Electronic structure engineering of heterogeneous ceria-incorporated Pt/C as an efficient catalyst for boosting DMFC performance

Abstract

The commercial development of direct methanol fuel cells (DMFCs) is hindered by the slow kinetics of both the methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) of Pt-based electrocatalysts. Modulating the electronic configuration of Pt with a low-electronegativity second component can accelerate reaction kinetics. Herein, heterogeneous PtCe–CeO₂/C was designed by alloying Pt with ultra-low-electronegativity Ce modulation and incorporating it with CeO₂ to accelerate intermediate conversion. As an efficient bifunctional catalyst, PtCe–CeO₂/C exhibits the MOR and ORR mass activities 3.6 and 9.4 times that of Pt/C and outperforms in DMFCs. The regulation of the electronic structure, intermediate adsorption, and the enhanced catalytic mechanism for the MOR and ORR on PtCe–CeO₂/C are clarified by experiments and theoretical calculations to comprehend the superiority in catalytic activity. Consequently, this work proposes an innovative strategy for deep electronic regulation of CeO₂-modified Pt-based materials with ultra-low-electronegativity Ce to understand the mechanism in electronic structure modulation and promote the reliable operation of DMFCs.