Closed-loop recyclable membranes enabled by covalent adaptable networks for water purification.

In the state-of-the-art membrane industry, membranes have linear life cycles and are commonly disposed of by landfill or incineration, sacrificing their sustainability. To date, little or no thought is given in the design phase to the end-of-life management of membranes. For the first time, we have innovated high-performance sustainable membranes, which can be closed-loop recycled after long-term usage for water purification. By synergizing membrane technology and dynamic covalent chemistry, covalent adaptable networks (CANs) with thermally reversible Diels-Alder (DA) adducts were synthesized and employed to fabricate integrally skinned asymmetric membranes via the nonsolvent-induced phase separation technique. Due to the stable and reversible features of CAN, the closed-loop recyclable membranes exhibit excellent mechanical properties and thermal and chemical stabilities as well as separation performance, which are comparable to or even higher than the state-of-the-art nonrecyclable membranes. Moreover, the used membranes can be closed-loop recycled with consistent properties and separation performance by depolymerization to remove contaminants, followed by refabrication into new membranes through the dissociation and reformation of DA adducts. This study may fill in the gaps in closed-loop recycling of membranes and inspire the advancement of sustainable membranes for a green membrane industry.

Knoevenagel C═C Metathesis Enabled Glassy Vitrimers with High Rigidity, Toughness, and Malleability.

Thermosets, characterized by their permanent cross-linked networks, present significant challenges in recyclability and brittleness. In this work, we explore a polarized Knoevenagel C═C metathesis reaction for the development of rigid yet tough and malleable thermosets. Initial investigation on small molecule model reactions reveals the feasibility of conducting the base-catalyzed C═C metathesis reaction in a solvent-free environment. Subsequently, thermosetting poly(α-cyanocinnamate)s (PCCs) were synthesized via Knoevenagel condensation between a triarm cyanoacetate star and a dialdehyde. The thermal and mechanical properties of the developed PCCs can be easily modulated by altering the structure of the dialdehyde. Remarkably, the introduction of ether groups into the PCC leads to a combination of high rigidity and toughness with Young's modulus of ∼1590 MPa, an elongation at break of ∼79%, and a toughness reaching ∼30 MJ m3. These values are competitive to traditional thermosets, in Young's modulus but far exceed them in ductility and toughness. Moreover, the C═C metathesis facilitates stress relaxation within the bulk polymer networks, thus rendering PCCs excellent malleability and reprocessability. This work overcomes the traditional limitations of thermosets, introducing groundbreaking insights for the design of rigid yet tough and malleable thermosets, and contributing significantly to the sustainability of materials.

Recyclable, Malleable, and Strong Thermosets Enabled by Knoevenagel Adducts.

Plastic recycling is critical for waste management and achieving a circular economy, but it entails difficult trade-offs between performance and recyclability. Here, we report a thermoset, poly(α-cyanocinnamate) (PCC), synthesized using Knoevenagel condensation between terephthalaldehyde (TPA) and a triarm cyanoacetate star, that tackles this difficulty by harnessing its intrinsically conjugated and dynamic chemical characteristics. PCCs exhibit extraordinary thermal and mechanical properties with a typical Tg of ∼178 °C, Young's modulus of 3.8 GPa, and tensile strength of 102 MPa, along with remarkable flexibility and dimensional and chemical stabilities. Furthermore, end-of-life PCCs can be selectively degraded and partially recycled back into one starting monomer TPA for a new production cycle or reprocessed through dynamic exchange aided by cyanoacetate chain-ends. This study lays the scientific groundwork for the design of robust and recyclable thermosets, with transformative potential in plastic engineering.

Catalyst-Free α-Acetyl Cinnamate/Acetoacetate Exchange to Enable High Creep-Resistant Vitrimers.

Vitrimers represent an emerging class of polymeric materials that combine the desirable characteristics of both thermoplastics and thermosets achieved through the design of dynamic covalent bonds within the polymer networks. However, these materials are prone to creep due to the inherent instability of dynamic covalent bonds. Consequently, there are pressing demands for the development of robust and stable dynamic covalent chemistries. Here, we report a catalyst-free α-acetyl cinnamate/acetoacetate (α-AC/A) exchange reaction to develop vitrimers with remarkable creep resistance. Small-molecule model studies revealed that the α-AC/A exchange occurred at temperatures above 140 °C in bulk, whereas at 120 °C, this reaction was absent. For demonstration in the case of polymers, copolymers derived from common vinyl monomers were crosslinked with terephthalaldehyde to produce α-AC/A vitrimers with tunable thermal and mechanical performance. All resulting α-AC/A vitrimers exhibited high stability, especially in terms of creep resistance at 120 °C, while retaining commendable reprocessability when subjected to high temperatures. This work showcases the α-AC/A exchange reaction as a novel and robust dynamic covalent chemistry capable of imparting both reprocessability and high stability to cross-linked networks.

Ultrafast Self-Healing Elastomer with Closed-Loop Recyclability.

The loss of function after prolonged periods of use is inevitable for all materials including plastics. Hence, self-healing capabilities are a key development to prolong the service lifetime of materials. One of such self-healing capabilities can be achieved by integrating dynamic bonds such as boronic ester linkages into polymeric materials, however the rate of self-healing in these materials is insufficient and current methods to accelerate it are limited. In this study, we report the rational design, synthesis and characterization of a fluorinated elastomer (FBE15) that utilizes enhanced interaction between polymer chains afforded by strong dipole-dipole interactions from -CF3, which showed a significant increase in binding energy to -7.71 Kcal/mol from -5.51 Kcal/mol, resulting in increased interaction between the boronic ester linkages and improving self-healing capabilities of boronic ester materials, drastically reducing the time required for stress relaxation by 900 %. The bulk elastomer is capable of ultrafast self-healing in a one-click fashion that can happen in mere seconds, which can then be stretched to 150 % of its original length. By utilising the dynamic cross-linking, FBE15 is also capable of both mechanical reprocessing into the same materials and chemical recycling into its starting materials, respectively, further allowing reconstruction of the elastomers that have comparable properties to the original ones at the end of its service lifespan.

Contact-electro-catalytic CO2 reduction from ambient air.

Traditional catalytic techniques often encounter obstacles in the search for sustainable solutions for converting CO2 into value-added products because of their high energy consumption and expensive catalysts. Here, we introduce a contact-electro-catalysis approach for CO2 reduction reaction, achieving a CO Faradaic efficiency of 96.24%. The contact-electro-catalysis is driven by a triboelectric nanogenerator consisting of electrospun polyvinylidene fluoride loaded with single Cu atoms-anchored polymeric carbon nitride (Cu-PCN) catalysts and quaternized cellulose nanofibers (CNF). Mechanistic investigation reveals that the single Cu atoms on Cu-PCN can effectively enrich electrons during contact electrification, facilitating electron transfer upon their contact with CO2 adsorbed on quaternized CNF. Furthermore, the strong adsorption of CO2 on quaternized CNF allows efficient CO2 capture at low concentrations, thus enabling the CO2 reduction reaction in the ambient air. Compared to the state-of-the-art air-based CO2 reduction technologies, contact-electro-catalysis achieves a superior CO yield of 33 µmol g-1 h-1. This technique provides a solution for reducing airborne CO2 emissions while advancing chemical sustainability strategy.

Revamping Triboelectric Output by Deep Trap Construction.

High output performance is critical for building triboelectric nanogenerators (TENGs) for future multifunctional applications. Unfortunately, the high triboelectric charge dissipation rate has a significant negative impact on its electrical output performance. Herein, a new tribolayer is designed through introducing self-assembled molecules with large energy gaps on commercial PET fibric to form carrier deep traps, which improve charge retention while decreasing dissipation rates. The deep trap density of the PET increases by two orders of magnitude, resulting in an 86% reduction in the rate of charge dissipation and a significant increase in the charge density that can be accumulated on tribolayer during physical contact. The key explanation is that increasing the density of deep traps improves the dielectric's ability to store charges, making it more difficult for the triboelectric charges trapped by the tribolayer to escape from the deep traps, lowering the rate of charge dissipation. This TENG has a 1300% increase in output power density as a result of altering the deep trap density, demonstrating a significant improvement. This work describes a simple yet efficient method for building TENGs with ultra-high electrical output and promotes their practical implementation in the sphere of the Internet of Things.

In-situ forming dynamic covalently crosslinked nanofibers with one-pot closed-loop recyclability.

Polymeric nanofibers are attractive nanomaterials owing to their high surface-area-to-volume ratio and superior flexibility. However, a difficult choice between durability and recyclability continues to hamper efforts to design new polymeric nanofibers. Herein, we integrate the concept of covalent adaptable networks (CANs) to produce a class of nanofibers ⎯ referred to dynamic covalently crosslinked nanofibers (DCCNFs) via electrospinning systems with viscosity modulation and in-situ crosslinking. The developed DCCNFs possess homogeneous morphology, flexibility, mechanical robustness, and creep resistance, as well as good thermal and solvent stability. Moreover, to solve the inevitable issues of performance degradation and crack of nanofibrous membranes, DCCNF membranes can be one-pot closed-loop recycled or welded through thermal-reversible Diels-Alder reaction. This study may unlock strategies to fabricate the next generation nanofibers with recyclable features and consistently high performance via dynamic covalent chemistry for intelligent and sustainable applications.

Advances in Single-component inorganic nanostructures for photoacoustic imaging guided photothermal therapy.

Phototheranostic based on photothermal therapy (PTT) and photoacoustic imaging (PAI), as one of avant-garde medical techniques, have sparked growing attention because it allows noninvasive, deeply penetrative, and highly selective and effective therapy. Among a variety of phototheranostic nanoagents, single-component inorganic nanostructures are found to be novel and attractive PAI and PTT combined nanotheranostic agents and received tremendous attention, which not only exhibit structural controllability, high tunability in physiochemical properties, size-dependent optical properties, high reproducibility, simple composition, easy functionalization, and simple synthesis process, but also can be endowed with multiple therapeutic and imaging functions, realizing the superior therapy result along with bringing less foreign materials into body, reducing systemic side effects and improving the bioavailability. In this review, according to their synthetic components, conventional single-component inorganic nanostructures are divided into metallic nanostructures, metal dichalcogenides, metal oxides, carbon based nanostructures, upconversion nanoparticles (UCNPs), metal organic frameworks (MOFs), MXenes, graphdiyne and other nanostructures. On the basis of this category, their detailed applications in PAI guide PTT of tumor treatment are systematically reviewed, including synthesis strategies, corresponding performances, and cancer diagnosis and therapeutic efficacy. Before these, the factors to influence on photothermal effect and the principle of in vivo PAI are briefly presented. Finally, we also comprehensively and thoroughly discussed the limitation, potential barriers, future perspectives for research and clinical translation of this single-component inorganic nanoagent in biomedical therapeutics.

Polyelectrolyte Hydrogels for Tissue Engineering and Regenerative Medicine.

Polyelectrolyte hydrogels are emerging materials for tissue engineering and regenerative medicine applications due to their tunable biochemical properties, electrical conductivity, biocompatibility and similar network structure to the extracellular matrix in mammalian bodies. In this review, representative polyelectrolyte hydrogels carrying anionic, cationic, ampholytic, zwitterionic and ionic liquid moieties are systemically cataloged to express their chemical structures and preparation strategies. Recent advance of polyelectrolyte hydrogels in tissue engineering and regenerative medicine for drug delivery, skin healing, bone regeneration, cardiac tissue repair and anti-biofouling coating are also highlighted. Eventually, the outlook and challenges of polyelectrolyte hydrogels and their biomedical material applications are also discussed to offer future directions.