2026-04-18T01:22:04Zhttps://recercat.cat/oai/request

oai:recercat.cat:2072/4725512024-11-04T07:01:33Zcom_2072_98col_2072_378192

00925njm 22002777a 4500 dc Carrasco, Sergio author Orcajo, Gisela author Martínez Castillejo, Fernando author Imaz, Inhar author Kavak, Safiyye author Arenas Esteban, Daniel author Maspoch Comamala, Daniel author Bals, Sara author Calleja, Guillermo author Horcajada, Patricia author 2023 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. http://hdl.handle.net/2072/472551 Hf/porphyrin-based metal-organic framework PCN-224 for CO2 cycloaddition with epoxides