3D hierarchical heterostructure NiFe LDH@NiCoP/NF electrodes are prepared successfully on nickel foam with special interface engineering and synergistic effects. This research finds that the as-prepared NiFe LDH@NiCoP/NF electrodes have a more sophisticated inner structure and intensive interface than a simple physical mixture. The NiFe LDH@NiCoP/NF electrodes require an overpotential as low as 120 and 220 mV to deliver 10 mA cm −2 for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in 1 m KOH, respectively. Tafel and electrochemical impedance spectroscopy further reveal a favorable kinetic during electrolysis. Specifically, the NiFe LDH@NiCoP/NF electrodes are simultaneously used as cathode and anode for overall water splitting, which requires a cell voltage of 1.57 V at 10 mA cm −2 . Furthermore, the synergistic effect of the heterostructure improves the structural stability and promotes the generation of active phases during HER and OER, resulting in excellent stability over 100 h of continuous operation. Moreover, the strategy and interface engineering of the introduced heterostructure can also be used to prepare other bifunctional and cost-efficient electrocatalysts for various applications.

Self-healing materials emerge as a fascinating class of materials important for various technological applications. However, achieving the synergistic characteristics of high conductivity, room-temperature self-healing ability, and decent mechanical properties still remains a critical challenge. Here we develop for the first time a hybrid gel based on self-assembled supramolecular gel and nanostructured polypyrrole that synergizes the dynamic assembly/disassembly nature of metal-ligand supramolecule and the conductive nanostructure of polypyrrole hydrogel and exhibits features of high conductivity (12 S m(-1)), appealing mechanical and electrical self-healing property without any external stimuli, and enhanced mechanical strength and flexibility. The attractive characteristics of the hybrid gel are further demonstrated by a flexible yet self-healable electrical circuit. Our work shows the great potential of self-healing hybrid gel system in flexible electronics and provides a useful strategy to design multifunctional self-healing materials.

Reducing green hydrogen production costs is essential for developing a hydrogen economy. Developing cost-effective electrocatalysts for water electrolysis is thus of great research interest. Among various material candidates, transition metal phosphides (TMP) have emerged as robust bifunctional electrocatalysts for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) due to their various phases and tunable electronic structure. Recently, heterostructured catalysts have exhibited significantly enhanced activities toward HER/OER. The enhancement can be attributed to the increased amount of accessible active sites, accelerated mass/charge transfer, and optimized adsorption of intermediates, which arise from the synergistic effects of the heterostructure. Herein, a comprehensive overview of the recent progress of bifunctional TMP-based heterostructure is introduced to provide an insight into their preparation and corresponding reaction mechanisms. It starts with summarizing general fundamental aspects of HER/OER and the synergistic effect of heterostructures for enhanced catalytic activity. Next, the innovational strategies to design and construct bifunctional TMP-based heterostructures with enhanced overall water splitting activity, as well as the related mechanisms, are discussed in detail. Finally, a summary and perspective for further opportunities and challenges are highlighted for the further development of bifunctional TMP-based heterostructures from the points of practical application and mechanistic studies.

Polymer networks can have a range of desirable properties such as mechanical strength, wide compositional diversity between different materials, permanent porosity, convenient processability and broad solvent compatibility. Designing polymer networks from the bottom up with new structural motifs and chemical compositions can be used to impart dynamic features such as malleability or self-healing, or to allow the material to respond to environmental stimuli. However, many existing systems exhibit only one operational state that is defined by the material's composition and topology; or their responsiveness may be irreversible and limited to a single network property (such as stiffness). Here we use cooperative self-assembly as a design principle to prepare a material that can be switched between two topological states. By using networks of polymer-linked metal-organic cages in which the cages change shape and size on irradiation, we can reversibly switch the network topology with ultraviolet or green light. This photoswitching produces coherent changes in several network properties at once, including branch functionality, junction fluctuations, defect tolerance, shear modulus, stress-relaxation behaviour and self-healing. Topology-switching materials could prove useful in fields such as soft robotics and photo-actuators as well as providing model systems for fundamental polymer physics studies.

A novel giant surfactant possessing a well-defined hydrophilic head and a hydrophobic polymeric tail, polystyrene-(carboxylic acid-functionalized polyhedral oligomeric silsesquioxane) conjugate (PS-APOSS), has been designed and synthesized via living anionic polymerization, hydrosilylation, and thiol-ene "click" chemistry. PS-APOSS forms micelles in selective solvents, and the micellar morphology can be tuned from vesicles to wormlike cylinders and further to spheres by increasing the degree of ionization of the carboxylic acid. The effect of APOSS-APOSS interactions was proven to be essential in the morphological transformation of the micelles. The PS tails in these micellar cores were found to be highly stretched in comparison with those in traditional amphiphilic block copolymers, and this can be explained in terms of minimization of free energy. This novel class of giant surfactants expands the scope of macromolecular amphiphiles and provides a platform for the study of the basic physical principles of their self-assembly behavior.

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The syntheses, characterization, and emission properties of three tetragonal prismatic cages, 4a-4c, constructed from eight 90° Pt(II) acceptors, four linear dipyridyl ligands, and two tetraphenylethene (TPE)-based sodium benzoate ligands, are described. These cages are emissive in dilute solutions due to the metal-coordination-induced partial restriction of intramolecular rotation of their TPE units, while the dipyridyl moieties, which act as the pillars as well as the solvents, strongly influence these emissions. Specifically, cages 4a and 4b, bearing a 4,4'-dipyridine and a 1,2-di(4-pyridyl)ethylene as their pillar parts, respectively, display good emissions in common organic solvents at 485-493 nm that are derived from the TPE units. In contrast, cage 4c, with its BODIPY-based dipyridyl unit, exhibits two emission bands at 462-473 and 540-545 nm, originating from the TPE and BODIPY fluorophores, respectively. Moreover, cage 4b has been employed as a turn-on fluorescent sensor for thiol-containing amino acids via a self-destructive reaction, while the cage can also be regenerated via the addition of Pt(II) acceptors. The studies described herein not only enrich the ongoing research on fluorescent materials but also pave the way to prepare stimuli-responsive supramolecular coordination complexes.

Herein, we report the preparation of a multifunctional metallacage-core supramolecular gel by orthogonal metal coordination and host-guest interactions. A tetragonal prismatic cage with four appended 21-crown-7 (21C7) moieties in its pillar parts was first prepared via the metal-coordination-driven self-assembly of cis-Pt(PEt)(OTf), tetraphenylethene (TPE)-based sodium benzoate ligands and linear dipyridyl ligands. Further addition of a bisammonium linker to the cage delivered a supramolecular polymer network via the host-guest interactions between the 21C7 moieties and ammonium salts, which formed a supramolecular gel at relatively higher concentrations. Due to the incorporation of a TPE derivative as the fluorophore, the gel shows emission properties. Multiple stimuli responsiveness and good self-healing properties were also observed because of the dynamic metal coordination and host-guest interactions used to stabilize the whole network structure. Moreover, the storage and loss moduli of the gel are 10-fold those of the gel without the metallacage cores, indicating that the rigid metallacage plays a significant role in enhancing the stiffness of the gel. The studies described herein not only enrich the functionalization of fluorescent metallacages via elegant ligand design but also provide a way to prepare stimuli-responsive and self-healing supramolecular gels as robust and smart materials.