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2018 Volume 34 Issue 6
2018, 34(6): 1007-1017
doi: 10.11862/CJIC.2018.150
Abstract:
Photovoltaics have been received considerable attention as renewable clean energy, which convert solar energy to electric power via a green way. Shifting solar irradiation photons from UV to visible region by down conversion materials for more efficient photo-electric conversion has been attracted great academic attentions as a viable way for photovoltaic performance enhancement. In this text, we review the research progress on the development of down conversion materials for solar cells, and focus on the luminescent metal-complexes system. We also provide an outlook for the future of the down conversion materials in photovoltaics, and summarize the existed problems and the approaches to further development.
Photovoltaics have been received considerable attention as renewable clean energy, which convert solar energy to electric power via a green way. Shifting solar irradiation photons from UV to visible region by down conversion materials for more efficient photo-electric conversion has been attracted great academic attentions as a viable way for photovoltaic performance enhancement. In this text, we review the research progress on the development of down conversion materials for solar cells, and focus on the luminescent metal-complexes system. We also provide an outlook for the future of the down conversion materials in photovoltaics, and summarize the existed problems and the approaches to further development.
2018, 34(6): 1018-1027
doi: 10.11862/CJIC.2018.134
Abstract:
Two new chiral Cu(Ⅱ) coordination polymers, {[Cu((1R, 2R)-3-bcpb)]Cl2}n (1) and {[Cu((1R, 2R)-3-bcpb)2](ClO4)2·2H2O·2CH3OH}n (2) ((1R, 2R)-3-bcpb=N, N'-((1R, 2R)-cyclohexane-1, 2-diyl)bis(N-(pyridin-3-ylmethyl)benz-amide)), have been assembled with a chiral V-shaped bidentate ligand and different Cu(Ⅱ) salts, in which 1 is a 1D linear chain, while 2 displays a 2D (4, 4) topology. 1 can be directly transformed to 2 by the introduction of AgClO4, and 2 can also be directly converted to 1 by the addition of NaCl in methanol under solvothermal conditions. CD spectra and SHG response of the complexes confirm that their bulk samples are both of structural chirality.
Two new chiral Cu(Ⅱ) coordination polymers, {[Cu((1R, 2R)-3-bcpb)]Cl2}n (1) and {[Cu((1R, 2R)-3-bcpb)2](ClO4)2·2H2O·2CH3OH}n (2) ((1R, 2R)-3-bcpb=N, N'-((1R, 2R)-cyclohexane-1, 2-diyl)bis(N-(pyridin-3-ylmethyl)benz-amide)), have been assembled with a chiral V-shaped bidentate ligand and different Cu(Ⅱ) salts, in which 1 is a 1D linear chain, while 2 displays a 2D (4, 4) topology. 1 can be directly transformed to 2 by the introduction of AgClO4, and 2 can also be directly converted to 1 by the addition of NaCl in methanol under solvothermal conditions. CD spectra and SHG response of the complexes confirm that their bulk samples are both of structural chirality.
Syntheses and Crystal Structures of Hg(Ⅱ) and Cd(Ⅱ) Complexes Derived from a Bis(pyridylurea) Ligand
2018, 34(6): 1028-1034
doi: 10.11862/CJIC.2018.112
Abstract:
A bis(pyridylurea) ligand(L) was synthesized from the reaction of bis(2-aminophenyl) ether with 4-isocyanatopyridine. HgCl2 and Cd(ClO4)2 reacted with L to give two coordination polymers {[Hg(L)Cl2]·2DMF}n (1) and {[Cd(L)2(H2O)2](ClO4)2·4DMF·2H2O·2CH3OH}n (2), respectively. The ligand was characterized by 1H NMR, MS, FTIR, and elemental analysis. The structures of the ligand and two complexes were analyzed via single crystal X-ray diffraction, and the structural analysis indicated that both complexes show a one-dimensional chain structure. Their thermal stabilities and vapor adsorptions for MeOH were further investigated.CCDC: 1588599, L; 1588600, 1; 1588601, 2
A bis(pyridylurea) ligand(L) was synthesized from the reaction of bis(2-aminophenyl) ether with 4-isocyanatopyridine. HgCl2 and Cd(ClO4)2 reacted with L to give two coordination polymers {[Hg(L)Cl2]·2DMF}n (1) and {[Cd(L)2(H2O)2](ClO4)2·4DMF·2H2O·2CH3OH}n (2), respectively. The ligand was characterized by 1H NMR, MS, FTIR, and elemental analysis. The structures of the ligand and two complexes were analyzed via single crystal X-ray diffraction, and the structural analysis indicated that both complexes show a one-dimensional chain structure. Their thermal stabilities and vapor adsorptions for MeOH were further investigated.CCDC: 1588599, L; 1588600, 1; 1588601, 2
2018, 34(6): 1035-1042
doi: 10.11862/CJIC.2018.111
Abstract:
Four bis(tricyclohexyltin)pyridinedicarboxylates, {[(2, 6-Hpydc)SnCy3]·MeOH}n (1), [(2, 6-pydc)Sn2Cy6(H2O)]·PhH (2), [(3, 5-pydc)Sn2Cy6(MeOH)]·MeOH (3) and[(3, 5-pydc)Sn2Cy6(H2O)]·EtOH (4), have been prepared by the microwave-assisted solvothermal reaction of tricyclohexyltin hydroxide with 2, 6-H2pydc and 3, 5-H2pydc (H2pydc=pyridinedicarboxylic acid), respectively. Compounds 1~4 have been characterized by elemental, IR, (1H, 13C and 119Sn) NMR and single crystal X-ray diffraction analyses. The distorted tetrahedral and trigonal bipyramid geometry is formed by the tin and ligand atoms. These compounds has a 2D network with macrocyclic supramolecular by the hydrogen bonding interaction of the neighboring molecule. The antitumor activity showed that compounds 1 and 3 have higher activities than cisplatin in HT-29, HepG2, MCF-7, KB and A549 cell line in vitro.
Four bis(tricyclohexyltin)pyridinedicarboxylates, {[(2, 6-Hpydc)SnCy3]·MeOH}n (1), [(2, 6-pydc)Sn2Cy6(H2O)]·PhH (2), [(3, 5-pydc)Sn2Cy6(MeOH)]·MeOH (3) and[(3, 5-pydc)Sn2Cy6(H2O)]·EtOH (4), have been prepared by the microwave-assisted solvothermal reaction of tricyclohexyltin hydroxide with 2, 6-H2pydc and 3, 5-H2pydc (H2pydc=pyridinedicarboxylic acid), respectively. Compounds 1~4 have been characterized by elemental, IR, (1H, 13C and 119Sn) NMR and single crystal X-ray diffraction analyses. The distorted tetrahedral and trigonal bipyramid geometry is formed by the tin and ligand atoms. These compounds has a 2D network with macrocyclic supramolecular by the hydrogen bonding interaction of the neighboring molecule. The antitumor activity showed that compounds 1 and 3 have higher activities than cisplatin in HT-29, HepG2, MCF-7, KB and A549 cell line in vitro.
2018, 34(6): 1043-1050
doi: 10.11862/CJIC.2018.111a
Abstract:
Soft/hard magnetic Ni0.5Zn0.5Fe2O4/SrFe12O19 composite fibers with porous structure are prepared using a combination of sol-gel and electrospinning method. The crystal structure, micromorphology and electromagnetic properties of the as-prepared composite fibers are characterized by thermogravimetric analyzer (TG-DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectrometry (EDS), N2 adsorpation-desorpation and vector network analyzer (VNA). The results indicate that after being heat treatment at 900℃, the obtained composite fibers are of three-dimensional porous structure. When the mass ratio of soft phase/hard phase is 1:3, the composite fiber has a large surface area value (55 m2·g-1). The microwave absorption properties results demonstrate that when the coating layer thickness is 3.5 mm, the composite fiber has a minimum reflection loss (RL) value (-31.9 dB). At the same time, the bandwidth of the RL values less than -10 dB in the frequency range of 2~18 GHz reaches 10.5 GHz, which covers all X-band (8.2~12.4 GHz) and Ku-band (12.4~18 GHz) and shows excellent wide band microwave absorption performance.
Soft/hard magnetic Ni0.5Zn0.5Fe2O4/SrFe12O19 composite fibers with porous structure are prepared using a combination of sol-gel and electrospinning method. The crystal structure, micromorphology and electromagnetic properties of the as-prepared composite fibers are characterized by thermogravimetric analyzer (TG-DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectrometry (EDS), N2 adsorpation-desorpation and vector network analyzer (VNA). The results indicate that after being heat treatment at 900℃, the obtained composite fibers are of three-dimensional porous structure. When the mass ratio of soft phase/hard phase is 1:3, the composite fiber has a large surface area value (55 m2·g-1). The microwave absorption properties results demonstrate that when the coating layer thickness is 3.5 mm, the composite fiber has a minimum reflection loss (RL) value (-31.9 dB). At the same time, the bandwidth of the RL values less than -10 dB in the frequency range of 2~18 GHz reaches 10.5 GHz, which covers all X-band (8.2~12.4 GHz) and Ku-band (12.4~18 GHz) and shows excellent wide band microwave absorption performance.
2018, 34(6): 1051-1058
doi: 10.11862/CJIC.2018.123
Abstract:
Layered organo-titanosilicate materials with a micro sphere morphology (denoted as ms-LOTS) were synthesized via the aerosol-assisted self-assembly (AASA) method. The morphology and materials' structure of ms-LOTS was characterized by SEM, XRD and FT-IR. The temperature and concentration play an important role in catalytic activity. The ms-LOTS with a uniform sphere size of 2~4 μm were successfully prepared by the optimization of synthetic condition (350℃ and low concentration). At room temperature, ms-LOTS show improved catalytic performance in the epoxidation of cyclohexene.
Layered organo-titanosilicate materials with a micro sphere morphology (denoted as ms-LOTS) were synthesized via the aerosol-assisted self-assembly (AASA) method. The morphology and materials' structure of ms-LOTS was characterized by SEM, XRD and FT-IR. The temperature and concentration play an important role in catalytic activity. The ms-LOTS with a uniform sphere size of 2~4 μm were successfully prepared by the optimization of synthetic condition (350℃ and low concentration). At room temperature, ms-LOTS show improved catalytic performance in the epoxidation of cyclohexene.
2018, 34(6): 1059-1064
doi: 10.11862/CJIC.2018.113
Abstract:
g-C3N4 nanotubes were prepared by pyrolysis of a mixture of melamine and ammonium bicarbonate via a simple and convenient method. The morphology and catalytic properties of the photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared spectroscopy (IR), N2 adsorption-desorption, ultraviolet-visible diffuse reflectance spectroscopy and UV-visible spectroscopy. The photocatalytic activity of g-C3N4 nanotubes to rhodamine B degradation was investigated. The photocatalytic activity of the g-C3N4 nanotubes under the visible light irradiation was effectively promoted because the tube structure can effectively promote the photo-electron transfer. The degradation percentage of rhodamine B was 95 and 99.4% at 60 and 120 min respective. The g-C3N4 nanotubes also displayed high recyclability.
g-C3N4 nanotubes were prepared by pyrolysis of a mixture of melamine and ammonium bicarbonate via a simple and convenient method. The morphology and catalytic properties of the photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared spectroscopy (IR), N2 adsorption-desorption, ultraviolet-visible diffuse reflectance spectroscopy and UV-visible spectroscopy. The photocatalytic activity of g-C3N4 nanotubes to rhodamine B degradation was investigated. The photocatalytic activity of the g-C3N4 nanotubes under the visible light irradiation was effectively promoted because the tube structure can effectively promote the photo-electron transfer. The degradation percentage of rhodamine B was 95 and 99.4% at 60 and 120 min respective. The g-C3N4 nanotubes also displayed high recyclability.
2018, 34(6): 1065-1070
doi: 10.11862/CJIC.2018.130
Abstract:
With the help of nanotechnology, a kind of Pt/Fe bimetallic nanoparticles with different ratio of nPt/nFe was prepared with PVP as protective agent and ethylene glycol as the reducing agent. And then the desired Pt-FeOx catalysts with different microstructural environment were obtained by following oxidation treatment and used as catalysts for CO oxidation. The results show that the number of FeOx species affects both the valence of Pt species and the redox properties of Fe species themselves. These properties have a direct and indirect effect on the activation of CO and oxygen molecules. It can be concluded that the presence of appropriate FeOx species around Pt is beneficial to the construction of highly active CO oxidation catalysts.
With the help of nanotechnology, a kind of Pt/Fe bimetallic nanoparticles with different ratio of nPt/nFe was prepared with PVP as protective agent and ethylene glycol as the reducing agent. And then the desired Pt-FeOx catalysts with different microstructural environment were obtained by following oxidation treatment and used as catalysts for CO oxidation. The results show that the number of FeOx species affects both the valence of Pt species and the redox properties of Fe species themselves. These properties have a direct and indirect effect on the activation of CO and oxygen molecules. It can be concluded that the presence of appropriate FeOx species around Pt is beneficial to the construction of highly active CO oxidation catalysts.
2018, 34(6): 1071-1078
doi: 10.11862/CJIC.2018.136
Abstract:
A relativistic density functional theory (DFT) was used to systematically examine a series of uranyl and transuranyl complexes of N-donor macrocyclic ligands, [(AnO2)(Ln)]2-(labeled as nAn; n=1~3; An=U, Np and Pu). Further comparison was made with[(UO2)(L0)]2-(A) that was experimentally synthesized. Cavities of L1 and L2 macrocycles are found to match well with actinyl ions, but the one of L3 is a lot larger. Consequently, the L3 complexes have to adopt distorted geometry to energetically stabilize systems. Infrared vibrational spectra presented that the An=O stretching frequencies decrease in going from U, Np to Pu. This agrees with the trend of optimized bond lengths of An=O and bond orders. Topological analyses of quantum theory of atoms in molecule (QTAIM) indicate that the An-N bonds have largely ionic character. Depending on different actinyl source, free energies reacting with various macrocyclic ligands were calculated around 146.4 kJ·mol-1, comparable to the calculated values of A. Time-dependent DFT calculations on four uranyl complexes well reproduced absorption spectra of experimentally reported analogue. The absorption bands in the near-IR and visible region have large contribution from ligand-to-metal charge transfer (LMCT), which is responsible for changes of solution color in the process of macrocyclic ligand sensing uranyl species.
A relativistic density functional theory (DFT) was used to systematically examine a series of uranyl and transuranyl complexes of N-donor macrocyclic ligands, [(AnO2)(Ln)]2-(labeled as nAn; n=1~3; An=U, Np and Pu). Further comparison was made with[(UO2)(L0)]2-(A) that was experimentally synthesized. Cavities of L1 and L2 macrocycles are found to match well with actinyl ions, but the one of L3 is a lot larger. Consequently, the L3 complexes have to adopt distorted geometry to energetically stabilize systems. Infrared vibrational spectra presented that the An=O stretching frequencies decrease in going from U, Np to Pu. This agrees with the trend of optimized bond lengths of An=O and bond orders. Topological analyses of quantum theory of atoms in molecule (QTAIM) indicate that the An-N bonds have largely ionic character. Depending on different actinyl source, free energies reacting with various macrocyclic ligands were calculated around 146.4 kJ·mol-1, comparable to the calculated values of A. Time-dependent DFT calculations on four uranyl complexes well reproduced absorption spectra of experimentally reported analogue. The absorption bands in the near-IR and visible region have large contribution from ligand-to-metal charge transfer (LMCT), which is responsible for changes of solution color in the process of macrocyclic ligand sensing uranyl species.
2018, 34(6): 1079-1085
doi: 10.11862/CJIC.2018.148
Abstract:
Two novel ruthenium-arene complexes of general formula[Ru(η6-p-cymene)(L)Cl]Cl, where L=4, 4'-dimethyl-2, 2'-bipyridine (1), 4'-methyl-(2, 2'-bipyridine)-4-carbaldehyde oxime (2), were synthesized. They were characterized by elemental analysis, mass spectrometry and 1H NMR spectroscopy. The hydrolytic property and binding activity of complexes with CT-DNA and serum proteins were detected by UV spectroscopy and fluorescence spectroscopy; the cytotoxic assay was also conducted. The results indicated that 1 is more dynamically stable in the aqueous solution than 2. Complexes 1 and 2 bind to DNA double helix structure via intercalation with the binding constants of 7.8×103 L·mol-1 (1) and 1.86×104 L·mol-1 (2), respectively. These complexes also exhibit strong interaction with protein and cause quiescent quenching of proteins with the binding constants of 1.04×105 L·mol-1 (1) and 8.62×104 L·mol-1 (2), respectively. Strong binding ability between complexes and protein may be the reason of low cytotoxicity.
Two novel ruthenium-arene complexes of general formula[Ru(η6-p-cymene)(L)Cl]Cl, where L=4, 4'-dimethyl-2, 2'-bipyridine (1), 4'-methyl-(2, 2'-bipyridine)-4-carbaldehyde oxime (2), were synthesized. They were characterized by elemental analysis, mass spectrometry and 1H NMR spectroscopy. The hydrolytic property and binding activity of complexes with CT-DNA and serum proteins were detected by UV spectroscopy and fluorescence spectroscopy; the cytotoxic assay was also conducted. The results indicated that 1 is more dynamically stable in the aqueous solution than 2. Complexes 1 and 2 bind to DNA double helix structure via intercalation with the binding constants of 7.8×103 L·mol-1 (1) and 1.86×104 L·mol-1 (2), respectively. These complexes also exhibit strong interaction with protein and cause quiescent quenching of proteins with the binding constants of 1.04×105 L·mol-1 (1) and 8.62×104 L·mol-1 (2), respectively. Strong binding ability between complexes and protein may be the reason of low cytotoxicity.
2018, 34(6): 1086-1094
doi: 10.11862/CJIC.2018.144
Abstract:
The shape-controlled hollow sphere Cu2O nanomaterials were prepared by one-step solvothermal method, and used Cu(NO3)2·3H2O as raw material, ethylene glycol as reductant and polyvinylpyrrolidone (PVP) as surfactant. In this study, the influence of different mass ratios of Cu(NO3)2·3H2O and PVP (wCu(NO3)2·3H2O/wPVP) and reaction time on the crystal structures, morphologies, surface area and optical properties of Cu2O was researched. The photocatalytic mechanism of Cu2O nanocrystals are also investigated. The results show that the photocatalytic activity of Cu2O hollow spheres covered by nano-thorns is best when wCu(NO3)2·3H2O/wPVP=45, and at the 1 h of irradiation, the photodegradation efficiency of methyl orange solution can reach up to 94.3%.
The shape-controlled hollow sphere Cu2O nanomaterials were prepared by one-step solvothermal method, and used Cu(NO3)2·3H2O as raw material, ethylene glycol as reductant and polyvinylpyrrolidone (PVP) as surfactant. In this study, the influence of different mass ratios of Cu(NO3)2·3H2O and PVP (wCu(NO3)2·3H2O/wPVP) and reaction time on the crystal structures, morphologies, surface area and optical properties of Cu2O was researched. The photocatalytic mechanism of Cu2O nanocrystals are also investigated. The results show that the photocatalytic activity of Cu2O hollow spheres covered by nano-thorns is best when wCu(NO3)2·3H2O/wPVP=45, and at the 1 h of irradiation, the photodegradation efficiency of methyl orange solution can reach up to 94.3%.
2018, 34(6): 1095-1102
doi: 10.11862/CJIC.2018.164
Abstract:
A novel sandwich-like nanocomposites of rGO/Fe3O4@mSiO2 were successfully fabricated through a facile method. The morphology and properties of nanocomposites were characterized by SEM, TEM, FTIR, XRD and N2 adsorption-desorption. As a result, it was observed that the nanocomposites exhibit the saturation magnetization of 32 emu·g-1, and possess abundant pores with a large surface area as much as 217 m2·g-1. The loading capacity of Pentafluorouracil (5-FU) with the nanocomposites was high(57.34%). The formation mechanism of rGO/Fe3O4@mSiO2 was discussed. Additionally, the synergistic anticancer efficacy of as-prepared nanocomposites against HeLa cell line was investigated by MTT assay and cell fluorescence microscopic imaging analysis. The results indicated that 5-FU loaded in the nanocoposites is effectively delivered to tumor lesion sites under the action of magnetic targeting. Moreover, the rGO/Fe3O4@mSiO2 nanocomposites have excellent photothermal conversion properties under light conditions, and show significant killing effect on HeLa cells.
A novel sandwich-like nanocomposites of rGO/Fe3O4@mSiO2 were successfully fabricated through a facile method. The morphology and properties of nanocomposites were characterized by SEM, TEM, FTIR, XRD and N2 adsorption-desorption. As a result, it was observed that the nanocomposites exhibit the saturation magnetization of 32 emu·g-1, and possess abundant pores with a large surface area as much as 217 m2·g-1. The loading capacity of Pentafluorouracil (5-FU) with the nanocomposites was high(57.34%). The formation mechanism of rGO/Fe3O4@mSiO2 was discussed. Additionally, the synergistic anticancer efficacy of as-prepared nanocomposites against HeLa cell line was investigated by MTT assay and cell fluorescence microscopic imaging analysis. The results indicated that 5-FU loaded in the nanocoposites is effectively delivered to tumor lesion sites under the action of magnetic targeting. Moreover, the rGO/Fe3O4@mSiO2 nanocomposites have excellent photothermal conversion properties under light conditions, and show significant killing effect on HeLa cells.
2018, 34(6): 1103-1109
doi: 10.11862/CJIC.2018.146
Abstract:
Nanoporous Ni and Ni-Co alloys were prepared by a method of rapid quenching and de-alloying, and the samples were corroded and annealed to synthesize the nanoporous NiO and NiCo2O4 material respectively. The composition, morphology and microstructure of NiO and NiCo2O4 were analyzed by XRD, SEM, TEM and N2 adsorption-desorption. The electrochemical performance was investigated by cyclic voltammetry and galvanostatic charge-discharge. The results show that the porous NiO has a uniform "mud crack" structure. The specific capacitance of nanoporous NiO is 375 F·g-1 at current density of 1 A·g-1 and its retention ratio remains at 67.5% when the current density increases to 20 A·g-1. After galvanostatic charge-discharge 1 000 cycles at 4 A·g-1, the retention ratio of specific capacitance is 81.7%. The porous NiCo2O4 has a lamellar structure. The specific capacitance of nanoporous NiCo2O4 is 674 F·g-1 at current density of 1 A·g-1 and its retention ratio remains at 72.0% when the current density increases to 20 A·g-1. After galvanostatic charge-discharge 1 000 cycles at 4 A·g-1, the retention ratio of specific capacitance is 92.9%. NiCo2O4 shows superior supercapacitive performance because of the mechanical stability of the bicontinuous nanoporous structure.
Nanoporous Ni and Ni-Co alloys were prepared by a method of rapid quenching and de-alloying, and the samples were corroded and annealed to synthesize the nanoporous NiO and NiCo2O4 material respectively. The composition, morphology and microstructure of NiO and NiCo2O4 were analyzed by XRD, SEM, TEM and N2 adsorption-desorption. The electrochemical performance was investigated by cyclic voltammetry and galvanostatic charge-discharge. The results show that the porous NiO has a uniform "mud crack" structure. The specific capacitance of nanoporous NiO is 375 F·g-1 at current density of 1 A·g-1 and its retention ratio remains at 67.5% when the current density increases to 20 A·g-1. After galvanostatic charge-discharge 1 000 cycles at 4 A·g-1, the retention ratio of specific capacitance is 81.7%. The porous NiCo2O4 has a lamellar structure. The specific capacitance of nanoporous NiCo2O4 is 674 F·g-1 at current density of 1 A·g-1 and its retention ratio remains at 72.0% when the current density increases to 20 A·g-1. After galvanostatic charge-discharge 1 000 cycles at 4 A·g-1, the retention ratio of specific capacitance is 92.9%. NiCo2O4 shows superior supercapacitive performance because of the mechanical stability of the bicontinuous nanoporous structure.
2018, 34(6): 1110-1120
doi: 10.11862/CJIC.2018.149
Abstract:
Three coordination polymers of cadmium and zinc {[Cd2(CPhIDC)(bimb)]·H2O}n (1), {[Cd2(CPhIDC)(phen)2]·3H2O}n (2), {[Zn2(CPhIDC)(bpp)]·1.5H2O}n (3), (H4CPhIDC=2-(4'-carboxyphenyl)-1H-imidazole-4, 5-dicar-boxylic acid, bimb=1, 4-bis(imidazoL-1-yl)butane, phen=1, 10-phenanthroline, bpp=1, 3-di(pyridin-4-yl)propane) have been synthesized by solvothermal reaction and characterized by IR, EA and PXRD. Single crystal X-ray diffraction shows that the H4CPhIDC ligand presents fully deprotonated motifs of CPhIDC4- in three corresponding polymers. Moreover, the fully deprotonated ligands coordinate in the μ4 and μ5 manner to generate 2D and 3D polymers, displaying three different coordination modes. Complexes 1 and 3 exhibit 3D structures with (3, 4, 5)-connected frameworks with (5·6·7)(4·52·6·72)(4·52·6·74·82) topology, but the metal ions and auxiliary ligands are different. 2 displays a 2D wave-like fishing nets structure with 44·62 topology. The fluorescence spectra in the solid state and DNA binding properties of the polymers and ligand are investigated.
Three coordination polymers of cadmium and zinc {[Cd2(CPhIDC)(bimb)]·H2O}n (1), {[Cd2(CPhIDC)(phen)2]·3H2O}n (2), {[Zn2(CPhIDC)(bpp)]·1.5H2O}n (3), (H4CPhIDC=2-(4'-carboxyphenyl)-1H-imidazole-4, 5-dicar-boxylic acid, bimb=1, 4-bis(imidazoL-1-yl)butane, phen=1, 10-phenanthroline, bpp=1, 3-di(pyridin-4-yl)propane) have been synthesized by solvothermal reaction and characterized by IR, EA and PXRD. Single crystal X-ray diffraction shows that the H4CPhIDC ligand presents fully deprotonated motifs of CPhIDC4- in three corresponding polymers. Moreover, the fully deprotonated ligands coordinate in the μ4 and μ5 manner to generate 2D and 3D polymers, displaying three different coordination modes. Complexes 1 and 3 exhibit 3D structures with (3, 4, 5)-connected frameworks with (5·6·7)(4·52·6·72)(4·52·6·74·82) topology, but the metal ions and auxiliary ligands are different. 2 displays a 2D wave-like fishing nets structure with 44·62 topology. The fluorescence spectra in the solid state and DNA binding properties of the polymers and ligand are investigated.
2018, 34(6): 1121-1126
doi: 10.11862/CJIC.2018.135
Abstract:
Two new isomorphic coordination polymers, [M(btec)0.5(H2L)]n (M=Co(Ⅱ) (1), Cu(Ⅱ) (2); H4btec=1, 2, 4, 5-benzenetetracarboxylic acid; H2L=3-(1H-pyrazol-4-yl)-5-(pyridin-2-yl)-1, 2, 4-triazole), have been synthesized under hydrothermal conditions. Compounds 1 and 2 were structurally characterized by elemental analysis, single crystal X-ray diffraction analysis, infrared spectroscopy and powder X-ray diffraction analysis. Single crystal X-ray diffraction measurement reveals that compounds 1 and 2 are isostructural structure and all crystallize in the orthorhombic system, space group Pbca. Compounds 1 and 2 have same 2D structure, which are connected by N…H…O hydrogen bonds to generate 3D frameworks. In addition, magnetic studies indicate that 1 show weak ferromagnetic exchange through carboxylate bridges between metal ions, and there is typical paramagnetic behavior in 2.
Two new isomorphic coordination polymers, [M(btec)0.5(H2L)]n (M=Co(Ⅱ) (1), Cu(Ⅱ) (2); H4btec=1, 2, 4, 5-benzenetetracarboxylic acid; H2L=3-(1H-pyrazol-4-yl)-5-(pyridin-2-yl)-1, 2, 4-triazole), have been synthesized under hydrothermal conditions. Compounds 1 and 2 were structurally characterized by elemental analysis, single crystal X-ray diffraction analysis, infrared spectroscopy and powder X-ray diffraction analysis. Single crystal X-ray diffraction measurement reveals that compounds 1 and 2 are isostructural structure and all crystallize in the orthorhombic system, space group Pbca. Compounds 1 and 2 have same 2D structure, which are connected by N…H…O hydrogen bonds to generate 3D frameworks. In addition, magnetic studies indicate that 1 show weak ferromagnetic exchange through carboxylate bridges between metal ions, and there is typical paramagnetic behavior in 2.
2018, 34(6): 1127-1136
doi: 10.11862/CJIC.2018.143
Abstract:
Geometries, electronic structure, and bonding nature of a series of mono-manganese-substituted Keggin-type (POMs) with atmospheric small molecules X (X=H2O, N2, O2, NO, N2O, CO and CO2) have been studied based on density functional theory (DFT) method with M06L functional. Due to the poly-anionic nature of polyoxometalates (POMs), the counterions effects have firstly been considered by means of a full treatment of the cesium salt Cs4[PW11O39MnⅢH2O]. DFT-M06L calculations show that the key geometric a nd electronic parameters are almost constants as change of the four Cs counterions. The optimized calculations for[PW11O39MnⅢH2O]4-both in gas phase and solution provide an analogous result, no significant variation of key geometric and electronic parameters was found when compared with the cesium salt. The calculated relative energy of different spin states indicates that the lowest energy spin state is the high-spin quintet state for[PW11O39MnⅢX]4-(X=H2O, N2, N2O, CO and CO2), triplet state for[PW11O39MnⅢO2]4-, and doublet state for[PW11O39MnⅢNO]4-. The calculated adsorption energy of those atmospheric small molecules over the porphyrin-like POM ligand increases in the following order:N2 < N2O < CO≈CO2 < O2 < H2O < NO. The Mn-NO POM complex provides considerable adsorption energy. Mulliken population analysis shows that coordination of NO ligand to the MnⅢ center in its doublet ground state arises from an antiferromagnetic coupling between an intermediate-spin MnⅢ center and NO· unit.
Geometries, electronic structure, and bonding nature of a series of mono-manganese-substituted Keggin-type (POMs) with atmospheric small molecules X (X=H2O, N2, O2, NO, N2O, CO and CO2) have been studied based on density functional theory (DFT) method with M06L functional. Due to the poly-anionic nature of polyoxometalates (POMs), the counterions effects have firstly been considered by means of a full treatment of the cesium salt Cs4[PW11O39MnⅢH2O]. DFT-M06L calculations show that the key geometric a nd electronic parameters are almost constants as change of the four Cs counterions. The optimized calculations for[PW11O39MnⅢH2O]4-both in gas phase and solution provide an analogous result, no significant variation of key geometric and electronic parameters was found when compared with the cesium salt. The calculated relative energy of different spin states indicates that the lowest energy spin state is the high-spin quintet state for[PW11O39MnⅢX]4-(X=H2O, N2, N2O, CO and CO2), triplet state for[PW11O39MnⅢO2]4-, and doublet state for[PW11O39MnⅢNO]4-. The calculated adsorption energy of those atmospheric small molecules over the porphyrin-like POM ligand increases in the following order:N2 < N2O < CO≈CO2 < O2 < H2O < NO. The Mn-NO POM complex provides considerable adsorption energy. Mulliken population analysis shows that coordination of NO ligand to the MnⅢ center in its doublet ground state arises from an antiferromagnetic coupling between an intermediate-spin MnⅢ center and NO· unit.
2018, 34(6): 1137-1142
doi: 10.11862/CJIC.2018.108
Abstract:
The title complex[Ag2(HL)(NO3)2]n (1) (HL=1-(3-ethylpyrazin-2-yl)ethylidene-4-phenylsemicarbazide) has been synthesized and characterized by single crystal X-ray diffraction, elemental analysis and IR spectroscopy.X-ray diffraction analysis results show that in 1, HL acts as a neutral tetradentate ligand to connect with two Ag(Ⅰ) centers, one of which adopts a distorted square pyramid coordination geometry involving one HL ligand with ON2 donor set (carbonyl O, imine N, and pyrazine N1 atoms) and two monodentate nitrate anions; while the other one is four-coordinated with one monodentate nitrate anion, one bidentate nitrate anion and pyrazine N4 atom, thus giving a planar square coordination geometry.Adjacent Ag(Ⅰ) ions are further connected by bridged nitrate anions to form a 2D framework; Moreover, the fluorescence spectra indicate that the interaction of the complex 1 with DNA is stronger than that of the ligand HL.
The title complex[Ag2(HL)(NO3)2]n (1) (HL=1-(3-ethylpyrazin-2-yl)ethylidene-4-phenylsemicarbazide) has been synthesized and characterized by single crystal X-ray diffraction, elemental analysis and IR spectroscopy.X-ray diffraction analysis results show that in 1, HL acts as a neutral tetradentate ligand to connect with two Ag(Ⅰ) centers, one of which adopts a distorted square pyramid coordination geometry involving one HL ligand with ON2 donor set (carbonyl O, imine N, and pyrazine N1 atoms) and two monodentate nitrate anions; while the other one is four-coordinated with one monodentate nitrate anion, one bidentate nitrate anion and pyrazine N4 atom, thus giving a planar square coordination geometry.Adjacent Ag(Ⅰ) ions are further connected by bridged nitrate anions to form a 2D framework; Moreover, the fluorescence spectra indicate that the interaction of the complex 1 with DNA is stronger than that of the ligand HL.
2018, 34(6): 1143-1148
doi: 10.11862/CJIC.2018.141
Abstract:
Two ternary complexes of neodymium ions, [Nd(TTA)3(TPPO)2] (1) and[Nd(BFA)3(TPPO)2] (2), based on 4, 4, 4-trifluoro-1-(2-thienyl)-1, 3-butanedione(TTA), 4, 4, 4-trifluoro-1-phenyl-1, 3-butanedione(BFA) and triphenyl-phosphineoxide(TPPO) have been synthesized by mild condition and the single crystals suitable for X-ray measurement were obtained. The structures of the two Nd complexes were determined in solid states by X-ray diffraction. Single crystal analysis revealed that the complexes are both eight-coordinated with one center Nd ion and eight O atoms from ligands and crystallize in triclinic symmetry with P1 space group. The complexes were characterized by elemental analysis, IR spectroscopy and thermogravimetric. Furthermore, photophysical studies on the complexes were carried out, which shows luminescence in near-infrared area.
Two ternary complexes of neodymium ions, [Nd(TTA)3(TPPO)2] (1) and[Nd(BFA)3(TPPO)2] (2), based on 4, 4, 4-trifluoro-1-(2-thienyl)-1, 3-butanedione(TTA), 4, 4, 4-trifluoro-1-phenyl-1, 3-butanedione(BFA) and triphenyl-phosphineoxide(TPPO) have been synthesized by mild condition and the single crystals suitable for X-ray measurement were obtained. The structures of the two Nd complexes were determined in solid states by X-ray diffraction. Single crystal analysis revealed that the complexes are both eight-coordinated with one center Nd ion and eight O atoms from ligands and crystallize in triclinic symmetry with P1 space group. The complexes were characterized by elemental analysis, IR spectroscopy and thermogravimetric. Furthermore, photophysical studies on the complexes were carried out, which shows luminescence in near-infrared area.
2018, 34(6): 1149-1158
doi: 10.11862/CJIC.2018.140
Abstract:
A novel one-dimensional structured (1D) TiO2-coated CdTe@C nanowires support for Au nanoparticles (CdTe@C@TiO2-Au) is synthesized for photocatalysis application. The structure and properties of the prepared photocatalysts are investigated by X-ray powder diffraction (XRD), scanning transmission electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), and UV-Vis instruments (DRS). As an example of applications, the photodegradation of rhodamine B (RhB) is investigated under the simulated sunlight irradiation. It is found that the photocatalytic activities of these catalysts are 1D CdTe@C@TiO2-Au heteronanowires > CdTe@C@TiO2 nanowires > pure TiO2. Moreover, the degradation rates can reach 95.3% for CdTe@C@TiO2-Au with 270 min of irradiation time. This outcome is attributed to the localized surface plasmon resonance (LSPR) of Au nanoparticles largely enhanced visible light absorption, the efficient photogenerated electron separation of the prepared catalyst and CdTe@C nanowires photosensitized TiO2 structures.
A novel one-dimensional structured (1D) TiO2-coated CdTe@C nanowires support for Au nanoparticles (CdTe@C@TiO2-Au) is synthesized for photocatalysis application. The structure and properties of the prepared photocatalysts are investigated by X-ray powder diffraction (XRD), scanning transmission electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), and UV-Vis instruments (DRS). As an example of applications, the photodegradation of rhodamine B (RhB) is investigated under the simulated sunlight irradiation. It is found that the photocatalytic activities of these catalysts are 1D CdTe@C@TiO2-Au heteronanowires > CdTe@C@TiO2 nanowires > pure TiO2. Moreover, the degradation rates can reach 95.3% for CdTe@C@TiO2-Au with 270 min of irradiation time. This outcome is attributed to the localized surface plasmon resonance (LSPR) of Au nanoparticles largely enhanced visible light absorption, the efficient photogenerated electron separation of the prepared catalyst and CdTe@C nanowires photosensitized TiO2 structures.
2018, 34(6): 1159-1165
doi: 10.11862/CJIC.2018.142
Abstract:
Zero dimensional dinuclear copper(Ⅱ) coordination compound and 3D manganese(Ⅱ) coordination polymer, namely[Cu2(Hdppa)2(4, 4'-bipy)(H2O)4]·4, 4'-bipy·6H2O (1) and {[Mn3(μ5-dppa)2(4, 4'-bipy)(H2O)2]·4H2O}n (2), have been constructed hydrothermally using H3dppa, 4, 4'-bipy (H3dppa=5-(3, 4-dicarboxylphenyl)picolinic acid, 4, 4'-bipy=4, 4'-bipyridine), and copper or manganese chlorides. Single-crystal X-ray diffraction analyses revealed that two compounds crystallize in the triclinic or monoclinic system, space group P1 or C2/c. In compound 1, one 4, 4'-bipy ligand bridges neighboring Cu(Ⅱ) ions to form a discrete dinuclear copper(Ⅱ) structure. These Cu2 units are assembled to a 3D supramolecular framework through O-H…O/N hydrogen bond. In compound 2, neighboring Mn(Ⅱ) ions are bridged by the carboxylate groups of μ5-dppa3- ligands, producing a double-helix Mn(Ⅱ) chain subunit. The adjacent double-helix chains subunits are further linked by the dppa3- blocks and 4, 4'-bipy ligands into a 3D framework. Magnetic studies for compound 2 demonstrate an antiferromagnetic coupling between the adjacent Mn(Ⅱ) centers.
Zero dimensional dinuclear copper(Ⅱ) coordination compound and 3D manganese(Ⅱ) coordination polymer, namely[Cu2(Hdppa)2(4, 4'-bipy)(H2O)4]·4, 4'-bipy·6H2O (1) and {[Mn3(μ5-dppa)2(4, 4'-bipy)(H2O)2]·4H2O}n (2), have been constructed hydrothermally using H3dppa, 4, 4'-bipy (H3dppa=5-(3, 4-dicarboxylphenyl)picolinic acid, 4, 4'-bipy=4, 4'-bipyridine), and copper or manganese chlorides. Single-crystal X-ray diffraction analyses revealed that two compounds crystallize in the triclinic or monoclinic system, space group P1 or C2/c. In compound 1, one 4, 4'-bipy ligand bridges neighboring Cu(Ⅱ) ions to form a discrete dinuclear copper(Ⅱ) structure. These Cu2 units are assembled to a 3D supramolecular framework through O-H…O/N hydrogen bond. In compound 2, neighboring Mn(Ⅱ) ions are bridged by the carboxylate groups of μ5-dppa3- ligands, producing a double-helix Mn(Ⅱ) chain subunit. The adjacent double-helix chains subunits are further linked by the dppa3- blocks and 4, 4'-bipy ligands into a 3D framework. Magnetic studies for compound 2 demonstrate an antiferromagnetic coupling between the adjacent Mn(Ⅱ) centers.
2018, 34(6): 1166-1172
doi: 10.11862/CJIC.2018.133
Abstract:
Au films with three-dimensional (3D) hierarchical pores consisting of interconnected dendrite walls were successfully fabricated by a strategy of cathodic deposition utilizing the hydrogen bubble dynamic template. The deposition conditions like potential, deposition time, H2SO4 concentration, precursor concentrations were investigated in detail. Herein, 3D Au porous films (3D PGFs) with dendritic walls could also be prepared by square wave potential (SWP). The morphology of foam films were characterized by scanning electron microscopy (SEM). The 3D PGFs comprised of nanodendrites show good electrocatalytic activities in enzyme-free detection of glucose.
Au films with three-dimensional (3D) hierarchical pores consisting of interconnected dendrite walls were successfully fabricated by a strategy of cathodic deposition utilizing the hydrogen bubble dynamic template. The deposition conditions like potential, deposition time, H2SO4 concentration, precursor concentrations were investigated in detail. Herein, 3D Au porous films (3D PGFs) with dendritic walls could also be prepared by square wave potential (SWP). The morphology of foam films were characterized by scanning electron microscopy (SEM). The 3D PGFs comprised of nanodendrites show good electrocatalytic activities in enzyme-free detection of glucose.
2018, 34(6): 1173-1182
doi: 10.11862/CJIC.2018.137
Abstract:
A unique core-shell Co3O4@δ-MnO2/Pt arrays-type cathode on Ni foam has been fabricated by a facile, controlled hydrothermal approach. The array-type structure facilitates the electrode wetting and oxygen gas transport and supplies free volume for Li2O2 loading. The Co3O4@δ-MnO2/Pt cathode exhibits high catalytic effect for ORR and OER, where thin-layered Li2O2 shows conformal growth along the surface of the Co3O4@δ-MnO2/Pt arrays with the array-type structure remained. This growth behavior of Li2O2 renders easy decomposition of Li2O2 upon charge. Li-O2 cells with Co3O4@δ-MnO2/Pt delivers a high discharge capacity (2 480 mAh·g-1 at 100 mA·g-1) and long cycle life (65 cycles at 200 mA·g-1 with a limited capacity of 500 mAh·g-1), which are better than those with Co3O4 or Co3O4@δ-MnO2 cathodes.
A unique core-shell Co3O4@δ-MnO2/Pt arrays-type cathode on Ni foam has been fabricated by a facile, controlled hydrothermal approach. The array-type structure facilitates the electrode wetting and oxygen gas transport and supplies free volume for Li2O2 loading. The Co3O4@δ-MnO2/Pt cathode exhibits high catalytic effect for ORR and OER, where thin-layered Li2O2 shows conformal growth along the surface of the Co3O4@δ-MnO2/Pt arrays with the array-type structure remained. This growth behavior of Li2O2 renders easy decomposition of Li2O2 upon charge. Li-O2 cells with Co3O4@δ-MnO2/Pt delivers a high discharge capacity (2 480 mAh·g-1 at 100 mA·g-1) and long cycle life (65 cycles at 200 mA·g-1 with a limited capacity of 500 mAh·g-1), which are better than those with Co3O4 or Co3O4@δ-MnO2 cathodes.
2018, 34(6): 1183-1191
doi: 10.11862/CJIC.2018.143a
Abstract:
Porous BiVO4 thin films have been prepared on the fluorine doped tin oxide (SnO2:F) coated glass substrates through a facile spin-coating strategy for water splitting application. The film thickness was tuned by varying the deposition cycles and the precursor concentration, respectively. The influences of electrolyte composition, film thickness and surface modification were investigated on the actual photoelectrochemical (PEC) performance of the as-annealed BiVO4 porous films. The results show that the PEC activity of BiVO4 can be enhanced effectively by adding a hole scavenger Na2SO3 with suitable amount into the electrolyte, or modified the surface with a co-catalyst Co-Pi. These methods can suppress the carrier recombination that occurs at the solid/liquid interface. The highest photocurrent density (4.3 mA·cm-2 at a bias of 0.6 V (vs SCE)) was achieved in the BiVO4 samples which were synthesized at the optimal condition and characterized under a visible-light irradiation intensity of 100 mW·cm-2, using a 0.1 mol·L-1 Na2SO4+0.1 mol·L-1 Na2SO3 electrolyte. Additionally, a facile PEC bio-sensor is constructed by using a BiVO4 film anode, leading to an acceptable sensitivity for detecting the glutathione (GSH). In a word, it is demonstrated that the PEC performance of BiVO4 is dependent on both the light harvesting and carrier diffusion process.
Porous BiVO4 thin films have been prepared on the fluorine doped tin oxide (SnO2:F) coated glass substrates through a facile spin-coating strategy for water splitting application. The film thickness was tuned by varying the deposition cycles and the precursor concentration, respectively. The influences of electrolyte composition, film thickness and surface modification were investigated on the actual photoelectrochemical (PEC) performance of the as-annealed BiVO4 porous films. The results show that the PEC activity of BiVO4 can be enhanced effectively by adding a hole scavenger Na2SO3 with suitable amount into the electrolyte, or modified the surface with a co-catalyst Co-Pi. These methods can suppress the carrier recombination that occurs at the solid/liquid interface. The highest photocurrent density (4.3 mA·cm-2 at a bias of 0.6 V (vs SCE)) was achieved in the BiVO4 samples which were synthesized at the optimal condition and characterized under a visible-light irradiation intensity of 100 mW·cm-2, using a 0.1 mol·L-1 Na2SO4+0.1 mol·L-1 Na2SO3 electrolyte. Additionally, a facile PEC bio-sensor is constructed by using a BiVO4 film anode, leading to an acceptable sensitivity for detecting the glutathione (GSH). In a word, it is demonstrated that the PEC performance of BiVO4 is dependent on both the light harvesting and carrier diffusion process.
2018, 34(6): 1192-1198
doi: 10.11862/CJIC.2018.147
Abstract:
A bis-Schiff base N, N'-bis(3, 5-difluorosalicylidene)-1, 3-diaminopropane) (H2L) was prepared. Reaction of H2L and manganese acetate with ammonium thiocyanate or sodium azide in methanol gave complexes[MnL(NCS)(OH2)] (1) and[MnL(μ1, 3-N3)]n (2), respectively. H2L and the complexes were characterized by elemental analysis, IR spectra, 1H NMR spectra, and the crystal structures of the complexes were analyzed by single crystal X-ray diffraction. The Schiff base ligand coordinates to the Mn atom through the imino nitrogen and phenolate oxygen. The thiocyanate ligand coordinates to the Mn atom through the nitrogen atom, and the azide ligand coordinates to the Mn atom, with a bridging mode, through two terminal nitrogen atoms. In both complexes, the Mn atoms adopt octahedral coordination. The Schiff base and the complexes were tested for their Jack bean urease inhibitory activities. For complex 1, the inhibition rate at concentration of 100 μmol·L-1 on the urease is (52.0±3.1)%, and the IC50 value is (81.0±3.7) μmol·L-1. While for complex 2, it has no activity against the urease. Molecular docking study of complex 1 was performed to study the inhibition.
A bis-Schiff base N, N'-bis(3, 5-difluorosalicylidene)-1, 3-diaminopropane) (H2L) was prepared. Reaction of H2L and manganese acetate with ammonium thiocyanate or sodium azide in methanol gave complexes[MnL(NCS)(OH2)] (1) and[MnL(μ1, 3-N3)]n (2), respectively. H2L and the complexes were characterized by elemental analysis, IR spectra, 1H NMR spectra, and the crystal structures of the complexes were analyzed by single crystal X-ray diffraction. The Schiff base ligand coordinates to the Mn atom through the imino nitrogen and phenolate oxygen. The thiocyanate ligand coordinates to the Mn atom through the nitrogen atom, and the azide ligand coordinates to the Mn atom, with a bridging mode, through two terminal nitrogen atoms. In both complexes, the Mn atoms adopt octahedral coordination. The Schiff base and the complexes were tested for their Jack bean urease inhibitory activities. For complex 1, the inhibition rate at concentration of 100 μmol·L-1 on the urease is (52.0±3.1)%, and the IC50 value is (81.0±3.7) μmol·L-1. While for complex 2, it has no activity against the urease. Molecular docking study of complex 1 was performed to study the inhibition.
