Matrix effects can significantly hamper the accuracy and precision of the analysis results of perfluorinated acids （PFAs） in environmental solid samples. Several methods, such as standard addition, isotopically labe...Matrix effects can significantly hamper the accuracy and precision of the analysis results of perfluorinated acids （PFAs） in environmental solid samples. Several methods, such as standard addition, isotopically labeled internal standards, clean-up of SPE （solid phase extraction） eluents by dispersive graphitized carbon sorbent and substitution of eletrospray ionization （ESI） source by atmosphere pressure photoionization （APPI） source, were demonstrated for elimination of matrix effects in quantitative analysis of PFAs in solid samples. The resuRs indicate that matrix effects can be effectively eliminated by standard addition, but instrumental analysis time will be multiplied. Isotopically labeled internal standards can effectively negate matrix effects of PFAs with the same perfluorocarbon chain length, but is not valid for the other analytes. Although APPI can eliminate matrix effects for all analytes, it is only suitable for analysis of high pollution levels samples. Clean-up of SPE eluents by dispersive graphitized carbon sorbent not only effectively negate the impact of matrix effect, but also avoid frequent clean of the ESI in order to maintain instrumental sensitivity. Therefore, the best method for elimination of matrix effects is the usage of dispersive graphitized carbon sorbent for clean-up of SPE elution.展开更多
The photodegradation of persistent and bioaccumulative perftuorooctanoic acid （PFOA） in water by 185 nm vacuum ultraviolet （VUV） light was examined to develop an effective technology to deal with PFOA pollution. P...The photodegradation of persistent and bioaccumulative perftuorooctanoic acid （PFOA） in water by 185 nm vacuum ultraviolet （VUV） light was examined to develop an effective technology to deal with PFOA pollution. PFOA degraded very slowly under irradiation of 254 nm UV light. However, 61.7% of initial PFOA was degraded by 185 nm VUV light within 2 h, and defluorination ratio reached 17.1%. Pseudo first-order-kinetics well simulated its degradation and defluorination. Besides, fluoride ion formed in water, 4 shorter-chain perfluorinated carboxylic acids （PFCAs）, that is, perfluoroheptanoic acid, perfluorohexanoic acid, perfluoropentanoic acid, and perfluorobutanoic acid. These were identified as intermediates by LC-MS measurement. These PFCAs consecutively formed and further degraded with irradiation time. According to the mass balance calculation, no other byproducts were formed. It was proposed that PFCAs initially are decarboxylated by 185 nm light, and the radical thus formed reacts with water to form shorter-chain PFCA with one less CF2 unit.展开更多
The novel perfluorinated vinyl ether containing sulfonimide and phosphonic acid functionalities, CF2 = CFOCF2CF(CF3)-OCF2CF2SO2NHSO2(CF2)2P(O)(OH)2, has been synthesized by multiple reaction steps. It is a very strong...The novel perfluorinated vinyl ether containing sulfonimide and phosphonic acid functionalities, CF2 = CFOCF2CF(CF3)-OCF2CF2SO2NHSO2(CF2)2P(O)(OH)2, has been synthesized by multiple reaction steps. It is a very strong bi-functional acid and exhibits a high degree of stability in aqueous solution at an elevated temperature. These properties make it an attractive monomer for the preparation of the co-polymer with TFE to obtain the high quality ionomer membrane and proton conductor.展开更多
将三乙胺作用后的全氟磺酸离子膜(PFSA)与咪唑基离子液体进行掺杂改性,分别以甲醇及水为介质制备了复合膜A和B,采用交流阻抗法测定了膜的电导率,结果表明,当温度从30℃升至90℃时,含5%、10%、15%和20%离子液体的复合膜A的电导率为0.92&#...将三乙胺作用后的全氟磺酸离子膜(PFSA)与咪唑基离子液体进行掺杂改性,分别以甲醇及水为介质制备了复合膜A和B,采用交流阻抗法测定了膜的电导率,结果表明,当温度从30℃升至90℃时,含5%、10%、15%和20%离子液体的复合膜A的电导率为0.92×10^(-5)~3.52×10^(-5)S·cm^(-1),复合膜B的电导率为0.59×10^(-5)~2.38×10^(-5)S·cm^(-1),而PFSA的电导率为0.30×10^(-5)~1.21×10^(-5)S·cm^(-1),复合膜较PFSA膜的电导率增大2~3倍,膜的电导率随温度的升高而增大;测定了-25~0℃时PFSA及复合膜的电导率,由Arrhenius方程求解的复合膜A、B的活化能E为1.62~2.47 k J/mol。展开更多
基金Foundation item: Projects(51108197, 51205215) supported by the National Natural Science Foundation of ChinaProjects(2011J05135, 2011J01318) supported by the Natural Science Foundation of Fujian Province, China+1 种基金Project(11QZR08) supported by the Scientific Research Foundation of Overseas Chinese Affairs Office of the State Council,ChinaProject(10BS213) supported by the Scientific Research Foundation for Advanced Talents,Huaqiao University,China
文摘Matrix effects can significantly hamper the accuracy and precision of the analysis results of perfluorinated acids （PFAs） in environmental solid samples. Several methods, such as standard addition, isotopically labeled internal standards, clean-up of SPE （solid phase extraction） eluents by dispersive graphitized carbon sorbent and substitution of eletrospray ionization （ESI） source by atmosphere pressure photoionization （APPI） source, were demonstrated for elimination of matrix effects in quantitative analysis of PFAs in solid samples. The resuRs indicate that matrix effects can be effectively eliminated by standard addition, but instrumental analysis time will be multiplied. Isotopically labeled internal standards can effectively negate matrix effects of PFAs with the same perfluorocarbon chain length, but is not valid for the other analytes. Although APPI can eliminate matrix effects for all analytes, it is only suitable for analysis of high pollution levels samples. Clean-up of SPE eluents by dispersive graphitized carbon sorbent not only effectively negate the impact of matrix effect, but also avoid frequent clean of the ESI in order to maintain instrumental sensitivity. Therefore, the best method for elimination of matrix effects is the usage of dispersive graphitized carbon sorbent for clean-up of SPE elution.
基金Project supported by the National Natural Science Foundation of China (No. 20577026) the New Century Excellent Talents in University (No. NCET-04-0090).
文摘The photodegradation of persistent and bioaccumulative perftuorooctanoic acid （PFOA） in water by 185 nm vacuum ultraviolet （VUV） light was examined to develop an effective technology to deal with PFOA pollution. PFOA degraded very slowly under irradiation of 254 nm UV light. However, 61.7% of initial PFOA was degraded by 185 nm VUV light within 2 h, and defluorination ratio reached 17.1%. Pseudo first-order-kinetics well simulated its degradation and defluorination. Besides, fluoride ion formed in water, 4 shorter-chain perfluorinated carboxylic acids （PFCAs）, that is, perfluoroheptanoic acid, perfluorohexanoic acid, perfluoropentanoic acid, and perfluorobutanoic acid. These were identified as intermediates by LC-MS measurement. These PFCAs consecutively formed and further degraded with irradiation time. According to the mass balance calculation, no other byproducts were formed. It was proposed that PFCAs initially are decarboxylated by 185 nm light, and the radical thus formed reacts with water to form shorter-chain PFCA with one less CF2 unit.
文摘The novel perfluorinated vinyl ether containing sulfonimide and phosphonic acid functionalities, CF2 = CFOCF2CF(CF3)-OCF2CF2SO2NHSO2(CF2)2P(O)(OH)2, has been synthesized by multiple reaction steps. It is a very strong bi-functional acid and exhibits a high degree of stability in aqueous solution at an elevated temperature. These properties make it an attractive monomer for the preparation of the co-polymer with TFE to obtain the high quality ionomer membrane and proton conductor.
文摘将三乙胺作用后的全氟磺酸离子膜(PFSA)与咪唑基离子液体进行掺杂改性,分别以甲醇及水为介质制备了复合膜A和B,采用交流阻抗法测定了膜的电导率,结果表明,当温度从30℃升至90℃时,含5%、10%、15%和20%离子液体的复合膜A的电导率为0.92×10^(-5)~3.52×10^(-5)S·cm^(-1),复合膜B的电导率为0.59×10^(-5)~2.38×10^(-5)S·cm^(-1),而PFSA的电导率为0.30×10^(-5)~1.21×10^(-5)S·cm^(-1),复合膜较PFSA膜的电导率增大2~3倍,膜的电导率随温度的升高而增大;测定了-25~0℃时PFSA及复合膜的电导率,由Arrhenius方程求解的复合膜A、B的活化能E为1.62~2.47 k J/mol。
