Enhanced catalytic activity and stability for the electrooxidation of formic acid on lead modified shape controlled platinum nanoparticles

- Lead modified 111-Pt NPs display one of the highest current density values reported for FAOR at 0.5 V in 0.1 M HCOOH solution.
- Lead adatom presents a combined third body and bifunctional catalytic effect as modifier on Pt NPs.
- High catalyst stability is displayed at maximum lead coverage.
- SECM emerges as a suitable and fast tool to perform preliminary tests of electrocatalytic activity.

High catalytic activity for formic acid oxidation reaction (FAOR) is demonstrated in Pb modified shape-controlled Pt nanoparticles (NPs). Cyclic voltammetry is used to follow the effective modification of Pt NPs by Pb. Octahedral shaped Pt NPs (having a (111) preferential surface structure) modified by Pb are proved the most active electrocatalyst studied towards FAOR and display a catalytic activity of c.a. 7 mA cm−2 at 0.5 V in 0.1 M formic acid solution. This current density represents an enhancement factor of 29.5 with respect to the unmodified Pt NPs and this is 2.7 and 2.3 times higher than that found on Tlθ/100-Pt NPs and Sbθ/111-Pt NPs, respectively, some of the most active electrocatalysts based on adatoms modified Pt NPs reported so far. This outstanding activity is displayed at maximum Pb coverage and also confers a wide electrocatalyst stability over the entire potential range studied. FAOR is also studied using scanning electrochemical microscopy (SECM) by the micropipette delivery/substrate collection (MD/SC) working mode as a preliminary rapid test to identify active electrocatalysts. In particular, the remarkable activity enhancement exhibited by a Pt ultramicroelectrode (100 μm diameter) modified by Pb is rapidly imaged by SECM providing preliminary catalyst performance information. Thus, this technique emerges as a suitable and fast method to test, and in some cases quantify, catalyst activity for reactions of interest in fuel cell applications.

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