Functionally Antagonistic Hybrid Electrode with Hollow Tubular Graphene Mesh and Nitrogen‐Doped Crumpled Graphene for High‐Performance Ionic Soft Actuators

Ionic soft actuators, which exhibit large mechanical deformations under low electrical stimuli, are attracting attention in recent years with the advent of soft and wearable electronics. However, a key challenge for making high‐performance ionic soft actuators with large bending deformation and fast actuation speed is to develop a stretchable and flexible electrode having high electrical conductivity and electrochemical capacitance. Here, a functionally antagonistic hybrid electrode with hollow tubular graphene meshes and nitrogen‐doped crumpled graphene is newly reported for superior ionic soft actuators. Three‐dimensional network of hollow tubular graphene mesh provides high electrical conductivity and mechanically resilient functionality on whole electrode domain. On the contrary, nitrogen‐doped wrinkled graphene supplies ultrahigh capacitance and stretchability, which are indispensably required for improving electrochemical activity in ionic soft actuators. Present results show that the functionally antagonistic hybrid electrode greatly enhances the actuation performances of ionic soft actuators, resulting in much larger bending deformation up to 620%, ten times faster rise time and much lower phase delay in a broad range of input frequencies. This outstanding enhancement mostly attributes to exceptional properties and synergistic effects between hollow tubular graphene mesh and nitrogen‐doped crumpled graphene, which have functionally antagonistic roles in charge transfer and charge injection, respectively.     

Mutually Exclusive p‐Type and n‐Type Hybrid Electrode of MoS2 and Graphene for Artificial Soft Touch Fingers

Future smart mobile electronics and wearable robotics that can perform delicate activities controlled by artificial intelligence can require rapid motion actuators working at low voltages with acceptable safety and improved energy efficiency. Accordingly, ionic soft actuators can have great potential over other counterparts because they exhibit gentle movements at low voltages, less than 2 V. However, these actuators currently show deficient performances at sub‐1 V voltages in the high‐frequency range because of the lack of electrode materials with the vital antagonistic properties of high capacitance and good conductivity. Herein, a mutually exclusive nanohybrid electrode (pMoS₂‐nSNrGO) is reported consisting of oxide‐doped p‐type molybdenum‐disulfide and sulfur‐nitrogen‐codoped n‐type reduced‐graphene‐oxide. The pMoS₂‐nSNrGO electrode derives high capacitance from MoS₂ and good charge transfer between the two components from p‐n nano‐junctions, resulting in excellent actuation performances (670% improvement compared with rGO electrode at 0.5 V and 1 Hz, together with fast responses up to 15 Hz). With such excellent performances, these actuators can be successfully applied to realize an artificial soft robotic finger system for delicately touching the fragile surfaces of smartphones and tablets. The mutually exclusive pMoS₂‐nSNrGO electrode can open a new way to develop high‐performance soft actuators for soft robotic applications in the future.     

Metal–Organic Framework‐Derived Graphitic Nanoribbons Anchored on Graphene for Electroionic Artificial Muscles

To achieve large bending displacement and fast response time under ultralow input voltages, as well as improved durability, advanced high‐performance ionic actuators still face crucial design challenges that must be resolved. Here, hierarchically porous and unzipped graphitic nanoribbons anchored on graphene as an efficient electrode material for high‐performance electroionic artificial muscles are reported. Using controlled solvothermal and pyrolysis methods, nanoarchitectured carbon is derived from a self‐templated potassium‐based metal–organic frameworks–graphene hybrid. The newly designed ionic actuator demonstrates excellent actuation performance, including large bending displacement (17.4 mm) and a strain difference of 0.51% at 0.5 V AC input, very fast response time (700 ms) at 0.5 V DC input, wide frequency response (0.1–15 Hz), and excellent cycling stability (92%) after 25 000 cycles without any delamination of electrodes under continuous electrical operation. The breakthrough in actuation performance mainly stems from the unzipping of hollow nanorods to hierarchical porous graphitic nanoribbons anchored on graphene with the enlarged surface area, large pore volume, stronger mechanical integrity, and emerging charge storage and transport ability. Further, the electroionic actuator shows promise when applied in the demonstration of a biomimicking Venus flytrap.     

Graphene‐Based Actuator with Integrated‐Sensing Function

Flexible actuators have important applications in artificial muscles, robotics, optical devices, and so on. However, most of the conventional actuators have only actuation function, lacking in real‐time sensing signal feedbacks. Here, to break the limitation and add functionality in conventional actuators, a graphene‐based actuator with integrated‐sensing function is reported, which avoids the dependence on image post‐processing for actuation detection and realizes real‐time measurement of the shape‐deformation amplitudes of the actuator. The actuator is able to show a large bending actuation (curvature of 1.1 cm^?1) based on a dual‐mode actuation mechanism when it is driven by near infrared light. Meanwhile, the relative resistance change of the actuator is ?17.5%. The sensing function is attributed to piezoresistivity and thermoresistivity of the reduced graphene oxide and paper composite. This actuator can be used as a strain sensor to monitor human motions. A smart gripper based on the actuators demonstrates perfect integration of the actuating and sensing functions, which can not only grasp and release an object, but also sense every actuation state of the actuator. The developed integrated‐sensing actuator is hopeful to open new application fields in soft robotics, artificial muscles, flexible wearable devices, and other integrated‐multifunctional devices.     

Fast‐Response,Stiffness‐Tunable Soft Actuator by Hybrid Multimaterial 3D Printing

Soft robots have the appealing advantages of being highly flexible and adaptive to complex environments. However, the low‐stiffness nature of the constituent materials makes soft robotic systems incompetent in tasks requiring relatively high load capacity. Despite recent attempts to develop stiffness‐tunable soft actuators by employing variable stiffness materials and structures, the reported stiffness‐tunable actuators generally suffer from limitations including slow responses, small deformations, and difficulties in fabrication with microfeatures. This work presents a paradigm to design and manufacture fast‐response, stiffness‐tunable (FRST) soft actuators via hybrid multimaterial 3D printing. The integration of a shape memory polymer layer into the fully printed actuator body enhances its stiffness by up to 120 times without sacrificing flexibility and adaptivity. The printed Joule‐heating circuit and fluidic cooling microchannel enable fast heating and cooling rates and allow the FRST actuator to complete a softening–stiffening cycle within 32 s. Numerical simulations are used to optimize the load capacity and thermal rates. The high load capacity and shape adaptivity of the FRST actuator are finally demonstrated by a robotic gripper with three FRST actuators that can grasp and lift objects with arbitrary shapes and various weights spanning from less than 10 g to up to 1.5 kg.     

Bio‐Inspired All‐Organic Soft Actuator Based on a π–π Stacked 3D Ionic Network Membrane and Ultra‐Fast Solution Processing

Next generation electronic products, such as wearable electronics, flexible displays, and smart mobile phones, will require the use of unprecedented electroactive soft actuators for haptic and stimuli‐responsive devices and space‐saving bio‐mimetic actuation. Here, a bio‐inspired all‐organic soft actuator with a π–π stacked and 3D ionic networked membrane based on naphthalene‐tetracarboxylic dianhydride (Ntda) and sulfonated polyimide block copolymers (SPI) is presented, utilizing an ultra‐fast solution process. The π–π stacked and self‐assembled 3D ionic networked membrane with continuous and interconnected ion transport nanochannels is synthesized by introducing simple and strong atomic level regio‐specific interactions of hydrophilic and hydrophobic SPI co‐blocks with cations and anions in the ionic liquid. Furthermore, a facile and ultrafast all‐solution process involving solvent blending, dry casting, and solvent dropping is developed to produce electro‐active soft actuators with highly conductive polyethylenedioxythiophene (PEDOT):polystyrenesulfonate (PSS) electrodes. Ionic conductivity and ion exchange capacity of the π–π stacked Ntda‐SPI membrane can be increased up to 3.1 times and 3.4 times of conventional SPI, respectively, resulting in a 3.2 times larger bending actuation. The developed bio‐inspired soft actuator is a good candidate for satisfying the tight requirements of next generation soft electronic devices due to its key benefits such as low operating voltage and comparatively large strains, as well as quick response and facile processability.     

Near‐Infrared Light‐Driven,Highly Efficient Bilayer Actuators Based on Polydopamine‐Modified Reduced Graphene Oxide

Near‐infrared (NIR) light‐driven bilayer actuators capable of fast, highly efficient, and reversible bending/unbending motions toward periodic NIR light irradiation are fabricated by exploiting the photothermal conversion and humidity‐sensitive properties of polydopamine‐modified reduced graphene oxide (PDA‐RGO). The bilayer actuator comprises a PDA‐RGO layer prepared by a filtration method, and this layer is subsequently spin‐coated with a layer of UV‐cured Norland Optical Adhesive (NOA)‐63. Given the hydrophilicity of PDA, the PDA‐RGO layer can absorb water to swell and lose water to shrink. The intrinsic NIR absorbance of RGO sheets convertes NIR light into thermal energy, which transfers the humidity‐responsive PDA‐RGO layer to be NIR light‐responsive. Considering that the shape of the NOA‐63 layer remains unchanged under NIR light, periodic NIR light irradiation leads to asymmetric shrinkage/expansion of the bilayer, which enables fast and reversible bending/unbending motions of the bilayer actuator. We demonstrate that compared with a poly(ethylenimine)‐modified graphene oxide layer, the PDA‐RGO layer is unique in fabricating highly efficient bilayer actuators. A NIR light‐driven walking device capable of performing quick worm‐like motion on a ratchet substrate is built by connecting two polyethylene terephthalate plates as claws on opposite ends of the PDA‐RGO/NOA‐63 bilayer actuator.     

Facile Solid‐State Growth of 3D Well‐Interconnected Nitrogen‐Rich Carbon Nanotube–Graphene Hybrid Architectures for Lithium–Sulfur Batteries

Constructing 3D carbon structures built from carbon nanotubes (CNTs) and graphene has been considered as an effective approach to achieve superior properties in energy conversion and storage because of the synergistic combination of the advantages of each building block. Herein, a facile solid‐state growth strategy is reported for the first time to fabricate highly nitrogen doped CNT–graphene 3D nanostructures without the necessity to use chemical vapor deposition. As cathode hosts for lithium–sulfur batteries, the hybrid architectures exhibit reversible capacities of 1314 and 922 mAh g^?1 at 0.2 and 1 C, respectively, and a capacity retention of 97% after 200 cycles at a high rate of 2 C, revealing their great potential for energy storage application.     

Shape Control of Mn3O4 Nanoparticles on Nitrogen‐Doped Graphene for Enhanced Oxygen Reduction Activity

Three kinds of Mn₃O₄ nanoparticles with different shapes (spheres, cubes, and ellipsoids) are selectively grown on nitrogen‐doped graphene sheets through a two‐step liquid‐phase procedure. These non‐precious hybrid materials display an excellent ORR activity and good durability. The mesoporous microstructure, nitrogen doping, and strong bonding between metal species and doped graphene are found to facilitate the ORR catalytic process. Among these three kinds of Mn₃O₄ particles, the ellipsoidal particles on nitrogen‐doped graphene exhibit the highest ORR activity with a more positive onset‐potential of –0.13 V (close to that of Pt/C, –0.09 V) and a higher kinetic limiting current density (J_K) of 11.69 mA cm^–2 at –0.60 V. It is found that the ORR performance of hybrid materials can be correlated to the shape of Mn₃O₄ nanocrystals, and specifically to the exposed crystalline facets associated with a given shape. The shape dependence of Mn₃O₄ nanoparticles integrated with nitrogen‐doped graphene on the ORR performance, reported here for the first time, may advance the development of fuel cells and metal‐air batteries.     

High‐Performance Wearable Micro‐Supercapacitors Based on Microfluidic‐Directed Nitrogen‐Doped Graphene Fiber Electrodes

Fiber‐shaped micro‐supercapacitors (micro‐SCs) have attracted enormous interest in wearable electronics due to high flexibility and weavability. However, they usually present a low energy density because of inhomogeneity and less pores. Here, we demonstrate a microfluidic‐directed strategy to synthesize homogeneous nitrogen‐doped porous graphene fibers. The porous fibers‐based micro‐SCs utilize solid‐state phosphoric acid/polyvinyl alcohol (H₃PO₄/PVA) and 1‐ethyl‐3‐methylimidazolium tetrafluoroborate/poly(vinylidenefluoride‐co‐hexafluoropropylene) (EMIBF₄/PVDF‐HFP) electrolytes, which show significant improvements in electrochemical performances. Ultralarge capacitance (1132 mF cm^?2), high cycling‐stability, and long‐term bending‐durability are achieved based on H₃PO₄/PVA. Additionally, high energy densities of 95.7–46.9 µWh cm^?2 at power densities of 1.5–15 W cm^?2 are obtained in EMIBF₄/PVDF‐HFP. The key to higher performances stems from microfluidic‐controlled fibers with a uniformly porous network, large specific surface area (388.6 m² g^?1), optimal pyridinic nitrogen (2.44%), and high electric conductivity (30785 S m^?1) for faster ion diffusion and flooding accommodation. By taking advantage of these remarkable merits, this study integrates micro‐SCs into flexible and fabric substrates to power audio–visual electronics. The main aim is to clarify the important role of microfluidic techniques toward the architecture of electrodes and promote development of wearable electronics.     

Engineering the Photocatalytic Behaviors of g/C3N4‐Based Metal‐Free Materials for Degradation of a Representative Antibiotic

Graphitic carbon nitride (g/C₃N₄) is of promise as a highly efficient metal‐free photocatalyst, yet engineering the photocatalytic behaviours for efficiently and selectively degrading complicated molecules is still challenging. Herein, the photocatalytic behaviors of g/C₃N₄ are modified by tuning the energy band, optimizing the charge extraction, and decorating the cocatalyst. The combination shows a synergistic effect for boosting the photocatalytic degradation of a representative antibiotic, lincomycin, both in the degradation rate and the degree of decomposition. In comparison with the intrinsic g/C₃N₄, the structurally optimized photocatalyst shows a tenfold enhancement in degradation rate. Interestingly, various methods and experiments demonstrate the specific catalytic mechanisms for the multiple systems of g/C₃N₄‐based photocatalysts. In the degradation, the active species, including ·O₂^?, ·OH, and h⁺, have different contributions in the different photocatalysts. The intermediate, H₂O₂, plays an important role in the photocatalytic process, and the detailed functions and originations are clarified for the first time.     

Multiaxial and Transparent Strain Sensors Based on Synergetically Reinforced and Orthogonally Cracked Hetero‐Nanocrystal Solids

Wearable strain sensors are widely researched as core components in electronic skin. However, their limited capability of detecting only a single axial strain, and their low sensitivity, stability, opacity, and high production costs hinder their use in advanced applications. Herein, multiaxially highly sensitive, optically transparent, chemically stable, and solution‐processed strain sensors are demonstrated. Transparent indium tin oxide and zinc oxide nanocrystals serve as metallic and insulating components in a metal–insulator matrix and as active materials for strain gauges. Synergetic sensitivity‐ and stability‐reinforcing agents are developed using a transparent SU‐8 polymer to enhance the sensitivity and encapsulate the devices, elevating the gauge factor up to over 3000 by blocking the reconnection of cracks caused by the Poisson effect. Cross‐shaped patterns with an orthogonal crack strategy are developed to detect a complex multiaxial strain, efficiently distinguishing strains applied in various directions with high sensitivity and selectivity. Finally, all‐transparent wearable strain sensors with Ag nanowire electrodes are fabricated using an all‐solution process, which effectively measure not only the human motion or emotion, but also the multiaxial strains occurring during human motion in real time. The strategies can provide a pathway to realize cost‐effective and high‐performance wearable sensors for advanced applications such as bio‐integrated devices.     

Electrochemically Inert g‐C3N4 Promotes Water Oxidation Catalysis

Electrode surface wettability is critically important for heterogeneous electrochemical reactions taking place in aqueous and nonaqueous media. Herein, electrochemically inert g‐C₃N₄ (GCN) is successfully demonstrated to significantly enhance water oxidation by constructing a superhydrophilic catalyst surface and promoting substantial exposure of active sites. As a proof‐of‐concept application, superhydrophilic GCN/Ni(OH)₂ (GCNN) hybrids with monodispersed Ni(OH)₂ nanoplates strongly anchored on GCN are synthesized for enhanced water oxidation catalysis. Owing to the superhydrophilicity of functionalized GCN, the surface wettability of GCNN (contact angle 0°) is substantially improved as compared with bare Ni(OH)₂ (contact angle 21°). Besides, GCN nanosheets can effectively suppress Ni(OH)₂ aggregation to help expose more active sites. Benefiting from the well‐defined catalyst surface, the optimal GCNN hybrid shows significantly enhanced electrochemical performance over bare Ni(OH)₂ nanosheets, although GCN is electrochemically inert. In addition, similar catalytic performance promotion resulting from wettability improvement induced by incorporation of hydrophilic GCN is also successfully demonstrated on Co(OH)₂. The present results demonstrate that, in addition to developing new catalysts, building efficient surface chemistry is also vital to achieve extraordinary water oxidation performance.     

Carbon‐Based Photothermal Actuators

Actuators that can convert environmental stimuli into mechanical work are widely used in intelligent systems, robots, and micromechanics. To produce robust and sensitive actuators of different scales, efforts are devoted to developing effective actuating schemes and functional materials for actuator design. Carbon‐based nanomaterials have emerged as preferred candidates for different actuating systems because of their low cost, ease of processing, mechanical strength, and excellent physical/chemical properties. Especially, due to their excellent photothermal activity, which includes both optical absorption and thermal conductivities, carbon‐based materials have shown great potential for use in photothermal actuators. Herein, the recent advances in photothermal actuators based on various carbon allotropes, including graphite, carbon nanotubes, amorphous carbon, graphene and its derivatives, are reviewed. Different photothermal actuating schemes, including photothermal effect–induced expansion, desorption, phase change, surface tension gradient creation, and actuation under magnetic levitation, are summarized, and the light‐to‐heat and heat‐to‐work conversion mechanisms are discussed. Carbon‐based photothermal actuators that feature high light‐to‐work conversion efficiency, mechanical robustness, and noncontact manipulation hold great promise for future autonomous systems.     

An Autonomous Soft Actuator with Light‐Driven Self‐Sustained Wavelike Oscillation for Phototactic Self‐Locomotion and Power Generation

Mimicking the intelligence of biological organisms in artificial systems to design smart actuators that act autonomously in response to constant environmental stimuli is crucial to the construction of intelligent biomimetic robots and devices, but remains a great challenge. Here, a light‐driven autonomous carbon‐nanotube‐based bimorph actuator is developed through an elaborate structural design. This curled droplet‐shaped actuator can be simply driven by constant white light irradiation, self‐propelled by a light‐mechanical negative feedback loop created by light‐driven actuation, time delay in the photothermal response along the actuator, and good elasticity from the curled structure, performing a continuously self‐oscillating motion in a wavelike fashion, which mimics the human sit‐up motion. Moreover, this autonomous self‐oscillating motion can be further tuned by controlling the intensity and direction of the incident light. The autonomous actuator with continuous wavelike oscillating motion shows immense potential in light‐driven biomimetic soft robots and optical‐energy‐harvesting devices. Furthermore, a self‐locomotive artificial snake with phototaxis is constructed, which autonomously and continuously crawls toward the light source in a wave‐propagating manner under constant light irradiation. This snake can be placed on a substrate made of triboelectric materials to realize continuous electric output when exposed to constant light illumination.     

Preparation of Highly Ordered Nitrogen‐Containing Mesoporous Carbon from a Gelatin Biomolecule and its Excellent Sensing of Acetic Acid

Novel nitrogen‐containing mesoporous carbon with well‐ordered pores (NMC‐G) and high basicity is synthesized using a low‐cost single‐molecule precursor, gelatin biomolecule, and SBA‐15 as a template via nanocasting method. The obtained materials are thoroughly characterized. It is found that the prepared materials have excellent textural properties such as high specific surface areas, huge pore volumes, and large pore diameters. The pore diameter of the materials can also be controlled with a simple adjustment of the pore diameter of the hard templates. The C/N ratio of the samples is calculated to be ≈6.01, which is slightly higher than that observed for mesoporous carbon nitride samples. X‐ray photoelectron spectroscopy (XPS) reveals the presence of sp² hybridized carbon in aromatic ring structure attached to amino groups. The materials could adsorb a huge quantity of CO₂. The sensing capability of the materials with different pore diameters for different adsorbates including ethanol, acetic acid, aniline, toluene, and ammonia is also investigated. Among the materials with different pore diameters studied, the material with the highest basicity and the largest pore diameter (NMC‐G‐150) showed excellent sensing performance with a high selectivity of adsorption for acetic acid molecule.