Modification of Kaolin with Carbon Quantum Dots as Composite for Methylene Blue Removal: Literature Review and Experiment

Nonni Soraya Sambudi, Yuvan Sithambaran, Khee Chung Hui, Muhammad Wahyu Nugraha, Norashikin Ahmad Kamal, Noorfidza Yub Harun, Suriati Sufian


The modification of kaolin with nano-size fillers has exhibited excellent performance in the adsorption process. Carbon quantum dots (CQDs) are the new generation of nanoparticles that have attracted interest for their utilization as modifiers. In this study, a composite of metakaolin(MK)/CQDs was synthesized and tested for methylene blue (MB) removal. The heating and acid-alkali treatment of kaolin transformed it into MK. The interaction between MK and CQDs was analyzed using XPS to detect the binding of pyridic NH2 and C-N. By loading CQDs into the kaolin matrix, the surface area was improved and the removal of MB increased. For a lower MB concentration at 5 ppm, the removal efficiency could reach 96%. The composite exhibited good regeneration through the recyclability test.


Adsorption; Carbon quantum dots; Kaolin; Methylene blue

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Alfred, M. O., Omorogie, M. O., Bodede, O., Moodley, R., Ogunlaja, A., Adeyemi, O. G., and Unuabonah, E. I. (2020). Solar-active clay-TiO2 nanocomposites prepared via biomass assisted synthesis: Efficient removal of ampicillin, sulfamethoxazole and artemether from water. Chemical Engineering Journal, 398, 125544.

Anshar, A. M., Taba, P., and Raya, I. (2016). Kinetic and thermodynamics studies the adsorption of phenol on activated carbon from rice husk activated by ZnCl2. Indonesian Journal of Science and Technology, 1(1), 47-60.

Asuha, S., Fei, F., Wurendaodi, W., Zhao, S., Wu, H., and Zhuang, X. (2020). Activation of kaolinite by a low-temperature chemical method and its effect on methylene blue adsorption. Powder Technology, 361, 624-632.

Awad, A. M., Shaikh, S. M., Jalab, R., Gulied, M. H., Nasser, M. S., Benamor, A., and Adham, S. (2019). Adsorption of organic pollutants by natural and modified clays: a comprehensive review. Separation and Purification Technology, 228, 115719.

Boukhemkhem, A., and Rida, K. (2017). Improvement adsorption capacity of methylene blue onto modified Tamazert kaolin. Adsorption Science and Technology, 35(9-10), 753-773.

Boushehrian, M. M., Esmaeili, H., and Foroutan, R. (2020). Ultrasonic assisted synthesis of Kaolin/CuFe2O4 nanocomposite for removing cationic dyes from aqueous media. Journal of Environmental Chemical Engineering, 8(4), 103869.

Caballero, L. R., Paiva, M. d. D. M., Fairbairn, E. d. M. R., and Toledo Filho, R. D. (2019). Thermal, mechanical and microstructural analysis of metakaolin based geopolymers. Materials Research, 22, 1-8.

Chai, J. B., Au, P. I., Mubarak, N. M., Khalid, M., Ng, W. P. Q., Jagadish, P., and Abdullah, E. C. (2020). Adsorption of heavy metal from industrial wastewater onto low-cost Malaysian kaolin clay–based adsorbent. Environmental Science and Pollution Research, 27(12), 13949-13962.

Chargui, H., Hajjaji, W., Wouters, J., Yans, J., and Jamoussi, F. (2018). Direct orange 34 dye fixation by modified kaolin. Clay Minerals, 53(2), 271-287.

Chung Hui, K., Lun Ang, W., and Soraya Sambudi, N. (2021). Nitrogen and bismuth-doped rice husk-derived carbon quantum dots for dye degradation and heavy metal removal. Journal of Photochemistry and Photobiology A: Chemistry, 418, 113411.

Chung, H. K., Wongso, V., Sambudi, N. S., and Isnaeni. (2020). Biowaste-derived carbon dots/hydroxyapatite nanocomposite as drug delivery vehicle for acetaminophen. Journal of Sol-Gel Science and Technology, 93(1), 214-223.

Çiftçi, H. (2022). Removal of methylene blue from water by ultrasound-assisted adsorption using low-cost bentonites. Chemical Physics Letters, 802, 139758.

David, M. K., Okoro, U. C., Akpomie, K. G., Okey, C., and Oluwasola, H. O. (2020). Thermal and hydrothermal alkaline modification of kaolin for the adsorptive removal of lead(II) ions from aqueous solution. SN Applied Sciences, 2(6), 1134.

de la Luz-Asunción, M., Pérez-Ramírez, E. E., Martínez-Hernández, A. L., García-Casillas, P. E., Luna-Bárcenas, J. G., and Velasco-Santos, C. (2020). Adsorption and kinetic study of Reactive Red 2 dye onto graphene oxides and graphene quantum dots. Diamond and Related Materials, 109, 108002.

de Oliveira, M. C. A., de L. Oliveira, E. G., Pires, I. C. B., Candido, I. C. M., Rakov, N., de Oliveira, H. P., and Maciel, G. S. (2020). Carbon dots-doped electrospun fibers for simultaneous metal ion detection and adsorption of dyes. Advanced Fiber Materials, 2(6), 302-313.

Dewi, R., Shamsuddin, N., Bakar, M. S. A., Santos, J. H., Bilad, M. R., and Lim, L. H. (2021). Progress in emerging contaminants removal by adsorption/membrane filtration-based technologies: A review. Indonesian Journal of Science and Technology, 6(3), 577-618.

Fadillah, G., Yudha, S. P., Sagadevan, S., Fatimah, I., and Muraza, O. (2020). Magnetic iron oxide/clay nanocomposites for adsorption and catalytic oxidation in water treatment applications. Open Chemistry, 18(1), 1148-1166.

Fadzil, M. A., Nurhasri, M. M., Norliyati, M. A., Hamidah, M. S., Ibrahim, M. W., and Assrul, R. Z. (2017). Characterization of kaolin as nano material for high quality construction. MATEC Web of Conferences, 103, 09019.

Fatimah, S., Ragadhita, R., Al Husaeni, D. F., and Nandiyanto, A. B. D. (2010). How to calculate crystallite size from x-ray diffraction (XRD) using Scherrer method. ASEAN Journal of Science and Engineering, 2(1), 65-76.

Fei, F., Gao, Z., Wu, H., Wurendaodi, W., Zhao, S., and Asuha, S. (2020). Facile solid-state synthesis of Fe3O4/kaolinite nanocomposites for enhanced dye adsorption. Journal of Solid State Chemistry, 291, 121655.

Ferrazzo, S. T., Tímbola, R. d. S., Bragagnolo, L., Prestes, E., Korf, E. P., Prietto, P. D. M., and Ulsen, C. (2020). Effects of acidic attack on chemical, mineralogical, and morphological properties of geomaterials. Environmental Science and Pollution Research, 27(30), 37718-37732.

Fiandini, M., Ragadhita, R. I. S. T. I., Nandiyanto, A. B. D., and Nugraha, W. C. (2020). Adsorption characteristics of submicron porous carbon particles prepared from rice husk. Journal of Engineering Science and Technology, 15, 022-031.

Gasparini, E., Tarantino, S. C., Ghigna, P., Riccardi, M. P., Cedillo-González, E. I., Siligardi, C., and Zema, M. (2013). Thermal dehydroxylation of kaolinite under isothermal conditions. Applied Clay Science, 80, 417-425.

Golubeva, O. Y., Alikina, Y. A., and Kalashnikova, T. A. (2020). Influence of hydrothermal synthesis conditions on the morphology and sorption properties of porous aluminosilicates with kaolinite and halloysite structures. Applied Clay Science, 199, 105879.

Guggenheim, s., and Martin, R. T. (1995). Definition of clay and clay mineral: joint report of the AIPEA and CMS Nomenclature Committees. Clay Minerals, 30(3), 257-259.

He, H., Chai, K., Wu, T., Qiu, Z., Wang, S., and Hong, J. (2022). Adsorption of rhodamine b from simulated waste water onto kaolin-bentonite composites. Materials, 15(12), 4058.

He, K., Chen, G., Zeng, G., Chen, A., Huang, Z., Shi, J., and Hu, L. (2018). Enhanced removal performance for methylene blue by kaolin with graphene oxide modification. Journal of the Taiwan Institute of Chemical Engineers, 89, 77-85.

Hens, S. C., Shenderova, O., and Turner, S. (2012). Producing photoluminescent species from sp2 carbons. Fullerenes, Nanotubes and Carbon Nanostructures, 20(4-7), 502-509.

Jawad, A. H., and Abdulhameed, A. S. (2020). Mesoporous Iraqi red kaolin clay as an efficient adsorbent for methylene blue dye: Adsorption kinetic, isotherm and mechanism study. Surfaces and Interfaces, 18, 100422.

Kandisa, R. V., Saibaba, K. N., Shaik, K. B., and Gopinath, R. (2016). Dye removal by adsorption: a review. Journal of bioremediation and Biodegradation, 7(6), 371.

Katheresan, V., Kansedo, J., and Lau, S. Y. (2018). Efficiency of various recent wastewater dye removal methods: A review. Journal of Environmental Chemical Engineering, 6(4), 4676-4697.

Khan, I., Ullah, H., Khairun Azizi, A., Sufian, S., Man, Z., Siyal, A., and Rehman, M. (2017). The pyrolysis kinetics of the conversion of Malaysian kaolin to metakaolin. Applied Clay Science, 146, 152-161.

Khan, M. I. (2020). Adsorption of methylene blue onto natural Saudi Red Clay: isotherms, kinetics and thermodynamic studies. Materials Research Express, 7(5), 055507.

Khuluk, R. H., and Rahmat, A. (2019). Removal of methylene blue by adsorption onto activated carbon from coconut shell (Cocous Nucifera L.). Indonesian Journal of Science and Technology, 4(2), 229-240.

Kuila, U., and Prasad, M. (2013). Specific surface area and pore-size distribution in clays and shales. Geophysical Prospecting, 61(2), 341-362.

Lan, T., Li, P., Rehman, F. U., Li, X., Yang, W., and Guo, S. (2019). Efficient adsorption of Cd2+ from aqueous solution using metakaolin geopolymers. Environmental Science and Pollution Research, 26(32), 33555-33567.

Lellou, S., Kadi, S., Guemou, L., Schott, J., and Benhebal, H. (2020). Study of methylene blue adsorption by modified kaolinite by dimethyl sulfoxide. Ecological Chemistry and Engineering S-Chemia I Inzynieria Ekologiczna S, 27(2), 225-239.

Lertcumfu, N., Jaita, P., Thammarong, S., Lamkhao, S., Tandorn, S., Randorn, C., and Rujijanagul, G. (2020). Influence of graphene oxide additive on physical, microstructure, adsorption, and photocatalytic properties of calcined kaolinite-based geopolymer ceramic composites. Colloids And Surfaces A: Physicochemical And Engineering Aspects, 602, 125080.

Li, F., Li, T., Sun, C., Xia, J., Jiao, Y., and Xu, H. (2017). Selenium-doped carbon quantum dots for free-radical scavenging. Angewandte Chemie International Edition, 56(33), 9910-9914.

Li, X.-y., Han, D., Xie, J.-f., Wang, Z.-b., Gong, Z.-q., and Li, B. (2018). Hierarchical porous activated biochar derived from marine macroalgae wastes (Enteromorpha prolifera): facile synthesis and its application on Methylene Blue removal. RSC Advances, 8(51), 29237-29247.

Liu, F., Zhang, W., Chen, W., Wang, J., Yang, Q., Zhu, W., and Wang, J. (2017a). One-pot synthesis of NiFe2O4 integrated with EDTA-derived carbon dots for enhanced removal of tetracycline. Chemical Engineering Journal, 310, 187-196.

Liu, K., Luo, L., Zhou, W., Yang, J., Xiao, H., Hong, Z., and Yang, H. (2013). Study of behaviors of aluminum overlayers deposited on uranium via AES, EELS, and XPS. Applied Surface Science, 270, 184–189.

Liu, X., Li, J. X., Huang, Y. S., Wang, X. X., Zhang, X. D., and Wang, X. K. (2017b). Adsorption, aggregation, and deposition behaviors of carbon dots on minerals. Environmental Science and Technology, 51(11), 6156-6164.

Liu, X., Li, J. X., Wu, X. H., Zeng, Z., Wang, X. L., Hayat, T., and Zhang, X. D. (2017). Adsorption of carbon dots onto Al2O3 in aqueous: Experimental and theoretical studies. Environmental Pollution, 227, 31-38.

Liu, X., Wu, Y., Li, M., Jiang, J., Guo, L., Wang, W., and Duan, P. (2020). Effects of graphene oxide on microstructure and mechanical properties of graphene oxide-geopolymer composites. Construction and Building Materials, 247, 118544.

Long, C., Jiang, Z., Shangguan, J., Qing, T., Zhang, P., and Feng, B. (2021). Applications of carbon dots in environmental pollution control: A review. Chemical Engineering Journal, 406, 126848.

Loutfi, M., Mariouch, R., Mariouch, I., Belfaquir, M., and ElYoubi, M. S. (2022). Adsorption of methylene blue dye from aqueous solutions onto natural clay: Equilibrium and kinetic studies. Materials Today: Proceedings, 2022, 412.

Meigoli Boushehrian, M., Esmaeili, H., and Foroutan, R. (2020). Ultrasonic assisted synthesis of Kaolin/CuFe2O4 nanocomposite for removing cationic dyes from aqueous media. Journal of Environmental Chemical Engineering, 8(4), 103869.

Mohapi, M., Sefadi, J. S., Mochane, M. J., Magagula, S. I., and Lebelo, K. (2020). Effect of LDHs and other clays on polymer composite in adsorptive removal of contaminants: a review. Crystals, 10(11), 957.

Mudgal, M., Singh, A., Chouhan, R. K., Acharya, A., and Srivastava, A. K. (2021). Fly ash red mud geopolymer with improved mechanical strength. Cleaner Engineering and Technology, 4, 100215.

Mustapha, S., Ndamitso, M., Abdulkareem, A., Tijani Oladejo, J., Mohammed, A., and Shuaib, D. T. (2019). Potential of using kaolin as a natural adsorbent for the removal of pollutants from tannery wastewater. Heliyon, 5, e02923.

Mustapha, S., Tijani, J. O., Ndamitso, M. M., Abdulkareem, S. A., Shuaib, D. T., Mohammed, A. K., and Sumaila, A. (2020). The role of kaolin and kaolin/ZnO nanoadsorbents in adsorption studies for tannery wastewater treatment. Scientific Reports, 10(1), 13068.

Nandiyanto, A. B. D. A., Nissa Nur; Taufik, Refika Safitri Rizkia. (2022a). Investigation of adsorption performance of calcium carbonate microparticles prepared from eggshells waste. Journal of Engineering Science and Technology, 17(3), 1934-1943.

Nandiyanto, A. B. D., Oktiani, R., and Ragadhita, R. (2019). How to read and interpret FTIR spectroscope of organic material. Indonesian Journal of Science and Technology, 4(1), 97-118.

Nandiyanto, A. B. D., Putri, S. R., Anggraeni, S., Kurniwan, T. (2022b). Isotherm adsorption OF 3000-µm natural zeolite. Journal of Engineering Science and Technology, 17(4), 2447-2460.

Natarajan, S., Bajaj, H. C., and Tayade, R. J. (2018). Recent advances based on the synergetic effect of adsorption for removal of dyes from waste water using photocatalytic process. Journal of Environmental Sciences, 65, 201-222.

Niu, S., Xie, X., Wang, Z., Zheng, L., Gao, F., and Miao, Y. (2021). Enhanced removal performance for Congo red by coal-series kaolin with acid treatment. Environmental Technology, 42(10), 1472-1481.

Nugraha, M. W., Zainal Abidin, N. H., Supandi, and Sambudi, N. S. (2021). Synthesis of tungsten oxide/ amino-functionalized sugarcane bagasse derived-carbon quantum dots (WO3/N-CQDs) composites for methylene blue removal. Chemosphere, 277, 130300.

Obinna, E. M. (2022). Physicochemical properties of human hair using Fourier transform infra-red (FTIR) and scanning electron microscope (SEM). ASEAN Journal for Science and Engineering in Materials, 1(2), 71-74.

Patawat, C., Silakate, K., Chuan-Udom, S., Supanchaiyamat, N., Hunt, A. J., and Ngernyen, Y. (2020). Preparation of activated carbon from Dipterocarpus alatus fruit and its application for methylene blue adsorption. RSC Advances, 10(36), 21082-21091.

Pillay, D. L., Olalusi, O. B., Awoyera, P. O., Rondon, C., Echeverría, A. M., and Kolawole, J. T. (2020). A review of the engineering properties of metakaolin based concrete: Towards combatting chloride attack in coastal/marine structures. Advances in Civil Engineering, 2020, 1-13.

Prihastuti, H., and Kurniawan, T. (2022). Conversion of indonesian coal fly ash into zeolites for ammonium adsorption. ASEAN Journal for Science and Engineering in Materials, 1(2), 75-84.

Ragadhita, R., and Nandiyanto, A. B. D. (2021). How to calculate adsorption isotherms of particles using two-parameter monolayer adsorption models and equations. Indonesian Journal of Science and Technology, 6(1), 205-234.

Ragadhita, R., and Nandiyanto, A. B. D. (2022). Curcumin adsorption on zinc imidazole framework-8 particles: Isotherm adsorption using Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich models. Journal of Engineering Science and Technology, 17(2), 1078-1089.

Ragadhita, R., Nandiyanto, A. B. D., Nugraha, W. C., and Mudzakir, A. (2019). Adsorption isotherm of mesopore-free submicron silica particles from rice husk. Journal of Engineering Science and Technology, 14(4), 2052-2062.

Raj, A. M., and Chirayil, G. T. (2017). Tunable direct band gap photoluminescent organic semiconducting nanoparticles from lignite. Scientific Reports, 7(1), 1-9.

Rani, U. A., Ng, L. Y., Ng, C. Y., and Mahmoudi, E. (2020). A review of carbon quantum dots and their applications in wastewater treatment. Advances in Colloid and Interface Science, 278, 102124.

Rashad, A. M. (2013). Metakaolin as cementitious material: History, scours, production and composition – A comprehensive overview. Construction and Building Materials, 41, 303-318.

Ratlam, C., Phanichphant, S., and Sriwichai, S. (2020). Development of dopamine biosensor based on polyaniline/carbon quantum dots composite. Journal of Polymer Research, 27(7), 1-12.

Sen Gupta, S., and Bhattacharyya, K. G. (2012). Adsorption of heavy metals on kaolinite and montmorillonite: A review. Physical Chemistry Chemical Physics, 14(19), 6698-6723.

Shi, W., Guo, F., Wang, H., Liu, C., Fu, Y., Yuan, S., and Kang, Z. (2018). Carbon dots decorated magnetic ZnFe2O4 nanoparticles with enhanced adsorption capacity for the removal of dye from aqueous solution. Applied Surface Science, 433, 790-797.

Shu, Z., Li, T. T., Zhou, J., Chen, Y., Yu, D. X., and Wang, Y. X. (2014). Template-free preparation of mesoporous silica and alumina from natural kaolinite and their application in methylene blue adsorption. Applied Clay Science, 102, 33-40.

Sukamto, S., and Rahmat, A. (2023). Evaluation of ftir, macro and micronutrients of compost from black soldier fly residual: in context of its use as fertilizer. ASEAN Journal of Science and Engineering, 3(1), 21-30.

Sullivan, M. S., Chorzepa, M. G., Hamid, H., Durham, S. A., and Kim, S. S. (2018). Sustainable materials for transportation infrastructures: Comparison of three commercially-available metakaolin products in binary cementitious systems. Infrastructures, 3(3), 17.

Tan, T. C. N., and Sen, T. K. (2020). Aqueous-phase methylene blue (MB) dye removal by mixture of eucalyptus bark (EB) biomass and kaolin clay (KC) adsorbents: kinetics, thermodynamics, and isotherm modeling. Separation Science and Technology, 55(6), 1036-1050.

Thommes, M., Kaneko, K., Neimark, A. V., Olivier, J. P., Rodriguez-Reinoso, F., Rouquerol, J., and Sing, K. S. W. (2015). Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure and Applied Chemistry, 87(9-10), 1051-1069.

Vakalova, T. V., Reshetova, A. A., Revva, I. B., Rusinov, P. G., and Balamygin, D. I. (2019). Effect of thermochemical activation of clay raw materials on phase formation, microstructure and properties of aluminosilicate proppants. Applied Clay Science, 183, 105335.

Valeev, D., Shoppert, A., Mikhailova, A., and Kondratiev, A. (2020). Acid and acid-alkali treatment methods of al-chloride solution obtained by the leaching of coal fly ash to produce sandy grade alumina. Metals, 10(5), 585.

Wongso, V., Chen, C. J., Razzaq, A., Kamal, N. A., and Sambudi, N. S. (2019). Hybrid kaolin/TiO2 composite: Effect of urea addition towards an efficient photocatalyst for dye abatement under visible light irradiation. Applied Clay Science, 180, 105158.

Wongso, V., Sambudi, N. S., and Sufian, S. (2021). The effect of hydrothermal conditions on photoluminescence properties of rice husk-derived silica-carbon quantum dots for methylene blue degradation. Biomass Conversion and Biorefinery, 11(6), 2641-2654.

Wongso, V., Sambudi, N. S., Sufian, S., Isnaeni, and Abdullah, B. (2019). The effect of pH in the synthesis of carbon quantum dots from rice husk on their photoluminescence properties. IOP Conference Series: Earth and Environmental Science, 268, 012087.

Yahaya Pudza, M., Zainal Abidin, Z., Abdul Rashid, S., Md Yasin, F., Noor, A. S. M., and Issa, M. A. (2020). Eco-friendly sustainable fluorescent carbon dots for the adsorption of heavy metal ions in aqueous environment. Nanomaterials, 10(2), 315.

Yang, J., Hou, B., Wang, J., Tian, B., Bi, J., Wang, N., and Huang, X. (2019). Nanomaterials for the removal of heavy metals from wastewater. Nanomaterials, 9(3), 424.

Ye, N., Chen, Y., Yang, J., Liang, S., Hu, Y., Hu, J., and Xiao, B. (2017). Transformations of Na, Al, Si and Fe species in red mud during synthesis of one-part geopolymers. Cement and Concrete Research, 101, 123-130.

Yin, W.-M., Wang, Y., Hou, Y.-C., Sun, Y., Zhang, J.-G., Sun, H.-L., and Guo, Y.-R. (2020). Petaloid-array hierarchically structured carbon Dots/Mg(OH)2 composite: Design, characterization and removal/recovery of cadmium via slowly releasing. Chemical Engineering Journal, 401, 125961.

Yolanda, Y. D., and Nandiyanto, A. B. D. (2022). How to read and calculate diameter size from electron microscopy images. ASEAN Journal of Science and Engineering Education, 2(1), 11-36.

Zainal Abidin, N. H., Wongso, V., Hui, K. C., Cho, K., Sambudi, N. S., Ang, W. L., and Saad, B. (2020). The effect of functionalization on rice-husks derived carbon quantum dots properties and cadmium removal. Journal of Water Process Engineering, 38, 101634.

Zare Pirhaji, J., Moeinpour, F., Mirhoseini Dehabadi, A., and Yasini Ardakani, S. A. (2020). Synthesis and characterization of halloysite/graphene quantum dots magnetic nanocomposite as a new adsorbent for Pb(II) removal from water. Journal of Molecular Liquids, 300, 112345.

Zhang, Q., Zhang, Y., Chen, J., and Liu, Q. (2019). Hierarchical structure kaolinite nanospheres with remarkably enhanced adsorption properties for methylene blue. Nanoscale Research Letters, 14(1), 1-9.

Zhang, T., Wang, W., Zhao, Y., Bai, H., Wen, T., Kang, S., and Komarneni, S. (2021). Removal of heavy metals and dyes by clay-based adsorbents: From natural clays to 1D and 2D nano-composites. Chemical Engineering Journal, 420, 127574.

Zhang, Y., Chen, S., Feng, X., Yu, J., and Jiang, X. (2019b). Self-assembly of sponge-like kaolin/chitosan/reduced graphene oxide composite hydrogels for adsorption of Cr(VI) and AYR. Environmental Science and Pollution Research, 26(28), 28898-28908.



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