Chemical Warfare Agents Detoxification Properties of Zirconium Metal−Organic Frameworks by Synergistic Incorporation of Nucleophilic and Basic Sites Gil-San-Millán, Rodrigo López-Maya, Elena Hall, Morgan Muñoz Padial, Natalia Peterson, Gregory W. DeCoste, Jared B. Rodríguez-Albelo, Luisa Marleny Oltra Ferrero, Juan Enrique Barea Martínez, Elisa María Rodríguez Navarro, Jorge Andrés Nerve agents Catalysis Hydrolysis toxic gases degradation Adsorption Porous coordination framework Phosphotriesterase The authors are grateful to generous funding from Spanish MINECO (CTQ2014-53486-R; CTQ2015-70724-R), EU Feder funding, and the Joint Science and Technology Office for Chemical Biological Defense (JSTO–CBD) under project BA13PHM210. 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. 2026-02-16T08:03:02Z 2026-02-16T08:03:02Z 2017-06-27 journal article Gil-San-Millan, Rodrigo et al. ACS Appl. Mater. Interfaces 2017, 9, 28, 23967–23973. DOI: 10.1021/acsami.7b06341 https://hdl.handle.net/10481/111003 10.1021/acsami.7b06341 eng http://creativecommons.org/licenses/by-nc-nd/4.0/ open access Attribution-NonCommercial-NoDerivatives 4.0 Internacional American Chemical Society