J. Segner

Bio: J. Segner is an academic researcher from Ludwig Maximilian University of Munich. The author has contributed to research in topics: Desorption & Scattering. The author has an hindex of 11, co-authored 14 publications receiving 2021 citations.

A molecular beam study of the catalytic oxidation of CO on a Pt(111) surface

Abstract: The oxidation of carbon monoxide catalyzed by Pt(111) was studied in ultrahigh vacuum using reactive molecular beam–surface scattering. Under all conditions studied, the reaction follows a Langmuir–Hinshelwood mechanism: the combination of a chemisorbed CO molecule and an oxygen adatom. When both reactants are at low coverage, the reaction proceeds with an activation energy E*LH =24.1 kcal/mole and a pre‐exponential υ4 =0.11 cm2 particles−1 sec−1. At very high oxygen coverage, E*LH decreases to about 11.7 kcal/mole and υ4 to about 2×10−6 cm2 particles−1 sec−1. This is largely attributed to the corresponding increase in the energy of the adsorbed reactants. When a CO molecule incident from the gas phase strikes the surface presaturated with oxygen, it enters a weakly held precursor state to chemisorption. Desorption from this state causes a decrease in chemisorption probability with temperature. Once chemisorbed, the CO molecule then has almost unit probability of reacting to produce CO2 below 540 K. The CO2 product angular distribution varies from cosγ to cos4γ depending sensitively upon the adsorbed reactant concentrations.

Why gold is the noblest of all the metals

Abstract: THE unique role that gold plays in society is to a large extent related to the fact that it is the most noble of all metals: it is the least reactive metal towards atoms or molecules at the interface with a gas or a liquid. The inertness of gold does not reflect a general inability to form chemical bonds, however—gold forms very stable alloys with many other metals. To understand the nobleness of gold, we have studied a simple surface reaction, the dissociation of H2 on the surface of gold and of three other metals (copper, nickel and platinum) that lie close to it in the periodic table. We present self-consistent density-functional calculations of the activation barriers and chemisorption energies which clearly illustrate that nobleness is related to two factors: the degree of filling of the antibonding states on adsorption, and the degree of orbital overlap with the adsorbate. These two factors, which determine both the strength of the adsorbate-metal interaction and the energy barrier for dissociation, operate together to the maxima] detriment of adsorbate binding and subsequent reactivity on gold.

Theoretical surface science and catalysis—calculations and concepts

Abstract: The application of density functional theory to calculate adsorption properties, reaction pathways, and activation energies for surface chemical reactions is reviewed. Particular emphasis is placed on developing concepts that can be used to understand and predict variations in reactivity from one transition metal to the next or the effects of alloying, surface structure, and adsorbate-adsorbate interactions on the reactivity. Most examples discussed are concerned with the catalytic properties of transition metal surfaces, but it is shown that the calculational approach and the concepts developed to understand trends in reactivity for metals can also be used for sulfide and oxide catalysts.

Thermally stable Pt/mesoporous silica core–shell nanocatalysts for high-temperature reactions

Abstract: Recent advances in colloidal synthesis enabled the precise control of the size, shape and composition of catalytic metal nanoparticles, enabling their use as model catalysts for systematic investigations of the atomic-scale properties affecting catalytic activity and selectivity. The organic capping agents stabilizing colloidal nanoparticles, however, often limit their application in high-temperature catalytic reactions. Here, we report the design of a high-temperature-stable model catalytic system that consists of a Pt metal core coated with a mesoporous silica shell (Pt@mSiO2). Inorganic silica shells encaged the Pt cores up to 750 ∘C in air and the mesopores providing direct access to the Pt core made the Pt@mSiO2 nanoparticles as catalytically active as bare Pt metal for ethylene hydrogenation and CO oxidation. The high thermal stability of Pt@mSiO2 nanoparticles enabled high-temperature CO oxidation studies, including ignition behaviour, which was not possible for bare Pt nanoparticles because of their deformation or aggregation. The results suggest that the Pt@mSiO2 nanoparticles are excellent nanocatalytic systems for high-temperature catalytic reactions or surface chemical processes, and the design concept used in the Pt@mSiO2 core–shell catalyst can be extended to other metal/metal oxide compositions. Colloidal synthesis can help to precisely control the shape and composition of catalytic metal nanoparticles, but it has so far proved difficult to use these particles in high-temperature reactions. Core–shell structures capable of isolating Pt-mesoporous silica nanoparticles have now been shown to be catalytically active for ethylene hydrogenation and CO oxidation at high temperature.