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2019 Volume 35 Issue 11
2019, 35(11): 1905-1920
doi: 10.11862/CJIC.2019.227
Abstract:
Dye-sensitized solar cells (DSSCs) are the third generation photovoltaic cells developed by Michael Grätzel et al. It has the advantages of low preparation cost, simple manufacturing process, adjustable optical performance and high photoelectric conversion efficiency. Photosensitizer is the core component of DSSCs, transmitting electrons to semiconductor conduction band by absorbing visible light, which is very important to the electronic cycle of the whole battery. Noble metal complexes such as N719 are widely used as photosensitizers, but they are very expensive and difficult to realize large-scale industrialization. Therefore, the search for low-cost non-noble metal photosensitizers is a challenge in this field. Polyoxometalates (POMs) are a kind of molecular-based nanomaterials with nano-size and molecular inorganic semiconductor materials. The oxygen-enriched surface of polyoxometalates can be activated and modified. The absorption spectrum can cover the visible and even near infrared regions. It has appropriate redox potential, good thermal stability and solubility. A series of studies have shown that surface polyoxometalates can be used as photosensitizers in DSSCs. In this paper, based on the work accumulated by our research group in the field of POMs and solar cells over the years and the work of domestic and foreign peer experts, the application of polyoxometalates-based photosensitizers in DSSCs is reviewed in detail. Firstly, the research significance of DSSCs, the introduction of polyoxometalates, the measurement and adjustment of energy levels of polyoxometalates are described. After that, we mainly reviewed the use of polyoxometalates as photosensitizers and co-sensitizers in DSSCs. Finally, we summarized and prospected the development prospects of polyoxometalates photosensitizers in the field of DSSCs. This review may be of interest to researchers in the fields of polyoxometalates chemistry, material chemistry and emerging interdisciplinary disciplines. It also provides new ideas for the research of photosensitizers for solar cells.
Dye-sensitized solar cells (DSSCs) are the third generation photovoltaic cells developed by Michael Grätzel et al. It has the advantages of low preparation cost, simple manufacturing process, adjustable optical performance and high photoelectric conversion efficiency. Photosensitizer is the core component of DSSCs, transmitting electrons to semiconductor conduction band by absorbing visible light, which is very important to the electronic cycle of the whole battery. Noble metal complexes such as N719 are widely used as photosensitizers, but they are very expensive and difficult to realize large-scale industrialization. Therefore, the search for low-cost non-noble metal photosensitizers is a challenge in this field. Polyoxometalates (POMs) are a kind of molecular-based nanomaterials with nano-size and molecular inorganic semiconductor materials. The oxygen-enriched surface of polyoxometalates can be activated and modified. The absorption spectrum can cover the visible and even near infrared regions. It has appropriate redox potential, good thermal stability and solubility. A series of studies have shown that surface polyoxometalates can be used as photosensitizers in DSSCs. In this paper, based on the work accumulated by our research group in the field of POMs and solar cells over the years and the work of domestic and foreign peer experts, the application of polyoxometalates-based photosensitizers in DSSCs is reviewed in detail. Firstly, the research significance of DSSCs, the introduction of polyoxometalates, the measurement and adjustment of energy levels of polyoxometalates are described. After that, we mainly reviewed the use of polyoxometalates as photosensitizers and co-sensitizers in DSSCs. Finally, we summarized and prospected the development prospects of polyoxometalates photosensitizers in the field of DSSCs. This review may be of interest to researchers in the fields of polyoxometalates chemistry, material chemistry and emerging interdisciplinary disciplines. It also provides new ideas for the research of photosensitizers for solar cells.
2019, 35(11): 1921-1933
doi: 10.11862/CJIC.2019.237
Abstract:
Metal-organic frameworks (MOFs) are porous coordination polymers with periodic network structures constructed from metal ions/clusters and organic ligands through coordination interactions. Typically, MOFs always have advantageous features of regular pore structures, large specific surface areas, high porosity, designable structures and modifiable pore walls. By virtue of these unique characteristics, the study of MOFs is moving from the coordination chemistry to a broad range of academic disciplines, which is becoming one of the hot topics in intercrossed multi-disciplines. Recent studies show that MOFs are promising candidate precursors for functional carbon materials. On the one hand, the specific surface area and porosity are still kept in the MOF-derived carbon materials and various heteroatoms (e.g., N, S, P, and B) can be uniformly doped into the prepared carbon frameworks. On the other hand, the composition, morphology and size of the resultant carbon materials can also be tuned precisely by choosing the appropriate MOF precursors. Currently, MOF-derived hollow carbon materials have drawn widespread attention, mainly because the hollow structures are favorable for alleviating the volume change and impact in the electrochemical processes. Furthermore, hollow structures are more likely to achieve maximum performance benefiting from the fast mass transport and full exposure of active sites. As a result of these properties, MOF-derived hollow carbon materials have shown many applications in a variety of energy devices and areas, such as secondary batteries, capacitors, and electrochemical catalysis. Here, a comprehensive overview of recent developments of MOF-derived hollow carbon materials is provided, including their preparation processes and applications in lithium-ion batteries, lithium-sulfur/selenium batteries, sodium-ion batteries, supercapacitors, and oxygen reduction reaction. Finally, the current challenges and development trends in the future of MOF-derived hollow carbon materials are also discussed.
Metal-organic frameworks (MOFs) are porous coordination polymers with periodic network structures constructed from metal ions/clusters and organic ligands through coordination interactions. Typically, MOFs always have advantageous features of regular pore structures, large specific surface areas, high porosity, designable structures and modifiable pore walls. By virtue of these unique characteristics, the study of MOFs is moving from the coordination chemistry to a broad range of academic disciplines, which is becoming one of the hot topics in intercrossed multi-disciplines. Recent studies show that MOFs are promising candidate precursors for functional carbon materials. On the one hand, the specific surface area and porosity are still kept in the MOF-derived carbon materials and various heteroatoms (e.g., N, S, P, and B) can be uniformly doped into the prepared carbon frameworks. On the other hand, the composition, morphology and size of the resultant carbon materials can also be tuned precisely by choosing the appropriate MOF precursors. Currently, MOF-derived hollow carbon materials have drawn widespread attention, mainly because the hollow structures are favorable for alleviating the volume change and impact in the electrochemical processes. Furthermore, hollow structures are more likely to achieve maximum performance benefiting from the fast mass transport and full exposure of active sites. As a result of these properties, MOF-derived hollow carbon materials have shown many applications in a variety of energy devices and areas, such as secondary batteries, capacitors, and electrochemical catalysis. Here, a comprehensive overview of recent developments of MOF-derived hollow carbon materials is provided, including their preparation processes and applications in lithium-ion batteries, lithium-sulfur/selenium batteries, sodium-ion batteries, supercapacitors, and oxygen reduction reaction. Finally, the current challenges and development trends in the future of MOF-derived hollow carbon materials are also discussed.
2019, 35(11): 1934-1956
doi: 10.11862/CJIC.2019.230
Abstract:
Due to the advantages of their easy regulated composition, structure and size along with the excellent electronic storage and redox activity, polyoxometalates have broad application prospects in the fields of catalytic, photoelectric, and magnetic, etc. It is much favored by chemists especially in the field of catalysis. Polyoxometalates are easy to deactivate due to the agglomeration in the catalytic process, and its specific surface area is low. The introduction of polyoxometalates into a well-structured, porous framework material can better solve the above problems. Therefore, these materials have become one of the research hotspots in the field of polyoxometalates chemistry. In this paper, the polyoxometalate-based host-guest framework materials are classified according to their synthetic methods, namely in situ synthesis, impregnation synthesis and mechanical grinding synthesis, and their advantages or disadvantages are discussed separately. We further summarize the performance and application of these materials in the fields of catalysis, dye adsorption and degradation, proton conduction and photoelectric sensing, and prospect its future development trend.
Due to the advantages of their easy regulated composition, structure and size along with the excellent electronic storage and redox activity, polyoxometalates have broad application prospects in the fields of catalytic, photoelectric, and magnetic, etc. It is much favored by chemists especially in the field of catalysis. Polyoxometalates are easy to deactivate due to the agglomeration in the catalytic process, and its specific surface area is low. The introduction of polyoxometalates into a well-structured, porous framework material can better solve the above problems. Therefore, these materials have become one of the research hotspots in the field of polyoxometalates chemistry. In this paper, the polyoxometalate-based host-guest framework materials are classified according to their synthetic methods, namely in situ synthesis, impregnation synthesis and mechanical grinding synthesis, and their advantages or disadvantages are discussed separately. We further summarize the performance and application of these materials in the fields of catalysis, dye adsorption and degradation, proton conduction and photoelectric sensing, and prospect its future development trend.
2019, 35(11): 1957-1973
doi: 10.11862/CJIC.2019.250
Abstract:
In recent years, with the development of material science, organic-inorganic composites with excellent mechanical properties and specific functions have become a hot research topic. The natural processes of biomineralization have produced widely distributed biominerals with a wide variety of unique composite materials and excellent mechanical properties, such as tooth, bone, pearl, shellfish, sea urchin thorn, marine bloodworm jaw. The characteristics of biominerals structure and mineralization mechanisms in natural composite materials provide a theoretical basis for biomimetic design and synthesis of materials with specific structure, specific function and excellent mechanical properties. By learning the principle of biomineralization, biomimetic mineralization is a crystallization process, by which an organic matrix regulates the nucleation of inorganic minerals, and grows into organic-inorganic hybrid minerals with ordered structures and advanced functions. This paper reviews the natural reinforced composite materials with high hardness and high toughness fabricated by natural biomineralization process, and a number of artificial organic-inorganic reinforced composite materials inspired by the reinforcing and toughening mechanisms in biomineralization.
In recent years, with the development of material science, organic-inorganic composites with excellent mechanical properties and specific functions have become a hot research topic. The natural processes of biomineralization have produced widely distributed biominerals with a wide variety of unique composite materials and excellent mechanical properties, such as tooth, bone, pearl, shellfish, sea urchin thorn, marine bloodworm jaw. The characteristics of biominerals structure and mineralization mechanisms in natural composite materials provide a theoretical basis for biomimetic design and synthesis of materials with specific structure, specific function and excellent mechanical properties. By learning the principle of biomineralization, biomimetic mineralization is a crystallization process, by which an organic matrix regulates the nucleation of inorganic minerals, and grows into organic-inorganic hybrid minerals with ordered structures and advanced functions. This paper reviews the natural reinforced composite materials with high hardness and high toughness fabricated by natural biomineralization process, and a number of artificial organic-inorganic reinforced composite materials inspired by the reinforcing and toughening mechanisms in biomineralization.
2019, 35(11): 1987-1998
doi: 10.11862/CJIC.2019.246
Abstract:
Similar to single-molecular magnets (SMMs), single-molecule toroics (SMTs) are defined as molecules with toroidal magnetic bi-stability. This type of compounds is characterized by the "vortex" spatial distribution of the weakly coupled magnetic moments, resulting in zero total magnetic momentum, but a non-vanishing toroidal magnetic moment. SMTs offer broad application prospects in quantum computing and information storage, and can also be used as a multiferroic materials with magneto-electric coupling effect. Great effort has been paid in the synthesis of SMTs since the first observation of the SMT behavior of typical [Dy3] molecules, and researchers are committed to the investigation of SMTs with enhanced molecular toroidal magnetization. In this review, several representative examples with SMT behavior will be addressed to provide a down to date overview of the burgeoning SMT complexes reported in recent years. Accordingly, we aim to illuminate the factors governing the arrangement of toroidal magnetic moments and the synthetic strategy on designing SMTs, and ultimately enlighten the study of SMTs with enhanced toroidal magnetization.
Similar to single-molecular magnets (SMMs), single-molecule toroics (SMTs) are defined as molecules with toroidal magnetic bi-stability. This type of compounds is characterized by the "vortex" spatial distribution of the weakly coupled magnetic moments, resulting in zero total magnetic momentum, but a non-vanishing toroidal magnetic moment. SMTs offer broad application prospects in quantum computing and information storage, and can also be used as a multiferroic materials with magneto-electric coupling effect. Great effort has been paid in the synthesis of SMTs since the first observation of the SMT behavior of typical [Dy3] molecules, and researchers are committed to the investigation of SMTs with enhanced molecular toroidal magnetization. In this review, several representative examples with SMT behavior will be addressed to provide a down to date overview of the burgeoning SMT complexes reported in recent years. Accordingly, we aim to illuminate the factors governing the arrangement of toroidal magnetic moments and the synthetic strategy on designing SMTs, and ultimately enlighten the study of SMTs with enhanced toroidal magnetization.
2019, 35(11): 1999-2012
doi: 10.11862/CJIC.2019.239
Abstract:
Zinc ion recharge battery is a promising energy storage device with excellent charge-discharge performance, high power density and energy density, low cost, high safety and environment friendly. Metal zinc has been regarded as an ideal anode material for aqueous recharge batteries due to its excellent conductivity, relatively low redox potential, high theoretic capacity and low cost. As the negative electrode material of zinc ion recharge battery, metal zinc has some problems such as dendrite growth, corrosion and passivation, which result in the limit of the reversible capacity and cycle life of zinc ion recharge battery. However, the performance of zinc anode can be improved by controlling its morphology and surface modification. Herein, we review the development of anode materials for zinc ion batteries, including metal zinc anode, composite zinc anode and zinc alloy, and the prospects for zinc anode.
Zinc ion recharge battery is a promising energy storage device with excellent charge-discharge performance, high power density and energy density, low cost, high safety and environment friendly. Metal zinc has been regarded as an ideal anode material for aqueous recharge batteries due to its excellent conductivity, relatively low redox potential, high theoretic capacity and low cost. As the negative electrode material of zinc ion recharge battery, metal zinc has some problems such as dendrite growth, corrosion and passivation, which result in the limit of the reversible capacity and cycle life of zinc ion recharge battery. However, the performance of zinc anode can be improved by controlling its morphology and surface modification. Herein, we review the development of anode materials for zinc ion batteries, including metal zinc anode, composite zinc anode and zinc alloy, and the prospects for zinc anode.
2019, 35(11): 2013-2030
doi: 10.11862/CJIC.2019.232
Abstract:
Single-molecule magnets have attracted extensive attention for their potential applications in high-density data storage, molecular spintronics and quantum information processing. Single-molecule magnets with single spin-carrier center, denoted single-ion magnets, feature simple structures, outstanding designability and advantages for studying magneto-structure correlation. Typical single-ion magnets and their magnetic relaxation dynamics are reviewed in this paper.
Single-molecule magnets have attracted extensive attention for their potential applications in high-density data storage, molecular spintronics and quantum information processing. Single-molecule magnets with single spin-carrier center, denoted single-ion magnets, feature simple structures, outstanding designability and advantages for studying magneto-structure correlation. Typical single-ion magnets and their magnetic relaxation dynamics are reviewed in this paper.
2019, 35(11): 1974-1986
doi: 10.11862/CJIC.2019.231
Abstract:
Acidic pH in tumor tissues provides a powerful platform for accurate tumor diagnosis and efficient therapy. The pH-sensitive iridium, ruthenium and platinum metal complexes have attracted increasing attention due to their high physicochemical stability, favorable spectral properties and tumor targetability. In this review, we summarize formation mechanisms of the acidic tumor microenvironment and recent advances on the acidic microenvironment-sensitive metal complexes of iridium, ruthenium and platinum for tumor imaging chemotherapy agents.
Acidic pH in tumor tissues provides a powerful platform for accurate tumor diagnosis and efficient therapy. The pH-sensitive iridium, ruthenium and platinum metal complexes have attracted increasing attention due to their high physicochemical stability, favorable spectral properties and tumor targetability. In this review, we summarize formation mechanisms of the acidic tumor microenvironment and recent advances on the acidic microenvironment-sensitive metal complexes of iridium, ruthenium and platinum for tumor imaging chemotherapy agents.
2019, 35(11): 2031-2037
doi: 10.11862/CJIC.2019.223
Abstract:
Iron is the most abundant essential transition metal in human body, and iron disorder has been reported to be associated with many diseases. Therefore, the development of fluorescent probes for Fe2+/Fe3+ imaging and offering spatial-temporal information of Fe2+/Fe3+ is of great significance. We chose BODIPY with good stability and high quantum yield as the fluorophore, and the terpyridine with high binding ability to Fe2+ as a chelating group. The probe BTPY for Fe2+ was constructed by integrating BODIPY with terpyridine at α-position by a vinyl group to form a large conjugated system. The NIR emission at 678 nm and the visible excitation at 582 nm suggest that this probe has the potential for in vivo imaging in animal model. BTPY was able to selectively bind Fe2+/Fe3+ with a bathochromic absorption shift from 573 to 607 nm and the solution color changed from red to pale blue. In addition, Fe2+ caused BTPY fluorescence quenching while Fe3+ did not significantly affect the fluorescence. Combining with the spectra change of absorption and emission, this probe can be used for visual detection of iron ions and is able to distinguish Fe2+ from Fe3+.
Iron is the most abundant essential transition metal in human body, and iron disorder has been reported to be associated with many diseases. Therefore, the development of fluorescent probes for Fe2+/Fe3+ imaging and offering spatial-temporal information of Fe2+/Fe3+ is of great significance. We chose BODIPY with good stability and high quantum yield as the fluorophore, and the terpyridine with high binding ability to Fe2+ as a chelating group. The probe BTPY for Fe2+ was constructed by integrating BODIPY with terpyridine at α-position by a vinyl group to form a large conjugated system. The NIR emission at 678 nm and the visible excitation at 582 nm suggest that this probe has the potential for in vivo imaging in animal model. BTPY was able to selectively bind Fe2+/Fe3+ with a bathochromic absorption shift from 573 to 607 nm and the solution color changed from red to pale blue. In addition, Fe2+ caused BTPY fluorescence quenching while Fe3+ did not significantly affect the fluorescence. Combining with the spectra change of absorption and emission, this probe can be used for visual detection of iron ions and is able to distinguish Fe2+ from Fe3+.
2019, 35(11): 2038-2044
doi: 10.11862/CJIC.2019.228
Abstract:
The reactions of dipyridin-2-yl-(4-(2-pyridin-4-yl-vinyl)-phenyl)-amine (ppvppa) with various silver(Ⅰ) salts afforded three one-dimensional (1D) coordination polymers {[Ag(ppvppa)]BF4}n (1), {[Ag(ppvppa)]PF6}n (2) and {[Ag(ppvppa)]NO3}n (3). When analogous reactions of ppvppa with Ni(Ⅱ) salt was carried out under solvothermal conditions, another 1D coordination polymer {[Ni(ppvppa)(2, 3-NDC)(H2O)]·2H2O}n (4) was obtained. Complexes 1~4 were characterized by elemental analysis, infrared spectrum (IR), thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD) and single crystal X-ray diffraction. Complexes 1~3 have similar 1D cationic chain structures in which the dimeric[Ag(ppvppa)]2 units are interconnected by ppvppa ligands. Complex 4 holds a double chain structure in which the[Ni2(ppvppa)2(H2O)2] units are interlinked by pairs of 2, 3-NDC ligands. In the solid state, Ag(Ⅰ)-based complexes 1~3 showed good luminescent properties while no luminescence was observed for Ni(Ⅱ)-based complex 4. Complexes 1 and 4 as representative samples showed relatively prompt, rapid anodic photocurrent responses, which were steady and reproducible after ten on/off cycles. The photocurrent values were calculated to be 2 μA for 1 and 6 μA for 4, respectively, which were greater than that observed for a blank ITO electrode.
The reactions of dipyridin-2-yl-(4-(2-pyridin-4-yl-vinyl)-phenyl)-amine (ppvppa) with various silver(Ⅰ) salts afforded three one-dimensional (1D) coordination polymers {[Ag(ppvppa)]BF4}n (1), {[Ag(ppvppa)]PF6}n (2) and {[Ag(ppvppa)]NO3}n (3). When analogous reactions of ppvppa with Ni(Ⅱ) salt was carried out under solvothermal conditions, another 1D coordination polymer {[Ni(ppvppa)(2, 3-NDC)(H2O)]·2H2O}n (4) was obtained. Complexes 1~4 were characterized by elemental analysis, infrared spectrum (IR), thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD) and single crystal X-ray diffraction. Complexes 1~3 have similar 1D cationic chain structures in which the dimeric[Ag(ppvppa)]2 units are interconnected by ppvppa ligands. Complex 4 holds a double chain structure in which the[Ni2(ppvppa)2(H2O)2] units are interlinked by pairs of 2, 3-NDC ligands. In the solid state, Ag(Ⅰ)-based complexes 1~3 showed good luminescent properties while no luminescence was observed for Ni(Ⅱ)-based complex 4. Complexes 1 and 4 as representative samples showed relatively prompt, rapid anodic photocurrent responses, which were steady and reproducible after ten on/off cycles. The photocurrent values were calculated to be 2 μA for 1 and 6 μA for 4, respectively, which were greater than that observed for a blank ITO electrode.
2019, 35(11): 2045-2050
doi: 10.11862/CJIC.2019.233
Abstract:
Core-shell-structured MoOx/C microspheres were prepared through the calcination of a MoO3/resin precursor obtained by a hydrothermal method. Upon calcination, carbonized resin reduced hexagonal MoO3 into monoclinic MoO2. A small amount of monoclinic MoO2 was further oxidized to orthorhombic MoO3, forming core-shell MoOx/C microspheres. The hierarchical MoOx/C microspheres showed excellent electrochemical lithium storage performance when used as an anode material for lithium-ion batteries. High reversible capacities of 640.6 mAh· g-1 was maintained at 100 mA·g-1 after 100 cycles, demonstrating the high reversible capacity and excellent cycle performance of the MoOx/C microspheres for lithium storage.
Core-shell-structured MoOx/C microspheres were prepared through the calcination of a MoO3/resin precursor obtained by a hydrothermal method. Upon calcination, carbonized resin reduced hexagonal MoO3 into monoclinic MoO2. A small amount of monoclinic MoO2 was further oxidized to orthorhombic MoO3, forming core-shell MoOx/C microspheres. The hierarchical MoOx/C microspheres showed excellent electrochemical lithium storage performance when used as an anode material for lithium-ion batteries. High reversible capacities of 640.6 mAh· g-1 was maintained at 100 mA·g-1 after 100 cycles, demonstrating the high reversible capacity and excellent cycle performance of the MoOx/C microspheres for lithium storage.
2019, 35(11): 2051-2056
doi: 10.11862/CJIC.2019.242
Abstract:
SAPO-11 molecular sieves were synthesized by adding seed crystals to reduce the amount of organic amine template. The morphology of crystal and the degree of crystallinity were the best by adding 4% crystal seed and the ratio of template to Al2O3 (ntemplate/nAl2O3) of 0.6 when other technological conditions remained unchanged. Using castor oil hydrodeoxidized production (HDO) as raw material, the selectivity of the catalyst at 623 K was 66.1% and the conversion rate was 79.8%.
SAPO-11 molecular sieves were synthesized by adding seed crystals to reduce the amount of organic amine template. The morphology of crystal and the degree of crystallinity were the best by adding 4% crystal seed and the ratio of template to Al2O3 (ntemplate/nAl2O3) of 0.6 when other technological conditions remained unchanged. Using castor oil hydrodeoxidized production (HDO) as raw material, the selectivity of the catalyst at 623 K was 66.1% and the conversion rate was 79.8%.
Co-pyrolysis Characteristics of Sewage Sludge and Vinegar Residue and Migration Law of Alkali Metals
2019, 35(11): 2057-2065
doi: 10.11862/CJIC.2019.252
Abstract:
The synergetic effects during co-pyrolysis of sewage sludge and vinegar residue were investigated concerning the product distribution and reaction kinetics by thermogravimetric analysis and vacuum fixed bed reactor, and the alkali metals migration rules was analyzed by atomic absorption spectrophotometer. Results indicated that there is a significantly synergetic effect during the co-pyrolysis process. Kinetics was analyzed by Kissinger-Akahira-Sunose(KAS) method, and the activation energies needed were 35.38%~29.49% decreased for the decomposition of mixture compared with theoretical calculation and the devolatilization index were 3.5×10-8 lower than calculation. The synergetic effect resulted in an increase in gas yields but a decrease in char yield and liquid. The presence of vinegar residue promoted the devolatilization of sewage sludge, improved the syngas (H2+CO) content in the gaseous products, and promoted the cracking reactions of large aromatic rings in the resulted char. In addition, the co-pyrolysis process has a good effect on increasing phenols and esters of its bio-oil. At the end of pyrolysis process, the exhalation rate of alkali elements reached 79.19%~86.73%.
The synergetic effects during co-pyrolysis of sewage sludge and vinegar residue were investigated concerning the product distribution and reaction kinetics by thermogravimetric analysis and vacuum fixed bed reactor, and the alkali metals migration rules was analyzed by atomic absorption spectrophotometer. Results indicated that there is a significantly synergetic effect during the co-pyrolysis process. Kinetics was analyzed by Kissinger-Akahira-Sunose(KAS) method, and the activation energies needed were 35.38%~29.49% decreased for the decomposition of mixture compared with theoretical calculation and the devolatilization index were 3.5×10-8 lower than calculation. The synergetic effect resulted in an increase in gas yields but a decrease in char yield and liquid. The presence of vinegar residue promoted the devolatilization of sewage sludge, improved the syngas (H2+CO) content in the gaseous products, and promoted the cracking reactions of large aromatic rings in the resulted char. In addition, the co-pyrolysis process has a good effect on increasing phenols and esters of its bio-oil. At the end of pyrolysis process, the exhalation rate of alkali elements reached 79.19%~86.73%.
2019, 35(11): 2066-2072
doi: 10.11862/CJIC.2019.234
Abstract:
Two binuclear Fe(Ⅱ) complexes of bis-pyridylhydrazone Schiff base ligands HLx (x=1, 2) have been successfully synthesized and characterized by infrared spectroscopy, X-ray single crystal diffraction and magnetic susceptibility measurements. Single-crystal structural determinations reveal that the Fe(Ⅱ) ion is chelated by two pyridylhydrazone Schiff base ligands to form a FeN4O2 distorted octahedral structure and four free perchlorates serve as charge balancing anions. Intermolecular π…π stacking is present in the complexes, connecting adjacent[Fe2(HLx)2]4+ cations to form supramolecular chains. Magnetic susceptibility measurement shows that the complexes are both in the high-spin state, meanwhile complex 2 exhibits weak intermolecular ferromagnetic coupling.
Two binuclear Fe(Ⅱ) complexes of bis-pyridylhydrazone Schiff base ligands HLx (x=1, 2) have been successfully synthesized and characterized by infrared spectroscopy, X-ray single crystal diffraction and magnetic susceptibility measurements. Single-crystal structural determinations reveal that the Fe(Ⅱ) ion is chelated by two pyridylhydrazone Schiff base ligands to form a FeN4O2 distorted octahedral structure and four free perchlorates serve as charge balancing anions. Intermolecular π…π stacking is present in the complexes, connecting adjacent[Fe2(HLx)2]4+ cations to form supramolecular chains. Magnetic susceptibility measurement shows that the complexes are both in the high-spin state, meanwhile complex 2 exhibits weak intermolecular ferromagnetic coupling.
2019, 35(11): 2073-2077
doi: 10.11862/CJIC.2019.249
Abstract:
HfO2 nanoparticles with size of 4 nm were prepared through solvothermal process, and the lattice thermal expansion of nano and bulk HfO2 was studied by X-ray atom pair distribution function (PDF) method. The results showed that in nanoscale HfO2, the lattice thermal expansion along a and c axis increased, while b axis slightly decreased, and eventually volumetric thermal expansion increased. Meanwhile, the anisotropy of the thermal expansion of the nanosized HfO2 is larger than that of the bulk. The origin was that size effect induced a large structural distortion, mainly the reduction of the next nearest neighbor Hf-O-Hf bond angle, and then heating process triggered the relaxation of the distortion to equilibrium position.
HfO2 nanoparticles with size of 4 nm were prepared through solvothermal process, and the lattice thermal expansion of nano and bulk HfO2 was studied by X-ray atom pair distribution function (PDF) method. The results showed that in nanoscale HfO2, the lattice thermal expansion along a and c axis increased, while b axis slightly decreased, and eventually volumetric thermal expansion increased. Meanwhile, the anisotropy of the thermal expansion of the nanosized HfO2 is larger than that of the bulk. The origin was that size effect induced a large structural distortion, mainly the reduction of the next nearest neighbor Hf-O-Hf bond angle, and then heating process triggered the relaxation of the distortion to equilibrium position.
2019, 35(11): 2078-2082
doi: 10.11862/CJIC.2019.251
Abstract:
The catalytic activity of metal catalysts is closely related to its coordination unsaturation:The higher coordination unsaturation is, the better catalytic effect is in general. The single-atom catalyst (SAC or ad-atom) model has the smallest coordination number on metal surface and thus exhibits high catalytic activity, but the stability of SAC still need to be studied in detail. In this work, we used LAMMPS (large-scale atomic/molecular massively parallel simulator) for large-scale molecular dynamics simulation based on Reactive Force Field (ReaxFF) to study the thermal stability of the single atom model. The simulation results show that only Fe1/Fe(100) catalyst can be stable at high temperature (>500 K), while other SAC models will occur that single atom aggregates to form large nanoparticles or moves to subsurface as temperature increases. In the meanwhile, the dynamic behavior of Ni1/Ni(111) catalyst under H2 and O2 atmosphere was also studied was found that compared with simulation results in vacuum, the H2 and O2 atmosphere improved the stability of the catalyst to some extent.
The catalytic activity of metal catalysts is closely related to its coordination unsaturation:The higher coordination unsaturation is, the better catalytic effect is in general. The single-atom catalyst (SAC or ad-atom) model has the smallest coordination number on metal surface and thus exhibits high catalytic activity, but the stability of SAC still need to be studied in detail. In this work, we used LAMMPS (large-scale atomic/molecular massively parallel simulator) for large-scale molecular dynamics simulation based on Reactive Force Field (ReaxFF) to study the thermal stability of the single atom model. The simulation results show that only Fe1/Fe(100) catalyst can be stable at high temperature (>500 K), while other SAC models will occur that single atom aggregates to form large nanoparticles or moves to subsurface as temperature increases. In the meanwhile, the dynamic behavior of Ni1/Ni(111) catalyst under H2 and O2 atmosphere was also studied was found that compared with simulation results in vacuum, the H2 and O2 atmosphere improved the stability of the catalyst to some extent.
2019, 35(11): 2083-2088
doi: 10.11862/CJIC.2019.236
Abstract:
A biological metal-organic framework (BioMOF) ZnBTCA was prepared by the solvent-thermal method, which showed interesting host-guest chemistry in CO2 gas adsorption process. It was found that the adsorption enthalpy of CO2 increased with the increase of adsorption capacity. Using four models to fit the adsorption isotherm of CO2, we modeled and predicted the binary mixture selectivity by the ideal adsorbed solution theory (IAST), and tried to find a reasonable explanation for the abnormal adsorption behavior of ZnBTCA. ZnBTCA has high adsorption selectivity for CO2 in CO2/N2 and CO2/CH4 binary systems due to the molecular sieve effect. This is attributed to the fact that ZnBTCA has NH2, N-active site, and a large number of guest cations in the pores. The counterbalancing (CH3)2NH2+ could not be evacuated through thermal activation, and the accessible micropore volume was reduced as a result.
A biological metal-organic framework (BioMOF) ZnBTCA was prepared by the solvent-thermal method, which showed interesting host-guest chemistry in CO2 gas adsorption process. It was found that the adsorption enthalpy of CO2 increased with the increase of adsorption capacity. Using four models to fit the adsorption isotherm of CO2, we modeled and predicted the binary mixture selectivity by the ideal adsorbed solution theory (IAST), and tried to find a reasonable explanation for the abnormal adsorption behavior of ZnBTCA. ZnBTCA has high adsorption selectivity for CO2 in CO2/N2 and CO2/CH4 binary systems due to the molecular sieve effect. This is attributed to the fact that ZnBTCA has NH2, N-active site, and a large number of guest cations in the pores. The counterbalancing (CH3)2NH2+ could not be evacuated through thermal activation, and the accessible micropore volume was reduced as a result.
2019, 35(11): 2089-2094
doi: 10.11862/CJIC.2019.253
Abstract:
A new copper(Ⅱ) complex [Cu2(μ-L-κO, O)2Cl2] (1) with 4-(2-hydroxy-3-chloro)phenyl-2, 2':6', 2'-tribi-pyridine(HL) as ligand was synthesized and characterized by elemental analysis, NMR, ESI-MS as well as single crystal X-ray diffraction analysis. Complex 1 is a binuclear structure, and the central copper(Ⅱ) is coordinated by one Cl- anion, two N atoms and two hydroxyl O atoms from L- to form five-coordination distorted square-pyramid geometric configurations; two copper centers are bridged by two hydroxyl O atoms. MTT assay was employed to test the inhibitory activities of complex 1 against five selected cancer cell lines. The results showed that inhibition rate of MGC80-3 cells was the highest, reaching(84.30±1.28)%, and its IC50 value was(3.36±0.43) μmol·L-1. Flow cytometry analytical results indicated that complex 1 could induce apoptosis of MGC80-3 cells. Under the complex 1 concentration of 4.5 μmol·L-1, the MGC80-3 cell apoptosis percentage was 42.2%. Complex 1 arrested MGC80-3 cells in G1 phase, thereby inhibiting the growth of tumor cells.
A new copper(Ⅱ) complex [Cu2(μ-L-κO, O)2Cl2] (1) with 4-(2-hydroxy-3-chloro)phenyl-2, 2':6', 2'-tribi-pyridine(HL) as ligand was synthesized and characterized by elemental analysis, NMR, ESI-MS as well as single crystal X-ray diffraction analysis. Complex 1 is a binuclear structure, and the central copper(Ⅱ) is coordinated by one Cl- anion, two N atoms and two hydroxyl O atoms from L- to form five-coordination distorted square-pyramid geometric configurations; two copper centers are bridged by two hydroxyl O atoms. MTT assay was employed to test the inhibitory activities of complex 1 against five selected cancer cell lines. The results showed that inhibition rate of MGC80-3 cells was the highest, reaching(84.30±1.28)%, and its IC50 value was(3.36±0.43) μmol·L-1. Flow cytometry analytical results indicated that complex 1 could induce apoptosis of MGC80-3 cells. Under the complex 1 concentration of 4.5 μmol·L-1, the MGC80-3 cell apoptosis percentage was 42.2%. Complex 1 arrested MGC80-3 cells in G1 phase, thereby inhibiting the growth of tumor cells.
2019, 35(11): 2095-2100
doi: 10.11862/CJIC.2019.238
Abstract:
Using a metal-organic framework (MOF) called CYCU-3 with one-dimensional (1D) mesoporous channels as the host material, the polymerization of pyrrole was carried out in the pores by iodine oxidation method to obtain the composite material PPy@CYCU-3. Powdered X-ray diffraction (PXRD), scanning electron microscopy (SEM), thermogravimetry (TG), infrared (IR), fluorescence spectroscopy, etc. were used to characterize the synthesized CYCU-3, Py@CYCU-3 which is obtained after adsorption of pyrrole and PPy@CYCU-3 in pores. It is demonstrated that the polymerization in the pores was successful. In addition, CYCU-3 remained structurally stable and its morphology did not change during the polymerization. The composite PPy@CYCU-3 is multifunctional material with porosity and electrical conductivity. Nitrogen adsorption measurement indicated that the material was a typical microporous material with a BET specific surface area of 420 m2·g-1. Conductivity tests indicate that the material has a conductivity of 10-7 S·cm-1, which is six orders of magnitude higher than the conductivity of CYCU-3 (σ≈10-13 S·cm-1) and it is a semiconductor material.
Using a metal-organic framework (MOF) called CYCU-3 with one-dimensional (1D) mesoporous channels as the host material, the polymerization of pyrrole was carried out in the pores by iodine oxidation method to obtain the composite material PPy@CYCU-3. Powdered X-ray diffraction (PXRD), scanning electron microscopy (SEM), thermogravimetry (TG), infrared (IR), fluorescence spectroscopy, etc. were used to characterize the synthesized CYCU-3, Py@CYCU-3 which is obtained after adsorption of pyrrole and PPy@CYCU-3 in pores. It is demonstrated that the polymerization in the pores was successful. In addition, CYCU-3 remained structurally stable and its morphology did not change during the polymerization. The composite PPy@CYCU-3 is multifunctional material with porosity and electrical conductivity. Nitrogen adsorption measurement indicated that the material was a typical microporous material with a BET specific surface area of 420 m2·g-1. Conductivity tests indicate that the material has a conductivity of 10-7 S·cm-1, which is six orders of magnitude higher than the conductivity of CYCU-3 (σ≈10-13 S·cm-1) and it is a semiconductor material.
2019, 35(11): 2101-2107
doi: 10.11862/CJIC.2019.245
Abstract:
A novel heteropolymolybdate containing mixed-valence antimony[(CH3)4N]8Na41H17[(SbⅢ3O3)(SbⅤMo6O24)2]6 ·162H2O (1) has been successfully synthesized by reaction of (NH4)6Mo7O24·4H2O, Sb2O3 and Sb2O5 in a conventional aqueous method. This structure was structurally characterized by single-crystal X-ray diffraction, TG analysis, PXRD and IR spectrum. The results show that compound 1 contains a sandwich polyoxoanion[(Sb3O3)(SbMo6O24)2]11-, and further forms a two-dimensional structure through Na+ connection. In addition, compound 1 also exhibits intriguing allochroic properties. It can change color from yellowy to cyan yellow/sepia when heated or irradiated by Xe lamp (full wave-band, P=300 W).
A novel heteropolymolybdate containing mixed-valence antimony[(CH3)4N]8Na41H17[(SbⅢ3O3)(SbⅤMo6O24)2]6 ·162H2O (1) has been successfully synthesized by reaction of (NH4)6Mo7O24·4H2O, Sb2O3 and Sb2O5 in a conventional aqueous method. This structure was structurally characterized by single-crystal X-ray diffraction, TG analysis, PXRD and IR spectrum. The results show that compound 1 contains a sandwich polyoxoanion[(Sb3O3)(SbMo6O24)2]11-, and further forms a two-dimensional structure through Na+ connection. In addition, compound 1 also exhibits intriguing allochroic properties. It can change color from yellowy to cyan yellow/sepia when heated or irradiated by Xe lamp (full wave-band, P=300 W).
2019, 35(11): 2108-2116
doi: 10.11862/CJIC.2019.224
Abstract:
Two nanosized zirconium-based molecular capsules (Zr-MCs), namely[Cp3Zr3(μ3-O)(μ2-OH)3]2(BPDC)3Cl2 ·H2O (Zr-MC-1) and[Cp3Zr3(μ3-O)(μ2-OH)3]2(NDC)3Cl2·3H2O (Zr-MC-2), have been synthesized by reacting zirconocenedichloride (Cp2ZrCl2) with 4, 4'-biphenyldicarboxylic acid (4, 4'-H2BPDC) and 2, 6-naphthalenedicar-boxylic acid (2, 6-H2NDC), respectively, which are constructed by two trinuclear zirconocene building blocks and three linear carboxylate ligands. They were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, IR spectroscopy, thermogravimetric analysis and N2 adsorption-desorption tests. In addition, the fluorescence spectra indicate that Zr-MC-1 and Zr-MC-2 are deep-blue and blue emitting materials with emission peaks at 404 and 456 nm, respectively.
Two nanosized zirconium-based molecular capsules (Zr-MCs), namely[Cp3Zr3(μ3-O)(μ2-OH)3]2(BPDC)3Cl2 ·H2O (Zr-MC-1) and[Cp3Zr3(μ3-O)(μ2-OH)3]2(NDC)3Cl2·3H2O (Zr-MC-2), have been synthesized by reacting zirconocenedichloride (Cp2ZrCl2) with 4, 4'-biphenyldicarboxylic acid (4, 4'-H2BPDC) and 2, 6-naphthalenedicar-boxylic acid (2, 6-H2NDC), respectively, which are constructed by two trinuclear zirconocene building blocks and three linear carboxylate ligands. They were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, IR spectroscopy, thermogravimetric analysis and N2 adsorption-desorption tests. In addition, the fluorescence spectra indicate that Zr-MC-1 and Zr-MC-2 are deep-blue and blue emitting materials with emission peaks at 404 and 456 nm, respectively.
2019, 35(11): 2117-2124
doi: 10.11862/CJIC.2019.229
Abstract:
Two isostructural lanthanide (Ln) compounds with N-succinopyridine (HL) ligand, namely[Ln(HL)2(H2O)4]Cl3 (Ln=Pr (1), Eu (2)), have been synthesized and structurally characterized. Both 1 and 2 feature 1D chains with metal ions double-bridged by carboxyl ligands, which are further interconnected through hydrogen bonds to yield a 3D supramolecular architecture. Variable temperature magnetic susceptibility measurements revealed the presence of antiferromagnetic interaction between Pr(Ⅲ) ions for 1 but weak ferromagnetic interactions between Eu(Ⅲ) ions for 2. Solid-state luminescence measurement showed that 2 emitted intense red luminescence, but no characteristic peak of 1 was observed due to the large energy gap of the Pr(Ⅲ) ion.
Two isostructural lanthanide (Ln) compounds with N-succinopyridine (HL) ligand, namely[Ln(HL)2(H2O)4]Cl3 (Ln=Pr (1), Eu (2)), have been synthesized and structurally characterized. Both 1 and 2 feature 1D chains with metal ions double-bridged by carboxyl ligands, which are further interconnected through hydrogen bonds to yield a 3D supramolecular architecture. Variable temperature magnetic susceptibility measurements revealed the presence of antiferromagnetic interaction between Pr(Ⅲ) ions for 1 but weak ferromagnetic interactions between Eu(Ⅲ) ions for 2. Solid-state luminescence measurement showed that 2 emitted intense red luminescence, but no characteristic peak of 1 was observed due to the large energy gap of the Pr(Ⅲ) ion.
2019, 35(11): 2125-2135
doi: 10.11862/CJIC.2019.244
Abstract:
Here, we reported the synthesis and FITC-functionalized of mesoporous silica nanoparticles (MSNs) for tracing bioimaging and sustained drug release. Firstly, the MSNs-FITC were synthesized through one-pot method and characterized by SEM, TEM, FT-IR, XRD and the N2 adsorption-desorption isotherm respectively. Then a classic anticancer drug doxorubicin (DOX) was loaded into the MSNs-FITC. The DOX-loaded nanocarriers exhibited obviously pH dependent release behavior with accelerated release rate in acidic environment. Meanwhile, the in vitro cytotoxicity evaluation exhibited that the nude MSNs-FITC were highly biocompatible. Furthermore, the confocal laser scanning microscope (CLSM) images indicated that MSNs-FITC could penetrate into living cells effectively and dose-depended internalization of MSNs-FITC were further investigated by flow cytometry analysis (FCM).
Here, we reported the synthesis and FITC-functionalized of mesoporous silica nanoparticles (MSNs) for tracing bioimaging and sustained drug release. Firstly, the MSNs-FITC were synthesized through one-pot method and characterized by SEM, TEM, FT-IR, XRD and the N2 adsorption-desorption isotherm respectively. Then a classic anticancer drug doxorubicin (DOX) was loaded into the MSNs-FITC. The DOX-loaded nanocarriers exhibited obviously pH dependent release behavior with accelerated release rate in acidic environment. Meanwhile, the in vitro cytotoxicity evaluation exhibited that the nude MSNs-FITC were highly biocompatible. Furthermore, the confocal laser scanning microscope (CLSM) images indicated that MSNs-FITC could penetrate into living cells effectively and dose-depended internalization of MSNs-FITC were further investigated by flow cytometry analysis (FCM).
2019, 35(11): 2136-2144
doi: 10.11862/CJIC.2019.247
Abstract:
Through postsynthetic modification (PSM) of metal-organic frameworks with perfluoroacetyl and perfluoropropionyl as functional groups, hydrophobic frameworks (UiO-66-F1 and UiO-66-F2) were obtained. Both frameworks exhibited lipophilicity, which indicates that they are potential absorbents for liposoluble solvent. The crystallinity, stability, and exceptional porosity of modified MOFs decreased slightly compared to those of UiO-66-NH2. Their Brunauer-Emmett-Teller (BET) specific surface areas were 810 and 610 m2·g-1 for UiO-66-F1 and UiO-66-F2, respectively. Suitable pore size and hydrophobic microenvironment made the frameworks easier to adsorb organic pollutants in water. Furthermore, they showed an obvious increase in adsorption capacity for a variety of organic solvents and endowed outstanding recycling performance without a significant reduction in adsorption capacity after recycle ten times.
Through postsynthetic modification (PSM) of metal-organic frameworks with perfluoroacetyl and perfluoropropionyl as functional groups, hydrophobic frameworks (UiO-66-F1 and UiO-66-F2) were obtained. Both frameworks exhibited lipophilicity, which indicates that they are potential absorbents for liposoluble solvent. The crystallinity, stability, and exceptional porosity of modified MOFs decreased slightly compared to those of UiO-66-NH2. Their Brunauer-Emmett-Teller (BET) specific surface areas were 810 and 610 m2·g-1 for UiO-66-F1 and UiO-66-F2, respectively. Suitable pore size and hydrophobic microenvironment made the frameworks easier to adsorb organic pollutants in water. Furthermore, they showed an obvious increase in adsorption capacity for a variety of organic solvents and endowed outstanding recycling performance without a significant reduction in adsorption capacity after recycle ten times.
2019, 35(11): 2145-2151
doi: 10.11862/CJIC.2019.225
Abstract:
Reactions of 2, 6-di(1H-imidazol-1-yl)naphthalene (L) and dicarboxylic acid ligands with corresponding metal salts under solvothermal conditions gave rise to three new metal-organic frameworks (MOFs)[Co(L)(AIP)]·2DMF (1), [Co(L)(AIP)]·DMF (2) and[Co(L)(IDC)(H2O)2]·0.5L·H2O (3) (H2AIP=5-aminoisophthalic acid, H2IDC=4, 4'-iminodibenzoic acid). The MOFs have been structurally characterized by single-crystal and powder X-ray diffraction analyses, elemental analyses, infrared spectra (IR) and thermogravimetric analysis (TGA). MOF 1 crystallizes in monoclinic space group C2/c, while 2 and 3 are triclinic space group P1. MOFs 1 and 3 have distinct infinite one-dimensional (1D) chain structures, and 2 is a two-dimensional (2D) network, which are further linked together by hydrogen bonding interactions to give the eventual three-dimensional (3D) supramolecular architectures. Furthermore, the thermal stability and photoluminescence property of the MOFs were investigated, and it was found that 3 can efficiently detect acetone molecules via fluorescent quenching.
Reactions of 2, 6-di(1H-imidazol-1-yl)naphthalene (L) and dicarboxylic acid ligands with corresponding metal salts under solvothermal conditions gave rise to three new metal-organic frameworks (MOFs)[Co(L)(AIP)]·2DMF (1), [Co(L)(AIP)]·DMF (2) and[Co(L)(IDC)(H2O)2]·0.5L·H2O (3) (H2AIP=5-aminoisophthalic acid, H2IDC=4, 4'-iminodibenzoic acid). The MOFs have been structurally characterized by single-crystal and powder X-ray diffraction analyses, elemental analyses, infrared spectra (IR) and thermogravimetric analysis (TGA). MOF 1 crystallizes in monoclinic space group C2/c, while 2 and 3 are triclinic space group P1. MOFs 1 and 3 have distinct infinite one-dimensional (1D) chain structures, and 2 is a two-dimensional (2D) network, which are further linked together by hydrogen bonding interactions to give the eventual three-dimensional (3D) supramolecular architectures. Furthermore, the thermal stability and photoluminescence property of the MOFs were investigated, and it was found that 3 can efficiently detect acetone molecules via fluorescent quenching.
2019, 35(11): 2152-2158
doi: 10.11862/CJIC.2019.235
Abstract:
The optical properties of a metal-free tetra(aryl)porphyrin with two N, N-di(2-pyridylmethyl)amino groups (Porphyrin-2-DPA) upon respective addition of different metal ion were investigated. Systemic studies show that the rigid π-conjugated tetrapyrrole macrocyclic moiety of Porphyrin-2-DPA is employed not only as the sensitive signaling fluorophore but also as the primary receptor with excellent binding affinity and distinctive selectivity to metal ion, which together with the no-conjugated DPA auxiliary receptor endows Porphyrin-2-DPA the sensitive versatile sensor to Pb2+/Cu2+ on the basis of dual-optical signals.
The optical properties of a metal-free tetra(aryl)porphyrin with two N, N-di(2-pyridylmethyl)amino groups (Porphyrin-2-DPA) upon respective addition of different metal ion were investigated. Systemic studies show that the rigid π-conjugated tetrapyrrole macrocyclic moiety of Porphyrin-2-DPA is employed not only as the sensitive signaling fluorophore but also as the primary receptor with excellent binding affinity and distinctive selectivity to metal ion, which together with the no-conjugated DPA auxiliary receptor endows Porphyrin-2-DPA the sensitive versatile sensor to Pb2+/Cu2+ on the basis of dual-optical signals.
2019, 35(11): 2159-2167
doi: 10.11862/CJIC.2019.241
Abstract:
Two complexes 1~2 (1={[Co2(pddb)2(μ2-H2O)(H2O)2]·2DMA·5H2O}n and 2={[Ni2(pddb)2(μ2-H2O)(H2O)2]·2DMA·5H2O}n, H2pddb=3, 3'-(pyridine-3, 5-diyl) dibenzoic acid, DMA=N, N-dimethylacetamide) have been synth-esized and identified by Infrared spectroscopy (IR), elemental analysis, thermogravimetric analysis (TG) and single crystal X-ray diffraction. Structural analyses show that 1 and 2 are isostructural, and display a 3D (3, 6)-connected net with the point symbol (42·6)·(44·62·88·10). Besides, the UV-Vis absorption spectra in solid state, the magnetic properties and catalytic activity of 1~2 were investigated. Between the proximal Co(Ⅱ)/Ni(Ⅱ) ions, the variable-temperature (2~300 K) magnetic susceptibilities of 1~2 display antiferromagnetic coupling. Furthermore, 1 have been verified to be effectual catalysts for the oxidation of arylacycloalkanes in aqueous medium.
Two complexes 1~2 (1={[Co2(pddb)2(μ2-H2O)(H2O)2]·2DMA·5H2O}n and 2={[Ni2(pddb)2(μ2-H2O)(H2O)2]·2DMA·5H2O}n, H2pddb=3, 3'-(pyridine-3, 5-diyl) dibenzoic acid, DMA=N, N-dimethylacetamide) have been synth-esized and identified by Infrared spectroscopy (IR), elemental analysis, thermogravimetric analysis (TG) and single crystal X-ray diffraction. Structural analyses show that 1 and 2 are isostructural, and display a 3D (3, 6)-connected net with the point symbol (42·6)·(44·62·88·10). Besides, the UV-Vis absorption spectra in solid state, the magnetic properties and catalytic activity of 1~2 were investigated. Between the proximal Co(Ⅱ)/Ni(Ⅱ) ions, the variable-temperature (2~300 K) magnetic susceptibilities of 1~2 display antiferromagnetic coupling. Furthermore, 1 have been verified to be effectual catalysts for the oxidation of arylacycloalkanes in aqueous medium.
2019, 35(11): 2168-2176
doi: 10.11862/CJIC.2019.240
Abstract:
Two new daidzein derivatives containing nitrogen, 4', 7-bis(((sodium glycinate)carbonyl)methoxy) isoflavone (L1) and 4', 7-bis((hydrazinocarbonyl) methoxy) isoflavone (L2), have been synthesized and characterized by elemental analysis, IR and 1H NMR. The antioxidant properties of the daidzein derivatives were studied by evaluating its ability to capture the hydroxyl free radical, the superoxide anion free radical, and to protect erythrocytes of human blood against oxidative damage induced from AAPH (2, 2'-azobis(2-amidinopropane) hydrochloride). Results of the experiments suggest that the daidzein derivatives show excellent antioxidant activity in physiological pH condition compared with vitamin C. Especially in the hydroxyl radical scavenging activity and suppressing the hemolysis of erythrocytes of human blood, the antioxidant capacity of the daidzein derivatives is more outstanding. The IC50 values of the daidzein derivatives were in the range of 0.1~1 μmol·L-1 on hydroxyl free radical scavenging activity, which was 104 times higher than that of vitamin C.
Two new daidzein derivatives containing nitrogen, 4', 7-bis(((sodium glycinate)carbonyl)methoxy) isoflavone (L1) and 4', 7-bis((hydrazinocarbonyl) methoxy) isoflavone (L2), have been synthesized and characterized by elemental analysis, IR and 1H NMR. The antioxidant properties of the daidzein derivatives were studied by evaluating its ability to capture the hydroxyl free radical, the superoxide anion free radical, and to protect erythrocytes of human blood against oxidative damage induced from AAPH (2, 2'-azobis(2-amidinopropane) hydrochloride). Results of the experiments suggest that the daidzein derivatives show excellent antioxidant activity in physiological pH condition compared with vitamin C. Especially in the hydroxyl radical scavenging activity and suppressing the hemolysis of erythrocytes of human blood, the antioxidant capacity of the daidzein derivatives is more outstanding. The IC50 values of the daidzein derivatives were in the range of 0.1~1 μmol·L-1 on hydroxyl free radical scavenging activity, which was 104 times higher than that of vitamin C.
2019, 35(11): 2177-2184
doi: 10.11862/CJIC.2019.248
Abstract:
In this study, an unusual luminescence behavior from two polyhedral oligomeric silsesquioxane (POSS) monomers, aminopropyl isobutyl POSS (AIPOSS) and octal isobutyl POSS (OIPOSS) was observed after heating and stirring in their tetrahydrofuran (THF) solution. The chemical structures of these POSS samples were characterized before and after the heat treatment in THF by means of 1H and 29Si nuclear magnetic resonance (NMR) spectroscopy, and Fourier transform infrared (FTIR) spectroscopy. The valence state of silicon in the POSS sample was determined by X-ray photoelectron spectroscopy (XPS) as well. The characterization results showed that there is no obvious change in their structures, except tiny difference of the 1H NMR spectra. Photoluminescence (PL) properties of the treated/untreated POSS were studied in detail. According to the PL and structure characterization results, it is speculated that this unusual luminescence from the treated POSS is most likely caused by the adsorption effect of the POSS cage, forming the POSS/solvent adducts, which lead to the change of the electronic structure of the POSS, and consequently the luminescence of the treated POSS.
In this study, an unusual luminescence behavior from two polyhedral oligomeric silsesquioxane (POSS) monomers, aminopropyl isobutyl POSS (AIPOSS) and octal isobutyl POSS (OIPOSS) was observed after heating and stirring in their tetrahydrofuran (THF) solution. The chemical structures of these POSS samples were characterized before and after the heat treatment in THF by means of 1H and 29Si nuclear magnetic resonance (NMR) spectroscopy, and Fourier transform infrared (FTIR) spectroscopy. The valence state of silicon in the POSS sample was determined by X-ray photoelectron spectroscopy (XPS) as well. The characterization results showed that there is no obvious change in their structures, except tiny difference of the 1H NMR spectra. Photoluminescence (PL) properties of the treated/untreated POSS were studied in detail. According to the PL and structure characterization results, it is speculated that this unusual luminescence from the treated POSS is most likely caused by the adsorption effect of the POSS cage, forming the POSS/solvent adducts, which lead to the change of the electronic structure of the POSS, and consequently the luminescence of the treated POSS.
2019, 35(11): 2185-2191
doi: 10.11862/CJIC.2019.243
Abstract:
Hierarchically structured flower-like Bi2WO6 was fabricated via a simple template-free hydrothermal method. The as-prepared Bi2WO6 was applied in the removal of tetracycline antibiotics presented in aqueous phases under visible irradiation. The photocatalyst were characterized by a series of physical characterizations including powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy, UV-Vis diffuse reflectance spectra, nitrogen adsorption desorption test etc. The Bi2WO6 photocatalysts showed excellent degradation capacity towards tetracycline antibiotics (tetracycline (TC) and oxytetracycline (OTC)). Moreover, the TC degradation rates were generally higher in relatively alkaline solutions. The Bi2WO6 photocatalysts exhibited excellent stability and could be recycled for reuse.
Hierarchically structured flower-like Bi2WO6 was fabricated via a simple template-free hydrothermal method. The as-prepared Bi2WO6 was applied in the removal of tetracycline antibiotics presented in aqueous phases under visible irradiation. The photocatalyst were characterized by a series of physical characterizations including powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy, UV-Vis diffuse reflectance spectra, nitrogen adsorption desorption test etc. The Bi2WO6 photocatalysts showed excellent degradation capacity towards tetracycline antibiotics (tetracycline (TC) and oxytetracycline (OTC)). Moreover, the TC degradation rates were generally higher in relatively alkaline solutions. The Bi2WO6 photocatalysts exhibited excellent stability and could be recycled for reuse.
