Over the past several years, the term PFAS (per- and polyfluoroalkyl substances) has grown to be emblematic of environmental contamination, garnering public, scientific, and regulatory concern. PFAS are synthesized by two processes, direct fluorination (e.g., electrochemical fluorination) and oligomerization (e.g., fluorotelomerization). More than a megatonne of PFAS is produced yearly, and thousands of PFAS wind up in end-use products. Atmospheric and aqueous fugitive releases during manufacturing, use, and disposal have resulted in the global distribution of these compounds. Volatile PFAS facilitate long-range transport, commonly followed by complex transformation schemes to recalcitrant terminal PFAS, which do not degrade under environmental conditions and thus migrate through the environment and accumulate in biota through multiple pathways. Efforts to remediate PFAS-contaminated matrices still are in their infancy, with much current research targeting drinking water.
Over the past 25 years, microwave (MW) chemistry has moved from a laboratory curiosity to a well-established synthetic technique used in many academic and industrial laboratories around the world. Although the overwhelming number of MW-assisted applications today are still performed on a laboratory (mL) scale, we expect that this enabling technology may be used on a larger, perhaps even production, scale in conjunction with radio frequency or conventional heating. Microwave chemistry is based on two main principles, the dipolar mechanism and the electrical conductor mechanism. The dipolar mechanism occurs when, under a very high frequency electric field, a polar molecule attempts to follow the field in the same alignment. When this happens, the molecules release enough heat to drive the reaction forward. In the second mechanism, the irradiated sample is an electrical conductor and the charge carriers, ions and electrons, move through the material under the influence of the electric field and lead to polarization within the sample. These induced currents and any electrical resistance will heat the sample. This Account summarizes a microwave (MW)-assisted synthetic approach for producing silver nanostructures. MW heating has received considerable attention as a promising new method for the one-pot synthesis of metallic nanostructures in solutions. Researchers have successfully demonstrated the application of this method in the preparation of silver (Ag), gold (Au), platinum (Pt), and gold-palladium (Au-Pd) nanostructures. MW heating conditions allow not only for the preparation of spherical nanoparticles within a few minutes but also for the formation of single crystalline polygonal plates, sheets, rods, wires, tubes, and dendrites. The morphologies and sizes of the nanostructures can be controlled by changing various experimental parameters, such as the concentration of metallic salt precursors, the surfactant polymers, the chain length of the surfactant polymers, the solvents, and the operation reaction temperature. In general, nanostructures with smaller sizes, narrower size distributions, and a higher degree of crystallization have been obtained more consistently via MW heating than by heating with a conventional oil-bath. The use of microwaves to heat samples is a viable avenue for the greener synthesis of nanomaterials and provides several desirable features such as shorter reaction times, reduced energy consumption, and better product yields.
A correlation was developed to estimate the adsorption equilibrium capacity of various adsorbents and organic compounds using a combination of Polanyi potential theory and linear solvation energy relationships (LSERs). Polanyi theory provided the basic mathematical form for the correlation. LSERs were used to normalize the Polanyi theory based on the fundamental interaction forces between the solvent, adsorbate, and adsorbent expected in aqueous-phase adsorption. The correlation was developed using 56 organic compounds and eight adsorbents. The following classes of organic compounds were used: (i) halogenated aliphatics, (ii) aromatics and halogenated aromatics, (iii) polyfunctional organic compounds and (iv) sulfonated aromatics. The adsorbents were (i) three coal-based activated carbons (F-300, F-400, and APA), (ii) one coconut shell based activated carbon (580-26), (iii) one unspecified activated carbon, and (iv) three synthetic polymeric adsorbents (XAD-4, XAD-7, and XEN-563). The proposed correlation, which considers the fundamental solvent−adsorbate−adsorbent interaction forces, showed a significant improvement in predicting the adsorption capacity over a correlation that considered only van der Waals forces. However, the correlations did not predict the adsorption capacities of highly soluble organic compounds such as polysulfonated aromatics and polyfunctional organic compounds.
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