Fuel cells represent a promising technology for clean power generation because they convert chemical energy (fuel) into electrical energy with high efficiency and low-to-none emission of pollutants. Direct ethanol fuel cells (DEFCs) have several advantages compared to the most studied hydrogen and methanol fuel cells. First and foremost, ethanol is a non-toxic liquid, which lowers the investment of handling facilities because the current infrastructure for gasoline can be largely used. Second, ethanol can be conveniently produced from biomass, hence is carbon neutral which mitigates increasing atmospheric CO2. Last but not least, if completely oxidized to CO2, ethanol has a higher energy density than methanol since it can deliver 12 electrons per molecule. The almost exclusive oxidation to acetic acid overshadows the attractiveness of DEFCs considerably, as the energy density is divided by 3. The standard potential of acetic acid formation indicates that a reaction path including acetic acid, leads to inevitable potential losses of about 0.4 V (difference between ideal potential for CO2 and acetic acid "production"). The development of alkaline DEFCs had also been hampered by the lack of stable and efficient anion exchange membranes. Fortunately, this challenge has been well tackled in recent years,8,9 making the development of alkaline fuel cells (AFCs) which are of particular technological interest due to their simple designs and ability to operate at low temperatures (25-100 °C). In alkaline conditions, the kinetic of both the cathodic oxygen reduction and the anodic ethanol oxidation is facilitated. Furthermore, the expensive Pt catalyst can be replaced by the lower-cost and more active transition metals such as Pd. The main objectives of this project are: i) to provide detailed fundamental understanding of ethanol oxidation reaction on transition metal surfaces in alkaline media, ii) to propose the best rational catalyst design strategies to cleave the C–C bond during ethanol electrooxidation. To achieve these goals two methodologies are used, i.e., in-situ identification of ethanol electrooxidation products using polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) and mechanistic investigation using computational studies in the framework of density functional theory (DFT). The PM-IRRAS technique was advanced in this project to the level of distinguishing electrooxidation products at the surface of the nanoparticles (electrode) and in the bulk-phase of the electrolyte. This new PM-IRRAS utility makes it possible to detect molecules such as CO2 which desorbs from the catalyst surface as soon as they are formed. The DFT insights in this project, provides an explanation as to why it is difficult to break the C–C bond in ethanol and is used for screening the top candidate metals for further studies.