Supporting information: Resonance-promoted formic acid oxidation via dynamic electrocatalytic modulation

The activity of platinum group metals have placed majority of these catalysts far above other types of metal catalysts,turnover frequencies have typically landed them on top of the volcano curves of most chemical reactions. However, itsbiggest attraction is also the reason for its lack of practicality; two of the biggest problems involving platinum groupmetals include lack of selectivity control, and susceptibility to poison . Hydrodeoxygenation (HDO) is a key chemistryin pushing forward more bio-derived feedstocks in the industry, succinic acid -through HDO- has been highlighted as apotential alternative to maleic anhydride for the production of 1,4-butanediol, gamma-butyrolactone andtetrahydrofuran. However, upgrading these carboxylic acids proves problematic over the preferred catalysts (noblemetals) because of a lack of selectivity control. These active catalysts facilitate a multitude of undesired reactions suchas hydrogenolysis, decarbonylation, decarboxylation, and methanation, which all lead to a slew of low-value products .It is widely reported that the addition of oxophilic “promoter metals,” such as Sn can be used to tune the selectivity ofnoble metals during the HDO of carboxylic acids ; however, their mechanism of action is poorly understood. Anothercommon problem in both upgrading and extracting energy (fuel cells) from carboxylic acids is formation of carbonmonoxide, which has a tendency to inhibit reaction rates. A new approach has been brought to the forefront in moderncatalyst operation, dynamic catalysis. This involves the use of an external stimuli in order to oscillate between energystate ; these different states will manipulate the rate determining steps (rds) in a reaction mechanism, bouncingbetween different rds’s has the potential operate at rates magnitudes higher than operating under a static condition. Inthis poster, we use two separate approaches for solving the practical limitations of platinum group metals. First, we use propionic acid HDO as a model system for tackling selectivity control over supported Pt catalysts. Whilesuccinic acid HDO might be more practical to an industrial setting, a simpler molecule is ideal for a fundamental studyas it captures all the essential chemistries expected without a product stream being overcrowded. We will dissect HDOactivity over monometallic Pt using experimental and computational techniques, providing macroscopic insight onreaction pathways and major inhibitors to HDO selectivity. This shall play a crucial role in understanding how theaddition of an oxophilic promoter, Sn, can intrinsically tune the catalytic activity towards higher yields of HDO products. Second, we explore the effect of dynamic catalysis on carboxylic acid oxidation using electric fields. Formic acidoxidation will be used as a model reaction for the production of carbon dioxide, this is common reaction in fuel cells.Oscillating in between different applied potentials will allow us to observe this concept experimentally and the degreeto which a rate increase can be achieved using a potentiodynamic approach while also overcoming the hurdle ofproduct inhibition.