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2016 Volume 33 Issue 5
2016, 33(5): 489-503
doi: 10.11944/j.issn.1000-0518.2016.05.150210
Abstract:
Great attention has recently been gained because of the power conversion efficiency has rapidly increased from about 3% to 20.1% over the past six years since perovskite has been applied in solar cells in 2009. In this article, we propose to review the development in perovskite solar cells, introduce the property and preparation method of perovskite, summarize the structure and mechanism of perovskite solar cells, discuss how to break through and solve the problems in perovskite solar cells, state the impressive development, and present our outlook of the progress of perovskite solar cells.
Great attention has recently been gained because of the power conversion efficiency has rapidly increased from about 3% to 20.1% over the past six years since perovskite has been applied in solar cells in 2009. In this article, we propose to review the development in perovskite solar cells, introduce the property and preparation method of perovskite, summarize the structure and mechanism of perovskite solar cells, discuss how to break through and solve the problems in perovskite solar cells, state the impressive development, and present our outlook of the progress of perovskite solar cells.
2016, 33(5): 504-512
doi: 10.11944/j.issn.1000-0518.2016.05.150287
Abstract:
Converting solar energy to hydrogen by water splitting is a major trend of the future energy development. Water oxidation is in the most important and complex step in the conversion. So it is critical to design a stable and efficient catalyst for the water oxidation. The development of Ruthenium-based water oxidation catalyst tends to maturity. However, its utilization is limited by the high price and low reserves. In recent years, iron as the same group of ruthenium for catalytic oxidation of water has received increasing attention. Here we summarize the progress of classification of iron-based water oxidation catalyst, the preparation method, and the catalytic system and mechanism. By analyzing current problems, we try to provide some reference for further design of water oxidation catalysts.
Converting solar energy to hydrogen by water splitting is a major trend of the future energy development. Water oxidation is in the most important and complex step in the conversion. So it is critical to design a stable and efficient catalyst for the water oxidation. The development of Ruthenium-based water oxidation catalyst tends to maturity. However, its utilization is limited by the high price and low reserves. In recent years, iron as the same group of ruthenium for catalytic oxidation of water has received increasing attention. Here we summarize the progress of classification of iron-based water oxidation catalyst, the preparation method, and the catalytic system and mechanism. By analyzing current problems, we try to provide some reference for further design of water oxidation catalysts.
2016, 33(5): 513-523
doi: 10.11944/j.issn.1000-0518.2016.05.150212
Abstract:
Porous organic polymers(POPs) are a new type of porous materials that consist of pure organic groups. The application of POPs in water contaminants removal have attracted widespread interest in recent years. This article briefly reviews the most recent developments in this field, and discusses the adsorption mechanism, impact factors and the future developments.
Porous organic polymers(POPs) are a new type of porous materials that consist of pure organic groups. The application of POPs in water contaminants removal have attracted widespread interest in recent years. This article briefly reviews the most recent developments in this field, and discusses the adsorption mechanism, impact factors and the future developments.
2016, 33(5): 524-532
doi: 10.11944/j.issn.1000-0518.2016.05.160100
Abstract:
Conducting polyaniline(ES) was prepared using acidic phosphate(HPAA) as dopant of emeraldine base(EB), which can be dispersed in nanoscale in the polyurethane or polyurethane acrylates based matrix, subsequently, ultraviolet-thermal double cured polyaniline anti-corrosion coating without any heavy metals was prepared. The anti-corrosion layer was obtained by ultraviolet light curing in 3~5 s and subsequent thermal curing at 80 ℃ in 1~3 min. Particle size of ES increases with increasing mass fraction of ES in the coating matrix, meanwhile, the aggregation of ES molecules is enhanced. This is because ES is not miscible in polyurethane or polyurethane acrylates in the coating system. The particle size of ES can be controlled between 80 nm and 750 nm, it is ca. 80~119 nm when the mass fraction of the ES in the coating is 1.0%, and is increased to 500~750 nm when mass fraction of ES is 5.0%. The increase of particle size of ES is accompanied by the increase of porosity of anti-corrosion coating, leading to poorer anti-corrosion performance. The absolute impedance at 0.1 Hz(|Z|0.1 Hz) of 1.0 % ES anti-corrosion coating protected mild steel can maintain 1.0×108 Ω·cm2 after 2160 h immersion in 3.5% NaCl solution, while that from UV curing coating protected mild steel is 1.0×107 Ω·cm2,indicating better anti-corrosion performance of this double cured coating. The double cured anti-corrosion coating does not show any red rust and blister after 500 h cross scratch neutral salt spray test, while the rust is observed in the UV-cured anti-corrosion coating, though the rusted frontier around the scratch is still less than 1 mm.
Conducting polyaniline(ES) was prepared using acidic phosphate(HPAA) as dopant of emeraldine base(EB), which can be dispersed in nanoscale in the polyurethane or polyurethane acrylates based matrix, subsequently, ultraviolet-thermal double cured polyaniline anti-corrosion coating without any heavy metals was prepared. The anti-corrosion layer was obtained by ultraviolet light curing in 3~5 s and subsequent thermal curing at 80 ℃ in 1~3 min. Particle size of ES increases with increasing mass fraction of ES in the coating matrix, meanwhile, the aggregation of ES molecules is enhanced. This is because ES is not miscible in polyurethane or polyurethane acrylates in the coating system. The particle size of ES can be controlled between 80 nm and 750 nm, it is ca. 80~119 nm when the mass fraction of the ES in the coating is 1.0%, and is increased to 500~750 nm when mass fraction of ES is 5.0%. The increase of particle size of ES is accompanied by the increase of porosity of anti-corrosion coating, leading to poorer anti-corrosion performance. The absolute impedance at 0.1 Hz(|Z|0.1 Hz) of 1.0 % ES anti-corrosion coating protected mild steel can maintain 1.0×108 Ω·cm2 after 2160 h immersion in 3.5% NaCl solution, while that from UV curing coating protected mild steel is 1.0×107 Ω·cm2,indicating better anti-corrosion performance of this double cured coating. The double cured anti-corrosion coating does not show any red rust and blister after 500 h cross scratch neutral salt spray test, while the rust is observed in the UV-cured anti-corrosion coating, though the rusted frontier around the scratch is still less than 1 mm.
2016, 33(5): 533-541
doi: 10.11944/j.issn.1000-0518.2016.05.150198
Abstract:
An asymmetric diacetylene derivative bearing naphthyl group, 4-(4-(4-(6-(hexyloxy)-2-naphthalen)-1-(1,3-butadiynyl))-3-vinyl-phenylethynyl)-N,N-dimethylbenzenamine, was successfully synthesized by multi-step Sonogashira reactions. The structure of the compound was confirmed with 1H and 13C NMR spectroscopy and elemental analysis. Its liquid crystalline property and optical birefringence were characterized by differential scanning calorimetry(DSC), polarized light microscopy(POM) and Abbe refractometer. The absorption and emission spectra of the compound were obtained with the ultraviolet-visible absorption spectrometer and fluorescence spectrometer, respectively. The compound exhibits the nematic phase in liquid crystal state and high optical birefringence of 0.47. The peak of the photoluminescence(PL) of the compound in chloroform is at 470 nm and the quantum efficiency is 97%. The double-layer devices ITO/PEDOT/liquid crystal compound/Mg:Ag(10:1)/Ag(ITO:indium tin oxide, PEDOT:poly(3,4-ethylene-dioxythiophene thiophene)) is fabricated with a low onset voltage(6.75 V). The peak of electroluminescence(EL) is at 503 nm, and the maximum brightness value is 150 cd/m2(14.75 V). The diacetylene derivative is a promising material for liquid crystal display or organic light-emitting device.
An asymmetric diacetylene derivative bearing naphthyl group, 4-(4-(4-(6-(hexyloxy)-2-naphthalen)-1-(1,3-butadiynyl))-3-vinyl-phenylethynyl)-N,N-dimethylbenzenamine, was successfully synthesized by multi-step Sonogashira reactions. The structure of the compound was confirmed with 1H and 13C NMR spectroscopy and elemental analysis. Its liquid crystalline property and optical birefringence were characterized by differential scanning calorimetry(DSC), polarized light microscopy(POM) and Abbe refractometer. The absorption and emission spectra of the compound were obtained with the ultraviolet-visible absorption spectrometer and fluorescence spectrometer, respectively. The compound exhibits the nematic phase in liquid crystal state and high optical birefringence of 0.47. The peak of the photoluminescence(PL) of the compound in chloroform is at 470 nm and the quantum efficiency is 97%. The double-layer devices ITO/PEDOT/liquid crystal compound/Mg:Ag(10:1)/Ag(ITO:indium tin oxide, PEDOT:poly(3,4-ethylene-dioxythiophene thiophene)) is fabricated with a low onset voltage(6.75 V). The peak of electroluminescence(EL) is at 503 nm, and the maximum brightness value is 150 cd/m2(14.75 V). The diacetylene derivative is a promising material for liquid crystal display or organic light-emitting device.
2016, 33(5): 542-548
doi: 10.11944/j.issn.1000-0518.2016.05.150314
Abstract:
Four new bi-aryl and tri-aryl compounds containing pyridine ring were synthesized by using 2-bromopyridine-5-carbaldehyde and 5-bromopyridine-2-carbaldehyde as starting materials. The total yields are around 20%~30%. Thermal analysis results show that the bi-aryl compounds exhibit no mesophase, while the tri-aryl compounds exhibit nematic phase during both heating and cooling process. For the compound with nitrogen atoms located at the ortho position of n-butyl group, its melting point is decreased by 11.7 ℃ and its clearing point is increased by 6.3 ℃, and the mesophase range is broadened by 18 ℃, compared with the reference terphenyl compound(2c). Optic-electronic property analysis results show that the birefringence is improved when one of benzene ring in the reference compounds(1c or 2c) is replaced by with pyridine ring. Besides, the dielectric anisotropy values are increased when the nitrogen atoms locate at ortho position of n-butyl, and the threshold voltage and saturation voltage are decreased. The rule of the dielectric anisotropy variation is explained by conformation energy calculation of three-ring isomers.
Four new bi-aryl and tri-aryl compounds containing pyridine ring were synthesized by using 2-bromopyridine-5-carbaldehyde and 5-bromopyridine-2-carbaldehyde as starting materials. The total yields are around 20%~30%. Thermal analysis results show that the bi-aryl compounds exhibit no mesophase, while the tri-aryl compounds exhibit nematic phase during both heating and cooling process. For the compound with nitrogen atoms located at the ortho position of n-butyl group, its melting point is decreased by 11.7 ℃ and its clearing point is increased by 6.3 ℃, and the mesophase range is broadened by 18 ℃, compared with the reference terphenyl compound(2c). Optic-electronic property analysis results show that the birefringence is improved when one of benzene ring in the reference compounds(1c or 2c) is replaced by with pyridine ring. Besides, the dielectric anisotropy values are increased when the nitrogen atoms locate at ortho position of n-butyl, and the threshold voltage and saturation voltage are decreased. The rule of the dielectric anisotropy variation is explained by conformation energy calculation of three-ring isomers.
2016, 33(5): 549-553
doi: 10.11944/j.issn.1000-0518.2016.05.150412
Abstract:
Three novel stable nicotinamide adenine dinucleotide(NAD+) analogs were synthesized and characterized by 1H NMR, 13C NMR, 31P NMR and HRMS. The NAD+ analogs show good stability after heating at 80 ℃ for 24 h. Cyclic voltammetry(CV) measurement of the electrochemical properties of NAD+ analogs shows that they remain good redox activities.
Three novel stable nicotinamide adenine dinucleotide(NAD+) analogs were synthesized and characterized by 1H NMR, 13C NMR, 31P NMR and HRMS. The NAD+ analogs show good stability after heating at 80 ℃ for 24 h. Cyclic voltammetry(CV) measurement of the electrochemical properties of NAD+ analogs shows that they remain good redox activities.
2016, 33(5): 554-564
doi: 10.11944/j.issn.1000-0518.2016.05.150267
Abstract:
Twenty-two novel Mannich bases of 5-alkyl-1,2,4-triazole were designed and synthesized to evaluate their biological activities. The plant growth regulating activity, herbicidal activity and the inhibitory activity on cell division cycle protein 25B(CDC25B) of those molecules were screened. Most of the molecules exhibit good cytokinin activity and herbicidal activity, indicating their potential as novel pesticide. One of these molecules performs good inhibitory activity against CDC25B, and is a potential leading compound for anti-concer drug design.
Twenty-two novel Mannich bases of 5-alkyl-1,2,4-triazole were designed and synthesized to evaluate their biological activities. The plant growth regulating activity, herbicidal activity and the inhibitory activity on cell division cycle protein 25B(CDC25B) of those molecules were screened. Most of the molecules exhibit good cytokinin activity and herbicidal activity, indicating their potential as novel pesticide. One of these molecules performs good inhibitory activity against CDC25B, and is a potential leading compound for anti-concer drug design.
2016, 33(5): 565-570
doi: 10.11944/j.issn.1000-0518.2016.05.150318
Abstract:
With acid-treated montmorillonite supported zinc chloride(H-mont/ZnCl2) as the catalyst, phenols, alcohols, and carboxylic acid were reacted with di-tert-butyl dicarbonate to give tert-butyl ether and tert-butyl ester derivatives at 120 ℃ in sealed tube with yields ranging from 61% to 75%, which is simple and environmentally friendly. All the compounds synthesized were confirmed by 1H NMR and ESI-MS. The effect of solvent, temperature, metal ion and some other factors to the reaction were investigated. A possible mechanism for this reaction was proposed. Provided a new method for this type of synthesis in the future.
With acid-treated montmorillonite supported zinc chloride(H-mont/ZnCl2) as the catalyst, phenols, alcohols, and carboxylic acid were reacted with di-tert-butyl dicarbonate to give tert-butyl ether and tert-butyl ester derivatives at 120 ℃ in sealed tube with yields ranging from 61% to 75%, which is simple and environmentally friendly. All the compounds synthesized were confirmed by 1H NMR and ESI-MS. The effect of solvent, temperature, metal ion and some other factors to the reaction were investigated. A possible mechanism for this reaction was proposed. Provided a new method for this type of synthesis in the future.
2016, 33(5): 571-576
doi: 10.11944/j.issn.1000-0518.2016.05.150418
Abstract:
Hydrofloride modified Pt/ZSM-5 catalysts were studied and applied in benzene alkylation with methanol. The effects of acidity and pore structures of the catalysts were studied by NH3-TPD and N2 adsorption. The results show that the acidity and the amount of acidic sites of Pt/ZSM-5 are increased by HF modification and the catalytic performance in benzene methylation with methanol is also enhanced. The selectivity of toluene and xylene can reach to 92.20% when 3%HF-0.2%Pt/ZSM-5 catalyst is used in benzene methylation with methanol. When the loading of HF is more than 6%, partially removed aluminum and silicon from the zeolite framework will block the pores of zeolite resulting in decreasing diffusions of reactants and products, and eventually reducing catalytic performance of zeolites. The calculated activation energy of benzene methylation with methanol in HF modified Pt/ZSM-5 catalyst is 118 kJ/mol.
Hydrofloride modified Pt/ZSM-5 catalysts were studied and applied in benzene alkylation with methanol. The effects of acidity and pore structures of the catalysts were studied by NH3-TPD and N2 adsorption. The results show that the acidity and the amount of acidic sites of Pt/ZSM-5 are increased by HF modification and the catalytic performance in benzene methylation with methanol is also enhanced. The selectivity of toluene and xylene can reach to 92.20% when 3%HF-0.2%Pt/ZSM-5 catalyst is used in benzene methylation with methanol. When the loading of HF is more than 6%, partially removed aluminum and silicon from the zeolite framework will block the pores of zeolite resulting in decreasing diffusions of reactants and products, and eventually reducing catalytic performance of zeolites. The calculated activation energy of benzene methylation with methanol in HF modified Pt/ZSM-5 catalyst is 118 kJ/mol.
2016, 33(5): 577-582
doi: 10.11944/j.issn.1000-0518.2016.05.150296
Abstract:
[PMo8V6O42][Co(Phen)2][Him]2·2H3O·3H2O(1) was prepared by hydrothermal synthesis method and characterized by means of IR, Raman, UV, XRD and XPS. Its photocatalytic performance toward degradation of methylene blue wastewater was investigated. Under the optimized conditions, i.e., catalyst dosage of 50 mg/L, 4 mg/L methylene blue at pH=1 and the reaction time 220 min, 99.2% of the methylene blue is degraded photocatalytically. The kinetics of the photodegradation of methylene blue is satisfied by the pseudo-first-order equation, with a constant at 0.0144 min-1, and fitting coefficient of 0.9918. The photocatalyst also exhibits good reusability. The degradation rate for methylene blue still keeps at 92.4% after 4 recycles.
[PMo8V6O42][Co(Phen)2][Him]2·2H3O·3H2O(1) was prepared by hydrothermal synthesis method and characterized by means of IR, Raman, UV, XRD and XPS. Its photocatalytic performance toward degradation of methylene blue wastewater was investigated. Under the optimized conditions, i.e., catalyst dosage of 50 mg/L, 4 mg/L methylene blue at pH=1 and the reaction time 220 min, 99.2% of the methylene blue is degraded photocatalytically. The kinetics of the photodegradation of methylene blue is satisfied by the pseudo-first-order equation, with a constant at 0.0144 min-1, and fitting coefficient of 0.9918. The photocatalyst also exhibits good reusability. The degradation rate for methylene blue still keeps at 92.4% after 4 recycles.
2016, 33(5): 583-590
doi: 10.11944/j.issn.1000-0518.2016.05.160123
Abstract:
Nano gold-zinc titanate(Nano Au-ZnTiO3) composite plasmonic photocatalyst were prepared by a sol-gel process and photodeposition method. The obtained samples were characterized by powder X-ray diffraction(XRD), field emission scanning electron microscopy(FE-SEM), UV-Vis diffuse reflectance spectra, fluorescence spectra, photocurrent density and photocatalytic hydrogen production activity. The results indicate that ZnTiO3 sintered at 900 ℃ shows a mixed phase composed of cubic and hexagonal with a approximately spherical morphology in the size range of 50~100 nm. An intense absorption band centered at 525 nm of Nano Au-ZnTiO3 can be observed in visible light region due to the surface plasma resonance effect of Au nanoparticles. Under the irradiation of visible light, the Nano Au-ZnTiO3 plasmonic photocatalyst shows excellent photocatalytic activity in hydrogen evolution from water splitting.
Nano gold-zinc titanate(Nano Au-ZnTiO3) composite plasmonic photocatalyst were prepared by a sol-gel process and photodeposition method. The obtained samples were characterized by powder X-ray diffraction(XRD), field emission scanning electron microscopy(FE-SEM), UV-Vis diffuse reflectance spectra, fluorescence spectra, photocurrent density and photocatalytic hydrogen production activity. The results indicate that ZnTiO3 sintered at 900 ℃ shows a mixed phase composed of cubic and hexagonal with a approximately spherical morphology in the size range of 50~100 nm. An intense absorption band centered at 525 nm of Nano Au-ZnTiO3 can be observed in visible light region due to the surface plasma resonance effect of Au nanoparticles. Under the irradiation of visible light, the Nano Au-ZnTiO3 plasmonic photocatalyst shows excellent photocatalytic activity in hydrogen evolution from water splitting.
2016, 33(5): 591-598
doi: 10.11944/j.issn.1000-0518.2016.05.150417
Abstract:
Lead telluride nanorods were successfully synthesized by a simple glucose-assisted solvothermal method. The structure characteristics of these as-prepared samples were studied by X-ray diffraction pattern(XRD), field emission scanning electron microscopy(FESEM), transmission electron microscopy(TEM), high resolution transmission electron microscopy(HRTEM) and energy dispersive spectrometer(EDS). The results show that the products are PbTe with a cubic structure. The diameter and length of PbTe nanorods obtained are 50 and 500 nm, respectively. Some reaction factors influencing the formation of PbTe nanorods were systematically investigated. The morphology of the obtained products can be controlled by changing the amount of glucose, the reaction time, the reaction temperature and the amount of polyvinyl pyrrolidone(PVP). The mechanism for the formation of PbTe nanorods is discussed.
Lead telluride nanorods were successfully synthesized by a simple glucose-assisted solvothermal method. The structure characteristics of these as-prepared samples were studied by X-ray diffraction pattern(XRD), field emission scanning electron microscopy(FESEM), transmission electron microscopy(TEM), high resolution transmission electron microscopy(HRTEM) and energy dispersive spectrometer(EDS). The results show that the products are PbTe with a cubic structure. The diameter and length of PbTe nanorods obtained are 50 and 500 nm, respectively. Some reaction factors influencing the formation of PbTe nanorods were systematically investigated. The morphology of the obtained products can be controlled by changing the amount of glucose, the reaction time, the reaction temperature and the amount of polyvinyl pyrrolidone(PVP). The mechanism for the formation of PbTe nanorods is discussed.
2016, 33(5): 599-605
doi: 10.11944/j.issn.1000-0518.2016.05.150333
Abstract:
The probe 4-hydroxy-benzoyl-(2-hydroxy-naphthalene-formaldehyde) hydrazone(L) was synthesized and evaluated. The UV-Vis and fluorescence spectra suggested that probe L has highly Al3+-selective affinity over others commonly coexistent metal ions by fluorescence enhancing. Meanwhile, the color change of probe L solution after addition of Al3+ is obvious. 1H NMR titration, job-plot, and (MALDI-TOF) results indicate that the complex molar ratio of Al3+/L is 1:2. The binding constant of Al3+/L is calculated to be 1.3×104 L/mol by nonlinear curve-fitting based on the UV-Vis titration data, and the detection limit reaches 3.71×10-6 L/mol. The UV-Vis and fluorescence emission titration experiment show that a wide range and low detection limit can be achieved in the present sensing system. This result suggests that the probe L has potential application in determination of trace Al3+ ions.
The probe 4-hydroxy-benzoyl-(2-hydroxy-naphthalene-formaldehyde) hydrazone(L) was synthesized and evaluated. The UV-Vis and fluorescence spectra suggested that probe L has highly Al3+-selective affinity over others commonly coexistent metal ions by fluorescence enhancing. Meanwhile, the color change of probe L solution after addition of Al3+ is obvious. 1H NMR titration, job-plot, and (MALDI-TOF) results indicate that the complex molar ratio of Al3+/L is 1:2. The binding constant of Al3+/L is calculated to be 1.3×104 L/mol by nonlinear curve-fitting based on the UV-Vis titration data, and the detection limit reaches 3.71×10-6 L/mol. The UV-Vis and fluorescence emission titration experiment show that a wide range and low detection limit can be achieved in the present sensing system. This result suggests that the probe L has potential application in determination of trace Al3+ ions.
2016, 33(5): 606-610
doi: 10.11944/j.issn.1000-0518.2016.05.150367
Abstract:
A novel method for the determination of 2,4,6-trinitrophenol has been developed based on fluorescent quenching of riboflavin by 2,4,6-trinitrophenol(TNP) in aqueous solutions. The proposed fluorescent quenching method for TNP detection at pH=6.2 using 0.2 mol/L phosphate(NaH2PO4-Na2HPO4) as buffer solution responses within 1 min and with a broad linear relationship from 2.5 to 1000 μmol/L(r=0.9938). The limit of detection for TNP is 0.55 μmol/L. When 5.00 and 20.00 μmol/L TNP is added to different water samples, the recovery ranges from 98.2% to 103.5%. Furthermore, this method is simple, selective, and with wide linear range. Therefore, it can be applied in the determination of 2,4,6-trinitrophenol in real samples.
A novel method for the determination of 2,4,6-trinitrophenol has been developed based on fluorescent quenching of riboflavin by 2,4,6-trinitrophenol(TNP) in aqueous solutions. The proposed fluorescent quenching method for TNP detection at pH=6.2 using 0.2 mol/L phosphate(NaH2PO4-Na2HPO4) as buffer solution responses within 1 min and with a broad linear relationship from 2.5 to 1000 μmol/L(r=0.9938). The limit of detection for TNP is 0.55 μmol/L. When 5.00 and 20.00 μmol/L TNP is added to different water samples, the recovery ranges from 98.2% to 103.5%. Furthermore, this method is simple, selective, and with wide linear range. Therefore, it can be applied in the determination of 2,4,6-trinitrophenol in real samples.
