Symmetry-Breaking Synthesis of Multicomponent Nanoparticles

Multicomponent nanoparticles (MCNs) composed of disparate inorganic colloidal components have attracted great attention from researchers in both the academic and industrial community, because of their unique properties and diverse applications in energy conversion and storage; heterogeneous catalysis; optics and electronics; and biomedical imaging, diagnosis, and therapy. Compared with single-component nanoparticles (NPs), new or advanced properties of MCNs arise from the synergistic effect between their constituent components and the presence of nanoscale interfaces between distinct materials within the particles. Consequently, the spatial arrangement of nanoscale domains of MCNs becomes equally important in property or function control of MCNs as their size, shape, and composition, if not more. In particular, compositionally asymmetric MCNs may outperform their symmetric counterparts in many of their applications. To this end, the seed-mediated growth (SMG) method, which involves depositing a second material onto seed NPs, has been considered as the most common strategy for the synthesis of asymmetric MCNs with desired complexity. In this approach, the control of symmetry breaking during MCN growth is usually achieved by manipulating the growth kinetics or using seed NPs with asymmetric shapes or surfaces. Although great progress has been made in the past decade, there remains a challenge to control the shape, orientation and organization of colloidal components of MCNs with a high yield and reproducibility. Recently, several unconventional methods have been developed as an important addition to the synthetic toolbox for the production of complex MCNs that otherwise may not be readily attainable. This Account summarizes recent advancements on the development of unconventional synthetic strategies for breaking the growth symmetry in the synthesis of asymmetric MCNs. We start with a brief discussion of the achievements and limitations of the conventional strategies for symmetry breaking synthesis. In the subsequent section, we present three unconventional approaches toward symmetry-breaking synthesis of asymmetric MCNs, namely, surface-protected growth, interface-guided growth, and welding-induced synthesis. First, we discuss how commonly used soft agents (e.g., collapsed polymer) and hard agents (e.g., silica) can be asymmetrically coated on seed NPs to template the asymmetric growth of secondary material, generating a broad range of MCNs with complex architectures. The unique features and key factors of this surface-protected synthesis are discussed from the viewpoints of the surface chemistry of seed NPs. We further discuss the use of a solid/liquid or liquid/liquid interface to guide the synthesis of Janus or more complex MCNs through two general mechanisms; that is, selective blocking or impeding the access of precursors to one side of seed NPs and interfacial reaction-enabled generation of asymmetric seeds for further growth. Finally, we discuss a symmetry-breaking method beyond the SMG mechanism, directed welding of as-synthesized single-component NPs. Moreover, we discuss how the unique structural symmetry and compositional arrangement of these MCNs significantly alter the physical and chemical properties of MCNs, thus facilitating their performance in exemplary applications of photocatalysis and electrocatalysis. We finally conclude this Account with a summary of recent progress and our future perspective on the future challenges.