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2018 Volume 34 Issue 3
2018, 34(3): 415-420
doi: 10.11862/CJIC.2018.076
Abstract:
Fullerene (C60) thin films have been prepared on SiO2 substrates by vacuum deposition under different substrate temperature ranging from 30 to 190℃ and deposition pressure of 1×10-4 and 1×10-1 Pa. The effect of crystallinity and grain size on the mobility of the deposited C60 thin films are investigated. X-ray diffraction and atomic force microscopy observation indicates that both the crystallinity and the grain size of the C60 films increase with increasing substrate temperature. And the grain size of the films increase and the crystallinity keep almost unchanged with increasing deposition pressure. Field-effect measurements indicate that the mobilities of the C60 thin films are closely correlated with their crystallinities, and the increased crystallinity of the films gives the improved mobility. Different from the films of planar organic semiconducrors molecules, for the spherical C60 molecules films, the larger grain size could lead to the lower mobility.
Fullerene (C60) thin films have been prepared on SiO2 substrates by vacuum deposition under different substrate temperature ranging from 30 to 190℃ and deposition pressure of 1×10-4 and 1×10-1 Pa. The effect of crystallinity and grain size on the mobility of the deposited C60 thin films are investigated. X-ray diffraction and atomic force microscopy observation indicates that both the crystallinity and the grain size of the C60 films increase with increasing substrate temperature. And the grain size of the films increase and the crystallinity keep almost unchanged with increasing deposition pressure. Field-effect measurements indicate that the mobilities of the C60 thin films are closely correlated with their crystallinities, and the increased crystallinity of the films gives the improved mobility. Different from the films of planar organic semiconducrors molecules, for the spherical C60 molecules films, the larger grain size could lead to the lower mobility.
2018, 34(3): 436-444
doi: 10.11862/CJIC.2018.053
Abstract:
Two novel complexes, [CoⅡCo4Ⅲ(salhn)4(N3)6(CH3OH)2(H2O)2]·4CH3OH·2H2O (1) and[Cu2(salhn)(N3)2]n (2) (H2salhn=N, N'-bis(salicylidene)hydrazine), were synthesized and structurally characterized by X-ray single-crystal diffraction. Complex 1 is a zigzag-like penta-nuclear[CoⅡCo4Ⅲ] cobalt cluster, while complex 2 consists of a 1D chain containing subunit[Cu2(salhn)(N3)2]. Both complexes possess bridged azide with the end-on (EO, μ-1, 1) coordination fashion. The magnetic measurements indicate that 1 and 2 both show antiferromagnetic behaviors.
Two novel complexes, [CoⅡCo4Ⅲ(salhn)4(N3)6(CH3OH)2(H2O)2]·4CH3OH·2H2O (1) and[Cu2(salhn)(N3)2]n (2) (H2salhn=N, N'-bis(salicylidene)hydrazine), were synthesized and structurally characterized by X-ray single-crystal diffraction. Complex 1 is a zigzag-like penta-nuclear[CoⅡCo4Ⅲ] cobalt cluster, while complex 2 consists of a 1D chain containing subunit[Cu2(salhn)(N3)2]. Both complexes possess bridged azide with the end-on (EO, μ-1, 1) coordination fashion. The magnetic measurements indicate that 1 and 2 both show antiferromagnetic behaviors.
2018, 34(3): 515-524
doi: 10.11862/CJIC.2018.038
Abstract:
Two new three-dimensional supramolecular complexes {[Zn2(pzdc)(L)2(H2O)]·H2O}n (1) and[Mn(μ2-O)(H2O)2(HL)]·NIPH (2) (H2pzdc=pyrazine-2, 3-dicarboxylic acid, H2NIPH=5-nitroisophthalic acid, HL=3-(2-pyridyl)pyrazole) have been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, UV spectrum, TG, fluorescence spectrum, single-crystal and powder X-ray diffraction. Complex 1 shows two-dimensional (2D) network, and complex 2 is zero-dimensional structure. They are further extended into a three-dimensional supramolecular network structure through hydrogen bonds and π-π interactions. Moreover, natural bond orbital (NBO) was analyzed by using the PBE0/LANL2DZ method built in Gaussian 09 program. The calculation results indicate the distinct covalent interaction between the coordinated atoms and Zn(Ⅱ), Mn(Ⅱ) ion, respectively.
Two new three-dimensional supramolecular complexes {[Zn2(pzdc)(L)2(H2O)]·H2O}n (1) and[Mn(μ2-O)(H2O)2(HL)]·NIPH (2) (H2pzdc=pyrazine-2, 3-dicarboxylic acid, H2NIPH=5-nitroisophthalic acid, HL=3-(2-pyridyl)pyrazole) have been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, UV spectrum, TG, fluorescence spectrum, single-crystal and powder X-ray diffraction. Complex 1 shows two-dimensional (2D) network, and complex 2 is zero-dimensional structure. They are further extended into a three-dimensional supramolecular network structure through hydrogen bonds and π-π interactions. Moreover, natural bond orbital (NBO) was analyzed by using the PBE0/LANL2DZ method built in Gaussian 09 program. The calculation results indicate the distinct covalent interaction between the coordinated atoms and Zn(Ⅱ), Mn(Ⅱ) ion, respectively.
2018, 34(3): 525-533
doi: 10.11862/CJIC.2018.035
Abstract:
Two trinuclear Co(Ⅱ) complexes, [Co3L(OAc)2(CH3CH2OH)2]·2CH3CH2OH·2CHCl3 (1) and[Co3L(OAc)2(C3H7OH)2] (2) were synthesized by the reaction of a new Salamo-type bisoxime chelating ligand of 4, 4'-dinitro-2, 2'-(1, 2-ethylenedioxybis(nitrilomethylidyne))diphenol (H2L) with cobalt(Ⅱ) acetate tetrahydrate in different solvents. Complexes 1 and 2 were characterized by elemental analyses, IR and UV-Vis spectra, and single crystal X-ray diffraction methods. In complexes 1 and 2, there are two ligand L2- moieties (which provide N2O2 donors), two acetate ions, two coordinated ethanol or n-propanol molecules, respectively. Although the two complexes were synthesized in different solvents, it is worthwhile that the Co(Ⅱ) ions in the structures of the two complexes adopt slightly distorted hexa-coordinated geometries. As a result, solvent effect was assumed to have played a crucial role in their coordination environment. In addition, when excited at 450 nm, the complexes 1 and 2 show an intense photoluminescence with maximum emission at ca. 568 and 566 nm, respectively.
Two trinuclear Co(Ⅱ) complexes, [Co3L(OAc)2(CH3CH2OH)2]·2CH3CH2OH·2CHCl3 (1) and[Co3L(OAc)2(C3H7OH)2] (2) were synthesized by the reaction of a new Salamo-type bisoxime chelating ligand of 4, 4'-dinitro-2, 2'-(1, 2-ethylenedioxybis(nitrilomethylidyne))diphenol (H2L) with cobalt(Ⅱ) acetate tetrahydrate in different solvents. Complexes 1 and 2 were characterized by elemental analyses, IR and UV-Vis spectra, and single crystal X-ray diffraction methods. In complexes 1 and 2, there are two ligand L2- moieties (which provide N2O2 donors), two acetate ions, two coordinated ethanol or n-propanol molecules, respectively. Although the two complexes were synthesized in different solvents, it is worthwhile that the Co(Ⅱ) ions in the structures of the two complexes adopt slightly distorted hexa-coordinated geometries. As a result, solvent effect was assumed to have played a crucial role in their coordination environment. In addition, when excited at 450 nm, the complexes 1 and 2 show an intense photoluminescence with maximum emission at ca. 568 and 566 nm, respectively.
2018, 34(3): 534-538
doi: 10.11862/CJIC.2018.087
Abstract:
Two complexes, [Li(L)2]ClO4 (1) and[Na(L)2]ClO4 (2) based on L (L=2-(5-chloroquinolin-8-yloxy)-1-(pyrrolidin-1-yl)ethanone) were synthesized and characterized by the X-ray diffraction analyses. The results show that complex 1 was isostructural with 2. The metal ion in each complex with a distorted octahedron geometry is surrounded by two acetamide ligands with N2O4 donor set. In addition, the structure of the perchlorate salt of L, namely (HL)ClO4·H2O was demonstrated. The fluorescence properties of all compounds have been investigated in detail.
Two complexes, [Li(L)2]ClO4 (1) and[Na(L)2]ClO4 (2) based on L (L=2-(5-chloroquinolin-8-yloxy)-1-(pyrrolidin-1-yl)ethanone) were synthesized and characterized by the X-ray diffraction analyses. The results show that complex 1 was isostructural with 2. The metal ion in each complex with a distorted octahedron geometry is surrounded by two acetamide ligands with N2O4 donor set. In addition, the structure of the perchlorate salt of L, namely (HL)ClO4·H2O was demonstrated. The fluorescence properties of all compounds have been investigated in detail.
2018, 34(3): 539-544
doi: 10.11862/CJIC.2018.058
Abstract:
Two new lead coordination polymers, namely, [Pb4(μ3-O)2L2]n (1), [Pb3(μ4-O)2L]n (2) (H2L=N-acetic-5-oxygen-nicotinic acid) have been prepared by the reaction of Pb(NO3)2 with H2L and characterized by elemental analysis, IR and single crystal X-ray diffraction. Polymer 1 crystallizes in the monoclinic C2/c space group, and features[Pb4(μ3-O)2]n rigid inorganic chains, which are further linked by L2- ligands to form a 3D framework. Polymer 2 crystallizes in the orthorhombic P212121 space group, and displays a 3D framework with[Pb3(μ4-O)2]n inorganic chains. The thermodynamic stability and fluorescence properties of 2 were investigated.
Two new lead coordination polymers, namely, [Pb4(μ3-O)2L2]n (1), [Pb3(μ4-O)2L]n (2) (H2L=N-acetic-5-oxygen-nicotinic acid) have been prepared by the reaction of Pb(NO3)2 with H2L and characterized by elemental analysis, IR and single crystal X-ray diffraction. Polymer 1 crystallizes in the monoclinic C2/c space group, and features[Pb4(μ3-O)2]n rigid inorganic chains, which are further linked by L2- ligands to form a 3D framework. Polymer 2 crystallizes in the orthorhombic P212121 space group, and displays a 3D framework with[Pb3(μ4-O)2]n inorganic chains. The thermodynamic stability and fluorescence properties of 2 were investigated.
2018, 34(3): 545-550
doi: 10.11862/CJIC.2018.060
Abstract:
Two Zn(Ⅱ) coordination complexes, [Zn2(L)2Cl4] (1) and[Zn(L)2Cl2]·2H2O (2) (L=4-pyridiyl-NH-1, 2, 3-triazole) are synthesized by reaction of ZnCl2·2H2O with rigid ligand L. Single crystal diffraction reveals that 1 and 2 crystallizes in space groups, P1 and P21/n, respectively. In the structures of 1 and 2, supramolecular interactions play important role in forming 3D structures. Photoluminescent properties of 1 and 2 in solid state and dilute methanolic solutions have been investigated in detail.
Two Zn(Ⅱ) coordination complexes, [Zn2(L)2Cl4] (1) and[Zn(L)2Cl2]·2H2O (2) (L=4-pyridiyl-NH-1, 2, 3-triazole) are synthesized by reaction of ZnCl2·2H2O with rigid ligand L. Single crystal diffraction reveals that 1 and 2 crystallizes in space groups, P1 and P21/n, respectively. In the structures of 1 and 2, supramolecular interactions play important role in forming 3D structures. Photoluminescent properties of 1 and 2 in solid state and dilute methanolic solutions have been investigated in detail.
2018, 34(3): 551-559
doi: 10.11862/CJIC.2018.059
Abstract:
The CuNPs@Cu(Ⅱ)-AMTD metal-organic gel composites was prepared by in situ growth of copper nanoparticles within gel matrix. The resulting material has been characterized by IR, SPR, SEM, TEM, EDX and XPS. It was found that CuNPs@Cu(Ⅱ)-AMTD composites exhibit excellent catalytic activities on the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) and other nitroarenes by NaBH4 in aqueous solution. The mechanism of the catalytic reaction has also been discussed.
The CuNPs@Cu(Ⅱ)-AMTD metal-organic gel composites was prepared by in situ growth of copper nanoparticles within gel matrix. The resulting material has been characterized by IR, SPR, SEM, TEM, EDX and XPS. It was found that CuNPs@Cu(Ⅱ)-AMTD composites exhibit excellent catalytic activities on the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) and other nitroarenes by NaBH4 in aqueous solution. The mechanism of the catalytic reaction has also been discussed.
2018, 34(3): 560-568
doi: 10.11862/CJIC.2018.078
Abstract:
By Reactions of Cu(Ⅱ), Co(Ⅱ) with H2PPCA ligand (H2PPCA=5-pyrazin-2-yl-1H-pyrazole-3-carboxylic acid) in the same hydrothermal conditions resulted in two distinct structural metal-organic frameworks (MOFs), namely, [Cu(PPCA)(H2O)]·H2O (HPU-7) and {[Co(PPCA)(H2O)]·H2O}n (HPU-8). HPU-7 that obtained from CuCl2·2H2O at 160℃ is a dinuclear cluster based on Cu(Ⅱ) ions and PPCA2- ligands. HPU-8 synthesized by Co(NO3)2·6H2O at 160℃ exhibits a 4, 4-connected 2D layer connected by dinuclear Co(Ⅱ) clusters and the skeletons of the PPCA2- ligands. The structural differences are dependent on the coordination geometries of central metal ions. And due to the structural differences, the two complexes display different photodegradation efficiencies toward methylene blue (MB).
By Reactions of Cu(Ⅱ), Co(Ⅱ) with H2PPCA ligand (H2PPCA=5-pyrazin-2-yl-1H-pyrazole-3-carboxylic acid) in the same hydrothermal conditions resulted in two distinct structural metal-organic frameworks (MOFs), namely, [Cu(PPCA)(H2O)]·H2O (HPU-7) and {[Co(PPCA)(H2O)]·H2O}n (HPU-8). HPU-7 that obtained from CuCl2·2H2O at 160℃ is a dinuclear cluster based on Cu(Ⅱ) ions and PPCA2- ligands. HPU-8 synthesized by Co(NO3)2·6H2O at 160℃ exhibits a 4, 4-connected 2D layer connected by dinuclear Co(Ⅱ) clusters and the skeletons of the PPCA2- ligands. The structural differences are dependent on the coordination geometries of central metal ions. And due to the structural differences, the two complexes display different photodegradation efficiencies toward methylene blue (MB).
2018, 34(3): 579-588
doi: 10.11862/CJIC.2018.067
Abstract:
LuF3:Yb3+, Er3+ microcrystals codoped with Yb3+ nYB3+/nLu3+=5%~15%) and Er3+ ions (nEr3+/nLu3+=1%~5%) were synthesized by a facile hydrothermal process at different pH values. It is found that the pH value has a crucial effect on synthesis of the orthorhombic phase LuF3:Yb3+, Er3+. Under 980 nm excitation, LuF3:Yb3+, Er3+ phosphors exhibit strong green upconversion (UC) emission bands centered at 523 (2H11/2→4I15/2) and 539 nm (4S3/2→4I15/2) and weak red emissions near 660 nm (4F9/2→4I15/2). The optimum doping concentrations of Er3+ and Yb3+ for the highest emission intensity were determined by using X-ray diffraction (XRD) and photoluminescence (PL) analyses. Concentration dependent studies reveal that the optimal composition is 10% Yb3+ and 2% Er3+ co-doping concen-tration with a strong green emission. A possible UC mechanism for LuF3:Yb3+, Er3+ depends on the pump power is discussed. The temperature dependence of the fluorescence intensity ratios (FIR) for the two green UC emission bands peaked at 523 and 539 nm was studied in the range of 293~573 K under excitation by a 980 nm diode laser and the maximum sensitivity was approximately 15.3×10-4 K-1 at 490 K. This indicates that LuF3:Yb3+, Er3+ phosphors are potential candidates for optical temperature sensors with high sensitivity.
LuF3:Yb3+, Er3+ microcrystals codoped with Yb3+ nYB3+/nLu3+=5%~15%) and Er3+ ions (nEr3+/nLu3+=1%~5%) were synthesized by a facile hydrothermal process at different pH values. It is found that the pH value has a crucial effect on synthesis of the orthorhombic phase LuF3:Yb3+, Er3+. Under 980 nm excitation, LuF3:Yb3+, Er3+ phosphors exhibit strong green upconversion (UC) emission bands centered at 523 (2H11/2→4I15/2) and 539 nm (4S3/2→4I15/2) and weak red emissions near 660 nm (4F9/2→4I15/2). The optimum doping concentrations of Er3+ and Yb3+ for the highest emission intensity were determined by using X-ray diffraction (XRD) and photoluminescence (PL) analyses. Concentration dependent studies reveal that the optimal composition is 10% Yb3+ and 2% Er3+ co-doping concen-tration with a strong green emission. A possible UC mechanism for LuF3:Yb3+, Er3+ depends on the pump power is discussed. The temperature dependence of the fluorescence intensity ratios (FIR) for the two green UC emission bands peaked at 523 and 539 nm was studied in the range of 293~573 K under excitation by a 980 nm diode laser and the maximum sensitivity was approximately 15.3×10-4 K-1 at 490 K. This indicates that LuF3:Yb3+, Er3+ phosphors are potential candidates for optical temperature sensors with high sensitivity.
2018, 34(3): 589-596
doi: 10.11862/CJIC.2018.073
Abstract:
Two new 1D cadmium/cobalt-based coordination polymers, {[Cd2(CH3O-ip)2(ethanol)2(H2O)4]·3H2O}n (1) and {[Co2(CH3O-ip)2(dmbpy)(H2O)4]·H2O·C2H3N}n (2) (CH3O-H2ip=5-methoxyisophthalic acid, dmbpy=2, 2'-dimethyl -4, 4'-bipyridine, C2H3N=acetonitrile), were synthesized in mixed solvent and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA), powder X-ray diffraction and single-crystal X-ray diffraction. Both complexes are synthesized using dual linkers (CH3O-H2ip and dmbpy). Complex 1 is a wave-like chain and further connected into 2D network through O-H…O hydrogen bonds, whereas 2 shows a ladder chain and further linked into 3D supramolecular framework by O-H…O, O-H…N and C-H…O hydrogen bonds. Furthermore, the luminescence property of 1 and the catalytic degradation of methyl orange in a Fenton-like process of 1~2 are also investigated.
Two new 1D cadmium/cobalt-based coordination polymers, {[Cd2(CH3O-ip)2(ethanol)2(H2O)4]·3H2O}n (1) and {[Co2(CH3O-ip)2(dmbpy)(H2O)4]·H2O·C2H3N}n (2) (CH3O-H2ip=5-methoxyisophthalic acid, dmbpy=2, 2'-dimethyl -4, 4'-bipyridine, C2H3N=acetonitrile), were synthesized in mixed solvent and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA), powder X-ray diffraction and single-crystal X-ray diffraction. Both complexes are synthesized using dual linkers (CH3O-H2ip and dmbpy). Complex 1 is a wave-like chain and further connected into 2D network through O-H…O hydrogen bonds, whereas 2 shows a ladder chain and further linked into 3D supramolecular framework by O-H…O, O-H…N and C-H…O hydrogen bonds. Furthermore, the luminescence property of 1 and the catalytic degradation of methyl orange in a Fenton-like process of 1~2 are also investigated.
2018, 34(3): 597-604
doi: 10.11862/CJIC.2018.085
Abstract:
A novel surface enhanced Raman spectroscopy (SERS) substrate was fabricated via a simple galvanic displacement reaction, where large scale of silver dendritic were uniformly and symmetrically formed on anodic aluminum oxide (AAO) membrane. The morphology, distribution and density of these silver dendritic films could be tuned easily just by controlling the reaction time as well as the concentration of AgNO3. Such active SERS substrate exhibits extremely high sensitivity, excellent reproducibility and good stability. Raman signal sensitivity for rhodamine 6G (R6G) was tested as low as 1×10-11 mol·L-1. Additionally, the as-synthesized robust substrate displays good stability under an ambient condition for several months. This 3D eco-friendly AAO membrane based substrate provides not only high density of SERS hot spots, but also a very large area for capturing target analytes. It has potential applications for the detection of trace organic contaminants in the environment.
A novel surface enhanced Raman spectroscopy (SERS) substrate was fabricated via a simple galvanic displacement reaction, where large scale of silver dendritic were uniformly and symmetrically formed on anodic aluminum oxide (AAO) membrane. The morphology, distribution and density of these silver dendritic films could be tuned easily just by controlling the reaction time as well as the concentration of AgNO3. Such active SERS substrate exhibits extremely high sensitivity, excellent reproducibility and good stability. Raman signal sensitivity for rhodamine 6G (R6G) was tested as low as 1×10-11 mol·L-1. Additionally, the as-synthesized robust substrate displays good stability under an ambient condition for several months. This 3D eco-friendly AAO membrane based substrate provides not only high density of SERS hot spots, but also a very large area for capturing target analytes. It has potential applications for the detection of trace organic contaminants in the environment.
2018, 34(3): 605-613
doi: 10.11862/CJIC.2018.069
Abstract:
Two cadmium(Ⅱ) coordination polymers, [CdI(TIPA)(CDC)0.5]n (1) and {[Cd(TIPA)(MPDA)]·H2O}n (2), (TIPA=tris(4-imidazolylphenyl)amine, H2CDC=1, 4-cyclohexanedicarboxylic acid, H2MPDA=5-methylisophthalic acid), have been synthesized and characterized by IR spectroscopy, elemental analyses and single-crystal X-ray diffraction. Structural analyses reveal that complex 1 features a rare 2D→2D polyrotaxane network with (3, 4)-connected (4.52)(4.53.72) topology, which is further interlinked into a higher-dimensional supramolecular framework by intermolecular weak interactions, whereas complex 2 has a two-dimensional (3, 5)-connected novel network with (42.67.8)(42.6) topology and shows a 2D→3D parallel-parallel polycatenation framework. The results show that the carboxylates exert obvious influence on the resulting architectures. Meanwhile, the solid-state photoluminescence of two complexes at room temperature was also investigated.
Two cadmium(Ⅱ) coordination polymers, [CdI(TIPA)(CDC)0.5]n (1) and {[Cd(TIPA)(MPDA)]·H2O}n (2), (TIPA=tris(4-imidazolylphenyl)amine, H2CDC=1, 4-cyclohexanedicarboxylic acid, H2MPDA=5-methylisophthalic acid), have been synthesized and characterized by IR spectroscopy, elemental analyses and single-crystal X-ray diffraction. Structural analyses reveal that complex 1 features a rare 2D→2D polyrotaxane network with (3, 4)-connected (4.52)(4.53.72) topology, which is further interlinked into a higher-dimensional supramolecular framework by intermolecular weak interactions, whereas complex 2 has a two-dimensional (3, 5)-connected novel network with (42.67.8)(42.6) topology and shows a 2D→3D parallel-parallel polycatenation framework. The results show that the carboxylates exert obvious influence on the resulting architectures. Meanwhile, the solid-state photoluminescence of two complexes at room temperature was also investigated.
2018, 34(3): 421-426
doi: 10.11862/CJIC.2018.040
Abstract:
Three-dimensional highly branched snowflake-like silver powder (3DHBS) has been one-step synthesized by reducing silver nitrate with ascorbic acid under the protection of polyvinyl alcohol in aqueous solution at room temperature. The microstructure of 3DHBS was investigated in details through different characteristic methods including X-ray diffraction (XRD) and scanning electron microscopy (SEM), and the possible formation mechanism was proposed based upon it. Additionally, 3DHBS exhibits superior catalytic activity for the hydrogenation reduction of p-nitrophenol.
Three-dimensional highly branched snowflake-like silver powder (3DHBS) has been one-step synthesized by reducing silver nitrate with ascorbic acid under the protection of polyvinyl alcohol in aqueous solution at room temperature. The microstructure of 3DHBS was investigated in details through different characteristic methods including X-ray diffraction (XRD) and scanning electron microscopy (SEM), and the possible formation mechanism was proposed based upon it. Additionally, 3DHBS exhibits superior catalytic activity for the hydrogenation reduction of p-nitrophenol.
Crystal Structural Prediction and the Genes of Structure-Property Relationshp for Hafnium Monoboride
2018, 34(3): 427-435
doi: 10.11862/CJIC.2018.080
Abstract:
Using the crystal structure prediction software USPEX based on the evolutionary algorithms, structural prediction were performed for searching the real ground state structure of HfB. Under the condition of ground state, two new HfB crystal structures were found (P6m2 and R3m), in which P6m2 structure has the lowest energy than the reported HfB crystal structures (Pnma, Cmcm, I41/amd and Fm3m). In these structures, the B atoms represented three different forms, including two-dimensional grapheme (P6m2 and R3m), zig-zag chain (Pnma, Cmcm and I41/amd) and isolated atoms (Fm3m), respectively, resulting their significant chemical bonding chara-cteristics, high temperature stability and toughness characteristics difference.
Using the crystal structure prediction software USPEX based on the evolutionary algorithms, structural prediction were performed for searching the real ground state structure of HfB. Under the condition of ground state, two new HfB crystal structures were found (P6m2 and R3m), in which P6m2 structure has the lowest energy than the reported HfB crystal structures (Pnma, Cmcm, I41/amd and Fm3m). In these structures, the B atoms represented three different forms, including two-dimensional grapheme (P6m2 and R3m), zig-zag chain (Pnma, Cmcm and I41/amd) and isolated atoms (Fm3m), respectively, resulting their significant chemical bonding chara-cteristics, high temperature stability and toughness characteristics difference.
2018, 34(3): 445-453
doi: 10.11862/CJIC.2018.047
Abstract:
Three-dimensional structures of monolayer and hollow carbon nanocages were obtained by a facile method. These nanocages with controlled wall thickness are synthesized by catalytic templating on magnesium oxides (MgO), nucleating in situ during annealing of basic magnesium carbonate, using absolute ethyl alcohol as an inexpensive precursor of carbon, and following the MgO dissolution by dilute nitric acid solution. The obtained CNCs show a specific surface area as high as 906 m2·g-1, and conduct an adsorption capacity of 542.6 mg·g-1 for aqueous crystal violet under experimental conditions. The hydrophilia of as-prepared CNCs can be significantly improved through a simple modification by treating CNCs with sodium dodecyl benzene sulfonate, and the hydrophilic CNCs can capture CV molecules with an adsorption capacity saturated in 748.4 mg·g-1. The pristine and modified CNCs were extensively characterized by XRD, FT-IR, TEM, XPS and BET surface measurement, and the structure-performance of CNCs is careful correlated. The chemical adsorption mechanism during the removal of CV by CNCs is identified, and the interactions between CV and CNCs, through π-π and electrovalent bonds are proposed.
Three-dimensional structures of monolayer and hollow carbon nanocages were obtained by a facile method. These nanocages with controlled wall thickness are synthesized by catalytic templating on magnesium oxides (MgO), nucleating in situ during annealing of basic magnesium carbonate, using absolute ethyl alcohol as an inexpensive precursor of carbon, and following the MgO dissolution by dilute nitric acid solution. The obtained CNCs show a specific surface area as high as 906 m2·g-1, and conduct an adsorption capacity of 542.6 mg·g-1 for aqueous crystal violet under experimental conditions. The hydrophilia of as-prepared CNCs can be significantly improved through a simple modification by treating CNCs with sodium dodecyl benzene sulfonate, and the hydrophilic CNCs can capture CV molecules with an adsorption capacity saturated in 748.4 mg·g-1. The pristine and modified CNCs were extensively characterized by XRD, FT-IR, TEM, XPS and BET surface measurement, and the structure-performance of CNCs is careful correlated. The chemical adsorption mechanism during the removal of CV by CNCs is identified, and the interactions between CV and CNCs, through π-π and electrovalent bonds are proposed.
2018, 34(3): 454-460
doi: 10.11862/CJIC.2018.052
Abstract:
In this work, micron CuS crystals were successfully prepared by solvothermal route with CuCl2·2H2O and CH4N2S as the reactant, and the effect of different reaction medium on the morphology, crystal structure and the yield of the synthesized CuS crystals had been investigated. The result show that the CuS crystals prepared with the N, N-dimethylformamide (DMF) as solvent were micron-scale hexagonal flower like shape crystals. And the micron flower-like CuS crystals were synthesized by using the ethylene glycol or the mixture with DMF and deionized water as solvent. With the increase of the proportion of water in the solvent, the yield of CuS crystal increases first and then decreases. The max yield of 64.5% was achieved when the ratio of VDMF:VH2O is 1:1. The CuS crystals obtained with VDMF:VH2O=2:1 show good photocatalytic activity and the decolorized rate of rhodamine B pollutant solution can reach 96.7% under the natural light irradiation simulated by xenon lamp in 2.5 h.
In this work, micron CuS crystals were successfully prepared by solvothermal route with CuCl2·2H2O and CH4N2S as the reactant, and the effect of different reaction medium on the morphology, crystal structure and the yield of the synthesized CuS crystals had been investigated. The result show that the CuS crystals prepared with the N, N-dimethylformamide (DMF) as solvent were micron-scale hexagonal flower like shape crystals. And the micron flower-like CuS crystals were synthesized by using the ethylene glycol or the mixture with DMF and deionized water as solvent. With the increase of the proportion of water in the solvent, the yield of CuS crystal increases first and then decreases. The max yield of 64.5% was achieved when the ratio of VDMF:VH2O is 1:1. The CuS crystals obtained with VDMF:VH2O=2:1 show good photocatalytic activity and the decolorized rate of rhodamine B pollutant solution can reach 96.7% under the natural light irradiation simulated by xenon lamp in 2.5 h.
2018, 34(3): 461-466
doi: 10.11862/CJIC.2018.049
Abstract:
The synthesis of ZSM-5 zeolite by seeded dry-gel conversion method using water glass as a cheap silica source was studied. The products were characterized using XRD, SEM, TEM, FTIR, N2 adsorption-desorption and NH3-TPD. The crystallization process of ZSM-5 zeolite was investigated in detail. The results show that ZSM-5 zeolite can be synthesized when the ratio of nSiO2/nAl2O3 is 30~70, nNa2O/nSiO2 is 0.12~0.2, even in the absence of external bulk water. The added of external bulk water can accelerate the crystallization speed. Compared with the products synthesized by conventional hydrothermal synthesis method, the dry-gel synthesized ZSM-5 zeolite show much smaller crystal size and much shorter crystallization time.
The synthesis of ZSM-5 zeolite by seeded dry-gel conversion method using water glass as a cheap silica source was studied. The products were characterized using XRD, SEM, TEM, FTIR, N2 adsorption-desorption and NH3-TPD. The crystallization process of ZSM-5 zeolite was investigated in detail. The results show that ZSM-5 zeolite can be synthesized when the ratio of nSiO2/nAl2O3 is 30~70, nNa2O/nSiO2 is 0.12~0.2, even in the absence of external bulk water. The added of external bulk water can accelerate the crystallization speed. Compared with the products synthesized by conventional hydrothermal synthesis method, the dry-gel synthesized ZSM-5 zeolite show much smaller crystal size and much shorter crystallization time.
2018, 34(3): 467-474
doi: 10.11862/CJIC.2018.064
Abstract:
Porous carbon nitride nanosheet was prepared by the simple oxygen etching using melamine and thiourea as precursors respectively. The porous g-C3N4 (TCNS) nanosheet prepared by thiourea is thinner than the porous carbon nitride (MCNS) nanosheet prepared by melamine, and the monolayer thickness is about 30 nm. Meanwhile, TCNS demonstrates an obvious layered structure and a band gap of 3.03 eV, which is higher than that of graphitic carbon nitride (2.77 eV). An enlarged band gap can give carrier stronger ability of oxidation reduction for photocatalysis. The larger specific surface area (114 m2·g-1) can provide more active sites, and the nanosheet structure can effectively promote the separation and transfer of electrons and holes, which makes TCNS have higher photocatalytic activity.
Porous carbon nitride nanosheet was prepared by the simple oxygen etching using melamine and thiourea as precursors respectively. The porous g-C3N4 (TCNS) nanosheet prepared by thiourea is thinner than the porous carbon nitride (MCNS) nanosheet prepared by melamine, and the monolayer thickness is about 30 nm. Meanwhile, TCNS demonstrates an obvious layered structure and a band gap of 3.03 eV, which is higher than that of graphitic carbon nitride (2.77 eV). An enlarged band gap can give carrier stronger ability of oxidation reduction for photocatalysis. The larger specific surface area (114 m2·g-1) can provide more active sites, and the nanosheet structure can effectively promote the separation and transfer of electrons and holes, which makes TCNS have higher photocatalytic activity.
2018, 34(3): 475-482
doi: 10.11862/CJIC.2018.063
Abstract:
The Sr-doped perovskite oxides La1-xSrxCoO3 (x=0, 0.2, 0.4, 0.6, 0.8), as the electrocatalyst for bi-functional oxygen electrode, were synthesized by sol-gel method. The test results show that Sr-doped La1-xSrxCoO3 has higher electrocatalytic activities than LaCoO3. In addition, La0.6Sr0.4CoO3 reveal excellent catalytic activity for the oxygen evolution reaction and oxygen reduction reaction, reaching a maximum of 0.244 A·cm-2 (at -0.6 V vs Hg/HgO) and 0.303 A·cm-2 (at 1 V vs Hg/HgO). In order to further improve the catalytic activity of the catalyst, α-MnO2 nano-wires as bi-functional catalyst was prepared by hydrothermal synthesis and added into the La0.6Sr0.4CoO3. The activities of bi-functional catalysts of α-MnO2/La0.6Sr0.4CoO3 were markedly superior compared with α-MnO2 or La0.6Sr0.4CoO3 perovskite oxide when the mass fraction of 40% α-MnO2, demonstrating a synergistic effect, which was responsible for the improvement of electrochemical catalytic activity and stability of the bi-functional oxygen electrode.
The Sr-doped perovskite oxides La1-xSrxCoO3 (x=0, 0.2, 0.4, 0.6, 0.8), as the electrocatalyst for bi-functional oxygen electrode, were synthesized by sol-gel method. The test results show that Sr-doped La1-xSrxCoO3 has higher electrocatalytic activities than LaCoO3. In addition, La0.6Sr0.4CoO3 reveal excellent catalytic activity for the oxygen evolution reaction and oxygen reduction reaction, reaching a maximum of 0.244 A·cm-2 (at -0.6 V vs Hg/HgO) and 0.303 A·cm-2 (at 1 V vs Hg/HgO). In order to further improve the catalytic activity of the catalyst, α-MnO2 nano-wires as bi-functional catalyst was prepared by hydrothermal synthesis and added into the La0.6Sr0.4CoO3. The activities of bi-functional catalysts of α-MnO2/La0.6Sr0.4CoO3 were markedly superior compared with α-MnO2 or La0.6Sr0.4CoO3 perovskite oxide when the mass fraction of 40% α-MnO2, demonstrating a synergistic effect, which was responsible for the improvement of electrochemical catalytic activity and stability of the bi-functional oxygen electrode.
2018, 34(3): 483-489
doi: 10.11862/CJIC.2018.061
Abstract:
1, 10-phenanthroline Cu(Ⅱ) complexes (CuPhen) were successfully encapsulated in the cavities of conventional zeolite-Y and hierarchical zeolite-Y hosts obtained via post-treatment by the flexible ligand method. The physicochemical properties of the prepared hybrids were characterized by X-ray diffraction, TEM, Fourier transform infrared spectroscopy, Ultraviolet-visible spectroscopy and N2 adsorption-desorption. A comparative study on the catalytic performances of the Cu complexes encapsulated in the different zeolite-Y hosts was carried out with different substrates. The results show that the hierarchical zeolite-Y exhibites superior host performance to the conventional zeolite-Y, and Cu complexes encapsulated in hierarchical zeolite-Y has higher catalytic activities in various cycloalkane oxidation reactions than those in the conventional zeolite-Y using H2O2 as the oxidant. In addition, Cu complexes encapsulated in the hierarchical zeolite-Y exhibites the same stability and reusability as those in the conventional zeolite-Y.
1, 10-phenanthroline Cu(Ⅱ) complexes (CuPhen) were successfully encapsulated in the cavities of conventional zeolite-Y and hierarchical zeolite-Y hosts obtained via post-treatment by the flexible ligand method. The physicochemical properties of the prepared hybrids were characterized by X-ray diffraction, TEM, Fourier transform infrared spectroscopy, Ultraviolet-visible spectroscopy and N2 adsorption-desorption. A comparative study on the catalytic performances of the Cu complexes encapsulated in the different zeolite-Y hosts was carried out with different substrates. The results show that the hierarchical zeolite-Y exhibites superior host performance to the conventional zeolite-Y, and Cu complexes encapsulated in hierarchical zeolite-Y has higher catalytic activities in various cycloalkane oxidation reactions than those in the conventional zeolite-Y using H2O2 as the oxidant. In addition, Cu complexes encapsulated in the hierarchical zeolite-Y exhibites the same stability and reusability as those in the conventional zeolite-Y.
2018, 34(3): 490-498
doi: 10.11862/CJIC.2018.065
Abstract:
Silk fibroin nanofibers solution (SFFs) was processed through controlling silk protein molecules self-assembly process, which were incorporated with vancomycin (VCM) to calcium sulfate (CS) for infective calcium sulfate-based materials. Surface morphology of the material was observed using SEM. Structure of the materials was studied with XRD. Drug release property of materials was evaluated using UV absorbance. Mechanical property of the materials was tested using computer-controlled electronic universal testing machine. Antibacterial property was illustrated by inhibition zone. Cytocompatibility was assessed by MTT assay. The results show that the addition of SFFs can not only effectively reduce the degradation rate of the composite material, but also enhance toughness and water resistance comparing to water as setting liquid. And the compressive strength first increased, then decreased as the concentration of SFFs from 0.017 5 to 2.1 mg·mL-1. The results also show that the composite with controllable setting time has excellent antibacterial properties and drug slow-release performance in a week as well as better cell proliferation with MC-3T3.
Silk fibroin nanofibers solution (SFFs) was processed through controlling silk protein molecules self-assembly process, which were incorporated with vancomycin (VCM) to calcium sulfate (CS) for infective calcium sulfate-based materials. Surface morphology of the material was observed using SEM. Structure of the materials was studied with XRD. Drug release property of materials was evaluated using UV absorbance. Mechanical property of the materials was tested using computer-controlled electronic universal testing machine. Antibacterial property was illustrated by inhibition zone. Cytocompatibility was assessed by MTT assay. The results show that the addition of SFFs can not only effectively reduce the degradation rate of the composite material, but also enhance toughness and water resistance comparing to water as setting liquid. And the compressive strength first increased, then decreased as the concentration of SFFs from 0.017 5 to 2.1 mg·mL-1. The results also show that the composite with controllable setting time has excellent antibacterial properties and drug slow-release performance in a week as well as better cell proliferation with MC-3T3.
2018, 34(3): 499-506
doi: 10.11862/CJIC.2018.072
Abstract:
An efficient route for the synthesis of Cu and Ni doped ZnO was developed in the presence of Zn(NO3)2, CuSO4 and Ni(NO3)2 with Gemini surfactant as the soft template. Moreover, the photocatalyst was prepared by a hydrothermal method, and its structure was unambiguously configured by XRD, SEM-EDX, UV-Vis DRS and PL as well. In this paper, different influence parameters to synthesize the ZnO photocatalyst were investigated, such as reaction time, temperature, the doping amount of the Cu and Ni. By adopting the newly synthesized photocatalyst in the degradation of model pollutant RhB, the optimal conditions to afford the ZnO were finally developed. The results show that the degradation efficiency could reach 96.9% in the condition that hydrothermal process 130℃ for 8 h, calcination 500℃ for 3 h, and 10 mg·L-1 RhB under the irradiation of 250 W high pressure mercury lamp with 0.8 g·L-1 1.0%Cu-3.0%Ni/ZnO as photocatalyst.
An efficient route for the synthesis of Cu and Ni doped ZnO was developed in the presence of Zn(NO3)2, CuSO4 and Ni(NO3)2 with Gemini surfactant as the soft template. Moreover, the photocatalyst was prepared by a hydrothermal method, and its structure was unambiguously configured by XRD, SEM-EDX, UV-Vis DRS and PL as well. In this paper, different influence parameters to synthesize the ZnO photocatalyst were investigated, such as reaction time, temperature, the doping amount of the Cu and Ni. By adopting the newly synthesized photocatalyst in the degradation of model pollutant RhB, the optimal conditions to afford the ZnO were finally developed. The results show that the degradation efficiency could reach 96.9% in the condition that hydrothermal process 130℃ for 8 h, calcination 500℃ for 3 h, and 10 mg·L-1 RhB under the irradiation of 250 W high pressure mercury lamp with 0.8 g·L-1 1.0%Cu-3.0%Ni/ZnO as photocatalyst.
2018, 34(3): 507-514
doi: 10.11862/CJIC.2018.075
Abstract:
Mesoporous carbon/graphene composite was firstly synthesized by hard-template method. Then, different quinone molecules were introduced to improve the capacitive performance of the composite. The results show that mesoporous carbon/graphene composite with 30% (w/w) loading of butylhydroquinone shows the best capacitive performance. This sample exhibits specific capacitance of 355 and 226 F·g-1 at the current density of 0.5 and 30 A·g-1, respectively, highlighting its good rate performance.
Mesoporous carbon/graphene composite was firstly synthesized by hard-template method. Then, different quinone molecules were introduced to improve the capacitive performance of the composite. The results show that mesoporous carbon/graphene composite with 30% (w/w) loading of butylhydroquinone shows the best capacitive performance. This sample exhibits specific capacitance of 355 and 226 F·g-1 at the current density of 0.5 and 30 A·g-1, respectively, highlighting its good rate performance.
2018, 34(3): 569-578
doi: 10.11862/CJIC.2018.071
Abstract:
Two new metal-organic coordination polymers, [Co2(1, 4-bib)2(5-hipa)2]n (1) (5-H2hipa=5-hydroxyisophth-alic acid, 1, 4-bib=1, 4-bis(1-imidazolyl)benzene), [Co(Hbpt)(4, 4'-bidpe)]n (2) (H3bpt=biphenyl-3, 4', 5-tricarboxylic acid, 4, 4'-bidpe=4, 4'-bis(imidazol-1-yl)diphenyl ether) were obtained under solvothermal conditions and chara-cterized structurally. The meta benzenedicarboxylates in 5-hipa2- and Hbpt2- connect the Co(Ⅱ) ions into 1D carboxylate-cobalt chain structures with 8-membered ring Co2O4C2 and 16-membered Co2O4C10 ring alternately. And the bis(imidazole) ligands further link the adjacent 1D carboxylate-cobalt chains to construct an interesting two-dimensional layered structure, respectively. The adjacent layers[Co2(1, 4-bib)2(5-hipa)2] in complex 1 are linked with each other by hydrogen bonding to generate an interesting 3D supramolecular framework. While the hydrogen bonding only exits within the layers of 2. Furthermore, the complex 1/Vulcan XC-72R composite can catalyze the oxygen reduction reaction through a 2e/4e mixed reduction pathway.
Two new metal-organic coordination polymers, [Co2(1, 4-bib)2(5-hipa)2]n (1) (5-H2hipa=5-hydroxyisophth-alic acid, 1, 4-bib=1, 4-bis(1-imidazolyl)benzene), [Co(Hbpt)(4, 4'-bidpe)]n (2) (H3bpt=biphenyl-3, 4', 5-tricarboxylic acid, 4, 4'-bidpe=4, 4'-bis(imidazol-1-yl)diphenyl ether) were obtained under solvothermal conditions and chara-cterized structurally. The meta benzenedicarboxylates in 5-hipa2- and Hbpt2- connect the Co(Ⅱ) ions into 1D carboxylate-cobalt chain structures with 8-membered ring Co2O4C2 and 16-membered Co2O4C10 ring alternately. And the bis(imidazole) ligands further link the adjacent 1D carboxylate-cobalt chains to construct an interesting two-dimensional layered structure, respectively. The adjacent layers[Co2(1, 4-bib)2(5-hipa)2] in complex 1 are linked with each other by hydrogen bonding to generate an interesting 3D supramolecular framework. While the hydrogen bonding only exits within the layers of 2. Furthermore, the complex 1/Vulcan XC-72R composite can catalyze the oxygen reduction reaction through a 2e/4e mixed reduction pathway.
