Switching acidic and basic catalysis through supramolecular functionalization in a porous 3D covalent imine-based material
Luis-Barrerra, Javier (Universidad Autónoma de Madrid. Departamento de Química Orgánica)
Cano, Rafael (Universidad Autónoma de Madrid. Departamento de Química Inorgánica)
Imani-Shakibaei, Ghazaleh (Universidad Autónoma de Madrid. Departamento de Química Orgánica)
Heras-Domingo, Javier (Universitat Autònoma de Barcelona. Departament de Química)
Pérez-Carvajal, Javier (Institut Català de Nanociència i Nanotecnologia)
Imaz, Inhar (Institut Català de Nanociència i Nanotecnologia)
Maspoch Comamala, Daniel (Institut Català de Nanociència i Nanotecnologia)
Solans Monfort, Xavier (Universitat Autònoma de Barcelona. Departament de Química)
Aleman Lara, Jose Julian (Universidad Autónoma de Madrid. Departamento de Química Orgánica)
Mas Balleste, Ruben (Universidad Autónoma de Madrid. Departamento de Química Inorgánica)

Date:	2019
Abstract:	Non-covalent inclusion of small acid and base molecules (CHCOOH and NEt) in an imine structure based on micrometre COF-300 crystals and amorphous nanoparticles results in the facile modulation of their acid-base properties. Such a strategy results in the triggering of acidic/basic catalytic activity of the otherwise inactive materials towards ring-opening epoxide and Knoevenagel condensation reactions. For both reactions, amorphous nanoparticles are better catalysts than micrometre crystals as they exhibit a higher external surface area. The found activities and stability of this supramolecular functionalization are modulated by confinement effects, which are rationalized with the help of DFT calculations. All results obtained suggest that the reactions catalysed by these functionalized materials occur confined to pores closer to the material surface, which makes size-discrimination phenomena possible, and explains the major activity of the nanoparticulated material.
Grants:	Ministerio de Economía y Competitividad RTI2018-095038-B-I00 Ministerio de Economía y Competitividad CTQ2017-89132-P
Note:	Altres ajuts: European Structural Funds (S2018/NMT-4367). Generalitat de Catalunya (SGR XSM is grateful for the Professor Agregat Serra Húnter position). R. C. thanks to CAM for the "Atracción de Talento" fellowship.
Rights:	Tots els drets reservats.
Language:	Anglès
Document:	Article ; recerca ; Versió acceptada per publicar
Subject:	Acid-base property ; Amorphous nanoparticles ; Confinement effects ; External surfaces ; Functionalizations ; Functionalized materials ; Knoevenagel condensation ; Material surface
Published in:	Catalysis science & technology, Vol. 9, issue 21 (Nov. 2019) , p. 6007-6014, ISSN 2044-4761

DOI: 10.1039/c9cy01527b

Postprint 10 p, 1.1 MB

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Research literature > UAB research groups literature > Research Centres and Groups (research output) > Experimental sciences > Catalan Institute of Nanoscience and Nanotechnology (ICN2)
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Articles > Published articles