Matthew B. Boucher

Isolated metal atom geometries as a strategy for selective heterogeneous hydrogenations.

Tuning Hydrogen Adsorption Heterogeneous metal catalysts for hydrogenating unsaturated organic compounds need to bind molecular hydrogen strongly enough that it dissociates and forms adsorbed hydrogen atoms, but must not bind these atoms too strongly, or the transfer to the organic molecule will be impeded. Kyriakou et al. (p. 1209) examined surface alloy catalysts created when palladium (Pd) atoms are adsorbed on a copper (Cu) surface using scanning tunneling microscopy and desorption techniques under ultrahigh vacuum conditions. The Pd atoms could bind hydrogen dissociatively—which, under these conditions, the Cu surfaces could not—allowing the Cu surface to take up adsorbed hydrogen atoms. These weakly bound hydrogen atoms were able to selectively hydrogenate styrene and acetylene. Palladium atoms adsorbed on a copper surface activate hydrogen adsorption for subsequent hydrogenation reactions. 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.

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.

Variables affecting homogeneous acid catalyst recoverability and reuse after esterification of concentrated omega-9 polyunsaturated fatty acids in vegetable oil triglycerides.

Global concerns regarding greenhouse gas emissions combined with soaring oil prices have driven the search for renewable diesel fuels derived from either virgin or waste vegetable oils, dubbed “bio-diesels”. A key challenge in the emerging bio-diesel industry is cost-effective pre-treatment of waste vegetable oils to reduce free-fatty acid content prior to transesterification. This article reports, for the first time, recoverability and reusability of hydrochloric and sulfuric acid catalysts for efficient pre-treatment of waste cooking oils for subsequent conversion to bio-diesels. Esterification of omega-9 polyunsaturated fatty acids, particularly 18:2,18:3 linoleic acid with methanol and a homogenous acid catalyst was investigated over a range of fatty acid concentrations. It was determined that greater than 95% by weight of each catalyst was recovered after esterification under all conditions investigated. When recovered methanol was used, containing recovered catalyst and water, it was determined that hydrochloric acid catalyzed esterification exhibits a higher tolerance to water accumulation. After sulfuric acid was recovered and re-used, the observed rate constant decreased more than 50% to a value comparable to that observed for hydrochloric acid at more than three times the water concentration.

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.

Mode‐Selective Electrical Excitation of a Molecular Rotor

Understanding and actuating the rotation of individual molecules on surfaces is a crucial step towards the development of nanoscale devices such as fluid pumps, sensors, delay lines, and microwave signaling applications. Recently a new, stable and robust system of molecular rotors consisting of thioether molecules (RSR) bound to metal surfaces has offered a method with which to study the rotation of individual molecules as a function of temperature, molecular chemistry, proximity of neighboring molecules, and surface structure. Arrhenius plots for the rotation of dibutyl sulfide yielded a rotational barrier of 1.2 0.1 kJ mol . While these results revealed that small amounts of thermal energy are capable of inducing rotation, thermodynamics dictates that thermal energy alone cannot be used to perform useful work in the absence of a temperature gradient. Therefore, for molecules to meet their full potential as components in molecular machines, methods for coupling them to external sources of energy that selectively excite the desired motions must be devised. Herein we describe a study of the electrical excitation of individual dibutyl sulfide (Bu2S) molecular rotors with electrons from a scanning tunneling microscope (STM) tip. Action spectroscopy was used to measure the effect of electron energy on the rate of rotation. The results revealed that tunneling electrons above a threshold energy excited a C H vibration in the rotor s alkyl tail that coupled selectively to rotation of the whole molecule. The Au ACHTUNGTRENNUNG{111} 22 p3 surface chosen for the study consists of domains of surface atoms with both hcp and fcc packing separated by narrow soliton walls with an intermediate packing structure. Therefore, molecular rotors in both areas were studied independently and the results were compared. For simplicity we only present data for fcc-adsorbed rotors in this communication (see Supporting Information for hcp data). Figure 1 a shows an STM image of an individual dibutyl sulfide molecular rotor on a Au ACHTUNGTRENNUNG{111} surface at 7 K. When imaging at 7 K under non-perturbative conditions (V=0.3 V, I= 10 pA), the molecules were static and appeared in STM images as crescent-shaped protrusions. Figure 1 b shows an image of a di-

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.

Investigation into the relationship between the gravity vector and the flow vector to improve performance in two-phase continuous flow biodiesel reactor

The following study analyzes the performance of a continuous flow biodiesel reactor/separator. The reactor achieves high conversion of vegetable oil triglycerides to biodiesel while simultaneously separating co-product glycerol. The influence of the flow direction, relative to the gravity vector, on the reactor performance was measured. Reactor performance was assessed by both the conversion of vegetable oil triglycerides to biodiesel and the separation efficiency of removing the co-product glycerol. At slightly elevated temperatures of 40-50 degrees C, an overall feed of 1.2 L/min, a 6:1 M ratio of methanol to vegetable oil triglycerides, and a 1-1.3 wt.% potassium hydroxide catalyst loading, the reactor converted more than 96% of the pretreated waste vegetable oil to biodiesel. The reactor also separated 36-95% of the glycerol that was produced. Tilting the reactor away from the vertical direction produced a large increase in glycerol separation efficiency and only a small decrease in conversion.