Untersuchungen zur chemischen Stabilität von Cu3(btc)2 (HKUST‐1) durch N2‐Adsorption, Röntgenpulverdiffraktometrie und EPR‐Spektroskopie

Pöppl, Andreas; Jee, Bettina; Icker, Maik; Hartmann, Martin; Himsl, Dieter

doi:10.1002/cite.201000020

Cited by 14 publications

(13 citation statements)

References 22 publications

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“…Taking into account that the collapse of the HKUST‐1 pore network is caused by hydrolysis, it was also plausible to expect that a dehydration of the resulting non‐porous material could lead to a reconstruction of HKUST‐1. Even so, dehydration experiments in vacuum (100 °C during 3–48 h and 150 °C during 16 h) were not successful in recovering the HKUST‐1 structure (Supporting Information, Figure S1), which is in agreement with previously reported observations . Both of these results pointed towards the need of a minimal amount of solvent in order to provide certain flexibility for the structure to be reconstructed.…”

Section: Resultssupporting

confidence: 89%

Solvent‐Mediated Reconstruction of the Metal–Organic Framework HKUST‐1 (Cu₃(BTC)₂)

Majano

Martin

Hammes

et al. 2014

Adv Funct Materials

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3855 www.MaterialsViews.com wileyonlinelibrary.com IntroductionMetal-organic frameworks (MOFs) are innovative materials built out of metal nodes and organic ligands forming extended, crystalline porous structures. They exhibit remarkable properties (high surface area, defi ned metal sites, and accessible porous structure), which remain unmatched for prospective applications in gas sorption, separation, catalysis and biomedicine. [1][2][3][4][5][6] Nevertheless, up to date their industrial scope has barely breached scaled-up syntheses of a handful of structures. As a result of the characteristic ionic and fl exible nature of their framework, the most signifi cant barrier for MOF application has been their hydrothermal stability, [ 7 ] which directly impacts the fi nal stage of their life cycle. While the stability of some MOF structures can reach temperatures up to 500 °C (e.g., Al-benzenedicarboxylate [ 8 ] and ZIF-8), [ 9 ] extensive research has been focused on delaying their so-far inevitable degradation, with special interest on water-related effects. Explored approaches include use of mixed linkers, [ 10 ] hydrophobization of the linker, [ 11 ] variation of the framework through functionalization, [12][13][14] encapsulation of polyoxometalates, [ 15 ] isolation of crystals from humidity by carbon layers, [ 16 ] generation of interpenetrated structures [ 17 ] and theoretical work on the effect of solvent coordination. [ 18 ] Unfortunately most of these routes raise the operational cost or they are not amenable for industrial application. Thus, a general optimization for any selected application by removing water or just fi nding a compromise between the present of water and a certain degradation degree of the MOF material remains as the only viable route for fi ghting or minimizing its deterioration by humidity.In spite of some reports presenting a rather integral approach for MOF application, [ 19 ] the fi nal and critical step of MOF lifetime has been largely ignored. While porous aluminosilicate materials such as zeolites do not present practically any hazard after their lifetime is exhausted, spent MOF materials would result in a potentially problematic mixture of metallic and aromatic compounds, which would require expensive solvent extraction and work-up. This poses fi nancial and ecological issues deterring their adoption into industrial applications and underlines the urgent need for material recovery strategies after their degradation.A general mechanistic picture of MOF degradation by water has been known for quite some time. [ 7 ] Basically, water molecules gradually coordinate the metal nodes, structurally weakening the framework with increasing coordination and ligand displacement. [ 20 ] Finally, this results in the complete hydrolysis of the metal-linker bond followed by the collapse of the framework, resulting in a material containing the protonated (carboxylic) linker and the metal hydroxide. [ 7,[21][22][23] Such a degradation path has also been verifi ed for HKUST-1 (Cu 3 (BTC) 2 , BTC = 1,...

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Section: Resultssupporting

confidence: 89%

Solvent‐Mediated Reconstruction of the Metal–Organic Framework HKUST‐1 (Cu₃(BTC)₂)

Majano

Martin

Hammes

et al. 2014

Adv Funct Materials

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“…[33,34] It is well-known that massive hydration conditions or water cycles seriously compromise the structure and the performances of HKUST-1. [8,15,21,[35][36][37][38][39][40][41][42][43][44][45] However, only few works face the water degradation issue at atomic scale level.…”

Section: Hkust-1mentioning

confidence: 99%

“…Depending on the water content inside HKUST-1 network, different decomposition products may be observed. [35,43,57,58] One of the most significant identifications of such products has been done by Todaro and co-authors, by the use of EPR spectroscopy. [35] In the following the structural processes taking in HKUST-1 upon interaction with air moisture for a long time will be explained in detail.…”

Section: Details About the Hkust-1 Degradation Processmentioning

confidence: 99%

“…[35] Combining their results with other similar studies, the main stages of the decomposition pathway identified until now are resumed in the following paragraphs. [35,37,43,44,55] First stage: the water adsorption on the Cu sites. As above mentioned, the preferential adsorption site in HKUST-1 is on the copper, and then the first stage is the simple adsorption of the water molecule on the Cu 2+ ions.…”

Section: Details About the Hkust-1 Degradation Processmentioning

confidence: 99%

“…Todaro and co-authors suggested that the E'2(Cu) center is stable enough to be considered the final stage of the decomposition process. [35] In contrast, Pöppl and co-authors [43] have also studied the degradation process occurred in HKUST-1 upon exposure to air moisture, and they individuated a strong similarity between the spectroscopic parameters of the final product of the decomposed HKUST-1 and those of the [Cu(H2O)6] 2+ monomeric complexes. [43,44] For this reason, they suggest that in the final products of the decomposition process of HKUST-1 exposed to air there are coppers completely cut off from the framework and possibly arranged in mononuclear complexes.…”

Section: Reviewmentioning

confidence: 99%

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Water Stability of Metal-Organic Framework HKUST-1

Terracinaa¹,

Buscarino²

2021

General Chemistry

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Metal-organic frameworks (MOFs) are a new class of crystalline porous materials, having wide pores which provide extremely high specific surface areas, larger than those typically observed in more common p orous materials like zeolites or activated carbons. This peculiar property combined with the frequent presence of open-metal sites, makes them very promising for a broad range of applications, spacing from gas storage or separation, drug delivery, toxic air removal, chemical detectors, etc. However, the industrialization of MOFs is still facing difficulties because of their low stability to water or even air moisture, a substance difficult to avoid in applications like those mentioned. Another issue concerning MOF industrialization consists in the low bulk density of the micrometric powder grains, which typically constitute such materials. Unfortunately, their low mechanical stability seems to make difficult even to enhance the packaging by simple mechanical compaction. In this review, we will particularly focus on the current state of art involving the MOF HKUST-1, especially on the degradation process involved when this MOF interacts with water molecules. Furthermore, we will show the connection between water and mechanical stability, bringing to attention of a study where solid tablets of HKUST-1 powder have been realized without any loss of crystallinity or porosity because of an accurate study on the effects of different degree of hydration during the tableting phases. In addition, in order to highlight the causes of damages induced in the framework upon interaction with water, a comparison with other two copper carboxylate MOFs will be shown, namely STAM-1 and STAM-17-OEt, which differ from HKUST-1 uniquely for the organic ligands.

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BTC, btc

Sloby¹

2020

Catalysis From a to Z

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Untersuchungen zur chemischen Stabilität von Cu₃(btc)₂ (HKUST‐1) durch N₂‐Adsorption, Röntgenpulverdiffraktometrie und EPR‐Spektroskopie

Abstract: Kupfertrimesat Cu 3 (btc) 2 , auch bekannt als HKUST-1, ist einer der ältesten und bekannte-

Cited by 14 publications

References 22 publications

Solvent‐Mediated Reconstruction of the Metal–Organic Framework HKUST‐1 (Cu₃(BTC)₂)

Solvent‐Mediated Reconstruction of the Metal–Organic Framework HKUST‐1 (Cu₃(BTC)₂)

Water Stability of Metal-Organic Framework HKUST-1

BTC, btc

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Untersuchungen zur chemischen Stabilität von Cu3(btc)2 (HKUST‐1) durch N2‐Adsorption, Röntgenpulverdiffraktometrie und EPR‐Spektroskopie

Abstract: Kupfertrimesat Cu 3 (btc) 2 , auch bekannt als HKUST-1, ist einer der ältesten und bekannte-

Cited by 14 publications

References 22 publications

Solvent‐Mediated Reconstruction of the Metal–Organic Framework HKUST‐1 (Cu3(BTC)2)

Solvent‐Mediated Reconstruction of the Metal–Organic Framework HKUST‐1 (Cu3(BTC)2)

Water Stability of Metal-Organic Framework HKUST-1

BTC, btc

Contact Info

Product

Resources

About

Untersuchungen zur chemischen Stabilität von Cu₃(btc)₂ (HKUST‐1) durch N₂‐Adsorption, Röntgenpulverdiffraktometrie und EPR‐Spektroskopie

Solvent‐Mediated Reconstruction of the Metal–Organic Framework HKUST‐1 (Cu₃(BTC)₂)

Solvent‐Mediated Reconstruction of the Metal–Organic Framework HKUST‐1 (Cu₃(BTC)₂)