The surface of solid catalysts is one of the most important factors where the interface with reaction products governs the reaction kinetics. Herein, the crystal phase of palladium–copper nanoparticles (PdCu NPs) is controlled to modulate their surface atomic arrangement, which will govern the growth dynamics of discharge products on their surfaces and thus the catalytic performances in non‐aqueous lithium–oxygen (Li‐O₂) batteries. First‐principles calculations and experimental validations reveal that homogeneous nucleation and distribution of discharge products are observed on the surface of body‐centered cubic PdCu NPs, promoting the oxygen reduction/evolution reaction (ORR/OER) activities in Li‐O₂ batteries. However, the agglomerates formed on the surface of its face‐centered cubic homologue deteriorates ORR/OER activities, which worsen the battery performances. For the first time, this work theoretically and experimentally demonstrates how the crystal phase modulation regulates the nucleation behaviors and growth dynamics of discharge products for ORR/OER.

中文翻译：

---

通过双金属催化剂的晶体结构调节来调节催化动力学

固体催化剂的表面是与反应产物的界面决定反应动力学的最重要因素之一。在此，控制钯-铜纳米颗粒（PdCu NPs）的晶相以调节其表面原子排列，这将控制放电产物在其表面上的生长动力学，从而控制在非水锂-氧（Li- O ₂）电池。第一性原理计算和实验验证表明，在以人体为中心的立方PdCu NPs表面观察到均匀的成核和放电产物分布，从而促进了Li-O _2中的氧还原/演化反应（ORR / OER）活性电池。但是，在其面心立方同系物表面上形成的附聚物会降低ORR / OER活性，从而使电池性能恶化。这项工作首次在理论上和实验上证明了晶体相位调制如何调节ORR / OER放电产物的成核行为和生长动力学。