Metal-Oxide Nanostructures Fabricated from Laser-Assisted Synthesis Technique

Background Rising levels of greenhouse gases in our atmosphere such as CO 2 are contributing to global rises in temperature, acidification of the oceans, and more extreme weather conditions. Hydrogenation of CO 2 to form carbon-based products is of great importance to reduce CO 2 levels and generate carbon-based compounds that can be used for industrial purposes. Copper- and nickel- based nanocatalysts have promising catalytic activity toward CO 2 hydrogenation, and have great interest to replace expensive and rare Pt- and Pd-based catalysts. Methods Focusing high powered laser pulses onto the surface of a silicon wafer immersed in liquid solutions containing nickel nitrate or copper nitrate in alkaline media leads to the formation of Cu, Ni or copper-nickel phyllosilicates (PS). The laser pulses remove Si atoms from the wafer, allowing them to interact with the surrounding liquid where the Cu 2+ or Ni 2+ ions incorporate themselves into the forming phyllosilicate structure. The well-dispersed Cu and Ni atoms throughout the structure lead to a highly catalytically active material. Results The Cu-PS and Ni-PS nanostructures were synthesized, and the formation mechanisms from different experimental parameters were investigated. The Cu-PS selectively converted CO 2 to methanol below 500ºC, and formed methanol and methane above 500ºC. Conclusions The synthesis of Cu-PS and Ni-PS nanostructured catalysts were achieved using a reactive laser ablation in liquid technique, and the products displayed catalytic activity toward the hydrogenation of CO 2 , with temperature-dependent selectivity toward methanol and methane.https://scholarscompass.vcu.edu/gradposters/1095/thumbnail.jp

Probing Coherent Vibrations of Organic Phosphonate Radical Cations with Femtosecond Time-Resolved Mass Spectrometry

Organic phosphates and phosphonates are present in a number of cellular components that can be damaged by exposure to ionizing radiation. This work reports femtosecond time-resolved mass spectrometry (FTRMS) studies of three organic phosphonate radical cations that model the DNA sugar-phosphate backbone: dimethyl methylphosphonate (DMMP), diethyl methylphosphonate (DEMP), and diisopropyl methylphosphonate (DIMP). Upon ionization, each molecular radical cation exhibits unique oscillatory dynamics in its ion yields resulting from coherent vibrational excitation. DMMP has particularly well-resolved 45 fs (732 ± 28 cm−1) oscillations with a weak feature at 610–650 cm−1, while DIMP exhibits bimodal oscillations with a period of ∼55 fs and two frequency features at 554 ± 28 and 670–720 cm−1. In contrast, the oscillations in DEMP decay too rapidly for effective resolution. The low- and high-frequency oscillations in DMMP and DIMP are assigned to coherent excitation of the symmetric O–P–O bend and P–C stretch, respectively. The observation of the same ionization-induced coherently excited vibrations in related molecules suggests a possible common excitation pathway in ionized organophosphorus compounds of biological relevance, while the distinct oscillatory dynamics in each molecule points to the potential use of FTRMS to distinguish among fragment ions produced by related molecules

Probing Coherent Vibrations of Organic Phosphonate Radical Cations with Femtosecond Time-Resolved Mass Spectrometry

Organic phosphates and phosphonates are present in a number of cellular components that can be damaged by exposure to ionizing radiation. This work reports femtosecond time-resolved mass spectrometry (FTRMS) studies of three organic phosphonate radical cations that model the DNA sugar-phosphate backbone: dimethyl methylphosphonate (DMMP), diethyl methylphosphonate (DEMP), and diisopropyl methylphosphonate (DIMP). Upon ionization, each molecular radical cation exhibits unique oscillatory dynamics in its ion yields resulting from coherent vibrational excitation. DMMP has particularly well-resolved 45 fs (732 ± 28 cm−1) oscillations with a weak feature at 610–650 cm−1, while DIMP exhibits bimodal oscillations with a period of ∼55 fs and two frequency features at 554 ± 28 and 670–720 cm−1. In contrast, the oscillations in DEMP decay too rapidly for effective resolution. The low- and high-frequency oscillations in DMMP and DIMP are assigned to coherent excitation of the symmetric O–P–O bend and P–C stretch, respectively. The observation of the same ionization-induced coherently excited vibrations in related molecules suggests a possible common excitation pathway in ionized organophosphorus compounds of biological relevance, while the distinct oscillatory dynamics in each molecule points to the potential use of FTRMS to distinguish among fragment ions produced by related molecules

Roles of Free Electrons and H2O2 in the Optical Breakdown-Induced Photochemical Reduction of Aqueous [AuCl4]-

Free electrons and H2O2 formed in an optical breakdown plasma are found to directly control the kinetics of [AuCl4]− reduction to form Au nanoparticles (AuNPs) during femtosecond laser-assisted synthesis of AuNPs. The formation rates of both free electrons and H2O2 strongly depend on the energy and duration of the 800 nm laser pulses over the ranges of 10−2400 μJ and 30−1500 fs. By monitoring the conversion of [AuCl4]− to AuNPs using in situ UV−vis spectroscopy during laser irradiation, the first- and second-order rate constants in the autocatalytic rate law, k1 and k2, were extracted and compared to the computed free electron densities and experimentally measured H2O2 formation rates. For laser pulse energies of 600 μJ and lower at all pulse durations, the first-order rate constant, k1, was found to be directly proportional to the theoretically calculated plasma volume, in which the electron density exceeds the threshold value of 1.8 × 1020 cm−3. The second-order rate constant, k2, was found to correlate with the measured H2O2 formation rate at all pulse energies and durations, resulting in the empirical relationship k2 ≈ H2O20.5. We have demonstrated that the relative composition of free electrons and H2O2 in the optical breakdown plasma may be controlled by changing the pulse energy and duration, which may make it possible to tune the size and dispersity of AuNPs and other metal nanoparticle products synthesized with femtosecond laser-based methods

Alien Registration- Tibbetts, Liva M. (Brooklin, Hancock County)

https://digitalmaine.com/alien_docs/19607/thumbnail.jp

Undoped Electron-Hole Bilayers in a GaAs/AlGaAs Double Quantum Well

We present the fabrication details of completely undoped electron-hole bilayer devices in a GaAs/AlGaAs double quantum well heterostructure with a 30 nm barrier. These devices have independently tunable densities of the two-dimensional electron gas and two-dimensional hole gas. We report four-terminal transport measurements of the independently contacted electron and hole layers with balanced densities from $1.2 \times 10^{11}$cm$^{-2}$ down to $4 \times 10^{10}$ cm$^{-2}$ at $T = 300 mK$. The mobilities can exceed $1 \times 10^{6}$ cm$^{2}$ V$^{-1}$ s$^{-1}$ for electrons and $4 \times 10^{5}$ cm$^{2}$ V$^{-1}$ s$^{-1}$ for holes.Comment: 3 pages, 3 figure

Radical Chemistry in a Femtosecond Laser Plasma: Photochemical Reduction of Ag+ in Liquid Ammonia Solution

Plasmas with dense concentrations of reactive species such as hydrated electrons and hydroxyl radicals are generated from focusing intense femtosecond laser pulses into aqueous media. These radical species can reduce metal ions such as Au3+ to form metal nanoparticles (NPs). However, the formation of H2O2 by the recombination of hydroxyl radicals inhibits the reduction of Ag+ through back-oxidation. This work has explored the control of hydroxyl radical chemistry in a femtosecond laser-generated plasma through the addition of liquid ammonia. The irradiation of liquid ammonia solutions resulted in a reaction between NH3 and OH·, forming peroxynitrite and ONOO−, and significantly reducing the amount of H2O2 generated. Varying the liquid ammonia concentration controlled the Ag+ reduction rate, forming 12.7 ± 4.9 nm silver nanoparticles at the optimal ammonia concentration. The photochemical mechanisms underlying peroxynitrite formation and Ag+ reduction are discussed

Conserved Vibrational Coherence in the Ultrafast Rearrangement of 2-Nitrotoluene Radical Cation

2-Nitrotoluene (2-NT) is a good model for both photolabile protecting groups for organic synthesis and the military explosive 2,4,6-trinitrotoluene (TNT). In addition to the direct C−NO2 bond-cleavage reaction that initiates detonation in TNT, 2-NT undergoes an H atom attack reaction common to the photolabile 2-nitrobenzyl group, which forms the aci-nitro tautomer. In this work, femtosecond pump−probe measure- ments with mass spectrometric detection and density functional theory (DFT) calculations demonstrate that the initially prepared vibrational coherence in the 2-NT radical cation (2- NT+) is preserved following H atom attack. Strong-field adiabatic ionization is used to prepare 2-NT+, which can overcome a modest 0.76 eV energy barrier to H atom attack to form the aci-nitro tautomer as soon as ∼20−60 fs after ionization. Once formed, the aci-nitro tautomer spontaneously loses −OH to form C7H6NO+, which exhibits distinctly faster oscillations in its ion yield (290 fs period) as compared to the 2-NT+ ion (380 fs period). The fast oscillations are attributed to the coherent torsional motion of the aci-nitro tautomer, which has a significantly faster computed torsional frequency (86.9 cm−1) than the 2- NT+ ion (47.9 cm−1). Additional DFT calculations identify reaction pathways leading to the formation of the dissociation products C7H6NO+, C7H7+, and C6H6N+. Collectively, these results reveal a rich picture of coherently and incoherently driven dissociation pathways in 2-NT+

Life to Those Shadows: Kevin Brownlow Talks about a Career in Films

Life to Those Shadows: Kevin Brownlow Talks about a Career in Film