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.
The electrochemical production of hydrogen and hydrocarbons is considered to play a decisive role in the conversion and storage of excess amounts of renewable energy. The electrocatalysis of the oxygen evolution reaction (OER), however, faces significant challenges for practical implementation of electrolyzers. In this work, a comparative study on the activity and stability of oxidized polycrystalline noble metals during the OER is presented. All studied metals exhibit transient and steady-state dissolution. Transient dissolution takes place during oxide formation and reduction. Steady-state dissolution depends on the OER mechanism on each surface: On metals such as Ru and Au, for which oxygen from the oxide participates in the OER, the Tafel slope is low and the dissolution rate is high. In contrast, on metals for which oxygen evolves directly from adsorbed water, such as Pt and presumably Pd, the Tafel slopes are high and the dissolution rates are low. This should be considered in the design of optimal OER catalysts.The conventional energy strategy based on the deployment of fossil fuels comprises two serious drawbacks: depletion of irretrievable fuels and environmental concerns upon their exploitation. As a consequence, the growing general interest in the concept of sustainable renewable energy has boosted the implementation of alternative energy supply technologies over recent years. [1] Particularly, the utilization of energy from sun and wind is considered as an adoptable scenario in the energy paradigm shift, as each of them is capable of covering the global energy demand, which is estimated to be 17 TW in 2030. [2] Unlike traditional energy supplies, however, the production of electricity from sun and wind is intermittent, which creates a terawatt-scale challenge: fluctuations in energy supply by variation of seasonal weather conditions must be efficiently leveled off. Consequently, besides production itself, conversion and storage of enormous amounts of energy during peak production hours as well as its constant distribution to end users during downtime is an essential piece of the puzzle. One approach capable of handling the terawatt scale is the conversion of electrical energy and storage in the form of chemical bonds as, for example, hydrogen (through water reduction) or hydrocarbons (through carbon dioxide reduction). [3] For instance, these fuels can be produced electrochemically in electrolyzers [4] and then utilized at local fuel cell factories or transported to consumers on demand. [5] The essential counterreaction in an electrolyzer for either technology (water or CO 2 reduction) will be the oxygen evolution reaction (OER). However, the high energy required for the rearrangement of the chemical bonds of water during the OER is actually a bottleneck in the production costs compared to other technologies such as reforming. [3a, 6] Namely, sluggish electrode kinetics and detachment of evolved gas bubbles can severely restrict efficiency. [7] Moreover, the catalyst activity needs to be sustained...
Platinum is one of the most important electrode materials for continuous electrochemical energy conversion due to its high activity and stability. The resistance of this scarce material towards dissolution is however limited under the harsh operational conditions that can occur in fuel cells or other energy conversion devices. In order to improve the understanding of dissolution of platinum, we therefore investigate this issue with an electrochemical flow cell system connected to an inductively coupled plasma mass spectrometer (ICP-MS) capable of online quantification of even small traces of dissolved elements in solution. The electrochemical data combined with the downstream analytics are used to evaluate the influence of various operational parameters on the dissolution processes in acidic electrolytes at room temperature. Platinum dissolution is a transient process, occurring during both positive-and negative-going sweeps over potentials of ca. 1.1 V RHE and depending strongly on the structure and chemistry of the formed oxide. The amount of anodically dissolved platinum is thereby strongly related to the number of low-coordinated surface sites, whereas cathodic dissolution depends on the amount of oxide formed and the timescale. Thus, a tentative mechanism for Pt dissolution is suggested based on a place exchange of oxygen atoms from surface to sub-surface positions.
Electrochemical dissolution of gold and platinum in 0.1 M HClO 4 , 0.1 M H 2 SO 4 , and 0.05 M NaOH is investigated. The qualitative picture of both metals' dissolution is pH-independent. Oxidation/reduction of the metal's surface leads to the transient dissolution peaks which we label A 1 and C 1 on the dissolution profiles. Commencement of the oxygen evolution reaction (OER) results in the additional dissolution peak A 2 . Quantitatively, there are important differences. The amount of gold transiently dissolved in alkaline medium is more than an order of magnitude higher in comparison to that in acidic medium. Oppositely, steady-state gold dissolution in base in the potential region of OER is hindered. The transient dissolution of platinum is by a factor of two higher in base. It is suggested that variation of the pH does not change the mechanism of the OER on platinum. Consequently, the dissolution rate of platinum is equal in acidic and alkaline electrolytes. As an explanation of the observed difference in gold dissolution, a difference in the thickness of compact oxide formed in acid and base is suggested. Growth of a thicker compact oxide in the alkaline medium explains the increased transient and the decreased steady-state dissolution of gold. Platinum and gold are perhaps the most frequently studied metals in electrochemistry. In particular, they constitute important model systems in the context of fundamental investigations of the mechanism and kinetics of the initial stages of metal oxidation. Surface processes during transition of adsorbed hydroxyl groups to, initially, compact couple of monolayers thickness and, later, relatively thick bulk phase oxides have occupied electrochemists for many decades. In the earliest works, investigations were directed toward the general problem of metal passivity, hotly debated at the beginning of the twentieth century. [1][2][3] In the 1960s and 1970s, the rapid development of fuel cells and application of platinum as a catalyst for the hydrogen oxidation and the oxygen reduction reactions (HOR and ORR) re-stimulated research efforts on noble metal oxidation. As adsorbed intermediates and other oxygenated species present on the catalyst surface were believed to have a poisoning effect on the rate of the ORR, understanding of the oxygen-platinum interaction was of substantial importance. The great progress in the development of electrochemical experimental techniques and surface analytics in these years significantly contributed to new insights of electrocatalysis at the solid-liquid interface. The understanding of noble metal oxidation is, however, not only crucial for these reactions but also the essential step in the comprehension of dissolution. Despite its importance in general and as a basis for the current work, the description of the theories and models for noble metal oxidation over the last century is beyond the scope of the present article. The interested reader is therefore referred to a comprehensive work published by Conway, and references therein. Plat...
The electrochemical stability of thermally prepared Ir oxide films is investigated using a scanning flow cell (SFC)-inductively coupled plasma mass-spectrometer (ICP-MS) setup under transient and stationary potential and/or current conditions. Time-resolved dissolution rates provide important insights into critical conditions for material breakdown and a fully quantitative in-situ assessment of the electrochemical stability during oxygen evolution reaction (OER) conditions. In particular, the results demonstrate that stability and OER activity of the IrOx catalysts strongly depend on the chemical and structural nature of Ir oxide species and their synthesis conditions. (C) 2014 The Authors. Published by Elsevier B.V
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