Igor Yu. Skobelev

Metal–organic frameworks of the MIL-101 family as heterogeneous single-site catalysts

In this short review paper, we survey our recent findings in the catalytic applications of mesoporous metal–organic frameworks of the MIL-101 family (Fe- and Cr-MIL-101) and demonstrate their potential in two types of liquid-phase processes: (i) selective oxidation of hydrocarbons with green oxidants—O2 and tert-butyl hydroperoxide—and (ii) coupling reaction of organic oxides with CO2. A comparison with conventional single-site catalysts is made with special attention to issues of the catalysts resistance to metal leaching and the nature of catalysis.

Nanomodification of gold surface by picosecond soft x-ray laser pulse

We show experimentally the possibility of nanostructuring (about 20 nm) of gold surface by picosecond soft x-ray single pulse with low fluence of ∼20 mJ/cm2. The nanometer-scale changes of the surface structure are due to the splash of molten gold under fluence gradient of the laser beam. In addition, the ablation process occurs at slightly higher fluence of ∼50 mJ/cm2. The atomistic model of ablation is developed which reveals that the low threshold fluence of this process is due to the build-up of the high electron pressure and the comparatively low electron-ion energy relaxation rate in gold. The calculated ablation depths as a function of the irradiation fluence are in good agreement with the experimental data measured for gold surface modification with ultra-short duration soft x-ray and visible lasers.

Nanoscale surface modifications and formation of conical structures at aluminum surface induced by single shot exposure of soft x-ray laser pulse

We irradiated the soft x-ray laser (SXRL) pulses having a wavelength of 13.9 nm, a duration time of 7 ps, and fluences of up to 27 mJ/cm2 to aluminum (Al) surface. After the irradiation process, the modified surface was observed with the visible microscope, the scanning electron microscope, and the atomic force microscope. The surface modifications caused by the SXRL pulses were clearly seen, and it was found that the conical structures having about 70–150 nm in diameters were formed under a single pulse shot. The conical structures were formed in the features with the average depth of about 40 nm, and this value was in accordance with the attenuation length of the SXRL beam for Al. However, those conical structures were deconstructed under the multiple pulse shots exposure. Thermomechanical modeling of SXRL laser interaction with Al surface, which explains nanostructure surface modification, was provided.

Spallative ablation of dielectrics by X-ray laser

A short laser pulse in wide range of wavelengths, from infrared to X-ray, disturbs electron–ion equilibrium and increases pressure in a heated layer. The case where the pulse duration τL is shorter than acoustic relaxation time ts is considered in the paper. It is shown that this short pulse may cause thermomechanical phenomena such as spallative ablation regardless of wavelength. While the physics of electron–ion relaxation strongly depends on wavelength and various electron spectra of substances: there are spectra with an energy gap in semiconductors and dielectrics opposed to gapless continuous spectra in metals. The paper describes entire sequence of thermomechanical processes from expansion, nucleation, foaming, and nanostructuring to spallation with particular attention to spallation by X-ray pulse.

Enhanced K α output of Ar and Kr using size optimized cluster target irradiated by high-contrast laser pulses

We observed that increasing the clusters size and laser pulse contrast can enhance the X-ray flux emitted by femtosecond-laser-driven-cluster plasma. By focusing a high contrast laser (10(-10)) on large argon clusters, high flux Kα-like X-rays (around 2.96 keV) is generated with a total flux of 2.5 × 10(11) photons/J in 4π and a conversion efficiency of 1.2 × 10-4. In the case of large Kr clusters, the best total flux for L-shell X-rays is 5.3 × 1011 photons/J with a conversion efficiency of 1.3 × 10-4 and, for the Kα X-ray (12.7 keV), it is 8 × 10(8) photons/J with a conversion efficiency of 1.6 × 10-6. Using this X-ray source, a single-shot high-performance X-ray imaging is demonstrated.

Alkene Epoxidation Catalyzed by Ti-Containing Polyoxometalates: Unprecedented β-Oxygen Transfer Mechanism.

A DFT study revealed that the mechanism of alkene epoxidation with hydrogen peroxide catalyzed by Ti-containing polyoxometalates (POMs) depends on the Ti coordination environment: For rigid and hindered Ti centers, the unprecedented β-oxygen transfer from the titanium hydroperoxo species becomes favored over the α-oxygen one. Improving the model for catalyst description, the calculations were able to reproduce the Arrhenius activation energy values determined in kinetic studies. Unlike protonation, the possible ion-pairing between POMs and countercations has a minor effect on the electrophlicity of the catalyst and, consequently, on the activity of epoxidation.

Mechanistic Insights into Oxidation of 2-Methyl-1-naphthol with Dioxygen: Autoxidation or a Spin-Forbidden Reaction?

Oxidation of 2-methyl-1-naphthol (MNL) with molecular oxygen proceeds efficiently under mild reaction conditions (3 atm O(2), 60-80 °C) in the absence of any catalyst or sensitizer and produces 2-methyl-1,4-naphthoquinone (MNQ, menadione, or vitamin K(3)) with selectivity up to 80% in nonpolar solvents. (1)H NMR and (1)H,(1)H-COSY studies revealed the formation of 2-methyl-4-hydroperoxynaphthalene-1(4H)-one (HP) during the reaction course. Several mechanistic hypotheses, including conventional radical autoxidation, electron transfer mechanisms, photooxygenation, and thermal intersystem crossing (ISC), have been evaluated using spectroscopic, mass-spectrometric, spin-trapping, (18)O(2) labeling, kinetic, and computational techniques. Several facts collectively implicate that ISC contributes significantly into MNL oxidation with O(2) at elevated pressure: (i) the reaction rate is unaffected by light; (ii) C-C-coupling dimers are practically absent; (iii) the reaction is first order in both MNL and O(2); (iv) the observed activation parameters (ΔH(‡) = 8.1 kcal mol(-1) and ΔS(‡) = -50 eu) are similar to those found for the spin-forbidden oxidation of helianthrene with (3)O(2) (Seip, M.; Brauer, H.-D. J. Am. Chem. Soc.1992, 114, 4486); and (v) the external heavy atom effect (2-fold increase of the reaction rate in iodobenzene) points to spin inversion in the rate-limiting step.

Imaging spectroscopy of high-temperature plasma sources

The imaging spectrograph with spherical crystal and transmission grating have been used to obtain the high spectrally and spatially resolved images of plasma X-ray microsources (fast z -pinch) as well as of laser-produced plasma flares up to 5 mm in extent. The spectral resolution λ/Δλ = 2·10 4 have been achieved using a quartz spherical mirror with the curvature radius 500 mm. Using a transmission grating spectrometer, the spectral density of power about 10 5 W/A in the “water window” has been measured in experiments with a fast z -pinch large pulse storage facility.

Propagation-based phase-contrast enhancement of nanostructure images using a debris-free femtosecond-laser-driven cluster-based plasma soft x-ray source and an LiF crystal detector

We demonstrate in-line phase-contrast imaging of nanothickness foils by using a relatively large, polychromatic, debris-free femtosecond-laser-driven cluster-based plasma soft x-ray source, and a high-resolution, large dynamic range LiF crystal detector. The spatial coherence length of radiation in our setup reached a value of 5 microm on the sample plane, which is enough to observe phase-contrast enhancement in the images registered by the detector placed only a few hundred micrometers behind the object. We have developed a tabletop soft x-ray emission source, which emits radiation within a 4pi sr solid angle, and which allows one to obtain contact and propagation-based phase-contrast imaging of nanostructures with 700 nm spatial resolutions. This advance could be of utility for metrology applications.

The role of hollow atoms in the spectra of an ultrashort-pulse-laser-driven Ar cluster target

An investigation is made of the role of hollow atoms in the spectra of an ultrashort-pulse-laser-driven Ar cluster target. Experimental measurements are presented from an Ar cluster-gas target using short-pulse lasers with various intensities, durations, and contrasts. Calculations in support of these measurements have been performed using a detailed atomic kinetics model with the ion distributions found from solution of the time-dependent rate equations. The calculations are in good agreement with the measurements and the role of hollow atoms in the resulting complicated spectra is analyzed. It is demonstrated that, although the presence of hollow atoms is estimated to add only around 2% to the total line emission, signatures of hollow atom spectra can be identified in the calculations, which are qualitatively supported by the experimental measurements.