Ni Ziyue, Zhu Yuanmin, Liu Junjun, Yang Lin, Sun Peng, Gu Meng, Huang Zhifeng
Department of Physics Hong Kong Baptist University (HKBU) Kowloon Tong Kowloon Hong Kong SAR China.
Department of Materials Science and Engineering Southern University of Science and Technology (SUSTech) Shenzhen 518055 China.
Adv Sci (Weinh). 2020 Oct 27;7(23):2001321. doi: 10.1002/advs.202001321. eCollection 2020 Dec.
Metal chiral nanoparticles (CNPs), composed of atomically chiral lattices, are an emerging chiral nanomaterial showing unique asymmetric properties. Chirality transmission from the host CNPs mediated with galvanic replacement reactions (GRRs) has been carried out to extend their compositional space from the unary to binary. Further compositional extension to, e.g., the ternary is of fundamental interest and in practical demand. Here, layer-by-layer glancing angle deposition is used to dope galvanically "inert" dopant Au in the host Cu CNPs to generate binary Cu:Au CNPs. The "inert" dopants serve as structural scaffold to assist the chirality transmission from the host to the third metals (M: Pt and Ag) cathodically precipitating in the CNPs, enabling the formation of polycrystalline ternary Cu:Au:M CNPs whose compositions are tailored with engineering the GRR duration. More scaffold Au atoms are favored for the faster chirality transfer, and the Au-assisted chirality transfer follows the first-order kinetics with the reaction rate coefficient of ≈0.3 h at room temperature. This work provides further understanding of the GRR-mediated chirality transfer and paves the way toward enhancing the application functions in enantiodifferentiation, enantioseperation, asymmetric catalysis, bioimaging, and biodetection.
由原子手性晶格组成的金属手性纳米粒子（CNPs）是一种新兴的手性纳米材料，具有独特的不对称性质。通过电置换反应（GRRs）介导的主体CNPs的手性传递已被用于将其组成空间从一元扩展到二元。进一步将组成扩展到例如三元，具有重要的基础研究意义和实际需求。在这里，采用逐层掠角沉积法在主体铜CNPs中掺杂电“惰性”掺杂剂金，以生成二元铜:金CNPs。“惰性”掺杂剂作为结构支架，协助手性从主体传递到在CNPs中阴极沉淀的第三种金属（M：铂和银），从而能够形成多晶三元铜:金:M CNPs，其组成可通过设计GRR持续时间来定制。更多的支架金原子有利于更快的手性转移，并且金辅助的手性转移遵循一级动力学，室温下反应速率系数约为0.3 h⁻¹。这项工作进一步加深了对GRR介导的手性转移的理解，并为增强对映体分化、对映体分离、不对称催化、生物成像和生物检测中的应用功能铺平了道路。
