Intriguing Catalytic Activity of Surface Active Gold-Platinum Islands on Nano-Porous Au in Determining Efficient Direct Formic Acid Oxidation Pathway

Gold-platinum nano-porous structures (Au100-xPtx NPoS) with unique surface enriched Au−Pt islands are synthesised through a galvanic replacement strategy from Au100-xAg2x nano-alloys with ultra-low platinum loading (x=1.25, 2.5 and 5). Formic acid oxidation reaction (FAOR) on Au100-xPtx/C NPoS shows a distinct peak at around 0.5 V related to CO2 formation. A characteristic peak at around 1.5 V increases with increasing FA concentration owing to the direct FAOR by nano-porous Au centers. FAOR peaks and If/Ib peak current ratios indicates that, Au100-xPtx/C NPoS facilitates direct FAOR pathway unlike HiSPEC Pt/C (dehydration pathway). Based on the enhanced chrono-amperometric response, Tafel behaviour and mass activity values, Au97.5Pt2.5/C NPoS (5.5 A/mgPt) reflects as the optimal catalyst for efficient FAOR. The intriguing catalytic role of surface enriched Au−Pt islands present on nano-porous Au greatly helps in determining the superior FAOR activity in Au97.5Pt2.5/C NPoS towards direct dehydrogenation pathway at ultra-low Pt content compared to other NPoS and HiSPEC Pt/C catalysts.