DALTON TRANSACTIONS
·
2018
·Vol. 47
·期 18
·6394-6403
·
IF 4.099
Yanqin Li,Qi Gao,Lijuan Zhang,Yunshan Zhou,Yuxu Zhong,Ying Ying,Mingcai Zhang,Chunqian Huang,Yong'an Wang
Currently extensive effort is compulsively expended to decontaminate efficiently banned chemical war agents. In this work, H5PV2Mo10O40 molecules have been encapsulated in mesoporous MIL-101(Cr), which features two types of mesoporous cages (internal diameters of 29 Å and 34 Å) and microporous windows (diameters of 12 Å and 16 Å), leading to the formation of a new composite H5PV2Mo10O40@MIL-101(Cr) through a simple impregnation method. The composite was characterized thoroughly by elemental analysis, FT-IR spectroscopy, powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, TG/DTA, and textural analysis thereby confirming the encapsulation of the H5PV2Mo10O40 into MIL-101(Cr). The decontamination efficiency of sulfur mustard (4 μL HD in 40 μL of petroleum ether) by 20 mg of the composite is found to be 97.39% in 120 min under ambient conditions. GC-MS analysis on the decontaminated products using 2-chloroethyl ethyl sulfide (CEES), which has been widely used as a simulant of sulfur mustard, showed that MIL-101(Cr) just decontaminates CEES by adsorption, while CEES can be decontaminated under ambient conditions by a synergetic combination of adsorption of MIL-101(Cr) and subsequent chemical oxidation degradation to nontoxic 2-chloroethyl ethyl sulfoxide (CEESO) due to the presence of highly dispersed H5PV2Mo10O40 within the composites.
研究领域:
材料科学
·
化学工程
·
环境科学
✓ 已验证
DOI
高影响因子
JOURNAL OF HAZARDOUS MATERIALS
·
2017
·
IF 6.065
Sanping Zhao,Hailing Xi,Yanjun Zuo,Qi Wang,Zhicheng Wang,Zengyuan Yan
13 C NMR spectra showed that peroxymonocarbonate (HCO 4 − ) was generated in the NaHCO 3 -activated H 2 O 2 solution and pH was a key factor in its production. A cycle for the bicarbonate anion was proposed as HCO 3 − → HCO 3 → (CO 2 ) 2 * → CO 2 (aq) → HCO 4 − (H 2 CO 4 ) → HCO 3 − ( HCO 3 ) basing on the results of NMR, electron paramagnetic resonance, chemiluminescence analysis. In this cycle, (CO 2 ) 2 * was the key intermediate and (CO 2 ) 2 * → 2CO 2 + hv was the rate controlling step. Thioanisole and paraoxon, the simulants of sulfur mustard gas and nerve gas, respectively, were efficiently decontaminated by the NaHCO 3 -activated H 2 O 2 solution. While HCO 4 − was the primary oxidant for the oxidation of thioanisole, O 2 − generated during the decomposition of HCO 4 − or H 2 O 2 led to the secondary oxidation of the sulfide. Paraoxon was degraded in the NaHCO 3 -activated H 2 O 2 solution via nucleophilic substitution by OOH − and OH − , and the degradation rate increased exponentially with increasing pH. Alkali metal ions had a catalytic effect on the degradation of paraoxon. Mustard gas and soman degraded efficiently into nontoxic products in NaHCO 3 -activated H 2 O 2 . A pH range of 9–10 was found to be optimum for the broad-spectrum decontamination of chemical warfare agents and other eco-toxicants using NaHCO 3 -activated H 2 O 2 .
研究领域:
化学
·
环境科学
·
生物学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Materials Chemistry B
·
2017
·Vol. 5
·期 30
·6138-6146
·
IF 4.543
Lijuan Zhang,Junmei Sun,Yunshan Zhou,Yuxu Zhong,Ying Ying,Yanqin Li,Yanqin Liu,Zareen Zuhra,Chunqian Huang
Cu3(BTC)2 (H3BTC = 1,3,5-benzenetricarboxylic acid) was anchored onto the surface of carboxymethylated chitosan non-woven fabrics by a controllable layer-by-layer technique in alternating solution baths of Cu(OAc)2·H2O and H3BTC solutions, and the resulting [Cu3(BTC)2]n@chitosan non-woven fabric composite materials (n = number of alternate deposition cycles) were thoroughly characterized. The results showed that the composite materials not only exhibited excellent decontamination ability against sulfur mustard (HD), with an enhanced degradation rate of HD with increasing n, but also possessed remarkable haemostasis performance. The degradation efficiency of sulfur mustard by [Cu3(BTC)2]4@chitosan was found to be much higher than that of pristine [Cu3(BTC)2]4. The inherent haemostatic capabilities of the chitosan non-woven fabrics were not affected by the growth of Cu3(BTC)2 on the surface of chitosan. Oral and histological toxicity examinations of the pristine Cu3(BTC)2 sample showed that damage and toxicity in the viscera of mice was very low, even if the intra-gastric administration dose of Cu3(BTC)2 reached a very high level (50 mg of Cu3(BTC)2 per kg of mouse). The results have shown that the as-prepared composite can be used safely as a promising haemostatic decontaminant with good recyclability against sulfur mustard.
研究领域:
材料科学
·
生物医学工程
·
化学
✓ 已验证
DOI
高影响因子
DALTON TRANSACTIONS
·
2021
·Vol. 50
·期 28
·9796-9803
·
IF 4.39
Yanyan Wu,Jing Dong,Chengpeng Liu,Xiaoting Jing,Huifang Liu,Yue Guo,Yingnan Chi,Changwen Hu
Keggin-type polyoxometalates (POMs) were immobilized on poly(diallyldimethylammonium chloride) (PDDA) functionalized reduced graphene oxide (rGO) by a facile and broad-spectrum hydrothermal method. The prepared POMs@PDDA-rGO composites (POM = H3PMo12O40, H3PW12O40, H5PMo10V2O40) have been thoroughly characterized using a series of techniques. The three composites can catalyze the oxidative decontamination of a sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES) in the order of PMo12@PDDA-rGO > PMo10V2@PDDA-rGO > PW12@PDDA-rGO. Notably, under ambient conditions PMo12@PDDA-rGO can convert 99% of CEES within 30 min in the presence of nearly stoichiometric aqueous H2O2 (3 wt%) and its catalytic activity is significantly higher than that of homogeneous H3PMo12O40. XPS spectral analysis and control experiments indicate that the Mo center of POM is reduced from +6 to +5 during the hydrothermal process, and the excellent catalytic performance is related to the reduction of Mo. Moreover, the PMo12@PDDA-rGO composite is stable during the decontamination process and it can be used for at least five cycles without loss of activity.
研究领域:
材料科学
·
环境科学
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2024
·
IF 8.3
Xingqi Huang,Wenming Chen,Haibo Wang,Lingce Kong,Jingjing Zhang,Chonglin Zhao,Yanjun Zuo
Manganese oxides with porous structure and abundant active sites show potential in degrading sulfur mustard (HD). However, there is an interface effect between the oily liquid HD and nano oxides, and the powder is prone to agglomeration, which leads to incomplete contact and limited degradation ability. Here, we demonstrate a simple hydrothermal method for preparing MnO2/Ti3C2 composites to address this problem. The influence of morphology and crystal structure on performance are examined. Herein, flower-like MnO2 is loaded onto the surface or interlayer of Ti3C2-MXene nanosheets during in situ formation, significantly expanding the specific surface area. It also provides abundant acid–base sites and oxygen vacancies for the degradation of simulants 2-chloro-ethyl-ethyl thioether (2-CEES) without external energy, resulting in a reaction half-life as fast as 12.5 min. The relationship between structure and performance is clearly elaborated through temperature-programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), and X-ray absorption fine structure (XAFS) analyses. Based on in situ attenuated total reflection–Fourier transform infrared (ATR–FTIR) analysis, gas chromatography–mass spectrometry (GC–MS) analysis, and density functional theory (DFT) calculation, the proposed degradation pathway of the 2-CEES molecule is a synergistic effect of hydrolysis, elimination, and oxidation. Furthermore, the products are nontoxic or low toxic. Metal oxide/MXene composites are first illustrated for their potential use in degrading sulfur mustard, suggesting new insights into these materials as novel decontamination for decomposing chemical warfare agents.
研究领域:
材料科学
·
环境科学
·
化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF HAZARDOUS MATERIALS
·
2024
·
IF 12.2
Xingqi Huang,Haibo Wang,Lingce Kong,Zihao Chen,Jingjing Zhang,Yanjun Zuo,Wenming Chen
The microwave-assisted hydrothermal method has facilitated the straightforward and efficient production of nanoscale Ce x Zr 1−x O 2 /Ti 3 C 2 T x composites. This technique has greatly shortened the synthesis time several hours required by conventional hydrothermal method to merely 10 min. Due to the unique mechanism of microwave-hydrothermal synthesis, composites with excellent crystallinity, uniform particle size, and superior degradation capabilities can be obtained without calcination. Our investigation systematically explores the influence of various factors including mineralizer concentration, dispersant types, synthesis duration, cerium-to-zirconium ratio, as well as MXene content on the material properties. Optimal degradation of 2-chloroethyl ethyl sulfide (2-CEES), sulfur mustard simulants, is achieved using PEG1000 as the dispersant, a cerium-to-zirconium ratio of 1:2, along with 15 mL of MXene, resulting in a remarkably short half-life of only 6.5 min. Furthermore, it is confirmed that the incorporation of cerium atoms into ZrO 2 lattice, forming a solid solution that is deposited onto the interlayer and surface of Ti 3 C 2 T x nanosheets, with the composite particles measuring approximately 5.01 nm. The reduced size and increased specific surface area, coupled with the synergistic effects of oxygen vacancies and acid-base sites, ultimately contribute to the hydrolysis and elimination reactions occurring on 2-CEES. This research offers fresh perspectives on the development of novel materials for the degradation of chemical warfare agents.
研究领域:
材料科学
·
环境化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
DALTON TRANSACTIONS
·
2020
·Vol. 49
·期 24
·8122-8135
·
IF 4.174
Jialin Yu,Qi Gao,Lijuan Zhang,Yunshan Zhou,Yuxu Zhong,Jianbo Yin,Yuanyuan Zhou,Fangsheng Tao,Yong'an Wang
ε-[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 96.4% (within 120 min) and 99.5% (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 ε-[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.
研究领域:
化学
·
生物学
·
医学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Applied Nano Materials
·
2019
·
IF 0
Xueyan Zhang,Yiming Li,Yue Li,Shengtian Wang,Xiaohong Wang
“Click reactions” are widely used for the synthesis and modification of new materials due to their fascinating advantages (e.g., highly efficient and selective, mild reaction conditions, and lack of side reactions). Redox-active metal-substituted polyoxotungstates (MSPs) were covalently immobilized on a graphene surface by using a “click” reaction between the azido group of K1.5Cs5.5[γ-SiW10O39Cu2(N3)2] (SiW10Cu2(N3)2) and the alkynyl groups on functionalized graphene. This novel strategy allowed for controllable formation of interfacial catalysts (SiW10Cu2/GO) with a single MSP molecule being loaded on the surface of graphene. This interfacing between a single polyoxometalate (POM) molecule and graphene results in several advantages combined with redox properties and higher thermal stability due to the POMs, electronic band structure of graphene, special hydrophobic environment, and single molecular dispersing sites. This SiW10Cu2/GO catalyst exhibited excellent stability and highly efficient reactivity or selectivity for dismutation of H2O2 and oxidation of 2-chloroethyl ethyl sulfide (CEES). SiW10Cu2/GO was active for evolving oxygen from H2O2 dismutation at a rate of 1.35 × 10–1 μmol s–1, which was much higher than that by using its parent SiW10Cu2(N3)2 (1.89 × 10–2 μmol s–1) and similar to that of the reported [Ru4(μ-OH)2(μ-O)4(H2O)4][γ-SiW10O36]210– (1.24 × 10–1 μmol s–1) catalyst. Therefore, this activity permitted it to mimic catalase (H2O2 → H2O + O2) as an inorganic synzyme at 27 °C. The simultaneous generation of O2 and highly selective detoxification of CEES to nontoxic sulfoxide CEESO demonstrated the potential for personnel protection against chemical warfare agents. Moreover, SiW10Cu2/GO exhibited higher activity for the oxidation of CEES to sulfide CEESO with higher selectivity in the presence of O2. Furthermore, recycling and leaching experiments indicated that no significant leaching of POMs was observed from graphene. In addition, the produced CEESO did not aggregate on the catalyst hybrids.
研究领域:
材料科学
·
催化化学
·
环境化学
✓ 已验证
产品关联
DOI
ANALYTICAL CHEMISTRY
·
2024
·
IF 6.7
Shuya Liu,Yongxian Guo,Yifei Jiang,Yanjun Gong,Qiongzheng Hu,Li Yu
Real-time detection and effective degradation of toxic gases have attracted considerable attention in environmental monitoring and human health. Here, we demonstrate a solvent-assisted dynamic assembly strategy to strongly enhance the detection and degradation performance for 2-chloroethyl ethyl sulfide (CEES, as a sulfur mustard simulant) via confinement of a conjugated polymer in metal–organic frameworks (MOFs). The conjugated polymer poly(9,9-di-n-octylfluorene-altbenzothiadiazole) (F8BT) is infiltrated into one-dimensional nanochannels of the Zr-based topological MOF NU-1000 in a single-chain manner, which is caused by the nanoconfinement effect and the steric hindrance between 9,9-dioctylfluorene units and benzothiadiazole units. The obtained F8BT⊂NU-1000 composites provide a high specific surface area and abundant active sites. Based on the cooperative effect of F8BT and NU-1000, rapid and sensitive detection of CEES has been achieved. Moreover, the F8BT⊂NU-1000 composites can selectively oxidize CEES into 2-chloroethyl ethyl sulfoxide (CEESO) under mild photooxidation conditions. Overall, this study opens a new avenue for the fabrication of conjugated polymer/MOF hybrid materials that show great potential for the sensitive detection and effective removal of hazardous chemicals.
研究领域:
环境科学
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
DALTON TRANSACTIONS
·
2019
·Vol. 48
·期 16
·5285-5291
·
IF 4.052
Xiangrong Sun,Jing Dong,Zhen Li,Huifang Liu,Xiaoting Jing,Yingnan Chi,Changwen Hu
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.
研究领域:
化学
·
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF HAZARDOUS MATERIALS
·
2021
·
IF 10.588
Wangsheng Xu,Haoming Bao,Hongwen Zhang,Hao Fu,Qian Zhao,Yue Li,Weiping Cai
Surface Enhanced Raman Spectroscopy (SERS) could be a powerful technique for detecting trace gaseous sulfur-mustard, but it is still challenging due to the difficulty in efficiently capturing sulfur-mustard molecules by normal SERS substrates. Here, a chemically trapping strategy is presented for such detection via coating an ultrathin metal-oxide sensing layer on a SERS substrate. In the strategy, a SERS substrate Au-wrapped Si nanocone array is designed and fabricated by Si wafer-based organic template-etching and appropriate Au deposition, and coated with an ultrathin CuO for chemically capturing sulfur-mustard molecules. The validity of such strategy has been demonstrated via taking the gaseous 2-chloroethyl ethyl sulfide (a simulant of sulfur-mustard, or 2-CEES for short) as the target molecules. The response of the CuO-coated SERS substrate to the gaseous 2-CEES is detectable within 10 min, and the lowest detectable concentration is 10 ppb or less. Further experiments have shown that there exists an optimal CuO coating thickness which is about 6 nm. The CuO coating-based capture of 2-CEES molecules is attributed to the surface hydroxyl-induced specific adsorption, which is subject to the pseudo-second-order kinetics and Freundlich-typed model. This study presents the practical SERS chips and new route for the trace detection of gaseous sulfur-mustard.
研究领域:
化学
·
材料科学
·
分析化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Water Process Engineering
·
2023
·
IF 7
Ruixue Wang,Zhongwen Li,Xiaosen Li,Peiwen Guo,Haibo Wang,Xuan Guo,Jinyi Zhong
Atmospheric pressure plasma jet (APPJ), as an emerging clean and efficient technology, has been found a great potential for chemical warfare agents (CWAs) decontamination. In this study, we first proposed APPJ for the degradation of sulfur mustard (HD) and its surrogate 2-chloroethyl ethyl sulfide (2-CEES) in water. Under optimal conditions, the degradation efficiency of 2-CEES and HD reached 100 % after 5 min or 6 min plasma treatment. The degradation products of 2-CEES and HD were mainly non-toxic alcohols or low toxic sulfones, which can be degraded and converted into some small molecules (HCl, SO 2 , or CO 2 ) under further plasma treatment. We then identified two dominant short-lived reactive species (·OH and 1 O 2 ) and long-lived reactive molecule (H 2 O 2 ) and distinguished the effect of these three active particles during the degradation process of 2-CEES in water. This work provides detailed evidence of a novel decontamination strategy for HD and 2-CEES.
研究领域:
环境科学
·
化学工程
·
等离子体技术
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）