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Understanding photochemical pathways of laser-induced metal ion reduction through byproduct analysisLaser-induced reduction of metal ions is attracting increasing attention as a sustainable route to ligand-free metal nanoparticles. In this work, we investigate the photochemical reactions involved in reduction of Ag + and [AuCl 4 ] − upon interaction with lasers with nanosecond and femtosecond pulse duration, using strong-field ionization mass spectrometry and spectroscopic assays to identify stable molecular byproducts. Whereas Ag + in aqueous isopropyl alcohol (IPA) is reduced through plasma-mediated mechanisms upon femtosecond laser excitation, low-fluence nanosecond laser excitation induces electron transfer from IPA to Ag + . Both nanosecond and femtosecond laser excitation of aqueous [AuCl 4 ] − produce reactive chlorine species by Au–Cl bond homolysis. Formation of numerous volatile products by IPA decomposition during both femtosecond and nanosecond laser excitation of [AuCl 4 ] − is attributed to enhanced optical breakdown by the Au nanoparticle products of [AuCl 4 ] − reduction. These mechanistic insights can inform the design of laser synthesis procedures to improve control over metal nanoparticle properties and enhance byproduct yields.more » « less
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Abstract Gold (Au)- and ceria (CeO2)-based catalysts are amongst the most active catalysts for the gas phase CO oxidation reaction. Nevertheless, nanosized Au and CeO2catalysts may encounter heat-induced sintering in thermochemical catalytic reactions. Herein, we report on the rational one-pot synthesis of ceria-reduced graphene oxide (CeO2-RGO) using a facile ethylenediamine (EDA)-assisted solvothermal method. Standalone RGO and free-standing CeO2were also prepared using the same EDA-assisted method for comparison. We then incorporated Au into the prepared samples by colloidal reduction and evaluated the catalytic activity of the different catalysts for CO oxidation. The RGO-supported CeO2surpassed the free-standing CeO2, exhibiting a 100% CO conversion at 285oC compared to 340oC in the case of CeO2. Interestingly, the RGO-supported Au/CeO2catalysts outperformed the Au/CeO2catalysts and achieved a 100% CO conversion at 76oC compared to 113oC in the case of Au/CeO2. Additionally, the Au/CeO2-RGO catalyst demonstrated remarkable room-temperature activity with simultaneous 72% CO conversion. This outstanding performance was attributed to the unique dispersion and size characteristics of the RGO-supported CeO2and Au catalysts in the ternary Au/CeO2-RGO nanocomposite, as revealed by TEM and XPS, among other techniques.more » « less
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null (Ed.)A highly porous adsorbent based on a metal–organic framework was successfully designed and applied as an innovative adsorbent in the solid phase for the heavy metal removal. MIL-125 was densely decorated by 2-imino-4-thiobiuret functional groups, which generated a green, rapid, and efficacious adsorbent for the uptake of Hg( ii ) and Pb( ii ) from aqueous solutions. ITB-MIL-125 showed a high adsorption affinity toward mercury( ii ) ions of 946.0 mg g −1 due to covalent bond formation with accessible sulfur-based functionality. Different factors were studied, such as the initial concentration, pH, contact time, and competitive ions, under same circumstances at the room temperature. Moreover, the experimental adsorption data were in excellent agreement with the Langmuir adsorption isotherm and pseudo-second order kinetics. At a high concentration of 100 ppm mixture of six metals, ITB-MIL-125 exhibited a high adsorption capacity, reaching more than 82% of Hg( ii ) compared to 62%, 30%, 2%, 1.9%, and 1.6% for Pb( ii ), Cu( ii ), Cd( ii ), Ni( ii ), and Zn( ii ), respectively.more » « less
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null (Ed.)Laser photoreduction of metal ions onto graphene oxide (GO) is a facile, environmentally friendly method to produce functional metal–GO nanocomposites for a variety of applications. This work compares Au–GO nanocomposites prepared by photoreduction of [AuCl 4 ] − in aqueous GO solution using laser pulses of nanosecond (ns) and femtosecond (fs) duration. The presence of GO significantly accelerates the [AuCl 4 ] − photoreduction rate, with a more pronounced effect using ns laser pulses. This difference is rationalized in terms of the stronger interaction of the 532 nm laser wavelength and long pulse duration with the GO. Both the ns and fs lasers produce significant yields of sub-4 nm Au nanoparticles attached to GO, albeit with different size distributions: a broad 5.8 ± 1.9 nm distribution for the ns laser and two distinct distributions of 3.5 ± 0.8 and 10.1 ± 1.4 nm for the fs laser. Despite these differences, both Au–GO nanocomposites had the same high catalytic activity towards p -nitrophenol reduction as compared to unsupported 4–5 nm Au nanoparticles. These results point to the key role of GO photoexcitation in catalyzing metal ion reduction and indicate that both ns and fs lasers are suitable for producing functional metal–GO nanocomposites.more » « less
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