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

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. This article is protected by copyright. All rights reserved.

[1]  Rebecca L. Melen,et al.  An International Study Evaluating Elemental Analysis , 2022, ACS central science.

[2]  M. Gaultois,et al.  Exploring the Role of Cluster Formation in UiO Family Hf Metal-Organic Frameworks with in Situ X-ray Pair Distribution Function Analysis. , 2021, Journal of the American Chemical Society.

[3]  A. Morris,et al.  Defect Level and Particle Size Effects on the Hydrolysis of a Chemical Warfare Agent Simulant by UiO-66. , 2021, Inorganic chemistry.

[4]  C. Ochsenfeld,et al.  Understanding disorder and linker deficiency in porphyrinic zirconium-based metal–organic frameworks by resolving the Zr8O6 cluster conundrum in PCN-221 , 2021, Nature Communications.

[5]  J. Gascón,et al.  The Current Status of MOF and COF Applications. , 2021, Angewandte Chemie.

[6]  Ryan P. Lively,et al.  How Reproducible are Surface Areas Calculated from the BET Equation? , 2021, Advanced materials.

[7]  Yong Lu,et al.  A Low-Strain Potassium-Rich Prussian Blue Analogue Cathode for High Power Potassium-Ion Batteries. , 2021, Angewandte Chemie.

[8]  G. Giri,et al.  Controlling Polymorphism and Orientation of NU-901/NU-1000 Metal–Organic Framework Thin Films , 2020 .

[9]  J. Hupp,et al.  Node-Accessible Zirconium MOFs. , 2020, Journal of the American Chemical Society.

[10]  O. Farha,et al.  A historical overview of the activation and porosity of metal-organic frameworks. , 2020, Chemical Society reviews.

[11]  P. Adelhelm,et al.  How Certain Are the Reported Ionic Conductivities of Thiophosphate-Based Solid Electrolytes? An Interlaboratory Study , 2019, ACS Energy Letters.

[12]  O. Farha,et al.  Controlling the polymorphism and topology transformation in porphyrinic zirconium metal-organic frameworks via mechanochemistry. , 2019, Journal of the American Chemical Society.

[13]  A. Goodwin,et al.  Hidden diversity of vacancy networks in Prussian blue analogues , 2019, Nature.

[14]  M. Biserčić,et al.  The quest for optimal water quantity in the synthesis of metal-organic framework MOF-5 , 2019, Microporous and Mesoporous Materials.

[15]  O. Farha,et al.  Interrogating Kinetic versus Thermodynamic Topologies of Metal-Organic Frameworks via Combined Transmission Electron Microscopy and X-ray Diffraction Analysis. , 2019, Journal of the American Chemical Society.

[16]  Jie Zhu,et al.  Synthesis and Defect Characterization of Phase-Pure Zr-MOFs Based on Meso-tetracarboxyphenylporphyrin. , 2019, Inorganic chemistry.

[17]  C. Lamberti,et al.  Water as a structure-driving agent between the UiO-66 and MIL-140A metal-organic frameworks. , 2019, Chemical communications.

[18]  B. Iversen,et al.  The Chemistry of Nucleation: In Situ Pair Distribution Function Analysis of Secondary Building Units During UiO-66 MOF Formation. , 2019, Chemistry.

[19]  M. Wasielewski,et al.  A concentrated array of copper porphyrin candidate qubits , 2018, Chemical science.

[20]  Zhaohui Li,et al.  Catalysis and photocatalysis by metal organic frameworks. , 2018, Chemical Society reviews.

[21]  Peyman Z. Moghadam,et al.  Engineering new defective phases of UiO family metal–organic frameworks with water , 2018, Journal of Materials Chemistry A.

[22]  Nghia T. Vo,et al.  Control of Metal-Organic Framework Crystallization by Metastable Intermediate Pre-equilibrium Species. , 2018, Angewandte Chemie.

[23]  J. R. Schmidt,et al.  In Situ, Time-Resolved, and Mechanistic Studies of Metal-Organic Framework Nucleation and Growth. , 2018, Chemical reviews.

[24]  Aamod V. Desai,et al.  Guest-Responsive Metal-Organic Frameworks as Scaffolds for Separation and Sensing Applications. , 2017, Accounts of chemical research.

[25]  Marco Taddei,et al.  When defects turn into virtues: the curious case of zirconium-based metal-organic frameworks , 2017 .

[26]  Helge Reinsch,et al.  Synthesis of MOFs: a personal view on rationalisation, application and exploration. , 2017, Dalton transactions.

[27]  M. Wahiduzzaman,et al.  Polymorphous Al-MOFs Based on V-Shaped Linker Molecules: Synthesis, Properties, and in Situ Investigation of Their Crystallization. , 2017, Inorganic chemistry.

[28]  L. Brammer,et al.  Solvent-switchable continuous-breathing behaviour in a diamondoid metal-organic framework and its influence on CO2 versus CH4 selectivity. , 2017, Nature chemistry.

[29]  Wei-Jian Xu,et al.  Controlling Two-Step Phase Transitions and Dielectric Responses by A-Site Cations in Two Perovskite-like Coordination Polymers , 2016 .

[30]  Diego A. Gómez-Gualdrón,et al.  Framework-Topology-Dependent Catalytic Activity of Zirconium-Based (Porphinato)zinc(II) MOFs. , 2016, Journal of the American Chemical Society.

[31]  Hai‐Long Jiang,et al.  Porphyrinic Metal–Organic Framework Catalyzed Heck-Reaction: Fluorescence “Turn-On” Sensing of Cu(II) Ion , 2016 .

[32]  K. Sumida,et al.  Emerging applications of metal–organic frameworks , 2016 .

[33]  T. Verstraelen,et al.  Thermodynamic Insight in the High-Pressure Behavior of UiO-66: Effect of Linker Defects and Linker Expansion , 2016, Chemistry of materials : a publication of the American Chemical Society.

[34]  Hong-Cai Zhou,et al.  Zr-based metal-organic frameworks: design, synthesis, structure, and applications. , 2016, Chemical Society reviews.

[35]  Xiang Jiang,et al.  Solid state reconstructive phase transition from porous supramolecular network to porous coordination polymer. , 2016, Chemical communications.

[36]  J. Bernstein,et al.  Disappearing Polymorphs Revisited , 2015, Angewandte Chemie.

[37]  François-Xavier Coudert,et al.  Defect-dependent colossal negative thermal expansion in UiO-66(Hf) metal-organic framework. , 2015, Physical chemistry chemical physics : PCCP.

[38]  Jihye Park,et al.  A highly stable porphyrinic zirconium metal-organic framework with shp-a topology. , 2014, Journal of the American Chemical Society.

[39]  P. Behrens,et al.  Insight into the mechanism of modulated syntheses: in situ synchrotron diffraction studies on the formation of Zr-fumarate MOF , 2014 .

[40]  C. Serre,et al.  In situ energy-dispersive X-ray diffraction for the synthesis optimization and scale-up of the porous zirconium terephthalate UiO-66. , 2014, Inorganic chemistry.

[41]  J. Fraser Stoddart,et al.  Metal-organic framework thin films composed of free-standing acicular nanorods exhibiting reversible electrochromism , 2013 .

[42]  Dawei Feng,et al.  Construction of ultrastable porphyrin Zr metal-organic frameworks through linker elimination. , 2013, Journal of the American Chemical Society.

[43]  Hong‐Cai Zhou,et al.  Metal-organic frameworks based on previously unknown Zr8/Hf8 cubic clusters. , 2013, Inorganic chemistry.

[44]  Dawei Feng,et al.  An exceptionally stable, porphyrinic Zr metal-organic framework exhibiting pH-dependent fluorescence. , 2013, Journal of the American Chemical Society.

[45]  S. Nguyen,et al.  Vapor-phase metalation by atomic layer deposition in a metal-organic framework. , 2013, Journal of the American Chemical Society.

[46]  Stefan Kaskel,et al.  Zr- and Hf-Based Metal–Organic Frameworks: Tracking Down the Polymorphism , 2013 .

[47]  Shengqian Ma,et al.  Biomimetic catalysis of a porous iron-based metal-metalloporphyrin framework. , 2012, Inorganic chemistry.

[48]  Zhangwen Wei,et al.  Zirconium-metalloporphyrin PCN-222: mesoporous metal-organic frameworks with ultrahigh stability as biomimetic catalysts. , 2012, Angewandte Chemie.

[49]  D. Cascio,et al.  Synthesis, structure, and metalation of two new highly porous zirconium metal-organic frameworks. , 2012, Inorganic chemistry.

[50]  P. Behrens,et al.  Modulated synthesis of Zr-fumarate MOF , 2012 .

[51]  Peter Behrens,et al.  Modulated synthesis of Zr-based metal-organic frameworks: from nano to single crystals. , 2011, Chemistry.

[52]  K. Lillerud,et al.  A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability. , 2008, Journal of the American Chemical Society.

[53]  Gérard Férey,et al.  Flexible porous metal-organic frameworks for a controlled drug delivery. , 2008, Journal of the American Chemical Society.

[54]  Michael Krumrey,et al.  Reproducibility in X-ray reflectometry: results from the first world-wide round-robin experiment , 2008 .

[55]  Michael O’Keeffe,et al.  Exceptional chemical and thermal stability of zeolitic imidazolate frameworks , 2006, Proceedings of the National Academy of Sciences.

[56]  D. Balzar,et al.  Size–strain line-broadening analysis of the ceria round-robin sample , 2004 .

[57]  J. Bauer,et al.  Ritonavir: An Extraordinary Example of Conformational Polymorphism , 2001, Pharmaceutical Research.

[58]  Nicolaas A. Vermeulen,et al.  Best Practices for the Synthesis, Activation, and Characterization of Metal–Organic Frameworks , 2017 .

[59]  Zhangwen Wei,et al.  Metal − Organic Frameworks Based on Previously Unknown Zr 8 / Hf 8 Cubic Clusters , 2013 .

[60]  J. THE GLASS TRANSITION TEMPERATURE OF POLYSTYRENE Results of a round robin test , 2022 .