Competition between Mononuclear and Binuclear Copper Sites across Different Zeolite Topologies.

A key challenge for metal-exchanged zeolites is the determination of metal cation speciation and nuclearity under synthesis and reaction conditions. Copper-exchanged zeolites, which are widely used in automotive emissions control and potential catalysts for partial methane oxidation, have in particular evidenced a wide variety of Cu structures that are observed to change with exposure conditions, zeolite composition, and topology. Here, we develop predictive models for Cu cation speciation and nuclearity in CHA, MOR, BEA, AFX, and FER zeolite topologies using interatomic potentials, quantum chemical calculations, and Monte Carlo simulations to interrogate this vast configurational and compositional space. Model predictions are used to rationalize experimentally observed differences between Cu-zeolites in a wide-body of literature, including nuclearity populations, structural variations, and methanol per Cu yields. Our results show that both topological features and commonly observed Al-siting biases in MOR zeolites increase the population of binuclear Cu sites, explaining the small population of mononuclear Cu sites observed in these materials relative to other zeolites such as CHA and BEA. Finally, we used a machine learning classification model to determine the preference to form mononuclear or binuclear Cu sites at different Al configurations in 200 zeolites in the international zeolite database. Model results reveal several zeolite topologies at extreme ends of the mononuclear vs binuclear spectrum, highlighting synthetic options for realization of zeolites with strong Cu nuclearity preferences.

Rhodium Catalyst Structural Changes during, and Their Impacts on the Kinetics of, CO Oxidation.

Catalysts can undergo structural changes during the reaction, affecting the number and/or the shape of active sites. For example, Rh can undergo interconversion between nanoparticles and single atoms when CO is present in the reaction mixture. Therefore, calculating a turnover frequency in such cases can be challenging as the number of active sites can change depending on the reaction conditions. Here, we use CO oxidation kinetics to track Rh structural changes occurring during the reaction. The apparent activation energy, considering the nanoparticles as the active sites, was constant in different temperature regimes. However, in a stoichiometric excess of O2, there were observed changes in the pre-exponential factor, which we link to changes in the number of active Rh sites. An excess of O2 enhanced CO-induced Rh nanoparticle disintegration into single atoms, affecting catalyst activity. The temperature at which these structural changes occur depend on Rh particle size, with small particle sizes disintegrating at higher temperature, relative to the temperature required to break apart bigger particles. Rh structural changes were also observed during in situ infrared spectroscopic studies. Combining CO oxidation kinetics and spectroscopic studies allowed us to calculate the turnover frequency before and after nanoparticle redispersion into single atoms.

Solvation and Mobilization of Copper Active Sites in Zeolites by Ammonia: Consequences for the Catalytic Reduction of Nitrogen Oxides.

ConspectusCopper-exchanged chabazite (Cu-CHA) zeolites are catalysts used in diesel emissions control for the abatement of nitrogen oxides (NOx) via selective catalytic reduction (SCR) reactions with ammonia as the reductant. The discovery of these materials in the early 2010s enabled a step-change improvement in diesel emissions aftertreatment technology. Key advantages of Cu-CHA zeolites over prior materials include their effectiveness at the lower temperatures characteristic of diesel exhaust, their durability under high-temperature hydrothermal conditions, and their resistance to poisoning from residual hydrocarbons present in exhaust. Fundamental catalysis research has since uncovered mechanistic and kinetic features that underpin the ability of Cu-CHA to selectively reduce NOx under strongly oxidizing conditions and to achieve improved NOx conversion relative to other zeolite frameworks, particularly at low exhaust temperatures and with ammonia instead of other reductants.One critical mechanistic feature is the NH3 solvation of exchanged Cu ions at low temperatures (<523 K) to create cationic Cu-amine coordination complexes that are ionically tethered to anionic Al framework sites. This ionic tethering confers regulated mobility that facilitates interconversion between mononuclear and binuclear Cu complexes, which is necessary to propagate SCR through a Cu2+/Cu+ redox cycle during catalytic turnover. This dynamic catalytic mechanism, wherein single and dual metal sites interconvert to mediate different half-reactions of the redox cycle, combines features canonically associated with homogeneous and heterogeneous reaction mechanisms.In this Account, we describe how a unified experimental and theoretical interrogation of Cu-CHA catalysts in operando provided quantitative evidence of regulated Cu ion mobility and its role in the SCR mechanism. This approach relied on new synthetic methods to prepare model Cu-CHA zeolites with varied active-site structures and spatial densities in order to verify that the kinetic and mechanistic models describe the catalytic behavior of a family of materials of diverse composition, and on new computational approaches to capture the active-site structure and dynamics under conditions representative of catalysis. Ex situ interrogation revealed that the Cu structure depends on the conditions for the zeolite synthesis, which influence the framework Al substitution patterns, and that statistical and electronic structure models can enumerate Cu site populations for a known Al distribution. This recognition unifies seemingly disparate spectroscopic observations and inferences regarding Cu ion structure and responses to different external conditions. SCR rates depend strongly on the Cu spatial density and zeolite composition in kinetic regimes where Cu+ oxidation with O2 becomes rate-limiting, as occurs at lower temperatures and under fuel-rich conditions. Transient experiments, ab initio molecular dynamics simulations, and statistical models relate these sensitivities to the mobility constraints imposed by the CHA framework on NH3-solvated Cu ions, which regulate the pore volume accessible to these ions and their ability to pair and complete the catalytic cycle. This highlights the key characteristics of the CHA framework that enable superior performance under low-temperature SCR reaction conditions.This work illustrates the power of precise control over a catalytic material, simultaneous kinetic and spectroscopic interrogation over a wide range of reaction conditions, and computational strategies tailored to capture those reaction conditions to reveal in microscopic detail the mechanistic features of a complex and widely practiced catalysis. In doing so, it highlights the key role of ion mobility in catalysis and thus potentially a more general phenomenon of reactant solvation and active site mobilization in reactions catalyzed by exchanged metal ions in zeolites.

Consequences of exchange-site heterogeneity and dynamics on the UV-visible spectrum of Cu-exchanged SSZ-13.

The speciation and structure of Cu ions and complexes in chabazite (SSZ-13) zeolites, which are relevant catalysts for nitrogen oxide reduction and partial methane oxidation, depend on material composition and reaction environment. Ultraviolet-visible (UV-Vis) spectra of Cu-SSZ-13 zeolites synthesized to contain specific Cu site motifs, together with ab initio molecular dynamics and time-dependent density functional theory calculations, were used to test the ability to relate specific spectroscopic signatures to specific site motifs. Geometrically distinct arrangements of two framework Al atoms in six-membered rings are found to exchange Cu2+ ions that become spectroscopically indistinguishable after accounting for the finite-temperature fluctuations of the Cu coordination environment. Nominally homogeneous single Al exchange sites are found to exchange a heterogeneous mixture of [CuOH]+ monomers, O- and OH-bridged Cu dimers, and larger polynuclear complexes. The UV-Vis spectra of the latter are sensitive to framework Al proximity, to precise ligand environment, and to finite-temperature structural fluctuations, precluding the precise assignment of spectroscopic features to specific Cu structures. In all Cu-SSZ-13 samples, these dimers and larger complexes are reduced by CO to Cu+ sites at 523 K, leaving behind isolated [CuOH]+ sites with a characteristic spectroscopic identity. The various mononuclear and polynuclear Cu2+ species are distinguishable by their different responses to reducing environments, with implications for their relevance to catalytic redox reactions.

Zeolite Adsorption Free Energies from ab Initio Potentials of Mean Force.

The ability of metal-exchanged zeolites to chemisorb small gas molecules is key to their performance as heterogeneous catalysts and gas-separating agents. Here, we propose and evaluate an ab initio potential of mean force (PMF) method for computing adsorption free energies of representative small molecules to Cu-exchanged sites in SSZ-13 zeolite. We show that Cu ions are mobilized by adsorbates and, as a result, computed free energies are significantly more negative than those obtained from a conventional harmonic oscillator model. PMF-derived free energies are consistent with available experiment and, in many cases, with a dynamics-based quasi-harmonic analysis (QHA). The PMF approach avoids the artificial partitioning of degrees of freedom intrinsic to the QHA. On the basis of the PMF results, we propose a simple correlation to estimate free energies from computed adsorption energies and gas-phase entropies.

Dynamic multinuclear sites formed by mobilized copper ions in NO x selective catalytic reduction.

Copper ions exchanged into zeolites are active for the selective catalytic reduction (SCR) of nitrogen oxides (NO x ) with ammonia (NH3), but the low-temperature rate dependence on copper (Cu) volumetric density is inconsistent with reaction at single sites. We combine steady-state and transient kinetic measurements, x-ray absorption spectroscopy, and first-principles calculations to demonstrate that under reaction conditions, mobilized Cu ions can travel through zeolite windows and form transient ion pairs that participate in an oxygen (O2)-mediated CuI→CuII redox step integral to SCR. Electrostatic tethering to framework aluminum centers limits the volume that each ion can explore and thus its capacity to form an ion pair. The dynamic, reversible formation of multinuclear sites from mobilized single atoms represents a distinct phenomenon that falls outside the conventional boundaries of a heterogeneous or homogeneous catalyst.

Catalysis in a Cage: Condition-Dependent Speciation and Dynamics of Exchanged Cu Cations in SSZ-13 Zeolites.

The relationships among the macroscopic compositional parameters of a Cu-exchanged SSZ-13 zeolite catalyst, the types and numbers of Cu active sites, and activity for the selective catalytic reduction (SCR) of NOx with NH3 are established through experimental interrogation and computational analysis of materials across the catalyst composition space. Density functional theory, stochastic models, and experimental characterizations demonstrate that within the synthesis protocols applied here and across Si:Al ratios, the volumetric density of six-membered-rings (6MR) containing two Al (2Al sites) is consistent with a random Al siting in the SSZ-13 lattice subject to Löwenstein's rule. Further, exchanged Cu(II) ions first populate these 2Al sites before populating remaining unpaired, or 1Al, sites as Cu(II)OH. These sites are distinguished and enumerated ex situ through vibrational and X-ray absorption spectroscopies (XAS) and chemical titrations. In situ and operando XAS follow Cu oxidation state and coordination environment as a function of environmental conditions including low-temperature (473 K) SCR catalysis and are rationalized through first-principles thermodynamics and ab initio molecular dynamics. Experiment and theory together reveal that the Cu sites respond sensitively to exposure conditions, and in particular that Cu species are solvated and mobilized by NH3 under SCR conditions. While Cu sites are spectroscopically and chemically distinct away from these conditions, they exhibit similar turnover rates, apparent activation energies and apparent reaction orders at the SCR conditions, even on zeolite frameworks other than SSZ13.

Isolation of the copper redox steps in the standard selective catalytic reduction on Cu-SSZ-13.

Operando X-ray absorption experiments and density functional theory (DFT) calculations are reported that elucidate the role of copper redox chemistry in the selective catalytic reduction (SCR) of NO over Cu-exchanged SSZ-13. Catalysts prepared to contain only isolated, exchanged Cu(II) ions evidence both Cu(II) and Cu(I) ions under standard SCR conditions at 473 K. Reactant cutoff experiments show that NO and NH3 together are necessary for Cu(II) reduction to Cu(I). DFT calculations show that NO-assisted NH3 dissociation is both energetically favorable and accounts for the observed Cu(II) reduction. The calculations predict in situ generation of Brønsted sites proximal to Cu(I) upon reduction, which we quantify in separate titration experiments. Both NO and O2 are necessary for oxidation of Cu(I) to Cu(II), which DFT suggests to occur by a NO2 intermediate. Reaction of Cu-bound NO2 with proximal NH4(+) completes the catalytic cycle. N2 is produced in both reduction and oxidation half-cycles.