Enhanced sonocatalytic degradation of carbamazepine and salicylic acid using a metal-organic framework

Abstract

A metal-organic framework (MOF) was used as a sonocatalyst for ultrasonic (US) processes, to improve the degradation of two selected pharmaceutical active compounds (PhACs); carbamazepine (CBM) and salicylic acid (SA). The intrinsic characteristics of the MOF were characterized using a porosimeter (N₂-BET) and scanning electron microscope (SEM). Various experiments were carried out under conditions with different US frequencies (28 and 1000 kHz), US power densities (45-180 W L^-1), pH conditions (3.5, 7, and 10.5), and temperatures (293, 303, and 313 K) to investigate the degradation rates of the selected PhACs. Improved removal rates of PhACs were demonstrated within 60 min at 28 kHz (46% for SA; 47% for CBM) and 1000 kHz (60% for SA; 99% for CBM) with an MOF concentration of 45 mg L^-1 in the US/MOF system, in comparison to 28 kHz (20% for SA; 25% for CBM) and 1000 kHz (37% for SA; 97% for CBM) under the 'US only' process. The removal of CBM was greater than that of SA under all experimental conditions due to the intrinsic properties of the PhACs. The degradation rates of PhACs are related to the quantity of H₂O₂; degradation is thus mostly affected by OH oxidation, which is generated by the dissociation of water molecules. The advantages of the 'US/MOF system' are as follows: (i) dispersion of MOF by US can improve sites and reactivity with respect to adsorption between the adsorbate (PhACs) and the adsorbent (MOF), and (ii) dispersed MOF acted as additional nuclei for water molecule pyrolysis, leading to the production of more OH. Therefore, based on the synergy indices, which were calculated using the removal rate constants [k₁ (min^-1)] of the pseudo-first order kinetic model, the 'US/MOF system' can potentially be used to treat organic pollutants (e.g., PhACs).

Keywords: Metal-organic framework; Pharmaceuticals; Sonocatalytic degradation; Water treatment.