Chemical Warfare Agents Detoxification Properties of Zirconium Metal–Organic Frameworks by Synergistic Incorporation of Nucleophilic and Basic Sites

• DOI: 10.1021/acsami.7b06341
• Publication Date: 2017-06-27T12:43:34Z
• Authors: Rodrigo Gil-San-M...; Elena López-Maya; Morgan Hall; Natalia M. Padial; Gregory W. Peterson; Jared B. DeCoste; L. Marleny Rodríg...; J. Enrique Oltra; Elisa Barea; Jorge A. R. Navarro
• Keywords: 02 engineering and technology; 0210 nano-technology

The development of protective self-detoxifying materials is an important societal challenge to counteract risk attacks employing highly toxic chemical warfare agents (CWAs). In this work, we have developed bifunctional zirconium metal–organic frameworks (MOFs) incorporating variable amounts nucleophilic amino residues by means formation 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 x 0, 0.25, 0.5, 0.75, 1. a second step, UiO-66-xNH2 UiO-67-x(NH2)2 been postsynthetically modified introduction basic lithium tert-butoxide (LiOtBu) on oxohydroxometallic clusters MOFs yield UiO-66-xNH2@LiOtBu UiO-67-x(NH2)2@LiOtBu materials. results show that combination pre postsynthetic modifications these MOF series gives rise fine-tuning catalytic activity toward hydrolytic degradation both simulants real CWAs in unbuffered aqueous solutions. Indeed, UiO-66-0.25NH2@LiOtBu able hydrolyze (diisopropylfluorophosphate (DIFP), 2-chloroethylethylsulfide (CEES), (soman (GD), sulfur mustard (HD)) quickly solution. These are related suitable robustness, nucleophilicity, basicity, accessibility porous framework.