Facile dissociation of reactants and weak binding of intermediates are key requirements for efficient and selective catalysis. However, these two variables are intimately linked in a way that does not generally allow the optimization of both properties simultaneously. By using desorption measurements in combination with high-resolution scanning tunneling microscopy, we show that individual, isolated Pd atoms in a Cu surface substantially lower the energy barrier to both hydrogen uptake on and subsequent desorption from the Cu metal surface. This facile hydrogen dissociation at Pd atom sites and weak binding to Cu allow for very selective hydrogenation of styrene and acetylene as compared with pure Cu or Pd metal alone.
Using a combination of low-temperature scanning tunneling microscopy and density functional theory it is demonstrated how the nature of an inert host metal of an alloy can affect the thermodynamics and kinetics of a reaction pathway in a much more profound way than simply a dilution, electronic, or geometric effect. This study reveals that individual, isolated Pd atoms can promote H2 dissociation and spillover onto a Cu(111) surface, but that the same mechanism is not observed for an identical array of Pd atoms in Au(111).
For molecules to be used as components in molecular machines, methods that couple individual molecules to external energy sources and that selectively excite motion in a given direction are required. Significant progress has been made in the construction of molecular motors powered by light and by chemical reactions, but electrically driven motors have not yet been built, despite several theoretical proposals for such motors. Here we report that a butyl methyl sulphide molecule adsorbed on a copper surface can be operated as a single-molecule electric motor. Electrons from a scanning tunnelling microscope are used to drive the directional motion of the molecule in a two-terminal setup. Moreover, the temperature and electron flux can be adjusted to allow each rotational event to be monitored at the molecular scale in real time. The direction and rate of the rotation are related to the chiralities of both the molecule and the tip of the microscope (which serves as the electrode), illustrating the importance of the symmetry of the metal contacts in atomic-scale electrical devices.
This paper describes a fundamental, single-molecule study of the motion of a set of thioethers supported on Au surfaces. Thioethers constitute a simple, robust system with which molecular rotation can be actuated both thermally and mechanically. Low-temperature scanning tunneling microscopy allowed the measurement of the rotation of individual molecules as a function of temperature and the quantification of both the energetic barrier and pre-exponential factor of the motion. The results suggest that movement of the second CH(2) group from the S atom over the surface is responsible for the barrier. Through a series of single-molecule manipulation experiments, we have switched the rotation on and off reversibly by moving the molecules toward or away from one another. Arrhenius plots for individual dibutyl sulfide molecules reveal that the torsional barrier to rotation is approximately 1.2 kJ/mol, in good agreement with the temperature at which the molecule's appearance changes from a linear to a hexagonal shape in the STM images. The thioether backbone constitutes an excellent test bed for studying the details of molecular rotation at the single-molecule level.
Water-gas shift chemistry provides a useful method for producing hydrogen from coal; however, fuel cell applications demand that this hydrogen be free of impurities. Due to their unique properties, Pd/Cu alloys represent an import class of materials used for H purification membranes and also serve as the active metals in many heterogeneous catalysts. Little is known about how Pd and Cu interact electronically in these mixed systems and there is debate in the literature over the direction of charge transfer between the two species. This study used the differential conductance (dI/dV) spectroscopy capabilities of a low-temperature scanning tunneling microscope (STM) to investigate the atomic-scale electronic structure of Pd/Cu surface alloys. dI/ dV spectroscopy gives a direct measure of the local density of states of surface sites with subnanometer precision. Results from this work demonstrate that individual, isolated Pd atoms in a Cu lattice are almost electronically identical to their host atoms. Over an energy range that spans 1 eV on either side of the Fermi level, the only significant electronic difference between isolated Pd and their host Cu atoms is that Pd atoms have a very slightly depleted electron density in the region of the Cu surface state maximum.
Palladium and its alloys play a central role in a wide variety of industrially important applications such as hydrogen reactions, separations, storage devices, and fuel‐cell components. Alloy compositions are complex and often heterogeneous at the atomic‐scale and the exact mechanisms by which many of these processes operate have yet to be discovered. Herein, scanning tunneling microscopy (STM) has been used to investigate the atomic‐scale structure of Pd–Au and Pd–Cu bimetallics created by depositing Pd on both Au(111) and Cu(111) single crystals at a variety of surface temperatures. We demonstrated that individual, isolated Pd atoms in an inert Cu matrix are active for the dissociation of hydrogen and subsequent spillover onto Cu sites. Our results indicated that H spillover was facile on Pd–Cu at 420 K but that no H was found under the same H2 flux on a Pd–Au sample with identical atomic composition and geometry. In the case of Au, significant H uptake was only observed when larger ensembles of Pd were present in the form of nanoparticles. We report experimental evidence for hydrogen’s ability to reverse the tendency of Pd to segregate into the Au surface at catalytically relevant temperatures and our STM images reveal a novel H‐induced striped structure in which Pd atoms aggregated on top of the surface in regularly spaced rows. These results demonstrate the powerful influence an inert substrate has on the catalytic activity of Pd atoms supported in or on its surface and reveal how the atomic‐scale geometry of Pd–Au alloys is greatly affected by the presence of hydrogen.
Pd/Au bimetallic alloys catalyze many important reactions ranging from the synthesis of vinyl acetate and hydrogen peroxide to the oxidation of carbon monoxide and trimerization of acetylene. It is known that the atomic-scale geometry of these alloys can dramatically affect both their reactivity and selectivity. However, there is a distinct lack of experimental characterization and quantification of ligand and ensemble effects in this system. Low-temperature, ultrahigh vacuum scanning tunneling microscopy is used to investigate the atomic-scale geometry of Pd/Au111 near-surface alloys and to spectroscopically probe their local electronic structure. The results reveal that the herringbone reconstruction of Au111 provides entry sites for the incorporation of Pd atoms in the Au surface and that the degree of mixing is dictated by the surface temperature. At catalytically relevant temperatures the distribution of low coverages of Pd in the alloy is random, except for a lack of nearest neighbor pairs in both the surface and subsurface sites. Scanning tunneling spectroscopy is used to examine the electronic structure of the individual Pd atoms in surface and subsurface sites. This work reveals that in both surface and subsurface locations, Pd atoms display a very similar electronic structure to the surrounding Au atoms. However, individual surface and subsurface Pd atoms are depleted of charge in a very narrow region at the band edge of the Au surface state. dI/dV images of the phenomena demonstrate the spatial extent of this electronic perturbation.
Recent single-molecule experiments indicated that thioethers (dialkyl sulfides) on gold surfaces act as thermallyor mechanically activated molecular rotors, although the mechanisms for these phenomena are not yet clearly understood. Here we present theoretical and experimental investigations of the rotational dynamics of these thioether molecules. Single-molecule studies utilizing low-temperature scanning tunneling microscopy allowed us to determine rotational rates and activation energies for the rotation of symmetric dialkyl sulfides. It was found that the rotational energy barriers increased as a function of alkyl chain length but then quickly saturated. Molecular dynamics simulations have also been performed in order to understand the molecular rotations of thioethers, and our theoretical calculations agree well with experimental observations. It is argued that the observed rotational dynamics of dialkyl sulfides are determined by the effective interactions with the surface and the flexibility of the alkyl chains. These results suggest possible ways to control and utilize thioether rotors at the single-molecule level.
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