Ordered alloy formation for Pt3Fe/C, PtFe/C and Pt5.75Fe5.75Cuy/CO2-reduction electro-catalysts

Carbon supported Pt3Fe, PtFe and Pt5.75Fe5.75Cu catalysts are prepared via the impregnation of Fe and/or Cu-nitrate precursor salts onto a preformed nano-sized Pt/C catalyst. They are referred to as Pt3Fe/C, PtFe/C and Pt5.75Fe5.75Cu/C catalysts and the subscripts refer to the nominal Pt, Fe and Cu atomic ratios. The final catalysts are obtained by annealing the impregnated samples in a H2 enriched atmosphere. Pt5.75Fe6.75/C, Pt5.75Cu6.75/C and Pt5.75Fe5.75Cu2/C catalysts were also made. The as-prepared catalysts are characterized using X-ray diffraction, transmission electron microscopy, standard electrochemical methods and probed for the electrochemical O2 reduction reaction (orr). Rietveld analyses reveal that [Fm-3m] Pt, cubic [Pm-3m] Pt3Fe and tetragonal [P4/mmm] PtFe structure types are made. In case of the Pt5.75Fe5.75Cu/C catalyst, a nano-sized carbon-supported single-phase catalyst of [P4/mmm] structure is found to be made at 800°C, with Pt and Fe ordered on separate lattice planes, while Cu is distributed randomly onto both Pt and Fe atomic planes. The PtFe/C equivalent catalyst contains in addition a separate Fe phase as well as a slightly disordered [P4/mmm] phase. Pt5.75Cu6.75/C forms a disordered cubic [Fm-3m] alloy structure. The activity toward the orr was measured after 70 potential cycling, which can cause beneficial changes to the catalysts. In case of the specific orr activity, a dependence on the catalyst series is observed as follows: Pt5.75Fe5.75Cu/C [P4/mmm]>PtFe/C [P4/mmm]>Pt3Fe/C [Pm-3m]≈Pt5.75Cu6.75/C [Fm-3m]>Pt/C [Fm-3m]. The highest orr mass activities are also found for the Pt5.75Fe5.75Cu/C and subsequently for the PtFe/C catalysts. Estimated orr activities are well within the range reported in the literature. In fact the specific orr activities compare to results reported for so called de-alloyed catalyst that are among the highest orr mass activities reported in the recent literature.