Versatile waste wood-chitosan composites for 2,4-D and paraquat adsorption: Isotherm modelling and thermodynamic evaluation.

2,4-dichlorophenoxy acetic acid (2,4-D) and 1,1-dimethyl-4,4-bipiridinium chloride (paraquat) are among the most widely used herbicides and are known to be toxic. Fabrication of green adsorbents which are capable of removing both herbicides remains a challenge. Here, we fabricate a novel adsorbent from tropical waste wood and use a facile, chitosan-mediated N-heteroatom functionalization technique to augment surface nitrogen and improve specific surface area. The addition of 20 wt% chitosan to the waste wood feedstock prior to activation, increased specific surface area by 300 m/g (∼25%) and nitrogen content by 7-fold. This functionalized material removed 69% of 2,4-D and 82% of paraquat at initial concentrations of 4 ppm and 40 ppm from model solutions at pH 7. It also removed 39% 2,4-D and 93% paraquat from binary mixtures demonstrating its versatility. 2,4-D adsorption increased with chitosan addition suggesting synergistic effects between protonated amine functions and the anionic herbicide form. Paraquat adsorption was negatively correlated with chitosan addition, implying antagonistic interaction between protonated amine functions and quaternary nitrogen atoms on herbicide molecules. Adsorption of both herbicides was spontaneous, entropically favored and exothermic with ΔG °: 19.2 kJ/mol and -28.8 kJ/mol; ΔS °: 7.42 and 28.6 J/Kmol and ΔH °: 17.0 kJ/mol and -20.1 kJ/mol for 2,4-D and paraquat respectively. Chitosan addition therefore provides a facile and green alternative for N-heteroatom functionalization, and these nitrogen-doped materials are promising candidates for the removal of multiple herbicides from aqueous systems.