Direct Ethanol Fuel Cells: Cleavage of the C-C Bond on Different Pt-M Catalysts Using Reactivity Descriptors through Density Functional Theory
The use of ethanol in this fuel cell offers advantages such as its non-toxicity, renewability, high energy density (8 kWh/kg, compared with 33 kWh/kg for hydrogen and about of 11 kWh/kg for gasoline), and its easy production in large quantities [4-6], despite this advantage of ethanol as fuel, the research to achieve the C-C bond cleavage in this molecule on several Pt-Metal (Pt-M) alloys is still in development.
Complete oxidation of ethanol implies the cleavage of the C-C bond, whose mechanism is currently not completely understood. The most accepted mechanism proposes that ethanol oxidation on Pt-based catalysts occurs through an initial adsorption step and then a series of dehydrogenation reactions occurs to produce adsorbed acetaldehyde CH3CHO and acetyl CH3CO. Acetyl could react with OH molecules, formed by H2O oxidation to OH-, producing acetic acid CH3COOH, considered a final product in ethanol oxidation because of the difficulty of further oxidation. This partial oxidation of ethanol is considered the most favorable route on actual catalysts, but it only releases 4 electrons [5, 6].
To achieve the complete oxidation to CO2 and to avoid the partial oxidation of ethanol is necessary to gain understanding of the C-C bond cleavage after of the first dehydrogenation steps, so in this work the C-C cleavage step of the ethanol oxidation is described on Pt and different Pt-M catalytic alloys (Pt-Sn, Pt-Re) using reactivity descriptors (representative molecules showing destabilization on catalytic alloys, for instance CHCO) .
The reactivity descriptors are characterized calculating their binding energies, electron density, density of states, and electron localization function. With this data and analyzing the reactivity surface of the descriptors on each catalytic alloy, a comparison of the behavior of the C-C bond cleavage on the different metallic alloys is presented based on the chemical bonding theory. Also available experimental data are compared with the theoretical calculations carried out with density functional theory.
 S Abdullah, S.K. Kamarudin, U.A. Hasran, M.S. Masdar, and W.R.W. Daud. Modeling and simulation of a direct ethanol fuel cell: An overview. Journal of Power Sources, 262:401–406, September 2014.
 Jiujun Zhang. PEM Fuel Cell Electrocatalysts and Catalyst Layers. Springer London, London, 2008.
 Annett Rabis, Paramaconi Rodriguez, and Thomas J. Schmidt. Electrocatalysis for Polymer Electrolyte Fuel Cells: Recent Achievements and Future Challenges. ACS Catalysis, 2(5):864–890, May 2012.
 Shuqin Song and Panagiotis Tsiakaras. Recent progress in direct ethanol proton exchange membrane fuel cells (DE-PEMFCs). Applied Catalysis B: Environmental, 63(3- 4):187–193, March 2006.
C Lamy. The direct ethanol fuel cell: a challenge to convert bioethanol cleanly into electric energy. In Pierluigi Barbaro and Claudio Bianchini, editors, Catalysis for Sustainable Energy Production, chapter 1, pages 1–46. WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany., 2009.
 M.Z.F. Kamarudin, S.K. Kamarudin, M.S. Masdar, and W.R.W. Daud. Review: Direct ethanol fuel cells. International Journal of Hydrogen Energy, pages 1–16, September 2012.
 J K Nørskov, T Bligaard, J Rossmeisl, and C H Christensen. Towards the computational design of solid catalysts. Nature chemistry, 1(1):37–46, April 2009.