Citation: Tong-Ming SUN, Meng YOU, Dan-Qi WANG, Ying CUI, Hui-Hui CUI, Miao WANG, Yan-Feng TANG. Simple synthesis of hierarchical ZnO microspheres for organic dyes removal[J]. Chinese Journal of Inorganic Chemistry, ;2023, 39(6): 1131-1138. doi: 10.11862/CJIC.2023.067 shu

Simple synthesis of hierarchical ZnO microspheres for organic dyes removal

School of Chemistry and Chemical Engineering, Nantong University, Nantong, Jiangsu 226019, China

Corresponding author: Miao WANG, wangmiao@ntu.edu.cn Yan-Feng TANG, tangyf@ntu.edu.cn
Received Date: 2 March 2023
Revised Date: 14 April 2023

Figures(5)

Uniform and dispersed 3D hierarchical nanosheets-assembled ZnO microspheres were fabricated by a simple ethylene glycol (EG)-assisted solvothermal route, in which hexamethylenetetramine (HMTA) was selected as a functional agent. A series of controllable experiments proved that HMTA and the solvent play vital roles in the formation of hierarchical microspheres. The assembly of 2D nanosheets to construct the 3D hierarchical structures not only increases the specific surface area of the products but also builds more charge transport channels. The samples were evaluated as adsorbents for the removal of some organic dyes from the aqueous solution in dark. Resultantly, the hierarchical nanosheets-assembled ZnO microspheres showed excellent removal rate and selectivity for anionic dyes. Taking Congo red (CR) as a representative dye, it can be removed 95.67% after five adsorption cycles due to the synergistic effects of hierarchical structures, large surface areas, and electrostatic attraction. The kinetics studies confirmed that the adsorption of CR onto ZnO microspheres is physisorption and followed the pseudo-second-order kinetic and Langmuir isotherm models.
- ZnO,
- hierarchical structures,
- nanomaterials,
- organic dyes,
- adsorption
1. [1]
  Kausar A, Iqbal M, Javed A, Aftab K, Nazli Z H, Bhatti H N, Nouren S. Dyes adsorption using clay and modified clay: A review[J]. J. Mol. Liq., 2018,256:395-407. doi: 10.1016/j.molliq.2018.02.034
2. [2]
  Molla A, Li Y, Mandal B, Kang S G, Hur S H, Chung J S. Selective adsorption of organic dyes on graphene oxide: Theoretical and experimental analysis[J]. Appl. Surf. Sci., 2019,464:170-177. doi: 10.1016/j.apsusc.2018.09.056
3. [3]
  Yu F, Li Y, Han S, Ma J. Adsorptive removal of antibiotics from aqueous solution using carbon materials[J]. Chemosphere, 2016,153:365-385. doi: 10.1016/j.chemosphere.2016.03.083
4. [4]
  Li Y H, Lai Z, Huang Z J, Wang H Y, Zhao C X, Ruan G H, Du F Y.. Fabrication of BiOBr/MoS₂/graphene oxide composites for efficient adsorption and photocatalytic removal of tetracycline antibiotics.[J]. Appl. Surf. Sci., 2021,550149342. doi: 10.1016/j.apsusc.2021.149342
5. [5]
  Du F Y, Sun L L, Tan W, Wei Z Y, Nie H G, Huang Z J, Ruan G H, Li J P. Magnetic stir cake sorptive extraction of trace tetracycline anti-biotics in food samples: preparation of metal-organic framework-embedded polyHIPE monolithic composites, validation and application[J]. Anal. Bioanal. Chem., 2019,411:2239-2248. doi: 10.1007/s00216-019-01660-1
6. [6]
  Tian C G, Zhang Q, Wu A P, Jiang M J, Liang Z L, Jiang B J, Fu H G.. Cost-effective large-scale synthesis of ZnO photocatalyst with excellent performance for dye photodegradation[J]. Chem. Commun., 2012,48:2858-2860. doi: 10.1039/c2cc16434e
7. [7]
  Goktas S, Goktas A. A comparative study on recent progress in efficient ZnO based nanocomposite and heterojunction photocatalysts: A review[J]. J. Alloy. Compd., 2021,863158734. doi: 10.1016/j.jallcom.2021.158734
8. [8]
  Weldegebrieal G K. Synthesis method, antibacterial and photocatalytic activity of ZnO nanoparticles for azo dyes in wastewater treatment: A review[J]. Chem. Commun., 2020,120108140.
9. [9]
  Movahedi T, Norouzbeigi R. Synthesis of flower-like micro/nano ZnO superhydrophobic surfaces: Additive effect optimization via designed experiments[J]. J. Alloy. Compd., 2019,795:483-492. doi: 10.1016/j.jallcom.2019.04.343
10. [10]
  Wang M, Guo Y Y, Zhu Z Q, Liu Q, Sun T M, Cui H H, Tang Y F. Diethanolamine-assisted and morphology controllable synthesis of ZnO with enhanced photocatalytic activities[J]. Mater. Lett., 2021,299130114. doi: 10.1016/j.matlet.2021.130114
11. [11]
  WU S S, YI B, WANG R, LAN D H, TAN N Y.. Enhancing photocatalytic performance of flower-like BiOBr for degradation of rhodamine B by ZnO modification[J]. Chinese J. Inorg. Chem., 2022,38(2):211-219.
12. [12]
  YAO Y F, YUAN J Y, SHEN M, DU B, XING R. Synthesis and photocatalytic performance of ZnO micro/nano materials induced by amphiphilic calixarene.[J]. Chinese J. Inorg. Chem., 2022,38(2):261-273.
13. [13]
  ZHONG W, XIA Y F, ZHAI H L, GAO Y, LI S H, L C X. Preparation by co-precipitation method and photocatalytic performance on the degradation of dyes of Ce³⁺-doped nano-ZnO[J]. Chinese J. Inorg. Chem., 2020,36(1):40-52.
14. [14]
  Kataria N, Garg V K. Removal of Congo red and brilliant green dyes from aqueous solution using flower shaped ZnO nanoparticles[J]. J. Environ. Chem., 2017,5:5420-5428. doi: 10.1016/j.jece.2017.10.035
15. [15]
  Chauhan A K, Kataria N, Garg V.. Green fabrication of ZnO nanoparticles using Eucalyptus spp. leaves extract and their application in wastewater remediation[J]. Chemosphere, 2020,247125803. doi: 10.1016/j.chemosphere.2019.125803
16. [16]
  Guo Y Y, Liu N, Sun T M, Cui H H, Wang J, Wang M, Wang M M, Tang Y F. Rational structural design of ZnOHF nanotube-assembled microsphere adsorbents for high efficient Pb²⁺ removal[J]. CrystEngComm, 2020,22:7543-7548. doi: 10.1039/D0CE01279C
17. [17]
  Guo Y Y, Mo Y X, Cui H H, Wang M, Tang Y F, Sun T M. Green and facile synthesis of hierarchical ZnOHF microspheres for rapid and selective adsorption of cationic dyes[J]. J. Mol. Liq., 2021,329115529. doi: 10.1016/j.molliq.2021.115529
18. [18]
  Yu X Y, Luo T, Jia Y, Xu R X, Gao C, Zhang Y X, Liu J H, Huang X J. Three-dimensional hierarchical flower-like Mg-Al-layered double hydroxides: highly efficient adsorbents for As and Cr removal[J]. Nanoscale, 2012,4:3466-3474. doi: 10.1039/c2nr30457k
19. [19]
  Zhang G L, Cao D J, Wang X S, Guo S Y, Yang Z Z, Cui P, Wang Q, Dou Y, Cheng S, Shen H. α-Calcium sulfate hemihydrate with a 3D hierarchical straw-sheaf morphology for use as a remove Pb²⁺ adsorbent[J]. Chemosphere, 2022,287132025. doi: 10.1016/j.chemosphere.2021.132025
20. [20]
  Gao M, Wang W M, Cao M B, Yang H B, Li Y S. Constructing hydrangea-like hierarchical zinc-zirconium oxide microspheres for accelerating fluoride elimination[J]. J. Mol. Liq., 2020,317111133.
21. [21]
  El -Nahas S, Abd El-sadek M S, Salman H M, Elkady M M.. Controlled morphological and physical properties of ZnO nanostructures synthesized by domestic microwave route[J]. Mater. Chem. Phys., 2021,258123885. doi: 10.1016/j.matchemphys.2020.123885
22. [22]
  Cho S H, Jung S H, Lee K H. Morphology-controlled growth of ZnO nanostructures using microwave irradiation: From basic to complex structures[J]. J. Phys. Chem. C, 2008,112:12769-12776.
23. [23]
  Bao Y, Wang C, Ma J Z. Morphology control of ZnO microstructures by varying hexamethylenetetramine and trisodium citrate concentration and their photocatalytic activity[J]. Mater. Des., 2016,101:7-15. doi: 10.1016/j.matdes.2016.03.158
24. [24]
  Lv S, Wang C G, Xing S X. Hexamethylenetetramine-induced synthesis of hierarchical NiO nanostructures on nickel foam and their electrochemical properties[J]. J. Alloy. Compd., 2014,603:90-196.
25. [25]
  Gao X D, Li X M, Yu W D. Synthesis and characterization of flower-like ZnO nanostructures via an ethylenediamine-meditated solution route[J]. J. Solid State Chem., 2005,178:1139-1144. doi: 10.1016/j.jssc.2004.10.020
26. [26]
  Li C, Lin Y, Li F, Zhu L H, Sun D M, Shen L, Chen Y, Ruan S P. Hexagonal ZnO nanorings: Synthesis, formation mechanism and trimethylamine sensing properties[J]. RSC Adv., 2015,5:80561-80567. doi: 10.1039/C5RA14793J
27. [27]
  Huang Z B, Zhang Y Q, Tang F Q. Solution-phase synthesis of single-crystalline magnetic nanowires with high aspect ratio and uniformity[J]. Chem. Commun., 2005,3:342-344.
28. [28]
  Zhang X, Ai Z H, Jia F L, Zhang L Z. Generalized one-pot synthesis, characterization, and photocatalytic activity of hierarchical BiOX (X = Cl, Br, I) nanoplate microspheres[J]. J. Phys. Chem. C, 2008,112:747-753.
29. [29]
  Zhong L S, Hu J S, Liang H P, Cao A M, Song W G, Wan L G. Self-assembled 3D flowerlike iron oxide nanostructures and their applica-tion in water treatment[J]. Adv. Mater., 2006,18:2426-2431.
30. [30]
  Wang M, Yang X, Tian S Q, Guo Y Y, Sun T M, Wang M M, Tang Y F. Constructing novel hierarchical porous hydrangea-like ZnWO₄ microspheres with enhanced photocatalytic performance[J]. Mater. Lett., 2020,264127417.
1. [1]
  Irshad Ahmad , Yifei Zhang , Ayman Al-Qattan , S. AlFaify , Gao Li . Unlocking the engineering of solar-driven ZnO composites: From fundaments to sustainable and eco-friendly chemical energy. Chinese Journal of Structural Chemistry, 2025, 44(11): 100700-100700. doi: 10.1016/j.cjsc.2025.100700
2. [2]
  Chuansong LIN , Chuqing ZHANG , Shixiong LI . A Ni(Ⅱ) metal-organic framework based on the 4, 4′-biphenyldicarboxylic acid ligand and its adsorption performance for tetracycline. Chinese Journal of Inorganic Chemistry, 2026, 42(3): 593-605. doi: 10.11862/CJIC.20250278
3. [3]
  Bing Shen , Tongwei Yuan , Wenshuang Zhang , Yang Chen , Jiaqiang Xu . Complex shell Fe-ZnO derived from ZIF-8 as high-quality acetone MEMS sensor. Chinese Chemical Letters, 2024, 35(11): 109490-. doi: 10.1016/j.cclet.2024.109490
4. [4]
  Yang WANG , Lulu ZHANG , Hanjiang HE , Xia ZHANG , Xiaohong SUN , Fan WANG , Shuli WANG . In situ construction of ammonium phosphomolybdate@ZIF-8 composite for Rb⁺ and Cs⁺ adsorption performance. Chinese Journal of Inorganic Chemistry, 2026, 42(4): 826-842. doi: 10.11862/CJIC.20250332
5. [5]
  Shuanglin TIAN , Tinghong GAO , Yutao LIU , Qian CHEN , Quan XIE , Qingquan XIAO , Yongchao LIANG . First-principles study of adsorption of Cl₂ and CO gas molecules by transition metal-doped g-GaN. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1189-1200. doi: 10.11862/CJIC.20230482
6. [6]
  Bowen Liu , Jianjun Zhang , Han Li , Bei Cheng , Chuanbiao Bie . MOF-derived ZnO/PANI S-scheme heterojunction for efficient photocatalytic phenol mineralization coupled with H₂O₂ generation. Acta Physico-Chimica Sinica, 2025, 41(10): 100121-0. doi: 10.1016/j.actphy.2025.100121
7. [7]
  Muhammad Riaz , Rakesh Kumar Gupta , Di Sun , Mohammad Azam , Ping Cui . Selective adsorption of organic dyes and iodine by a two-dimensional cobalt(II) metal-organic framework. Chinese Journal of Structural Chemistry, 2024, 43(12): 100427-100427. doi: 10.1016/j.cjsc.2024.100427
8. [8]
  Mengmeng SUN , Rui JIANG , Tianyi ZHAO , Jimin YANG . Fabrication of carboxyl-modified UiO-67 nanomaterials and their highly efficient removal mechanism of anionic dye. Chinese Journal of Inorganic Chemistry, 2026, 42(3): 499-506. doi: 10.11862/CJIC.20250281
9. [9]
  Xiaoyu YANG , Yejun ZHANG , Yu ZOU , Hongchao YANG , Jiang JIANG , Qiangbin WANG . Research progress of inorganic X-ray nanoscintillators. Chinese Journal of Inorganic Chemistry, 2025, 41(10): 1929-1952. doi: 10.11862/CJIC.20250122
10. [10]
  Jie Ma , Jianxiang Wang , Jianhua Yuan , Xiao Liu , Yun Yang , Fei Yu . The regulating strategy of hierarchical structure and acidity in zeolites and application of gas adsorption: A review. Chinese Chemical Letters, 2024, 35(11): 109693-. doi: 10.1016/j.cclet.2024.109693
11. [11]
  Qiang MA , Yiming ZHU , Meiqi HUA , Guangyu LU , Xingdong WANG , Hailong YU , Huan PANG , Yuping LI . Research progress on metal-organic frameworks as comprehensive carrier platforms for delivering anti-glioma drugs. Chinese Journal of Inorganic Chemistry, 2026, 42(4): 657-667. doi: 10.11862/CJIC.20250250
12. [12]
  Peng XU , Shasha WANG , Nannan CHEN , Ao WANG , Dongmei YU . Preparation of three-layer magnetic composite Fe₃O₄@polyacrylic acid@ZiF-8 for efficient removal of malachite green in water. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 544-554. doi: 10.11862/CJIC.20230239
13. [13]
  Zeyu XU , Anlei DANG , Bihua DENG , Xiaoxin ZUO , Yu LU , Ping YANG , Wenzhu YIN . Evaluation of the efficacy of graphene oxide quantum dots as an ovalbumin delivery platform and adjuvant for immune enhancement. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1065-1078. doi: 10.11862/CJIC.20240099
14. [14]
  Jingke LIU , Jia CHEN , Yingchao HAN . Nano hydroxyapatite stable suspension system: Preparation and cobalt adsorption performance. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1763-1774. doi: 10.11862/CJIC.20240060
15. [15]
  Fugui XI , Du LI , Zhourui YAN , Hui WANG , Junyu XIANG , Zhiyun DONG . Functionalized zirconium metal-organic frameworks for the removal of tetracycline from water. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 683-694. doi: 10.11862/CJIC.20240291
16. [16]
  Ting YANG , Jia AN , Jinyu ZHANG , Ruonan FAN , Rong YAN , Xiaoxia JING , Panpan CHANG , Wei YAN . Synergistic enhancement of ion migration and sulfur conversion kinetics in lithium-sulfur batteries by CeO₂/g-C₃N₄. Chinese Journal of Inorganic Chemistry, 2026, 42(3): 519-530. doi: 10.11862/CJIC.20250274
17. [17]
  Qin′ai FENG , Jianjun LI , Lili ZHANG , Linxin WU , Huiling WANG , Wenjing HOU , Lei WANG , Mingjie REN . Amphiphilic surface modification of magnetic adsorbents and its adsorption properties of two microplastics. Chinese Journal of Inorganic Chemistry, 2026, 42(4): 789-807. doi: 10.11862/CJIC.20250208
18. [18]
  Peipei DING , Jingying DUAN , Haoran XU , Xinru FANG , Xingyu LIU , Juntao YAN , Chunlei WANG . Preparation and adsorption properties of poplar catkin-derived porous carbon by ethanol solvothermal method. Chinese Journal of Inorganic Chemistry, 2026, 42(6): 1203-1214. doi: 10.11862/CJIC.20250370
19. [19]
  Cong JI , Hao WANG , Willie Forkpah DELEAU , Xinxin JING , Dapeng LI , Zhengying WU , Linbing SUN . Magnetic calcium-rich CaFe₂O₄: Synthesis and adsorption performance for phosphates in water bodies. Chinese Journal of Inorganic Chemistry, 2026, 42(6): 1131-1145. doi: 10.11862/CJIC.20260063
20. [20]
  Junliang Zhou , Tian-Bing Ren , Lin Yuan . The strategy to improve the brightness of organic small-molecule fluorescent dyes for imaging. Chinese Chemical Letters, 2025, 36(8): 110644-. doi: 10.1016/j.cclet.2024.110644

Get Citation

PDF

XML

Metrics

PDF Downloads(6)
Abstract views(5244)
HTML views(257)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142