@misc{10481/111003,
year = {2017},
month = {6},
url = {https://hdl.handle.net/10481/111003},
abstract = {The development of protective self-detoxifying materials is an important societal challenge to counteract risk of attacks employing highly toxic chemical warfare agents (CWAs). In this work, we have developed bifunctional zirconium metal−organic frameworks (MOFs) incorporating variable amounts of nucleophilic amino residues by means of formation of the mixed ligand [Zr6O4(OH)4(bdc)6(1−x)(bdc-NH2)6x] (UiO-66-xNH2) and [Zr6O4(OH)4(bpdc)6(1−x)(bpdc-(NH2)2)6x] (UiO-
67-x(NH2)2) systems where bdc = benzene-1,4-dicarboxylate; bdc- NH2= benzene-2-amino-1,4-dicarboxylate; bpdc = 4,4′-biphenyldicarboxylate; bpdc-(NH2)2 = 2,2′-diamino-4,4′-biphenyldicarboxylate and x = 0, 0.25, 0.5, 0.75, 1. In a second step, the UiO-66-xNH2 and UiO-67- x(NH2)2 systems have been postsynthetically modified by introduction of highly basic lithium tert-butoxide (LiOtBu) on the oxohydroxometallic clusters of the mixed ligand MOFs to yield UiO-66-xNH2@LiOtBu and UiO-67-x(NH2)2@LiOtBu materials. The results show that the combination of pre and postsynthetic modifications on these MOF series gives rise to fine-tuning of the catalytic activity toward the hydrolytic degradation of both simulants and real CWAs in unbuffered aqueous solutions. Indeed, UiO-66-0.25NH2@LiOtBu is able to hydrolyze both CWAs simulants (diisopropylfluorophosphate (DIFP), 2-chloroethylethylsulfide (CEES), and real CWAs (soman (GD), sulfur mustard (HD)) quickly in aqueous solution. These results are related to a suitable combination of robustness, nucleophilicity, basicity, and accessibility to the porous framework.},
organization = {Departamento de Química Inorgánica},
organization = {Spanish Ministry MINECO (CTQ2014-53486-R; CTQ2015-70724-R)},
organization = {Joint Science and Technology Office for Chemical Biological Defense (JSTO−CBD) BA13PHM210},
publisher = {American Chemical Society},
keywords = {Nerve agents},
keywords = {Catalysis},
keywords = {Hydrolysis},
keywords = {toxic gases},
keywords = {degradation},
keywords = {Adsorption},
keywords = {Porous coordination framework},
keywords = {Phosphotriesterase},
title = {Chemical Warfare Agents Detoxification Properties of Zirconium Metal−Organic Frameworks by Synergistic Incorporation of Nucleophilic and Basic Sites},
doi = {10.1021/acsami.7b06341},
author = {Gil-San-Millán, Rodrigo and López-Maya, Elena and Hall, Morgan and Muñoz Padial, Natalia and Peterson, Gregory W. and DeCoste, Jared B. and Rodríguez-Albelo, Luisa Marleny and Oltra Ferrero, Juan Enrique and Barea Martínez, Elisa María and Rodríguez Navarro, Jorge Andrés},
}