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HKUST-1 is a metal-organic framework (MOF) which plays a significant roleboth in applicative and basic fields of research, thanks to its outstandingproperties of adsorption and catalysis but also because it is a referencematerial for the study of many general properties of MOFs. Its metallic groupcomprises a pair of Cu2+ ions chelated by four carboxylate bridges, forming astructure known as paddle-wheel unit, which is the heart of the material.However, previous studies have well established that the paddle-wheel isincline to hydrolysis. In fact, the prolonged exposure of the material tomoisture promotes the hydrolysis of Cu-O bonds in the paddle-wheels, sobreaking the crystalline network. The main objective of the presentexperimental investigation is the determination of the details of thestructural defects induced by this process in the crystal and it has beensuccessfully pursued by coupling the electron paramagnetic resonancespectroscopy with other more commonly considered techniques, as X-raydiffraction, surface area estimation and scanning electron microscopy. Thanksto this original approach we have recognized three stages of the process ofdecomposition of HKUST-1 and we have unveiled the details of the correspondingequilibrium structures of the paddle-wheels at the atomic scale level.

Decomposition Process of Carboxylate MOF HKUST-1 Unveiled at the Atomic Scale Level