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A novel plastic with useful properties can easily be recycled again and again Since the synthesis of the first synthetic polymer in 1907, the low cost, durability, safeness, and processability of polymers have led to ever-expanding uses throughout the global economy. Polymers, commonly called plastics, have become so widely used that global production is expected to exceed 500 million metric tons by 2050. This rising production, combined with rapid disposal and poor mechanisms for recycling, has led to the prediction that, by 2050, there will be more plastic in the sea than fish ( 1 ). On page 398 of this issue, Zhu et al. ( 2 ) report an important step toward addressing this problem with the synthesis of a plastic with mechanical properties comparable to those of commercially available plastics, but with an intrinsically infinite recyclability.

The global energy demand has been projected to rise over 28% by 2040, calling for more renewable resources such as lignocellulosic biomass to produce biofuels, and for green and efficient processing technologies. Actual limitations of processing technologies include high cost and high-energy consumption. Here, deep eutectic solvents appear as a green alternative to harmful organic solvents. For biomass pretreatment, deep eutectic solvent-based techniques require about 28% less energy and remove 40.7% of lignin. Deep eutectic solvents can be recycled up to five times. Here we review deep eutectic solvents with focus on properties, toxicity, recyclability, techno-economy and applications in biomass conversion.

Vitrimers are a new class of cross-linked materials that are capable of network topology alternation through the associative dynamic bond-exchange mechanism, which has recently been invented to solve the problem of conventional cross-linked materials, such as poor recyclability and healability. Thus far, the concept of vitrimers has been applied to various commercial polymers, e.g., polyesters, polylactides, polycarbonates, polydimethylsiloxanes, polydienes, polyurethanes, polyolefins, poly(meth)acrylates, and polystyrenes, by utilizing different compatible bond-exchange reactions. In this review article, the concept of vitrimers is described by clarifying the difference from thermoplastics and supramolecular systems; in addition, the term “associative bond-exchange” in vitrimers is explained by comparison with the “dissociative” term. Several useful functions attained by the vitrimer concept (including recyclability and healability) are demonstrated, and recent molecular designs of vitrimers are classified into groups depending on the types of molecular frameworks. This review specifically focuses on the vitrimer molecular designs with commercial polymer-based frameworks, which provide useful hints for the practical application of the vitrimer concept.

Stretchable ionic conductors are considerable to be the most attractive candidate for next-generation flexible ionotronic devices. Nevertheless, high ionic conductivity, excellent mechanical properties, good self-healing capacity and recyclability are necessary but can be rarely satisfied in one material. Herein, we propose an ionic conductor design, dynamic supramolecular ionic conductive elastomers (DSICE), via phase-locked strategy, wherein locking soft phase polyether backbone conducts lithium-ion (Li + ) transport and the combination of dynamic disulfide metathesis and stronger supramolecular quadruple hydrogen bonds in the hard domains contributes to the self-healing capacity and mechanical versatility. The dual-phase design performs its own functions and the conflict among ionic conductivity, self-healing capability, and mechanical compatibility can be thus defeated. The well-designed DSICE exhibits high ionic conductivity (3.77 × 10 −3 S m −1 at 30 °C), high transparency (92.3%), superior stretchability (2615.17% elongation), strength (27.83 MPa) and toughness (164.36 MJ m −3 ), excellent self-healing capability (~99% at room temperature) and favorable recyclability. This work provides an interesting strategy for designing the advanced ionic conductors and offers promise for flexible ionotronic devices or solid-state batteries. Stretchable ionic conductors are attractive candidates for flexible ionotronics but combining high conductivity with excellent mechanical properties is challenging. Herein, the authors combine these properties in a dynamic supramolecular ionic conductive elastomer enabling lithium-ion transport in the soft phase and dynamic disulfide and supramolecular hydrogen bonding in the hard segments.

The diffusion limitations on gas storage and catalytic reaction of microporous materials can often be overcome if they are incorporated into a mesoporous structure with much larger pores. Shen et al. grew ordered arrays of microcrystals of the ZIF-8 metal-organic framework, in which zinc ions are bridged by 2-methylimidazole linkers, inside a porous polystyrene template. These materials showed higher reaction rates for the Knoevenagel reaction between benzaldehydes and malononitriles and better catalyst recyclability. Science , this issue p. 206 A double-solvent method and templating are used to grow ordered arrays of metal-organic framework microcrystals. We constructed highly oriented and ordered macropores within metal-organic framework (MOF) single crystals, opening up the area of three-dimensional–ordered macro-microporous materials (that is, materials containing both macro- and micropores) in single-crystalline form. Our methodology relies on the strong shaping effects of a polystyrene nanosphere monolith template and a double-solvent–induced heterogeneous nucleation approach. This process synergistically enabled the in situ growth of MOFs within ordered voids, rendering a single crystal with oriented and ordered macro-microporous structure. The improved mass diffusion properties of such hierarchical frameworks, together with their robust single-crystalline nature, endow them with superior catalytic activity and recyclability for bulky-molecule reactions, as compared with conventional, polycrystalline hollow, and disordered macroporous ZIF-8.

The additive manufacturing of photopolymer resins by means of vat photopolymerization enables the rapid fabrication of bespoke 3D-printed parts. Advances in methodology have continually improved resolution and manufacturing speed, yet both the process design and resin technology have remained largely consistent since its inception in the 1980s 1 . Liquid resin formulations, which are composed of reactive monomers and/or oligomers containing (meth)acrylates and epoxides, rapidly photopolymerize to create crosslinked polymer networks on exposure to a light stimulus in the presence of a photoinitiator 2 . These resin components are mostly obtained from petroleum feedstocks, although recent progress has been made through the derivatization of renewable biomass 3 – 6 and the introduction of hydrolytically degradable bonds 7 – 9 . However, the resulting materials are still akin to conventional crosslinked rubbers and thermosets, thus limiting the recyclability of printed parts. At present, no existing photopolymer resin can be depolymerized and directly re-used in a circular, closed-loop pathway. Here we describe a photopolymer resin platform derived entirely from renewable lipoates that can be 3D-printed into high-resolution parts, efficiently deconstructed and subsequently reprinted in a circular manner. Previous inefficiencies with methods using internal dynamic covalent bonds 10 – 17 to recycle and reprint 3D-printed photopolymers are resolved by exchanging conventional (meth)acrylates for dynamic cyclic disulfide species in lipoates. The lipoate resin platform is highly modular, whereby the composition and network architecture can be tuned to access printed materials with varied thermal and mechanical properties that are comparable to several commercial acrylic resins. A photopolymer platform derived from renewable lipoates can be 3D-printed into high-resolution parts, which possess properties comparable to some commercial acrylic resins, and then recycled to produce a re-printable resin.

Metallic alloys containing multiple principal alloying elements have created a growing interest in exploring the property limits of metals and understanding the underlying physical mechanisms. Refractory high-entropy alloys have drawn particular attention due to their high melting points and excellent softening resistance, which are the two key requirements for high-temperature applications. Their compositional space is immense even after considering cost and recyclability restrictions, providing abundant design opportunities. However, refractory high-entropy alloys often exhibit apparent brittleness and oxidation susceptibility, which remain important challenges for their processing and application. Here, utilizing natural-mixing characteristics among refractory elements, we designed a Ti 38 V 15 Nb 23 Hf 24 refractory high-entropy alloy that exhibits >20% tensile ductility in the as-cast state, and physicochemical stability at high temperatures. Exploring the underlying deformation mechanisms across multiple length scales, we observe that a rare β′-phase plays an intriguing role in the mechanical response of this alloy. These results reveal the effectiveness of natural-mixing tendencies in expediting high-entropy alloy discovery. A refractory high-entropy alloy was designed with the composition chosen based on the natural-mixing characteristics among refractory elements; this alloy demonstrates good tensile ductility in the as-cast state and physicochemical stability at high temperatures.

Some polymers, such as polyethylene terephthalate in soft drink bottles, can be depolymerized back to the starting monomers. This makes it possible to repolymerize true virgin material for repeated use. Zhu et al. developed a polymer based on a five-membered ring cyclic monomer derived from γ-butyrolactone that could be produced at ambient temperature and mild conditions (see the Perspective by Sardon and Dove). The high-molecular-weight polymer exhibited high crystallinity and thermal stability. However, at hot enough conditions, or at lower temperatures in the presence of a zinc chloride catalyst, the polymer could be returned to its starting monomers and thus recycled into new material. Science , this issue p. 398 ; see also p. 380 A highly crystalline, stable polymer can be repeatedly broken down into monomers and recycled. The development of chemically recyclable polymers offers a solution to the end-of-use issue of polymeric materials and provides a closed-loop approach toward a circular materials economy. However, polymers that can be easily and selectively depolymerized back to monomers typically require low-temperature polymerization methods and also lack physical properties and mechanical strengths required for practical uses. We introduce a polymer system based on γ-butyrolactone (GBL) with a trans-ring fusion at the α and β positions. Such trans-ring fusion renders the commonly considered as nonpolymerizable GBL ring readily polymerizable at room temperature under solvent-free conditions to yield a high–molecular weight polymer. The polymer has enhanced thermostability and can be repeatedly and quantitatively recycled back to its monomer by thermolysis or chemolysis. Mixing of the two enantiomers of the polymer generates a highly crystalline supramolecular stereocomplex.

Carbon-defect engineering in metal single-atom catalysts by simple and robust strategy, boosting their catalytic activity, and revealing the carbon defect-catalytic activity relationship are meaningful but challenging. Herein, we report a facile self-carbon-thermal-reduction strategy for carbon-defect engineering of single Fe-N 4 sites in ZnO-Carbon nano-reactor, as efficient catalyst in Fenton-like reaction for degradation of phenol. The carbon vacancies are easily constructed adjacent to single Fe-N 4 sites during synthesis, facilitating the formation of C-O bonding and lowering the energy barrier of rate-determining-step during degradation of phenol. Consequently, the catalyst Fe-NCv-900 with carbon vacancies exhibits a much improved activity than the Fe-NC-900 without abundant carbon vacancies, with 13.5 times improvement in the first-order rate constant of phenol degradation. The Fe-NCv-900 shows high activity (97% removal ratio of phenol in only 5 min), good recyclability and the wide-ranging pH universality (pH range 3-9). This work not only provides a rational strategy for improving the Fenton-like activity of metal single-atom catalysts, but also deepens the fundamental understanding on how periphery carbon environment affects the property and performance of metal-N 4 sites. Designing carbon-defect engineering is significant for boosting the catalytic performance of metal single-atom sites catalysts. Herein, the authors report a self-carbon-thermal-reduction strategy for carbon defect engineering to boost the Fenton-like activity of single Fe-N 4 sites.

Functionalizing porous materials with capping agents generates hybrid materials with enhanced properties, while the challenge is how to improve the selectivity and maintain the porosity of the parent framework. Herein, we developed a “Cage-on-MOF” strategy to tune the recognition and catalytic properties of MOFs without impairing their porosity. Two types of porous coordination cages (PCCs) of opposite charges containing secondary binding groups were developed to coordinatively functionalize two distinct porous MOFs, namely MOF@PCC nanocomposites. We demonstrated that the surface-capped PCCs can act as “modulators” to effectively tune the surface charge, stability, and adsorption behavior of different host MOF particles. More importantly, the MOF@PCCs can serve as selective heterogeneous catalysts for condensation reactions to achieve reversed product selectivity and excellent recyclability. This work sets the foundation for using molecular cages as porous surface-capping agents to functionalize and manipulate another porous material, without affecting the intrinsic properties of the parent framework. Functionalising porous materials is a route to enhancing properties of hybrid materials. Here authors present a “Cage-on-MOF” strategy to modify the surface of mesoporous MOFs by using molecular cages to achieve selective dyes adsorption behavior and heterogeneous catalysis.