Unraveling the Role of Base and Catalyst Polarization in Alcohol Oxidation on Au and Pt in Water

Alcohol oxidation by O2 to carboxylic acid can be operated in water using noble-metal catalysts, but relies on the undesirable addition of a base such as sodium hydroxide. Using periodic density functional theory (DFT), we built a model including the chemisorption of hydroxide anion at the metal/water interface to rationalize the pivotal role of the added base on the catalytic activity. We demonstrate that the role of the base is to polarize the surface and that a similar promotion could be obtained by tuning the electronic properties of additives, alloy, and support