Nitrogen and Sulfur Co-Doped Graphene Composite Aerogel Microspheres Supporting Pt Electrode-Catalyzed Methanol Electro-Oxidation Reaction

Nitrogen and sulfur co-doped graphene composite aerogel microspheres containing pyrolyzed carbon (NS-GAMs@C) are prepared by pressure-spraying the graphene oxide (GO) dispersion with water-soluble phenolic resin and thiourea, followed by freeze shaping, freeze-drying, and high-temperature carbonization. The resulting NS-GAMs@C possesses interconnected porous structures with large surface areas and high doping levels of N/S elements. Furthermore, the platinum nanoparticles (Pt NPs) are grown onto the NS-GAMs@C via a solvothermal reduction reaction to obtain the Pt/NS-GAMs@C microspheres with an average particle size of ∼32.25 μm. The residual carbon species in situ formed by the high-temperature carbonization of phenolic resin can act as intercalation compounds to reduce the self-stacking of graphene sheets, which contributes to an enhanced specific surface area and doping level. The N/S co-doping in NS-GAMs@C improves the interaction between the Pt and carriers, reduces the size of Pt NPs, ensures their even distribution, and increases the proportion of highly active Pt (111) crystal planes. Consequently, the methanol oxidation activity of Pt/NS-GAMs@C is significantly improved compared to undoped materials. Specifically, the optimized Pt/NS-GAMs@C composites demonstrate a remarkable mass activity of 840.11 mA·mg^-1 Pt for methanol electrooxidation, which is approximately 2.39, 3.94, 3.41, and 1.75 times higher than that of commercial Pt/C, Pt/rGO (reduced GO), Pt/GAMs without doping, and Pt/NS-GAB@C (bulk aerogel), respectively. Additionally, the Pt/NS-GAMs@C exhibits long-term electrocatalytic stability. This research provides a novel catalyst system based on aerogel microspheres for methanol electrooxidation fuel cells.