Tunable zirconium-based metal organic frameworks synthesis for dibutyl phthalate efficient removal: An investigation of adsorption mechanism on macro and micro scale

The tunable porous structure of metal organic frameworks (MOFs) plays a crucial role in determining their adsorption performance. In this study, we developed and employed a strategy involving monocarboxylic acid assistance to synthesize a series of zirconium-based MOFs (UiO-66-F₄) for the removal of aqueous phthalic acid esters (PAEs). The adsorption mechanisms were investigated by combining batch experiments, characterization and theoretical simulation. By adjusting the affecting factors (i.e., initial concentration, pH values, temperature, contact time and interfering substance), the adsorption behavior was confirmed as a spontaneous and exothermic chemisorption process. The Langmuir model provided a good fit, and the maximum expected adsorption capacity of di-n-butyl phthalate (DnBP) on UiO-66-F₄(PA) was calculated to be 530.42 mg·g^-1. Besides, through carrying out the molecular dynamics (MD) simulation, the multistage adsorption process in the form of DnBP clusters was revealed on a microcosmic scale. The independent gradient model (IGM) method showed the types of weak interactions of inter-fragments or between DnBP and UiO-66-F₄. Furthermore, the synthesized UiO-66-F₄ displayed excellent removal efficiency (>96 % after 5 cycles), satisfactory chemical stability and reusability in the regeneration process. Hence, the modulated UiO-66-F₄ will be regarded as a promising adsorbent for PAEs separation. This work will provide referential significance in tunable MOFs development and actual applications of PAEs removal.