Rationally tailoring the coordination environments of metal single atoms (SAs) is an effective approach to promote their catalytic performances, which, however, remains as a challenge to date. Here, we report a novel misplaced deposition strategy for the fabrication of differently coordinated dual-metal hetero-SAs. Systematic characterization results imply that the as-synthesized dual-metal hetero-SAs (exemplified by Cu and Co) are affixed to a hierarchical carbon support via Cu–C₄ and Co–N₄ coordination bonds. Density functional theory studies reveal that the strong synergistic interactions between the asymmetrically deployed CuC₄ and CoN₄ sites lead to remarkably polarized charge distributions, i.e., electron accumulation and deficiency around CuC₄ and CoN₄ sites, respectively. The obtained CuC₄/CoN₄@HC catalyst exhibits significantly enhanced capability in substrate adsorption and O₂ activation, achieving superior catalytic performances in the oxidative esterification of aromatic aldehydes in comparison with the Cu- and Co-based SA counterparts.

中文翻译：

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不同配位的双金属杂单原子高效协同催化

合理地调整金属单原子（SAs）的配位环境是提高其催化性能的有效方法，然而，迄今为止，这仍然是一个挑战。在这里，我们报告了一种新颖的错位沉积策略，用于制造不同协调的双金属异质 SA。系统表征结果表明，合成的双金属异质-SAs（以Cu和Co为例）通过Cu-C ₄和Co-N ₄配位键固定在分级碳载体上。密度泛函理论研究表明，不对称部署CUC之间的密切协同相互作用₄和CON ₄位点导致显着极化的电荷分布，即分别围绕CuC ₄和CoN ₄位点的电子积累和缺陷。将所得到的CUC ₄ / CON ₄ @HC催化剂表现出显著增强在基板吸附和O能力₂活化，实现芳族醛的氧化酯化优良的催化性能与CU-和Co基SA对应比较。