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First-Principles Microkinetic Model for Ammonia Synthesis on Fe(110) under Nonequilibrium Programmable Heating and Quenching Operation
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From microkinetic model to process: understanding the role of the boron nitride surface and gas phase chemistry in the oxidative dehydrogenation of propane
In the oxidative dehydrogenation of propane over boron nitride, propylene selectivity is lost due to unselective gas-phase chemistry.
Coupling Microkinetics with Continuum Transport Models to Understand Electrochemical CO 2 Reduction in Flow Reactors
Not Available
REFINING AUTOMATICALLY GENERATED MICROKINETIC MECHANISMS IN A WORKFLOW.
Abstract not provided.
A study of microkinetic adjustments required to match shock wave experiments and Monte Carlo Direct Simulation for a wide Mach number range
Shock wave thickness predictions from Monte Carlo Direct Simulations, using differential scattering and the Maitland-Smith-Aziz interatomic potential, underpredict experiments as shock Mach numbers increase above about 4. Examination of several sources of data has indicated that at relatively high energies the repulsive portion of accepted potentials such as the Maitland-Smith-Aziz may be too steep. An Exponential-6 potential due to Ross, based on high energy molecular beam scattering data and shock velocity measurements in liquid argon, has been combined with the lower energy portion of the Maitland-Smith-Aziz potential. When this hybrid potential is used in Monte Carlo Direct Simulations, agreement with experiments is improved over the previous predictions using the pure Maitland-Smith-Aziz form.
Unraveling the CO Oxidation Mechanism over Highly Dispersed Pt Single Atom on Anatase TiO 2 (101)
Catalysts with noble metals deposited as single atoms on metal oxide supports have recently been studied extensively due to their maximized metal utilization and potential for performing difficult chemical conversions owing to their unique electronic properties. Understanding of the reaction mechanisms on supported single-metal atoms is still limited but is highly important for designing more efficient catalysts. In this study, we report the complexity of the CO oxidation reaction mechanism on Pt single atoms supported on anatase TiO 2 (Pt SA /a-TiO 2 ) by coupling density functional theory (DFT) calculations and microkinetic analysis with kinetic measurements, in situ/operando infrared, and X-ray absorption spectroscopies. Starting from the adsorbed Pt SA occupying an O vacancy induced by reductive pretreatment, we show that CO oxidation follows a complex mechanism consisting of initiation steps to reorganize the active site and multibranch reactive cycles, with the Pt SA /a-TiO 2 catalyst not returning to its initial configuration. The initiation step consists of CO and O 2 adsorption healing the O vacancy, followed by CO oxidation using gas-phase CO to form Pt(CO). The reactive cycle alternates O 2 adsorption and dissociation to oxidize the catalyst to Pt(O)(O)(CO) and branching pathways of competing Langmuir–Hinshelwood (LH)- or Eley–Rideal (ER)-type CO oxidation steps to reduce it again to Pt(CO). In situ/operando infrared experiments, including cryogenic CO adsorption and isotopic CO exchange, confirm the combined involvement of strongly adsorbed CO and gas-phase CO in an Eley–Rideal step along the reaction cycle. Microkinetic modeling shows that Pt single atoms are present in a mixture of Pt(CO), Pt(CO)(O 2 ), Pt(O)(CO)(O 2 ), and Pt(CO)(CO 3 ) structures as the main intermediates during steady-state CO oxidation, all having the C–O vibrational stretch close to the experimentally observed value of 2115 cm –1 . Microkinetic modeling also shows that the fractional orders of CO and O 2 measured experimentally originate from multiple steps with a high degree of rate control and not from a simple competitive adsorption. The results demonstrate the complex reaction pathways that even CO oxidation on a simple single-atom system can follow, providing mechanistic insights for designing efficient Pt-based single-atom catalysts. Here, we further show that microkinetic modeling results are sensitive to changes in energies of intermediate and transition states within errors of density functional theory, which can ultimately lead to incorrect conclusions regarding the reaction pathways and most abundant reaction intermediates if not accounted for by experiments.
Kinetics of low-temperature methane activation on IrO 2 (1 1 0): Role of local surface hydroxide species
The ability of the IrO 2 (1 1 0) surface to promote CH 4 activation at low temperatures (~150 K) suggests possibilities for developing IrO 2 -based catalysts to selectively convert light alkanes to high-value chemicals. In this study, we present experimental results and microkinetic simulations, based on density functional theory (DFT) calculations, of temperature programmed reaction spectra (TPRS) obtained for CH 4 σ-complexes adsorbed on IrO 2 (1 1 0), and focus on clarifying how surface OH groups modify the branching between CH 4 desorption, activation and subsequent reactions during TPRS. Our DFT results predict that surface OH groups strongly destabilize CH 4 σ-complexes on IrO 2 (1 1 0) in addition to deactivating surface O-atoms that are needed to achieve CH 4 activation at low temperature. We demonstrate that a microkinetic model that incorporates the influence of surface OH groups on the CH 4 binding and reactivity reproduces experimental TPRS results which show that adsorbed CH 4 σ-complexes preferentially dissociate at low CH 4 coverage, but that an increasing fraction of the adsorbed CH 4 desorbs at low temperature (~120 K) with increasing initial CH 4 or H coverage. The simulations reveal that low-temperature CH4 desorption during TPRS arises primarily from CH 4 σ-complexes that are kinetically-trapped between adjacent surface OH groups, and are thus destabilized and unable to access reactive O-atoms. In addition, when the effect of adjacent OH groups is incorporated we find that the PBE-D3 functional incorporating dispersion provides CH 4 binding energies that agree more closely with that obtained from the TPRS experiments. Overall, our results demonstrate that the local effect of adjacent OH groups must be incorporated into any microkinetic models to properly capture the selectivity between extensive and partial oxidation in alkane conversion on IrO 2 (1 1 0) under reaction conditions.
Ethane Dehydrogenation on Single and Dual Centers of Ga-modified γ-Al 2 O 3
Density-functional theory calculations and microkinetic analysis are used to investigate the efficacy of Ga-modified γ-Al 2 O 3 (110) surfaces for the catalytic dehydrogenation of ethane and elucidate the synergy between Ga and Al sites. The model surfaces are modified by either Ga grafting or doping. We consider and analyze numerous active sites and rank them using microkinetic analysis. The kinetic parameters obtained from microkinetic modelling are compared with experimental values for ethane dehydrogenation over Ga 2 O 3 -Al 2 O 3 mixed oxides prepared by co-precipitation. The dominant reaction pathway proceeds via heterolytic C-H bond dissociation to a surface proton and a metal-carbanion intermediate that undergoes β-hydride elimination. We find that grafted Ga sites are catalytically inactive. In contrast, Ga-doped sites exhibit fivefold enhancement in catalytic activity when compared to the sites on pristine Al 2 O 3 , owed to the synergy between neighboring AlIII and GaIV sites. Furthermore, we model and investigate the effect of surface hydroxylation, demonstrate how surface water interferes with the aforementioned synergy between AlIII and GaIV sites and discuss the implications for the catalytic activity of the modified surfaces. Here, an increase in the partial pressure of H 2 O significantly increases the apparent activation energies of dehydrogenation and interestingly changes the most active site.
Hydrogen Dissociation Controls 1-Hexyne Selective Hydrogenation on Dilute Pd-in-Au Catalysts
Increasing the selectivity of the catalytic hydrogenation of alkynes to alkenes is of major importance for the processing of petrochemicals and the production of fine chemicals. Achieving high selectivity for alkene formation at high conversions, however, remains a long-standing challenge in heterogeneous catalysis. Here, the mechanism and origin of the high selectivity of dilute Pd-in-Au catalysts has been studied by a combination of first-principles calculations, microkinetic simulations, and isotopic exchange hydrogenation experiments using Pd 0.04 Au 0.96 nanoparticles embedded in raspberry colloid-templated silica. The Pd is predominantly in the form of isolated atoms, only surrounded by Au atoms, based on prior studies. The simulations indicate that the rate-limiting process for 1-hexyne hydrogenation on Pd monomers in Au(111) is H 2 dissociation, which has a large free energy barrier of 0.86 eV at 363 K and 0.2 bar of H 2 . The C–H bond formation steps, on the other hand, proceed with lower barriers, which contrasts with previous studies of extended Pd catalysts. The microkinetic simulations identify the sizable H 2 dissociation barrier and the small barrier for the hydrogenation of 1-hexyne as key factors that lead to a high selectivity for the production of 1-hexene from 1-hexyne, even at high conversion. The unconventional H 2 dissociation limiting process in combination with the low coverage of weakly bound hydrocarbon intermediates explains the near-zero order of 1-hexyne found experimentally. Furthermore, the partial hydrogenation of 1-hexyne to form 1-hexene is shown to be an irreversible process from our isotopic exchange hydrogenation experiments and is explained by the strongly exothermic nature of the reaction. Diluting active species, like Pd, in a less active host metal, like Au, hence appears promising as a means of tuning the binding energy of reactants and altering reaction profiles, leading to distinct kinetic behavior for an optimal catalytic activity and selectivity. Furthermore, the combination of microkinetic modeling, density functional theory calculations, and isotopic exchange experiments is thus demonstrated to be an effective approach to modeling important catalytic phenomena.
Enhanced Selectivity for C 2 H 4 Production from C 2 H 6 on Partially Chlorinated IrO 2 (110) Surfaces
Modifying metal oxide surfaces to limit their oxidizing activity can provide a means of improving catalytic selectivity toward the partial oxidation of light alkanes. Here, in this study, we investigated the oxidation of C 2 H 6 on Cl-modified IrO 2 (110) surfaces using temperature-programmed reaction spectroscopy (TPRS) and first-principles microkinetic modeling. We find that substituting Cl for O in the IrO 2 (110) surface enhances the selectivity for C 2 H 6 conversion to C 2 H 4 during TPRS by suppressing extensive oxidation to CO x products, while also either enhancing C 2 H 4 production or altering it to a lesser extent, depending on the initial C 2 H 6 coverage. The C 2 H 4 selectivity increased with increasing C 2 H 6 and Cl coverage, but reached a limiting value below 50%. The Cl coverage changed negligibly during C 2 H 6 oxidation, and the surface reactivity decreased only marginally for Cl coverages up to 0.5 ML (monolayer). TPRS simulations using a microkinetic model predict C 2 H 4 and CO x product yields as a function of the Cl coverage that agree closely with the experimental results. According to the simulations, C 2 H 6 conversion to C 2 H 4 occurs on Cl-IrO 2 (110) by the hydrogenation of C 2 H 3 * species adsorbed in blocked states, in which neighboring sites are occupied only by unreactive HO and Cl species. The microkinetic modeling shows that H-hopping away from surface HO groups provides a relatively efficient route for C 2 H 3 * to escape blocked configurations and dehydrogenate, and that this process can limit the C 2 H 4 selectivity on Cl-IrO 2 (110) under the conditions studied. Overall, our results demonstrate that Cl-substitution into IrO 2 (110) enhances the selectivity for C 2 H 4 production from C 2 H 6 and provides insights into the reaction mechanism that can guide strategies to further improve the C 2 H 4 selectivity.
A self-adjusting platinum surface for acetone hydrogenation
We show that platinum displays a self-adjusting surface that is active for the hydrogenation of acetone over a wide range of reaction conditions. Reaction kinetics measurements under steady-state and transient conditions at temperatures near 350 K, electronic structure calculations employing density-functional theory, and microkinetic modeling were employed to study this behavior over supported platinum catalysts. The importance of surface coverage effects was highlighted by evaluating the transient response of isopropanol formation following either removal of the reactant ketone from the feed, or its substitution with a similarly structured species. The extent to which adsorbed intermediates that lead to the formation of isopropanol were removed from the catalytic surface was observed to be higher following ketone substitution in comparison to its removal, indicating that surface species leading to isopropanol become more strongly adsorbed on the surface as the coverage decreases during the desorption experiment. This phenomenon occurs as a result of adsorbate–adsorbate repulsive interactions on the catalyst surface which adjust with respect to the reaction conditions. Reaction kinetics parameters obtained experimentally were in agreement with those predicted by microkinetic modeling when the binding energies, activation energies, and entropies of adsorbed species and transition states were expressed as a function of surface coverage of the most abundant surface intermediate (MASI, C 3 H 6 OH*). It is important that these effects of surface coverage be incorporated dynamically in the microkinetic model (e.g., using the Bragg–Williams approximation) to describe the experimental data over a wide range of acetone partial pressures.
Rhodium Single–Atom Catalysts on Titania for Reverse Water Gas Shift Reaction Explored by First Principles Mechanistic Analysis and Compared to Nanoclusters
The thermocatalytic reduction of CO2 by H2 often proceeds via two competing reaction mechanisms—the reverse water gas shift reaction (rWGSR, CO2 + H2 ⇌ CO + H2O) and methanation (CO2 + 4H2 ⇌ CH4 + 2H2O). Atomically dispersed Rh1 catalysts on TiO2 show high selectivity toward the rWGSR compared with larger Rh nanoclusters, but the origin of this size-dependent selectivity has not been fully explained. Here we report density functional theory (DFT) calculations and microkinetic simulations that clarify the Rh1 active sites and rWGSR pathway on anatase TiO2(101), as well as the high rWGSR selectivity of Rh1 compared with supported Rhx (x = 2–8 atoms) nanoclusters. DFT-computed formation energies, vibrational frequency analysis, and microkinetic modeling suggest three plausible active sites: Rh1 on titania (Rh1/TiO2(101)), Rh1 with a nearby hydroxyl group (Rh1OH/TiO2(101)), and Rh1 near an oxygen vacancy at a three-fold coordinated site (Rh1 near O3cvac). Predicted turnover frequencies and apparent activation barriers for Rh1 indicate a faster reaction involving CO2 dissociation assisted by a support oxygen vacancy via Rh1 near O3cvac, as well as slower reactions involving Rh1OH/TiO2(101) or Rh1/TiO2(101) through a COOH intermediate. Furthermore, these Rh1 sites are selective toward CO rather than CH4 because of the weak adsorption of CO, large barrier for C-O bond dissociation, and the lack of nearby metal sites for H2 dissociation, in contrast to Rhx nanoclusters, including Rh2 dimers.
Effects of water on the kinetics of acetone hydrogenation over Pt and Ru catalysts
We employed an approach combining reaction kinetics measurements at steady state conditions, electronic structure calculations employing density functional theory, and microkinetic modeling for acetone hydrogenation to provide insights into the effects of water on metal catalyst surfaces for the hydrogenation of oxygenates over a wide range of reaction conditions. Elucidation of the repulsive interactions due to adsorbed water molecules at various reaction conditions provides a basis to formulate rate expressions for heterogeneous catalytic processes of biomass oxygenates. Reaction kinetics experiments were carried out at partial pressures of H 2 , acetone, water and helium in the range of 0.51-0.79, 0.02-0.13, 0.08-0.23, 0-0.28 atm, respectively. We show that the addition of water enhances the hydrogenation rate at 353 K and 1 atm on oxophilic metal catalysts such as Ru/C, whereas the same promotional effect of water is not observed for Pt-based catalysts. Microkinetic model predictions for the hydrogenation of acetone on Ru in the absence and presence of water, using enthalpies and entropies obtained from DFT calculations, were in agreement with the experimentally observed reaction orders and activation barriers. The model shows that a water-assisted hydroxypropyl path is expected to be the favored path on Ru with a rate-determining step of H-OH-mediated hydrogenation of C 3 H 6 OH (i.e., the hydroxypropyl intermediate formed by H 2 O-mediated initial hydrogenation of acetone) to produce isopropyl alcohol (IPA). Furthermore, hydrogen, acetone, hydroxypropyl intermediate and hydroxyl species were predicted to be abundant on the Ru surface with a high coverage of nearly 85%. Lastly, the combined studies of computational and experimental catalysis on hydrogenation reactions help to elucidate the mechanistic role of water on metal catalyzed reactions for producing chemical building blocks from biomass-derived oxygenates.