A highly active surface can endow the electrocatalysts with extraordinary catalytic performances. However, it remains challenging to tailor the atomic packing characteristics and thus the physical and chemical characteristics of the electrocatalysts . Herein, penta-twinned Pd nanowires (NWs) with abundant high-energy atomic steps (i.e., stepped Pd) are synthesized by seeded synthesis on Pd NWs enclosed by (1 0 0) facets. Benefiting from the catalytically active atomic steps, such as [ n (1 0 0) × m (1 1 1)] on the surface, the resultant stepped Pd NWs can work as an effective electrocatalyst for the ethanol oxidation reaction (EOR) and ethylene glycol oxidation reaction (EGOR), which are essential anode reactions in direct alcohol fuel cells (DAFCs). Compared with commercial Pd/C, the Pd nanowires bound by (1 0 0) facets and atomic steps both display enhanced catalytic activity and stability towards the EOR and EGOR. Importantly, the mass activities of the stepped Pd NWs toward the EOR and EGOR are 6.38 and 7.98 A mg Pd −1 , which are 3.1 and 2.6 times those of Pd NWs enclosed by (1 0 0) facets, respectively. Besides, our synthetic strategy also enables the formation of bimetallic Pd-Cu nanowires with abundant atomic steps. This work not only demonstrates a simple yet effective strategy to obtain mono- or bi-metallic nanowires with abundant atomic steps, but also highlights the significant role of atomic steps for boosting the activity of electrocatalysts.
Platinum (Pt)-based nanocatalysts with a high density of surface atomic steps hold great prospects in electrocatalysis. However, the structural instability under harsh redox conditions is still a rigorous challenge. Here, we demonstrate that ternary PtCoRh alloyed spiral nanowires (SNWs), which have the advantages of one-dimensional nanowires, alloy synergy, surface atomic steps, and anti-corrosive Rh incorporation, can serve as active and robust MOR electrocatalysts in acidic media. The results showed that the Pt77Co11Rh12 SNWs delivered the highest mass activity (1.48 A mg−1) and specific activity (4.76 mA cm−2), as well as the best durability in the long-term MOR test, compared with the Pt85Co10Rh5 and Pt85Co15 SNWs and Pt black. Further inspections of the morphology, composition, and electronic structure revealed that the incorporated Rh atoms not only stabilized the highly rugged SNWs and the easily leaching Co atoms but also delicately tuned the electron transfer among the three metallic elements, leading to the enhancement of MOR activity, structural stability and anti-CO-poisoning ability. Our work provides a rational strategy for the development of highly efficient and durable alcohol oxidation electrocatalysts.
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