An Account on BiVO4 as Photocatalytic Active Matter.

Photocatalytic materials are gaining popularity and research investment for developing light-driven micromotors. While most of the early work used highly stable TiO2 as a material to construct micromotors, mostly in combination with noble metals, other semiconductors offer a wider range of properties, including independence from high-energy UV light. This review focuses on our work with BiVO4 which has shown promise due to its small band gap and resulting ability to absorb blue light. Additionally, this salt's well-defined crystal structures lead to exploitable charge separation on different crystal facets, providing sufficient asymmetry to cause active propulsion. These properties have given rise to fascinating physical and chemical behaviors that show how rich and variable active matter can become. Here, we present the synthesis of different BiVO4 microparticles and their material properties that make them excellent candidates as active micromotors. A critical factor in understanding inherently asymmetric micromotors is knowledge of their flow fields. However, due to their small size and the need to use even smaller tracer particles to avoid perturbing the flow field, measuring flow fields at the microscale is a difficult task. We also present these first results, which allow us to demonstrate the correlation between chemical reactivity and the flow generated, leading to active motion. Due to the nontoxic nature of BiVO4, these visible-light-responsive microswimmers have been used to study the first steps toward applications, even in sensitive areas such as food technology. Although these initial tests are far from being realized, we have to face the fact that a single microswimmer will not be able to perform macroscale tasks. Therefore, we present the reader with the first simple studies of collective motion, hoping for many new contributions to the field. The one-step synthesis of BiVO4 clearly paves the way for studies requiring large numbers of particles. We predict that the combination of promising applications for a nontoxic material which is readily synthesized in large quantities will contribute pivotally to advance the field of active matter beyond the proof-of-concept stage.

Combining photocatalytic collection and degradation of microplastics using self-asymmetric Pac-Man TiO2.

Microplastics are a significant environmental threat and the lack of efficient removal techniques further amplifies this crisis. Photocatalytic semiconducting nanoparticles have the potential to degrade micropollutants, among them microplastics. The hydrodynamic effects leading to the propulsion of micromotors can lead to the accumulation of microplastics in close vicinity of the micromotor. Incorporating these different properties into a single photocatalytic micromotor (self-propulsion, phoretic assembly of passive colloids and photocatalytic oxidation of contaminants), we achieve a highly scalable, inherently-asymmetric Pac-Man TiO2 micromotor with the ability to actively collect and degrade microplastics. The target microplastics are homogeneous polystyrene microspheres (PS) to facilitate the optical degradation measurements. We cross-correlate the degradation with catalytic activity studies and critically evaluate the timescales required for all involved processes.

Pair Interaction between Two Catalytically Active Colloids.

Due to the intrinsically complex non-equilibrium behavior of the constituents of active matter systems, a comprehensive understanding of their collective properties is a challenge that requires systematic bottom-up characterization of the individual components and their interactions. For self-propelled particles, intrinsic complexity stems from the fact that the polar nature of the colloids necessitates that the interactions depend on positions and orientations of the particles, leading to a 2d - 1 dimensional configuration space for each particle, in d dimensions. Moreover, the interactions between such non-equilibrium colloids are generically non-reciprocal, which makes the characterization even more complex. Therefore, derivation of generic rules that enable us to predict the outcomes of individual encounters as well as the ensuing collective behavior will be an important step forward. While significant advances have been made on the theoretical front, such systematic experimental characterizations using simple artificial systems with measurable parameters are scarce. Here, two different contrasting types of colloidal microswimmers are studied, which move in opposite directions and show distinctly different interactions. To facilitate the extraction of parameters, an experimental platform is introduced in which these parameters are confined on a 1D track. Furthermore, a theoretical model for interparticle interactions near a substrate is developed, including both phoretic and hydrodynamic effects, which reproduces their behavior. For subsequent validation, the degrees of freedom are increased to 2D motion and resulting trajectories are predicted, finding remarkable agreement. These results may prove useful in characterizing the overall alignment behavior of interacting self-propelling active swimmer and may find direct applications in guiding the design of active-matter systems involving phoretic and hydrodynamic interactions.

Active BiVO4 Swimmers Propelled by Depletion Gradients Caused by Photodeposition.

Artificial active matter often self-propels by creating gradients of one or more species or quantities. For chemical swimmers, most frequently either O2 or H+ that are created in certain catalytic reactions are causing the interfacial flows which drive the self-propulsion. While the palette of reactions is extending constantly, especially toward more bio-compatible fuels, the depletion of species is often overlooked. Here, the photodeposition of metal species on BiVO4 micro swimmers is considered. During the photodeposition reaction, metal ions are removed from the solution creating a depleted region around the particle. The ability of this depletion to drive active motion of artificial micro swimmers, as well as the influences of different metal ions and counter ions on the motion are investigated and cross compared.

Determination of the swimming mechanism of Au@TiO2 active matter and implications on active-passive interactions.

Non-equilibrium dynamic assembly attracts considerable attention due to the possibility of forming diverse structures that can potentially lead to functional materials. Despite significant progress in understanding and modelling, the complexity of the system implies that different phases of the assembly formation are governed by different interactions. It is clear that both, hydrodynamic and chemical interactions stem from the activity of the particle, but correlation to specific chemical species remains not yet understood. Here, we investigate the origin of the main driving forces for light-driven Au@TiO2 micromotors and look at the implication this causes for the interactions between active and passive particles. We develop precision experimental measurements of the photochemical reaction rate, which are correlated with the observed speed of Au@TiO2 micromotors. The comparison with two distinct models allows the conclusion that the dominant propulsion mechanism of the active particles is self-electrophoresis based on the self-generated H+ gradient. We verify this assumption by adding salt and confirm the dependence of the expected swimming behaviour on salt concentration and investigate the consequences for raft formation in COMSOL simulations.

Colloidal Active Matter Mimics the Behavior of Biological Microorganisms-An Overview.

This article provides a review of the recent development of biomimicking behaviors in active colloids. While the behavior of biological microswimmers is undoubtedly influenced by physics, it is frequently guided and manipulated by active sensing processes. Understanding the respective influences of the surrounding environment can help to engineering the desired response also in artificial swimmers. More often than not, the achievement of biomimicking behavior requires the understanding of both biological and artificial microswimmers swimming mechanisms and the parameters inducing mechanosensory responses. The comparison of both classes of microswimmers provides with analogies in their dependence on fuels, interaction with boundaries and stimuli induced motion, or taxis.

Beyond Janus Geometry: Characterization of Flow Fields around Nonspherical Photocatalytic Microswimmers.

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 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 because of the high spatial resolution of measured flow fields around pinned BiVO4 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.

Hydrodynamically Controlled Self-Organization in Mixtures of Active and Passive Colloids.

Active particles are known to exhibit collective behavior and induce structure in a variety of soft-matter systems. However, many naturally occurring complex fluids are mixtures of active and passive components. The authors examine how activity induces organization in such multi-component systems. Mixtures of passive colloids and colloidal micromotors are investigated and it is observed that even a small fraction of active particles induces reorganization of the passive components in an intriguing series of phenomena. Experimental observations are combined with large-scale simulations that explicitly resolve the near- and far-field effects of the hydrodynamic flow and simultaneously accurately treat the fluid-colloid interfaces. It is demonstrated that neither conventional molecular dynamics simulations nor the reduction of hydrodynamic effects to phoretic attractions can explain the observed phenomena, which originate from the flow field that is generated by the active colloids and subsequently modified by the aggregating passive units. These findings not only offer insight into the organization of biological or synthetic active-passive mixtures, but also open avenues to controlling the behavior of passive building blocks by means of small amounts of active particles.

Microswimming by oxidation of dibenzylamine.

Chemiophoretic nano- and micromotors require a constant flow of product molecules to maintain a gradient that enables their propulsion. Apart from a smaller number of redox reactions that have been used, catalytic reactions are the main source of energy with the obvious benefit of making on-board fuel storage obsolete. However, the decomposition of H2O2 seems to strongly dominate the literature and although motion in H2O through water splitting is becoming more popular, so far only a few different reactions have been used for propulsion of photocatalytic microswimmers. Here, we investigate the possibility of extending the range of possible fuelling reactions to organic reactions with high significance in organic synthesis - the oxidation of amines to imines. Herein, motion of the microswimmers is analysed at different amine concentrations and light intensities. The findings thereof are correlated with the reaction products identified and quantified by gas chromatography (GC).

Upstream Rheotaxis of Catalytic Janus Spheres.

Fluid flow is ubiquitous in many environments that form habitats for microorganisms. Therefore, it is not surprising that both biological and artificial microswimmers show responses to flows that are determined by the interplay of chemical and physical factors. In particular, to deepen the understanding of how different systems respond to flows, it is crucial to comprehend the influence played by swimming pattern. The tendency of organisms to navigate up or down the flow is termed rheotaxis. Early theoretical studies predicted a positive rheotactic response for puller-type spherical Janus micromotors. However, recent experimental studies have focused on pusher-type Janus particles, finding that they exhibit cross-stream migration in externally applied flows. To study the response to the flow of swimmers with a qualitatively different flow pattern, we introduce Cu@SiO2 micromotors that swim toward their catalytic cap. On the basis of experimental observations, and supported by flow field calculations using a model for self-electrophoresis, we hypothesize that they behave effectively as a puller-type system. We investigate the effect of externally imposed flow on these spherically symmetrical Cu@SiO2 active Janus colloids, and we indeed observe a steady upstream directional response. Through a simple squirmer model for a puller, we recover the major experimental observations. Additionally, the model predicts a "jumping" behavior for puller-type micromotors at high flow speeds. Performing additional experiments at high flow speeds, we capture this phenomenon, in which the particles "roll" with their swimming axes aligned to the shear plane, in addition to being dragged downstream by the fluid flow.

A Platform for Stop-Flow Gradient Generation to Investigate Chemotaxis.

The ability of artificial microswimmers to respond to external stimuli and the mechanistical details of their origins belong to the most disputed challenges in interdisciplinary science. Therein, the creation of chemical gradients is technically challenging, because they quickly level out due to diffusion. Inspired by pivotal stopped flow experiments in chemical kinetics, we show that microfluidics gradient generation combined with a pressure feedback loop for precisely controlling the stop of the flows, can enable us to study mechanistical details of chemotaxis of artificial Janus micromotors, based on a catalytic reaction. We find that these copper Janus particles display a chemotactic motion along the concentration gradient in both, positive and negative direction and we demonstrate the mechanical reaction of the particles to unbalanced drag forces, explaining this behaviour.

Highly Efficient Active Colloids Driven by Galvanic Exchange Reactions.

Micromotors are propelled by a variety of chemical reactions, with most of them being of catalytic nature. There are, however, systems based on redox reactions, which show clear benefits for efficiency. Here, we broaden the spectrum of suitable reactions to galvanic exchange processes, or an electrochemical replacement of a solid metal layer with dissolved ionic species of a more noble metal. We study the details of motility and the influence of different reaction parameters to conclude that these galvanophoretic processes circumvent several steps that lose efficiency in catalytic micromotors. Furthermore, we investigate the chemical process, the charge, and flow conditions that lead to this highly efficient new type of active motility. Toward a better understanding of the underlying processes, we propose an electrokinetic model that we numerically solve via finite elements.

Semiconductor-Based Microswimmers: Attention to Detail Matters.

Colloidal active matter is known for its sensitivity to external conditions; for example, the swimming speeds depend strongly on substrates, fuel concentration, and in the case of light-driven colloids, the illumination. While these points are regularly considered, the nanoscopic material properties of the motor bodies are often barely mentioned, but they are highly influential in the case of photocatalysts. In order to demonstrate the influence of subtle differences in chemical composition and interfacing between the different material compounds, we designed a system based on colloidal titania spheres asymmetrized by different nanoscale cobalt oxide species. We examine how the material properties and combinations lead to highly specific catalytic activity and cross-relate the subtle differences to the typical active behaviors of these complex materials.

Microfluidics for Microswimmers: Engineering Novel Swimmers and Constructing Swimming Lanes on the Microscale, a Tutorial Review.

This paper provides an updated review of recent advances in microfluidics applied to artificial and biohybrid microswimmers. Sharing the common regime of low Reynolds number, the two fields have been brought together to take advantage of the fluid characteristics at the microscale, benefitting microswimmer research multifold. First, microfluidics offer simple and relatively low-cost devices for high-fidelity production of microswimmers made of organic and inorganic materials in a variety of shapes and sizes. Microscale confinement and the corresponding fluid properties have demonstrated differential microswimmer behaviors in microchannels or in the presence of various types of physical or chemical stimuli. Custom environments to study these behaviors have been designed in large part with the help of microfluidics. Evaluating microswimmers in increasingly complex lab environments such as microfluidic systems can ensure more effective implementation for in-field applications. The benefits of microfluidics for the fabrication and evaluation of microswimmers are balanced by the potential use of microswimmers for sample manipulation and processing in microfluidic systems, a large obstacle in diagnostic and other testing platforms. In this review various ways in which these two complementary technology fields will enhance microswimmer development and implementation in various fields are introduced.

Impact of Segmented Magnetization on the Flagellar Propulsion of Sperm-Templated Microrobots.

Technical design features for improving the way a passive elastic filament produces propulsive thrust can be understood by analyzing the deformation of sperm-templated microrobots with segmented magnetization. Magnetic nanoparticles are electrostatically self-assembled on bovine sperm cells with nonuniform surface charge, producing different categories of sperm-templated microrobots. Depending on the amount and location of the nanoparticles on each cellular segment, magnetoelastic and viscous forces determine the wave pattern of each category during flagellar motion. Passively propagating waves are induced along the length of these microrobots using external rotating magnetic fields and the resultant wave patterns are measured. The response of the microrobots to the external field reveals distinct flow fields, propulsive thrust, and frequency responses during flagellar propulsion. This work allows predictions for optimizing the design and propulsion of flexible magnetic microrobots with segmented magnetization.

Active spheres induce Marangoni flows that drive collective dynamics.

For monolayers of chemically active particles at a fluid interface, collective dynamics is predicted to arise owing to activity-induced Marangoni flow even if the particles are not self-propelled. Here, we test this prediction by employing a monolayer of spherically symmetric active [Formula: see text] particles located at an oil-water interface with or without addition of a nonionic surfactant. Due to the spherical symmetry, an individual particle does not self-propel. However, the gradients produced by the photochemical fuel degradation give rise to long-ranged Marangoni flows. For the case in which surfactant is added to the system, we indeed observe the emergence of collective motion, with dynamics dependent on the particle coverage of the monolayer. The experimental observations are discussed within the framework of a simple theoretical mean-field model.

Study of Active Janus Particles in the Presence of an Engineered Oil-Water Interface.

We present a systematic study of motion of Pt@SiO2 Janus particles at a liquid-liquid interface. A special microfluidic trap is used for creating such an interface. The increased surface energy of the large surface results in partial wetting of the substrate, leaving patches of oil on the glass surface. This allows us to directly compare the motion at the two interfaces, i.e., oil-water and solid-water interface within the same setting, guaranteeing identical conditions in terms of additional parameters. The propulsion behavior of Janus particles is found to be quantitatively similar at both surfaces. The interplay of reaction product absorption by oil, slip locking by surfactant, microscale friction, lubrication efficiency, and potential Marangoni effect controls the resemblance of motion characteristics at the two interfaces. Additionally, we also observed guidance effect on the Janus particles by the pinning line of oil patches, similar to solid side walls.

Apparent phototaxis enabled by Brownian motion.

Biomimetic behaviour in artificially created active matter that allows deterministic and controlled motility has become of growing interest in recent years. It is well known that phototrophic bacteria optimize their position with respect to light by phototaxis. Here, we describe how our fully artificial, magnetic and photocatalytic microswimmers undergo a specific type of behaviour that strongly resembles phototaxis: when crossing an illuminated stripe the particles repeatedly turn back towards the light once they reach the dark region, without any obvious reason for the particles to do so. In order to understand the origin of this behaviour we analyze different influences and elucidate through experiments and theoretical considerations that this behavior arises from a combination of orientational stabilization through activity and destabilizing Brownian motion. This interplay shows beautifully how simple physical effects can combine into complex behaviours.

IRONSperm: Sperm-templated soft magnetic microrobots.

We develop biohybrid magnetic microrobots by electrostatic self-assembly of nonmotile sperm cells and magnetic nanoparticles. Incorporating a biological entity into microrobots entails many functional advantages beyond shape templating, such as the facile uptake of chemotherapeutic agents to achieve targeted drug delivery. We present a single-step electrostatic self-assembly technique to fabricate IRONSperms, soft magnetic microswimmers that emulate the motion of motile sperm cells. Our experiments and theoretical predictions show that the swimming speed of IRONSperms exceeds 0.2 body length/s (6.8 ± 4.1 µm/s) at an actuation frequency of 8 Hz and precision angle of 45°. We demonstrate that the nanoparticle coating increases the acoustic impedance of the sperm cells and enables localization of clusters of IRONSperm using ultrasound feedback. We also confirm the biocompatibility and drug loading ability of these microrobots, and their promise as biocompatible, controllable, and detectable biohybrid tools for in vivo targeted therapy.

Active Assembly of Spheroidal Photocatalytic BiVO4 Microswimmers.

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.