NiAl Layered Double Hydroxide/Rice Husk Composite for the Efficient Removal of Malachite Green

Neza Rahayu Palapa(1), Tarmizi Taher(2), Normah Normah(3), Aldes Lesbani(4*)

(1) Graduate School of Mathematics and Natural Sciences, Faculty of Mathematics and Natural Sciences, Universitas Sriwijaya, Jl. Palembang Prabumulih Km. 32, Ogan Ilir 30662, Indonesia
(2) Department of Environmental Engineering, Faculty of Infrastructure and Regional, Institut Teknologi Sumatera, Jl. Terusan Ryacudu, Way Hui, Lampung Selatan 35365, Indonesia
(3) Research Center of Inorganic Materials and Coordination Complexes, Faculty of Mathematics and Natural Sciences, Universitas Sriwijaya, Jl. Palembang Prabumulih Km. 32, Ogan Ilir 30662, Indonesia
(4) Graduate School of Mathematics and Natural Sciences, Faculty of Mathematics and Natural Sciences, Universitas Sriwijaya, Jl. Palembang Prabumulih Km. 32, Ogan Ilir 30662, Indonesia Research Center of Inorganic Materials and Coordination Complexes, Faculty of Mathematics and Natural Sciences, Universitas Sriwijaya, Jl. Palembang Prabumulih Km. 32, Ogan Ilir 30662, Indonesia
(*) Corresponding Author


Rice husk biochar (BC) loaded NiAl layered double hydroxide (LDH) has been synthesized to form NiAl LDH/BC composite through a co-precipitation method. NiAl LDH/BC has been used as an adsorbent to remove malachite green from water efficiently. The specific surface area analysis revealed that the surface area of NiAl LDH/BC composite increased five times, from 92.6 to 438.9 m2/g, compared to the original NiAl LDH. The adsorption studies revealed that NiAl LDH/BC composite followed the pseudo-second-order kinetic adsorption model while the isotherm followed the Langmuir monolayer adsorption model. The maximum adsorption capacity of NiAl LDH/BC composite prepared with a ratio of 1:1 and 1:0.5 achieved 185.1 mg/g and 142.9 mg/g, respectively, which is twice higher than the pristine ones (NiAl LDH). The thermodynamic parameters, determined at 303, 313, 323, and 333 K, revealed that the adsorption process was spontaneous and endothermic. The NiAl LDH/BC composite was tested for three consecutive adsorption-desorption cycles to investigate its reusability performance. It is found that their adsorption performance slightly decreased to 71.8% and 68.3% for NiAl LDH/BC composite 1:0.5 and 1:1, respectively. Therefore, it could be considered that the synthesized NiAl LDH/BC exhibited a good and efficient adsorbent for malachite greed removal.


NiAl LDH; biochar; adsorption; kinetic study; thermodynamic study; malachite green

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[1] Srivastava, S., Sinha, R., and Roy, D., 2004, Toxicological effects of malachite green, Aquat. Toxicol., 66 (3), 319–329.

[2] Bielska, M., Sobczyńska, A., and Prochaska, K., 2009, Dye-surfactant interaction in aqueous solutions, Dyes Pigm., 80 (2), 201–205.

[3] Bekçi, Z., Özveri, C., Seki, Y., and Yurdakoç, K., 2008, Sorption of malachite green on chitosan bead, J. Hazard. Mater., 154 (1-3), 254–261.

[4] Weber, E.J., and Adams, R.L., 1995, Chemical- and sediment-mediated reduction of the azo dye Disperse Blue 79, Environ. Sci. Technol., 29 (5), 1163–1170.

[5] Ratna, and Padhi, B.S., 2012, Pollution due to synthetic dyes toxicity & carcinogenicity studies and remediation, Int. J. Environ. Sci., 3 (3), 940–955.

[6] Panswad, T., and Luangdilok, W., 2000, Decolorization of reactive dyes with different molecular structures under different environmental conditions, Water Res., 34 (17), 4177–4184.

[7] Siregar, P.M.S.B.N., Palapa, N.R., Wijaya, A., Fitri, E.S., and Lesbani, A., 2021, Structural stability of Ni/Al layered double hydroxide supported on graphite and biochar toward adsorption of Congo red, Sci. Technol. Indones., 6 (2), 85–95.

[8] Boutemak, K., Taoualit, N., Cheknane, B., Laslouni, O., Djeddou, S., Medaoud, K., Mazouni, I., and Aoudj, S., 2019, Equilibrium, kinetic and thermodynamic study of green malachite and rhodamine-B dyes sorption on olive pomace, Chem. Eng. Trans., 73, 277–282.

[9] Esan, O.S., Kolawole, A.O., and Olumuyiwa, A.C., 2019, The removal of single and binary basic dyes from synthetic wastewater using bentonite clay adsorbent, Am. J. Polym. Sci. Technol., 5 (1), 16–28.

[10] Matpang, P., Sriuttha, M., and Piwpuan, N., 2017, Effects of malachite green on growth and tissue accumulation in pak choy (Brassica chinensis Tsen & Lee ), Agric. Nat. Resour., 51 (2), 96–102.

[11] Li, J., Fan, Q., Wu, Y., Wang, X., Chen, C., Tang, Z., and Wang, X., 2016, Magnetic polydopamine decorated with Mg-Al LDH nanoflakes as a novel bio-based adsorbent for simultaneous removal of potentially toxic metals and anionic dyes, J. Mater. Chem. A, 4 (5), 1737–1746.

[12] Oldring, P.K.T., and Nehring, U., 2007, Packing Materials - 7. Metal Packing for Foodstuffs, ILSI Europe Report Series, ILSI Europe Packaging Materials Task Force, Washington, DC, US.

[13] Krishna Murthy, T.P., Gowrishankar, B.S., Chandra Prabha, M.N., Kruthi, M., and Hari Krishna, R., 2019, Studies on batch adsorptive removal of malachite green from synthetic wastewater using acid treated coffee husk: Equilibrium, kinetics and thermodynamic studies, Microchem. J., 146 192–201.

[14] Qu, W., Yuan, T., Yin, G., Xu, S., Zhang, Q., and Su, H., 2019, Effect of properties of activated carbon on malachite green adsorption, Fuel, 249, 45–53.

[15] Nidheesh, P.V., Zhou, M., and Oturan, M.A., 2018, An overview on the removal of synthetic dyes from water by electrochemical advanced oxidation processes, Chemosphere, 197 210–227.

[16] Shankar, Y.S., Ankur, K., Bhushan, P., and Mohan, D., 2019, “Utilization of Water Treatment Plant (WTP) Sludge for Pretreatment of Dye Wastewater Using Coagulation/Flocculation” in Advances in Waste Management, Eds. Kalamdhad, A., Singh, J., and Dhamodharan, K., Springer Singapore, 107–121.

[17] Dahri, M.K., Kooh, M.R.R., and Lim, L.B.L., 2014, Water remediation using low cost adsorbent walnut shell for removal of malachite green: Equilibrium, kinetics, thermodynamic and regeneration studies, J. Environ. Chem. Eng., 2 (3), 1434–1444.

[18] Robinson, T., McMullan, G., Marchant, R., and Nigam, P., 2001, Remediation of dyes in textile effluent: A critical review on current treatment technologies with a proposed alternative, Bioresour. Technol., 77 (3), 247–255.

[19] Dai, L., Zhu, W., He, L., Tan, F., Zhu, N., Zhou, Q., He, M., and Hu, G., 2018, Calcium-rich biochar from crab shell: An unexpected super adsorbent for dye removal, Bioresour. Technol., 267, 510–516.

[20] Fil, BA, 2016, Isotherm, kinetic, and thermodynamic studies on the adsorption behavior of malachite green dye onto montmorillonite clay, Part. Sci. Technol., 34 (1), 118–126.

[21] Abdelrahman, E.A., 2018, Synthesis of zeolite nanostructures from waste aluminum cans for efficient removal of malachite green dye from aqueous media, J. Mol. Liq., 253, 72–82.

[22] Chen, Y., Lin, Y.C., Ho, S.H., Zhou, Y., and Ren, N., 2018, Highly efficient adsorption of dyes by biochar derived from pigments-extracted macroalgae pyrolyzed at different temperature, Bioresour. Technol., 259, 104–110.

[23] Palapa, N.R., Juleanti, N., Mohadi, R., Taher, T., Rachmat, A., and Lesbani, A., 2020, Copper aluminum layered double hydroxide modified by biochar and its application as an adsorbent for procion red, J. Water Environ. Technol., 18 (6), 359–371.

[24] Blaisi, N.I., Zubair, M., Ihsanullah, I., Ali, S., Kazeem, T.S., Manzar, M.S., Al-Kutti, W., and Al Harthi, M.A., 2018, Date palm ash-MgAl-layered double hydroxide composite: Sustainable adsorbent for effective removal of methyl orange and eriochrome black-T from aqueous phase, Environ. Sci. Pollut. Res., 25 (34), 34319–34331.

[25] Chen, J., 2011, “Chapter 18 - Host-Guest Functional Materials” in Modern Inorganic Synthetic Chemistry, Eds. Xu. R., Pang, W., and Huo, Q., Elsevier, Amsterdam, 405–428.

[26] Shan, R., Yan, L., Yang, Y., Yang, K., Yu, S., Yu, H., Zhu, B., and Du, B., 2015, Highly efficient removal of three red dyes by adsorption onto Mg-Al-layered double hydroxide, J. Ind. Eng. Chem., 21, 561–568.

[27] Zhu, Z., Ouyang, S., Li, P., Shan, L., Ma, R., and Zhang, P., 2020, Persistent organic pollutants removal via hierarchical flower-like layered double hydroxide: Adsorption behaviors and mechanism investigation, Appl. Clay Sci., 188, 105500.

[28] Starukh, H., and Levytska, S., 2019, The simultaneous anionic and cationic dyes removal with Zn–Al layered double hydroxides, Appl. Clay Sci., 180, 105183.

[29] Palapa, N.R., Juleanti, N., Normah, N., Taher, T., and Lesbani, A., 2020, Unique adsorption properties of malachite green on interlayer space of Cu-Al and Cu-Al-SiW12O40 layered double hydroxides, Bull. Chem. React. Eng. Catal., 15 (3), 653–661.

[30] Wang, T., Li, C., Wang, C., and Wang, H., 2018, Biochar/MnAl-LDH composites for Cu(ΙΙ) removal from aqueous solution, Colloids Surf., A, 538 443–450.

[31] Lestari, N.A., 2019, Reduction of CO2 emission by integrated biomass gasification-solid oxide fuel cell combined with heat recovery and in-situ CO2 utilization, Evergreen, 6 (3), 254–261.

[32] Tareq, R., Akter, N., and Azam, M.S., 2019, “Chapter 10 - Biochars and Biochar Composites: Low-Cost Adsorbents for Environmental Remediationin” in Biochar from Biomass and Waste, Eds., Ok, Y.S., Tsang, D.C.W., Bolan, N., and Novak, J.M., Elsevier Inc., Amsterdam, Netherland, 169–209.

[33] Jerai, F., Miyazaki, T., Saha, B.B., and Koyama, S., 2015, Overview of adsorption cooling system based on activated carbon: Alcohol Pair, Evergreen, 2 (1), 30–40.

[34] Huang, D., Liu, C., Zhang, C., Deng, R., Wang, R., Xue, W., Luo, H., Zeng, G., Zhang, Q., and Guo, X., 2019, Cr(VI) removal from aqueous solution using biochar modified with Mg/Al-layered double hydroxide intercalated with ethylenediaminetetraacetic acid, Bioresour. Technol., 276, 127–132.

[35] Meili, L., Lins, P.V., Zanta, C.L.P.S., Soletti, J.I., Ribeiro, L.M.O., Dornelas, C.B., Silva, T.L., and Vieira, M.G.A., 2019, MgAl-LDH/biochar composites for methylene blue removal by adsorption, Appl. Clay Sci., 168, 11–20.

[36] Wan, S., Wang, S., Li, Y., and Gao, B., 2017, Functionalizing biochar with Mg–Al and Mg–Fe layered double hydroxides for removal of phosphate from aqueous solutions, J. Ind. Eng. Chem., 47, 246–253.

[37] Ravuru, S.S., Jana, A., and De, S., 2019, Synthesis of NiAl-layered double hydroxide with nitrate intercalation: Application in cyanide removal from steel industry effluent, J. Hazard. Mater., 373, 791–800.

[38] Kajjumba, G.W., Emik, S., Öngen, A., Özcan, H.K., and Ayd, S., 2019, “Modelling of Adsorption Kinetic Processes—Errors, Theory and Application” in Modelling of Adsorption Kinetic Processes — Errors, Theory and Application, Eds. Edebali, S., IntechOpen, Rijeka, Croatia.

[39] Aljeboree, A.M., Alkaim, A.F., and Al-Dujaili, A.H., 2015, Adsorption isotherm, kinetic modeling and thermodynamics of crystal violet dye on coconut husk-based activated carbon, Desalin. Water Treat., 53 (13), 3656–3667.

[40] Shaji, A., and Zachariah, A.K., 2017, “Chapter 9 - Surface Area Analysis of Nanomaterials” in Thermal and Rheological Measurement Techniques for Nanomaterials Characterization, Eds. Thomas, S., Thomas, R., Zachariah, A.K., and Mishra, R.K., Elsevier Inc., Amsterdam, Netherlands, 197–231.

[41] Parida, K.M., and Mohapatra, L., 2012, Carbonate intercalated Zn/Fe layered double hydroxide: A novel photocatalyst for the enhanced photo degradation of azo dyes, Chem. Eng. J., 179 131–139.

[42] James, J., and Rao, M.S., 1986, Silica from rice husk through thermal decomposition, Thermochim. Acta, 97, 329–336.

[43] Mohapatra, S., Sakthivel, R., Roy, G.S., Varma, S., Singh, S.K., and Mishra, D.K., 2011, Synthesis of β-SiC powder from bamboo leaf in a DC extended thermal plasma reactor, Mater. Manuf. Processes, 26 (11), 1362–1368.

[44] Gholami, P., Khataee, A., Soltani, R.D.C., Dinpazhoh, L., and Bhatnagar, A., 2020, Photocatalytic degradation of gemifloxacin antibiotic using Zn-Co-LDH@biochar nanocomposite, J. Hazard. Mater., 382, 121070.

[45] Lesbani, A., Asri, F., Palapa, N.R., Taher, T., and Rachmat, A., 2020, Efficient removal of methylene blue by adsorption using composite based Ca/Al layered double hydroxide-biochar, Global NEST J., 22 (2), 250–257.

[46] Harizi, I., Chebli, D., Bouguettoucha, A., Rohani, S., and 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 J. Sci. Eng., 44 (6), 5245–5261.

[47] Abukhadra, M.R., Sayed, M.A., Rabie, A.M., and Ahmed, S.A., 2019, Surface decoration of diatomite by Ni/NiO nanoparticles as hybrid composite of enhanced adsorption properties for malachite green dye and hexavalent chromium, Colloids Surf., A, 577, 583–593.

[48] Bagheri, R., Ghaedi, M., Asfaram, A., Alipanahpour Dil, E., and Javadian, H., 2019, RSM-CCD design of malachite green adsorption onto activated carbon with multimodal pore size distribution prepared from Amygdalus scoparia: Kinetic and isotherm studies, Polyhedron, 171, 464–472.

[49] Jiang, F., Dinh, D.M., and Hsieh, Y.L., 2017, Adsorption and desorption of cationic malachite green dye on cellulose nanofibril aerogels, Carbohydr. Polym., 173, 286–294.

[50] Rajabi, M., Mahanpoor, K., and Moradi, O., 2019, Preparation of PMMA/GO and PMMA/GO-Fe3O4 nanocomposites for malachite green dye adsorption: Kinetic and thermodynamic studies, Composites, Part B, 167, 544–555.

[51] Raghu, M.S., Kumar, K.Y., Prashanth, M.K., Prasanna, B.P., Vinuth, R., and Pradeep Kumar, C.B., 2017, Adsorption and antimicrobial studies of chemically bonded magnetic graphene oxide-Fe3O4 nanocomposite for water purification, J. Water Process Eng., 17, 22–31.

[52] Palapa, N.R., Taher, T., Wijaya, A., and Lesbani, A., 2021, Modification of Cu/Cr layered double hydroxide by Keggin type polyoxometalate as adsorbent of malachite green from aqueous solution, Sci. Technol. Indones., 6 (3), 209–217.

[53] Zhang, J., Liu, M., Yang, T., Yang, K., and Wang, H., 2016, A novel magnetic biochar from sewage sludge: Synthesis and its application for the removal of malachite green from wastewater, Water Sci. Technol., 74 (8), 1971–1979.

[54] Sharifpour, E., Alipanahpour Dil, E., Asfaram, A., Ghaedi, M., and Goudarzi, A., 2019, Optimizing adsorptive removal of malachite green and methyl orange dyes from simulated wastewater by Mn-doped CuO-nanoparticles loaded on activated carbon using CCD-RSM: Mechanism, regeneration, isotherm, kinetic, and thermodynamic studies, Appl. Organomet. Chem., 33 (3), e4768.

[55] Normah, N., Palapa, N.R., Taher, T., Mohadi, R., Utami, H.P., and Lesbani, A., 2021, The ability of composite Ni/Al-carbon based material toward readsorption of iron(II) in aqueous solution, Sci. Technol. Indones., 6 (3), 156–165.

[56] Naushad, M., Alqadami, A.A., AlOthman, Z.A., Alsohaimi, I.H., Algamdi, M.S., and Aldawsari, A.M., 2019, Adsorption kinetics, isotherm and reusability studies for the removal of cationic dye from aqueous medium using arginine modified activated carbon, J. Mol. Liq., 293, 111442.

[57] Nishimura, S., Takagaki, A., and Ebitani, K., 2010, Monodisperse iron oxide nanoparticles embedded in Mg-Al hydrotalcite as a highly active, magnetically separable, and recyclable solid base catalyst, Bull. Chem. Soc. Jpn., 83 (7), 846–851.


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