Chen Lihui, Hu Haifeng, Chen Yuzhou, Gao Jing, Li Guohua
College of Chemical Engineering, Zhejiang University of Technology, 18, Chaowang Road, Hangzhou, 310014, P. R. China.
State Key Breeding Base of Green Chemistry Synthesis Technology, Zhejiang University of Technology, 18, Chaowang Road, Hangzhou, 310032, P. R. China.
Chemistry. 2021 May 6;27(26):7444-7452. doi: 10.1002/chem.202100006. Epub 2021 Mar 16.
A crucial parameter in the design of semiconductor nanoparticles (NPs) with controllable optical, magnetic, electronic, and catalytic properties is the morphology. Herein, we demonstrate the potential of additive metal cations with variable valency to direct the morphology evolution of copper-deficient Cu S nanoparticles in the process of seed-mediated growth. In particular, the djurleite Cu S seed could evolve from disk into tetradecahedron in the presence of tin(IV) cations, whereas they merely formed sharp hexagonal nanodisks with tin(II) cations. In addition to djurleite Cu S, the tin(IV) cations could be generalized to direct the growth of roxbyite Cu S and covellite CuS nanodisk seeds into tetradecahedra. We further perform pseudomorphic cation exchanges of Cu S tetradecahedra with Zn and Cd to produce polyhedral zinc sulfide (ZnS) and cadmium sulfide (CdS) NPs. Moreover, we achieve Cu S/ZnS and Cu S/CdS tetradecahedral heterostructures via partial cation exchange, which are otherwise inaccessible by traditional synthetic approaches.
在设计具有可控光学、磁性、电子和催化特性的半导体纳米颗粒（NP）时，一个关键参数是形态。在此，我们展示了具有可变价态的添加金属阳离子在种子介导生长过程中引导缺铜硫化亚铜纳米颗粒形态演变的潜力。特别是，在锡（IV）阳离子存在的情况下，硫铜银矿硫化亚铜种子可以从圆盘状演变成十四面体，而在锡（II）阳离子存在时，它们仅形成尖锐的六边形纳米盘。除了硫铜银矿硫化亚铜，锡（IV）阳离子可以推广到引导硫铜锌矿硫化亚铜和靛铜矿硫化铜纳米盘种子生长成十四面体。我们进一步用锌和镉对硫化亚铜十四面体进行赝同形阳离子交换，以制备多面体硫化锌（ZnS）和硫化镉（CdS）纳米颗粒。此外，我们通过部分阳离子交换实现了硫化亚铜/硫化锌和硫化亚铜/硫化镉十四面体异质结构，而这是传统合成方法无法实现的。
