Login In
2022 Volume 38 Issue 1
2022, 38(1): 1-13
doi: 10.11862/CJIC.2022.006
Abstract:
Mesoporous carbon nanomaterials have received tremendous attention in many areas because they have fast transport channels, high electrical conductivity, large specific surface area, and outstanding chemical stability. Realizing controllable synthesis and precise modification of mesoporous carbon nanomaterial is a hotspot and a focus of current research. Based on this, the research progress in the preparation and modification of mesoporous carbon nanomaterial is analyzed and summarized. The existing issues and future research direction are also discussed.
Mesoporous carbon nanomaterials have received tremendous attention in many areas because they have fast transport channels, high electrical conductivity, large specific surface area, and outstanding chemical stability. Realizing controllable synthesis and precise modification of mesoporous carbon nanomaterial is a hotspot and a focus of current research. Based on this, the research progress in the preparation and modification of mesoporous carbon nanomaterial is analyzed and summarized. The existing issues and future research direction are also discussed.
2022, 38(1): 14-20
doi: 10.11862/CJIC.2022.014
Abstract:
α -Al2O3 ceramic hollow fiber membranes were prepared by a combined phase-inversion and sintering method. Effects of TiO2 doping on sintering behavior and surface property of hollow fiber membranes were investigated extensively. The results showed that a solid reaction between TiO2 and α-Al2O3 could promote the sintering of α - Al2O3 hollow fibers. When the doping TiO2 content (molar fraction) was 1% - 2%, the sintering temperature of hollow fibers could decrease to 1 400 ℃ while the mechanical strength was unchanged. The hydroxyl active sites on the surface of the fibers increased with the doping amount of TiO2, which was helpful to the growth of the CHA zeolite membrane on the prepared fibers. High-quality CHA zeolite membranes could be prepared on the α-Al2O3 hollow fibers doped with a molar fraction of 1%-3% TiO2, which showed high separation factors above 10 000 for pervaporation dehydration of ethanol/water (9∶1, w/w) mixture.
α -Al2O3 ceramic hollow fiber membranes were prepared by a combined phase-inversion and sintering method. Effects of TiO2 doping on sintering behavior and surface property of hollow fiber membranes were investigated extensively. The results showed that a solid reaction between TiO2 and α-Al2O3 could promote the sintering of α - Al2O3 hollow fibers. When the doping TiO2 content (molar fraction) was 1% - 2%, the sintering temperature of hollow fibers could decrease to 1 400 ℃ while the mechanical strength was unchanged. The hydroxyl active sites on the surface of the fibers increased with the doping amount of TiO2, which was helpful to the growth of the CHA zeolite membrane on the prepared fibers. High-quality CHA zeolite membranes could be prepared on the α-Al2O3 hollow fibers doped with a molar fraction of 1%-3% TiO2, which showed high separation factors above 10 000 for pervaporation dehydration of ethanol/water (9∶1, w/w) mixture.
2022, 38(1): 21-30
doi: 10.11862/CJIC.2022.023
Abstract:
There are some key problems for oxygen reduction reaction (ORR), such as the slow kinetic process and high cost of Pt/C catalysts. To overcome this problem, the ball - type metallophthalocyanines containing aldehyde substituents M2Pc2(TA)4 (M=Zn, Co, Fe) were synthesized. The metallophthalocyanine was then supported on the reduced graphene oxide (rGO) surface to obtain a composite catalyst M2Pc2(TA)4/rGO using the"π-π assembly" technology, and the morphology and microstructure were characterized. The results showed that the metallophthalocyanine was loaded on the surface of rGO through the"π-π stacking"effect, and the agglomeration phenomenon of the metallophthalocyanines was prevented. Cyclic voltammetry and linear sweep voltammetry were used to evaluate the catalytic activity of composites for ORR. The results suggested that rGO promotes the transfer of electrons in ORR and effectively enhances the electrocatalytic activity, based on the synergistic effect between rGO and balltype metallophthalocyanine. The catalytic mechanism reveals that the ORR is a four-electron electrocatalytic process. The catalytic activity is related to the d electron of the central metal. The electrocatalytic activity test was displayed in the order of Fe2Pc2(TA)4/rGO>Zn2Pc2(TA)4/rGO>Co2Pc2(TA)4/rGO.
There are some key problems for oxygen reduction reaction (ORR), such as the slow kinetic process and high cost of Pt/C catalysts. To overcome this problem, the ball - type metallophthalocyanines containing aldehyde substituents M2Pc2(TA)4 (M=Zn, Co, Fe) were synthesized. The metallophthalocyanine was then supported on the reduced graphene oxide (rGO) surface to obtain a composite catalyst M2Pc2(TA)4/rGO using the"π-π assembly" technology, and the morphology and microstructure were characterized. The results showed that the metallophthalocyanine was loaded on the surface of rGO through the"π-π stacking"effect, and the agglomeration phenomenon of the metallophthalocyanines was prevented. Cyclic voltammetry and linear sweep voltammetry were used to evaluate the catalytic activity of composites for ORR. The results suggested that rGO promotes the transfer of electrons in ORR and effectively enhances the electrocatalytic activity, based on the synergistic effect between rGO and balltype metallophthalocyanine. The catalytic mechanism reveals that the ORR is a four-electron electrocatalytic process. The catalytic activity is related to the d electron of the central metal. The electrocatalytic activity test was displayed in the order of Fe2Pc2(TA)4/rGO>Zn2Pc2(TA)4/rGO>Co2Pc2(TA)4/rGO.
2022, 38(1): 31-38
doi: 10.11862/CJIC.2022.024
Abstract:
Three electrode materials of nickel - cobalt hydroxide, nickel - iron hydroxide, and nickel - cobalt - iron hydroxide were synthesized on nickel foam (NF) via a one - step solvothermal method. The electrochemical tests showed that the ternary nickel-cobalt-iron metal electrode with the best energy storage performance outperforms the other two binary metal electrodes, and it could reach an area capacitance of 5.11 F·cm-2 at a current density of 2 mA·cm-2. To further investigate the practical application, an asymmetric supercapacitor was assembled with NiCoFeOH/NF as the positive electrode and activated carbon as the negative electrode, respectively, and the device achieved a maximum energy density of 5.994 Wh·m-2 at a power density of 46.814 W·m-2. The results show that the excellent performance of NiCoFe - OH/NF can be attributed to loosen flocculent structure, which provides larger specific surface area per unit volume and subsequently store more electric charges, as well as facilitate electron/ion transportation, reduce the contact resistance between active material and electrolyte, and increase the electrical conductivity.
Three electrode materials of nickel - cobalt hydroxide, nickel - iron hydroxide, and nickel - cobalt - iron hydroxide were synthesized on nickel foam (NF) via a one - step solvothermal method. The electrochemical tests showed that the ternary nickel-cobalt-iron metal electrode with the best energy storage performance outperforms the other two binary metal electrodes, and it could reach an area capacitance of 5.11 F·cm-2 at a current density of 2 mA·cm-2. To further investigate the practical application, an asymmetric supercapacitor was assembled with NiCoFeOH/NF as the positive electrode and activated carbon as the negative electrode, respectively, and the device achieved a maximum energy density of 5.994 Wh·m-2 at a power density of 46.814 W·m-2. The results show that the excellent performance of NiCoFe - OH/NF can be attributed to loosen flocculent structure, which provides larger specific surface area per unit volume and subsequently store more electric charges, as well as facilitate electron/ion transportation, reduce the contact resistance between active material and electrolyte, and increase the electrical conductivity.
2022, 38(1): 39-45
doi: 10.11862/CJIC.2022.005
Abstract:
The oxygen atom transfer (OAT) reaction pathway of the reaction between styrene and manganese(Ⅴ)-oxo corrole complexes (MnⅤO corrole) was investigated using the density functional theory B3LYP method. The calculation results showed that the oxygen atom attacked the β carbon atom of the olefinic double bond in styrene to form a transition state, and the direct oxygen atom transfer pathway was determined via the intrinsic reaction coordinate method (IRC) and the minimum -energy crossing point (MECP) calculation. The meso -pentafluorophenyl group of MnⅤO corrole can change the electrophilicity of the manganese atom and increase electrostatic repulsion between the substituent and the oxygen atom, leading to the improvement of oxygen transferability of MnⅤO corrole. With the increase of the pentafluorophenyl group number at the MnⅤO corrole, the reaction energy barrier decreases accordingly. Furthermore, the reaction energy barrier of the triplet state is significantly lower than that of the singlet state pathway, indicating that spin exchange is prone to occur and the reaction proceeds via triplet state pathway. In the OAT reaction pathway, the reactants in singlet state reach to MECP position firstly, and then change to the triplet state with spin over easily. After that, the reactants follow the triplet state pathway with a lower transition state to achieve the product.
The oxygen atom transfer (OAT) reaction pathway of the reaction between styrene and manganese(Ⅴ)-oxo corrole complexes (MnⅤO corrole) was investigated using the density functional theory B3LYP method. The calculation results showed that the oxygen atom attacked the β carbon atom of the olefinic double bond in styrene to form a transition state, and the direct oxygen atom transfer pathway was determined via the intrinsic reaction coordinate method (IRC) and the minimum -energy crossing point (MECP) calculation. The meso -pentafluorophenyl group of MnⅤO corrole can change the electrophilicity of the manganese atom and increase electrostatic repulsion between the substituent and the oxygen atom, leading to the improvement of oxygen transferability of MnⅤO corrole. With the increase of the pentafluorophenyl group number at the MnⅤO corrole, the reaction energy barrier decreases accordingly. Furthermore, the reaction energy barrier of the triplet state is significantly lower than that of the singlet state pathway, indicating that spin exchange is prone to occur and the reaction proceeds via triplet state pathway. In the OAT reaction pathway, the reactants in singlet state reach to MECP position firstly, and then change to the triplet state with spin over easily. After that, the reactants follow the triplet state pathway with a lower transition state to achieve the product.
2022, 38(1): 46-52
doi: 10.11862/CJIC.2022.016
Abstract:
Two organotin carboxylate compounds, tri(o-bromobenzyl)tin thiophene 2-carboxylate (1) and tri(o-bromobenzyl)tin cinnamate (2), have been synthesized. Compounds 1 and 2 were characterized by elemental analysis, IR spectroscopy, NMR (1H, 13C, and 119Sn), thermogravimetric analysis, and single-crystal X-ray diffraction. The study on compounds 1 and 2 has been performed with quantum chemistry calculation and in vitro anticancer activity. The results showed that the tin atoms in compounds 1 and 2 have distorted tetrahedral geometry. Compounds 1 and 2 had strong inhibitory activities against human breast cancer cells (MCF - 7), human non - small cell cancer cells (A549), and human lung cancer cell lines (H460).
Two organotin carboxylate compounds, tri(o-bromobenzyl)tin thiophene 2-carboxylate (1) and tri(o-bromobenzyl)tin cinnamate (2), have been synthesized. Compounds 1 and 2 were characterized by elemental analysis, IR spectroscopy, NMR (1H, 13C, and 119Sn), thermogravimetric analysis, and single-crystal X-ray diffraction. The study on compounds 1 and 2 has been performed with quantum chemistry calculation and in vitro anticancer activity. The results showed that the tin atoms in compounds 1 and 2 have distorted tetrahedral geometry. Compounds 1 and 2 had strong inhibitory activities against human breast cancer cells (MCF - 7), human non - small cell cancer cells (A549), and human lung cancer cell lines (H460).
2022, 38(1): 53-62
doi: 10.11862/CJIC.2022.009
Abstract:
The composite of CeTiO4/g-C3N4-x (CTO/CN-x, x g was the addition amount of g-C3N4) was successfully prepared via a simple solid method synthesis. The as-synthesized catalysts were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), N2 adsorption-desorption test, X -ray photoelectron spectroscopy (XPS), UV -Vis diffuse reflectance spectra (UV -Vis DRS), and electrochemical test. It was found that CTO and CN layered nanoplates were closely combined to form heterostructure. CTO/CN-x composite photocatalyst exhibited outstanding visible light response, and it could improve the separation and mobility of photogenerated hole-electron pair. The photocatalytic activity of composite material was assessed by degradation of rhodamine B under simulated sunlight for 140 min. Compared to pure CTO and CN, CTO/CN-x composite showed the enhancement of photocatalytic activity, and the optimum reaction rate constant was 0.020 2 min-1 for CTO/CN-6 (The addition amount of g-C3N4 was 6 g). The enhanced photocatalytic performance was mainly ascribed to the structure of heterostructure, which could reduce the recombination of CTO photocarriers and improve the transfer of photocarriers.
The composite of CeTiO4/g-C3N4-x (CTO/CN-x, x g was the addition amount of g-C3N4) was successfully prepared via a simple solid method synthesis. The as-synthesized catalysts were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), N2 adsorption-desorption test, X -ray photoelectron spectroscopy (XPS), UV -Vis diffuse reflectance spectra (UV -Vis DRS), and electrochemical test. It was found that CTO and CN layered nanoplates were closely combined to form heterostructure. CTO/CN-x composite photocatalyst exhibited outstanding visible light response, and it could improve the separation and mobility of photogenerated hole-electron pair. The photocatalytic activity of composite material was assessed by degradation of rhodamine B under simulated sunlight for 140 min. Compared to pure CTO and CN, CTO/CN-x composite showed the enhancement of photocatalytic activity, and the optimum reaction rate constant was 0.020 2 min-1 for CTO/CN-6 (The addition amount of g-C3N4 was 6 g). The enhanced photocatalytic performance was mainly ascribed to the structure of heterostructure, which could reduce the recombination of CTO photocarriers and improve the transfer of photocarriers.
2022, 38(1): 63-72
doi: 10.11862/CJIC.2022.021
Abstract:
Nitrogen-doped carbon fiber (NCF) loaded bimetal selenide nanoparticle material ((Ni, Co)Se2/NCF) was synthesized by calcination and selenium treatment using electrospun fibers as the precursor. A series of related characterization was carried out, and the hydrogen evolution properties of the materials were studied under acidic and alkaline conditions. (Ni, Co)Se2 nanoparticles were anchored in NCF, which effectively prevents the aggregation of nanoparticles and provides more catalytic active sites. The electrocatalytic hydrogen evolution test results showed that in 1 mol·L-1 KOH solution, the overpotential of (Ni, Co)Se2/NCF was 123.3 mV at the current density of 10 mA·cm-2, and the Tafel slope was 144.0 mV·dec-1. In 0.5 mol·L-1 H2SO4 solution, the overpotential of hydrogen evolution required for (Ni, Co)Se2/NCF to reach the current density of 10 mA·cm-2 was 95.5 mV, and the Tafel slope was 115.2 mV·dec-1, indicating excellent electrocatalytic hydrogen evolution performance.
Nitrogen-doped carbon fiber (NCF) loaded bimetal selenide nanoparticle material ((Ni, Co)Se2/NCF) was synthesized by calcination and selenium treatment using electrospun fibers as the precursor. A series of related characterization was carried out, and the hydrogen evolution properties of the materials were studied under acidic and alkaline conditions. (Ni, Co)Se2 nanoparticles were anchored in NCF, which effectively prevents the aggregation of nanoparticles and provides more catalytic active sites. The electrocatalytic hydrogen evolution test results showed that in 1 mol·L-1 KOH solution, the overpotential of (Ni, Co)Se2/NCF was 123.3 mV at the current density of 10 mA·cm-2, and the Tafel slope was 144.0 mV·dec-1. In 0.5 mol·L-1 H2SO4 solution, the overpotential of hydrogen evolution required for (Ni, Co)Se2/NCF to reach the current density of 10 mA·cm-2 was 95.5 mV, and the Tafel slope was 115.2 mV·dec-1, indicating excellent electrocatalytic hydrogen evolution performance.
2022, 38(1): 73-83
doi: 10.11862/CJIC.2022.001
Abstract:
Porous Fe2O3 nanorods and nitrogen-doped reduced graphene oxide (N-RGO) composite materials obtained by electrospinning were used as the carrier to successfully prepare clean and highly active Pt/Fe2O3/N-RGO catalyst by photoreduction method. The synthesis mechanism of the photoreduction reaction and the sintering resistance of the catalyst were further studied. During visible light irradiation, the efficient light absorption of Fe2O3 facilities the generation of photoelectrons and holes, while N-RGO highly prolongs the lifetime of photogenerated carriers. In this case, partially reduced Fe2+ in Pt/Fe2O3/N-RGO has a strong reduction ability, which can make PtCl62- reduce on the surface of Fe2O3 and nucleate rapidly, and grow into Pt nanoparticles with a diameter of about 2.13 nm. Methanol as a hole scavenger can effectively and quickly consume the photo-generated holes on the surface of the carrier, which causes the electrons accumulated in the conduction band to undergo a reduction reaction with PtCl62-, and greatly accelerates the formation rate of Pt nanoparticles. Fe2O3 nanorods with ultra-high porosity provide numerous nucleation sites for Pt nanoparticles. N-RGO sheets with abundant defects can shorten the diffusion path of Fe2O3 photocarriers and improve the efficiency of Pt photo-deposition. Besides, its characteristic wrinkle structure can act as a physical barrier to prevent Pt nanoparticles from agglomeration. Due to the strong interaction between metal and carrier, the size of Pt nanoparticles remained at 2.67 nm even after aging at 500 ℃. Pt/Fe2O3/N-RGO catalyst still had excellent thermal stability and catalytic activity after aging at 400 ℃, with a reaction rate constant of up to 22.2 L·g-1·s-1, which was about 1.6 times of that before aging.
Porous Fe2O3 nanorods and nitrogen-doped reduced graphene oxide (N-RGO) composite materials obtained by electrospinning were used as the carrier to successfully prepare clean and highly active Pt/Fe2O3/N-RGO catalyst by photoreduction method. The synthesis mechanism of the photoreduction reaction and the sintering resistance of the catalyst were further studied. During visible light irradiation, the efficient light absorption of Fe2O3 facilities the generation of photoelectrons and holes, while N-RGO highly prolongs the lifetime of photogenerated carriers. In this case, partially reduced Fe2+ in Pt/Fe2O3/N-RGO has a strong reduction ability, which can make PtCl62- reduce on the surface of Fe2O3 and nucleate rapidly, and grow into Pt nanoparticles with a diameter of about 2.13 nm. Methanol as a hole scavenger can effectively and quickly consume the photo-generated holes on the surface of the carrier, which causes the electrons accumulated in the conduction band to undergo a reduction reaction with PtCl62-, and greatly accelerates the formation rate of Pt nanoparticles. Fe2O3 nanorods with ultra-high porosity provide numerous nucleation sites for Pt nanoparticles. N-RGO sheets with abundant defects can shorten the diffusion path of Fe2O3 photocarriers and improve the efficiency of Pt photo-deposition. Besides, its characteristic wrinkle structure can act as a physical barrier to prevent Pt nanoparticles from agglomeration. Due to the strong interaction between metal and carrier, the size of Pt nanoparticles remained at 2.67 nm even after aging at 500 ℃. Pt/Fe2O3/N-RGO catalyst still had excellent thermal stability and catalytic activity after aging at 400 ℃, with a reaction rate constant of up to 22.2 L·g-1·s-1, which was about 1.6 times of that before aging.
2022, 38(1): 84-92
doi: 10.11862/CJIC.2022.025
Abstract:
The synergistic photoanode coating strategy was applied to inhibit the charge recombination processes at the photoanode/electrolyte interface and improve the photovoltaic performance of Zn-Cu-In-Se (ZCISe) quantum dotsensitized solar cells (QDSC). On the surface of ZCISe QD-sensitized photoanode, ZnS and SiO2 layers were successively coated by the solution route to form double passivation coating layers. This double-layer treatment offers more effective charge recombination inhibition than the traditional ZnS single coating layer, thus obtaining higher photovoltaic performance for the resulting QDSC. The results indicated that with the coating of ZnS/SiO2 double passivation layers, the efficiency was increased from 12.17% corresponding to cells with the traditional single ZnS coating to 13.23%. This is mainly due to the effective inhibition of the charge recombination processes at the photoanode/electrolyte interface, and the charge collection efficiency is improved accordingly.
The synergistic photoanode coating strategy was applied to inhibit the charge recombination processes at the photoanode/electrolyte interface and improve the photovoltaic performance of Zn-Cu-In-Se (ZCISe) quantum dotsensitized solar cells (QDSC). On the surface of ZCISe QD-sensitized photoanode, ZnS and SiO2 layers were successively coated by the solution route to form double passivation coating layers. This double-layer treatment offers more effective charge recombination inhibition than the traditional ZnS single coating layer, thus obtaining higher photovoltaic performance for the resulting QDSC. The results indicated that with the coating of ZnS/SiO2 double passivation layers, the efficiency was increased from 12.17% corresponding to cells with the traditional single ZnS coating to 13.23%. This is mainly due to the effective inhibition of the charge recombination processes at the photoanode/electrolyte interface, and the charge collection efficiency is improved accordingly.
2022, 38(1): 93-102
doi: 10.11862/CJIC.2022.019
Abstract:
To overcome the shortcomings of poor antitumor drug targeting, low efficacy, and high toxicity, a pH regulated drug delivery system (YMS-DOX) through hydrogen bonds and van der Waals force was constructed to acquire high drug loading capacity and better therapeutic efficiency based on Y-type molecular sieve (YMS) as nano-carrier and doxorubicin (DOX) as the model drug. The successful formation of YMS-DOX was confirmed by using UV-Vis, FT-IR, particle size and potential measurement, and fluorescence spectroscopy. Interestingly, with the assistance of citric acid buffer solution (pH=9.0), YMS nanocarrier loading DOX achieved nearly 99.61% loading efficiency. In vitro drug release showed that YMS had low premature drug release under physiological conditions (pH=7.4), while greatly enhanced in the tumor microenvironment (pH=4.5) 3.8 times compared to normal tissue, indicating YMSDOX can be effectively released in the tumor site. Excitingly, when dendritic (DC) cells and breast cancer (MM -231) cells were treated with YMS-DOX, the results demonstrated that YMS-DOX preferentially accumulated much more in tumor cells than in normal cells, which implies that YMS-DOX can selectively kill tumor cells. In addition, assessment by flow cytometry apoptosis assay illustrated that YMS-DOX could induce cell apoptosis and inhibit cell migration.
To overcome the shortcomings of poor antitumor drug targeting, low efficacy, and high toxicity, a pH regulated drug delivery system (YMS-DOX) through hydrogen bonds and van der Waals force was constructed to acquire high drug loading capacity and better therapeutic efficiency based on Y-type molecular sieve (YMS) as nano-carrier and doxorubicin (DOX) as the model drug. The successful formation of YMS-DOX was confirmed by using UV-Vis, FT-IR, particle size and potential measurement, and fluorescence spectroscopy. Interestingly, with the assistance of citric acid buffer solution (pH=9.0), YMS nanocarrier loading DOX achieved nearly 99.61% loading efficiency. In vitro drug release showed that YMS had low premature drug release under physiological conditions (pH=7.4), while greatly enhanced in the tumor microenvironment (pH=4.5) 3.8 times compared to normal tissue, indicating YMSDOX can be effectively released in the tumor site. Excitingly, when dendritic (DC) cells and breast cancer (MM -231) cells were treated with YMS-DOX, the results demonstrated that YMS-DOX preferentially accumulated much more in tumor cells than in normal cells, which implies that YMS-DOX can selectively kill tumor cells. In addition, assessment by flow cytometry apoptosis assay illustrated that YMS-DOX could induce cell apoptosis and inhibit cell migration.
2022, 38(1): 103-110
doi: 10.11862/CJIC.2022.026
Abstract:
The bis(3-ethoxysalicylaldehyde) 1, 3-benzyldiacyl hydrazone (H4L) ligand was prepared by the reaction of 3-ethoxysalicylaldehyde with benzene-1, 3-dicarbohydrazide in ethanol solution. Bis(3-ethoxysalicylaldehyde) 1, 3benzyldiacyl hydrazone tetrabutyl(phenyl)ditin, Bu4Sn2L (T1) and Ph4Sn2L (T2), were synthesized by solvothermal reaction of H4L with dibutyltin oxide and triphenyltin hydroxide in methanol, respectively. The structures of ligand and complexes were characterized by elemental analysis, IR, UV-Vis spectroscopy, NMR, and single-crystal X-ray diffraction. The molecular formula of H4L is C26H26N4O6. The crystal of H4L belongs to the monoclinic system and space group C2/c. Two formylhydrazide (3-ethoxy)salicylaldehydes are cis-symmetric configuration. The molecular formula of T1 is C42H58N4O6Sn2. The crystal of T1 belongs to the orthorhombic system and space group Pbcn. The two formylhydrazide (3-ethoxy)salicylaldehyde chains of H4L turn inward 180°, and a distorted trigonal bipyramid is formed by the coordination of coordinating atoms with tin. The molecular structure is axis-symmetric about C2…C4. The molecular formula of T2 is C50H42N4O6Sn2. The crystal of T2 belongs to the triclinic system, space group P1. One formylhydrazide (3-ethoxy)salicylaldehyde of H4L keeps the original configuration, and the other formylhydrazide (3-ethoxy)salicylaldehyde turns inward 180°. Two coordination chains with different configuration orientations were formed, which coordinated with diphenyltin to form a binuclear trans-asymmetric distorted trigonal bipyramid complexes. The fluorescence properties of trichloromethane solutions of H4L, T1, T2 (50 μmol·L-1) were tested. The results showed that H4L had weak fluorescence at 520 nm, and T1 and T2 had 14-15 times stronger fluorescence emission peaks than the ligand at 518 nm.
The bis(3-ethoxysalicylaldehyde) 1, 3-benzyldiacyl hydrazone (H4L) ligand was prepared by the reaction of 3-ethoxysalicylaldehyde with benzene-1, 3-dicarbohydrazide in ethanol solution. Bis(3-ethoxysalicylaldehyde) 1, 3benzyldiacyl hydrazone tetrabutyl(phenyl)ditin, Bu4Sn2L (T1) and Ph4Sn2L (T2), were synthesized by solvothermal reaction of H4L with dibutyltin oxide and triphenyltin hydroxide in methanol, respectively. The structures of ligand and complexes were characterized by elemental analysis, IR, UV-Vis spectroscopy, NMR, and single-crystal X-ray diffraction. The molecular formula of H4L is C26H26N4O6. The crystal of H4L belongs to the monoclinic system and space group C2/c. Two formylhydrazide (3-ethoxy)salicylaldehydes are cis-symmetric configuration. The molecular formula of T1 is C42H58N4O6Sn2. The crystal of T1 belongs to the orthorhombic system and space group Pbcn. The two formylhydrazide (3-ethoxy)salicylaldehyde chains of H4L turn inward 180°, and a distorted trigonal bipyramid is formed by the coordination of coordinating atoms with tin. The molecular structure is axis-symmetric about C2…C4. The molecular formula of T2 is C50H42N4O6Sn2. The crystal of T2 belongs to the triclinic system, space group P1. One formylhydrazide (3-ethoxy)salicylaldehyde of H4L keeps the original configuration, and the other formylhydrazide (3-ethoxy)salicylaldehyde turns inward 180°. Two coordination chains with different configuration orientations were formed, which coordinated with diphenyltin to form a binuclear trans-asymmetric distorted trigonal bipyramid complexes. The fluorescence properties of trichloromethane solutions of H4L, T1, T2 (50 μmol·L-1) were tested. The results showed that H4L had weak fluorescence at 520 nm, and T1 and T2 had 14-15 times stronger fluorescence emission peaks than the ligand at 518 nm.
2022, 38(1): 111-118
doi: 10.11862/CJIC.2022.020
Abstract:
FeFe-based Prussian blue (NaFeHCF) is a promising cathode material for sodium-ion batteries (SIBs). However, how to effectively control the synthesis parameters to improve the cycling stability of NaFeHCF in sodiumion batteries remains to be addressed. In this work, NaFeHCF powders were prepared through the co-precipitation method, and the synergetic effects of a complexing agent (with or without sodium citrate) and reaction temperature (0-80 ℃) on the physical and electrochemical properties of NaFeHCF were investigated in detail. The results showed that NaFeHCF powders synthesized with the addition of a complexing agent and at a temperature slightly above room temperature (40 ℃) exhibited the most appropriate properties in terms of morphology, grain size, and crystallinity. Therefore, the SIB cathode using this material showed the highest cycling stability, being able to deliver a discharge capacity of 83.5 mAh·g-1 after 1 500 cycles at the current density of 120 mA·g-1 with capacity retention of 79.4%.
FeFe-based Prussian blue (NaFeHCF) is a promising cathode material for sodium-ion batteries (SIBs). However, how to effectively control the synthesis parameters to improve the cycling stability of NaFeHCF in sodiumion batteries remains to be addressed. In this work, NaFeHCF powders were prepared through the co-precipitation method, and the synergetic effects of a complexing agent (with or without sodium citrate) and reaction temperature (0-80 ℃) on the physical and electrochemical properties of NaFeHCF were investigated in detail. The results showed that NaFeHCF powders synthesized with the addition of a complexing agent and at a temperature slightly above room temperature (40 ℃) exhibited the most appropriate properties in terms of morphology, grain size, and crystallinity. Therefore, the SIB cathode using this material showed the highest cycling stability, being able to deliver a discharge capacity of 83.5 mAh·g-1 after 1 500 cycles at the current density of 120 mA·g-1 with capacity retention of 79.4%.
2022, 38(1): 119-126
doi: 10.11862/CJIC.2022.012
Abstract:
Ba0.6Sr0.4TiO3 (BST)/poly(vinylidene fluoride) (PVDF)-poly(methyl methacrylate) (PMMA) composite films were prepared by tape casting and hot pressing. The effects of PMMA content on the phase structure and electrical properties of the composites were studied. The results showed that the BST phase was uniformly dispersed in the polymer matrix. The interface between the two polymers is not clear, which is attributed to the good compatibility between PMMA and PVDF. With the increase of PMMA content, the dielectric constant of the composites is negatively correlated with the breakdown strength and dielectric tunability. BST/PVDF-PMMA15 composite with PMMA content (volume fraction) of 15% showed the best dielectric properties with the dielectric constant of 23.2, the dielectric loss of 0.07, the breakdown strength of 1 412 kV·cm-1, and the dielectric tunability was 26.2% under the DC bias of 550 kV·cm-1.
Ba0.6Sr0.4TiO3 (BST)/poly(vinylidene fluoride) (PVDF)-poly(methyl methacrylate) (PMMA) composite films were prepared by tape casting and hot pressing. The effects of PMMA content on the phase structure and electrical properties of the composites were studied. The results showed that the BST phase was uniformly dispersed in the polymer matrix. The interface between the two polymers is not clear, which is attributed to the good compatibility between PMMA and PVDF. With the increase of PMMA content, the dielectric constant of the composites is negatively correlated with the breakdown strength and dielectric tunability. BST/PVDF-PMMA15 composite with PMMA content (volume fraction) of 15% showed the best dielectric properties with the dielectric constant of 23.2, the dielectric loss of 0.07, the breakdown strength of 1 412 kV·cm-1, and the dielectric tunability was 26.2% under the DC bias of 550 kV·cm-1.
2022, 38(1): 127-136
doi: 10.11862/CJIC.2022.010
Abstract:
A kind of three-dimensional flower-like CeO2/TiO2 heterojunction as photocatalysts was designed by the solvothermal method. The photocatalytic activity was evaluated by the decomposition of methyl orange (MO) under xenon lamp irradiation. The results showed that the flower-like structure was composed of thin nanosheets, on which many CeO2 particles were uniformly attached. The molar ratio of Ce to Ti (nCe/nTi) and the solvothermal time influenced on the photocatalytic performance. When nCe/nTi=0.1 and the solvothermal time was 6 h, the photocatalytic activity of CeO2/TiO2 reached the best, and the degradation rate reached 95% under xenon lamp irradiation for 50 min. The results suggested that the photocatalytic activity of CeO2/TiO2 heterojunction was greatly improved, compared to TiO2, which was mainly the function of heterojunction formed by CeO2 and TiO2, and was conducive to the separation of photogenerated electrons and holes.
A kind of three-dimensional flower-like CeO2/TiO2 heterojunction as photocatalysts was designed by the solvothermal method. The photocatalytic activity was evaluated by the decomposition of methyl orange (MO) under xenon lamp irradiation. The results showed that the flower-like structure was composed of thin nanosheets, on which many CeO2 particles were uniformly attached. The molar ratio of Ce to Ti (nCe/nTi) and the solvothermal time influenced on the photocatalytic performance. When nCe/nTi=0.1 and the solvothermal time was 6 h, the photocatalytic activity of CeO2/TiO2 reached the best, and the degradation rate reached 95% under xenon lamp irradiation for 50 min. The results suggested that the photocatalytic activity of CeO2/TiO2 heterojunction was greatly improved, compared to TiO2, which was mainly the function of heterojunction formed by CeO2 and TiO2, and was conducive to the separation of photogenerated electrons and holes.
2022, 38(1): 137-144
doi: 10.11862/CJIC.2022.015
Abstract:
A novel thermal-stable and water-stable Zn(Ⅱ)-based metal-organic framework (MOF), [Zn2(bcpp)2(1, 4bib)2]·1.5H2O (1) was synthesized by solvothermal method based on 3, 5-bis(4-carboxylphenoxy)pyridine (H2bcpp) and 1, 4 - bis(1 - imidazoly)benzene (1, 4 - bib). Complex 1 belongs to the monoclinic system with space group I2/a, which exhibits a 1D tubular structure. The adjacent 1D tubular structures are interpenetrated with each other to obtain a 3D supramolecular structure. Moreover, complex 1 exhibits excellent photoluminescence property, which can be applied as a"turn-off"fluorescence probe to detect Fe3+ ion and pesticide 2, 6-dichloro-4-nitroaniline in an aqueous solution with high selectivity and sensitivity.
A novel thermal-stable and water-stable Zn(Ⅱ)-based metal-organic framework (MOF), [Zn2(bcpp)2(1, 4bib)2]·1.5H2O (1) was synthesized by solvothermal method based on 3, 5-bis(4-carboxylphenoxy)pyridine (H2bcpp) and 1, 4 - bis(1 - imidazoly)benzene (1, 4 - bib). Complex 1 belongs to the monoclinic system with space group I2/a, which exhibits a 1D tubular structure. The adjacent 1D tubular structures are interpenetrated with each other to obtain a 3D supramolecular structure. Moreover, complex 1 exhibits excellent photoluminescence property, which can be applied as a"turn-off"fluorescence probe to detect Fe3+ ion and pesticide 2, 6-dichloro-4-nitroaniline in an aqueous solution with high selectivity and sensitivity.
2022, 38(1): 145-152
doi: 10.11862/CJIC.2022.002
Abstract:
Three new LnⅢ2 complexes based on a polydentate Schiff base ligand, namely [Ln2(L)2(acac)2(CH3OH)2]·2CH3OH (Ln=Sm (1), Gd (2), Ho (3), H2L=pyridine-2-carboxylic acid (1-methyl-3-oxo-butylidene)-hydrazide, Hacac =acetylacetone), have been synthesized by using solvothermal method. The crystal structures and magnetic properties of these complexes have been systematically studied. The crystal structures measurement results reveal that complexes 1-3 are isostructural and each eight-coordinated Ln (Ⅲ) ion possesses a square antiprism geometry; the adjacent central rare earth Ln(Ⅲ) ions are connected by two μ2-O to form a parallelogram [Ln2O2] core. The magnetic study showed that complex 2 displayed significant magnetic refrigeration property with a larger magnetic entropy (-ΔSmax) of 31.9 J·K-1·kg-1 at ΔH=70 kOe and T=2.0 K; while complex 3 shows slow magnetic relaxation behavior.
Three new LnⅢ2 complexes based on a polydentate Schiff base ligand, namely [Ln2(L)2(acac)2(CH3OH)2]·2CH3OH (Ln=Sm (1), Gd (2), Ho (3), H2L=pyridine-2-carboxylic acid (1-methyl-3-oxo-butylidene)-hydrazide, Hacac =acetylacetone), have been synthesized by using solvothermal method. The crystal structures and magnetic properties of these complexes have been systematically studied. The crystal structures measurement results reveal that complexes 1-3 are isostructural and each eight-coordinated Ln (Ⅲ) ion possesses a square antiprism geometry; the adjacent central rare earth Ln(Ⅲ) ions are connected by two μ2-O to form a parallelogram [Ln2O2] core. The magnetic study showed that complex 2 displayed significant magnetic refrigeration property with a larger magnetic entropy (-ΔSmax) of 31.9 J·K-1·kg-1 at ΔH=70 kOe and T=2.0 K; while complex 3 shows slow magnetic relaxation behavior.
2022, 38(1): 153-160
doi: 10.11862/CJIC.2022.008
Abstract:
A Mn-based metal-organic framework (Mn-MOF) was selected as the precursors to prepare the Mn-MOF derivative (Mn2O3) microspheres. The Mn2O3 microspheres had a homogenous size of ca. 4 μm, with perfect sphere morphology, rough surface, good crystallinity and high yield. At the same time, the movement behavior of Mn2O3 micromotors under different conditions and the degradation properties of methyl blue (MB) were studied. As-prepared Mn2O3 micromotors had excellent autonomous movement ability, and their moving speed can reach 81.32 μm·s-1 in 10% H2O2 solution. Experimental results show that with the addition of H2O2, the Mn2O3 micromotors can effectively remove MB through degradation within 5 min.
A Mn-based metal-organic framework (Mn-MOF) was selected as the precursors to prepare the Mn-MOF derivative (Mn2O3) microspheres. The Mn2O3 microspheres had a homogenous size of ca. 4 μm, with perfect sphere morphology, rough surface, good crystallinity and high yield. At the same time, the movement behavior of Mn2O3 micromotors under different conditions and the degradation properties of methyl blue (MB) were studied. As-prepared Mn2O3 micromotors had excellent autonomous movement ability, and their moving speed can reach 81.32 μm·s-1 in 10% H2O2 solution. Experimental results show that with the addition of H2O2, the Mn2O3 micromotors can effectively remove MB through degradation within 5 min.
2022, 38(1): 161-170
doi: 10.11862/CJIC.2022.004
Abstract:
Two cobalt(Ⅱ) coordination polymers, namely [Co2(μ3-deta)(H2biim)3(H2O)2]n (1) and {[Co2((μ6-deta)(phen)2]·H2O}n (2), have been constructed hydrothermally using H4deta (2, 3, 3', 4' - diphenyl ether tetracarboxylic acid), H2biim (2, 2'-biimidazole), phen (1, 10-phenanthroline), and cobalt chloride at 160 ℃. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses, and single-crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that compounds 1 and 2 crystallize in the triclinic and monoclinic systems, space groups P1 and P21/c, respectively. Compound 1 discloses a 1D chain structure, and compound 2 features a 2D network. The catalytic activities in Knoevenagel condensation reaction of the compounds were investigated. Compound 1 exhibited excellent catalytic activity in Knoevenagel condensation reaction at room temperature.
Two cobalt(Ⅱ) coordination polymers, namely [Co2(μ3-deta)(H2biim)3(H2O)2]n (1) and {[Co2((μ6-deta)(phen)2]·H2O}n (2), have been constructed hydrothermally using H4deta (2, 3, 3', 4' - diphenyl ether tetracarboxylic acid), H2biim (2, 2'-biimidazole), phen (1, 10-phenanthroline), and cobalt chloride at 160 ℃. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses, and single-crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that compounds 1 and 2 crystallize in the triclinic and monoclinic systems, space groups P1 and P21/c, respectively. Compound 1 discloses a 1D chain structure, and compound 2 features a 2D network. The catalytic activities in Knoevenagel condensation reaction of the compounds were investigated. Compound 1 exhibited excellent catalytic activity in Knoevenagel condensation reaction at room temperature.
2022, 38(1): 171-180
doi: 10.11862/CJIC.2022.017
Abstract:
Three salen - type centrosymmetric dinuclear Dy (Ⅲ) complexes, [Dy2(Hhms)2(C(CH3)3COO)2(H2O)4](NO3)2 (1), [Dy2(Hhms)2(C14H9COO)2(C2H5OH)2(CH3OH)2][ZnCl4] (2), and [Dy2(Hhms)2(C6H3(NH2)2COO)2Cl2]·2CH3CN (3) (H2hms=(2-hydroxy-3-methoxybenzylidene)-semicarbazide), were isolated with different substituted carboxylic acid ligand, and were characterized structurally and magnetically. Structural analyses illustrate that the Dy (Ⅲ) ions in complexes 1 and 2 maintain similar monocapped square-antiprism geometries, but the coordination mode of carboxylate in 1 is different from that in 2; complexes 2 and 3 possess similar phenoxy oxygen and carboxylate bridged structure whereas the coordination geometries around the Dy(Ⅲ) ions are different between 3 and 2 due to the difference of coordinated small molecules. Magnetic characterizations reveal that significant single - molecule magnet (SMM) behavior was observed under zero dc field for complex 3, with an effective energy barrier to the reversal of magnetization of 96 K. Conversely, complex 1 only showed fast quantum tunneling relaxation even 2 was SMM-silent. Furthermore, the magneto-structural correlations in these Dy2 complexes were discussed. The results indicate that utility of carboxylate ligand substituent can give rise to good modulation in the molecular anisotropy and symmetry, hence the enhanced magnetic relaxation.
Three salen - type centrosymmetric dinuclear Dy (Ⅲ) complexes, [Dy2(Hhms)2(C(CH3)3COO)2(H2O)4](NO3)2 (1), [Dy2(Hhms)2(C14H9COO)2(C2H5OH)2(CH3OH)2][ZnCl4] (2), and [Dy2(Hhms)2(C6H3(NH2)2COO)2Cl2]·2CH3CN (3) (H2hms=(2-hydroxy-3-methoxybenzylidene)-semicarbazide), were isolated with different substituted carboxylic acid ligand, and were characterized structurally and magnetically. Structural analyses illustrate that the Dy (Ⅲ) ions in complexes 1 and 2 maintain similar monocapped square-antiprism geometries, but the coordination mode of carboxylate in 1 is different from that in 2; complexes 2 and 3 possess similar phenoxy oxygen and carboxylate bridged structure whereas the coordination geometries around the Dy(Ⅲ) ions are different between 3 and 2 due to the difference of coordinated small molecules. Magnetic characterizations reveal that significant single - molecule magnet (SMM) behavior was observed under zero dc field for complex 3, with an effective energy barrier to the reversal of magnetization of 96 K. Conversely, complex 1 only showed fast quantum tunneling relaxation even 2 was SMM-silent. Furthermore, the magneto-structural correlations in these Dy2 complexes were discussed. The results indicate that utility of carboxylate ligand substituent can give rise to good modulation in the molecular anisotropy and symmetry, hence the enhanced magnetic relaxation.
