of Li dendrite growth. Therefore, the obtained Li@NF-Cu3P@Cu composite anode exhibited excellent cycling stability in both the symmetric and full cells.
The Cu3P nanoflake array was uniformly coated onto the commercial Cu foam skeleton(NF-Cu3P@Cu)through an in-situ growth method, and then used as a highly efficient 3D host for stable lithium metal anodes. The Cu3P nanoflake array with high lithiophilicity could provide abundant and homogenous active-sites for Li nucleation, leading to the fast nucleation and homogenous deposition of Li metal into the NF-Cu3P@Cu. Furthermore, during the electrochemical deposition process of Li metal, the Cu3P nanoflake array could be lithiated to form the fastion conductor Li3P, which ensures fast and uniform diffusion of Li+ in the NF-Cu3P@Cu, thus resulting in the effective suppression of Li dendrite growth. Therefore, the obtained Li@NF-Cu3P@Cu composite anode exhibited excellent cycling stability in both the symmetric and full cells.
2021, 37(4): 717-727
doi: 10.11862/CJIC.2021.060
Abstract:
Herein, Fe species modified urchin-like Nb2O5 nanospheres were prepared by directly introducing Fe3+ cations into the system on the basis of synthesizing urchin-like Nb2O5 nanospheres via hydrothermal method. The synthesized samples were characterized in detail by power X-ray diffraction(XRD), Fourier transform infrared spectroscopy(FT-IR), scanning electron microscopy(SEM), transmission electron microscopy(TEM), N2 adsorption-desorption test, X-ray photoelectron spectroscopy(XPS), UV-Vis absorption spectroscopy(UV-Vis) and photoluminescence emission spectroscopy(PL). The results indicated that Fe3+ cations had no obvious effect on the morphology and hexagonal structure of Nb2O5, but could increase the specific surface area of samples. The Fe species of Fe2O3 and Fe(Ⅱ)NbxOy with low crystallinity were most likely to be form in situ on the Nb2O5 surface during the experiment and uniformly dispersed. Compared with pure urchin-like Nb2O5 nanospheres, the Fe species modified Nb2O5 samples exhibited high photocatalytic activity under full light irradiation, and they could selectively degrade quasiphenothiazine dyes of methylene blue(MB) and toluidine blue(TB) with a high efficiency.One of the reasons is that Fe species can form coordination adsorption with N and S in quasi-phenothiazine dye molecules. Moreover, Fe species can separate photoexcited electrons of Nb2O5 and then decrease the recombination of photoexcited electron/hole by their matched conduction band(CB) with Nb2O5, and leading to the improvement of hole oxidation activity. Furthermore, Fenton reaction under the presence of trace H2O2 quickly consumes photoelectrons and generates a number of ·OH radicals to oxidize dye molecules.
Herein, Fe species modified urchin-like Nb2O5 nanospheres were prepared by directly introducing Fe3+ cations into the system on the basis of synthesizing urchin-like Nb2O5 nanospheres via hydrothermal method. The synthesized samples were characterized in detail by power X-ray diffraction(XRD), Fourier transform infrared spectroscopy(FT-IR), scanning electron microscopy(SEM), transmission electron microscopy(TEM), N2 adsorption-desorption test, X-ray photoelectron spectroscopy(XPS), UV-Vis absorption spectroscopy(UV-Vis) and photoluminescence emission spectroscopy(PL). The results indicated that Fe3+ cations had no obvious effect on the morphology and hexagonal structure of Nb2O5, but could increase the specific surface area of samples. The Fe species of Fe2O3 and Fe(Ⅱ)NbxOy with low crystallinity were most likely to be form in situ on the Nb2O5 surface during the experiment and uniformly dispersed. Compared with pure urchin-like Nb2O5 nanospheres, the Fe species modified Nb2O5 samples exhibited high photocatalytic activity under full light irradiation, and they could selectively degrade quasiphenothiazine dyes of methylene blue(MB) and toluidine blue(TB) with a high efficiency.One of the reasons is that Fe species can form coordination adsorption with N and S in quasi-phenothiazine dye molecules. Moreover, Fe species can separate photoexcited electrons of Nb2O5 and then decrease the recombination of photoexcited electron/hole by their matched conduction band(CB) with Nb2O5, and leading to the improvement of hole oxidation activity. Furthermore, Fenton reaction under the presence of trace H2O2 quickly consumes photoelectrons and generates a number of ·OH radicals to oxidize dye molecules.
2021, 37(4): 728-734
doi: 10.11862/CJIC.2021.077
Abstract:
SSZ-13 zeolite with good crystallinity was prepared by using tetraethyl ammonium hydroxide as organic template and Y zeolite with low molar ratio of SiO2 to Al2O3(nSiO2/nAl2O3) as aluminum source. The effect of different compositions of pre-gels on the synthesis of SSZ-13 was investigated, and the crystallinity, morphology and nSiO2/nAl2O3 in the process of hydrothermal reaction were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM) and inductively coupled plasm(ICP) to reveal the synthesis mechanism of SSZ-13. NH3 selective catalytic reduction(NH3-SCR) of NOx shows that the SSZ-13 catalysts with Cu loading(mass fraction of 3%) had excellent catalytic activity, which provides the possibility for its wide application in industry.
SSZ-13 zeolite with good crystallinity was prepared by using tetraethyl ammonium hydroxide as organic template and Y zeolite with low molar ratio of SiO2 to Al2O3(nSiO2/nAl2O3) as aluminum source. The effect of different compositions of pre-gels on the synthesis of SSZ-13 was investigated, and the crystallinity, morphology and nSiO2/nAl2O3 in the process of hydrothermal reaction were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM) and inductively coupled plasm(ICP) to reveal the synthesis mechanism of SSZ-13. NH3 selective catalytic reduction(NH3-SCR) of NOx shows that the SSZ-13 catalysts with Cu loading(mass fraction of 3%) had excellent catalytic activity, which provides the possibility for its wide application in industry.
