Application of a manganese dioxide/amine-functionalized metal-organic framework nanocomposite as a bifunctional adsorbent-catalyst for the room-temperature removal of gaseous aromatic hydrocarbons

Abstract

A high surface area (883 m2·g−1) nanocomposite composed of an amine-functionalized metal–organic framework (NH2-UiO-66 (U6N)) and manganese dioxide (MnO2@U6N) was prepared as bifunctional adsorbent-catalyst for the purification of multiple aromatic volatile organic compounds (VOCs) such as benzene (B), toluene (T), m-xylene (X), and styrene (S), i.e., BTXS. The performance of MnO2@U6N was assessed for BTXS removal both as single- and multi-component systems at room temperature (RT (20 °C)) under dark conditions. MnO2@U6N exhibited superior catalytic-adsorption activity for the RT removal of BTXS. The removal performance of MnO2@U6N against BTXS was then assessed across varying levels of flow rate, VOC concentration, adsorbent/catalyst mass, and relative humidity. To better understand the catalytic-adsorption activity, two types of non-linear kinetic models (pseudo-first-order and pseudo-second-order) were utilized to simulate the experimentally obtained data. In-situ diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS) analysis was also conducted to interpret the removal mechanism of BTXS. Their adsorption capacity (mg·g−1) values are estimated to increase in the order of B (21.1) < T (66.0) < X (79.1) < S (129.7). It is suggested that the adsorbed aromatic VOC molecules on the surface of MnO2@U6N should react with active oxygen species (lattice and adsorbed oxygen) to yield the environmentally benigh end products (i.e., carbon dioxide and water) along with various intermediates (e.g., alkoxides, aldehydes, phenolates, carboxylates, and anhydrides). Accordingly, the VOC removal potential of MnO2@U6N has been validated through the synergistic combination between adsorption (primary process) and catalysis (subordinate process) at RT.