Metal-support interactions in catalysis impose fundamental limitations on maximum activity. Here, we show that the constraint relationship of local electronic and geometric structures of carbon-supported palladium (Pd) catalysts can be broken through the synergy between the Pd-Pd and the Pd-B coupling interaction, producing a class of densely populated entities with unique negatively charged properties. A volcano-shaped curve that depicts the relationship between Pd Bader charge and neighboring atomic distance is established, thereby optimizing catalytic performance. Acetaldehyde manufacture via acetylene hydration is used as our study case. Outstanding performance can be triggered over the densely populated Pd single-atom and nanoparticle co-catalytic sites compared with individual Pd sites. The effect is attributed to the negative charge and high-density effect of Pd-BN₃ sites, which easily adapt their structures to binding C₂H₂ and H₂O and varying reaction routes. This approach provides practical insights for the design of Pd-based catalysts comprising well-defined electronic and geometric structures.

中文翻译：

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用于乙醛制造的单个原子和相邻纳米颗粒的 d 电子的相互自调节


催化中的金属-载体相互作用对最大活性施加了根本限制。在这里，我们表明，碳负载钯 （Pd） 催化剂的局部电子和几何结构的约束关系可以通过 Pd-Pd 和 Pd-B 耦合相互作用之间的协同作用来打破，从而产生一类具有独特负电荷特性的密集实体。建立了一条描述 Pd Bader 电荷与相邻原子距离之间关系的火山形曲线，从而优化了催化性能。通过乙炔水合制造乙醛被用作我们的研究案例。与单个 Pd 位点相比，可以在密集的 Pd 单原子和纳米颗粒共催化位点上触发出色的性能。这种效应归因于 Pd-BN₃ 位点的负电荷和高密度效应，它们很容易使其结构适应结合 C₂H₂ 和 H₂O 以及不同的反应路线。这种方法为设计由定义明确的电子和几何结构组成的 Pd 基催化剂提供了实用的见解。