Catalytic probe reactions

Through the combined use of catalytic probe reactions, Mossbauer, EXAFS, XPS, XRD, it has been demonstrated that the anticipated particle structures for the half-SMAD and full SMAD procedures are close to reality.(40-42) Thus, 119Sn Mossbauer, a bulk solid analysis technique, revealed the relative amounts of Sn, Pt-Sn alloy, SnO, and Sn02 present in the catalysts. It was possible to differentiate Sn° from Pt-Sn alloy through supporting evidence of XPS and selective oxidation, since it was found that ultra-fine Sn° particles were much more susceptible to oxidation than Pt-Sn alloy particles. Also, since the full SMAD Pt°-Sn°/Al203 catalysts behaved much differently than Pt°/Al203, it is clear that the SMAD catalysts are not made up of separate Pt° and Sn particles. 

The measure of acidity/basicity and discrimination between Lewis and Bronsted acidity is a delicate task This topic is the subject of other chapters of this series Molecular Sieves - Science and Technology (cf. Volume 4, Chapter 1, Volume 5, Chapter 2, Volume 6, Chapters 3-6), to which the reader is referred for detailed information. We limit to note that means for measuring the acidity and basicity of MTS are the same as with other systems titration, adsorption volumetry, gravimetry and microcalorimetry, temperature-programmed desorption (basically of ammonia), infrared and NMR spectroscopies and catalytic probe reactions. 

Use of catalytic probe reactions. Chemical probes of surface structure have been underutilized. The ideal catalytic probe reaction would be gentle (operate at low temperature) and would be sufficiently well understood to provide information characterizing the catalytic site. Reaction probes which have been widely used are olefin hydrogenation, olefin and paraffin isomerization, and paraffin hydroge-... 

Develop new catalytic probe reactions, in particular for oxidation catalysis. 

Bars, J.L., Specht, U., Bradley, J.S., and Blackmond, D.G., A catalytic probe of the surface of colloidal palladium particles using heck coupling reactions, Langmuir, 15, 7621, 1999. 

A typical probe reaction for estimating catalytic properties in selective hydrogenations is the hydrogenation of cinnamaldehyde. This molecule contains both a C=C and a C=0 double bond, thus the formation of hydrocinnamaldehyde and/or cinnamyl alcohol by reduction of the one or the other, or the formation of phenyl propanol in the case of complete reduction may indicate the potential of the catalyst for other fine chemical transformations. Indeed, this reaction was one of the first to be tested by CNT-supported catalysts [120]. Noble metals show a high activity in this reaction and... 

Lercher, J.A., Jentys, A., and Brait, A. (2008) Catalytic test reactions for probing the acidity and basicity of zeolites. Mol. Sieves, 6,153-212. 

G.M. Hamminga, G. Mul and J.A. Moulijn, Applicability of fiber-optic-based Raman probes for on-line reaction monitoring of high-pressure catalytic hydrogenation reactions, Appl. Spectrosc., 61, 470 78 (2007). 

The present chapter will primarily focus on oxidation reactions over supported vanadia catalysts because of the widespread applications of these interesting catalytic materials.5 6,22 24 Although this article is limited to well-defined supported vanadia catalysts, the supported vanadia catalysts are model catalyst systems that are also representative of other supported metal oxide catalysts employed in oxidation reactions (e.g., Mo, Cr, Re, etc.).25 26 The key chemical probe reaction to be employed in this chapter will be methanol oxidation to formaldehyde, but other oxidation reactions will also be discussed (methane oxidation to formaldehyde, propane oxidation to propylene, butane oxidation to maleic anhydride, CO oxidation to C02, S02 oxidation to S03 and the selective catalytic reduction of NOx with NH3 to N2 and H20). This chapter will combine the molecular structural and reactivity information of well-defined supported vanadia catalysts in order to develop the molecular structure-reactivity relationships for these oxidation catalysts. The molecular structure-reactivity relationships represent the molecular ingredients required for the molecular engineering of supported metal oxide catalysts. 

Here we report the synthesis and catalytic application of a new porous clay heterostructure material derived from synthetic saponite as the layered host. Saponite is a tetrahedrally charged smectite clay wherein the aluminum substitutes for silicon in the tetrahedral sheet of the 2 1 layer lattice structure. In alumina - pillared form saponite is an effective solid acid catalyst [8-10], but its catalytic utility is limited in part by a pore structure in the micropore domain. The PCH form of saponite should be much more accessible for large molecule catalysis. Accordingly, Friedel-Crafts alkylation of bulky 2, 4-di-tert-butylphenol (DBP) (molecular size (A) 9.5x6.1x4.4) with cinnamyl alcohol to produce 6,8-di-tert-butyl-2, 3-dihydro[4H] benzopyran (molecular size (A) 13.5x7.9x 4.9) was used as a probe reaction for SAP-PCH. This large substrate reaction also was selected in part because only mesoporous molecular sieves are known to provide the accessible acid sites for catalysis [11]. Conventional zeolites and pillared clays are poor catalysts for this reaction because the reagents cannot readily access the small micropores. 

Zamaraev and Thomas provide a concise summary of work done with a family of classic catalytic test reactions—dehydration of butyl alcohols—to probe the workings of acidic molecular sieve catalysts. This chapter echoes some of the themes stated by Pines and Manassen, who wrote about alcohol dehydration reactions catalyzed by solid acids in the 1966 volume of Advances in Catalysis. 

Homogeneous catalysis is, of course, a major field in it s own right, as catalytic transformations are important synthetic tools. However, catalysis is also a potentially sensitive probe for nanoparticle properties and surface chemistry, since catalytic reactions are ultimately carried out on the particle surface. In the case of bimetallic DENs, catalytic test reactions have provided clear evidence for the modification of one metal by another. DENs also provide the opportunity to undertake rational control experiments not previously possible to evaluate changes in catalytic activity as a function of particle composition. 

Catalytic superactivity of electron-deficient Pd for neopentane conversion was recently verified for Pd/NaHY (157, 170). The reaction rate was positively correlated with the proton content of the catalyst. Samples that contained all the protons generated during H2 reduction of the catalysts were two orders of magnitude more active than silica-supported Pd. Samples prepared by reduction of Pd(NH3)2+NaY displayed on intermediate activity. It was suggested that Pd-proton adducts are highly active sites in neopentane conversion. With methylcyclopentane as a catalytic probe, all Pd/NaY samples deactivated rapidly and coke was deposited. Two types of coke were found (by temperature-programmed oxidation), one of... 

In this last example, the catalytic exchange reaction can be regarded as a probe to study the oxidation of the surface of Cu2S by H2S. 

In the current investigation we have extended these types of experiments to cover the influence of sulfur on the catalytic properties of iron. Since C2H4 does not readily undergo decomposition on iron surfaces we elected to use the decomposition of CO/H2 and CO/C2H4/H2 mixtures at 600 0 as the probe reactions in this work. For this purpose, both the amount of solid carbon and the gas phase product distribution arising from the decomposition of these mixtures have been used to monitor variations in the catalytic behavior of both pure and sulfur contaminated iron particles. 

The catalytic oxidation of sulphurous acid in aqueous medium to sulphuric acid [138, 84] has been suggested as a probe reaction for the ability of a carbon to activate molecular oxygen at ambient conditions. Besides this remarkable property the reaction is of interest in atmospheric chemistry where it provides a sink for all nonphotochemically oxidized sulfur dioxide [215]. Carbon plays a special role in this environmental application as both pure carbon and active particles (iron oxide [84] for example) anchored to carbon can act as efficient catalysts. The detailed analysis of the reactivity of various types of carbon [138] reveal that basic surface oxides (see Fig. 23) are important to fix the educt HSOj ion. It was found, in addition, that the... 

The acid or base strength is defined by comparing the interaction between the sites and reference (probe) molecules. For example, the acid strength is the ability of the site to convert an adsorbed reference neutral base into its conjugate acid. This process may be monitored by following the colour changes of the indicators or by such techniques as IR or NMR spectroscopies. Several criteria must be considered in the selection of these probes their pK value must be adapted to the acidity or basicity of the surface under study the size of the probe molecules should ensure that all sites are readily accessible finally, the probe should be selected so that its interaction with the surface is easily studied by the available experimental techniques. Catalytic test reactions are sometimes used... 

Dealuminated Y zeolites which have been prepared by hydrothermal and chemical treatments show differences in catalytic performance when tested fresh however, these differences disappear after the zeolites have been steamed. The catalytic behavior of fresh and steamed zeolites is directly related to zeolite structural and chemical characteristics. Such characteristics determine the strength and density of acid sites for catalytic cracking. Dealuminated zeolites were characterized using X-ray diffraction, porosimetry, solid-state NMR and elemental analysis. Hexadecane cracking was used as a probe reaction to determine catalytic properties. Cracking activity was found to be proportional to total aluminum content in the zeolite. Product selectivity was dependent on unit cell size, presence of extraframework alumina and spatial distribution of active sites. The results from this study elucidate the role that zeolite structure plays in determining catalytic performance. 

The structural features of dealuminated zeolite samples were characterized using X-ray powder diffraction, porosimetry and solid-state NMR measurements. Hexadecane cracking was used as a probe reaction to investigate catalytic properties of pure zeolites. 

The development of new catalytic materials needs to be complemented with detailed studies of the surface chemistry of catalysis at the molecular level in order to better define the requirements for the catalytic active sites. The wide array of modem spectroscopies available to surface scientists today is ideally suited for this task (see Surfaces). Surface science studies on catalysis typically probe reaction intermediates on model metal samples under well controlled conditions. This kind of study is traditionally carried out in ultrahigh vacuum (UHV) systems such as that shown in Figure 10. Single crystals or other well-defined metal surfaces are cleaned and characterized in situ by physical and chemical means, and then probed using a battery of surface sensitive techniqnes snch as photoelectron (XPS and UPS), electron energy loss (ELS... 

Methanol conversion was adopted as a probe reaction to explore the catalytic activity of M" -TSM, because methanol is a simple molecule that transforms into easily assignable compounds and is converted into different products through different routes employing different catalysts. Methanol is decomposed into carbon monoxide and hydrogen over metal catalysts [including Ni (77)], is dehydrogenated into formaldehyde or methyl formate over Zn- or Cu-containing catalysts (78), and is dehydrated into dimethyl ether and successively into hydrocarbons over acid catalysts (79). 

The oxidation of propylene has been chosen as a probe reaction to study the catalytic activity of Cu Pd -TSM. The olefin oxidation in an acidic solution of Cu(II) and Pd(U) chlorides, well known as the Wacker reaction, is achieved when olefins are selectively oxidized to ketones or aldehydes by hydrated Pd, leaving Pd . The Pd is oxidized back to Pd by 2Cu, and the resulting Cu is reoxidized by dissolved oxygen. Because the corrosive nature of the catalyst solution is a serious disadvantage for practical use, supported copper-palladium catalysts have been proposed to operate the reaction in a gas flow reactor (40). 

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