Lignin derived hydrophobic deep eutectic solvents for the extraction of nanoplastics from water.

As a growing concern in aqueous systems, micro- and nano-plastics, especially nanoplastics (NPs), have been widely detected in the environment and organisms, posing a potential threat to ecosystems and human health. Hydrophobic deep eutectic solvents (HDESs) have emerged as environmentally friendly solvents that have shown promise for extracting pollutants from water, either for detection or removal purposes. Herein, we investigated the extraction of polystyrene (PS) and polyethylene terephthalate (PET) NPs from aqueous solution using lignin based HDESs as sustainable solvents. Rapid extraction of both PET and PS NPs was observed with the high extraction efficiency achieved (> 95%). The extraction capacities for PET and PS could reach up to 525.877 mg/mL and 183.520 mg/mL, respectively, by the Thymol-2,6-dimethoxyphenol 1:2 HDES. Moreover, the extraction mechanism was studied using various techniques including Fourier-transform infrared analysis, contact angle measurements, molecular dynamics simulation, kinetics, and isotherm studies. This work lays a foundational basis for the future development of innovative HDES-based technologies in the detection and remediation of NPs as part of the grand challenge of plastic pollution.

Process intensification strategies for green solvent mediated biomass pretreatment.

Demonstrated to be highly effective for lignocellulosic biomass pretreatment, deep eutectic solvent (DES) has attracted increasing attention owing to its advantages of simple synthesis, relatively low chemical cost, and better biocompatibility as compared to certain ionic liquids. Here we provide a critical review of the status of the design/selection of DES for the pretreatment of biomass feedstocks with an emphasis on the process intensification strategies: 1) integration of microwave, ultrasound, and high solid extrusion for pretreating biomass, 2) one-pot DES pretreatment, enzymatic hydrolysis, and fermentation, 3) strategies for DES recycling and product recovery; and 4) recent progress on molecular simulations toward understanding the interactions between DES and biomass compounds such as lignin and cellulose. Lastly, we provide perspectives toward cost-effective, continuous, high-solid, environmental-benign, and industrial-relevant applications and point to future research directions to address the challenges associated with DES pretreatment.

Negative Thermal Expansion HfV2O7 Nanostructures for Alleviation of Thermal Stress in Nanocomposite Coatings.

A primary mode of failure of thin-film coatings is the mismatch in thermal expansion coefficients of the substrate and the coating, which results in accumulation of interfacial stresses and ultimately in film delamination. While much attention has been devoted to modulation of interfacial bonding to mitigate delamination, current strategies are constrained in their generalizability and have had limited success in imbuing resistance to prolonged thermal cycling. We demonstrate here the incorporation of rigid thermal expansion compensators within polymeric films as a generalizable strategy for minimizing thermal mismatch with the substrate. Nanostructures of the isotropic negative thermal expansion (NTE) material HfV2O7 have been prepared based on the reaction of nanoparticulate precursors. The NTE behavior, derived from transverse oxygen displacement within the cubic structure, has been examined using temperature-variant powder X-ray diffraction, Raman spectroscopy, electron microscopy, and selected-area electron diffraction measurements. HfV2O7 initially crystallizes in a 3 × 3 × 3 superlattice but undergoes phase transformations to stabilize a cubic structure that exhibits strong and isotropic NTE with a coefficient of thermal expansion (CTE) = -6.7 × 10-6 °C-1 across an extended temperature range of 130-700 °C. Incorporation of HfV2O7 in a high-temperature thermoset polybenzimidazole enables the reduction of compressive stress by 67.3% for a relatively small loading of 26.6 vol % HfV2O7. Based on a composite model, we demonstrate that HfV2O7 can reduce the thermal expansion coefficient of polymer nanocomposite films, even at low volume fractions, as a result of its substantially higher elastic modulus compared to the continuous polymer matrix. By changing the volume fraction of HfV2O7, the overall coefficients of thermal expansion of the film can be tuned to match a range of substrates, thereby mitigating thermal stresses and resolving a fundamental challenge for high-temperature composites and nanocomposite coatings.