Huang Jia-Hong, Cui Yao, Luo Peng, Wang Zhao-Yang, Zang Shuang-Quan
College of Chemistry, Zhengzhou University, Zhengzhou, 450001, China.
College of Chemistry and Chemical Engineering, Henan Polytechnic University, Jiaozuo, 454000, China.
Adv Sci (Weinh). 2025 Sep;12(33):e01186. doi: 10.1002/advs.202501186. Epub 2025 Jun 29.
Heterostructured composite materials with multiple components have potential applications in diverse aspects, as they tend to exhibit superior physicochemical properties than the sum of their single counterparts. However, the fabrication of heterostructures composed of atomic-precise metal nanoclusters (NCs) is seldom reported owing to their inherent instability, leading to the decomposition of metal NCs during the formation of peripheral layers. Here, a spontaneously formed amorphous-crystalline heterostructured Ag@Ag is discovered, wherein the amorphous Ag NCs are enveloped by a single crystal of Ag NCs. The formation of Ag@Ag involves three stages, including initial crystallization of Ag NCs, partial decomposition (self-sacrifice) of Ag NCs enabling Ag assembly, and epitaxial-growth crystallization of the Ag NCs. The partially decomposed Ag NCs provide starting materials for the formation and crystallization of Ag NCs to encapsulate the Ag seeds, while the residual Ag loses its crystallinity in solution simultaneously. This work not only reports a novel class of heterostructured materials for the first time but also provides new insights into the macroscopic co-assembly of distinct silver clusters.
具有多种成分的异质结构复合材料在多个方面具有潜在应用，因为它们往往表现出比其单一对应物总和更优异的物理化学性质。然而，由原子精确的金属纳米团簇（NCs）组成的异质结构的制备很少被报道，这是由于其固有的不稳定性，导致在形成外围层的过程中金属纳米团簇分解。在此，发现了一种自发形成的非晶-晶体异质结构Ag@Ag，其中非晶态Ag纳米团簇被Ag纳米团簇的单晶所包裹。Ag@Ag的形成涉及三个阶段，包括Ag纳米团簇的初始结晶、使Ag组装的Ag纳米团簇的部分分解（自我牺牲）以及Ag纳米团簇的外延生长结晶。部分分解的Ag纳米团簇为Ag纳米团簇的形成和结晶提供起始材料以包裹Ag种子，而残余的Ag同时在溶液中失去其结晶性。这项工作不仅首次报道了一类新型的异质结构材料，还为不同银簇的宏观共组装提供了新的见解。
