Developing superior oxidation resistance of high-entropy diborides is critical for extending their potential applications in harsh environments. Herein, we developed non-equimolar (Hf,Zr,Ta,W)B₂ high-entropy diborides with superior oxidation resistance by adjusting W contents for the first time. The as-fabricated (Hf_0.28Zr_0.28Ta_0.28W_0.15)B₂ samples are predicted to possess superior oxidation resistance at 1473–1773 K through the oxidation depth quantitative analysis obtained by machine learning, which is attributed to the reason that the moderate WO₃ can effectively inhibit the volatilization of B₂O₃. Furthermore, a four-layered structure is found in the generated product layers at 1773 K, which is due to the preferential oxidation of Hf and Zr elements at low oxygen partial pressure and the different diffusion activation energies of oxide products. The preferential oxidation of Hf and Zr elements is further demonstrated by the computational phase stability diagrams, and oxygen adsorption energies and charge transfer between oxygen atoms and different metal adsorption sites via first-principles calculations. Such superior performance endows (Hf_0.28Zr_0.28Ta_0.28W_0.15)B₂ with potential applications as ultrahigh-temperature structural materials.

开发高熵二硼化物的优异抗氧化性对于扩展其在恶劣环境中的潜在应用至关重要。在此，我们首次通过调整W含量开发出具有优异抗氧化性的非等摩尔(Hf,Zr,Ta,W)B _{2高熵二硼化物。}通过机器学习获得的氧化深度定量分析预测制备的 (Hf _0.28 Zr _0.28 Ta _0.28 W _0.15 )B ₂样品在 1473–1773 K 具有优异的抗氧化性，这是由于适度的 WO _{3能有效抑制B 2} O ₃的挥发. 此外，在 1773 K 时，在生成的产物层中发现了四层结构，这是由于 Hf 和 Zr 元素在低氧分压下优先氧化以及氧化物产物的不同扩散活化能。Hf 和 Zr 元素的优先氧化通过计算相稳定性图、氧吸附能和氧原子与不同金属吸附位点之间的电荷转移通过第一性原理计算得到进一步证明。如此优越的性能赋予了(Hf _0.28 Zr _0.28 Ta _0.28 W _0.15 )B ₂作为超高温结构材料的潜在应用。