A Conceptual Framework to Understand the Self-Assembly of Chemically Active Colloids.

Colloids that generate chemicals, or "chemically active colloids", can interact with their neighbors and generate patterns via forces arising from such chemical gradients. Examples of such assemblies of chemically active colloids are abundant in the literature, but a unified theoretical framework is needed to rationalize the scattered results. Combining experiments, theory, Brownian dynamics, and finite element simulations, we present here a conceptual framework for understanding how immotile, yet chemically active, colloids assemble. This framework is based on the principle of ionic diffusiophoresis and diffusioosmosis and predicts that a chemically active colloid interacts with its neighbors through short- and long-range interactions that can be either repulsive or attractive, depending on the relative diffusivity of the released cations and anions, and the relative zeta potential of a colloidal particle and the planar surface on which it resides. As a result, 4 types of pairwise interactions arise, leading to 4 different types of colloidal assemblies with distinct patterns. Using short-range attraction and long-range attraction (SALR) systems as an example, we show quantitative agreement between the framework and experiments. The framework is then applied to rationalize a wide range of patterns assembled from chemically active colloids in the literature exhibiting other types of pairwise interactions. In addition, the framework can predict what the assembly looks like with minimal experimental information and help infer ionic diffusivity and zeta potential values in systems where these values are inaccessible. Our results represent a solid step toward building a complete theory for understanding and controlling chemically active colloids, from the molecular level to their mesoscopic superstructures and ultimately to the macroscopic properties of the assembled materials.

Chemical Micromotors Move Faster at Oil-Water Interfaces.

Many real-world scenarios involve interfaces, particularly liquid-liquid interfaces, that can fundamentally alter the dynamics of colloids. This is poorly understood for chemically active colloids that release chemicals into their environment. We report here the surprising discovery that chemical micromotors─colloids that convert chemical fuels into self-propulsion─move significantly faster at an oil-water interface than on a glass substrate. Typical speed increases ranged from 3 to 6 times up to an order of magnitude and were observed for different types of chemical motors and interfaces made with different oils. Such speed increases are likely caused by faster chemical reactions at an oil-water interface than at a glass-water interface, but the exact mechanism remains unknown. Our results provide valuable insights into the complex interactions between chemical micromotors and their environments, which are important for applications in the human body or in the removal of organic pollutants from water. In addition, this study also suggests that chemical reactions occur faster at an oil-water interface and that micromotors can serve as a probe for such an effect.

Reversing a Platinum Micromotor by Introducing Platinum Oxide.

Understanding and controlling the swimming direction of a synthetic nano- and micromotor holds fundamental and applied significance. Here, we focus on platinum-containing Janus colloids that catalytically decompose H2 O2 into O2 , an archetypical model of chemical micromotor. We discover that platinum oxides (primarily PtO) are produced on Pt films sputter-coated in O2 plasma, and PtO reverses the motor possibly by self-electrophoresis. Using this knowledge, micromotors moving in either direction were fabricated by intentionally introducing or removing PtO. These findings challenge the conventional wisdom that a Pt micromotor is powered by Pt alone, and open up new avenues for controlling the swimming directions of a micro- and nanomachine.

Generic Rules for Distinguishing Autophoretic Colloidal Motors.

Distinguishing the operating mechanisms of nano- and micromotors powered by chemical gradients, i.e. "autophoresis", holds the key for fundamental and applied reasons. In this article, we propose and experimentally confirm that the speeds of a self-diffusiophoretic colloidal motor scale inversely to its population density but not for self-electrophoretic motors, because the former is an ion source and thus increases the solution ionic strength over time while the latter does not. They also form clusters in visually distinguishable and quantifiable ways. This pair of rules is simple, powerful, and insensitive to the specific material composition, shape or size of a colloidal motor, and does not require any measurement beyond typical microscopy. These rules are not only useful in clarifying the operating mechanisms of typical autophoretic micromotors, but also in predicting the dynamics of unconventional ones that are yet to be experimentally realized, even those involving enzymes.

Better fuels for photocatalytic micromotors: a case study of triethanolamine.

Efficient fuels are critical for designing photocatalytic micromotors with high performance. We discover that 0.5 mM of triethanolamine can power TiO2-Pt motors at 35 µm s-1 without producing bubbles, a significant improvement over conventional fuels such as water, H2O2 or hydroquinone. The effectiveness of hole scavengers such as triethanolamine can be generalized to other photocatalytic micromotors containing a heterojunction with an n-type (but not a p-type) semiconductor.

Active, Yet Little Mobility: Asymmetric Decomposition of H2O2 Is Not Sufficient in Propelling Catalytic Micromotors.

A popular principle in designing chemical micromachines is to take advantage of asymmetric chemical reactions such as the catalytic decomposition of H2O2. Contrary to intuition, we use Janus micromotors half-coated with platinum (Pt) or catalase as an example to show that this ingredient is not sufficient in powering a micromotor into self-propulsion. In particular, by annealing a thin Pt film on a SiO2 microsphere, the resulting microsphere half-decorated with discrete Pt nanoparticles swims ∼80% more slowly than its unannealed counterpart in H2O2, even though they both catalytically produce comparable amounts of oxygen. Similarly, SiO2 microspheres half-functionalized with the enzyme catalase show negligible self-propulsion despite high catalytic activity toward decomposing H2O2. In addition to highlighting how surface morphology of a catalytic cap enables/disables a chemical micromotor, this study offers a refreshed perspective in understanding how chemistry powers nano- and microscopic objects (or not): our results are consistent with a self-electrophoresis mechanism that emphasizes the electrochemical decomposition of H2O2 over nonelectrochemical pathways. More broadly, our finding is a critical piece of the puzzle in understanding and designing nano- and micromachines, in developing capable model systems of active colloids, and in relating enzymes to active matter.

Light-powered active colloids from monodisperse and highly tunable microspheres with a thin TiO2 shell.

The emerging field of active matter, and its subset active colloid, is in great need of good model systems consisting of moving entities that are uniform and highly tunable. In this article, we address this challenge by introducing core-shell SiO2-TiO2 microspheres, prepared by chemically coating a thin layer of TiO2 on an inert core, that are highly monodisperse in size (polydispersity 4.1%) and regular in shape (circularity 0.93). Compared with similar samples prepared by the classic sol-gel method, Janus TiO2-Pt active colloids prepared with core-shell TiO2 spheres move faster and boast a much clearer Janus interface. Moreover, a unique feature of these core-shell TiO2 microspheres is their great tunability in the colloid size, shell thickness, and even the type of the core particle. These advantages are highlighted in two examples, one demonstrating a TiO2-Pt active colloid with a magnetic core that enables magnetic manipulation, and the other demonstrating the collective expansion and contraction of a uniform cluster of core-shell TiO2 colloids under UV light illumination. We believe that TiO2 microspheres produced by this core-shell technique compare favorably with many other types of active colloids being employed as model systems, and thus open up many research possibilities.

Synergistic Speed Enhancement of an Electric-Photochemical Hybrid Micromotor by Tilt Rectification.

A hybrid micromotor is an active colloid powered by more than one power source, often exhibiting expanded functionality and controllability than those of a singular energy source. However, these power sources are often applied orthogonally, leading to stacked propulsion that is just a sum of two independent mechanisms. Here, we report that TiO2-Pt Janus micromotors, when subject to both UV light and AC electric fields, move up to 90% faster than simply adding up the speed powered by either source. This unexpected synergy between light and electric fields, we propose, arises from the fact that an electrokinetically powered TiO2-Pt micromotor moves near a substrate with a tilted Janus interface that, upon the application of an electric field, becomes rectified to be vertical to the substrate. Control experiments with magnetic fields and three types of micromotors unambiguously and quantitatively show that the tilting angle of a micromotor correlates positively with its instantaneous speed, reaching maximum at a vertical Janus interface. Such "tilting-induced retardation" could affect a wide variety of chemically powered micromotors, and our findings are therefore helpful in understanding the dynamics of micromachines in confinement.

A practical guide to active colloids: choosing synthetic model systems for soft matter physics research.

Synthetic active colloids that harvest energy stored in the environment and swim autonomously are a popular model system for active matter. This emerging field of research sits at the intersection of materials chemistry, soft matter physics, and engineering, and thus cross-talk among researchers from different backgrounds becomes critical yet difficult. To facilitate this interdisciplinary communication, and to help soft matter physicists with choosing the best model system for their research, we here present a tutorial review article that describes, in appropriate detail, six experimental systems of active colloids commonly found in the physics literature. For each type, we introduce their background, material synthesis and operating mechanisms and notable studies from the soft matter community, and comment on their respective advantages and limitations. In addition, the main features of each type of active colloid are summarized into two useful tables. As materials chemists and engineers, we intend for this article to serve as a practical guide, so those who are not familiar with the experimental aspects of active colloids can make more informed decisions and maximize their creativity.

Bimetallic coatings synergistically enhance the speeds of photocatalytic TiO2 micromotors.

The design of powerful, more biocompatible microrobots calls for faster catalytic reactions. Here we demonstrate a two-fold increase in the speed of photocatalytic TiO2-metal Janus micromotors via a Au/Ag bi-layered coating. Electrochemical measurements show that such a bimetallic coating is a better photocatalyst than either metal alone. Similarly, an additional sputtered Ag layer could also significantly increase the speed of Pt-PS or TiO2-Pt micromotors, suggesting that applying bimetallic coatings is a generalizable strategy in the design of faster catalytic micromotors.

2.6 V aqueous symmetric supercapacitors based on phosphorus-doped TiO2 nanotube arrays.

Increasing the voltage window of an electrode material is effective for improving the energy density of aqueous symmetric supercapacitors. Herein, a novel aqueous symmetric supercapacitor equipped with a high cell voltage window of 2.6 V was assembled by P-doped TiO2 nanotube arrays on a Ti sheet. The arrays exhibit a wide potential range of about 1.2 V as the cathode, and a stable wide potential range of 1.4 V as the anode was also obtained. These wide potential windows in the cathode and anode render the symmetric supercapacitor with a very large working voltage window reaching 2.6 V, and thus a high volumetric energy density (1.65 mW h cm-3). These results suggest that P-doped TiO2 nanotube arrays can be promising candidates for energy storage devices.

High-Performance Photoelectrochemical Water Oxidation with Phosphorus-Doped and Metal Phosphide Cocatalyst-Modified g-C3 N4 Formation Through Gas Treatment.

Graphitic carbon nitride (g-C3 N4 ) has been widely explored as a photocatalyst for water splitting. The anodic water oxidation reaction (WOR) remains a major obstacle for such processes, with issues such as low surface area of g-C3 N4 , poor light absorption, and low charge-transfer efficiency. In this work, such longtime concerns have been partially addressed with band gap and surface engineering of nanostructured graphitic carbon nitride (g-C3 N4 ). Specifically, surface area and charge-transfer efficiency are significantly enhanced through architecting g-C3 N4 on nanorod TiO2 to avoid aggregation of layered g-C3 N4 . Moreover, a simple phosphide gas treatment of TiO2 /g-C3 N4 configuration not only narrows the band gap of g-C3 N4 by 0.57 eV shifting it into visible range but also generates in situ a metal phosphide (M=Fe, Cu) water oxidation cocatalyst. This TiO2 /g-C3 N4 /FeP configuration significantly improves charge separation and transfer capability. As a result, our non-noble-metal photoelectrochemical system yields outstanding visible light (>420 nm) photocurrent: approximately 0.3 mA cm-2 at 1.23 V and 1.1 mA cm-2 at 2.0 V versus RHE, which is the highest for a g-C3 N4 -based photoanode. It is expected that the TiO2 /g-C3 N4 /FeP configuration synthesized by a simple phosphide gas treatment will provide new insight for producing robust g-C3 N4 for water oxidation.

Tubular morphology preservation and doping engineering of Sn/P-codoped hematite for photoelectrochemical water oxidation.

Tubular hematite with high-concentration, uniform doping is regarded as a promising material for photoelectrochemical water oxidation. However, the high-temperature annealing commonly used for activating doped hematite inevitably causes deformation of the tubular structure and an increase in the trap states. In the present work, Sn-doped tubular hematite on fluorine-doped tin oxide (FTO) is successfully obtained at 750 °C from a Sn-coated FeOOH tube precursor. Sn/P codoping, which is rarely considered for hematite, is also achieved via a gas phase reaction in phosphide atmosphere. The tubular morphology allows the dopant to diffuse from both the inner and outer surfaces, thus decreasing the doping profile in the radial direction. The even distribution of Sn and P synergetically increases the carrier density of hematite by one order of magnitude, which shortens the width of the depletion layer to ca. 2.3 nm (compared with 19.3 nm for the pristine sample) and leads to prolonged carrier lifetime and efficient charge separation. In addition, this codoping protocol does not introduce additional surface trap states, as evidenced by the increased charge injection efficiency and surface kinetic analysis using intensity modulated photocurrent spectroscopy (IMPS). As a result, the morphology- and doping-engineered hematite exhibits photocurrents of 0.9 mA cm-2 at 1.23 V and 3.8 mA cm-2 at 2.0 V vs. RHE under AM 1.5 G illumination (100 mW cm-2) in 1.0 M NaOH, representing 4.5-fold and 4.8-fold enhancements, respectively, compared with the photocurrents of undoped hematite. The present method is shown to be effective for preparing multi-element-doped hematite nanotubes and may find broad application in the development of other nanotubular photoelectrodes with or without doping for efficient and robust water oxidation.

Brand new 1D branched CuO nanowire arrays for efficient photoelectrochemical water reduction.

Developing high surface area nanostructured electrodes with fast charge separation is one of the main challenges for exploring cupric oxide (CuO)-based photocathodes in solar-driven hydrogen production applications. Herein, brand new 1D branched CuO nanowire arrays have been achieved on fluorine-doped tin oxide-coated glass (FTO) through a two-step wet chemical redox reaction. X-ray diffraction patterns, Raman spectra and X-ray photoelectron spectroscopy confirm the pure phase characteristic of the resulting branched CuO. In addition to the enlarged surface area of this advanced functional structure as compared with that of the 1D wire trunk, the charge injection and separation have been improved by rationally controlling the density of defects and size of branches. As a result, the optimized branched CuO exhibits photocurrent as high as 3.6 mA·cm-2 under AM 1.5G (100 mW·cm-2) illumination and 3.0 mA·cm-2 under visible light (λ > 420 nm) at 0.2 V vs. RHE in 0.5 M Na2SO4, which are 2.8- and 3.0-fold greater than those of 1D wire samples, respectively. In addition, the solution-processed approach established herein seems quite favourable for large-scale and low-cost manufacturing.