Geometric Engineering of Porous PtCu Nanotubes with Ultrahigh Methanol Oxidation and Oxygen Reduction Capability.

Platinum (Pt), as a commonly used electrocatalyst in direct methanol fuel cells (DMFCs), suffers from sluggish kinetics of both the methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR). Geometric engineering has been proven effective for improving the MOR and ORR activities. Thus, by modulating the Pt precursor and poly(vinylpyrrolidone) (PVP) dosages, different porous PtCu nanotubes constructed by hollow nanospheres, solid alloy, and Pt-rich skinned nanoparticles, respectively, are successfully synthesized. Among them, the solid PtCu alloy nanoparticle coherent nanotubes exhibit the specific activity 9.42 times higher than Pt/C toward MOR, while the hollow PtCu alloy nanosphere coherent nanotubes show the specific activity 4.85 times higher than Pt/C toward ORR. The different Pt:Cu ratios of hollow nanospheres, solid alloy, and Pt-rich skinned nanoparticles cause the differences in electron transfer from Cu to Pt as well as electronic structures of Pt. As a result, the binding energies of intermediates can be regulated, leading to the enhancement in MOR and ORR.