Tailoring N Configurations for Enhanced Methanol Oxidation on Pt Nanoparticles

Abstract Direct methanol fuel cells (DMFCs) face significant challenges due to sluggish methanol oxidation reaction (MOR) kinetics and catalyst poisoning by carbon intermediates (e.g., CO ads ). To address this, we rationally designed nitrogen‐doped carbon (NC) carriers with tailored N‐configurations (pyridinic‐N, pyrrolic‐N, and graphitic‐N) via controlled pyrolysis temperatures (700–1000 °C) and anchored Pt nanoparticles (NPs) to enhance metal‐support interaction (MSI). The NC‐900 carrier achieved optimal N‐configuration distribution (56.7% pyridinic‐N, 25.2% pyrrolic‐N, 18.1% graphitic‐N) and the highest defect density ( I D /I G = 1.12), enabling ultra‐dispersed Pt NPs (1.69 nm) and strong electron donation to Pt. XPS confirmed a 61.2% Pt° content in Pt/NPC‐900, facilitating efficient methanol adsorption/activation. In alkaline media, Pt/NPC‐900 delivered a record mass activity of 4687.5 mA mg −1 Pt ‐ 4.36 × higher than Pt/PC—along with exceptional stability (79.6 % current retention after 500 cycles). In situ Raman spectroscopy revealed a non‐CO pathway, circumventing poisoning intermediates. This work establishes a precise N‐configuration engineering strategy to optimize MSI for next‐generation DMFC catalysts.