- Postsynthetic Incorporation of a Singlet Oxygen Photosensitizer in a Metal–Organic Framework for Fast and Selective Oxidative Detoxification of Sulfur Mustard
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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
- 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.
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- A mixed-ligand strategy regulates thorium-based MOFs
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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
- 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
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- Combining Two into One: A Dual-Function H5PV2Mo10O40?MOF-808 Composite as a Versatile Decontaminant for Sulfur Mustard and Soman
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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.
- Gao, Qi,Huang, Chengcheng,Liu, Jie,Wang, Yong'An,Yu, Jialin,Zhang, Lijuan,Zhong, Yuxu,Zhou, Yuanyuan,Zhou, Yunshan
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- Rapid Destruction of Two Types of Chemical Warfare Agent Simulants by Hybrid Polyoxomolybdates Modified by Carboxylic Acid Ligands
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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.
- Hou, Yujiao,An, Haiyan,Zhang, Yumeng,Hu, Tao,Yang, Wei,Chang, Shenzhen
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- A simple and controlled oxidative decontamination of sulfur mustard and its simulants using ozone gas
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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.
- Ramakrishna,Krishna,Saini, Bijendra,Gopi,Swetha,Chandra Shekar
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- Building a shp: A Rare-Earth Metal-Organic Framework and Its Application in a Catalytic Photooxidation Reaction
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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;
- Quezada-Novoa, Victor,Titi, Hatem M.,Sarjeant, Amy A.,Howarth, Ashlee J.
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- A novel polyoxovanadate-based Co-MOF: Highly efficient and selective oxidation of a mustard gas simulant by two-site synergetic catalysis
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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
- Dang, Tian-Yi,Li, Xiao-Hui,Liu, Shu-Mei,Liu, Shu-Xia,Lu, Ying,Tian, Hong-Rui,Zhang, Zhong
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- 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
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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
- Boring,Geletii,Hill
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- V= O Functionalized {Tm2}-Organic Framework Designed by Postsynthesis Modification for Catalytic Chemical Fixation of CO2and Oxidation of Mustard Gas
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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.
- Chen, Hongtai,Fan, Liming,Hu, Tuoping,Zhang, Xiutang
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- In Situ Ligand-Transformation-Involved Synthesis of Inorganic-Organic Hybrid Polyoxovanadates as Efficient Heterogeneous Catalysts for the Selective Oxidation of Sulfides
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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.
- Wang, Xiang,Zhang, Tong,Li, Yunhui,Lin, Jiafeng,Li, Huan,Wang, Xiu-Li
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- The reactions of singlet oxygen with β-chlorosulfides. The role of hydroperoxy sulfonium ylides in the oxidative destruction of chemical warfare simulants
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The reactions of singlet oxygen with 2-chloroethyl ethyl sulfide and 3- chlorothiane are reported, In both cases elimination of HCl to produce α,β- unsaturated sulfoxides is observed. The experimental results implicate a hydroperoxy sulfonium ylide as a transition state or intermediate in an E2 or E1cb elimination, respectively.
- Toutchkine, Alexei,Clennan, Edward L.
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- A Polyoxoniobate–Polyoxovanadate Double-Anion Catalyst for Simultaneous Oxidative and Hydrolytic Decontamination of Chemical Warfare Agent Simulants
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A novel double-anion complex, H13[(CH3)4N]12[PNb12O40(VVO)2?(VIV4O12)2]?22 H2O (1), based on bicapped polyoxoniobate and tetranuclear polyoxovanadate was synthesized, characterized by routine techniques and used in the catalytic decontamination of chemical warfare agents. Under mild conditions, 1 catalyzes both hydrolysis of the nerve agent simulant, diethyl cyanophosphonate (DECP) and selective oxidation of the sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES). In the oxidative decontamination system 100 % CEES was transformed selectively to nontoxic 2-chloroethyl ethyl sulfoxide and vinyl ethyl sulfoxide using nearly stoichiometric 3 % aqueous H2O2 with a turnover frequency (TOF) of 16 000 h?1. Importantly, the catalytic activity is maintained even after ten recycles and CEES is completely decontaminated in 3 mins without formation of the highly toxic sulfone by-product. A three-step oxidative mechanism is proposed.
- Dong, Jing,Hu, Jufang,Chi, Yingnan,Lin, Zhengguo,Zou, Bo,Yang, Song,Hill, Craig L.,Hu, Changwen
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- Hollow Lindqvist-like-Shaped {V6} Cluster-Based Metal-Organic Framework for the Highly Efficient Detoxification of Mustard Gas Simulant
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A polyoxovanadate-based nickel-organic framework, [Ni(bib)2]{V2O6}({V6}-MOF, bib = 1,4-bis(1H-imidazoly-1-yl)benzene), was facilely prepared under gentle hydrothermal conditions and structurally characterized. Single-crystal X-ray diffraction analysis ind
- Tian, Hong-Rui,Zhang, Zhong,Dang, Tian-Yi,Liu, Shu-Mei,Lu, Ying,Liu, Shu-Xia
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- Ferrocene-Linkage-Facilitated Charge Separation in Conjugated Microporous Polymers
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Conjugated microporous polymers (CMPs) have full access to the organic synthesis toolbox and feature-rich functionality, structural diversity, and high surface area. We incorporated ferrocene (Fc) into the backbones of CMPs and systematically engineered their optical energy gaps. Compared with the CMPs without Fc units yet adopting a similar molecular orbital level, Fc-based CMPs can sufficiently generate reactive oxygen species (ROS) under visible light. The resultant ROS are able to effectively decompose the absorbed pollutants, including organic dyes and chemical warfare agents. Specifically, Fc-based CMPs significantly outperform commercial TiO2 (P25) in the degradation of methylene blue and are capable of converting 2-chloroethyl ethyl sulfide (a mustard gas simulant) into a completely nontoxic product.
- Ma, Li,Liu, Yilin,Liu, Yi,Jiang, Shuyi,Li, Ping,Hao, Yuchen,Shao, Pengpeng,Yin, Anxiang,Feng, Xiao,Wang, Bo
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- Efficient and selective oxidation of sulfur mustard using singlet oxygen generated by a pyrene-based metal-organic framework
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A pyrene-based metal-organic framework (MOF) NU-1000 was used as a heterogeneous photocatalyst for the degradation of a sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES). Using irradiation from a commercially available and inexpensive ultraviole
- Liu, Yangyang,Buru, Cassandra T.,Howarth, Ashlee J.,Mahle, John J.,Buchanan, James H.,Decoste, Jared B.,Hupp, Joseph T.,Farha, Omar K.
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- Organic reactivity in microemulsion systems
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Sulfides are oxidized at a remarkably fast rate ( 15 s, 23 °C) when dissolved in an oil-in-water microemulsion containing a 2-fold excess of hypochlorite. Sulfoxide is formed exclusively and quantitatively. As much as 1 mL of sulfide can be oxidized by 15 mL of microemulsion. The process is much faster than phase-transfer catalysis and requires no stirring since the microemulsions are homogeneous. The cosurfactant in the microemulsion (a low molecular weight alcohol) is shown to play a central role in the oxidation by acting as an intermediary between the oil-soluble mustard and the water-soluble fact that microemulsions represent a "community" of molecules that function only by virtue of cooperative action. Each of the six componets (water, hydrocarbon, surfactant, oxidant, and sulfide) has its own particular residence site and its own particular role in the reaction. Self-assembly converts what might have been a useless and intractable mixture into a functioning system that destroys objectionable compounds.
- Menger,Elrington
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- Chemoselective Oxidation of Sulfides to Sulfoxides with Urea-Hydrogen Peroxide Complex Catalysed by Diselenide
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A highly selective catalytic oxidation system has been developed for the conversion of sulfides into the corresponding sulfoxides using urea-hydrogen peroxide as stoichiometric oxidant in the presence of a catalytic quantity of diphenyl diselenide.
- Bulman Page, Philip C.,Buckley, Benjamin R.,Elliott, Claire,Chan, Yohan,Dreyfus, Nicolas,Marken, Frank
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- Carbazole-based bis-imidazole ligand-involved synthesis of inorganic-organic hybrid polyoxometalates as electrochemical sensors for detecting bromate and efficient catalysts for selective oxidation of thioether
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Considering the potential application on preparing electrode and catalyst materials of inorganic-organic hybrid polyoxometalates, a bis-imidazole ligand with carbazole as a connector, 3,6-di(1H-imidazol-1-yl)-9H-carbazole (L), was used for preparing inorg
- Li, Huan,Lin, Jiafeng,Wang, Chenying,Wang, Xiang,Wang, Xiuli
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p. 4437 - 4445
(2022/02/21)
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- Electropolymerization of Metal Clusters Establishing a Versatile Platform for Enhanced Catalysis Performance
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Atomically precise metal clusters are attractive as highly efficient catalysts, but suffer from continuous efficiency deactivation in the catalytic process. Here, we report the development of an efficient strategy that enhances catalytic performance by electropolymerization (EP) of metal clusters into hybrid materials. Based on carbazole ligand protection, three polymerized metal-cluster hybrid materials, namely Poly-Cu14cba, Poly-Cu6Au6cbz and Poly-Cu6Ag4cbz, were prepared. Compared with isolated metal clusters, metal clusters immobilizing on a biscarbazole network after EP significantly improved their electron-transfer ability and long-term recyclability, resulting in higher catalytic performance. As a proof-of-concept, Poly-Cu14cba was evaluated as an electrocatalyst for reducing nitrate (NO3?) to ammonia (NH3), which exhibited ≈4-fold NH3 yield rate and ≈2-fold Faraday efficiency enhancement compared to that of Cu14cba with good durability. Similarly, Poly-Cu6Au6cbz showed 10 times higher photocatalytic efficiency towards chemical warfare simulants degradation than the cluster counterpart.
- Cai, Jinmeng,Gong, Chun-Hua,Han, Zhen,Li, Si,Li, Yao,Mak, Thomas C. W.,Wang, Qian-You,Wang, Shan,Wang, Yi-Man,Zang, Shuang-Quan
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supporting information
(2022/01/20)
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- Flow neutralisation of sulfur-containing chemical warfare agents with Oxone: packed bedvs.aqueous solution
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The oxidative neutralisation of sulfur-containing CWAs (yperite and VX simulants) with Oxone has been developed in flow systems. In order to reach full selectivity towards harmless decomposition products, Oxone has to be used either in solid form (blister agent detoxification) or aqueous form (nerve agent detoxification).
- Carrasqueira, Philippe,Chataigner, Isabelle,Delaune, Antonin,Jean, Ludovic,Legros, Julien,Mansour, Sergui,Monbaliu, Jean-Christophe M.,Picard, Baptiste,Renard, Pierre-Yves
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supporting information
p. 2925 - 2930
(2021/05/07)
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- Covalent Organic Frameworks toward Diverse Photocatalytic Aerobic Oxidations
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Photoactive two-dimensional covalent organic frameworks (2D-COFs) have become promising heterogenous photocatalysts in visible-light-driven organic transformations. Herein, a visible-light-driven selective aerobic oxidation of various small organic molecules by using 2D-COFs as the photocatalyst was developed. In this protocol, due to the remarkable photocatalytic capability of hydrazone-based 2D-COF-1 on molecular oxygen activation, a wide range of amides, quinolones, heterocyclic compounds, and sulfoxides were obtained with high efficiency and excellent functional group tolerance under very mild reaction conditions. Furthermore, benefiting from the inherent advantage of heterogenous photocatalysis, prominent sustainability and easy photocatalyst recyclability, a drug molecule (modafinil) and an oxidized mustard gas simulant (2-chloroethyl ethyl sulfoxide) were selectively and easily obtained in scale-up reactions. Mechanistic investigations were conducted using radical quenching experiments and in situ ESR spectroscopy, all corroborating the proposed role of 2D-COF-1 in photocatalytic cycle.
- Liu, Shuyang,Tian, Miao,Bu, Xiubin,Tian, Hua,Yang, Xiaobo
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supporting information
p. 7738 - 7744
(2021/05/07)
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- COVALENT ORGANIC FRAMEWORKS AND APPLICATIONS AS PHOTOCATALYSTS
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Described herein are covalent organic frameworks. The covalent organic frameworks have unique structural and physical properties, which lends them to be versatile in a number of different applications and uses. In one aspect, the covalent organic frameworks are composed of a plurality of fused aromatic groups and electron-deficient chromophores. The covalent organic frameworks are useful as photocatalysts in a number of different applications.
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Paragraph 00146; 00169
(2021/05/21)
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- Immobilized Regenerable Active Chlorine within a Zirconium-Based MOF Textile Composite to Eliminate Biological and Chemical Threats
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The most recent global health crisis caused by the SARS-CoV-2 outbreak and the alarming use of chemical warfare agents highlight the necessity to produce efficient protective clothing and masks against biohazard and chemical threats. However, the developm
- Cheung, Yuk Ha,Ma, Kaikai,Van Leeuwen, Hans C.,Wasson, Megan C.,Wang, Xingjie,Idrees, Karam B.,Gong, Wei,Cao, Ran,Mahle, John J.,Islamoglu, Timur,Peterson, Gregory W.,De Koning, Martijn C.,Xin, John H.,Farha, Omar K.
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supporting information
p. 16777 - 16785
(2021/10/21)
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- Self-assembly of three Ag-polyoxovanadates frameworks for their efficient construction of C–N bond and detoxification of simulant sulfur mustard
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Three imidazole-modified Ag-polyoxovanadates frameworks (APFs) with a controllable molar ratio of Ag+ to polyoxovanadates (POVs) [Ag(IM)2]2V4O12?2Ag(IM)2 (APF-1), [Ag2(1-eIM)sub
- Cui, Yanan,Huang, Xianqiang,Li, Jikun,Shen, Guodong,Xue, Zechun,Yang, Guoping,Yao, Qingxia,Zhang, Yalin,Zhou, Jinhong
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supporting information
(2021/11/18)
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- Two Novel Polyoxometalate-Based Metal-Organic Complexes with Chiral Waugh-Type [MnMo9O32]6- Anions as High-Efficiency Catalytic Oxidative Desulfurization Catalysts
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Two novel polyoxometalates (POMs)-based metal-organic complexes (MOCs) [Co3(4-H2dpye)(MnMo9O32)(H2O)10]·H2O (1) and [Co3(4-H2dpyb)(MnMo9O32)(H2O)12]·4H2O (2) have been designed and synthesized under hydrothermal conditions by introducing the chiral Waugh-
- Liu, Qianqian,Lin, Hongyan,Wang, Xiu-Li,Wang, Xiang,Xu, Na,Tian, Yuan,Yang, Lin,Li, Xiran,Sun, Jiaying
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p. 7015 - 7022
(2021/11/30)
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- Heterometallic CeIV/ VVOxo Clusters with Adjustable Catalytic Reactivities
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Heterometallic CeIV/M oxo clusters are underexplored yet and can benefit from synergistic properties from combining cerium and other metal cations to produce efficient redox catalysts. Herein, we designed and synthesized a series of new Ce12V6 oxo clusters with different capping ligands: Ce12V6-SO4, Ce12V6-OTs (OTs: toluenesulfonic acid), and Ce12V6-NBSA (NBSA: nitrobenzenesulfonic acid). Single crystal X-ray diffraction (SCXRD) for all three structures reveals a Ce12V6 cubane core formulated [Ce12(VO)6O24]18+ with cerium on the edges of the cube, vanadyl capping the faces, and sulfate on the corners. While infrared spectroscopy (IR), ultraviolet-visible spectroscopy (UV-vis), electrospray ionization mass spectrometry (ESI-MS), and proton nuclear magnetic resonance (1H NMR) proved the successful coordination of the organic ligands to the Ce12V6 core, liquid phase 51V NMR and small-angle X-ray scattering (SAXS) confirmed the integrity of the clusters in the organic solutions. Furthermore, functionalization of the Ce12V6 core with organic ligands both provides increased solubility in term of homogeneous application and introduces porosity to the assemblies of Ce12V6-OTs and Ce12V6-NBSA in term of heterogeneous application, thus allowing more catalytic sites to be accessible and improving reactivity as compared to the nonporous and less soluble Ce12V6-SO4. Meanwhile, the coordinated ligands also influenced the electronic environment of the catalytic sites, in turn affecting the reactivity of the cluster, which we probed by the selective oxidation of 2-chloroethyl ethyl sulfide (CEES). This work provides a strategy to make full use of the catalytic sites within a class of inorganic sulfate capped clusters via organic ligand introduction.
- Brunson, Kieran,Colliard, Ian,Farha, Omar K.,Gong, Xinyi,Idrees, Karam B.,Ma, Kaikai,Notestein, Justin M.,Nyman, May,Son, Florencia A.,Wang, Xingjie,Wasson, Megan C.,Wu, Yufang,Xie, Haomiao,Zhang, Xuan
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supporting information
p. 21056 - 21065
(2021/12/17)
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- Preparation of a porphyrin-polyoxometalate hybrid and its photocatalytic degradation performance for mustard gas simulant 2-chloroethyl ethyl sulfide
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By combining 5,10,15,20-tetra(4-chlorine)phenylporphyrin (TClPP) and α-Keggin polyoxometalate H5PV2Mo10O40 (H5PVMo) via a simple ion-exchange method, an organic-inorganic hybrid material [C44H28N4Cl4]1.5[H2PMo10V2O40]·2C2H6O (H2TClPP-H2PVMo) was prepared and thoroughly characterized by a variety of techniques. The homogeneous photocatalytic degradation of 2-chloroethyl ethyl sulfide (CEES) (5 μL) by H2TClPP-H2PVMo (1 × 10?6 mol/L) was studied in methanol and methanol-water mixed solvent (v/v = 1:1), in which the degradation rate of CEES reached 99.52% and 99.14%, respectively. The reaction followed first-order reaction kinetics, and the half-life and kinetic constant in methanol and the mixed solvent were respectively 33.0 min, ?0.021 min?1 and 15.7 min, ?0.043 min?1. Mechanism analysis indicated that under visible light irradiation in the air, CEES was degraded via oxidation and alcoholysis/hydrolysis in methanol and the mixed solvent. O2·? and 1O2 generated by H2TClPP-H2PVMo selectively oxidized CEES into a nontoxic sulfoxide. Singlet oxygen capture experiments showed that H2TClPP-H2PVMo (? = 0.73) had a higher quantum yield of singlet oxygen than TClPP (? = 0.35) under an air atmosphere and visible light irradiation.
- Tao, Fangsheng,Tian, Shubo,Wang, Yong'an,Yang, Ying,Zhang, Lijuan,Zhong, Yuxu,Zhou, Yunshan
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supporting information
(2022/01/03)
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- Effect of crystallographic structure of MnO2 on degradation of 2-CEES
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In this study, four MnO2 samples with different crystallographic structures (α-, β-, δ- and γ-MnO2) were synthesized by the hydrothermal method. The relationship between the characteristics of the four crystalline samples and their degradation ability against 2-chloroethyl ethyl sulfide (2-CEES), a simulant of the chemical warfare agent sulfur mustard, and the relevant reaction mechanism were investigated. Characterization data indicated that the various crystal types displayed different specific surface areas, frequency of lattice defects, amounts of adsorbed/inserted water, and numbers and strength of basic sites. The combined effects of these differences caused different degradation activity in 2-CEES degradation to be observed. The reaction followed pseudo-first-order kinetics, whereby γ-MnO2 exhibited the highest degradation activity. The mechanism of 2-CEES degradation was studied by gas chromatography and infrared spectroscopy methods, and data indicated the key role played by substrate hydrolysis and oxidation in the degradation process.
- Guo, Yueting,Kong, Lingce,Lei, Meiling,Xin, Yi,Zuo, Yanjun,Chen, Wenming
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- A New Hexa-TiIV-Substituted Sandwich-Type Polyoxotungstate: Hydrothermal Synthesis, Structure, and Oxidative Decontamination of Chemical Warfare Agent Simulant
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A new hexa-TiIV-substituted sandwich-type silicotungstate, Na2(H2enMe)4[Ti6(μ-O)9(A-α-SiW9O34H2)2]·16H2O (1, enMe = 1,2-diaminopropane) has been synthesized under mild hydrothermal conditions and characterized by FT-IR spectroscopy, elemental analysis, thermogravimetric analysis, single-crystal and powder X-ray diffraction. Compound 1 contains a dimeric polyoxoanion with two [A-α-SiW9O34]10– Keggin moieties sandwiching a trigonal-prismatic [Ti6(μ-O9)]6+ cluster. The catalytic performance of 1 was evaluated for the oxidative decontamination of chemical warfare agent, i.e. sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES), using H2O2 under ambient conditions, showing that 1 is an excellent catalyst for the rapid and complete transformation from CEES to nontoxic 2-chloroethyl ethyl sulfoxide (CEESO) with 100 % selectivity. In addition, 1 exhibits good stability and recyclability.
- Qin, Dan,Sun, Jun-Jun,Wang, Yue-Lin,Yang, Guo-Yu
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p. 475 - 479
(2020/02/04)
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- A safe and compact flow platform for the neutralization of a mustard gas simulant with air and light
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A low footprint, mobile, robust and frugal chemical neutralization technology is reported for the oxidative neutralization of a mustard gas simulant. It relies on the inherent properties of a highly engineered continuous flow setup and carefully optimized and simple, yet robust, experimental conditions. The neutralization protocol uses only non-toxic, widely available and cheap chemicals. The continuous flow setup integrates a singlet oxygen generator and exploits its oxidative power to neutralize 2-chloroethyl ethyl sulfide (CEES), the most common thioether mustard gas simulant. The flow reactor can be connected to either pressurized oxygen or air and handles CEES as a 1 M solution in EtOH containing a trace amount (0.06 molpercent) of a non-toxic and widely available photosensitizer (Methylene Blue). Upon irradiation with visible light (orange or white light), total and highly selective neutralization towards the corresponding non-toxic sulfoxide (1-chloro-2-(ethylsulfinyl)ethane, CEESO) is obtained with reactor effluents containing less than 1percent of the corresponding potentially toxic sulfone (1-chloro-2-(ethylsulfonyl)ethane, CEESO2). With a low footprint (L × W × H 94 × 42 × 40 cm), this neutralization technology can be equipped on a vehicle for on-site interventions, localized at a neutralization facility or both. This experimental work is also supported with the computational rationalization of the reactivity of CEES towards singlet oxygen.
- Bianchi, Pauline,Emmanuel, Noémie,Legros, Julien,Monbaliu, Jean-Christophe M.
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supporting information
p. 4105 - 4115
(2020/07/30)
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- Supramolecular Porous Organic Nanocomposites for Heterogeneous Photocatalysis of a Sulfur Mustard Simulant
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Efficient heterogeneous photosensitizing materials require both large accessible surface areas and excitons of suitable energies and with well-defined spin structures. Confinement of the tetracationic cyclophane (ExBox4+) within a nonporous anionic polystyrene sulfonate (PSS) matrix leads to a surface area increase of up to 225 m2 g?1 in ExBox?PSS. Efficient intersystem crossing is achieved by combining the spin-orbit coupling associated to Br heavy atoms in 1,3,5,8-tetrabromopyrene (TBP), and the photoinduced electron transfer in a TBP?ExBox4+ supramolecular dyad. The TBP?ExBox4+ complex displays a charge transfer band at 450 nm and an exciplex emission at 520 nm, indicating the formation of new mixed-electronic states. The lowest triplet state (T1, 1.89 eV) is localized on the TBP and is close in energy with the charge separated state (CT, 2.14 eV). The homogeneous and heterogeneous photocatalytic activities of the TBP?ExBox4+, for the elimination of a sulfur mustard simulant, has proved to be significantly more efficient than TBP and ExBox+4, confirming the importance of the newly formed excited-state manifold in TBP?ExBox4+ for the population of the low-lying T1 state. The high stability, facile preparation, and high performance of the TBP?ExBox?PSS nanocomposites augur well for the future development of new supramolecular heterogeneous photosensitizers using host–guest chemistry.
- Atilgan, Ahmet,Beldjoudi, Yassine,Deria, Pravas,Enciso, Alan E.,Hupp, Joseph T.,Roy, Indranil,Stoddart, J. Fraser,Wasielewski, Michael R.,Weber, Jacob A.,Young, Ryan M.,Yu, Jierui
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- Inorganic-organic hybrid polyoxovanadates based on [V4O12]4-or [VO3]22-clusters: Controllable synthesis, crystal structures and catalytic properties in selective oxidation of sulfides
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By rationally controlling hydrothermal conditions, three new inorganic-organic hybrid polyoxovanadates (POVs) [Ni2(1-vIM)7H2O][V4O12]·H2O (1), [Cu2(1-vIM)8][V4O12]·H2O (2) and [Co(1-vIM)H2O][VO3]2 (3) (1-vIM = 1-vinylimidazole) have been synthesized and thoroughly characterized by single X-ray diffraction (SXRD), powder X-ray diffraction (PXRD), infrared spectroscopy (FT-IR), and elemental analyses (EA). Interestingly, complexes 1 and 2 have similar structures including [V4O12]4- clusters; complex 3, however, was isolated as a structure by including the [VO3]22- cluster under a different synthetic condition compared with those of 1 and 2. Both complexes 1 and 2 display an interesting 3D supramolecular structure, and complex 3 shows a 2D two parallel networks supramolecular structure linked by a [Co2O2] unit due to the different coordination environments of the central metals. Three inorganic-organic hybrid POVs asheterogeneous catalysts are active in the selective oxidation of sulfides to produce sulfoxides or sulfones with high conversion and high selectivity (up to 99.5 for sulfoxides and 98.5% for sulfones respectively catalyzed by 1). Complex 1 is also used as catalyst in the oxidative CEES (2-chloroethyl ethyl sulfide, a sulfur mustard simulant) abatement with high activity and selectivity towardthe corresponding sulfoxide. Moreover, complex 1 can be reused at least three times in sulfoxidationreactions without losing its activity.
- Guo, Daigaojie,Han, Yinfeng,He, Guofang,Hu, Changwen,Huang, Xianqiang,Li, Jikun,Wang, Congcong,Wei, Chuanping,Zhang, Jianping
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p. 14148 - 14157
(2020/11/02)
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- Post-synthetically elaborated BODIPY-based porous organic polymers (POPs) for the photochemical detoxification of a sulfur mustard simulant
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Designing new materials for the effective detoxification of chemical warfare agents (CWAs) is of current interest given the recent use of CWAs. Although halogenated borondipyrromethene derivatives (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene or BDP or BODIPY) at the 2 and 6 positions have been extensively explored as efficient photosensitizers for generating singlet oxygen (1 O2) in homogeneous media, their utilization in the design of porous organic polymers (POPs) has remained elusive due to the difficulty of controlling polymerization processes through cross-coupling synthesis pathways. Our approach to overcome these difficulties and prepare halogenated BODIPYbased porous organic polymers (X-BDP-POP where X = Br or I) represents an attractive alternative through post-synthesis modification (PSM) of the parent hydrogenated polymer. Upon synthesis of both the parent polymer, H-BDP-POP, and its post-synthetically modified derivatives, Br-BDP-POP and I-BDP-POP, the BET surface areas of all POPs have been measured and found to be 640, 430, and 400 m2 g-1, respectively. In addition, the insertion of heavy halogen atoms at the 2 and 6 positions of the BODIPY unit leads to the quenching of fluorescence (both polymer and solution-phase monomer forms) and the enhancement of phosphorescence (particularly for the iodo versions of the polymers and monomers), as a result of efficient intersystem crossing. The heterogeneous photocatalytic activities of both the parent POP and its derivatives for the detoxification of the sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES), have been examined; the results show a significant enhancement in the generation of singlet oxygen (1 O2). Both the bromination and iodination of H-BDP-POP served to shorten by 5-fold of the time needed for the selective and catalytic photo-oxidation of CEES to 2-chloroethyl ethyl sulfoxide (CEESO).
- Atilgan, Ahmet,Beldjoudi, Yassine,Cetin, Furkan M.,Cetin, M. Mustafa,Deria, Pravas,Farha, Omar K.,Hupp, Joseph T.,Islamoglu, Timur,Liu, Jian,Stern, Charlotte L.,Stoddart, J. Fraser,Yu, Jierui
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supporting information
p. 18554 - 18564
(2020/12/01)
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- Efficient Catalytic Oxidative Desulfurization toward Thioether and Sulfur Mustard Stimulant by Polyoxomolybdate-Resorcin[4]arene-Based Metal-Organic Materials
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The design and synthesis of effective and recyclable oxidative desulfurization catalysts is of great importance in view of environmental protection and human health. Herein, a family of polyoxomolybdate-based inorganic-organic hybrid materials, namely, [Mn(TMR4A)(H2O)4][Mo6O19]·0.5CH3CH2OH·H2O (1), [Ni(TMR4A)(H2O)4][Mo6O19]·0.5CH3CH2OH·H2O (2), [Zn(TMR4A)(H2O)4][Mo6O19]·0.5CH3CH2OH·H2O (3), and [Co2(TMR4A)2(H2O)4(β-Mo8O26)]·CH3CN·12H2O (4), were assembled by the functionalized resorcin[4]arene ligand (TMR4A) with polyoxomolybdate and metal ions under solvothermal conditions. In isostructural 1-3, the [M(TMR4A)(H2O)4]2+ species (M = MnII, NiII, ZnII) and [Mo6O19]2- anions are held together via C-H···O hydrogen bonds to give a 3D supramolecular architecture. In 4, two [Co(TMR4A)(H2O)2]2+ cations were linked by one [β-Mo8O26]4- anion to produce an attractive molecular dimer. Remarkably, 1-4, as recyclable heterogeneous catalysts, exhibit efficient catalytic oxidation desulfurization activities toward thioethers. Particularly, 1, as a representative example, features selective catalytic oxidation for sulfur mustard simulant. Moreover, their electrochemical properties were also studied.
- Guo, Ting-Ting,Ma, Jian-Fang,Yang, Jin,Yu, Ming-Yue
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supporting information
(2020/04/02)
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- Self-assembly of polyoxovanadate-capped polyoxoniobates and their catalytic decontamination of sulfur mustard simulants
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We report the synthesis and characterization of two discrete vanadoniobates, H6Cs4Na5K7[V5Nb23O80]·28H2O (1) and H6Cs4Na5K8[V6Nb23O81]·34H2O (2), based on a brand new {Nb23} and a 5/6-nuclear polyoxovanadate cap. The two vanadoniobates as heterogeneous catalysts can effectively promote the oxidative decontamination of sulfur mustard simulants. This journal is
- Zhen, Ni,Dong, Jing,Lin, Zhengguo,Li, Xiaoxia,Chi, Yingnan,Hu, Changwen
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supporting information
p. 13967 - 13970
(2020/11/20)
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- A dual-function all-inorganic intercluster salt comprising the polycation ?-[Al13O4(OH)24(H2O)12]7+and polyanion α-[PMo10V2O40]5-for detoxifying sulfur mustard and soman
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?-[Al13O4(OH)24(H2O)12]7+, which shares similarity with the phosphotriesterase active site ZnII-OH-ZnII, was specially chosen to interact with the cluster α-PMo10V2O405- to form a new three-dimensional intercluster, which crystallized in the monoclinic space group P21/m with Z = 2, for the decontamination of chemical warfare agents. The experimental results showed that 50 mg of the compound decontaminated 96.4percent (within 120 min) and 99.5percent (within 40 min) of sulfur mustard (HD) (4 μL) and soman (GD) (4 μL), respectively, in ambient conditions. The decontamination processes followed first-order reaction kinetics with a rate constant and half-life of 0.01234 min-1 and 56.15 min for HD and 0.1198 min-1 and 5.78 min for GD, respectively. It was concluded that the α-PMo10V2O405- moiety was responsible for the catalytic oxidation of HD into non-toxic sulfoxide, while the ?-[Al13O4(OH)24(H2O)12]7+ moiety was responsible for the catalytic hydrolysis of HD and GD into nontoxic hydrolysates. Besides, the compound showed notable efficacy for the decontamination of HD on guinea pig skin and of GD on Kunming mouse skin, indicating high potential for use in human skin protection and treatment. This journal is
- Gao, Qi,Tao, Fangsheng,Wang, Yong'An,Yin, Jianbo,Yu, Jialin,Zhang, Lijuan,Zhong, Yuxu,Zhou, Yuanyuan,Zhou, Yunshan
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p. 8122 - 8135
(2020/07/10)
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- Mono-transition-metal-substituted polyoxometalate intercalated layered double hydroxides for the catalytic decontamination of sulfur mustard simulant
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The Keggin-type mono-transition-metal-substituted [PW11M(H2O)O39]5? (PW11M, M = Ni, Co, Cu) were intercalated into Zn2Cr-based layered double hydroxide (Zn2Cr-LDH) by an exfoliation-reassembly method and the synthesized Zn2Cr-LDH-PW11M composites were thoroughly characterized by Fourier transform infrared (FT-IR) spectroscopy, powder X-ray diffraction (PXRD), solid state 31P nuclear magnetic resonance (31P NMR) spectroscopy, thermogravimetric analysis (TGA), inductively coupled plasma atomic emission spectroscopy (ICP-AES), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The three composites can be used as heterogeneous catalysts to promote the oxidative decontamination of the sulfur mustard simulant 2-chloroethyl ethyl sulfide (CEES). Interestingly, a cooperative effect between the PW11M cluster and Zn2Cr-LDH is evidenced by the fact that the composites have a higher catalytic performance than either of the individual constituents alone. The catalytic activity of Zn2Cr-LDH-PW11M is significantly influenced by the substituted transition metals, showing the order: Zn2Cr-LDH-PW11Ni > Zn2Cr-LDH-PW11Co > Zn2Cr-LDH-PW11Cu. Under ambient conditions, the Zn2Cr-LDH-PW11Ni composite can convert 98% of CEES in 3 h using nearly stoichiometric 3% aqueous H2O2 with the selectivity of 94% for the nontoxic product 2-chloroethyl ethyl sulfoxide (CEESO). Moreover, the decontaminating material, Zn2Cr-LDH-PW11Ni, is stable to leaching and can be readily reused for up to ten cycles without obvious loss of its activity.
- Sun, Xiangrong,Dong, Jing,Li, Zhen,Liu, Huifang,Jing, Xiaoting,Chi, Yingnan,Hu, Changwen
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supporting information
p. 5285 - 5291
(2019/04/26)
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- Porphyrinic Silver Cluster Assembled Material for Simultaneous Capture and Photocatalysis of Mustard-Gas Simulant
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Silver cluster-assembled materials (SCAMs), by virtue of their tunable structure, accessible surface area and excellent stability, hold great promise as highly efficient catalysts. Herein, we report a new SCAM [Ag12(StBu)6
- Cao, Man,Pang, Rui,Wang, Qian-You,Han, Zhen,Wang, Zhao-Yang,Dong, Xi-Yan,Li, Shun-Fang,Zang, Shuang-Quan,Mak, Thomas C. W.
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supporting information
p. 14505 - 14509
(2019/09/10)
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- A versatile and recyclable molecularly imprinted polymer as an oxidative catalyst of sulfur derivatives: A new possible method for mustard gas and v nerve agent decontamination
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A molecularly imprinted polymer containing a porphyrin unit was developed as a biomimetic heterogenous catalyst for the oxidation of sulfur derivatives. Its catalytic efficiency under mild conditions and its easy recovery represent a great asset for the design of new decontamination tools for yperite and VX.
- Mohamed, Sophie,Balieu, Sébastien,Petit, Emilie,Galas, Ludovic,Schapman, Damien,Hardouin, Julie,Baati, Rachid,Estour, Fran?ois
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supporting information
p. 13243 - 13246
(2019/11/16)
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- Stabilization of an Unprecedented Hexanuclear Secondary Building Unit in a Thorium-Based Metal-Organic Framework
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The crystal structures of thorium clusters are important for understanding the formation and transformation mechanisms of actinide species in solution, which can in turns benefit nuclear waste processing and management. However, stabilizing thorium clusters in aqueous solution is quite challenging because of their fast olation and oxolation reactions. Here, we report a thorium-based metal-organic framework, NU-905, with the formula [Th6(μ3-O)2(HCOO)4(H2O)6(TCPP)4] [TCPP = tetrakis(4-carboxyphenyl)porphyrin], synthesized by a solvothermal reaction in N,N-dimethylformamide and water at 120 °C. NU-905 contains a hexanuclear secondary building unit (SBU), [Th6(μ3-O)2(HCOO)4(H2O)6], which has never been reported previously. The SBUs are capped and bridged by the tetratopic linker TCPP to form a three-dimensional network with scu topology. The activated NU-905 exhibits permanent porosity and shows high catalytic activity for the selective photooxidation of a mustard gas simulant.
- Li, Peng,Goswami, Subhadip,Otake, Ken-Ichi,Wang, Xingjie,Chen, Zhijie,Hanna, Sylvia L.,Farha, Omar K.
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supporting information
p. 3586 - 3590
(2019/04/05)
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- Versatile catalysts constructed from hybrid polyoxomolybdates for simultaneously detoxifying sulfur mustard and organophosphate simulants
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Chemical warfare agents (CWAs) containing sulfur mustard and organophosphates are among the most toxic materials known to mankind and have caused lots of casualties during wars and terrorist attacks. Development of catalysts with selective oxidation and hydrolysis abilities for detoxification of these two types of CWAs is highly desired. Here, we report a series of carboxylic acid modified polyoxomolybdate derivatives with high catalytic performance in the degradation two typical chemical warfare agent simulants: 2-chloroethyl ethyl sulfide (CEES) and diethyl cyanophosphonate (DECP), at room temperature. Our results demonstrate that CEES can be highly-selectively degraded to the corresponding far less toxic 2-chloroethyl ethyl sulfoxide (CEESO) with the oxidant H2O2 within 12 minutes, and DECP is almost completely hydrolysed to nontoxic products within 10 minutes. The catalytic activities of these compounds were found to be influenced by the metal cations, carboxylic acid ligands and heteroatoms of polyoxoanions. The corresponding order is respectively Co2+ > Ni2+, Zn2+, Mn2+; PABA > Ala, Ac; AsMo > TeMo.
- Hou, Yujiao,An, Haiyan,Chang, Shenzhen,Zhang, Jie
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p. 2445 - 2455
(2019/06/13)
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- Destruction of chemical warfare agent simulants by air and moisture stable metal NHC complexes
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The cooperative effect of both NHC and metal centre has been found to destroy chemical warfare agent (CWA) simulants. Choice of both the metal and NHC is key to these transformations as simple, monodentate N-heterocyclic carbenes in combination with silver or vanadium can promote stoichiometric destruction, whilst bidentate, aryloxide-tethered NHC complexes of silver and alkali metals promote breakdown under mild heating. Iron-NHC complexes generated in situ are competent catalysts for the destruction of each of the three targetted CWA simulants.
- Weetman, Catherine,Notman, Stuart,Arnold, Polly L.
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supporting information
p. 2568 - 2574
(2018/02/28)
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- Highly Efficient and Selective Photooxidation of Sulfur Mustard Simulant by a Triazolobenzothiadiazole-Moiety-Functionalized Metal-Organic Framework in Air
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A photoactive triazolobenzothiadiazole (TBTD)-conjugated terphenyldicarboxylate (TPDC) linker was introduced into a porous and robust UiO-68 isoreticular zirconium metal-organic framework (denoted as UiO-68-TBTD) by the de novo synthetic approach of mixed TPDC struts. Under blue-light-emitting-diode irradiation, UiO-68-TBTD can serve as a heterogeneous photocatalyst for the highly efficient and selective oxidation of a sulfur mustard simulant (2-chloroethyl ethyl sulfide) to the corresponding much less toxic sulfoxide product, with a half-life of only 3 min in the open air atmosphere.
- Zhang, Wen-Qiang,Cheng, Ke,Zhang, He,Li, Qiu-Yan,Ma, Zheng,Wang, Zixuan,Sheng, Jialing,Li, Yinwei,Zhao, Xinsheng,Wang, Xiao-Jun
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supporting information
p. 4230 - 4233
(2018/04/23)
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- Thermally induced migration of a polyoxometalate within a metal-organic framework and its catalytic effects
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The polyoxometalate (POM), H3PW12O40, was postsynthetically incorporated into the metal-organic framework (MOF), NU-1000. The POM@MOF composite, PW12@NU-1000, was activated under mild conditions, resulting in a material whose diffraction pattern and spectroscopic properties differ from the same material heated at elevated temperatures. These discrepancies, corroborated by difference envelope density analyses, were attributed to the POM residing either in the mesoporous or microporous channels of NU-1000. As a testament to the importance of catalyst accessibility, the POM's locational change also induced a change in the composite's rate and selectivity toward oxidizing 2-chloroethyl ethyl sulfide.
- Buru, Cassandra T.,Platero-Prats, Ana. E.,Chica, Daniel G.,Kanatzidis, Mercouri G.,Chapman, Karena W.,Farha, Omar K.
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supporting information
p. 7389 - 7394
(2018/05/14)
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- Oxidation studies on mustard gas, and the first crystal structure of a metal-mustard gas complex
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Attempts to selectively oxidize mustard gas [(ClCH2CH2)2S, abbreviated as BCES] to the non-toxic sulfoxide using a trans-Ru(TMP)(O)2/O2 catalyst (TMP = porphyrin dianion of 5,10,15,20-tetramesitylporphyrin) have led to isolation and characterization, including an X-ray structure, of trans-Ru(TMP)(BCES)2, the first such report of a metal-mustard gas complex.
- Rajapakse, Nimal,Mehraban, Shahram,Pacheco, Andrew,Patrick, Brian O.,James, Brian R.
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- Oxidative Detoxification of Sulfur-Containing Chemical Warfare Agents by Electrophilic Iodine
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Mild oxidation of sulfur-containing chemical warfare agents was performed in organic medium by electrophilic iodine reagents. Kinetic experiments on sulfur mustard (HD) showed rapid (t1/2 1/2 ~ 90 min). Higher donor number solvents, such as THF, DMF, or DMSO, showed slower rates with both iodine and NIS. The oxidation of the nerve agent O-ethyl-S-2-(N,N-diisopropylaminoethyl)methylphosphonothioate (VX) selectively to the nontoxic ethyl methylphosphonic acid product exhibited fast rates (t1/2 = 6 min) using NIS in DMSO solution. In all other solvents tested with VX, rates were slower (t1/2 ~ 30-70 min). Oxidation experiments under the same conditions with chloroethyl ethyl sulfide (HD simulant) and O,S-diethyl methylphosphonothioate (VX simulant) led to much faster reaction rates. These transformations are believed to proceed through electrophilic iodine attack on the sulfur moiety and display solvent dependency based on the agents' structural and chemical properties.
- Smolkin, Boris,Levi, Noam,Karton-Lifshin, Naama,Yehezkel, Lea,Zafrani, Yossi,Columbus, Ishay
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supporting information
p. 13949 - 13955
(2018/11/30)
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- A Versatile Self-Detoxifying Material Based on Immobilized Polyoxoniobate for Decontamination of Chemical Warfare Agent Simulants
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A decontaminating composite, Mg3Al-LDH-Nb6, has been successfully prepared by immobilizing Lindqvist [H3Nb6O19]5? (Nb6) into a Mg3Al-based layered double hydroxide (Mg3Al-LDH). To our knowledge, this represents the first successful approach to the immobilization of polyoxoniobate. As a versatile catalyst, Mg3Al-LDH-Nb6 can effectively catalyze the degradation of both vesicant and nerve agent simulants by multiple pathways under mild conditions. Specifically, the sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES), is converted into the corresponding nontoxic 2-chloroethyl ethyl sulfoxide (CEESO) by selective oxidation, whereas the Tabun (G-type nerve agent) simulant, diethyl cyanophosphonate (DECP), and the VX (V-type nerve agent) simulant, O,S-diethyl methylphosphonothioate (OSDEMP), are detoxified through hydrolysis and perhydrolysis, respectively. A possible mechanism is proposed on the basis of control experiments and spectroscopic studies. The Mg3Al-LDH-Nb6 composite exhibits remarkable robustness and can be readily reused for up to ten cycles with negligible loss of its catalytic activity. More importantly, a protective “self-detoxifying” material has easily been constructed by integrating Mg3Al-LDH-Nb6 into textiles. In this way, the flexible and permeable properties of textiles have been combined with the catalytic activity of polyoxoniobate to remove 94 % of CEES in 1 h by using nearly stoichiometric dilute H2O2 (3 %) as oxidant with 96 % selectivity.
- Dong, Jing,Lv, Hongjin,Sun, Xiangrong,Wang, Yin,Ni, Yuanman,Zou, Bo,Zhang, Nan,Yin, Anxiang,Chi, Yingnan,Hu, Changwen
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supporting information
p. 19208 - 19215
(2019/01/03)
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- Oxidative Neutralization of Mustard-Gas Simulants in an On-Board Flow Device with In-Line NMR Monitoring
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The fast and effective neutralization of the mustard-gas simulant 2-chloroethyl ethyl sulfide (CEES) using a simple and portable continuous flow device is reported. Neutralization takes place through a fully selective sulfoxidation by a stable source of hydrogen peroxide (alcoholic solution of urea–H2O2 adduct/MeSO3H freshly prepared). The reaction progress can be monitored with an in-line benchtop NMR spectrometer, allowing a real-time adjustment of reaction conditions. Inherent features of millireactors, that is, perfect control of mixing, heat and reaction time, allowed the neutralization of 25 g of pure CEES within 46 minutes in a 21.5 mL millireactor (tR=3.9 minutes). This device, which relies on affordable and nontoxic reagents, fits into a suitcase, and can be deployed by police/military forces directly on the attack site.
- Picard, Baptiste,Gouilleux, Boris,Lebleu, Thomas,Maddaluno, Jacques,Chataigner, Isabelle,Penhoat, Ma?l,Felpin, Fran?ois-Xavier,Giraudeau, Patrick,Legros, Julien
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supporting information
p. 7568 - 7572
(2017/06/13)
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- Polyoxometalate-based gelating networks for entrapment and catalytic decontamination
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We report the synthesis and characterization of a new class of organic/inorganic hybrid polymers composed of covalently-bound 1,3,5-benzenetricarboxamide linkers and anionic polyoxovanadate clusters with varying counter-cations. These materials form gels within seconds upon contact with polar aprotic organic liquids and catalyze the degradation of odorants and toxic molecules under mild conditions including aerobic oxidation of thiols, hydrogen peroxide-catalyzed oxidation of sulfides, and hydrolysis of organophosphate chemical warfare agent analogues.
- Sullivan, Kevin P.,Neiwert, Wade A.,Zeng, Huadong,Mehta, Anil K.,Yin, Qiushi,Hillesheim, Daniel A.,Vivek, Skanda,Yin, Panchao,Collins-Wildman, Daniel L.,Weeks, Eric R.,Liu, Tianbo,Hill, Craig L.
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supporting information
p. 11480 - 11483
(2017/10/23)
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- Decontamination and remediation of the sulfur mustard simulant CEES with “off-the-shelf” reagents in solution and gel states: A proof-of-concept study
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The decontamination and remediation of sulfur mustard chemical warfare agents remains an ongoing challenge. Herein, we report the use of “off-the-shelf” metal salts alongside commercially available peroxides to catalyze the degradation of the simulant 2-chloroethyl ethyl sulfide (CEES) in solution and encapsulated within a supramolecular gel.
- Hiscock, Jennifer R.,Bustone, Gianluca P.,Clark, Ewan R.
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p. 497 - 500
(2018/08/17)
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- Controllable Synthesis of Lindqvist Alkoxopolyoxovanadate Clusters as Heterogeneous Catalysts for Sulfoxidation of Sulfides
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Six alkoxohexavanadate-based Cu- or Co-POVs [Cu(dpa)(acac)(H2O)]2[V6O13(OMe)6] (1), [Cu(phen)(acac)(MeOH)]2[V6O13(OMe)6] (2), [Co(dpa)(acac)2]2[V6O13(OMe)6]·2MeOH (3), [Co(phen)(acac)2]2[V6O13(OMe)6] (4), [Cu(dpa)(acac)]2[VIV2VV4O12(OMe)7] (5), and [Cu(dpa)(acac)(MeOH)]2[VIV2VV4O11(OMe)8] (6) (POV = polyoxovanadate; dpa = 2,2′-dipyridine amine; phen = 1,10-phenanthroline; acac = acetylacetone anion) have been synthesized by controlling the reaction conditions and characterized by single-crystal X-ray diffraction and powder X-ray diffraction analyses, FT-IR spectroscopy, element analyses, and X-ray photoelectron spectroscopy. In compounds 1-4 and 6, Cu or Co complexes and alkoxohexavanadate anions are assembled through electrostatic interactions. Differently, in compound 5, seven-methoxo-substituted Lindqvist-type [V6O12(OMe)7]2- are bridged to Cu complex via terminal O atoms by coordination bonds. All compounds 1-6 exhibit excellent heterogeneous catalytic performance in oxidative desulfurization and CEES ((2-chloroethyl) ethyl sulfide, a sulfur mustard simulant) abatement with H2O2 as oxidant. Among them, the catalytic activity of 6 [conv. of DBT (dibenzothiophene) up to 100% in 6 h; conv. of CEES reached 100% and selectivity of CEESO ((2-chloroethyl) ethyl sulfoxide) up to 85% after 4 h] outperforms others and can be reused without losing its activity.
- Li, Ji-Kun,Dong, Jing,Wei, Chuan-Ping,Yang, Song,Chi, Ying-Nan,Xu, Yan-Qing,Hu, Chang-Wen
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p. 5748 - 5756
(2017/05/22)
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- Adsorption of a Catalytically Accessible Polyoxometalate in a Mesoporous Channel-type Metal-Organic Framework
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A Keggin-type polyoxometalate (H3PW12O40) was incorporated into a mesoporous Zr-based MOF (NU-1000) via an impregnation method in aqueous media, resulting in the hybrid material, PW12@NU-1000. The POM@MOF composite was characterized by a suite of physical methods, indicating the retention of crystallinity and high porosity of the parent MOF. The hybrid material was also stable to leaching in aqueous media at varying pH. Finally, the material was tested as a heterogeneous catalyst for the oxidation of 2-chloroethyl ethyl sulfide using hydrogen peroxide as the oxidant. PW12@NU-1000 was shown to have a higher catalytic activity than either of the individual constituents alone.
- Buru, Cassandra T.,Li, Peng,Mehdi, B. Layla,Dohnalkova, Alice,Platero-Prats, Ana E.,Browning, Nigel D.,Chapman, Karena W.,Hupp, Joseph T.,Farha, Omar K.
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p. 5174 - 5181
(2017/07/04)
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- Efficient Metal-Free Aerobic Photooxidation of Sulfides to Sulfoxides Mediated by a Vitamin B2Derivative and Visible Light
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We have developed a metal-free process for the aerobic photooxygenation of sulfides to sulfoxides mediated by riboflavin tetraacetate or riboflavin (vitamin B2) photocatalysts and visible light (450 nm) in an acetonitrile-water (85:15 v/v) mixture. The optimised solvent system leads to both singlet-oxygen and electron-transfer pathways in photooxygenation, thus allowing oxidation of electron-poor and electron-rich thioanisoles, dialkyl sulfides and sterically hindered sulfides. Besides having a broad substrate scope, the method has very short reaction times and requires low catalyst loading (down to 0.1 mol%). These properties are due to the high photocatalyst stability and the extremely high quantum yields (1.3 for thioanisole oxygenation). Moreover, the method is chemoselective, producing only sulfoxides without overoxidation to sulfones. Taking into account the broad substrate scope, high selectivity and high efficiency, this method distinguishes itself from those previously reported. Other advantages include easy work-up of the reaction mixture, the availability and biodegradability of the photocatalysts and mild reaction conditions. We demonstrated, on a preparative scale, its practical application in the synthesis of the psychostimulant modafinil, in the selective oxidation of methionine derivatives, and in the detoxification of mustard gas. (Figure presented.).
- Nevesely, Tomá?,Svobodová, Eva,Chudoba, Josef,Sikorski, Marek,Cibulka, Radek
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p. 1654 - 1663
(2016/10/13)
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- Supramolecular Activation of Hydrogen Peroxide in the Selective Sulfoxidation of Thioethers by a Self-Assembled Hexameric Capsule
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An efficient metal-free organocatalytic activation of hydrogen peroxide (H2O2) towards thioethers leading to the corresponding sulfoxides in high yields at room temperature within hours was promoted by the hexameric capsule formed by
- La Sorella, Giorgio,Sperni, Laura,Strukul, Giorgio,Scarso, Alessandro
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p. 3443 - 3449
(2016/11/13)
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