27998-62-5Relevant academic research and scientific papers
Postsynthetic Incorporation of a Singlet Oxygen Photosensitizer in a Metal–Organic Framework for Fast and Selective Oxidative Detoxification of Sulfur Mustard
Howarth, Ashlee J.,Buru, Cassandra T.,Liu, Yangyang,Ploskonka, Ann M.,Hartlieb, Karel J.,McEntee, Monica,Mahle, John J.,Buchanan, James H.,Durke, Erin M.,Al-Juaid, Salih S.,Stoddart, J. Fraser,DeCoste, Jared B.,Hupp, Joseph T.,Farha, Omar K.
, p. 214 - 218 (2017)
A fullerene-based photosensitizer is incorporated postsynthetically into a Zr6-based MOF, NU-1000, for enhanced singlet oxygen production. The structural organic linkers in the MOF platform also act as photosensitizers which contribute to the o
A mixed-ligand strategy regulates thorium-based MOFs
Huang, Zhi-Wei,Hu, Kong-Qiu,Mei, Lei,Kong, Xiang-He,Yu, Ji-Pan,Liu, Kang,Zeng, Li-Wen,Chai, Zhi-Fang,Shi, Wei-Qun
, p. 983 - 987 (2020)
Two novel thorium-based organic frameworks (Th-IHEP-5 and Th-IHEP-6) were assembled from a hexanuclear thorium cluster, porphyrin derivative ligand and linear carboxylic acid ligands via a mixed-ligand strategy. As a stable heterogeneous catalyst, Th-IHEP
Combining Two into One: A Dual-Function H5PV2Mo10O40?MOF-808 Composite as a Versatile Decontaminant for Sulfur Mustard and Soman
Gao, Qi,Huang, Chengcheng,Liu, Jie,Wang, Yong'An,Yu, Jialin,Zhang, Lijuan,Zhong, Yuxu,Zhou, Yuanyuan,Zhou, Yunshan
, (2020)
Due to the unpredictable nature of a battlefield environment, in the simultaneous degradation of sulfur mustard and nerve agents it is preferable to use just one decontaminant. Herein, the new composite HPVMo?MOF-808 (HPVMo = H5PV2Mo10O40) was deliberately synthesized via a simple impregnation method and thoroughly characterized. The results showed that the decontamination rate of the composites (30-40 mg) with optimal HPVMo loadings for HD (4 μL) and GD (4 μL) under ambient conditions was 97.2% (within 120 min) and 90.8% (within 30 min), respectively. Due to the combinational/synergistic effect of MOF-808 and encapsulated homogeneously dispersed HPVMo, the composite can very efficiently oxidize HD to nontoxic products in a single system, while retaining the inherent excellence of MOF-808 in hydrolytically degrading GD. The decontamination process was found to follow first-order reaction kinetics, and the rate constant and half-life of the composite for HD and GD were 0.0231 min-1, 30.13 min and 0.0795 min-1, 8.72 min, respectively. In addition, experimental results in guinea pigs and Kunming mice used as animal models showed that the composite provided effective skin protection against HD and GD, showing great potential for application in skin decontamination and protection.
Rapid Destruction of Two Types of Chemical Warfare Agent Simulants by Hybrid Polyoxomolybdates Modified by Carboxylic Acid Ligands
Hou, Yujiao,An, Haiyan,Zhang, Yumeng,Hu, Tao,Yang, Wei,Chang, Shenzhen
, p. 6062 - 6069 (2018)
Four chain-like hybrid compounds based on mixed carboxylic acid ligands-modified polyoxomolybdates, K2H[(H2O)4M][AsMo6O21(Ala)(PHBA)2]·nH2O 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 (CEES) and diethyl cyanophosphonate (DECP), at room temperature. The catalytic results were analyzed and confirmed by GC-FID, GC-MS, and 1HNMR 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.
A simple and controlled oxidative decontamination of sulfur mustard and its simulants using ozone gas
Ramakrishna,Krishna,Saini, Bijendra,Gopi,Swetha,Chandra Shekar
, p. 965 - 970 (2016)
A simple and efficient oxidative decontamination method was developed for sulfur mustard (HD), a potential chemical warfare agent. The method involves treatment of chemical warfare agent HD and its simulants, i.e., dimethyl sulfide, diethyl sulfide, and 2-chloroethyl ethyl sulfide with ozone gas at ambient conditions in acetonitrile solvent. Ozone gas readily oxidizes sulfur mustard in a controlled manner to give its corresponding nontoxic sulfoxide. This transformation is selective and takes place even at subzero temperatures. The oxidation products of HD and its simulants were monitored and quantified by gas chromatography and gas chromatography–mass spectrometry.
Building a shp: A Rare-Earth Metal-Organic Framework and Its Application in a Catalytic Photooxidation Reaction
Quezada-Novoa, Victor,Titi, Hatem M.,Sarjeant, Amy A.,Howarth, Ashlee J.
, p. 4163 - 4169 (2021)
The design and synthesis of new metal-organic frameworks (MOFs) is important from both a fundamental and application standpoint. In this work, a novel, highly connected rare-earth (RE) MOF with an shp topology is reported, named RE-CU-10 (RE, rare-earth;
A novel polyoxovanadate-based Co-MOF: Highly efficient and selective oxidation of a mustard gas simulant by two-site synergetic catalysis
Dang, Tian-Yi,Li, Xiao-Hui,Liu, Shu-Mei,Liu, Shu-Xia,Lu, Ying,Tian, Hong-Rui,Zhang, Zhong
, p. 12398 - 12405 (2020)
Two novel polyoxovanadate-based metal-organic frameworks (MOFs), [Co(bib)]{V2O6} (V-Co-MOF) and [Ni(en)(bib)]{V2O6}·2H2O (V-Ni-MOF) (bib = 1,4-bis(1H-imidazoly-1-yl)benzene, en = ethylenediamine) were facilely synthesized under mild hydrothermal condition
A homogeneous catalyst for selective O2 oxidation at ambient temperature. Diversity-based discovery and mechanistic investigation of thioether oxidation by the Au(III)Cl2NO3(thioether)/O2 system
Boring,Geletii,Hill
, p. 1625 - 1635 (2001)
A library of inorganic complexes with reversible redox chemistry and/or the ability to catalyze homogeneous oxidations by peroxides, including but not limited to combinations of polyoxometalate anions and redox-active cations, was constructed. Evaluation
V= O Functionalized {Tm2}-Organic Framework Designed by Postsynthesis Modification for Catalytic Chemical Fixation of CO2and Oxidation of Mustard Gas
Chen, Hongtai,Fan, Liming,Hu, Tuoping,Zhang, Xiutang
, p. 5005 - 5013 (2021)
In terms of recently documented references, the introduction of V= O units into porous MOF/COF frameworks can greatly improve their original performance and expand their application prospects due to a change in their electronegativity. In this work, by a cation-exchange strategy, a consummate combination of separate 4f [Tm2(CO2)8] SBUs and 3d [VIVO(H2O)2] units generated the functionalized porous metal-organic framework {(Me2NH2)2[VO(H2O)][Tm2(BDCP)2]·3DMF·3H2O}n (NUC-11), in which [Tm2(CO2)8] SBUs constitute the fundamental 3D host framework of {[Tm2](BDCP)2}n along with [VIVO(H2O)2] units being further docked on the inner wall of channels by covalent bonds. Significantly, NUC-11 represents the first example of V= O modified porous MOFs, in which uncoordinated carboxylic groups (-CO2H) further grasp the functional [VIVO(H2O)2] units on the initial basic skeleton along with the formation of covalent bonds as fixed ropes. Furthermore, activated samples of NUC-11 displayed a good catalytic performance for the chemical synthesis of carbonates from related epoxides and CO2 with high conversion rate. Moreover, by employing NUC-11 as a catalyst, a simulator of mustard gas, 2-chloroethyl ethyl sulfide, could be quickly and efficiently oxidized into low-toxicity products of oxidized sulfoxide (CEESO). Thus, this study offers a brand new view for the design and synthesis of functional-units-modified porous MOFs, which could be potentially applied as an excellent candidate in the growing field of efficient catalysis.
In Situ Ligand-Transformation-Involved Synthesis of Inorganic-Organic Hybrid Polyoxovanadates as Efficient Heterogeneous Catalysts for the Selective Oxidation of Sulfides
Wang, Xiang,Zhang, Tong,Li, Yunhui,Lin, Jiafeng,Li, Huan,Wang, Xiu-Li
, p. 17583 - 17590 (2020)
By intentionally involving in situ ligand transformation in the reaction system, two inorganic-organic hybrid polyoxovanadates (POVs), [Co(HDTBA)V2O6] (1) and [Ni(H2O)2(DTBA)2V2O4(OH)2]·4H2O (2), have been synthesized by using a hydrothermal method, where the 3,5-di[1,2,4]triazol-1-ylbenzoic acid (HDTBA) ligand originated from in situ hydrolysis of 3,5-di[1,2,4]triazol-1-ylbenzonitrile in the self-assembly process. The inorganic layers [Co2(V4O12)]n containing [V4O12]4- circle clusters were linked by HDTBA ligands to yield a 3D framework structure of compound 1. There existed a kind of binuclear [(DTBA)2V2O4(OH)2]2- vanadium cluster grafted directly by two DTBA ligands through the sharing of carboxyl oxygen atoms in compound 2, further extended into a 2D layer by nickel centers. The investigations on the catalytic properties indicated that compounds 1 and 2 as heterogeneous catalysts, especially 2, owned satisfying catalytic performances for catalyzing the selective oxidation of sulfides to sulfoxides in the presence of tert-butyl hydroperoxide as an oxidant, accompanied by excellent conversion of 100% and selectivity of above 99%, providing a promising way for developing inorganic-organic hybrid POVs as effective heterogeneous catalysts for catalyzing the selective oxidation of sulfides.
