Enzymatic Modification of Walnut Shell for High-Efficiency Adsorptive Methylene Blue Removal

Developing energy-efficient and environmentally benign synthesis protocols is crucial to agricultural waste-based adsorbent preparation. This study prepared novel walnut shell-derived adsorbents by enzymatic modification using a green process, and the as-prepared material was used for methylene blue (MB) removal from wastewater. The results showed that under the optimized conditions (100 mg L^-1 methylene blue (MB) solution, pH 7, 30 °C, 120 min adsorption time, and 0.14 g adsorbent dosage), WS-1 exhibited an MB removal efficiency of 93.67%, which was only slightly lower than that of WS-2 that was prepared by further carbonization of WS-1 using the low-temperature hydrothermal method (99.01%). Kinetic analysis confirmed WS-1 exhibited pseudo-second-order adsorption kinetics, which were generally similar to those of WS-2. However, the results obtained by the isotherm model followed by the Langmuir model of WS-1 indicated monolayer adsorption involving combined weak chemisorption and physisorption, which was different from the WS-2 (followed the Freundlich model that inferred multilayer chemisorption). In conclusion, this study successfully converted walnut shells, a type of agricultural waste, into functional adsorbents by a novel, simple, and greener enzymatic modification method, thereby achieving dual benefits of waste valorization and wastewater treatment.