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2013 Volume 30 Issue 6
2013, 30(6): 611-616
doi: 10.3724/SP.J.1095.2013.20394
Abstract:
2-Phenyl benzothiophene is an important compound and has been widely used in the synthesis of medicines,pesticides and functional materials,and so on. Much research concern has been made on its synthesis. Sereval synthetic routes have been developed for the synthesis of 2-phenyl benzothiophene over the past decades. In this short review,we briefly summarized the recent progress in this field using benzo[b] thiophene,2-benzo[b] thiophene boronic acid and substituted benzene as substrates and made some comments on the future perspectives of the synthetic methodology.
2-Phenyl benzothiophene is an important compound and has been widely used in the synthesis of medicines,pesticides and functional materials,and so on. Much research concern has been made on its synthesis. Sereval synthetic routes have been developed for the synthesis of 2-phenyl benzothiophene over the past decades. In this short review,we briefly summarized the recent progress in this field using benzo[b] thiophene,2-benzo[b] thiophene boronic acid and substituted benzene as substrates and made some comments on the future perspectives of the synthetic methodology.
2013, 30(6): 617-622
doi: 10.3724/SP.J.1095.2013.20323
Abstract:
Two novel organic dyes with double D-π-A branches were designed and synthesized as sensitizers for dye sensitized solar cells(DSSCs). These dyes were characterized by mass spectrometry(MS),proton nuclear magnetic resonance spectrometry(1H NMR),and carbon nuclear magnetic resonance spectrometry (13C NMR). The photophysical and electrochemical properties of these two dyes were studied.Relatively high light to electricity conversion efficiency(η) of 4.10% was achieved using dye DP2 as a sensitizer (open-circuit photovoltage Voc=0.63 V,short-circuit photocurrent density Jsc=8.59 × 10-3 A/cm2 and fill factor FF=0.76) under 100 × 10-3 W/cm2(AM 1.5G). An efficiency of 3.38% for DSSCs based on dye DP1 was observed under the same conditions.
Two novel organic dyes with double D-π-A branches were designed and synthesized as sensitizers for dye sensitized solar cells(DSSCs). These dyes were characterized by mass spectrometry(MS),proton nuclear magnetic resonance spectrometry(1H NMR),and carbon nuclear magnetic resonance spectrometry (13C NMR). The photophysical and electrochemical properties of these two dyes were studied.Relatively high light to electricity conversion efficiency(η) of 4.10% was achieved using dye DP2 as a sensitizer (open-circuit photovoltage Voc=0.63 V,short-circuit photocurrent density Jsc=8.59 × 10-3 A/cm2 and fill factor FF=0.76) under 100 × 10-3 W/cm2(AM 1.5G). An efficiency of 3.38% for DSSCs based on dye DP1 was observed under the same conditions.
2013, 30(6): 623-627
doi: 10.3724/SP.J.1095.2013.20368
Abstract:
Using nitrofluorene and acrylic esters as precursors,a series of Michael addition products with high yields of 79%~87% was obtained under microwave irradiation(500 W) for 4~5 min in the presence of sodium hydroxide. The strcutures of products were characterized by IR,1H NMR,MS and elemental analysis. The crystal structure of compound 3b was determined by single X-ray diffraction analysis.
Using nitrofluorene and acrylic esters as precursors,a series of Michael addition products with high yields of 79%~87% was obtained under microwave irradiation(500 W) for 4~5 min in the presence of sodium hydroxide. The strcutures of products were characterized by IR,1H NMR,MS and elemental analysis. The crystal structure of compound 3b was determined by single X-ray diffraction analysis.
2013, 30(6): 628-632
doi: 10.3724/SP.J.1095.2013.20352
Abstract:
Using 7-deoxycholic acid(1) as a starting material,3,12-dioxy-7-deoxycholic acid(2) was obtained by oxidation with Jones reagent. Then the N,N-bis(2-chloroethyl)-3,12-dioxy-7-deoxycholic amide(4) was synthesized by the reaction of compound 2 with bis(2-chloroethyl) amine. Furthermore,N,N-bis(2chloroethyl)-12-oxy-3-hydroximino-7-deoxycholic amide (5) and N,N-bis(2-chloroethyl)-12-oxy-3thiosemicarbazone-7-deoxycholic amide(6) were prepared by the functional group transformation of 3-carbonyl on compound 4. The antiproliferative activities of compounds against HeLa cells were assayed and the result showed that the compounds displayed distinct cytotoxicity.
Using 7-deoxycholic acid(1) as a starting material,3,12-dioxy-7-deoxycholic acid(2) was obtained by oxidation with Jones reagent. Then the N,N-bis(2-chloroethyl)-3,12-dioxy-7-deoxycholic amide(4) was synthesized by the reaction of compound 2 with bis(2-chloroethyl) amine. Furthermore,N,N-bis(2chloroethyl)-12-oxy-3-hydroximino-7-deoxycholic amide (5) and N,N-bis(2-chloroethyl)-12-oxy-3thiosemicarbazone-7-deoxycholic amide(6) were prepared by the functional group transformation of 3-carbonyl on compound 4. The antiproliferative activities of compounds against HeLa cells were assayed and the result showed that the compounds displayed distinct cytotoxicity.
2013, 30(6): 633-637
doi: 10.3724/SP.J.1095.2013.20356
Abstract:
Thiourea(TU) chitosan(CTS)-Ag+ complex was prepared by the reaction of thiourea chitosan with a trace amount of silver ion in homogeneous solution,and was characterized by FT-IR. Antimicrobial activities of CTS,TU-CTS,TU-CTS-Ag+ complex and AgNO3 were evaluated against E.coli and S.aureus in vitro,and the minimum inhibition concentration(MIC) and the minimum bactericidal concentration(MBC) were determined. The results show that the complex has stronger antimicrobial activities than chitosan and thiourea chitosan. The MIC and MBC of thiourea chitosan Ag+ complex are both 100 mg/L (free silver ion content 0.032 mg/L),lower than the MIC and MBC for AgNO3,which are both 120 g/L.
Thiourea(TU) chitosan(CTS)-Ag+ complex was prepared by the reaction of thiourea chitosan with a trace amount of silver ion in homogeneous solution,and was characterized by FT-IR. Antimicrobial activities of CTS,TU-CTS,TU-CTS-Ag+ complex and AgNO3 were evaluated against E.coli and S.aureus in vitro,and the minimum inhibition concentration(MIC) and the minimum bactericidal concentration(MBC) were determined. The results show that the complex has stronger antimicrobial activities than chitosan and thiourea chitosan. The MIC and MBC of thiourea chitosan Ag+ complex are both 100 mg/L (free silver ion content 0.032 mg/L),lower than the MIC and MBC for AgNO3,which are both 120 g/L.
2013, 30(6): 638-642
doi: 10.3724/SP.J.1095.2013.20331
Abstract:
Epoxidized safflower seed oil was prepared using hydrogen peroxide as oxidant,formic acid as oxygen carrier,and strong acidic cation exchange resin as catalyst. The optimized reaction conditions are:with the presence of ethylene diamine tetraacetic acid as stabilizer,the precursor ratio for m(safflower seed oil):m(88% formic acid):m(H2O230%):m(cation exchange resin) is 1:0.244:1.665:0.035,the reaction temperature is 60℃,the reaction time is 6 h and the stirring rate is 400 r/min,the epoxy value is above 7.0.
Epoxidized safflower seed oil was prepared using hydrogen peroxide as oxidant,formic acid as oxygen carrier,and strong acidic cation exchange resin as catalyst. The optimized reaction conditions are:with the presence of ethylene diamine tetraacetic acid as stabilizer,the precursor ratio for m(safflower seed oil):m(88% formic acid):m(H2O230%):m(cation exchange resin) is 1:0.244:1.665:0.035,the reaction temperature is 60℃,the reaction time is 6 h and the stirring rate is 400 r/min,the epoxy value is above 7.0.
2013, 30(6): 643-647
doi: 10.3724/SP.J.1095.2013.20326
Abstract:
Effect of additives on the decomposition behavior of the carbon fiber reinforced epoxy resin cured with anhydride in subcritical water was investigated. IR and GC-MS results show that the decomposition is ascribed to cleavage of ester bond. KOH and phenol does not exhibit the synergetic effect on the decomposition of anhydride cured epoxy resin. Alkaline conditions are found to be favorable to the cleavage of ester linkages. The carbon fiber reinforced methyl-tetrahydrophalic anhydride(MeTHPA) cured epoxy resin composite was totally decomposed with the addition of 0.2 mol/L KOH at 250℃ for 60 min. The tensile strength and morphology of the recycled carbon fibers are not influenced.
Effect of additives on the decomposition behavior of the carbon fiber reinforced epoxy resin cured with anhydride in subcritical water was investigated. IR and GC-MS results show that the decomposition is ascribed to cleavage of ester bond. KOH and phenol does not exhibit the synergetic effect on the decomposition of anhydride cured epoxy resin. Alkaline conditions are found to be favorable to the cleavage of ester linkages. The carbon fiber reinforced methyl-tetrahydrophalic anhydride(MeTHPA) cured epoxy resin composite was totally decomposed with the addition of 0.2 mol/L KOH at 250℃ for 60 min. The tensile strength and morphology of the recycled carbon fibers are not influenced.
2013, 30(6): 648-654
doi: 10.3724/SP.J.1095.2013.20317
Abstract:
The imidazole,acrylonitrile,bromooctane were used to synthesize a new cationic polymerizable ionic liquid surfactant named chlorinated-1-octyl-3-(4-butylacrylate-based) imidazole(PMOIH8). Using 2-chloropropylamide(MPC) as the initiator,Cu0 powder and tris-(2-dimethylamino ethyl) amine(Me6-TREN) as the catalyst,a new kind of copolymer acrylamide/acrylic ester was synthesized via single electron transfer living radical polymerization(SET-LRP) of acrylamide with PMOIH8. The resulting polymers were analyzed by FT-IR,MS and 1H NMR,and the results showed that the polymers were target products. The relative molecular mass and the distribution of the resulting polymer were determined by GPC. The relative molecular mass of polymers is within the ramge of 2 × 103~14 × 103,and the relative molecular mass distribution is within the range of 1.21~1.75. Various factors which might affect the SET-LRP such as catalyst and initiator were discussed. The results showed that as the amount of catalyst reduced,the polymerization rate decreased and the polymerization rate constant(kpapp) reduced from 0.0168 min-1 to 0.0065 min-1,while the relative molecular mass distribution Mw/Mn increased from 1.25~1.71 to 1.32~1.75,and the initiator efficiency decreased,Ieff=90.24%. As the amount of initiator increased,the relative molecular mass distribution of the resulting polymer was narrower with Mw/Mn reduced from 1.25~1.71 to 1.21~1.68,while the polymerization rate constant(kpapp) increased from 0.0168 min-1 to 0.0201 min-1,and the initiator efficiency increased,Ieff=93.17%.
The imidazole,acrylonitrile,bromooctane were used to synthesize a new cationic polymerizable ionic liquid surfactant named chlorinated-1-octyl-3-(4-butylacrylate-based) imidazole(PMOIH8). Using 2-chloropropylamide(MPC) as the initiator,Cu0 powder and tris-(2-dimethylamino ethyl) amine(Me6-TREN) as the catalyst,a new kind of copolymer acrylamide/acrylic ester was synthesized via single electron transfer living radical polymerization(SET-LRP) of acrylamide with PMOIH8. The resulting polymers were analyzed by FT-IR,MS and 1H NMR,and the results showed that the polymers were target products. The relative molecular mass and the distribution of the resulting polymer were determined by GPC. The relative molecular mass of polymers is within the ramge of 2 × 103~14 × 103,and the relative molecular mass distribution is within the range of 1.21~1.75. Various factors which might affect the SET-LRP such as catalyst and initiator were discussed. The results showed that as the amount of catalyst reduced,the polymerization rate decreased and the polymerization rate constant(kpapp) reduced from 0.0168 min-1 to 0.0065 min-1,while the relative molecular mass distribution Mw/Mn increased from 1.25~1.71 to 1.32~1.75,and the initiator efficiency decreased,Ieff=90.24%. As the amount of initiator increased,the relative molecular mass distribution of the resulting polymer was narrower with Mw/Mn reduced from 1.25~1.71 to 1.21~1.68,while the polymerization rate constant(kpapp) increased from 0.0168 min-1 to 0.0201 min-1,and the initiator efficiency increased,Ieff=93.17%.
2013, 30(6): 655-660
doi: 10.3724/SP.J.1095.2013.20504
Abstract:
Polypropylene/calcium carbonate-maleic anhydride-polypropylene wax(PP/CaCO3-MAH-PPW) composites were prepared by means of in situ solid phase graft copolymerization using MAH and PPW as the main raw materials. Compared with PP/PP-g-MAH/CaCO3 composites using MAH grafted with PP(PP-g-MAH) as compatibilizer,PP/CaCO3-MAH-PPW composites exhibit higher impact resistance,bending and processing properties. The results show that a good dispersion of calcium carbonate and an appropriate interface bonding between CaCO3 and PP are the key factors in order to obtain the composite with good toughness. When m(PP):m(CaCO3)=100:20,the notched impact strength of PP/CaCO3-MAH-PPW composite reaches a maximum,which is 1.19 times as high as that of the matrix resin.
Polypropylene/calcium carbonate-maleic anhydride-polypropylene wax(PP/CaCO3-MAH-PPW) composites were prepared by means of in situ solid phase graft copolymerization using MAH and PPW as the main raw materials. Compared with PP/PP-g-MAH/CaCO3 composites using MAH grafted with PP(PP-g-MAH) as compatibilizer,PP/CaCO3-MAH-PPW composites exhibit higher impact resistance,bending and processing properties. The results show that a good dispersion of calcium carbonate and an appropriate interface bonding between CaCO3 and PP are the key factors in order to obtain the composite with good toughness. When m(PP):m(CaCO3)=100:20,the notched impact strength of PP/CaCO3-MAH-PPW composite reaches a maximum,which is 1.19 times as high as that of the matrix resin.
2013, 30(6): 661-666
doi: 10.3724/SP.J.1095.2013.20591
Abstract:
Poly(octylene 2,5-furandicarboxylate)(POF) was synthesized via the direct esterification method starting from 2,5-furandicarboxylic acid(FDCA) and 1,8-octylene glycol(1,8-ODO),in which tetrabutyl titanate was chosen as catalyst. Effect of the molar ratio of F-DCA to 1,8-ODO,dosage of tetrabutyl titanate,esterification temperature,polycondensation temperature on the esterification and polycondensation processes were studied in details. The optimized process conditions are:n(FDCA):n(1,8-ODO)=1:1.2,tetrabutyl titanate dosage is 3 × 10-3 mol/mol FDCA,esterification temperature is 240℃,polycondensation temperature is 260℃,polycondensation time is 300 min. The relative molecular mass of the condensation product is the highest(ηSP/ρ=2.1 dL/g),and the carboxylic group content is the lowest(5.8 mol/t). Compared with ethylene glycol,using the 1,8-ODO reduced the molar ratio of FDCA to 1,8-ODO,and reduced the consumption of alcohol,meanwhile we got a high molecular mass polymer. The results of gas chromatography mass spectrometry(GC-MS) confirmed the composition of the esterification distillate and polycondensation product extractives. The results were found to be:the main ingredient of esterification distillate is H2O,and the other component is 1,8-ODO; polycondensation product extractives are composed of cyclohexanone(56%),(Z)-3-octene alcohol(18%),4-methyl-3-amylene-2-ketone(17%),4-hydro-xy-4-methyl-2pentan-one(9%).
Poly(octylene 2,5-furandicarboxylate)(POF) was synthesized via the direct esterification method starting from 2,5-furandicarboxylic acid(FDCA) and 1,8-octylene glycol(1,8-ODO),in which tetrabutyl titanate was chosen as catalyst. Effect of the molar ratio of F-DCA to 1,8-ODO,dosage of tetrabutyl titanate,esterification temperature,polycondensation temperature on the esterification and polycondensation processes were studied in details. The optimized process conditions are:n(FDCA):n(1,8-ODO)=1:1.2,tetrabutyl titanate dosage is 3 × 10-3 mol/mol FDCA,esterification temperature is 240℃,polycondensation temperature is 260℃,polycondensation time is 300 min. The relative molecular mass of the condensation product is the highest(ηSP/ρ=2.1 dL/g),and the carboxylic group content is the lowest(5.8 mol/t). Compared with ethylene glycol,using the 1,8-ODO reduced the molar ratio of FDCA to 1,8-ODO,and reduced the consumption of alcohol,meanwhile we got a high molecular mass polymer. The results of gas chromatography mass spectrometry(GC-MS) confirmed the composition of the esterification distillate and polycondensation product extractives. The results were found to be:the main ingredient of esterification distillate is H2O,and the other component is 1,8-ODO; polycondensation product extractives are composed of cyclohexanone(56%),(Z)-3-octene alcohol(18%),4-methyl-3-amylene-2-ketone(17%),4-hydro-xy-4-methyl-2pentan-one(9%).
2013, 30(6): 667-672
doi: 10.3724/SP.J.1095.2013.20349
Abstract:
Single crystalline nanoarrays of ZnO were in situ grown on cheap zinc foil at 140℃ for 12 h in p-aminopyridine(p-APD,1.0 mol/L) medium through a simple one-step hydrothermal method. The crystal features and morphology of the products were characterized and observed by X-ray diffraction(XRD),scanning electron microscopy(SEM) and high-resolution transmission electron microscopy(HRTEM),respectively. The possible synthetic mechanism of the ZnO was discussed. The as-prepared ZnO shows a high photocatalytic ability towards the degradation of Rhodamine B under UV irradiation.
Single crystalline nanoarrays of ZnO were in situ grown on cheap zinc foil at 140℃ for 12 h in p-aminopyridine(p-APD,1.0 mol/L) medium through a simple one-step hydrothermal method. The crystal features and morphology of the products were characterized and observed by X-ray diffraction(XRD),scanning electron microscopy(SEM) and high-resolution transmission electron microscopy(HRTEM),respectively. The possible synthetic mechanism of the ZnO was discussed. The as-prepared ZnO shows a high photocatalytic ability towards the degradation of Rhodamine B under UV irradiation.
2013, 30(6): 673-676
doi: 10.3724/SP.J.1095.2013.20367
Abstract:
Ag3PO4/WO3 composite was prepared by an ion-exchange method. The prepared samples were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM) and UV-Vis absorption spectroscopy. The photocatalytic activity of the different samples were evaluated by photocatalytic degradation of methyl orange aqueous solutions under visible-light irradiation(λ > 420 nm). The results showed that Ag3PO4/WO3 exhibited much higher photocatalytic activity and stability than pristine Ag3PO4. The reason is that the photoinduced electrons on the conduct band of Ag3PO4 can be easily transferred to WO3,resulting in the increase of the separation of photogenerated carriers and the reduction of Ag3PO4.
Ag3PO4/WO3 composite was prepared by an ion-exchange method. The prepared samples were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM) and UV-Vis absorption spectroscopy. The photocatalytic activity of the different samples were evaluated by photocatalytic degradation of methyl orange aqueous solutions under visible-light irradiation(λ > 420 nm). The results showed that Ag3PO4/WO3 exhibited much higher photocatalytic activity and stability than pristine Ag3PO4. The reason is that the photoinduced electrons on the conduct band of Ag3PO4 can be easily transferred to WO3,resulting in the increase of the separation of photogenerated carriers and the reduction of Ag3PO4.
2013, 30(6): 677-682
doi: 10.3724/SP.J.1095.2013.20363
Abstract:
According to the nature of copper,γ-amino propyl methyl di-ethoxy-silane(KH-902) is selected to modify copper. FT-IR,digital microscope,TG,SEM and EDS have been used to characterize the modified copper and the copper-filled conductive adhesive. The results show that the addition of silane coupling agent KH-902 can improve the antioxidation ability. When the addition of KH-902 is 3%,it can significantly improve not only the oxidation resistance of the copper-filled conductive adhesive in high temperature curing,but also the dispersion of copper in the epoxy resin colloid system,and make the combination between copper and copper better,which is the superior conductivity of system with bulk resistance rate of 1.31 × 10-2 Ω·cm.
According to the nature of copper,γ-amino propyl methyl di-ethoxy-silane(KH-902) is selected to modify copper. FT-IR,digital microscope,TG,SEM and EDS have been used to characterize the modified copper and the copper-filled conductive adhesive. The results show that the addition of silane coupling agent KH-902 can improve the antioxidation ability. When the addition of KH-902 is 3%,it can significantly improve not only the oxidation resistance of the copper-filled conductive adhesive in high temperature curing,but also the dispersion of copper in the epoxy resin colloid system,and make the combination between copper and copper better,which is the superior conductivity of system with bulk resistance rate of 1.31 × 10-2 Ω·cm.
2013, 30(6): 683-689
doi: 10.3724/SP.J.1095.2013.20337
Abstract:
Polarization curves and AC impedance spectroscopy were used to investigate the effects of different concentrations of stabilizer phenyl thiourea(PHTU) on the electrochemical properties of electroless Ni-P coatings on a 6063 aluminum alloy. The polarization curves show that the coatings formed in phenyl thioureacontaining electroless nickel solution have a more positive corrosion potential(Ecorr) and pitting corrosion potential(Epit),and a lower corrosion current density(icorr) than the bare aluminum alloy. To explain the electrochemical properties of the coatings,a simple equivalent circuit is designed. Electrochemical parameters of EIS,such as the surface resistance(Rcoat) and capacitance(Qcoat),charge transfer resistance(Rct) and double layer capacitance(Qdl),have been obtained by fitting the EIS plots.The EIS results show that the coatings formed in 6~10 mg/L PHTU electroless nickel solution present a higher resistance(Rcoat and Rct) and lower capacitance(Qcoat and Qdl) values. The EIS and polarization curve results indicate that the prepared coatings have a better corrosion resistance and the EIS and polarization curve results are in agreement with each other. The morphology and composition of the Ni-P coatings have been examined by using a SEM and EDS,respectively. The results show the coating surface is in a uniform state and the mass fraction of P element on the coating surface is more than 10%.
Polarization curves and AC impedance spectroscopy were used to investigate the effects of different concentrations of stabilizer phenyl thiourea(PHTU) on the electrochemical properties of electroless Ni-P coatings on a 6063 aluminum alloy. The polarization curves show that the coatings formed in phenyl thioureacontaining electroless nickel solution have a more positive corrosion potential(Ecorr) and pitting corrosion potential(Epit),and a lower corrosion current density(icorr) than the bare aluminum alloy. To explain the electrochemical properties of the coatings,a simple equivalent circuit is designed. Electrochemical parameters of EIS,such as the surface resistance(Rcoat) and capacitance(Qcoat),charge transfer resistance(Rct) and double layer capacitance(Qdl),have been obtained by fitting the EIS plots.The EIS results show that the coatings formed in 6~10 mg/L PHTU electroless nickel solution present a higher resistance(Rcoat and Rct) and lower capacitance(Qcoat and Qdl) values. The EIS and polarization curve results indicate that the prepared coatings have a better corrosion resistance and the EIS and polarization curve results are in agreement with each other. The morphology and composition of the Ni-P coatings have been examined by using a SEM and EDS,respectively. The results show the coating surface is in a uniform state and the mass fraction of P element on the coating surface is more than 10%.
2013, 30(6): 690-697
doi: 10.3724/SP.J.1095.2013.20385
Abstract:
The spinel-type NiFe2O4 powders have been synthesized by a hydroxide co-precipitation method. The Ni/NiFe2O4 composite coating was prepared through electro-deposition in Watt nickel plating by adding some NiFe2O4 powders. The optimized plating conditions for the composite electro-deposition were investigated by varying parameters,such as the plating solution pH and the cathode current density jk. The composition and structure of the Ni/NiFe2O4 composite coating were characterized by scanning electron microscopy(SEM),energy X-ray diffraction(XRD) and dispersive spectrometer(EDS). The results show that the NiFe2O4 mass content in the Ni/NiFe2O4 composite coating is the highest(55.15%) at optimized plating conditions of a solution pH=5.8~6.0 and a cathodic current density jk=40 × 10-3~60 × 10-3 A/cm2. In 5 mol/L KOH solution,the electro-catalytic properties towards the oxygen evolution reaction(OER) of the Ni/NiFe2O4 composite electrode was studied using cyclic voltammetry,steady-state polarization,and chronoamperometry. Compared with the nickel electrode,the electro-catalytic properties towards OER of the Ni/NiFe2O4 electrode is higher and the apparent activation energy is decreased by 62.07 kJ/mol,and its specific surface area is 23.02 times as large as that of the nickel electrode. The constant-potential electrolysis with long time for OER shows that the stability of the Ni/NiFe2O4 composite electrode is good.
The spinel-type NiFe2O4 powders have been synthesized by a hydroxide co-precipitation method. The Ni/NiFe2O4 composite coating was prepared through electro-deposition in Watt nickel plating by adding some NiFe2O4 powders. The optimized plating conditions for the composite electro-deposition were investigated by varying parameters,such as the plating solution pH and the cathode current density jk. The composition and structure of the Ni/NiFe2O4 composite coating were characterized by scanning electron microscopy(SEM),energy X-ray diffraction(XRD) and dispersive spectrometer(EDS). The results show that the NiFe2O4 mass content in the Ni/NiFe2O4 composite coating is the highest(55.15%) at optimized plating conditions of a solution pH=5.8~6.0 and a cathodic current density jk=40 × 10-3~60 × 10-3 A/cm2. In 5 mol/L KOH solution,the electro-catalytic properties towards the oxygen evolution reaction(OER) of the Ni/NiFe2O4 composite electrode was studied using cyclic voltammetry,steady-state polarization,and chronoamperometry. Compared with the nickel electrode,the electro-catalytic properties towards OER of the Ni/NiFe2O4 electrode is higher and the apparent activation energy is decreased by 62.07 kJ/mol,and its specific surface area is 23.02 times as large as that of the nickel electrode. The constant-potential electrolysis with long time for OER shows that the stability of the Ni/NiFe2O4 composite electrode is good.
2013, 30(6): 698-704
doi: 10.3724/SP.J.1095.2013.20577
Abstract:
Electrochemical codeposition of Al-Li-La alloys were investigated in molten LiCl-KCl-AlCl3-La2O3 system. The results showed that chlorination of La2O3 by AlCl3 led to the formation of LaCl3 in the molten salts and promote the electrolytic preparation of Al-Li-La alloys. Transient electrochemical techniques,such as cyclic voltammetry and chronopotentiometry,were used to study the reaction mechanism. The electrochemical codeposition of Al,Li and La occurred when cathodic current densities were higher than 0.25 A/cm2 in the LiCl-KCl-AlCl3-La2O3 melts. The influencing factors such as electrolytic temperature,cathodic current density and electrolysis times on alloys were studied and the optimum electrolysis conditions were:a molten salt mixture of LiCl:KCl:AlCl3:La2O3=45:45:5:2(mass raito),an electrolytic temperature of 650℃,a cathode current density of 12.5 A/cm2,and electrolysis time of 1 h. X-ray diffraction(XRD) indicated that the Al-LiLa alloys obtained by electrocodeposition mainly consisted of Al2La,and βLi phases.
Electrochemical codeposition of Al-Li-La alloys were investigated in molten LiCl-KCl-AlCl3-La2O3 system. The results showed that chlorination of La2O3 by AlCl3 led to the formation of LaCl3 in the molten salts and promote the electrolytic preparation of Al-Li-La alloys. Transient electrochemical techniques,such as cyclic voltammetry and chronopotentiometry,were used to study the reaction mechanism. The electrochemical codeposition of Al,Li and La occurred when cathodic current densities were higher than 0.25 A/cm2 in the LiCl-KCl-AlCl3-La2O3 melts. The influencing factors such as electrolytic temperature,cathodic current density and electrolysis times on alloys were studied and the optimum electrolysis conditions were:a molten salt mixture of LiCl:KCl:AlCl3:La2O3=45:45:5:2(mass raito),an electrolytic temperature of 650℃,a cathode current density of 12.5 A/cm2,and electrolysis time of 1 h. X-ray diffraction(XRD) indicated that the Al-LiLa alloys obtained by electrocodeposition mainly consisted of Al2La,and βLi phases.
2013, 30(6): 705-709
doi: 10.3724/SP.J.1095.2013.20364
Abstract:
Li-rich cathode material of Li[Li0.2Mn0.4Fe0.4]O2 was prepared by co-precipitation,and was modified by surface coating with Al2O3. The modified samples were characterized by X-ray diffraction,scanning electron microscopy,and electrochemical tests. It was found that the 4.0% Al2O3 coated Li[Li0.2Mn0.4Fe0.4]O2 exhibited a good cycling performance compared with the bare Li[Li0.2Mn0.4Fe0.4]O2. The discharge capacity loss of the surface coated Li[Li0.2Mn0.4Fe0.4]O2 after 50 cycling was about 9%.
Li-rich cathode material of Li[Li0.2Mn0.4Fe0.4]O2 was prepared by co-precipitation,and was modified by surface coating with Al2O3. The modified samples were characterized by X-ray diffraction,scanning electron microscopy,and electrochemical tests. It was found that the 4.0% Al2O3 coated Li[Li0.2Mn0.4Fe0.4]O2 exhibited a good cycling performance compared with the bare Li[Li0.2Mn0.4Fe0.4]O2. The discharge capacity loss of the surface coated Li[Li0.2Mn0.4Fe0.4]O2 after 50 cycling was about 9%.
2013, 30(6): 710-715
doi: 10.3724/SP.J.1095.2013.30188
Abstract:
A new carbamate functionalized ionic liquid stationary phase(ImPh-Carb-Silica) for highperformance liquid chromatography was prepared by bonding 4,4'-diphenylmethylene-bis[2-(1-imidazolyl)-3phenyl-1-propanol carbamate] (ImPh-Carb) onto silica particles. The structure of ImPh-Carb was characterized by 1H NMR,13C NMR,MS and FTIR,and the bonded stationary phase was also characterized by FTIR and element analysis,and the bonding amount of ImPh-Carb-Silica stationary phase was about 0.19 mmol/g,according to the nitrogen content. The chromatographic performances of the stationary phase were evaluated using aromatic hydrocarbons,phenols and organophosphorus pesticides as solutes in reversedphase and normal-phase chromatographic modes,and the effect of the content of mobile phase on retention factor(lg k) of analytes was studied. The results show that the functionalized ionic liquid stationary phase provides a multiple-interaction mechanism with analytes including hydrophobic,hydrogen bonding,π-π,and dipole-induce/dipole interactions. The stationary phase can be simultaneously performed in reversed-phase and normal-phase chromatographic modes,and it demonstrates its superiority in separation of phenols and organophosphorus pesticides under normal-phase chromatographic mode.
A new carbamate functionalized ionic liquid stationary phase(ImPh-Carb-Silica) for highperformance liquid chromatography was prepared by bonding 4,4'-diphenylmethylene-bis[2-(1-imidazolyl)-3phenyl-1-propanol carbamate] (ImPh-Carb) onto silica particles. The structure of ImPh-Carb was characterized by 1H NMR,13C NMR,MS and FTIR,and the bonded stationary phase was also characterized by FTIR and element analysis,and the bonding amount of ImPh-Carb-Silica stationary phase was about 0.19 mmol/g,according to the nitrogen content. The chromatographic performances of the stationary phase were evaluated using aromatic hydrocarbons,phenols and organophosphorus pesticides as solutes in reversedphase and normal-phase chromatographic modes,and the effect of the content of mobile phase on retention factor(lg k) of analytes was studied. The results show that the functionalized ionic liquid stationary phase provides a multiple-interaction mechanism with analytes including hydrophobic,hydrogen bonding,π-π,and dipole-induce/dipole interactions. The stationary phase can be simultaneously performed in reversed-phase and normal-phase chromatographic modes,and it demonstrates its superiority in separation of phenols and organophosphorus pesticides under normal-phase chromatographic mode.
2013, 30(6): 716-722
doi: 10.3724/SP.J.1095.2013.20366
Abstract:
A simple colorimetric assay for rapid and selective sensing toxic heavy metal ion,cadmium ion(Cd2+),has been developed using gold nanoparticles(AuNPs) decorated with 6-mercaptopurine(MP) and peptide CALNN. MP is employed as a chelating ligand through the N group at the end of MP,and CALNN is served not only as a stabilizer,but also as a factor of high selectivity. AuNPs solution exhibits a gradual color change from red to blue with increasing the concentration of Cd2+,which leads to an easily measurable change in absorption spectrum of AuNPs solution and naked eye detection. A simple assay with high selectivity and fast response(within 5 min) is presented,and the limit of detection(LOD) for Cd2+ was calculated to be 350 nmol/L.
A simple colorimetric assay for rapid and selective sensing toxic heavy metal ion,cadmium ion(Cd2+),has been developed using gold nanoparticles(AuNPs) decorated with 6-mercaptopurine(MP) and peptide CALNN. MP is employed as a chelating ligand through the N group at the end of MP,and CALNN is served not only as a stabilizer,but also as a factor of high selectivity. AuNPs solution exhibits a gradual color change from red to blue with increasing the concentration of Cd2+,which leads to an easily measurable change in absorption spectrum of AuNPs solution and naked eye detection. A simple assay with high selectivity and fast response(within 5 min) is presented,and the limit of detection(LOD) for Cd2+ was calculated to be 350 nmol/L.
2013, 30(6): 723-729
doi: 10.3724/SP.J.1095.2013.20357
Abstract:
Ultra performance liquid chromatography(UPLC) was used to determine the content of lignans of Schisandra fruits with different growth characteristics. The antioxidant activity of these samples was also studied. In order to screen the superior kinds of these samples,principal component analysis,cluster analysis and stepwise discrimination analysis were used to analyze the above data. Principal component analysis and cluster analysis results divided the origin samples into three categories. The correct rate for screening the superior kinds of Schisandra fruits via stepwise discrimination analysis is 90%.
Ultra performance liquid chromatography(UPLC) was used to determine the content of lignans of Schisandra fruits with different growth characteristics. The antioxidant activity of these samples was also studied. In order to screen the superior kinds of these samples,principal component analysis,cluster analysis and stepwise discrimination analysis were used to analyze the above data. Principal component analysis and cluster analysis results divided the origin samples into three categories. The correct rate for screening the superior kinds of Schisandra fruits via stepwise discrimination analysis is 90%.
2013, 30(6): 730-732
doi: 10.3724/SP.J.1095.2013.20506
Abstract:
The cadmium carboxylate/silica composite materials(CCSM) were prepared through the combined use of nucleophilic substitution,hydrolysis of siloxane,and condensation of silanol. The CdS nanoparticles of cubic and hexagonal structures were prepared in situ in CCSM by vulcanization. The emission peak of CdS nanoparticles in CCSM belongs to the red fluorescence at 672 nm(one of the three primary colors),suggesting that the CdS/silica composite materials have a potential application as optical devices.
The cadmium carboxylate/silica composite materials(CCSM) were prepared through the combined use of nucleophilic substitution,hydrolysis of siloxane,and condensation of silanol. The CdS nanoparticles of cubic and hexagonal structures were prepared in situ in CCSM by vulcanization. The emission peak of CdS nanoparticles in CCSM belongs to the red fluorescence at 672 nm(one of the three primary colors),suggesting that the CdS/silica composite materials have a potential application as optical devices.
