Zn<sup>2+</sup>/GaOOH纳米线的制备、表征与荧光性能

田俐; 李岩; 吴杰灵; 刘强; 易益涛; 陈丽娟

doi:10.13801/j.cnki.fhclxb.20210818.001

Zn²⁺/GaOOH纳米线的制备、表征与荧光性能

doi: 10.13801/j.cnki.fhclxb.20210818.001

湖南科技大学　材料科学与工程学院，高温耐磨材料及制备技术湖南省国防科技重点实验室，精细聚合物可控制备及功能应用湖南省重点实验室，新能源储存与转换先进材料湖南省重点实验室，湘潭 411201

基金项目: 国家自然科学基金(51202066)；教育部新世纪优秀人才支持计划项目(NCET-13-0784)；湖南科技大学大学生科研创新计划(SRIP)项目(YZ2064)

详细信息

通讯作者:
田俐，博士，教授，博士生导师，研究方向为纳米光电材料　E-mail：849050031@qq.com

中图分类号: TB383.1
计量
- 文章访问数: 1213
- HTML全文浏览量: 551
- PDF下载量: 84
- 被引次数: 0
出版历程
- 收稿日期: 2021-06-07
- 修回日期: 2021-07-18
- 录用日期: 2021-07-31
- 网络出版日期: 2021-08-18
- 刊出日期: 2022-07-30

Preparation, characterization and photoluminescence of Zn²⁺/GaOOH nanowires

School of Materials Science and Engineering, Hunan Provincial Key Defense Laboratory of High Temperature Wear-resisting Materials and Preparation Technology, Hunan Provincial Key Laboratory of Controllable Preparation and Functional Application of Fine Polymers, Hunan Provincial Key Laboratory of Advanced Materials for New Energy Storage and Conversion, Hunan University of Science and Technology, Xiangtan 411201, China

摘要

摘要: 羟基氧化镓(GaOOH)是一类宽带隙的半导体材料，在光催化降解有机染料、甲醇燃料电池、锂离子电池和生物光学成像方面有着潜在的应用前景。本研究以乙二胺四乙酸二钠(Na₂Y)为模板剂，选取醋酸锌和硝酸镓为反应源，在简便易操作的水热条件下制备了Zn²⁺/GaOOH纳米线。采用XRD、SEM、HRTEM、EDS对材料进行了物相、成分、形貌与微结构表征。所制备的Zn²⁺/GaOOH纳米线长度达数十微米、直径约为100 nm，粗细均匀；Zn²⁺/GaOOH晶体呈现单晶的特性，纳米线沿<110>晶向生长。反应源及其摩尔量强烈地影响着产物的物相和形貌。当控制硝酸镓为1.5 mmol不变，Zn(Ac)₂为1.0 mmol，Na₂Y为0.5 mmol时，生成ZnGa₂O₄；Na₂Y为1.0~1.7 mmol时，生成Zn²⁺/GaOOH纳米线。改变Zn(Ac)₂为2.0 mmol，当Na₂Y 为1.5 mmol时，得到尖晶石型结构的ZnGa₂O₄。详细探究了Zn∶Ga∶Y摩尔量比例影响产物的物相和形貌的规律，结果显示当控制Zn∶Ga∶Y=2∶3∶3时，可以得到相纯均一的Zn²⁺/GaOOH纳米线。荧光测试表明，紫外光照射Zn²⁺/GaOOH纳米线，在蓝绿光区域的469 nm 波长处有很强的发射峰，归因于阴离子空位缺陷激发重组后的发射。随着激发波长蓝移，其发射峰强度增加，214 nm时强度最大。相对于ZnGa₂O₄纳米颗粒而言，在226 nm激发波长下，Zn²⁺/GaOOH纳米线在469 nm 波长处有更高的发射峰强度，Zn²⁺/GaOOH纳米线比ZnGa₂O₄纳米颗粒具有更好的荧光性能。
- GaOOH /
- 纳米线 /
- 水热合成 /
- 荧光性能 /
- 半导体材料 /
- Zn²⁺
Abstract: Gallium oxide hydroxide (GaOOH) is a kind of semiconductor material with broad-band gap and has extensive potential applications in the fields such as photocatalytic degradation of organic dyes, direct methanol fuel cell, lithium ion battery, bioluminescent imaging and so on. In our study, Zn²⁺/GaOOH nanowires have been synthesized via a facile and controllable hydrothermal method with zinc acetate and gallium nitrate as reactants and ethylenediaminetetraacetic acid disodium salt (Na₂Y) as template. The products were characterized by XRD、SEM、HRTEM and EDS techniques. The length of the as-prepared uniform Zn²⁺/GaOOH nanowires is up to several micrometers and the diameter is about 100 nm. Zn²⁺/GaOOH is single crystalline and grew along crystalline direction <110>. The phase and morphology of Zn²⁺/GaOOH are affected by reactants and their amounts. Keeping the reactant amount of 1.5 mmol gallium nitrate stand, Zn²⁺/GaOOH nanowires form with 1.0 mmol zinc acetate and 1.0-1.7 mmol Na₂Y, while spinel ZnGa₂O₄ nanoparticles obtain with 0.5 mmol Na₂Y. When the reactant amount of zinc acetate is changed to 2.0 mmol, only spinel ZnGa₂O₄ nanoparticles can be obtained with the reactant amount of 1.5 mmol gallium nitrate. The detail of the effects of the products by Zn∶Ga∶Y mole ratios on the phase and morphology was studied, showing the forming condition of phase-pure and uniform Zn²⁺/GaOOH nanowires with the Zn∶Ga∶Y mole ratio of 2∶3∶3. The result of photoluminescence determination shows that Zn²⁺/GaOOH nanowires exhibit strong PL emission in the blue-green wavelength range, attribute to the recombination of the defect-related excitations through an excitation-excitation collision process. The strongest PL emission is at 469 nm with the excitaton of 214 nm. The intensity of the emission peak at 469 nm rises with the blue-transiton of excitation wavelength. Zn²⁺/GaOOH nanowires show higher intensity of the emission peak at 469 nm by the excitation wavelength of 226 nm, accompany with ZnGa₂O₄ nanoparticles, indicating more excellent photoluminescence performance.
- GaOOH /
- nanowires /
- hydrothermal synthesis /
- photoluminescence /
- semiconductor material /
- Zn²⁺

HTML全文

图 1 α-GaOOH的XRD图谱(a)和标准卡片(b)

Figure 1. XRD patterns of the α-GaOOH product (a) and standard card (b)

下载: 全尺寸图片幻灯片

图 2 Zn²⁺/GaOOH的EDS图谱

Figure 2. EDS spectrum of Zn²⁺/GaOOH

下载: 全尺寸图片幻灯片

图 3 Zn²⁺/GaOOH纳米线不同放大倍数的SEM图像：(a) 2000 倍；(b) 5000 倍；(c) 10000 倍；(d) 20000倍

Figure 3. SEM images of Zn²⁺/GaOOH nanowires with different magnification: (a) 2 000 times; (b) 5000 times; (c) 10000 times; (d) 20000 times

下载: 全尺寸图片幻灯片

图 4 Zn²⁺/GaOOH纳米线的TEM图像，显示了Zn²⁺/GaOOH单晶的特性和生长方向：(a)低倍；(b)单根Zn²⁺/GaOOH纳米线；(c)高倍放大的单根Zn²⁺/GaOOH纳米线；(d) HRTEM

Figure 4. TEM images of Zn²⁺/GaOOH nanowires, showing single crystalline character and growth orientation of the Zn²⁺/GaOOH nanowires:(a) Low-magnification; (b) Single Zn²⁺/GaOOH nanowire; (c) Higher-magnification Zn²⁺/GaOOH nanowire; (d) HRTEM

下载: 全尺寸图片幻灯片

图 5 Zn²⁺/GaOOH纳米线的FTIR图谱

Figure 5. FTIR spectrum of Zn²⁺/GaOOH nanowires

下载: 全尺寸图片幻灯片

图 6 反应体系中加入不同摩尔量的Zn(Ac)₂所制得Zn²⁺/GaOOH的XRD图谱

Figure 6. XRD patterns of Zn²⁺/GaOOH prepared with different contents of Zn(Ac)₂

下载: 全尺寸图片幻灯片

图 7 加入不同摩尔量的反应源Zn(Ac)₂所制得Zn²⁺/GaOOH的SEM图像：(a) 0.8 mmol；(b) 2.0 mmol

Figure 7. SEM images of Zn²⁺/GaOOH obtained at different molar amounts of Zn(Ac)₂: (a) 0.8 mmol; (b) 2.0 mmol

下载: 全尺寸图片幻灯片

图 8 反应体系中加入不同摩尔量的Na₂Y所制备的Zn²⁺/GaOOH的XRD图谱

Figure 8. XRD patterns of Zn²⁺/GaOOH prepared with different contents of Na₂Y

下载: 全尺寸图片幻灯片

图 9 反应体系中加入不同摩尔量的Na₂Y所制得Zn²⁺/GaOOH的SEM图像：(a) 0.5 mmol；(b) 1.0 mmol；(c) 1.2 mmol；(d) 1.7 mmol

Figure 9. SEM images of Zn²⁺/GaOOH prepared with different contents of Na₂Y: (a) 0.5 mmol；(b) 1.0 mmol；(c) 1.2 mmol；(d) 1.7 mmol

下载: 全尺寸图片幻灯片

图 10 反应源摩尔比对 Zn²⁺/GaOOH纳米线形貌和物相的影响

Figure 10. Effects of reactants mole ratios on the phase and morphology of Zn²⁺/GaOOH nanowires

下载: 全尺寸图片幻灯片

图 11 Zn²⁺/GaOOH在不同激发波长下的荧光发射图谱

Figure 11. Fluorescence emission spectra of Zn²⁺/GaOOH nanowires at different excitation wavelengths

下载: 全尺寸图片幻灯片

图 12 Zn²⁺/GaOOH (a)和ZnGa₂O₄(b)的荧光发射图谱

Figure 12. Fluorescence emission spectra of Zn²⁺/GaOOH (a) and ZnGa₂O₄(b)

下载: 全尺寸图片幻灯片

参考文献(27)

[1]	HUANG M H, WU Y Y, FERCK H, et al. Catalytic growth of zinc oxide nanowiresby vapor transport[J]. Advanced Materials,2001,13(2):113-116. doi: 10.1002/1521-4095(200101)13:2<113::AID-ADMA113>3.0.CO;2-H
[2]	TIAN L, CHEN L. Liquid-phase preparation and electrochemical property of LiFePO₄/C nanowires[J]. Journal of Central South University. 2014, 21: 477-481.
[3]	辛国祥, 王蒙蒙, 翟耀, 等. 一步法合成具有优异循环性能的聚苯胺纳米线/自支撑石墨烯复合材料[J]. 复合材料学报, 2021, 38(4):251-261. XIN Guoxiang, WANG Mengmeng, ZHAI Yao, et al. One-step synthesis of polyaniline nanowire/self- supported graphene composite with excellent cycling stability[J]. Acta Materiae Composi-tae Sinica,2021,38(4):251-261(in Chinese).
[4]	TIAN L, SUN Q L, XU X J, et al. Controlled synthesis and formation mechanism of monodispersive lanthanum vanadate nanowires with monoclinic structure[J]. Journal of Solid State Chemistry,2013,200:123-127. doi: 10.1016/j.jssc.2013.01.039
[5]	XU L, SU Y, ZHOU Q, et al. Self-assembled catalyst growth and optical properties of single-crystalline ZnGa₂O₄ nanowires[J]. Crystal Growth & Design. 2007, 7(4): 810-814.
[6]	KIM H S, HWANG S O, MYUNG Y, et al. Three-dimensional structure of helical and zigzagged nanowires using electron tomography[J]. Nano Letters,2008,8(2):551-557. doi: 10.1021/nl072829i
[7]	ADAMS T W, VINUEZA N R, ROMANYUK O, et al. Nanostructured GaOOH modifified with reactive yellow, red and blue water-soluble dyes[J]. AIP Advances,2019,9:025005. doi: 10.1063/1.5080353
[8]	MURUGANANDHAM M, SURI R, SILLANPA M, et al. Catalytic activity evaluation of mesoporous α-GaOOH microspheres self-assembly[J]. Journal of Industrial and Engi-neering Chemistry,2015,26:348-353. doi: 10.1016/j.jiec.2014.12.008
[9]	HUANG P Q, LUAN J F. Structure and photocatalytic performance of rice husk-like Ba-doped GaOOH under light irradiation [J]. RSC Advances, 2019, 9: 19930-19939.
[10]	MURUGANANDHAM M, SURI R, ABDEL WAHED M S M, et al. Solvothermal synthesis of mesoporous α-GaOOH semi-nanospheres[J]. Materials Letters,2013,111:137-139. doi: 10.1016/j.matlet.2013.08.071
[11]	CHEN K, HE C, GUO D, et al. Low-voltage-worked photodetector based on Cu₂O/GaOOH shell-core heterojunction nanorod arrays[J]. Journal of Alloys and Compounds,2018,755:199-205. doi: 10.1016/j.jallcom.2018.04.219
[12]	LIANG H F, MENG F, LAMB B K, et al. Solution growth of screw dislocation driven α-GaOOH nanorod arrays and their conversion to porous ZnGa₂O₄nanotubes [J]. Chemi-cal Materials, 2017, 29: 7278-7287.
[13]	HSU Y H, NGUYEN A T, CHIU Y H, et al. Au-decorated GaOOH nanorods enhanced the performance of directmethanol fuel cells under light illumination[J]. Applied Catalysis B: Environmental,2016,185:133-140. doi: 10.1016/j.apcatb.2015.11.049
[14]	FENG J J, FU B, FANG L, et al. Uniform gallium oxyhydro-xide nanorod anodes with superior lithium-ion storage[J]. RSC Advances,2019,9:34896-34901. doi: 10.1039/C9RA07064H
[15]	ZHENG Y N, FAN M, LI K, et al. Ultraviolet-induced Ostwald ripening strategy towards a mesoporous Ga₂O₃/GaOOH heterojunction composite with a controllable structure for enhanced photocatalytic hydrogen evolution[J]. Catalysis Science & Technology,2020,10:2882-2892.
[16]	PRAKASAM B, LAHTINEN M, MURUGANANDHAM M, et al. Synthesis of self-assembled α-GaOOH microrods and 3D hierarchical architectures with flower like morphology and their conversion to α-Ga₂O₃[J]. Materials Letters,2015,158:370-372. doi: 10.1016/j.matlet.2015.05.044
[17]	LERTANANTAWONG B, RICHES J D, MULLANE A P O. Room temperature electrochemical synthesis of crystalline GaOOH nanoparticles from expanding liquid metals[J]. Langmuir, 2018, 34(26): 7604-7611.
[18]	XU X, BI K, HUANG K, et al. Controlled fabrication of α-GaOOH with a novel needle-like submicrontubular structure and its enhanced photocatalytic performance[J]. Journal of Alloys and Compounds,2015,644:485-490. doi: 10.1016/j.jallcom.2015.03.088
[19]	SHI L, ZHANG J, WU S, et al. Phase evolution of Ga₂O₃produced from morphology-controllable α-GaOOH nanocrystals [J]. Journal of the American Ceramic Society, 2014, 97(8): 2607-2614.
[20]	SUN M, LI D Z, ZHANG W J, et al. Rapid microwave hydrothermal synthesis of GaOOH nanorods with photocatalytic activity toward aromatic compounds[J]. Nanotechnology,2010,21(35):355601. doi: 10.1088/0957-4484/21/35/355601
[21]	KREHULA S, RISTIC M, KUBUKI S, et al. The formation and microstructural properties of uniform α-GaOOH particles and their calcination products[J]. Journal of Alloys and Compounds,2015,620:217-227. doi: 10.1016/j.jallcom.2014.09.134
[22]	TIAN L, LI Y, WANG H F, et al. Controlled preparation and self-assembly of NdVO₄ nanocrystals[J]. Journal of Rare Earths,2018,36:179-183. doi: 10.1016/j.jre.2017.04.010
[23]	TIAN L, CHENS M, LIU Q, et al. Effect of Eu³⁺-doping on morphology and fluorescent properties of neodymium vanadate nanorod-arrays[J]. Transactions Nonferrous Metals Society of China,2020,30:1031-1037. doi: 10.1016/S1003-6326(20)65274-8
[24]	田俐, 刘强, 李岩. 一种GaOOH, Zn²⁺一维纳米材料的制备方法: 中国专利, ZL 201910233072.3[P]. 2021-02-02. TIAN Li, LIU Qiang, LI Yan. A preparation method of a one-dimension nanomaterials GaOOH, Zn²⁺: Chinese patent, ZL 201910233072.3[P]. 2021-02-02 (in Chinese).
[25]	WU S, ZHANG J, SHI L, et al. Template-free synthesis of α-GaOOH hyperbranched nanoarchitectures via crystal splitting and their optical properties[J]. RSC Advances,2014,4:8209-8215. doi: 10.1039/c3ra46931j
[26]	PEI L Z, QUAN Y, FANG D, et al. Synthesis and characterization of gallium oxide nanowires via a hydrothermal me-thod[J]. Materials Chemistry and Physics,2010,121(1-2):142-146. doi: 10.1016/j.matchemphys.2010.01.009
[27]	梁建, 王晓斌, 张艳, 等. GaOOH和Ga₂O₃的制备及光学性能研究[J]. 人工晶体学报, 2013, 42(5):804-814. doi: 10.3969/j.issn.1000-985X.2013.05.006 LIANG Jian, WANG Xiaobin, ZHANG Yan, et al. Synthesis and optical properties of GaOOH and Ga₂O₃[J]. Journal of Synthetic Crystals,2013,42(5):804-814(in Chinese). doi: 10.3969/j.issn.1000-985X.2013.05.006