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 (Au 100‐x Pt x NPoS) with unique surface enriched Au−Pt islands are synthesised through a galvanic replacement strategy from Au 100‐x Ag 2x nano‐alloys with ultra‐low platinum loading (x=1.25, 2.5 and 5). Formic acid oxidation reaction (FAOR) on Au 100‐x Pt x /C NPoS shows a distinct peak at around 0.5 V related to CO 2 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 I f /I b peak current ratios indicates that, Au 100‐x Pt x /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, Au 97.5 Pt 2.5 /C NPoS (5.5 A/mg Pt ) 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 Au 97.5 Pt 2.5 /C NPoS towards direct dehydrogenation pathway at ultra‐low Pt content compared to other NPoS and HiSPEC Pt/C catalysts.