RESUMO
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.
Assuntos
Metanol , Nanotubos , Ligas/química , Catálise , Metanol/química , Nanotubos/química , Oxirredução , Oxigênio/química , Platina/química , PorosidadeRESUMO
The amount of active sites of a catalyst is of great importance to enhance the oxygen evolution reaction (OER) activity. Here, the sheet-on-sheet strategy is proposed to effectively increase the density of active sites of NiFe layered double hydroxide (NiFe LDH) catalyst in terms of structural engineering. As a non-precious electrocatalyst for the OER, NiFe LDH is grown directly on CuO nanosheets. As a result, the received NiFe LDH/CuO nanosheet catalyst with sheet-on-sheet structure shows an ultralow overpotential of 270 mV at 20 mA cm-2, much lower than that of RuO2 as a benchmark. The CuO nanosheets, as substrate, play the vital role in downsizing the NiFe LDH, leading to the raised active site density.