纳米二氧化锰的制备及其应用研究进展

doi:10.15541/jim20200105

摘要/Abstract

摘要：

二氧化锰作为一种重要的过渡金属氧化物, 因其储量丰富、晶型多样、性能优异而备受关注。将二氧化锰纳米化后, 其颗粒尺寸变小、比表面积变大、材料性能优化、应用领域得以拓宽。本文在引言部分从介绍二氧化锰的应用着手, 指出纳米化和晶型多变对二氧化锰的结构和性能有着重要的影响。正文部分主要从纳米二氧化锰的制备方法和纳米二氧化锰的应用两个方面对近年来的研究进展进行了总结和评述。(1)介绍了水热法、溶胶-凝胶法、化学沉淀法、固相合成法等纳米二氧化锰的制备方法, 对各种制备方法的优点与缺点以及所制备纳米二氧化锰的形貌与性能进行了总结。(2)综述了纳米二氧化锰在储能电极、电致变色器件、催化剂、生物传感器等领域的应用研究进展。纳米二氧化锰可作为电池的正极材料和超级电容器的电极材料。通过调控二氧化锰的晶型和复合制备的含锰复合氧化物用于锂离子电池的正极材料, 可提高电池的容量并改善循环稳定性。作为锂离子动力电池的正极材料已有产业化应用, 在新能源汽车领域具有良好的应用前景。由于纯二氧化锰本身的颜色主要是在棕色和黄色之间变化, 光调制幅度较小, 因此作为电致变色器件的电极材料, 通常将其与其它光调制幅度较大的材料进行复合使用。如聚苯胺/二氧化锰杂化电致变色薄膜较纯聚苯胺薄膜在形貌、结构和电致变色性能上有巨大差异, 显示出更高的光调制幅度、着色效率和循环稳定性。纳米二氧化锰在乙苯的催化转化和空气污染物的催化消除方面发挥重要作用。纳米二氧化锰能够增大电流响应、降低检出限, 使检测的灵敏度大大提高, 近年来在生物传感器领域逐渐被大家重视并得到广泛应用, 如二氧化锰纳米片辅助荧光偏振生物传感器可有效检测环境水样中Ag⁺, PtAu-MnO₂二元纳米结构修饰的石墨烯纸在非酶葡萄糖检测中表现出良好的传感性能。在结语部分, 分析了当前纳米二氧化锰的制备和应用方面存在的问题, 指出了纳米二氧化锰在锂离子电池正极材料和电致变色器件中应用的发展方向, 并对其未来的发展前景进行了展望。

关键词: 纳米二氧化锰, 水热法, 储能电极, 电致变色

Abstract:

As an important transition metal oxide, manganese dioxide (MnO₂) has attracted more and more attention due to its abundant reserves, varied crystal types and excellent material properties. Nanostructured MnO₂ has smaller size and larger specific surface area, that makes it can further optimize its material properties and expand its application fields. In the introduction, this article starts with the introduction of the application of manganese dioxide, and points out that nanostructuring and variability in crystal form have an important influence on the structure and properties of manganese dioxide. The main text summarizes and reviews the research progress in recent years from two aspects: the preparation methods and the applications of nanostructured MnO₂. (1) This paper introduces the progress in the preparation methods of nanostructured MnO₂ including hydrothermal, Sol-Gel, chemical precipitation, solid-phase synthesis. Then the advantages and disadvantages of preparation methods, the morphologies and properties of nanostructured MnO₂ are summarized. (2) The applications of nanostructured MnO₂ including energy-storage electrodes, electrochromic devices, catalysts and bio-sensors are reviewed. Nanostructured MnO₂ can be used as the cathode material of batteries and the electrode material of supercapacitors. Manganese- containing composite oxides prepared by adjusting the crystal form of MnO₂ and compounding are used as the cathode material of the lithium ion batteries, which can increase the capacities and improve the cycle stability of batteries. It has been industrialized as a cathode material for lithium-ion power batteries, and has good application prospects in the field of new energy vehicles. As the electrode material of electrochromic devices, MnO₂ is usually used by combining with other materials with large optical modulations since the color of pure MnO₂ mainly changes between brown and yellow and its optical modulation is small. For example, polyaniline/MnO₂ hybrid electrochromic film has a great difference in morphology, structure and electrochromic performance compared with pure polyaniline film, showing higher optical modulation, coloration efficiency and cycle stability. Nanostructured MnO₂ plays important roles in the catalytic conversion of ethylbenzene and the catalytic elimination of air pollutants. Nanostructured MnO₂ can increase the current response, reduce the detection limit, and greatly improve the sensitivity of detection. In recent years, it has been gradually paid attention to and widely used in the field of biosensors. For example, MnO₂ nanosheets assisted fluorescence polarization biosensors can be effective in detection of Ag⁺ in environmental water samples, PtAu-MnO₂ binary nanostructures modified graphene paper show good sensing performance in non-enzymatic glucose detection. In conclusion part, current existing problems are analyzed. The development direction of nanostructured MnO₂ applied in lithium-ion battery cathode materials and electrochromic devices are pointed out. The future prospects for development of nanostructured MnO₂ are discussed.

Key words: nanostructured manganese oxide, hydrothermal, energy-storage electrodes, electrochromism

中图分类号:

TQ174

王金敏, 于红玉, 马董云. 纳米二氧化锰的制备及其应用研究进展[J]. 无机材料学报, 2020, 35(12): 1307-1314.

WANG Jinmin, YU Hongyu, MA Dongyun. Progress in the Preparation and Application of Nanostructured Manganese Dioxide[J]. Journal of Inorganic Materials, 2020, 35(12): 1307-1314.

图/表 7

图1 在碳布上两步合成MnO2空心多面体纳米结构的制备过程示意图[13]

Fig. 1 Schematic illustration for the two-step preparation process of MnO2 hollow polyhedrons nanostructures assembled on carbon cloth[13]

图2 采用溶胶-凝胶法与模板法相结合, 以(a) AAO模板A和(b) AAO模板B制备的纳米MnO2的扫描电镜照片[23]

Fig. 2 SEM images of nanostructured MnO2 fabricated by using Sol-Gel and template methods with (a) AAO template A and (b) AAO template B[23]

图3 MnO2纳米片组装体的(a) FESEM、(b, c) TEM和(d) HRTEM照片, (d)中插图为SAED花样[28]

Fig. 3 (a) FESEM, (b, c) TEM and (d) HRTEM images of MnO2 assembled nanosheets with inset in (d) showing the corresponding SAED pattern [28]

图4 在1 mol/L Na2SO4电解质溶液、2.1 A/g电流密度下δ-MnO2的电容保持率, 插图为相应的δ-MnO2的充放电曲线[16]

Fig. 4 Capacitance retention of δ-MnO2 at current density of 2.1 A/g in 1 mol/L Na2SO4 electrolyte with inset showing the corresponding charge-discharge curves[16]

图5 (a) PANI、(b) MnO2和(c) PANI/MnO2在不同电压下的紫外-可见光透过率光谱, (c)中的插图为PANI/MnO2杂化膜电沉积在ITO/玻璃上的褪色态(上, 浅绿黄色)和着色态(下, 深青绿色)的照片; (d) PANI、MnO2和PANI/MnO2杂化膜在λ680nm (-0.4 V/+0.4 V, 每周期60 s)的响应时间曲线[47]

Fig. 5 UV-Vis transmittance spectra of (a) PANI, (b) MnO2, and (c) PANI/MnO2 at different potentials with insets in (c) showing the photos of PANI/MnO2 hybrid film electrodeposited on ITO/glass at bleached (upper, light greenish yellow) and colored state (lower, dark bluish green), and (d) switching curves comparison between PANI, MnO2, and PANI/MnO2 hybrid films at λ680 nm (-0.4 V/+0.4 V, 60 s/cycle)[47]

图6 (a)纳米棒状、类丝状、管状α-MnO2和花状球形Mn2O3的SEM照片; (b)在甲苯浓度为10-3、甲苯/O2的摩尔比为1/400和空速为20000 mL/(g?h)的条件下甲苯的转化率随反应温度的变化曲线[51]

Fig. 6 (a) SEM images of rod-like α-MnO2, wire-like α-MnO2, tube-like α-MnO2, and flower-like Mn2O3; (b) Toluene conversion as a function of reaction temperature over the catalysts under the conditions of a toluene concentration of 10-3, toluene/ O2 = 1/400 (mol/mol), and a space velocity of 20000 mL/(g?h)[51]

图7 在MnO2纳米片(80 μg/mL)存在下, 加入不同浓度Ag+的荧光偏振值(FP), 插图为ΔFP与Ag+的浓度之间的线性关系[52]

Fig. 7 Measurement of FP following the addition of various concentrations of Ag+ in the presence of MnO2 nanosheets (80 μg/mL) with inset showing the linear relationship between ΔFP and Ag+ concentration[52]

参考文献 53

[1]	SUN K, LI S Y, WAIGI M G, et al. Nano-MnO₂-mediated transformation of triclosan with humic molecules present: kinetics, products, and pathways. Environmental Science & Pollution Research, 2018,25(15):14416-14425. DOI URL PMID
[2]	SEO J K, SHIN J W, CHUNG H, et al. Intercalation and conversion reactions of nanosized β-MnO₂ cathode in the secondary Zn/MnO₂ alkaline battery. The Journal of Physical Chemistry C, 2018,122(21):11177-11185.
[3]	XUE F, WU S, WANG M X, et al. A three-dimensional graphene/ CNT/MnO₂ hybrid as supercapacitor electrode. Integrated Ferroelectrics, 2018,190(1):156-163.
[4]	GU X, YUE J, LI L J, et al. General synthesis of MnO_x (MnO₂, Mn₂O₃, Mn₃O₄, MnO) hierarchical microspheres as lithium-ion battery anodes. Electrochimica Acta, 2015,184:250-256.
[5]	FENG Q, KANOH H, OOI K. Manganese oxide porous crystals. Journal of Materials Chemistry, 1999,9(2):319-333.
[6]	POST J E. Manganese oxide minerals: crystal structures and economic and environmental significance. Proceedings of the National Academy of Sciences, 1999,96(7):3447-3454.
[7]	JIA Z J, WANG J, WANG Y, et al. Interfacial synthesis of δ-MnO₂ nano-sheets with a large surface area and their application in electrochemical capacitors. Journal of Materials Science & Technology, 2016,32(2):147-152.
[8]	HUANG Y J, LI W S. Preparation of manganese dioxide for oxygen reduction in zinc air battery by hydro thermal method. Journal of Inorganic Materials, 2013,28(3):341-346.
[9]	WEN J G, RUAN X Y, ZHOU Z T. Characterization of MnO₂ aerogels prepared via supercritical drying technique. Journal of Inorganic Materials, 2009,24(3):521-524.
[10]	XIAO X Z, YI Q F. Synthesis and electochemical capacity of MnO₂/SMWCNT/PANI ternarycomposites. Journal of Inorganic Materials, 2013,28(8):825-830.
[11]	DARR J A, ZHANG J Y, MAKWANA N M, et al. Continuous hydrothermal synthesis of inorganic nanoparticles: applications and future directions. Chemical Reviews, 2017,117(17):11125-11238. DOI URL PMID
[12]	ZHAO P, YAO M Q, REN H B, et al. Nanocomposites of hierarchical ultrathin MnO₂ nanosheets/hollow carbon nanofibers for high-performance asymmetric supercapacitors. Applied Surface Science, 2019,463:931-938.
[13]	WU F F, GAO X B, XU X L, et al. Boosted Zn storage performance of MnO₂ nanosheet-assembled hollow polyhedron grown on carbon cloth via a facile wet-chemical synthesis. ChemSusChem, 2020,13(6):1537-1545. DOI URL PMID
[14]	LU C J, ZHU F Q, YIN J G, et al. Synthesis of α-MnO₂ nanowires via facile hydrothermal method and their application in Li-O₂ battery. Journal of Inorganic Materials, 2018,33(9):1029-1034.
[15]	ZHU K, WANG C, CAMARGO P H C, et al. Investigating the effect of MnO₂ band gap in hybrid MnO₂-Au materials over the SPR-mediated activities under visible light. Journal of Materials Chemistry A, 2019,7(3):925-931.
[16]	WANG L, MA W L, LI Y H, et al. Synthesis of δ-MnO₂ with nanoflower-like architecture by a microwave-assisted hydrothermal method. Journal of Sol-Gel Science and Technology, 2017,82:85-91.
[17]	MA Z C, WEI X Y, XING S T, et al. Hydrothermal synthesis and characterization of surface-modified δ-MnO₂ with high Fenton-like catalytic activity. Catalysis Communications, 2015,67:68-71.
[18]	LIU D Y, DONG L M, SHAN L W, et al. Preparation of Fe-MnO₂/RGO electrode and electrochemical properties. Ferroelectrics, 2019,546(1):41-47.
[19]	XIE Y M, WANG L J, GUO Q Y, et al. Preparation of MnO₂/porous carbon material with core-shell structure and its application in supercapacitor. Journal of Materials Science Materials in Electronics, 2018,29(10):1-8.
[20]	MATHUR A, HALDER A. One step synthesis of bifunctional iron-doped manganese oxide nanorods for rechargeable zinc-air batteries. Catalysis Science & Technology, 2019,9(5):1245-1254.
[21]	JITTIARPORN P, BADILESCU S, Al SAWAFTA M N, et al. Electrochromic properties of Sol-Gel prepared hybrid transition metal oxides - a short review. Journal of Science: Advanced Materials and Devices, 2017,2(3):286-300. DOI URL
[22]	MOHAMED M A, SALLEH W N W, JAAFAR J, et al. Carbon as amorphous shell and interstitial dopant in mesoporous rutile TiO₂: bio-template assisted Sol-Gel synthesis and photocatalytic activity. Applied Surface Science, 2017,393:46-59. DOI URL
[23]	WANG X Y, WANG X Y, HUANG W G, et al. Sol-Gel template synthesis of highly ordered MnO₂ nanowire arrays. Journal of Power Sources, 2005,140(1):211-215.
[24]	赵娜英, 卞洁鹏, 杨雪健, 等. 溶胶-凝胶法制备掺镧改性纳米MnO₂. 化工新型材料, 2019,47(5):164-171.
[25]	李哲, 汤化伟, 王百年. 纳米MnO₂负载硅藻土对苯酚废水的吸附性能研究. 合肥工业大学学报(自然科学版), 2016,39(5):695-700.
[26]	THEISS F L, AYOKO G A, FROST R L. Synthesis of layered double hydroxides containing Mg²⁺, Zn²⁺, Ca²⁺ and Al³⁺ layer cations by co-precipitation methods-a review. Applied Surface Science, 2016,383:200-213.
[27]	LI X L, ZHU J F, JIAO Y H, et al. Manganese dioxide morphology on electrochemical performance of Ti₃C₂T_x@MnO₂ composites. Journal of Inorganic Materials, 2020,35(1):119-125.
[28]	MAHAMALLIK P, SAHA S, PAL A. Tetracycline degradation in aquatic environment by highly porous MnO₂ nanosheet assembly. Chemical Engineering Journal, 2015,276:155-165.
[29]	吴昊天, 张振忠, 赵芳霞, 等. 低温固相法制备的纳米α-MnO₂的性能. 电池, 2015,45(3):157-159.
[30]	龚良玉. 固相合成MnO₂纳米棒的电容性能及其PbO改性研究. 青岛农业大学学报(自然科学版), 2011,28(2):157-161.
[31]	李娟, 夏熙. 纳米MnO₂的固相合成及其电化学性能的研究(Ι): 纳米γ-MnO₂的合成及表征. 高等学校化学学报, 1999,20(9):1434-1437.
[32]	SHIN J, SEO J K, YAYLIAN R, et al. A review on mechanistic understanding of MnO₂ in aqueous electrolyte for electrical energy storage systems. International Materials Reviews, 2019: 1-32.
[33]	SHAFI P M, BOSE A C. Structural evolution of tetragonal MnO₂ and its electrochemical behavior. AIP Conference Proceedings, 2016,1731(1):050038.
[34]	HAN S D, KIM S, LI D G, et al. Mechanism of Zn insertion into nanostructured δ-MnO₂: a nonaqueous rechargeable Zn metal battery. Chemistry of Materials, 2017,29(11):4874-4884.
[35]	ZERAATI A S, ARJMAND M, SUNDARARAJ U. Silver nanowire/MnO₂ nanowire hybrid polymer nanocomposites: materials with high dielectric permittivity and low dielectric loss. ACS Applied Materials & Interfaces, 2017,9(16):14328-14336. DOI URL PMID
[36]	REHMAN S, TANG T Y, ALI Z, et al. Integrated design of MnO₂@carbon hollow nanoboxes to synergistically encapsulate polysulfides for empowering lithium sulfur batteries. Small, 2017,13(20):1700087.
[37]	LUO P F, HUANG Z. Fabrication of scandium-doped lithium manganese oxide as a high-rate capability cathode material for lithium energy storage. Solid State Ionics, 2019,338:20-24.
[38]	WANG Y M, WANG F, FENG X J. Porous nest-like LiMnPO₄ microstructures assembled by nanosheets for lithium ion battery cathodes. Journal of Materials Science: Materials in Electronics, 2018,29(2):1426-1434.
[39]	李俊豪, 冯斯桐, 张圣洁, 等. 高性能磷酸锰锂正极材料的研究进展. 材料导报, 2019,33(9):2854-2861.
[40]	ZHAO J X, WANG G H, ZHANG Q, et al. An underlying intercalation ion for fast-switching and stable electrochromism. Journal of Materials Science Materials in Electronics, 2019,30(13):12753-12756.
[41]	LIU Y R, RYOTA S, CHEUK L H, et al. Electrochromic triphenylamine-based cobalt (II) complex nanosheets. Journal of Materials Chemistry C, 2019,7(30):9159-9166.
[42]	CHEN C W, BRIGEMAN A N, HO T J, et al. Normally transparent smart window based on electrically induced instability in dielectrically negative cholesteric liquid crystal. Optical Materials Express, 2018,8(3):691.
[43]	TONG Z Q, LIU S K, LI X G, et al. Achieving rapid Li-ion insertion kinetics in TiO₂ mesoporous nanotube arrays for bifunctional high-rate energy storage smart windows. Nanoscale, 2018,10:3254-3261. DOI URL PMID
[44]	CANNAVALE A, AYR U, FIORITO F, et al. Smart electrochromic windows to enhance building energy efficiency and visual comfort. Energies, 2020,13(6):1449.
[45]	BECHINGER C, FERRERE S, ZABAN A, et al. Photoelectrochromic windows and displays. Nature, 1996,383(6601):608-610.
[46]	CHO S I, KWON W J, CHOI S J, et al. Nanotube-based ultrafast electrochromic display. Advanced Materials, 2005,17(2):171-175.
[47]	ZHOU D, CHE B Y, LU X H. Rapid one-pot electrodeposition of polyaniline/manganese dioxide hybrids: a facile approach to stable high-performance anodic electrochromic materials. Journal of Materials Chemistry C, 2017(5):1758-1766.
[48]	SAKAI N, EBINA Y, TAKADA K, et al. Electrochromic films composed of MnO₂ nanosheets with controlled optical density and high coloration efficiency. Journal of the Electrochemical Society, 2005,152(12):E384-E389.
[49]	FALAHATGAR S S, GHODSI F E, TEPEHAN F Z, et al. Electrochromic performance of Sol-Gel derived amorphous MnO₂-ZnO nanogranular composite thin films. Journal of Non-Crystalline Solids, 2015,427:1-9.
[50]	LYU W M, YANG L, FAN B B, et al. Silylated MgAl LDHs intercalated with MnO₂ nanowires: highly efficient catalysts for the solvent-free aerobic oxidation of ethylbenzene. Chemical Engineering Journal, 2015,263:309-316.
[51]	WANG F, DAI H X, DENG J G, et al. Manganese oxides with rod-, wire-, tube-, and flower-like morphologies: highly effective catalysts for the removal of toluene. Environmental Science & Technology, 2012,46(7):4034-4041. DOI URL PMID
[52]	QI L, YAN Z, HUO Y, et al. MnO₂ nanosheet-assisted ligand-DNA interaction-based fluorescence polarization biosensor for the detection of Ag⁺ ions. Biosensors and Bioelectronics, 2017,87:566-571. DOI URL PMID
[53]	XIAO F, LI Y Q, GAO H C, et al. Growth of coral-like PtAu-MnO₂ binary nanocomposites on free-standing graphene paper for flexible nonenzymatic glucose sensors. Biosensors & Bioelectronics, 2013,41:417-423. DOI URL PMID