In situ growth of metal-organic framework HKUST-1 in a polymer monolith as efficient sorbent for Polycyclic Aromatic Hydrocarbons derivatives

MARTÍNEZ PÉREZ-CEJUELA, HECTOR; HERRERO-MARTÍNEZ, JOSÉ MANUEL; SIMÓ-ALFONSO, ERNESTO; GUIÑEZ, MARÍA

Congreso; XXII Reunión de la Sociedad Española de Química Analítica; 2019

Metal-organic frameworks (MOFs) are a type of highly ordered porous coordination polymers composed of inorganic clusters or chains of metal ions linked together by organic ligands in 2D- or 3D-networks. In the last years, they have received great attention as novel attractive materials for its use as stationary phases in the field of separation sciences due to their fascinating properties such as large surface areas, high porosity, chemical tunability and excellent chemical and thermal stability [1, 2]. Despite its good characteristics, the direct use of MOFs as micro-/nanocrystals is somewhat limited since its packing in solid-phase extraction (SPE) cartridges is troublesome and separation in dispersive mode implies centrifugation or filtration steps. To overcome these limitations, an attractive strategy is the combination of MOF particles with other substrate materials such as organic polymer monoliths for its use in sample preparation. This combination would allow the synthesis of hybrid monoliths supports (composites), which incorporate the best features of both materials. Thus, the porous polymer monoliths have distinct advantages of easy in situ preparation, variable chemical properties, and large chemical stability.On the other hand, over the last years, attention has been paid to polycyclic aromatic hydrocarbon derivatives, such as nitrated polycyclic aromatic hydrocarbons (N-PAHs) and oxygenated PAHs (O-PAHs), which are emitted primarily by combustion sources and post-emission transformation of PAHs [3]. Some of these derivatives are more toxic, having a greater threat to human health, than some PAHs, due to their direct-acting mutagenicity and carcinogenicity. For this reason, monitoring trace levels of these analytes in complex samples is relevant, being the development of efficient and selective SPE protocols mandatory.In this work, the in situ synthesis of HKUST-1 onto the surface of organic polymer based on methacrylic acid monolith is described. This composite was applied as SPE sorbent for the extraction and preconcentration of N-PAHs and O-PAHs in aquatic samples. Hybrid polymer was morphologically characterized and its potential as SPE phase to isolate PAH derivatives was evaluated. The analytical properties of interest as extraction sorbent were also established (loading capacity, breakthrough volume, preconcentration capacity, etc.). To our knowledge, this is the first time that a hybrid material, built layer-by-layer self-assembly method, is used as sorbent to extract successfully these pollutants from environmental water samples