Leveraging bismuth immiscibility to create highly concave noble-metal nanoparticles
Leveraging bismuth immiscibility to create highly concave noble-metal nanoparticles
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DOI：
10.1016/j.chempr.2024.02.002
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发表时间：
2024-02
期刊：
影响因子：
23.5
通讯作者：
Melissa E. King;Yuting Xu;Porvajja Nagarajan;Noah L. Mason;Anthony J. Branco;Connor S. Sullivan;Samantha M. Silva;Sangmin Jeong;Fanglin Che;Michael B. Ross
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文献类型：
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作者：
Melissa E. King;Yuting Xu;Porvajja Nagarajan;Noah L. Mason;Anthony J. Branco;Connor S. Sullivan;Samantha M. Silva;Sangmin Jeong;Fanglin Che;Michael B. Ross
具有结构和电子学差异的金属的纳米级集成虽然对于操纵表面吸附很重要，但通常不会在胶体合成中产生具有明确形态的结构。为了创建具有异常配位不足表面的结构，我们利用面心立方贵金属与菱面体Bi的不相容性来合成具有可控介电常数的定义明确的纳米结构。使用Au，可以实现三种不同的形态：凹四面体、星形八角体（对偶四面体）和凹星形八角体。用Pd合成凹四面体。结构和成分分析表明，实现这些形貌只需要0.66 × 10− 6摩尔的表面Bi。电催化实验和模拟表明，与非Bi导向的凹纳米颗粒相比，凹Au结构对醇氧化具有高度活性，并且表面Bi是吸附的关键。这种不混溶元素的整合提供了一种强大的策略，用于精确地产生高活性纳米颗粒。
The nanoscale integration of metals with differences in structure and electronics, although important for manipulating surface adsorption, does not typically yield structures with well-defined morphologies in colloidal synthesis. To create structures with unusually undercoordinated surfaces, we leverage the immiscibility of face-centered cubic noble metals with rhombohedral Bi to synthesize well-defined nanostructures with controllable concavity. With Au, three distinct morphologies can be achieved: concave tetrahedra, stella octangula (dual tetrahedron), and concave stella octangula. With Pd, we synthesize concave tetrahedra. Structural and compositional analysis shows that only ∼6 × 10−6moles of surface Bi are needed for realizing these morphologies. Electrocatalytic experiments and simulations reveal that, compared with non-Bi-directed concave nanoparticles, the concave Au architectures are highly active toward alcohol oxidation and that surface Bi is critical for adsorption. This integration of immiscible elements provides a powerful strategy for creating highly active nanoparticles with precision.