Photocatalytic micromotors are developing rapidly and environmental applications seem very promising and within reach. However, the complex synthesis strategies, jointly with the large band gaps of most efficient swimmers inhibit both, applications and upscaling. Herein, a simple solvothermal synthesis of well defined, catalytically active BiVO4 microparticles, which can propel efficiently without asymmetrization is presented. Those microparticles respond to blue and UV light and are able to switch between different motion strategies, similar to bacterial microswimmers. These behavioral changes are controlled by changing the pH value of the environment.
We create single-component photocatalytic bismuth vanadate (BiVO4) microswimmers with a spheroidal shape that move individually upon irradiation without any asymmetrization step. These particles form active assemblies which we investigate combining an experimental approach with numerical simulations and analytical calculations. We systematically explore the speed and assembly of the swimmers into clusters of up to four particles and find excellent agreement between experiment and theory, which helps us to understand motion patterns and speed trends. Moreover, different batches of particles can be functionalized separately, making them ideal candidates to fulfill a multitude of tasks, such as sensing or environmental remediation. To exemplify this, we coat our swimmers with silica (SiO2) and selectively couple some of their modules to fluorophores in a way which does not inhibit self-propulsion. The present work establishes spheroidal BiVO4 microswimmers as a versatile platform to design multifunctional microswimmers.
Chemiophoretic nano- and micromotors require a constant flow of product molecules to maintain a gradient that enables their propulsion. Besides a smaller number of redox reactions that have been used,...
Catalytic microswimmers that move by a phoretic mechanism in response to a self-induced chemical gradient are often obtained by the design of spherical janus microparticles, which suffer from multi-step fabrication and low yields. Approaches such as irregular particle shapes, local excitation or intrinsic asymmetry are on the rise to facilitate manufacturing, but the effects on the generation of motion remain poorly understood. In this work, single crystalline BiVO4 microswimmers are presented that rely on a strict inherent asymmetry of charge-carrier distribution under illumination. The origin of the asymmetrical flow pattern is elucidated becauseof the high spatial resolution of measured flow fields around pinned BiVO4 colloids. As a result the flow from oxidative to reductive particle sides was confirmed. Distribution of oxidation and reduction reactions suggests a dominant self-electrophoretic motion mechanism with a source quadrupole as the origin of the induced flows. It is shown that the symmetry of the flow fields is broken by self-shadowing of the particles and synthetic surface defects that impact the photocatalytic activity of the microswimmers. The results demonstrate the complexity of symmetry breaking in nonspherical microswimmers and are leading the way towards understanding ofpropulsion mechanisms of phoretic colloids of various shapes.
Catalytic microswimmers that move by a phoretic mechanism in response to a self-induced chemical gradient are often obtained by the design of spherical janus microparticles, which suffer from multi-step fabrication and low yields. Approaches that circumvent laborious multi-step fabrication include the exploitation of the possibility of nonuniform catalytic activity along the surface of irregular particle shapes, local excitation or intrinsic asymmetry. Unfortunately, the effects on the generation of motion remain poorly understood. In this work, single crystalline BiVO 4 microswimmers are presented that rely on a strict inherent asymmetry of charge-carrier distribution under illumination. The origin of the asymmetrical flow pattern is elucidated because of the high spatial resolution of measured flow fields around pinned BiVO 4 colloids. As a result the flow from oxidative to reductive particle sides is confirmed. Distribution of oxidation and reduction reactions suggests a dominant self-electrophoretic motion mechanism with a source quadrupole as the origin of the induced flows. It is shown that the symmetry of the flow fields is broken by self-shadowing of the particles and synthetic surface defects that impact the photocatalytic activity of the microswimmers. The results demonstrate the complexity of symmetry breaking in nonspherical microswimmers and emphasize the role of self-shadowing for photocatalytic microswimmers. The findings are leading the way toward understanding of propulsion mechanisms of phoretic colloids of various shapes.
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