Tuning Catalytic Activity in Ultrathin Bimetallic Nanowires via Surface Segregation: Some Insights

The efficiency of heterogeneous catalysts critically depends on the nature of the surface. We present results on controlling the composition in ultrathin bimetallic AuPd. AuPd wires were grown using Au nanowire templates; the surface composition could be tuned by increasing the amount of Pd. Further, segregation of Pd to the surface could be induced in alloyed nanowires by annealing under a controlled CO atmosphere. Electrocatalytic activity of these bimetallic systems is assessed for the methanol oxidation reaction (MOR). While the MOR potential shows a monotonic increase with Pd content, the specific activity displays a typical volcano-type behavior. The CO-annealed nanowires show a lowering of potential owing to a higher Pd content on the surface while still maintaining the specific activity. These findings provide clear strategies to independently control the reaction potential and the activities of nanocatalysts. The experimental findings are well supported by the theoretical investigations using density functional theory (DFT) calculations.