Regularities of oxygen chemisorption on coked exchanged Y zeolites

Two types of paramagnetic centers have been revealed in the composition of coke formation products on zeolite surfaces. The oxygen effect on the paramagnetic properties of these systems is determined by the concentration of these centers, which in turn characterizes the structure of coke precursors on their surface.

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Theoretical study of the adsorption of ethylene on alkali‐exchanged zeolites

The structures of alkali‐exchanged faujasite (X–FAU, X = Li⁺ or Na⁺ ion) and ZSM‐5 (Li–ZSM‐5) zeolites and their interactions with ethylene have been investigated by means of quantum cluster and embedded cluster approaches at the B3LYP/6‐31G(d, p) level of theory. Inclusion of the Madelung potential from the zeolite framework has a significant effect on the structure and interaction energies of the adsorption complexes and leads to differentiation of different types of zeolites (ZSM‐5 and FAU) that cannot be drawn from a typical quantum cluster model, H₃SiO(X)Al(OH)₂OSiH₃. The Li–ZSM‐5 zeolite is predicted to have a higher Lewis acidity and thus higher ethylene adsorption energy than the Li–FAU zeolites (16.4 vs. 14.4 kcal/mol), in good agreement with the known acidity trend of these two zeolites. On the other hand, the cluster models give virtually the same adsorption energies for both zeolite complexes (8.9 vs. 9.1 kcal/mol). For the larger cation‐exchanged Na–FAU complex, the adsorption energy (11.6 kcal/mol) is predicted to be lower than that of Li–FAU zeolites, which compares well with the experimental estimate of about 9.6 kcal/mol for ethylene adsorption on a less acidic Na–X zeolite. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 94: 333–340, 2003     

Study of thermodynamic characteristics of CO adsorption on Li exchanged zeolites

The experimental thermodynamic characteristics of CO probe molecule adsorption on lithium exchanged zeolites of MFI, FAU, MCM-58, MCM-22, MCM-36 and MCM-49 structure was investigated by joint volumetry-calorimetry method. Consideration was given to the interpretation of the heat evolved when a probe molecule was adsorbed on the surface. In particular, the number and strength of adsorption sites were discussed as functions of zeolite structure and concentration of extra-framework cation. In addition, the obtained thermodynamic data and energy distribution functions were discussed together with results obtained from FTIR spectroscopy and theoretical DFT calculations.     

The lability of carbon monoxide adsorbed on rhodium

Carbon monoxide which is retained by a rhodium surface after heating to 573 K exchanges with gas phase carbon monoxide at 293 K. The retained species is postulated as *–C=O–*.

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, 573 , 293 . *–C=O–*.

     

CuCl改性Y型分子筛的CO吸附性能研究

利用自发单层分散原理,讨论了在NaY,NH4Y,CuY分子筛上CuCl分散改性情况,并对所得到的改性分子筛进行了CO吸附性能研究。实验结果表明,在低CuCl担载量时,CuCl可在这三种载体表面达到原子水平分散,其分散容量分别为0.58g/gNaY,0.68g/gNH4Y和0.41g/gCuY。由于CO与Cu^+可生配位化合物,经CuCl改性的Y型分子筛对CO显示出较高吸附性能。其中,0.6gCuCl/gNH4Y分子筛表现出最高的CO吸附容量,在室温、常压下可达123mL/gNH4Y.     

Coadsorption of carbon monoxide and copper atoms on rhodium electroplates

The partial removal of copper atoms from a preliminarily formed Cu_ad layer and the adsorption of Cu²⁺ cations in the presence of a CO_ads monolayer were demonstrated for Rh/Pt electrodes by means of transients of current and potentiodynamic and analytical measurements. The electrooxidation of the mixed CO_ads + Cu_ad layer in the course of anodic potential scans is shown to be accompanied by simultaneous removal of both species in a wide potentials range.Translated from Elektrokhimiya, Vol. 41, No. 3, 2005, pp. 367–370.Original Russian Text Copyright © 2005 by Gladysheva, Podlovchenko.     

Dicarboxylate rhodium complexes with diolefins and carbon monoxide

Dinuclear rhodium complexes of the type [Rh₂(C₂O₄)(diolefin)₂] (diolefin)₂  1,5-cyclooctadiene, 2,5-norbornadiene and tetrafluorobenzobarrelene) with bridging oxalate ligands have been obtained by reaction of [Rh(acac)(diolefin)] with oxalic acid (2: 1 mol ratio). The use of a 1 : 1 molar ratio affords [Rh(HC₂O₄)(COD)], that reacts with [Ir(acac)(COD)] yielding the heterodinuclear [(COD)Rh(C₂O₄)Ir(COD)] complex. Treatment of [Rh₂(C₂O₄)(diolefin)₂] complexes with phenanthroline type ligands leads to ionic complexes of formula [Rh(diolefin) (phen)][Rh(C₂O₄)(diolefin)]. Bubbling of carbon monoxide through solutions of the diolefin complexes leads to the formation of carbonylrhodium species of formula [Rh₂(C₂O₄)(CO)₂L₂] (L = CO, PPh₃t-BuNC) or [Rh(CO)₂(phen)] - [Rh(C₂O₄)(CO)₂]. Other related malonate complexes are also described.     

An infrared study of the oxidation of carbon monoxide over supported rhodium catalysts

The reaction of carbon monoxide and oxygen over supported rhodium films has been studied using infrared spectroscopy. The focus of the work was the reactivity of the various CO/Rh/X (X = Al₂O₃, SiO₂, TiO₂) surface states for supported catalysts having high and low Rh loading. Under the reaction conditions the “linear CO” species was the most stable toward oxidation, but this could have been a result of an oxidized Rh surface. A new CO/Rh surface species has been proposed which exhibits an infrared band at 2000 cm⁻¹ for a 0.5% Rh/TiO₂ film. This species is believed to be a bridged carbonyl between Rh¹⁺ and the TiO₂ support.     

Efficient electrochemical conversion of carbon monoxide by rhodium octaethylporphyrin adsorbed on carbon black

We have found efficient electrocatalytic removal of CO by rhodium octaethylporphyrin on carbon black at a wide potential range. Using carbon-supported rhodium octaethylporphyrin, we have separated the Rh(II) state participating reaction and the Rh(III) state participating reaction with CO. We have clearly demonstrated electrocatalytic CO oxidation by rhodium(III) porphyrin. The onset potential for CO oxidation is much lower than that for CO oxidation by conventional Pt/Ru catalysts and cobalt porphyrin.     

Heat of adsorption of carbon dioxyde and ethene on zeolites a exchanged with Li+, Ni2+ and Cu2+

Various contents of Li⁺, Ni²⁺ or Cu²⁺ were introduced in zeolite NaA by conventional cation exchange. Crystal damages are observed on samples having suffered the lowerpH. The heat of adsorption of CO₂ and C₂H₄ was determined by isothermal calorimetry. Very high initial heats (100–120 kJ mol^?1) are found in NaA as well as in Li⁺ exchanged samples, perhaps due to chemisorption on alkaline cations; they vanish when Ni²⁺ or Cu²⁺ replaces more than 20% of Na⁺, in like manner with Co²⁺ or ZnI²⁺. For the adsorption of C₂H₄, high initial heats are absent in the case of NaA, but gradually appear when divalent cations are introduced. Apart from these strong initial values, the heats of adsorption present a plateauvs. the adsorbed amount. Abnormal low values at the plateau are indicative of crystal damages.     

Reversible adsorption of carbon monoxide on cupric oxide

Conclusions A gas chromatographic study of the reaction of CO with CuO enabled us to observe that, besides chemisorption, the reversible physical adsorption of CO on CuO occurs.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1626–1627, July, 1981.     

Size-dependent carbon monoxide adsorption on neutral gold clusters

We report on experiments probing the reactivity of neutral Au(n) clusters, n = 9-68, with carbon monoxide. The gold clusters are produced in a pulsed laser vaporization cluster source, operated at room temperature (RT) or at liquid-nitrogen temperature (LNT), pass through a low-pressure reaction cell containing CO gas, and are subsequently laser ionized. The reaction probabilities are determined by recording mass abundance spectra with time-of-flight mass spectrometry. The main observations are a strong temperature dependence and a remarkable size dependence. Upon cooling of the cluster source to LNT, the reactivity increases substantially. At LNT, the reaction probabilities for Au(n) with the first CO molecule are about a factor 10 higher than at RT. Moreover, adsorption of two, three, and even four CO molecules is observed, in contrast to RT clusters which at most adsorb one CO molecule. This temperature dependence is related to the lifetime of the cluster-molecule complexes, being much longer for cold clusters. The observed striking size dependence is similar at both temperatures and is discussed in terms of the electronic structure effects.     

A comparative FT-IR spectroscopic study of methanethiol and methanol adsorption on sodium X and Y zeolites

Adsorption of CH₃SH and CH₃OH on activated NaX and NaY zeolites has been studied by IR spectroscopy. Only NaX is able to provoke the dissociative adsorption of CH₃SH at room temperature and that of CH₃OH at 623 K. Results are discussed taking into account sodium cations in the S_III position.     

The adsorption of carbon monoxide on a platinum electrode

The adsorption of CO from 0.5 M H₂SO₄ solution on platinum has been studied using CO labelled with C-14. The adsorption of CO on Pt occurs in the potential range of hydrogen adsorption as well as in the double layer region. In the whole potential range the rate of adsorption follows first order kinetics. From the surface concentrations and charges for oxidation of adsorbed species it follows that the product of chemisorption consists at least of two kinds of species. One of them is the COOH radical probably formed by the reaction of CO with water.     

Physico-chemical characterization of ferric exchanged y zeolites

Ferric exchanged Y zeolites are prepared by ion exchange and are characterized by X-ray diffraction, thermal analysis, IR and visible spectroscopy. The number of hexa-aquo complexes, [Fe(OH)(H₂O)₅]²⁺, in supercages is determined from thermal analysis, and cation distribution at different sites is discussed. The visible spectra confirmed the formation of hexa-aquo complexes of iron in freshly prepared hydrated FeNaY zeolites. The migragtion of ferric ions from the supercage to the sodalite cage or hexagonal prism takes place on activation of Fe³⁺Y zeolites at 500°C for 2–10 h. The thermal stability of the activated samples is discussed on the basis of X-ray and thermal analysis.     

The electro-oxidation of chemisorbed carbon monoxide on polycrystalline rhodium in acid solution

The electrooxidation of CO adsorbed on Rh in 1 M HClO₄ at room temperature exhibits a complex potentiodynamic E/I profile which depends on the oxygen-containing species present on the electrode. The electrochemical behaviour of the system is explained through the participation of two CO-adsorbed states and the interaction of the latter with electrosorbed oxygen. The electro-oxidation of CO adsorbed on Rh can be correlated with the reaction occurring on Pt.     

Characterization of CuY zeolites after dehydration,oxidation and reduction with carbon monoxide An adsorption and 129Xe nuclear magnetic resonance spectroscopy study

The adsorption isotherms and ¹²⁹Xe nuclear magnetic resonance (NMR) chemical shifts of xenon and the adsorption isotherms of carbon monoxide of Cu(II)- and Cu(I)-exchanged zeolites NaY were measured. The former zeolites of 53, 75, and 95% exchange degrees were investigated after various pretreatment steps comprising dehydration, oxidation and reduction with CO at 420°C as well as long-term CO reduction at 470°C. The Cu(I)Y zeolite of 70% exchange degree was prepared via a solid-state exchange procedure with CuCl and subjected to dehydration at 420°C. In all cases, except the dehydrated zeolites, almost linear xenon adsorption isotherms and linear ¹²⁹Xe NMR chemical shift _versus xenon concentration curves running parallel to each other are obtained. In contrast, the chemical shift curves for the dehydrated zeolites are non-linear at low xenon concentrations turning towards negative chemical shift values at very low pressures. The whole body of the experimental xenon data can be explained quantitatively with a unifying approach on the basis of a site adsorption model where the sites are (i) two types of cuprous ions of much different adsorption strength and ¹²⁹Xe chemical shift, (ii) Na⁺ cations, (iii) Lewis acid sites generated through autoreduction and reduction of Cu²⁺ by CO, and (iv) framework sites free of cations. These five types of sites are each characterized by Langmuir adsorption isotherm constants and local ¹²⁹Xe NMR chemical shifts. The adsorption site concentrations in the various zeolites are evaluated. The supercage Cu(I) concentration values are in nice agreement with the results deduced from the CO adsorption isotherm measurements.