Competitive adsorption of Alizarin Red S and Bromocresol Green from aqueous solutions using brookite TiO2 nanoparticles: experimental and molecular dynamics simulation.

In this work, the effective adsorption and the subsequent photodegradation activity, of TiO2 brookite nanoparticles, for the removal of anionic dyes, namely, Alizarin Red S (ARS) and Bromocresol Green (BCG) were studied. Batch adsorption experiments were conducted to investigate the effect of both dyes' concentration, contact time, and temperature. Photodegradation experiments for the adsorbed dyes were achieved using ultraviolet light illumination (6 W, λ = 365 nm). The single adsorption isotherms were fitted to the Sips model. The binary adsorption isotherms were fitted using the Extended-Sips model. The results of adsorption isotherms showed that the estimated maximum adsorption uptakes in the binary system were around 140 mg g-1 and 45.5 mg g-1 for ARS and BCG, respectively. In terms of adsorption kinetics, the uptake toward ARS was faster than BCG molecules in which the equilibrium was obtained in 7 min for ARS, while it took 180 min for BCG. Moreover, the thermodynamics results showed that the adsorption process was spontaneous for both anionic dyes. All these macroscopic competitive adsorption results indicate high selectivity toward ARS molecules in the presence of BCG molecules. Additionally, the TiO2 nanoparticles were successfully regenerated using UV irradiation. Moreover, molecular dynamics computational modeling was performed to understand the molecules' optimum coordination, TiO2 geometry, adsorption selectivity, and binary solution adsorption energies. The simulation energies distribution exhibits lower adsorption energies for ARS in the range from - 628 to - 1046 [Formula: see text] for both single and binary systems. In addition to that, the water adsorption energy was found to be between - 42 and - 209 [Formula: see text].

New Synthesis Routes toward Improvement of Natural Filler/Synthetic Polymer Interfacial Crosslinking.

Among the critical issues dictating bio-composite performance is the interfacial bonding between the natural fibers and polymer matrix. In this regard, this article presents new synthesis routes comprising the treatment and functionalization of both date palm powder (DPP) filler and a polypropylene (PP) matrix to enhance filler-polymer adhesion in the newly developed bio-composites. Specifically, four bio-composite forms are considered: untreated DPP filled PP (DPP-UT/PP), treated DPP filled PP (DPP-T/PP), treated DPP filled functionalized PP using 2-isocyanatoethyl methacrylate (DPP-T/PP-g-IEM), and treated and functionalized DPP using 4-toluenesulfonyl chloride filled functionalized PP using 2-acrylamide ((DPP-T)-g-TsCl/PP-g-AcAm). The functional groups created on the surface of synthesized PP-g-IEM react with activated hydroxyl groups attached to the filler, resulting in chemical crosslinking between both components. Similarly, the reaction of TsCl with NH2 chemical groups residing on the mating surfaces of the filler and polymer generates an amide bond in the interface region. Fourier transform infrared spectroscopy (FTIR) is used to confirm the successful coupling between the filler and polypropylene matrix after applying the treatment and functionalization schemes. Owing to the introduced crosslinking, the DPP-T/PP-g-IEM bio-composite exhibits the best mechanical properties as compared to the neat polymer, unfunctionalized polymer-based bio-composite, and (DPP-T)-g-TsCl/PP-g-AcAm counterpart. The applied compatibilizers assist in reducing the water uptake of the manufactured bio-composites, increasing their durability.