Four-electron oxygen reduction reaction (4e-ORR), a key pathway in energy conversion, is preferred over the two-electron reduction pathway that falls short in dissociating dioxygen molecules. Gold surfaces exhibit high sensitivity of the ORR pathway to its atomic structures. A long-standing puzzle remains unsolved: why the Au surfaces with {100} sub-facets were exceptionally capable to catalyze the 4e-ORR in alkaline solution, though limited within a narrow potential window. Herein we report the discovery of a dominant 4e-ORR over the whole potential range on {310} surface of Au nanocrystal shaped as truncated ditetragonal prism (TDP). In contrast, ORR pathways on single-crystalline facets of shaped nanoparticles, including {111} on nano-octahedra and {100} on nanocubes, are similar to their single-crystal counterparts. Combining our experimental results with density functional theory calculations, we elucidate the key role of surface proton transfers from co-adsorbed H₂O molecules in activating the facet- and potential-dependent 4e-ORR on Au in alkaline solutions. These results elucidate how surface atomic structures determine the reaction pathways via bond scission and formation among weakly adsorbed water and reaction intermediates. The new insight helps in developing facet-specific nanocatalysts for various reactions.

中文翻译：

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表面质子转移促进碱性溶液中金纳米晶体表面的四电子氧还原

四电子氧还原反应（4e-ORR）是能量转换中的关键途径，它比在解离双氧分子方面欠缺的两电子还原途径更可取。金表面表现出ORR途径对其原子结构的高度敏感性。一个长期存在的难题仍未解决：为什么具有{100}亚面的Au表面在碱溶液中具有出色的催化4e-ORR的能力，尽管局限在狭窄的潜在窗口之内。本文中，我们报告了在形状为截顶的双四角棱镜（TDP）的Au纳米晶体的{310}表面上，在整个电势范围内发现了显性4e-ORR。相反，成形纳米颗粒的单晶面上的ORR路径，包括纳米八面体上的{111}和纳米立方体上的{100}，与它们的单晶对应物相似。_2个O分子在碱性溶液中激活Au上依赖于面和电位的4e-ORR。这些结果阐明了表面原子结构如何通过键断裂和弱吸附水和反应中间体之间的形成决定反应途径。新的见解有助于开发用于各种反应的特定于面的纳米催化剂。