Seeded Growth of Metal Nitrides on Noble-Metal Nanoparticles To Form Complex Nanoscale Heterostructures
Seeded Growth of Metal Nitrides on Noble-Metal Nanoparticles To Form Complex Nanoscale Heterostructures
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DOI：
10.1021/acs.chemmater.9b01638
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发表时间：
2019-06-25
影响因子：
8.6
通讯作者：
Schaak, Raymond E.
中科院分区：
文献类型：
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作者：
Lord, Robert W.;Holder, Cameron F.;Schaak, Raymond E.
通过直接固-固界面整合多种材料的胶态异质结构纳米颗粒在广泛的应用中是期望的。然而，化学、结构、界面和合成方面的考虑限制了可以掺入这种混合构建体中的材料的范围。金属氮化物是异质结构纳米颗粒的吸引人的组分，因为它们独特而多样的电子，光子和催化性质，但它们的合成具有挑战性。在这里，我们证明了模型金属氮化物系统Cu 3 N和Cu 3 PdN可以在各种贵金属种子颗粒上在溶液中生长，以形成异质结构金属金属氮化物纳米颗粒库。形成的纳米异质结构的类型取决于贵金属种子颗粒的形态和沉积的材料。Cu 3 PdN在Pt纳米立方体种子上生长的途径涉及Cu的初始非选择性沉积，随后在角落处沿着局部沉积Pd，伴随着氮的掺入和Cu 3 PdN的结晶。因此，在种子颗粒角落处的优先Pd沉积驱动Cu 3 PdN生长期间的区域选择性，导致Pt Cu 3 PdN异质结构纳米颗粒的形成。对于晶种颗粒，没有高度刻面，以及Cu 3 N，没有观察到局部沉积，不同类型的核壳和合金纳米颗粒的形式。Cu 3 PdN也选择性地沉积在Pt Fe 3 O 4混合纳米颗粒的立方体形状的Pt域的暴露的角上，形成复杂的Fe 3 O 4 Pt Cu 3 PdN异质三聚体。这些观察结果提供了有用的见解，将金属氮化物纳米异质结构使用种子生长过程。
Colloidal heterostructured nanoparticles that integrate multiple materials through direct solid solid interfaces are desirable across a wide range of applications. However, chemical, structural, interfacial, and synthetic considerations have limited the scope of materials that can be incorporated into such hybrid constructs. Metal nitrides are appealing components of heterostructured nanoparticles because of their unique and diverse electronic, photonic, and catalytic properties, but they can be challenging to synthesize. Here, we demonstrate that the model metal nitride systems Cu3N and Cu3PdN can be grown in solution on various noble-metal seed particles to form a library of heterostructured metal metal nitride nanoparticles. The types of nanoscale heterostructures that form depend on both the morphology of the noble-metal seed particle and the material being deposited. The pathway by which Cu3PdN grows on Pt nanocube seeds involves initial nonselective deposition of Cu, followed by localized deposition of Pd at the corners along with concomitant incorporation of nitrogen and crystallization of Cu3PdN. Preferential Pd deposition at seed particle corners therefore drives regioselectivity during the growth of Cu3PdN, leading to the formation of Pt Cu3PdN heterostructured nanoparticles. For seed particles that are not highly faceted, as well as Cu3N, localized deposition is not observed, and different types of core shell and alloy nanoparticles form. Cu3PdN also deposits selectively on the exposed corners of the cube-shaped Pt domains of Pt Fe3O4 hybrid nanoparticles, forming complex Fe3O4 Pt Cu3PdN heterotrimers. These observations provide useful insights for incorporating metal nitrides into nanoscale heterostructures using seeded growth processes.