Citation: Nan-Nan CHEN, Meng-Jia WANG, Yu-Feng QIAN, Meng-Ke ZHENG, Peng XU. Activated magnetic porous carbon microspheres: Preparation based on electrostatic spraying and adsorption on methylene blue[J]. Chinese Journal of Inorganic Chemistry, ;2023, 39(3): 575-584. doi: 10.11862/CJIC.2023.025 shu

Activated magnetic porous carbon microspheres: Preparation based on electrostatic spraying and adsorption on methylene blue

College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, China

Corresponding author: Peng XU, xupeng@njfu.edu.cn
Received Date: 14 October 2022
Revised Date: 15 February 2023

Figures(7)

Activated magnetic porous carbon microspheres (A‐Fe₃O₄/C) based on chitosan (CS) were prepared using a two‐step synthesis method. The prepared A‐Fe₃O₄/C was employed as an adsorbent to remove the methylene blue (MB) from water. First, magnetic microspheres Fe₃O₄/CS were prepared through electrostatic spraying with CS and FeCl₂/FeCl₃ as the precursor. Subsequently, Fe₃O₄/CS was converted into A‐Fe₃O₄/C using a combination method of high‐temperature carbonization and alkali activation. The obtained magnetic microspheres were systematically characterized by scanning electron microscopy, Fourier transform infrared, and specific surface area analyzer, and several major factors of the adsorption‐based removal were studied (e.g., pH of the solution, adsorbent dosage, temperature, contact time, as well as alkali activator). The removal efficiency was significantly dependent on the pH of the solution, and high pH values facilitated the removal of MB from water. The adsorption to MB was consistent with the pseudo ‐ second ‐ order kinetic equation, and the adsorption process was expressed using the Langmuir isotherm model. The maximum adsorption capacity of MB was examined as 300.6 mg·g^-1. Notably, the synthesized adsorbent could be effectively regenerated and repeatedly used without significant capacity loss after six cycles.
- carbonization,
- activation,
- electrostatic spray,
- Fe₃O₄,
- adsorption
1. [1]
  Wang H, Shao Y, Mei S L, Lu Y, Zhang M, Sun J K, Matyjaszewski K, Antonietti M, Yuan J Y. Polymer-derived heteroatom-doped porous carbon materials[J]. Chem. Rev., 2020,120(17):9363-9419. doi: 10.1021/acs.chemrev.0c00080
2. [2]
  Kannan C, Muthuraja K, Devi M R. Hazardous dyes removal from aqueous solution over mesoporous aluminophosphate with textural porosity by adsorption[J]. J. Hazard. Mater., 2013,244:10-20.
3. [3]
  Zhang X T, Liu H W, Taguchi T, Meng Q B, Sato O, Fujishima A. Slow interfacial charge recombination in solid-state dye-sensitized solar cell using Al₂O₃-coated nanoporous TiO ₂ films[J]. Sol. Energy Mater. Sol. Cells, 2003,81(2):197-203.
4. [4]
  Errais E, Duplay J, Elhabiri M, Elhabiri M, Khodja M, Ocampo R, Baltenweck-Guyot R, Darragi F. Anionic RR120 dye adsorption onto raw clay: Surface properties and adsorption mechanism[J]. Colloid Surf. A-Physicochem. Eng. Asp., 2012,403:69-78. doi: 10.1016/j.colsurfa.2012.03.057
5. [5]
  Zhu Y F, Zhang L X, Schappacher F M, Pöttgen R, Shi J L, Kaskel S. Synthesis of magnetically separable porous carbon microspheres and their adsorption properties of phenol and nitrobenzene from aqueous solution[J]. J. Phys. Chem. C, 2008,112(23):8623-8628. doi: 10.1021/jp8010684
6. [6]
  Luo X G, Lei X J, Cai N, Xie X P, Xue Y A, Yu F Q. Removal of heavy metal ions from water by magnetic cellulose-based beads with embedded chemically modified magnetite nanoparticles and activated carbon[J]. ACS Sustain. Chem. Eng., 2016,4(7):3960-3969. doi: 10.1021/acssuschemeng.6b00790
7. [7]
  Liu J, Qiao S Z, Hu Q H, Lu G Q. Magnetic nanocomposites with mesoporous structures: Synthesis and applications[J]. Small, 2011,7(4):425-443. doi: 10.1002/smll.201001402
8. [8]
  Ma J, Ma Y, Yu F. A novel one-pot route for large-scale synthesis of novel magnetic CNTs/Fe@C hybrids and their applications for binary dye removal[J]. ACS Sustain. Chem. Eng., 2018,6(7):8178-8191. doi: 10.1021/acssuschemeng.7b04668
9. [9]
  Yin C Y, Wei Y J, Wang F W, Chen Y H, Bao X. Magnetic hierarchical porous carbon sphere prepared for removal of organic pollutants in water[J]. Mater. Lett., 2013,104:64-67. doi: 10.1016/j.matlet.2013.03.143
10. [10]
  Liu Y, Fan X L, Jia X K, Chen X, Zhang A B, Zhang B L, Zhang Q Y. Preparation of magnetic hyper-cross-linked polymers for the efficient removal of antibiotics from water[J]. ACS Sustain. Chem. Eng., 2017,6(1):210-222.
11. [11]
  Qiu J, Wu X Y, Qiu T T. High electromagnetic wave absorbing performance of activated hollow carbon fibers decorated with CNTs and Ni nanoparticles[J]. Ceram. Int., 2016,42(4):5278-5285. doi: 10.1016/j.ceramint.2015.12.056
12. [12]
  Zhu M Y, Diao G W. Review on the progress in synthesis and application of magnetic carbon nanocomposites[J]. Nanoscale, 2011,3(7):2748-2767. doi: 10.1039/c1nr10165j
13. [13]
  Xie L L, Jin Z H, Dai Z D, Chang Y L, Jiang X, Wang H L. Porous carbons synthesized by templating approach from fluid precursors and their applications in environment and energy storage: A review[J]. Carbon, 2020,170:100-118. doi: 10.1016/j.carbon.2020.07.034
14. [14]
  Rider D A, Liu K, Eloi J C, Vanderark L, Yang L, Wang J Y, Grozea D, Lu Z H, Russell T P, Manners I. Nanostructured magnetic thin films from organometallic block copolymers: Pyrolysis of self-assembled polystyrene-block-poly(ferrocenylethylmethylsilane)[J]. ACS Nano, 2008,2(2):263-270. doi: 10.1021/nn7002629
15. [15]
  Ruan Z J, Li Z. Recent progress of magnetic nanomaterials from cobalt-containing organometallic polymer precursors[J]. Polym. Chem., 2019,11(4):764-778.
16. [16]
  Ruan Z J, Rong W H, Zhan X J, Li Q Q, Li Z. POSS containing organometallic polymers: Synthesis, characterization and solid-state pyrolysis behavior[J]. Polym. Chem., 2014,5(20):5994-6002. doi: 10.1039/C4PY00555D
17. [17]
  Gou Y Z, Tong X, Zhang Q C, Wang H, Wang B, Xie S, Wang Y D. Synthesis of hyperbranched polyferrocenylsilanes as preceramic polymers for Fe/Si/C ceramic microspheres with porous structures[J]. J. Mater. Sci., 2015,50(24):7975-7984. doi: 10.1007/s10853-015-9362-9
18. [18]
  Nakamura K, Suzuki N, Takase T. Preparation of magnetic carbon nanofibers derived from bacterial cellulose alloyed with magnetic fluid[J]. Diam. Relat. Mat., 2022,124108938. doi: 10.1016/j.diamond.2022.108938
19. [19]
  Tian K S, Wang J Y, Guo W C, Li R F, Cao L, Xu Z P, Wang H Y. Yolk-shell Fe₃ O₄@Void@N-carbon nanostructures based on one-step deposition of SiO₂ and resorcinol-3-aminophenol-formaldehyde (R-APF) cocondensed resin dual layers onto Fe₃O₄ nanoclusters[J]. Macromol. Rapid Commun., 2020,41(17)2000307. doi: 10.1002/marc.202000307
20. [20]
  Hu T, Li Y M, Gao W, Wang X F, Tian Y. Engineering of rich nitrogen-doped and magnetic mesoporous carbon nanospheres with predictable size uniformity for acid dye molecules adsorption[J]. Microporous Mesoporous Mat., 2019,279:234-244. doi: 10.1016/j.micromeso.2018.12.034
21. [21]
  Jiang W, Zhang X J, Sun Z D, Fang Y, Li F S, Chen K, Huang C X. Preparation and mechanism of magnetic carbonaceous polysaccharide microspheres by low-temperature hydrothermal method[J]. J. Magn. Magn. Mater., 2011,323(22):2741-2747. doi: 10.1016/j.jmmm.2011.05.058
22. [22]
  Zhang B L, Yu H Y, Wang J Q, Chen X, Zhang H P, Zhang Q Y. Fe₃O₄@SiO₂@CCS porous magnetic microspheres as adsorbent for removal of organic dyes in aqueous phase[J]. J. Alloy. Compd., 2018,735:1986-1996. doi: 10.1016/j.jallcom.2017.11.349
23. [23]
  Xu P, Zheng M K, Chen N N, Wu Z G, Xu N F, Tang J G, Teng Z G. Uniform magnetic chitosan microspheres with radially oriented channels by electrostatic droplets method for efficient removal of acid blue[J]. J. Taiwan Inst. Chem. Eng., 2019,104:210-218. doi: 10.1016/j.jtice.2019.09.016
24. [24]
  Gao Y, Xu S P, Yue Q Y, Wu Y W, Gao B Y. Chemical preparation of crab shell-based activated carbon with superior adsorption performance for dye removal from wastewater[J]. J. Taiwan Inst. Chem. Eng., 2016,61:327-335. doi: 10.1016/j.jtice.2015.12.023
25. [25]
  Jin Q, Li Y D, Yang D S, Cui J H. Chitosan-derived three-dimensional porous carbon for fast removal of methylene blue from wastewater[J]. RSC Adv., 2017,8(3):1255-1264.
26. [26]
  Guo L, An Q D, Xiao Z Y, Zhai S R, Cui L. Inherent N-doped honeycomb-like carbon/Fe₃O₄ composites with versatility for efficient microwave absorption and wastewater treatment[J]. ACS Sustain. Chem. Eng., 2019,7(10):9237-9248. doi: 10.1021/acssuschemeng.9b00067
27. [27]
  Thommes M, Kaneko K, Neimark A V, Olivier J P, Rodriguez-Reinoso F, Rouquerol J, Sing K S W. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report)[J]. Pure Appl. Chem., 2015,87(9/10):1051-1069.
28. [28]
  Gobi K, Mashitah M D, Vadivelu V M. Adsorptive removal of methylene blue using novel adsorbent from palm oil mill effluent waste activated sludge: Equilibrium, thermodynamics and kinetic studies[J]. Chem. Eng. J., 2011,171(3):1246-1252. doi: 10.1016/j.cej.2011.05.036
29. [29]
  Kyzas G Z, Deliyanni E A, Lazaridis N K. Magnetic modification of microporous carbon for dye adsorption[J]. Chem. Eng. J., 2014,430:166-173.
30. [30]
  Chagovets V V, Kosevich M V, Stepanian S G, Boryak O A, Shelkovsky V S, Orlov V V, Leontiev V S, Pokrovskiy V A, Adamowicz L, Karachevtsev V A. Noncovalent interaction of methylene blue with carbon nanotubes: Theoretical and mass spectrometry characterization[J]. J. Phys. Chem. C, 2012,116(38):20579-20590. doi: 10.1021/jp306333c
31. [31]
  Ahsan M A, Katla S K, Islam M T, Hernandez-Viezcas J A, Martinez L M, Díaz-Moreno C A, Lopez J, Singamaneni S R, Banuelos J, Gardea-Torresdey J, Noveron J C. Adsorptive removal of methylene blue, tetracycline and Cr(Ⅵ) from water using sulfonated tea waste[J]. Environ. Technol. Innov., 2018,11:23-40. doi: 10.1016/j.eti.2018.04.003
32. [32]
  Zhou Q, Gao Q, Luo W J, Yan C J, Ji Z N, Duan P. One-step synthesis of amino-functionalized attapulgite clay nanoparticles adsorbent by hydrothermal carbonization of chitosan for removal of methylene blue from wastewater[J]. Colloid Surf. A-Physicochem. Eng. Asp., 2015,470:248-257. doi: 10.1016/j.colsurfa.2015.01.092
33. [33]
  Wei S H, Kamali A R. Waste plastic derived Co₃Fe₇/CoFe₂O₄@carbon magnetic nanostructures for efficient dye adsorption[J]. J. Alloy. Compd., 2021,886161201. doi: 10.1016/j.jallcom.2021.161201
1. [1]
  Yongxin LIU , Xingchen LI , Hongjia LIU , Danni LI , Tao ZHANG , Xi CHEN . Enhancement effect of Fe₃O₄ conversion to MIL-100(Fe) on activation of persulfate for degradation of antibiotic. Chinese Journal of Inorganic Chemistry, 2025, 41(12): 2503-2513. doi: 10.11862/CJIC.20250169
2. [2]
  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
3. [3]
  Xiaonan Liu , Zhi Lei , Maoxia Lu , Dongwei Ma , Chuan Wang , Zehong Wu , Daohai Zhang . Construction of Fe₃O₄@ZIF-67 based flexible multifunctional hydrogels for electromagnetic interference shielding and strain sensing. Acta Physico-Chimica Sinica, 2026, 42(10): 100354-0. doi: 10.1016/j.actphy.2026.100354
4. [4]
  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
5. [5]
  Qinwen Zheng , Xin Liu , Lintao Tian , Yi Zhou , Libing Liao , Guocheng Lv . Mechanism of Fenton catalytic degradation of Rhodamine B induced by microwave and Fe₃O₄. Chinese Chemical Letters, 2025, 36(4): 109771-. doi: 10.1016/j.cclet.2024.109771
6. [6]
  Chang-An Xu , Yue Yu , Yuanming Tan , Shuxi Gao , Hao Pang . Reduced graphene oxide/Fe₃O₄ composite material integrated with electromagnetic wave absorption, thermal conductivity and corrosion resistance. Chinese Chemical Letters, 2026, 37(7): 112118-. doi: 10.1016/j.cclet.2025.112118
7. [7]
  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
8. [8]
  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
9. [9]
  Yan'e LIU , Shengli JIA , Yifan JIANG , Qinghua ZHAO , Yi LI , Xinshu CHANG . MoO₃/cellulose derived carbon aerogel: Fabrication and performance as cathode for lithium-sulfur battery. Chinese Journal of Inorganic Chemistry, 2025, 41(8): 1565-1573. doi: 10.11862/CJIC.20250054
10. [10]
  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
11. [11]
  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
12. [12]
  Ruiying Liu , Li Zhao , Baishan Liu , Jiayuan Yu , Yujie Wang , Wanqiang Yu , Di Xin , Chaoqiong Fang , Xuchuan Jiang , Riming Hu , Hong Liu , Weijia Zhou . Modulating pollutant adsorption and peroxymonosulfate activation sites on Co3O4@N,O doped-carbon shell for boosting catalytic degradation activity. Chinese Journal of Structural Chemistry, 2024, 43(8): 100332-100332. doi: 10.1016/j.cjsc.2024.100332
13. [13]
  Xiaoyang Sun , Peiyao Yang , Zhiming Liu , Shilin Zhang , Houzheng Ou , Bin Li , Yongpeng Lei , Xiangcui Liu . Simulating the reflectance and polarization spectra of vegetation via electrostatic adsorption. Chinese Chemical Letters, 2026, 37(8): 112284-. doi: 10.1016/j.cclet.2025.112284
14. [14]
  Cunjun Li , Wencong Liu , Xianlei Chen , Liang Li , Shenyu Lan , Mingshan Zhu . Adsorption and activation of peroxymonosulfate on BiOCl for carbamazepine degradation: The role of piezoelectric effect. Chinese Chemical Letters, 2024, 35(10): 109652-. doi: 10.1016/j.cclet.2024.109652
15. [15]
  Yue Li , Minghao Fan , Conghui Wang , Yanxun Li , Xiang Yu , Jun Ding , Lei Yan , Lele Qiu , Yongcai Zhang , Longlu Wang . 3D layer-by-layer amorphous MoS_x assembled from [Mo₃S₁₃]^2- clusters for efficient removal of tetracycline: Synergy of adsorption and photo-assisted PMS activation. Chinese Chemical Letters, 2024, 35(9): 109764-. doi: 10.1016/j.cclet.2024.109764
16. [16]
  Yuwei Liu , Yihui Zhu , Weijian Duan , Yizhuo Yang , Haorui Tuo , Chunhua Feng . Electrocatalytic nitrate reduction on Fe, Fe₃O₄, and Fe@Fe₃O₄ cathodes: Elucidating structure-sensitive mechanisms of direct electron versus hydrogen atom transfer. Chinese Chemical Letters, 2025, 36(6): 110347-. doi: 10.1016/j.cclet.2024.110347
17. [17]
  Huazhe Wang , Chenghuan Qiao , Chuchu Chen , Bing Liu , Juanshan Du , Qinglian Wu , Xiaochi Feng , Shuyan Zhan , Wan-Qian Guo . Synergistic adsorption and singlet oxygenation of humic acid on alkali-activated biochar via peroxymonosulfate activation. Chinese Chemical Letters, 2025, 36(5): 110244-. doi: 10.1016/j.cclet.2024.110244
18. [18]
  Yuan CONG , Yunhao WANG , Wanping LI , Zhicheng ZHANG , Shuo LIU , Huiyuan GUO , Hongyu YUAN , Zhiping ZHOU . Construction and photocatalytic properties toward rhodamine B of CdS/Fe₃O₄ heterojunction. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2241-2249. doi: 10.11862/CJIC.20240219
19. [19]
  Qing ZHANG , Kexin ZHOU , Yanjun GUO , Guangjun CHEN , Bai HE , Bo YU , Songshan JIANG , Guoyuan YUAN , Huidong QIU . Preparation, functional modification, and applications of Fe₃O₄ nanoparticles. Chinese Journal of Inorganic Chemistry, 2026, 42(7): 1383-1411. doi: 10.11862/CJIC.20250344
20. [20]
  Tiantian Long , Hongmei Luo , Jingbo Sun , Fengniu Lu , Yi Chen , Dong Xu , Zhiqin Yuan . Carbonization-engineered ultrafast chemical reaction on nanointerface. Chinese Chemical Letters, 2025, 36(3): 109728-. doi: 10.1016/j.cclet.2024.109728

Get Citation

PDF

XML

Metrics

PDF Downloads(5)
Abstract views(2207)
HTML views(299)

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