Author
J. Matthiesen
Bio: J. Matthiesen is an academic researcher. The author has contributed to research in topics: Catalysis & Reaction rate. The author has an hindex of 1, co-authored 1 publications receiving 1081 citations.
Papers
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TL;DR: In this paper, it was shown that the reaction rate under given reaction conditions shows a maximum as a function of dissociative adsorption energy of the key reactant, and that for most conditions this maximum is in the same range of reaction energies.
1,218 citations
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TL;DR: In this paper, the stability of reaction intermediates of electrochemical processes on the basis of electronic structure calculations was analyzed and a detailed description of the free energy landscape of the electrochemical oxygen reduction reaction over Pt(111) as a function of applied bias was presented.
Abstract: We present a method for calculating the stability of reaction intermediates of electrochemical processes on the basis of electronic structure calculations. We used that method in combination with detailed density functional calculations to develop a detailed description of the free-energy landscape of the electrochemical oxygen reduction reaction over Pt(111) as a function of applied bias. This allowed us to identify the origin of the overpotential found for this reaction. Adsorbed oxygen and hydroxyl are found to be very stable intermediates at potentials close to equilibrium, and the calculated rate constant for the activated proton/electron transfer to adsorbed oxygen or hydroxyl can account quantitatively for the observed kinetics. On the basis of a database of calculated oxygen and hydroxyl adsorption energies, the trends in the oxygen reduction rate for a large number of different transition and noble metals can be accounted for. Alternative reaction mechanisms involving proton/electron transfer to ...
7,711 citations
TL;DR: The emphasis of this review is on the origin of the electrocatalytic activity of nanostructured catalysts toward a series of key clean energy conversion reactions by correlating the apparent electrode performance with their intrinsic electrochemical properties.
Abstract: A fundamental change has been achieved in understanding surface electrochemistry due to the profound knowledge of the nature of electrocatalytic processes accumulated over the past several decades and to the recent technological advances in spectroscopy and high resolution imaging. Nowadays one can preferably design electrocatalysts based on the deep theoretical knowledge of electronic structures, via computer-guided engineering of the surface and (electro)chemical properties of materials, followed by the synthesis of practical materials with high performance for specific reactions. This review provides insights into both theoretical and experimental electrochemistry toward a better understanding of a series of key clean energy conversion reactions including oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The emphasis of this review is on the origin of the electrocatalytic activity of nanostructured catalysts toward the aforementioned reactions by correlating the apparent electrode performance with their intrinsic electrochemical properties. Also, a rational design of electrocatalysts is proposed starting from the most fundamental aspects of the electronic structure engineering to a more practical level of nanotechnological fabrication.
3,918 citations
TL;DR: The first steps towards using computational methods to design new catalysts are reviewed and how, in the future, such methods may be used to engineer the electronic structure of the active surface by changing its composition and structure are discussed.
Abstract: Over the past decade the theoretical description of surface reactions has undergone a radical development. Advances in density functional theory mean it is now possible to describe catalytic reactions at surfaces with the detail and accuracy required for computational results to compare favourably with experiments. Theoretical methods can be used to describe surface chemical reactions in detail and to understand variations in catalytic activity from one catalyst to another. Here, we review the first steps towards using computational methods to design new catalysts. Examples include screening for catalysts with increased activity and catalysts with improved selectivity. We discuss how, in the future, such methods may be used to engineer the electronic structure of the active surface by changing its composition and structure.
3,023 citations
TL;DR: A density functional theory database of hydrogen chemisorption energies on close packed surfaces of a number of transition andnoble metals is presented in this article, where the bond energies are used to understand the trends in the exchange current for hydrogen evolution.
Abstract: Department of Physics, Technical University Munich, D-85748 Garching, GermanyA density functional theory database of hydrogen chemisorption energies on close packed surfaces of a number of transition andnoble metals is presented. The bond energies are used to understand the trends in the exchange current for hydrogen evolution. Avolcano curve is obtained when measured exchange currents are plotted as a function of the calculated hydrogen adsorptionenergies and a simple kinetic model is developed to understand the origin of the volcano. The volcano curve is also consistent withPt being the most efficient electrocatalyst for hydrogen evolution.© 2005 The Electrochemical Society. @DOI: 10.1149/1.1856988# All rights reserved.Manuscript submitted May 10, 2004; revised manuscript received August 12, 2004. Available electronically January 24, 2005.
2,623 citations
TL;DR: The overall catalytic activities for these reaction as a function of a more fundamental property, a descriptor, OH-M(2+δ) bond strength (0 ≤ δ ≤ 1.5), provide the foundation for rational design of 'active sites' for practical alkaline HER and OER electrocatalysts.
Abstract: Design and synthesis of materials for efficient electrochemical transformation of water to molecular hydrogen and of hydroxyl ions to oxygen in alkaline environments is of paramount importance in reducing energy losses in water–alkali electrolysers. Here, using 3d-M hydr(oxy)oxides, with distinct stoichiometries and morphologies in the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) regions, we establish the overall catalytic activities for these reaction as a function of a more fundamental property, a descriptor, OH–M2+δ bond strength (0 ≤ δ ≤ 1.5). This relationship exhibits trends in reactivity (Mn < Fe < Co < Ni), which is governed by the strength of the OH–M2+δ energetic (Ni < Co < Fe < Mn). These trends are found to be independent of the source of the OH, either the supporting electrolyte (for the OER) or the water dissociation product (for the HER). The successful identification of these electrocatalytic trends provides the foundation for rational design of ‘active sites’ for practical alkaline HER and OER electrocatalysts. Efficient electrochemical transformation of water to molecular hydrogen and of hydroxyl ions to oxygen in alkaline environments is important for reducing energy losses in water–alkali electrolysers. Insight into the activities of hydr(oxy)oxides on platinum catalyst surfaces for hydrogen and oxygen evolution reactions should prove significant for designing practical alkaline electrocatalysts.
2,271 citations