N-Doped Carbon Nanotube Shell Encapsulating the NiFe Metal Core for Enhanced Catalytic Stability in Methanol Oxidation Reaction by the Structural Cooperation Mechanism

Exploitation of high-efficiency catalysts toward methanol oxidation is a pivotal step to promote the commercialization of direct methanol fuel cells. Herein, a strategy is demonstrated to prepare nitrogen-doped carbon nanotubes with NiFe metal particles (NiFe@N-CNT) as the carrier material of Pt nanoparticles. Combining SEM and TEM, NiFe metal particles are fully encapsulated in N-CNTs, and they form the metal core and carbon nanotube shell structure based on the structural cooperation mechanism. Surprisingly, the as-prepared Pt/NiFe@N-CNT catalyst shows superior catalytic activity (1023 mA mg–1Pt) compared to commercial Pt/C (392 mA mg–1Pt), Pt/Ni@N-CNT (331 mA mg–1Pt), and Pt/Fe@N-CNT (592 mA mg–1Pt). After 1000 cycles, Pt/NiFe@N-CNT maintains the optimal catalytic activity (588 mA mg–1Pt), and its mass activity loss is 42.5%, which is better than those of commercial Pt/C (64.0%), Pt/Ni@N-CNT (67.7%), and Pt/Fe@N-CNT (59.6%) catalysts, indicating that the Pt/NiFe@N-CNT catalyst achieves excellent catalytic activity and stability, which stems chiefly from the homodispersed Pt nanoparticles and the generation of the metal core–carbon nanotube shell based on the structural cooperation mechanism. This study reports the facile construction of a metal core–carbon nanotube shell structure, which intrinsically ameliorates structural collapse of carrier material, thereby improving the catalytic stability of the Pt-based catalyst and broadening the view for design of other desire catalysts in methanol oxidation.