It is well known that acid-volatile sulfide (AVS) plays an important role in influencing the toxicity of divalent cationic metals within anoxic sediments. In studying sediment core samples collected from tidal flats w...It is well known that acid-volatile sulfide (AVS) plays an important role in influencing the toxicity of divalent cationic metals within anoxic sediments. In studying sediment core samples collected from tidal flats within the Jiaozhou Bay, China, we found that the AVS concentration gradually increases with depth and decreases from high tidal flat to low tidal flat areas. We evaluated the chemical activity and bioavailability of heavy metals in the tidal flat based on the molar ratio of simultaneously ex- tracted metals (SEM) and AVS. The value of SEM/AVS is generally less than 1 in this area except for the surface layer, which suggests that the heavy metals only have chemical activity in the surface layer. SEM is most highly concentrated at the boundary of the redox layer. SEM have similar depth distributions throughout the tidal flat. The aeration of low tidal flat sediment indicates that SEM gradually move to deeper sites via interstitial water.展开更多
Sodium-treated sepiolite(Na Sep)-supported transition metal catalysts(TM/Na Sep;TM = Cu, Fe, Ni, Mn, and Co) were synthesized via a rotary evaporation method. Physicochemical properties of the as-synthesized samples w...Sodium-treated sepiolite(Na Sep)-supported transition metal catalysts(TM/Na Sep;TM = Cu, Fe, Ni, Mn, and Co) were synthesized via a rotary evaporation method. Physicochemical properties of the as-synthesized samples were characterized by means of various techniques, and their catalytic activities for HCHO(0.2%) oxidation were evaluated. Among the samples, Cu/Na Sep exhibited superior performance, and complete HCHO conversion was achieved at 100 ℃(GHSV = 240000 m L/(g·h)). Additionally, the sample retained good catalytic activity during a 42 h stability test. A number of factors, including elevated acidity, the abundance of oxygen species, and favorable low-temperature reducibility, were responsible for the excellent catalytic activity of Cu/Na Sep. According to the results of the in-situ DRIFTS characterization, the HCHO oxidation mechanism was as follows:(i) HCHO was rapidly decomposed into dioxymethylene(DOM) species on the Cu/Na Sep surface;(ii) DOM was then immediately converted to formate species;(iii) the resultant formate species were further oxidized to carbonates;(iv) the carbonate species were eventually converted to CO2 and H2O.展开更多
The design and synthesis of highly active non-noble metal oxide catalysts, such as transition- and rare-earth-metal oxides, have attracted significant attention because of their high efficiency and low cost and the re...The design and synthesis of highly active non-noble metal oxide catalysts, such as transition- and rare-earth-metal oxides, have attracted significant attention because of their high efficiency and low cost and the resultant potential applications for the degradation of volatile organic compounds(VOCs). The structure-activity relationships have been well-studied and used to facilitate design of the structure and composition of highly active catalysts. Recently, non-noble metal oxides with porous structures have been used as catalysts for deep oxidation of VOCs, such as aromatic hydrocarbons, aliphatic compounds, aldehydes, and alcohols, with comparable activities to their noble metal counterparts. This review summarizes the growing literature regarding the use of porous metal oxides for the catalytic removal of VOCs, with emphasis on design of the composition and structure and typical synthetic technologies.展开更多
Arrays of chemical vapor sensors based on graphene field effect transistors functionalized with single-stranded DNA have been demonstrated. Standard photolithographic processing was adapted for use on large-area graph...Arrays of chemical vapor sensors based on graphene field effect transistors functionalized with single-stranded DNA have been demonstrated. Standard photolithographic processing was adapted for use on large-area graphene by including a metal protection layer, which protected the graphene from contamination and enabled fabrication of high quality field-effect transistors (GFETs). Processed graphene devices had hole mobilities of 1,640 ± 250 cm2.V-1.s-1 and Dirac voltages of 15 ± 10 V under ambient conditions. Atomic force microscopy was used to verify that the graphene surface remained uncontaminated and therefore suitable for controlled chemical functionalization. Single-stranded DNA was chosen as the functionalization layer due to its affinity to a wide range of target molecules and π-π stacking interaction with graphene, which led to minimal degradation of device characteristics. The resulting sensor arrays showed analyte- and DNA sequence-dependent responses down to parts-per-billion concentrations. DNA/GFET sensors were able to differentiate among chemically similar analytes, including a series of carboxylic acids, and structural isomers of carboxylic acids and pinene. Evidence for the important role of electrostatic chemical gating was provided by the observation of understandable differences in the sensor response to two compounds that differed only by the replacement of a (deprotonating) hydroxyl group by a neutral methyl group. Finally, target analytes were detected without loss of sensitivity in a large background of a chemically similar, volatile compound. These results motivate further development of the DNA/graphene sensor family for use in an electronic olfaction system.展开更多
基金This work is supported by the National Natural Science Foundation of China(40476063).
文摘It is well known that acid-volatile sulfide (AVS) plays an important role in influencing the toxicity of divalent cationic metals within anoxic sediments. In studying sediment core samples collected from tidal flats within the Jiaozhou Bay, China, we found that the AVS concentration gradually increases with depth and decreases from high tidal flat to low tidal flat areas. We evaluated the chemical activity and bioavailability of heavy metals in the tidal flat based on the molar ratio of simultaneously ex- tracted metals (SEM) and AVS. The value of SEM/AVS is generally less than 1 in this area except for the surface layer, which suggests that the heavy metals only have chemical activity in the surface layer. SEM is most highly concentrated at the boundary of the redox layer. SEM have similar depth distributions throughout the tidal flat. The aeration of low tidal flat sediment indicates that SEM gradually move to deeper sites via interstitial water.
文摘Sodium-treated sepiolite(Na Sep)-supported transition metal catalysts(TM/Na Sep;TM = Cu, Fe, Ni, Mn, and Co) were synthesized via a rotary evaporation method. Physicochemical properties of the as-synthesized samples were characterized by means of various techniques, and their catalytic activities for HCHO(0.2%) oxidation were evaluated. Among the samples, Cu/Na Sep exhibited superior performance, and complete HCHO conversion was achieved at 100 ℃(GHSV = 240000 m L/(g·h)). Additionally, the sample retained good catalytic activity during a 42 h stability test. A number of factors, including elevated acidity, the abundance of oxygen species, and favorable low-temperature reducibility, were responsible for the excellent catalytic activity of Cu/Na Sep. According to the results of the in-situ DRIFTS characterization, the HCHO oxidation mechanism was as follows:(i) HCHO was rapidly decomposed into dioxymethylene(DOM) species on the Cu/Na Sep surface;(ii) DOM was then immediately converted to formate species;(iii) the resultant formate species were further oxidized to carbonates;(iv) the carbonate species were eventually converted to CO2 and H2O.
基金supported by the National High Technology Research and Development Program of China(2012AA062702)the strategic project of the Chinese Academy of Sciences(XDB05050000)
文摘The design and synthesis of highly active non-noble metal oxide catalysts, such as transition- and rare-earth-metal oxides, have attracted significant attention because of their high efficiency and low cost and the resultant potential applications for the degradation of volatile organic compounds(VOCs). The structure-activity relationships have been well-studied and used to facilitate design of the structure and composition of highly active catalysts. Recently, non-noble metal oxides with porous structures have been used as catalysts for deep oxidation of VOCs, such as aromatic hydrocarbons, aliphatic compounds, aldehydes, and alcohols, with comparable activities to their noble metal counterparts. This review summarizes the growing literature regarding the use of porous metal oxides for the catalytic removal of VOCs, with emphasis on design of the composition and structure and typical synthetic technologies.
基金This research was supported by the Nano/Bio Interface Center through the National Science Foundation Nanoscale Science and Engineering Center (NSEC) DMR08-32802, and the work involved use of its facilities. Support from Lockheed Martin is also gratefully acknowledged. M.L. acknowledges the support of the Science, Mathematics, And Research for Transformation (SMART) Fellowship.
文摘Arrays of chemical vapor sensors based on graphene field effect transistors functionalized with single-stranded DNA have been demonstrated. Standard photolithographic processing was adapted for use on large-area graphene by including a metal protection layer, which protected the graphene from contamination and enabled fabrication of high quality field-effect transistors (GFETs). Processed graphene devices had hole mobilities of 1,640 ± 250 cm2.V-1.s-1 and Dirac voltages of 15 ± 10 V under ambient conditions. Atomic force microscopy was used to verify that the graphene surface remained uncontaminated and therefore suitable for controlled chemical functionalization. Single-stranded DNA was chosen as the functionalization layer due to its affinity to a wide range of target molecules and π-π stacking interaction with graphene, which led to minimal degradation of device characteristics. The resulting sensor arrays showed analyte- and DNA sequence-dependent responses down to parts-per-billion concentrations. DNA/GFET sensors were able to differentiate among chemically similar analytes, including a series of carboxylic acids, and structural isomers of carboxylic acids and pinene. Evidence for the important role of electrostatic chemical gating was provided by the observation of understandable differences in the sensor response to two compounds that differed only by the replacement of a (deprotonating) hydroxyl group by a neutral methyl group. Finally, target analytes were detected without loss of sensitivity in a large background of a chemically similar, volatile compound. These results motivate further development of the DNA/graphene sensor family for use in an electronic olfaction system.