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Carcinogenic health concerns over arsenic in drinking water caused the USEPA to reduce the maximum contaminant level (MCL) from 50 to 10 ppb, effective on January 23, 2006. This has forced many smaller utilities into expensive treatment or discontinuation of water distribution. Researchers throughout the world are working to develop an inexpensive method for arsenic removal to meet this MCL. Aluminum silicates, or zeolites, are naturally occurring ionic sorbents. Modification of a zeolite may enhance adsorption capacities and ion selectivity. This research investigates the arsenic adsorption capacities of a modified Chabazite. This adsorption, coupled with a hollow fiber, microfiltration membrane substrate, allows for the use of finer zeolite particles. Powdered zeolite creates a cake layer on the filtration surface through which the arsenic solution must filter. The research goal was to develop an overall mathematical model for the adsorption of arsenic through the adsorption equilibrium isotherms, the cake layer, and the microfiltration operational settings. Baseline adsorption isotherms where performed in distilled water. Solutions containing counter ions were then used to determine any counter-effects. The final isotherms were found using dechlorinated tap water, which is similar to many groundwaters found in the United States. Various runs were used to determine the most efficient modification and loading rate.Initial characterization of the membrane system defined membrane permeability and inherent arsenic rejection. Variable mass loading in both deadend and crossflow filtration determined that the cake layer was not compressible due to linear pressure increases. This process also determined the maximum cake layer permissible hydraulically on the membrane surface. Membrane system operational characteristics and arsenic dosing were chosen to adhere to these parameters as well as the adsorption isotherms. Adsorption runs were conducted which varied the flux through the membrane, the arsenic feed concentration, and the cake layer thickness. Through the data collected, a mathematical model based on irreversible adsorption was developed. This novel approach to arsenic removal and the predictive mathematical model can be used as an effective method for removal of aqueous arsenic, and may provide small water utilities with a cost effective way to meet the recommended new MCL.

<p>Zeolites contain distinct Brønsted acid site (H⁺) ensembles that arise from differences in the arrangement of framework Al atoms (Al−O(−Si−O)x−Al) between isolated (x ≥3) and paired (x=1,2) configurations, the latter defined by their ability to exchange certain divalent cations (e.g., Cu²⁺, Co²⁺). Manipulation of the synthesis conditions used to prepare MFI zeolites has been proposed to influence the proximity of framework Al atoms, but in a manner that is neither determined randomly nor by any simple predictive rules. Moreover, the effects of proton proximity have been studied for hydrocarbon catalysis in MFI zeolites, but interpretations of catalytic phenomena are convoluted by effects of the distribution of framework Al atoms among different crystallographic tetrahedral sites (T-sites) and diverse pore environments (i.e., confining environments) present in MFI. This work instead focuses on the chabazite (CHA) framework, which contains a single crystallographically-distinct lattice tetrahedral site (T-site) that allows clarifying how synthesis conditions influence Al proximity, and in turn, how H⁺ site proximity influences catalysis independent of T-site location. </p> <p> Selective quantification of the number and type of H⁺ site ensembles present in a given zeolite allows for more rigorous normalization of reaction rates by the number of active sites, but also for probing the number and identity of active sites on bifunctional catalysts that contain mixtures of Brønsted and Lewis acid sites. Gaseous NH₃ titrations can be used to count the total number of protons on small-pore CHA zeolites, which are inaccessible to larger amine titrants (e.g., pyridine, alkylamines), and can be used to quantify the exchange stoichiometry of extraframework metal cations (e.g., Cu²⁺, [CuOH]⁺) that are stabilized at different framework Al arrangements. Additionally, paired Al sites in CHA zeolites can be titrated selectively by divalent Co²⁺ cations, whose sole presence is validated by measuring UV-Visible spectra, counting residual protons after Co²⁺ exchange, and titration of paired Al with other divalent cations (e.g., Cu²⁺). These different titration procedures enabled reliable and reproducible quantification of different Al arrangements, and recognition of the effects of different synthetic methods on the resulting arrangement of framework Al atoms in CHA zeolites. </p> <p>Upon the advent of this suite of characterization and titration tools, different synthetic methods were developed to crystallize CHA zeolites at constant composition (e.g., Si/Al = 15) but with systematic variation in their paired Al content. The substitution of N,N,N-trimethyl-1-adamantylammonium (TMAda⁺) cations for Na⁺ in the synthesis media (Na⁺/TMAda⁺<2), while holding all other synthetic variables constant, resulted in CHA zeolites of similar composition (Si/Al = 15) and organic content (ca. 1 TMAda⁺ per cage), but with percentages of paired Al (0-44%) that increased with the total amount of sodium retained on the zeolite product. This result suggests that sodium atoms are occluded near the ammonium group of TMAda⁺ leading to the formation of a paired Al site. Replacement of Na⁺ by other alkali cations in the synthesis media allowed for the crystallization of CHA (Si/Al = 15) at higher ratios of alkali to TMAda⁺than accessible by Na⁺, likely due to the ability of different alkali cations to favor (or inhibit) crystallization of other zeolite phases. Incorporation of different alkali cations during CHA crystallization influences the formation of paired Al sites in different ways, likely reflecting the nature of different alkali to preferentially occupy different positions within the CHA framework. <i>Ab initio</i> molecular dynamics simulations were used to assess the stability of various Al-Al arrangements in the presence of combinations of alkali and TMAda⁺ cations, and provide thermodynamic insight into electrostatic interactions between cationic structure-directing agents that stabilize paired Al sites in CHA. </p> <p> Using these synthetic procedures to prepare CHA zeolites of similar composition, but with varied arrangements of framework Al, the catalytic consequences of framework Al arrangement were investigated using acid and redox catalysis. The low-temperature (473 K) selective catalytic reduction of NOx with NH₃ (NH₃-SCR) was investigated over Cu-exchanged CHA zeolites containing various Al arrangements. Cu cations exchange as both divalent Cu²⁺ and monovalent [CuOH]⁺ complexes, which exchange at paired and isolated Al sites, respectively, and turnover with similar SCR rates (473 K). <i>In situ</i> and <i>operando</i> X-ray absorption spectroscopy (XAS) were used to monitor the oxidation state and coordination environment of Cu as a function of time and environmental conditions. Rationalization of these experimental observations by first-principles thermodynamics and <i>ab initio</i> molecular dynamics simulations revealed that both Cu²⁺ and [CuOH]⁺ complexes are solvated by NH₃ and undergo reduction to Cu⁺ upon oxidation of NO with NH₃. Cu⁺ cations become mobilized by coordination with NH₃ under reaction conditions (473 K, equimolar NO and NH₃ feed), and activate O₂ through a dicopper complex formed dynamically during reaction. These results implicate the spatial density of nominally site-isolated Cu cations and, in turn, the arrangement of anionic framework Al atoms that anchor such cationic Cu complexes, influence the kinetics of O₂ activation in selective oxidation reactions, manifested as SCR rates (per 1000 A³) that depend quadratically on Cu density (per 1000 A³) and become rate-limiting processes in practice at low temperatures.</p> <p>Furthermore, first-order and zero-order rate constants (415 K, per H⁺) of methanol dehydration, a probe reaction of acid strength and confinement effects in solid Brønsted acids, are nearly one order of magnitude larger on paired than on isolated protons in CHA zeolites, reflecting differences in prevalent mechanisms and apparent enthalpic and entropic barriers at these different active site ensembles. Yet, these differences in rate constants and activation parameters at isolated and paired protons do not persist within larger pore zeolites (e.g., MFI). <i>In situ </i>IR spectra measured during steady-state methanol dehydration catalysis (415 K, 0.05-22 kPa CH₃OH) reveal that surface methoxy species are present in CHA zeolites containing paired protons, but not in CHA zeolites containing only isolated protons or MFI zeolites, providing evidence that sequential dehydration pathways via methoxy intermediates become accessible on paired protons in CHA. Density functional theory is used to provide atomistic detail of confined intermediates and transition states at isolated and paired protons in CHA and MFI zeolites, indicating that paired protons in CHA preferentially stabilize dehydration transition states that are partially-confined within the 8-membered ring (8-MR) of CHA. These findings provide evidence that catalytic diversity for the same stoichiometric reaction among zeolites of fixed structure and composition, even for frameworks containing a single T-site, can be introduced deliberately through synthetic control of the atomic arrangement of matter. </p>

This thesis is focused on theoretical study of influence of the silanol nest defects on the hydrolysis of zeolite Chabazite under harsh steaming conditions. The motivation of the thesis was a recent experiment proving that the silanol nest defect enhances the hydrolysis of a zeolite. The harsh steaming conditions have been chosen as some important technological processes involving zeolites require high temperatures and have water vapour present. The study was performed by using density functional theory calculations. To investigate the influence of the defect two models were used a reference pristine model and a defected model containing the silanol nest defect. The two models were pure siliceous Chabazite periodical models with supercell containing 36 and 35 Si tetrahedra respectively. A multi-step hydrolysis leading to detachment of a Si(OH)4 cluster from the zeolite, known as total desilication, was calculated for the two models. Multiple possible paths of the hydrolysis were discovered, compared and discussed on both models. Both the most favourable hydrolysis paths of the two model as well as their arithmetic means were compared. The experimentally set expectations that a silanol nest defect enhances the hydrolysis of the zeolite have been met.

The translational self-diffusion, the librations, and the reorientational motions of guest water molecules in the zeolite chabazite are examined by Molecular Dynamics (MD) computer simulations at different temperatures and loadings, including at room temperature, at which the experiments are carried out. Satisfactory agreement is found between the computed and measured translational self-diffusion coefficients. It is, however, furthermore found that the way in which the long-range electrostatic interactions are computed has an effect on the self-diffusion at high loadings and temperatures. The spectral densities of the librational motions of water are found to be similar to those in aqueous salt solutions. The reorientations of the water molecules, on the other hand, are much slower than in the liquids, and very anisotropic. The vector in direction of the molecular dipole moment reorients only very slowly, at the time scale of the simulations, due to the attraction to the almost immobile Ca++-ions and the walls of the zeolite. The other two vectors seem to undergo jump-reorientations rather than reorientations by a diffusion process. Hyper dynamics boost potential method has been applied to the MD simulations to estimate the self-diffusion coefficients of Ca++ ions in dehydrated chabazite. Because of our system is very complicated, the self-diffusion of Ca++ ions can only be roughly estimated. The Ca++ ions diffusion is small enough to confirm that the cation motion can be neglected in the normal MD simulation.

Nanosized SSZ-13 was synthesized hydrothermally by applying N,N,N-trimethyl-1-adamantammonium hydroxide (TMAdaOH) as a structure-directing agent. In the next step, the quantity of TMAdaOH in the initial synthesis mixture of SSZ-13 was reduced by half. Furthermore, we varied the sodium hydroxide concentration. After ion-exchange with copper ions (Cu2+ and Cu+), the Cu-SSZ-13 catalysts were characterized to explore their framework composition (XRD, solid-state NMR, ICP-OES), texture (N2-sorption, SEM) and acid/redox properties (FT-IR, TPR-H2, DR UV-Vis, EPR). Finally, the materials were tested in the selective catalytic reduction of NOx with ammonia (NH3-SCR). The main difference between the Cu-SSZ-13 catalysts was the number of Cu2+ in the double six-membered ring (6MRs). Such copper species contribute to a high NH3-SCR activity. Nevertheless, all materials show comparable activity in NH3-SCR up to 350 °C. Above 350 °C, NO conversion decreased for Cu-SSZ-13(2–4) due to side reaction of NH3 oxidation.

The translational self-diffusion, the librations, and the reorientational motions of guest water molecules in the zeolite chabazite are examined by Molecular Dynamics (MD) computer simulations at different temperatures and loadings, including at room temperature, at which the experiments are carried out. Satisfactory agreement is found between the computed and measured translational self-diffusion coefficients. It is, however, furthermore found that the way in which the long-range electrostatic interactions are computed has an effect on the self-diffusion at high loadings and temperatures. The spectral densities of the librational motions of water are found to be similar to those in aqueous salt solutions. The reorientations of the water molecules, on the other hand, are much slower than in the liquids, and very anisotropic. The vector in direction of the molecular dipole moment reorients only very slowly, at the time scale of the simulations, due to the attraction to the almost immobile Ca++-ions and the walls of the zeolite. The other two vectors seem to undergo jump-reorientations rather than reorientations by a diffusion process. Hyper dynamics boost potential method has been applied to the MD simulations to estimate the self-diffusion coefficients of Ca++ ions in dehydrated chabazite. Because of our system is very complicated, the self-diffusion of Ca++ ions can only be roughly estimated. The Ca++ ions diffusion is small enough to confirm that the cation motion can be neglected in the normal MD simulation.

[ES] En este trabajo estudiamos dos reacciones catalíticas relevantes para la industria y la localización del anión fluoruro en la zeolita RTH, sintetizada en medio fluoruro. El capítulo 3 es el primer capítulo de resultados, donde se estudia la reducción quimioselectiva del nitroestireno en las superficies Ni(111), Co(111), Cu(111) y Pd(111). El mecanismo generalmente aceptado de esta reacción está basado en el esquema propuesto por Haber en 1898, en el que la reacción puede transcurrir por dos rutas, la directa y la de condensación. En este capítulo exploramos ambas rutas, y observamos que la ruptura de los enlaces N-O y la consecuente formación de enlaces metal-O está más favorecida que la formación de enlaces N-H en las superficies Ni(111) y Co(111), debido al carácter oxofílico de ambos metales. Las etapas más lentas involucran la formación de enlaces N-H. En las superficies de metales nobles como Pt(111) y Pd(111) se observa el comportamiento contrario. La superficie Cu(111) es un caso intermedio comparado con los metales nobles y no nobles. Además, el nitroestireno interactúa con los átomos de Cu de la superficie solo a través de grupo nitro, con lo cual es un candidato ideal para alcanzar selectividades cerca del 100%. Sin embargo, la superficie Cu(111) no es capaz de activar la molécula de H2. En este sentido, proponemos un catalizador bimetálico basado en Cu, dopado con otro metal capaz de activar al H2, tales como el Pd o el Ni. En los capítulos 4 y 5 se ha estudiado la reducción catalítica selectiva de los óxidos de nitrógeno (SCR, en inglés) con amoníaco. Usando métodos de DFT, hemos encontrado rutas para la oxidación de NO a NO2, nitritos y nitratos con energías de activación relativamente bajas. También, hemos encontrado que la reducción de Cu2+ a Cu+ requiere la participación simultánea de NO y NH3. Posteriormente, hemos estudiado la influencia del NH3 en este sistema con métodos de dinámica molecular. El NH3 interacciona fuertemente con el Cu+ de forma que dos moléculas de este gas son suficientes para romper la coordinación del catión Cu+ con los oxígenos del anillo 6r, y formar el complejo lineal [Cu(NH3)2]+. Además, los cationes Cu2+ pueden ser estabilizados fuera de la red mediante la formación del complejo tetraamincobre(II). Debido a la presencia de los cationes Cu+ y Cu2+ coordinados a la red de la zeolita, aparecen bandas en la región entre 800-1000 cm-1 del espectro infrarrojo. El análisis de las frecuencias IR de varios modelos con Cu+ y Cu2+ coordinados al anillo 6r, o formando complejos con amoniaco indica que cuando los cationes Cu+ y Cu2+ están coordinados a los oxígenos del anillo 6r aparecen vibraciones entre 830 y 960 cm-1. Frecuencias en esta zona también se obtienen en los casos en que NO, NO2, O2 y combinaciones de dos de ellos están adsorbidos en Cu+ y Cu2+. Sin embargo, cuando los cationes Cu+ y Cu2+ están fuera del anillo (no hay enlaces entre los cationes de cobre y los oxígenos del anillo 6r) no se obtienen vibraciones de IR en esta región del espectro. Estos resultados indican que con el seguimiento del espectro IR durante la reacción SCR es posible determinar si los cationes Cu+ y Cu2+ están coordinados o no al anillo de 6r en las etapas de oxidación y reducción. Por último, hemos simulado el desplazamiento químico de 19F, δiso,, en la zeolita sintetizada RTH. El análisis del δiso de los distintos modelos utilizados nos ha permitido reconocer la simetría del material sintetizado, el cual pertenece al grupo espacial P1 y la nueva celda unidad ha sido confirmada experimentalmente por difracción de rayos X. Finalmente, hemos asignado la señal experimental que aparece en el espectro de 19F a -67.2_ppm, al F- localizado en un sitio T2, el cual es a su vez la posición más estable. Además, la señal a -71.8 ppm se ha asignado al anión F- localizado en un sitio T4. / [CA] En aquest treball estudiem dues reaccions catalítiques rellevants per a la indústria i la localització de l'anió fluorur en la zeolita RTH, sintetitzada al mig fluorur. El capítol 3 és el primer capítol de resultats, on s'estudia la reducció quimioselectiva del nitroestireno en les superfícies Ni(111), Co(111), Cu(111) i Pd(111). El mecanisme generalment acceptat d'aquesta reacció està basat en l'esquema proposat per Haver-hi en 1898, en el qual la reacció pot transcórrer per dues rutes, la directa i la de condensació. En aquest capítol explorem totes dues rutes, i observem que la ruptura dels enllaços N-O i la conseqüent formació d'enllaços metall-O està més afavorida que la formació d'enllaços N-H en les superfícies Ni(111) i Co(111), a causa del caràcter oxofílico de tots dos metalls. Les etapes més lentes involucren la formació d'enllaços N-H. En les superfícies de metalls nobles com Pt(111) i Pd(111) s'observa el comportament contrari. La superfície Cu(111) és un cas intermedi comparat amb els metalls nobles i no nobles. A més, el nitroestireno interactua amb els àtoms de Cu de la superfície sol a través de grup nitre, amb la qual cosa és un candidat ideal per a aconseguir selectivitats prop del 100%. No obstant això, la superfície Cu(111) no és capaç d'activar la molècula d'H2. En aquest sentit, proposem un catalitzador bimetàl·lic basat en Cu, dopat amb un altre metall capaç d'activar a l'H2, com ara el Pd o el Ni. En els capítols 4 i 5 hem estudiat la reducció catalítica selectiva dels òxids de nitrogen (SCR, en anglés) amb amoníac. Usant mètodes de DFT, hem trobat rutes per a l'oxidació de NO a NO2, nitrits i nitrats amb energies d'activació relativament baixes. També, hem trobat que la reducció de Cu2+ a Cu+ requereix la participació simultània de NO i NH3. Posteriorment, hem estudiat la influència del NH3 en aquest sistema amb mètodes de dinàmica molecular. El NH3 interacciona fortament amb el Cu+ de manera que dues molècules d'aquest gas són suficients per a trencar la coordinació del catió Cu+ amb els oxígens de l'anell 6r, i formar el complex lineal [Cu(NH3)2]+. A més, els cations Cu2+ poden ser estabilitzats fora de la xarxa mitjançant la formació del complex tetraamincobre(II). A causa de la presència dels cations Cu+ i Cu2+ coordinats a la xarxa de la zeolita, apareixen bandes a la regió entre 800-1000 cm-1 de l'espectre infraroig. L'anàlisi de les freqüències IR de diversos models amb Cu+ i Cu2+ coordinats a l'anell 6r, o formant complexos amb amoníac indica que quan els cations Cu+ i Cu2+ estan coordinats als oxígens de l'anell 6r apareixen vibracions entre 830 i 960 cm-1. Freqüències en aquesta zona també s'obtenen en els casos en què NO, NO2, O2 i combinacions de dues d'ells estan adsorbidos en Cu+ i Cu2+. No obstant això, quan els cations Cu+ i Cu2+ estan fora de l'anell (no hi ha enllaços entre els cations de coure i els oxígens de l'anell 6r) no s'obtenen vibracions d'IR en aquesta regió de l'espectre. Aquests resultats indiquen que amb el seguiment de l'espectre IR durant la reacció SCR és possible determinar si els cations Cu+ i Cu2+ estan coordinats o no a l'anell de 6r en les etapes d'oxidació i reducció. Finalment, hem simulat el desplaçament químic de 19F, δiso, en la zeolita sintetitzada RTH. L'anàlisi del δiso dels diferents models utilitzats ens ha permés reconéixer la simetria del material sintetitzat, el qual pertany al grup espacial P1 i la nova cel·la unitat ha sigut confirmada experimentalment per difracció de raigs X. Finalment, hem assignat el senyal experimental que apareix en l'espectre de 19F a -67.2 ppm, al F- localitzat en un lloc T2, el qual és al seu torn la posició més estable. A més, el senyal a -71.8 ppm s'ha assignat a l'anió F- localitzat en un lloc T4. / [EN] In this work, we have studied two heterogeneous catalytic reactions and the localization of the fluoride anion in the as-made RTH framework, synthesized in fluoride medium. The first results, included in chapter 3, correspond to the chemoselective reduction of nitrostyrene on different metal surfaces, i.e, Ni(111), Co(111), Cu(111) and Pd(111). Until very recently, the reduction of the nitro group was explained on the basis of the general mechanism proposed by Haber in 1898 where the reaction can follow two routes, the direct and condensation route. We have explored the relevant elementary steps of both routes and found that because of the oxophilic nature of Ni and Co, the steps involving the dissociation of N-O bonds and formation of metal-O bonds are significantly favored compared with the other steps on both metal surfaces. In addition, the most demanding steps in terms of energy involve the formation of N-H bonds. These findings are in contrast to those of noble metals such as Pt and Pd, where the opposite behavior is observed. The behavior of Cu(111) lies in between the aforementioned cases, and also no chemical bonds between the carbon atoms of the aromatic ring of nitrostyrene and the Cu(111) surface is formed. For this reason, it might be an ideal candidate to achieve nearly 100 % selectivity. However, the Cu(111) surface does not seem to activate the H2 molecule. In this regard, we propose a bimetallic Cu-based catalyst whose surface is doped with atoms of a H2-activating metal, such as Ni or Pd. On another matter, we have also investigated the selective catalytic reduction of nitrogen oxides (SCR-NOx) and the main results are presented in the following two chapters, 4 and 5. By using static DFT methods, we found pathways for the oxidation of NO to NO2, nitrites and nitrates with relatively low activation energies. We also found, in agreement with experimental reports, that the reduction of Cu2+ to Cu+ requires the simultaneous participation of NO and NH3. Later, molecular dynamics simulations allowed us to assess the influence of NH3. The strong interaction of NH3 with the Cu+ cation is evidenced by its ability to detach Cu+ from the zeolite framework and form the mobile linear complex [Cu(NH3)2]+. Cu+ is no longer coordinated to the zeolite framework in the presence of two NH3 molecules. This observation and the fact that the T-O-T vibrations of the framework produce bands in the 800-1000 cm-1 region of the IR spectrum when perturbed by the coordination of Cu+ and Cu2+ cations, indicate that bands in the 800-1000 cm-1 regions should be observed when both copper cations are bonded to the framework oxygens. Finally, we have also studied NMR properties of the as-made pure silica RTH framework, aiming at locating the compensating fluoride anion. The calculation of the 19F chemical shift in different T sites and comparison with the experimental NMR spectra shows that the as-made RTH belongs to the P-1 space group with 16 Si, 32 O atoms, one fluoride anion and one OSDA cation. These results have been confirmed experimentally by XRD. In addition, we have assigned the experimental signal of 19F at -67.2 ppm to the fluoride anion in a T2 site, which in turn is the most stable location found, and the signal of -71.8 ppm to a fluoride anion sitting in a T4 site. / My acknowledgements to “La Caixa foundation” for the financial support through “La Caixa−Severo Ochoa” International PhD Fellowships (call 2015), to the Spanish Supercomputing Network (RES), to the Centre de Càlcul de la Universitat de València, to the Flemish Supercomputer Center (VSC) of Ghent University for the computational resources and technical support, and to the Spanish Government through the MAT2017-82288-C2-1-P programme / Millan Cabrera, R. (2021). Computational study of heterogeneous catalytic systems. Kinetic and structural insights from Density Functional Theory [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/161934 / TESIS

<p>Although Cu-SSZ-13 zeolites are used commercially in diesel engine exhaust after-treatment for abatement of toxic NO_x pollutants via selective catalytic reduction (SCR) with NH₃, molecular details of its active centers and mechanistic details of the redox reactions they catalyze, specifically of the Cu(I) to Cu(II) oxidation half-reaction, are not well understood. A detailed understanding of the SCR reaction mechanism and nature of the Cu active site would provide insight into their catalytic performance and guidance on synthesizing materials with improved low temperature (< 473 K) reactivity and stability against deactivation (e.g. hydrothermal, sulfur oxides). We use computational, titration, spectroscopic, and kinetic techniques to elucidate (1) the presence of two types of Cu²⁺ ions in Cu-SSZ-13 materials, (2) molecular details on how these Cu cations, facilitated by NH₃ solvation, undergo a reduction-oxidation catalytic cycle, and (3) that sulfur oxides poison the two different types of Cu²⁺ ions to different extents at via different mechanisms. </p><p><br></p> <p> </p> <p>Copper was exchanged onto H-SSZ-13 samples with different Si:Al ratios (4.5, 15, and 25) via liquid-phase ion exchange using Cu(NO₃)₂ as the precursor. The speciation of copper started from the most stable Cu²⁺ coordinated to two anionic sites on the zeolite framework to [CuOH]⁺ coordinated to only one anionic site on the zeolite framework with increasing Cu:Al ratios. The number of Cu²⁺ and [CuOH]⁺ sites was quantified by selective NH₃ titration of the number of residual Brønsted acid sites after Cu exchange, and by quantification of Brønsted acidic Si(OH)Al and CuOH stretching vibrations from IR spectra. Cu-SSZ-13 with similar Cu densities and anionic framework site densities exhibit similar standard SCR rates, apparent activation energies, and orders regardless of the fraction of Z₂Cu and ZCuOH sites, indicating that both sites are equally active within measurable error for SCR. </p><p><br></p> <p> </p> <p>The standard SCR reaction uses O₂ as the oxidant (4NH₃ + 4NO + O₂ -> 6H₂O + 4N₂) and involves a Cu(I)/Cu(II) redox cycle, with Cu(II) reduction mediated by NO and NH₃, and Cu(I) oxidation mediated by NO and O₂. In contrast, the fast SCR reaction (4NH₃ + 2NO + 2NO₂ -> 6H₂O + 4N₂) uses NO₂ as the oxidant. Low temperature (437 K) standard SCR reaction kinetics over Cu-SSZ-13 zeolites depend on the spatial density and distribution of Cu ions, varied by changing the Cu:Al and Si:Al ratio. Facilitated by NH₃ solvation, mobile Cu(I) complexes can dimerize with other Cu(I) complexes within diffusion distances to activate O₂, as demonstrated through X-ray absorption spectroscopy and density functional theory calculations. Monte Carlo simulations are used to define average Cu-Cu distances. In contrast with O₂-assisted oxidation reactions, NO₂ oxidizes single Cu(I) complexes with similar kinetics among samples of varying Cu spatial density. These findings demonstrate that low temperature standard SCR is dependent on Cu spatial density and requires NH₃ solvation to mobilize Cu(I) sites to activate O₂, while in contrast fast SCR uses NO₂ to oxidize single Cu(I) sites. </p><p><br></p> <p> </p> <p>We also studied the effect of sulfur oxides, a common poison in diesel exhaust, on Cu-SSZ-13 zeolites. Model Cu-SSZ-13 samples exposed to dry SO₂ and O₂ streams at 473 and 673 K. These Cu-SSZ-13 zeolites were synthesized and characterized to contain distinct Cu active site types, predominantly either divalent Cu²⁺ ions exchanged at proximal framework Al sites (Z₂Cu), or monovalent CuOH+ complexes exchanged at isolated framework Al sites (ZCuOH). On the model Z₂Cu sample, SCR turnover rates (473 K, per Cu) catalyst decreased linearly with increasing S content to undetectable values at equimolar S:Cu molar ratios, while apparent activation energies remained constant at ~65 kJ mol^-1, consistent with poisoning of each Z₂Cu site with one SO₂-derived intermediate. On the model ZCuOH sample, SCR turnover rates also decreased linearly with increasing S content, yet apparent activation energies decreased monotonically from ~50 to ~10 kJ mol^-1, suggesting that multiple phenomena are responsible for the observed poisoning behavior and consistent with findings that SO₂ exposure led to additional storage of SO₂-derived intermediates on non-Cu surface sites. Changes to Cu²⁺ charge transfer features in UV-Visible spectra were more pronounced for SO₂-poisoned ZCuOH than Z₂Cu sites, while X-ray diffraction and micropore volume measurements show evidence of partial occlusion of microporous voids by SO₂-derived deposits, suggesting that deactivation may not only reflect Cu site poisoning. Density functional theory calculations are used to identify the structures and binding energies of different SO₂-derived intermediates at Z₂Cu and ZCuOH sites. It is found that bisulfates are particularly low in energy, and residual Brønsted protons are liberated as these bisulfates are formed. These findings indicate that Z₂Cu sites are more resistant to SO₂ poisoning than ZCuOH sites, and are easier to regenerate once poisoned. </p>