Valentin N. Parmon

Metal-support interactions in cobalt-aluminum co-precipitated catalysts: XPS and CO adsorption studies

Cobalt-aluminum catalysts were prepared using either the precipitation of Co 2+ in the presence of freshly prepared Zn-Al hydrotalcite (the promoted sample) or the co-precipitation of Co 2+ and Al 3+ (the unpromoted samples). The evolution of the initial hydrotalcite-like structure was monitored during its calcination and the reductive treatment by means of XPS. It was shown that at 480 ◦ C the reduction of the calcined samples results in the formation of Co 0 species, the further reduction at 650 ◦ C results in an increase of the amount of the Co 0 species. The samples reduced at 650 ◦ C chemisorb readily carbon monoxide at 77 K, while the sample reduced at 480 ◦ C does not chemisorb CO at 77 K. At elevated temperatures, all reduced samples are found to be able to chemisorb CO. Terminal CO moieties as well as monodentate carbonates, formates and carboxyl species were detected at the surface of the reduced samples at their exposure to the CO medium at the elevated temperature. The intensity of the IR absorption bands of chemisorbed CO are found proportional to the surface fraction of the Co 0 species, measured by XPS. The apparent red shift of the IR absorption bands is observed for CO adsorbed on the samples reduced at 480 ◦ C. The obtained data correlate with the catalytic properties of the Co-Al samples in hydrogenation reactions. The conclusion on the existence of a strong metal–support interaction in the samples under the study is made.

Iron complexes in zeolites as a new model of methane monooxygenase

Iron complexes in the ZSM-5 zeolite matrix (α-centers) are shown to perform single-turnover cycles of methane oxidation to methanol at room temperature when nitrous oxide is used as a source of oxygen. The origin of carbon and oxygen in the product methanol was traced using13C and18O isotopes. Probable structure of α-sites as well as mechanistic features of the reaction allow to consider this system as a first successful model of methane monooxygenase.

Understanding Methane Aromatization on a Zn-Modified High-Silica Zeolite†

Methane is the principle constituent of natural gas and also the most inert of the saturated hydrocarbons. Its conversion into more commercially useful chemicals and liquid fuels represents one of the most important challenges in modern catalysis. Coaromatization of methane and light hydrocarbons (paraffins and olefins) at 700–800 K is one of the alternative methods for the conversion of methane. It has been reported recently that the conversion of methane during coaromatization with higher alkanes or alkenes (C2–C6) at 670–870 K in the presence of bifunctional catalysts (mainly, high-silica ZSM-5 or ZSM-11 zeolites, modified with gallium or zinc) may reach 20–40%. However, previous experiments in which C-labeled methane was used did not confirm the presence of the C-labeled atoms from the methane in the aromatization products. This result gave rise to scepticism as to whether methane-involved aromatization occurred at all. Herein we report that transfer of isotopically C-labeled atoms from methane into the aromatic products does occur to a high degree during the co-conversion of methane and propane on the Zn-modified high-silica zeolite BEA. We have identified the nature of the intermediates formed during the activation of methane and established how the conversion of methane into aromatic compounds occurs. Figure 1 shows the C CP/MAS NMR spectra of the products (in their adsorbed state on the zeolite catalyst) which are formed from methane and propane at 823–873 K. The spectrum of the products formed from unlabeled CH4 and C3H8 exhibits only a weak signal at d = 8.5 ppm from methane (Figure 1a). When unlabeled CH4 was replaced with CH4, the spectrum of the reaction products showed two new signals, which undoubtedly belong to hydrocarbons containing the C labels from the CH4 (Figure 1b). The carbon atoms of the C-labeled methane molecules are incorporated into both methyl groups (signal at d = 20 ppm) and aromatic rings (d = 130 ppm) of the methyl-substituted aromatic compounds (Figure 1b,c). According to GC-MS analysis of the products extracted from the zeolite, a mixture of benzene and toluene, as well as mand p-xylenes (BTX) with C enrichment is formed from CH4 and unlabeled propane at 773–823 K (Figure 2). The presence of singly (C1), doubly ( C2), and triply ( C3) labeled molecules of BTX (Figure 2b) provides proof for the incorporation of C-labeled methane into both the methyl groups and the carbon atoms of the aromatic rings of BTX. Neat propane converts on Zn/H-BEA into a mixture of aromatic products and methane at lower temperature (573– 723 K; Figure 1d). According to the H MAS NMR spectra, approximately 1.6–1.7 methane molecules are produced per reacted propane molecule. The possible overall reaction which describe the aromatization of propane can be described by Equation (1). Figure 1. C CP/MAS NMR spectra of products in the adsorbed state formed from methane and propane on zeolite Zn/H-BEA: a) from CH4 and C3H8 at 823 K for 15 min; b,c) from CH4 and C3H8 at 823 K for 15 min (b) and at 873 K for 15 min (c); d) from [1-C]C3H8 at 723 K for 15 min. Asterisks (*) in Figures 1, 3, and 4 denote the spinning side bands.

Modulation effects in the electron spin echo resulting from hyperfine interaction with a nucleus of an arbitrary spin

Abstract Exact analytic expressions for the modulation effects in two- and three-pulse electron spin echoes resulting from the hyperfine interaction of an electron and a nucleus with an arbitrary spin are derived. The two-pulse envelope modulation is calculated numerically for some nuclei for which modulation effects are most often observed experimentally. Applicability requirements of the conventional approximate formula for analysis of the ESE modulation effects are considered.

Hydroxides of transition metals as artificial catalysts for oxidation of water to dioxygen

Abstract Hydroxides of transition metals cations like Fe(III), Co(III), Mn(III), Ru(IV), etc., appear to be efficient artificial catalysts in oxidation of water to O 2 . The paper describes some catalytic properties of these hydroxides. The hydroxide-based catalysts for the water oxidation can be obtained in three modifications: bulky (individual and binary), supported on the ion exchange resins or conventional oxide supports (SiO 2 , TiO 2 , Al 2 O 3 , zeolites), and colloidal catalysts stabilized by starch. The possible mechanism of the catalytic reaction, including the stage of the formation of peroxocomplexes as intermediates is under discussion. Some similarities are drawn between the catalytic properties of hydroxide catalysts and those of the manganese-based oxygen evolving complex of the Photosystem II of green plants.

Oxide catalysts for ammonia oxidation in nitric acid production: properties and perspectives

Abstract This paper generalizes the results of long-term efforts aimed at research and development of industrial oxide catalysts for ammonia oxidation in the nitric acid production within two-bed (Pt gauzes+monolithic oxide layers) technology of the high pressure process. Main factors determining performance of precious metals and oxides in the high-temperature ammonia oxidation are considered. The surface oxygen bonding strength determined by the surface atomic structure appears to be the most important. From this point of view, existing approaches to synthesis of mixed oxide systems including perovskites with controlled nitric oxide selectivity and good stability in the high-temperature process of ammonia oxidation are analyzed. Main features of the bulk oxide monolithic catalysts production technology and principles of a two-bed system design based upon the process mathematical modeling are briefly outlined. Proven economic benefits of this technology recently commercialized in Russia at nitric acid plants are debated.

On the influence of the metal loading on the structure of carbon-supported PtRu catalysts and their electrocatalytic activities in CO and methanol electrooxidation

PtRu (1:1) catalysts supported on low surface area carbon of the Sibunit family (S(BET) = 72 m(2) g(-1)) with a metal percentage ranging from 5 to 60% are prepared and tested in a CO monolayer and for methanol oxidation in H(2)SO(4) electrolyte. At low metal percentage small (<2 nm) alloy nanoparticles, uniformly distributed on the carbon surface, are formed. As the amount of metal per unit surface area of carbon increases, particles start coalescing and form first quasi two-dimensional, and then three-dimensional metal nanostructures. This results in a strong enhancement of specific catalytic activity in methanol oxidation and a decrease of the overpotential for CO monolayer oxidation. It is suggested that intergrain boundaries connecting crystalline domains in nanostructured PtRu catalysts produced at high metal-on-carbon loadings provide active sites for electrocatalytic processes.

Hydrogen Production by Steam Reforming of Ethanol: A Two Step Process

A two-layer fixed-bed catalytic reactor for hydrogen production by steam reforming of ethanol is proposed. In this reactor ethanol is first converted to acetaldehyde over a Cu-based catalyst and then acetaldehyde is converted to a hydrogen-rich mixture over a Ni-based catalyst. It is shown that the use of such type of reactor prevents coke formation and provides hydrogen yields closed to equilibrium.

Cobalt–aluminum co-precipitated catalysts and their performance in the Fischer–Tropsch synthesis

Cobalt–aluminum catalysts were prepared using either Co2+ precipitation onto freshly prepared Mg–Al or Zn–Al hydrotalcite (promoted samples) or co-precipitation of Co2+ and Al3+ (non-promoted samples). The evolution of initial hydrotalcite structure was monitored during its calcination and reductive treatment. It has been shown that, at moderate temperatures, hydrotalcites results decomposition yields a Co oxide phase supported by a highly defective inverted spinel-like structure. Cations Co2+ enter the support structure, and occupy both tetrahedral and octahedral positions. Octahedron coordinated Co species are reduced at 580–620°C. After the reduction at 470–480°C catalyst phase composition shows Co0 supported on inverted spinel-like structure, which contains Co2+ in the octahedral coordination. Further reduction at 600°C transforms the support to ‘ideal’ spinel, which contains no octahedron coordinated Co2+. Chemical properties of the Co–Al catalysts, including their performance in the Fischer–Tropsch synthesis (FTS), were found to depend on the catalyst reduction temperature, and thus on the support structure. Metal-support interaction is supposed to explain the observed properties of metallic cobalt.

Possible Impact of Heterogeneous Photocatalysis on the Global Chemistry of the Earth's Atmosphere

Abstract Photochemistry is recognized to be important for various physicochemical processes in the atmosphere, such as formation of the ozone layer and smogs, degradation of waste substances, etc. [1]. However, up to the present the emphasis in atmospheric photochemistry has been mainly on the study of photochemical reactions that occur with molecules directly excited by absorption of light quanta. However, the major components and impurities of the earths atmosphere (such as nitrogen, oxygen, water, carbon dioxide, methane, methane halides, etc.) are totally transparent to most solar radiation. Electronically excited states of these molecules are formed only upon absorption of vacuum ultraviolet light quanta with energy hv ≥ 5 eV (i.e., with wavelength λ ≤ 200 nm). Only a small portion of the energy of solar light is found in this spectral region. In other words, most of the energy of the solar flux cannot participate in such direct photochemical reactions.