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The alteration of surface functional properties via incorporation of foreign atoms is supposed to be a key strategy for the enhanced catalytic performance of noble-metal based nanocatalysts (NCs). In the present study, carbon-supported palladium (Pd)-based NCs including Pd, PdPt and PdRuPt have been prepared via a polyol reduction method under the same reduction conditions as for formic acid oxidation reaction (FAOR) applications. By cross-referencing the results of the microscopic, spectroscopic and electrochemical analysis we demonstrated that adding a small amount of platinum (Pt) into Pd NCs ( i.e. PdPt NCs) significantly promotes the FAOR performance as compared to that of Pd NCs via weakening the CO ads bond strength at a lower voltage (0.875 V vs. NHE) than Pd (0.891 V vs. NHE). Of special relevance, the PdPt NC shows a mass activity (MA) of 1.0 A mg -1 and 1.9 A mg -1 , respectively, in the anodic and cathodic scan. These values are ∼1.7-fold (0.6 A mg -1 ) and ∼4.8-fold (0.4 A mg -1 ) higher than those of Pd NC. Moreover, PdPt NC retains a higher MA (54 mA mg -1 ) than that of Pd NC (9 mA mg -1 ) after chronoamperometric (CA) stability tests over 2000 s. Meanwhile, further addition of ruthenium (Ru) ( i.e. PdRuPt NCs) outstandingly enhances the CO tolerance during the CA test via removal of adsorbed CO ads and thus shows the highest MA (62 mA mg -1 ) after CA testing, which is higher than that of PdPt (54 mA mg -1 ) and Pd (9 mA mg -1 ) NCs. The intriguing results obtained in this study have great significance to provide further strategic opportunities for tuning the surface electronic properties of Pd-based NCs to design Pd-based NCs with improved electrochemical performance.

Promoting formic acid oxidation performance of Pd nanoparticles via Pt and Ru atom mediated surface engineering