Interface Engineering of PdPt Ultrafine Ethanol Electro‐Oxidation Nanocatalysts by Bacterial Soluble Extracellular Polymeric Substances (s‐EPS) to Break through Sabatier Principle

Abstract Unsatisfactory performance of ethanol oxidation reaction (EOR) catalysts hinders the application of direct ethanol fuel cells (DEFCs), while traditional alloy catalysts (like PdPt) is cursed by Sabatier principle due to countable active site types. However, bacterial soluble extracellular polymeric substances (s‐EPS) owning abundent functional groups may help breacking through it by contrusting different active sites on PdPt and inducing them to play synergy effect, which is called interface engineering. Using s‐EPS to engineer catalysts is more green and consumes lower energy compared to chemical reagents. Herein, PdPt alloy nanoparticles (≈2.1 nm) are successfully in situ synthesized by/on s‐EPS of Bacillus megaterium , an ex‐holotype. Tryptophan residuals are proved as the main reductant. In EOR, PdPt@s‐EPS shows higher activity (3.89 mA cm ⁻² ) than Pd@s‐EPS, Pt@s‐EPS, Pt/C and most reported akin catalysts. Its stability and durability are excellent, too. DFT modelling further demonstrates that, interface engineering by s‐EPS breaks through Sabatier principle, by the synergy of diverse sites owning different degrees of d‐p orbital hybridization. This work not only makes DEFCs closer to practice, but provides a facile and green strategy to design more catalysts.