How reproducible is the synthesis of Zr–porphyrin metal–organic frameworks? An interlaboratory study

Hanna L. B. Boström, Sebastian Emmerling, Fabian Heck, Charlotte Koschnick, Andrew J. Jones, Matthew J. Cliffe, Rawan Al Natour, Mickaele Bonneau, Vincent Guillerm, Osama Shekhah, Mohamed Eddaoudi, Javier Lopez-Cabrelles, Shuhei Furukawa, María Romero-Angel, Carlos Martí-Gastaldo, Minliang Yan, Amanda J. Morris, Ignacio Romero-Muñiz, Ying Xiong, Ana E. Platero-PratsJocelyn Roth, Wendy L. Queen, Kalle S. Mertin, Danielle E. Schier, Neil R. Champness, Hamish H.-M. Yeung, Bettina V. Lotsch

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

Abstract

Metal–organic frameworks (MOFs) are a rapidly growing class of materials that offer great promise in various applications. However, the synthesis remains challenging: for example, a range of crystal structures can often be accessed from the same building blocks, which complicates the phase selectivity. Likewise, the high sensitivity to slight changes in synthesis conditions may cause reproducibility issues. This is crucial, as it hampers the research and commercialisation of affected MOFs. Here, we present the first-ever interlaboratory study of the synthetic reproducibility of two Zr–porphyrin MOFs, PCN-222 and PCN-224, to investigate the scope of this problem. For PCN-222, only one sample out of ten was phase pure and of the correct symmetry, while for PCN-224, three were phase pure, although none of these show the spatial linker order characteristic of PCN-224. Instead, these samples resemble dPCN-224 (disordered PCN-224), which was recently reported by us. The variability in thermal behavior, defect content, and BET surface area of the synthesised samples are also studied. Our results have important ramifications for field of metal–organic frameworks and their crystallisation, by highlighting the synthetic challenges associated with a multi-variable synthesis space and flat energy landscapes characteristic of MOFs.
Original languageEnglish (US)
JournalAdvanced Materials
DOIs
StatePublished - Sep 5 2023

Bibliographical note

KAUST Repository Item: Exported on 2023-09-08
Acknowledgements: HLBB acknowledges financial support from the Alexander von Humboldt Foundation. V.Duppel is gratefully acknowledged for collecting the SEM images and S.Krause for use-ful discussions. MJC acknowledges the School of Chemistry, University of Nottingham, for support from the Hobday bequest. AJJ acknowledges funding provided by the EPSRC under grant number :EPSRC/SFICDT in Sustainable Chemistry- Atoms 2 Products (EP/S022236/1). RN, MB, VG,OS and ME acknowledge the support of the King Abdullah University of Science and Technology (KAUST). CMG and MR Aacknowledge FPI Scholarships PRE2018-083327 and MCIN/AEI/10.13039/501100011033 (projects PID2020-118117RB-I00&EUR2021-121999) for funding. Virginia Tech Nanoscale Characterization and Fabrication Laboratory were used for SEM and X.Yang, H.Cornell, M.J.Bortner and Y.Yao are thanked for assistance with analysis. The NCFL facilities are supported by Nano Earth and National Nanotechnology Coordinated Infrastructure who are funded by ECCS1542100 and ECCS2025151. This work was supported by PID2021-123839OB-I00 and EUR2020-112294 funded by MCIN/AEI/10.13039/501100011033 and by the European Union Nex tGeneration EU/PRTR. A.E.P.-P. acknowledges the financial support from the Spanish Ministry of Science and Innovation through the MaríadeMaeztu Programme for Units of Excellence in R&D445(CEX2018-000805-M). A.E.P.-P. acknowledges the Spanish Ministry of Science and Innovation for a Ramón y Cajal fellowship (RYC2018-024328-I).I.R.-M.acknowledges FPI-UAM2019 fellowship fromUAM.We are grateful to N.S to ck(Kiel) fo ruseful discussions. HHMY acknowledges the EPSRC grant EP/W010151/1,.Unlocking the pre-nucleation state as a route to materials discovery in MOFs . NRC gratefully acknowledges the support of the EPSRC(EP/S002995/1).

ASJC Scopus subject areas

  • Mechanics of Materials
  • General Materials Science
  • Mechanical Engineering

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