电子束辐照制备钼酸锰纳米材料
李敏敏1,曹 凡1,贾双凤1,郑 赫1,王建波1,2*,赵东山1
(武汉大学物理科学与技术学院,电子显微镜中心,人工微结构教育部重点实验室和高等研究院,湖北 武汉430072;2. 中南大学轻质高强结构材料重点实验室,湖南 长沙410083)
摘要 在透射电子显微镜中,利用电子束辐照诱导的方法合成了钼酸锰片状纳米材料。研究发现在电子束辐照前,由于Mn、O等的相对含量不同样品可以分为两类。其中Mn和O含量较低的样品经电子束辐照后的产物为Mn2Mo3O8纳米片和MoO2纳米颗粒。而Mn和O含量较高的则主要生成六角结构的新相MnxMo3O8。进一步分析发现,MnxMo3O8的生成可能是因为样品中Mn相对含量较高,导致Mn、Mo和O原子层堆垛方式发生了改变。同时也初步确定了MnxMo3O8的晶胞参数为aH2= 0.59 nm,cH2= 6.24 nm。研究结果不仅提供了利用电子束辐照制备钼酸盐纳米材料的新方法,同时也促进了对钼酸锰材料的认识。
关键词 钼酸锰;电子束辐照;电子显微学
中图分类号:TG146. 4 + 12;TG115. 21+ 5. 3 文献标识码:A doi:10.3969/j.issn.1000-6281.2017.04.005
Synthesis of the manganese molybdate nanomaterials through electron beam irradiation
LI Min-min1, CAO Fan1, JIA Shuang-feng1, ZHENG He1, WANG Jian-bo1,2*, ZHAO Dong-shan1
(1. School of Physics and Technology, Center for Electron Microscopy, MOE Key Laboratory of Artificial Micro- and Nano-structures, and Institute for Advanced Studies, Wuhan University, Wuhan Hubei 430072; 2. Science and Technology on High Strength Structural Materials Laboratory, Central South University, Changsha Hunan 410083, China)
Abstract Manganese molybdate nanosheets are synthesized through electron beam (e-beam) irradiation inside a transmission electron microscope. There are two kinds of samples before e-beam irradiation, according to the different contents of Mn and O. After irradiated by the e-beam, Mn2Mo3O8 nanosheets and MoO2 nanoparticles are synthesized through the sample with lower Mn and O contents, while mainly MnxMo3O8 with higher Mn and O contents. Furthermore, the generation of the new hexagonal MnxMo3O8 phase can be ascribed to higher Mn content in the initial reactant, which results in the different stacking of Mn, Mo and O atoms. Meanwhile, the lattice parameters of MnxMo3O8 is determined to be aH2 = 0.59 nm, cH2 = 6.24 nm. The results not only provide a new strategy for the synthesis of molybdate nanomaterials by electron beam irradiation, but also facilitate the understanding of manganese molybdate materials.
Keywords manganese molybdate; electron beam radiation; electron microscopy
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[1] MCALISTER S P. Unusual ferrimagnetism in Mn2Mo3O8 and Sm2In [J].J Appl Phys, 1984, 55(6): 2343-2345.
[2] EHRENBERG H, SCHWARZ B, WEITZEL H. Magnetic phase diagrams of α-MnMoO4 [J]. J Magn Magn Mater, 2006, 305(1): 57-62.
[3] MI Y, HUANG Z Y, ZHOU Z G, et al. Room-temperature synthesis of MnMoO4·H2O nanorods by the microemulsion-based method and its photocatalytic performance[J]. J Phys: Conf Ser, 2009, 188(1): 012056.
[4] GHOSH D, GIRI S, MONIRUZZAMAN M, et al. α-MnMoO4/graphene hybrid composite: high energy density supercapacitor electrode material[J]. Dalton Trans, 2014, 43(28): 11067-11076.
[5] SENTHILKUMAR B, SELVAN R K, MEYRICK D, et al. Synthesis and characterization of manganese molybdate for symmetric capacitor applications [J]. Int J Electrochem Sci, 2015, 10(1): 185-193.
[6] PURUSHOTHAMAN K K, CUBA M, MURALIDHARAN G. Supercapacitor behavior of α-MnMoO4 nanorods on different electrolytes[J]. Mater Res Bull, 2012, 47(11): 3348-3351.
[7] KIM S S, OGURA S, IKUTA H, et al. Reaction mechanisms of MnMoO4for high capacity anode material of Li secondary battery [J]. Solid State Ionics, 2002, 146(3): 249-256.
[8] DAS B, REDDY M V, KRISHNAMOORTHI C, et al. Carbothermal synthesis, spectral and magnetic characterization and Li-cyclability of the Mo-cluster compounds, LiYMo3O8 and Mn2Mo3O8[J]. Electrochim Acta, 2009, 54(12): 3360-3373.
[9] PETNIKOTA S, MARKA S K, SRIKANTH V V, et al. Elucidation of few layered graphene-complex metal oxide (A2Mo3O8, A= Co, Mn and Zn) composites as robust anode materials in Li ion batteries [J]. Electrochim Acta, 2015, 178: 699-708.
[10] SUN Y M, HU X L, LUO W, et al. Hierarchical self-assembly of Mo3O8–graphene nanostructures and their enhanced lithium-storage properties [J].J Mater Chem, 2011, 21(43): 17229-17235.
[11] SLEIGHT A W, CHAMBERLAND B L. Transition metal molybdates of the type AMoO4 [J]. Inorg Chem, 1968, 7(8): 1672-1675.
[12] CAO F, ZHENG H, JIA S F, et al. Atomistic observation of phase transitions in calcium sulfates under electron irradiation [J]. J Phys Chem C, 2015, 119(38): 22244-22248.
[13] ZHOU Z, TIAN H, LI J X. Electron beam induced ZnO quantum dot growth [J]. J Chin Electr Microsc Soc,2016, 35(4): 298-302.
[14] KIM J U, CHA S H, SHIN K, et al. Synthesis of gold nanoparticles from gold(I)-alkanethiolate complexes with supramolecular structures through electron beam irradiation in TEM [J]. J Am Chem Soc, 2005, 127(28): 9962-9963.
[15] SEPULVEDA-GUZMAN S, ELIZONDO-VILLARREAL N, FERRER D, et al. In situ formation of bismuth nanoparticles through electron-beam irradiation in a transmission electron microscope [J]. Nanotechnology, 2007, 18(33): 335604.
[16] TROIANI H E, CAMACHO-BRAGADO A, ARMENDARIZ V, et al. Synthesis of carbon onions by gold nanoparticles and electron irradiation [J]. Chem Mater, 2003, 15(5): 1029-1031.
[17] LIU Z Q, HASHIMOTO H, SUKEDAI E, et al.In situ observation of the formation of Fe3O4 inFe4N (001) due to electron irradiation [J]. Phys Rev Lett, 2003, 90(25): 255504.
[18] DIAZ-DROGUETT D E, ZUNIGA A, SOLORZANO G, et al. Electron beam-induced structural transformations of MoO3 and MoO3−x crystalline nanostructures[J]. J Nanopart Res, 2012, 14(1): 1-9.
[19] WANG D, SU D S, SCHLÖGL R.Electron beam induced transformation of MoO3 to MoO2 and a new phase MoO[J].Z Anorg Allg Chem, 2004, 630(7): 1007-1014.
[20] JIA S F, SANG H Q, ZHANG W J, et al. Ordered and twinned structure in hexagonal-based potassium tungsten bronze nanosheets [J]. J Appl Cryst, 2013, 46(6): 1817-1822.
[21] KRAUSE H B, MOULTON W G and MORRIS R C. Investigation of superlattices in KxWO3 inrelation to electric transport properties [J]. Acta Cryst Sect B: Struct Sci, 1985, 41(1): 11-21.
[22] MCCARROLL W H, KATZ L,WARD R.Some ternary oxides of tetravalent molybdenum [J]. J Am Chem Soc, 1957, 79(20): 5410-5414.
[23] TORARDI C C,MCCARLEY R E. Synthesis, crystal structures, and properties of lithium zinc molybdenum oxide (LiZn2Mo3O8), zinc molybdenum oxide (Zn3Mo3O8), and scandium zinc molybdenum oxide (ScZnMo3O8), reduced derivatives containing the Mo3O13 cluster unit [J]. Inorg Chem, 1985, 24(4): 476-481.
[24] GALL P,GOUGEON P. Li2GeMo3O8: a novel reduced molybdenum oxide containing Mo3O13 cluster units [J].Acta Cryst Sect E: Cryst Commun, 2016, 72(7): 995-997.
[25] CARLSON C D, BROUGH L F, EDWARDS P A, et al.Synthesis, structure and properties of Mn1.5Mo8O11, a unique structure type among compounds having infinite chains of trans-edge-shared octahedral cluster units [J].J Less Common Met, 1989, 156(1): 325-339.
[26] GALL P,GOUGEON P. Redetermination of Mn1.44Mo8O11: evidence of pairwise distortion of octahedral molybdenum chains [J].Acta Cryst Sect E: Struct Rep, 2006, 62(7): 155-157.
[27] TORARDI C C,MCCARLEY R E. Synthesis and structure of Ba5(Mo4O6)8: a compound having the NaMo4O6 structure type and superlattice ordering of barium ions[J].J Less Common Met, 1986, 116(1): 169-186.