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2022 Volume 38 Issue 8
2022, 38(8): 1441-1450
doi: 10.11862/CJIC.2022.133
Abstract:
The past decade has witnessed an explosion of research into organic‐inorganic hybrid perovskites due to their outstanding optoelectronic properties, including high flexibility, high absorption/emission efficiency, large defect tolerance, and long‐distance carrier diffusion. Recently, chiral hybrid perovskites, combing the unique properties of perovskites and chiral materials, show promising potential in the applications of the three‐dimensional display, optical information processing, quantum optics, biological probe, and spintronics, etc. Particularly, chiral hybrid perovskites exhibit robust circularly polarized light emission and sensitive circularly polarized light detection, as the present chiral molecules can rotate the light polarization plane differently and/or absorb the left‐handed (σ-) and right‐handed (σ+) circularly polarized light differently. Considering that circularly polarized light can create nonequilibrium spin polarization between the two Rashba‐split bands, chiral perovskites are promising for chiro‐spintronic and chiro‐optoelectronic applications. Chiral perovskites can be sorted as one‐dimensional, two‐dimensional, and three‐dimensional structures according to the space distributions of organic and inorganic components. This work demonstrates the crystal structure, and optical and optoelectronic properties of chiral perovskite of different dimensionalities, including the circular dichroism, the photoluminescence, and photodetection properties under the excitation of circularly polarized light. Considering the van der Waals coupling layered structure of two‐dimensional chiral perovskites, we also introduce the work on their two‐dimensional heterostructures combined with other two‐dimensional materials. Last, the important challenges and promising directions of chiral perovskites are summarized in aspects of material design and device exploration.
The past decade has witnessed an explosion of research into organic‐inorganic hybrid perovskites due to their outstanding optoelectronic properties, including high flexibility, high absorption/emission efficiency, large defect tolerance, and long‐distance carrier diffusion. Recently, chiral hybrid perovskites, combing the unique properties of perovskites and chiral materials, show promising potential in the applications of the three‐dimensional display, optical information processing, quantum optics, biological probe, and spintronics, etc. Particularly, chiral hybrid perovskites exhibit robust circularly polarized light emission and sensitive circularly polarized light detection, as the present chiral molecules can rotate the light polarization plane differently and/or absorb the left‐handed (σ-) and right‐handed (σ+) circularly polarized light differently. Considering that circularly polarized light can create nonequilibrium spin polarization between the two Rashba‐split bands, chiral perovskites are promising for chiro‐spintronic and chiro‐optoelectronic applications. Chiral perovskites can be sorted as one‐dimensional, two‐dimensional, and three‐dimensional structures according to the space distributions of organic and inorganic components. This work demonstrates the crystal structure, and optical and optoelectronic properties of chiral perovskite of different dimensionalities, including the circular dichroism, the photoluminescence, and photodetection properties under the excitation of circularly polarized light. Considering the van der Waals coupling layered structure of two‐dimensional chiral perovskites, we also introduce the work on their two‐dimensional heterostructures combined with other two‐dimensional materials. Last, the important challenges and promising directions of chiral perovskites are summarized in aspects of material design and device exploration.
2022, 38(8): 1451-1469
doi: 10.11862/CJIC.2022.130
Abstract:
Large‐scale electrical energy storage (EES) technology with high safety, low cost, and high stability determines the future energy structure adjustment and smart grid construction. Rechargeable Zn batteries (RZBs) would be an ideal candidate for EES devices because of their intrinsic environment‐friendly and cost‐effective properties. Although substantial progress has been achieved in RZBs in the past several years, the state‐of‐art RZBs are plagued by severe side‐reactions like cathode materials dissolution, dendrites growth, Zn corrosion, and hydrogen evolution, which are associated with the active free water and hydrated Zn(OH)62+ ion in common aqueous solution. In this review, the electrolyte strategies including concentration, additives, and solvation structure modulation for improving Zn cycling performance are discussed in detail. This paper combines reviews and perspectives on electrolyte strategies, which would shed light on the development of high‐performance RZBs.
Large‐scale electrical energy storage (EES) technology with high safety, low cost, and high stability determines the future energy structure adjustment and smart grid construction. Rechargeable Zn batteries (RZBs) would be an ideal candidate for EES devices because of their intrinsic environment‐friendly and cost‐effective properties. Although substantial progress has been achieved in RZBs in the past several years, the state‐of‐art RZBs are plagued by severe side‐reactions like cathode materials dissolution, dendrites growth, Zn corrosion, and hydrogen evolution, which are associated with the active free water and hydrated Zn(OH)62+ ion in common aqueous solution. In this review, the electrolyte strategies including concentration, additives, and solvation structure modulation for improving Zn cycling performance are discussed in detail. This paper combines reviews and perspectives on electrolyte strategies, which would shed light on the development of high‐performance RZBs.
First-Principles Calculation of H/CO2 Interaction in Plasma: A Density Functional Theory-Based Study
2022, 38(8): 1470-1476
doi: 10.11862/CJIC.2022.158
Abstract:
An in-depth understanding of the microscopic mechanism of the reaction of hydrogen isotopes with CO2 under irradiation conditions can provide data support for the optimal design of the deuterium-tritium fuel cycle process for fusion reactors. Based on this, the microscopic reaction mechanism of H2 and CO2 under the condition of plasma discharge was studied by first-principles calculation, and the influences of different temperatures and hydrogen isotope effect on the reaction process were studied. The principal calculation was carried out by the Gaussian 09 software package. The enthalpies and activation energies of these reactions were measured at the level of M06-2X/6-311++G (3d2f, 3p2d). Four initial reaction paths are obtained by using the intrinsic reaction coordinate (IRC) algorithm and finding the transition state of the combined reaction. The thermodynamic easiness of the two pathways to produce CH4 and CH3OH and the influence of different hydrogen isotopes on each reaction were compared and studied. It is found that the spontaneous decay of tritium or the high-energy electrons in the plasma will induce hydrogen isotopes to react with CO2 to form products such as CO, H2O, CH4, and CH3OH; after the high-energy electrons induce the dissociation of CO2, there are four initial reaction paths. Complex reactions can occur on their own, and there are two tendencies to this complex reaction. Raising the reaction temperature has a certain promoting effect on the conversion of CO2 into organic matter (CH4 and CH3OH).
An in-depth understanding of the microscopic mechanism of the reaction of hydrogen isotopes with CO2 under irradiation conditions can provide data support for the optimal design of the deuterium-tritium fuel cycle process for fusion reactors. Based on this, the microscopic reaction mechanism of H2 and CO2 under the condition of plasma discharge was studied by first-principles calculation, and the influences of different temperatures and hydrogen isotope effect on the reaction process were studied. The principal calculation was carried out by the Gaussian 09 software package. The enthalpies and activation energies of these reactions were measured at the level of M06-2X/6-311++G (3d2f, 3p2d). Four initial reaction paths are obtained by using the intrinsic reaction coordinate (IRC) algorithm and finding the transition state of the combined reaction. The thermodynamic easiness of the two pathways to produce CH4 and CH3OH and the influence of different hydrogen isotopes on each reaction were compared and studied. It is found that the spontaneous decay of tritium or the high-energy electrons in the plasma will induce hydrogen isotopes to react with CO2 to form products such as CO, H2O, CH4, and CH3OH; after the high-energy electrons induce the dissociation of CO2, there are four initial reaction paths. Complex reactions can occur on their own, and there are two tendencies to this complex reaction. Raising the reaction temperature has a certain promoting effect on the conversion of CO2 into organic matter (CH4 and CH3OH).
2022, 38(8): 1487-1498
doi: 10.11862/CJIC.2022.166
Abstract:
In this work, the Bi3TaO7/Ti3C2 composite photocatalysts were in-situ deposited on the surface of 2D Ti3C2 by electrostatic adsorption and solvothermal treatment using bismuth nitrate pentahydrate and tantalum pentachloride as the Bi and Ta sources, respectively. The effects of 2D Ti3C2 nanosheets on the microstructure of Bi3TaO7/ Ti3C2 were investigated by various physicochemical characterizations. The photocatalytic properties of as‐prepared samples were evaluated by visible light degradation of sodium sulfadiazine (SD‐Na) aqueous solution. The experimental results showed that the photocatalytic performance of the Bi3TaO7/Ti3C2 composites was significantly enhanced. Under the optimal conditions (the mass ratio of Ti3C2 to Bi3TaO7 was 0.02), the obtained BT2 sample exhibited the highest photocatalytic activity for degrading the SD‐Na aqueous solution and the apparent rate constant k value was 2.8 times higher than that of the pure Bi3TaO7 sample. The significant improvement of the Bi3TaO7/ Ti3C2 composite is attributed to the formation of heterojunction structure on the interface between Ti3C2 and Bi3TaO7, resulting in the rapid transfer and separation of photogenerated carriers.
In this work, the Bi3TaO7/Ti3C2 composite photocatalysts were in-situ deposited on the surface of 2D Ti3C2 by electrostatic adsorption and solvothermal treatment using bismuth nitrate pentahydrate and tantalum pentachloride as the Bi and Ta sources, respectively. The effects of 2D Ti3C2 nanosheets on the microstructure of Bi3TaO7/ Ti3C2 were investigated by various physicochemical characterizations. The photocatalytic properties of as‐prepared samples were evaluated by visible light degradation of sodium sulfadiazine (SD‐Na) aqueous solution. The experimental results showed that the photocatalytic performance of the Bi3TaO7/Ti3C2 composites was significantly enhanced. Under the optimal conditions (the mass ratio of Ti3C2 to Bi3TaO7 was 0.02), the obtained BT2 sample exhibited the highest photocatalytic activity for degrading the SD‐Na aqueous solution and the apparent rate constant k value was 2.8 times higher than that of the pure Bi3TaO7 sample. The significant improvement of the Bi3TaO7/ Ti3C2 composite is attributed to the formation of heterojunction structure on the interface between Ti3C2 and Bi3TaO7, resulting in the rapid transfer and separation of photogenerated carriers.
2022, 38(8): 1499-1511
doi: 10.11862/CJIC.2022.165
Abstract:
Complex [MnH2L(DMSO)2] (1) and coordination polymer {[La(H2L)2]2[La2(H2L)2(DMF)5(H2O)] ·2DMF· 2H2O}n (2) (DMSO=dimethyl sulfoxide, DMF=N, N‐dimethylformamide) having 2, 6‐diacetylpyridine salicylhydrazone derivative (2, 6‐((o‐OH)C6H4C=ONHN=C(CH3))2C5H3N, H4L) as ligand were synthesized and characterized by IR, UV‐Vis, elemental analysis and further by single‐crystal X‐ray diffraction. Complex 1 belongs to an orthorhombic crystal system with space group P212121, and coordination polymer 2 crystallizes in a triclinic crystal system with space group P1. Moreover, the in vitro antitumor activities of complex 1 and coordination polymer 2 were evaluated by CCK‐8 assay in the colon (HCT116) and colorectal adenocarcinoma (DLD‐1) cancer cell lines. And the resulting IC50 values were estimated to be as low as (23.69±1.226) μmol·L-1 and (41.06±1.013) μmol·L-1 for complex 1 or (57.61±1.034) μmol·L-1 and (61.36±1.029) μmol·L-1 for complex 2 against HCT116 and DLD‐1 cells, respectively, proving cytotoxic activities of complex 1 and coordination polymer 2 against these two cancer cell lines.
Complex [MnH2L(DMSO)2] (1) and coordination polymer {[La(H2L)2]2[La2(H2L)2(DMF)5(H2O)] ·2DMF· 2H2O}n (2) (DMSO=dimethyl sulfoxide, DMF=N, N‐dimethylformamide) having 2, 6‐diacetylpyridine salicylhydrazone derivative (2, 6‐((o‐OH)C6H4C=ONHN=C(CH3))2C5H3N, H4L) as ligand were synthesized and characterized by IR, UV‐Vis, elemental analysis and further by single‐crystal X‐ray diffraction. Complex 1 belongs to an orthorhombic crystal system with space group P212121, and coordination polymer 2 crystallizes in a triclinic crystal system with space group P1. Moreover, the in vitro antitumor activities of complex 1 and coordination polymer 2 were evaluated by CCK‐8 assay in the colon (HCT116) and colorectal adenocarcinoma (DLD‐1) cancer cell lines. And the resulting IC50 values were estimated to be as low as (23.69±1.226) μmol·L-1 and (41.06±1.013) μmol·L-1 for complex 1 or (57.61±1.034) μmol·L-1 and (61.36±1.029) μmol·L-1 for complex 2 against HCT116 and DLD‐1 cells, respectively, proving cytotoxic activities of complex 1 and coordination polymer 2 against these two cancer cell lines.
2022, 38(8): 1512-1522
doi: 10.11862/CJIC.2022.170
Abstract:
To investigate the electronic, optical, and magnetic properties of the cluster ConMoS (n=1-5) at the theoretical level and to clarify its inherent relevance, the structure of the cluster was optimized and analyzed at the B3LYP/def2-TZVP quantum chemical level and multiple spin multiplexes based on topological principles and density functional theory. The results show that there are 21 stable configurations of the cluster ConMoS, which mostly exist in stereo form, and the conformation na is the most stable and the overall cluster stability tends to be more stable as the cluster size increases; the analysis of NPA (natural population analysis) charge, electrostatic potential, electrophilic index, ionization potential, optical electronegativity, and refractive index, etc. shows that metal atoms have a high probability of losing electrons and non-metal atoms are relatively more likely to gain electrons; the configuration 5a in the cluster Co5MoS has high electron gain and loss ability, reactivity, and refractive index in the most stable configuration, but it is the least chemically stable; Co and Mo atoms are prone to nucleophilic reactions and S atoms are prone to electrophilic reactions, and the active site is predicted provisionally from the electrostatic potential extreme site; the analysis of the spin population, atomic magnetic moments, orbital magnetic moments, and density of states of the cluster reveals that the magnetic properties of the cluster are mainly provided by the d orbital of the Co atom, the non-metallic atom S contributes less to the magnetic properties and the orbital hybridisation has an effect on the magnetic properties to some extent, the cluster Co3MoS exhibits more stable and excellent magnetic properties than other size clusters. It is concluded that the cluster Co3MoS has a good performance in magnetic properties and configuration 5a has some potential in the field of activity and optics.
To investigate the electronic, optical, and magnetic properties of the cluster ConMoS (n=1-5) at the theoretical level and to clarify its inherent relevance, the structure of the cluster was optimized and analyzed at the B3LYP/def2-TZVP quantum chemical level and multiple spin multiplexes based on topological principles and density functional theory. The results show that there are 21 stable configurations of the cluster ConMoS, which mostly exist in stereo form, and the conformation na is the most stable and the overall cluster stability tends to be more stable as the cluster size increases; the analysis of NPA (natural population analysis) charge, electrostatic potential, electrophilic index, ionization potential, optical electronegativity, and refractive index, etc. shows that metal atoms have a high probability of losing electrons and non-metal atoms are relatively more likely to gain electrons; the configuration 5a in the cluster Co5MoS has high electron gain and loss ability, reactivity, and refractive index in the most stable configuration, but it is the least chemically stable; Co and Mo atoms are prone to nucleophilic reactions and S atoms are prone to electrophilic reactions, and the active site is predicted provisionally from the electrostatic potential extreme site; the analysis of the spin population, atomic magnetic moments, orbital magnetic moments, and density of states of the cluster reveals that the magnetic properties of the cluster are mainly provided by the d orbital of the Co atom, the non-metallic atom S contributes less to the magnetic properties and the orbital hybridisation has an effect on the magnetic properties to some extent, the cluster Co3MoS exhibits more stable and excellent magnetic properties than other size clusters. It is concluded that the cluster Co3MoS has a good performance in magnetic properties and configuration 5a has some potential in the field of activity and optics.
2022, 38(8): 1523-1532
doi: 10.11862/CJIC.2022.150
Abstract:
The geometric structures, electronic, and thermodynamic properties of vanadium doped boron clusters, VB2n- (n=8 -12), were investigated systemically by using CALYPSO searching method and density functional theory. It is found that vanadium atom doping significantly modifies the structures of the boron clusters and strong the chem- ical activity of systems. A drum-shaped structure is the global minimum for VB16- cluster with C2v point symmetry. Tubular-shaped VB18- and VB20- with C2v and Cs symmetry exhibit a metal-centred tubular with a B 2 unit over the B16 and B 18 drum, respectively. For VB22- and VB24- clusters, vanadium atom tends to encapsulate into boron cages. Based on the lowest energy structures, the charge transfer and polarizability were explored, the photoelectron spec- tra, infrared spectra, and Raman spectra were simulated, the fluxional bonds and aromatic properties were analyzed. At last, the thermodynamic properties were investigated, the thermodynamics parameters were discussed for the lowest energy structures of VB2n- (n=8-12) clusters.
The geometric structures, electronic, and thermodynamic properties of vanadium doped boron clusters, VB2n- (n=8 -12), were investigated systemically by using CALYPSO searching method and density functional theory. It is found that vanadium atom doping significantly modifies the structures of the boron clusters and strong the chem- ical activity of systems. A drum-shaped structure is the global minimum for VB16- cluster with C2v point symmetry. Tubular-shaped VB18- and VB20- with C2v and Cs symmetry exhibit a metal-centred tubular with a B 2 unit over the B16 and B 18 drum, respectively. For VB22- and VB24- clusters, vanadium atom tends to encapsulate into boron cages. Based on the lowest energy structures, the charge transfer and polarizability were explored, the photoelectron spec- tra, infrared spectra, and Raman spectra were simulated, the fluxional bonds and aromatic properties were analyzed. At last, the thermodynamic properties were investigated, the thermodynamics parameters were discussed for the lowest energy structures of VB2n- (n=8-12) clusters.
2022, 38(8): 1533-1540
doi: 10.11862/CJIC.2022.161
Abstract:
Two organotin heterocyclic carboxylate complexes di(o - bromobenzyl)tin bis(2-pyridinecarboxylate) (1) and tri(2-methyl-2-phenyl propyl)tin 3-indole butyrate (2) have been synthesized by a solvothermal method using methanol as solvent. The complexes were characterized by elemental analysis, IR spectroscopy, NMR (1H, 13C, and 119Sn), X-ray diffraction, and thermogravimetric analysis. The crystal structures of the complexes were determined by X-ray single-crystal diffraction. The results show that the complexes have a single tin core structure, and the tin atoms are six-coordinate distorted octahedron configuration and four-coordinate distorted tetrahedron configuration respectively. The stabilities, orbital energies, and composition characteristics of some frontier molecular orbitals of 1 and 2 have been carefully investigated with quantum chemistry calculation. In addition, the in vitro antitumor activities suggest that 1 and 2 had higher activities than cisplatinum against human hepatoma cells (HUH7), human lung cancer cells (A549), human epidermal cancer cells (A431), human colon cancer cells (HCT-116), and breast cancer cells (MDA-MB-231).
Two organotin heterocyclic carboxylate complexes di(o - bromobenzyl)tin bis(2-pyridinecarboxylate) (1) and tri(2-methyl-2-phenyl propyl)tin 3-indole butyrate (2) have been synthesized by a solvothermal method using methanol as solvent. The complexes were characterized by elemental analysis, IR spectroscopy, NMR (1H, 13C, and 119Sn), X-ray diffraction, and thermogravimetric analysis. The crystal structures of the complexes were determined by X-ray single-crystal diffraction. The results show that the complexes have a single tin core structure, and the tin atoms are six-coordinate distorted octahedron configuration and four-coordinate distorted tetrahedron configuration respectively. The stabilities, orbital energies, and composition characteristics of some frontier molecular orbitals of 1 and 2 have been carefully investigated with quantum chemistry calculation. In addition, the in vitro antitumor activities suggest that 1 and 2 had higher activities than cisplatinum against human hepatoma cells (HUH7), human lung cancer cells (A549), human epidermal cancer cells (A431), human colon cancer cells (HCT-116), and breast cancer cells (MDA-MB-231).
2022, 38(8): 1541-1548
doi: 10.11862/CJIC.2022.148
Abstract:
In this work, 3D flower - like Ni(OH)2/Ni@NG composite electrodes were prepared by combining 3D Ni(OH)2/Ni with nitrogen-doped reduced graphene oxide(rGO)using de-alloying and two-step hydrothermal synthesis.Characterization of the phase, valence distribution, and microstructure of electrodes by X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), scanning electron microscopy(SEM), and transmission electron microscopy(TEM).In addition, the electrocatalytic hydrogen evolution reaction(HER)performance was tested in 1 mol·L-1 KOH solution.The results showed that the three-dimensional structure of Ni(OH)2/Ni increased the active area of the electrode, and the complexation with N-doped rGO significantly improved the electron/ion transport rate with an overpotential of 108 mV(η10)and a Tafel slope of 114.9 mV·dec-1, which exhibited good HER catalytic activity.The Ni(OH)2/Ni@NG electrode showed good stability by both the 1 000-turn cyclic voltammetry method and the chronopotentiometry test.
In this work, 3D flower - like Ni(OH)2/Ni@NG composite electrodes were prepared by combining 3D Ni(OH)2/Ni with nitrogen-doped reduced graphene oxide(rGO)using de-alloying and two-step hydrothermal synthesis.Characterization of the phase, valence distribution, and microstructure of electrodes by X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), scanning electron microscopy(SEM), and transmission electron microscopy(TEM).In addition, the electrocatalytic hydrogen evolution reaction(HER)performance was tested in 1 mol·L-1 KOH solution.The results showed that the three-dimensional structure of Ni(OH)2/Ni increased the active area of the electrode, and the complexation with N-doped rGO significantly improved the electron/ion transport rate with an overpotential of 108 mV(η10)and a Tafel slope of 114.9 mV·dec-1, which exhibited good HER catalytic activity.The Ni(OH)2/Ni@NG electrode showed good stability by both the 1 000-turn cyclic voltammetry method and the chronopotentiometry test.
2022, 38(8): 1549-1556
doi: 10.11862/CJIC.2022.169
Abstract:
Thin bismuth bromide oxide (BiOBr) flake was prepared by photochemical reaction under dilute acid con- dition, and a new type of bismuth oxide/polypyrrole (BiOBr/PPy) composite was prepared in-situ through a one-step polymerization reaction of pyrrole dispersed in an aqueous solution containing ammonium persulfate and cetyltri- methylammonium bromide. The scanning electron microscope, transmission electron microscope, X-ray diffraction, Raman spectra, X-ray photoelectron spectra, ultraviolet and visible spectra, and fluorescence spectra were used to characterize the crystal structure, morphology feature, and photoelectric characteristics of the samples. The results showed that PPy was successfully modified onto BiOBr flakes with strong interaction and close contact. Compared with pure BiOBr, BiOBr/PPy composite showed superior visible light absorption efficiency and enhanced photocatalytic degradation activity of methyl orange (MO) dye. By optimizing the combination ratio of PPy and BiOBr, the deg- radation efficiency of MO (30 mg·L-1) by BiOBr/PPy-2 with a ca. 7% mass fraction of BiOBr was 87.3% in 50 min photoreaction, and the cyclic photocatalytic activity was reduced but still higher than that of pure BiOBr and pure PPy (10.4%). These results indicated that the strong interaction and good interface combination between BiOBr and PPy can effectively promote the separation efficiency of photogenerated electrons and holes. The photogenic holes separated and free radicals derived in this reaction played an important role in oxidative degradation of dye.
Thin bismuth bromide oxide (BiOBr) flake was prepared by photochemical reaction under dilute acid con- dition, and a new type of bismuth oxide/polypyrrole (BiOBr/PPy) composite was prepared in-situ through a one-step polymerization reaction of pyrrole dispersed in an aqueous solution containing ammonium persulfate and cetyltri- methylammonium bromide. The scanning electron microscope, transmission electron microscope, X-ray diffraction, Raman spectra, X-ray photoelectron spectra, ultraviolet and visible spectra, and fluorescence spectra were used to characterize the crystal structure, morphology feature, and photoelectric characteristics of the samples. The results showed that PPy was successfully modified onto BiOBr flakes with strong interaction and close contact. Compared with pure BiOBr, BiOBr/PPy composite showed superior visible light absorption efficiency and enhanced photocatalytic degradation activity of methyl orange (MO) dye. By optimizing the combination ratio of PPy and BiOBr, the deg- radation efficiency of MO (30 mg·L-1) by BiOBr/PPy-2 with a ca. 7% mass fraction of BiOBr was 87.3% in 50 min photoreaction, and the cyclic photocatalytic activity was reduced but still higher than that of pure BiOBr and pure PPy (10.4%). These results indicated that the strong interaction and good interface combination between BiOBr and PPy can effectively promote the separation efficiency of photogenerated electrons and holes. The photogenic holes separated and free radicals derived in this reaction played an important role in oxidative degradation of dye.
2022, 38(8): 1557-1566
doi: 10.11862/CJIC.2022.156
Abstract:
In this study, by using the solid and liquid coating method, LiCoO2 was dual-coated by lithium titanate (Li4Ti5O12) and polypyrrole (PPy). The coating layers not only protect the surface of LiCoO2 at high voltage but also increase its ion conductivity and electronic conductivity. According to the result of the electrochemistry test, when the mass ratio of active material, conductive agent, and binder was 80∶10∶10, the capacity retention of the modified material after 300 cycles at 0.5C (1C=180 mA·g-1) was 76.9%. Its reversible capacity was 150 mAh·g-1 at 5C cur- rent density. Due to the improvement of electric conductive of dual-coated LiCoO2, when this mass ratio was 90∶3∶ 7, the capacity retention after 200 cycles at 0.5C was 82.8%. Its reversible capacity was 130 mAh·g-1 at 5C current density. As shown in X-ray photoelectron spectra, the coating layers can keep stability during cycling and prevent side reactions on the surface.
In this study, by using the solid and liquid coating method, LiCoO2 was dual-coated by lithium titanate (Li4Ti5O12) and polypyrrole (PPy). The coating layers not only protect the surface of LiCoO2 at high voltage but also increase its ion conductivity and electronic conductivity. According to the result of the electrochemistry test, when the mass ratio of active material, conductive agent, and binder was 80∶10∶10, the capacity retention of the modified material after 300 cycles at 0.5C (1C=180 mA·g-1) was 76.9%. Its reversible capacity was 150 mAh·g-1 at 5C cur- rent density. Due to the improvement of electric conductive of dual-coated LiCoO2, when this mass ratio was 90∶3∶ 7, the capacity retention after 200 cycles at 0.5C was 82.8%. Its reversible capacity was 130 mAh·g-1 at 5C current density. As shown in X-ray photoelectron spectra, the coating layers can keep stability during cycling and prevent side reactions on the surface.
2022, 38(8): 1567-1576
doi: 10.11862/CJIC.2022.163
Abstract:
Employing Co(NO3)2 and Eu(NO3)3 as raw materials, a series of porous Co/Eu bimetallic ‐oxide catalysts were synthesized through an oxalate‐pyrolysis method, and their catalytic performances in activating peroxymonosulfate (PMS) for degradation of methylene blue (MB) were evaluated. The results showed that the sample with a Co/Eu molar ratio (nCo/nEu) of 9 (Co9Eu1) exhibited the most excellent catalytic property towards PMS decomposition for MB removal. The degradation ratio of MB was 86.66% in the system of Co9Eu1/PMS, while it was only 52.62% for the counterpart, under the reaction conditions: catalyst addition of 0.10 g·L-1, PMS concentration of 0.6 mmol·L-1, and a reaction temperature of 25 ℃. The outstanding catalytic performance of Co9Eu1 is attributed to the electron ‐ deficient property of Eu3+, which can enhance the polarization of PMS adsorbed on the surface of the catalyst and then make PMS easier to be activated by the primary catalytic component of Co3O4. Meanwhile, it is found that both C2O42- and HCO3- anions have obvious inhibitory effects on the degradation efficiency of MB in the Co9Eu1/PMS reaction system. In addition, quenching experiments and electron paramagnetic resonance spectroscopies (EPR) identify that reactive oxygen species (SO4-·, ·OH and ·O2-) and non‐radical reactive oxygen species (1O2) both exist in the reaction system. Among them, SO4-· plays a key role in MB oxidative degradation process. Furthermore, no significant changes in catalytic performance in four consecutive cycles was observed.
Employing Co(NO3)2 and Eu(NO3)3 as raw materials, a series of porous Co/Eu bimetallic ‐oxide catalysts were synthesized through an oxalate‐pyrolysis method, and their catalytic performances in activating peroxymonosulfate (PMS) for degradation of methylene blue (MB) were evaluated. The results showed that the sample with a Co/Eu molar ratio (nCo/nEu) of 9 (Co9Eu1) exhibited the most excellent catalytic property towards PMS decomposition for MB removal. The degradation ratio of MB was 86.66% in the system of Co9Eu1/PMS, while it was only 52.62% for the counterpart, under the reaction conditions: catalyst addition of 0.10 g·L-1, PMS concentration of 0.6 mmol·L-1, and a reaction temperature of 25 ℃. The outstanding catalytic performance of Co9Eu1 is attributed to the electron ‐ deficient property of Eu3+, which can enhance the polarization of PMS adsorbed on the surface of the catalyst and then make PMS easier to be activated by the primary catalytic component of Co3O4. Meanwhile, it is found that both C2O42- and HCO3- anions have obvious inhibitory effects on the degradation efficiency of MB in the Co9Eu1/PMS reaction system. In addition, quenching experiments and electron paramagnetic resonance spectroscopies (EPR) identify that reactive oxygen species (SO4-·, ·OH and ·O2-) and non‐radical reactive oxygen species (1O2) both exist in the reaction system. Among them, SO4-· plays a key role in MB oxidative degradation process. Furthermore, no significant changes in catalytic performance in four consecutive cycles was observed.
2022, 38(8): 1577-1585
doi: 10.11862/CJIC.2022.153
Abstract:
BiOCl0.5Br0.5/BiPO4 double‐layer heterojunction thin film photocatalyst was successfully prepared on Bi plate by one‐pot electrochemical method. The crystal structure, elemental composition and valence, morphology and optical property were characterized. The as‐obtained double‐layer film consisted of BiOCl0.5Br 0.5 solid solution layer at the bottom and BiPO4 nanoparticles layer at the top. The interface internal electric field of BiOCl0.5Br0.5/BiPO4 composite film led the photo‐induced electrons and holes to shift in the opposite direction, thus improving the photocatalytic performance of BiOCl0.5Br0.5/BiPO4 composite film. The results displayed that the photodegradation efficiency of phenol reached 99.97% after 120 min under simulated sunlight irradiation, which was nearly 1.69 times and 1.20 times more than that of BiOCl/BiPO4 and BiOBr/BiPO4 composite films, respectively. Besides, the hole (h+) and hydroxyl radical (·OH) played a crucial role in the photodegradation process of phenol. The improved photocatalytic performance of BiOCl 0.5Br0.5/BiPO4 composite film can be ascribed to the broadened absorbance spectra range and efficient separation of photo‐induced charge carriers.
BiOCl0.5Br0.5/BiPO4 double‐layer heterojunction thin film photocatalyst was successfully prepared on Bi plate by one‐pot electrochemical method. The crystal structure, elemental composition and valence, morphology and optical property were characterized. The as‐obtained double‐layer film consisted of BiOCl0.5Br 0.5 solid solution layer at the bottom and BiPO4 nanoparticles layer at the top. The interface internal electric field of BiOCl0.5Br0.5/BiPO4 composite film led the photo‐induced electrons and holes to shift in the opposite direction, thus improving the photocatalytic performance of BiOCl0.5Br0.5/BiPO4 composite film. The results displayed that the photodegradation efficiency of phenol reached 99.97% after 120 min under simulated sunlight irradiation, which was nearly 1.69 times and 1.20 times more than that of BiOCl/BiPO4 and BiOBr/BiPO4 composite films, respectively. Besides, the hole (h+) and hydroxyl radical (·OH) played a crucial role in the photodegradation process of phenol. The improved photocatalytic performance of BiOCl 0.5Br0.5/BiPO4 composite film can be ascribed to the broadened absorbance spectra range and efficient separation of photo‐induced charge carriers.
2022, 38(8): 1477-1486
doi: 10.11862/CJIC.2022.155
Abstract:
The cobalt(Ⅱ) complexes containing terpyridine (terpy) and its derivatives compose a large family of Co(Ⅱ) SCO-active (SCO=spin-crossover) compounds and the reported cases are mainly built from homoleptic type terpy ligands. Herein we report the SCO properties in three mononuclear cobalt (Ⅱ) complexes constructed from complementary terpy ligand pairing. Their SCO behaviors are largely affected by the substituents of terpy at the 4-position. The archetypical complex 1 and its CF3-substituted one 3 showed a gradual and incomplete spin transition from the low spin state of S=1/2 to the high spin state of S=3/2. The fluorine-substituted complex 2 exhibited a solventdependent spin transition phenomenon. The solvated form which contains three lattice water molecules showed a similar gradually incomplete spin transition. Whereas the entire removal of water molecules resulted in a repeatable thermal hysteresis loop with a width of ca. 50 K. Impressively, the adsorption and desorption of water molecules are reversible in structure and magnetism. In addition, absorption spectroscopy and cyclic voltammetry show that the substituent on the ligands can regulate the electronic structures of the central cobalt ion.
The cobalt(Ⅱ) complexes containing terpyridine (terpy) and its derivatives compose a large family of Co(Ⅱ) SCO-active (SCO=spin-crossover) compounds and the reported cases are mainly built from homoleptic type terpy ligands. Herein we report the SCO properties in three mononuclear cobalt (Ⅱ) complexes constructed from complementary terpy ligand pairing. Their SCO behaviors are largely affected by the substituents of terpy at the 4-position. The archetypical complex 1 and its CF3-substituted one 3 showed a gradual and incomplete spin transition from the low spin state of S=1/2 to the high spin state of S=3/2. The fluorine-substituted complex 2 exhibited a solventdependent spin transition phenomenon. The solvated form which contains three lattice water molecules showed a similar gradually incomplete spin transition. Whereas the entire removal of water molecules resulted in a repeatable thermal hysteresis loop with a width of ca. 50 K. Impressively, the adsorption and desorption of water molecules are reversible in structure and magnetism. In addition, absorption spectroscopy and cyclic voltammetry show that the substituent on the ligands can regulate the electronic structures of the central cobalt ion.
Chemical Modification of Cyclen to Raise the Phase Transition Temperature of Its Perrhenic Compounds
2022, 38(8): 1586-1592
doi: 10.11862/CJIC.2022.162
Abstract:
A methyl-substituted 1, 4, 7, 10-tetraazacyclododecane (N-methyl-1, 4, 7, 10-tetraazacyclododecane, Me-cyclen) was isolated by chemical modification of 1, 4, 7, 10-tetraazacyclododecane (cyclen) with iodomethane. Reactions of cyclen and Me-cyclen with two equivalents of HReO4 led to phase transition molecules (cyclen)(ReO4)2 (1) and (Me -cyclen)(ReO 4)2 (2), respectively. Differential scanning calorimetry and dielectric studies revealed that compounds 1 and 2 show reversible phase transition with temperatures at 324 K for 1 and 384 K for 2. The research results demonstrate a way that the high-temperature phase transition organic-inorganic hybrid materials can be obtained by reducing molecular symmetry through chemical modification of organic amines.
A methyl-substituted 1, 4, 7, 10-tetraazacyclododecane (N-methyl-1, 4, 7, 10-tetraazacyclododecane, Me-cyclen) was isolated by chemical modification of 1, 4, 7, 10-tetraazacyclododecane (cyclen) with iodomethane. Reactions of cyclen and Me-cyclen with two equivalents of HReO4 led to phase transition molecules (cyclen)(ReO4)2 (1) and (Me -cyclen)(ReO 4)2 (2), respectively. Differential scanning calorimetry and dielectric studies revealed that compounds 1 and 2 show reversible phase transition with temperatures at 324 K for 1 and 384 K for 2. The research results demonstrate a way that the high-temperature phase transition organic-inorganic hybrid materials can be obtained by reducing molecular symmetry through chemical modification of organic amines.
2022, 38(8): 1593-1600
doi: 10.11862/CJIC.2022.151
Abstract:
In this work, three water-soluble compounds (tiopronin, cysteamine, and mercaptoglycerol) which contain a thiol group have been used to initiate CO - release from a diiron hexacarbonyl complex [Fe2(μ-SCH2CH(OH)CH2 (OH))2(CO)6] (1). To overcome forming precipitates during the CO-releasing process, we investigated using ethylene- diaminetetraacetic acid (EDTA) as the agent to solubilize products derived from the decomposition. Our results sug- gest that EDTA not only successfully prevents the CO-releasing system from forming precipitates, but also synergis- tically facilitates the CO-release from complex 1. Despite the fact that the chosen ligands possess a thiol functional group, their behaviors in promoting the CO-release from complex 1 are rather different, which can be exploited to tune the CO-releasing rate in potential applications.
In this work, three water-soluble compounds (tiopronin, cysteamine, and mercaptoglycerol) which contain a thiol group have been used to initiate CO - release from a diiron hexacarbonyl complex [Fe2(μ-SCH2CH(OH)CH2 (OH))2(CO)6] (1). To overcome forming precipitates during the CO-releasing process, we investigated using ethylene- diaminetetraacetic acid (EDTA) as the agent to solubilize products derived from the decomposition. Our results sug- gest that EDTA not only successfully prevents the CO-releasing system from forming precipitates, but also synergis- tically facilitates the CO-release from complex 1. Despite the fact that the chosen ligands possess a thiol functional group, their behaviors in promoting the CO-release from complex 1 are rather different, which can be exploited to tune the CO-releasing rate in potential applications.
2022, 38(8): 1601-1608
doi: 10.11862/CJIC.2022.152
Abstract:
A new coordination polymer (CP), [Co5(L)2(μ3‐OH)2(H2O)8]n (1) (H4L=1‐(3, 5‐dicarboxybenzyl)‐1H‐pyrazole‐3, 5‐dicarboxylic acid), was synthesized by hydrothermal method and characterized by single‐crystal X‐ray diffraction, elemental analyses, infrared spectroscopic analysis, and thermogravimetric analysis. The crystallographic analysis indicates that complex 1 crystallizes in the triclinic system with a space group of P1 and exhibits a 3D network structure. Each of the three Co(Ⅱ) ions in the molecule adopts a six‐coordinated pattern, forming a slightly twisted octahedral coordination configuration. The variable temperature magnetic susceptibility measurements indicate that there are antiferromagnetic interactions between the Co(Ⅱ) ions in complex 1. The fluorescence sensing experiments demonstrate that complex 1 exhibits fluorescent quenching to Hg2+ with high sensitivity and selectivity. Additionally, the Co(Ⅱ)‐CP sensor could be successfully used to assay the content of Hg2+ in Yanhe River water samples.
A new coordination polymer (CP), [Co5(L)2(μ3‐OH)2(H2O)8]n (1) (H4L=1‐(3, 5‐dicarboxybenzyl)‐1H‐pyrazole‐3, 5‐dicarboxylic acid), was synthesized by hydrothermal method and characterized by single‐crystal X‐ray diffraction, elemental analyses, infrared spectroscopic analysis, and thermogravimetric analysis. The crystallographic analysis indicates that complex 1 crystallizes in the triclinic system with a space group of P1 and exhibits a 3D network structure. Each of the three Co(Ⅱ) ions in the molecule adopts a six‐coordinated pattern, forming a slightly twisted octahedral coordination configuration. The variable temperature magnetic susceptibility measurements indicate that there are antiferromagnetic interactions between the Co(Ⅱ) ions in complex 1. The fluorescence sensing experiments demonstrate that complex 1 exhibits fluorescent quenching to Hg2+ with high sensitivity and selectivity. Additionally, the Co(Ⅱ)‐CP sensor could be successfully used to assay the content of Hg2+ in Yanhe River water samples.
2022, 38(8): 1609-1622
doi: 10.11862/CJIC.2022.167
Abstract:
A new Ag(Ⅰ) complex, [Ag(Qina) (Tpp)2]·1.5H2O (Qina=2 ‐ quinolinecarboxylate, Tpp=triphenylphosphine), was synthesized and successfully obtained as a single crystal. The structure of the complex was characterized by single‐crystal X‐ray diffraction, IR, NMR, and powder X‐ray diffraction. The results show that the complex belongs to monoclinic crystal system, C2/c space group, and the unit cell parameters are a=3.195 90(13) nm, b= 1.210 96(4) nm, c=2.319 74(7) nm, β=102.166(4)°, V=8.776 0(5) nm3, and Z=8. The supramolecular structures and weak intermolecular force of the complex were deduced by Hirshfeld surface analysis. Meanwhile, the biological activities of the complex were tested by evaluating DNA ‐ binding efficacy, antibacterial activity, and in vitro toxic activity of cancer cells.
A new Ag(Ⅰ) complex, [Ag(Qina) (Tpp)2]·1.5H2O (Qina=2 ‐ quinolinecarboxylate, Tpp=triphenylphosphine), was synthesized and successfully obtained as a single crystal. The structure of the complex was characterized by single‐crystal X‐ray diffraction, IR, NMR, and powder X‐ray diffraction. The results show that the complex belongs to monoclinic crystal system, C2/c space group, and the unit cell parameters are a=3.195 90(13) nm, b= 1.210 96(4) nm, c=2.319 74(7) nm, β=102.166(4)°, V=8.776 0(5) nm3, and Z=8. The supramolecular structures and weak intermolecular force of the complex were deduced by Hirshfeld surface analysis. Meanwhile, the biological activities of the complex were tested by evaluating DNA ‐ binding efficacy, antibacterial activity, and in vitro toxic activity of cancer cells.
2022, 38(8): 1623-1632
doi: 10.11862/CJIC.2022.168
Abstract:
Herein, a mitochondria-targeting fluorescent probe Cou-Py has been designed and synthesized for sensing hypochlorite (ClO-). Cou-Py exhibited very weak fluorescence due to the C=N isomerization of the oxime group in the excited state and recovers fluorescence within 5 s based on a ClO--triggered deoximation reaction. Additionally, Cou-Py showed high selectivity toward ClO- over other reactive oxygen species (ROS) and owned a low detection limit (6.87 nmol·L-1) for ClO-. Importantly, Cou-Py has been successfully employed for visualizing ClO- in the mitochondria of MCF-7 cells as well as zebrafish larvae.
Herein, a mitochondria-targeting fluorescent probe Cou-Py has been designed and synthesized for sensing hypochlorite (ClO-). Cou-Py exhibited very weak fluorescence due to the C=N isomerization of the oxime group in the excited state and recovers fluorescence within 5 s based on a ClO--triggered deoximation reaction. Additionally, Cou-Py showed high selectivity toward ClO- over other reactive oxygen species (ROS) and owned a low detection limit (6.87 nmol·L-1) for ClO-. Importantly, Cou-Py has been successfully employed for visualizing ClO- in the mitochondria of MCF-7 cells as well as zebrafish larvae.
2022, 38(8): 1633-1642
doi: 10.11862/CJIC.2022.164
Abstract:
A new inorganic-organic hybrid (H2L)2(HL)2L(PMo12O40)2·2H2O (marked as PMo12) derived from the selfassembling of N-containing ligands L (L=1, 3-bis(1-imidazolyl) propane) and inorganic polyoxometalates (H3PMo12O40) have been hydrothermally synthesized. The compound was characterized by infrared spectroscopy (IR), thermal gravity (TG), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and single-crystal X-ray diffraction. Studies on single-crystal X-ray diffraction reveal that the compound displays 3D structures. Then a bisphenol A (BPA) electrochemical sensor based on PMo12 and multi-walled carbon nanotubes (MWCNTs) has been successfully constructed. The detection limit was 0.5 μmol·L-1 (S/N=3) in a range of 1-20 μmol·L-1, and the sensor had good anti-interference and stability.
A new inorganic-organic hybrid (H2L)2(HL)2L(PMo12O40)2·2H2O (marked as PMo12) derived from the selfassembling of N-containing ligands L (L=1, 3-bis(1-imidazolyl) propane) and inorganic polyoxometalates (H3PMo12O40) have been hydrothermally synthesized. The compound was characterized by infrared spectroscopy (IR), thermal gravity (TG), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and single-crystal X-ray diffraction. Studies on single-crystal X-ray diffraction reveal that the compound displays 3D structures. Then a bisphenol A (BPA) electrochemical sensor based on PMo12 and multi-walled carbon nanotubes (MWCNTs) has been successfully constructed. The detection limit was 0.5 μmol·L-1 (S/N=3) in a range of 1-20 μmol·L-1, and the sensor had good anti-interference and stability.
2022, 38(8): 1643-1654
doi: 10.11862/CJIC.2022.160
Abstract:
The performance of energy storage materials is substantially dependent on their nanostructures. Herein, Ni-1, 3, 5-benzenetricarboxylate (Ni-BTC) and Ni-1, 4-benzoate (Ni-BDC) metal-organic frameworks with different morphologies were controllably synthesized using a facile solvothermal method by simply adjusting the solvent, including Ni-BTC blocks, nanospheres, and double-pyramid structures and Ni-BDC nanosheets, nanoflowers and blocks structures, and their electrochemical performance as supercapacitors was thoroughly investigated. Moreover, our study showed that the supercapacitor performance of the electrode materials obtained for Ni-BTC and Ni-BDC electrodes in pure N, N-dimethylformamide (DMF) solvent was better than those prepared with pure ethanol (EtOH) and DMF/EtOH (50:50, V/V) as solvent.
The performance of energy storage materials is substantially dependent on their nanostructures. Herein, Ni-1, 3, 5-benzenetricarboxylate (Ni-BTC) and Ni-1, 4-benzoate (Ni-BDC) metal-organic frameworks with different morphologies were controllably synthesized using a facile solvothermal method by simply adjusting the solvent, including Ni-BTC blocks, nanospheres, and double-pyramid structures and Ni-BDC nanosheets, nanoflowers and blocks structures, and their electrochemical performance as supercapacitors was thoroughly investigated. Moreover, our study showed that the supercapacitor performance of the electrode materials obtained for Ni-BTC and Ni-BDC electrodes in pure N, N-dimethylformamide (DMF) solvent was better than those prepared with pure ethanol (EtOH) and DMF/EtOH (50:50, V/V) as solvent.
2022, 38(8): 1655-1662
doi: 10.11862/CJIC.2022.154
Abstract:
The nanocomposites of LiAlO2 coated Si nanoparticles (Si@LiAlO2) have been successfully synthesized by the solvothermal method and heat treatment. Si@LiAlO2 formed a dendritic structure with openings and channels between the dendrites. As anode material for lithiumion batteries, electrochemical results showed that as-prepared Si@LiAlO2 nanocomposite achieved a reversible capacity of 364.1 mAh·g-1 after 100 cycles at a current density of 100 mA·g-1. The superior cycling performance is attributed to the nanocomposite dendritic structure, in which nanosized Si particles shorten the diffusion path of lithium ions and the LiAlO2 coating, the voids, and openings between the dendrites help buffer volume changes during charging and discharging.
The nanocomposites of LiAlO2 coated Si nanoparticles (Si@LiAlO2) have been successfully synthesized by the solvothermal method and heat treatment. Si@LiAlO2 formed a dendritic structure with openings and channels between the dendrites. As anode material for lithiumion batteries, electrochemical results showed that as-prepared Si@LiAlO2 nanocomposite achieved a reversible capacity of 364.1 mAh·g-1 after 100 cycles at a current density of 100 mA·g-1. The superior cycling performance is attributed to the nanocomposite dendritic structure, in which nanosized Si particles shorten the diffusion path of lithium ions and the LiAlO2 coating, the voids, and openings between the dendrites help buffer volume changes during charging and discharging.
2022, 38(8): 1663-1671
doi: 10.11862/CJIC.2022.157
Abstract:
The 2, 6-lutidine- 3, 5-dicarboxylic acid (H2L1) was used as the main ligand, 1, 10-phenanthroline (L2) as the auxiliary ligand, and the complexes [Dy2(L1)3 (L2)2]n (1), {[Tb2(L1)3 (L2)2]·5H2O}n (2), and {[Eu2(L1)3(L2)2]·5H2O}n (3) were synthesized by solvothermal reaction with dysprosium nitrate pentahydrate, terbium nitrate hexahydrate, and europium nitrate hexahydrate, respectively. The structures and properties of the complexes were characterized by single - crystal X - ray diffraction, IR, fluorescence spectroscopy, and thermogravimetric analysis. The results show that complexes 1-3 all use rare-earth ions as metal nodes to connect with ligands L12- and L2 to form an infinitely extending 1D chain structure.
The 2, 6-lutidine- 3, 5-dicarboxylic acid (H2L1) was used as the main ligand, 1, 10-phenanthroline (L2) as the auxiliary ligand, and the complexes [Dy2(L1)3 (L2)2]n (1), {[Tb2(L1)3 (L2)2]·5H2O}n (2), and {[Eu2(L1)3(L2)2]·5H2O}n (3) were synthesized by solvothermal reaction with dysprosium nitrate pentahydrate, terbium nitrate hexahydrate, and europium nitrate hexahydrate, respectively. The structures and properties of the complexes were characterized by single - crystal X - ray diffraction, IR, fluorescence spectroscopy, and thermogravimetric analysis. The results show that complexes 1-3 all use rare-earth ions as metal nodes to connect with ligands L12- and L2 to form an infinitely extending 1D chain structure.
