Enhancing Hydrogen Oxidation and Evolution Kinetics by Tuning the Interfacial Hydrogen‐Bonding Environment on Functionalized Platinum Surfaces

Abstract Developing efficient catalytic systems for the hydrogen oxidation and evolution reactions (HOR/HER) is essential in the world's transition to renewable energy. There is a growing recognition that the HOR/HER activity depends on properties of the electrochemical interface, rather than just the composition and structure of the catalyst. Herein, we demonstrate that specifically adsorbed organic additives (theophylline derivatives) could enhance the intrinsic HOR/HER activity in base on polycrystalline Pt by up to a factor of 3 via introducing weakly hydrogen‐bonded water, as confirmed by in situ surface enhanced infrared and Raman spectroscopies. Optimal HOR/HER activity is achieved on a 7‐n‐butyltheophylline decorated Pt surface, which sufficiently disrupts the hydrogen bonding network in the double layer without depleting the interfacial water. This work demonstrates the promise of electrochemical interfacial engineering as a strategy to boost electrocatalytic performance.