Metal-organic frameworks as chemical nanoreactors for the preparation of catalytically active metal compounds

Abstract

[EN] Since the emergence of metal¿organic frameworks (MOFs), a myriad of thrilling properties and applications, in a wide range of fields, have been reported for these materials, which mainly arise from their porous nature and rich host¿guest chemistry. However, other important features of MOFs that offer great potential rewards have been only barely explored. For instance, despite the fact that MOFs are suitable candidates to be used as chemical nanoreactors for the preparation, stabilization and characterization of unique functional species, that would be hardly accessible outside the functional constrained space offered by MOF channels, only very few examples have been reported so far. In particular, we outline in this feature recent advances in the use of highly robust and crystalline oxamato- and oxamidato-based MOFs as reactors for the in situ preparation of well-defined catalytically active single atom catalysts (SACS), subnanometer metal nanoclusters (SNMCs) and supramolecular coordination complexes (SCCs). The robustness of selected MOFs permits the post-synthetic (PS) in situ preparation of the desired catalytically active metal species, which can be characterised by single-crystal X-ray diffraction (SC-XRD) taking advantage of its high crystallinity. The strategy highlighted here permits the always challenging large-scale preparation of stable and well-defined SACs, SNMCs and SCCs, exhibiting outstanding catalytic activities.This work was supported by the MICINN (Spain) (Projects PID2019-104778GB-I00, PID2020-115100GB-I00, and Excellence Unit Maria de Maeztu CEX2019-000919-M) and the Ministero dell Istruzione, dell Universita` e della Ricerca (Italy). The work has also been funded by Generalitat Valenciana, Prometeo Grupos de Investigacio¿n de Excelencia (PROMETEU/2021/ 054). D. A. acknowledges the financial support of the Fondazione CARIPLO/ Economia Circolare: ricerca per un futuro sostenibile 2019, Project code: 2019 2090, MOCA. Thanks are also extended to the 2019 Post-doctoral Junior LeaderRetaining Fellowship, la Caixa Foundation (ID100010434 and fellowship code LCF/BQ/PR19/11700011), the Generalitat Valenciana (SEJI/2020/034) and the Ramo¿n y Cajal program (J. F.-S.). E. P. acknowledges the financial support of the European Research Council under the European Union s Horizon 2020 research and innovation programme/ERC Grant Agreement No 814804, MOF-reactors. This study forms part of the Advanced Materials programme and was supported by MCIN with funding from European Union NextGenerationEU (PRTR-C17.I1) and by Generalitat Valenciana (MFA/2022/048).Escamilla, P.; Guerra, WD.; Leyva Perez, A.; Armentano, D.; Ferrando-Soria, J.; Pardo, E. (2023). Metal-organic frameworks as chemical nanoreactors for the preparation of catalytically active metal compounds. Chemical Communications. 59. https://doi.org/10.1039/d2cc05686k5