以Ce(NH4)2(NO2)6为原料,H2BDC为配体,采用热熔剂法合成了金属有机框架材料Ce-MOF。利用电镜、X射线衍射、热重、红外光谱以及X射线光电子能谱等技术对Ce-MOF的形貌、结构和化学性质等进行分析研究,并探索其对神经毒剂模拟剂甲基对氧磷(DMNP)的催化降解效果。结果表明:Ce-MOF具有良好的化学稳定性和热稳定性,并具有优良催化性能,可以快速降解DMNP。研究揭示了Ce-MOF是一种新型的水解去除神经性毒剂模拟物的活性物质,对催化降解和清除神经性毒剂具有巨大潜力。
Ce-MOF metal-organic framework material was synthesized by hot flux method using Ce(NH4)2(NO2)6 as raw material and H2BDC as ligand.The morphology,size,phase structure and chemical properties of Ce-MOF were studied by using SEM,TEM,XRD,TGA,FT-IR and XPS techniques.Then,the catalytic degradation of dimethyl p-nitrophenylphosphate (DMNP),a simulant of nerve agent,was investigated.The results shown that Ce-MOF had good chemical stability and thermal stability,and had excellent catalytic performance,which can quickly degrade DMNP.The results revealed that Ce-MOF was a novel active substance for hydrolytic removal of DMNP,and had great potential for catalytic degradation and removal of nerve agents.
[1] Barthold C L,Schier J G.Organic phosphorus compounds-nerve agents[J].Critical Care Clinics,2005,21(4):673-689.
[2] Mohammad M,Anahita A,Mahdi B M.Clinical management of organophosphorus nerve agents'poisonings[J].Basic and Clinical Toxicology of Organophosphorus Compounds,2014,DOI:10.1007/978-1-4471-5625-3-7.
[3] Tsai P C,Bigley A,Li Y C,et al.Stereoselective hydrolysis of organophosphate nerve agents by the bacterial phosphotriesterase[J].Biochemistry,2010,49(37):7978-7987.
[4] Kinnan M K,Creasy W R,Fullmer L B,et al.Nerve agent degradation with polyoxoniobates[J].European Journal of Inorganic Chemistry,2014(14):2361-2367.
[5] Wagner G W.Hydrogen peroxide-based decontamination of chemical warfare agents[J].Main Group Chemistry,2010,9(3):257-263.
[6] Edwards D R,Liu C T,Garrett G E,et al.Leaving group assistance in the La3+-catalyzed cleavage of dimethyl (O-methoxycarbonyl) aryl phosphate triesters in methanol[J].Journal of the American Chemical Society,2009,131(38):13738-13748.
[7] Liu T,Neverov A A,Tsang J S W,et al.Mechanistic studies of La3+- and Zn2+-catalyzed methanolysis of aryl phosphate and phosphorothioate triesters.Development of artificial phosphotriesterase systems[J].Organic & Biomolecular Chemistry,2005,3(8):1525-1533.
[8] Kang B,Kurutz J W,Youm K T,et al.Catalytically active supramolecular porphyrin boxes:acceleration of the methanolysis of phosphate triesters via a combination of increased local nucleophilicity and reactant encapsulation[J].Chemical Science,2012,3(6):1938-1944.
[9] 刘红岩,孙晓红,林京玉,等.纳米金属氧化物对化学战剂消毒效果的评价[J].国际药学研究杂志,2015,42(5):606-609.
[10] Wagner G W,Procell L R,O'Connor R J,et al.Reactions of VX,GB,GD,and HD with nanosize Al2O3 formation of aluminophosphonates[J].Journal of the American Chemical Society,2001,123(8):1636-1644.
[11] Furukawa H,Cordova K E,O'Keeffe M,et al.The chemistry and applications of metal-organic frameworks[J].Science,2013,341:1230444.
[12] Jiao L,Wang Y,Jiang H L,et al.Metal-organic frameworks as platforms for catalytic applications[J].Advanced Materials,2017,30(37):1703663.
[13] Hu Z C,Deibert B J,Li J.Luminescent metal-organic frameworks for chemical sensing and explosive detection[J].Chemical Society Reviews,2014,43:5815-5840.
[14] Katz M J,Mondloch J E,Totten R K,et al.Simple and compelling biomimetic metal-organic framework catalyst for the degradation of nerve agent simulants[J].Angewandte Chemie,2014,126(2):507-511.
[15] Xu Can,Qu Xiaogang.Cerium oxide nanoparticle:a remarkably versatile rare earth nanomaterial for biological applications[J].NPG Asia Materials,2014,6:1-16.
[16] Lammert M,Wharmby M T,Smolders S,et al.Cerium-based metal organic frameworks with Uio-66 architecture:synthesis,properties and redox catalytic activity[J].Chemical Communications,2015,51(63):12578-12581.
[17] Hassan M H,Andreescu D,Andreescu S.Cerium oxide nanoparticles stabilized within metal-organic frameworks for the degradation of nerve agents[J].ACS Applied Nano Materials,2020,3(4):3288-3294.
[18] Sangeetha S,Krishnamurthy G.Electrochemical and photocatalytic applications of Ce-MOF[J].Bulletin of Materials Science,2020,43(1):269.
[19] Luo Z,Fan S,Gu C,et al.Metal-organic framework (MOF)-based nanomaterials for biomedical applications[J].Current Medicinal Chemistry,2019,26(18):3341-3369.
[20] Kim H K,Yun W S,Kim M B,et al.A chemical route to activation of open metal sites in the copper-based metal-organic framework materials HKUST-1 and Cu-MOF-2[J].Journal of the American Chemical Society,2015,137(31):10009-10015.
[21] Zheng Xiaofang,Huang Yumei,Duan Jingui,et al.A microporous Zn(Ⅱ)-MOF with open metal sites:structure and selective adsorption properties[J].Dalton Transactions,2014,43(22):8311-8317.
[22] Katz M J,Moon S Y,Mondloch J E,et al.Exploiting parameter space in MOFs:a 20-fold enhancement of phosphate-ester hydrolysis with UiO-66-NH2[J].Chemical Science,2015,6(4):2286-2291.
[23] Mondloch J E,Katz M J,Isley W C,et al.Destruction of chemical warfare agents using metal-organic frameworks[J].Nature Materials,2015,14(5):512-516.
[24] Li P,Klet R C,Moon S Y,et al.Synthesis of nanocrystals of Zr-based metal-organic frameworks with csq-net:significant enhancement in the degradation of a nerve agent simulant[J].Chemical Communications,2015,51(54):10925-10928.
[25] Moon S Y,Liu Y Y,Hupp J T,et al.Instantaneous hydrolysis of nerve-agent simulants with a six-connected zirconium-based metal-organic framework[J].Angewandte Chemie International Edition,2015,54(23):6795-6799.
