Reactive Force Field Development for Propane Dehydrogenation on Platinum Surfaces.

Propane dehydrogenation (PDH) is an on-purpose catalytic technology to produce propylene from propane that operates at high temperatures, 773-973 K. Several key industry players have been active in developing new catalysts and processes with improved carbon footprint and economics, where Pt-based catalysts have played a central role. The optimization of these catalytic systems through computational and atomistic simulations requires large-scale models that account for their reactivity and dynamic properties. To address this challenge, we developed a new reactive ReaxFF force field (2023-Pt/C/H) that enables large-scale simulations of PDH reactions catalyzed on Pt surfaces. The optimization of force-field parameters relies on a large training set of density functional theory (DFT) calculations of Pt-catalyzed PDH mechanism, including geometries, adsorption and relative energies of reaction intermediates, and key C-H and C-C bond-breaking/forming reaction steps on the Pt(111) surface. The internal validation supports the accuracy of the developed 2023-Pt/C/H force-field parameters, resulting in mean absolute errors (MAE) against DFT data of 14 and 12 kJ mol-1 for relative energies of intermediates and energy barriers, respectively. We demonstrated the applicability of the 2023-Pt/C/H force field with reactive molecular dynamics simulations of propane on different Pt surface topologies and temperatures. The simulations successfully model the formation of propene in the gas phase as well as competitive, unproductive reactions such as deep dehydrogenation and C-C bond cleavage that produce H, C1 and C2 adsorbed species responsible of catalytic deactivation of Pt surface. Results show the following reactivity order: Pt(111) < Pt(100) < Pt(211), and that for the stepped Pt(211) surface, propane activation occurs on low-coordinated Pt atoms at the steps. The measured selectivity as a function of surface topology follows the same trend as activity, the Pt(211) facet being the most selective. The 2023-Pt/C/H reactive force field can also describe the increase of reactivity with the temperature. From these simulations, we were able to estimate the Arrhenius activation energy, 73 kJ mol-1, whose value is close to those reported experimentally for PDH catalyzed by large, supported Pt nanoparticles . The newly developed 2023-Pt/C/H reactive force field can be used in subsequent investigations of different Pt topologies and of collective effects such as temperature, propane pressure, or H surface coverage.

Automated MUltiscale simulation environment.

Multiscale techniques integrating detailed atomistic information on materials and reactions to predict the performance of heterogeneous catalytic full-scale reactors have been suggested but lack seamless implementation. The largest challenges in the multiscale modeling of reactors can be grouped into two main categories: catalytic complexity and the difference between time and length scales of chemical and transport phenomena. Here we introduce the Automated MUltiscale Simulation Environment AMUSE, a workflow that starts from Density Functional Theory (DFT) data, automates the analysis of the reaction networks through graph theory, prepares it for microkinetic modeling, and subsequently integrates the results into a standard open-source Computational Fluid Dynamics (CFD) code. We demonstrate the capabilities of AMUSE by applying it to the unimolecular iso-propanol dehydrogenation reaction and then, increasing the complexity, to the pre-commercial Pd/In2O3 catalyst employed for the CO2 hydrogenation to methanol. The results show that AMUSE allows the computational investigation of heterogeneous catalytic reactions in a comprehensive way, providing essential information for catalyst design from the atomistic to the reactor scale level.

Metal-Support Interactions in Heterogeneous Catalysis: DFT Calculations on the Interaction of Copper Nanoparticles with Magnesium Oxide.

Oxide supports play an important role in enhancing the catalytic properties of transition metal nanoparticles in heterogeneous catalysis. How extensively interactions between the oxide support and the nanoparticles impact the electronic structure as well as the surface properties of the nanoparticles is hence of high interest. In this study, the influence of a magnesium oxide support on the properties of copper nanoparticles with different size, shape, and adsorption sites is investigated using density functional theory (DFT) calculations. By proposing simple models to reduce the cost of the calculations while maintaining the accuracy of the results, we show using the nonreducible oxide support MgO as an example that there is no significant influence of the MgO support on the electronic structure of the copper nanoparticles, with the exception of adsorption directly at the Cu-MgO interface. We also propose a simplified methodology that allows us to reduce the cost of the calculations, while the accuracy of the results is maintained. We demonstrate in addition that the Cu nanowire model corresponds well to the nanoparticle model, which reduces the computational cost even further.

Microfabrication Enables Quantification of Interfacial Activity in Thermal Catalysis.

A myriad of heterogeneous catalysts comprises multiple phases that need to be precisely structured to exert their maximal contribution to performance through electronic and structural interactions at their peripheries. In view of the nanometric, tridimensional, and anisotropic nature of these materials, a quantification of the interface and the impact of catalytic sites located there on the global performance is a highly challenging task. Consequently, the true origin of catalysis often remains subject of debate even for widely studied materials. Herein, an integrated strategy based on microfabricated catalysts and a custom-designed reactor is introduced for determining interfacial contributions upon catalytic activity assessment under process-relevant conditions, which can be easily implemented in the common catalysis research infrastructure and will accelerate the rational design of multicomponent heterogeneous catalysts for diverse applications. The method is validated by studying the high-pressure continuous-flow hydrogenation of CO and CO2 over Cu-ZnO catalysts, revealing linear correlations between the methanol formation rate and the interface between the metal and the oxide. Characterization of fresh and used materials points to the model catalyst preparation as the current challenge of the methodology that can be addressed through further development of nanotechnological tools.

Atomic-scale engineering of indium oxide promotion by palladium for methanol production via CO2 hydrogenation.

Metal promotion is broadly applied to enhance the performance of heterogeneous catalysts to fulfill industrial requirements. Still, generating and quantifying the effect of the promoter speciation that exclusively introduces desired properties and ensures proximity to or accommodation within the active site and durability upon reaction is very challenging. Recently, In2O3 was discovered as a highly selective and stable catalyst for green methanol production from CO2. Activity boosting by promotion with palladium, an efficient H2-splitter, was partially successful since palladium nanoparticles mediate the parasitic reverse water-gas shift reaction, reducing selectivity, and sinter or alloy with indium, limiting metal utilization and robustness. Here, we show that the precise palladium atoms architecture reached by controlled co-precipitation eliminates these limitations. Palladium atoms replacing indium atoms in the active In3O5 ensemble attract additional palladium atoms deposited onto the surface forming low-nuclearity clusters, which foster H2 activation and remain unaltered, enabling record productivities for 500 h.

Advances in the preparation of highly selective nanocatalysts for the semi-hydrogenation of alkynes using colloidal approaches.

In the last decade, the semi-hydrogenation of alkynes has experienced significant advances in terms of fine control of alkene selectivity and prevention of the over-hydrogenation reaction. Such advances have been possible to a large extent through the progress in colloidal methods for the preparation of metallic nanoparticles. The present review describes the contributions in the field of the selective hydrogenation of alkynes involving the utilization of colloidal methodologies. These approaches permit the fine modulation of several parameters affecting the catalytic performance of the active phase such as the particle size, the bulk and the surface structure and composition. For the transformation of liquid substrates, the nature of the stabilizers, the reducing agents and the metal precursors employed for the synthesis of the catalysts can be tuned to enhance the alkene selectivity. In contrast, in catalytic transformations of gaseous substrates, the presence of adsorbed species at the metal surface usually gives detrimental results while the interplay between the support and the active phase appears to be a more convincing alternative for catalyst tuning.

Effect of the Polymeric Stabilizer in the Aqueous Phase Fischer-Tropsch Synthesis Catalyzed by Colloidal Cobalt Nanocatalysts.

A series of small and well defined cobalt nanoparticles were synthesized by the chemical reduction of cobalt salts in water using NaBH4 as a reducing agent and using various polymeric stabilizers. The obtained nanocatalysts of similar mean diameters (ca. 2.6 nm) were fully characterized and tested in the aqueous phase Fischer-Tropsch Synthesis (AFTS). Interestingly, the nature and structure of the stabilizers used during the synthesis of the CoNPs affected the reduction degree of cobalt and the B-doping of these NPs and consequently, influenced the performance of these nanocatalysts in AFTS.

Operando Synchrotron X-ray Powder Diffraction and Modulated-Excitation Infrared Spectroscopy Elucidate the CO2 Promotion on a Commercial Methanol Synthesis Catalyst.

Optimal amounts of CO2 are added to syngas to boost the methanol synthesis rate on Cu-ZnO-Al2 O3 in the industrial process. The reason for CO2 promotion is not sufficiently understood at the particle level due to the catalyst complexity and the high demands of characterization under true reaction conditions. Herein, we applied operando synchrotron X-ray powder diffraction and modulated-excitation infrared spectroscopy on a commercial catalyst to gain insights into its morphology and surface chemistry. These studies unveiled that Cu and ZnO agglomerate and ZnO particles flatten under CO/H2 and/or CO2 /H2 . Under the optimal CO/CO2 /H2 mixture, sintering is prevented and ZnO crystals adopt an elongated shape due to the minimal presence of the H2 O byproduct, enhancing the water-gas shift activity and thus the methanol production. Our results provide a rationale to the CO2 promotion emphasizing the importance of advanced analytical methods to establish structure-performance relations in heterogeneous catalysis.

Indium Oxide as a Superior Catalyst for Methanol Synthesis by CO2 Hydrogenation.

Methanol synthesis by CO2 hydrogenation is attractive in view of avoiding the environmental implications associated with the production of the traditional syngas feedstock and mitigating global warming. However, there still is a lack of efficient catalysts for such alternative processes. Herein, we unveil the high activity, 100 % selectivity, and remarkable stability for 1000 h on stream of In2 O3 supported on ZrO2 under industrially relevant conditions. This strongly contrasts to the benchmark Cu-ZnO-Al2 O3 catalyst, which is unselective and experiences rapid deactivation. In-depth characterization of the In2 O3 -based materials points towards a mechanism rooted in the creation and annihilation of oxygen vacancies as active sites, whose amount can be modulated in situ by co-feeding CO and boosted through electronic interactions with the zirconia carrier. These results constitute a promising basis for the design of a prospective technology for sustainable methanol production.

First-principles elucidation of the surface chemistry of the C(2)H(x) (x = 0-6) adsorbate series on Fe(100).

Ab initio total-energy calculations of the elementary reaction steps leading to acetylene, ethylene and ethane formation and their decomposition on Fe(100) are described. Alongside the endothermicity of all the formation reactions, the crucial role played by adsorbed ethyl as main precursor towards both ethylene and ethane formation, characterises Fe(100) surface reactivity towards C(2)H(x) (x = 0-6) hydrocarbon formation in the low coverage limit. A comprehensive scheme based on three viable mechanisms towards ethyl formation on Fe(100), including methyl/methylene coupling, methyl/methylidyne coupling followed by one hydrogenation and methyl/carbon coupling followed by two hydrogenations, is the main result of this article.

A DFT study of the adsorption and dissociation of CO on sulfur-precovered Fe100.

Sulfur is known to be a poison to several catalytic reactions, e.g., the Fischer-Tropsch synthesis (FTS), in which it affects drastically the performance of both iron- and cobalt-based catalysts. However, despite the importance of this industrial process, little is known about what elementary steps are poisoned by sulfur. In the present article, we report, using density functional theory, the effect of sulfur on one of the most relevant reactions in the FTS: the dissociation of carbon monoxide over iron surfaces. We have studied the adsorption and dissociation of CO on Fe(100)-S-p(2 x 2) (theta(S) = 0.25 ML) and on Fe(100)-S-c(2 x 2) (theta(S) = 0.50 ML). We have found surface configurations that correlate well with the desorption features observed in temperature-programmed desorption mass spectroscopy. In addition, we have calculated the activation energy of CO dissociation on Fe(100)-S-p(2 x 2), which, interestingly, is very similar to the activation energy of CO dissociation on the sulfur-free Fe(100) surface. However, the sign of the reaction changes by the presence of sulfur; CO dissociation is highly exothermic on the sulfur-free Fe(100) surface, whereas on the Fe(100)-S-p(2 x 2) surface, it is slightly endothermic. Moreover, according to our results, the influence of sulfur in the CO dissociation seems to be short-ranged.

Atom-molecule interactions on transition metal surfaces: a DFT Study of CO and several atoms on Rh(100), Pd(100) and Ir(100).

Density functional theory (DFT) calculations have been performed to determine the interaction energy between a CO probe molecule and all atoms from the first three rows of the periodic table coadsorbed on Rh(100), Pd(100) and Ir(100) metal surfaces. Varying the coverage of CO or the coadsorbed atom proved to have a profound effect on the strength of the interaction energy. The general trend, however, is the same in all cases: the interaction energy becomes more repulsive when moving towards the right along a row of elements, and reaches a maximum somewhere in the middle of a row of elements. The absolute value of the interaction energy between an atom-CO pair ranges from about -0.40 eV (39 kJ mol(-1)) attraction to +0.70 eV (68 kJ mol(-1)) repulsion, depending on the coadsorbate, the metal and the coverage. The general trend in interaction energies seems to be a common characteristic for several transition metals.

Acetylene decomposition on Rh(100): theory and experiment.

The decomposition of acetylene on a Rh(100) single crystal was studied by a combination of experimental techniques [static secondary ion mass spectrometry (SSIMS), temperature-programmed desorption (TPD), and low-energy electron diffraction (LEED)] to gain insight into the reaction pathway and the nature of the reaction intermediates. The experimental techniques were combined with a computational approach using density functional theory (DFT). Acetylene adsorbs irreversibly on the Rh(100) surface and eventually decomposes to atomic carbon and gas-phase hydrogen. The combination of experimental and computational results enabled us to determine the most likely reaction pathway for the decomposition process.

The influence of promoters and poisons on carbon monoxide adsorption on Rh(100): a DFT study.

Density functional theory calculations were performed to determine the pairwise lateral interaction energies between carbon monoxide and coadsorbed elements from the first three rows of the periodic table on a Rh(100) surface. The atoms were placed in a c(2x2) arrangement of fourfold hollow sites and the carbon monoxide probe molecule in a p(2x2) arrangement, so that each CO molecule had four atoms as nearest neighbours. The alkali atoms show an attractive interaction with CO while the other atoms show a repulsive interaction. For second-row elements the maximum repulsion is at nitrogen and for third-row elements at sulphur. Attempts to correlate the interaction energies with properties of the system, such as electronegativity, distances, or change in work function, failed, which implies that each combination of adsorbates needs to be calculated separately.

Testing the pairwise additive potential approximation using DFT: coadsorption of CO and N on Rh (100).

The interaction between adsorbates is a key issue in surface science, because these interactions can influence strongly the properties of chemisorbed species with consequences for the thermodynamics and kinetics of surface processes. The simplest representation of adsorbate-adsorbate interactions is based on the assumption that all interactions are pairwise additive. This approach has been satisfactorily used in the modeling of temperature-programmed desorption (TPD) spectra using both continuum and Monte Carlo methods. However, the energies estimated within the pairwise approximation have never been compared to the energies calculated using density functional theory (DFT) methods. We demonstrate that the pairwise additive potential approximation is indeed a good representation of the adsorbate-adsorbate interactions, and that we do not need to include three-body interactions or higher-order terms to estimate the perturbation of the adsorption energy of an adsorbate by the presence of other coadsorbates. Moreover, we show for the first time how DFT can be used to explain the desorption features that one finds in TPD experiments, thus linking the TPD desorption features with actual microscopic configurations.