Impact of Electrolyte Composition on Bulk Electrolysis of Furfural over Platinum Electrodes**

Abstract Partial oxidation of furanic biomass derivatives such as furfural is of interest for the sustainable production of chemicals including furoic acid, maleic acid, and 2,5‐furandicarboxylic acid (FDCA). The oxidative bulk electrolysis of furfural is here investigated on platinum electrodes in acidic media. The effects of potential, concentration, pH, and supporting anion are studied, and selectivity trends are coupled with attenuated total reflectance surface‐enhanced infrared absorption spectroscopy (ATR‐SEIRAS) to illuminate adsorbate structures that influence the catalysis. Increasing potential is found to shift selectivity from primarily C 5 products to C 4 products, coincident with oxidation of the Pt surface. Selectivity changes are also observed moving from pH 1 to pH 4, with an increase in C 5 products at higher pH. Changing from the weakly adsorbing perchlorate anion to the specifically‐adsorbing phosphate anion results in a number of changes that manifest differently depending on potential and pH. Selectivity to furoic acid is found to be highest above the pKa of phosphoric acid due to the strongly adsorbed phosphate ions suppressing flat‐lying configurations of furfural that lead to C−C cleavage. These results point toward opportunities to use electrolyte engineering to tune selectivity and optimize surface conditions to disfavor binding of inhibitory products.