Preparation effects on the activity of Cu-ZSM-5 catalysts for NO decomposition

Effects of Cu-ZSM-5 catalyst preparation on the activity of over-exchanged copper for NO decomposition are reported. The Cu-ZSM-5 catalysts were prepared by incorporating Cu²⁺ cations into ZSM-5 zeolites from an aqueous cupric acetate solution adjusted to different pH values by adding either acetic anhydride or aqueous ammonia in the solution. The Cu²⁺ exchange levels increased with increasing pH level. STEM/EDX analysis identified CuO particles (5–6 nm) on the zeolite surface for the materials exchanged at pH>6. Conversion and kinetics measurements of NO decomposition to N₂ over these catalysts showed that the over-exchanged copper was not active. Short-time wash with aqueous ammonia removed this copper. The catalyst activity correlated very well with the amount of copper remaining in the ZSM-5 channels.     

Does Density of Cationic Sites Affect Catalytic Activity of Co Zeolites in Selective Catalytic Reduction of NO with Methane?

Selective catalytic reduction of NO with methane (CH₄-SCR) in an excess of oxygen over Co ions located in ZSM-5 of various Si/Al composition and in ferrierite, mordenite, chabazite and beta zeolite was investigated. From the comparison of the dependence of the TOF values per Co ion for NO conversion to N₂ and Co ions distribution among the cationic sites on total Co ion concentration, the catalytic activity of the individual Co ions was estimated. The -type Co²⁺ ions, located in the main channel of mordenite and ferrierite and coordinated above the rectangle of four framework oxygens of the channel wall exhibit the highest activity in these zeolites. On the other hand, the -type Co²⁺ ions coordinated in the plane of four oxygens of the deformed six-member ring located in the channel intersection of ZSM-5 and in channels of beta zeolite control the activity of these Co zeolites. The sequence of activity of Co²⁺ ions in CH₄-SCR of NO was FER Co>ZSM-5 Co>BEA CoZSM-5 CoFER CoMOR CoCHA CoMOR Co. A correlation between the activity of the individual Co ions in CH₄-SCR of NO and a distance between the cationic sites was observed.     

Variable‐temperature IR spectroscopic studies of CO adsorbed on Na‐ZSM‐5 and Na‐Y zeolites

CO interacts with extraframework alkali metal cations (M⁺=) of zeolites to form both M⁺CO and M⁺OC species. By using variabletemperature FTIR spectroscopy, these Cbonded and Obonded species were found to be in a temperaturedependent equilibrium. For the same cation, the difference in interaction energy depends upon the zeolite framework. Thus, for the equilibrium process ZNa⁺=CO ZNa⁺OC, where Z represents the zeolite framework, H ⁰ was found to take the values 3.8 and 2.4 kJ mol^– for CO/NaZSM5 and CO/NaY, respectively. The Cbonded species show always the highest cation–CO interaction energy.     

Acetone conversion to isobutene in high selectivity using zeolite β catalyst

The catalytic activity of the proton forms of zeolite and ZSM-5 are compared for the conversion of acetone. Zeolite demonstrates markedly enhanced selectivity to isobutene and selectivities of >80% can be achieved for conversions up to 65%. In contrast high selectivities to isobutene with ZSM-5 can be attained only at very low conversions (5%).     

Aromatization of n-butane over new LD-HBS catalysts. Effect of the gallium oxide support

It is shown that even pure quartz, other silicas or aluminas can enhance the aromatization activity of a ZSM-5 zeolite. Incorporation of gallium oxide onto these supports increases further the production of aromatics. The use of supported gallium oxide co-catalyst obtained by co-evaporation of a colloidal silica and a Ga salt has led to extremely high aromatization performance for the hybrid catalyst.     

Mechanisms of Iron Activation on Fe-Containing Zeolites and the Charge of α-Oxygen

According to previous Mössbauer data [1] -sites formation at the activation of Fe-containing zeolites is accompanied by irreversible self-reduction of the iron, proceeding without participation of an external reducing agent. Reduced Fe²⁺ ions are inert to O₂ but are reversibly oxidized to Fe³⁺ by N₂O, generating the -oxygen species, O, which provide selective oxidation of hydrocarbons.In this work, the mechanism of -sites formation was studied via quantitative measurement of the dioxygen amount desorbed into the gas phase at the step of self-reduction. A prominent role of the zeolite matrix chemical composition has been revealed. For example, with zeolites of Al–Si composition (FeZSM-5 and Fe-), heating to 900 °C in a closed vacuum space leads to irreversible evolution of O₂, which is accompanied by the immediate formation of -sites. Similar heating of B–Si and Ti–Si zeolites also leads to dioxygen evolution; however, this evolution is reversible and is not accompanied by formation of -sites. Activation of these zeolites occurs only in the presence of water vapor. Stoichiometric measurements showed that in terms of charge one regular O^2- ion, removed at the activation, is equivalent to two -oxygen atoms. So, -oxygen is identified as an ion-radical species O ^-., whose unique oxidation properties still distinguish it from the generally observed O^-. radicals.The mechanism of -sites formation is proposed, in which the process of strong chemical stabilization of reduced Fe²⁺ atoms in the zeolite structure is a key step, making impossible the reoxidation of the iron with O₂.     

Mechanism of Microwave Heating of Zeolite A

The mechanism of microwave heating of A zeolite was studied by comparing the heating properties, cation distributions and dielectric properties of 3A, 4A and 5A zeolites. It was easy to heat hydrated 4A zeolite to a glowing (melting) temperature by microwave (2.45 GHz) radiation from room temperature but was difficult to heat the same zeolite with little hydration. When 4A zeolite was preheated to 120°C, it could be easily heated by microwave radiation. However, 3A zeolite was not heated by microwaves under the above condition used for 4A zeolite. 3A zeolite with little hydration at room temperature could not be heated by microwaves but could be heated after hydrating it to 5 H₂O per unit cell (puc) or preheating 3A to 254°C. 5A zeolite could not be heated at all. The easiness of microwave heating was in the order of 4A < 3A 5A. There are differences in the cation distribution among these zeolites, i.e., 5A zeolite has no cations on the 4- and 8-membered oxygen ring sites but the other two have. It was expected from dielectric properties reported so far that the cation on 4-ring site can absorb microwave at <450°C with a higher efficiency but cations in other locations are ineffective for absorption. The following mechanism for the microwave heating was proposed: In the initial period, the hydratedzeolite absorbs the microwaves through its adsorbed water and its temperature rises. The adsorbed water completes desorption by ca. 400–470°C. In this temperature range the zeolite begins to absorb microwaves and the absorption efficiency becomes high with increasing temperature. When zeolite reaches 450–500°C thermal runaway starts. 5A zeolite cannot reach thermal runaway conditions because of absence of cation on 4-ring site. The adsorbed water plays the role of preheating agent in the initial period of microwave heating. Its role, however, can be substituted by other ways, e.g., preheating by conventional heating.     

Studies on the mechanism of ZSM-5 formation

The nucleation of (Al-free) zeolite precursor gels was studied using X-ray diffraction,²⁹Si FT-NMR, and ion exchange. Results suggest that in ZSM-5 nucleation, the channel intersections are first formed. These clathrate-like units, each containing essentially one TPA⁺ cation, are initially randomly connected, but progressively anneal with rearrangement under the influence of OH^– ions to form the ZSM-5 framework.     

On the preparation and properties of CuZSM-5 catalysts for NO decomposition

Equilibrium exchange isotherms were determined for the exchange of Cu²⁺ with NaZSM-5 at varying Cu(Ac)₂ concentrations in solutions of constant volume and zeolite weight. At low Cu²⁺ levels the solid scavenged all the copper ions. When copper could be detected in the equilibrated solutions, overexchange was observed. The extent of overexchange was higher at pH 6 than at pH 4. These results were analyzed in relation to catalytic activity.On leave from the Central Institute for Chemistry, Hungarian Academy of Sciences, H1525 Budapest, Hungary.     

Alkylation of benzene with ethane over platinum-loaded zeolite catalyst

Alkylation of benzene with ethane was carried out using various zeolite catalysts at temperature ranges of 400–550°C. Loading of platinum onto zeolite greatly enhanced the yield of ethylbenzene. Among the zeolites tested, H-ZSM5 and H-MCM22 showed catalytic activities. By contrast, mordenite did not yield ethylbenzene. Moderate acid strength distribution is the key factor of zeolite catalysts. Optimum catalyst and conditions for this reaction are as follows. The platinum-loaded H-ZSM5 catalyst containing 6.8 wt% Pt, at a reaction temperature of 500°C, afforded ethylbenzene and styrene formation rates of 14.2 and 0.8 mmolh^–1g-cat^–1, respectively (benzene-based yields 7.3 and 0.4%). In the alkylation of benzene with ethane over platinum-loaded H-ZSM5, ethene was initially formed from ethane over the metallic platinum. Then the alkylation proceeded over the acid sites of H-ZSM5.     

Vapor‐phase synthesis of acetophenone in benzene acylation over CeHZSM‐5(30) zeolite

The benzene acylation was carried out with acetic anhydride as an acylating agent in vapor phase over HZSM5, Si/Al =30 and 280, HY and Ce, Vmodified HZSM5(30) zeolite catalysts at atmospheric pressure. The yield of acylated product acetophenone was found to be 82.1 wt% with 95.0% selectivity at 86.4 wt% conversion of acetic anhydride over Cemodified HZSM5(30) where Brønsted acidic sites are active for this reaction.     

1H broad-line and MAS NMR: application to the study of acid sites of desilicated zeolite ZSM-5

Broad-line¹H NMR study of desilicated zeolite ZSM-5 was carried out as a function of the number of adsorbed water molecules in amounts lower than or equal to that of the Brønsted acid sites. The dissociation coefficient of the acid OH groups, currently associated with the acid strength, was shown not to be affected by the selective removal of Si from the zeolite ZSM-5 framework which resulted in more Brønsted acid sites per unit surface area. On the other hand, by using MAS NMR, bridging Brønsted acid sites hydrogen-bonded to the zeolite framework were identified on the anhydrous surface of the desilicated ZSM-5. Moreover, MAS NMR spectra of the desilicated zeolite partially rehydrated showed the presence of some Lewis acid sites.     

Texture prediction of Bi2Te3 electroplated layers using Hartman's theory of crystal growth

An experimental study of electroplated thin films of bismuth telluride, R3m crystal structure, shows that fibre textures are observed during the growth of the layers. Several orientations 00.1, 10.10, 11.0, 10.4, 10.8, 01.5 and 10.0 are developed during the deposition process, then reach a final orientation. Hartman's theory of crystal growth based on the periodic bond chain (PBC) in a crystal lattice is usually applied. This explains the equilibrium shape of a crystal defined by F faces and the faces observed during the growth (S and K faces). It also successfully predicts the orientations observed in bismuth telluride from the beginning to the end of the layer deposition. The theory may also be applied to other deposition processes.     

Surface complexes in zeolite-catalysed acylation reactions detected by13C MAS NMR spectroscopy

The state of the acylating agent acetyl chloride, adsorbed on a series of proton and metal ion exchanged zeolites X, Y (faujasite) and ZSM-5, was investigated by¹³C MAS NMR spectroscopy. The observed carbonyl signals were assigned to two species: chemisorbed acetyl chloride bound to lattice oxygen (signals near 182 ppm), and acetyl chloride complexed with counter cations in the lattice (signals near 172 ppm). In a few cases signals were observed which have been assigned to free acylium cation stabilized on the surface of the solid (signal 160–165 ppm). Experiments in which toluene was adsorbed on to ZnY pretreated with acetyl chloride showed the participation of various adsorbed species in the acylation reaction of toluene.     

Specific features of the phase transformations occurring during the sintering process of the beta-alumina based ceramics and their properties

Conclusions During the sintering process of beta-alumina obtained using the method of plasmochemical synthesis, the structural transformation occurs and it is accompanied by the separation of the excess Na₂O and the formation of an intergranular meltlike phase that is saturated with sodium and is characterized by high dielectric properties.The quantity of the meltlike phase and the magnitude of the /( + ) ratio determine the degree of stabilization (stability) and the final resistivity of the material and depend on the initial chemical composition and the heating rate maintained during the sintering process.It was shown that when the duration of residence of the material in the hot zone of the furnace is increased or when the specimens sintered maintaining high heating rates are subjected to additional heat treatment, one observes the occurrance of the reverse structural transformation that is characterized by an increase of the phase ratio /( + ) 1, a reduction in the quantity of the meltlike phase right up to its complete disappearance, and a decrease of the electrical resistivity of the material.In the materials having a large excess quantity of sodium oxide, the process of crystallization of the intergranular NaAlO₂ phase occurs simultaneously with the second phase transformation.The best ceramic and electrophysical parameters were obtained when sintering the material contained 7.9% Na₂O.Translated from Ogneupory, No. 3, pp. 13–18, March, 1990.     

Enhancement of βα-recrystallization in β-form isotactic polypropylene during heating after roll deformation

Summary -form isotactic polypropylene shows -recrystallization behavior (recrystallization from - to -form) during slow heating. This is enhanced by deformation. -form specimen with uniaxially oriented lamellae was deformed by rolling, and -recrystallization was studied by DSC and x-ray diffraction. The result showed that (1) — recrystallization is promoted with the degree of deformation. (2) Deformed specimen shows -recrystallization from considerably low temperature compared with the undeformed one. (3) The recrystallized -form is c-axis-oriented along the roll direction. From these results the -recrystallization mechanism was discussed in view of -nucleus formation by deformation.     

Interaction of Two Diffusion Flames Spreading Along a Metal Substrate Wetted with Different Fuels

The paper reports an experimental and theoretical study of the interaction of two diffusion flames propagating over the surface of two different liquid fuels applied to both sides of a thin metal substrate. It is shown that in this system, there may be formation of a unified complex — a doublesided flame which has the properties of a steadystate flame with a peculiar structures. Some velocity and structural dependences for doublesided flames are determined. A mathematical model for a doublesided flame is proposed that adequately describes experimental relations. A physical model for a doublesided flame with a pulsating flame of the heavier fuel is formulated.     

Synthesis of statistical polydiene networks by reaction of liquid polyenes with telechelic siloxanes

The present investigation concerns the synthesis of statistical networks similar to vulcanized rubber. We have used liquid precursor polymers: polybutadiene (PB) and polyisoprene (PI) with telechelic siloxanes. The reactivity of the polydienes can be classified as follows: PB units 1,2 PI units 3,4 PI units 1,4 0. The network formation is a function of the ratio R = nb, of pendent double bonds/nb. of SiH. For R 1 the networks are rather hard and brittle, for 8 R 10 they are soft and elastic, whereas for R 16 the gels obtained are very soft and sticky.     

Titanium silicate molecular sieves (TS-1 and TS-2) catalyzed Michael reaction of silyl enol ethers with α,β unsaturated carbonyl compounds

The Michael addition reaction has been carried out with silyl enol ether and Michael acceptors such as acrylates, and , - unsaturated ketones over aluminum-free titanium silicates (TS-1 and TS-2) in the absence of H₂O₂. The reaction was carried out slightly above room temperature (40°C) in the presence of dry solvents giving moderate to good yield. The effect of various modified zeolites like RE-Y, La-Y, steamed-Y, Na-Y, VS-1, SnS-1, Zn/ZSM-5 and different solvents has been studied. The catalytic activity is explained on the basis of oxophilic Lewis acidity of titanium silicate molecular sieves.     

Textural and structural studies on nickel hydroxide electrodes. II. Turbostratic nickel (II) hydroxide submitted to electrochemical redox cycling

The textural and structural modifications involved in electrochemical redox cycling of turbostratic nickel (II) hydroxide has been investigated using X-ray diffraction and electron microscopy methods. It was found that during the first cycles, different phenomena compete: redox reactions which occur in the solid state, and ageing reactions via the solution. For the first galvanostatic charge performed at the C/5 rate in 4.5 N KOH, the direct oxidation of (II) to (III) and the ageing of (II) to (II) via the solution followed by the oxidation to (III) are in competition. The study of the discharge mechanism shows that the direct reduction (III)(II) is parallel to the reduction (III)(II) and the ageing of the turbostratic hydroxide via the solution. After the first cycle it was established that the alpha-generated (II) active phase consisted of a mixture of two kinds of particles, the oxidation of which follows two paths: (II)/(III) for the thicker particles and for the thinner (II)/(III), but these latter (II) particles aged via the solution by Oswald ripening and the (II)/(III) couples swung to (II)/(III).