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.

Cooperative and Competitive Occlusion of Organic and Inorganic Structure-Directing Agents within Chabazite Zeolites Influences Their Aluminum Arrangement.

We combine experiment and theory to investigate the cooperation or competition between organic and inorganic structure-directing agents (SDAs) for occupancy within microporous voids of chabazite (CHA) zeolites and to rationalize the effects of SDA siting on biasing the framework Al arrangement (Al-O(-Si-O)x-Al, x = 1-3) among CHA zeolites of essentially fixed composition (Si/Al = 15). CHA zeolites crystallized using mixtures of TMAda+ and Na+ contain one TMAda+ occluded per cage and Na+ co-occluded in an amount linearly proportional to the number of 6-MR paired Al sites, quantified by Co2+ titration. In contrast, CHA zeolites crystallized using mixtures of TMAda+ and K+ provide evidence that three K+ cations, on average, displace one TMAda+ from occupying a cage and contain predominantly 6-MR isolated Al sites. Moreover, CHA crystallizes from synthesis media containing more than 10-fold higher inorganic-to-organic ratios with K+ than with Na+ before competing crystalline phases form, providing a route to decrease the amount of organic SDA needed to crystallize high-silica CHA. Density functional theory calculations show that differences in the ionic radii of Na+ and K+ determine their preferences for siting in different CHA rings, which influences their energy to co-occlude with TMAda+ and stabilize different Al configurations. Monte Carlo models confirm that energy differences resulting from Na+ or K+ co-occlusion promote the formation of 6-MR and 8-MR paired Al arrangements, respectively. These results highlight opportunities to exploit using mixtures of organic and inorganic SDAs during zeolite crystallization in order to more efficiently use organic SDAs and influence framework Al arrangements.

Comparison of Coverage-Dependent Binding Energy Models for Mean-Field Microkinetic Rate Predictions.

The binding energies of adsorbates at catalytic surfaces are in general functions of adsorbate coverage, with corresponding consequences for equilibrium surface coverages and reaction rates under relevant conditions. This coverage dependence is commonly incorporated into mean-field microkinetic models by writing adsorption energies as an algebraic function of coverage and parametrizing against density functional theory models. In this work, we compare the performance of three different analytical coverage-dependent forms, including linear and piecewise models and a logarithmic form inspired by Wilson's activity model, against accurate results obtained from a lattice-based cluster expansion (CE) representation of adsorbate interactions combined with a Monte Carlo evaluation of reaction rates. We take as a model system O2 dissociation-limited NO oxidation to NO2 over Pt(111), parametrize all models against the same set of previously reported coverage-dependent NO and O binding energies, and solve kinetic models under the same set of assumptions. Steady-state coverages from the analytical models are similar to each other and the ensemble-averaged CE result, other than the discontinuities in O and NO coverages that appear in the piecewise model. Predicted steady-state rates differ more substantially, reflecting the sensitivity of the O2 dissociation activation energy to coverage-dependent binding energies. The activity model predicts reaction rates reliably at low temperatures and systematically deviates from CE rates at high temperatures, where minority surface sites, having low local coverage around vacant pairs, dominate overall reaction rates. The results highlight the challenges of developing coverage-dependent microkinetic models that are reliable across a range of conditions.

Role of Molecular Modeling in the Development of CO2-Reactive Ionic Liquids.

Ionic liquids (ILs) have gained considerable attention in recent years as CO2-reactive solvents that could be used to improve the economic efficiency of industrial-scale CO2 separations. Researchers have demonstrated that IL physical and chemical properties can be optimized for a given application through chemical functionalization of both cations and anions. The tunability of ILs presents both a great potential and a significant challenge due to the complex chemistries and the many ways in which ILs can be made to react with CO2. However, computer simulations have demonstrated great potential in understanding the behavior of ILs from the underlying molecular interactions. In the present review, we examine how computer simulations have aided in the design of ILs that chemically bind CO2. We present the historical development of CO2-reactive ILs while highlighting the insights provided by molecular modeling which aided in understanding IL behavior to further experimental findings. We also provide a brief discussion of simulations focused on ionic liquids that physically dissolve CO2. We conclude with a discussion of areas where simulations can yet be used to advance the current understanding of these complex systems and an outlook on the use of computer simulations in the design of optimal ILs for CO2 separations.

Water-Mediated Reduction of Aqueous N-Nitrosodimethylamine with Pd.

Pd-catalyzed reduction has emerged as a promising treatment strategy to remove the recalcitrant disinfection byproduct N-nitrosodimethylamine (NDMA). However, the reaction pathways remain unexplored, and questions remain about how water solvent influences NDMA reduction mechanisms and selectivity. Here, we compute the energies and barriers of all relevant elementary steps in NDMA reduction by H2 on Pd(111) using density functional theory. We further calculate water-assisted H-shuttling for all hydrogenation reactions explicitly and include water solvation for all elementary reactions implicitly. We parametrize microkinetic models to predict product formation rates and selectivities over a wide range of NDMA concentrations. We show that H2O-mediated H-shuttling lowers the reaction barriers for all hydrogenation reactions involved in NDMA reduction while implicit solvation has negligible impact on the reaction and activation energies. We further conduct batch experiments with SiO2-supported Pd nanoparticles and compare them with the microkinetic models. The predicted rates, selectivity, and apparent activation energy from the model parametrized with both explicit H2O-mediated H-shuttling and implicit solvation correspond well with experimental observations. Models that ignore water as an H-shuttle or solvent fail to recover the experimental rates and apparent activation energy. We identified the rate-determining steps of the reaction and show the reaction flow pathways of the complicated reaction network. Finally, we demonstrate that water-mediated H-shuttling changes the rate-determining steps and reaction flows of elementary reactions.

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.

Kinetic Monte Carlo Analysis Reveals Non-mean-field Active Site Dynamics in Cu-Zeolite-Catalyzed NO x Reduction.

Copper-exchanged chabazite (Cu-CHA) zeolites are the preferred catalysts for the selective catalytic reduction of NO x with NH3. The low temperature (473 K) SCR mechanism proceeds through a redox cycle between mobile and ammonia-solvated Cu(I) and Cu(II) complexes, as demonstrated by multiple experimental and computational investigations. The oxidation step requires two Cu(I) to migrate into the same cha cage to activate O2 and form a binuclear Cu(II)-di-oxo complex. Prior steady state and transient kinetic experiments find that the apparent rate constants for oxidation (per Cu ion) are sensitive to catalyst composition and follow nonmean-field kinetics. We develop a nonmean-field kinetic model for NO x SCR that incorporates a composition-dependent Cu(I) volumetric footprint centered at anionic [AlO4]- tetrahedral sites on the CHA lattice. We use Bayesian optimization to parameterize a kinetic Monte Carlo model against available experimental composition-dependent SCR rates and in situ Cu(II) fractions. We find that both rates and Cu(II) fractions of a majority of catalyst compositions can be captured by single oxidation and reduction rate constants combined with a composition-dependent Cu(I) cation footprint, highlighting the contributions of both Cu and Al densities to steady-state SCR performance of Cu-CHA. The work illustrates a pathway for extracting robust molecular insights from the kinetics of a dynamic catalytic system.

Observation and Characterization of Vibrationally Active Surface Species Accessed with Nonthermal Nitrogen Plasmas.

Polycrystalline Ni, Pd, Cu, Ag, and Au foils exposed to nonthermal plasma (NTP)-activated N2 are found to exhibit a vibrational feature near 2200 cm-1 in polarization-modulation infrared reflection-absorption spectroscopy (PM-IRAS) observations that are not present in the same materials exposed to N2 under nonplasma conditions. The feature is similar to that reported elsewhere and is typically assigned to chemisorbed N2. We employ a combination of temperature-dependent experiments, sequential dosing, X-ray photoelectron spectroscopy, isotopic labeling, and density functional theory calculations to characterize the feature. Results are most consistent with a triatomic species, likely NCO, with the C and O likely originating from ppm-level impurities in the ultrahigh-purity (UHP) Ar and/or N2 gas cylinders. The work highlights the potential for nonthermal plasmas to access adsorbates inaccessible thermally as well as the potential contributions of ppm-level impurities to corrupt the interpretation of plasma catalytic chemistry.

Climbing the Hydrogen Evolution Volcano with a NiTi Shape Memory Alloy.

Alkaline water electrolysis is a sustainable way to produce green hydrogen using renewable electricity. Even though the rates of the cathodic hydrogen evolution reaction (HER) are 2-3 orders of magnitude less under alkaline conditions than under acidic conditions, the possibility of using non-precious metal catalysts makes alkaline HER appealing. We identify a novel and facile route for substantially improving HER performance via the use of commercially available NiTi shape memory alloys, which upon heating undergo a phase transformation from the monoclinic martensite to the cubic austenite structure. While the room-temperature performance is modest, austenitic NiTi outperforms Pt (which is the state-of-the-art HER electrocatalyst) in terms of current density by ≤50% at 80 °C. Surface ensembles presented by the austenite phase are computed with density functional theory to bind hydrogen more weakly than either metallic Ni or Ti and to have binding energies ideally suited for HER.

Solid-state covalent capture of CO2 by using N-heterocyclic carbenes.

Capture me! The first report of an N-heterocyclic carbene (NHC) as a solid-state carbon capture reagent is presented. Experimental and theoretical measurements demonstrate the ability of the NHC to react rapidly and stoichiometrically with CO2 at low partial pressures.

Development and application of effective pairwise potentials for UO2(n+), NpO2(n+), PuO2(n+), and AmO2(n+) (n = 1, 2) ions with water.

Intra- and intermolecular force field parameters for the interaction of actinyl ions (AnO2(n+), where, An = U, Np, Pu, Am and n = 1, 2) with water have been developed using quantum mechanical calculations. Water was modeled with the extended simple point charge potential (SPC/E). The resulting force field consists of a simple form in which intermolecular interactions are modeled with pairwise Lennard-Jones functions plus partial charge terms. Intramolecular bond stretching and angle bending are treated with harmonic functions. The new potentials were used to carry out extensive molecular dynamics simulations for each hydrated ion. Computed bond lengths, bond angles and coordination numbers agree well with known values and previous simulations. Hydration free energies, computed from molecular dynamics simulations as well as from quantum simulations with a solvation model, were in reasonable agreement with estimated experimental values.

Interplay between subsurface ordering, surface segregation, and adsorption on Pt-Ti(111) near-surface alloys.

Using the first-principles cluster expansion (CE) method, we studied the subsurface ordering of Pt/Pt-Ti(111) surface alloys and the effect of this ordering on segregation and adsorption behavior. The clusters included in the CE are optimized by a genetic algorithm to better describe the interactions between Pt and Ti atoms in the subsurface layer. Similar to bulk Pt-Ti alloys, Pt-Ti(111) subsurface alloys show a strong ordering tendency. A series of stable ordered Pt-Ti subsurface structures are identified from the two-dimensional (2D) CE. As an indication of the connection between the 2D and the bulk ordering, the CE predicts a ground-state Pt(8)Ti structure in the (111) subsurface layer, which is the same ordering as the close-packed plane of the bulk Pt(8)Ti compound. We carried out Monte Carlo simulations (MC) using the CE Hamiltonian to study the finite temperature stability of the Pt-Ti subsurface structures. The MC results show that subsurface structures in the Pt-rich range have higher order-disorder transition temperatures than their Ti-rich subsurface counterparts. We calculate the binding energy of different adsorbates (O, S, H, and NO) on Pt-terminated and Ti-segregated surfaces of ordered PtTi and Pt(8)Ti subsurface alloys. The binding of these adsorbates is generally stronger on Ti-segregated surfaces than Pt-terminated surfaces. The adsorption-induced Ti surface segregation is determined by two factors: (i) the unfavorable energy penalty for the Ti atom to segregate to the clean surface and (ii) the favorable energy decrease from stronger adsorbate binding on the Ti-segregated surface. The two factors introduce similar magnitude in energy change for the S and NO adsorption on Ti-segregated surfaces of PtTi subsurface alloys. We predict an adsorption-induced Ti surface segregation that is dependent on the atomic configurations of the Ti-segregated surfaces resulting from the competition of the two factors.

Influence of dipole-dipole interactions on coverage-dependent adsorption: CO and NO on Pt(111).

Density functional theory (DFT) calculations of energetic, geometric, vibrational, and electrostatic properties of different arrangements of CO and NO at quarter and half monolayer coverage on Pt(111) are presented. Differences in the extents of electron back-donation from the Pt surface to these molecules cause the low-coverage adsorbate dipoles to have opposite signs at atop and more highly coordinated bridge or fcc sites. These dipoles of opposite sign occupy adjacent positions in the experimentally observed atop-bridge or atop-fcc high -coverage arrangements, leading to attractive electrostatic interactions and concomitant changes in dipole moments, bond lengths, and vibrational frequencies. The interaction energies are estimated by charge partitioning to extract individual dipoles from the mixed arrangement and by calculations of field-dipole interactions. These estimated dipole interactions contribute significantly (20-60%) to the DFT-calculated relative stability of mixed arrangements over atop-, bridge-, or fcc-only arrangements and thus play an important role in coverage-dependent adsorption. We further extend these analyses to a range of molecules with varying dipole moments and show that the general nature of these interactions is not limited to CO and NO.

Critical review of Pd-based catalytic treatment of priority contaminants in water.

Catalytic reduction of water contaminants using palladium (Pd)-based catalysts and hydrogen gas as a reductant has been extensively studied at the bench-scale, but due to technical challenges it has only been limitedly applied at the field-scale. To motivate research that can overcome these technical challenges, this review critically analyzes the published research in the area of Pd-based catalytic reduction of priority drinking water contaminants (i.e., halogenated organics, oxyanions, and nitrosamines), and identifies key research areas that should be addressed. Specifically, the review summarizes the state of knowledge related to (1) proposed reaction pathways for important classes of contaminants, (2) rates of contaminant reduction with different catalyst formulations, (3) long-term sustainability of catalyst activity with respect to natural water foulants and regeneration strategies, and (4) technology applications. Critical barriers hindering implementation of the technology are related to catalyst activity (for some contaminants), stability, fouling, and regeneration. New developments overcoming these limitations will be needed for more extensive field-scale application of this technology.

First-principles-guided design of ionic liquids for CO2 capture.

The identification of sorbents that combine selectively and reversibly with CO(2) is essential for efficient and economical abatement of ever-increasing CO(2) emissions. Room temperature ionic liquids (ILs) are a promising class of potential absorbents, especially when modified to chemically combine with CO(2). In this perspective we describe the evolution of IL-based CO(2) capture chemistries over the last ten years and in particular the important role that first principles simulations have played in helping guide those developments. Current anion-functionalized ILs achieve high CO(2) capture efficiencies tailorable to a wide range of separation conditions and avoid the viscosity problems that plagued the earliest amine-functionalized, CO(2)-reactive ILs. Further progress is needed to develop ILs able to meet all the requirements of a CO(2) separation system, and simulations will play a central role in those developments.

Observation and rationalization of nitrogen oxidation enabled only by coupled plasma and catalyst.

Heterogeneous catalysts coupled with non-thermal plasmas (NTP) are known to achieve reaction yields that exceed the contributions of the individual components. Rationalization of the enhancing potential of catalysts, however, remains challenging because the background contributions from NTP or catalysts are often non-negligible. Here, we first demonstrate platinum (Pt)-catalyzed nitrogen (N2) oxidation in a radio frequency plasma afterglow at conditions at which neither catalyst nor plasma alone produces significant concentrations of nitric oxide (NO). We then develop reactor models based on reduced NTP- and surface-microkinetic mechanisms to identify the features of each that lead to the synergy between NTP and Pt. At experimental conditions, NTP and thermal catalytic NO production are suppressed by radical reactions and high N2 dissociation barrier, respectively. Pt catalyzes NTP-generated radicals and vibrationally excited molecules to produce NO. The model construction further illustrates that the optimization of productivity and energy efficiency involves tuning of plasma species, catalysts properties, and the reactor configurations to couple plasma and catalysts. These results provide unambiguous evidence of synergism between plasma and catalyst, the origins of that synergy for N2 oxidation, and a modeling approach to guide material selection and system optimization.