Revolutionizing CO2 Electrolysis: Fluent Gas Transportation within Hydrophobic Porous Cu2O.

The success of electrochemical CO2 reduction at high current densities hinges on precise interfacial transportation and the local concentration of gaseous CO2. However, the creation of efficient CO2 transportation channels remains an unexplored frontier. In this study, we design and synthesize hydrophobic porous Cu2O spheres with varying pore sizes to unveil the nanoporous channel's impact on gas transfer and triple-phase interfaces. The hydrophobic channels not only facilitate rapid CO2 transportation but also trap compressed CO2 bubbles to form abundant and stable triple-phase interfaces, which are crucial for high-current-density electrocatalysis. In CO2 electrolysis, in situ spectroscopy and density functional theory results reveal that atomic edges of concave surfaces promote C-C coupling via an energetically favorable OC-COH pathway, leading to overwhelming CO2-to-C2+ conversion. Leveraging optimal gas transportation and active site exposure, the hydrophobic porous Cu2O with a 240 nm pore size (P-Cu2O-240) stands out among all the samples and exhibits the best CO2-to-C2+ productivity with remarkable Faradaic efficiency and formation rate up to 75.3 ± 3.1% and 2518.2 ± 8.1 µmol h-1 cm-2, respectively. This study introduces a novel paradigm for efficient electrocatalysts that concurrently addresses active site design and gas-transfer challenges.

Bioinspired Gas Manipulation for Regulating Multiphase Interactions in Electrochemistry.

The manipulation of gas in multiphase interactions plays a crucial role in various electrochemical processes. Inspired by nature, researchers have explored bioinspired strategies for regulating these interactions, leading to remarkable advancements in design, mechanism, and applications. This paper provides a comprehensive overview of bioinspired gas manipulation in electrochemistry. It traces the evolution of gas manipulation in gas-involving electrochemical reactions, highlighting the key milestones and breakthroughs achieved thus far. The paper then delves into the design principles and underlying mechanisms of superaerophobic and (super)aerophilic electrodes, as well as asymmetric electrodes. Furthermore, the applications of bioinspired gas manipulation in hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO2RR), and other gas-involving electrochemical reactions are summarized. The promising prospects and future directions in advancing multiphase interactions through gas manipulation are also discussed.

Superaerophilic/Superaerophobic NiFe-LDHs Electrode for Enhancing Overall Water Splitting in Alkaline Media.

Overall water splitting, as a critical approach to producing green hydrogen, is greatly impeded by the mass transfer of gaseous bubbles and dissolved gas molecules. Herein, a bifunctional superaerophilic/superaerophobic (SAL/SAB) NiFe layered-double-hydroxides (LDHs) electrode has been developed, which can drive H2 and O2 bubbles out of the reaction system by asymmetric Laplace pressure and accelerate dissolved gases diffusion through reducing their diffusion distance. Consequently, the SAL/SAB NiFe-LDHs electrode exhibits excellent HER activity with an overpotential of -76 mV at -10 mA cm-2 and outstanding oxygen evolution reaction activity with an overpotential of 253 mV at 100 mA cm-2. The bifunctional SAL/SAB NiFe-LDHs electrode is further utilized in overall water splitting, which can achieve 10 mA cm-2 with a cell voltage of 1.54 V. This work provides an efficient strategy to improve the efficiency of overall water splitting and can stimulate new electrode design in various gas-involved processes.

Bioinspired Underwater Superoleophilic Two-Dimensional Surface with Asymmetric Oleophobic Barriers for Unidirectional and Long-Distance Oil Transport.

Unidirectional and long-distance liquid transport is critically important to a range of practical applications, e.g., water harvesting, microfluidics, and chemical reactions. Great efforts have been made on liquid manipulation; most of which, however, are limited in the air environment. It is still a great challenge to achieve unidirectional and long-distance oil transport in an aqueous environment. Herein, we have successfully fabricated an underwater superoleophilic two-dimensional surface (USTS) with asymmetric oleophobic barriers to arbitrarily manipulate oil in aqueous medium. The behavior of oil on USTS was carefully investigated, of which the unidirectional spreading capability was originated from the anisotropic spreading resistance resulted from the asymmetric oleophobic barriers. Accordingly, an underwater oil/water separation device has been developed, which can achieve continuous and efficient oil/water separation and further prevent the secondary pollution caused by oil volatilization.

Superaerophilic/superaerophobic cooperative electrode for efficient hydrogen evolution reaction via enhanced mass transfer.

Hydrogen evolution reaction (HER), as an effective method to produce green hydrogen, is greatly impeded by inefficient mass transfer, i.e., bubble adhesion on electrode, bubble dispersion in the vicinity of electrode, and poor dissolved H2 diffusion, which results in blocked electrocatalytic area and large H2 concentration overpotential. Here, we report a superaerophilic/superaerophobic (SAL/SAB) cooperative electrode to efficiently promote bubble transfer by asymmetric Laplace pressure and accelerate dissolved H2 diffusion through reducing diffusion distance. Benefiting from the enhanced mass transfer, the overpotential for the SAL/SAB cooperative electrode at -10 mA cm-2 is only -19 mV, compared to -61 mV on the flat Pt electrode. By optimizing H2SO4 concentration, the SAL/SAB cooperative electrode can achieve ultrahigh current density (-1867 mA cm-2) at an overpotential of -500 mV. We can envision that the SAL/SAB cooperative strategy is an effective method to improve HER efficiency and stimulate the understanding of various gas-involved processes.

Bioinspired Metalation of the Metal-Organic Framework MIL-125-NH2 for Photocatalytic NADH Regeneration and Gas-Liquid-Solid Three-Phase Enzymatic CO2 Reduction.

Coenzyme NADH regeneration is crucial for sustained photoenzymatic catalysis of CO2 reduction. However, light-driven NADH regeneration still suffers from the low regeneration efficiency and requires the use of a homogeneous Rh complex. Herein, a Rh complex-based electron transfer unit was chemically attached onto the linker of the MIL-125-NH2 . The coupling between the light-harvesting iminopyridine unit and electron-transferring Rh-complex facilitated the photo-induced electron transfer for the NADH regeneration with the yield of 66.4 % in 60 mins for 5 cycles. The formate dehydrogenase was further deposited onto the hydrophobic layer of the membrane by a reverse filtering technique, which forms the gas-liquid-solid reaction interface around the enzyme site. It gave an enhanced formic acid yield of 9.5 mM in 24 hours coupled with the in situ regenerated NADH. The work could shed light on the construction of integrated inorganic-enzyme hybrid systems for artificial photosynthesis.

Bioinspired Anisotropic Slippery Cilia for Stiffness-Controllable Bubble Transport.

Bubbles play a crucial role in multidisciplinary industrial applications, e.g., heat transfer and mass transfer. However, existing methods to manipulate bubbles still face many challenges, such as buoyancy inhibition, hydrostatic pressure, gas dissolving, easy deformability, and so on. To circumvent these constraints, here we develop a bioinspired anisotropic slippery cilia surface to achieve an elegant bubble transport by tuning its elastic modulus, which results from the different contacts of bubbles with cilia, i.e., soft cilia will be easily bent by the bubble motion, while hard cilia will pierce into the bubble, consequently leading to the asymmetric three-phase contact line and resistance force. Moreover, a real-time and arbitrarily directional bubble manipulation is also demonstrated by applying an external magnetic field, enabling the scalable operation of bubbles in a remote manner. Our work exhibits a strategy of regulating bubble behavior smartly, which will update a wide range of gas-related sciences or technologies including gas evolution reactions, heat transfer, microfluidics, and so on.

Liquid-Assisted Single-Layer Janus Membrane for Efficient Unidirectional Liquid Penetration.

Unidirectional liquid penetration plays an important role in many fields, such as microfluidic devices, biological medical, liquid printing, and oil/water separation. Although there are some progresses in the liquid unidirectional penetration using a variety of Janus membranes with anisotropic wettability, it still remains a great difficulty for single-layer Janus membranes with straight pore to balance spontaneous liquid penetration in positive direction and superior liquid resistance in the reverse direction. Herein, a liquid-assisted strategy for single-layer Janus membrane is developed, which can efficiently decrease the critical breakthrough pressure from superhydrophobic side to hydrophilic side and show little influence on that in the reverse direction. Consequently, unidirectional water penetration with high hydraulic pressure difference can be achieved. The Laplace pressure change along the thickness of the single-layer Janus membranes is further discussed, and the mechanism by which the auxiliary liquid decreases the critical breakthrough pressure is revealed. Furthermore, this Janus membrane with unidirectional water penetration "diode" performance can be used to prevent liquid backflow in intravenous transfusion. It is believed that this work can open an avenue for people to design single-layer Janus membrane with high pressure difference and find wide applications in unidirectional liquid transport.

Integrated Bundle Electrode with Wettability-Gradient Copper Cones Inducing Continuous Generation, Directional Transport, and Efficient Collection of H2 Bubbles.

The hydrogen evolution reaction (HER), as an efficient process of converting various energies into high-purity hydrogen, has attracted much attention from both scientific research studies and industrial productions. However, its wide applications still confront considerable difficulties, for example, bubble coverage on the electrode and bubble dispersion in the electrolyte, which will disturb current distribution and isolate active sites from reaction ions resulting in a high reaction overpotential and large Ohmic voltage drop. Consequently, timely removing the generated gas bubbles from the electrode as well as avoiding their direct release into the electrolyte can be an effective approach to address these issues. In this work, we have developed an elegant electrode, that is, the integrated bundle electrode with wettability-gradient copper cones, which is endowed with the multifunctions of continuous generation, direct transport, and efficient collection of hydrogen bubbles. All processes are proceeding on the electrode, which not only remove the generated hydrogen bubbles efficiently but also prevent the hydrogen bubbles from releasing into the electrolyte, which should greatly advance the development of water electrolysis and offer inspirations for people to fabricate more efficient HER devices.

Bioinspired Two-Dimensional Structure with Asymmetric Wettability Barriers for Unidirectional and Long-Distance Gas Bubble Delivery Underwater.

Gas bubble manipulations in liquid have long been a concern because of their vital roles in various gas-related fields. To deal with the weakness in long-distance gas transportation of previous works, we took inspiration from the ridgelike structure on Nepenthes pitcher's peristome and successfully prepared a two-dimensional superaerophilic surface decorated with asymmetric aerophobic barriers capable of unidirectional and long-distance gas bubble delivery. For the first time, this process was investigated by in situ bubble-releasing experiments recorded by a high-speed camera and finite element modeling, which demonstrates a kinetic process regulated by the anisotropic motion resistance arising from the patterns. Furthermore, the Nepenthes alata-inspired two-dimensional surface (NATS) was integrated into a water electrolysis system for H2 directional transportation and efficient collection. As a result, the NATS design was proved to be a potential solution for facile manipulation of gas bubbles and provides a simple, adaptive, and reliable strategy for long-range gas transport underwater.

Designing Flexible but Tough Slippery Track for Underwater Gas Manipulation.

Lubricant-infused slippery surface exhibits a series of superior properties such as pressure tolerance, self-healing, oil-repellence, etc. Especially when being applied in an aqueous environment, the reliable bubble manipulating ability of slippery surface offers great opportunities to develop advanced systems in the field of gas transport, water splitting, etc. To improve the strength and the functionality of slippery surfaces, a sliced lubricant-infused slippery (SLIS) track is presented here, possessing both flexibility and toughness for underwater bubble manipulation. The rigid slippery slices with hydrophobic porous structure are linked by the liquid bridge of silicone oil, resulting in a continuous lubricant layer for bubble transfer. Taking advantage of this unique assembled structure, the in situ bubble controlling process, that is, pinning and moving, is achieved via the stretching/releasing of an elastic SLIS track. Besides, on the basis of the integrated design, a hypothesis of underwater gas mining is proved in the all-in-one process including the micro-bubble generation, bubble collection, and gas transport. The current design paves an avenue to reinforce the structure of slippery surfaces, and should promote the function of underwater bubble manipulation toward real-world applications.

Durable Underwater Superoleophobic Coatings via Dispersed Micro Particle-Induced Hierarchical Structures Inspired by Pomfret Skin.

Underwater superoleophobic materials due to its excellent antioil and self-cleaning performance have attracted tremendous attention. Current underwater superoleophobic surfaces usually use complex methods to construct the surface structure limiting the yield and not suitable for large-scale production. Here, inspired by the superoleophobicity of pomfret skin, we developed a strategy to fabricate superoleophobic coatings with hierarchical micro/nano structures by doping hydrophilic micro silica particle in calcium alginate hydrogel. The introduction of micro particles significantly reduces the adhesion of oil and improves the mechanical properties of the coatings. The prepared coatings also survived in high temperature and high salinity environment and the dried for free-standing films. The free-standing dry coating films can be used like wallpaper to decorate the targeted surface and endow them with underwater superoleophobicity. We expect that this work will provide a new method for designing underwater superoleophobic coatings and the wallpaper-like coating films allow large-scale production and will also promote the commercialization of oil-repellent materials.

A Multi-Bioinspired Dual-Gradient Electrode for Microbubble Manipulation toward Controllable Water Splitting.

Clean energy generated from total water splitting is expected to be an affordable, sustainable, and reliable resource but it remains a challenge to gain pure fuel with a controllable pathway. Here, a simple and economical strategy that enables in situ separation of H2 /O2 product by manipulating the generated gas phases with the aid of multi-bioinspired electrodes is proposed. This versatile electrode is based on a Janus asymmetric foam with dual gradients, i.e., the wettability gradient promotes the one-way gas penetration and the geometry gradient boosts the spontaneous on-surface transport in the horizontal direction, which cooperatively facilitates self-driven 3D bubble transport in an aqueous environment. Benefitting from the 3D bionic electrode, the limited distance between the cathode and the anode can be reduced to 1 mm, and the corresponding current density is enhanced 1.5 times as compared with the common condition. This Janus triangular electrode with dual directionality elucidates 3D smart bubble manipulation during overall water splitting and should offer a great opportunity to develop advanced electrochemical processes toward complicated environments such as confined space and zero gravity.

Bioinspired Slippery Cone for Controllable Manipulation of Gas Bubbles in Low-Surface-Tension Environment.

Manipulating bubbles in surfactant solutions or oil mediums is of vital importance in daily life and industries concerned with cosmetics, food, fermentation, mineral flotation, etc. However, realizing controllable regulation of a bubble's behavior is quite challenging in a low-surface-tension aqueous environment, which is mainly attributed to the strong affinity of liquid molecules to a solid surface to prevent the efficient interaction of gas bubbles with the solid surface. To address these issues, herein, we have taken inspiration from cactus spines and pitcher plants to develop a slippery copper cone (SCC), which can facilely manipulate gas bubble in surfactant solutions (as low as ∼29.9 mN/m, 20 °C), e. g., directional and continuous transportation of gas bubbles. This intriguing capability mainly originates from the cooperation of the conical morphology engendering a Laplace pressure and the slippery surface with low friction force but high affinity to bubbles. In addition, the SCC also shows an elegant capability of transporting gas bubbles in various organic solvents, such as formamide (57.4 mN/m, 20 °C), glycol (46.5 mN/m, 20 °C), dibutyl phthalate (37.0 mN/m, 20 °C), and dimethylformamide (35.8 mN/m, 20 °C). Furthermore, the prepared SCC also demonstrated distinguished feasibility in antibuoyancy bubble delivery, efficient collection of acidic CO2 microbubbles, and the underwater reaction of hydrogen and oxygen, endowing it with promising applications in various complex low-surface-tension environments.

Is Superhydrophobicity Equal to Underwater Superaerophilicity: Regulating the Gas Behavior on Superaerophilic Surface via Hydrophilic Defects.

Superhydrophobic surfaces have long been considered as superaerophilic surfaces while being placed in the aqueous environment. However, versatile gas/solid interacting phenomena were reported by utilizing different superhydrophobic substrates, indicating that these two wetting states cannot be simply equated. Herein, we demonstrate how the hydrophilic defects on the superhydrophobic track manipulate the underwater gas delivery, without deteriorating the water repellency of the surface in air. The versatile gas-transporting processes can be achieved on the defected superhydrophobic surfaces; on the contrary, in air, a water droplet is able to roll on those surfaces indistinguishably. Results show that the different media pressures applied on the two wetting states determine the diversified fluid-delivering phenomena; that is, the pressure-induced hydrophilic defects act as a gas barrier to regulate the bubble motion behavior under water. Through the rational incorporation of hydrophilic defects, a series of gas-transporting behaviors are achieved purposively, for example, gas film delivery, bubble transporting, and anisotropic bubble gating, which proves the feasibility of this underwater air-controlling strategy.

Bioinspired Pressure-Tolerant Asymmetric Slippery Surface for Continuous Self-Transport of Gas Bubbles in Aqueous Environment.

Biosurfaces with geometry-gradient structures or special wettabilities demonstrate intriguing performance in manipulating the behaviors of versatile fluids. By mimicking natural species, that is, the cactus spine with a shape-gradient morphology and the Picher plant with a lubricated inner surface, we have successfully prepared an asymmetric slippery surface by following the processes of CO2-laser cutting, superhydrophobic modification, and the fluorinert infusion. The asymmetric morphology will cause the deformation of gas bubbles and subsequently engender an asymmetric driven force on them. Due to the infusion of fluorinert, which has a low surface energy (∼16 mN/m, 25 °C) and an easy fluidic property (∼0.75 cP, 25 °C), the slippery surface demonstrates high adhesive force (∼300 µN) but low friction force on the gas bubbles. Under the cooperation of the asymmetric morphology and fluorinert infused surface, the fabricated asymmetric slippery surface is applicable to the directional and continuous bubble delivery in an aqueous environment. More importantly, due to the hard-compressed property of fluorinert, the asymmetric slippery surface is facilitated with distinguished bubble transport capability even in a pressurized environment (∼0.65 MPa), showing its feasibility in practical industrial production. In addition, asymmetric slippery surfaces with a snowflake-like structure and a star-shaped structure were successfully fabricated for the real-world applications, both of which illustrated reliable performances in the continuous generation, directional transportation, and efficient collection of CO2 and H2 microbubbles.

Superwettability of Gas Bubbles and Its Application: From Bioinspiration to Advanced Materials.

Gas bubbles in aqueous media are common and inevitable in, for example, agriculture and industrial processes. The behaviors of gas bubbles on solid interfaces, including generation, growth, coalescence, release, transport, and collection, are crucial to gas-bubble-related applications, which are always determined by gas-bubble wettability on solid interfaces. Here, the recent progress regarding the study of interfaces with gas-bubble superwettability in aqueous media, i.e., superaerophilicity and superaerophobicity, is summarized. Some examples illustrate how to design microstructures and chemical compositions to achieve reliable and effective manipulation of gas-bubble wettability on artificial interfaces. These designed interfaces exhibit excellent performance in gas-evolution reactions, gas-adsorption reactions, and directional gas-bubble transportation. Moreover, progress in the theoretical investigation of gas-bubble superwettability is reported. Lastly, some challenges are presented, such as the reliable manipulation of gas-bubble wettability and the establishment of mature theory for exactly and systematically explaining gas-bubble wetting phenomena.

Foolproof Method for Fast and Reversible Switching of Water-Droplet Adhesion by Magnetic Gradients.

Reversible switching of water-droplet adhesion on solid surfaces is of great significance for smart devices, such as microfluidics. In this work, we designed a foolproof method for fast and reversible magnet-controlled switching of water-droplet adhesion surfaces by doping iron powders in soft poly(dimethylsiloxane). The water adhesion is adjusted by magnetic field-induced structure changes, avoiding complex chemical or physical surface design. The regulation process is so convenient that only tens of milliseconds are needed. The on-site responsive mechanism extends its use to unusual curved surfaces. Moreover, the excellent reversibility and stability make the film an ideal candidate for real-time applications.

Unidirectional Wetting Properties on Multi-Bioinspired Magnetocontrollable Slippery Microcilia.

Here, a smart fluid-controlled surface is designed, via the rational integration of the unique properties of three natural examples, i.e., the unidirectional wetting behaviors of butterfly's wing, liquid-infused "slippery" surface of the pitcher plant, and the motile microcilia of micro-organisms. Anisotropic wettability, lubricated surfaces, and magnetoresponsive microstructures are assembled into one unified system. The as-prepared surface covered by tilted microcilia achieves significant unidirectional droplet adhesion and sliding. Regulating by external magnet field, the directionality of ferromagnetic microcilia can be synergistically switched, which facilitates a continuous and omnidirectional-controllable water delivery. This work opens an avenue for applications of anisotropic wetting surfaces, such as complex-flow distribution and liquid delivery, and extend the design approach of multi-bioinspiration integration.

Superhydrophobic Cones for Continuous Collection and Directional Transportation of CO2 Microbubbles in CO2 Supersaturated Solutions.

Microbubbles are tiny bubbles with diameters below 50 µm. Because of their minute buoyant force, the microbubbles stagnate in aqueous media for a long time, and they sometimes cause serious damage. Most traditional methods chosen for elimination of gas bubbles utilize buoyancy forces including chemical methods and physical methods, and they only have a minor effect on microbubbles. Several approaches have been developed to collect and transport microbubbles in aqueous media. However, the realization of innovative strategies to directly collect and transport microbubbles in aqueous media remains a big challenge. In nature, both spider silk and cactus spines take advantage of their conical-shaped surface to yield the gradient of Laplace pressure and surface free energy for collecting fog droplets from the environment. Inspired by this, we introduce here the gradient of Laplace pressure and surface free energy to the interface of superhydrophobic copper cones (SCCs), which can continuously collect and directionally transport CO2 microbubbles (from tip side to base side) in CO2-supersaturated solution. A gas layer was formed when the microbubbles encounter the SCCs. This offers a channel for microbubble directional transportation. The efficiency of microbubble transport is significantly affected by the apex angle of SCCs and the carbon dioxide concentration. The former provides different gradients of Laplace pressure as the driving force. The latter represents the capacity, which offers the quantity of CO2 microbubbles for collection and transportation. We believe that this approach provides a simple and valid way to remove microbubbles.