Droplet confined binary colloidal co-assembly into hierarchical Supraparticles with controllable morphology

Huan Liu; Shijian Huang; Zhenping Liu; Lang Chen; Jiamei Chen; Xinyi Li; Mengjun Liu; Haoqiang Feng; Weilong Xu; Ruizhi Yang; Minmin Zhang; Lingling Shui

doi:10.1016/j.jcis.2025.138344

Droplet confined binary colloidal co-assembly into hierarchical Supraparticles with controllable morphology

J Colloid Interface Sci. 2025 Dec 15;700(Pt 1):138344. doi: 10.1016/j.jcis.2025.138344. Epub 2025 Jul 3.

Authors

Huan Liu¹, Shijian Huang¹, Zhenping Liu², Lang Chen¹, Jiamei Chen³, Xinyi Li¹, Mengjun Liu¹, Haoqiang Feng², Weilong Xu², Ruizhi Yang⁴, Minmin Zhang¹, Lingling Shui⁵

Affiliations

¹ Guangdong Provincial Key Laboratory of Nanophotonic Functional Materials and Devices, Guangdong Basic Research Center of Excellence for Structure and Fundamental Interactions of Matter, School of Optoelectronic Science and Engineering, South China Normal University, Guangzhou 510006, China.
² International Joint Laboratory of Optofluidic Technology and System (LOTS), National Center for International Research on Green Optoelectronics, South China Academy of Advanced Optoelectronics, South China Normal University, Guangzhou 510006, China.
³ International Joint Laboratory of Optofluidic Technology and System (LOTS), National Center for International Research on Green Optoelectronics, South China Academy of Advanced Optoelectronics, South China Normal University, Guangzhou 510006, China; Department of Pharmacy, Shenzhen Bao'an Traditional Chinese Medicine Hospital, Guangzhou University of Chinese Medicine, Shenzhen 518133, China.
⁴ Soft Condensed Matter, Debye Institute for Nanomaterials Science, Utrecht University, Princetonplein 1, 3584 CC, Utrecht, the Netherlands.
⁵ Guangdong Provincial Key Laboratory of Nanophotonic Functional Materials and Devices, Guangdong Basic Research Center of Excellence for Structure and Fundamental Interactions of Matter, School of Optoelectronic Science and Engineering, South China Normal University, Guangzhou 510006, China. Electronic address: shuill@m.scnu.edu.cn.

PMID: 40639168
DOI: 10.1016/j.jcis.2025.138344

Abstract

Physically confined assembly of binary colloidal mixtures in emulsion droplets provides a versatile platform for engineering supraparticles with tunable morphologies and functionalities. While single-component and hard-sphere colloidal assemblies have been extensively studied, the co-assembly of binary soft colloids presents unresolved challenges in architecture control and functional integration. In this work, we investigate the co-assembly performance of emulsion droplet confined binary soft colloids of spherical polystyrene nanoparticles (PS) and wire-like carbon nanotubes (CNTs). The supraparticles of CNT/PS with various architectures have been obtained by varying the solvent removal dynamics and the binary colloidal composition. We find out that the binary colloidal size and mass ratio govern the CNT/PS supraparticle structural diversity, ranging from core-shell, core-semishell, garnet-like to densely packed architectures. Spontaneous emulsification and microphase segregation drive the transformation from core-shell to core-semishell architectures, revealing the critical role of fluid dynamics and confinement effects. This understanding of mechanism enables the rational design of hybrid magnetic supraparticles, demonstrating the broad applicability of such an approach. By establishing clear composition-structure correlations, this work advances the controlled co-assembly of binary colloids into hierarchical supraparticles, offering a pathway for constructing functional materials with tailored complexity.

Keywords: Carbon nanotubes; Co-assembly; Microfluidics; Polystyrene; Supraparticles.