Carrasco, SergioOrcajo, GiselaMartínez, FernandoImaz, InharKavak, SafiyyeArenas-Esteban, DanielMaspoch, DanielBals, SaraCalleja, GuillermoHorcajada, Patricia2023-10-162023-10-162023Sergio Carrasco, Gisela Orcajo, Fernando Martínez, Inhar Imaz, Safiyye Kavak, Daniel Arenas-Esteban, Daniel Maspoch, Sara Bals, Guillermo Calleja, Patricia Horcajada, Hf/porphyrin-based metal-organic framework PCN-224 for CO2 cycloaddition with epoxides, Materials Today Advances, Volume 19, 2023, 100390, ISSN 2590-0498, https://doi.org/10.1016/j.mtadv.2023.1003902590-0498https://hdl.handle.net/10115/24909S.C. acknowledges the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie (MSCA-COFUND) grant agreement No 754382 (GOT Energy Talent). S.C. and P.H. acknowledge “Comunidad de Madrid” and European Regional Development Fund-FEDER 2014-2020-OE REACT-UE 1 for their financial support to VIRMOF-CM project associated to R&D projects in response to COVID-19. The authors acknowledge H2020-MSCA-ITN-2019 HeatNMof (ref. 860942), the M-ERA-NET C-MOF-cell (grant PCI2020-111998 funded by MCIN/AEI /10.13039/501100011033 and European Union NextGenerationEU/PRTR) project, and Retos Investigación MOFSEIDON (grant PID2019-104228RB-I00 funded by MCIN/AEI/10.13039/501100011033) project. This work has been also supported by the Regional Government of Madrid (Project ACES2030-CM, S2018/EMT-4319) and the Universidad Rey Juan Carlos IMPULSO Project (grant MATER M − 3000). S.K acknowledges the Flemish Fund for Scientific Research (FWO Vlaanderen) through a PhD research grant (1181122 N).Herein, we describe for the first time the synthesis of the highly porous Hf-tetracarboxylate porphyrinbased metal-organic framework (MOF) (Hf)PCN-224(M) (M ¼ H2, Co2þ). (Hf)PCN-224(H2) was easily and efficiently prepared following a simple microwave-assisted procedure with good yields (56e67%; spacetime yields: 1100e1270 kg m3 $day1 ), 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 Co2þ 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 CO2 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 CO2, room temperature, 18 e24 h). Twelve epoxides were tested, obtaining from moderate to excellent conversions (35e96%). 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.engAtribución 4.0 Internacionalhttp://creativecommons.org/licenses/by/4.0/MOFHafniumPorphyrinPCNCO2Cycloadditioninfo:eu-repo/semantics/article10.1016/j.mtadv.2023.100390info:eu-repo/semantics/openAccess