Shape-Controlled First-Row Transition Metal Vanadates for Electrochemical and Photoelectrochemical Water Splitting.

Transition metal vanadates (MVs) possess abundant electroactive sites, short ion diffusion pathways, and optical properties that make them suitable for various electrochemical (EC) and photoelectrochemical (PEC) applications. While these materials are commonly used in energy storage devices like batteries and capacitors, their shape-controlled 1D and 2D morphologies have gained equal popularity in water splitting (WS) technology in recent times. This review focuses on recent progress made on various first-row (3d, 4 s) transition metal vanadates (t-MVs) having controlled one-dimensional (fiber, wire, or rod) and two-dimensional (layered or sheet) morphologies with a specific emphasis on copper vanadates (CuV), cobalt vanadates (CoV), iron vanadates (FeV), and nickel vanadates (NiV). The review covers different aspects of shape-controlled 1D and 2D t-MVs including optoelectrical properties, wet chemistry synthesis, and electrochemical (EC-WS) and photoelectrochemical water splitting (PEC-WS) performance in terms of onset potential, overpotential, and long-term stability or high cyclic performance. The review concludes by providing some possible thoughts on how to promote the water-splitting attributes of shape-controlled t-MVs more effectively.

Surface-Templated Polymer Microparticle Synthesis Based on Droplet Microarrays.

Polymer microparticle synthesis based on the surface-templated method is a simple and environmentally friendly method to produce various microparticles. Unique particles with different compositions can be fabricated by simply annealing a polymer on a liquid-repellent surface. However, there are hurdles to producing particles of homogeneous sizes with large quantities and varying the shape of particles. Here, a new approach to synthesizing multiple polymer microparticles using micropatterns with wettability contrast is presented. Polymer microparticles are formed in two steps. First, a layer of poly(sodium-4-styrenesulfonate) is deposited on the hydrophilic regions by dipping and withdrawing this micropattern from a polymer solution, and an array of microdroplets is formed. A dewetting-inducing layer on the pattern is introduced, and then target polymer patches are sequentially generated on it. By annealing over Tg, the contact line of the target polymer patch is freely receded, creating a particle form. The size and shape of the microparticle can be controlled by varying the micropatterns. In addition, it is demonstrated that microparticles made of polymer blends or polymer/nanoparticle composite are easily produced. This versatile method offers the potential of surface-templated synthesis to tailor polymer microparticles with different sizes, shapes, and functionalities in various research and applications.

Cracking of Colloidal Films to Generate Rectangular Fragments.

Cracks are common in nature. Cracking is known as an irreversible and uncontrollable process. To control the cracking patterns, many researchers have proposed methods to prepare notches for stress localization on films. In this work, we investigate a method of controlling cracks by making microscale pyramid patterns that have notches between the pyramids. After preparing pyramid patterns consisting of colloidal particles with organic residue, we annealed them to induce volume shrinkage and cracking between the pyramids. We studied the effect of film thickness on cracking and the generation of rectangular fragments consisting of multiple pyramids. The area of rectangular fragments was in good agreement with the results of scaling analysis. The concept of controlling cracks by imprinting notches on a film and the relationship with the film thickness can guide the study of cracking phenomena.

Liquid-Repellent Metal Oxide Photocatalysts.

Metal oxide photocatalysts (MOPCs) decompose organic molecules under illumination. However, the application of MOPCs in industry and research is currently limited by their intrinsic hydrophilicity because MOPCs can be wetted by most liquids. To achieve liquid repellency, the surface needs to possess a low surface energy, but most organic molecules with low surface energy are degraded by photocatalytic activity. Herein, current methods to achieve liquid repellency on MOPCs, while preventing degradation of hydrophobic coatings, are reviewed. Classically, composite materials containing MOPCs and hydrophobic organic compounds possess good liquid repellency. However, composites normally form irregular coatings and are hard to prepare on surfaces such as those that are mesoporous or nanostructured. In addition, the adhesion of composites to substrates is often weak, resulting in delamination. Recent studies have shown that the direct grafting reaction of polydimethylsiloxane (PDMS) from silicone oil (methyl-terminated PDMS) under illumination results in a stable polymer brush. This easy and simple grafting method allows us to create stable liquid-repellent surfaces on MOPCs of various types, structures, and sizes. In particular, super-liquid-repellent drops with an underlying air layer can be created on PDMS-grafted nano-/microstructured MOPCs. Potential applications of surfaces combining liquid repellency and photocatalytic activity are also discussed; thus offering new ways of using MOPCs in a wider range of applications.

Mechanoresponsive Tuning of Anisotropic Wetting on Hierarchically Structured Patterns.

Here, we propose a simple mechanoresponsive system on patterned soft surfaces to manipulate both anisotropy and orientation of liquid wetting. On the poly(dimethylsiloxane) embedding line patterned structures, additional topographies, such as wrinkles and cracks, can be provided by applying compressive and tensile stress, respectively. This tunable hierarchy of structures with the different scales and directions of lines, wrinkles, and cracks allow the mechanoresponsive control of anisotropic wetting in a single platform. In addition, the wetting behavior on those surfaces is precisely investigated based on the concept of critical contact angle to overcome the ridges in a step flow.

Controlling the Structure of Supraballs by pH-Responsive Particle Assembly.

Supraballs of various sizes and compositions can be fabricated via drying of drops of aqueous colloidal dispersions on super-liquid-repellent surfaces with no chemical waste and energy consumption. A "supraball" is a particle composed of colloids. Many properties, such as mechanical strength and porosity, are determined by the ordering of a colloidal assembly. To tune such properties, a colloidal assembly needs to be controlled when supraballs are formed during drying. Here, we introduce a method to control a colloidal assembly of supraballs by adjusting the dispersity of the colloids. Supraballs are fabricated on superamphiphobic surfaces from colloidal aqueous dispersions of polystyrene microparticles carrying pH-responsive poly[2-(diethylamino)ethyl methacrylate]. Drying of dispersion drops at pH 3 on superamphiphobic surfaces leads to the formation of spherical supraballs with densely packed colloids. The pH 10 supraballs are more oblate and consist of more disordered colloids than the pH 3 supraballs, caused by particle aggregates with random sizes and shapes in the pH 10 dispersion. Thus, the shape, crystallinity, porosity, and mechanical properties could be controlled by pH, which allows broader uses of supraballs.

A Photocatalytically Active Lubricant-Impregnated Surface.

Lubricant impregnated surfaces (LISs) exhibit sliding angles below 5°. A LIS is presented that possesses photocatalytic activity as well as improved liquid repellency. In a single-step reaction, the surface of photocatalytic mesoporous TiO2 substrate is modified by grafting polydimethylsiloxane (PDMS) brush and the residual non-bound PDMS serves as lubricant. Since the lubricant and the hydrophobic layer are chemically identical, the grafting PDMS layer is stably swollen by the lubricant PDMS, which inhibits direct contact of liquid drops to the solid substrate. Liquid drops such as water, methanol, and even low-surface-tension fluorocarbons, slide on the surface with tilt angles below 1°. The surface exhibits long-term stable photocatalytic activity while retaining its liquid repellency. This photocatalytic activity allows photocatalytic chemistry, for example, decomposition of organics, on LIS to be carried out.

Cylindrical chains of water drops condensing on microstructured lubricant-infused surfaces.

We studied the condensation of water drops on a micro-structured lubricant-infused surfaces. Hierarchical micro-prism surfaces were fabricated by soft imprinting with wet TiO2 nanoparticle paste. After hydrophobization, the patterned surfaces were infused with silicone oil as a lubricant. When cooling at high humidity (over 80%), water drops nucleate and start growing on the surface. Once they have reached a certain size, the drops at neighboring channels of the micro-prisms attract each other and spontaneously form cylindrical chains. These chains of drops align perpendicular to the prism array. The morphology and the length-to-width ratio of the chains of drops depend on the thickness of the lubricant layer. This new concept of water drop alignment on lubricant-infused surfaces offers a new route for pattern formation with condensed drops.

Silicone Brushes: Omniphobic Surfaces with Low Sliding Angles.

Losing contact: Omniphobic surfaces can be readily produced by acid-catalyzed graft polycondensation of dimethyldimethoxysilane (PDMS). Droplets show a very small contact angle hysteresis as well as a low sliding angle of only a few degrees. The nm-thick PDMS layer is neither easily washed away nor depleted. This method offers a novel approach towards the preparation of super-liquid-repelling surfaces.

Enhancing Resistance to Wetting Transition through the Concave Structures.

Water-repellent superhydrophobic surfaces are ubiquitous in nature. The fundamental understanding of bio/bio-inspired structures facilitates practical applications surmounting metastable superhydrophobicity. Typically, the hierarchical structure and/or reentrant morphology have been employed hitherto to suppress the Cassie-Baxter to Wenzel transition (CWT). Herein, a new design concept is reported, an effect of concave structure, which is vital for the stable superhydrophobic surface. The thermodynamic and kinetic stabilities of the concave pillars are evaluated by continuous exposure to various hydrostatic pressures and sudden impacts of water droplets with various Weber numbers (We), comparing them to the standard superhydrophobic normal pillars. Specifically, the concave pillar exhibits reinforced impact resistance preventing CWT below a critical We of ≈27.6, which is ≈1.6 times higher than that of the normal pillar (≈17.0). Subsequently, the stability of underwater air film (plastron) is investigated at various hydrostatic pressures. The results show that convex air caps formed at the concave cavities generate downward Laplace pressure opposing the exerted hydrostatic pressure between the pillars, thus impeding the hydrostatic pressure-dependent underwater air diffusion. Hence, the effects of trapped air caps contributing to the stable Cassie-Baxter state can offer a pioneering strategy for the exploration and utilization of superhydrophobic surfaces.

Evaporation-driven Supraparticle Synthesis by Self-Lubricating Colloidal Dispersion Microdrops.

The surface-templated evaporation-driven (S-TED) method that uses liquid-repellent surfaces has attracted considerable attention for its use in fabricating supraparticles of defined shape, size, and porosity. However, challenges in achieving mass production have impeded the widespread adoption of the S-TED method. To overcome this limit, we introduce an evaporation-driven "multiple supraparticle" synthesis by drying arrays of self-lubricating colloidal dispersion microdrops. To facilitate this synthetic method, a hydrophilic micropattern is prepared on a hydrophobic substrate as a template. During the removal of the substrate out of a dispersion, liquid drops are trapped and generate a microdrop array. To produce supraparticles, the contact lines of the trapped drops must be able to recede freely during evaporation. However, hydrophilic micropatterns induce strong contact line pinning for microdrops that hinders supraparticle formation. Herein, we solve this contradiction by employing an Ouzo-like colloidal dispersion, where we can control the wettability of the drop trapping domain. The self-lubrication effect provided by the Ouzo-like solution enables smooth movement of the drops' contact lines during evaporation, thereby resulting in the successful fabrication of supraparticle arrays even within the trapping domain. This strategy offers a promising and scalable approach for large-scale evaporation-driven supraparticle synthesis with a potential for extension to various primary colloidal particles, further broadening its applicability.

Bandgap Engineering of Melon using Highly Reduced Graphene Oxide for Enhanced Photoelectrochemical Hydrogen Evolution.

The uncondensed form of polymeric carbon nitrides (PCN), generally known as melon, is a stacked 2D structure of poly(aminoimino)heptazine. Melon is used as a photocatalyst in solar energy conversion applications, but suffers from poor photoconversion efficiency due to weak optical absorption in the visible spectrum, high activation energy, and inefficient separation of photoexcited charge carriers. Experimental and theoretical studies are reported to engineer the bandgap of melon with highly reduced graphene oxide (HRG). Three HRG@melon nanocomposites with different HRG:melon ratios (0.5%, 1%, and 2%) are prepared. The 1% HRG@melon nanocomposite shows higher photocurrent density (71 µA cm-2 ) than melon (24 µA cm-2 ) in alkaline conditions. The addition of a hole scavenger further increases the photocurrent density to 630 µA cm-2 relative to the reversible hydrogen electrode (RHE). These experimental results are validated by calculations using density functional theory (DFT), which revealed that HRG results in a significant charge redistribution and an improved photocatalytic hydrogen evolution reaction (HER).

Multimodal Enzyme-Carrying Suprastructures for Rapid and Sensitive Biocatalytic Cascade Reactions.

Colloidal assemblies of mesoporous suprastructures provide effective catalysis in an advantageous volume-confined environment. However, typical fabrication methods of colloidal suprastructures are carried out under toxic or harmful conditions for unstable biomolecules, such as, biocatalytic enzymes. For this reason, biocatalytic enzymes have rarely been used with suprastructures, even though biocatalytic cascade reactions in confined environments are more efficient than in open conditions. Here, multimodal enzyme- and photocatalyst-carrying superstructures with efficient cascade reactions for colorimetric glucose detection are demonstrated. The suprastructures consisting of various functional nanoparticles, including enzyme-carrying nanoparticles, are fabricated by surface-templated evaporation driven suprastructure synthesis on polydimethylsiloxane-grafted surfaces at ambient conditions. For the fabrication of suprastructures, no additional chemicals and reactions are required, which allows maintaining the enzyme activities. The multimodal enzymes (glucose oxidase and peroxidase)-carrying suprastructures exhibit rapid and highly sensitive glucose detection via two enzyme cascade reactions in confined geometry. Moreover, the combination of enzymatic and photocatalytic cascade reactions of glucose oxidase to titanium dioxide nanoparticles is successfully realized for the same assay. These results show promising abilities of multiple colloidal mixtures carrying suprastructures for effective enzymatic reactions and open a new door for advanced biological reactions and enzyme-related works.

Imbibition-induced selective wetting of liquid metal.

Herein, we present the imbibition-induced, spontaneous, and selective wetting characteristics of gallium-based liquid metal alloys on a metallized surface with micro-scale topographical features. Gallium-based liquid metal alloys are fascinating materials that have enormous surface tension; therefore, they are difficult to pattern into films. The complete wetting of eutectic alloy of gallium and indium is realized on microstructured copper surfaces in the presence of HCl vapor, which removes the native oxide from the liquid metal alloy. This wetting is numerically explained based on the Wenzel's model and imbibition process, revealing that the dimensions of the microstructures are critical for effective imbibition-driven wetting of the liquid metal. Further, we demonstrate that the spontaneous wetting of the liquid metal can be directed selectively along the microstructured region on the metallic surface to create patterns. This simple process enables the uniform coating and patterning of the liquid metal over large areas without an external force or complex processing. We demonstrate that the liquid metal-patterned substrates maintain electrical connection even in a stretched state and after repetitive stretching cycles.

Designing the shape of supraparticles by controlling the apparent contact angle and contact line friction of droplets.

Surface-templated evaporation-driven supraparticle synthesis is a versatile method for supraparticle fabrication. A supraparticle is formed by drying droplet of a colloidal dispersion on liquid repellent surfaces, allowing precise control of the size and mean composition of the supraparticles. The crucial factor determining the morphology is the motion of the contact line of the dispersion droplet on the liquid repellent surface. Here, we study effects of (i) the apparent contact angle and (ii) the contact line friction of a droplet on the shape of the supraparticle. In order to change the initial apparent contact angle of the dispersion droplet a surfactant was added to decrease surface tension. In addition, two different liquid repellent surfaces were used: a polydimethysiloxane (PDMS) grafted surface and a lubricated surface. Both surfaces exhibited distinctly different contact line friction during evaporation. As the initial contact angle of a droplet decreases and friction of a contact line increases, flatter supraparticles are fabricated. By using this simple manipulation principle, eventually, various shapes of supraparticles can be obtained, such as mushroom, hemispherical, convex lens, and disk shapes. This study presents fundamental and critical information that allow us to manipulate the shape of a supraparticle via surface-templated evaporation-driven synthesis that increases the scalability of supraparticles for use in a wide range of applications.

Fluorocarbon lubricant impregnated nanoporous oxide for omnicorrosion-resistant stainless steel.

Corrosion protection coatings have been required for long-term uses of metallic materials applied in various environments incorporating liquid and/or vapor phase corrosion reactants. In this study, we introduce a fluorocarbon lubricant impregnated nanoporous oxide (FLINO) coating on stainless steel for realizing effective resistances against corrosive media in both liquid and vapor phases. The FLINO layer on stainless steel significantly enhances corrosion resistances with superior durability and self-healing capability. The combination of nanoporous structure and fluorocarbon lubricant layer provides an outstanding atmospheric corrosion resistance, which has been a serious issue to be overcome on corrosion-resistant coatings. Therefore, the FLINO coating exhibiting stable and remarkable corrosion resistance against both liquid and vaporized corrosive media, called omnicorrosion-resistance, gives a new route for the versatile protection of metallic materials in various environments encompassing both underwater and atmospheric applications.

Porous supraparticle assembly through self-lubricating evaporating colloidal ouzo drops.

The assembly of colloidal particles from evaporating suspension drops is seen as a versatile route for the fabrication of supraparticles for various applications. However, drop contact line pining leads to uncontrolled shapes of the emerging supraparticles, hindering this technique. Here we report how the pinning problem can be overcome by self-lubrication. The colloidal particles are dispersed in ternary drops (water, ethanol, and anise-oil). As the ethanol evaporates, oil microdroplets form ('ouzo effect'). The oil microdroplets coalesce and form an oil ring at the contact line, levitating the evaporating colloidal drop ('self-lubrication'). Then the water evaporates, leaving behind a porous supraparticle, which easily detaches from the surface. The dispersed oil microdroplets act as templates, leading to multi-scale, fractal-like structures inside the supraparticle. Employing this method, we could produce a large number of supraparticles with tunable shapes and high porosity on hydrophobic surfaces.

Optimizing Hydrophobicity and Photocatalytic Activity of PDMS-Coated Titanium Dioxide.

Polydimethylsiloxane (PDMS) can be linked to the surface of metal-oxide photocatalysts by immersion and UV illumination. The surfaces become hydrophobic and keep their hydrophobicity even under extended UV exposure. Titanium dioxide (TiO2) is a prominent example of a metal-oxide photocatalyst. Here, we studied the influence of a grafted PDMS layer on the photocatalytic activity and wetting properties of TiO2. By varying the molecular weight of PDMS, we controlled the thickness of the polymer layer from 0.6 to 5.5 nm. We recommend a PDMS molecular weight of 6.0 kDa. It leads to a grafted PDMS layer thickness of 2.2 nm, a receding contact angle of 94°,  a low contact angle hysteresis of 9°, and the layer is still photocatalytically active.

Shaping the Assembly of Superparamagnetic Nanoparticles.

Superparamagnetism exists only in nanocrystals, and to endow micro/macro-materials with superparamagnetism, superparamagnetic nanoparticles have to be assembled into complex materials. Most techniques currently used to produce such assemblies are inefficient in terms of time and material. Herein, we used evaporation-guided assembly to produce superparamagnetic supraparticles by drying ferrofluid droplets on a superamphiphobic substrate in the presence of an external magnetic field. By tuning the concentration of ferrofluid droplets and controlling the magnetic field, barrel-like, cone-like, and two-tower-like supraparticles were obtained. These assembled supraparticles preserved the superparamagnetism of the original nanoparticles. Moreover, other colloids can easily be integrated into the ferrofluid suspension to produce, by co-assembly, anisotropic binary supraparticles with additional functions. Additionally, the magnetic and anisotropic nature of the resulting supraparticles was harnessed to prepare magnetically actuable microswimmers.

Development of Multimodal Antibacterial Surfaces Using Porous Amine-Reactive Films Incorporating Lubricant and Silver Nanoparticles.

Anti-biofouling has been improved by passive or active ways. Passive antifouling strategies aim to prevent the initial adsorption of foulants, while active strategies aim to eliminate proliferative fouling by destruction of the chemical structure and inactivation of the cells. However, neither passive antifouling strategies nor active antifouling strategies can solely resist biofouling due to their inherent limitations. Herein, we successfully developed multimodal antibacterial surfaces for waterborne and airborne bacteria with the benefit of a combination of antiadhesion (passive) and bactericidal (active) properties of the surfaces. We elaborated multifunctionalizable porous amine-reactive (PAR) polymer films from poly(pentafluorophenyl acrylate) (PPFPA). Pentafluorophenyl ester groups in the PAR films facilitate creation of multiple functionalities through a simple postmodification under mild condition, based on their high reactivity toward various primary amines. We introduced amine-containing poly(dimethylsiloxane) (amine-PDMS) and dopamine into the PAR films, resulting in infusion of antifouling silicone oil lubricants and formation of bactericidal silver nanoparticles (AgNPs), respectively. As a result, the PAR film-based lubricant-infused AgNPs-incorporated surfaces demonstrate outstanding antibacterial effects toward both waterborne and airborne Escherichia coli, suggesting a new door for development of an effective multimodal anti-biofouling surface.