Hf/porphyrin-based metal-organic framework PCN-224 for CO2 cycloaddition with epoxides
Carrasco, Sergio (IMDEA Energy Institute)
Orcajo, Gisela (Universidad Rey Juan Carlos)
Martínez Castillejo, Fernando (Universidad Rey Juan Carlos)
Imaz, Inhar (Institut Català de Nanociència i Nanotecnologia)
Kavak, Safiyye (University of Antwerp)
Arenas Esteban, Daniel (University of Antwerp)
Maspoch Comamala, Daniel (Institut Català de Nanociència i Nanotecnologia)
Bals, Sara (University of Antwerp)
Calleja, Guillermo (Universidad Rey Juan Carlos)
Horcajada, Patricia (IMDEA Energy Institute)

Data:	2023
Resum:	Herein, we describe for the first time the synthesis of the highly porous Hf-tetracarboxylate porphyrin-based metal-organic framework (MOF) (Hf)PCN-224(M) (M = H, Co). (Hf)PCN-224(H) was easily and efficiently prepared following a simple microwave-assisted procedure with good yields (56-67%; space-time yields: 1100-1270 kg m·day), high crystallinity and phase purity by using trifluoromethanesulfonic acid and benzoic acid as modulators in less than 30 min. By simply introducing a preliminary step (10 min), 5,10,15,20-(tetra-4-carboxyphenyl)porphyrin linker (TCPP) was quantitatively metalated with Co without additional purification and/or time consuming protection/deprotection steps to further obtain (Hf)PCN-224(Co). (Hf)PCN-224(Co) was then tested as catalyst in CO cycloaddition reaction with different epoxides to yield cyclic carbonates, showing the best catalytic performance described to date compared to other PCNs, under mild conditions (1 bar CO, room temperature, 18-24 h). Twelve epoxides were tested, obtaining from moderate to excellent conversions (35-96%). Moreover, this reaction was gram scaled-up (x50) without significant loss of yield to cyclic carbonates. (Hf)PCN-224(Co) maintained its integrity and crystallinity even after 8 consecutive runs, and poisoning was efficiently reverted by a simple thermal treatment (175 °C, 6 h), fully recovering the initial catalytic activity.
Ajuts:	Agencia Estatal de Investigación PID2019-104228RB-I00 European Commission 754382 European Commission 860942 Agencia Estatal de Investigación PCI2020-111998
Drets:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, fins i tot amb finalitats comercials, sempre i quan es reconegui l'autoria de l'obra original.
Llengua:	Anglès
Document:	Article ; recerca ; Versió publicada
Publicat a:	Materials Today Advances, Vol. 19 (August 2023) , art. 100390, ISSN 2590-0498

DOI: 10.1016/j.mtadv.2023.100390

11 p, 1.9 MB

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