Modification of Cu/Cr Layered Double Hydroxide by Keggin Type Polyoxometalate as Adsorbent of Malachite Green from Aqueous Solution

Neza Rahayu Palapa, Tarmizi Taher, Alfan Wijaya, Aldes Lesbani


Modification of Cu/Cr layered double hydroxides (LDHs) has been conducted by intercalation using Keggin type polyoxometalate [a-SiW12O40]4- to form CuCr-[a-SiW12O40].  The materials were analyzed by XRD, FTIR, and surface area analyses. Furthermore, materials were used as selectivity adsorbents of cationic dyes such as malachite green, rhodamine-B and methylene blue. The malachite green is more selective than others from an aqueous solution. The adsorption of malachite green showed that the adsorption capacity of CuCr-[a-SiW12O40] was higher than pristine LDHs. The adsorption process was followed pseudo second order kinetic model and Langmuir isotherm adsorption. The Qmax value of CuCr-[a-SiW12O40] reached 55.322 mg/g at 323 K after 100 minutes adsorption time. Thermodynamic parameters such as  ΔG, ΔH and ΔS confirm that the adsorption process was endothermic, spontaneous, and more favorable at high temperatures. The intercalated material was higher structural stability toward reusability adsorbent than pristine LDHs.


Abbas, M. (2020). Experimental investigation of activated carbon prepared from apricot stones material (ASM) adsorbent for removal of malachite green (MG) from aqueous solution. Adsorption Science and Technology, 38(1–2), 24–45.
Altaf, M., Ahmad, N., Cheng, C., Shoaib, S., & Shah, A. (2020). Applied Clay Science Surface induced growth of ZIF-67 at Co-layered double hydroxide : Removal of methylene blue and methyl orange from water. Applied Clay Science, 190(March), 105564.
Benselka-Hadj Abdelkader, N., Bentouami, A., Derriche, Z., Bettahar, N., & de Ménorval, L. C. (2011). Synthesis and characterization of Mg-Fe layer double hydroxides and its application on adsorption of Orange G from aqueous solution. Chemical Engineering Journal, 169(1–3), 231–238.
Bi, B., Xu, L., Xu, B., & Liu, X. (2011). Heteropoly blue-intercalated layered double hydroxides for cationic dye removal from aqueous media. Applied Clay Science, 54(3–4), 242–247.
Bulut, E., Özacar, M., & Şengil, I. A. (2008). Adsorption of malachite green onto bentonite: Equilibrium and kinetic studies and process design. Microporous and Mesoporous Materials, 115(3), 234–246.
Carriazo, D., Lima, S., Martín, C., Pillinger, M., Valente, A. A., & Rives, V. (2007). Metatungstate and tungstoniobate-containing LDHs: Preparation, characterisation and activity in epoxidation of cyclooctene. Journal of Physics and Chemistry of Solids, 68(10), 1872–1880.
Dahri, M. K., Kooh, M. R. R., & Lim, L. B. L. (2014). Water remediation using low cost adsorbent walnut shell for removal of malachite green: Equilibrium, kinetics, thermodynamic and regeneration studies. Journal of Environmental Chemical Engineering, 2(3), 1434–1444.
Dai, L., Zhu, W., He, L., Tan, F., Zhu, N., Zhou, Q., et al. (2018). Calcium-rich biochar from crab shell: An unexpected super adsorbent for dye removal. Bioresource Technology (Vol. 267).
Daniel, S., & Thomas, S. (2020). Layered double hydroxides: fundamentals to applications. Layered Double Hydroxide Polymer Nanocomposites. Elsevier Ltd.
Das, S., Dash, S. K., & Parida, K. M. (2018). Kinetics, Isotherm, and Thermodynamic Study for Ultrafast Adsorption of Azo Dye by an Efficient Sorbent: Ternary Mg/(Al + Fe) Layered Double Hydroxides. ACS Omega, 3(3), 2532–2545.
Doǧan, M., & Alkan, M. (2003). Adsorption kinetics of methyl violet onto perlite. Chemosphere, 50(4), 517–528.
Elmoubarki, R., Mahjoubi, F. Z., Elhalil, A., Tounsadi, H., Abdennouri, M., Sadiq, M., et al. (2017). Ni/Fe and Mg/Fe layered double hydroxides and their calcined derivatives: Preparation, characterization and application on textile dyes removal. Journal of Materials Research and Technology, 6(3), 271–283.
Gholami, P., Khataee, A., Soltani, R. D. C., Dinpazhoh, L., & Bhatnagar, A. (2020). Photocatalytic degradation of gemifloxacin antibiotic using Zn-Co-LDH@biochar nanocomposite. Journal of Hazardous Materials, 382(March 2019), 121070.
Giscard, D., Kamgaing, T., Temgoua, R. C. T., Ymele, E., Tchieno, F. M. M., & Tonlé, I. K. (2016). Intercalation of oxalate ions in the interlayer space of a layered double hydroxide for nickel ions adsorption. International Journal of Basic and Applied Sciences, 5(2), 144.
Harizi, I., Chebli, D., Bouguettoucha, A., Rohani, S., & Amrane, A. (2019). A New Mg–Al–Cu–Fe-LDH Composite to Enhance the Adsorption of Acid Red 66 Dye: Characterization, Kinetics and Isotherm Analysis. Arabian Journal for Science and Engineering, 44(6), 5245–5261.
Jarrah, N., Muazu, N. D., Zubair, M., & Al-Harthi, M. (2019). Enhanced adsorptive performance of Cr(VI) onto layered double hydroxide-bentonite composite: Isotherm, kinetic and thermodynamic studies. Separation Science and Technology (Philadelphia), 55(11), 1897–1909.
Jaśkaniec, S., Hobbs, C., Seral-Ascaso, A., Coelho, J., Browne, M. P., Tyndall, D., et al. (2018). Low-temperature synthesis and investigation into the formation mechanism of high quality Ni-Fe layered double hydroxides hexagonal platelets. Scientific Reports, 8(1), 4–11.
Lee, Y. C., Amini, M. H. M., Sulaiman, N. S., Mazlan, M., & Boon, J. G. (2018). Batch adsorption and isothermic studies of malachite green dye adsorption using leucaena leucocephala biomass as potential adsorbent in water treatment. Songklanakarin Journal of Science and Technology, 40(3), 563–569.
Legagneux, N., Jeanneau, E., Basset, J. M., & Lefebvre, F. (2009). Trialkyl tin salts of polyoxometalates: Synthesis and characterization of [α-SiW12O40][(CH3)3Sn(DMSO)2]4·2DMSO. Journal of Molecular Structure, 921(1–3), 300–306.
Lesbani, A, Asri, F., Palapa, N. R., Taher, T., & Rachmat, A. (2020). Efficient removal of methylene blue by adsorption using composite based Ca / Al layered double hydroxide-biochar. Global NEST Journal, 22(2), 250–257.
Lesbani, A, Taher, T., Palapa, N. R., Mohadi, R., & Yuliana, A. (2020). Methyl orange dye removal using Ni / Fe-NO 3 and Ni / Fe- [ α-SiW 12 O 40 ] layered double hydroxides Methyl orange dye removal using Ni / Fe-NO 3 and Ni / Fe- [ α -SiW 12 O 40 ] layered double hydroxides, (3), 0–7.
Lesbani, Aldes, Hensen, H., Taher, T., Hidayati, N., Mohadi, R., & Andreas, R. (2018). Intercalation of Zn/Al layered double hydroxides with Keggin ion as adsorbent of cadmium(II). AIP Conference Proceedings, 2026(Ii).
Lesbani, Aldes, Marpaung, A., Verawaty, M., Rizki Amalia, H., & Mohadi, R. (2016). Catalytic Desulfurization of Benzothiophene Using Keggin Type Polyoxometalates as catalyst. The Journal of Pure and Applied Chemistry Research, 4(1), 5–11.
Lesbani, Aldes, Taher, T., Neza, ·, Palapa, R., Mohadi, R., Rachmat, A., & Mardiyanto, ·. (2020). Preparation and utilization of Keggin-type polyoxometalate intercalated Ni-Fe layered double hydroxides for enhanced adsorptive removal of cationic dye. SN Applied Sciences, 2, 470.
Liao, X. J., & Chen, G. S. (2016). A hybrid hydrogel based on clay nanoplatelets and host-guest inclusion complexes. Chinese Chemical Letters, 27(4), 583–587.
Long, D. L., Tsunashima, R., & Cronin, L. (2010). Polyoxometalates: Building blocks for functional nanoscale systems. Angewandte Chemie - International Edition, 49(10), 1736–1758.
Ma, S., Wang, J., Du, L., Sun, Y., Gu, Q., Sun, G., & Yang, X. (2013). A new method for fast intercalation of bulk crown ether guest into LDH. Journal of Colloid and Interface Science, 393(1), 29–35.
Mall, I. D., Srivastava, V. C., Agarwal, N. K., & Mishra, I. M. (2005). Adsorptive removal of malachite green dye from aqueous solution by bagasse fly ash and activated carbon-kinetic study and equilibrium isotherm analyses. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 264(1–3), 17–28.
Mohadi, R., Palapa, N. R., & Lesbani, A. (2021). Preparation of Ca/Al-Layered Double Hydroxides/Biochar Composite with High Adsorption Capacity and Selectivity toward Cationic Dyes in Aqueous. Bulletin of Chemical Reaction Engineering & Catalysis, 16(2), 244–252.
Naseeruteen, F., Hamid, N. S. A., Suah, F. B. M., Ngah, W. S. W., & Mehamod, F. S. (2018). Adsorption of malachite green from aqueous solution by using novel chitosan ionic liquid beads. International Journal of Biological Macromolecules (Vol. 107). Elsevier B.V.
Nijs, H., Bock, M. D. E., & Vansant, E. F. (1999). Comparative Study of the Synthesis and Properties of Polyoxometalate Pillared Layered Double Hydroxides ( POM-LDHs ). Journal of Porous Materials, 110, 101–110.
Obike, A. I., Igwe, J. C., Emeruwa, C. N., & Uwakwe, K. J. (2018). Equilibrium and kinetic studies of Cu (II), Cd (II), Pb (II) and Fe (II) adsorption from aqueous solution using cocoa (Theobroma cacao) pod husk. Journal of Applied Sciences and Environmental Management, 22(2), 182.
Oktriyanti, M., Palapa, N. R., & Lesbani, A. (2020). Effective Removal of Iron ( II ) from Aqueous Solution by Adsorption using Zn / Cr Layered Double Hydroxides Intercalated with Keggin Ion. Journal of Ecological Engineering, 21(5), 63–71.
Oliveira, J. A., Cunha, F. A., & Ruotolo, L. A. M. (2019). Synthesis of zeolite from sugarcane bagasse fly ash and its application as a low-cost adsorbent to remove heavy metals. Journal of Cleaner Production, 229, 956–963.
Ouassif, H., Moujahid, E. M., Lahkale, R., Sadik, R., Bouragba, F. Z., Sabbar, E. mouloudi, & Diouri, M. (2020). Zinc-Aluminum layered double hydroxide: High efficient removal by adsorption of tartrazine dye from aqueous solution. Surfaces and Interfaces, 18, 100401.
Palapa, N R, Taher, T., Mohadi, R., & Lesbani, A. (2020). Thermodynamic study of direct dye adsorption process onto Zn-Al-NO 3 and Zn- Fe-NO 3 layered double hydroxides Thermodynamic Study of Direct Dye Adsorption Process, 040052(3).
Palapa, Neza Rahayu, Juleanti, N., Normah, N., Taher, T., & Lesbani, A. (2020). Unique Adsorption Properties of Malachite Green on Interlayer Space of Cu-Al and Cu-Al-SiW 12 O 40 Layered Double Hydroxides, 15(3), 653–661.
Palapa, Neza Rahayu, Mohadi, R., Rachmat, A., & Lesbani, A. (2020). Adsorption Study of Malachite Green Removal from Aqueous Solution Using Cu / M 3 + ( M 3 + = Al , Cr ) Layered Double Hydroxide. Mediterranean Journal of Chemistry, 10(1), 33–45.
Palapa, Neza Rahayu, Taher, T., Mohadi, R., Said, M., & Lesbani, A. (2018). Synthesis of Ni/Al layered double hydroxides (LDHs) for adsorption of malachite green and direct yellow dyes from solutions: Kinetic and thermodynamic. AIP Conference Proceedings, 2026.
Palapa, Neza Rahayu, Taher, T., Rahayu, B. R., Mohadi, R., Rachmat, A., & Lesbani, A. (2020). CuAl LDH/Rice Husk Biochar Composite for Enhanced Adsorptive Removal of Cationic Dye from Aqueous Solution. Bulletin of Chemical Reaction Engineering & Catalysis, 15(2), 525–537.
Parida, K. M., & Mohapatra, L. (2012). Carbonate intercalated Zn/Fe layered double hydroxide: A novel photocatalyst for the enhanced photo degradation of azo dyes. Chemical Engineering Journal, 179, 131–139.
Qu, W., Yuan, T., Yin, G., Xu, S., Zhang, Q., & Su, H. (2019). Effect of properties of activated carbon on malachite green adsorption. Fuel, 249(February), 45–53.
Rajabi, M., Mirza, B., Mahanpoor, K., Mirjalili, M., Najafi, F., Moradi, O., et al. (2016). Adsorption of malachite green from aqueous solution by carboxylate group functionalized multi-walled carbon nanotubes: Determination of equilibrium and kinetics parameters. Journal of Industrial and Engineering Chemistry, 34, 130–138.
Shan, R. ran, Yan, L. guo, Yang, Y. ming, Yang, K., Yu, S. jun, Yu, H. qin, et al. (2015). Highly efficient removal of three red dyes by adsorption onto Mg-Al-layered double hydroxide. Journal of Industrial and Engineering Chemistry, 21.
Silaen, L., Palapa, N. R., Juleanti, N., Mohadi, R., & Lesbani, A. (2020). Efficient Adsorption of Cadmium ( II ) on Zn / M 3 + ( M 3 + = Al , Cr ). ARPN Journal, 15(18), 1967–1975.
Siregar, P. M. S. B. N., Palapa, N. R., Wijaya, A., Fitri, E. S., & Lesbani, A. (2021). Structural stability of ni/al layered double hydroxide supported on graphite and biochar toward adsorption of congo red. Science and Technology Indonesia, 6(2), 85–95.
Srinivasan, S., & Sadasivam, S. K. (2018). Exploring docking and aerobic-microaerophilic biodegradation of textile azo dye by bacterial systems. Journal of Water Process Engineering, 22(January), 180–191.
Starukh, H., & Levytska, S. (2019). The simultaneous anionic and cationic dyes removal with Zn–Al layered double hydroxides. Applied Clay Science, 180(June), 0–5.
Sun, X., Dong, J., Li, Z., Liu, H., Jing, X., Chi, Y., & Hu, C. (2019). Mono-transition-metal-substituted polyoxometalate intercalated layered double hydroxides for the catalytic decontamination of sulfur mustard simulant. Dalton Transactions, 48(16), 5285–5291.
Taher, T., Christina, M. M., Said, M., Hidayati, N., Ferlinahayati, F., & Lesbani, A. (2019). Removal of iron(II) using intercalated Ca/Al layered double hydroxides with [-SiW 12 O 40 ] 4-. Bulletin of Chemical Reaction Engineering & Catalysis, 14(2), 260–267.
Taher, T., Mohadi, R., Rohendi, D., & Lesbani, A. (2017). Kinetic and thermodynamic adsorption studies of congo red on bentonite. AIP Conference Proceedings, 1823.
Xu, M., Bi, B., Xu, B., Sun, Z., & Xu, L. (2018). Polyoxometalate-intercalated ZnAlFe-layered double hydroxides for adsorbing removal and photocatalytic degradation of cationic dye. Applied Clay Science, 157(January), 86–91.
Xu, Y., Li, Z., Su, K., Fan, T., & Cao, L. (2018). Mussel-inspired modification of PPS membrane to separate and remove the dyes from the wastewater. Chemical Engineering Journal, 341, 371–382.
Yang, R., Liu, S. X., Tang, Q., Li, S. J., & Liang, D. D. (2012). Synthesis, structure, and catalytic activity of Keggin-type polyoxometalate coordinated Cu(I): {[Cu(py) 2] 4[SiW 12O 40]}, via hydrothermal decarboxylation. Journal of Coordination Chemistry, 65(5), 891–897.
Yun, S. K., & Pinnavaia, T. J. (1996). Layered Double Hydroxides Intercalated by Polyoxometalate Anions with Keggin , Dawson , and Finke Structures. Inorganic Chem, 35(96), 6853–6860.
Zhu, Y., Rong, J., Zhang, T., Xu, J., Dai, Y., & Qiu, F. (2018). Facile and Controlled Fabrication of Cu–Al Layered Double Hydroxide Nanosheets/Laccase Hybrid Films: A Route to Efficient Biocatalytic Removal of Congo Red from Aqueous Solutions. ACS Applied Nano Materials, 1(1), 284–292.
Zubair, M., Daud, M., McKay, G., Shehzad, F., & Al-Harthi, M. A. (2017). Recent progress in layered double hydroxides (LDH)-containing hybrids as adsorbents for water remediation. Applied Clay Science, 143(March), 279–292.


Neza Rahayu Palapa (Primary Contact)
Tarmizi Taher
Alfan Wijaya
Aldes Lesbani
Palapa, N. R., Taher, T., Wijaya, A., & Lesbani, A. (2021). Modification of Cu/Cr Layered Double Hydroxide by Keggin Type Polyoxometalate as Adsorbent of Malachite Green from Aqueous Solution. Science and Technology Indonesia, 6(3), 209–217.

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