Accelerate Synthesis of Metal-Organic Frameworks by a Robotic Platform and Bayesian Optimization.

Synthesis of materials with desired structures, e.g., metal-organic frameworks (MOFs), involves optimization of highly complex chemical and reaction spaces due to multiple choices of chemical elements and reaction parameters/routes. Traditionally, realizing such an aim requires rapid screening of these nonlinear spaces by experimental conduction with human intuition, which is quite inefficient and may cause errors or bias. In this work, we report a platform that integrates a synthesis robot with the Bayesian optimization (BO) algorithm to accelerate the synthesis of MOFs. This robotic platform consists of a direct laser writing apparatus, precursor injecting and Joule-heating components. It can automate the MOFs synthesis upon fed reaction parameters that are recommended by the BO algorithm. Without any prior knowledge, this integrated platform continuously improves the crystallinity of ZIF-67, a demo MOF employed in this study, as the number of operation iterations increases. This work represents a methodology enabled by a data-driven synthesis robot, which achieves the goal of material synthesis with targeted structures, thus greatly shortening the reaction time and reducing energy consumption. It can be easily generalized to other material systems, thus paving a new route to the autonomous discovery of a variety of materials in a cost-effective way in the future.

4D Printing of shape-memory polymeric scaffolds for adaptive biomedical implantation.

4D printing has shown great potential in a variety of biomedical applications due to the adaptability and minimal invasiveness of fabricated devices. However, commonly employed shape memory polymers (SMPs) possess undesirable transition temperatures (Ttranss), leading to complications in implantation operations. Herein, we demonstrate 4D printing of a new SMP named poly(glycerol dodecanoate) acrylate (PGDA) with a Ttrans in a range of 20 °C - 37 °C making it appropriate for shape programming at room temperature and then shape deployment within the human body. In addition, the material possesses suitable rheological properties to allow for the fabrication of a variety of delicate 3D structures such as "triangular star", "six-petal flower", "honeycomb", "tube", tilted "truncated hollow cones", as well as overhanging "bridge", "cage", and "mesh". The printed 3D structures show shape memory properties including a large fixity ratio of 100% at 20 °C, a large recovery ratio of 98% at 37 °C, a stable cyclability of > 100 times, and a fast recovery speed of 0.4 s at 37 °C. Moreover, the Young's moduli of the printed structures can be decreased by 5 times due to the phase transition of PGDA, which is compatible with biological tissues. Finally, in vitro stenting and in vivo vascular grafting demonstrated the geometrical and mechanical adaptivity of the printed constructs for biomedical implantation. This newly developed PGDA SMP based 4D printing technology has the potential to pave a new route to the fabrication of shape memory scaffolds for personalized biomedical applications.

4D Printing Elastic Composites for Strain-Tailored Multistable Shape Morphing.

Three-dimensional (3D) morphing structures with multistable shapes that can be quantitatively and reversibly altered are highly desired in many potential applications ranging from soft robots to wearable electronics. In this study, we present a 4D printing method for fabricating multistable shape-morphing structures that can be quantitatively controlled by the applied strains. The structures are printed by a two-nozzle 3D printer that can spatially distribute phase change wax microparticles (MPs) in the elastomer matrix. The wax MPs can retain the residual strain after the prestrained elastomer composite is relaxed because of the solid-liquid phase change. Thanks to high design freedom of the 3D printing, spatial distribution of the wax MPs can be programmed, leading to an anisotropic stress field in the elastomer composite. This causes the out-of-plane deformations such as curling, folding, and buckling. These deformations are multistable and can be reprogrammed because of the reversible phase change of the wax MPs. What's more, characteristics of deformations such as curvatures and folding angles are linearly dependent on the applied strains, suggesting that these deformations are quantitatively controllable. Finally, the applications of the strained-tailored multistable shape morphing 3D structures in the assembly of 3D electronics and adaptive wearable sensors were demonstrated.

Deterministic Self-Morphing of Soft-Stiff Hybridized Polymeric Films for Acoustic Metamaterials.

We reported a soft-stiff hybridized polymeric film that can self-morph to dedicated three-dimensional (3D) structures for application in acoustic metamaterials. The hybridized film was fabricated by laterally adhering a soft and responsive poly(N-isopropylacrylamide) (PNIPAM) hydrogel to stiff and passive SU-8 patterns. Upon thermal stimulation, deformation of the tough PNIPAM hydrogel was locally constrained by the stiff SU-8 patterns, thereby causing laterally nonuniform strain to their interfaces for mechanically buckling the hybridized films to 3D structures. Combined with finite element analysis, we demonstrated that the stiff SU-8 patterns effectively alleviated the uncontrollability and uncertainty during the self-morphing process, which was caused by unexpected mutual deformation between the active and passive domains in the self-morphing materials. Therefore, deterministic self-buckling to dedicated 3D structures was physically realized such as a wave-shaped peak-valley structure, 3D checkerboard patterns, and Gaussian curved surfaces from the hybridized polymeric films. Finally, we demonstrated that the self-morphed 3D structures with predesigned patterns can be used as acoustic materials for subwavelength noise control. This transformative way of constructing 3D structures by self-morphing of the hybridized polymeric films will be a substantial progress in fabricating smart and multifunctional materials for widespread applications in metamaterials, soft robotics, and 3D electronics.

Reprogrammable 3D Shaping from Phase Change Microstructures in Elastic Composites.

Herein, we demonstrate reprogrammable 3D structures that are assembled from elastic composite sheets made from elastic materials and phase change microparticles. By controlling the phase change of the microparticles by localized thermal patterning, anisotropic residual strain is generated in the pre-stretched composite sheets and then triggers 3D structure assembly when the composite sheets are released from the external stress. Modulation of the geometries and location of the thermal patterns leads to complex 2D-3D shaping behaviors such as bending, folding, buckling, and wrinkling. Because of the reversible phase change of the microparticles, these programmed 3D structures can later be recovered to 2D sheets once they are heated for reprogramming different 3D structures. To predict the 3D structures assembled from the 2D composite sheets, finite element modeling was employed, which showed reasonable agreement with the experiments. The demonstrated strategy of reversibly programming 3D shapes by controlling the phase change microstructures in the elastic composites offers unique capabilities in fabricating functional devices such as a rewritable "paper" and a shape reconfigurable pneumatic actuator.

Stimulus Responsive 3D Assembly for Spatially Resolved Bifunctional Sensors.

3D electronic/optoelectronic devices have shown great potentials for various applications due to their unique properties inherited not only from functional materials, but also from 3D architectures. Although a variety of fabrication methods including mechanically guided assembly have been reported, the resulting 3D devices show no stimuli-responsive functions or are not free standing, thereby limiting their applications. Herein, the stimulus responsive assembly of complex 3D structures driven by temperature-responsive hydrogels is demonstrated for applications in 3D multifunctional sensors. The assembly driving force, compressive buckling, arises from the volume shrinkage of the responsive hydrogel substrates when they are heated above the lower critical solution temperature. Driven by the compressive buckling force, the 2D-formed membrane materials, which are pre-defined and selectively bonded to the substrates, are then assembled to 3D structures. They include "tent," "tower," "two-floor pavilion," "dome," "basket," and "nested-cages" with delicate geometries. Moreover, the demonstrated 3D bifunctional sensors based on laser induced graphene show capability of spatially resolved tactile sensing and temperature sensing. These multifunctional 3D sensors would open new applications in soft robotics, bioelectronics, micro-electromechanical systems, and others.

Chemically Interconnected Thermotropic Polymers for Transparency-Tunable and Impact-Resistant Windows.

Thermotropic polymers with the capability of thermally tuning transparency are widely applied in smart windows and energy-saving windows, playing a critical role in enhancing comfort level and energy efficiency of indoor spaces. Usually, thermotropic polymer systems are constructed by physically dispersing phase transition materials in transparent hosting materials. However, bad interfaces universally exist in these systems, resulting in poor mechanical properties, weak interfaces to substrates, or bad long-term stability. Herein, we demonstrate a novel chemically interconnected thermotropic polymer, which is obtained by reacting dodecanedioic acid (DDA) with glycerol. In the system, some of DDA molecules were cross-linked to form a polyester network, poly(glycerol-dodecanoate) (PGD). Other grafted but non-cross-linked DDA molecules form semicrystalline domains, which possess a solid-liquid phase transition within the PGD matrix. The phase transition offers the resulting hybrid materials with tunable optical transparency. The PGD-DDA system shows stable performance after 100 heating-cooling cycles. In addition, when applied for window coating, it results in tough interfacial bonding to glass substrates with toughness of >6910 J m-2 below its transition temperature and >135 J m-2 above its transition temperature. It increases the impact resistance of the window by multiple times.

A Supramolecular Coordination-Polymer-Derived Electrocatalyst for the Oxygen Evolution Reaction.

An iron oxide decorated nickel iron alloy nanoparticle/porous graphene hybrid exhibits high electrocatalytic activity and excellent durability toward oxygen evolution reaction (OER). It displays a low overpotential of 274 mV at 10 mA cm-2 , and low Tafel slope of 37 mV dec-1 , showing a superior performance to the state-of-the-art RuO2 OER electrocatalyst.

Rapid Synthesis of Zeolitic Imidazole Frameworks in Laser-Induced Graphene Microreactors.

Various approaches to synthesize zeolitic imidazole frameworks (ZIFs) have been developed, such as solvothermal, sonochemical, microfluidic, and mechanochemical reactions. However, most of them are time consuming and involve complex processing steps, thus they cannot rapidly screen potential candidates to obtain ZIFs on demand. Such a challenge calls for efficient synthetic approaches. Herein, this challenge is overcome by employing two nonconventional heating strategies, that is, microwave and Joule heating, which are induced by laser-induced graphene (LIG) microreactors, to rapidly synthesize ZIFs. In the first reaction, the LIG acts as a susceptor that absorbs electromagnetic energy, which is converted into heat. In the latter one, LIG acts an electrical conductor that converts electrical energy to heat. Both of them can rapidly heat up the reactor, accelerating the crystal growth for synthesizing ZIFs with well-controlled morphology and crystallinity. To demonstrate a conceptual application, a ZIF-67/LIG composite was converted into Co/CoNC/LIG by a CO2 laser-induced process. It showed excellent performance in the oxygen reduction reaction with a half-wave potential (E1/2 ) of 0.798 V, and superior methanol tolerance and long-term stability. These rapid and facile synthesis methodologies will enable quick optimization of reaction conditions and fast screening of compound libraries for searching new materials, paving the way to high-throughput and autonomous nanomanufacturing.

Mechanically Guided Assembly of Monolithic Three-Dimensional Structures from Elastomer Composites.

Mechanically guided assembly is considered a facile and scalable methodology for fabrication of three-dimensional (3D) structures. However, most of the previous methods require multistep processes for bonding bi- or multilayers and only result in non-freestanding 3D structures because of usage of a supporting elastomer substrate. Herein, we report a functional elastomer composite that can be transformed to a freestanding and monolithic 3D structure driven by the mechanically guided assembly. Photolithography can be used to selectively tune the mechanical properties of UV-exposed regions which exhibit enhanced ductility compared with the nonexposed regions. Thus, a gradient of the residual strain in the thickness direction makes the films assemble into 3D structures. These 3D structures are also predicted by our computational models using finite element simulations, which yields a reasonable agreement with the experiments. The systematically designed 2D structures with varied patterns can be transformed to various 3D structures with the control of the residual strain gradient, via key processing parameters including pre-strain, film thickness, and UV exposure time. By integrating different active electronic components on the fabricated 3D structures, potential applications of this 3D platform in electronics were demonstrated. This study offers a unique capability in constructing monolithic and freestanding 3D assembly, paving new routes to many applications such as wearable electronics, smart textiles, soft robotics, and structural health monitoring.

4D printing of a self-morphing polymer driven by a swellable guest medium.

There is a significant need of advanced materials that can be fabricated into functional devices with defined three-dimensional (3D) structures for application in tissue engineering, flexible electronics, and soft robotics. This need motivates an emerging four-dimensional (4D) printing technology, by which printed 3D structures consisting of active materials can transform their configurations over time in response to stimuli. Despite the ubiquity of active materials in performing self-morphing processes, their potential for 4D printing has not been fully explored to date. In this study, we demonstrate 4D printing of a commercial polymer, SU-8, which has not been reported to date in this field. The working principle is based on a self-morphing process of the printed SU-8 structures through spatial control of the swelling medium inside the polymer matrix by a modified process. To understand the self-morphing behavior, fundamental studies on the effect of the geometries including contours and filling patterns were carried out. A soft electronic device as an actuator was demonstrated to realize an application of this programmable polymer using the 3D printing technology. These studies provide a new paradigm for application of SU-8 in 4D printing, paving a new route to the exploration of more potential candidates by this demonstrated strategy.

Bioinspired multi-responsive soft actuators controlled by laser tailored graphene structures.

By exploiting aligned cellulose fibrils as geometrically constraining structures, plants can achieve a complex programmable shape change in response to environmental stimuli. Inspired by this natural prototype, a series of manmade materials with aligned structures have been developed and employed in self-morphing materials. However, in these cases, the constraining materials are fabricated and aligned in separate processes. In botanic systems, a more efficient way is adopted, in which the aligned microstructures are simultaneously synthesized and aligned in one bottom-up process. Herein, we report a bioinspired bottom-up approach to fabricate laser induced graphene (LIG) structures which resemble the aligned microstructures of the cellulose fibrils in plants. Such LIG structures serve as geometrically constraining materials to precisely control the shape changing behaviors of soft actuators made from polymer and LIG layers. Meanwhile, the LIG structures also serve as functional materials to absorb photo and electrical energy to stimulate motions of the soft actuators. Taking advantage of the geometrically constraining effect from the aligned LIG structures, a series of programmable actuations stimulated by electricity, light, organic vapor, and moisture were demonstrated. Furthermore, the soft actuators also act as soft grippers and walking robots upon different stimuli, indicating their potential applications in soft robotics, electronics, microelectromechanical systems, and others.

Reversible Self-Assembly of 3D Architectures Actuated by Responsive Polymers.

An assembly of three-dimensional (3D) architectures with defined configurations has important applications in broad areas. Among various approaches of constructing 3D structures, a stress-driven assembly provides the capabilities of creating 3D architectures in a broad range of functional materials with unique merits. However, 3D architectures built via previous methods are simple, irreversible, or not free-standing. Furthermore, the substrates employed for the assembly remain flat, thus not involved as parts of the final 3D architectures. Herein, we report a reversible self-assembly of various free-standing 3D architectures actuated by the self-folding of smart polymer substrates with programmed geometries. The strategically designed polymer substrates can respond to external stimuli, such as organic solvents, to initiate the 3D assembly process and subsequently become the parts of the final 3D architectures. The self-assembly process is highly controllable via origami and kirigami designs patterned by direct laser writing. Self-assembled geometries include 3D architectures such as "flower", "rainbow", "sunglasses", "box", "pyramid", "grating", and "armchair". The reported self-assembly also shows wide applicability to various materials including epoxy, polyimide, laser-induced graphene, and metal films. The device examples include 3D architectures integrated with a micro light-emitting diode and a flex sensor, indicting the potential applications in soft robotics, bioelectronics, microelectromechanical systems, and others.

Bioinspired Programmable Polymer Gel Controlled by Swellable Guest Medium.

Responsive materials with functions of forming three-dimensional (3D) origami and/or kirigami structures have a broad range of applications in bioelectronics, metamaterials, microrobotics, and microelectromechanical (MEMS) systems. To realize such functions, building blocks of actuating components usually possess localized inhomogeneity so that they respond differently to external stimuli. Previous fabrication strategies lie in localizing nonswellable or less-swellable guest components in their swellable host polymers to reduce swelling ability. Herein, inspired by ice plant seed capsules, we report an opposite strategy of implanting swellable guest medium inside nonswellable host polymers to locally enhance the swelling inhomogeneity. Specifically, we adopted a skinning effect induced surface polymerization combined with direct laser writing to control gradient of swellable cyclopentanone (CP) in both vertical and lateral directions of the nonswellable SU-8. For the first time, the laser direct writing was used as a novel strategy for patterning programmable polymer gel films. Upon stimulation of organic solvents, the dual-gradient gel films designed by origami or kirigami principles exhibit reversible 3D shape transformation. Molecular dynamics (MD) simulation illustrates that CP greatly enhances diffusion rates of stimulus solvent molecules in the SU-8 matrix, which offers the driving force for the programmable response. Furthermore, this bioinspired strategy offers unique capabilities in fabricating responsive devices such as a soft gripper and a locomotive robot, paving new routes to many other responsive polymers.

Monolithic and Flexible ZnS/SnO2 Ultraviolet Photodetectors with Lateral Graphene Electrodes.

A continuing trend of miniaturized and flexible electronics/optoelectronic calls for novel device architectures made by compatible fabrication techniques. However, traditional layer-to-layer structures cannot satisfy such a need. Herein, a novel monolithic optoelectronic device fabricated by a mask-free laser direct writing method is demonstrated in which in situ laser induced graphene-like materials are employed as lateral electrodes for flexible ZnS/SnO2 ultraviolet photodetectors. Specifically, a ZnS/SnO2 thin film comprised of heterogeneous ZnS/SnO2 nanoparticles is first coated on polyimide (PI) sheets by a solution process. Then, CO2 laser irradiation ablates designed areas of the ZnS/SnO2 thin film and converts the underneath PI into highly conductive graphene as the lateral electrodes for the monolithic photodetectors. This in situ growth method provides good interfaces between the graphene electrodes and the semiconducting ZnS/SnO2 resulting in high optoelectronic performance. The lateral electrode structure reduces total thickness of the devices, thus minimizing the strain and improving flexibility of the photodetectors. The demonstrated lithography-free monolithic fabrication is a simple and cost-effective method, showing a great potential for developement into roll-to-roll manufacturing of flexible electronics.