期刊
ACS APPLIED MATERIALS & INTERFACES
卷 9, 期 28, 页码 23967-23973出版社
AMER CHEMICAL SOC
DOI: 10.1021/acsami.7b06341
关键词
nerve agents; catalysis; hydrolysis; toxic gases; degradation; adsorption; porous coordination frameworks; phosphotriesterase
资金
- Spanish MINECO [CTQ2014-53486-R, CTQ2015-70724-R]
- EU Feder funding
- Joint Science and Technology Office for Chemical Biological Defense (JSTO-CBD) [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-xNH(2)) and [Zr6O4(OH)(4)(bpdc)(6(1-x))(bpdc-(NH2)(2))(6x)] (UiIO67-x(NH2)(2)) systems where bdc = benzene-1,4-dicarboxylate; bdcNH2= 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.S, 0.75, 1. In a second step, the UiO-66-xNH(2) and UiO-67x(NH2)(2) systems have been postsynthetically modified by introduction of highly basic lithium tert-butoxide (LiO1Bu) on the oxohydroxometallic dusters of the mixed ligand MOFs to yield UiO-66-xNH(2)@ 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-66-0.25NH(2)@LiO Bu 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.
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