Photocatalytic Degradation of Methylene Blue Over Layered Double Hydroxides Using Various Divalent Metal Ions

  • Guoxiang PanEmail author
  • Minhong Xu
  • Kai Zhou
  • Yue Meng
  • Haifeng Chen
  • Yuhua Guo
  • Tao Wu


To apply hydrotalcites more effectively to the problem of dye wastewater, the effects of divalent metal ions on the structure and stability of hydrotalcites, especially on their photocatalytic activity, were compared. In the present study, M/Cr hydrotalcites (M3Cr-CO3-LDHs) (in which M = Mg, Co, Ni, Cu, Zn), where the M/Cr molar ratio was 3, were prepared by the co-precipitation method. The structures and properties were characterized using powder X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric-differential thermal analysis (TG-DTA), and UV-Visible diffuse reflectance spectroscopy (UV-Vis DRS). The results showed that five kinds of M3Cr-CO3-LDHs were synthesized successfully, and the layered structure of the samples obtained was regular and the crystal phase was single. When methylene blue (MB) solution was exposed to ZnCr-CO3-LDHs, H2O2, and visible light irradiation, more than 90.67% of the methylene blue (MB) was removed after 140 min. The photocatalytic activity of the samples was in the order: Co3Cr-CO3-LDHs > Mg3Cr-CO3-LDHs > Cu3Cr-CO3-LDHs > Zn3Cr-CO3-LDHs > Ni3Cr-CO3-LDHs. The results of a catalytic mechanism study showed that photocatalytic degradation of MB involved a demethylation reaction, with the reactive species containing •O2-, •OH, and h+.


Co-precipitation Method M3Cr-CO3-LDHs Methylene Blue Photocatalytic Degradation 



This Project is supported by Zhejiang Provincial Natural Science Foundation of China (No. LY17E040001; No. LQ19E040001).


  1. Adeleke, J. T., Theivasanthi, T., Thiruppathi, M., Swaminathan, M., Akomolafe, T., & Alabi, A. B. (2018). Photocatalytic degradation of methylene blue by ZnO/NiFe2O4 nanoparticles. Applied Surface Science, 455, 195–200. Scholar
  2. Alijani, M., Kaleji, B. K., & Rezaee, S. (2017). Highly visible-light active with Co/Sn co-doping of TiO2 nanoparticles for degradation of methylene blue. Journal of Materials Science Materials in Electronics, 28, 15345–15353. Scholar
  3. Bohac, P., & Bujdak, J. (2018). Prepublication: tuning the photophysical properties of cyanine dyes with clay minerals. Clays and Clay Minerals, 66, 127–137. Scholar
  4. Chen, Q., He, Q. Q., Lv, M. M., Liu, X. T., Wang, J., & Lv, J. P. (2014). The vital role of PANI for the enhanced photocatalytic activity of magnetically recyclable N–K2Ti4O9/MnFe2O4/PANI composites. Applied Surface Science, 311, 230–238. Scholar
  5. Chen, Y. F., Bao, Y., & Wang, X. Q. (2016). Green emission of Tb-doped Mg-Al layered double hydroxide response to L-lysine. Journal of Fluorescence, 26, 813–820. Scholar
  6. Comelli, N. A., Ruiz, M. L., Aparicio, M. S. L., Merino, N. A., & Ponzi, M. I. (2018). Influence of the synthetic conditions on the composition, morphology of cumgal hydrotalcites and their use as catalytic precursor in diesel soot combustion reactions. Applied Clay Science, 157, 148–157. Scholar
  7. Crossland, E. J. W., Noel, N., Sivaram, V., Leijtens, T., Alexander-Webber, J. A., & Snaith, H. J. (2013). Mesoporous TiO2 single crystals delivering enhanced mobility and optoelectronic device performance. Nature, 495, 215–219. Scholar
  8. Da, S. E., Prevot, V., Forano, C., Wong-Wah-Chung, P., Burrows, H. D., & Sarakha, M. (2014). Heterogeneous photocatalytic degradation of pesticides using decatungstate intercalated macroporous layered double hydroxides. Environmental Science & Pollution Research International, 21, 11218–11227. Scholar
  9. Fu, S., Zheng, Y., Zhou, X., Ni, Z., & Xia, S. (2019). Visible light promoted degradation of gaseous volatile organic compounds catalyzed by au supported layered double hydroxides: influencing factors, kinetics and mechanism. Journal of Hazardous Materials, 363, 41–54. Scholar
  10. Gao, Z., Sasaki, K., & Qiu, X. (2018). Structural memory effect of Mg-Al and Zn-Al layered double hydroxides in the presence of different natural humic acids: process and mechanism. Langmuir, 34, 5386–5395. Scholar
  11. Hibino, T., Yamashita, Y., Kosuge, K., & Tsunashima, A. (1995). Decarbonation behavior of Mg-Al-CO3 hydrotalcite-like compounds during heat treatment. Clays and Clay Minerals, 43, 427–432. Scholar
  12. Ishibashi, K., Fujishima, A., Watanabe, T., & Hashimoto, K. (2000). Quantum yields of active oxidative species formed on TiO2, photocatalyst. Journal of Photochemistry & Photobiology A Chemistry, 134, 139–142. Scholar
  13. Karataş, D.˙z., Senol-Arslan, D., & Ozdemir, O. (2018). Experimental and atomic modeling of the adsorption of acid azo dye 57 to sepiolite. Clays and Clay Minerals, 66, 426–437. Scholar
  14. Kuzyaka, D., Galioglu, S., Altın, İ., Sökmen, M., & Akata, B. (2018). The effect of microporous vanadosilicate Am-6 thin films as photocatalysts for the degradation of methylene blue. Journal of Photochemistry & Photobiology A Chemistry, 366, 127–135. Scholar
  15. Li, P., Yu, F., Altaf, N., Zhu, M., Li, J., Dai, B., & Wang, Q. (2018). Two-dimensional layered double hydroxides for reactions of methanation and methane reforming in C1 Chemistry. Materials,11, 221–246. Scholar
  16. Mao, N., Zhou, C. H., Tong, D. S., Yu, W. H., & Cynthia Lin, C. X. (2017). Exfoliation of layered double hydroxide solids into functional nanosheets. Applied Clay Science, 144, 60–78. Scholar
  17. Pan, G. X., Cao, F., Ni, Z. M., Li, X. N., Chen, H. F., Tang, P. S., & Xu, M. H. (2011). Preparation of NiMgAl layered double hydroxides and hydrogen production from aqueous-phase reforming of ethylene glycol. Journal of the Chinese Ceramic Society, 39, 585–589. Scholar
  18. Pan, G. X., Ni, Z. M., Cao, F., & Li, X. N. (2012). Hydrogen production from aqueous-phase reforming of ethylene glycol over Ni/Sn/Al hydrotalcite derived catalysts. Applied Clay Science, 58, 108–113. Scholar
  19. Pan, X., Wang, L. J., Sun, X. Q., Xu, B. H., & Wang, X. (2013). Ternary Titania–Cobalt Ferrite–polyaniline nanocomposite: a magnetically recyclable hybrid for adsorption and photodegradation of dyes under visible light. Industrial & Engineering Chemistry Research, 52, 10105–10113. Scholar
  20. Prevot, V., Forano, A., & Besse, J. P. (2005). Hydrolysis in polyol: new route for hybrid-layered double hydroxides preparation. Chemistry of Materials, 17, 6695–6701. Scholar
  21. Ray, S. K., Dhakal, D., Kshetri, Y. K., & Lee, S. W. (2017). Cu-α-NiMoO4 photocatalyst for degradation of Methylene blue with pathways and antibacterial performance. Journal of Photochemistry & Photobiology A Chemistry, 348, 18–32. Scholar
  22. Rives, V., Prieto, O., Dubey, A., & Kannan, S. (2003). Synergistic effect in the hydroxylation of phenol over CoNiAl ternary hydrotalcites. Journal of Catalysis, 220, 161–171. Scholar
  23. Sels, B. F., De Vos, D. E., & Jacobs, P. A. (2001). Hydrotalcite-like anionic clays in catalytic organic reactions. Catalysis Reviews, 43, 443–488. Scholar
  24. Shang, Y., Xi, C., Liu, W., Tan, P., Chen, H., Wu, L., & Pan, J. (2017). Photocorrosion inhibition and high-efficiency photoactivity of porous g-C3N4/Ag2CrO4 composites by simple microemulsion-assisted co-precipitation method. Applied Catalysis B Environmental, 204, 78–88. Scholar
  25. Tichit, D., Gerardin, C., Durand, R., & Coq, B. (2006). Layered double hydroxides: precursors for multifunctional catalysts. Topics in Catalysis, 39, 89–96. Scholar
  26. Vialat, P., Leroux, F., Taviot-Gueho, C., Villemure, G., & Mousty, C. (2013). Insights into the electrochemistry of (CoxNi(1−x))2Al–NO3 layered double hydroxides. Electrochimica Acta, 107, 599–610. Scholar
  27. Wang, L., Wang, D., Dong, X. Y., Zhang, Z. J., Pei, X. F., Chen, X. J., & Jin, J. A. (2011). Layered assembly of graphene oxide and Co-Al layered double hydroxide nanosheets as electrode materials for supercapacitors. Chemical Communications, 47, 3556–3668. Scholar
  28. Xia, S. J., Liu, F. X., Ni, Z. M., Shi, W., Xue, J. L., & Qian, P. P. (2014). Ti-based layered double hydroxides: efficient photocatalysts for azo dyes degradation under visible light. Applied Catalysis B: Environmental, 144, 570–579. Scholar
  29. Xiang, Q., Yu, J., & Wong, P. K. (2011). Quantitative characterization of hydroxyl radicals produced by various photocatalysts. Journal of Colloid & Interface Science, 357, 163–167. Scholar
  30. Xiong, P., Chen, Q., He, M. Y., Sun, X. Q., & Wang, X. (2012). Cobalt ferrite–polyaniline heteroarchitecture: a magnetically recyclable photocatalyst with highly enhanced performances. Journal of Materials Chemistry, 22, 17485–17493. Scholar
  31. Xu, M., Pan, G., Meng, Y., Guo, Y., Wu, T., & Chen, H. (2019). Effect of Ce3+ on the photocatalytic activity of MAlCe ternary hydrotalcites-like compounds in methylene blue photodegradation. Applied Clay Science, 170, 46–56. Scholar
  32. Yang, Z. H., Qian, W. M., Chu, Y. M., & Zhang, W. (2018). On approximating the arithmetic-geometric mean and complete elliptic integral of the first kind. Journal of Mathematical Analysis and Applications, 462, 1714–1726. Scholar
  33. Yang, Z. H., Chu, Y. M., & Zhang, W. (2019). High accuracy asymptotic bounds for the complete elliptic integral of the second kind. Applied Mathematics and Computation, 348, 552–564. Scholar
  34. Yuan, B., Wei, J., Hu, T., Yao, H. B., Jiang, Z. H., Fang, Z. W., & Chu, Z. Y. (2015). Simple synthesis of g-C3N4/rGO hybrid catalyst for the photocatalytic degradation of rhodamine B. Chinese Journal of Catalysis, 36, 1009–1016. Scholar
  35. Zhang, T. Y., Oyama, T., Aoshima, A., Hidaka, H., Zhao, J. C., & Serpone, N. (2001). Photooxidative n-demethylation of methylene blue in aqueous TiO2 dispersions under UV irradiation. Journal of Photochemistry & Photobiology A Chemistry, 140, 163–172. Scholar
  36. Zhang, X., Wang, L., Zhou, X., Ni, Z., & Xia, S. (2018). Investigation into the enhancement of property and the difference of mechanism onto visible light degradation of gaseous toluene catalyzed by ZnAl layered double hydroxides before and after Au supporting. ACS Sustainable Chemistry & Engineering, 6, 13395–13407. Scholar
  37. Zhao, Y. F., Zhang, S., Li, B., Yan, H., He, S., Tian, L., & Duan, X. (2011). A Family of Visible-Light Responsive Photocatalysts Obtained by Dispersing CrO6 Octahedra into a Hydrotalcite Matrix. Chemistry -A European Journal, 17, 13175–13181. Scholar
  38. Zhou, C. H. (2010). Emerging trends and challenges in synthetic clay-based materials and layered double hydroxides. Applied Clay Science, 48, 1–4. Scholar
  39. Zhou, C. H. & Keeling, J. (2013). Fundamental and applied research on clay minerals: from climate and environment to nanotechnology. Applied Clay Science, 74, 3–9. . CrossRefGoogle Scholar
  40. Zhou, C. H., Li, Z. Z., Ai, Q. W., Tian, H. C., & Hong, P. H. (2016). Current fundamental and applied research into clay minerals in china. Applied Clay Science, 119, 3–7. Scholar

Copyright information

© The Clay Minerals Society 2019
AE: Chun-Hui Zhou

Authors and Affiliations

  • Guoxiang Pan
    • 1
    • 2
    Email author
  • Minhong Xu
    • 1
  • Kai Zhou
    • 1
  • Yue Meng
    • 1
  • Haifeng Chen
    • 1
  • Yuhua Guo
    • 1
  • Tao Wu
    • 1
  1. 1.Department of Materials EngineeringHuzhou UniversityHuzhouPeople’s Republic of China
  2. 2.Zhejiang Huayuan Pigment Co., LtdDeqingPeople’s Republic of China

Personalised recommendations