In Situ Growth Strategy to Construct "Four-In-One" Separators with Functionalized Polyphosphazene Coatings for Safe and Stable Lithium-Sulfur Batteries.

Lithium-sulfur batteries (LSBs) are facing many challenges, such as the inadequate conductivity of sulfur, the shuttle effect caused by lithium polysulfide (LiPSs), lithium dendrites, and the flammability, which have hindered their commercial applications. Herein, a "four-in-one" functionalized coating is fabricated on the surface of polypropylene (PP) separator by using a novel flame-retardant namely InC-HCTB to meet these challenges. InC-HCTB is obtained by cultivating polyphosphazene on the surface of carbon nanotubes with an in situ growth strategy. First, this unique architecture fosters an enhanced conductive network, bolstering the bidirectional enhancement of both ionic and electronic conductivities. Furthermore, InC-HCTB effectively inhibits the shuttle effect of LiPSs. LSBs exhibit a remarkable capacity of 1170.7 mA h g-1 at 0.2 C, and the capacity degradation is a mere 0.0436% over 800 cycles at 1 C. Third, InC-HCTB coating serves as an ion migration network, hindering the growth of lithium dendrites. More importantly, InC-HCTB exhibits notable flame retardancy. The radical trapping action in the gas phase and the protective effect of the shielded char layer in the condensed phase are simulated and verified. This facile in situ growth strategy constructs a "four-in-one" functional separator coating, rendering InC-HCTB a promising additive for the large-scale production of safe and stable LSBs.

Paralysis caused by dinotefuran at environmental concentration via interfering the Ca2+-ROS-mitochondria pathway in Chironomus kiiensis.

Introduction: Dinotefuran as the third-generation of neonicotinoid insecticides is extensively used in agriculture worldwide, posing a potential toxic threat to non-target animals and humans. However, the chronic toxicity mechanism related to mitochondria damage of dinotefuran to non-target animals at environmental concentration is unclear. Methods: In this study, the mitochondria damage and oxidative stress of dinotefuran on Chironomus kiiensis were investigated at environmental concentrations by long-term exposure. At the same time, relevant gene expressions of these toxicity indexes were measured as sensitive ecotoxicity biomarkers to reflect the toxic effects of dinotefuran on Chironomidae. Results: Our present study showed that chronic exposure to environmental concentrations of dinotefuran resulted in behavioral inhibition in the larvae of Chironomidae. For burrowing inhibition of 10 days, the lowest observed-effect concentration (LOEC) and 50% inhibitory concentration (IC50) were 0.01 (0.01-0.04) and 0.60 (0.44-0.82) µg/L, respectively. Dinotefuran promoted the release of intracellular calcium ions (Ca2+) in Chironomidae via dysregulating the gene expressions of atp2b, camk ii, and calm. Subsequently, the disruption of the Ca2+ signaling pathway induced oxidative stress by raising reactive oxygen species (ROS), hydrogen peroxide (H2O2), and malonaldehyde (MDA) levels. Thus, the over-release of Ca2+ and ROS disordered the normal functioning of mitochondrial-related pathways by dysregulating the expressions of mitochondria-related genes of atpef0a, sdha, and cyt b. Conclusion: Our findings showed that low environmental concentrations of dinotefuran caused paralysis of the midge via interfering the Ca2+-ROS-mitochondria pathway. These results provided data support for assessing the potential environmental risk of dinotefuran.

A free radical interlocking co-deposition strategy based on the oxidative pyrolysis mechanism of polyethylene terephthalate to achieve green energy recovery.

Accidental combustion and energy recovery of polyethylene terephthalate (PET) result in the formation of harmful organic substances and excessive emissions of CO2 and CO. This paper presents our recent efforts to unravel the formation mechanism of these harmful substances during the PET combustion process using thermal analysis and simulation calculations (DFT, CDFT, and ReaxFF). Our findings reveal that PET oxidative pyrolysis produces free radicals, harmful small molecule gases, and CO2. The interaction between aromatic free radicals and oxygen initiates unstable peroxy bonds, triggering uncontrollable chain exothermic reactions and producing oxygenated polycyclic aromatic hydrocarbon (OPAH) precursors. We propose a straightforward and eco-friendly free radical interlocking co-deposition inhibition strategy for PET by incorporating polycarbonate (PC). This strategy aims to facilitate green energy recovery by curbing OPAH formation and reducing CO2 and CO emissions during PET waste combustion. Our investigation into the oxidative pyrolysis of PET challenges conventional wisdom dominated by C-H bond fracture, paving the way for efficient, low-pollution green energy recovery.

Enhancing the flame retardancy of polylactic acid nonwoven fabric through solvent-free transparent coating.

Polylactic acid (PLA) nonwovens, recognized as eco-friendly substitutes for petroleum-based synthetic fibers, face a significant challenge due to their inherent flammability. This work addresses this concern by synthesizing a hyperbranched polyphosphoramide flame retardant (TPDT) through a one-step polycondensation process without using solvent and catalyst. TPDT is subsequently applied to PLA nonwovens using a dip-pad finishing technique. Notably, with a mere 7 wt% weight gain of TPDT, the PLA nonwovens exhibit a substantial increase in the limited oxygen index (LOI) value, reaching 32.3 %. Furthermore, the damaged area in the vertical burning test is reduced by approximately 69.2 %. In the cone calorimeter test, 17 wt% weight gain of TPDT results in a 51.4 % decrease in peak heat release rate and a 56.0 % reduction in total heat release compared to the control PLA. Additionally, char residue increases from 1.5 wt% to 31.1 wt% after combustion. The strong affinity between TPDT and PLA molecules persists even after repeated abrasion, ensuring sustained flame retardancy. Importantly, the introduction of TPDT also imparts increased softness to the PLA nonwovens. This work addresses this concern by synthesizing a hyperbranched polyphosphoramide flame retardant (TPDT) through a solvent-free, catalyst-free, and one-step polycondensation process.

Mechanical, Thermal Stability, and Flame Retarding Properties of Phosphorus-Modified PET Blended with DOPO-POSS.

In this study, an antidroplet flame retardant system based on FRPET (phosphorus-containing copolyester) is constructed with DOPO-POSS (polyhedral oligomeric silsesquioxane containing DOPO) as an additive flame retardant. It is demonstrated that DOPO-POSS has good dispersibility at a lower amount. When the amount of DOPO-POSS is 9 wt %, the residual char of DOPO-POSS/FRPET at 700 °C increases to 23.56 from 18.16% of FRPET, and the maximum thermal weight loss rate also reduces. What is more is that the limiting oxygen index increases to 33 from 26% of FRPET. The flame burning time is shortened to 4.95 from 20.8 s, the phenomenon of self-extinguishing of the fire occurs, and the vertical combustion level is increased from V-2 to V-0. Compared with FRPET, the peak of the heat release rate decreases by 66.0%, the total heat release decreases by 32.4%, the flame retardancy index (FRI) reaches an excellent value, and the condensed-phase products significantly improve. The Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy-energy dispersive X-ray spectrometry (SEM-EDX), thermogravimetric-FTIR (TG-FTIR), and pyrolysis-gas chromatograph/mass spectrometry (Py-GC/MS) results indicate that DOPO-POSS contributes to the formation of char layers and decomposes to generate free radicals with a quenching effect. In a word, DOPO-POSS is an effective radical trapper and charring agent for PET and exerts a flame retardancy effect in gaseous and condensed phases simultaneously.

Preparation of Carbon Dots with Ultrahigh Fluorescence Quantum Yield Based on PET Waste.

Environmentally friendly polyethylene terephthalate-based carbon dots (PET-CDs) with ultrahigh fluorescence quantum yield were prepared with waste PET textiles as raw materials. First, oligomers were prepared from the reaction of waste PET textile and ethylene glycol by the microwave method. Then, the mixture without isolation and purification as well as pyromellitic acid and urea were adopted as precursors for the preparation of PET-CDs by the hydrothermal method. It was found that the as-prepared PET-CDs had a spherical structure with an average particle size of 2.8 nm. The carbon core of PET-CDs was a graphene-like structure doped with nitrogen atoms in the form of pyrrole nitrogen and the surface contained -NH2, which is convenient for modification and functionalization with various materials in the form of chemical bonds. The as-prepared PET-CDs exhibit excitation-independent emission properties in the range from 340 to 440 nm, and the best excitation and emission wavelengths of PET-CDs are 406 and 485 nm, respectively, while the fluorescence quantum yield is 97.3%. In terms of the application, the as-prepared PET-CDs could be adopted as a fluorescence probe for the detection of Fe3+, and the limit of detection is as low as 0.2 µmol/L. The mechanism of PET-CDs by Fe3+ was found to be the static quenching mechanism. In addition, PET-CDs can be used in LEDs and fluorescent anticounterfeiting.

Simple and Green Synthesis of Carbonized Polymer dots from Nylon 66 Waste Fibers and its Potential Application.

Carbonized polymer dots (CPDs) have attracted widespread attention owing to their unique properties and are usually prepared from monomers of polymers or polymers. To reduce the waste of high-value petropolymers and environmental pollution, a simple and green method for the preparation of CPDs using a hydrothermal technique based on the cross-linking enhanced emission effect was proposed, in which nylon 66 waste fibers were used as a precursor and glutaraldehyde as a cross-linking agent. The as-prepared CPDs possessed polymer/carbon hybrid structures with a 3.5 nm average diameter, and hydroxyl (-OH), carboxyl (-COOH), and amino (-NH2) groups were present on the surface of CPDs. It can be found that the as-prepared CPDs display excitation-dependent photoluminescence emission, which is mainly attributed to the molecular state luminescence center. Because the molecular state fluorescence of CPDs could be affected by the presence of Fe3+ and the change of pH values, the as-prepared CPDs can be used as a probe for the detection of the concentration of Fe3+ and the pH variations of solution. The fluorescence intensity of CPDs was selectively quenched by Fe3+ in the range from 1 to 145 µM. In virtue of the static quenching of CPDs by Fe3+, a sensing system was fabricated for the quantitative detection of Fe3+, and its limit of detection was 0.1 µM. Based on the electrostatic doping/charging of CPDs, a pH sensor was fabricated. It showed that the fluorescence intensity of CPDs decreased along with the increase of pH from 2.60 to 12.6. What is more, the CPDs were found to be an alternative to traditional fluorescent inks for encryption and information storage.