Facile synthesis of fully ordered L1₀-FePt nanoparticles with controlled Pt-shell thicknesses for electrocatalysis

We report a simple one-step approach for the synthesis of ~4 nm uniform and fully L1₀-ordered face-centered tetragonal (fct) FePt nanoparticles (NPs) embedded in ~60 nm MCM-41 (fct-FePt NPs@MCM-41). We controlled the Pt-shell thickness of the fct-FePt NPs by treating the fct-FePt NPs@MCM-41 with acetic acid (HOAc) or hydrochloric acid (HCl) under sonication, thereby etching the surface Fe atoms of the NPs. The fct-FePt NPs deposited onto the carbon support (fct-FePt NP/C) were prepared by mixing the fct-FePt NPs@MCM-41 with carbon and subsequently removing the MCM-41 using NaOH. We also developed a facile method to synthesize acid-treated fct-FePt NP/C by using a HF solution for simultaneous surface-Fe etching and MCM-41 removal. We studied the effects of both surface-Fe etching and Pt-shell thickness on the electrocatalytic properties of fct-FePt NPs for the methanol oxidation reaction (MOR). Compared with the non-treated fct-FePt NP/C catalyst, the HOAc-treated and HCl-treated catalysts exhibit up to 34% larger electrochemically active surface areas (ECASAs); in addition, the HCl-treated fct-FePt NP (with ~1.0 nm Pt shell)/C catalyst exhibits the highest specific activity. The HF-treated fct-FePt NP/C exhibits an ECASA almost 2 times larger than those of the other acid-treated fct-FePt NP/C catalysts and shows the highest mass activity (1, 435 mA·mg_Pt^–1, 2.3 times higher than that of the commercial Pt/C catalyst) and stability among the catalysts tested. Our findings demonstrate that the surface-Fe etching for the generation of the Pt shell on fct-FePt NPs and the Pt-shell thickness can be factors for optimizing the electrocatalysis of the MOR.