Quaternary ammonium-functionalized rosin-derived resin for the high-performance capture of caramels: Experiments and quantum chemical theory simulations

Abstract

Water contamination caused by discharge of spent washes containing colorants remains controversial. In this study, rosin-derived strongly basic macroporous anion-adsorption resin (RSBMAR) was designed as an advanced adsorbent for scavenging caramel, the most recalcitrant colorant in spent washes. Toxicity tests suggest that RSBMAR is environmentally friendly and hardly threatens aquatic organisms. RSBMAR exhibits outstanding caramel capture efficiency because of its rich target quaternary ammonium (−R4N+) and protonated tertiary amine (−R3NH+) groups, abundant porous structure, large specific surface area, excellent thermal stability, and good sphericity. The caramel adsorption capacity of RSBMAR was 165.86 mg/g and the decolorization efficiency reached 96.75%. After five cycles, the spent RSBMAR maintained a high decolorization rate, indicating excellent renewability. Multiple characterizations indicated that caramel capture was largely mediated by charge interaction between −R4N+/−R3NH+ (RSBMAR) and −RCOO−/−RCOOH (caramel), followed by H-bonds. Quantum chemical theory simulations, including electrostatic potential, local ionization energy, frontier molecular orbitals, and independent gradient model analyses, further visualized caramel capture mechanisms at atomic level. Hirshfeld surface analysis revealed that RSBMAR acts as both an H-bond donor and acceptor during caramel uptake. Dynamic adsorption was performed to treat real wastewater, laying the foundation for the industrial application of RSBMAR.