Cao Guolin, Yang Sha, Ren Ji-Chang, Liu Wei
Nano and Heterogeneous Materials Center, School of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing, China.
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China.
Nat Commun. 2025 Feb 1;16(1):1251. doi: 10.1038/s41467-025-56421-9.
High-entropy alloys (HEAs) present a vast compositional space for fine-tuning electrocatalytic activities, leveraging millions of distinct active sites on the surface. However, the intricate local chemical environment poses challenges to the rational and efficient design of HEA electrocatalysts with high reactivity. Here, focusing on noble-metal HEAs for oxygen reduction reactions, we propose a straightforward yet effective descriptor for quantitively determining the local reactivities of HEAs. This descriptor is based on a linear combination of the intrinsic d-band filling of the active center and the neighborhood electronegativity. Our model offers an accurate and robust description of the binding strengths of intermediates with different adsorption configurations on HEAs, supported by external density functional theory calculations. Importantly, the local environmental electronegativity of the HEA surface is strongly related to the d-band profile of the center atom(s) embedded within. Finally, we establish a library of activity maps for HEAs encompassing nine noble-metal elements, suggesting that Pd-rich and Ir-rich alloys, such as Pd-Ag, Ir-Pt, Ir-Au compositions, hold promise as potential candidates for optimal electrocatalysts.
高熵合金（HEAs）为微调电催化活性提供了广阔的成分空间，利用其表面数百万个不同的活性位点。然而，复杂的局部化学环境给合理高效地设计具有高反应活性的HEA电催化剂带来了挑战。在此，针对用于氧还原反应的贵金属HEAs，我们提出了一种简单而有效的描述符，用于定量确定HEAs的局部反应活性。该描述符基于活性中心的固有d带填充和邻域电负性的线性组合。我们的模型对不同吸附构型的中间体在HEAs上的结合强度提供了准确而稳健的描述，外部密度泛函理论计算对此提供了支持。重要的是，HEA表面的局部环境电负性与嵌入其中的中心原子的d带轮廓密切相关。最后，我们建立了一个涵盖九种贵金属元素的HEAs活性图谱库，表明富含钯和铱的合金，如Pd-Ag、Ir-Pt、Ir-Au成分，有望成为最佳电催化剂的潜在候选材料。
