Colloidal ionogels: Controlled assembly and self-propulsion upon tunable swelling

Active colloids driven out of thermal equilibrium serve as building blocks for smart materials with tunable structures and functions. Using chemical energy to drive colloids is advantageous but requires precise control over chemical release. To address this, we developed colloidal ionogels-polymer microspheres infused with ionic liquids-that show controlled assembly and self-propulsion upon tunable swelling. For example, we synthesized microspheres of polymethylmethacrylate loaded with ionic liquid [Bmim][PF₆], which were released from the colloidal ionogel upon swelling in alcohol-water mixtures and dissociated into cations and anions of different diffusivities. The resulting electric field leads to four types of pair-wise colloidal interactions via ionic diffusiophoresis and diffusioosmosis, giving rise to four types of self-assembled superstructures. These interactions were precisely modulated by altering the swelling conditions and the ionic liquids used. Additionally, partially blocking the ionogel's surface induces anisotropic swelling and asymmetric ion release, turning the colloidal ionogel into a self-propelled Janus colloidal motor powered by ionic self-diffusiophoresis, reaching speeds of several µm/s and lasting about 100 s. These findings indicate that colloidal ionogels are smart colloidal building blocks with highly tunable pair-wise interactions, self-assembled structures, and self-propulsion, offering potential applications in biomedical sensing, environmental monitoring, and photonics.