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A computational study of ethane cracking in cluster models of zeolite H-ZSM-5.

Description: Protolytic cracking of ethane by zeolites has been studied using quantum-chemical techniques and a cluster model of the zeolite Broensted acid site. Previous computational studies have utilized small cluster models and have not accounted for the long-range effects of the zeolite lattice. These studies have found reaction barriers for cracking which are significantly higher than experimental values. In this work we used a larger zeolite cluster model containing five tetrahedral (Si, Al) atoms (denoted 5T) and searched for stationary points along one possible reaction path for cracking at the HF/6-31 G(d) level of theory. This path involves a multi-step cracking reaction, in which the proton is first transferred from the acid site to the adsorbed ethane molecule to form an ion-pair equilibrium complex. Subsequently the proton attacks the C-C bond to complete the cracking process. The activation barrier for cracking was calculated, including corrections for (i) vibrational energies at the experimental reaction temperature of 773 K; (ii) electron correlation and an extended basis set at the B3LYP/6-311+G(3df,2p) level; and (iii) the influence of the surrounding zeolite lattice in H-ZSM-5. The barrier we obtain, 53 {+-} 5 kcal/mol, is significantly smaller than previous theoretical results and is in good agreement with typical experimental values for small hydrocarbons. Work is currently in progress to extend this study by carrying out geometry optimization of these complexes using the B3LYP method of density functional theory.
Date: August 21, 1998
Creator: Zygmunt, S. A.
Partner: UNT Libraries Government Documents Department

Computational studies of Bronsted acid sites in zeolites

Description: The authors have performed high-level ab initio calculations using both Hartree-Fock (HF) and Moller-Plesset perturbation theory (MP2) to study the geometry and energetics of the adsorption complex involving H{sub 2}O and the Bronsted acid site in the zeolite H-ZSM-5. In these calculations, which use aluminosilicate cluster models for the zeolite framework with as many a 28 T atoms (T = Si, Al), we included geometry optimization in the local vicinity of the acid site at the HF/6-31G(d) level of theory, and have calculated corrections for zero-point energies, extensions for zero-point energies, extensions to higher basis sets, and the influence of electron correlation. Results for the adsorption energy and geometry of this complex are reported and compared with previous theoretical and experimental values.
Date: January 1, 1995
Creator: Curtiss, L.A.; Iton, L.E. & Zygmunt, S.A.
Partner: UNT Libraries Government Documents Department

Catalytic Deprotection of Acetals In Strongly Basic Solution Usinga Self-Assembled Supramolecular 'Nanozyme'

Description: Acetals are among the most commonly used protecting groups for aldehydes and ketones in organic synthesis due to their ease of installation and resistance to cleavage in neutral or basic solution.[1] The common methods for hydrolyzing acetals almost always involve the use of either Broensted acid or Lewis acid catalysts.[2] Usually aqueous acids or organic solutions acidified with organic or inorganic acids have been used for reconversion of the acetal functionality to the corresponding carbonyl group; however, recently a number of reports have documented a variety of strategies for acetal cleavage under mild conditions. These include the use of Lewis acids such as bismuth(III)[3] or cerium(IV),[4, 5] functionalized silica gel, such as silica sulfuric acid[6] or silica-supported pyridinium p-toluene sulfonate,[7] or the use of silicon-based reagents such as TESOTf-2,6-Lutidine.[8] Despite these mild reagents, all of the above conditions require either added acid or overall acidic media. Marko and co-workers recently reported the first example of acetal deprotection under mildly basic conditions using catalytic cerium ammonium nitrate at pH 8 in a water-acetonitrile solution.[5] Also recently, Rao and co-workers described a purely aqueous system at neutral pH for the deprotection of acetals using {beta}-cyclodextrin as the catalyst.[9] Herein, we report the hydrolysis of acetals in strongly basic aqueous solution using a self-assembled supramolecular host as the catalyst. During the last decade, we have used metal-ligand interactions for the formation of well-defined supramolecular assemblies with the stoichiometry M{sub 4}L{sub 6}6 (M = Ga{sup III} (1 refers to K{sub 12}[Ga{sub 4}L{sub 6}]), Al{sup III}, In{sup III}, Fe{sup III}, Ti{sup IV}, or Ge{sup IV}, L = N,N{prime}-bis(2,3-dihydroxybenzoyl)-1,5-diaminonaphthalene) (Figure 1).[10] The metal ions occupy the vertices of the tetrahedron and the bisbidentate catecholamide ligands span the edges. The strong mechanical coupling of the ligands transfers the chirality from one metal center to the other, thereby ...
Date: July 26, 2007
Creator: Pluth, Michael D.; Bergman, Robert G. & Raymond, Kenneth N.
Partner: UNT Libraries Government Documents Department

Improved Catalysts for Heavy Oil Upgrading Based on Zeolite Y Nanoparticles Encapsulated Stable Nanoporous Host

Description: The addition of hydrothermally-aged zeolite Y precursor to an SBA-15 synthesis mixture under a mildly acidic condition resulted in the formation of mesoporous aluminosilicate catalyst, Al-SBA-15, containing strong Broensted acid sites and aluminum (Al) stabilized in a totally tetrahedral coordination. The physicochemical characteristics of the catalyst varied as a function of the synthesis conditions. The catalyst possessed surface areas ranging between 690 and 850 m{sup 2}/g, pore sizes ranging from 5.6 to 7.5 nm, and pore volumes up 1.03 cm{sup 3}, which were comparable to the parent SBA-15 synthesized under similar conditions. Two wt% Al was present in the catalyst that was obtained from the reaction mixture that contained the highest Al content. The Al remained stable in totally tetrahedral coordination after calcination at 550 C. The Al-SBA-15 mesoporous catalyst showed significant catalytic activity for cumene dealkylation, and the activity increased as the amount of zeolite precursor added to the SBA-15 mixture was increased. In preparation for the final phase of the project, the catalyst was embedded into psuedoboemite alumina (catapal B) matrix and then formed into pellets. In the final phase of the project, the pelletized catalyst will be evaluated for the conversion of heavy petroleum feedstocks to naphtha and middle distillates.
Date: September 30, 2006
Creator: Ingram, Conrad & Mitchell, Mark
Partner: UNT Libraries Government Documents Department


Description: Al-SBA-15 mesoporous catalysts with strong Broensted acid sites and Al stabilized in a totally tetrahedral coordination was synthesized from the addition of hydrothermally aged zeolite Y precursor to SBA-15 synthesis mixture under mildly acidic condition of pH 5.5. The materials possessed surface areas between 690 and 850 m{sup 2}/g, pore sizes ranging from 5.6 to 7.5 nm and pore volumes up 1.03 cm{sup 3}, which were comparable to parent SBA-15 synthesized under similar conditions. Up to 2 wt. % Al was present in the most aluminated sample that was investigated, and the Al remained stable in totally tetrahedral coordination, even after calcination at 550 C. The Al-SBA-15 mesoporous catalyst showed significant catalytic activity for cumene dealkylation, and activity increased as the amount of zeolite precursor added to the SBA-15 mixture was increased. The catalyst's activity was not affected by the aging time of the precursor for up to the 24 hr aging time investigated. This method of introducing Al and maintaining it in a total tetrahedral coordination is very effective, in comparison to other direct and post synthesis alumination methods reported. The catalytic performance of the zeolite Y/SBA-15 composite materials will be compared with that of pure SBA-15. The catalysts will then be evaluated for the conversion of heavy petroleum feedstocks.
Date: June 20, 2006
Creator: Ingram, Conrad & Mitchell, Mark
Partner: UNT Libraries Government Documents Department

Computational studies of water adsorption in zeolites

Description: We have performed high-level ab initio calculations using Hartree-Fock (HF) theory, Moller-Plesset perturbation theory (MP2), and density-functional theory (DFT) to study the geometry and energetics of the adsorption complex involving H{sub 2}O and the Bronsted acid site in the zeolite H-ZSM-5. These calculations use aluminosilicate cluster models for the zeolite framework with as many as 28 T atoms (T=Si, Al). We included geometry optimization in the local vicinity of the acid site at the MP2 and DFT levels of theory for the smallest cluster, while in the larger clusters this was done at the HF/6-31G(d) level of theory. We have also calculated corrections for zero-point energies, extensions to higher basis sets, and higher levels of electron correlation. Results for the adsorption energy and geometry of this complex are reported and compared with previous theoretical and experimental values.
Date: May 1, 1995
Creator: Zygmunt, S.A.; Curtiss, L.A. & Iton, L.E.
Partner: UNT Libraries Government Documents Department

Final Report: Acidic Properties of Doped Aerogels, April 19, 1993 - June 30, 1998

Description: Over this grant period we have studied extensively zirconia and alumina aerogels doped with a wide variety of dopants including silica, sulfate, phosphate, tungstate and combinations thereof. These results have deepened our understanding of the effects of dopants on acidic properties, which is the main goal of the project, and in particular led to the development of a hierarchy with which the Broensted acid strength of different samples can be meaningfully compared. We provide a more detailed description of several specific systems.
Date: June 30, 1998
Creator: Boyse, Raymond
Partner: UNT Libraries Government Documents Department

Understanding Nitrogen Fixation

Description: The purpose of our program is to explore fundamental chemistry relevant to the discovery of energy efficient methods for the conversion of atmospheric nitrogen (N{sub 2}) into more value-added nitrogen-containing organic molecules. Such transformations are key for domestic energy security and the reduction of fossil fuel dependencies. With DOE support, we have synthesized families of zirconium and hafnium dinitrogen complexes with elongated and activated N-N bonds that exhibit rich N{sub 2} functionalization chemistry. Having elucidated new methods for N-H bond formation from dihydrogen, C-H bonds and Broensted acids, we have since turned our attention to N-C bond construction. These reactions are particularly important for the synthesis of amines, heterocycles and hydrazines with a range of applications in the fine and commodity chemicals industries and as fuels. One recent highlight was the discovery of a new N{sub 2} cleavage reaction upon addition of carbon monoxide which resulted in the synthesis of an important fertilizer, oxamide, from the diatomics with the two strongest bonds in chemistry. Nitrogen-carbon bonds form the backbone of many important organic molecules, especially those used in the fertilizer and pharamaceutical industries. During the past year, we have continued our work in the synthesis of hydrazines of various substitution patterns, many of which are important precursors for heterocycles. In most instances, the direct functionalization of N{sub 2} offers a more efficient synthetic route than traditional organic methods. In addition, we have also discovered a unique CO-induced N{sub 2} bond cleavage reaction that simultaneously cleaves the N-N bond of the metal dinitrogen compound and assembles new C-C bond and two new N-C bonds. Treatment of the CO-functionalized core with weak Broensted acids liberated oxamide, H{sub 2}NC(O)C(O)NH{sub 2}, an important slow release fertilizer that is of interest to replace urea in many applications. The synthesis of ammonia, NH{sub 3}, from its ...
Date: May 25, 2012
Creator: Chirik, Paul J.
Partner: UNT Libraries Government Documents Department

Advance concepts for conversion of syngas to liquids. Quarterly progress report No. 4, July 30, 1995--October 29, 1995

Description: Substitution of transition metals for either aluminum and/or phosphorus in the AlPO{sub 4}-11 framework is found to afford novel heterogeneous catalysts for liquid phase hydroxylation of phenol with hydrogen peroxide. AlPO{sub 4}-11 is more active than SAPO-11 and MgAPO-11 for phenol conversion to hydroquinone. The Bronsted acid sites of SAPO-11 and MgAPO-11 may promote the decomposition of hydrogen peroxide to water and oxygen, thus leading to lower phenol conversions. Substitution of divalent and trivalent metal cations, such as Fe, Co and Mn appears to significantly improve the conversion of phenol. The activity follows the order of FeAPO-11>FeMnAPO-11>CoAPO-11>MnAPO-11{much_gt}ALPO{sub 4}-11. FeAPO-11, FeMnAPO-11 and AlPO{sub 4}-11 give similar product selectivities of about 1:1 hydroquitione (HQ) to catechol (CT). MnAPO-11 and CoAPO-11 favor the production of catechol, particularly at low conversions. FeAPO-11 and TS-1 (titanium silicate with MFI topology) are comparable for the phenol conversions with TS-1 giving higher selectivities toward hydroquinone. The external surfaces of the catalysts plays a significant role in these oxidation reactions. MeAPO molecular sieves may be complementary to the metal silicalite catalysts for the catalytic oxidations in the manufacture of fine chemicals.
Date: February 1, 1996
Creator: Dai, Pei-Shing Eugene; Petty, R.H.; Ingram, C. & Szostak, R.
Partner: UNT Libraries Government Documents Department


Description: A tungstena-zirconia (WZ) catalyst has been investigated for coupling methanol and isobutanol to unsymmetrical ethers, i.e. methyl isobutyl ether (MIBE) and compared with earlier studied sulfated-zirconia (SZ) and Nafion-H catalysts. In all cases, the ether synthesis mechanism is a dual site S{sub N}2 process involving competitive adsorption of reactants on proximal acid sites. At low reaction temperatures, methylisobutylether (MIBE) is the predominant product. However, at temperatures >135 C the WZ catalyst is very good for dehydration of isobutanol to isobutene. The surface acid sites of the WZ catalyst and a Nafion-H catalyst were diagnosed by high resolution X-ray photoelectron spectroscopy (XPS) of N 1s shifts after adsorption of amines. Using pyridine, ethylenediamine, and triethylamine, it is shown that WZ has heterogeneous strong Broensted acid sites. Theoretical study located the transition state of the alcohol coupling reaction on proximal Broensted acid sites and accounted well for XPS core-level shifts upon surface acid-base interactions. While computations have not been carried out with WZ, it is shown that the SZ catalyst is a slightly stronger acid than CF{sub 3}SO{sub 3}H (a model for Nafion-H) by 1.3-1.4 kcal/mol. A novel sulfated zirconia catalyst having proximal strong Broensted acid sites was synthesized and shown to have significantly enhanced activity and high selectivity in producing MIBE or isobutene from methanol/isobutanol mixtures. The catalyst was prepared by anchoring 1,2-ethanediol bis(hydrogen sulfate) salt precursor onto zirconium hydroxide, followed by calcination to remove the -(CH{sub 2}CH{sub 2})- bridging residues.
Date: March 1, 2003
Creator: Klier, Kamil; Herman, Richard G.; Kwon, Heock-Hoi; Shen, James G. C.; Ma, Qisheng; Hunsicker, Robert A. et al.
Partner: UNT Libraries Government Documents Department

Atomic polar tensors and acid-base properties of metal-oxide building blocks

Description: The sensitivity of the atomic polar tensor to compositional substituents is reported for the alkali silicate series. Rotational invariants, effective atomic charge (GAPT) and charge normalized anisotropy and dipole ([alpha][sub n] and [gamma][sub n]) are used to characterize the charge distribution and chemical environment of the atomic sites. Comparison of [alpha][sub n] and [gamma][sub n] with a series of known Bronsted and Lewis acids and bases suggests that these rotational invariants may act as indicators for metal-oxide site acidities. Basis set and electron correlation particularly affect the determined effective charge, but show minimal effect on [alpha] and [gamma] quantities.
Date: February 1, 1993
Creator: Ferris, K.F.
Partner: UNT Libraries Government Documents Department

Catalytic Synthesis of Oxygenates: Mechanisms, Catalysts and Controlling Characteristics

Description: This research focused on catalytic synthesis of unsymmetrical ethers as a part of a larger program involving oxygenated products in general, including alcohols, ethers, esters, carboxylic acids and their derivatives that link together environmentally compliant fuels, monomers, and high-value chemicals. The catalysts studied here were solid acids possessing strong Brønsted acid functionalities. The design of these catalysts involved anchoring the acid groups onto inorganic oxides, e.g. surface-grafted acid groups on zirconia, and a new class of mesoporous solid acids, i.e. propylsulfonic acid-derivatized SBA-15. The former catalysts consisted of a high surface concentration of sulfate groups on stable zirconia catalysts. The latter catalyst consists of high surface area, large pore propylsulfonic acid-derivatized silicas, specifically SBA-15. In both cases, the catalyst design and synthesis yielded high concentrations of acid sites in close proximity to one another. These materials have been well-characterization in terms of physical and chemical properties, as well as in regard to surface and bulk characteristics. Both types of catalysts were shown to exhibit high catalytic performance with respect to both activity and selectivity for the bifunctional coupling of alcohols to form ethers, which proceeds via an efficient SN2 reaction mechanism on the proximal acid sites. This commonality of the dual-site SN2 reaction mechanism over acid catalysts provides for maximum reaction rates and control of selectivity by reaction conditions, i.e. pressure, temperature, and reactant concentrations. This research provides the scientific groundwork for synthesis of ethers for energy applications. The synthesized environmentally acceptable ethers, in part derived from natural gas via alcohol intermediates, exhibit high cetane properties, e.g. methylisobutylether with cetane No. of 53 and dimethylether with cetane No. of 55-60, or high octane properties, e.g. diisopropylether with blending octane No. of 105, and can replace aromatics in liquid fuels.
Date: November 30, 2005
Creator: Klier, Kamil & Herman, Richard G.
Partner: UNT Libraries Government Documents Department

[Experimental and kinetic modeling of acid/base and redox reactions over oxide catalysts]

Description: The research has involved the characterization of catalyst acidity, [sup 2]D NMR studies of Bronsted acid sites, and kinetic, calorimetric, and spectroscopic studies of methylamine synthesis and related reactions over acid catalysts. Approach of this work was to explore quantitative correlations between factors that control the generation, type, strength, and catalytic properties of acid sites on zeolite catalysts. Microcalorimetry, thermogravimetric analysis, IR spectroscopy, and NMR spectroscopy have provided information about the nature and strength of acid sites in zeolites. This was vital in understanding the catalytic cycles involved in methylamine synthesis and related reactions over zeolite catalysts.
Date: January 1, 1993
Partner: UNT Libraries Government Documents Department

A preliminary investigation of acid-catalyzed polymerization reactions of shale oil distillates

Description: Sinor (1989) reported that a major specialty market may exist for shale oil as an asphalt blending material. Shale oil can be converted to an asphalt blending material by acid catalyzed condensation and polymerization reactions of the many molecular species comprising the composition of shale oil. To simplify the investigation, crude shale oil was separated by distillation into three distillates of different hydrocarbon and heteroaromatic compositions. These distillates were then treated with two different types of acids to determine the effect of acid type on the end products. Three western shale oil distillates, a naphtha, a middle distillate, and an atmospheric gas oil, were reacted with anhydrous AlCl{sub 3} and 85% H{sub 2}SO{sub 4} under low-severity conditions. At relatively low temperatures, little change in the hydrocarbon composition was noted for the AlCl{sub 3} reactions. AlCl{sub 3}{center dot} (a polymerized product and/or complex) was formed. However, it is assumed that the sludge was mainly the result of heteroaromatic-AlCl{sub 3} reactions.
Date: April 1, 1991
Creator: Netzel, D.A.
Partner: UNT Libraries Government Documents Department

Fine particle clay catalysts for coal liquefaction

Description: The efficient production of environmentally acceptable distillate fuels requires catalysts for hydrogenation and cleavage of the coal macromolecules and removal of oxygen, nitrogen, and sulfur heteroatoms. The goal of the proposed research is to develop new catalysts for the direct liquefaction of coal. This type of catalyst consists of fine clay particles that have been treated with reagents which form pillaring structures between the aluminosilicate layers of the clay. The pillars not only hold the layers apart but also constitute the active catalytic sites for hydrogenation of the coal and solvent used in the liquefaction. The pillaring catalytic sites are composed of pyrrhotite, which has been previously demonstrated to be active for coal liquefaction. The pyrrhotite sites are generated in situ by sulfiding the corresponding oxyiron species. The size of the catalyst will be less than 40 nm in order to promote intimate contact with the coal material. Since the clays and reagents for pillaring and activating the clays are inexpensive, the catalysts can be discarded after use, rather than regenerated by a costly process. The proposed work will evaluate methods for preparing the fine particle iron-pillared clay dispersions and for activating the particles to generate the catalysts. Characterization studies of the pillared clays and activated catalysts will performed. The effectiveness of the pillared clay dispersion for hydrogenation and coal liquefaction will be determined in several types of testing. 5 refs., 1 tab.
Date: January 1, 1991
Creator: Olson, E.S.
Partner: UNT Libraries Government Documents Department

Thermodynamic and kinetic aspects of surface acidity

Description: Our research in the general area of acid catalysis involves the characterization of solid acidity and the corresponding assessment of catalytic performance of acidic materials. Acid characterization studies are required to provide essential information about the type of acid site (i.e., Lewis versus Bronsted), the strength of the sites, and the mobility of molecules adsorbed on the acid sites. An accurate measure of acid strength is given by the heat of adsorption of a basic probe molecule on the acid site. A thermodynamic representation of the mobility of adsorbed species on these sites is given by the entropy of adsorption. Important techniques used in these acid site characterization studies include microcalorimetry, thermogravimetric measurements, temperature programmed desorption, infrared spectroscopy and solid state nuclear magnetic resonance. The combination of these acid site characterization studies with reaction kinetics measurements of selected catalytic processes allows the elucidation of possible relationships between surface thermodynamic and kinetic properties of acidic sites. Such relationships are important milestones in formulating effective strategies for the effective utilization of solid acid catalysts. Current work in this direction involves methylamine syntheses over various zeolites, and the basic probe molecules employed include ammonia, methanol, water and mono-, di- and tri-methylamines. 31 refs., 18 figs., 1 tab.
Date: January 1, 1992
Creator: Dumesic, J.A.
Partner: UNT Libraries Government Documents Department

Mechanism of hydrodenitrogenation (Part 4) infrared spectroscopy of acidic molybdena catalysts

Description: Mo oxide catalysts supported over a complete series of silica-aluminas have been characterized in the oxidic and reduced states, by means of total acidity measurements and by infrared spectroscopy. Ammonia chemisorption was used to titrate the total acidity of the catalysts, and IR absorption of adsorbed pyridine to distinguish Bronsted from Lewis acid sites. The formation of new acidity upon deposition of molybdena on silica-alumina supports was then explained on the basis of a simple surface model. The new acidity is of both Lewis and Bronsted type, the preponderance of one over the other depending on support composition, as well as loading and state of oxidation of Mo. High-alumina supports and low Mo loading favor dispersed Mo species, in particular bidentate and monodentate di-oxo Mo species. The latter is responsible for the new Bronsted acidity. Coordinative unsaturation of polymolybdates is responsible for the new Lewis acidity, which is increased upon reduction of Mo. High-silica supports favor monodentate species (high Bronsted acidity) up to 4 wt % MoO{sub 3}. Beyond that, polymolybdates species and Lewis acidity predominate. 7 refs., 4 figs.
Date: January 1, 1990
Creator: Miranda, R.
Partner: UNT Libraries Government Documents Department

Aluminum coordination and active sites on aluminas, Y zeolites and pillared silicates

Description: Effort was continued to characterize the nature of the Al species responsible for Lewis acidity in zeolites and in aluminas by NMR. While numerous techniques have been successful for scaling the acid strength of Broensted sites, the situation is not satisfactory for the Lewis acid sites. Initial rate of dehydrochlorination of 1,1,1-trichloroethane is sensitive to strength of Lewis acid sites. N-Butene isomerization has been extended to the new aluminas obtained from nano-sized precursors. O-Xylene isomerization was carried out in a recirculation reactor on H-mordenite samples containing Lewis or Broensted acid sites; effects of H[sub 2] and NO were also investigated. Cracking of methylcyclohexane and 3-methylpentane was investigated by EPR on H-mordenite. Sepiolite, a Mg silicate with zeolitic channels, had Al substituted for Si; the negative charge is balanced by, say, VO[sup 2+]. Transformation of ethanol into butadiene on this dual-function catalyst appears to result from a Prins reaction between acetaldeyde formed on the redox sites and ethylene resulting from dehydration of ethanol on Lewis sites.
Date: January 1, 1992
Creator: Fripiat, J.J.
Partner: UNT Libraries Government Documents Department