Skip to main content Accessibility help

Synthesis of metal–organic framework nanocrystals immobilized with 3D flowerlike Cu–Bi-layered double hydroxides for iodine efficient removal

  • Fang Yu (a1), Yuantao Chen (a1), Yunsheng Wang (a1), Chen Liu (a1) and Jianxian Qin (a1)...


The safe and efficient capture of radioactive iodine is highly necessary, but still remains an ongoing challenge. Herein, because of its special layer structure, CuBi–CO3-layered double hydroxides (CuBi–CO3-LDHs) are used to serve as a generic platform, and 3D hierarchical flowerlike ZIF-67/CuBi–CO3-LDH composites are synthesized by a simple coprecipitation method. After immobilization, the flowerlike morphology of CuBi–CO3-LDHs can be completely preserved and proved by scanning electron microscope. Various affecting factors on adsorption performance are investigated, including adsorbent dose, initial concentration of iodine, and temperature. The experimental and modeling results manifest that iodine adsorption is accurately elucidated by pseudo-second-order model, and the equilibrium isotherm is accordant with the Freundlich model. Moreover, the regeneration experiment indicates that ZIF-67/CuBi–CO3-LDH composites possess good stability and reusability for the removal of iodine. The possible adsorption mechanisms of iodine on ZIF-67/CuBi–CO3-LDHs involve particular layer structure and the strong interaction between nitrogen of imidazole ring and iodine, which were investigated by X-ray diffraction, energy-dispersive X-ray, and X-ray photoelectron spectroscopy spectra. The good performance for the iodine adsorption indicates that ZIF-67/CuBi–CO3-LDHs may be identified as a promising adsorbent in the field of iodine capture.


Corresponding author

a)Address all correspondence to this author. e-mail:


Hide All
1.Jie, Y., Luo, X., Bo, L., Jian, Z., Jian, F., Zhu, W., Wang, S., Zhang, Y., Lin, X., and Ping, C.: Bayberry tannin immobilized bovine serum albumin nanospheres: Characterization, irradiation stability and selective removal of uranyl ions from radioactive wastewater. J. Mater. Chem. A. 6, 15359 (2018).
2.Yu, M., Ohara, T., and Nishizawa, M.: Atmospheric behavior, deposition, and budget of radioactive materials from the Fukushima Daiichi nuclear power plant in March 2011. Geophys. Res. Lett. 38, 136 (2011).
3.Liu, R., Zhang, W., Chen, Y.T., Xu, C., Hu, G.Z., and Han, Z.: Highly efficient adsorption of iodine under ultrahigh pressure from aqueous solution. Sep. Purif. Technol. 233, 115999 (2020).
4.Yang, Y., Fan, G., and Li, F.: Synthesis of novel marigold-like carbonate-type Mg–Al layered double hydroxide micro-nanostructures via a two-step intercalation route. Mater. Lett. 116, 203 (2014).
5.Ao, Y.H., Wang, D.D., Wang, P.F., Wang, C., Hou, J., and Qian, J.: Enhanced photocatalytic properties of the 3D flower-like Mg–Al layered double hydroxides decorated with Ag2CO3 under visible light illumination. Mater. Res. Bull. 80, 23 (2016).
6.Sun, H.X., Chu, Z.Y., Hong, D.H., Zhang, G., Xie, Y., Li, L., and Shi, K.Y.: Three-dimensional hierarchical flower-like Mg–Al-layered double hydroxides: Fabrication, characterization and enhanced sensing properties to NOx at room temperature. J. Alloys Compd. 658, 561 (2016).
7.Zhang, J., Xie, X.L., Li, C.J., Wang, H., and Wang, L.J.: The role of soft colloidal templates in the shape evolution of flower-like Mg–Al-LDH hierarchical microstructures. RSC Adv. 5, 29757 (2015).
8.Jinesh, C.M., Rives, V., Carriazo, D., Antonyraj, C., and Kannan, S.: Influence of copper on the isomerization of eugenol for as-synthesized NiCuAl ternary hydrotalcites: An understanding through physicochemical study. Catal. Lett. 134, 337 (2010).
9.Chen, G., Qian, S., Tu, X., Wei, X., Zou, J., Leng, L., and Luo, S.: Enhancement photocatalytic degradation of rhodamine B on nano Pt intercalated Zn–Ti layered double hydroxides. Appl. Surf. Sci. 293, 345 (2014).
10.Sun, Y., Zhou, J., Cai, W., Zhao, R., and Yuan, J.: Hierarchically porous Ni Al-LDH nanoparticles as highly efficient adsorbent for p-nitrophenol from water. Appl. Surf. Sci. 349, 897 (2015).
11.Rives, V., Arco, M.D., and Martín, C.: Intercalation of drugs in layered double hydroxides and their controlled release: A review. Appl. Clay Sci. 88, 239 (2014).
12.Luo, S.L., Qian, L., Liao, M.L., Hua, X.R., and Xiao, D.: Surface and interface engineering of CoNi layered double hydroxides for efficient methanol oxidation reaction. RSC Adv. 7, 45294 (2017).
13.Tomohito, K., Kazuaki, H.S., and Toshiaki, Y.: Preparation of Cu–Al layered double hydroxide intercalated with ethylene diaminetetraacetate by coprecipitation and its uptake of rare earth ions from aqueous solution. Solid State Sci. 17, 28 (2013).
14.Kamellia, N., Soheila, D., and Marziye, S.: Study of 2,4-dichlorophenoxyacetic acid (2,4-D) removal by Cu–Fe-layered double hydroxide from aqueous solution. Appl. Surf. Sci. 280, 67 (2013).
15.Guo, Y.W., Zhu, Z.L., Qiu, Y.L., and Zhao, J.F.: Synthesis of mesoporous Cu/Mg/Fe layered double hydroxide and its adsorption performance for arsenate in aqueous solutions. RSC Adv. 5, 51868 (2015).
16.Guzmán-Vargas, A., Lima, E., Uriostegui-Ortega, G.A., Oliver-Tolentino, M.A., and Rodríguez, E.E.: Adsorption and subsequent partial photodegradation of methyl violet 2B on Cu/Al layered double hydroxides. Appl. Surf. Sci. 363, 372 (2016).
17.Butova, V.V., Soldatov, M.A., Guda, A.A., Lomachenko, K.A., and Lamberti, C.: Metal–organic frameworks: Structure, properties, methods of synthesis and characterization. Russ. Chem. Rev. 85, 280 (2016).
18.Braglia, L., Borfecchia, E., Maddalena, L., Øien, S., Lomachenko, K.A., Bugaev, A.L., Bordiga, S., Soldatov, A.V., Lillerud, K.P., and Lamberti, C.: Exploring structure and reactivity of Cu sites in functionalized UiO-67MOFs. Catal. Today 283, 89 (2017).
19.H He, S., P Li, Z., Ma, L.M., Wang, J.Q., and Yang, S.G.: Graphene oxide templated growth of MOFs with enhanced lithium-storage properties. New J. Chem. 41, 14209 (2017).
20.Yang, X.C. and Xu, Q.: Bimetallic metal–organic frameworks for gas storage and separation. Cryst. Growth Des. 17, 1450 (2017).
21.Janiak, C. and Vieth, J.K.: ChemInform abstract: MOFs, MILs and more: Concepts, properties and applications for porous coordination networks (PCNs). New J. Chem. 42, 2366 (2011).
22.Jahan, M., Liu, Z., and Loh, K.P.: A graphene oxide and copper-centered metal organic framework composite as a tri-functional catalyst for HER, OER, and ORR. Adv. Funct. Mater. 23, 5363 (2013).
23.Huang, J., Fang, G.Z., Liu, K., Zhou, J., Tang, X.K., Cai, K.N., and Liang, S.Q.: Controllable synthesis of highly uniform cuboid-shape MOFs and their derivatives for lithium-ion battery and photocatalysis applications. Chem. Eng. J. 322, 281 (2017).
24.Horcajada, P., Serre, C., Maurin, G., Ramsahye, N.A., Balas, F., Vallet-Reqí, M., Sebban, M., Taulelle, F., and Férey, G.: Flexible porous metal–organic frameworks for a controlled drug delivery. J. Am. Chem. Soc. 130, 6774 (2008).
25.Banerjee, R., Phan, A., Wang, B., Knobler, C., Furukawa, H., O’Keeffe, M., and Yaghi, O.M.: High-throughput synthesis of zeolitic imidazolate frameworks and application to CO2 capture. Science 319, 939 (2008).
26.Lia, Y.B., Jin, Z.L., and Zhao, T.S.: Performance of ZIF-67-derived fold polyhedrons for enhanced photocatalytic hydrogen evolution. Chem. Eng. J. 8, 123051 (2019).
27.Li, Z., Shao, M., Lei, Z., Zhang, R., Zhang, C., Wei, M., Evans, D.G., and Duan, X.: Directed growth of metal–organic frameworks and their derived carbon-based network for efficient electrocatalytic oxygen reduction. Adv. Mater. 28, 2337 (2016).
28.Iqbal, S., Hassan, M., Ryu, H.J., and Yun, J.: Environmentally benign and novel management route for radioactive corrosion products by hydroxyapatite. J. Nucl. Mater. 507, 218 (2018).
29.Santos, R.M.M.D., Santos, R.M.M., Gonçalves, R.G.L., Constantino, V.R.L., Costa, L.M., Silva, L.H.M., Tronto, J., and Garcia, F.: Removal of acid green 68:1 from aqueous solutions by calcined and uncalcined layered double hydroxides. Appl. Clay Sci. 80, 189 (2013).
30.Chakraborty, S., Sarkar, I., Haldar, K., Pal, S.K., and Chakraborty, S.: Synthesis of Cu–Al layered double hydroxide nanofluid and characterization of its thermal properties. Appl. Clay Sci. 107, 98 (2015).
31.He, M., Yao, J.F., Liu, Q., Wang, K., Chen, F.Y., and Wang, H.T.: Facile synthesis of zeolitic imidazolate framework-8 from a concentratedaqueous solution. Microporous Mesoporous Mater. 184, 55 (2014).
32.Kwon, H.T., Jeong, H.K., Lee, A.S., An, H.S., and Lee, J.S.: Heteroepitaxially grown zeolitic imidazolate framework membranes with unprecedented propylene/propane separation performances. J. Am. Chem. Soc. 137, 12304 (2015).
33.Santos, R.M.M.D., Gonçalves, R.G.L., Constantino, V.R.L., Santilli, C.V., Borges, P.D., Tronto, J., and Pin, F.G.: Adsorption of acid yellow 42 dye on calcined layered double hydroxide: Effect of time, concentration, pH and temperature. Appl. Clay Sci. 140, 132 (2017).
34.Xue, L.H., Gao, B., Wan, Y.S., Fang, J., Wang, S.S., Li, Y.C., Muñoz-Carpena, R., and Yang, L.Z.: High efficiency and selectivity of Mg Fe-LDH modified wheat-straw biochar in the removal of nitrate from aqueous solutions. J. Taiwan Inst. Chem. Eng. 63, 312 (2016).
35.Yang, Q.X., Lu, R., Ren, S.S., Zhou, H.M., Wu, Q.X., Zhen, Y.Y., Chen, Z.J., and Fang, S.M.: Magnetic beads embedded in poly (sodium-p-styrenesulfonate) and ZIF-67: Removal of nitrophenol from water. J. Solid State Chem. 265, 200 (2018).
36.Lia, G., Huang, Y., Lin, J., Yua, C., Liu, Z.Y., Fang, Y., Xue, Y.M., and Tang, C.C.: Effective capture and reversible storage of iodine using foam-like adsorbents consisting of porous boron nitride microfibers. Chem. Eng. J. 382, 122833 (2020).
37.Gholamia, P., Dinpazhoha, L., Khataee, A., Hassanib, A., and Bhatnagar, A.: Facile hydrothermal synthesis of novel Fe–Cu layered double hydroxide/biochar nanocomposite with enhanced sonocatalytic activity for degradation of cefazolin sodium. J. Hazard. Mater. 6, 120742 (2019).
38.Guan, C., Zhao, W., Hu, Y., Lai, Z., Li, X., Sun, S., Zhang, H., Cheetham, A.K., and Wang, J.: Cobalt oxide and N-doped carbon nanosheets derived from a single two-dimensional metal–organic framework precursor and their application in flexible asymmetric supercapacitors. Nanoscale Horiz. 2, 99 (2017).
39.Xin, Y.Y., Luo, T., Jia, Y., Xu, R.X., Gao, C., Zhang, Y.X., Liu, J.H., and Huang, X.J.: Three-dimensional hierarchical flower-like Mg–Al-layered double hydroxides:highly efficient adsorbents for As(V) and Cr(VI) removal. Nanoscale 4, 3466 (2012).
40.Liu, P.F., Tao, K., Li, G.C., Wu, M.K., Zhu, S.R., Yi, F.Y., Zhao, W.N., and Han, L.: In situ growth of ZIF-8 nanocrystals on layered double hydroxide nanosheets for enhanced CO2 capture. Dalton Trans. 45, 12632 (2016).
41.Xu, J., Deng, H., Song, J., Zhao, J., Zhang, L., and Hou, W.: Synthesis of hierarchical flower-like Mg2Al-Cl layered double hydroxide in a surfactant-free reverse microemulsion. J. Colloid Interface Sci. 505, 816 (2017).
42.Li, P. and Zeng, H.C.: Immobilization of metal–organic framework nanocrystals for advanced design of supported nanocatalysts. ACS Appl. Mater. Interfaces 8, 29551 (2016).
43.Singha, K., Latayeb, D.H., and Wasewar, K.L.: Removal of fluoride from aqueous solution by using bael (Aegle marmelos) shell activated carbon: Kinetic, equilibrium and thermodynamic study. J. Fluorine Chem. 194, 23 (2017).
44.Cai, J.J., Jiang, L.L., Wei, H.M., Wang, C.Q., Yu, L., and Zhang, L.X.: Preparation of carbon/cobalt composite from phenolic resin and ZIF-67 for efficient tannic acid adsorption. Microporous Mesoporous Mater. 287, 9 (2017).
45.Wang, Y.S., Chen, Y.T., Liu, C., Yu, F., Chi, Y.L., and Chi, C.L.: The effect of magnesium oxide morphology on adsorption of U(VI) from aqueous solution. Chem. Eng. J. 316, 936 (2017).
46.Zhang, M., Meng, J., Liu, Q.Y., Gu, S.Y., Zhao, L., Dong, M.Y., Zhang, J.X., Hou, H., and Guo, Z.H.: Corn stover-derived biochar for efficient adsorption of oxytetracycline from wastewater. J. Mater. Res. 34, 3050 (2019).
47.Hu, X., Zhang, H., and Sun, Z.: Adsorption of low concentration ceftazidime from aqueous solutions using impregnated activated carbon promoted by iron, copper and aluminum. Appl. Surf. Sci. 392, 332 (2017).
48.Li, S., Zeng, Z., and Xue, W.: Adsorption of lead ion from aqueous solution by modified walnut shell: Kinetics and thermodynamics. Environ. Technol. 2, 1 (2018).
49.Vijayalakshmi, K., Devi, B.M., Latha, S., Gomathi, T., Sudha, P.N., Venkatesan, J., and Anil, S.: Batch adsorption and desorption studies on the removal of lead(II) from aqueous solution using nanochitosan/sodium alginate/microcrystalline cellulose bead. Int. J. Biol. Macromol. 104, 1483 (2017).
50.Can, N., Omur, B.C., and Altındal, A.: Modeling of heavy metal ion adsorption isotherms onto metallophthalocyanine film. Sens. Actuators, B 237, 953 (2016).
51.Muthukumaran, C., Sivakumar, V.M., and Thirumarimurugan, M.: Adsorption isotherms and kinetic studies of crystal violet dye removal from aqueous solution using surfactant modified magnetic nanoadsorbent. J. Taiwan Inst. Chem. Eng 63, 354 (2016).
52.Gomes, R.F., deAzevedo, A.C., Pereira, A.G., Muniz, E.C., Fajardo, A.R., and Rodrigues, F.H.: Fast dye removal from water by starch-based nanocomposites. J. Colloid Interface Sci. 454, 200 (2015).
53.Chaudhry, S.A., Zaidi, Z., and Siddiqui, S.I.: Isotherm, kinetic and thermodynamics of arsenic adsorption onto iron–zirconium binary oxide-coated sand (IZBOCS): Modelling and process optimization. J. Mol. Liq. 229, 230 (2017).
54.Lagergren, S.: About the theory of so called adsorption of solution substances, Kungl Sven Vetenskapsakad Handlingar, 24, 1 (1989).
55.Zhang, X.W., Ge, Y.Z., Zhu, G.T., Tang, J.C., Xing, X.J., and Li, N.: Effect of acid and hydrothermal treatments on the multilayer adsorption of Cr(VI) and dyes on biomass-derived nano/mesoporous carbon. J. Mater. Res. 34, 3020 (2019).
56.Weber, W.J. and Morris, J.C.: Kinetics of adsorption on carbon from solution. J. Sanit. Eng. Div. 1, 12 (1963).
57.Kumar, P.S., Senthamarai, C., and Durgadevi, A.: Adsorption kinetics, mechanism, isotherm, and thermodynamic analysis of copper ions onto the surface modified agricultural waste. Environ. Prog. Sustainable Energy 33, 28 (2014).
58.Mashhadi, S., Sohrabi, R., Javadian, H., Ghasemi, M., Tyagi, I., Agarwal, S., and Gupta, V.K.: Rapid removal of Hg(II) from aqueous solution by rice straw activated carbon prepared by microwave-assisted H2SO4 activation: Kinetic, isotherm and thermodynamic studies. J. Mol. Liq. 215, 144 (2016).
59.Sari, A.A., Amriani, F., Muryanto, M., Triwulandari, E., Sudiyani, Y., Barlianti, V., Lotulung, P.D.N., and Hadibarata, T.: Mechanism, adsorption kinetics and applications of carbonaceous adsorbents derived from black liquor sludge. J. Taiwan Inst. Chem. Eng. 77, 236 (2017).
60.Wu, T., Mao, L.L., and Wang, H.Z.: Adsorption of fluoride from aqueous solution by using hybrid adsorbent fabricated with Mg/Fe composite oxide and alginate via a facile method. J. Fluorine Chem. 200, 8 (2017).
61.Lu, Y., Jiang, B., Fang, L., Ling, F.L., Gao, J.M., Wu, F., and Zhang, X.H.: High performance NiFe layered double hydroxide for methyl orangedye and Cr(VI) adsorption. Chemosphere 152, 415 (2016).
62.Tang, D.D. and Zhang, G.K.: Efficient removal of fluoride by hierarchical Ce–Fe bimetal oxides adsorbent: Thermodynamics, kinetics and mechanism. Chem. Eng. J. 283, 721 (2016).
63.Dkl, H., Chandra, V., Yoon, T., and Kim, K.S.: Radioactive iodine capture and storage from water using magnetite nanoparticles encapsulated in polypyrrole. J. Hazard. Mater. 344, 576 (2017).


Related content

Powered by UNSILO
Type Description Title
Supplementary materials

Yu et al. supplementary material
Figures S1-S5 and Tables S1-S2

 Word (594 KB)
594 KB

Synthesis of metal–organic framework nanocrystals immobilized with 3D flowerlike Cu–Bi-layered double hydroxides for iodine efficient removal

  • Fang Yu (a1), Yuantao Chen (a1), Yunsheng Wang (a1), Chen Liu (a1) and Jianxian Qin (a1)...


Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed.