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This study investigated the impact of cellulose nanofibers (CNFs) on montmorillonites (MMTs) exfoliation within thermoplastic starch (TPS) nanocomposites during the melt blending process. TPS nanocomposite films were manufactured using an internal mixer with a controlled ratio of CNFs and MMTs to evaluate the effect of individual and hybrid fillers on the material interactions and characteristics of the TPS composites. The incorporation of hybrid fillers resulted in notable enhancements in torque values and rheological properties, suggesting interactions between the starch, CNFs, and MMTs. The degree of MMT intercalation, obtained via X-ray diffraction analysis, decreased with the addition of CNFs, indicating that CNFs positively impacted MMT exfoliation. Scanning electron microscopy (SEM) images of cryo- and tensile-fractured samples highlighted the effectiveness of CNFs in facilitating MMT exfoliation and reinforcing interactions between the MMTs and TPS matrix. These interactions enhanced the tensile strength and Young's modulus by up to 95.8 % and 278.2 %, respectively, with a 1:1 weight ratio of CNFs to MMTs. Additionally, well-dispersed MMTs within the TPS matrix caused passivation and created tortuous paths, improving the water contact angle and decreasing the water vapor sorption. These synergistic effects of the hybrid filler, achieved through a melt blending process, indicate the potential use of TPS nanocomposites as an eco-friendly packaging material., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Using first principles calculations we unveil fundamental mechanism of hydrolysis reactions of two hazardous chemicals PCl 3 and POCl 3 with explicit molecular water clusters nearby. It is found that the water molecules play a key role as a catalyst significantly lowing activation barrier of the hydrolysis via transferring its protons to reaction intermediates. Interestingly, torsional angle of the molecular complex at transition state is identified as a vital descriptor on the reaction rate. Analysis of charge distribution over the complex further reinforces the finding with atomic level correlation between the torsional angle and variation of the orbital hybridization state of phosphorus (P) in the complex. Electronic charge separation (or polarization) enhances thermodynamic stability of the activated complex and reduces the activation energy through hydrogen bonding network with water molecules nearby. Calculated potential energy surfaces (PES) for the hydrolysis of PCl 3 and POCl 3 depict their two contrastingly different profiles of double- and triple-depth wells, respectively. It is ascribed to the unique double-bonding O=P in the POCl 3 . Our results on the activation free energy show well agreements with previous experimental data within 7kcalmol -1 deviation., (Copyright © 2017 Elsevier B.V. All rights reserved.)