Templated Growth of a Homochiral Thin Film Oxide.

Chiral surfaces are of growing interest for enantioselective adsorption and reactions. While metal surfaces can be prepared with a wide range of chiral surface orientations, chiral oxide surface preparation is more challenging. We demonstrate the chirality of a metal surface can be used to direct the homochiral growth of a thin film chiral oxide. Specifically, we study the chiral "29" copper oxide, formed by oxidizing a Cu(111) single crystal at 650 K. Surface structure spread single crystals, which expose a continuous distribution of surface orientations as a function of position on the crystal, enable us to systematically investigate the mechanism of chirality transfer between the metal and the surface oxide with high-resolution scanning tunneling microscopy. We discover that the local underlying metal facet directs the orientation and chirality of the oxide overlayer. Importantly, single homochiral domains of the "29" oxide were found in areas where the Cu step edges that templated growth were ≤20 nm apart. We use this information to select a Cu(239 241 246) oriented single crystal and demonstrate that a "29" oxide surface can be grown in homochiral domains by templating from the subtle chirality of the underlying metal crystal. This work demonstrates how a small degree of chirality induced by slight misorientation of a metal surface (∼1 sites/20 nm2) can be amplified by oxidation to yield a homochiral oxide with a regular array of chiral oxide pores (∼75 sites/20 nm2). This offers a general approach for making chiral oxide surfaces via oxidation of an appropriately "miscut" metal surface.

Adsorption and reaction of methanol on Fe3O4(001).

The interaction of methanol with iron oxide surfaces is of interest due to its potential in hydrogen storage and from a fundamental perspective as a chemical probe of reactivity. We present here a study examining the adsorption and reaction of methanol on magnetite Fe3O4(001) at cryogenic temperatures using a combination of temperature programmed desorption, x-ray photoelectron spectroscopy, and scanning tunneling microscopy. The methanol desorption profile from Fe3O4(001) is complex, exhibiting peaks at 140 K, 173 K, 230 K, and 268 K, corresponding to the desorption of intact methanol, as well as peaks at 341 K and 495 K due to the reaction of methoxy intermediates. The saturation of a monolayer of methanol corresponds to ∼5 molecules/unit cell (u.c.), which is slightly higher than the number of surface octahedral iron atoms of 4/u.c. We probe the kinetics and thermodynamics of the desorption of molecular methanol using inversion analysis. The deconvolution of the complex desorption profile into individual peaks allows for calculations of both the desorption energy and the prefactor of each feature. The initial 0.7 methanol/u.c. reacts to form methoxy and hydroxy intermediates at 180 K, which remain on the surface above room temperature after intact methanol has desorbed. The methoxy species react via one of two channels, a recombination reaction with surface hydroxyls to form additional methanol at ∼350 K and a disproportionation reaction to form methanol and formaldehyde at ∼500 K. Only 20% of the methoxy species undergo the disproportionation reaction, with most of them reacting via the 350 K pathway.

Chirality at two-dimensional surfaces: A perspective from small molecule alcohol assembly on Au(111).

The delicate balance between hydrogen bonding and van der Waals interactions determines the stability, structure, and chirality of many molecular and supramolecular aggregates weakly adsorbed on solid surfaces. Yet the inherent complexity of these systems makes their experimental study at the molecular level very challenging. In this quest, small alcohols adsorbed on metal surfaces have become a useful model system to gain fundamental insight into the interplay of such molecule-surface and molecule-molecule interactions. Here, through a combination of scanning tunneling microscopy and density functional theory, we compare and contrast the adsorption and self-assembly of a range of small alcohols from methanol to butanol on Au(111). We find that longer chained alcohols prefer to form zigzag chains held together by extended hydrogen bonded networks between adjacent molecules. When alcohols bind to a metal surface datively via one of the two lone electron pairs of the oxygen atom, they become chiral. Therefore, the chain structures are formed by a hydrogen-bonded network between adjacent molecules with alternating adsorbed chirality. These chain structures accommodate longer alkyl tails through larger unit cells, while the position of the hydroxyl group within the alcohol molecule can produce denser unit cells that maximize intermolecular interactions. Interestingly, when intrinsic chirality is introduced into the molecule as in the case of 2-butanol, the assembly changes completely and square packing structures with chiral pockets are observed. This is rationalized by the fact that the intrinsic chirality of the molecule directs the chirality of the adsorbed hydroxyl group meaning that heterochiral chain structures cannot form. Overall this study provides a general framework for understanding the effect of simple alcohol molecular adstructures on hydrogen bonded aggregates and paves the way for rationalizing 2D chiral supramolecular assembly.

Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C-H activation.

The recent availability of shale gas has led to a renewed interest in C-H bond activation as the first step towards the synthesis of fuels and fine chemicals. Heterogeneous catalysts based on Ni and Pt can perform this chemistry, but deactivate easily due to coke formation. Cu-based catalysts are not practical due to high C-H activation barriers, but their weaker binding to adsorbates offers resilience to coking. Using Pt/Cu single-atom alloys (SAAs), we examine C-H activation in a number of systems including methyl groups, methane and butane using a combination of simulations, surface science and catalysis studies. We find that Pt/Cu SAAs activate C-H bonds more efficiently than Cu, are stable for days under realistic operating conditions, and avoid the problem of coking typically encountered with Pt. Pt/Cu SAAs therefore offer a new approach to coke-resistant C-H activation chemistry, with the added economic benefit that the precious metal is diluted at the atomic limit.

Characterizing the geometric and electronic structure of defects in the "29" copper surface oxide.

The geometric and electronic structural characterization of thin film metal oxides is of fundamental importance to many fields such as catalysis, photovoltaics, and electrochemistry. Surface defects are also well known to impact a material's performance in any such applications. Here, we focus on the "29" oxide Cu2O/Cu(111) surface and we observe two common structural defects which we characterize using scanning tunneling microscopy/spectroscopy and density functional theory. The defects are proposed to be O vacancies and Cu adatoms, which both show unique topographic and spectroscopic signatures. The spatially resolved electronic and charge state effects of the defects are investigated, and implications for their reactivity are given.

Tackling CO Poisoning with Single-Atom Alloy Catalysts.

Platinum catalysts are extensively used in the chemical industry and as electrocatalysts in fuel cells. Pt is notorious for its sensitivity to poisoning by strong CO adsorption. Here we demonstrate that the single-atom alloy (SAA) strategy applied to Pt reduces the binding strength of CO while maintaining catalytic performance. By using surface sensitive studies, we determined the binding strength of CO to different Pt ensembles, and this in turn guided the preparation of PtCu alloy nanoparticles (NPs). The atomic ratio Pt:Cu = 1:125 yielded a SAA which exhibited excellent CO tolerance in H2 activation, the key elementary step for hydrogenation and hydrogen electro-oxidation. As a probe reaction, the selective hydrogenation of acetylene to ethene was performed under flow conditions on the SAA NPs supported on alumina without activity loss in the presence of CO. The ability to maintain reactivity in the presence of CO is vital to other industrial reaction systems, such as hydrocarbon oxidation, electrochemical methanol oxidation, and hydrogen fuel cells.

The interplay of covalency, hydrogen bonding, and dispersion leads to a long range chiral network: The example of 2-butanol.

The assembly of complex structures in nature is driven by an interplay between several intermolecular interactions, from strong covalent bonds to weaker dispersion forces. Understanding and ultimately controlling the self-assembly of materials requires extensive study of how these forces drive local nanoscale interactions and how larger structures evolve. Surface-based self-assembly is particularly amenable to modeling and measuring these interactions in well-defined systems. This study focuses on 2-butanol, the simplest aliphatic chiral alcohol. 2-butanol has recently been shown to have interesting properties as a chiral modifier of surface chemistry; however, its mode of action is not fully understood and a microscopic understanding of the role non-covalent interactions play in its adsorption and assembly on surfaces is lacking. In order to probe its surface properties, we employed high-resolution scanning tunneling microscopy and density functional theory (DFT) simulations. We found a surprisingly rich degree of enantiospecific adsorption, association, chiral cluster growth and ultimately long range, highly ordered chiral templating. Firstly, the chiral molecules acquire a second chiral center when adsorbed to the surface via dative bonding of one of the oxygen atom lone pairs. This interaction is controlled via the molecule's intrinsic chiral center leading to monomers of like chirality, at both chiral centers, adsorbed on the surface. The monomers then associate into tetramers via a cyclical network of hydrogen bonds with an opposite chirality at the oxygen atom. The evolution of these square units is surprising given that the underlying surface has a hexagonal symmetry. Our DFT calculations, however, reveal that the tetramers are stable entities that are able to associate with each other by weaker van der Waals interactions and tessellate in an extended square network. This network of homochiral square pores grows to cover the whole Au(111) surface. Our data reveal that the chirality of a simple alcohol can be transferred to its surface binding geometry, drive the directionality of hydrogen-bonded networks and ultimately extended structure. Furthermore, this study provides the first microscopic insight into the surface properties of this important chiral modifier and provides a well-defined system for studying the network's enantioselective interaction with other molecules.

Selective hydrogenation of 1,3-butadiene on platinum-copper alloys at the single-atom limit.

Platinum is ubiquitous in the production sectors of chemicals and fuels; however, its scarcity in nature and high price will limit future proliferation of platinum-catalysed reactions. One promising approach to conserve platinum involves understanding the smallest number of platinum atoms needed to catalyse a reaction, then designing catalysts with the minimal platinum ensembles. Here we design and test a new generation of platinum-copper nanoparticle catalysts for the selective hydrogenation of 1,3-butadiene,, an industrially important reaction. Isolated platinum atom geometries enable hydrogen activation and spillover but are incapable of C-C bond scission that leads to loss of selectivity and catalyst deactivation. γ-Alumina-supported single-atom alloy nanoparticle catalysts with <1 platinum atom per 100 copper atoms are found to exhibit high activity and selectivity for butadiene hydrogenation to butenes under mild conditions, demonstrating transferability from the model study to the catalytic reaction under practical conditions.

Significant quantum effects in hydrogen activation.

Dissociation of molecular hydrogen is an important step in a wide variety of chemical, biological, and physical processes. Due to the light mass of hydrogen, it is recognized that quantum effects are often important to its reactivity. However, understanding how quantum effects impact the reactivity of hydrogen is still in its infancy. Here, we examine this issue using a well-defined Pd/Cu(111) alloy that allows the activation of hydrogen and deuterium molecules to be examined at individual Pd atom surface sites over a wide range of temperatures. Experiments comparing the uptake of hydrogen and deuterium as a function of temperature reveal completely different behavior of the two species. The rate of hydrogen activation increases at lower sample temperature, whereas deuterium activation slows as the temperature is lowered. Density functional theory simulations in which quantum nuclear effects are accounted for reveal that tunneling through the dissociation barrier is prevalent for H2 up to ∼190 K and for D2 up to ∼140 K. Kinetic Monte Carlo simulations indicate that the effective barrier to H2 dissociation is so low that hydrogen uptake on the surface is limited merely by thermodynamics, whereas the D2 dissociation process is controlled by kinetics. These data illustrate the complexity and inherent quantum nature of this ubiquitous and seemingly simple chemical process. Examining these effects in other systems with a similar range of approaches may uncover temperature regimes where quantum effects can be harnessed, yielding greater control of bond-breaking processes at surfaces and uncovering useful chemistries such as selective bond activation or isotope separation.

Hydrogen Dissociation, Spillover, and Desorption from Cu-Supported Co Nanoparticles.

Co-Cu nanoparticles have recently been explored for Fischer-Tropsch synthesis (FTS) as a way to combine the long chain selectivity of Co with Cu's activity for alcohol formation in order to synthesize oxygenated transportation fuels. Depending on particle size, hydrogen dissociation can be a rate-determining step in cobalt-catalyzed FTS. To understand the fundamentals of uptake and release of hydrogen from the Co/Cu bimetallic system, we prepared well-defined Co nanoparticles on Cu(111). We demonstrate that hydrogen spills over from dissociation sites on the Co nanoparticles to the Cu(111) surface via the Co-Cu interface and that desorption of H occurs at a temperature that is lower than from Co or Cu alone, which we attribute to the Co-Cu interface sites. From this data, we have constructed an energy landscape for the facile dissociation, spillover, and desorption of hydrogen on the Co-Cu bimetallic system.

Single atom alloy surface analogs in Pd0.18Cu15 nanoparticles for selective hydrogenation reactions.

We report a novel synthesis of nanoparticle Pd-Cu catalysts, containing only trace amounts of Pd, for selective hydrogenation reactions. Pd-Cu nanoparticles were designed based on model single atom alloy (SAA) surfaces, in which individual, isolated Pd atoms act as sites for hydrogen uptake, dissociation, and spillover onto the surrounding Cu surface. Pd-Cu nanoparticles were prepared by addition of trace amounts of Pd (0.18 atomic (at)%) to Cu nanoparticles supported on Al2O3 by galvanic replacement (GR). The catalytic performance of the resulting materials for the partial hydrogenation of phenylacetylene was investigated at ambient temperature in a batch reactor under a head pressure of hydrogen (6.9 bar). The bimetallic Pd-Cu nanoparticles have over an order of magnitude higher activity for phenylacetylene hydrogenation when compared to their monometallic Cu counterpart, while maintaining a high selectivity to styrene over many hours at high conversion. Greater than 94% selectivity to styrene is observed at all times, which is a marked improvement when compared to monometallic Pd catalysts with the same Pd loading, at the same total conversion. X-ray photoelectron spectroscopy and UV-visible spectroscopy measurements confirm the complete uptake and alloying of Pd with Cu by GR. Scanning tunneling microscopy and thermal desorption spectroscopy of model SAA surfaces confirmed the feasibility of hydrogen spillover onto an otherwise inert Cu surface. These model studies addressed a wide range of Pd concentrations related to the bimetallic nanoparticles.

Molecular-scale perspective of water-catalyzed methanol dehydrogenation to formaldehyde.

Methanol steam reforming is a promising reaction for on-demand hydrogen production. Copper catalysts have excellent activity and selectivity for methanol conversion to hydrogen and carbon dioxide. This product balance is dictated by the formation and weak binding of formaldehyde, the key reaction intermediate. It is widely accepted that oxygen adatoms or oxidized copper are required to activate methanol. However, we show herein by studying a well-defined metallic copper surface that water alone is capable of catalyzing the conversion of methanol to formaldehyde. Our results indicate that six or more water molecules act in concert to deprotonate methanol to methoxy. Isolated palladium atoms in the copper surface further promote this reaction. This work reveals an unexpected role of water, which is typically considered a bystander in this key chemical transformation.

Controlling a spillover pathway with the molecular cork effect.

Spillover of reactants from one active site to another is important in heterogeneous catalysis and has recently been shown to enhance hydrogen storage in a variety of materials. The spillover of hydrogen is notoriously hard to detect or control. We report herein that the hydrogen spillover pathway on a Pd/Cu alloy can be controlled by reversible adsorption of a spectator molecule. Pd atoms in the Cu surface serve as hydrogen dissociation sites from which H atoms can spillover onto surrounding Cu regions. Selective adsorption of CO at these atomic Pd sites is shown to either prevent the uptake of hydrogen on, or inhibit its desorption from, the surface. In this way, the hydrogen coverage on the whole surface can be controlled by molecular adsorption at a minority site, which we term a 'molecular cork' effect. We show that the molecular cork effect is present during a surface catalysed hydrogenation reaction and illustrate how it can be used as a method for controlling uptake and release of hydrogen in a model storage system.