Acrylic fiber can be chemically converted to an amidoxime and carboxylate containing chelating adsorbent by a two-step synthesis method for extraction of uranium from seawater. A portion of the nitrile groups in the fiber is first converted to amidoxime using hydroxylamine followed by conversion of another portion of the nitrile groups to carboxylate with NaOH. At an optimized ratio of amidoxime/carboxylate (about 1 : 1), the chelating fiber in real seawater shows a higher uranium adsorption capacity and shorter saturation time compared with similar high-surface-area chelating fibers developed recently using a radiation-induced grafting method.
View Article and Find Full Text PDFHydrogen sulfide as a gas indicator molecule plays an important role in various human physiological processes. However, due to the high volatility and diffusivity of HS in biological systems, it is very difficult to implement a precise assay for HS detection. Compared with the destructive instrumental methods, assays based on fluorescence probes provide noninvasive and real-time detections of HS in living cells.
View Article and Find Full Text PDFNewly designed graphene cellular monoliths (GCMs) functionalized with hollow Pt-M nanoparticles (NPs) (Pt-M/GCM, M = Ni, Co) have been successfully achieved by a facile and powerful method on the basis of sonochemical-assisted reduction and gelatinization processes. First, hollow Pt-M (M = Ni, Co) NPs were synthesized and distributed on graphene oxide sheets (Pt-M/GO) by sodium borohydride reduction of metal precursors in the ultrasonic environment. Second, the hollow structure was further formed by ascorbic acid (AA) reduction of Pt precursors in gelatinization process.
View Article and Find Full Text PDFSupercritical fluid carbon dioxide (sc-CO2) is capable of depositing nanoparticles in small structures of silicon substrates because of its gas-like penetration, liquid-like solvation abilities, and near-zero surface tension. In nanometer-sized shallow wells on silicon surface, formation of two-dimensional (2D) monolayer metal nanoparticle (NP) clusters can be achieved using the sc-CO2 deposition method. Nanoparticles tend to fill nanostructured holes first, and then, if sufficient nanoparticles are available, they will continue to cover the flat areas nearby, unless defects or other surface imperfections are available.
View Article and Find Full Text PDFHerein, a facile ultrasonic-assisted strategy was proposed to fabricate the Pd-Pt alloy/multi-walled carbon nanotubes (Pd-Pt/CNTs) nanocomposites. A good number of Pd-Pt alloy nanoparticles with an average of 3.4 ± 0.
View Article and Find Full Text PDFThe feasibility of separating U from nitric acid solutions of mixed actinides using tri-n-butylphosphate (TBP)-modified supercritical fluid carbon dioxide (sc-CO2) was investigated. The actinides U, Np, Pu, and Am were extracted into sc-CO2 modified with TBP from a range of nitric acid concentrations, in the absence of, or in the presence of, a number of traditional reducing and/or complexing agents to demonstrate the separation of these metals from U under sc-CO2 conditions. The separation of U from Pu using sc-CO2 was successful at nitric acid concentrations of less than 3M in the presence of acetohydroxamic acid (AHA) or oxalic acid (OA) to mitigate Pu extraction, and the separation of U from Np was successful at nitric acid concentrations of less than 1M in the presence of AHA, OA, or sodium nitrite to mitigate Np extraction.
View Article and Find Full Text PDFUranium adsorbed on amidoxime-based polyethylene fiber in simulated seawater can be quantitatively eluted at room temperature using 1 M Na2CO3 containing 0.1 M H2O2. This efficient elution process is probably due to the formation of an extremely stable uranyl-peroxo-carbonato complex in the carbonate solution.
View Article and Find Full Text PDFLead sulfide (PbS) quantum dots stabilized by 1,2-benzenedimethanethiol can be synthesized by mixing Pb(NO3)2 and Na2S solutions in ethanol under ultrasound irradiation. The PbS quantum dots (2.7 and 3.
View Article and Find Full Text PDFIn this study, palladium nanoparticles embedded in monolithic microcellular high density polyethylene supports are synthesized as heterogeneous catalysts for remediation of 1,6-dichlorodibenzo-p-dioxin and 2,8-dichlorodibenzofuran in 200 atm of supercritical carbon dioxide containing 10 atm of hydrogen gas and at 50-90°C. Stepwise removal of chlorine atoms takes place first, followed by saturation of two benzene rings with slower reaction rates. The pseudo first order rate constant of initial hydrodechlorination for 2,8-dichlorodibenzofuran is 4.
View Article and Find Full Text PDFTechnologies such as thermal, oxidative, reductive, and microbial methods for the remediation of polychlorinated biphenyls (PCBs) have previously been reviewed. Based on energy consumption, formation of PCDD/F, and remediation efficiency, reductive methods have emerged as being advantageous for remediation of PCBs. However, many new developments in this field have not been systematically reviewed.
View Article and Find Full Text PDFUsing supercritical fluid CO(2) (Sc-CO(2)) as a medium, PbS nanoparticles can be uniformly deposited on surfaces of various substrates. Sc-CO(2) deposition of PbS nanoparticles on carbon-coated copper grids, into small holes in silicon, and formation of uniform PbS nanoparticle films on glass are described. Fluorescence spectra of PbS nanoparticles obtained from the films prepared by the Sc-CO(2) method indicate effective energy transfer between PbS nanoparticles of different sizes.
View Article and Find Full Text PDFNanometer-sized Pt, Rh, and bimetallic Pt-Rh particles can be deposited on surface of phenylacetic acid functionalized single-walled carbon nanotubes (SWCNTs) by a microemulsion method. The SWCNT-supported metallic nanoparticles show much greater catalytic activities compared with commercially available carbon-supported Pt and Rh catalysts for hydrogenation of neat benzene under mild experimental conditions. The bimetallic Pt-Rh nanoparticle catalyst synthesized by this method shows an enhanced activity relative to individual SWCNT-supported Pt and Rh nanoparticle catalysts.
View Article and Find Full Text PDFA common complication in fabricating arrays of TiO(2) nanotubes is that they agglomerate into tightly packed bundles during the inevitable solvent evaporation step. This problem is particularly acute for template-fabricated TiO(2) nanotubes, as the geometric tunability of this technique enables relatively large inter-pore spacings or, from another perspective, more space for lateral displacement. Our work showed that agglomeration results from the surface tension forces that are present as the ambient solvent is evaporated from the nanotube film.
View Article and Find Full Text PDFVery small (<10 nm) monodisperse gold nanoparticles (AuNPs) coated with a monolayer of decanethiol were prepared and their surface-enhanced infrared absorption (SEIRA) spectra were measured in the transmission mode. The AuNPs were prepared by the borohydride reduction of HAuCl(4) inside reverse micelles that were made by adding water to a hexane solution of sodium bis(2-ethylhexyl)sulfosuccinate (AOT). The gold nanoparticles were then stabilized by the addition of decanethiol.
View Article and Find Full Text PDFUranium dioxide can be dissolved directly in an imidazolium-based ionic liquid (IL) at room temperature with a tri-n-butylphosphate(TBP)-HNO(3) complex. The dissolution process follows pseudo first-order kinetics initially. Raman spectroscopic studies show the dissolved uranyl ions are coordinated with TBP in the IL phase with a molar ratio of (UO(2))(2+) : TBP = 1 : 2.
View Article and Find Full Text PDFCatalytic hydrogenation of polycyclic aromatic hydrocarbons (PAHs) with up to four fused benzene rings over high-density-polyethylene-stabilized palladium nanoparticles in supercritical carbon dioxide via in situ UV/Vis spectroscopy is presented. PAHs can be efficiently converted to saturated polycyclic hydrocarbons using this green technique under mild conditions at 20 MPa of CO₂ containing 1 MPa of H₂ at 40-50°C. Kinetic studies based on in situ UV/Vis spectra of the CO₂ phase reveal that the initial hydrogenation of a given PAH and the subsequent hydrogenations of its intermediates are pseudo-first-order.
View Article and Find Full Text PDFFluorescence of semiconducting single-walled carbon nanotubes (SWNTs) normally exhibits diameter-dependent oxidative quenching behaviour. This behaviour can be changed substantially to become an almost diameter-independent quenching phenomenon in the presence of electron-withdrawing nitroaromatic compounds, including o-nitrotoluene, 2,4-dinitrotoluene, and nitrobenzene. This change is observed for SWNTs suspended either in sodium dodecyl sulfate or in Nafion upon titration with hydrogen peroxide.
View Article and Find Full Text PDFRoom temperature ionic liquids form potentially important solvents in novel nuclear waste reprocessing methods, and the solvation, speciation, and complexation behaviors of actinides and lanthanides in room temperature ionic liquids is of current interest. In this study, the coordination environment of uranyl(VI) in solutions of the room temperature ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide containing either tetrabutylammonium nitrate or nitric acid was characterized using attenuated total reflection-Fourier transform infrared spectrometry. Both UO(2)(NO(3))(2) and UO(2)(NO(3))(3)(-) species were detected in solutions containing tetrabutylammonium nitrate.
View Article and Find Full Text PDFSilver sulfide and cadmium sulfide nanoparticles of controllable sizes are synthesized using a water-in-hexane microemulsion method and stabilized by dodecanethiol. The stabilized metal sulfide nanoparticles can be deposited homogenously on flat substrates forming ordered 2-D arrays in supercritical fluid carbon dioxide (Sc-CO(2)). The use of Sc-CO(2) leaves the particles unaffected by dewetting effects caused by traditional solvents and produces uniform arrays.
View Article and Find Full Text PDFA series of green techniques for synthesizing carbon nanotube-supported platinum nanoparticles and their high electrocatalytic activity toward methanol fuel cell applications are reported. The techniques utilize either the supercritical fluid carbon dioxide or water as a medium for depositing platinum nanoparticles on surfaces of multiwalled or single-walled carbon nanotubes. The catalytic properties of the carbon nanotubes-supported Pt nanoparticle catalysts prepared by four different techniques are compared for anodic oxidation of methanol and cathodic reduction of oxygen using cyclic voltammetry.
View Article and Find Full Text PDFSingle-walled carbon nanotubes (SWNTs) dispersed in sodium dodecyl sulfate (SDS) suspensions exhibit diameter-dependent protonation and oxidative quenching of their E11 fluorescence. This nanotube-diameter-based difference in solution chemistry is substantially changed when complexed with aromatic electron-accepting compounds such as nitrobenzene, o-nitrotoluene, 2,4-dinitrotoluene, and 9-nitroanthracene. SWNTs were suspended in aqueous SDS, and their emission spectra were measured as a function of pH and concentration of oxidizing agent (hypochlorite or hydrogen peroxide) to observe their protonation and oxidation behavior.
View Article and Find Full Text PDFHydrodechlorination of 4-chlorobiphenyl in supercritical fluid carbon dioxide (SF-CO(2)) catalyzed by palladium nanoparticles stabilized in high-density polyethylene beads proceeds by consecutive reactions to the final product bicyclohexyl. Each step of the reaction sequence, that is, 4-chlorobiphenyl --> biphenyl --> cyclohexylbenzene --> bicyclohexyl, follows pseudo-first-order kinetics. Arrhenius parameters of each reaction step were determined separately in SF-CO(2) by in situ absorption spectroscopy using a high-pressure fiber-optic cell.
View Article and Find Full Text PDFUranyl ions [UO(2)](2+) in aqueous nitric acid can be extracted into supercritical CO(2) (sc-CO(2)) by using an imidazolium-based ionic liquid with tri-n-butyl phosphate (TBP) as a complexing agent. The transfer of uranium from the ionic liquid to the supercritical fluid phase was monitored by UV/Vis spectroscopy using a high-pressure fiber-optic cell. The form of the uranyl complex extracted into the sc-CO(2) phase was identified to be [UO(2)(NO(3))(2)(TBP)(2)].
View Article and Find Full Text PDFSupercritical fluid carbon dioxide (SF-CO(2)) with small amounts of chemical modifier(s) provides a very effective sterilization technique that should be useful for destroying microorganism on heat-sensitive devices such as instruments flown on planetary-bound spacecraft. Under a moderate temperature (50 degrees C) and pressure (100 atm), spores of Bacillus pumilus strains ATCC 7061 and SAFR 032 can be effectively inactivated/eliminated from metal surfaces and small electronic devices in only 45 min using optimized modifier concentrations. Modifiers explored in this study included hydrogen peroxide (H(2)O(2)), tert-butyl hydroperoxide, formic acid, and Triton X-100.
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