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1.
Chemistry ; : e202402512, 2024 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-39146044

RESUMO

Mesoporous catalysts with a high specific surface area, accessible pore structures, and appropriate band edges are desirable for optimal charge transfer across the interfaces, suppress electron-hole recombination, and promote redox reactions at the active sites. The present study demonstrates the rational design of mesoporous ZnFe2O4@g-C3N4 magnetic nanocomposites (MNCs) with different pore sizes and pore volumes following a combination of facile thermal itching and thermal impregnation methods. The MNCs preserve the structural, morphological, and physical attributes of their counterparts while ensuring their effectiveness and superior catalytic capabilities. The morphological analysis confirms the successful grafting and confinement of ZnFe2O4 nanoparticles with the polymeric g-C3N4 nanosheets to form heterojunctions with numerous interfaces. The MNCs possess uniformly distributed small mesopores (pore size <4 nm), ample active sites, and a high specific surface area of 62.50 m2/g. The mesoporous ZnFe2O4@g-C3N4 notably improve hydrogen evolution rate and methylene blue dye degradation. The optimal loading weight of ZnFe2O4 is 20%, in which the MNCs display the highest hydrogen evolution rate of 1752 µmolg-1h-1 and photo-Fenton dye degradation rate constants of 0.147 min-1, upon solar-light illumination. Furthermore, the photocatalysts demonstrate recyclability over five consecutive cycles, confirming their stability, while easy separation using a simple magnet underscores practical utility.

2.
Environ Technol ; : 1-11, 2024 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-39150880

RESUMO

Silica fume (SF) is a major voluminous and bulky by-product of the ferrosilicon industry, and its disposal poses a significant environmental concern. To address this issue, a sustainable approach was employed to transform SF into silica powder using a precipitation method. The process involved calcination, acid precipitation, aging, and drying, utilising industrial by-products such as silica fume and calcium oxide. Various parameters, including hydrochloric acid concentration, water bath temperature, aging pH, aging temperature, and aging time, were systematically investigated to optimise the properties of the resulting silica product. The physical and chemical attributes of the processed silica were thoroughly examined using techniques such as X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), laser particle size analysis, and dibutyl phthalate (DBP) absorption tests. Under optimal conditions (hydrochloric acid concentration of 20%, water bath temperature of 90℃, aging pH 3-4, aging temperature of 90℃, and aging time of 8 hours), the resulting silica product achieved a purity of 98.5866%, a DBP absorption value of 2.85 mL/g, and a particle size of 6.07 µm, meeting national industry standards. This environmentally benign and cost-efficient synthesis route offers a practical solution for large-scale production.

3.
Macromol Rapid Commun ; : e2400493, 2024 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-39150331

RESUMO

Recently, renewable bio-based materials have received more and more attention due to environmental issues such as global warming and ecosystem destruction. In the present work, a series of isosorbide-based bioelastomers poly(isosorbide carbonate-co-butanediol aliphatic esters)s (PICBAs) are synthesized by a facile and economical two-step melt polycondensation. Due to the slightly self-crosslinking reaction of isosorbide, PICBAs exhibit excellent tensile strength and self-healing ability, the mechanical properties of PICBAs can recover over 95% after 48 h under room temperature. In addition, PICBAs can stick different substances, such as glass, rubber, plastic, and stones, and show better adhesive performance than 3M commercially available double-sided tape. Consequently, isosorbide-based bioelastomers PICBAs are of great potential to be used as environmentally friendly pressure-sensitive adhesives (PSA) in the future.

4.
Anal Chim Acta ; 1320: 343017, 2024 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-39142789

RESUMO

BACKGROUND: Hydrogen peroxide (H2O2) plays a vital role in human health and have been regarded as a crucial analyte in metabolic processes, redox transformations, foods research and medical fields. Especially, the long-time and excessive digestion of H2O2 may even cause severe diseases. Although conventional instrumental methods and nanozymes-based colorimetric methods have been developed to accomplish the quantitative analysis of H2O2, the drawbacks of instrument dependence, cost-effectiveness, short lifespan, non-portable and unsustainable detection efficacies will limit their applications in different detection scenarios. RESULTS: Herein, to address these challenges, we have proposed a novel strategy for nanozyme (RuO2) hydrogel preparation by the solid support from cross-linked polyvinyl alcohol (PVA) and chitosan (CS) to both inherit the dominant peroxidase-like (POD) activity and protect the RuO2 from losing efficacies. Taking advantages from the hydrogel, the encapsulated RuO2 were further prepared as the regularly spherical beads (PCRO) to exhibit the sustainable, recyclable, and robust catalysis. Moreover, the intrinsic color interferences which originated from RuO2 can be avoided by the encapsulation strategy to promote the detection accuracy. Meanwhile, the high mechanical strength of PCRO shows the high stability, reproducibility, and cyclic catalysis to achieve the recyclable detection performance and long lifetime storage (40 days), which enables the sensitively detection of H2O2 with the detection limit as lower to 15 µM and the wide detection linear range from 0.025 to 1.0 mM. SIGNIFICANCE: On the basis of the unique properties, PCRO has been further adopted to construct a smartphone detection platform to realize the instrument-free and visual analysis of H2O2 in multi-types of milk and real water samples through capturing, processing, and analyzing the RGB values from the colorimetric photographs. Therefore, PCRO with the advanced detection efficacies holds the great potential in achieving the portable and on-site analysis of targets-of-interest.


Assuntos
Quitosana , Hidrogéis , Peróxido de Hidrogênio , Álcool de Polivinil , Peróxido de Hidrogênio/química , Peróxido de Hidrogênio/análise , Quitosana/química , Álcool de Polivinil/química , Catálise , Hidrogéis/química , Colorimetria , Limite de Detecção
5.
Materials (Basel) ; 17(15)2024 Jul 26.
Artigo em Inglês | MEDLINE | ID: mdl-39124369

RESUMO

In the context of ecological sustainability, this study focuses on the effect of variables of pasture fibers on the thermal properties of slag bricks made from a green recyclable material. This experiment uses slag as the binder, sand as the aggregate, and pasture fiber as an additive. The experimental variables include the additive content ratio of the pasture fiber, the size of the pasture fiber, and the type of pasture fiber. Significance analysis of the experimental results of the thermal performance tests is carried out using Minitab 18.1.0 software, and the optimal ratios for the thermal performance of the composite samples are derived from the response optimizer and conformity analysis. The results of the experiment's test analysis using Minitab 18 software indicate that, with an increase in pasture fiber content, the thermal performance of the composite samples initially decreases before increasing. Additionally, the lower the thermal conductivity of the composite sample, the lower the apparent density and the higher the porosity. Incorporating pasture fibers into slag bricks, as revealed in this study, reduces the waste of pasture resources in pastoral areas and promotes the development of sustainable building materials with favorable thermal properties.

6.
Adv Sci (Weinh) ; : e2407596, 2024 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-39140246

RESUMO

Inspired by the Mimosa plant, this study herein develops a unique dynamic shape memory polymer (SMP) network capable of transitioning from hard to pliable with heat, featuring reversible actuation, self-healing, recyclability, and degradability. This material is adept at simulating the functionalities of artificial muscles for a variety of tasks, with a remarkable specific energy density of 1.8 J g-1-≈46 times higher than that of human skeletal muscle. As an intelligent manipulator, it demonstrates remarkable proficiency in identifying and handling items at high temperatures. Its suitable rate of shape recovery around human body temperature indicates its promising utility as an implant material for addressing acute obstructions. The dynamic covalent bonding within the network structure not only provides excellent resistance to solvents but also bestows remarkable abilities for self-healing, reprocessing, and degradation. These attributes significantly boost its practicality and environmental sustainability. Anticipated to promote advancements in the sectors of biomedical devices, soft robotics, and smart actuators, this SMP network represents a forward leap in simulating artificial muscles, marking a stride toward the future of adaptive and sustainable technology.

7.
Molecules ; 29(14)2024 Jul 13.
Artigo em Inglês | MEDLINE | ID: mdl-39064886

RESUMO

Nanoparticles have been widely applied to treat emulsion-containing wastewater in the form of chemical demulsifiers, such as SiO2, Fe3O4, and graphene oxide (GO). Owing to their asymmetric structures and selective adsorption, Janus nanoparticles show greater application potential in many fields. In the present work, the novel magnetic Janus graphene oxide (MJGO) nanoparticle was successfully prepared by grafting magnetic Fe3O4 to the surface of the JGO, and its demulsifying ability to treat a crude oil-in-water emulsion was evaluated. The MJGO structure and its magnetic intensity were verified by Fourier-transform infrared spectra (FTIR), transmission electron microscopy (TEM), X-ray diffraction (XRD), and magnetization saturation (MS) tests. Compared with GO and JGO, MJGO displayed the superior efficiency (>96%) to demulsify the crude oil-in-water emulsion, which can be attributed to the reduced electrostatic repulsion between MJGO and the emulsion droplets. Furthermore, the effects of pH and temperature on the demulsification performance of MJGO were also studied. Lastly, the recyclability of MJGO largely reduced the cost of demulsifiers in separating crude oil and water. The current research presents an efficient and recyclable demulsifier, which provides a new perspective for the structural design of nanomaterials and their application in the field of demulsification.

8.
Materials (Basel) ; 17(13)2024 Jul 02.
Artigo em Inglês | MEDLINE | ID: mdl-38998348

RESUMO

In the polymeric material industry, thermosets and related composites have played a substantial role in the production of rubber and plastics. One important subset of these is thermoset composites with carbon reinforcement. The incorporation of carbon fillers and fibers gives polymeric materials improved electrical and mechanical properties, among other benefits. However, the covalently crosslinked network of thermosets presents significant challenges for recycling and reprocessing because of its intractable nature. The introduction of vitrimer materials opens a new avenue to produce biodegradable and recyclable thermosets. Carbon-reinforced vitrimer composites are pursued for high-performance, long-lasting materials with attractive physical properties, the ability to be recycled and processed, and other features that respond uniquely to stimuli. The development of carbon-reinforced vitrimer composites over the last few years is summarized in this article. First, an overview of vitrimers and the methods used to prepare carbon fiber-reinforced vitrimer composites is provided. Because of the vitrimer nature of such composites, reprocessing, healing, and recycling are viable ways to greatly extend their service life; these approaches are thoroughly explained and summarized. The conclusion is our prediction for developing carbon-based vitrimer composites.

9.
Bioresour Technol ; 407: 131142, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39043277

RESUMO

In this study, a sustainable and environmentally friendly method was developed for the enrichment and purification of phycocyanin from Spirulina platensis. This was achieved by utilizing a temperature-sensitive polymer, Pluronic F68, in an aqueous two-phase solvent system. The phase behavior of the temperature-sensitive polymer-based biphasic system was evaluated. The extraction conditions were optimized by both single-factor experiments and response surface methodology. Under the optimal conditions, the upper polymer-rich phase was recycled for sustainable phycocyanin extraction, resulting in a grade of 3.23 during the third extraction cycle. Pluronic F68 could be efficiently recovered and reused during the extraction process. The interaction mechanism between Pluronic F68 and phycocyanin was systematically studied using FT-IR and fluorescence analysis. This was further complemented by static and dynamic calculation of molecular motion through molecular docking and molecular dynamics simulation, indicating that hydrophobic segment of Pluronic F68 played a key role in the binding process with phycocyanin.


Assuntos
Química Verde , Ficocianina , Poloxâmero , Spirulina , Temperatura , Ficocianina/química , Ficocianina/isolamento & purificação , Spirulina/química , Poloxâmero/química , Química Verde/métodos , Simulação de Acoplamento Molecular , Espectroscopia de Infravermelho com Transformada de Fourier , Água/química , Polímeros/química , Simulação de Dinâmica Molecular
10.
Adv Mater ; : e2406252, 2024 Jul 14.
Artigo em Inglês | MEDLINE | ID: mdl-39004888

RESUMO

Carbon fiber (CF)-reinforced polymers (CFRPs) demonstrate potential for use in personal protective equipment. However, existing CFRPs are typically rigid, nonrecyclable, and lack of tearing resistance. In this study, flexible, recyclable, and tearing resistant polyurethane (PU)-CF composites are fabricated through complexation of reversibly cross-linked PU elastomer binders with CF fabrics. The PU-CF composites possess a high strength of 767 MPa and a record-high fracture energy of 2012 kJ m-2. The high performance of the PU-CF composites originates from the well-engineered PU elastomer binders that are obtained by cross-linking polytetrahydrofuran chains with in situ-formed nanodomains composed of hierarchical supramolecular interactions of hydrogen and coordination bonds. When subjected to tearing, the force concentrated on the damaged regions of the PU-CF composites can be effectively distributed to a wider area through the PU binders, leading to a significantly enhanced tearing resistance of the composites. The strong interfacial adhesion between PU binders and the CF fabrics enables the fracture of the CF in bundles, thereby significantly enhancing the strength and fracture energy of the composites. Because of the dynamic nature of the PU elastomer binders, the PU-CF composites can be recycled through the dissociation of the PU elastomer binders.

11.
J Colloid Interface Sci ; 677(Pt A): 11-24, 2024 Jul 23.
Artigo em Inglês | MEDLINE | ID: mdl-39079212

RESUMO

The persistent release of tetracycline into the environment significantly endangers both ecosystems and human health. Zinc indium sulfide (ZnIn2S4) capable to degrade tetracycline pollutants under visible light irradiation has attracted extensive attentions and great effort has been devoted to augment its catalytic efficacy. In this work, we synthesized a p-n heterojunction, NiFe2O4/ZnIn2S4, to enhance the carrier migration rate and explained the intrinsic mechanism by density functional theory. When the heterojunction was formed, carriers traversed from the n-type NiFe2O4 to the p-type ZnIn2S4, instigating the emergence of a built-in electric field to facilitate the separation of carriers. 2 %-NiFe2O4/ZnIn2S4 exhibited excellent photocatalytic efficiency in tetracycline (TC) degradation and total organic carbon (TOC) removal. Compared to pure ZnIn2S4 and NiFe2O4, the TC degradation rates of 2 %-NiFe2O4/ZnIn2S4 were 2.0 times and 16.9 times higher, respectively. Additionally, 2 %-NiFe2O4/ZnIn2S4 had a saturation magnetization intensity of 3.05 emu/g, allowing for rapid recovery of the catalyst under a magnetic field. Superoxide radicals (O2-) and holes (h+) were the primary active species driving the degradation process. Furthermore, potential reaction pathways of tetracycline in this photocatalytic process were determined and bioconcentration factor and developmental toxicity of the intermediate products were accessed. This work held great potentials for wastewater treatment and provided a pathway for the development of magnetic recyclable photocatalysts.

12.
EFSA J ; 22(7): e8918, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-39071238

RESUMO

The EFSA Panel on Food Contact Materials, Enzymes and Processing Aids (CEP) assessed the safety of the recycling process Guolong (EU register number RECYC323), which uses the EREMA Basic technology. The input material is hot caustic washed and dried poly(ethylene terephthalate) (PET) flakes originating from collected post-consumer PET containers, including no more than 5% PET from non-food consumer applications. The flakes are heated in a ■■■■■ reactor under vacuum before being extruded. Having examined the challenge test provided, the Panel concluded that the ■■■■■ decontamination (step 2), for which a challenge test was provided, is critical in determining the decontamination efficiency of the process. The operating parameters to control the performance of this step are temperature, pressure and residence time. It was demonstrated that this recycling process is able to ensure a level of migration of potential unknown contaminants into food below the conservatively modelled migrations of 0.1 and 0.15 µg/kg food, derived from the exposure scenarios for infants and toddlers, when such recycled PET is used at up to 100%. Therefore, the Panel concluded that the recycled PET obtained from this process is not of safety concern when used at up to 100% for the manufacture of materials and articles for contact with all types of foodstuffs, including drinking water, for long-term storage at room temperature or below, with or without hotfill. Articles made of this recycled PET are not intended to be used in microwave or conventional ovens and such uses are not covered by this evaluation.

13.
Waste Manag Res ; : 734242X241262714, 2024 Jul 30.
Artigo em Inglês | MEDLINE | ID: mdl-39078048

RESUMO

This study tackles the growing global concern about municipal waste management, particularly in cities like the Grand Guayaquil Metropolitan Area (GGA). Through realistic field studies on in situ household waste generation and geographic information system (GIS) tools, this work offers a framework to predict the quantities and types of recyclable household waste for any metropolitan area in Latin America. Over 4 weeks, students collected, sorted and weighed recyclable waste types, including plastic, paper, metal, glass and fabric, from 776 sampled household of the GGA. ArcGIS survey tool identified household locations and allowed to survey different socio-demographic features. With the help of ArcGIS interpolation method, the total household waste generation for GGA was predicted, and the classification of the different types of recyclable waste was also spatially distributed for the study area. The report identified notable trends in plastic waste, specifically polyethylene terephthalate waste's steady prevalence and 42% growth rate, emphasizing the importance of enhanced recycling techniques. Spatial density maps showed a heterogeneous waste distribution across the GGA, emphasizing locations with higher waste output. This study demonstrates that improving recyclable waste collection can be accomplished with a moderately cheap expenditure by collaborating with academia to overcome knowledge gaps. This strategy provides opportunities to mitigate the environmental impacts of poor waste management.

14.
ACS Appl Mater Interfaces ; 16(26): 32887-32905, 2024 Jul 03.
Artigo em Inglês | MEDLINE | ID: mdl-38904545

RESUMO

Hydrogel bioelectronics has been widely used in wearable sensors, electronic skin, human-machine interfaces, and implantable tissue-electrode interfaces, providing great convenience for human health, safety, and education. The generation of electronic waste from bioelectronic devices jeopardizes human health and the natural environment. The development of degradable and recyclable hydrogels is recognized as a paradigm for realizing the next generation of environmentally friendly and sustainable bioelectronics. This review first summarizes the wide range of applications for bioelectronics, including wearable and implantable devices. Then, the employment of natural and synthetic polymers in hydrogel bioelectronics is discussed in terms of degradability and recyclability. Finally, this work provides constructive thoughts and perspectives on the current challenges toward hydrogel bioelectronics, providing valuable insights and guidance for the future evolution of sustainable hydrogel bioelectronics.


Assuntos
Hidrogéis , Dispositivos Eletrônicos Vestíveis , Hidrogéis/química , Humanos , Materiais Biocompatíveis/química , Polímeros/química , Eletrônica
15.
Angew Chem Int Ed Engl ; 63(34): e202405083, 2024 Aug 19.
Artigo em Inglês | MEDLINE | ID: mdl-38837601

RESUMO

Physical blending is an effective strategy for tailoring polymeric materials to specific application requirements. However, physically blended mixed plastics waste adds additional barriers in mechanical or chemical recycling. This difficulty arises from the intricate requirement for meticulous sorting and separation of the various polymers in the inherent incompatibility of mixed polymers during recycling. To overcome this impediment, this work furthers the emerging single-monomer - multiple-materials approach through the design of a bifunctional monomer that can not only orthogonally polymerize into two different types of polymers - specifically lactone-based polyester and CO2-based polycarbonate - but the resultant polymers and their mixture can also be depolymerized back to the single, original monomer when facilitated by catalysis. Specifically, the lactone/epoxide hybrid bifunctional monomer (BiLO) undergoes ring-opening polymerization through the lactone manifold to produce polyester, PE(BiLO), and is also applied to ring-opening copolymerization with CO2, via the epoxide manifold, to yield polycarbonate, PC(BiLO). Remarkably, a one-pot recycling process of a BiLO-derived PE/PC blend back to the constituent monomer BiLO in >99 % selectivity was achieved with a superbase catalyst at 150 °C, thereby effectively obviating the requirement for sorting and separation typically required for recycling of mixed polymers.

16.
ChemSusChem ; : e202400356, 2024 Jun 06.
Artigo em Inglês | MEDLINE | ID: mdl-38842466

RESUMO

Dynamic covalent chemistry (DCC) has revolutionized the field of polymer science by offering new opportunities for the synthesis, processability, and recyclability of polymers as well as in the development of new materials with interesting properties such as vitrimers and covalent organic frameworks (COFs). Many DCC linkages have been explored for this purpose, but recently, enamine-ones have proven to be promising dynamic linkages because of their facile reversible transamination reactions under thermodynamic control. Their high stability, stimuli-responsive properties, and tunable kinetics make them promising dynamic cross-linkers in network polymers. Given the rapid developments in the field in recent years, this review provides a critical and up-to-date overview of recent developments in enamine-one chemistry, including factors that control their dynamics. The focus of the review will be on the utility of enamine-ones in designing a variety of processable and self-healable polymers with important applications in vitrimers and recyclable closed-loop polymers. The use of enamine-one linkages in crystalline polymers, known as COFs and their applications are also summarized. Finally, we provide an outlook for future developments in this field.

17.
Macromol Rapid Commun ; : e2400260, 2024 Jun 02.
Artigo em Inglês | MEDLINE | ID: mdl-38824417

RESUMO

As the demand for sustainable polymers increases, most research efforts have focused on polyesters, which can be bioderived and biodegradable. Yet analogous polythioesters, where one of the oxygen atoms has been replaced by a sulfur atom, remain a relatively untapped source of potential. The incorporation of sulfur allows the polymer to exhibit a wide range of favorable properties, such as thermal resistance, degradability, and high refractive index. Polythioester synthesis represents a frontier in research, holding the promise of paving the way for eco-friendly alternatives to conventional polyesters. Moreover, polythioester research can also open avenues to the development of sustainable and recyclable materials. In the last 25 years, many methods to synthesize polythioesters have been developed. However, to date no industrial synthesis of polythioesters has been developed due to challenges of costs, yields, and the toxicity of the by-products. This review will summarize the recent advances in polythioester synthesis, covering step-growth polymerization, ring-opening polymerization (ROP), and biosynthesis. Crucially, the benefits and challenges of the processes will be highlighted, paying particular attention to their sustainability, with the aim of encouraging further exploration and research into the fast-growing field of polythioesters.

18.
ACS Appl Mater Interfaces ; 16(25): 32812-32823, 2024 Jun 26.
Artigo em Inglês | MEDLINE | ID: mdl-38878000

RESUMO

This study presents a novel three-dimensional (3D) printable gallium-carbon black-styrene isoprene styrene block copolymer (Ga-CB-SIS), offering a versatile solution for the rapid fabrication of stretchable and integrated sensor-heater-battery systems in wearable and recyclable electronics. The composite exhibits sinter-free characteristics, allowing for printing on various substrates, including heat-sensitive materials. Unlike traditional conductive inks, the Ga-CB-SIS composite, composed of gallium, carbon black, and styrene isoprene block copolymers, combines electrical conductivity, stretchability, and digital printability. By introducing carbon black as a filler material, the composite achieves promising electromechanical behavior, making it suitable for low-resistance heaters, batteries, and electrical interconnects. The fabrication process involves a simultaneous mixing and ball-milling technique, resulting in a homogeneous composition with a CB/Ga ratio of 4.3%. The Ga-CB-SIS composite showcases remarkable adaptability for digital printing on various substrates. Its self-healing property and efficient recycling technique using a deep eutectic solvent contribute to an environmentally conscious approach to electronic waste, with a high gallium recovery efficiency of ∼98%. The study's innovation extends to applications, presenting a fully digitally printed stretchable Ga-CB-SIS battery integrated with strain sensors and heaters, representing a significant leap in LM-based composites. This multifunctional and sustainable Ga-CB-SIS composite emerges as a key player in the future of wearable electronics, offering integrated circuits with sensing, heating, and energy storage elements.

19.
Angew Chem Int Ed Engl ; 63(32): e202404769, 2024 Aug 05.
Artigo em Inglês | MEDLINE | ID: mdl-38783562

RESUMO

Elastomeric solid polymer electrolytes (SPEs) are highly promising to address the solid-solid-interface issues of solid-state lithium metal batteries (LMBs), but compromises have to be made to balance the intrinsic trade-offs among their conductive, resilient and recyclable properties. Here, we propose a dual-bond crosslinking strategy for SPEs to realize simultaneously high ionic conductivity, elastic resilience and recyclability. An elastomeric SPE is therefore designed with hemiaminal dynamic covalent networks and Li+-dissociation co-polymer chains, where the -C-N- bond maintains the load-bearing covalent network under stress but is chemically reversible through a non-spontaneous reaction, the weaker intramolecular hydrogen bond is mechanically reversible, and the soft chains endow the rapid ion conduction. With this delicate structure, the optimized SPE elastomer achieves high elastic resilience without loading-unloading hysteresis, outstanding ionic conductivity of 0.2 mS cm-1 (25 °C) and chemical recyclability. Then, exceptional room-temperature performances are obtained for repeated Li plating/stripping tests, and stable cycling of LMBs with either LiFePO4 or 4.3 V-class LiFe0.2Mn0.8PO4 cathode. Furthermore, the recycled and reprocessed SPEs can be circularly reused in LMBs without significant performance degradation. Our findings provide an inspiring design principle for SPEs to address the solid-solid-interface and sustainability challenges of solid-state LMBs.

20.
Angew Chem Int Ed Engl ; 63(31): e202405653, 2024 Jul 29.
Artigo em Inglês | MEDLINE | ID: mdl-38764409

RESUMO

Dithioacetals are heavily used in organic, material and medical chemistries, and exhibit huge potential to synthesize degradable or recyclable polymers. However, the current synthetic approaches of dithioacetals and polydithioacetals are overwhelmingly dependent on external catalysts and organic solvents. Herein, we disclose a catalyst- and solvent-free acetal-thiol click-like reaction for synthesizing dithioacetals and polydithioacetals. High conversion, higher than acid catalytic acetal-thiol reaction, can be achieved. High universality was confirmed by monitoring the reactions of linear and cyclic acetals (including renewable bio-sourced furan-acetal) with aliphatic and aromatic thiols, and the reaction mechanism of monomolecular nucleophilic substitution (SN1) and auto-protonation (activation) by thiol was clarified by combining experiments and density functional theory computation. Subsequently, we utilize this reaction to synthesize readily recyclable polydithioacetals. By simple heating and stirring, linear polydithioacetals with M ‾ ${\bar M}$ w of ~110 kDa were synthesized from acetal and dithiol, and depolymerization into macrocyclic dithioacetal and repolymerization into polydithioacetal can be achieved; through reactive extrusion, a semi-interpenetrating polymer dynamic network with excellent mechanical properties and continuous reprocessability was prepared from poly(vinyl butyral) and pentaerythritol tetrakis(3-mercaptopropionate). This green and high-efficient synthesis method for dithioacetals and polydithioacetals is beneficial to the sustainable development of chemistry.

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