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2021 Volume 37 Issue 1
2021, 37(1): 1-15
doi: 10.11862/CJIC.2021.013
Abstract:
With the rapid development of nanomedicine, nanotherapeutic materials have attracted more and more attention due to their multifunctionality of diagnosis and treatment. Bismuth (Bi) based nanomaterials have excellent optical, electrical and magnetic properties, which make them have broad application in the field of integrated diagnosis and treatment of tumors. In this paper, we summarized the commonly used construction methods for Bi-based nanomaterials, and focused on their application in computed tomography (CT), photoacoustic imaging (PA), radiotherapy (RT), photothermal therapy (PTT) and synergy progress in applied research. At the same time, suggestions and prospects for further research progress in the future have been provided.
With the rapid development of nanomedicine, nanotherapeutic materials have attracted more and more attention due to their multifunctionality of diagnosis and treatment. Bismuth (Bi) based nanomaterials have excellent optical, electrical and magnetic properties, which make them have broad application in the field of integrated diagnosis and treatment of tumors. In this paper, we summarized the commonly used construction methods for Bi-based nanomaterials, and focused on their application in computed tomography (CT), photoacoustic imaging (PA), radiotherapy (RT), photothermal therapy (PTT) and synergy progress in applied research. At the same time, suggestions and prospects for further research progress in the future have been provided.
2021, 37(1): 16-22
doi: 10.11862/CJIC.2021.006
Abstract:
Sm2Ti2S2O5 (STSO) was prepared by a flux method using TiO2, TiS2 and Sm2O3 as reactants, and eutectic of LiCl and KCl (LiCl-KCl) or LiCl and CsCl (LiCl-CsCl) as flux. By analyzing X-ray diffraction patterns of the samples synthesized at different temperatures, it was firstly demonstrated that the threshold crystallization temperature of STSO was 520℃, much lower than the value of 650℃ that was reported previously as the lowest temperature for synthesizing STSO. Scanning electron microscope images showed that the synthesized STSO particles owned a platelike morphology. At the same temperature, LiCl-CsCl led to lower plate thickness than LiCl-KCl. The average photocatalytic H2 production rate showed volcano-like profile to synthesizing temperature, which was likely due to the effect of particle size and crystallinity on activity. Variation of hole sacrificial reagent showed that ascorbic acid produced much higher H2 evolution activity than Na2S-Na2SO3, triethylamine, triethanolamine and methanol. For the purpose of comparing with the literatures, Na2S-Na2SO3 was employed as sacrificial reagent in the following stability test. It was found that the as-prepared STSO exhibited stable H2 production over 20 h under visible light (Xe lamp, λ>420 nm) irradiation, and having nearly identical characterization results in XPS, XRD and TEM before and after photocatalytic reaction.
Sm2Ti2S2O5 (STSO) was prepared by a flux method using TiO2, TiS2 and Sm2O3 as reactants, and eutectic of LiCl and KCl (LiCl-KCl) or LiCl and CsCl (LiCl-CsCl) as flux. By analyzing X-ray diffraction patterns of the samples synthesized at different temperatures, it was firstly demonstrated that the threshold crystallization temperature of STSO was 520℃, much lower than the value of 650℃ that was reported previously as the lowest temperature for synthesizing STSO. Scanning electron microscope images showed that the synthesized STSO particles owned a platelike morphology. At the same temperature, LiCl-CsCl led to lower plate thickness than LiCl-KCl. The average photocatalytic H2 production rate showed volcano-like profile to synthesizing temperature, which was likely due to the effect of particle size and crystallinity on activity. Variation of hole sacrificial reagent showed that ascorbic acid produced much higher H2 evolution activity than Na2S-Na2SO3, triethylamine, triethanolamine and methanol. For the purpose of comparing with the literatures, Na2S-Na2SO3 was employed as sacrificial reagent in the following stability test. It was found that the as-prepared STSO exhibited stable H2 production over 20 h under visible light (Xe lamp, λ>420 nm) irradiation, and having nearly identical characterization results in XPS, XRD and TEM before and after photocatalytic reaction.
2021, 37(1): 23-32
doi: 10.11862/CJIC.2021.019
Abstract:
The binding of chlorpromazine (CPZ) to the C-terminal domain of Euplotes octocarinatus centrin (apoCEoCen) and the effect of CPZ on the protein function were studied by fluorescence spectra, isothermal titration calorimetry (ITC), circular dichroism (CD) and electrophoresis. The results illustrated that in 10 mmol·L-1 Hepes solution (pH=7.4) at room temperature, CPZ and apoC-EoCen were combined with a molar ratio of 1:1, in addition, the conditional binding constant was about 104 L·mol-1. The combination of CPZ leads to changes in the secondary structure of the protein, and the content of α-helix is reduced. It inhibits the aggregation of centrin induced by metal ions and reduces the fluorescence intensity of Tb3+ sensitization. CPZ suppresses the binding of centrin to xeroderma pigmentosum protein (XPC). The activity of apoC-EoCen nuclease is affected, which results in the decreased capability of protein to cut pBR322 DNA. The results indicate that chlorpromazine hydrochloride is a biological function antagonist of centrin, and it has a good regulatory effect on the function of centrin.
The binding of chlorpromazine (CPZ) to the C-terminal domain of Euplotes octocarinatus centrin (apoCEoCen) and the effect of CPZ on the protein function were studied by fluorescence spectra, isothermal titration calorimetry (ITC), circular dichroism (CD) and electrophoresis. The results illustrated that in 10 mmol·L-1 Hepes solution (pH=7.4) at room temperature, CPZ and apoC-EoCen were combined with a molar ratio of 1:1, in addition, the conditional binding constant was about 104 L·mol-1. The combination of CPZ leads to changes in the secondary structure of the protein, and the content of α-helix is reduced. It inhibits the aggregation of centrin induced by metal ions and reduces the fluorescence intensity of Tb3+ sensitization. CPZ suppresses the binding of centrin to xeroderma pigmentosum protein (XPC). The activity of apoC-EoCen nuclease is affected, which results in the decreased capability of protein to cut pBR322 DNA. The results indicate that chlorpromazine hydrochloride is a biological function antagonist of centrin, and it has a good regulatory effect on the function of centrin.
2021, 37(1): 33-38
doi: 10.11862/CJIC.2021.012
Abstract:
With 2-(2-pyridyl)benzothiophene (btp) as the primary ligand, 2-(1H-imidazo[4, 5-f] [1, 10]phenanthrolin-2 -yl)phenol (ipap) and 3-methyl-6-phenylimidazo[2, 1-b]thiazole (mpmt) as the auxiliary ligands, two platinum(Ⅱ) complexes, [(btp)Pt(ipap)]Cl and (btp)Pt(mpmt)Cl were synthesized, and the crystal structure of (btp)Pt(mpmt)Cl was determined. The luminescence of the complexes which is attributed to the metal-to-ligand charge transfer (MLCT) emission has internal quantum efficiency about 60% with emission peaks at 426 nm (blue) and 381 nm (purple). The orbital energy levels of HOMO/LUMO were -4.69 eV/-2.55 eV and -4.80 eV/-2.21 eV, respectively. The crystal structure discloses that the low conjugation of these complexes results in their short wavelength emission. CCDC:1978721, (btp)Pt(mpmt)Cl.
With 2-(2-pyridyl)benzothiophene (btp) as the primary ligand, 2-(1H-imidazo[4, 5-f] [1, 10]phenanthrolin-2 -yl)phenol (ipap) and 3-methyl-6-phenylimidazo[2, 1-b]thiazole (mpmt) as the auxiliary ligands, two platinum(Ⅱ) complexes, [(btp)Pt(ipap)]Cl and (btp)Pt(mpmt)Cl were synthesized, and the crystal structure of (btp)Pt(mpmt)Cl was determined. The luminescence of the complexes which is attributed to the metal-to-ligand charge transfer (MLCT) emission has internal quantum efficiency about 60% with emission peaks at 426 nm (blue) and 381 nm (purple). The orbital energy levels of HOMO/LUMO were -4.69 eV/-2.55 eV and -4.80 eV/-2.21 eV, respectively. The crystal structure discloses that the low conjugation of these complexes results in their short wavelength emission. CCDC:1978721, (btp)Pt(mpmt)Cl.
2021, 37(1): 39-46
doi: 10.11862/CJIC.2021.021
Abstract:
Herein, the deactivation problem of the MgF2 catalyst was solved via doping of Fe3+ into the catalyst. A series of Fe3+ doped MgF2 catalysts with different dopant concentrations were prepared via sol-gel method. The physio-chemical properties of the FeF3/MgF2 catalyst were examined by means of N2 gas adsorption-desorption, X-ray diffraction (XRD), energy dispersive X -ray spectrometer (EDS) and NH3 -temperature programmed desorption (NH3-TPD). Results show that small amount (molar fraction was less than 20%) of Fe3+ doping into MgF2 catalyst can effectively reduce the crystalline size of the catalyst. With concentration of Fe3+ below 20%, the specific surface area, surface acidity and catalytic activity towards the dehydrofluorination reaction of 1, 1-difluoroethane (R152a, C2H4F2) increased with the increasing of dopant concentration. In contrast, FeF3/MgF2 catalyst deactivation occurred when dopant concentration was greater than 20%.
Herein, the deactivation problem of the MgF2 catalyst was solved via doping of Fe3+ into the catalyst. A series of Fe3+ doped MgF2 catalysts with different dopant concentrations were prepared via sol-gel method. The physio-chemical properties of the FeF3/MgF2 catalyst were examined by means of N2 gas adsorption-desorption, X-ray diffraction (XRD), energy dispersive X -ray spectrometer (EDS) and NH3 -temperature programmed desorption (NH3-TPD). Results show that small amount (molar fraction was less than 20%) of Fe3+ doping into MgF2 catalyst can effectively reduce the crystalline size of the catalyst. With concentration of Fe3+ below 20%, the specific surface area, surface acidity and catalytic activity towards the dehydrofluorination reaction of 1, 1-difluoroethane (R152a, C2H4F2) increased with the increasing of dopant concentration. In contrast, FeF3/MgF2 catalyst deactivation occurred when dopant concentration was greater than 20%.
2021, 37(1): 47-54
doi: 10.11862/CJIC.2021.003
Abstract:
The α-MnO2 nanowires were used as the substrates for the in-situ growth of ZIF-67, and then converted into 3D α-MnO2@Co3O4 heterogeneous material by calcination, and its catalytic combustion of toluene performance was studied. The results show that Co3O4 nanoparticles with a particle size of about 12 nm grew uniformly on the outer surface of MnO2 nanowires, forming a heterogeneous interface. The composite material has better low-temperature reducibility and possesses more surface-active oxygen species. Compared with α-MnO2 nanowires, α-MnO2@Co3O4 exhibited more excellent toluene catalytic combustion performance with an ignition temperature (10% conversion) T10 of 202℃ and a complete combustion temperature (90% conversion) T90 of 235℃.
The α-MnO2 nanowires were used as the substrates for the in-situ growth of ZIF-67, and then converted into 3D α-MnO2@Co3O4 heterogeneous material by calcination, and its catalytic combustion of toluene performance was studied. The results show that Co3O4 nanoparticles with a particle size of about 12 nm grew uniformly on the outer surface of MnO2 nanowires, forming a heterogeneous interface. The composite material has better low-temperature reducibility and possesses more surface-active oxygen species. Compared with α-MnO2 nanowires, α-MnO2@Co3O4 exhibited more excellent toluene catalytic combustion performance with an ignition temperature (10% conversion) T10 of 202℃ and a complete combustion temperature (90% conversion) T90 of 235℃.
2021, 37(1): 55-64
doi: 10.11862/CJIC.2021.008
Abstract:
The composite α-(Fe, Cu)OOH/RGO was synthesized via one-step reflux method. The as-obtained catalyst was analyzed by means of X-ray powder diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and other characterization methods. With 30 mg·L-1 ciprofloxacin (CIP) as the target pollutant, the effect of the catalyst obtained under different synthesis conditions on the removal of CIP by H2O2 under visible light was investigated. The results show that α-(Fe, Cu)OOH nanorods were grown in situ on two-dimensional graphene sheets. The visible light absorption edge of α-(Fe, Cu)OOH/RGO composite material was red-shifted and the band gap was changed from 2.02 to 1.76 eV. Graphene composite could not only enhance the adsorption capacity of pollutants, but also accelerate the separation and transfer rate of photogenerated electrons, as well as improve the efficiency of electron conduction in the reaction system. The best catalytic performance was gained when the composite content (mass fraction) of graphene was 1%. The CIP was completely removed after 120 min when the addition of catalyst was 0.40 g·L-1 and the concentration of H2O2 was 0.10 mol·L-1. The removal efficiency of CIP reached to 90% even after fivetime reuse, which indicates that the catalyst has strong catalytic activity and good stability.
The composite α-(Fe, Cu)OOH/RGO was synthesized via one-step reflux method. The as-obtained catalyst was analyzed by means of X-ray powder diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and other characterization methods. With 30 mg·L-1 ciprofloxacin (CIP) as the target pollutant, the effect of the catalyst obtained under different synthesis conditions on the removal of CIP by H2O2 under visible light was investigated. The results show that α-(Fe, Cu)OOH nanorods were grown in situ on two-dimensional graphene sheets. The visible light absorption edge of α-(Fe, Cu)OOH/RGO composite material was red-shifted and the band gap was changed from 2.02 to 1.76 eV. Graphene composite could not only enhance the adsorption capacity of pollutants, but also accelerate the separation and transfer rate of photogenerated electrons, as well as improve the efficiency of electron conduction in the reaction system. The best catalytic performance was gained when the composite content (mass fraction) of graphene was 1%. The CIP was completely removed after 120 min when the addition of catalyst was 0.40 g·L-1 and the concentration of H2O2 was 0.10 mol·L-1. The removal efficiency of CIP reached to 90% even after fivetime reuse, which indicates that the catalyst has strong catalytic activity and good stability.
2021, 37(1): 65-73
doi: 10.11862/CJIC.2021.025
Abstract:
Using 3-mercaptopropyl trimethoxysilane(MPTS), 3-aminopropyl triethoxysilane(APTES) and citric acid (CA) as raw materials, the surface modified diatomite with mercapto (-SH) and amino/carboxyl (-NH2/-COOH) was prepared by water bath method and water bath/low temperature hydrothermal method, respectively. The samples were characterized by Fourier transform infrared spectroscopy, scanning electron microscope, N2 adsorption-desorption measurement, thermogravimetric analysis/differential scanning calorimetry, X-ray photoelectron spectroscopy and other technologies, and the preparation mechanism was discussed. When the pH value of heavy metal ion solution was 7 and the adsorption time was 4 h, the diatomite sample modified by MPTS showed the maximum adsorption capacities of 396 and 365 mg·g-1 towards Pb(Ⅱ) and Cd(Ⅱ), respectively, and the diatomite sample modified by APTES and CA showed the maximum adsorption capacities of 485 and 462 mg·g-1 towards Pb(Ⅱ) and Cd(Ⅱ), respectively.
Using 3-mercaptopropyl trimethoxysilane(MPTS), 3-aminopropyl triethoxysilane(APTES) and citric acid (CA) as raw materials, the surface modified diatomite with mercapto (-SH) and amino/carboxyl (-NH2/-COOH) was prepared by water bath method and water bath/low temperature hydrothermal method, respectively. The samples were characterized by Fourier transform infrared spectroscopy, scanning electron microscope, N2 adsorption-desorption measurement, thermogravimetric analysis/differential scanning calorimetry, X-ray photoelectron spectroscopy and other technologies, and the preparation mechanism was discussed. When the pH value of heavy metal ion solution was 7 and the adsorption time was 4 h, the diatomite sample modified by MPTS showed the maximum adsorption capacities of 396 and 365 mg·g-1 towards Pb(Ⅱ) and Cd(Ⅱ), respectively, and the diatomite sample modified by APTES and CA showed the maximum adsorption capacities of 485 and 462 mg·g-1 towards Pb(Ⅱ) and Cd(Ⅱ), respectively.
2021, 37(1): 74-84
doi: 10.11862/CJIC.2021.026
Abstract:
A new ternary Cu(Ⅱ) complex[Cu(HPBC)(L-Phe)(H2O)]ClO4 (1) was synthesized with 5-chloro-2-(2'-pyridyl) benzimidazole (HPBC) as the main ligand and L-phenylalaninate (L-Phe) as the auxiliary ligand. Complex 1 was characterized by elemental analysis, various spectroscopic methods and molar conductivity measurement, and the X-ray crystallographic study was used to determine the crystallographic structure of the complex, which exhibits a five-coordinated distorted square-pyramidal geometry. The binding property of the complex toward calf thymus DNA (CT-DNA) was studied by electronic absorption, competitive fluorescence titration, viscosity measurement and molecular docking technology, revealing that the complex mainly bound to DNA by an intercalative mode. The antibacterial activities (Listeria monocytogenes, Staphylococcus aureus and Escherichia coli) of Cu(ClO4)2, HPBC and the complex were tested by Oxford Cup method. In addition, the complex displayed favorable cytotoxic activities toward all the tested cancer cells such as SGC-7901, Bel-7402, HeLa and A549 with IC50 values of 1.69~2.50 μmol·L-1. Most importantly, the possible anticancer mechanism of the complex was explored by determining the morphological changes of cells (AO/EB double staining method) and cell cycle measurement analyses. The results revealed that the complex could induce apoptosis through the DNA binding pathway. CCDC:2032899.
A new ternary Cu(Ⅱ) complex[Cu(HPBC)(L-Phe)(H2O)]ClO4 (1) was synthesized with 5-chloro-2-(2'-pyridyl) benzimidazole (HPBC) as the main ligand and L-phenylalaninate (L-Phe) as the auxiliary ligand. Complex 1 was characterized by elemental analysis, various spectroscopic methods and molar conductivity measurement, and the X-ray crystallographic study was used to determine the crystallographic structure of the complex, which exhibits a five-coordinated distorted square-pyramidal geometry. The binding property of the complex toward calf thymus DNA (CT-DNA) was studied by electronic absorption, competitive fluorescence titration, viscosity measurement and molecular docking technology, revealing that the complex mainly bound to DNA by an intercalative mode. The antibacterial activities (Listeria monocytogenes, Staphylococcus aureus and Escherichia coli) of Cu(ClO4)2, HPBC and the complex were tested by Oxford Cup method. In addition, the complex displayed favorable cytotoxic activities toward all the tested cancer cells such as SGC-7901, Bel-7402, HeLa and A549 with IC50 values of 1.69~2.50 μmol·L-1. Most importantly, the possible anticancer mechanism of the complex was explored by determining the morphological changes of cells (AO/EB double staining method) and cell cycle measurement analyses. The results revealed that the complex could induce apoptosis through the DNA binding pathway. CCDC:2032899.
2021, 37(1): 85-94
doi: 10.11862/CJIC.2021.005
Abstract:
Novel 1D/0D ordered composite SnO2 nanocrystal electron transport layer (ETL) for pervoskite solar cells has been prepared by adjusting the density of one-dimensional (1D) nanorod arrays through adding functional additives in hydrothermal precursors, followed by depositing zero-dimensional (0D) nanoparticles between the nanorods. The effect of the NaCl additives in the precursor and the subsequent deposition of nanoparticles on the morphology, optical and interfacial charge transfer properties of the composite ETL was systematically studied, and the mechanism of the above effects on the photovoltaic performance of the device was discussed. The results show that the addition of NaCl in the precursor thins the rods' density, so that the following 0D nanoparticles penetrated smoothly into the gaps of 1D nanorods, inducing the obvious inhibitory effect on the perovskite/ETL and perovskite/FTO interface charge recombination, which is the direct reason for the increase in open circuit voltage and fill factor of the device. In summary, the excellent charge recombination inhibition (composite resistance was 2.9 times that of conventional 1D nanorod arrays ETL-2Cl) and efficient electron extraction performance (extraction rate and efficiency were 3.03×107 s-1 and 91.6%, respectively) of the novel 1D/0D ordered composite ETL-2P contributed to the better photoelectric performance of the device (with photoelectric efficiency of 12.15%).
Novel 1D/0D ordered composite SnO2 nanocrystal electron transport layer (ETL) for pervoskite solar cells has been prepared by adjusting the density of one-dimensional (1D) nanorod arrays through adding functional additives in hydrothermal precursors, followed by depositing zero-dimensional (0D) nanoparticles between the nanorods. The effect of the NaCl additives in the precursor and the subsequent deposition of nanoparticles on the morphology, optical and interfacial charge transfer properties of the composite ETL was systematically studied, and the mechanism of the above effects on the photovoltaic performance of the device was discussed. The results show that the addition of NaCl in the precursor thins the rods' density, so that the following 0D nanoparticles penetrated smoothly into the gaps of 1D nanorods, inducing the obvious inhibitory effect on the perovskite/ETL and perovskite/FTO interface charge recombination, which is the direct reason for the increase in open circuit voltage and fill factor of the device. In summary, the excellent charge recombination inhibition (composite resistance was 2.9 times that of conventional 1D nanorod arrays ETL-2Cl) and efficient electron extraction performance (extraction rate and efficiency were 3.03×107 s-1 and 91.6%, respectively) of the novel 1D/0D ordered composite ETL-2P contributed to the better photoelectric performance of the device (with photoelectric efficiency of 12.15%).
2021, 37(1): 95-102
doi: 10.11862/CJIC.2021.014
Abstract:
To reduce costs and improve performance of the positive electrode materials, the buffer solution method was used to prepare manganese and magnesium doped nickel hydroxide, labeled as Ni0.82Mn0.18-xMgx(OH)2 (x=0.06, 0.09, 0.12). XRD, XPS and SEM tests were used to characterize the crystal structure, manganese valence state and morphology of the samples. Cyclic voltammetry and constant current charge-discharge tests were used to study the influence of Mn and Mg doping ratio on the electrochemical performance of Ni(OH)2. The results showed that the samples doped Mn and Mg were all β-phase and the crystal particles were smaller; Ni0.82Mn0.09Mg0.09(OH)2 showed excellent electrode reaction reversibility and charge-discharge performance. Specific discharge capacity (290.6 mAh·g-1) of Ni0.82Mn0.09Mg0.09(OH)2 was better than that of the commercial β-Ni(OH)2 (281.1 mAh·g-1) at 100 mA·g-1; moreover, after cycling for 30 cycles at a current density of 500 mA·g-1, the specific discharge capacity of Ni0.82Mn0.09Mg0.09(OH)2 was no decay, indicating its cycle stability is better than that of the commercial β-Ni(OH)2.
To reduce costs and improve performance of the positive electrode materials, the buffer solution method was used to prepare manganese and magnesium doped nickel hydroxide, labeled as Ni0.82Mn0.18-xMgx(OH)2 (x=0.06, 0.09, 0.12). XRD, XPS and SEM tests were used to characterize the crystal structure, manganese valence state and morphology of the samples. Cyclic voltammetry and constant current charge-discharge tests were used to study the influence of Mn and Mg doping ratio on the electrochemical performance of Ni(OH)2. The results showed that the samples doped Mn and Mg were all β-phase and the crystal particles were smaller; Ni0.82Mn0.09Mg0.09(OH)2 showed excellent electrode reaction reversibility and charge-discharge performance. Specific discharge capacity (290.6 mAh·g-1) of Ni0.82Mn0.09Mg0.09(OH)2 was better than that of the commercial β-Ni(OH)2 (281.1 mAh·g-1) at 100 mA·g-1; moreover, after cycling for 30 cycles at a current density of 500 mA·g-1, the specific discharge capacity of Ni0.82Mn0.09Mg0.09(OH)2 was no decay, indicating its cycle stability is better than that of the commercial β-Ni(OH)2.
2021, 37(1): 103-109
doi: 10.11862/CJIC.2021.018
Abstract:
Two metal-organic frameworks (MOFs) of the same family, MIL-88B(Cr) and MIL-101(Cr), can be prepared under similar hydrothermal synthetic conditions via adjusting the concentration of acetic acid. Nanocrystals of MIL-101(Cr) with 100 nm average size and excellent SBET (3 543 m2·g-1) were obtained at relatively lower concentrations of acetic acid, while at higher concentrations the micro-sized MIL-88B(Cr) product with 'breathe' structure was formed. The products were characterized by powder X-ray diffraction, scanning electron microscopy, nitrogen physisorption measurement and thermal gravimetric analysis.
Two metal-organic frameworks (MOFs) of the same family, MIL-88B(Cr) and MIL-101(Cr), can be prepared under similar hydrothermal synthetic conditions via adjusting the concentration of acetic acid. Nanocrystals of MIL-101(Cr) with 100 nm average size and excellent SBET (3 543 m2·g-1) were obtained at relatively lower concentrations of acetic acid, while at higher concentrations the micro-sized MIL-88B(Cr) product with 'breathe' structure was formed. The products were characterized by powder X-ray diffraction, scanning electron microscopy, nitrogen physisorption measurement and thermal gravimetric analysis.
2021, 37(1): 110-120
doi: 10.11862/CJIC.2021.010
Abstract:
In this work, Ni0.88Co0.07Al0.05(OH)2 was synthesized by aluminum isopropoxide hydrolysis of nickel-cobalt hydroxide as raw material. The precursor was fully mixed with lithium source, and spherical LiNi0.88Co0.07Al0.05O2 cathode material was prepared through three sintering conditions. The crystalline structure, morphology and electrochemical performance were systematically characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), X-ray photoelectronic spectroscopy (XPS) and electrochemical tests. It is found that the synthesized LiNi0.88Co0.07Al0.05O2 after 500℃ for 3 h, and 700℃ for 14 h has a good comprehensive electrochemical performance. The discharge specific capacity at 0.2C was up to 192.2 mAh·g-1, the first charge-discharge efficiency was 81.6%, and the discharge specific capacity at 1C was 190.7 mAh·g-1, and still remain in 141.1 mAh·g-1 after 100 weeks, which shows the capacity retention rate of 73.4%.
In this work, Ni0.88Co0.07Al0.05(OH)2 was synthesized by aluminum isopropoxide hydrolysis of nickel-cobalt hydroxide as raw material. The precursor was fully mixed with lithium source, and spherical LiNi0.88Co0.07Al0.05O2 cathode material was prepared through three sintering conditions. The crystalline structure, morphology and electrochemical performance were systematically characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), X-ray photoelectronic spectroscopy (XPS) and electrochemical tests. It is found that the synthesized LiNi0.88Co0.07Al0.05O2 after 500℃ for 3 h, and 700℃ for 14 h has a good comprehensive electrochemical performance. The discharge specific capacity at 0.2C was up to 192.2 mAh·g-1, the first charge-discharge efficiency was 81.6%, and the discharge specific capacity at 1C was 190.7 mAh·g-1, and still remain in 141.1 mAh·g-1 after 100 weeks, which shows the capacity retention rate of 73.4%.
2021, 37(1): 121-130
doi: 10.11862/CJIC.2021.009
Abstract:
Four transition metal complexes, [Co(NO3) (H2O)2(L)2]NO3 (1), [Co2Cl4(L)2] ·CH2Cl2 (2), [Cd2(AcO)4(L)2] ·4CH3OH (3) and[Cd2(NO3)2(CH3OH)2(H2O)2(L)2](NO3)2·2H2O (4), were synthesized by employing a clamplike bipyridine ligand 3, 7-di(3-pyridyl)-1, 5-dioxa-3, 7-diazacyclooctane (L). Single-crystal X-ray analysis reveals that complex 1 is mononuclear structure; 2 is macrocyclic dimer; wheras 3 and 4 are rectangular dinuclear structures. The ligand molecules in these complexes has shown three types of coordination mode including mono-dentate, trans-bridge and cis-bridge. All of the complexes were also characterized by elemental analysis, IR, thermal stabilities and singlecrystal structure analysis.CCDC: 940778, 1; 915840, 2; 1446573, 3; 1446574, 4.
Four transition metal complexes, [Co(NO3) (H2O)2(L)2]NO3 (1), [Co2Cl4(L)2] ·CH2Cl2 (2), [Cd2(AcO)4(L)2] ·4CH3OH (3) and[Cd2(NO3)2(CH3OH)2(H2O)2(L)2](NO3)2·2H2O (4), were synthesized by employing a clamplike bipyridine ligand 3, 7-di(3-pyridyl)-1, 5-dioxa-3, 7-diazacyclooctane (L). Single-crystal X-ray analysis reveals that complex 1 is mononuclear structure; 2 is macrocyclic dimer; wheras 3 and 4 are rectangular dinuclear structures. The ligand molecules in these complexes has shown three types of coordination mode including mono-dentate, trans-bridge and cis-bridge. All of the complexes were also characterized by elemental analysis, IR, thermal stabilities and singlecrystal structure analysis.CCDC: 940778, 1; 915840, 2; 1446573, 3; 1446574, 4.
2021, 37(1): 131-139
doi: 10.11862/CJIC.2021.015
Abstract:
α-Ni(OH)2 nanoparticles with 5 nm average diameter were prepared under the existence of glucose in water solution, and the size of α-Ni(OH)2 nanoparticles was found to be controlled by the concentration of glucose. A possible mechanism of the preparation process was proposed. When the synthesis was processed without existence of the glucose, β-Ni(OH)2 was obtained. The super-small α-Ni(OH)2 nanoparticles showed strong adsorption ability to Li+ ions when pH value of the solution was about 7.0 under room temperature. Maximum adsorption capacity of the super-small α-Ni(OH)2 nanoparticles to Li+ was about 214 mg·g-1; however, the β-Ni(OH)2 with diameter above 1.0 μm was low than 30 mg·g-1. Freundlich equation analysis and SEM images of the adsorption products indicate multilayers' adsorption process to Li+ of α-Ni(OH)2 nanoparticles.
α-Ni(OH)2 nanoparticles with 5 nm average diameter were prepared under the existence of glucose in water solution, and the size of α-Ni(OH)2 nanoparticles was found to be controlled by the concentration of glucose. A possible mechanism of the preparation process was proposed. When the synthesis was processed without existence of the glucose, β-Ni(OH)2 was obtained. The super-small α-Ni(OH)2 nanoparticles showed strong adsorption ability to Li+ ions when pH value of the solution was about 7.0 under room temperature. Maximum adsorption capacity of the super-small α-Ni(OH)2 nanoparticles to Li+ was about 214 mg·g-1; however, the β-Ni(OH)2 with diameter above 1.0 μm was low than 30 mg·g-1. Freundlich equation analysis and SEM images of the adsorption products indicate multilayers' adsorption process to Li+ of α-Ni(OH)2 nanoparticles.
2021, 37(1): 140-150
doi: 10.11862/CJIC.2021.002
Abstract:
We systematically investigated Pd/FeOx for the reverse water gas shift (RWGS) reaction using a combination of ex situ and in situ characterizations, including transmission electron microscopy (TEM), Fourier-transform infrared (FTIR) spectroscopy, temperature-programmed desorption/reduction/oxidation (TPD/TPR/TPO), and X-ray photoelectron spectroscopy (XPS). A highly dispersed Pd/FeOx catalyst was synthesized using Pd(acac)2 as the precursor. The catalyst exhibited high activity, with CO2 conversion of ~29% and CO selectivity ogreater than 98% at 400℃, which are among the highest values in the literature. Moreover, Pd/SiO2 and Pd-Fe/SiO2 were further studied to determine the significant role of the Pd-FeOx interface in promoting the RWGS reaction. Semi-in situ XPS revealed the dynamic formation of Pdδ+-Fe2+ species at the Pd-FeOx interface; the species acted as highly active sites for CO2 dissociation. Our results also showed the formation of the Pdδ+-Fe2+ interface during the RWGS reaction remarkably enhanced the activity and selectivity of the Pd-FeOx catalyst for the reaction, benefiting CO2 adsorption, C=O dissociation, and CO desorption.
We systematically investigated Pd/FeOx for the reverse water gas shift (RWGS) reaction using a combination of ex situ and in situ characterizations, including transmission electron microscopy (TEM), Fourier-transform infrared (FTIR) spectroscopy, temperature-programmed desorption/reduction/oxidation (TPD/TPR/TPO), and X-ray photoelectron spectroscopy (XPS). A highly dispersed Pd/FeOx catalyst was synthesized using Pd(acac)2 as the precursor. The catalyst exhibited high activity, with CO2 conversion of ~29% and CO selectivity ogreater than 98% at 400℃, which are among the highest values in the literature. Moreover, Pd/SiO2 and Pd-Fe/SiO2 were further studied to determine the significant role of the Pd-FeOx interface in promoting the RWGS reaction. Semi-in situ XPS revealed the dynamic formation of Pdδ+-Fe2+ species at the Pd-FeOx interface; the species acted as highly active sites for CO2 dissociation. Our results also showed the formation of the Pdδ+-Fe2+ interface during the RWGS reaction remarkably enhanced the activity and selectivity of the Pd-FeOx catalyst for the reaction, benefiting CO2 adsorption, C=O dissociation, and CO desorption.
2021, 37(1): 151-156
doi: 10.11862/CJIC.2021.007
Abstract:
An aluminum amine compound (L)AlH(NMe2) (L=HC(C(Me)NAr)2, Ar=2, 6-iPr2C6H3) (1) protected by steric β-diketiminate ligand L has been synthesized successfully. A two-step synthesis method was employed to prepare the aluminum amine (L)AlH(NMe2) compound. The aluminum amine compound (L)AlH(NMe2) was identified via NMR spectroscopy, elemental analysis, infrared diffuse reflectance spectroscopy and X-ray single crystal diffraction analysis. The aluminum amine compound containing both Al-NMe2 and Al-H substitutes showed excellent catalytic performance on the ring-opening polymerization of ε-caprolactone. The molecular weight and molecular weight distribution of the resultant polycaprolactone were determined by high performance gel penetration chromatography.
An aluminum amine compound (L)AlH(NMe2) (L=HC(C(Me)NAr)2, Ar=2, 6-iPr2C6H3) (1) protected by steric β-diketiminate ligand L has been synthesized successfully. A two-step synthesis method was employed to prepare the aluminum amine (L)AlH(NMe2) compound. The aluminum amine compound (L)AlH(NMe2) was identified via NMR spectroscopy, elemental analysis, infrared diffuse reflectance spectroscopy and X-ray single crystal diffraction analysis. The aluminum amine compound containing both Al-NMe2 and Al-H substitutes showed excellent catalytic performance on the ring-opening polymerization of ε-caprolactone. The molecular weight and molecular weight distribution of the resultant polycaprolactone were determined by high performance gel penetration chromatography.
2021, 37(1): 157-170
doi: 10.11862/CJIC.2021.001
Abstract:
Carbon-based materials have been paid much attention due to their own good electroactivity and resources availability. Herein, we reported a simple and versatile synthesis strategy for the preparation of nitrogen-doped and metal-free carbon catalysts with excellent oxygen reduction reaction (ORR) electroactivity. Using dicyandiamide (DCD) as nitrogen source and sucrose, β-cyclodextrin and chitosan as different carbon sources, N-doped graphene-like nanosheet samples CN-nanosh(suc), CN-nanosh(cyc) and CN-nanosh(ch) were prepared by an easy pyrolysis of their mixture. The samples exhibited outstanding ORR electroactivity in alkaline media with a comparable performance to the benchmark Pt/C. Alkaline Zn-air battery with the prepared sample CN-nanosh(suc) as the cathodic catalyst displayed the maximum power density of 201.33 mW·cm-2, and its discharge time can last for more than 50 h at a constant current density of 100 mA·cm-2, which is close to the optimum values of the similar Zn-air battery with the metal-free cathodic electrocatalysts reported so far.
Carbon-based materials have been paid much attention due to their own good electroactivity and resources availability. Herein, we reported a simple and versatile synthesis strategy for the preparation of nitrogen-doped and metal-free carbon catalysts with excellent oxygen reduction reaction (ORR) electroactivity. Using dicyandiamide (DCD) as nitrogen source and sucrose, β-cyclodextrin and chitosan as different carbon sources, N-doped graphene-like nanosheet samples CN-nanosh(suc), CN-nanosh(cyc) and CN-nanosh(ch) were prepared by an easy pyrolysis of their mixture. The samples exhibited outstanding ORR electroactivity in alkaline media with a comparable performance to the benchmark Pt/C. Alkaline Zn-air battery with the prepared sample CN-nanosh(suc) as the cathodic catalyst displayed the maximum power density of 201.33 mW·cm-2, and its discharge time can last for more than 50 h at a constant current density of 100 mA·cm-2, which is close to the optimum values of the similar Zn-air battery with the metal-free cathodic electrocatalysts reported so far.
2021, 37(1): 171-179
doi: 10.11862/CJIC.2021.011
Abstract:
An effective approach of depositing NiS on CoNi2S4 was adopted to improve the performance of bimetallic cobalt/nickel-sulfide. The as-obtained CoNi2S4@NiS had an excellent specific capacitance of 1 433 F·g-1 at 1 A·g-1 and shows a superior rate performance of 69.6% at 10 A·g-1. A flexible solid-state asymmetric supercapacitor assembled with CoNi2S4@NiS and the reduced graphene oxide showed a high energy density of 36.6 Wh·kg-1 at a power density of 800 W·kg-1 and had a fantastic cycle performance of 78.7% retention after 10 000 cycles, indicating that the CoNi2S4@NiS nanocomposite is a promising electrode material for energy storage devices.
An effective approach of depositing NiS on CoNi2S4 was adopted to improve the performance of bimetallic cobalt/nickel-sulfide. The as-obtained CoNi2S4@NiS had an excellent specific capacitance of 1 433 F·g-1 at 1 A·g-1 and shows a superior rate performance of 69.6% at 10 A·g-1. A flexible solid-state asymmetric supercapacitor assembled with CoNi2S4@NiS and the reduced graphene oxide showed a high energy density of 36.6 Wh·kg-1 at a power density of 800 W·kg-1 and had a fantastic cycle performance of 78.7% retention after 10 000 cycles, indicating that the CoNi2S4@NiS nanocomposite is a promising electrode material for energy storage devices.
2021, 37(1): 180-188
doi: 10.11862/CJIC.2021.017
Abstract:
The folic acid (FA)-grafted magnetic FA-Fe3O4/ATP-P(NIPAM-AAM) composite microgels (attapulgite=ATP, N-isopropyl acrylamide=NIPAM, acrylamide=AAM) were prepared via a method of emulsion copolymerization. The as-prepared microgels were characterized by X-ray diffraction (XRD), vibrating sample magnetometer (VSM), thermogravimetric analysis (TG), infrared spectroscopy (IR), UV-visible spectroscopy (UV), scanning electron microscope (SEM) and transmission electron microscope (TEM). The dynamic light scattering (DLS) results show that the low critical solution temperature (LCST) of microgel was about 38.5℃. The drug delivery ability of the as-prepared microgels was evaluated by using doxorubicin hydrochloride (DOX) as the model drug. Based on the drug loading and releasing results, the presence of ATP increased the amount of drug loading and releasing. Compared with free DOX, the in vitro cytotoxicity of DOX loaded FA-Fe3O4/ATP-P(NIPAM-AAM) was decreased and the biocompatibility was improved. Those results indicate that the microgels of FA-Fe3O4/ATP-P(NIPAM-AAM) can be used in potential as a slow-release drug system. The in vitro cellular uptake test revealed that the microgels of FA-Fe3O4/ATP-P(NIPAM-AAM) at the assigned site were significantly richer than that of other sites. This result indicates that the microgels of FA-Fe3O4/ATP-P(NIPAM-AAM) composite are targeting and expectable in the application of targeted drug releasing.
The folic acid (FA)-grafted magnetic FA-Fe3O4/ATP-P(NIPAM-AAM) composite microgels (attapulgite=ATP, N-isopropyl acrylamide=NIPAM, acrylamide=AAM) were prepared via a method of emulsion copolymerization. The as-prepared microgels were characterized by X-ray diffraction (XRD), vibrating sample magnetometer (VSM), thermogravimetric analysis (TG), infrared spectroscopy (IR), UV-visible spectroscopy (UV), scanning electron microscope (SEM) and transmission electron microscope (TEM). The dynamic light scattering (DLS) results show that the low critical solution temperature (LCST) of microgel was about 38.5℃. The drug delivery ability of the as-prepared microgels was evaluated by using doxorubicin hydrochloride (DOX) as the model drug. Based on the drug loading and releasing results, the presence of ATP increased the amount of drug loading and releasing. Compared with free DOX, the in vitro cytotoxicity of DOX loaded FA-Fe3O4/ATP-P(NIPAM-AAM) was decreased and the biocompatibility was improved. Those results indicate that the microgels of FA-Fe3O4/ATP-P(NIPAM-AAM) can be used in potential as a slow-release drug system. The in vitro cellular uptake test revealed that the microgels of FA-Fe3O4/ATP-P(NIPAM-AAM) at the assigned site were significantly richer than that of other sites. This result indicates that the microgels of FA-Fe3O4/ATP-P(NIPAM-AAM) composite are targeting and expectable in the application of targeted drug releasing.
2021, 37(1): 189-189
doi: 10.11862/CJIC.2021.040
Abstract:
