Tuned to Perfection: Ironing Out the Defects in Metal–Organic Framework UiO-66

Shearer, Greig C.; Chavan, Sachin; Ethiraj, Jayashree; Vitillo, Jenny G.; Svelle, Stian; Olsbye, Unni; Lamberti, Carlo; Bordiga, Silvia; Lillerud, Karl Petter

doi:10.1021/cm501859p

Cited by 718 publications

(781 citation statements)

References 21 publications

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“…Structurally, Ti 5 UiO-66 is isomorphous to UiO-66; however post-synthetic exchange (PSE) 54 has been shown to increase polymer interaction, partially separate charge, increase surface area and further expose Ti (Table S3, ESI). [56][57][58] We propose that Ti 5 UiO-66's exposed Ti IV forms a chelation complex with PIM-1's terminal catechol groups (Figure 4). [59][60][61][62][63] Ti-Catechol complexes are highly stable and are used to bind molecules to titanium and titanium dioxide surfaces.…”

Section: Nano-additive Compatibilitymentioning

confidence: 97%

Physical aging in glassy mixed matrix membranes; tuning particle interaction for mechanically robust nanocomposite films

et al. 2016

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Despite the exceptional separation performance of modern glassy mixed matrix membranes, these materials are not being utilized to improve the performance of existing membrane technologies. Nano-sized additives can greatly enhance separation performance, and have recently been used to overcome age-related performance loss of high performance MMMs. However nano-additives also compromise the structural integrity of films and little is known on how physical aging affects their mechanical properties over time. A solution for both physical aging and mechanical instability is required before these high performance materials can be utilised in industrial membrane applications. Here, we examine physical aging in mixed matrix membranes through mechanical properties and single gas permeation measurements using three glassy polymers, Matrimid® 5218, poly-1-trimethylsilyl-1-propyne (PTMSP), and a Polymer of Intrinsic Microporosity (PIM-1); and a range of nano-scale additives; Silica, PAF-1, UiO-66, and Ti5UiO-66, each previously shown to enhance gas separation performance. We find polymer-additive interactions strongly influence local physical aging and play a key role in determining the overall material properties of glassy nanocomposite films. Strong interface interactions can slow physical aging, and may not correlate to reinforced or age-stable films. Whereas traditionally 'incompatible' nanocomposites exhibit mechanical properties that can improve over time and even outperform their native polymers.Tuning polymer-additive interactions is vital to achieving the physical aging, mechanical stability, and permselectivity requirements of advanced mixed matrix membrane technologies and reducing the enormous global energy cost of separation processes.

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Section: Nano-additive Compatibilitymentioning

confidence: 97%

Physical aging in glassy mixed matrix membranes; tuning particle interaction for mechanically robust nanocomposite films

et al. 2016

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“…51 On the other hand, when the cornerstone already contains another terminal ligand such as chlorine, dissociated water or a monocarboxylate (trifluoro acetate) instead of the original, a terephthalate, their removal by heat treatment becomes theoretically feasible at a temperature compatible with the thermal resistance of UiO-66, assuming a moderate linker vacancy concentration. 55 Vermoortele and co-workers demonstrated that the vacancy concentration per cluster (e.g. the Lewis site concentration) can be controlled from ca.…”

Section: Generation Of Linker Vacanciesmentioning

confidence: 99%

Origin of highly active metal–organic framework catalysts: defects? Defects!

2016

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a This article provides a comprehensive review of the nature of catalytic sites in MOFs. In the last decade, a number of striking studies have reported outstanding catalytic activities of MOFs. In all cases, the authors were intrigued as it was unexpected from the ideal structure. We demonstrate here that (surface) defects are at the origin of the catalytic activities for the reported examples. The vacancy of ligands or linkers systematically generates (surface) terminations which can possibly show Lewis and/or Brønsted acido-basic features. The engineering of catalytic sites at the nodes by the creation of defects (on purpose) appears today as a rational approach for the design of active MOFs. Similarly to zeolite post-treatments, postmodifications of MOFs by linker or metal cation exchange appear to be methods of choice. Despite the mild acidity of defective MOFs, we can account for very active MOFs in a number of catalytic applications which show higher performances than zeolites or benchmark catalysts.

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“…[5a, 6] Ideally,U iO-66 has a2 ,12-connected network with fcu-a topology,t he high connectivity of which allows for several sub-networks (e.g. bcu-a, reo-a,a nd hxg-a network [7] )o rhighly defected frameworks [8] upon connectivity reduction. Moreover,a ccompanied with the reduced connectivity,a vailable coordination sites on Zr 6 clusters can be generated, which is favorable for …”

mentioning

confidence: 99%

An In Situ One‐Pot Synthetic Approach towards Multivariate Zirconium MOFs

Sun

Feng

et al. 2016

Angewandte Chemie

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Chemically highly stable MOFs incorporating multiple functionalities are of great interest for applications under harsh environments.H erein, we presented af acile onepot synthetic strategy to incorporate multiple functionalities into stable Zr-MOFs from mixed ligands of different geometry and connectivity.V ia our strategy,tetratopic tetrakis(4-carboxyphenyl)porphyrin (TCPP) ligands were successfully integrated into UiO-66 while maintaining the crystal structure, morphology,a nd ultrahigh chemical stability of Integrating multi-functionality into metal-organic frameworks (MOFs) has attracted growing attention as it plays ac ritical role in realizing the potential of MOFs for aw ide range of applications.[1] To date,tremendous efforts have been made to develop strategies to incorporate multiple functionalities into MOFs.[2] Among them, mixed-ligand strategies have been extensively studied owing to the straightforward synthesis and preservation of the structural integrity of MOFs.[3] Remarkably,Y aghi and co-workers reported the synthesis of multifunctional MOFs,s o-called multivariate (MTV)-MOFs by mixing ligands and successfully introduced up to eight functionalities into MOF-5.[4] However,m ixedligand strategies generally require the use of ligands of the same geometry and connectivity (e.g.ligand derivatives) that are "indistinguishable" during the formation of MOFs to prevent generating mixed phases,w hich greatly limits the variety of ligand and functionality that can be incorporated into the MOF.I na ddition to the functionality,t he excellent stability is another prerequisite for practical applications of MOFs,especially for those under harsh conditions,inorder to guarantee the integrity of the framework. Although there have been af ew reported examples of MOFs containing mixed ligands of different symmetry and connectivity,t hose MOFs are mostly based on M 2+ metal species,w hich suffer from poor stability under harsh chemical conditions and thus their applications are severely restricted. Herein, we show that through one-pot thermodynamically controlled synthesis, multiple functionalities can be integrated into aZ r-MOF without forming separate domains even when mixing ligands of different size,s ymmetry,a nd connectivity.T he multifunctionalized Zr-MOFs obtained maintain the crystal structure,morphology,and stability of the parent MOF.Owing to the excellent stability of the parent MOF,our multi-functionalized Zr-MOFs exhibit high stability under harsh chemical environments.T herefore,o ur strategy goes beyond the limit of conventional mixed-ligand strategies and expands the diversity of functionality for stable MOFs modification, holding great potentials for exploring the applications of MOFs extensively.In recent years,Z r-MOFs have been intensively investigated owing to their considerably improved stability compared to common Zn/Cu/Cd-based MOFs.[5] Thev ersatile symmetry and connectivity of the Zr 6 cluster make it compatible with many different kinds of organic ligands to form MOFs.H owev...

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Tuned to Perfection: Ironing Out the Defects in Metal–Organic Framework UiO-66

Cited by 718 publications

References 21 publications

Physical aging in glassy mixed matrix membranes; tuning particle interaction for mechanically robust nanocomposite films

Physical aging in glassy mixed matrix membranes; tuning particle interaction for mechanically robust nanocomposite films

Origin of highly active metal–organic framework catalysts: defects? Defects!

An In Situ One‐Pot Synthetic Approach towards Multivariate Zirconium MOFs

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