Maximizing the leverage induced by Pt-O-Ce(III) interface structure to facilitate the non-CO pathway for methanol oxidation reaction

Cerium(III) oxygenated domain has been successfully decorated on the surface of PtCo particles. • The control of *CHO adsorption at Pt–O–Ce(III) interface achieves a non-CO pathway for MOR. • The *HCOOH deprotonation kinetics governed by the coverage of cerium(III) oxidation domain affects the overpotential of MOR. • The Ce-PtCo/C catalyst achieves a mass activity that is 4.8 times as high as that of Pt/C. The poisoning of *CO remains a longstanding challenge for Pt-based catalysts in methanol oxidation reaction (MOR). This study demonstrates that the non-CO pathway is governed by the moderate adsorption of *CHO species and the ability to rapidly oxidize intermediate, both of which can be fulfilled by the Pt-O-Ce(III) interface rather than Pt-O-Ce(IV). In contrast to traditional CeO 2 -supported Pt-based catalyst, this surface-modified Pt-based catalyst has been constructed with abundant Pt-O-Ce(III) interface, providing stable and sufficient active sites to simultaneously optimize the above two factors to catalyze MOR with non-CO pathway. Furthermore, we first reveal that the coverage of this Pt-O-Ce(III) interface is crucial. By rationally regulating the coverage of cerium(III) oxygenated domains, we modulate the thermodynamic adsorption properties of key intermediate species without affecting the subsequent deprotonation kinetics of *HCOOH, thereby achieving the maximum leverage. This novel catalyst steering the non-CO pathway shows promising application potential in actual DMFCs. Download: Download high-res image (137KB) Download: Download full-size image