Nanocomposite Hydrogel Actuators with Ordered Structures: From Nanoscale Control to Macroscale Deformations.

Flexible intelligent actuators with the characteristics of flexibility, safety and scalability, are highly promising in industrial production, biomedical fields, environmental monitoring, and soft robots. Nanocomposite hydrogels are attractive candidates for soft actuators due to their high pliability, intelligent responsiveness, and capability to execute large-scale rapid reversible deformations under external stimuli. Here, the recent advances of nanocomposite hydrogels as soft actuators are reviewed and focus is on the construction of elaborate and programmable structures by the assembly of nano-objects in the hydrogel matrix. With the help of inducing the gradient or oriented distributions of the nanounits during the gelation process by the external forces or molecular interactions, nanocomposite hydrogels with ordered structures are achieved, which can perform bending, spiraling, patterned deformations, and biomimetic complex shape changes. Given great advantages of these intricate yet programmable shape-morphing, nanocomposite hydrogel actuators have presented high potentials in the fields of moving robots, energy collectors, and biomedicines. In the end, the challenges and future perspectives of this emerging field of nanocomposite hydrogel actuators are proposed.

Rapid Printing and Patterning of Tough, Self-Healable, and Recyclable Hydrogel Thin-Films toward Flexible Sensing Devices.

Direct and rapid printing and surface patterning of hydrogel thin films are of great significance in the construction of advanced electronic devices, yet they are greatly underdeveloped due to the intrinsic contradiction between mechanical strength and self-healability as well as recyclability. Here, we present a universal and rapid slipping-directed route with a newly developed water-soluble star polymer hydrogel for direct and reproducible printing and patterning of freestanding functional thin films with precisely controlled thicknesses, components, and surface structures on a large scale. The resulting thin films combine the features of large transmittance (93%), tough mechanical strength (114 MPa), multiresponsive self-healability, recyclability, and remarkable multifunctionality. With the unique humidity-sensitive properties as motivation, diverse humidity-sensing devices including an actuating switch, a supercapacitive sensor, and a noncontact electronic skin are facilely constructed through the humidity-induced transverse, longitudinal, and patterning assembly techniques, respectively. The method presented here is universal and efficient in the fabrication and assembly of thin films with controlled configuration and functionality for advanced flexible electronics.

Double Confinement Hydrogel Network Enables Continuously Regenerative Solar-to-Hydrogen Conversion.

Soft matter catalyst system allowing controllable manipulation of the organized nanostructure and surface property holds the potential for renewable energy. Here we demonstrate the construction of a continuously regenerative hydrogel photocatalyst that confines the metal-thiolate coordination induced nanocavity into robust micro-sized spongy network for water splitting. Thanks to low vaporization enthalpy and fast proton mobility of water molecules confining in nanocavities, the composite delivers outstanding photocatalytic H2 production (TOF of 4568 H2 h-1 ), nearly 4.5 times higher than that on the catalyst without confinements. Incorporating with conductive polymers, the TOF is substantially improved to 7819 H2 h-1 . Impressively, continuous regeneration is for the first time achieved with H2 production retention improved from 24 % to 72 % by regulating optically-active catalyst surfaces. This optical regeneration method provides new avenues for sustainable solar energy conversion.

Autonomous Self-Healing of Highly Stretchable Supercapacitors at All Climates.

Realizing autonomous self-healing and high stretchability of flexible supercapacitors over a wide temperature range remains a big challenge because of simultaneous incorporation of self-healing, stretchable and temperature-tolerant elements into a device as well as unfavorable electrochemical kinetics in harsh conditions. Here, we demonstrate for the first time an autonomous self-healing and intrinsically stretchable supercapacitor that can work at all-climate environments assembled by universally self-healing and highly stretchable organohydrogel electrodes with record-high temperature-invariant conductivity of ∼965 S/cm. Benefiting from multiple hydrogen bonding and dynamic metal coordination combined with electrochemistry-favorable components and integrated device configuration, the supercapacitor exhibits outstanding long-term stability, high stretchability, instantaneous and complete capacitive self-healability, and real-time mechanical healing at harsh temperatures from -35 to 80 °C. The superiorities in stretchability, self-healability, and all-climate tolerance enable the supercapacitor presented here as the best performer among the flexible supercapacitors reported to date.

Ultrastretchable and Self-Healing Conductors with Double Dynamic Network for Omni-Healable Capacitive Strain Sensors.

Skin-mountable capacitive-type strain sensors with great linearity and low hysteresis provide inspiration for the interactions between human and machine. For practicality, high sensing performance, large stretchability, and self-healing are demanded but limited by stretchable electrode and dielectric and interfacial compatibility. Here, we demonstrate an extremely stretchable and self-healing conductor via both hard and soft tactics that combine conductive nanowire assemblies with double dynamic network based on π-π attractions and Ag-S coordination bonds. The obtained conductor outperforms the reported stretchable conductors by delivering an elongation of 3250%, resistance change of 223% at 2000% strain, high durability, and multiresponsive self-healability. Especially, this conductor accommodates large strain of 1500% at extremely knotted and twisted deformations. By sandwiching hydrogel conductors with a newly developed dielectric, ultrahigh stretchability and omni-healability are simultaneously achieved for the first time for a capacitive strain sensor inspired by metal-thiolate coordination chemistry, showing great potentials in wearable electronics and soft robotics.

A multi-responsive healable supercapacitor.

Self-healability is essential for supercapacitors to improve their reliability and lifespan when powering the electronics. However, the lack of a universal healing mechanism leads to low capacitive performance and unsatisfactory intelligence. Here, we demonstrate a multi-responsive healable supercapacitor with integrated configuration assembled from magnetic Fe3O4@Au/polyacrylamide (MFP) hydrogel-based electrodes and electrolyte and Ag nanowire films as current collectors. Beside a high mechanical strength, MFP hydrogel exhibits fast optical and magnetic healing properties arising from distinct photothermal and magneto-thermal triggered interfacial reconstructions. By growing electroactive polypyrrole nanoparticles into MFP framework as electrodes, the assembled supercapacitor exhibits triply-responsive healing performance under optical, electrical and magnetic stimuli. Notably, the device delivers a highest areal capacitance of 1264 mF cm-2 among the reported healable supercapacitors and restores ~ 90% of initial capacitances over ten healing cycles. These prominent performance advantages along with the facile device-assembly method make this emerging supercapacitor highly potential in the next-generation electronics.

Anisotropic and self-healing hydrogels with multi-responsive actuating capability.

Inspired by smart biological tissues, artificial muscle-like actuators offer fascinating prospects due to their distinctive shape transformation and self-healing function under external stimuli. However, further practical application is hindered by the lack of simple and general routes to fabricate ingenious soft materials with anisotropic responsiveness. Here, we describe a general in situ polymerization strategy for the fabrication of anisotropic hydrogels composed of highly-ordered lamellar network crosslinked by the metal nanostructure assemblies, accompanied with remarkably anisotropic performances on mechanical, optical, de-swelling and swelling behaviors. Owing to the dynamic thiolate-metal coordination as healing motifs, the composites exhibit rapid and efficient multi-responsive self-healing performance under NIR irradiation and low pH condition. Dependent on well-defined anisotropic structures, the hydrogel presents controllable solvent-responsive mechanical actuating performance. Impressively, the integrated device through a healing-induced assembly way can deliver more complicated, elaborate forms of actuation, demonstrating its great potentials as superior soft actuators like smart robots.

A Highly Stretchable and Real-Time Healable Supercapacitor.

In addition to a high specific capacitance, a large stretchability and self-healing properties are also essential to improve the practicality and reliability of supercapacitors in portable and wearable electronics. However, the integration of multiple functions into one device remains challenging. Here, the construction of a highly stretchable and real-time omni-healable supercapacitor is demonstrated by sandwiching the polypyrrole-incorporated gold nanoparticle/carbon nanotube (CNT)/poly(acrylamide) (GCP@PPy) hydrogel electrodes with a CNT-free GCP (GP) hydrogel as the electrolyte and chemically soldering an Ag nanowire film to the hydrogel electrode as the current collector. The newly developed dynamic metal-thiolate (M-SR, M = Au, Ag) bond-induced integrated configuration, with an intrinsically powerful electrode and electrolyte, enables the assembled supercapacitor to deliver an areal capacitance of 885 mF cm-2 and an energy density of 123 µWh cm-2 , which are among the highest-reported values for stretchable supercapacitors. Notably, the device exhibits a superhigh stretching strain of 800%, rapid optical healing capability, and significant real-time healability during the charge-discharge process. The exceptional performance combined with the facile assembly method confirms this multifunctional device as the best performer among all the flexible supercapacitors reported to date.

Self-healing and superstretchable conductors from hierarchical nanowire assemblies.

It is still a great challenge to improve deformability and fatigue-resistance of stretchable conductors when maintaining their high-level conductivity for practical use. Herein, a high-performance stretchable conductor with hierarchically ternary network and self-healing capability is demonstrated through in situ polymerizing N-isopropylacrylamide (NIPAM) on well-defined sulfur-containing molecule-modified Ag nanowire (AgNW) aerogel framework. Owing to hierarchical architecture from nanoscale to microscale and further to macroscale and strong interactions of polymer chains and AgNWs, the composite exhibits good conductivity of 93 S cm-1, excellent electromechanical stability up to superhigh tensile strain of 800% and strong fatigue-resistant ability through well accommodating the applied deformations and sharing external force in the network. Furthermore, the composite delivers a fast and strong healing capability induced by reversible Ag-S bonds, which enables the healed conductor to hold an impressive electromechanical property. These prominent demonstrations confirm this material as top performer for use as flexible, stretchable electronic devices.

Highly Tough Bioinspired Ternary Hydrogels Synergistically Reinforced by Graphene/Xonotlite Network.

The application fields of hydrogels are often severely limited by their weak mechanical performance. It is therefore highly demanded to develop an effective strategy to fabricate mechanically strong hydrogels. Herein, a kind of bioinspired ternary hydrogel consisting of graphene oxide (GO) nanosheets, xonotlite nanowires, and polyacrylamide (PAM) is constructed under the synergy of hydrogen bonding-induced GO/xonotlite network and the penetrated PAM chain network. Benefiting from the effective energy dissipation mechanism caused by double-network structural design and the strong hydrogen bonding interaction between two nanobuilding blocks, the gel exhibits a high toughness of 22 MJ m-3 at an elongation of 2750%. Even notched with 1/4 size, it still holds a large extensibility of 2180% its initial length. These high-performance hydrogels could be of great interest in the fields of tissue engineering and biomedical areas.

Templating Synthesis of Mesoporous Fe3C-Encapsulated Fe-N-Doped Carbon Hollow Nanospindles for Electrocatalysis.

Developing cost-efficient alternatives to the noble metal catalysts toward oxygen reduction reaction (ORR) has attracted much attention. Herein, a kind of mesoporous hollow spindlelike Fe-N-C electrocatalysts with iron carbide nanoparticles encased in the N-doped graphitic layers has been synthesized by a novel "reactive hard template" strategy through the Fe3+-assisted polymerization of dopamine on the Fe2O3 cores and the following calcinations. The Fe2O3 nanospindles not only as the hard template guide the formation of well-defined shape and structure of the catalyst but also as the reactive template provide Fe reservoir to generate Fe3C nanoparticles in the catalyst during the thermochemical process. The superiority in accessible active sites of Fe-N x species, Fe3C nanoparticles in graphenelike layers, and highly mesoporous hollow structure enables the catalysts to exhibit excellent ORR performances including high catalytic activity, outstanding long-term cycling stability, and good tolerance to methanol.

Two new alkylated furan derivatives with antifungal and antibacterial activities from the plant endophytic fungus Emericella sp. XL029.

Two new alkylated furan derivatives, 5-(undeca-3',5',7'-trien-1'-yl)furan-2-ol (1) and 5-(undeca-3',5',7'-trien-1'-yl)furan-2-carbonate (2), were isolated from the crude extract of the plant endophytic fungus Emericella sp. XL029 associated with the leaves of Panax notoginseng. The anti-agricultural pathogenic fungal assay indicated that compound 1 displayed significant activity against all tested fungi with minimum inhibitory concentrations (MIC) values from 25 to 3.1 µg/mL, while compound 2 displayed activity against all tested fungi except for Rhizoctonia solani and Fusarium oxysporum with MIC values from 50 to 12.5 µg/mL. Furthermore, compounds 1-2 also exhibited significant inhibitory activity against eight of thirteen tested bacteria with MIC values ranging from 50 to 6.3 µg/mL.

Stable Lithium Storage in Nitrogen-Doped Carbon-Coated Ferric Oxide Yolk-Shell Nanospindles with Preserved Hollow Space.

Iron oxide (Fe2 O3 ) is a promising anode material for next-generation high-energy lithium-ion batteries owing to its high theoretical specific capacity, but it suffers from unstable electrochemistry, as represented by a significant volume variation upon (de)lithiation and unstable solid-electrolyte interface. To target these issues, a double-coating synthetic route has been developed to prepare a yolk-shell-structured γ-Fe2 O3 /nitrogen-doped carbon composite, in which spindle-like γ-Fe2 O3 cores are encapsulated in the highly conductive carbon shell. Through precisely controlling the void space between the γ-Fe2 O3 core and the carbon shell, volume variation in γ-Fe2 O3 during (de)lithiation is well accommodated, while the composite maintains an intact and relatively dense structure, which stabilizes the solid-electrolyte interface and is beneficial for improving the practical energy density of the material. With a stabilized (de)lithiation electrochemistry and a synergistic storage effect between the two active components, the composite enables excellent lithium storage performance, in terms of reversible capacity, cycling ability, and rate capability.

Conductive Carbon Network inside a Sulfur-Impregnated Carbon Sponge: A Bioinspired High-Performance Cathode for Li-S Battery.

A highly conductive sulfur cathode is crucial for improving the kinetic performance of a Li-S battery. The encapsulation of sulfur in porous nanocarbons is expected to benefit the Li(+) migration, yet the e(-) conduction is still to be improved due to a low graphitization degree of a conventional carbon substrate, especially that pyrolyzed from carbohydrates or polymers. Aiming at facilitating the e(-) conduction in the cathode, here we propose to use ketjen black, a highly graphitized nanocarbon building block to form a conductive network for electrons in a biomass-derived, hierarchically porous carbon sponge by a easily scaled-up approach at a low cost. The specifically designed carbon host ensures a high loading and good retention of active sulfur, while also provides a faster electron transmission to benefit the lithiation/delithiation kinetics of sulfur. The sulfur cathode prepared from the carbon network shows excellent cycling and rate performance in a Li-S battery, rendering its practicality for emerging energy storage opportunities such as grids or automobiles.

2D Confined-Space Assisted Growth of Molecular-Level-Thick Polypyrrole Sheets with High Conductivity and Transparency.

Herein, the use of a 2D soft template system composed of hundred-nanometer-thick water/ethanol mixed layers sandwiched by lamellar bilayer membranes of a self-assembled amphiphilic molecule to produce ultrathin polyprrole (PPy) with a uniform thickness as thin as 3.8 nm and with large dimensions (>2 µm(2)) is presented. The obtained PPy nanosheets exhibit regioregularity with ordered chain alignment where the polymer chains in the nanosheets produced are well aligned with a clear interchain spacing as confirmed by small-angle X-ray scattering measurement. The molecular-level-thick PPy nanosheets exhibit extremely high conductivity up to 1330 S m(-1), thanks to the ordered alignment of polymer chains in the nanosheets, and a high transparency in both the visible region (transmittance >99%) and near-infrared region (transmittance >93%).

Organized Molecular Interface-Induced Noncrystallizable Polymer Ultrathin Nanosheets with Ordered Chain Alignment.

The orientation and state of organization of polymer chains play significant roles in determining the final properties and functions of these materials. Unlike most semicrystalline polymers, which have an inherent driving force toward crystallization, the means to control chain packing in noncrystallizable polymers is still restricted and remains a challenge. We report herein a 2D soft template-directed fabrication for ultrathin polyacrylamide nanosheets with a thickness as low as 3.5 nm and large dimensions (>20 µm). More importantly, the polymer chains in the nanosheets produced are well aligned with a clear interchain spacing. The formation of polymer nanosheets with ordered chain alignment was performed in a special solution containing a periodic sandwich structure of lamellar bilayer membranes and water layers that are hundreds of nanometers thick. It functions as a 2D orientation template to align the monomers in an orderly manner along the in-plane direction of the bimolecular membrane via hydrogen bonding.

Nanowire Oriented On-Surface Growth of Chiral Cystine Crystalline Nanosheets.

Exploration of an effective route to achieve the controlled growth of two-dimensional (2D) molecular crystal is of scientific significance yet greatly underdeveloped due to the complexity of weak intermolecular interactions, thus leading to difficulty of inducing anisotropic 2D growth. We report here a facile nanowire oriented on-surface growth strategy for the fabrication of cystine crystalline nanosheets with finely controlled thickness (1.1, 1.9, 2.9, and 4.8 nm which correspond to one layer, two layers, three layers, and five layers of crystal cystine, respectively) and large areas (>100 µm(2)). The cystine crystalline nanosheets display chirality delivered by chiral cysteine monomers, either l-cysteine or d-cysteine. The chiral nanosheets with structural precision and chemical diversity could serve as a novel 2D platform for constructing advanced hybrid materials.

Charge gradient-induced on-surface growth of ultralarge single-crystalline Ag nanomembranes for long surface plasmon propagation.

A facile strategy for the fabrication of ultralarge (edge length >50 µm), single-crystalline Ag nanomembranes is reported in this work. The Ag nanomembrane with an atomically smooth surface demonstrates a much longer surface plasmonic propagation length as compared to vacuum-deposited polycrystalline Ag film, representing superior plasmonic properties.

Free-standing, single-bilayer-thick polymeric nanosheets via spatially confined polymerization.

Polymeric nanosheets organized by molecular building blocks bearing specifically oriented reactive groups provide abundant and versatile strategies for tailoring structure and chemical functionality periodically over extended length scales that complement graphene. Here we report the bulk synthesis of free-standing polymeric nanosheets via spatially confined polymerization from an elaborate 2D supramolecular system composed of two liquid-crystalline lamellar bilayer membranes of a self-assembled nonionic surfactant--dodecylglyceryl itaconate (DGI)--sandwiched by a water layer. By employing a covalent polymerization on the lamellar bilayer membranes, single-bilayer-thick (4.2 nm), and large area (greater than 100 µm(2)) polymeric nanosheets of bilayer membranes are achieved. The polymeric nanosheets could serve as a well-defined 2D platform for post-functionalization for producing advanced hybrid materials by introducing the reactions on the hydroxyl groups at the head of DGI on the outer surfaces.

Novel polymer-free iridescent lamellar hydrogel for two-dimensional confined growth of ultrathin gold membranes.

Hydrogels are generally thought to be formed by nano- to micrometre-scale fibres or polymer chains, either physically branched or entangled with each other to trap water. Although there are also anisotropic hydrogels with apparently ordered structures, they are essentially polymer fibre/discrete polymer chains-based network without exception. Here we present a type of polymer-free anisotropic lamellar hydrogels composed of 100-nm-thick water layers sandwiched by two bilayer membranes of a self-assembled nonionic surfactant, hexadecylglyceryl maleate. The hydrogels appear iridescent as a result of Bragg's reflection of visible light from the periodic lamellar plane. The particular lamellar hydrogel with extremely wide water spacing was used as a soft two-dimensional template to synthesize single-crystalline nanosheets in the confined two-dimensional space. As a consequence, flexible, ultrathin and large area single-crystalline gold membranes with atomically flat surface were produced in the hydrogel. The optical and electrical properties were detected on a single gold membrane.