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At least 91 records · Page 5

Unraveling the adsorption-limited hydrogen oxidation reaction at palladium surface via in situ electron microscopy

Palladium (Pd) catalysts have been extensively studied for the direct synthesis of H 2 O through the hydrogen oxidation reaction at ambient conditions. This heterogeneous catalytic reaction not only holds considerable practical significance but also serves as a classical model for investigating fundamental mechanisms, including adsorption and reactions between adsorbates. Nonetheless, the governing mechanisms and kinetics of its intermediate reaction stages under varying gas conditions remain elusive. This is attributed to the intricate interplay between adsorption, atomic diffusion, and concurrent phase transformation of catalyst. Herein, the Pd-catalyzed, water-forming hydrogen oxidation is studied in situ, to investigate intermediate reaction stages via gas cell transmission electron microscopy. The dynamic behaviors of water generation, associated with reversible palladium hydride formation, are captured in real time with a nanoscale spatial resolution. Our findings suggest that the hydrogen oxidation rate catalyzed by Pd is significantly affected by the sequence in which gases are introduced. Through direct evidence of electron diffraction and density functional theory calculation, we demonstrate that the hydrogen oxidation rate is limited by precursors’ adsorption. These nanoscale insights help identify the optimal reaction conditions for Pd-catalyzed hydrogen oxidation, which has substantial implications for water production technologies. The developed understanding also advocates a broader exploration of analogous mechanisms in other metal-catalyzed reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Soft x-ray high-harmonic generation in an anti-resonant hollow core fiber driven by a 3 μ m ultrafast laser

High-harmonic upconversion driven by a mid-infrared femtosecond laser can generate coherent soft x-ray beams in a tabletop-scale setup. Here, we report on a compact ytterbium-pumped optical parametric chirped pulse amplifier (OPCPA) laser system seeded by an all-fiber front-end and employing periodically poled lithium niobate (PPLN) nonlinear media operated near the pulse fluence limits of current commercially available PPLN crystals. The OPCPA delivers 3 µm wavelength pulses with 775 µJ energy at 1 kHz repetition rate, with transform-limited 120 fs pulse duration, diffraction-limited beam quality, and ultrahigh 0.33% rms energy stability over >18 h. Using this laser, we generate soft x-ray high harmonics (HHG) in argon gas by focusing into a low-loss, high-pressure gas-filled anti-resonant hollow core fiber (ARHCF), generating coherent light at photon energies up to the argon L-edge (250 eV) and carbon K-edge (284 eV), with high beam quality and ∼1% rms energy stability. This work demonstrates soft x-ray HHG in a high-efficiency guided-wave phase matched geometry, overcoming the high losses inherent to mid-IR propagation in unstructured waveguides, or the short interaction lengths of gas cells or jets. The ARHCF can operate in the long term without damage and with the repetition rate, stability, and robustness required for demanding applications in spectromicroscopy and imaging. Finally, we discuss routes for further optimizing the soft x-ray HHG flux by driving He at higher laser intensities using either the signal (1.5 μm) or idler wavelengths (3 μm).

Femtosecond lasers

Transmission spectroscopy of CF 4 molecules in intense x-ray fields

The nonlinear interaction of x rays with matter is at the heart of understanding and controlling ultrafast molecular dynamics from an atom-specific viewpoint, providing new scientific and analytical opportunities to explore the structure and dynamics of small quantum systems. At increasingly high x-ray intensity, the sensitivity of ultrashort x-ray pulses to specific electronic states and emerging short-lived transient intermediates is of particular relevance for our understanding of fundamental multiphoton absorption processes. In this work, intense x-ray free-electron laser (XFEL) pulses at the European XFEL are combined with a gas cell and grating spectrometer for a high-intensity transmission spectroscopy study of multiphoton-induced ultrafast molecular fragmentation dynamics in CF 4 . This approach unlocks the direct intrapulse observation of transient fragments, including neutral atoms, by their characteristic absorption lines in the transmitted broadband x-ray spectrum. The dynamics with and without initially producing fluorine 𝐾-shell holes are studied by tuning the central photon energy. The absorption spectra are measured at different FEL intensities to observe nonlinear effects. Transient isolated fluorine atoms and ions are spectroscopically recorded within the ultrashort pulse duration of a few tens of femtoseconds. An isosbestic point that signifies the correlated transition between intact neutral CF 4 molecules and charged atomic fragments is observed near the fluorine 𝐾 edge. The dissociation dynamics and the multiphoton absorption-induced dynamics encoded in the spectra are theoretically interpreted. Overall, this study demonstrates the potential of high-intensity x-ray transmission spectroscopy to study ultrafast molecular dynamics with sensitivity to specific intermediate species and their electronic structure.

74 ATOMIC AND MOLECULAR PHYSICS

Improved photoionization mass spectrometer

Improved spectrometer for gas analysis lessens the intensity problem that occurs in obtaining dispersed ultraviolet radiation. A filter, consisting of a selectively transmitting gas cell, a thin film or mirror, or a predispersing grating, alleviates problems of interference from higher-order spectral lines and from scattered ultraviolet light.

Poshchenrieder, W. P.

Stark-effect modulation of a CO2 laser by NH2D.

Use of the molecular Stark effect in NH2D to modulate the 10.6-micron P(20) line of a CO2 laser, yielding a modulation depth of 40% from a 200-V/cm rms signal applied to a 19.7-cm gas cell external to the laser. NH2D was prepared by mixing ND3 and NH3. The absorption coefficient of the M = 4 Stark-split line was measured as a function of mixing ratio and pressure. The observed pressure-broadening coefficient was 32.5 MHz/torr.

Johnston, A. R.

Production of organic molecules by proton irradiation

Preliminary experiments were carried out to investigate the effectiveness of proton irradiation for producing organic chromophores. The source of the 2 MeV protons used in the experiments was a model Van de Graaff accelerator. The gas cells used were hollow aluminum cylinders. The test results show that energetic protons can be an effective energy source for the formation of complex molecules from simple ones. With the exception of sulfide compounds none of the molecules that were identified are colored. However, coloring agents could be contained in unresolvable fractions.

Scattergood, T.

A review of precision oscillators

Precision oscillators used in PTTI applications include quartz crystal, rubidium gas cell, cesium beam, and hydrogen maser oscillators. A general characterization and comparison of these devices is given including accuracy, stability, environmental sensitivity, size, weight, power consumption, availability and cost. Areas of special concern in practical applications are identified and a projection of future performance specifications is given. An attempt is made to predict physical and performance characteristics of new designs potentially available in the near future.

Hellwig, H.

The Stratospheric and Mesospheric Sounder (SAMS) experiment

Thermal emission and solar resonance fluorescence from the atmospheric limb are reported. Global measurements are made of radiation from the molecular species. The gas correlation spectroscopy technique based on the use of gas cells to select emission from chosen spectral lines or from particular parts of spectral lines is used. The source function and departure from the thermodynamic equilibrium between 80 and 130 kilometers associated with CO2 emission bands were investigated. The zonal wind velocity component along the line of sight is measured.

Drummond, J. R.

A 163 micron laser heterodyne radiometer for OH

A 163 micron (1.836 THz) radiometer developed for airplane and/or balloon platforms is described. The laser local oscillator is a CO2 pumped methanol laser operating at a frequency which is approx. 1 GHz from the J = 3/2 - 1/2 transition of OH. The laser is used directly as a local oscillator or is translated in frequency to closer coincidence with the OH emission, depending on achieved detector IF bandwidth. Frequency translation techniques which are described are diode mixing and a method of single sideband generation using an external Stark modulated gas cell. The photoconductive mixer used is a strained Ge crystal, doped with Ga, originally used as an incoherent detector. The uniaxial strain on the Ga doped Ge crystal shifts the threshold for photoconduction from 100/cm to frequencies as low as 50/cm. These detectors are currently being characterized as mixers in the laboratory. Of particular interest are the effect of local oscillator power and strain on IF, bandwidth detector impedance, and conversion loss. Preliminary results of these tests are described and compared with theorectical expectations.

Pickett, H. M.

Radiation hardness of Efratom M-100 rubidium frequency standard

The effects of nuclear radiation on rubidium gas cell frequency standards and components are presented, including the results of recent tests where a continuously operating rubidium frequency standard (Effratom, Model M-100) was subjected to simultaneous neutron/gamma radiation. At the highest neutron fluence 7.5 10 to the 12th power n/sq cm and total dose 11 krad(Si) tested, the unit operated satisfactorily; the total frequency change over the 2 1/2 hour test period due to all causes, including repeated retraction from and insertion into the reactor, was less than 1 x 10 to the -10th power. The effects of combined neutron/gamma radiation on rubidium frequency standard physics package components were also studied, and the results are presented.

English, T. C.

Thin metal film and multilayers experiment (A0138-3)

The sources of degradation of in state of the art and newly developed components and testing the usefulness of the concept of storing experiment samples in dry nitrogen under launch and space vacuum conditions during reentry mission phase were investigated. Ultraviolet (UV) and extreme ultraviolet (EUV) experiments suffer degradations during space missions of even 1 month duration. It is suggested that the degradation is due to condensation of outgassing products, followed by solar induced polymerization, however, penetrating charged particles are also known to produce volume effects. Degradation may also start immediately after manufacturing of the component due to oxidation, moisture, or chemical corrosion by atmospheric constituents such as CO2 and SO2. When the filters are used as windows for gas absorption cells or gas filters, or when they define the instrumental bandwidth by themselves. The effects of mechanical degradation by thermal cycling and/or dust may cause a dramatic impact.

Delaboudiniere, J. P.

Cell Separations in Microgravity and Development of a Space Bioreactor

A bioreactor optimized for operations in space is now being developed. The current research is focused on determining the optimum cell-bead ratios, medium content and proper maintenance conditions required to keep living cell specimens alive and healthy for the entire flight. The bioreactor development project has recently added a microprocessor/computer to the JSC prototype for control and data analysis. Appropriate new technology is being combined with the current bioreactor designs and tested to determine what specific features must be included in the fabrication of a bioreactor designed to operate for STS demonstration tests. Considerations include: (1) circulation and resupply of culture media; (2) sensors required to monitor temperature, cell growth, mass transport, and oxygen consumption; and (3) inflight control of shear stress on cells, gas transfer in microgravity, diffusion, and intracellular transport. These data and results from the JSC prototype bioreactor test will be used for the design and construction of a small space bioreactor for the Orbiter middeck.

Morrison, D. R.

A tandem mirror plasma source for hybrid plume plasma studies

A tandem mirror device to be considered as a hot plasma source for the hybrid plume rocket concept is discussed. The hot plamsa from this device is injected into an exhaust duct, which will interact with an annular hypersonic layer of neutral gas. The device can be used to study the dynamics of the hybrid plume, and to verify the numerical predictions obtained with computer codes. The basic system design is also geared towards low weight and compactness, and high power density at the exhaust. The basic structure of the device consists of four major subsystems: (1) an electric power supply; (2) a low temperature, high density plasma gun, such as a stream gun, an MPD source or gas cell; (3) a power booster in the form of a tandem mirror machine; and (4) an exhaust nozzle arrangement. The configuration of the tandem mirror section is shown.

Yang, T. F.

Support of validation of SAGE 2 data

An error analysis of differential absorption lidar (DIAL) measurements of stratospheric ozone from a Space Shuttle is discussed. A transmitter system consisting of a KrF excimer laser pumping gas cells of H2 or D2 producing output wavelengths in the near UV is shown to be useful for the measurement of ozone in an altitude range from 15 to 50 km.

Copeland, Gary E.

Error analysis of DIAL measurements of ozone by a Shuttle excimer lidar

Attention is given to an error analysis of DIAL measurements of stratospheric ozone from the Space Shuttle. It is shown that a transmitter system consisting of a KrF excimer laser pumping gas cells of H2 or D2 producing output wavelengths in the near UV is useful for the measurement of ozone in a 15-50-km altitude range. It is noted that for increased levels of stratospheric aerosols experienced after violent volcanic eruptions, the relative uncertainties of ozone densities will be large in the region below about 24 km.

Uchino, Osamu