Reaction stoichiometry directs the architecture of trimetallic nanostructures produced via galvanic replacement
Reaction stoichiometry directs the architecture of trimetallic nanostructures produced via galvanic replacement
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反应化学计量指导通过电取代产生的三金属纳米结构的结构
DOI：
10.1039/d2nr06632g
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发表时间：
2023
期刊：
影响因子：
6.7
通讯作者：
Skrabalak, Sara E.
中科院分区：
文献类型：
--
作者：
Kar, Nabojit;McCoy, Maximilian;Zhan, Xun;Wolfe, Joshua;Wang, Zhiyu;Skrabalak, Sara E.
单金属纳米粒子 (NP) 的电取代 (GR) 为有趣的双金属纳米结构提供了一种通用途径，已报道的例子有纳米盒、纳米笼、纳米壳、纳米环和异二聚体。用更贵重的金属替代双金属模板可以产生具有不同结构的三金属纳米结构，其中具体结构已被证明取决于参与金属的相对还原电位以及沉积相和模板金属相之间的晶格失配。现在，反应化学计量的作用被证明可以指导用双金属模板 GR 产生的多金属纳米结构的整体结构。具体来说，沉积在 NP 模板上的初始金属岛的数量取决于反应化学计量。这一结果是通过研究金属间 PdCu (i-PdCu) NP 与 AuCl2− (Au1+) 或 AuCl4− (Au3+) 之间的 GR 过程得出的，产生 i-PdCu-Au 异质结构。值得注意的是，在 GR 与 AuCl2− 的情况下形成多个 Au 域，而在 AuCl4− 的情况下仅形成单个 Au 域。这些不同的纳米粒子结构及其与反应化学计量的联系与 Stranski-Krastanov (SK) 生长一致，为如何利用 GR 过程的条件来实现具有不同定义结构的多金属纳米结构提供了一般指导。
Galvanic replacement (GR) of monometallic nanoparticles (NPs) provides a versatile route to interesting bimetallic nanostructures, with examples such as nanoboxes, nanocages, nanoshells, nanorings, and heterodimers reported. The replacement of bimetallic templates by a more noble metal can generate trimetallic nanostructures with different architectures, where the specific structure has been shown to depend on the relative reduction potentials of the participating metals and lattice mismatch between the depositing and template metal phases. Now, the role of reaction stoichiometry is shown to direct the overall architecture of multimetallic nanostructures produced by GR with bimetallic templates. Specifically, the number of initial metal islands deposited on a NP template depends on the reaction stoichiometry. This outcome was established by studying the GR process between intermetallic PdCu (i-PdCu) NPs and either AuCl2− (Au1+) or AuCl4− (Au3+), producing i-PdCu–Au heterostructures. Significantly, multiple Au domains form in the case of GR with AuCl2− while only single Au domains form in the case of AuCl4−. These different NP architectures and their connection to reaction stoichiometry are consistent with Stranski–Krastanov (SK) growth, providing general guidelines on how the conditions of GR processes can be used to achieve multimetallic nanostructures with different defined architectures.