Halogen-substituted thiophenol molecules on Cu(111)

Para-halosubstituted thiophenols (X-TPs, where X is Br, Cl, or F) form ordered islands and monolayers on Cu(111) at temperatures as low as 81 K. At incomplete coverages, all X-TPs adsorb with the dehydrogenated thiol group attached to the substrate and the substituted ring inclined toward the surface, as verified experimentally and theoretically. The structure of ordered islands has a pronounced dependence on the nature of the halogen substituent: while unsubstituted TP and pentafluoro-TP molecules do not self-assemble into extended ordered patterns at 81 K, X-TP molecules form a range of different structures which depend both on the size and electronegativity of the substituent, as well as on the coverage.     

Understanding the electrochemistry of “water-in-salt” electrolytes: basal plane highly ordered pyrolytic graphite as a model system

A new approach to expand the accessible voltage window of electrochemical energy storage systems, based on so-called “water-in-salt” electrolytes, has been expounded recently. Although studies of transport in concentrated electrolytes date back over several decades, the recent demonstration that concentrated aqueous electrolyte systems can be used in the lithium ion battery context has rekindled interest in the electrochemical properties of highly concentrated aqueous electrolytes. The original aqueous lithium ion battery conception was based on the use of concentrated solutions of lithium bis(trifluoromethanesulfonyl)imide, although these electrolytes still possess some drawbacks including cost, toxicity, and safety. In this work we describe the electrochemical behavior of a simple 1 : 1 electrolyte based on highly concentrated aqueous solutions of potassium fluoride (KF). Highly ordered pyrolytic graphite (HOPG) is used as well-defined model carbon to study the electrochemical properties of the electrolyte, as well as its basal plane capacitance, from a microscopic perspective: the KF electrolyte exhibits an unusually wide potential window (up to 2.6 V). The faradaic response on HOPG is also reported using K₃Fe(CN)₆ as a model redox probe: the highly concentrated electrolyte provides good electrochemical reversibility and protects the HOPG surface from adsorption of contaminants. Moreover, this electrolyte was applied to symmetrical supercapacitors (using graphene and activated carbon as active materials) in order to quantify its performance in energy storage applications. It is found that the activated carbon and graphene supercapacitors demonstrate high gravimetric capacitance (221 F g⁻¹ for activated carbon, and 56 F g⁻¹ for graphene), a stable working voltage window of 2.0 V, which is significantly higher than the usual range of water-based capacitors, and excellent stability over 10 000 cycles. These results provide fundamental insight into the wider applicability of highly concentrated electrolytes, which should enable their application in future of energy storage technologies.

The stability of water-in-salt electrolyte systems is investigated using highly concentrated solutions of KF(aq) with graphite as a model system.     

Effect of N2O pretreatment on fresh and regenerated Pd-Ag/α-Al2O3 catalysts during selective hydrogenation of acetylene

N₂O pretreatment has shown to result in enhancement of the performance of fresh commercial Pd-Ag/α-Al₂O₃ catalyst during selective acetylene hydrogenation. However, it showed no effect for the used and regenerated catalysts probably due to changes int he metal arrangement on the catalyst surface after regeneration.     

Oxadiazole-metal interface: from isolated molecules to pi-stacking

Derivatives of 2,5-diaryl-1,3,4-oxadiazole are used widely for electron transport in organic light emitting diodes (OLED). This study addresses the structure of 2,5-diphenyl-1,3,4-oxadiazole (PPD) molecules on Cu(111) using scanning tunneling microscopy (STM) and density function theory (DFT): at incomplete coverage, PPD molecules are found horizontally on the surface; once the surface area is insufficient to accommodate all adsorbates in this fashion, a pi-stacked film of vertically arranged molecules is formed. In contrast to bulk PPD, in this film, the molecules are arranged face-to-face at a separation of square root(3a0) = 4.4 A as imposed by the substrate interatomic spacing along the [-2 1 1] direction.     

Surface diffusive motion in a periodic and asymmetric potential

9,10-Dithioanthracene adsorbed on Cu(111) diffuses exclusively along the high-symmetry axis of the molecule-substrate system. Further reduction of the symmetry of the system by asymmetric methylation does not reduce the symmetry of the motion although it has a substantial effect on the diffusion rate (100-fold reduction) and renders the diffusion barrier asymmetric. This is in contrast to the behavior expected of a classical particle, and it provides a direct single-molecule-scale vista on the validity of The Principle of Microscopic Reversibility first formulated by Tolman in 1924, which despite its fundamental role has attracted little visualization.     

Steric blocking as a tool to control molecular film geometry at a metal surface

The application of steric blocking in surface science is exemplified by the control of surface patterns through the selective methylation of pentacenetetrone. Pentacenetetrones interact (with one another) on Cu(111) via intermolecular hydrogen bonding involving the carbonyl oxygen and the adjacent hydrogen atoms. Steric blocking of the intermolecular interaction by the successive insertion of inert methyl groups at terminal locations transforms a dense molecular pattern first into isolated double rows and eventually into single rows in a highly predictable fashion. Density functional theory modeling reveals the underlying energetics.     

Coverage and nearest-neighbor dependence of adsorbate diffusion

We present data on the coverage and nearest-neighbor dependences of the diffusion of CO on Cu(111) by time-lapsed scanning tunneling microscope (STM) imaging. Most notable is a maximum in diffusivity of CO at a local coverage of one molecule per 20 substrate atoms and a repulsion between CO molecules upon approach closer than three adsites, which in combination with a less pronounced increase in potential energy at the diffusion transition state, leads to rapid diffusion of CO molecules around one another. We propose a new method of evaluating STM-based diffusion data that provides all parameters necessary for the modeling of the dynamics of an adsorbate population.