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In many catalytic reactions lateral interactions between adsorbates are believed to have a strong influence on the reaction rates. We apply a microkinetic model to explore the effect of lateral interactions and how to efficiently take them into account in a simple catalytic reaction. Three different approximations are investigated: site, mean-field, and quasichemical approximations. The obtained results are compared to accurate Monte Carlo numbers. In the end, we apply the approximations to a real catalytic reaction, namely, ammonia synthesis. [ABSTRACT FROM AUTHOR]

We have studied the dissociative chemisorption and scattering of N2 on and from Ru(0001), using a six-dimensional quasiclassical trajectory method. The potential energy surface, which depends on all the molecular degrees of freedom, has been built applying a modified Shepard interpolation method to a data set of results from density functional theory, employing the RPBE generalized gradient approximation. The frozen surface and Born-Oppenheimer [Ann. Phys. (Leipzig) 84, 457 (1927)] approximations were used, neglecting phonons and electron-hole pair excitations. Dissociative chemisorption probabilities are found to be very small even for translational energies much higher than the minimum reaction barrier, in good agreement with experiment. A comparison to previous low dimensional calculations shows the importance of taking into account the multidimensional effects of N2 rotation and translation parallel to the surface. The new calculations strongly suggest a much smaller role of nonadiabatic effects than previously assumed on the basis of a comparison between low dimensional results and experiments [J. Chem. Phys. 115, 9028 (2001)]. Also in agreement with experiment, our theoretical results show a strong dependence of reaction on the initial vibrational state. Computed angular scattering distributions and parallel translation energy distributions are in good agreement with experiments on scattering, but the theory overestimates vibrational and rotational excitations in scattering. [ABSTRACT FROM AUTHOR]

First-principles calculations were used to predict outcome of catalysis in atomic-scale industrial ammonia production over ruthenium catalysts. It was shown that overall rates of ammonia production can be determined by applying various levels of theory to a range of relevant elementary reaction steps such as [N.sub.2] dissociation, [H.sub.2] dissociation and hydrogenation of the intermediate reactants.

Review: 30 refs. [ABSTRACT FROM AUTHOR]

Complexes of quantum dots with molecular catalysts are promising building blocks for photo-catalytic applications. Herein, we report the formation of stable complexes between colloidal CdTe quantum dots (CQDs) and two synthesized structurally different cobalt porphyrin derivatives (CoPp and CoPm, with phenyl and mesityl groups attached at the meso positions, respectively) through a sulfur bridge. Using both spectroscopy and computational methods, we found that the porphyrin adopts a "flat" binding mode on the CQD surface. We observed the coordination of the Co center on the CQD surface. This coordination is stronger for CoPp than for CoPm, resulting in a larger red shift in the absorption band. In addition, we measured a four fold increase in the electron transfer (ET) rate from the CQD to CoPp compared to that with CoPm by a transient absorption study and the charge recombination extended to tens of nanoseconds or longer depending on the structure of the porphyrin periphery. A spectrum measured after the ET points to a loss of coordination between the Co and CQD in a CoP/CQD complex. The experimental results are in agreement with density functional theory calculation results on the CoP complexes on CdTe surfaces, pointing to the porphyrin preferring to align along the CQD surface in the ground state. The change of porphyrin alignment from flat alignment before the excitation to upright alignment after the ET is a likely cause for the extended lifetime of the charge-separated (CS) state, due to an increase in the CS distance. Furthermore, the spectrum of the CS state can be assigned to catalytically active Co I P, proposing the applicability of the complexes in CO 2 reduction.

Coinage metals Cu, Ag, and Au are essential for modern electronics and their recycling from waste materials is becoming increasingly important to guarantee the security of their supply. Designing new sustainable and selective procedures that would substitute currently used processes is crucial. Here, we describe an unprecedented approach for the sequential dissolution of single metals from Cu, Ag, and Au mixtures using biomass-derived ionic solvents and green oxidants. First, Cu can be selectively dissolved in the presence of Ag and Au with a choline chloride/urea/H 2 O 2 mixture, followed by the dissolution of Ag in lactic acid/H 2 O 2 . Finally, the metallic Au, which is not soluble in either solution above, is dissolved in choline chloride/urea/Oxone. Subsequently, the metals were simply and quantitatively recovered from dissolutions, and the solvents were recycled and reused. The applicability of the developed approach was demonstrated by recovering metals from electronic waste substrates such as printed circuit boards, gold fingers, and solar panels. The dissolution reactions and selectivity were explored with different analytical techniques and DFT calculations. We anticipate our approach will pave a new way for the contemporary and sustainable recycling of multi-metal waste substrates., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The proton-coupled electron transfer (PCET) mechanism of the oxygen reduction reaction (ORR) is a long-standing enigma in electrocatalysis. Despite decades of research, the factors determining the microscopic mechanism of ORR-PCET as a function of pH, electrolyte, and electrode potential remain unresolved, even on the prototypical Pt(111) surface. Herein, we integrate advanced experiments, simulations, and theory to uncover the mechanism of the cation effects on alkaline ORR on well-defined Pt(111). We unveil a dual-cation effect where cations simultaneously determine i) the active electrode surface by controlling the formation of Pt-O and Pt-OH overlayers and ii) the competition between inner- and outer-sphere PCET steps. The cation-dependent transition from Pt-O to Pt-OH determines the ORR mechanism, activity, and selectivity. These findings provide direct evidence that the electrolyte affects the ORR mechanism and performance, with important consequences for the practical design of electrochemical systems and computational catalyst screening studies. Our work highlights the importance of complementary insight from experiments and simulations to understand how different components of the electrochemical interface contribute to electrocatalytic processes., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The underlying mechanism of cation effects on CO 2 RR remains debated. Herein, we study cation effects by simulating both outer-sphere electron transfer (OS-ET) and inner-sphere electron transfer (IS-ET) pathways during CO 2 RR via constrained density functional theory molecular dynamics (cDFT-MD) and slow-growth DFT-MD (SG-DFT-MD), respectively. Our results show without any cations, only OS-ET is feasible with a barrier of 1.21 eV. In the presence of K + (Li + ), OS-ET shows a very high barrier of 2.93 eV (4.15 eV) thus being prohibited. However, cations promote CO 2 activation through IS-ET with the barrier of only 0.61 eV (K + ) and 0.91 eV (Li + ), generating the key intermediate (adsorbed CO[Formula: see text]). Without cations, CO 2 -to-CO[Formula: see text](ads) conversion cannot proceed. Our findings reveal cation effects arise from short-range Coulomb interactions with reaction intermediates. These results disclose that cations modulate the inner- and outer-sphere pathways of CO 2 RR, offering substantial insights on the cation specificity in the initial CO 2 RR steps., (© 2023. The Author(s).)

Density functional theory-based molecular dynamics (DFT-MD) has been widely used for studying the chemistry of heterogeneous interfacial systems under operational conditions. We report frequently overlooked errors in thermostated or constant-temperature DFT-MD simulations applied to study (electro)catalytic chemistry. Our results demonstrate that commonly used thermostats such as Nosé-Hoover, Berendsen, and simple velocity-rescaling methods fail to provide a reliable temperature description for systems considered. Instead, nonconstant temperatures and large temperature gradients within the different parts of the system are observed. The errors are not a "feature" of any particular code but are present in several ab initio molecular dynamics implementations. This uneven temperature distribution, due to inadequate thermostatting, is well-known in the classical MD community, where it is ascribed to the failure in kinetic energy equipartition among different degrees of freedom in heterogeneous systems (Harvey et al . J. Comput. Chem. 1998, 726-740) and termed the flying ice cube effect. We provide tantamount evidence that interfacial systems are susceptible to substantial flying ice cube effects and demonstrate that the traditional Nosé-Hoover and Berendsen thermostats should be applied with care when simulating, for example, catalytic properties or structures of solvated interfaces and supported clusters. We conclude that the flying ice cube effect in these systems can be conveniently avoided using Langevin dynamics.

CO 2 adsorption and activation on a catalyst are key elementary steps for CO 2 conversion to various valuable products. In the present computational study, we screened different Cu-ZrO 2 interface structures and analyzed the influence of the interface structure on CO 2 binding strength using density functional theory calculations. Our results demonstrate that a Cu nanorod favors one position on both tetragonal and monoclinic ZrO 2 surfaces, where the bottom Cu atoms are placed close to the lattice oxygens. In agreement with previous calculations, we find that CO 2 prefers a bent bidentate configuration at the Cu-ZrO 2 interface and the molecule is clearly activated being negatively charged. Straining of the Cu nanorod influences CO 2 adsorption energy but does not change the preferred nanorod position on zirconia. Altogether, our results highlight that CO 2 adsorption and activation depend sensitively on the chemical composition and atomic structure of the interface used in the calculations. This structure sensitivity may potentially impact further catalytic steps and the overall computed reactivity profile.

Atomically precise metal nanoclusters, stabilized and functionalized by organic ligands, are emerging nanomaterials with potential applications in plasmonics, nano-electronics, bio-imaging, nanocatalysis, and as therapeutic agents or drug carriers in nanomedicine. The ligand layer has an important role in modifying the physico-chemical properties of the clusters and in defining the interactions between the clusters and the environment. While this role is well recognized from a great deal of experimental studies, there is very little theoretical information on dynamical processes within the layer itself. Here, we have performed extensive molecular dynamics simulations, with forces calculated from the density functional theory, to investigate thermal stability and dynamics of the ligand layer of the meta-mercaptobenzoic acid (m-MBA) protected Au68 and Au144 nanoclusters, which are the first two gold nanoclusters structurally solved to atomic precision by electron microscopy [Azubel et al., Science, 2014, 345, 909 and ACS Nano, 2017, 11, 11866]. We visualize and analyze dynamics of three distinct non-covalent interactions, viz., ligand-ligand hydrogen bonding, metal-ligand O[double bond, length as m-dash]C-OHAu interaction, and metal-ligand Ph(π)Au interaction. We discuss their relevance for defining, at the same time, the dynamic stability and reactivity of the cluster. These interactions promote the possibility of ligand addition reactions for bio-functionalization or allow the protected cluster to act as a catalyst where active sites are dynamically accessible inside the ligand layer.

Controlling the size and uniformity of metal clusters with atomic precision is essential for fine-tuning their catalytic properties, however for clusters deposited on supports, such control is challenging. Here, by combining X-ray absorption spectroscopy and density functional theory calculations, it is shown that supports play a crucial role in the evolution of monolayer-protected clusters into catalysts. Based on the acidic nature of the support, cluster-support interactions lead either to fragmentation of the cluster into isolated Au-ligand species or ligand-free metallic Au 0 clusters. On Lewis acidic supports that bind metals strongly, the latter transformation occurs while preserving the original size of the metal cluster, as demonstrated for various Au n sizes. These findings underline the role of the support in the design of supported catalysts and represent an important step toward the synthesis of atomically precise supported nanomaterials with tailored physico-chemical properties., (© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Water dissociation is an important reaction involved in many industrial processes. In this computational study, the dissociation of water is used as a model reaction for probing the activity of interfacial sites of globally optimized ZrO 2 supported Pt and Rh clusters under the framework of density functional theory. Our findings demonstrate that the perimeter sites of these small clusters can activate water, but the dissociation behavior varies considerably between sites. It is shown that the studied clusters break scaling relationships for water dissociation, suggesting that these catalysts may achieve activities beyond the maximum imposed by such relations. Furthermore, we observed large differences in the thermodynamics of the water dissociation reaction between global minimum and near-global minimum isomers of the clusters. Overall, our results highlight the uniqueness of interfacial sites in catalytic reactions and the need for developing new concepts and tools to deal with the associated complexity.

Copper-hydrides are known catalysts for several technologically important reactions such as hydrogenation of CO, hydroamination of alkenes and alkynes, and chemoselective hydrogenation of unsaturated ketones to unsaturated alcohols. Stabilizing copper-based particles by ligand chemistry to nanometer scale is an appealing route to make active catalysts with optimized material economy; however, it has been long believed that the ligand-metal interface, particularly if sulfur-containing thiols are used as stabilizing agent, may poison the catalyst. We report here a discovery of an ambient-stable thiolate-protected copper-hydride nanocluster [Cu 25 H 10 (SPhCl 2 ) 18 ] 3- that readily catalyzes hydrogenation of ketones to alcohols in mild conditions. A full experimental and theoretical characterization of its atomic and electronic structure shows that the 10 hydrides are instrumental for the stability of the nanocluster and are in an active role being continuously consumed and replenished in the hydrogenation reaction. Density functional theory computations suggest, backed up by the experimental evidence, that the hydrogenation takes place only around a single site of the 10 hydride locations, rendering the [Cu 25 H 10 (SPhCl 2 ) 18 ] 3- one of the first nanocatalysts whose structure and catalytic functions are characterized fully to atomic precision. Understanding of a working catalyst at the atomistic level helps to optimize its properties and provides fundamental insights into the controversial issue of how a stable, ligand-passivated, metal-containing nanocluster can be at the same time an active catalyst.