Regulating Hydrogen/Oxygen Species Adsorption via Built-in Electric Field -Driven Electron Transfer Behavior at the Heterointerface for Efficient Water Splitting.

Alkaline water electrolysis (AWE) plays a crucial role in the realization of a hydrogen economy. The design and development of efficient and stable bifunctional catalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are pivotal to achieving high-efficiency AWE. Herein, WC1-x/Mo2C nanoparticle-embedded carbon nanofiber (WC1-x/Mo2C@CNF) with abundant interfaces is successfully designed and synthesized. Benefiting from the electron transfer behavior from Mo2C to WC1-x, the electrocatalysts of WC1-x/Mo2C@CNF exhibit superior HER and OER performance. Furthermore, when employed as anode and cathode in membrane electrode assembly devices, the WC1-x/Mo2C@CNF catalyst exhibits enhanced catalytic activity and remarkable stability for 100 hours at a high current density of 200 mA cm-2 towards overall water splitting. The experimental characterizations and theoretical simulation reveal that modulation of the d-band center for WC1-x/Mo2C@CNF, achieved through the asymmetric charge distribution resulting from the built-in electric field induced by work function, enables optimization of adsorption strength for hydrogen/oxygen intermediates, thereby promoting the catalytic kinetics for overall water splitting. This work provides promising strategies for designing highly active catalysts in energy conversion fields.

Multishape Programming of Shape Memory Polymer Assemblies Fabricated by Vat Photopolymerization-Based 3D Printing and Interfacial Welding.

The combination of three-dimensional (3D) printing and shape memory polymers (SMP) enables programmable shape morphing of complex 3D structures, which is commonly termed four-dimensional (4D) printing. The process requirements of vat photopolymerization-based 3D printing impose limitations on the molecular structure design of SMPs, making it challenging to achieve triple- or multiple-shaped memory effects. Herein, we printed SMPs with different Tg values and obtained an SMP assembly through interfacial welding. The welding process is facilitated by the dynamic exchange of hindered urethane bonds at the interface. The resulting SMP assembly exhibits a quadruple shape memory effect, enabling programmable sequential deformation. The advantage of this approach is that the molecular design and the corresponding thermodynamic properties of different welding SMP components can be independently adjusted, enabling a greater range of shape and functional variations in the final 3D SMP assembly.

Chemical upcycling of commodity thermoset polyurethane foams towards high-performance 3D photo-printing resins.

Polyurethane thermosets are indispensable to modern life, but their widespread use has become an increasingly pressing environmental burden. Current recycling approaches are economically unattractive and/or lead to recycled products of inferior properties, making their large-scale implementation unviable. Here we report a highly efficient chemical strategy for upcycling thermoset polyurethane foams that yields products of much higher economic values than the original material. Starting from a commodity foam, we show that the polyurethane network is chemically fragmented into a dissolvable mixture under mild conditions. We demonstrate that three-dimensional photo-printable resins with tunable material mechanical properties-which are superior to commercial high-performance counterparts-can be formulated with the addition of various network reforming additives. Our direct upcycling of commodity foams is economically attractive and can be implemented with ease, and the principle can be expanded to other commodity thermosets.

Efficient synthesis of 6-membered cyclic monothiocarbonates from halohydrin and carbonyl sulfide.

We report herein an efficient method to synthesize 6-membered cyclic monothiocarbonates which are important intermediates for polymonothiocarbonate synthesis via the cycloaddition of carbonyl sulfide with 1,3-halohydrin using a low-cost base such as triethylamine and potassium carbonate. This protocol features excellent selectivity and efficiency, mild reaction conditions and easy-to-obtain starting materials.

3D printing of dynamic covalent polymer network with on-demand geometric and mechanical reprogrammability.

Delicate geometries and suitable mechanical properties are essential for device applications of polymer materials. 3D printing offers unprecedented versatility, but the geometries and mechanical properties are typically fixed after printing. Here, we report a 3D photo-printable dynamic covalent network that can undergo two independently controllable bond exchange reactions, allowing reprogramming the geometry and mechanical properties after printing. Specifically, the network is designed to contain hindered urea bonds and pendant hydroxyl groups. The homolytic exchange between hindered urea bonds allows reconfiguring the printed shape without affecting the network topology and mechanical properties. Under different conditions, the hindered urea bonds are transformed into urethane bonds via exchange reactions with hydroxyl groups, which permits tailoring of the mechanical properties. The freedom to reprogram the shape and properties in an on-demand fashion offers the opportunity to produce multiple 3D printed products from one single printing step.

Regenerative Living 4D Printing via Reversible Growth of Polymer Networks.

Living creatures possess complex geometries, exceptional adaptability, and continuous growing and regenerating characteristics, which are difficult for synthetic materials to imitate simultaneously. A living polymer network with these features is reported. The polymer can be digitally printed into arbitrary 3D shapes and subsequently undergoes growth via living polymerization of a monomer as the nutrient. This leads to macroscopic dimensional growth and transforms the printed amorphous network into a crystallizable network, resulting in geometric adaptability via a shape-memory mechanism. By controlling the localized growth, an initial homogeneous structure can be converted into a geometrically different heterogeneous structure composed of materials with different properties (crystallization and mechanical properties). After growth, the original network can be chemically regenerated for regrowth. With this regenerative living 4D printing, one 3D-printed seed template can be turned into different derivatives with distinct geometries and mechanical properties when repeated regeneration is conducted in different localized regions and the degree of regrowth is varied.

Reconfigurable Polymer Networks for Digital Light Processing 3D Printing.

To realize a wide range of applications using three-dimensional (3D) printing, it is urgent to develop 3D printing resins with different functions. However, the design freedom of the resin formulation is greatly limited to guarantee fast gelation during 3D printing. Herein, we report a reconfigurable polymer network that is compatible with digital light processing (DLP) 3D printing. The properties of the printed objects can be remanipulated by post-thermal treatment, during which the polymer network undergoes significant changes through the amidation of ester. The Young's modulus could be significantly reduced by 50 times. Specifically, a well-printed rigid part can be completely turned into a low-viscosity liquid. This strategy decouples the printing process and the final material properties, providing an efficient approach to print various functional objects.

Climbing-inspired twining electrodes using shape memory for peripheral nerve stimulation and recording.

Peripheral neuromodulation has been widely used throughout clinical practices and basic neuroscience research. However, the mechanical and geometrical mismatches at current electrode-nerve interfaces and complicated surgical implantation often induce irreversible neural damage, such as axonal degradation. Here, compatible with traditional 2D planar processing, we propose a 3D twining electrode by integrating stretchable mesh serpentine wires onto a flexible shape memory substrate, which has permanent shape reconfigurability (from 2D to 3D), distinct elastic modulus controllability (from ~100 MPa to ~300 kPa), and shape memory recoverability at body temperature. Similar to the climbing process of twining plants, the temporarily flattened 2D stiff twining electrode can naturally self-climb onto nerves driven by 37°C normal saline and form 3D flexible neural interfaces with minimal constraint on the deforming nerves. In vivo animal experiments, including right vagus nerve stimulation for reducing the heart rate and action potential recording of the sciatic nerve, demonstrate the potential clinical utility.

Synergetic Chemical and Physical Programming for Reversible Shape Memory Effect in a Dynamic Covalent Network with Two Crystalline Phases.

A recently emerged reversible shape memory effect greatly extends the capability of shape memory polymers and their practical potential. Physical confinement and chemical fixation are individually known to be effective in introducing network anisotropy essential for reversible shape memory. Herein, we demonstrate that synergetic combination of these two mechanisms effectively diversifies the shape-shifting behavior. Specifically, we introduce a transesterification catalyst into a network containing two crystalline phases: poly(ε-caprolactone) (PCL) and poly(ω-pentadecalactone) (PPDL). The reversible shape memory behavior of the resulting system can be programmed via the physical confinement by the PPDL phase and the chemical plasticity by the dynamic ester exchange. We illustrate that the two programming mechanisms can operate in a noninterfering way that allows achieving a synergetic benefit, notably realizing a zero-set reversible shape memory behavior. Our study points to a direction in diversifying the behaviors of reversible shape memory polymers and expands the scope for potential engineering devices.

Healable, Reconfigurable, Reprocessable Thermoset Shape Memory Polymer with Highly Tunable Topological Rearrangement Kinetics.

The unique capability of topological rearrangement for dynamic covalent polymer networks has enabled various unusual properties (self-healing, solid-state plasticity, and reprocessability) that are not found in conventional thermosets. Achieving these properties in one network in a synergetic fashion can open up new opportunities for shape memory polymer. To accomplish such a goal, the freedom to tune topological rearrangement kinetics is critical. This is, however, challenging to achieve. In this work, two sets of dynamic bonds (urethane and hindered urea) are incorporated into a hybrid network for synthesizing shape memory poly(urea-urethane). By changing the bond ratio, networks with highly tunable topological rearrangement kinetics are obtained. Combining self-healing, solid-state plasticity, and reprocessability in one such shape memory network leads to unusual versatility in its shape-shifting performance.

Catalyst-Free Thermoset Polyurethane with Permanent Shape Reconfigurability and Highly Tunable Triple-Shape Memory Performance.

Thermoset shape memory polymer (SMP) with dynamic covalent bonds in the network is a new class of SMPs for which the permanent shape can be reconfigured via topological rearrangement (plasticity). Catalyzed transcarbamoylation has recently been established as an effective exchange reaction for plasticity in cross-linked polyurethane networks. However, ensuring the plasticity severely constrains the network design which adversely affects the ability to tune other classical shape memory properties for practical applications. Facing this new challenge, we design an amorphous polyurethane system for which the cross-linking density can be adjusted in a wide range. We discovered that the use of an aromatic diisocyanate in the synthesis of the polyurethanes facilitates achieving plasticity without requiring any catalyst. The overall network design leads to tunable recovery stress and shape memory transition temperatures without sacrificing the plasticity. The versatility of our polyurethane SMP is further reflected in its triple-shape memory performance. We anticipate that our tunable polyurethanes will benefit a variety of potential SMP device applications.

Thermoset Shape-Memory Polyurethane with Intrinsic Plasticity Enabled by Transcarbamoylation.

Thermoset polymers are known for their superior thermomechanical properties, but the chemical crosslinking typically leads to intractability. This is reflected in the great differences between thermoset and thermoplastic shape-memory polymers; the former exhibit a robust shape memory but are not capable of redefining the permanent shape. Contrary to current knowledge, we reveal here that a classical thermoset shape-memory polyurethane is readily capable of permanent reshaping (plasticity) after a topological network rearrangement that is induced by transcarbamoylation. By employing the Jianzhi technique (also known as kirigami), unexpected shape-shifting versatility was observed for this otherwise classical material. As the essential carbamate moiety in polyurethanes is one of the most common polymer building units, we anticipate that our finding will have significant benefits beyond shape shifting.