Sunlight-powered self-excited oscillators for sustainable autonomous soft robotics.

As the field of soft robotics advances, full autonomy becomes highly sought after, especially if robot motion can be powered by environmental energy. This would present a self-sustained approach in terms of both energy supply and motion control. Now, autonomous movement can be realized by leveraging out-of-equilibrium oscillatory motion of stimuli-responsive polymers under a constant light source. It would be more advantageous if environmental energy could be scavenged to power robots. However, generating oscillation becomes challenging under the limited power density of available environmental energy sources. Here, we developed fully autonomous soft robots with self-sustainability based on self-excited oscillation. Aided by modeling, we have successfully reduced the required input power density to around one-Sun level through a liquid crystal elastomer (LCE)-based bilayer structure. The autonomous motion of the low-intensity LCE/elastomer bilayer oscillator "LiLBot" under low energy supply was achieved by high photothermal conversion, low modulus, and high material responsiveness simultaneously. The LiLBot features tunable peak-to-peak amplitudes from 4 to 72 degrees and frequencies from 0.3 to 11 hertz. The oscillation approach offers a strategy for designing autonomous, untethered, and sustainable small-scale soft robots, such as a sailboat, walker, roller, and synchronized flapping wings.

Tough Hydrogel Electrolytes for Anti-Freezing Zinc-Ion Batteries.

As the soaring demand for energy storage continues to grow, batteries that can cope with extreme conditions are highly desired. Yet, existing battery materials are limited by weak mechanical properties and freeze-vulnerability, prohibiting safe energy storage in devices that are exposed to low temperature and unusual mechanical impacts. Herein, a fabrication method harnessing the synergistic effect of co-nonsolvency and "salting-out" that can produce poly(vinyl alcohol) hydrogel electrolytes with unique open-cell porous structures, composed of strongly aggregated polymer chains, and containing disrupted hydrogen bonds among free water molecules, is introduced. The hydrogel electrolyte simultaneously combines high strength (tensile strength 15.6 MPa), freeze-tolerance (< -77 °C), high mass transport (10× lower overpotential), and dendrite and parasitic reactions suppression for stable performance (30 000 cycles). The high generality of this method is further demonstrated with poly(N-isopropylacrylamide) and poly(N-tertbutylacrylamide-co-acrylamide) hydrogels. This work takes a further step toward flexible battery development for harsh environments.

Esophagus-Inspired Actuator for Solid Transportation via the Synergy of Lubrication and Contractile Deformation.

Directional transportation of objects has important applications from energy transfer and intelligent robots to biomedical devices. Although breakthroughs in liquid migration on 2D surfaces or 3D tubular devices have been achieved, realizing smooth/on-demand transportation of constrained solids within a 3D cavity environment under harsh pressurized environment still remains a daunting challenge, where strong interface friction force becomes the main obstacle restricting the movement of solids. Inspired by typical feeding mechanism in natural esophagus system which synergistically couples a lubricating mucosa surface with the peristaltic contraction deformation of the cavity, herein, this challenge is addressed by constructing an esophagus-inspired layered tubular actuator with a slippery inner surface and responsive hydrogel matrix to realize spherical solid propulsion by photo(thermo)-induced cavity deformation. The as-constructed tubular actuator containing Fe3 O4 nanoparticles exhibits local volumetric shrinkage upon NIR-irradiation, which can generate large hydrodynamic pressure and considerable mechanical extrusion force (Fdriving force ≈ 0.18 N) to overcome low interface friction force (ffriction force ≈ 0.03 N), enabling on-demand transportation of constrained (pressure: 0.103 MPa) spherical solids over a long distance in an arbitrary direction. This actuator is anticipated to be used as bionic medicine transportation devices or artificial in vitro esophagus simulation systems, for example, to help formula eating-related physiotherapy plans for patients and astronauts.

Somatosensory actuator based on stretchable conductive photothermally responsive hydrogel.

Mimicking biological neuromuscular systems' sensory motion requires the unification of sensing and actuation in a singular artificial muscle material, which must not only actuate but also sense their own motions. These functionalities would be of great value for soft robotics that seek to achieve multifunctionality and local sensing capabilities approaching natural organisms. Here, we report a soft somatosensitive actuating material using an electrically conductive and photothermally responsive hydrogel, which combines the functions of piezoresistive strain/pressure sensing and photo/thermal actuation into a single material. Synthesized through an unconventional ice-templated ultraviolet-cryo-polymerization technique, the homogenous tough conductive hydrogel exhibited a densified conducting network and highly porous microstructure, achieving a unique combination of ultrahigh conductivity (36.8 milisiemens per centimeter, 103-fold enhancement) and mechanical robustness, featuring high stretchability (170%), large volume shrinkage (49%), and 30-fold faster response than conventional hydrogels. With the unique compositional homogeneity of the monolithic material, our hydrogels overcame a limitation of conventional physically integrated sensory actuator systems with interface constraints and predefined functions. The two-in-one functional hydrogel demonstrated both exteroception to perceive the environment and proprioception to kinesthetically sense its deformations in real time, while actuating with near-infinite degrees of freedom. We have demonstrated a variety of light-driven locomotion including contraction, bending, shape recognition, object grasping, and transporting with simultaneous self-monitoring. When connected to a control circuit, the muscle-like material achieved closed-loop feedback controlled, reversible step motion. This material design can also be applied to liquid crystal elastomers.

Tunable Sponge-Like Hierarchically Porous Hydrogels with Simultaneously Enhanced Diffusivity and Mechanical Properties.

Crosslinked polymers and gels are important in soft robotics, solar vapor generation, energy storage, drug delivery, catalysis, and biosensing. However, their attractive mass transport and volume-changing abilities are diffusion-limited, requiring miniaturization to avoid slow response. Typical approaches to improving diffusion in hydrogels sacrifice mechanical properties by increasing porosity or limit the total volumetric flux by directionally confining the pores. Despite tremendous efforts, simultaneous enhancement of diffusion and mechanical properties remains a long-standing challenge hindering broader practical applications of hydrogels. In this work, cononsolvency photopolymerization is developed as a universal approach to overcome this swelling-mechanical property trade-off. The as-synthesized poly(N-isopropylacrylamide) hydrogel, as an exemplary system, presents a unique open porous network with continuous microchannels, leading to record-high volumetric (de)swelling speeds, almost an order of magnitude higher than reported previously. This swelling enhancement comes with a simultaneous improvement in Young's modulus and toughness over conventional hydrogels fabricated in pure solvents. The resulting fast mass transport enables in-air operation of the hydrogel via rapid water replenishment and ultrafast actuation. The method is compatible with 3D printing. The generalizability is demonstrated by extending the technique to poly(N-tertbutylacrylamide-co-polyacrylamide) and polyacrylamide hydrogels, non-temperature-responsive polymer systems, validating the present hypothesis that cononsolvency is a generic phenomenon driven by competitive adsorption.

Solar anti-icing surface with enhanced condensate self-removing at extreme environmental conditions.

The inhibition of condensation freezing under extreme conditions (i.e., ultra-low temperature and high humidity) remains a daunting challenge in the field of anti-icing. As water vapor easily condensates or desublimates and melted water refreezes instantly, these cause significant performance decrease of most anti-icing surfaces at such extreme conditions. Herein, inspired by wheat leaves, an effective condensate self-removing solar anti-icing/frosting surface (CR-SAS) is fabricated using ultrafast pulsed laser deposition technology, which exhibits synergistic effects of enhanced condensate self-removal and efficient solar anti-icing. The superblack CR-SAS displays superior anti-reflection and photothermal conversion performance, benefiting from the light trapping effect in the micro/nano hierarchical structures and the thermoplasmonic effect of the iron oxide nanoparticles. Meanwhile, the CR-SAS displays superhydrophobicity to condensed water, which can be instantly shed off from the surface before freezing through self-propelled droplet jumping, thus leading to a continuously refreshed dry area available for sunlight absorption and photothermal conversion. Under one-sun illumination, the CR-SAS can be maintained ice free even under an ambient environment of -50 °C ultra-low temperature and extremely high humidity (ice supersaturation degree of ∼260). The excellent environmental versatility, mechanical durability, and material adaptability make CR-SAS a promising anti-icing candidate for broad practical applications even in harsh environments.

Atomic-scale ion transistor with ultrahigh diffusivity.

Biological ion channels rapidly and selectively gate ion transport through atomic-scale filters to maintain vital life functions. We report an atomic-scale ion transistor exhibiting ultrafast and highly selective ion transport controlled by electrical gating in graphene channels around 3 angstroms in height, made from a single flake of reduced graphene oxide. The ion diffusion coefficient reaches two orders of magnitude higher than the coefficient in bulk water. Atomic-scale ion transport shows a threshold behavior due to the critical energy barrier for hydrated ion insertion. Our in situ optical measurements suggest that ultrafast ion transport likely originates from highly dense packing of ions and their concerted movement inside the graphene channels.

Poly(vinyl alcohol) Hydrogels with Broad-Range Tunable Mechanical Properties via the Hofmeister Effect.

Hydrogels, exhibiting wide applications in soft robotics, tissue engineering, implantable electronics, etc., often require sophisticately tailoring of the hydrogel mechanical properties to meet specific demands. For examples, soft robotics necessitates tough hydrogels; stem cell culturing demands various tissue-matching modulus; and neuron probes desire dynamically tunable modulus. Herein, a strategy to broadly alter the mechanical properties of hydrogels reversibly via tuning the aggregation states of the polymer chains by ions based on the Hofmeister effect is reported. An ultratough poly(vinyl alcohol) (PVA) hydrogel as an exemplary material (toughness 150 ± 20 MJ m-3 ), which surpasses synthetic polymers like poly(dimethylsiloxane), synthetic rubber, and natural spider silk is fabricated. With various ions, the hydrogel's various mechanical properties are continuously and reversibly in situ modulated over a large window: tensile strength from 50 ± 9 kPa to 15 ± 1 MPa, toughness from 0.0167 ± 0.003 to 150 ± 20 MJ m-3 , elongation from 300 ± 100% to 2100 ± 300%, and modulus from 24 ± 2 to 2500 ± 140 kPa. Importantly, the ions serve as gelation triggers and property modulators only, not necessarily required to remain in the gel, maintaining the high biocompatibility of PVA without excess ions. This strategy, enabling high mechanical performance and broad dynamic tunability, presents a universal platform for broad applications from biomedicine to wearable electronics.

Heterogeneous Hydrogel Structures with Spatiotemporal Reconfigurability using Addressable and Tunable Voxels.

Stimuli-responsive hydrogels can sense environmental cues and change their volume accordingly without the need for additional sensors or actuators. This enables a significant reduction in the size and complexity of resulting devices. However, since the responsive volume change of hydrogels is typically uniform, their robotic applications requiring localized and time-varying deformations have been challenging to realize. Here, using addressable and tunable hydrogel building blocks-referred to as soft voxel actuators (SVAs)-heterogeneous hydrogel structures with programmable spatiotemporal deformations are presented. SVAs are produced using a mixed-solvent photopolymerization method, utilizing a fast reaction speed and the cononsolvency property of poly(N-isopropylacrylamide) (PNIPAAm) to produce highly interconnected hydrogel pore structures, resulting in tunable swelling ratio, swelling rate, and Young's modulus in a simple, one-step casting process that is compatible with mass production of SVA units. By designing the location and swelling properties of each voxel and by activating embedded Joule heaters in the voxels, spatiotemporal deformations are achieved, which enables heterogeneous hydrogel structures to manipulate objects, avoid obstacles, generate traveling waves, and morph to different shapes. Together, these innovations pave the way toward tunable, untethered, and high-degree-of-freedom hydrogel robots that can adapt and respond to changing conditions in unstructured environments.

4D Printable Tough and Thermoresponsive Hydrogels.

Hydrogels with attractive stimuli-responsive volume changing abilities are seeing emerging applications as soft actuators and robots. However, many hydrogels are intrinsically soft and fragile for tolerating mechanical damage in real world applications and could not deliver high actuation force because of the mechanical weakness of the porous polymer network. Conventional tough hydrogels, fabricated by forming double networks, dual cross-linking, and compositing, could not satisfy both high toughness and high stimuli responsiveness. Herein, we present a material design of combining responsive and tough components in a single hydrogel network, which enables the synergistic realization of high toughness and actuation performance. We showcased this material design in an exemplary tough and thermally responsive hydrogel based on PVA/(PVA-MA)-g-PNIPAM, which achieved 100 times higher toughness (∼10 MJ/m3) and 20 times higher actuation stress (∼10 kPa) compared to conventional PNIPAM hydrogels, and a contraction ratio of up to 50% simultaneously. The effects of salt concentration, polymer ratio, and structural design on the mechanical and actuation properties have been systematically investigated. Utilizing 4D printing, actuators of various geometries were fabricated, as well as lattice-architected hydrogels with macro-voids, presenting 4 times faster actuation speed compared to bulk hydrogel, in addition to the high toughness, actuation force, and contraction ratio.

Superhydrophobic photothermal icephobic surfaces based on candle soot.

Ice accumulation causes various problems in our daily life for human society. The daunting challenges in ice prevention and removal call for novel efficient antiicing strategies. Recently, photothermal materials have gained attention for creating icephobic surfaces owing to their merits of energy conservation and environmental friendliness. However, it is always challenging to get an ideal photothermal material which is cheap, easily fabricating, and highly photothermally efficient. Here, we demonstrate a low-cost, high-efficiency superhydrophobic photothermal surface, uniquely based on inexpensive commonly seen candle soot. It consists of three components: candle soot, silica shell, and polydimethylsiloxane (PDMS) brushes. The candle soot provides hierarchical nano/microstructures and photothermal ability, the silica shell strengthens the hierarchical candle soot, and the grafted low-surface-energy PDMS brushes endow the surface with superhydrophobicity. Upon illumination under 1 sun, the surface temperature can increase by 53 °C, so that no ice can form at an environmental temperature as low as -50 °C and it can also rapidly melt the accumulated frost and ice in 300 s. The superhydrophobicity enables the melted water to slide away immediately, leaving a clean and dry surface. The surface can also self-clean, which further enhances its effectiveness by removing dust and other contaminants which absorb and scatter sunlight. In addition, after oxygen plasma treatment, the surface can restore superhydrophobicity with sunlight illumination. The presented icephobic surface shows great potential and broad impacts owing to its inexpensive component materials, simplicity, ecofriendliness, and high energy efficiency.

Artificial phototropism for omnidirectional tracking and harvesting of light.

Many living organisms track light sources and halt their movement when alignment is achieved. This phenomenon, known as phototropism, occurs, for example, when plants self-orient to face the sun throughout the day. Although many artificial smart materials exhibit non-directional, nastic behaviour in response to an external stimulus, no synthetic material can intrinsically detect and accurately track the direction of the stimulus, that is, exhibit tropistic behaviour. Here we report an artificial phototropic system based on nanostructured stimuli-responsive polymers that can aim and align to the incident light direction in the three-dimensions over a broad temperature range. Such adaptive reconfiguration is realized through a built-in feedback loop rooted in the photothermal and mechanical properties of the material. This system is termed a sunflower-like biomimetic omnidirectional tracker (SunBOT). We show that an array of SunBOTs can, in principle, be used in solar vapour generation devices, as it achieves up to a 400% solar energy-harvesting enhancement over non-tropistic materials at oblique illumination angles. The principle behind our SunBOTs is universal and can be extended to many responsive materials and a broad range of stimuli.

Soft phototactic swimmer based on self-sustained hydrogel oscillator.

Oscillations are widely found in living organisms to generate propulsion-based locomotion often driven by constant ambient conditions, such as phototactic movements. Such environment-powered and environment-directed locomotions may advance fully autonomous remotely steered robots. However, most man-made oscillations require nonconstant energy input and cannot perform environment-dictated movement. Here, we report a self-sustained soft oscillator that exhibits perpetual and untethered locomotion as a phototactic soft swimming robot, remotely fueled and steered by constant visible light. This particular out-of-equilibrium actuation arises from a self-shadowing-enabled negative feedback loop inherent in the dynamic light-material interactions, promoted by the fast and substantial volume change of the photoresponsive hydrogel. Our analytical model and governing equation unveil the oscillation mechanism and design principle with key parameters identified to tune the dynamics. On this autonomous oscillator platform, we establish a broadly applicable principle for converting a continuous input into a discontinuous output. The modular design can be customized to accommodate various forms of input energy and to generate diverse oscillatory behaviors. The hydrogel oscillator showcases agile life-like omnidirectional motion in the entire three-dimensional space with near-infinite degrees of freedom. The large force generated by the powerful and long-lasting oscillation can sufficiently overcome water damping and effectively self-propel away from a light source. Such a hydrogel oscillator-based all-soft swimming robot, named OsciBot, demonstrated high-speed and controllable phototactic locomotion. This autonomous robot is battery free, deployable, scalable, and integratable. Artificial phototaxis opens broad opportunities in maneuverable marine automated systems, miniaturized transportation, and solar sails.

Structural phase transition in monolayer MoTe2 driven by electrostatic doping.

Monolayers of transition-metal dichalcogenides (TMDs) exhibit numerous crystal phases with distinct structures, symmetries and physical properties. Exploring the physics of transitions between these different structural phases in two dimensions may provide a means of switching material properties, with implications for potential applications. Structural phase transitions in TMDs have so far been induced by thermal or chemical means; purely electrostatic control over crystal phases through electrostatic doping was recently proposed as a theoretical possibility, but has not yet been realized. Here we report the experimental demonstration of an electrostatic-doping-driven phase transition between the hexagonal and monoclinic phases of monolayer molybdenum ditelluride (MoTe2). We find that the phase transition shows a hysteretic loop in Raman spectra, and can be reversed by increasing or decreasing the gate voltage. We also combine second-harmonic generation spectroscopy with polarization-resolved Raman spectroscopy to show that the induced monoclinic phase preserves the crystal orientation of the original hexagonal phase. Moreover, this structural phase transition occurs simultaneously across the whole sample. This electrostatic-doping control of structural phase transition opens up new possibilities for developing phase-change devices based on atomically thin membranes.