Effect of Keggin polyoxometalate on Cu(ii) speciation and its role in the assembly of Cu3(BTC)2 metal-organic framework

HKUST-1 is one of the popular metal-organic frameworks (MOFs). The formation of this MOF is significantly accelerated by adding Keggin polyoxometalate anions to the synthesis solution. In this paper the chemistry behind this observation was investigated. Upon addition of Keggin type H 3PW12O40 heter...

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Autores principales: Bajpe, S.R., Breynaert, E., Mustafa, D., Jobbágy, M., Maes, A., Martens, J.A., Kirschhock, C.E.A.
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Acceso en línea:http://hdl.handle.net/20.500.12110/paper_09599428_v21_n26_p9768_Bajpe
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spelling todo:paper_09599428_v21_n26_p9768_Bajpe2023-10-03T15:53:18Z Effect of Keggin polyoxometalate on Cu(ii) speciation and its role in the assembly of Cu3(BTC)2 metal-organic framework Bajpe, S.R. Breynaert, E. Mustafa, D. Jobbágy, M. Maes, A. Martens, J.A. Kirschhock, C.E.A. Acidic conditions Heteropoly acids Keggin ions Keggin polyoxometalate Keggin-type Metal organic framework Paddle wheels PH measurements Room temperature Synthesis solution XANES measurements Ethanol Hydrolysis Ions Oxides HKUST-1 is one of the popular metal-organic frameworks (MOFs). The formation of this MOF is significantly accelerated by adding Keggin polyoxometalate anions to the synthesis solution. In this paper the chemistry behind this observation was investigated. Upon addition of Keggin type H 3PW12O40 heteropolyacid the speciation of Cu2+ cations in ethanol:H2O mixture drastically changes. Combining EPR and XANES measurements with accurate pH measurements and prediction of Cu2+ hydrolysis provides strong evidence for surface induced hydrolysis and consequent dimerisation of monomeric Cu2+ species on Keggin ions in acidic conditions. This enables paddle wheel formation, hence explaining the instantaneous precipitation of Cu 3(BTC)2 at room temperature and the systematic encapsulation of Keggin ions in its pores. © 2011 The Royal Society of Chemistry. Fil:Jobbágy, M. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_09599428_v21_n26_p9768_Bajpe
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic Acidic conditions
Heteropoly acids
Keggin ions
Keggin polyoxometalate
Keggin-type
Metal organic framework
Paddle wheels
PH measurements
Room temperature
Synthesis solution
XANES measurements
Ethanol
Hydrolysis
Ions
Oxides
spellingShingle Acidic conditions
Heteropoly acids
Keggin ions
Keggin polyoxometalate
Keggin-type
Metal organic framework
Paddle wheels
PH measurements
Room temperature
Synthesis solution
XANES measurements
Ethanol
Hydrolysis
Ions
Oxides
Bajpe, S.R.
Breynaert, E.
Mustafa, D.
Jobbágy, M.
Maes, A.
Martens, J.A.
Kirschhock, C.E.A.
Effect of Keggin polyoxometalate on Cu(ii) speciation and its role in the assembly of Cu3(BTC)2 metal-organic framework
topic_facet Acidic conditions
Heteropoly acids
Keggin ions
Keggin polyoxometalate
Keggin-type
Metal organic framework
Paddle wheels
PH measurements
Room temperature
Synthesis solution
XANES measurements
Ethanol
Hydrolysis
Ions
Oxides
description HKUST-1 is one of the popular metal-organic frameworks (MOFs). The formation of this MOF is significantly accelerated by adding Keggin polyoxometalate anions to the synthesis solution. In this paper the chemistry behind this observation was investigated. Upon addition of Keggin type H 3PW12O40 heteropolyacid the speciation of Cu2+ cations in ethanol:H2O mixture drastically changes. Combining EPR and XANES measurements with accurate pH measurements and prediction of Cu2+ hydrolysis provides strong evidence for surface induced hydrolysis and consequent dimerisation of monomeric Cu2+ species on Keggin ions in acidic conditions. This enables paddle wheel formation, hence explaining the instantaneous precipitation of Cu 3(BTC)2 at room temperature and the systematic encapsulation of Keggin ions in its pores. © 2011 The Royal Society of Chemistry.
format JOUR
author Bajpe, S.R.
Breynaert, E.
Mustafa, D.
Jobbágy, M.
Maes, A.
Martens, J.A.
Kirschhock, C.E.A.
author_facet Bajpe, S.R.
Breynaert, E.
Mustafa, D.
Jobbágy, M.
Maes, A.
Martens, J.A.
Kirschhock, C.E.A.
author_sort Bajpe, S.R.
title Effect of Keggin polyoxometalate on Cu(ii) speciation and its role in the assembly of Cu3(BTC)2 metal-organic framework
title_short Effect of Keggin polyoxometalate on Cu(ii) speciation and its role in the assembly of Cu3(BTC)2 metal-organic framework
title_full Effect of Keggin polyoxometalate on Cu(ii) speciation and its role in the assembly of Cu3(BTC)2 metal-organic framework
title_fullStr Effect of Keggin polyoxometalate on Cu(ii) speciation and its role in the assembly of Cu3(BTC)2 metal-organic framework
title_full_unstemmed Effect of Keggin polyoxometalate on Cu(ii) speciation and its role in the assembly of Cu3(BTC)2 metal-organic framework
title_sort effect of keggin polyoxometalate on cu(ii) speciation and its role in the assembly of cu3(btc)2 metal-organic framework
url http://hdl.handle.net/20.500.12110/paper_09599428_v21_n26_p9768_Bajpe
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