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论文类型：期刊论文
发表时间：2018-07-01
发表刊物：ACS CATALYSIS
收录刊物：SCIE
卷号：8
期号：7
页面范围：6062-6069
ISSN号：2155-5435
关键字：hybrid polyoxomolybdates; carboxylic acids; catalysis; chemical warfare agents; destruction
摘要：Four chain-like hybrid compounds based on mixed carboxylic acid ligands-modified polyoxomolybdates, K2H[(H2O)(4)M] [AsMo6O21(Ala) (PHBA)(2)]center dot nH(2)O 1-4 (M = Co, Ni, Zn, Mn; Ala = alanine; PHBA = p-hydroxybenzonic acid), were prepared and characterized by elemental analysis, IR spectroscopy, solid diffuse reflective spectroscopy, TG analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. Four isostructural compounds 1-4 not only represent the extended architectures constructed from two different organic ligands-modified polyoxometalates but also can rapidly catalyze the degradation of two chemical warfare agent simulants, 2-chloroethyl ethyl sulfide (GEES) and diethyl cyanophosphonate (DECP), at room temperature. The catalytic results were analyzed and confirmed by GC-FID, GC-MS, and (HNMR)-H-1 techniques. Within 5 min, CEES was high-selectively oxidized to the corresponding nontoxic 2-chloroethyl ethyl sulfoxide (CEESO) using heterogeneous catalyst 1 with the oxidant H2O2 (conversion % = 98.5%, selectivity % > 99.9%). FTIR, PXRD techniques, and the following cycles also ascertained the stability and structural integrity of 1 in the oxidation reaction. Within 10 min, DECP can be almost entirely hydrolyzed to the nontoxic products catalyzed by 1 (conversion % = 99.0%). To our knowledge, they are in the rank of highly active catalysts for the degradation of CEES and DECP to date, accompanied by the advantages of steady reuse.