Multi‐Spectroscopic Interrogation of the Spatial Linker Distribution in Defect‐Engineered Metal–Organic Framework Crystals: The [Cu3(btc)2−x(cydc)x] Showcase: The [Cu3(btc)2−x(cydc)x] Showcase
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| Název: | Multi‐Spectroscopic Interrogation of the Spatial Linker Distribution in Defect‐Engineered Metal–Organic Framework Crystals: The [Cu3(btc)2−x(cydc)x] Showcase: The [Cu3(btc)2−x(cydc)x] Showcase |
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| Autoři: | Miguel Rivera‐Torrente, Matthias Filez, Florian Meirer, Bert M. Weckhuysen |
| Přispěvatelé: | Sub Inorganic Chemistry and Catalysis, Inorganic Chemistry and Catalysis |
| Zdroj: | Chemistry CHEMISTRY-A EUROPEAN JOURNAL |
| Informace o vydavateli: | Wiley, 2020. |
| Rok vydání: | 2020 |
| Témata: | ADSORPTION, ZEOLITES, microporous materials, FUNCTIONAL-GROUPS, Organic Chemistry, MORPHOLOGIES, Full Papers, HKUST-1, 01 natural sciences, Catalysis, 0104 chemical sciences, CU-BTC, FT-IR, Chemistry, metal–organic frameworks, Physics and Astronomy, crystal engineering, copper, ACID, Raman spectroscopy, HETEROGENEITY, POROUS COORDINATION-POLYMER, metal-organic frameworks, materials characterization |
| Popis: | In the past few years, defect‐engineered metal–organic frameworks (DEMOFs) have been studied due to the plethora of textural, catalytic, or magnetic properties that can be enhanced by carefully introducing defect sites into the crystal lattices of MOFs. In this work, the spatial distribution of two different non‐defective and defective linkers, namely 1,3,5‐benzenetricarboxylate (BTC) and 5‐cyano‐1,3‐benzenedicarboxylate (CYDC), respectively, has been studied in different DEMOF crystals of the HKUST‐1 topology. Raman micro‐spectroscopy revealed a nonhomogeneous distribution of defect sites within the [Cu3(btc)2−x(cydc)x] crystals, with the CYDC linker incorporated into defect‐rich or defect‐free areas of selected crystals. Additionally, advanced bulk techniques have shed light on the nature of the copper species, which is highly dynamic and directly affects the reactivity of the copper sites, as shown by probe molecule FTIR spectroscopy. Furthermore, electron microscopy revealed the effect of co‐crystallizing CYDC and BTC on the crystal size and the formation of mesopores, further corroborated by X‐ray scattering analysis. In this way we have demonstrated the necessity of utilizing micro‐spectroscopy along with a whole array of bulk spectroscopic techniques to fully describe multicomponent metal–organic frameworks. |
| Druh dokumentu: | Article Other literature type |
| Popis souboru: | application/pdf |
| Jazyk: | English |
| ISSN: | 1521-3765 0947-6539 |
| DOI: | 10.1002/chem.201905645 |
| Přístupová URL adresa: | https://pubmed.ncbi.nlm.nih.gov/31957120 https://lirias.kuleuven.be/3006508 https://www.ncbi.nlm.nih.gov/pubmed/31957120 https://europepmc.org/article/MED/31957120 https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201905645?af=R https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.201905645 https://chemistry-europe.onlinelibrary.wiley.com/doi/pdf/10.1002/chem.201905645 https://dspace.library.uu.nl/handle/1874/410871 https://biblio.ugent.be/publication/01JJY7HH81FBRFCNWZRBX63RYE/file/01JJYA63Q1W3ZKDNC08D3G3BT4 https://biblio.ugent.be/publication/01JJY7HH81FBRFCNWZRBX63RYE http://hdl.handle.net/1854/LU-01JJY7HH81FBRFCNWZRBX63RYE http://doi.org/10.1002/chem.201905645 |
| Rights: | CC BY |
| Přístupové číslo: | edsair.doi.dedup.....a073802137ce585f96b5ac7112d15d42 |
| Databáze: | OpenAIRE |
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Nájsť tento článok vo Web of Science | Abstrakt: | In the past few years, defect‐engineered metal–organic frameworks (DEMOFs) have been studied due to the plethora of textural, catalytic, or magnetic properties that can be enhanced by carefully introducing defect sites into the crystal lattices of MOFs. In this work, the spatial distribution of two different non‐defective and defective linkers, namely 1,3,5‐benzenetricarboxylate (BTC) and 5‐cyano‐1,3‐benzenedicarboxylate (CYDC), respectively, has been studied in different DEMOF crystals of the HKUST‐1 topology. Raman micro‐spectroscopy revealed a nonhomogeneous distribution of defect sites within the [Cu3(btc)2−x(cydc)x] crystals, with the CYDC linker incorporated into defect‐rich or defect‐free areas of selected crystals. Additionally, advanced bulk techniques have shed light on the nature of the copper species, which is highly dynamic and directly affects the reactivity of the copper sites, as shown by probe molecule FTIR spectroscopy. Furthermore, electron microscopy revealed the effect of co‐crystallizing CYDC and BTC on the crystal size and the formation of mesopores, further corroborated by X‐ray scattering analysis. In this way we have demonstrated the necessity of utilizing micro‐spectroscopy along with a whole array of bulk spectroscopic techniques to fully describe multicomponent metal–organic frameworks. |
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| ISSN: | 15213765 09476539 |
| DOI: | 10.1002/chem.201905645 |