Role of Energy Dissipation and Surface Mobility in Heterogeneous Catalysis by Metals

1998 ◽  
Vol 63 (11) ◽  
pp. 1851-1868 ◽  
Author(s):  
Zlatko Knor ◽  
Jan Plšek

The fundamental role of excess energy dissipation and of surface species mobility, both in the preparation of model metallic catalysts (bimetallic catalysts, bimetallic oxide-supported catalysts), and in the activation of reactant molecules on the catalyst surfaces (single crystals, bimetallic and bimetallic oxide-supported catalysts) are discussed. A generalized model of surface interactions is proposed which satisfactorily explains the trapping of particles from the gas phase at the atomic steps and recovery of the trapping sites due to migration of the trapped species towards flat terraces. Higher probability of encounter of these species with other reactants on flat terraces and easier desorption of the reaction products from there in comparison with the bound state at the edges of atomic steps can be expected. Results of FIM and FEM studies of Pt, Dy-W, Pd-W and Pd-Mo systems are used to illustrate selected features of the proposed general model.

2016 ◽  
Vol 2 (1) ◽  
pp. 41 ◽  
Author(s):  
Sh.S. Itkulova ◽  
K.Z. Zhunusova ◽  
I.S. Chanycheva ◽  
G.D. Zakumbaeva

<p>Mono- and bimetallic cobalt-containing catalysts supported on alumina have been investigated in the reaction of interaction between carbon dioxide and methane at variation of experiment temperature and pressure. It was shown, that the bimetallic catalysts have a high activity in this reaction in compare with monometallic ones. The main reaction products are carbon oxide, hydrogen, water and oxygenates. The yield of latter reaches 30% at certain conditions (P &gt; 0.5 MPa, T &lt; 853K). The maximum conversion of both methane (100%) and carbon dioxide (94%) is reached at lower pressure (0.1MPa) and 1023 K. In these conditions the synthesis-gas is a main reaction product. One of the advantages of the bimetallic catalysts is their resistance to coke formation.</p>


Author(s):  
V.P. Bondarenko ◽  
O.O. Matviichuk

Detail investigation of equilibrium chemical reactions in WO3–H2O system using computer program FacktSage with the aim to establish influence of temperature and quantity of water on formation of compounds of H2WO4 and WO2(OH)2 as well as concomitant them compounds, evaporation products, decomposition and dissociation, that are contained in the program data base were carried out. Calculations in the temperature range from 100 to 3000 °С were carried out. The amount moles of water added to 1 mole of WO3 was varied from 0 to 27. It is found that the obtained data by the melting and evaporation temperatures of single-phase WO3 are in good agreement with the reference data and provide additionally detailed information on the composition of the gas phase. It was shown that under heating of 1 mole single-phase WO3 up to 3000 °С the predominant oxide that exist in gaseous phase is (WO3)2. Reactions of it formation from other oxides ((WO3)3 and (WO3)4) were proposed. It was established that compound H2WO4 is stable and it is decomposed on WO3 and H2O under 121 °C. Tungsten Oxide Hydrate WO2(OH)2 first appears under 400 °С and exists up to 3000 °С. Increasing quantity of Н2О in system leads to decreasing transition temperature of WO3 into both liquid and gaseous phases. It was established that adding to 1 mole WO3 26 mole H2O maximum amount (0,9044–0,9171 mole) WO2(OH)2 under temperatures 1400–1600 °С can be obtained, wherein the melting stage of WO3 is omitted. Obtained data also allowed to state that that from 121 till 400 °С WO3–Н2O the section in the О–W–H ternary system is partially quasi-binary because under these temperatures in the system only WO3 and Н2O are present. Under higher temperatures WO3–Н2O section becomes not quasi-binary since in the reaction products WO3 with Н2O except WO3 and Н2O, there are significant amounts of WO2(OH)2, (WO3)2, (WO3)3, (WO3)4 and a small amount of atoms and other compounds. Bibl. 12, Fig. 6, Tab. 5.


2020 ◽  
pp. 130-135
Author(s):  
D.N. Korotaev ◽  
K.N. Poleshchenko ◽  
E.N. Eremin ◽  
E.E. Tarasov

The wear resistance and wear characteristics of cluster-gradient architecture (CGA) nanostructured topocomposites are studied. The specifics of tribocontact interaction under microcutting conditions is considered. The reasons for retention of high wear resistance of this class of nanostructured topocomposites are studied. The mechanisms of energy dissipation from the tribocontact zone, due to the nanogeometry and the structural-phase structure of CGA topocomposites are analyzed. The role of triboactivated deformation and diffusion processes in providing increased wear resistance of carbide-based topocomposites is shown. They are tested under the conditions of blade processing of heat-resistant titanium alloy.


Chemistry ◽  
2021 ◽  
Vol 3 (1) ◽  
pp. 338-359
Author(s):  
Magdalena Bonarowska ◽  
Zbigniew Kaszkur ◽  
Krzysztof Matus ◽  
Alicja Drelinkiewicz ◽  
Tomasz Szumełda ◽  
...  

We present an efficient strategy for synthesising the PdAu catalysts with a homogeneous PdAu alloy phase for environmentally important hydrodechlorination of tetrachloromethane in the gas phase. The synthesis of carbon-supported catalysts involved two major steps: (i) incorporation of palladium and gold nanoparticles into carbon support and (ii) activation of the catalysts. The critical part of this work was to find the optimal conditions for both steps. Thus, the incorporation of the nanoparticles was carried out in two ways, by impregnation and direct redox reaction method using acetone solutions of metal precursor salts. The activation was performed either by a conventional thermal reduction in hydrogen or flash irradiation in a microwave oven. The homogeneity and structure of the PdAu alloy were found to depend on the catalyst activation method critically. In all cases, we observed better homogeneity for catalysts that were subject to microwave irradiation. Moreover, the flash microwave irradiation of prepared catalysts provided catalysts of better stability and selectivity towards the desired products (hydrocarbons) in the hydrodechlorination of tetrachloromethane as compared to the catalyst obtained by conventional thermal activation in hydrogen.


ChemCatChem ◽  
2021 ◽  
Author(s):  
Alberto Villa ◽  
Ilaria Barlocco ◽  
Sofia Capelli ◽  
Xiuyuan Lu ◽  
Silvio Bellomi ◽  
...  

2020 ◽  
Vol 500 (3) ◽  
pp. 3414-3424
Author(s):  
Alec Paulive ◽  
Christopher N Shingledecker ◽  
Eric Herbst

ABSTRACT Complex organic molecules (COMs) have been detected in a variety of interstellar sources. The abundances of these COMs in warming sources can be explained by syntheses linked to increasing temperatures and densities, allowing quasi-thermal chemical reactions to occur rapidly enough to produce observable amounts of COMs, both in the gas phase, and upon dust grain ice mantles. The COMs produced on grains then become gaseous as the temperature increases sufficiently to allow their thermal desorption. The recent observation of gaseous COMs in cold sources has not been fully explained by these gas-phase and dust grain production routes. Radiolysis chemistry is a possible non-thermal method of producing COMs in cold dark clouds. This new method greatly increases the modelled abundance of selected COMs upon the ice surface and within the ice mantle due to excitation and ionization events from cosmic ray bombardment. We examine the effect of radiolysis on three C2H4O2 isomers – methyl formate (HCOOCH3), glycolaldehyde (HCOCH2OH), and acetic acid (CH3COOH) – and a chemically similar molecule, dimethyl ether (CH3OCH3), in cold dark clouds. We then compare our modelled gaseous abundances with observed abundances in TMC-1, L1689B, and B1-b.


2010 ◽  
Vol 2010 ◽  
pp. 1-15 ◽  
Author(s):  
Abdul-Majeed Azad ◽  
Desikan Sundararajan

Clean power source utilizing vast logistic fuel reserves (jet fuels, diesel, and coal) would be the main driver in the 21st century for high efficiency. Fuel processors are required to convert these fuels into hydrogen-rich reformate for extended periods in the presence of sulfur, and deliver hydrogen with little or no sulfur to the fuel cell stack. However, the jet and other logistic fuels are invariably sulfur-laden. Sulfur poisons and deactivates the reforming catalyst and therefore, to facilitate continuous uninterrupted operation of logistic fuel processors, robust sulfur-tolerant catalysts ought to be developed. New noble metal-supported ceria-based sulfur-tolerant nanocatalysts were developed and thoroughly characterized. In this paper, the performance of single metal-supported catalysts in the steam-reforming of kerosene, with 260 ppm sulfur is highlighted. It was found that ruthenium-based formulation provided an excellent balance between hydrogen production and stability towards sulfur, while palladium-based catalyst exhibited rapid and steady deactivation due to the highest propensity to sulfur poisoning. The rhodium supported system was found to be most attractive in terms of high hydrogen yield and long-term stability. A mechanistic correlation between the role of the nature of the precious metal and the support for generating clean desulfurized -rich reformate is discussed.


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