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1.
Adv Mater ; : e2406252, 2024 Jul 14.
Artículo en Inglés | MEDLINE | ID: mdl-39004888

RESUMEN

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.

2.
Materials (Basel) ; 17(13)2024 Jul 02.
Artículo en Inglés | MEDLINE | ID: mdl-38998348

RESUMEN

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.

3.
Bioresour Technol ; 407: 131142, 2024 Jul 21.
Artículo en Inglés | MEDLINE | ID: mdl-39043277

RESUMEN

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.

4.
Molecules ; 29(14)2024 Jul 13.
Artículo en Inglés | MEDLINE | ID: mdl-39064886

RESUMEN

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.

5.
EFSA J ; 22(7): e8918, 2024 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-39071238

RESUMEN

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.

6.
Waste Manag Res ; : 734242X241262714, 2024 Jul 30.
Artículo en Inglés | MEDLINE | ID: mdl-39078048

RESUMEN

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.

7.
J Colloid Interface Sci ; 677(Pt A): 11-24, 2024 Jul 23.
Artículo en Inglés | MEDLINE | ID: mdl-39079212

RESUMEN

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.

8.
ChemSusChem ; : e202400356, 2024 Jun 06.
Artículo en Inglés | MEDLINE | ID: mdl-38842466

RESUMEN

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.

9.
Macromol Rapid Commun ; : e2400260, 2024 Jun 02.
Artículo en Inglés | MEDLINE | ID: mdl-38824417

RESUMEN

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.

10.
Angew Chem Int Ed Engl ; : e202405083, 2024 Jun 04.
Artículo en Inglés | MEDLINE | ID: mdl-38837601

RESUMEN

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.

11.
ACS Appl Mater Interfaces ; 16(25): 32812-32823, 2024 Jun 26.
Artículo en Inglés | MEDLINE | ID: mdl-38878000

RESUMEN

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.

12.
ACS Appl Mater Interfaces ; 16(26): 32887-32905, 2024 Jul 03.
Artículo en Inglés | MEDLINE | ID: mdl-38904545

RESUMEN

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.


Asunto(s)
Hidrogeles , Dispositivos Electrónicos Vestibles , Hidrogeles/química , Humanos , Materiales Biocompatibles/química , Polímeros/química , Electrónica
13.
J Colloid Interface Sci ; 671: 325-335, 2024 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-38815369

RESUMEN

This present work demonstrated the functional transformation of 3D printed metal substrates into a new family of Surface-enhanced Raman Scattering substrates, a promising approach in developing SERS-based Point-of-care (PoC) analytical platforms. l-Powder Bed Fusion (l-PBF, Additive manufacturing or 3D printing technique) printed metal substrates have rough surfaces, and exhibit high thermal stability and intrinsic chemical inertness, necessitating a suitable surface functionalization approach. This present work demonstrated a unique multi-stage approach to transform l-PBF printed metal structures as recyclable SERS substrates by colloidal carbon templating, chemical vapor deposition, and electroless plating methods sequentially. The surface of the printed metal structures was functionalized using the colloidal carbon soot particles, that were formed by the eucalyptus oil flame deposition method. These carbon particles were shown to interact with the metals present in the printed structures by forming metal carbides and function as an adlayer on the surface. Subsequent deposition of TiO2 onto these templates led to strong grafting of TiO2 and retaining the fractal structure of the soot template onto the metal surface. Electroless deposition of silver nanoparticles resulted in the formation of fractally structured TiO2/Ag nanostructures and these functionalized printed metal structures were shown as excellent SERS substrates in enhancing the vibrational spectral features of Rhodamine B (RhB). The presence of TiO2 photocatalyst on the surface was shown to remove the RhB analyte from the surface under photochemical conditions, which enables the regeneration of SERS activity, and the substrate can be recycled. The migration of metals from the printed metal structures into the fractally ordered TiO2/Ag nanostructures was found to enhance the photocatalytic activity and increase the recyclability of these substrates. This study demonstrates the potential of 3D-printed Inconel metal substrates as next-generation recyclable SERS platforms, offering a substantial advancement over traditional colloidal, thin-film, flexible, and hard SERS substrates.

14.
Int J Biol Macromol ; 270(Pt 2): 132541, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38777012

RESUMEN

Bio-based polymers are materials of high interest given the harmful environmental impact that involves the use of non-biodegradable fossil products for industrial applications. These materials are also particularly interesting as bio-based ligands for the preparation of metal nanoparticles (MNPs), employed as catalysts for the synthesis of high value chemicals. In the present study, Ru (0) and Rh(0) Metal Nanoparticles supported on Sodium Carboxymethyl cellulose (MNP(0)s-CMCNa) were prepared by simply mixing RhCl3x3H2O or RuCl3 with an aqueous solution of CMCNa, followed by NaBH4 reduction. The formation of MNP(0)s-CMCNa was confirmed by FT-IR and XRD, and their size estimated to be around 1.5 and 2.2 nm by TEM analysis. MNP(0)s-CMCNa were employed for the hydrogenation of (E)-cinnamic aldehyde, furfural and levulinic acid. Hydrogenation experiments revealed that CMCNa is an excellent ligand for the stabilization of Rh(0) and Ru(0) nanoparticles allowing to obtain high conversions (>90 %) and selectivities (>98 %) with all substrates tested. Easy recovery by liquid/liquid extraction allowed to separate the catalyst from the reaction products, and recycling experiments demonstrated that MNPs-CS were highly efficiency up to three times in best hydrogenation conditions.


Asunto(s)
Carboximetilcelulosa de Sodio , Nanopartículas del Metal , Solubilidad , Agua , Carboximetilcelulosa de Sodio/química , Catálisis , Agua/química , Nanopartículas del Metal/química , Hidrogenación , Rutenio/química , Rodio/química
15.
Talanta ; 276: 126291, 2024 Aug 15.
Artículo en Inglés | MEDLINE | ID: mdl-38776774

RESUMEN

Developing a Surface-enhanced Raman spectroscopy (SERS) method with excellent detecting ability, good recyclability and analyzing multiple pollutants rapidly are critical for evaluation of water quality in emergency pollution affairs. While constructing a multifunctional substrate with these characteristics to realize the application of SERS in water quality monitoring remains a challenge. In this work, a reusable Au@R-Fe3O4/g-C3N4 SERS substrate is prepared by loading Au nanoparticles (Au NPs) on Fe3O4 nanorings (R-Fe3O4) and the formed Au@R-Fe3O4 is further combined with g-C3N4 nanosheets through a simple electrostatic assembly method. The Au@R-Fe3O4/g-C3N4 nanocomposite presents multifunction of magnetic enrichment, SERS signal enhancement, multiple pollutants analyzing, and photocatalytic activity, which achieves quantitative detection of rhodamine B (RhB), tetracycline hydrochloride (TC), and 4-chlorophenol (4-CP), with detection limits of 5.30 × 10-9, 7.50 × 10-8, 7.69 × 10-8 mol/L, respectively. Furthermore, the recyclable detection capability of Au@R-Fe3O4/g-C3N4 for multi components is demonstrated by the strong SERS signal after 9 cycles of "detection-degradation" processes. Combined with good uniformity and stability, this SERS method based on Au@R-Fe3O4/g-C3N4 substrate provides a new strategy for the multi-pollutants detection and degradation in water environment.

16.
Angew Chem Int Ed Engl ; 63(31): e202405653, 2024 Jul 29.
Artículo en Inglés | MEDLINE | ID: mdl-38764409

RESUMEN

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.

17.
Chemistry ; 30(39): e202400638, 2024 Jul 11.
Artículo en Inglés | MEDLINE | ID: mdl-38752324

RESUMEN

Ni single atom containing hollow carbon nanospheres with nitrogen doping has been synthesized by carbonization of Ni(NO3)2/phloroglucinol-formaldehyde polymer/silica composite. The samples have been characterized by powder X-ray diffraction, nitrogen adsorption/desorption, electron microscopic, Raman and X-ray photoelectron spectroscopic studies. The microstructure and surface area vary with the amount of Ni(NO3)2 employed in the syntheses and the carbonization environment. An optimized amount of nickel and argon as the carbonization gas afford Ni-1.0@N@HCN-Ar which possesses overall superior features. The uniformly dispersed Ni single atoms within the hollow porous carbon framework fully utilize all the electroactive sites thereby improving the supercapacitive performance. The specific capacitance of Ni-1.0@N@HCN-Ar reaches 777 F g-1 at 1 A g-1 with a Coulombic efficiency of 98.4 % and excellent recyclability. The energy and power density of Ni-1.0@N@HCN-Ar are found to be high; at 1 A g-1 its energy density is 155.4 Wh kg-1 with a power density of 600.3 W kg-1. At a high current density of 10 A g-1 the material shows a high energy density of 118.4 Wh kg-1 with excellent power density of 6003.4 W kg-1. A symmetric solid-state supercapacitor assembled with this material, Ni-1.0@N@HCN-Ar//Ni-1.0@N@HCN-Ar using H2SO4/PVA gel electrolyte shows a superior energy density value of 30 Wh kg-1 at a power density of 1200 W kg-1.

18.
Adv Mater ; 36(28): e2311758, 2024 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-38758171

RESUMEN

Thermoset elastomers have been extensively applied in many fields because of their excellent mechanical strengths and durable characteristics, such as an excellent chemical resistance. However, in the context of environmental issues, the nonrecyclability of thermosets has become a major barrier to the further development of these materials. Here, a well-tailored strategy is reported to solve this problem by introducing mismatched supramolecular interactions (MMSIs) into a covalently cross-linked poly(urethane-urea) network with dynamic acylsemicarbazide moieties. The MMSIs significantly strengthen and toughen the thermoset elastomer by effectively dissipating energy and resisting external stress. In addition, the elastomer recycling efficiency is improved 2.7-fold due to the superior reversibility of the MMSIs. The optimized thermoset elastomer features outstanding characteristics, including an ultrahigh tensile strength (110.8 MPa), an unprecedented tensile toughness (1245.2 MJ m-3), as well as remarkable resistance to chemical media, creep, and damage. Most importantly, it exhibits an extraordinary multirecyclability, and the 4th recycling efficiency remains close to 100%. This scalable method promotes the development of thermosets with both high performance and excellent recyclability, thereby providing valuable guidance for addressing the issue of nonrecyclability from a molecular design standpoint.

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

RESUMEN

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.
Molecules ; 29(9)2024 May 01.
Artículo en Inglés | MEDLINE | ID: mdl-38731574

RESUMEN

Bio-based polymers are attracting increasing interest as alternatives to harmful and environmentally concerning non-biodegradable fossil-based products. In particular, bio-based polymers may be employed as ligands for the preparation of metal nanoparticles (M(0)NPs). In this study, chitosan (CS) was used for the stabilization of Ru(0) and Rh(0) metal nanoparticles (MNPs), prepared by simply mixing RhCl3 × 3H2O or RuCl3 with an aqueous solution of CS, followed by NaBH4 reduction. The formation of M(0)NPs-CS was confirmed by Fourier Transform Infrared Spectroscopy (FT-IR), Differential Scanning Calorimetry (DSC), Thermal Gravimetric Analysis (TGA), Scanning Electron Microscopy (SEM), Energy-Dispersive X-ray Analysis (EDX), Transmission Electron Microscopy (TEM) and X-ray Diffraction (XRD). Their size was estimated to be below 40 nm for Rh(0)-CS and 10nm for Ru(0)-CS by SEM analysis. M(0)NPs-CS were employed for the hydrogenation of (E)-cinnamic aldehyde and levulinic acid. Easy recovery by liquid-liquid extraction made it possible to separate the catalyst from the reaction products. Recycling experiments demonstrated that M(0)NPs-CS were highly efficient up to four times in the best hydrogenation conditions. The data found in this study show that CS is an excellent ligand for the stabilization of Rh(0) and Ru(0) nanoparticles, allowing the production of some of the most efficient, selective and recyclable hydrogenation catalysts known in the literature.

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