A hybrid FeOx/CoOx/Pt ternary nanocatalyst for augmented catalysis of formic acid electro-oxidation

Platinum-based catalysts that have long been used as the anodes for the formic acid electro-oxidation (FAO) in the direct formic acid fuel cells (DFAFCs) were susceptible to retrogradation in performance due to CO poisoning that impaired the technology transfer in industry. This work is designed to overcome this challenge by amending the Pt surface sequentially with nanosized cobalt (nano-CoOx, fibril texture of ca. 200 nm in particle size) and iron (nano-FeOx, nanorods of particle size and length of 80 and 253 nm, respectively) oxides. This enriched the Pt surface with oxygenated groups that boosted FAO and mitigated the CO poisoning. The unfilled d-orbitals of the transition metals and their tendency to vary their oxidations states presumed their participation in a faster mechanism of FAO. Engineering the Pt surface in this FeOx/CoOx/Pt hierarchy resulted in a remarkable activity toward FAO, that exceeded four times that of the Pt catalyst with up to ca. 2.5 times improvement in the catalytic tolerance against CO poisoning. This associated a ca. - 32 mV shift in the onset potential of FAO which increased to - 40 mV with a post-activation of the same catalyst at - 0.5 in 0.2 mol L^-1 NaOH, displaying the catalyst's competitiveness in reducing overpotentials in DFAFCs. It also exhibited a favorable amelioration in the catalytic durability in long-termed chronoamperometric electrolysis. The electrochemical impedance spectroscopy and the CO stripping voltammetry were employed to elucidate the origin of enhancement.