Ternary Pt9RhFex Nanoscale Alloys as Highly Efficient Catalysts with Enhanced Activity and Excellent CO-Poisoning Tolerance for Ethanol Oxidation.

To address the problems of high cost and poor stability of anode catalysts in direct ethanol fuel cells (DEFCs), ternary nanoparticles Pt9RhFex (x = 1, 3, 5, 7, and 9) supported on carbon powders (XC-72R) have been synthesized via a facile method involving reduction by sodium borohydride followed by thermal annealing in N2 at ambient pressure. The catalysts are physically characterized by X-ray diffraction, scanning transmission electron microscopy, and X-ray photoelectron spectroscopy, and their catalytic performance for the ethanol oxidation reaction (EOR) is evaluated by cyclic and linear scan voltammetry, CO-stripping voltammograms, and chronopotentiometry. All the Pt9RhFex/C catalysts of different atomic ratios produce high EOR catalytic activity. The catalyst of atomic ratio composition 9:1:3 (Pt/Rh/Fe) has the highest activity and excellent CO-poisoning tolerance. Moreover, the enhanced EOR catalytic activity on Pt9RhFe3/C when compared to Pt9Rh/C, Pt3Fe/C, and Pt/C clearly demonstrates the presence of Fe improves catalytic performance. Notably, the onset potential for CO oxidation on Pt9RhFe3/C (0.271 V) is ∼55, 75, and 191 mV more negative than on Pt9Rh/C (0.326 V), Pt3Fe/C (0.346 V), and Pt/C (0.462 V), respectively, which implies the presence of Fe atoms dramatically improves CO-poisoning tolerance. Meanwhile, compared to the commercial PtRu/C catalyst, the peak potential on Pt9RhFe3/C for CO oxidation was just slightly changed after several thousand cycles, which shows high stability against the potential cycling. The possible mechanism by which Fe and Rh atoms facilitate the observed enhanced performance is also considered herein, and we conclude Pt9RhFe3/C offers a promising anode catalyst for direct ethanol fuel cells.