Thermal post-synthetic modification of Al-MIL-53–COOH : systematic investigation of the decarboxylation and condensation reaction

2012
journal article
article
68
cris.lastimport.wos2024-04-09T19:41:12Z
dc.abstract.enAluminium trimellitate [Al(OH)(BDC–COOH)] $\cdot0.9H_{2}O$ (1), the Al-MIL-53–COOH derivative, was discovered under solvothermal conditions using a high-throughput set-up suitable for microwave (MW)-assisted heating. The compound shows high structural flexibility. The large-pore (lp) form of the framework is obtained under large excess of $H_{2}O$ or after solvothermal treatment with N,N-dimethylformamide upon which [Al(OH)(BDC–COOH)] $\cdot$0.7DMF (2) is obtained. Exposure of the water rich lp form of 1 to ambient conditions leads to the transformation to the narrow-pore (np) form. Thermal activation of both compounds results in the formation of the empty lp form and the activation of 1 was studied in detail by in situ IR-spectroscopy. Depending on the activation temperature and time two post-synthetic modification (PSM) processes are observed: the partial decarboxylation and the formation of acid anhydride groups. Thus at high temperatures and long activation times [Al(OH)(BDC–OCOCO–BDC)$_{x/2}$ (BDC)$_{y}$](x+y= 1) is formed. Upon cooling in air the anhydride functionality still remains intact, but the np form is obtained in air due to the adsorption of $H_{2}O$ molecules. Sorption measurements of 1 confirm a preference for polar gases like $H_{2}O$ and $CO_{2}$ in comparison to $N_{2}$, $H_{2}$, and $CH_{4}$. The $N_{2}$ capacity depends strongly on the degree of decarboxylation.pl
dc.affiliationWydział Chemii : Zakład Chemii Nieorganicznejpl
dc.contributor.authorReimer, Nelepl
dc.contributor.authorGil, Barbara - 128059 pl
dc.contributor.authorMarszałek, Bartosz - 115142 pl
dc.contributor.authorStock, Norbertpl
dc.date.accessioned2015-09-07T11:13:46Z
dc.date.available2015-09-07T11:13:46Z
dc.date.issued2012pl
dc.description.number12pl
dc.description.physical4119-4125pl
dc.description.points35pl
dc.description.volume14pl
dc.identifier.doi10.1039/c2ce06649apl
dc.identifier.eissn1466-8033pl
dc.identifier.urihttp://ruj.uj.edu.pl/xmlui/handle/item/15355
dc.languageengpl
dc.language.containerengpl
dc.rightsDodaję tylko opis bibliograficzny*
dc.rights.licencebez licencji
dc.rights.uri*
dc.subtypeArticlepl
dc.titleThermal post-synthetic modification of Al-MIL-53–COOH : systematic investigation of the decarboxylation and condensation reactionpl
dc.title.journalCrystEngCommpl
dc.typeJournalArticlepl
dspace.entity.typePublication
cris.lastimport.wos
2024-04-09T19:41:12Z
dc.abstract.enpl
Aluminium trimellitate [Al(OH)(BDC–COOH)] $\cdot0.9H_{2}O$ (1), the Al-MIL-53–COOH derivative, was discovered under solvothermal conditions using a high-throughput set-up suitable for microwave (MW)-assisted heating. The compound shows high structural flexibility. The large-pore (lp) form of the framework is obtained under large excess of $H_{2}O$ or after solvothermal treatment with N,N-dimethylformamide upon which [Al(OH)(BDC–COOH)] $\cdot$0.7DMF (2) is obtained. Exposure of the water rich lp form of 1 to ambient conditions leads to the transformation to the narrow-pore (np) form. Thermal activation of both compounds results in the formation of the empty lp form and the activation of 1 was studied in detail by in situ IR-spectroscopy. Depending on the activation temperature and time two post-synthetic modification (PSM) processes are observed: the partial decarboxylation and the formation of acid anhydride groups. Thus at high temperatures and long activation times [Al(OH)(BDC–OCOCO–BDC)$_{x/2}$ (BDC)$_{y}$](x+y= 1) is formed. Upon cooling in air the anhydride functionality still remains intact, but the np form is obtained in air due to the adsorption of $H_{2}O$ molecules. Sorption measurements of 1 confirm a preference for polar gases like $H_{2}O$ and $CO_{2}$ in comparison to $N_{2}$, $H_{2}$, and $CH_{4}$. The $N_{2}$ capacity depends strongly on the degree of decarboxylation.
dc.affiliationpl
Wydział Chemii : Zakład Chemii Nieorganicznej
dc.contributor.authorpl
Reimer, Nele
dc.contributor.authorpl
Gil, Barbara - 128059
dc.contributor.authorpl
Marszałek, Bartosz - 115142
dc.contributor.authorpl
Stock, Norbert
dc.date.accessioned
2015-09-07T11:13:46Z
dc.date.available
2015-09-07T11:13:46Z
dc.date.issuedpl
2012
dc.description.numberpl
12
dc.description.physicalpl
4119-4125
dc.description.pointspl
35
dc.description.volumepl
14
dc.identifier.doipl
10.1039/c2ce06649a
dc.identifier.eissnpl
1466-8033
dc.identifier.uri
http://ruj.uj.edu.pl/xmlui/handle/item/15355
dc.languagepl
eng
dc.language.containerpl
eng
dc.rights*
Dodaję tylko opis bibliograficzny
dc.rights.licence
bez licencji
dc.rights.uri*
dc.subtypepl
Article
dc.titlepl
Thermal post-synthetic modification of Al-MIL-53–COOH : systematic investigation of the decarboxylation and condensation reaction
dc.title.journalpl
CrystEngComm
dc.typepl
JournalArticle
dspace.entity.type
Publication

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