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2017 Volume 33 Issue 11
2017, 33(11): 1897-1913
doi: 10.11862/CJIC.2017.249
Abstract:
Recently, the metal-free polymeric carbon nitride has drawn tremendous attention by virtue of its unique material composition and electronic structure, holding great promise in optical excitation related applications, such as photocatalysis, photoluminescence, and photoelectrochemistry. The investigation of photoexcitation processes dominated by energy band structure, charge carrier behaviors and excitonic effects in polymeric carbon nitride are of great significance in understanding mechanisms, optimizing performance and expanding application. Focusing on this topic, we review recent advances in research on the photoexcitation processes of polymeric carbon nitride-based materials, by beginning with a brief introduction of the characterization techniques in these works. We then discuss the charge carrier and exciton aspects in the photoexcitation processes. The principles of universal modification strategies on photoexcitation processes are summarized. Also, the applications of the photoexcitation processes in this polymeric semiconductor are highlighted.
Recently, the metal-free polymeric carbon nitride has drawn tremendous attention by virtue of its unique material composition and electronic structure, holding great promise in optical excitation related applications, such as photocatalysis, photoluminescence, and photoelectrochemistry. The investigation of photoexcitation processes dominated by energy band structure, charge carrier behaviors and excitonic effects in polymeric carbon nitride are of great significance in understanding mechanisms, optimizing performance and expanding application. Focusing on this topic, we review recent advances in research on the photoexcitation processes of polymeric carbon nitride-based materials, by beginning with a brief introduction of the characterization techniques in these works. We then discuss the charge carrier and exciton aspects in the photoexcitation processes. The principles of universal modification strategies on photoexcitation processes are summarized. Also, the applications of the photoexcitation processes in this polymeric semiconductor are highlighted.
2017, 33(11): 1914-1936
doi: 10.11862/CJIC.2017.265
Abstract:
Two-dimensional (2D) semiconducting materials have been widely used in optoelectronic devices, catalysis, biosensors and other fields due to their unique molecular structure and electronic properties, herein have attracted lots of attention. In this review, the development of traditional 2D materials as well as novel 2D material graphdiyne has been summarized. The review focused on the application of traditional 2D materials in the field of photodetector, investigated the influence of different material systems and their device structures on the performance of the photodetector. In addition, we further described the synthesis and application of graphdiyne. Finally, we summarized the opportunities and challenges of traditional 2D materials and graphdiyne in the application of energy conversion devices.
Two-dimensional (2D) semiconducting materials have been widely used in optoelectronic devices, catalysis, biosensors and other fields due to their unique molecular structure and electronic properties, herein have attracted lots of attention. In this review, the development of traditional 2D materials as well as novel 2D material graphdiyne has been summarized. The review focused on the application of traditional 2D materials in the field of photodetector, investigated the influence of different material systems and their device structures on the performance of the photodetector. In addition, we further described the synthesis and application of graphdiyne. Finally, we summarized the opportunities and challenges of traditional 2D materials and graphdiyne in the application of energy conversion devices.
2017, 33(11): 1937-1946
doi: 10.11862/CJIC.2017.242
Abstract:
Biominaralization based nanoparticle drug delivery systems that have the advantages of simple preparation, perfect biocompatibility, controlled drug release and easy to be modified have attracted a wide attention in field of clinical applications. This paper systematically elaborated the construction principle and classification of nanocarrier based on biomineralization, and the targeting strategy as well as stimulus response strategy of the caririers are discussed. The outlook of the clinical application is also prospected.
Biominaralization based nanoparticle drug delivery systems that have the advantages of simple preparation, perfect biocompatibility, controlled drug release and easy to be modified have attracted a wide attention in field of clinical applications. This paper systematically elaborated the construction principle and classification of nanocarrier based on biomineralization, and the targeting strategy as well as stimulus response strategy of the caririers are discussed. The outlook of the clinical application is also prospected.
2017, 33(11): 1959-1969
doi: 10.11862/CJIC.2017.244
Abstract:
Metal-organic frameworks (MOFs) have attracted remarkable attention of scientists because of their varied framework structures with definite channels/voids and potential applications in gas adsorption/storage and separation, chemical sensing, optics, magnetism, fluorescent probe and so on. In this review, we focus our attention on fluorescent recognition and sensing of solvent and small organic molecules based on MOFs. Recent research works in this field are summarized and the perspective of this area will be discussed.
Metal-organic frameworks (MOFs) have attracted remarkable attention of scientists because of their varied framework structures with definite channels/voids and potential applications in gas adsorption/storage and separation, chemical sensing, optics, magnetism, fluorescent probe and so on. In this review, we focus our attention on fluorescent recognition and sensing of solvent and small organic molecules based on MOFs. Recent research works in this field are summarized and the perspective of this area will be discussed.
2017, 33(11): 1970-1990
doi: 10.11862/CJIC.2017.257
Abstract:
With the development of nanotechnology, metal nanocomposite materials have received extensive attention due to their unique physiochemical properties and potential catalytic applications. In this article, the latest development of metal nanocomposite catalysts is systematically introduced. First, we present some important synthetic approaches to the metal nanocomposite catalyst. Secondly, in order to better optimize the structure-catalytic activity correlations and understand the catalytic mechanisms, we discuss the influence of some critical factors (e.g. particle size, shape, composition and support or ligand) of metal nanocomposite catalyst on catalytic activity and selectivity. Finally, we pay special attention to metal nanocomposite catalyst for the reduction of unsaturated bonds (N=O, N≡C and C=O), and the research trends of metal nanocomposite catalyst are prospected.
With the development of nanotechnology, metal nanocomposite materials have received extensive attention due to their unique physiochemical properties and potential catalytic applications. In this article, the latest development of metal nanocomposite catalysts is systematically introduced. First, we present some important synthetic approaches to the metal nanocomposite catalyst. Secondly, in order to better optimize the structure-catalytic activity correlations and understand the catalytic mechanisms, we discuss the influence of some critical factors (e.g. particle size, shape, composition and support or ligand) of metal nanocomposite catalyst on catalytic activity and selectivity. Finally, we pay special attention to metal nanocomposite catalyst for the reduction of unsaturated bonds (N=O, N≡C and C=O), and the research trends of metal nanocomposite catalyst are prospected.
2017, 33(11): 1991-2004
doi: 10.11862/CJIC.2017.243
Abstract:
It is always a great challenge to synthesize crystalline and porous polymer materials due to the random configuration and flexibility of polymers. However, polymer-metal coordination complexes (PMCCs) can exhibit high porosity and crystallinity because PMCCs possess not only the properties of polymers such as flexibility and good processability but also the properties of coordination complexes such as high crystallinity and porosity. Herein, this review article summarizes the methods how to construct porous and crystalline PMCCs including photo-induced polymerization method, coordination bond induced self-assembly method, two-step synthesis method and post-synthetic modification method. Finally, we discusse the characterization methods and the potential applications of PMCCs, and list the challenges and chances in the field.
It is always a great challenge to synthesize crystalline and porous polymer materials due to the random configuration and flexibility of polymers. However, polymer-metal coordination complexes (PMCCs) can exhibit high porosity and crystallinity because PMCCs possess not only the properties of polymers such as flexibility and good processability but also the properties of coordination complexes such as high crystallinity and porosity. Herein, this review article summarizes the methods how to construct porous and crystalline PMCCs including photo-induced polymerization method, coordination bond induced self-assembly method, two-step synthesis method and post-synthetic modification method. Finally, we discusse the characterization methods and the potential applications of PMCCs, and list the challenges and chances in the field.
2017, 33(11): 2045-2050
doi: 10.11862/CJIC.2017.246
Abstract:
The tetrathiafulvalene (TTF) functionalized 2, 6-di(pyrazin-2-yl)pyridine derivative, 4-tetrathiafulvalene-2, 6-di(pyrazin-2-yl)pyridine (L), was designed and synthesized. Based on L, one electrochemically active TTF-containing Fe(Ⅱ) complex, namely, [Fe(Ⅱ)(L)2](BF4)2·2.75CH3CN·0.25CH2Cl2 (1), was synthesized and characterized by IR, elemental analysis, and X-ray single crystal diffraction. The complex 1 is formed by ligands and iron(Ⅱ) in a tridentate fashion. Complex 1 exhibits a discrete structure and features diverse nonclassical hydrogen bonding interactions, π…π and S…S interactions. In addition, magnetic, electrochemical, and spectroelectrochemistry properties for complex 1 have been studied.
The tetrathiafulvalene (TTF) functionalized 2, 6-di(pyrazin-2-yl)pyridine derivative, 4-tetrathiafulvalene-2, 6-di(pyrazin-2-yl)pyridine (L), was designed and synthesized. Based on L, one electrochemically active TTF-containing Fe(Ⅱ) complex, namely, [Fe(Ⅱ)(L)2](BF4)2·2.75CH3CN·0.25CH2Cl2 (1), was synthesized and characterized by IR, elemental analysis, and X-ray single crystal diffraction. The complex 1 is formed by ligands and iron(Ⅱ) in a tridentate fashion. Complex 1 exhibits a discrete structure and features diverse nonclassical hydrogen bonding interactions, π…π and S…S interactions. In addition, magnetic, electrochemical, and spectroelectrochemistry properties for complex 1 have been studied.
2017, 33(11): 2051-2059
doi: 10.11862/CJIC.2017.251
Abstract:
The polar acyl hydrazine groups were introduced into a "pillar-layer" MOF, [Zn4(bpta)2(dipytz)2(H2O)2]·4DMF·H2O (1) (H4bpta=1, 1'-biphenyl-2, 2', 6, 6'-tetracarboxylic acid and dipytz=di-3, 6-(4-pyridyl)-1, 2, 4, 5-tetrazine), through the in-situ hydrolysis modification of the dipytz pillar ligand, and [Zn4(bpta)2(dipytzhydr)(H2O)2]·solvent (2) (dipytzhydr=1, 2-diisonicotinoylhydrazine) was obtained. The results of gas sorption measurement show that complex 2 has an enhanced CO2-framework affinity (initial CO2 adsorption enthalpies increase from 28.8 to 30.3 kJ·mol-1) and higher CO2/CH4 selectivity compared with that of complex 1. The present work indicates that in-situ hydrolysis modification is highly potential for the enhancement of CO2 adsorption performance of tetrazine functionalized MOFs.
The polar acyl hydrazine groups were introduced into a "pillar-layer" MOF, [Zn4(bpta)2(dipytz)2(H2O)2]·4DMF·H2O (1) (H4bpta=1, 1'-biphenyl-2, 2', 6, 6'-tetracarboxylic acid and dipytz=di-3, 6-(4-pyridyl)-1, 2, 4, 5-tetrazine), through the in-situ hydrolysis modification of the dipytz pillar ligand, and [Zn4(bpta)2(dipytzhydr)(H2O)2]·solvent (2) (dipytzhydr=1, 2-diisonicotinoylhydrazine) was obtained. The results of gas sorption measurement show that complex 2 has an enhanced CO2-framework affinity (initial CO2 adsorption enthalpies increase from 28.8 to 30.3 kJ·mol-1) and higher CO2/CH4 selectivity compared with that of complex 1. The present work indicates that in-situ hydrolysis modification is highly potential for the enhancement of CO2 adsorption performance of tetrazine functionalized MOFs.
2017, 33(11): 2060-2064
doi: 10.11862/CJIC.2017.256
Abstract:
A couple of pinene-containing europium(Ⅲ) complexes, Eu(TTA)3L1a (1a) and Eu(TTA)3L1b (1b) (TTA=thenoyltrifluoroacetonate, L1a=(+)-4, 5-bis(pinene)-2, 2'-bipyridine, L1b=(-)-4, 5-bis(pinene)-2, 2'-bipyridine), were prepared and characterized. The chiral characterization was confirmed by single crystal X-ray diffraction and distinct electronic circular dichroism (CD) signals. Complex 1a crystallizes in the polar space group P1, and a strongly distorted square-antiprism environment around the Eu(Ⅲ) ion is exhibited. Due to the non-centrosymmetric structure, distinct ferroelectric behavior of complex 1a was observed as expected.
A couple of pinene-containing europium(Ⅲ) complexes, Eu(TTA)3L1a (1a) and Eu(TTA)3L1b (1b) (TTA=thenoyltrifluoroacetonate, L1a=(+)-4, 5-bis(pinene)-2, 2'-bipyridine, L1b=(-)-4, 5-bis(pinene)-2, 2'-bipyridine), were prepared and characterized. The chiral characterization was confirmed by single crystal X-ray diffraction and distinct electronic circular dichroism (CD) signals. Complex 1a crystallizes in the polar space group P1, and a strongly distorted square-antiprism environment around the Eu(Ⅲ) ion is exhibited. Due to the non-centrosymmetric structure, distinct ferroelectric behavior of complex 1a was observed as expected.
2017, 33(11): 2083-2094
doi: 10.11862/CJIC.2017.253
Abstract:
Extra-large-pore and layered organically templated lanthanide sulfates have been prepared under solvothermal conditions. The extra-large-pore lanthanide sulfates, with the composition [(CH3)2NH2]9[Pr5(SO4)12]·2H2O (1), exhibit an interestingly intersecting 20-membered ring channels. The layered lanthanide sulfates, formulated as [H3O]3[(CH3)2NH2]3[Ln2(SO4)6] (Ln=Pr for 2, Nd for 3), can be considered as combination of double-stranded chains and 8-membered rings. The synthesis of three compounds demonstrates that large organic amine (1, 3, 5-triazine-2, 4, 6-triamine) may be used as the second structural directing agent to prevent the formation of high dimensional inorganic framework as well as inducing crystal the growth of 2D layer structural lanthanide sulfates. The magnetic property of compounds 1 and 3 has been investigated through the magnetic measurement over the temperature range of 2~300 K.
Extra-large-pore and layered organically templated lanthanide sulfates have been prepared under solvothermal conditions. The extra-large-pore lanthanide sulfates, with the composition [(CH3)2NH2]9[Pr5(SO4)12]·2H2O (1), exhibit an interestingly intersecting 20-membered ring channels. The layered lanthanide sulfates, formulated as [H3O]3[(CH3)2NH2]3[Ln2(SO4)6] (Ln=Pr for 2, Nd for 3), can be considered as combination of double-stranded chains and 8-membered rings. The synthesis of three compounds demonstrates that large organic amine (1, 3, 5-triazine-2, 4, 6-triamine) may be used as the second structural directing agent to prevent the formation of high dimensional inorganic framework as well as inducing crystal the growth of 2D layer structural lanthanide sulfates. The magnetic property of compounds 1 and 3 has been investigated through the magnetic measurement over the temperature range of 2~300 K.
2017, 33(11): 2005-2010
doi: 10.11862/CJIC.2017.247
Abstract:
Two new isomorphic coordination polymers, [MCl2(β-ala)]n (M=Co2+ (1) or Ni2+ (2), β-ala=3-aminopropi-onic acid), were constructed by assembling 3-aminopropionic acid and transition metal chlorides. Their reversible structural phase transitions were disclosed by differential scanning calorimetry (DSC), variable-temperature single-crystal X-ray diffraction and dielectric measurements. In 1 and 2, the adjacent M2+ ions are mix-bridged by two μ2-Cl- ions and a syn-syn carboxylate group from β-ala ligand, resulting in one-dimensional polymeric coor-dination chains. Both 1 and 2 undergo reversible phase transitions, which occur at critical temperature (Tc-heating, Tc-cooling) of 236, 224 K and 309, 302 K, respectively, with a change of space group between Pnam at the high-temperature phase (HTP) and Pna21 at the low-temperature phase (LTP). The phase transitions are mainly related to the dynamic change of ammonium ethyl group from two-fold disorder in HTP to static ordered state in LTP. Such order-disorder structural phase transitions lead to the coexistence of step-like dielectric anomaly and dielectric relaxation in the vicinity of the phase transition.
Two new isomorphic coordination polymers, [MCl2(β-ala)]n (M=Co2+ (1) or Ni2+ (2), β-ala=3-aminopropi-onic acid), were constructed by assembling 3-aminopropionic acid and transition metal chlorides. Their reversible structural phase transitions were disclosed by differential scanning calorimetry (DSC), variable-temperature single-crystal X-ray diffraction and dielectric measurements. In 1 and 2, the adjacent M2+ ions are mix-bridged by two μ2-Cl- ions and a syn-syn carboxylate group from β-ala ligand, resulting in one-dimensional polymeric coor-dination chains. Both 1 and 2 undergo reversible phase transitions, which occur at critical temperature (Tc-heating, Tc-cooling) of 236, 224 K and 309, 302 K, respectively, with a change of space group between Pnam at the high-temperature phase (HTP) and Pna21 at the low-temperature phase (LTP). The phase transitions are mainly related to the dynamic change of ammonium ethyl group from two-fold disorder in HTP to static ordered state in LTP. Such order-disorder structural phase transitions lead to the coexistence of step-like dielectric anomaly and dielectric relaxation in the vicinity of the phase transition.
2017, 33(11): 2017-2023
doi: 10.11862/CJIC.2017.239
Abstract:
Novel composites with nonlinear optical effect were prepared by exchanging the dimethylamine cation with DB and TM in MOFs (ZJU-28) channels. DB or TM cations with strong polar were arranged along one direction in crystal pores, leading to non-central symmetric crystal. Compared to original ZJU-28, the composite crystals, DB@ZJU-28 and TM@ZJU-28, possess strong second harmonic generation (SHG) and two-photon absorption fluorescence observed through confocal microscopy.
Novel composites with nonlinear optical effect were prepared by exchanging the dimethylamine cation with DB and TM in MOFs (ZJU-28) channels. DB or TM cations with strong polar were arranged along one direction in crystal pores, leading to non-central symmetric crystal. Compared to original ZJU-28, the composite crystals, DB@ZJU-28 and TM@ZJU-28, possess strong second harmonic generation (SHG) and two-photon absorption fluorescence observed through confocal microscopy.
2017, 33(11): 2065-2074
doi: 10.11862/CJIC.2017.250
Abstract:
The molecular docking, molecular dynamics (MD) simulation, and binding free energy analysis are used to gain the insight into the binding mechanism of three 1, 7-diazacarbazole derivatives (marked as M1, M2, and M3, respectively) with AChE at the atom level. The electrostatic and van der Waals (vdW) interactions of the three inhibitors with AChE are analyzed and discussed. The ranking of the computed binding free energies based on MM-PBSA method is consistent with the ranking of experimental bioactivities for the three inhibitors. The hydrogen-bond interactions of the inhibitors with S286 are favorable to the binding affinity of inhibitors to AChE. The van der Waals interactions, especially the key contacts with W279 and Y334 have larger contributions to the binding free energy and play an important role in distinguishing the bioactivities of M1(or M2) and M3.
The molecular docking, molecular dynamics (MD) simulation, and binding free energy analysis are used to gain the insight into the binding mechanism of three 1, 7-diazacarbazole derivatives (marked as M1, M2, and M3, respectively) with AChE at the atom level. The electrostatic and van der Waals (vdW) interactions of the three inhibitors with AChE are analyzed and discussed. The ranking of the computed binding free energies based on MM-PBSA method is consistent with the ranking of experimental bioactivities for the three inhibitors. The hydrogen-bond interactions of the inhibitors with S286 are favorable to the binding affinity of inhibitors to AChE. The van der Waals interactions, especially the key contacts with W279 and Y334 have larger contributions to the binding free energy and play an important role in distinguishing the bioactivities of M1(or M2) and M3.
2017, 33(11): 2075-2082
doi: 10.11862/CJIC.2017.252
Abstract:
The introduction of alkoxyl groups to 5, 6-positions of 1, 10-phenanthroline can not only lead to the enhancement of the reaction activity, but also increase the solubility of the targeted compounds. Crystal structure analyses reveal that the two alkoxyl groups at 5, 6-positions of 1, 10-phenanthroline adopt double six-membered ethylenedioxy cyclic conformation. Both TPA1 and TPA2 show selective recognition toward the silver ion. No obvious fluorescence quenching is found after the treatment of TPA1 and Ag+, in which a red shift of 47 nm in the fluorescence emission spectrum is observed. On the other hand, the two emission peaks at 415 and 542 nm in the fluorescence emission spectra are quenched when TPA2 is reacted with Ag+. However, the fluorescence quenching effect for Ag+ is not obvious in the case of TPA3, which makes it not a good candidate for the metal-ion recognition.
The introduction of alkoxyl groups to 5, 6-positions of 1, 10-phenanthroline can not only lead to the enhancement of the reaction activity, but also increase the solubility of the targeted compounds. Crystal structure analyses reveal that the two alkoxyl groups at 5, 6-positions of 1, 10-phenanthroline adopt double six-membered ethylenedioxy cyclic conformation. Both TPA1 and TPA2 show selective recognition toward the silver ion. No obvious fluorescence quenching is found after the treatment of TPA1 and Ag+, in which a red shift of 47 nm in the fluorescence emission spectrum is observed. On the other hand, the two emission peaks at 415 and 542 nm in the fluorescence emission spectra are quenched when TPA2 is reacted with Ag+. However, the fluorescence quenching effect for Ag+ is not obvious in the case of TPA3, which makes it not a good candidate for the metal-ion recognition.
2017, 33(11): 2095-2102
doi: 10.11862/CJIC.2017.241
Abstract:
Four lanthanide-organic frameworks (LOFs), [LnL1.5(DMA)]n (Ln=Eu (1), Gd (2), Tb (3), Dy (4); H2L=2, 2'-dinitro-4, 4'-biphenyldicarboxylic acid, DMA=N, N-dimethylacetylamide), have been prepared by the solvo-thermal reaction of H2L and Ln(NO3)3·6H2O. Their structures have been characterized by elemental analyses, IR, TGA, single-crystal and powder X-ray diffraction (XRD) studies. Crystal structure analyses show that LOFs 1~4 crystallize in the monoclinic system with C2/c space group. LOFs 1~4 are isomorphous and possess a binodal (3, 8)-connected three-dimensional (3D) topology network. All the LOFs exhibit high thermal stabilities (Td > 322 ℃). Furthermore, 1 displays characteristic luminescence of Eu(Ⅲ) ion while 3 only shows the emission peak of the L2- ligand.
Four lanthanide-organic frameworks (LOFs), [LnL1.5(DMA)]n (Ln=Eu (1), Gd (2), Tb (3), Dy (4); H2L=2, 2'-dinitro-4, 4'-biphenyldicarboxylic acid, DMA=N, N-dimethylacetylamide), have been prepared by the solvo-thermal reaction of H2L and Ln(NO3)3·6H2O. Their structures have been characterized by elemental analyses, IR, TGA, single-crystal and powder X-ray diffraction (XRD) studies. Crystal structure analyses show that LOFs 1~4 crystallize in the monoclinic system with C2/c space group. LOFs 1~4 are isomorphous and possess a binodal (3, 8)-connected three-dimensional (3D) topology network. All the LOFs exhibit high thermal stabilities (Td > 322 ℃). Furthermore, 1 displays characteristic luminescence of Eu(Ⅲ) ion while 3 only shows the emission peak of the L2- ligand.
2017, 33(11): 2110-2116
doi: 10.11862/CJIC.2017.230
Abstract:
The novel H2TNPP/TPA and H2TNPP/NaTP organic-inorganic hybrid nanocomposites [H2TNPP=tetrakis(4-N, N-diethylaminophenyl)porphyrin, TPA=the phosphotungstic acid and NaTP=sodium phosphotungstate] are fabricated by a simple QLS method. H-type molecular stacking mode with a tilted edge-on orientation of the H2TNPP has been formed in the hybrid films. The intermolecular face-to-face π-π interaction and film microstructures are effectively improved by introducing inorganic TPA and NaTP within the organic H2TNPP films, compared with the pure H2TNPP film. In particular, good film-conductivity, smaller grain size and large specific surface area of H2TNPP/NaTP hybrid film render it excellent sensing property for NO2 gas with the lowest detection limit of 0.094 mg·m-3 and highest sensitivity (43%) among the three kinds of films in room temperature, suggesting the great potential of semiconducting H2TNPP/NaTP organic-inorganic hybrid nanocomposites in the field of chemical sensors. The present result provides a new strategy to obtain high performance room-temperature gas sensors by the construction of organic/inorganic hybrid structure combined with a low-cost solution-based method.
The novel H2TNPP/TPA and H2TNPP/NaTP organic-inorganic hybrid nanocomposites [H2TNPP=tetrakis(4-N, N-diethylaminophenyl)porphyrin, TPA=the phosphotungstic acid and NaTP=sodium phosphotungstate] are fabricated by a simple QLS method. H-type molecular stacking mode with a tilted edge-on orientation of the H2TNPP has been formed in the hybrid films. The intermolecular face-to-face π-π interaction and film microstructures are effectively improved by introducing inorganic TPA and NaTP within the organic H2TNPP films, compared with the pure H2TNPP film. In particular, good film-conductivity, smaller grain size and large specific surface area of H2TNPP/NaTP hybrid film render it excellent sensing property for NO2 gas with the lowest detection limit of 0.094 mg·m-3 and highest sensitivity (43%) among the three kinds of films in room temperature, suggesting the great potential of semiconducting H2TNPP/NaTP organic-inorganic hybrid nanocomposites in the field of chemical sensors. The present result provides a new strategy to obtain high performance room-temperature gas sensors by the construction of organic/inorganic hybrid structure combined with a low-cost solution-based method.
2017, 33(11): 2117-2123
doi: 10.11862/CJIC.2017.248
Abstract:
A Pb-containing mixed halide, Pb7F12Br2, was synthesized and confirmed by single X-ray diffraction. Its nonlinear optical (NLO) and related properties have been studied systematically for the first time. It shows much wide energy band gap of 4.32 eV with large laser damage threshold (LDT) value of 25 MW·cm-2 that is higher than that of the currently commercialized infrared (IR) NLO material AgGaS2 measured at the same conditions ( < 5.2 MW·cm-2). Second harmonic generation (SHG) effect test shows that its powders exhibit phase-matching SHG response of about 1.5 times as strong as that of KDP (KH2PO4). Its powders also show good transparence in the region of 0.3~14 μm and exhibit excellent thermal stability with the decomposition temperature up to 650 ℃. Thus, it shows good comprehensive properties.
A Pb-containing mixed halide, Pb7F12Br2, was synthesized and confirmed by single X-ray diffraction. Its nonlinear optical (NLO) and related properties have been studied systematically for the first time. It shows much wide energy band gap of 4.32 eV with large laser damage threshold (LDT) value of 25 MW·cm-2 that is higher than that of the currently commercialized infrared (IR) NLO material AgGaS2 measured at the same conditions ( < 5.2 MW·cm-2). Second harmonic generation (SHG) effect test shows that its powders exhibit phase-matching SHG response of about 1.5 times as strong as that of KDP (KH2PO4). Its powders also show good transparence in the region of 0.3~14 μm and exhibit excellent thermal stability with the decomposition temperature up to 650 ℃. Thus, it shows good comprehensive properties.
2017, 33(11): 2147-2152
doi: 10.11862/CJIC.2017.272
Abstract:
Sulfur doped porous carbon (S-PC) were obtained by direct carbonization of sulfur containing phenolic resins, which were synthesized through one step reaction between phloroglucinol and benzo[b]thiophenc-3-carboxaldehyde under room temperature. The material was characterized by scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and N2 sorption-desorption experiments. The obtained porous carbons possess high surface area with abundant of micropores. What's more, ultra-high surface area of 997 m2·g-1 along with ultra-large micropore volume of 0.44 cm3·g-1 could be obtained after carefully regulation the concentration of reactants. Owing to these fascinating characters like high surface area and rich of micropores, both high CO2 uptake capacity (5.13 and 3.22 mmol·g-1 for 273 and 298 K respectively) and high selectivity was obtained, which indicating it's promising sorbents for CO2.
Sulfur doped porous carbon (S-PC) were obtained by direct carbonization of sulfur containing phenolic resins, which were synthesized through one step reaction between phloroglucinol and benzo[b]thiophenc-3-carboxaldehyde under room temperature. The material was characterized by scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and N2 sorption-desorption experiments. The obtained porous carbons possess high surface area with abundant of micropores. What's more, ultra-high surface area of 997 m2·g-1 along with ultra-large micropore volume of 0.44 cm3·g-1 could be obtained after carefully regulation the concentration of reactants. Owing to these fascinating characters like high surface area and rich of micropores, both high CO2 uptake capacity (5.13 and 3.22 mmol·g-1 for 273 and 298 K respectively) and high selectivity was obtained, which indicating it's promising sorbents for CO2.
2017, 33(11): 2011-2016
doi: 10.11862/CJIC.2017.254
Abstract:
A series of near infrared (NIR) luminescent complexes based on ErxYb1-x(TPB)3Bath (where TPB=4, 4, 4-tri-fluoro-1-phenyl-1, 3-butanedione, Bath=4, 7-diphenyl-1, 10-phenanthroline, x=0, 0.218, 0.799, 0.896, 0.987, 1, respectively) were prepared by selecting TPB and Bath as the first and second ligands, respectively. Luminescence properties of these complexes were investigated in detail. All these complexes exhibit the characteristic emission of the Yb3+ and/or Er3+ ion in the NIR region, and the emission intensity of Er3+ ion can be enhanced by modulating the nEr/nYb, which is related to the energy transfer from Yb3+ to Er3+ ions.
A series of near infrared (NIR) luminescent complexes based on ErxYb1-x(TPB)3Bath (where TPB=4, 4, 4-tri-fluoro-1-phenyl-1, 3-butanedione, Bath=4, 7-diphenyl-1, 10-phenanthroline, x=0, 0.218, 0.799, 0.896, 0.987, 1, respectively) were prepared by selecting TPB and Bath as the first and second ligands, respectively. Luminescence properties of these complexes were investigated in detail. All these complexes exhibit the characteristic emission of the Yb3+ and/or Er3+ ion in the NIR region, and the emission intensity of Er3+ ion can be enhanced by modulating the nEr/nYb, which is related to the energy transfer from Yb3+ to Er3+ ions.
2017, 33(11): 2024-2030
doi: 10.11862/CJIC.2017.231
Abstract:
Core-shell structure of SrTiO3/PVDF composite films cross-linked with silane coupling agent 3-aminopropyltriethoxysilane (3-APTS) were prepared by solution casting method and characterized by XRD, FTIR, TG, DSC, SEM, dielectric and ferroelectric test. SrTiO3 (ST) can be homogeneously distributed into PVDF matrix without obvious agglomeration in the presence of silane coupling agent, which may be related to the formation of core-shell structure in which 3-APTS acts as a cross-linker between polymer and inorganic material. The introduction of ST is helpful to improve the crystallinity, but will lead to a slight decrease in the electroactive β-phase content of composite films. The dielectric constant of composite film will increase up to 2.5 times larger than that of neat PVDF when the mass content of ST is up to 30%, and without leading to obvious increase of dielectric losses. Meanwhile, the Ps value of this film is increased up to about two times larger than that of pure PVDF. Our study suggests that the incorporation of surface modified ST into PVDF matrix is a useful way to obtain well dispersed film and improve its dielectric and ferroelectric property.
Core-shell structure of SrTiO3/PVDF composite films cross-linked with silane coupling agent 3-aminopropyltriethoxysilane (3-APTS) were prepared by solution casting method and characterized by XRD, FTIR, TG, DSC, SEM, dielectric and ferroelectric test. SrTiO3 (ST) can be homogeneously distributed into PVDF matrix without obvious agglomeration in the presence of silane coupling agent, which may be related to the formation of core-shell structure in which 3-APTS acts as a cross-linker between polymer and inorganic material. The introduction of ST is helpful to improve the crystallinity, but will lead to a slight decrease in the electroactive β-phase content of composite films. The dielectric constant of composite film will increase up to 2.5 times larger than that of neat PVDF when the mass content of ST is up to 30%, and without leading to obvious increase of dielectric losses. Meanwhile, the Ps value of this film is increased up to about two times larger than that of pure PVDF. Our study suggests that the incorporation of surface modified ST into PVDF matrix is a useful way to obtain well dispersed film and improve its dielectric and ferroelectric property.
2017, 33(11): 2031-2037
doi: 10.11862/CJIC.2017.245
Abstract:
A new 3D porous MOF, {[CuL]·x(Solvent)}n (1) have been successfully synthesized based upon a bifunctional organic ligand with two carboxyl groups and one nitrogen donor of 5-(quinolin-6-yl)isophthalic acid (H2L). MOF 1 exhibits an eea topological network with the point (Schläfli) symbol of {42.6}2{44.62.86.103}. Remarkably, desolvated 1 performs a high CH4 adsorption enthalpy and high methane uptake at high pressure and 298 K.
A new 3D porous MOF, {[CuL]·x(Solvent)}n (1) have been successfully synthesized based upon a bifunctional organic ligand with two carboxyl groups and one nitrogen donor of 5-(quinolin-6-yl)isophthalic acid (H2L). MOF 1 exhibits an eea topological network with the point (Schläfli) symbol of {42.6}2{44.62.86.103}. Remarkably, desolvated 1 performs a high CH4 adsorption enthalpy and high methane uptake at high pressure and 298 K.
2017, 33(11): 2103-2109
doi: 10.11862/CJIC.2017.238
Abstract:
Under weak base conditions, diruthenium(Ⅲ) tetrakis-N, N'-dimethylbenzamidinate (DMBA) nitrate Ru2(DMBA)4(NO3)2 was reacted with arylethyne ligands, where aryl=NAPme (N-methyl-1, 8-naphthalimide), NAPiso (N-isopropyl-1, 8-naphthalimide), Naphth (naphthalene) and Ant (anthracene), to afford four new compounds: trans-Ru2(DMBA)4(C2Ar)2 (Ar=NAPme, 1; NAPiso, 2; Naphth, 3; Ant, 4). Molecular structures of new compounds were determined using single crystal X-ray diffraction, and the Ru-Ru bond lengths (0.245 0~0.249 1 nm) are consis-tent with the existence of a Ru-Ru single bond. These compounds are diamagnetic and were further characterized with 1H NMR and UV-Vis-NIR spectroscopic techniques. Cyclic voltammograms of compounds 1~4 consist of two reversible one-electron processes, an oxidation and a reduction, and their potentials depend on the nature of Ar.
Under weak base conditions, diruthenium(Ⅲ) tetrakis-N, N'-dimethylbenzamidinate (DMBA) nitrate Ru2(DMBA)4(NO3)2 was reacted with arylethyne ligands, where aryl=NAPme (N-methyl-1, 8-naphthalimide), NAPiso (N-isopropyl-1, 8-naphthalimide), Naphth (naphthalene) and Ant (anthracene), to afford four new compounds: trans-Ru2(DMBA)4(C2Ar)2 (Ar=NAPme, 1; NAPiso, 2; Naphth, 3; Ant, 4). Molecular structures of new compounds were determined using single crystal X-ray diffraction, and the Ru-Ru bond lengths (0.245 0~0.249 1 nm) are consis-tent with the existence of a Ru-Ru single bond. These compounds are diamagnetic and were further characterized with 1H NMR and UV-Vis-NIR spectroscopic techniques. Cyclic voltammograms of compounds 1~4 consist of two reversible one-electron processes, an oxidation and a reduction, and their potentials depend on the nature of Ar.
2017, 33(11): 2124-2138
doi: 10.11862/CJIC.2017.255
Abstract:
Treatment of Cp3Ln with o-aminobenzamide followed by crystallization in a HMPA and toluene mixture affords the tetranuclear organolanthanide complexes [CpLn(μ-η2:η2-NHC6H4CONH)(μ3-η1:η1:η2-NHC6H4CONH)LnCp(HMPA)}2 (Ln=Yb, 1a; Er, 1b; Y, 1c). Reaction of 1 with PhNCO (nPhNCO/n1=4) in toluene gives the dianionic quinazolyldiolate (Quo) complexes [Cp2Ln(μ3-η2:η2:η1-Quo)]3Ln(HMPA)2 (Ln=Yb, 2a; Er, 2b; Y, 2c), indicating that one isocyanate molecule can undergo the tandem reaction with both NH and CONH of 1 to construct a quinazoly-ldiolate skeleton, companying with the elimination of PhNH2. However, 1a~1c react with iPrN=C=NiPr under the same conditions to give only the single ArNH addition products {Cp2Ln[μ-η1:η1:η2-iPrNC(NHiPr)NC6H4 CONH]}3Ln(HMPA)3 (Ln=Yb, 3a; Er, 3b; Y, 3c). Furthermore, treatment of Cp3Ln with o-aminobenzamide followed by reacting with iPrN=C=NiPr gave {CpLn[μ-η1:η2:η2-NHCOC6H4NC(NHiPr)NiPr]}2 (Ln=Yb, 4a; Er, 4b; Y, 4c). Noticeably, HMPA could induce the transformation of 4 into 3 by a ligand redistribution.
Treatment of Cp3Ln with o-aminobenzamide followed by crystallization in a HMPA and toluene mixture affords the tetranuclear organolanthanide complexes [CpLn(μ-η2:η2-NHC6H4CONH)(μ3-η1:η1:η2-NHC6H4CONH)LnCp(HMPA)}2 (Ln=Yb, 1a; Er, 1b; Y, 1c). Reaction of 1 with PhNCO (nPhNCO/n1=4) in toluene gives the dianionic quinazolyldiolate (Quo) complexes [Cp2Ln(μ3-η2:η2:η1-Quo)]3Ln(HMPA)2 (Ln=Yb, 2a; Er, 2b; Y, 2c), indicating that one isocyanate molecule can undergo the tandem reaction with both NH and CONH of 1 to construct a quinazoly-ldiolate skeleton, companying with the elimination of PhNH2. However, 1a~1c react with iPrN=C=NiPr under the same conditions to give only the single ArNH addition products {Cp2Ln[μ-η1:η1:η2-iPrNC(NHiPr)NC6H4 CONH]}3Ln(HMPA)3 (Ln=Yb, 3a; Er, 3b; Y, 3c). Furthermore, treatment of Cp3Ln with o-aminobenzamide followed by reacting with iPrN=C=NiPr gave {CpLn[μ-η1:η2:η2-NHCOC6H4NC(NHiPr)NiPr]}2 (Ln=Yb, 4a; Er, 4b; Y, 4c). Noticeably, HMPA could induce the transformation of 4 into 3 by a ligand redistribution.
2017, 33(11): 2139-2146
doi: 10.11862/CJIC.2017.258
Abstract:
The reaction of three divalent metal (Ⅱ) halides MCl2 (M=Pb2+, Cd2+, Co2+) with two equivalents of benzothiazole (btz) in the concentrated acid HCl at 80 ℃ resulted in the formation of the corresponding organic-inorganic hybrid compounds: (btzH)[(PbCl3)] (1), (btzH)2[CdCl4]·2H2O (2) and (btzH)2[CoCl4]·2H2O (3), in which the structures of compounds 2 and 3 are similar. All compounds have been characterized by XRD, IR, UV-Vis, EA, TG and single X-ray diffraction. Fluorescent investigation reveals that compounds 1~3 exhibit similar emission peaks at 393 nm, which are ascribed to the π…π transition of the btz ring.
The reaction of three divalent metal (Ⅱ) halides MCl2 (M=Pb2+, Cd2+, Co2+) with two equivalents of benzothiazole (btz) in the concentrated acid HCl at 80 ℃ resulted in the formation of the corresponding organic-inorganic hybrid compounds: (btzH)[(PbCl3)] (1), (btzH)2[CdCl4]·2H2O (2) and (btzH)2[CoCl4]·2H2O (3), in which the structures of compounds 2 and 3 are similar. All compounds have been characterized by XRD, IR, UV-Vis, EA, TG and single X-ray diffraction. Fluorescent investigation reveals that compounds 1~3 exhibit similar emission peaks at 393 nm, which are ascribed to the π…π transition of the btz ring.
2017, 33(11): 2038-2044
doi: 10.11862/CJIC.2017.240
Abstract:
Herein, Pt NPs of ca. 2.5 nm incorporated inside the mesopores of porphyrin-based MOF PCN-222, denoted as Pt@PCN-222, were prepared using double-solvent method followed by visible-light reduction. The obtained mesoporous MOF composite Pt@PCN-222 can effectively adsorb visible-light to promote the water splitting for hydrogen production, which gives a H2 yield of 253 μmol·g-1·h-1.
Herein, Pt NPs of ca. 2.5 nm incorporated inside the mesopores of porphyrin-based MOF PCN-222, denoted as Pt@PCN-222, were prepared using double-solvent method followed by visible-light reduction. The obtained mesoporous MOF composite Pt@PCN-222 can effectively adsorb visible-light to promote the water splitting for hydrogen production, which gives a H2 yield of 253 μmol·g-1·h-1.
