Triply Interlocked [2]catenanes: Rational Synthesis, Reversible Conversion Studies and Unprecedented Application in Photothermal Responsive Elastomer.

Triply interlocked [2]catenane complexes featuring two identical, mechanically interlocked units are extraordinarily rare chemical compounds, whose properties and applications remain open to detailed studies. Herein, we introduce the rational design of a new ligand precursor, L1, suitable for the synthesis of six triply interlocked [2]catenanes by coordination-driven self-assembly. The interlocked compounds can be reversibly converted into the corresponding simple triangular prism metallacage by addition of H2O or DMF solvents to their CH3OH solutions, thereby demonstrating the importance of π⋅⋅⋅π stacking and hydrogen bonding interactions in the formation of triply interlocked [2]catenanes. Moreover, extensive studies have been conducted to assess the remarkable photothermal conversion performance. Complex 6 a, exhibiting outstanding photothermal conversion performance (conversion efficiency in solution : 31.82 %), is used to prepare novel photoresponsive elastomer in combination with thermally activated liquid crystal elastomer. The resultant material displays robust response to near-infrared (NIR) laser and the capability of completely reforming the shape and reversible actuation, paving the way for the application of half-sandwich organometallic units in photo-responsive smart materials.

4D Printable liquid crystal elastomers with restricted nanointerfacial slippage for long-term-cyclic-stability photothermal actuation.

Liquid crystal elastomers (LCEs) blended with photothermal nanofillers can reversibly and rapidly deform their shapes under external optical stimuli. However, nanointerfacial slipping inevitably occurs between the LCE molecules and the nanofillers due to their weak physical interactions, eventually resulting in cyclic instability. This work presents a versatile strategy to fabricate nanointerfacial-slipping-restricted photoactuation elastomers by chemically bonding the nanofillers into a thermally actuatable liquid crystal network. We experimentally and theoretically investigated three types of metal-based nanofillers, including zero-dimensional (0D) nanoparticles, one-dimensional (1D) nanowires, and two-dimensional (2D) nanosheets. The toughly crosslinked nanointerface allows for remarkably promoted interfacial thermal conductivity and stress transfer. Therefore, the resultant actuators enable the realization of long-term-cyclic-stability 4D-printed flexible intelligent systems such as the optical gripper, crawling robot, light-powered self-sustained windmill, butterflies with fluttering wings, and intelligent solar energy collection system.

Near-Infrared Light-Driven MXene/Liquid Crystal Elastomer Bimorph Membranes for Closed-Loop Controlled Self-Sensing Bionic Robots.

More recently, soft actuators have evoked great interest in the next generation of soft robots. Despite significant progress, the majority of current soft actuators suffer from the lack of real-time sensory feedback and self-control functions, prohibiting their effective sensing and multitasking functions. Therefore, in this work, a near-infrared-driven bimorph membrane, with self-sensing and feedback loop control functions, is produced by layer by layer (LBL) assembling MXene/PDDA (PM) onto liquid crystal elastomer (LCE) film. The versatile integration strategy successfully prevents the separation issues that arise from moduli mismatch between the sensing and the actuating layers, ultimately resulting in a stable and tightly bonded interface adhesion. As a result, the resultant membrane exhibited excellent mechanical toughness (tensile strengths equal to 16.3 MPa (||)), strong actuation properties (actuation stress equal to 1.56 MPa), and stable self-sensing (gauge factor equal to 4.72) capabilities. When applying the near-infrared (NIR) laser control, the system can perform grasping, traction, and crawling movements. Furthermore, the wing actuation and the closed-loop controlled motion are demonstrated in combination with the insect microcontroller unit (MCU) models. The remote precision control and the self-sensing capabilities of the soft actuator pave a way for complex and precise task modulation in the future.

MXene Contact Engineering for Printed Electronics.

MXenes emerging as an amazing class of 2D layered materials, have drawn great attention in the past decade. Recent progress suggest that MXene-based materials have been widely explored as conductive electrodes for printed electronics, including electronic and optoelectronic devices, sensors, and energy storage systems. Here, the critical factors impacting device performance are comprehensively interpreted from the viewpoint of contact engineering, thereby giving a deep understanding of surface microstructures, contact defects, and energy level matching as well as their interaction principles. This review also summarizes the existing challenges of MXene inks and the related printing techniques, aiming at inspiring researchers to develop novel large-area and high-resolution printing integration methods. Moreover, to effectually tune the states of contact interface and meet the urgent demands of printed electronics, the significance of MXene contact engineering in reducing defects, matching energy levels, and regulating performance is highlighted. Finally, the printed electronics constructed by the collaborative combination of the printing process and contact engineering are discussed.

The Selective CO2 Adsorption and Photothermal Conversion Study of an Azo-Based Cobalt-MOF Material.

A new metal-organic framework (MOF), [Co2(L)2(azpy)]n (compound 1, H2L = 5-(pyridin-4-ylmethoxy)-isophthalic acid, azpy = 4,4'-azopyridine), was synthesized by a solvothermal method and further characterized by elemental analysis, IR spectra, thermogravimetric analysis, single-crystal and powder X-ray diffraction. The X-ray single-crystal diffraction analysis for compound 1 indicated that two cis L22- ligands connected to two cobalt atoms resulted in a macrocycle structure. Through a series of adsorption tests, we found that compound 1 exhibited a high capacity of CO2, and the adsorption capacity could reach 30.04 cm3/g. More interestingly, under 273 K conditions, the adsorption of CO2 was 41.33 cm3/g. In addition, when the Co-MOF was irradiated by a 730 nm laser, rapid temperature increases for compound 1 were observed (temperature variation in 169 s: 26.6 °C), showing an obvious photothermal conversion performance. The photothermal conversion efficiency reached 20.3%, which might be due to the fact that the parallel arrangement of azo units inhibited non-radiative transition and promoted photothermal conversion. The study provides an efficient strategy for designing MOFs for the adsorption of CO2 and with good photothermal conversion performance.

Recent advances in MXenes and their composites for wearable sensors.

Flexible wearable sensors have attracted significant interests and created high technological impact on human health monitoring, environmental pollutant detection and bimolecular identification. For sensors, the choice of sensing materials is a crucial priority. As a rising star in the family of two-dimensional materials, MXenes has metal-like electrical properties, adjustable surface chemical property, hydrophilicity and excellent mechanical properties, making them attractive for building different high-performance sensors. This study provides a comprehensive overview of recent advances in MXene-based sensor technology. The synthetic methods and basic properties of MXenes are first briefly introduced. The representative research progresses in MXene-based pressure sensors, strain sensors, gas sensors and electrochemical biosensors are then presented. Finally, the main challenges and future prospects of MXene-based materials in wearable sensor applications are discussed.

Intrinsic carbon nanotube liquid crystalline elastomer photoactuators for high-definition biomechanics.

Photoresponsive soft actuators with the unique merits of flexibility, contactless operation, and remote control have huge potential in technological applications of bionic robotics and biomedical devices. Herein, a facile strategy was proposed to prepare an intrinsically-photoresponsive elastomer by chemically grafting carbon nanotubes (CNTs) into a thermally-sensitive liquid-crystalline elastomer (LCE) network. Highly effective dispersion and nematic orientation of CNTs in the intrinsic LCE matrix were observed to yield anchoring energies ranging from 1.65 × 10-5 J m-2 to 5.49 × 10-7 J m-2, which significantly enhanced the mechanical and photothermal properties of the photoresponsive elastomer. When embedding an ultralow loading of CNTs (0.1 wt%), the tensile strength of the LCE increased by 420% to 13.89 MPa (||) and 530% to 3.94 MPa (⊥) and exhibited a stable response to repeated alternating cooling and heating cycles, as well as repeated UV and infrared irradiation. Furthermore, the shape transformation, locomotion, and photo-actuation capabilities allow the CNT/LCE actuator to be applied in high-definition biomechanical applications, such as phototactic flowers, serpentine robots and artificial muscles. This design strategy may provide a promising method to manufacture high-precision, remote-control smart devices.

Toward Application of Liquid Crystalline Elastomer for Smart Robotics: State of the Art and Challenges.

Liquid crystalline elastomers (LCEs) are lightly crosslinked polymers that combine liquid crystalline order and rubber elasticity. Owing to their unique anisotropic behavior and reversible shape responses to external stimulation (temperature, light, etc.), LCEs have emerged as preferred candidates for actuators, artificial muscles, sensors, smart robots, or other intelligent devices. Herein, we discuss the basic action, control mechanisms, phase transitions, and the structure-property correlation of LCEs; this review provides a comprehensive overview of LCEs for applications in actuators and other smart devices. Furthermore, the synthesis and processing of liquid crystal elastomer are briefly discussed, and the current challenges and future opportunities are prospected. With all recent progress pertaining to material design, sophisticated manipulation, and advanced applications presented, a vision for the application of LCEs in the next generation smart robots or automatic action systems is outlined.

A general gelation strategy for 1D nanowires: dynamically stable functional gels for 3D printing flexible electronics.

3D printing of functional inorganic nanowires has been accomplished using extruded nanowire-based inks obtained by incorporating nanofillers into polymeric matrices or thickeners. However, the presence of inactive additives poses a critical challenge for fully realizing the functionality of the nanowires in the printed structures, which remains a fundamental hurdle to overcome. Here, to construct 3D-printed electronics with high performance, we developed a versatile gelation strategy to obtain thixotropic nanowire gels through formation of dynamically stable 3D networks using small amounts of flexible, water-soluble and single-layer 2D nanosheets, such as graphene oxide and MXene, as physical cross-linkers. The nanosheets can knot-tie and stabilize the nanowire junctions in the aqueous suspension, leading to the formation of stable and thixotropic gels with viscosities up to ∼80 000 Pa s at 0.01 s-1 in the absence of polymer thickener. Gels of varioius metallic and semiconductive nanowires have been successfully prepared and printed into 3D and self-supported architectures via extrusion-based 3D-printing. The synergism of nanowires and nanosheets not only conquers the restraints of harsh post-treatments to remove additives after printing, but also maximizes the functionality of the nanowires in the printed architectures. The printed 3D structures solidified by ambient drying, coagulation, or freeze-drying exhibit remarkable functionalities. For example, the electrical conductivity of the 3D-printed silver nanowire-based architectures can reach 40 000 S cm-1. The feasibility of these functional nanowire gels was demonstrated by fabricating a series of printed flexible electronics via extrusion-based 3D-printing.

A Hierarchical Silver-Nanowire-Graphene Host Enabling Ultrahigh Rates and Superior Long-Term Cycling of Lithium-Metal Composite Anodes.

Metallic lithium (Li) is a promising anode for next-generation high-energy-density batteries, but its applications are still hampered due to the limited charging/discharging rate and poor cycling performance. Here, a hierarchical 3D porous architecture is designed with a binary network of continuous silver nanowires assembled on an interconnected 3D graphene skeleton as the host for Li-metal composite anodes, which offers a significant boost in both charging/discharging rates and long-term cycling performance for Li-metal batteries. This unique hierarchical binary network structure in conjunction with optimized material combination provides ultrafast, continuous, and smooth electron transportation channel and non-nucleation barrier sites to direct and confine Li deposition. It also offers outstanding mechanical strength and toughness to support massive Li deposition and buffer the internal stress fluctuations during long-term repeated Li stripping/plating thereby minimizing fundamental issues of dendrite formation and volume change even under ultrafast charging/discharging rates. As a result, the composite anode using this hierarchical host can work smoothly at an unprecedented high current density of 40 mA cm-2 over 1000 plating/stripping cycles with low overpotential (<120 mV) in symmetric cells. The as-constructed full cell, paired with LiNi0.5 Co0.2 Mn0.3 O2 cathode, also exhibits excellent rate capability and high-rate cycling stability.