{"title":"Probing water adsorption and stability under steam flow of Zr-based metal-organic frameworks using 91Zr solid-state NMR spectroscopy","authors":"Athulya Nadol, Florian Venel, Raynald Giovine, Maeva Leloire, Christophe Volkringer, Thierry Loiseau, Christel Gervais, Caroline Mellot-Draznieks, Bertrand Doumert, Julien Trébosc, Olivier Lafon, Frédérique Pourpoint","doi":"10.1039/d4sc04589k","DOIUrl":null,"url":null,"abstract":"The stability of metal-organic frameworks (MOFs) in the presence of water is crucial for a wide range of applications, including the production of freshwater, desiccation, humidity control, heat pumps/chillers and capture and separation of gas. In particular, their stability under steam flow is essential since most industrial streams contain water vapor. Nevertheless, to the best of our knowledge, the stability under steam flow of Zr-based MOFs, which are among the most widely studied MOFs, has not been investigated so far. We explore it herein for three UiO-like Zr-based MOFs built from the same Zr cluster but distinct organic linkers at temperature ranging from 80 to 200 °C. We demonstrate the possibility to acquire their 91Zr NMR spectra using high magnetic field (18.8 T) and low temperature (140 K) and to interpret them by comparing experimental data with NMR parameters calculated by DFT. NMR observation of this challenging isotope combined with more conventional techniques, such as N2 adsorption, X-ray diffraction, IR, 1H and 13C solid-state NMR spectroscopies, provides information on the possible collapse of the MOF framework but also on the adsorption of molecules into the pores. We notably show that UiO-66(Zr) and UiO-66-Fum(Zr) built from terephthalate and fumarate linkers, respectively, are stable over 24 h (and even over 7 days for UiO-66(Zr)) under steam flow at all investigated temperatures, whereas UiO-67-NH2 containing 2-amino-[1,1’-biphenyl]-4,4’-dicarboxylate linker degrades under steam flow at temperature ranging from 80 to 150 °C but is preserved at 200 °C. The lower stability of UiO-67-NH2 stems from its larger pores and its weaker Zr−O coordination bonds, whereas its preservation at 200 °C results from a more limited condensation of water in the pores.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":null,"pages":null},"PeriodicalIF":7.6000,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemical Science","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4sc04589k","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
The stability of metal-organic frameworks (MOFs) in the presence of water is crucial for a wide range of applications, including the production of freshwater, desiccation, humidity control, heat pumps/chillers and capture and separation of gas. In particular, their stability under steam flow is essential since most industrial streams contain water vapor. Nevertheless, to the best of our knowledge, the stability under steam flow of Zr-based MOFs, which are among the most widely studied MOFs, has not been investigated so far. We explore it herein for three UiO-like Zr-based MOFs built from the same Zr cluster but distinct organic linkers at temperature ranging from 80 to 200 °C. We demonstrate the possibility to acquire their 91Zr NMR spectra using high magnetic field (18.8 T) and low temperature (140 K) and to interpret them by comparing experimental data with NMR parameters calculated by DFT. NMR observation of this challenging isotope combined with more conventional techniques, such as N2 adsorption, X-ray diffraction, IR, 1H and 13C solid-state NMR spectroscopies, provides information on the possible collapse of the MOF framework but also on the adsorption of molecules into the pores. We notably show that UiO-66(Zr) and UiO-66-Fum(Zr) built from terephthalate and fumarate linkers, respectively, are stable over 24 h (and even over 7 days for UiO-66(Zr)) under steam flow at all investigated temperatures, whereas UiO-67-NH2 containing 2-amino-[1,1’-biphenyl]-4,4’-dicarboxylate linker degrades under steam flow at temperature ranging from 80 to 150 °C but is preserved at 200 °C. The lower stability of UiO-67-NH2 stems from its larger pores and its weaker Zr−O coordination bonds, whereas its preservation at 200 °C results from a more limited condensation of water in the pores.
期刊介绍:
Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.