One of the key objectives in fuel-cell technology is to improve and reduce Pt loading as the oxygen-reduction catalyst. Here, we show a fundamental relationship in electrocatalytic trends on Pt(3)M (M=Ni, Co, Fe, Ti, V) surfaces between the experimentally determined surface electronic structure (the d-band centre) and activity for the oxygen-reduction reaction. This relationship exhibits 'volcano-type' behaviour, where the maximum catalytic activity is governed by a balance between adsorption energies of reactive intermediates and surface coverage by spectator (blocking) species. The electrocatalytic trends established for extended surfaces are used to explain the activity pattern of Pt(3)M nanocatalysts as well as to provide a fundamental basis for the catalytic enhancement of cathode catalysts. By combining simulations with experiments in the quest for surfaces with desired activity, an advanced concept in nanoscale catalyst engineering has been developed.

The fuel cell is a promising alternative to environmentally unfriendly devices that are currently powered by fossil fuels. In the polymer electrolyte membrane fuel cell (PEMFC), the main fuel is hydrogen, which through its reaction with oxygen produces electricity with water as the only by-product. To make PEMFCs economically viable, there are several problems that should be solved; the main one is to find more effective catalysts than Pt for the oxygen reduction reaction (ORR), 1/2 O 2 + 2 H + + 2 e À = H 2 O. The design of inexpensive, stable, and catalytically active materials for the ORR will require fundamental breakthroughs, and to this end it is important to develop a fundamental understanding of the catalytic process on different materials. Herein, we describe how variations in the electronic structure determine trends in the catalytic activity of the ORR across the periodic table. We show that Pt alloys involving 3d metals are better catalysts than Pt because the electronic structure of the Pt atoms in the surface of these alloys has been modified slightly. With this understanding, we hope that electrocatalysts can begin to be designed on the basis of fundamental insight.

Electrochemistry will play a vital role in creating sustainable energy solutions in the future, particularly for the conversion and storage of electrical into chemical energy in electrolysis cells, and the reverse conversion and utilization of the stored energy in galvanic cells. The common challenge in both processes is the development of-preferably abundant-nanostructured materials that can catalyze the electrochemical reactions of interest with a high rate over a sufficiently long period of time. An overall understanding of the related processes and mechanisms occurring under the operation conditions is a necessity for the rational design of materials that meet these requirements. A promising strategy to develop such an understanding is the investigation of the impact of material properties on reaction activity/selectivity and on catalyst stability under the conditions of operation, as well as the application of complementary in situ techniques for the investigation of catalyst structure and composition.

Reducing noble metal loading and increasing specific activity of oxygen evolution catalysts are omnipresent challenges in proton exchange membrane (PEM) water electrolysis, which have recently been tackled by utilizing mixed oxides of noble and non-noble elements (e.g. perovskites, IrNiO x , etc.). However, proper verification of the stability of these materials is still pending. In this work dissolution processes of various iridium-based oxides are explored by introducing a new metric, defined as the ratio between amount of evolved oxygen and dissolved iridium. The so called Stability-number is independent of loading, surface area or involved active sites and thus, provides a reasonable comparison of diverse materials with respect to stability. Furthermore it can support the clarification of dissolution mechanisms and the estimation of a catalyst's lifetime. The case study on iridium-based perovskites shows that leaching of the non-noble elements in mixed oxides leads to formation of highly active amorphous iridium oxide, the instability of which is explained by participation of activated oxygen atoms, generating short-lived vacancies that favour dissolution. These insights are considered to guide further research which should be devoted to increasing utilization of pure crystalline iridium oxide, as it is the only known structure that guarantees a high durability in acidic conditions. In case amorphous iridium oxides are used, solutions for stabilization are needed.

The surface properties of PtM (M = Co, Ni, Fe) polycrystalline alloys are studied by utilizing Auger electron spectroscopy, low energy ion scattering spectroscopy, and ultraviolet photoemission spectroscopy. For each alloy initial surface characterization was done in an ultrahigh vacuum (UHV) system, and depending on preparation procedure it was possible to form surfaces with two different compositions. Due to surface segregation thermodynamics, annealed alloy surfaces form the outermost Pt-skin surface layer, which consists only platinum atoms, while the sputtered surfaces have the bulk ratio of alloying components. The measured valence band density of state spectra clearly shows the differences in electronic structures between Pt-skin and sputtered surfaces. Well-defined surfaces were hereafter transferred out from UHV and exposed to the acidic (electro)chemical environment. The electrochemical and post-electrochemical UHV surface characterizations revealed that Pt-skin surfaces are stable during and after immersion to an electrolyte. In contrast all sputtered surfaces formed Pt-skeleton outermost layers due to dissolution of transition metal atoms. Therefore, these three different near-surface compositions (Pt-skin, Pt-skeleton, and pure polycrystalline Pt) all having pure-Pt outermost layers are found to have different electronic structures, which originates from different arrangements of subsurface atoms of the alloying component. Modification in Pt electronic properties alters adsorption/catalytic properties of the corresponding bimetallic alloy. The most active systems for the electrochemical oxygen reduction reaction are established to be the Pt-skin near-surface composition, which also have the most shifted metallic d-band center position versus Fermi level.

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The particle size effect on the formation of OH adlayer, the CO bulk oxidation, and the oxygen reduction reaction (ORR) have been studied on Pt nanoparticles in perchloric acid electrolyte. From measurements of the CO displacement charge at controlled potential, the corresponding surface charge density versus potential curves yielded the potentials of total zero charge (pztc), which shifts approximately 35 mV negative by decreasing the particle size from 30 nm down to 1 nm. As a consequence, the energy of adsorption of OH is more enhanced, that is, at the same potential the surface coverage with OH increases by decreasing the particle size, which in turn affects the catalytic reactions thereon. The impact of the electronically induced potential shift in the OH adsorption is demonstrated at the CO bulk oxidation, in which adsorbed OH is an educt species and promotes the reaction, and the ORR, where it can act as a surface site blocking species and inhibits the reaction.