The transformation of CO_(2)into cyclic carbonates via atom-economical cycloadditions with epoxides has recently attracted tremendous attention.On one hand,though many heterogeneous catalysts have been developed for t...The transformation of CO_(2)into cyclic carbonates via atom-economical cycloadditions with epoxides has recently attracted tremendous attention.On one hand,though many heterogeneous catalysts have been developed for this reaction,they typically suffer from disadvantages such as the need for severe reaction conditions,catalyst loss,and large amounts of soluble co-catalysts.On the other hand,the development of heterogeneous catalysts featuring multiple and cooperative active sites,remains challenging and desirable.In this study,we prepared a series of porous organic catalysts(POP-PBnCl-TPPMg-x)via the copolymerization metal-porphyrin compounds and phosphonium salt monomers in various ratios.The resulting materials contain both Lewis-acidic and Lewis-basic active sites.The molecular-level combination of these sites in the same polymer allows these active sites to work synergistically,giving rise to excellent performance in the cycloaddition reaction of CO_(2)with epoxides,under mild conditions(40℃ and 1 atm CO_(2))in the absence of soluble co-catalysts.POP-PBnCl-TPPMg-12 can also efficiently fixate CO_(2)under low-CO_(2)-concentration(15%v/v N2)conditions representative of typical CO_(2)compositions in industrial exhaust gases.More importantly,this catalyst shows excellent recyclability and can easily be separated and reused at least five times while maintaining its activity.In view of their heterogeneous nature and excellent catalytic performance,the obtained catalysts are promising candidates for the transformation of industrially generated CO_(2)into high value-added chemicals.展开更多
Demineralisation plants of power stations are not able to remove organics in all cases to a satisfied degree. The present work focuses on natural organic matter (NOM) and its interaction with anion exchanger and ads...Demineralisation plants of power stations are not able to remove organics in all cases to a satisfied degree. The present work focuses on natural organic matter (NOM) and its interaction with anion exchanger and adsorber resins to optimize organics uptake. In this study, four different starches (one of them 14C-labelled) with different molecular size distributions were selected as model substances for the biopolymer fraction of NOM. Their uptake by various anion exchangers and adsorbers was measured in column experiments. Results are discussed in terms of size exclusion, anion exchange, adsorption, and hydrophilic/hydrophobic repulsion. In summary, at neutral pH, starch has been removed preferably by size-exclusion followed by adsorption, whereas anion exchange resins show higher uptake capacities than "pure" adsorber resins caused by stronger attraction between starch and polar functional groups of the anion exchangers. At acidic pH, the uptake of sulphate, as competitive adsorptive, leads to an earlier starch breakthrough at anion exchangers. Therefore, adsorbers are more effective. It was found that the higher the water content of the resins, the more effective the uptake is.展开更多
In this study we have successfully characterized the fluorescent components of chromophoric dissolved organic matter(CDOM) in the Yellow Sea and the East China Sea in autumn using excitation-emission matrix fluorescen...In this study we have successfully characterized the fluorescent components of chromophoric dissolved organic matter(CDOM) in the Yellow Sea and the East China Sea in autumn using excitation-emission matrix fluorescence spectroscopy(EEMs) combined with parallel factor analysis(PARAFAC).PARAFAC aids the characterization of fluorescence CDOM by decomposing the fluorescence matrices into individual components.Four humic-like components(C1,C2,C3,and C4),one marine biological production component(C6),and two protein-like components(C5 and C7) were identified by PARAFAC.We researched the distributional patterns of fluorescence intensity,regression analyses between salinity,chlorophyll a concentration and fluorescence intensities of individual fluorophore,and regression analysis between salinity and fluorescence intensities percent of individual fluorophore.The results revealed that C2 and C4 showed conservative mixing behavior,while C1 and C3 possessed conservative mixing behavior in high salinity region and additional behavior in low and middle salinity region,which were considered to be derived from riverine and degradation of organic matter from resuspended and/or sinking particles and show non-conservative mixing behavior.In addition to riverine sources,the tryptophan-like C5 may receive widespread addition(likely from photo-degradation or biodegradation),while the most likely sources for the one marine humic-like C6 and tyrosine-like C7 were biological activity and microbial processing of plankton-derived CDOM,which were suggested to be of autochthonous origin and biologically labile.The application of EEM-PARAFAC modeling presents a unique opportunity to observe compositional changes,different mixing behavior and temporal variability in CDOM in the Yellow Sea and the East China Sea.展开更多
文摘The transformation of CO_(2)into cyclic carbonates via atom-economical cycloadditions with epoxides has recently attracted tremendous attention.On one hand,though many heterogeneous catalysts have been developed for this reaction,they typically suffer from disadvantages such as the need for severe reaction conditions,catalyst loss,and large amounts of soluble co-catalysts.On the other hand,the development of heterogeneous catalysts featuring multiple and cooperative active sites,remains challenging and desirable.In this study,we prepared a series of porous organic catalysts(POP-PBnCl-TPPMg-x)via the copolymerization metal-porphyrin compounds and phosphonium salt monomers in various ratios.The resulting materials contain both Lewis-acidic and Lewis-basic active sites.The molecular-level combination of these sites in the same polymer allows these active sites to work synergistically,giving rise to excellent performance in the cycloaddition reaction of CO_(2)with epoxides,under mild conditions(40℃ and 1 atm CO_(2))in the absence of soluble co-catalysts.POP-PBnCl-TPPMg-12 can also efficiently fixate CO_(2)under low-CO_(2)-concentration(15%v/v N2)conditions representative of typical CO_(2)compositions in industrial exhaust gases.More importantly,this catalyst shows excellent recyclability and can easily be separated and reused at least five times while maintaining its activity.In view of their heterogeneous nature and excellent catalytic performance,the obtained catalysts are promising candidates for the transformation of industrially generated CO_(2)into high value-added chemicals.
文摘Demineralisation plants of power stations are not able to remove organics in all cases to a satisfied degree. The present work focuses on natural organic matter (NOM) and its interaction with anion exchanger and adsorber resins to optimize organics uptake. In this study, four different starches (one of them 14C-labelled) with different molecular size distributions were selected as model substances for the biopolymer fraction of NOM. Their uptake by various anion exchangers and adsorbers was measured in column experiments. Results are discussed in terms of size exclusion, anion exchange, adsorption, and hydrophilic/hydrophobic repulsion. In summary, at neutral pH, starch has been removed preferably by size-exclusion followed by adsorption, whereas anion exchange resins show higher uptake capacities than "pure" adsorber resins caused by stronger attraction between starch and polar functional groups of the anion exchangers. At acidic pH, the uptake of sulphate, as competitive adsorptive, leads to an earlier starch breakthrough at anion exchangers. Therefore, adsorbers are more effective. It was found that the higher the water content of the resins, the more effective the uptake is.
基金supported by the National High-Tech Research and Development Program of China(2009AA063005)the National Basic Research Program of China(2010CD428701)
文摘In this study we have successfully characterized the fluorescent components of chromophoric dissolved organic matter(CDOM) in the Yellow Sea and the East China Sea in autumn using excitation-emission matrix fluorescence spectroscopy(EEMs) combined with parallel factor analysis(PARAFAC).PARAFAC aids the characterization of fluorescence CDOM by decomposing the fluorescence matrices into individual components.Four humic-like components(C1,C2,C3,and C4),one marine biological production component(C6),and two protein-like components(C5 and C7) were identified by PARAFAC.We researched the distributional patterns of fluorescence intensity,regression analyses between salinity,chlorophyll a concentration and fluorescence intensities of individual fluorophore,and regression analysis between salinity and fluorescence intensities percent of individual fluorophore.The results revealed that C2 and C4 showed conservative mixing behavior,while C1 and C3 possessed conservative mixing behavior in high salinity region and additional behavior in low and middle salinity region,which were considered to be derived from riverine and degradation of organic matter from resuspended and/or sinking particles and show non-conservative mixing behavior.In addition to riverine sources,the tryptophan-like C5 may receive widespread addition(likely from photo-degradation or biodegradation),while the most likely sources for the one marine humic-like C6 and tyrosine-like C7 were biological activity and microbial processing of plankton-derived CDOM,which were suggested to be of autochthonous origin and biologically labile.The application of EEM-PARAFAC modeling presents a unique opportunity to observe compositional changes,different mixing behavior and temporal variability in CDOM in the Yellow Sea and the East China Sea.