School of Chemical Engineering and Advanced Materials, The University of Adelaide, Adelaide, SA, 5005, Australia.
Institute for Sustainability, Energy and Resources, The University of Adelaide, Adelaide, SA, 5005, Australia.
Nat Commun. 2023 Jan 21;14(1):354. doi: 10.1038/s41467-023-35913-6.
Heteroatom-doping is a practical means to boost RuO for acidic oxygen evolution reaction (OER). However, a major drawback is conventional dopants have static electron redistribution. Here, we report that Re dopants in ReRuO undergo a dynamic electron accepting-donating that adaptively boosts activity and stability, which is different from conventional dopants with static dopant electron redistribution. We show Re dopants during OER, (1) accept electrons at the on-site potential to activate Ru site, and (2) donate electrons back at large overpotential and prevent Ru dissolution. We confirm via in situ characterizations and first-principle computation that the dynamic electron-interaction between Re and Ru facilitates the adsorbate evolution mechanism and lowers adsorption energies for oxygen intermediates to boost activity and stability of ReRuO. We demonstrate a high mass activity of 500 A g (7811 A g) and a high stability number of S-number = 4.0 × 10 n n to outperform most electrocatalysts. We conclude that dynamic dopants can be used to boost activity and stability of active sites and therefore guide the design of adaptive electrocatalysts for clean energy conversions.
杂原子掺杂是提高 RuO 酸性析氧反应(OER)性能的一种实用方法。然而,主要缺点是传统掺杂剂具有静态电子再分布。在这里,我们报告了 ReRuO 中的 Re 掺杂剂经历了动态的电子接受-给予,自适应地提高了活性和稳定性,这与具有静态掺杂电子再分布的传统掺杂剂不同。我们表明,在 OER 过程中,(1)Re 掺杂剂在局域位势下接受电子以激活 Ru 位,(2)在大过电位下返回电子并防止 Ru 溶解。我们通过原位表征和第一性原理计算证实,Re 和 Ru 之间的动态电子相互作用促进了吸附物演化机制,并降低了氧中间体的吸附能,从而提高了 ReRuO 的活性和稳定性。我们展示了高质量活性 500 A g(7811 A g)和高稳定性数 S-number = 4.0 × 10 n n,优于大多数电催化剂。我们得出结论,动态掺杂剂可用于提高活性位点的活性和稳定性,从而指导用于清洁能源转化的自适应电催化剂的设计。