Pt-SiO2 Janus Particles and the Water/Oil Interface: A Competition between Motility and Thermodynamics.

Various aspects of the behavior of Janus particles near liquid/liquid interfaces have been studied through different experimental and theoretical realizations, but the effect of motility on the behavior of Janus particles near liquid/liquid interfaces has not been investigated, yet. Here, we demonstrate the ability to engineer the behavior of highly interfacial active Janus particles near a water/oil interface by introducing motility to the system. Passive, i.e., nonmotile, platinum-capped 8 µm silica (Pt-SiO2) Janus particles exhibit a strong tendency to attach to water/oil interfaces with the Pt-cap facing the oil and the SiO2 side facing the water phase. In contrast, we show that active, i.e., motile, 8 µm Pt-SiO2 Janus particles approach the interface, orient in a sideways fashion with the Janus boundary perpendicular to the interface, and then swim in the vicinity of the interface similar to observations reported near solid/liquid interfaces. Active Pt-SiO2 Janus particles near the water/oil interface show motility as a result of adding H2O2 to the particle solution. The decomposition of H2O2 into O2 and H2O creates a nonuniform gradient of O2 around the particle that hydrodynamically interacts with the water/decalin boundary. The interaction enables rotation of the particle within the swimming plane that is parallel to the interface but restricts rotation in and out of the swimming plane, thereby preventing adsorption to the liquid/liquid interface.

Floor- or Ceiling-Sliding for Chemically Active, Gyrotactic, Sedimenting Janus Particles.

Chemically active particles achieve motility without external forces and torques ("self-propulsion") due to catalytic chemical reactions at their surfaces, which change the chemical composition of the surrounding solution (called "chemical field") and induce hydrodynamic flow of the solution. By coupling the distortions of these fields back to its motion, a chemically active particle experiences an effective interaction with confining surfaces. This coupling can lead to a rich behavior, such as the occurrence of wall-bound steady states of "sliding". Most active particles are density mismatched with the solution and, thus, tend to sediment. Moreover, the often employed Janus spheres, which consist of an inert core material decorated with a cap-like, thin layer of a catalyst, are gyrotactic (i.e., "bottom-heavy"). Whether or not they may exhibit sliding states at horizontal walls depends on the interplay between the active motion and the gravity-driven sedimentation and alignment, such as the gyrotactic tendency to align the axis along the gravity direction being overcome by a competing, activity-driven alignment with a different orientation. It is therefore important to understand and quantify the influence of these gravity-induced effects on the behavior of model chemically active particles moving in the vicinity of walls. For model gyrotactic, self-phoretic Janus particles, here we study theoretically the occurrence of sliding states at horizontal planar walls that are either below ("floor") or above ("ceiling") the particle. We construct "state diagrams" characterizing the occurrence of such states as a function of the sedimentation velocity and of the gyrotactic response of the particle, as well as of the phoretic mobility of the particle. We show that in certain cases sliding states may emerge simultaneously at both the ceiling and the floor, while the larger part of the experimentally relevant parameter space corresponds to particles that would exhibit sliding states only either at the floor or at the ceiling-or there are no sliding states at all. These predictions are critically compared with the results of previous experimental studies, as well as with our dedicated experiments carried out with Pt-coated, polystyrene-core, or silica-core Janus spheres immersed in aqueous hydrogen peroxide solutions.

Experimental Study of the Motion of Patchy Particle Swimmers Near a Wall.

In this work, we demonstrate our ability to precisely tailor the surface activity of self-propelled active colloids by varying the size of the active area. The quasi two-dimensional autonomous motion of spherical patchy particle swimmers is studied in a chemical environment in the vicinity of a solid boundary. Oxidative decomposition of hydrogen peroxide into oxygen and water occurs only on a well-defined Pt-coated section of the polystyrene particle surface. The asymmetric distribution of product molecules interacting with the particle leads to the autonomous motion, which is characterized as the patch size varies from 11 to 25 to 50% of the particle surface area. The phoretic motion of patchy particle swimmers is analytically predicted by a model developed by Popescu et al. and shows good agreement with the experimentally observed velocities when the influence of the wall on the preferential rotational motion of the particles near the solid boundary is considered. The study illustrates the potential to precisely engineer the motion of particles by controlling their properties rather than depending on changes in the environment.