Definition of the Subject
More efficient energy conversion systems may help to reduce the use of fossil fuels and the emission of greenhouse gases. Polymer Electrolyte Membrane Fuel Cells are such devices which are of particular interest for automotive applications. Unfortunately, cost issues are still limiting the application of this technology in a highly competitive market. An important part of this is the inherently high cost of platinum which is commonly used as electrocatalyst. But recently, the replacement of platinum by NNMC has come into the focus of reach. The most promising approaches – comprising the use of crystalline phases and catalysts with molecular active centers – are described in this entry; limitations of both classes of materials are discussed.
Introduction
Although platinum and platinum alloys are the state-of-the-art electrocatalysts for PEM fuel cell applications, the platinum...
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Abbreviations
- R(R)DE:
-
Rotating (Ring) Disk Electrode. This technique is an electrochemical standard method; in this work, the measurements are performed to determine the catalytic activity towards the oxygen reduction in liquid oxygen–saturated electrolytes. Depending on the rotation rate, the diffusion-limited current changes. Measurements at different rotation rates enable the calculation of the kinetic current by using the Koutecky-Levich equation.
- Fe-N-C catalyst:
-
Group of catalysts for which it is believed that molecular FeN4- or FeN2+2-centers are responsible for the reduction of oxygen.
- Macrocycle:
-
Complex, organic molecule; in the context of this report, usually porphyrins, phthalocyanines, tetraazaannulenes, i.e., characterized by a tetrapyrrole core.
- NNMC:
-
Non-noble metal catalysts: Catalysts prepared without any noble metals. As a result, the fabrication costs of such materials should be essentially lower as all basic-components are cheap.
- ORR:
-
Oxygen Reduction Reaction. In this contribution, it stands for the electrochemical reduction of oxygen. The favored pathway is the direct reduction to water whereas the indirect pathway via the formation of peroxides is undesirable for fuel cell application.
- Pyrochelates:
-
Macrocycles which were heat-treated (T > 300°C). During pyrolysis, the initial molecular structure is transferred into a carbon matrix. As also some fractions of the molecular centers of the precursor are preserved, the resulting product is sometimes assigned as pyrochelate.
- Site density (SD):
-
Number of active sites per volume of catalyst. For the calculation of site densities of Me-N-C catalysts, often two assumptions have to be made: (1) the density is similar to other carbon-based catalysts (0.4 g/cm3) and (2) each metal atom is related to an active site. In some cases, authors determine the exact mass density and/or number of active sites, so that the value becomes more accurate. In all other cases, it is usually overestimated as not all metal atoms are associated with active sites.
- Transition metal chalcogenides:
-
A chemical compound which is composed of at least one chalcogen (O, S, Se, Te) anion and one or more transition metal cations.
- Turnover frequency (TOF):
-
The TOF gives the number of electrons which are transferred from the active site per site and second. Similar to the site density also here often assumptions have to be made.
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Kramm, U.I., Bogdanoff, P., Fiechter, S. (2012). Polymer Electrolyte Membrane Fuel Cells (PEM-FC) and Non-noble Metal Catalysts for Oxygen Reduction . In: Meyers, R.A. (eds) Encyclopedia of Sustainability Science and Technology. Springer, New York, NY. https://doi.org/10.1007/978-1-4419-0851-3_153
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