电子束辐照α-MoO3原子尺度结构演变的原位表征

电子束辐照α-MoO₃原子尺度结构演变的原位表征

王思铭，彭华雨，蒋仁辉，管晓溪，齐  孟，马龙辉，贾双凤，郑  赫^*，王建波^*

（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. 武汉大学苏州研究院，江苏 苏州215123；3. 武汉大学深圳研究院，广东 深圳518057）

摘  要    本文采用化学气相沉积法制备α-MoO₃纳米带，利用原位透射电子显微技术表征了在[010]_α、[100]_α和[001]_α方向电子束辐照下α-MoO₃纳米带的原子尺度结构演变。根据原位实验现象，本文提出了以氧空位和Mo原子迁移为核心的微观相变机制。本文发现三个方向会相变成由α-MoO₃以及正交相S1和S2共同构成的中间相，并且沿[010]_α方向观察到α-MoO₃经过中间相后最终相变成面心立方结构的MoO。本文加深了对α-MoO₃结构还原相变的理解，为调控α-MoO₃材料的结构和改善其性能提供了参考。

关键词   三氧化钼（α-MoO₃）；电子束辐照；相变；透射电子显微学（TEM）

中图分类号：TG146.4；TG111.5；TG115.21⁺5.3

文献标识码：Adoi:10.3969/j.issn.1000-6281.2021.05.002

Atomic-scale observation of the structure evolution of α-MoO₃ under electron beam irradiation

WANG Si-ming¹, PENG Hua-yu¹, JIANG Ren-hui¹, GUAN Xiao-xi¹, QI Meng¹, JIA Shuang-feng¹, ZHENG He^{1，2，3 *}, WANG Jian-bo^{1 *}

（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. Suzhou Institute of Wuhan University, Suzhou Jiangsu 215123；3. Wuhan University Shenzhen Research Institute, Shenzhen Guangdong 518057, China）

Abstract    In this paper, α-MoO₃ nanobelts were prepared by chemical vapor deposition method, and atomic-scale structure evolution of α-MoO₃ nanobelts was characterized by in-situ transmission electron microscopy under electron beam irradiation along [010]_α, [100]_α and [001]_α directions. Based on in-situ experimental phenomena, this paper has proposed a microscopic phase transition mechanism with oxygen vacancies and Mo atom migration as the core. This paper found that the three directions will transform into the intermediate phase composed of α-MoO₃ and orthogonal phases S1 and S2, and the α-MoO₃ will eventually transform into a face-centered cubic structure of MoO after passing through the intermediate phase along the [010]_α direction. This article has deepened the understanding of the reduction phase transition of the α-MoO₃ structure, and provided a reference for controlling the structure of α-MoO₃ material and improving its performance.

keywords    molybdenum trioxide (α-MoO₃); electron beam irradiation; phase transition; transmission electron microscopy (TEM)

 “全文下载请到同方知网，万方数据库或重庆维普等数据库中下载！”

[1] ZHANG J, LI C, GUAN W X, et al. Deactivation and regeneration study of a Co-promoted MoO3 catalyst in hydrogenolysis of dibenzofuran[J]. Industrial & Engineering Chemistry Research, 2020, 59(10): 4313-4321.

[2] SZKODA M, TRZCIŃSKI K, SIUZDAK K, et al. Photocatalytical properties of maze-like MoO3 microstructures prepared by anodization of Mo plate[J]. Electrochimica Acta, 2017, 228: 139-145.

[3] LIU Q W, WE Y W, ZHANG J W, et al. Plasmonic MoO3-x, nanosheets with tunable oxygen vacancies as efficient visible light responsive photocatalyst[J]. Applied Surface Science, 2019, 490: 395-402.

[4] FELIX A A, SILVA R A，ORLANDI M O. Layered α-MoO3 nanoplates for gas sensing applications[J]. CrystEngComm, 2020, 22(27): 4640-4649.

[5] RAHMAN F, ZAVABETI A, RAHMAN M A, et al. Dual selective gas sensing characteristics of 2D alpha-MoO3-x via a facile transfer process[J]. ACS Appl Mater Interfaces, 2019, 11(43): 40189-40195.

[6] WEI Z H, HAI Z Y, AKBARI M K, et al. Atomic layer deposition-developed two-dimensional α-MoO3 windows excellent hydrogen peroxide electrochemical sensing capabilities[J]. Sensors and Actuators B: Chemical, 2018, 262: 334-344.

[7] ANDRON I, MARICHEZ L, JUBERA V, et al. Photochromic behavior of ZnO/MoO3 interfaces[J]. ACS Appl Mater Interfaces, 2020, 12(41): 46972-46980.

[8] KIM H S, COOK J B, LIN H, et al. Oxygen vacancies enhance pseudocapacitive charge storage properties of MoO3-x[J]. Nature Materials, 2017, 16(4): 454-460.

[9] SHENG H W, ZHOU J J, LI B, et al. A thin, deformable, high-performance supercapacitor implant that can be biodegraded and bioabsorbed within an animal body[J]. Science Advances, 2021, 7(2): eabe3097.

[10] CROWLEY K, YE G, HE R, et al. α-MoO3 as a conductive 2D oxide: tunable n-type electrical transport via oxygen vacancy and fluorine doping[J]. ACS Applied Nano Materials, 2018, 1(11): 6407-6413.

[11] QIN P L, FANG G J, KE W J, et al. In situ growth of double-layer MoO3/MoS2 film from MoS2 for hole-transport layers in organic solar cell[J]. Journal of Materials Chemistry A, 2014, 2(8): 2742–2756.

[12] WU D, SHEN R, YANG R, et al. Mixed molybdenum oxides with superior performances as an advanced anode material for lithium-ion batteries[J]. Scientific Reports, 2017, 7: 44697.

[13] YU M H, SHAO H, WANG G, et al. Interlayer gap widened alpha-phase molybdenum trioxide as high-rate anodes for dual-ion-intercalation energy storage devices[J]. Nature Communications, 2020, 11(1): 1348.

[14] ZHANG G B, XIONG T F, YAN M Y, et al. α-MoO3-x by plasma etching with improved capacity and stabilized structure for lithium storage[J]. Nano Energy, 2018, 49: 555-563.

[15] DE CASTRO I A, DATTA R S, OU J Z, et al. Molybdenum oxides - from fundamentals to functionality[J]. Advanced Materials, 2017, 29(40): 1701619.

[16] POMERANTSEVA E, BONACCORSO F, FENG X, et al. Energy storage: the future enabled by nanomaterials[J]. Science, 2019, 366(6468): 969.

[17] MARTINEZ-GARCIA A, THAPA A K, DHARMADASA R, et al. High rate and durable, binder free anode based on silicon loaded MoO3 nanoplatelets[J]. Scientific Reports, 2015, 5: 10530.

[18] ZHANG W C, LIU Y J，GUO Z P. Approaching high-performance potassium-ion batteries via advanced design strategies and engineering[J]. Science Advances, 2019, 5(5): eaav7412.

[19] YIN Z Y, TORDJMAN M, LEE Y, et al. Enhanced transport in transistor by tuning transition-metal oxide electronic states interfaced with diamond[J]. Science Advances, 2018, 4(9): eaau0480.

[20] CHEN J，WEI Q. Phase transformation of molybdenum trioxide to molybdenum dioxide: an in-situ transmission electron microscopy investigation[J]. International Journal of Applied Ceramic Technology, 2017, 14(5): 1020-1025.

[21] WANG D, SU D S，SCHLOGL R. Electron beam induced transformation of MoO3 to MoO2 and a new phase MoO[J]. Zeitschrift Für Anorganische und Allgemeine Chemie, 2004, 630(7): 1007-1014.

[22] DIAZ-DROGUETT D E, ZUñIGA A, SOLORZANO G, et al. Electron beam-induced structural transformations of MoO3 and MoO3−x crystalline nanostructures[J].  Journal of Nanoparticle Research, 2012, 14(1): 679.

[23]PENG H Y, MENG W W, ZHENG H, et al. Probing the crystal and electronic structures of molybdenum oxide in redox process: implications for energy applications[J]. Acs Applied Energy Materials, 2019, 2(10): 7709-7716.

[24] 赵鹏辉, 曹凡, 贾双凤, 等. MoO3纳米带在外场作用下的相变[J]. 电子显微学报, 2017, 36(5): 429-435.

[25] BURSILL L A. Crystallographic shear in molybdenum trioxide[J]. Proceedings of the Royal Society of London A Mathematical and Physical Sciences, 1969, 311(1505): 267-290.

[26] THöNI W，HIRSCH P B. The reduction of MoO3 at low temperatures[J]. Philosophical Magazine, 2006, 33(4): 639-662.

[27] REESWINKEL T, MUSIC D，SCHNEIDER J M. Coulomb-potential-dependent decohesion of Magnéli phases[J]. Journal of Physics-condensed Matter, 2010, 22(29): 292203.

[28] MENG S, WU J B, ZHAO L G, et al. Atomistic insight into the redox reactions in Fe/oxide core–shell nanoparticles[J]. Chemistry of Materials, 2018, 30(20): 7306-7312.

[29] LIU H H, ZHENG H, LI L, et al. Atomic-scale observation of a two-stage oxidation process in Cu2O[J]. Nano Research, 2017, 10(7): 2344-2350.

[30] LI L Y, JIANG F, TU F F, et al. Atomic-scale study of cation ordering in potassium tungsten bronze nanosheets[J]. Advanced Science, 2017, 4(9): 1600537.

[31] CAO F, ZHENG H, JIA S F, et al. Atomistic observation of structural evolution during magnesium oxide growth[J]. The Journal of Physical Chemistry C, 2016, 120(47): 26873-26878.

[32] CAO F, ZHENG H, JIA S F, et al. Atomistic observation of phase transitions in calcium sulfates under electron irradiation[J]. The Journal of Physical Chemistry C, 2015, 119(38): 22244-22248.

[33] 郑赫, 曹凡, 胡帅帅, 等. 低维材料原子尺度动态结构演变[J]. 电子显微学报, 2019, 38(5): 436-444.

[34] ARASH A, AHMED T, GOVIND RAJAN A, et al. Large-area synthesis of 2D MoO3−x for enhanced optoelectronic applications[J]. 2D Materials, 2019, 6(3): 035031.

[35] KALANTAR-ZADEH K, TANG J, WANG M, et al. Synthesis of nanometre-thick MoO3 sheets[J]. Nanoscale, 2010, 2(3): 429-433.

[36] RAHMAN F, AHMED T, WALIA S, et al. Reversible resistive switching behaviour in CVD grown, large area MoOx[J]. Nanoscale, 2018, 10(42): 19711-19719.

[37] SENTHILKUMAR R, ANANDHABABU G, MAHALINGAM T, et al. Photoelectrochemical study of MoO3 assorted morphology films formed by thermal evaporation[J]. Journal of Energy Chemistry, 2016, 25(5): 798-804.

[38] ZHENG B J, WANG Z G, CHEN Y F, et al. Centimeter-sized 2D α-MoO3 single crystal: growth, Raman anisotropy, and optoelectronic properties[J]. 2D Materials, 2018, 5(4): 045011.

[39] DE CASTRO SILVA I, REINALDO A C, SIGOLI F A, et al. Raman spectroscopy-in situ characterization of reversibly intercalated oxygen vacancies in α-MoO3[J]. RSC Advances, 2020, 10(31): 18512-18518.

[40] 冯远皓, 柯小行，隋曼龄. 无机双钙钛矿太阳能电池材料Cs2AgBiBr6在电子束辐照下的降解行为研究[J]. 电子显微学报, 2020, 39（1）: 1-8.

[41] 管翔翔, 沈希, 张静, 等. 电子束辐照下LaCoO3/LaMnO3多层膜的结构演化[J]. 电子显微学报, 2019, 38(5): 464-469.

[42] WANG D, SU D S and SCHLöGL R. Crystallographic shear defect in molybdenum oxides: Structure and TEM of molybdenum sub-oxides Mo18O52 and Mo8O23[J]. Crystal Research and Technology, 2003, 38(2): 153-159.

[43] CAO F, JIA S F, ZHENG H, et al. Thermal-induced formation of domain structures in CuO nanomaterials[J]. Physical Review Materials, 2017, 1(5): 053401.

[44] 吕英豪, 李露颖, 刘辉辉, 等. 钾钨青铜材料中的W空位有序[J]. 电子显微学报, 2018, 37(6): 571-577.

[45] 李雷, 贾双凤, 文广玉, 等. 金属氧化物缺陷结构与微观力学形变机制[J]. 电子显微学报, 2020, 39(6): 642-649.

[46] 王正洲, 文广玉, 赵立功, 等. Al-O化合物中的有序超结构与取向畴[J]. 电子显微学报, 2020, 39(5): 487-497.

[47] SAYEDE A D, AMRIOU T, PERNISEK M, et al. An ab initio LAPW study of the α and β phases of bulk molybdenum trioxide, MoO3[J]. Chemical Physics, 2005, 316(1/2/3): 72-82.

[48] LAJAUNIE L, BOUCHER F, DESSAPT R, et al. Quantitative use of electron energy-loss spectroscopy Mo-M2,3 edges for the study of molybdenum oxides[J]. Ultramicroscopy, 2015, 149: 1-8.