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The origin of the enantiospecific decomposition of L- and D-tartaric acid on chiral Cu surfaces is elucidated on a structure-spread domed Cu(110) crystal by spatially resolved XPS and atomic-scale STM imaging. Extensive enantiospecific surface restructuring leads to the formation of surfaces vicinal to Cu(14,17,2) which are responsible for the enantiospecificity.
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We demonstrate that single-atom alloy catalysts can be made by exposing physical mixtures of monometallic supported Cu and Pd catalysts to vinyl acetate (VA) synthesis reaction conditions. This reaction induces the formation of mobile clusters of metal diacetate species that drive extensive metal nanoparticle restructuring, leading to atomic dispersion of the precious metal, smaller nanoparticle sizes than the parent catalysts, and high activity and selectivity for both VA synthesis and ethanol dehydrogenation reactions. This approach is scalable and appears to be generalizable to other alloy catalysts.
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Benzene, a high-volume chemical, is produced from larger molecules by inefficient and environmentally harmful processes. Recent changes in hydrocarbon feedstocks from oil to gas motivate research into small molecule upgrading. For example, the cyclotrimerization of acetylene reaction has been demonstrated on Pd, Pd alloy, and Cu surfaces and catalysts, but they are not 100% selective to benzene. We discovered that acetylene can be converted to benzene with 100% selectivity on the Ag(111) surface. Our temperature programmed desorption experiments reveal a threshold acetylene surface coverage of â¼one monolayer, above which benzene is formed. Furthermore, additional layers of acetylene increase the amount of benzene produced while retaining 100% selectivity. Our scanning tunneling microscopy images show that acetylene prefers square packing on the Ag(111) surface at low coverages, which converts to hexagonal packing when acetylene multilayers are present. Within this denser layer, features consistent with the proposed C4 intermediates of the cyclotrimerization process are observed. Density functional theory calculations demonstrate that the barrier for forming the crucial C4 intermediate generally decreases as acetylene multilayers are formed because the multilayer interacts more strongly with the surface in the transition state than in the initial state. Given that acetylene desorbs from Ag(111) at â¼90 K, the C4 intermediate on the pathway to benzene must be formed below this temperature, implying that if Ag-based heterogeneous catalysts can be run at sufficiently high pressure and low enough temperature, efficient and selective trimerization of acetylene to benzene may be possible.
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The identification of thermodynamic descriptors of catalytic performance is essential for the rational design of heterogeneous catalysts. Here, we investigate how spillover energy, a descriptor quantifying whether intermediates are more stable at the dopant or host metal sites, can be used to design single-atom alloys (SAAs) for formic acid dehydrogenation. Using theoretical calculations, we identify NiCu as a SAA with favorable spillover energy and demonstrate that formate intermediates produced after the initial O-H activation are more stable at Ni sites where rate-determining C-H activation occurs. Surface science experiments demonstrated that NiCu(111) SAAs are more reactive than Cu(111) while they still follow the formate reaction pathway. However, reactor studies of silica-supported NiCu SAA nanoparticles showed only a modest improvement over Cu resulting from surface coverage effects. Overall, this study demonstrates the potential of engineering SAAs using spillover energy as a design parameter and highlights the importance of adsorbate-adsorbate interactions under steady-state operation.
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Single-atom catalysts have received significant attention for their ability to enable highly selective reactions. However, many reactions require more than one adjacent site to align reactants or break specific bonds. For example, breaking a C-O or O-H bond may be facilitated by a dual site containing an oxophilic element and a carbophilic or "hydrogenphilic" element that binds each molecular fragment. However, design of stable and well-defined dual-atom sites with desirable reactivity is difficult due to the complexity of multicomponent catalytic surfaces. Here, we describe a new type of dual-atom system, trimetallic dual-atom alloys, which were designed via computation of the alloying energetics. Through a broad computational screening we discovered that Pt-Cr dimers embedded in Ag(111) can be formed by virtue of the negative mixing enthalpy of Pt and Cr in Ag and the favorable interaction between Pt and Cr. These dual-atom alloy sites were then realized experimentally through surface science experiments that enabled the active sites to be imaged and their reactivity related to their atomic-scale structure. Specifically, Pt-Cr sites in Ag(111) can convert ethanol, whereas PtAg and CrAg are unreactive toward ethanol. Calculations show that the oxophilic Cr atom and the hydrogenphilic Pt atom act synergistically to break the O-H bond. Furthermore, ensembles with more than one Cr atom, present at higher dopant loadings, produce ethylene. Our calculations have identified many other thermodynamically favorable dual-atom alloy sites, and hence this work highlights a new class of materials that should offer new and useful chemical reactivity beyond the single-atom paradigm.
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Recent experiments have demonstrated an intriguing phenomenon in which adsorption of a nonracemic mixture of aspartic acid (Asp) enantiomers onto an achiral Cu(111) metal surface leads to autoamplification of surface enantiomeric excess, ees, to values well above those of the impinging gas mixtures, eeg. This is particularly interesting because it demonstrates that a slightly nonracemic mixture of enantiomers can be further purified simply by adsorption onto an achiral surface. In this work, we seek a deeper understanding of this phenomena and apply scanning tunneling microscopy to image the overlayer structures formed by mixed monolayers of d- and l-Asp on Cu(111) over the full range of surface enantiomeric excess; ees = -1 (pure l-Asp) through ees = 0 (racemic dl-Asp) to ees = 1 (pure d-Asp). Both enantiomers of three chiral monolayer structures are observed. One is a conglomerate (enantiomerically pure), another is a racemate (equimolar mixture of d- and l-Asp); however, the third structure accommodates both enantiomers in a 2:1 ratio. Such solid phases of enantiomer mixtures with nonracemic composition are rare in 3D crystals of enantiomers. We argue that, in 2D, the formation of chiral defects in a lattice of one enantiomer is easier than in 3D, simply because the stress associated with the chiral defect in a 2D monolayer of the opposite enantiomer can be dissipated by strain into the space above the surface.
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Single-atom alloys (SAAs) have drawn significant attention in recent years due to their excellent catalytic properties. Controlling the geometry and electronic structure of this type of localized catalytic active site is of fundamental and technological importance. Dual-atom alloys (DAAs) consisting of a heterometallic dimer embedded in the surface layer of a metal host would bring increased tunability and a larger active site, as compared to SAAs. Here, we use computational studies to show that DAAs allow tuning of the active site electronic structure and reactivity. Interestingly, combining two SAAs into a dual-atom site can result in molecular-like hybridization by virtue of the free-atom-like electronic d states exhibited by many SAAs. DAAs can inherit the weak d-d interaction between dopants and hosts from the constituent SAAs, but exhibit new electronic and reactive properties due to dopant-dopant interactions in the DAA. We identify many heterometallic DAAs that we predict to be more stable than either the constituent SAAs or homometallic dual-atom sites of each dopant. We also show how both electronic and ensemble effects can modify the strength of CO adsorption. Because of the molecular-like interactions that can occur, DAAs require a different approach for tuning chemical properties compared to what is used for previous classes of alloys. This work provides insights into the unique catalytic properties of DAAs, and opens up new possibilities for tailoring localized and well-defined catalytic active sites for optimal reaction pathways.
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The relative stability of reactive intermediates and reactants on a surface, which dictates the rate and selectivity of catalytic reactions in both gas and liquid phases, is dependent on numerous factors. One well-established example is secondary interactions, such as van der Waals interactions between the catalyst surface and the pendant group of the intermediate, which can govern reaction selectivity for coupling reactions. Herein, we directly show that interactions between adsorbed reaction intermediates and reactant molecules increase the binding energy and affects the geometrical arrangement of coadsorbed reactant/solvent molecules. Evidence for this effect is demonstrated for the oxidative coupling reaction of methanol on a single crystal gold (Au(110)) surface. The rate-limiting reaction intermediate for methanol self-coupling, methoxy, stabilizes excess adsorbed methanol, which desorbs as a result of beta-hydride decomposition of the adsorbed methoxy. Direct molecular-scale imaging by scanning tunneling microscopy, supplemented by density functional theory, revealed interactive structures formed by methoxy and coadsorbed methanol. Interactions between the methoxy intermediate and coadsorbed methanol stabilizes a hydrogen-bonded network comprising methoxy and methanol by a minimum of 0.13 eV per methanol molecule. Inclusion of such interactions between reaction intermediates and coadsorbed reactants and solvents in kinetic models is important for microkinetic analysis of the rates and selectivities of catalytic reactions in both the gas and liquid phases whenever appreciable coverages of species from the ambient phase exist.
Assuntos
Ouro , Metanol , Catálise , Etanol , Ouro/química , Hidrogênio , Metanol/química , Solventes/químicaRESUMO
Single-atom alloy catalysts combine catalytically active metal atoms, present as dopants, with the selectivity of coinage metal hosts. Determining whether adsorbates stick at the dopant or spill over onto the host is key to understanding catalytic mechanisms on these materials. Despite a growing body of work, simple descriptors for the prediction of spillover energies (SOEs), i.e., the relative stability of an adsorbate on the dopant versus the host site, are not yet available. Using Density Functional Theory (DFT) calculations on a large set of adsorbates, we identify the dopant charge and the SOE of carbon as suitable descriptors. Combining them into a linear surrogate model, we can reproduce DFT-computed SOEs within 0.06 eV mean absolute error. More importantly, our work provides an intuitive theoretical framework, based on the concepts of electrostatic interactions and covalency, that explains SOE trends and can guide the rational design of future single-atom alloy catalysts.
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Dicarbonyl species are ubiquitous on Rh/oxide catalysts and are known to form on Rh+ centers. However, dicarbonyl species have never been directly observed on single-atom alloys (SAAs) where the active site is metallic. Herein, using surface science and theoretical modeling, we provide evidence of dicarbonyl species at isolated Rh sites on a RhCu(100) SAA. This approach not only enables us to directly visualize dicarbonyl species at Rh sites but also demonstrates that the transition between the mono- and dicarbonyl configuration can be achieved by changing surface temperature and CO pressure. Density functional theory calculations further support the mono- and dicarbonyl assignments and provide evidence that these species should be stable on other SAA combinations. Together, these results provide a picture of the structure and energetics of both the mono- and dicarbonyl configurations on the RhCu(100) SAA surface and should aid with IR assignments on SAA nanoparticle catalysts.
Assuntos
Ligas , CatáliseRESUMO
Elucidation of reaction mechanisms and the geometric and electronic structure of the active sites themselves is a challenging, yet essential task in the design of new heterogeneous catalysts. Such investigations are best implemented via a multipronged approach that comprises ambient pressure catalysis, surface science, and theory. Herein, we employ this strategy to understand the workings of NiAu single-atom alloy (SAA) catalysts for the selective nonoxidative dehydrogenation of ethanol to acetaldehyde and hydrogen. The atomic dispersion of Ni is paramount for selective ethanol to acetaldehyde conversion, and we show that even the presence of small Ni ensembles in the Au surface results in the formation of undesirable byproducts via C-C scission. Spectroscopic, kinetic, and theoretical investigations of the reaction mechanism reveal that both C-H and O-H bond cleavage steps are kinetically relevant and single Ni atoms are confirmed as the active sites. X-ray absorption spectroscopy studies allow us to follow the charge of the Ni atoms in the Au host before, under, and after a reaction cycle. Specifically, in the pristine state the Ni atoms carry a partial positive charge that increases upon coordination to the electronegative oxygen in ethanol and decreases upon desorption. This type of oxidation state cycling during reaction is similar to the behavior of single-site homogeneous catalysts. Given the unique electronic structure of many single-site catalysts, such a combined approach in which the atomic-scale catalyst structure and charge state of the single atom dopant can be monitored as a function of its reactive environment is a key step toward developing structure-function relationships that inform the design of new catalysts.
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Single-atom alloys (SAAs) make up a special class of alloy surface catalysts that offer well-defined, isolated active sites in a more inert metal host. The dopant sites are generally assumed to have little or no influence on the properties of the host metal, and transport of chemical reactants and products to and from the dopant sites is generally assumed to be facile. Here, by performing density functional theory calculations and surface science experiments, we identify a new physical effect on SAA surfaces, whereby adsorption is destabilized by ≤300 meV on host sites within the perimeter of the reactive dopant site. We identify periodic trends for this behavior and demonstrate a zone of exclusion around the reactive sites for a range of adsorbates and combinations of host and dopant metals. Experiments confirm an increased barrier for diffusion of CO toward the dopant on a RhCu SAA. This effect offers new possibilities for understanding and designing active sites with tunable energetic landscapes surrounding them.
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Carbon-carbon coupling is an important step in many catalytic reactions, and performing sp3-sp3 carbon-carbon coupling heterogeneously is particularly challenging. It has been reported that PdAu single-atom alloy (SAA) model catalytic surfaces are able to selectively couple methyl groups, producing ethane from methyl iodide. Herein, we extend this study to NiAu SAAs and find that Ni atoms in Au are active for C-I cleavage and selective sp3-sp3 carbon-carbon coupling to produce ethane. Furthermore, we perform ab initio kinetic Monte Carlo simulations that include the effect of the iodine atom, which was previously considered a bystander species. We find that model NiAu surfaces exhibit a similar chemistry to PdAu, but the reason for the similarity is due to the role the iodine atoms play in terms of blocking the Ni atom active sites. Specifically, on NiAu SAAs, the iodine atoms outcompete the methyl groups for occupancy of the Ni sites leaving the Me groups on Au, while on PdAu SAAs, the binding strengths of methyl groups and iodine atoms at the Pd atom active site are more similar. These simulations shed light on the mechanism of this important sp3-sp3 carbon-carbon coupling chemistry on SAAs. Furthermore, we discuss the effect of the iodine atoms on the reaction energetics and make an analogy between the effect of iodine as an active site blocker on this model heterogeneous catalyst and homogeneous catalysts in which ligands must detach in order for the active site to be accessed by the reactants.
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The formation of a two-phase surface molecular overlayer that transitions from isolated propene molecules to a highly ordered 1D chain structure on Cu(111) is elucidated through combined high-resolution STM imaging and DFT-based calculations. These models reveal how disordered molecules present in-between the 1D chains stabilizes the system as a whole.
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The atomic scale structure of the active sites in heterogeneous catalysts is central to their reactivity and selectivity. Therefore, understanding active site stability and evolution under different reaction conditions is key to the design of efficient and robust catalysts. Herein we describe theoretical calculations which predict that carbon monoxide can be used to stabilize different active site geometries in bimetallic alloys and then demonstrate experimentally that the same PdAu bimetallic catalyst can be transitioned between a single-atom alloy and a Pd cluster phase. Each state of the catalyst exhibits distinct selectivity for the dehydrogenation of ethanol reaction with the single-atom alloy phase exhibiting high selectivity to acetaldehyde and hydrogen versus a range of products from Pd clusters. First-principles based Monte Carlo calculations explain the origin of this active site ensemble size tuning effect, and this work serves as a demonstration of what should be a general phenomenon that enables in situ control over catalyst selectivity.
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Metal alloys are ubiquitous in many branches of heterogeneous catalysis, and it is now fairly well established that the local atomic structure of an alloy can have a profound influence on its chemical reactivity. While these effects can be difficult to probe in nanoparticle catalysts, model studies using well defined single crystal surfaces alloyed with dopants enable these structure-function correlations to be drawn. The first step in this approach involves understanding the alloying mechanism and the type of ensembles formed. In this study, we examined the atomic structure of RhCu single-atom alloys formed on Cu(111), Cu(100), and Cu(110) surfaces. Our results show a striking difference between Rh atoms alloying in Cu(111) vs the more open Cu(100) and Cu(110) surface facets. Unlike Cu(111) on which Rh atoms preferentially place-exchange with Cu atoms in the local regions above step edges leaving the majority of the Cu surface free of Rh, highly dispersed, homogeneous alloys are formed on the Cu(100) and (110) surfaces. These dramatically different alloying mechanisms are understood by quantifying the energetic barriers for atomic hopping, exchange, swapping, and vacancy filling events for Rh atoms on different Cu surfaces through theoretical calculations. Density functional theory results indicate that the observed differences in the alloying mechanism can be attributed to a faster hopping rate, relatively high atomic exchange barriers, and stronger binding of Rh atoms in the vicinity of step edges on Cu(111) compared to Cu(110) and Cu(100). These model systems will serve as useful platforms for examining structure sensitive chemistry on single-atom alloys.
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Selective hydrogenation of α,ß-unsaturated aldehydes to unsaturated alcohols is a challenging class of reactions, yielding valuable intermediates for the production of pharmaceuticals, perfumes, and flavorings. On monometallic heterogeneous catalysts, the formation of the unsaturated alcohols is thermodynamically disfavored over the saturated aldehydes. Hence, new catalysts are required to achieve the desired selectivity. Herein, the literature of three major research areas in catalysis is integrated as a step toward establishing the guidelines for enhancing the selectivity: reactor studies of complex catalyst materials at operating temperature and pressure, surface science studies of crystalline surfaces in ultrahigh vacuum, and first-principles modeling using density functional theory calculations. Aggregate analysis shows that bimetallic and dilute alloy catalysts significantly enhance the selectivity to the unsaturated alcohols compared to monometallic catalysts. This comprehensive review focuses primarily on the role of different metal surfaces as well as the factors that promote the adsorption of the unsaturated aldehyde via its CâO bond, most notably by electronic modification of the surface and formation of the electrophilic sites. Furthermore, challenges, gaps, and opportunities are identified to advance the rational design of efficient catalysts for this class of reactions, including the need for systematic studies of catalytic processes, theoretical modeling of complex materials, and model studies under ambient pressure and temperature.
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The conversions of surface-bound alkyl groups to alkanes and alkenes are important steps in many heterogeneously catalyzed reactions. On the one hand, while Pt is ubiquitous in industry because of its high activity toward C-H activation, many Pt-based catalysts tend to overbind reactive intermediates, which leads to deactivation by carbon deposition and coke formation. On the other hand, Cu binds intermediates more weakly than Pt, but activation barriers tend to be higher on Cu. We examine the reactivity of ethyl, the simplest alkyl group that can undergo hydrogenation and dehydrogenation via ß-elimination, and show that isolated Pt atoms in Cu enable low-temperature hydrogenation of ethyl, unseen on Cu, while avoiding the decomposition pathways on pure Pt that lead to coking. Furthermore, we confirm the predictions of our theoretical model and experimentally demonstrate that the selectivity of ethyl (de)hydrogenation can be controlled by changing the surface coverage of hydrogen.
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There are now many examples of single molecule rotors, motors, and switches in the literature that, when driven by photons, electrons, or chemical reactions, exhibit well-defined motions. As a step toward using these single molecule devices to perform useful functions, one must understand how they interact with their environment and quantify their ability to perform work on it. Using a single molecule rotary switch, we examine the transfer of electrical energy, delivered via electron tunneling, to mechanical motion and measure the forces the switch experiences with a noncontact q-plus atomic force microscope. Action spectra reveal that the molecular switch has two stable states and can be excited resonantly between them at a bias of 100 mV via a one-electron inelastic tunneling process which corresponds to an energy input of 16 zJ. While the electrically induced switching events are stochastic and no net work is done on the cantilever, by measuring the forces between the molecular switch and the AFM cantilever, we can derive the maximum hypothetical work the switch could perform during a single switching event, which is â¼55 meV, equal to 8.9 zJ, which translates to a hypothetical efficiency of â¼55% per individual inelastic tunneling electron-induced switching event. When considering the total electrical energy input, this drops to 1 × 10-7% due to elastic tunneling events that dominate the tunneling current. However, this approach constitutes a general method for quantifying and comparing the energy input and output of molecular-mechanical devices.