Abstract

Nitrogen doping in carbon materials can modify the employed carbon material’s electronic and structural properties, which helps in creating a stronger metal-support interaction. In this study, the role of nitrogen doping in improving the durability of Pt catalysts supported on a three-dimensional vertically aligned carbon nanofiber (VACNF) array towards oxygen reduction reaction (ORR) was explored. The nitrogen moieties present in the N-VACNF enhanced the metal-support interaction and contributed to a reduction in the Pt particle size from 3.1 nm to 2.3 nm. The Pt/N-VACNF catalyst showed better durability when compared to Pt/VACNF and Pt/C catalysts with similar Pt loading. DFT calculations validated the increase in the durability of the Pt NPs with an increase in pyridinic N and corroborated the molecular ORR pathway for Pt/N-VACNF. Moreover, the Pt/N-VACNF catalyst was found to have excellent tolerance towards methanol crossover.

Highlights

  • Platinum (Pt) nanoparticles (NPs) supported on amorphous carbon (Pt/C) are currently considered to be an effective catalyst for oxygen reduction reaction (ORR) with sluggish reaction kinetics

  • We explored an N-doped three-dimensional vertically aligned carbon nanofiber (VACNF) array as the catalyst support for ORR

  • As the VACNFs were plasma annealed, the NH3 plasma started to etch the sidewalls of carbon fibers confirmed from the decrease in diameter

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Summary

Introduction

Platinum (Pt) nanoparticles (NPs) supported on amorphous carbon (Pt/C) are currently considered to be an effective catalyst for oxygen reduction reaction (ORR) with sluggish reaction kinetics. The performance of Pt/C deteriorates in long-term operations due to the agglomeration or dissolution of Pt NPs [2]. Another factor that affects long-term performance is the oxidation of the underlying carbon support, i.e., carbon corrosion [3]. Pt on the surface can further catalyze the oxidation of carbon and thereby increasing the agglomeration or dissolution of Pt NPs [7]. To address these issues, various reports have recommended reducing the Pt loading or replacing it completely with non-noble metal catalysts. When the Pt loading is reduced, it is very challenging to maintain the catalytic activity and durability

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