Local coordination environment (LCE) manipulation has emerged as a significant approach for modulating the electrocatalytic behavior of low-dimensional nanomaterials. However, challenges persist in accurately identifying active sites and understanding dynamic changes during operation. Here, we underscore the influence of LCE on the electrochemical production of H₂O₂, utilizing the Pd cluster as a model catalyst. Density functional theory (DFT) calculations illustrate the role of first- and second-coordinated sulfur and oxygen in modulating the binding strength of HOO*. Guided by DFT screening, the as-prepared Pd cluster (Pd_x/HMCS) catalyst presents exceptional catalytic performance with a high mass activity of 4.06 A mg^–1 at 0.45 V and selectivity above 94%. The Pd_x/HMCS catalyst also delivers promising potential for industrial practices with a production rate of 16.3 mol g_cat^–1 h^–1 in flow cell evaluation. Elaborated in situ characterizations confirm that under operation, oxygen migrates from the second coordination sphere (CS) to the first CS to achieve oxygen coverage on the catalyst surface. Such an oxygen migration phenomenon and the optimized first and second coordination environment give rise to the outstanding performance.

中文翻译：

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电催化剂中电位驱动的配位氧迁移用于可持续 H2O2 合成


局部配位环境 （LCE） 操纵已成为调节低维纳米材料电催化行为的重要方法。然而，准确识别活跃部位和了解运行过程中的动态变化仍然存在挑战。在这里，我们利用 Pd 簇作为模型催化剂，强调了 LCE 对 H₂O₂ 电化学产生的影响。密度泛函理论 （DFT） 计算说明了一级和二级配位硫和氧在调节 HOO* 结合强度中的作用。在 DFT 筛选的引导下，制备的 Pd 簇 （Pd_x/HMCS） 催化剂表现出优异的催化性能，在 0.45 V 下具有 4.06 A mg^–1 的高质量活性，选择性高于 94%。Pd_x/HMCS 催化剂在流通池评估中具有 16.3 mol g_cat^–1 h^–1 的生产率，为工业实践提供了广阔的潜力。详细的原位表征证实，在操作中，氧气从第二配位球 （CS） 迁移到第一 CS，以实现氧气在催化剂表面的覆盖。这样的氧迁移现象和优化的第一和第二配位环境产生了出色的性能。