Are Au nanoparticles on oxygen free supports catalytically active?

Gold nanoparticles Au NPs on oxygen free supports were examined using near ambient pressure X ray photoelectron spectroscopy NAP XPS under CO oxidation conditions, and ex situ using scanning electron microscopy SEM and transmission electron microscopy TEM . Our observations demonstrate that Au NPs supported on carbon materials are inactive, regardless of the preparation method. Ozone O3 treatment of carbon supports leads oxygen functionalization of the supports. When subsequently exposed to a CO feed, CO is oxidized by the functionalized sites of the carbon support via a stoichiometric pathway. Microscopy reveals that the reaction with CO does not change the morphology of the Au NPs. In situ XPS reveals that the O3 treatment gives rise to additional Au 4f and O 1s peaks at binding energies of 85.25 85.6 eV and 529.4 530 eV, respectively, which are assigned to the presence of Au oxide. A surface oxide phase is formed during the activation of Au NPs supported on Au foil by O3 treatment. However, this phase decomposes in vacuum and the remaining low coordinative atoms do not have sufficient catalytic properties to oxidize CO, so the size reduction of Au NPs and or oxidation of Au NPs is not sufficient to activate A

Interactive Surface Chemistry of CO2 and NO2 on Metal Oxide Surfaces: Competition for Catalytic Adsorption Sites and Reactivity

Cataloged from PDF version of article.Interactive surface chemistry of CO2 and NO2 on BaOx/Pt(111) model catalyst surfaces were investigated via X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption (TPD) techniques with a particular emphasis on the competition between different adsorbates for the catalytic adsorption sites and adsorbate-induced morphological changes. After NO2 adsorption, nitrated BaO x/Pt(111) surfaces do not reveal available adsorption sites for CO2 at 323 K, irrespective of the presence/absence of exposed Pt sites on the surface. Although NO2 adsorption on thick BaO x(>10MLE)/Pt(111) overlayers at 323 K leads to the formation of predominantly nitrate species, NO2 adsorption on the corresponding carbonated surface leads to the formation of coexisting nitrates and nitrites. The presence of carbonates on BaOx/Pt(111) overlayers does not prevent NO2 uptake. Carbonated BaOx(1.5 MLE)/Pt(111) surfaces (with exposed Pt sites) obtained via CO2 adsorption can also further interact with NO2, forming surface nitrate/nitrite species, accompanied by the transformation of surface carbonates into bulk carbonate species. These results suggest that the nitrate formation process requires the presence of two adjacent unoccupied adsorption sites. It is apparent that in the presence of both NO2 and CO2, carbonate species formed on Lewis base (O2-) sites enable the formation of nitrites on Lewis acid (Ba2+) sites. Thermal aging, nitration, and carbonation have a direct impact on the morphology of the two-/three-dimensional (2D/3D) BaO x aggregates on Pt(111). While thermal aging in vacuum leads to the sintering of the BaOx domains, nitration and carbonation results in redispersion and spreading of the BaOx domains on the Pt(111) substrate. © 2013 American Chemical Society.

Combined in situ XPS and PTRMS study of ethylene epoxidation over silver

Ethylene epoxidation over silver was investigated by combined in-situ X-ray photoelectron spectroscopy (XPS) and proton-transfer reaction mass-spectrometry (PTRMS) at temperatures from 300 to 520 K and in the pressure range from 0.07 to 1 mbar. Ethylene oxide was present among the reaction products at T 420 ≥ K and P ≥ 0.3 mbar. The catalytically active surface contains two oxygen species – nucleophilic and electrophilic oxygen. The observed correlation between the abundance of electrophilic oxygen and the yield of ethylene oxide expressed as C2H4O partial pressure indicates that namely this oxygen species oxidizes ethylene to ethylene oxide. Opposite trend is observed for nucleophilic oxygen: the higher is the abundance of this species, the lower is the yield of ethylene oxide. This result is in line with the known fact that nucleophilic oxygen due to its oxidic nature is active in total oxidation of ethylene to CO2 and H2O. The low activity of silver at T < 420 K is caused by the presence of carbonates and carbonaceous residues at the silver surface that reduce the available silver surface area for the catalytic reaction. Reduction of the surface area available for the formation of active species due to accumulation of the embedded oxygen species explains also the decrease of the rate of ethylene oxide formation with time observed for T 470 ≥ K

Oxygen transport in Pr nickelates: Elucidation of atomic-scale features

Pr2NiO4+δ oxide with a layered Ruddlesden–Popper structure is a promising material for SOFC cathodes and oxygen separation membranes due to a high oxygen mobility provided by the cooperative mechanism of oxygen migration involving both interstitial oxygen species and apical oxygen of the NiO6 octahedra. Doping by Ca improves thermodynamic stability and increases electronic conductivity of Pr2 − xCaxNiO4+δ, but decreases oxygen mobility due to decreasing the oxygen excess and appearing of 1–2 additional slow diffusion channels at x ≥ 0.4, probably, due to hampering of cooperative mechanism of migration. However, atomic-scale features of these materials determining oxygen migration require further studies. In this work characteristics of oxygen diffusion in Pr2 − xCaxNiO4+δ (x = 0–0.6) are compared with results of the surface analysis by X-ray photoelectron spectroscopy and modeling of the interstitial oxygen migration by the plane-wave density functional theory calculations. According to the X-ray photoelectron spectroscopy data, the surface is enriched by Pr for undoped sample and by Ca for doped ones. The O1s peak at ~531 eV corresponding to a weakly bound form of surface oxygen located at Pr cations disappears at ~500 °C. Migration of interstitial oxygen was modeled for a I4/mmm phase of Pr2NiO4+δ. The interstitial oxygen anion repulses the apical one in the NiO6 octahedra pushing it into the tetrahedral site between Pr cations. The calculated activation barrier of this migration is equal to 0.585 eV, which reasonably agrees with the experimental value of 0.83 eV obtained by the oxygen isotope exchange method. At the same time, for the model compound Ca2NiO4+δ, obtained by isomorphic substitution of Pr by Ca in Pr2NiO4+δ, calculations implied formation of the peroxide ion comprised of interstitial and lattice oxygen species not revealed in the case of incomplete substitution (up to PrCaNiO4+δ composition). Hence, calculations in the framework of the plane-wave density functional theory provide a realistic estimation of specificity of oxygen migration features in Pr2NiO4+δ doped by alkaline-earth metals. © 2019 Elsevier B.V.Russian Science Foundation, RSF: 16-13-00112Support by Russian Science Foundation (Project 16-13-00112 ) is gratefully acknowledged

Constructing g-C3N4/Cd1−xZnxS-Based Heterostructures for Efficient Hydrogen Production under Visible Light

Two types of photocatalysts, 1%Pt/Cd1−x Znx S/g-C3 N4 (x = 0.2–0.3) and Cd1−x Znx S/1% Pt/g-C3 N4 (x = 0.2–0.3), were synthesized by varying the deposition order of platinum, and a solid solution of cadmium and zinc sulfides onto the surface of g-C3 N4. The characterization of photo-catalysts showed that, for 1%Pt/Cd1−x Znx S/g-C3 N4, small platinum particles were deposited onto a solid solution of cadmium and zinc sulfides; in the case of Cd1−x Znx S/1%Pt/g-C3 N4, enlarged platinum clusters were located on the surface of graphitic carbon nitride. Based on the structure of the photocatalysts, we assumed that, in the first case, type II heterojunctions and, in the latter case, S-scheme heterojunctions were realized. The activity of the synthesized samples was tested in hydrogen evolution from triethanolamine (TEOA) basic solution under visible light (λ = 450 nm). A remarkable increase in hydrogen evolution rate compared to single-phase platinized 1%Pt/Cd1−x Znx S photocat-alysts was observed only in the case of ternary photocatalysts with platinum located on the g-C3 N4 surface, Cd1−x Znx S/1%Pt/g-C3 N4. Thus, we proved using kinetic experiments and characterization techniques that, for composite photocatalysts based on Cd1−x Znx S and g-C3 N4, the formation of the S-scheme mechanism is more favorable than that for type II heterojunction. The highest activity, 2.5 mmol H2 g−1 h−1, with an apparent quantum efficiency equal to 6.0% at a wavelength of 450 nm was achieved by sample 20% Cd0.8 Zn0.2 S/1% Pt/g-C3 N4. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.Funding: This work was supported by the Ministry of Science and Higher Education of the Russian Federation within the governmental order for Boreskov Institute of Catalysis (project AAAA-A21-121011390009-1) and was also funded by the Russian Foundation for Basic Research (project No. 20-33-70086). A.S.V. and I.A.W. thank Minobrnauki research project FEUZ-2020-0059 for financial support

КОМПЬЮТЕРНАЯ ТОМОГРАФИЯ В ДИАГНОСТИКЕ И ДИФФЕРЕНЦИАЛЬНОЙ ДИАГНОСТИКЕ ПНЕВМОКОНИОЗА

Introduction. Pneumoconiosis is a disease caused by exposure industrial dust.The aim of the work was to determine the diagnostic effectiveness of radiation research methods in its diagnosis and systematize CT semiotics.Materials and methods. 105 mining and metallurgical workers were surveyed. All patients underwent a clinical and radiological examination.Results. In addition to focal and interstitial changes, nodular changes were detected, and the presence of a cavity was not always a sign of tuberculosis. The sensitivity of CT was 98,94%, the specificity was 90,0%.Conclusion. CT is necessary for all patients with suspected pneumoconiosis. The combination of the disseminated process in the lungs and professional harmfulness is not decisive in making a diagnosis, a comprehensive approach is necessary.Введение. Пневмокониоз — профессиональное заболевание от воздействия промышленной пыли.Цель работы: определить диагностическую эффективность лучевых методов исследования в его диагностике и систематизировать КТ-семиотику.Материалы и методы. Обследовано 105 работников горнодобывающей промышленности и металлургии. Всем пациентам проведено комплексное клинико-лучевое обследование.Результаты. Кроме очаговых и интерстициальных изменений, определялись узловые формы, причем наличие полости не всегда являлось признаком присоединения туберкулеза. Чувствительность КТ составила 98,94%, специфичность — 90,0%.Заключение. Необходимо проведение КТ пациентам при подозрении на пневмокониоз. У пациентов с диссеминацией наличие профессиональной вредности не является определяющим критерием в постановке диагноза, необходим комплексный подход