Lignin serves as one of the most important molecular fossils for tracing Terrestrial Organic Matters （TOMs） in marine environment. Extraction and derivatization of lignin oxidation products （LOPs） are crucial for ...Lignin serves as one of the most important molecular fossils for tracing Terrestrial Organic Matters （TOMs） in marine environment. Extraction and derivatization of lignin oxidation products （LOPs） are crucial for accurate quantification of lignin in marine sediment. Here we report a modification of the conventional alkaline cupric oxide （CuO） oxidation method, the modification consisting in a solid phase extraction （SPE） and a novel on-column derivatization being employed for better efficiency and reproducibility. In spiking blanks, recoveries with SPE for the LOPs are between 77.84% and 99.57% with relative standard deviations （RSDs） ranging from 0.57% to 8.04% （n=3）, while those with traditional liquid-liquid extraction （LLE） are from 44.52% to 86.16% With RSDs being from 0.53% to 13.14% （n=3）. Moreover, the reproducibility is greatly improved with SPE, with less solvent consumption and shorter processing time. The average efficiency of on-column derivatization for LOPs is 100.8%±0.68%, which is significantly higher than those of in-vial or in-syringe derivatization, thus resulting in still less consumption of derivatizing reagents.Lignin in the surface sediments sampled from the south of Yangtze River estuary, China, was determined with the established method. Recoveries of 72.66% to 85.99% with standard deviation less than 0.01mg/10g dry weight are obtained except for p-hydroxybenzaldehyde. The lignin content ∑8 （produced from 10g dry sediment） in the research area is between 0.231 and 0.587mg. S/V and C/V ratios （1.028 ± 0.433 and 0.192±0.066, respectively） indicate that the TOMs in this region are originated from a mixture of woody and nonwoody angiosperm plants; the high values or （Ad/Al）v suggest that the TOMs has been highly degraded.展开更多
Atomistic potentials for cupric element and cupric oxide are derived based on the analytical bond-order scheme that was presented by Brenner [Brenner D W, Erratum： Empirical potential for hydrocarbons for use in simu...Atomistic potentials for cupric element and cupric oxide are derived based on the analytical bond-order scheme that was presented by Brenner [Brenner D W, Erratum： Empirical potential for hydrocarbons for use in simulating the chemical vapor deposition of diamond films, Phys. Rev. B 1992, 46 1948]. In this paper, for the pure cupric element, the energy and structural parameters for several bulk phases as well as dimmer structure are well reproduced. The reference data are taken from our density functional theory calculations and the available experiments. The model potential also provides a good description of the bulk properties of various solid structures of cupric oxide compound structures, including cohesive energies, lattice parameters, and elastic constants.展开更多
Chemical warfare agents(CWAs)are extremely lethal substances used in warfare and terrorism,capable of causing permanent damage even in small doses,despite medical intervention.Therefore,detection,protection,and detoxi...Chemical warfare agents(CWAs)are extremely lethal substances used in warfare and terrorism,capable of causing permanent damage even in small doses,despite medical intervention.Therefore,detection,protection,and detoxification of CWAs are vital for the safety of first responders,military personnel,and civilians,driving significant research in this area.Herein,we designed and synthesized a poly(-diallyldimethylammonium chloride)(PDDA)mediated cupric oxide(CuO)functionalized activated carbon fabric(ACF),termed ACF@PDDA-CuO,as an adsorbent filter material for self-detoxifying chemical protective clothing.PDDA,a positively charged polyelectrolyte,effectively binds in-situ synthesized CuO to the negatively charged ACF surface,serving as a suitable binder.This study demonstrates the synergistic effects of PDDA-CuO functionalization on ACF,where PDDA treatment enhanced mechanical and comfort properties,and CuO crystal growth significantly improved detoxification efficacy against the CWA Nerve Agent Sarin.Comprehensive analyses,including FTIR,BET surface area analysis,SEM,EDS,TEM,STEM,TGA,XPS,and XRD,confirmed the uniform deposition of CuO and PDDA on the ACF surface.The Cu content on ACF@PDDA-CuO samples was measured via iodometric titration.The materials were evaluated for tensile strength,air permeability,water vapor permeability,nerve agent(Sarin)detoxification,and blister agent(Sulfur Mustard)breakthrough time to assess their applicability for protective clothing.The optimized PDDA-CuO on ACF detoxified 82.04%of Sarin within 18 h,compared to 25.22%by ACF alone,and enhanced tensile strength by 23.67%,air permeability by 24.63%,and water vapor permeability by 3.94%,while maintaining protection against Sulfur Mustard for 24 h.These findings indicate that ACF@PDDA-CuO is a promising candidate for CWA protective clothing,offering robust protection with enhanced comfort.展开更多
Maintaining a residual disinfectant/oxidant(e.g., chlorine and chlorine dioxide), is a generally used strategy to control microbial contaminants and bacterial regrowth in distribution systems. Secondarily oxidant, suc...Maintaining a residual disinfectant/oxidant(e.g., chlorine and chlorine dioxide), is a generally used strategy to control microbial contaminants and bacterial regrowth in distribution systems. Secondarily oxidant, such as hypobromous acid(HOBr), can be formed during chlorination of bromide-containing waters. The decay of oxidants and formation of disinfection byproducts(DBPs) due to the interaction between oxidants and selected metal oxides were studied. Selected metal oxides generally enhanced the decay of these halogencontaining oxidants via three pathways:(1) catalytic disproportionation to yield an oxidized form of halogen(i.e., halate) and reduced form(halide for chlorine and bromine or chlorite for chlorine dioxide),(2) oxygen formation, and(3) oxidation of a metal in a reduced form(e.g., cuprous oxide) to a higher oxidation state. Cupric oxide(Cu O) and nickel oxide(Ni O)showed significantly strong abilities for the first pathway, and oxygen formation was a side reaction. Cuprous oxide can react with oxidants via the third pathway, while goethite was not involved in these reactions. The ability of Cu O on catalytic disproportionation of HOBr remained stable up to four cycles. In chlorination process, bromate formation tends to be important(exceeding 10 μg/L) when initial bromide concentration is above 400 μg/L in the presence of dissolved organic matter. Increasing initial bromide concentrations increased the formation of DBPs and calculated cytotoxicity, and the maximum was observed at p H8.6 during chlorination process. Therefore, the possible disinfectant loss and DBP formation should be carefully considered in drinking water distribution systems.展开更多
Different from the classical configuration CuO/CeO2 catalyst,the inverse configuration CeO2 /CuO catalyst （atomic ratio of Ce/Cu=10/100） was prepared by impregnation method.Five calcination temperatures were selecte...Different from the classical configuration CuO/CeO2 catalyst,the inverse configuration CeO2 /CuO catalyst （atomic ratio of Ce/Cu=10/100） was prepared by impregnation method.Five calcination temperatures were selected to investigate the interaction between CeO2 and CuO support.It is found that as calcination temperature increased from 500 to 900 C,sintering of CeO2 particles on the support occurred together with the diffusion of a portion of Ce 4＋ ions into CuO crystals,forming solid solution.Formation of interface complex Ce-O-Cu was suggested by TPR measurements.The catalyst calcined at 700 C gives the highest activity for preferential oxidation of CO in excess H2 stream.展开更多
Cupric oxide （CuO） and copper-cuprous oxide （Cu-Cu2O） nanoparticles were prepared by a simple hydrothermal method for the synthesis of diethyi carbonate （DEC） from ethanol. During these syntheses, varying NaOH a...Cupric oxide （CuO） and copper-cuprous oxide （Cu-Cu2O） nanoparticles were prepared by a simple hydrothermal method for the synthesis of diethyi carbonate （DEC） from ethanol. During these syntheses, varying NaOH and glucose concentrations were applied to explore and pinpoint the active species. It was found that PdCl2/CuO and PdCI2/Cu-Cu2O both catalysts exhibited good thermal stability and morphology. The results of catalytic tests showed that the catalysts prepared with 5 mol/L NaOH show superior catalytic performances because of their lower extent of agglomeration. It is noteworthy that the PdC12/Cu-Cu2O catalysts were the most active, especially the PdCl2/Cu-Cu2O catalyst prepared with 10 mmol glucose and having a higher Cu2O concentration. In Pd（ll）-Cu（II） （PdCl2/CuO） catalysts, there is an induction period, during which Pd（II） is reduced to Pd（0）, that must occur prior to electron transfer between Pd and Cu, and this can slow the catalytic reaction. To further pinpoint the active species, PdCl2/Cu-Cu2O catalysts with different Cu2O contents were prepared by controlling the dosages of glucose. The maximum DEC yield obtained with these catalysts was 151.9 mg.g-1.h-1, corresponding to an ethanol conversion of 7.2% and 97.9% DEC selectivity on an ethanol basis. Therefore, it was concluded that Cu＋ was the active species in this catalytic system, possibly because a higher proportion of Cu＋ reduces the Pd2＋ concentration and limits the CO oxidation side reaction, thus increasing DEC selectivity. In addition, Cu＋ promotes electron transfer between Pd and Cu without an induction period, which could also promote the catalytic activity.展开更多
Nanoflake-based flower-like CuO nanostruc- tures have been synthesized through thermal decomposi- tion of [Cu（NH3）4]2＋ solution without any surfactants and catalysts at low temperature. The products are character- ...Nanoflake-based flower-like CuO nanostruc- tures have been synthesized through thermal decomposi- tion of [Cu（NH3）4]2＋ solution without any surfactants and catalysts at low temperature. The products are character- ized by X-ray diffraction （XRD） and field-emission scanning electron microscopy （FESEM）. The possible formation process based on the aggregation-recrystalliza- tion mechanism is proposed. Finally, the obtained flower- like CuO hierarchical nanostructures have been used as the photocatalyst in the experiments. It is found that the as- prepared flower-like CuO hierarchical nanostructures exhibit superior photocatalytic property on photocatalytic decomposition of Rhodamine B due to their hierarchical structures.展开更多
基金supported by the National Basic Research Program of China (973 Program, Grant No. 2010CB428901)the National Natural Science Foundation of China (NSFC, Grant No. 41020164005,41276067)the team of 973 Program Grant No. 2010CB428701 for the help during sampling
文摘Lignin serves as one of the most important molecular fossils for tracing Terrestrial Organic Matters （TOMs） in marine environment. Extraction and derivatization of lignin oxidation products （LOPs） are crucial for accurate quantification of lignin in marine sediment. Here we report a modification of the conventional alkaline cupric oxide （CuO） oxidation method, the modification consisting in a solid phase extraction （SPE） and a novel on-column derivatization being employed for better efficiency and reproducibility. In spiking blanks, recoveries with SPE for the LOPs are between 77.84% and 99.57% with relative standard deviations （RSDs） ranging from 0.57% to 8.04% （n=3）, while those with traditional liquid-liquid extraction （LLE） are from 44.52% to 86.16% With RSDs being from 0.53% to 13.14% （n=3）. Moreover, the reproducibility is greatly improved with SPE, with less solvent consumption and shorter processing time. The average efficiency of on-column derivatization for LOPs is 100.8%±0.68%, which is significantly higher than those of in-vial or in-syringe derivatization, thus resulting in still less consumption of derivatizing reagents.Lignin in the surface sediments sampled from the south of Yangtze River estuary, China, was determined with the established method. Recoveries of 72.66% to 85.99% with standard deviation less than 0.01mg/10g dry weight are obtained except for p-hydroxybenzaldehyde. The lignin content ∑8 （produced from 10g dry sediment） in the research area is between 0.231 and 0.587mg. S/V and C/V ratios （1.028 ± 0.433 and 0.192±0.066, respectively） indicate that the TOMs in this region are originated from a mixture of woody and nonwoody angiosperm plants; the high values or （Ad/Al）v suggest that the TOMs has been highly degraded.
基金Project supported by the Doctoral Program of Higher Education of China(Grant No.20111415120002)the National Natural Science Foundation of China(Grant Nos.11204199,61178067,and 51135007)+1 种基金the Program for the Outstanding Innovative Teams of Higher Learning Institutions of Shanxi Province,Chinathe Youth Foundation of Taiyuan University of Science and Technology,China(Grant No.20113020)
文摘Atomistic potentials for cupric element and cupric oxide are derived based on the analytical bond-order scheme that was presented by Brenner [Brenner D W, Erratum： Empirical potential for hydrocarbons for use in simulating the chemical vapor deposition of diamond films, Phys. Rev. B 1992, 46 1948]. In this paper, for the pure cupric element, the energy and structural parameters for several bulk phases as well as dimmer structure are well reproduced. The reference data are taken from our density functional theory calculations and the available experiments. The model potential also provides a good description of the bulk properties of various solid structures of cupric oxide compound structures, including cohesive energies, lattice parameters, and elastic constants.
基金Defence Research and Development Establishment(DRDE),DRDO,Gwalior-474002,(India)for his keen interestencouragement.The DRDE accession number for this manuscript is DRDE-IREC-130-28/03/2024.
文摘Chemical warfare agents(CWAs)are extremely lethal substances used in warfare and terrorism,capable of causing permanent damage even in small doses,despite medical intervention.Therefore,detection,protection,and detoxification of CWAs are vital for the safety of first responders,military personnel,and civilians,driving significant research in this area.Herein,we designed and synthesized a poly(-diallyldimethylammonium chloride)(PDDA)mediated cupric oxide(CuO)functionalized activated carbon fabric(ACF),termed ACF@PDDA-CuO,as an adsorbent filter material for self-detoxifying chemical protective clothing.PDDA,a positively charged polyelectrolyte,effectively binds in-situ synthesized CuO to the negatively charged ACF surface,serving as a suitable binder.This study demonstrates the synergistic effects of PDDA-CuO functionalization on ACF,where PDDA treatment enhanced mechanical and comfort properties,and CuO crystal growth significantly improved detoxification efficacy against the CWA Nerve Agent Sarin.Comprehensive analyses,including FTIR,BET surface area analysis,SEM,EDS,TEM,STEM,TGA,XPS,and XRD,confirmed the uniform deposition of CuO and PDDA on the ACF surface.The Cu content on ACF@PDDA-CuO samples was measured via iodometric titration.The materials were evaluated for tensile strength,air permeability,water vapor permeability,nerve agent(Sarin)detoxification,and blister agent(Sulfur Mustard)breakthrough time to assess their applicability for protective clothing.The optimized PDDA-CuO on ACF detoxified 82.04%of Sarin within 18 h,compared to 25.22%by ACF alone,and enhanced tensile strength by 23.67%,air permeability by 24.63%,and water vapor permeability by 3.94%,while maintaining protection against Sulfur Mustard for 24 h.These findings indicate that ACF@PDDA-CuO is a promising candidate for CWA protective clothing,offering robust protection with enhanced comfort.
基金supported by the Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences (Project No. 20Z01KLDWST)。
文摘Maintaining a residual disinfectant/oxidant(e.g., chlorine and chlorine dioxide), is a generally used strategy to control microbial contaminants and bacterial regrowth in distribution systems. Secondarily oxidant, such as hypobromous acid(HOBr), can be formed during chlorination of bromide-containing waters. The decay of oxidants and formation of disinfection byproducts(DBPs) due to the interaction between oxidants and selected metal oxides were studied. Selected metal oxides generally enhanced the decay of these halogencontaining oxidants via three pathways:(1) catalytic disproportionation to yield an oxidized form of halogen(i.e., halate) and reduced form(halide for chlorine and bromine or chlorite for chlorine dioxide),(2) oxygen formation, and(3) oxidation of a metal in a reduced form(e.g., cuprous oxide) to a higher oxidation state. Cupric oxide(Cu O) and nickel oxide(Ni O)showed significantly strong abilities for the first pathway, and oxygen formation was a side reaction. Cuprous oxide can react with oxidants via the third pathway, while goethite was not involved in these reactions. The ability of Cu O on catalytic disproportionation of HOBr remained stable up to four cycles. In chlorination process, bromate formation tends to be important(exceeding 10 μg/L) when initial bromide concentration is above 400 μg/L in the presence of dissolved organic matter. Increasing initial bromide concentrations increased the formation of DBPs and calculated cytotoxicity, and the maximum was observed at p H8.6 during chlorination process. Therefore, the possible disinfectant loss and DBP formation should be carefully considered in drinking water distribution systems.
文摘Different from the classical configuration CuO/CeO2 catalyst,the inverse configuration CeO2 /CuO catalyst （atomic ratio of Ce/Cu=10/100） was prepared by impregnation method.Five calcination temperatures were selected to investigate the interaction between CeO2 and CuO support.It is found that as calcination temperature increased from 500 to 900 C,sintering of CeO2 particles on the support occurred together with the diffusion of a portion of Ce 4＋ ions into CuO crystals,forming solid solution.Formation of interface complex Ce-O-Cu was suggested by TPR measurements.The catalyst calcined at 700 C gives the highest activity for preferential oxidation of CO in excess H2 stream.
基金supported by the National Natural Science Foundation of China(21106054)~~
文摘Cupric oxide （CuO） and copper-cuprous oxide （Cu-Cu2O） nanoparticles were prepared by a simple hydrothermal method for the synthesis of diethyi carbonate （DEC） from ethanol. During these syntheses, varying NaOH and glucose concentrations were applied to explore and pinpoint the active species. It was found that PdCl2/CuO and PdCI2/Cu-Cu2O both catalysts exhibited good thermal stability and morphology. The results of catalytic tests showed that the catalysts prepared with 5 mol/L NaOH show superior catalytic performances because of their lower extent of agglomeration. It is noteworthy that the PdC12/Cu-Cu2O catalysts were the most active, especially the PdCl2/Cu-Cu2O catalyst prepared with 10 mmol glucose and having a higher Cu2O concentration. In Pd（ll）-Cu（II） （PdCl2/CuO） catalysts, there is an induction period, during which Pd（II） is reduced to Pd（0）, that must occur prior to electron transfer between Pd and Cu, and this can slow the catalytic reaction. To further pinpoint the active species, PdCl2/Cu-Cu2O catalysts with different Cu2O contents were prepared by controlling the dosages of glucose. The maximum DEC yield obtained with these catalysts was 151.9 mg.g-1.h-1, corresponding to an ethanol conversion of 7.2% and 97.9% DEC selectivity on an ethanol basis. Therefore, it was concluded that Cu＋ was the active species in this catalytic system, possibly because a higher proportion of Cu＋ reduces the Pd2＋ concentration and limits the CO oxidation side reaction, thus increasing DEC selectivity. In addition, Cu＋ promotes electron transfer between Pd and Cu without an induction period, which could also promote the catalytic activity.
文摘Nanoflake-based flower-like CuO nanostruc- tures have been synthesized through thermal decomposi- tion of [Cu（NH3）4]2＋ solution without any surfactants and catalysts at low temperature. The products are character- ized by X-ray diffraction （XRD） and field-emission scanning electron microscopy （FESEM）. The possible formation process based on the aggregation-recrystalliza- tion mechanism is proposed. Finally, the obtained flower- like CuO hierarchical nanostructures have been used as the photocatalyst in the experiments. It is found that the as- prepared flower-like CuO hierarchical nanostructures exhibit superior photocatalytic property on photocatalytic decomposition of Rhodamine B due to their hierarchical structures.
