• International Journal of Technology (IJTech)
  • Vol 12, No 2 (2021)

Micro-structured Materials for the Removal of Heavy Metals using a Natural Polymer Composite

Micro-structured Materials for the Removal of Heavy Metals using a Natural Polymer Composite

Title: Micro-structured Materials for the Removal of Heavy Metals using a Natural Polymer Composite
Eny Kusrini, Karina Ayuningtyas, Dias Puspitaning Mawarni, Lee D. Wilson, Muhammad Sufyan, Arif Rahman, Yohanes Eko Adi Prasetyanto, Anwar Usman

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Cite this article as:
Kusrini, E., Ayuningtyas, K., Mawarni, D.P., Wilson, L.D., Sufyan, M., Rahman, A., Prasetyanto, Y.E.A., Usman, A., 2021. Micro-structured Materials for the Removal of Heavy Metals using a Natural Polymer Composite. International Journal of Technology. Volume 12(2), pp. 275-286

Eny Kusrini Department of Chemical Engineering, Faculty of Engineering, Universitas Indonesia, Kampus Baru UI Depok, 16424, Indonesia
Karina Ayuningtyas Department of Chemical Engineering, Faculty of Engineering, Universitas Indonesia, Kampus Baru UI Depok, 16424, Indonesia
Dias Puspitaning Mawarni Department of Medical, Faculty of Medical, Universitas Pembangunan Nasional Veteran Jakarta, Jakarta 12450, Indonesia
Lee D. Wilson Department of Chemistry, University of Saskatchewan, 110 Science Place, Room 156 Thorvaldson Building, Saskatoon, Saskatchewan, Canada S7N 5C9
Muhammad Sufyan Department of Computer Science, Faculty of computer science and Information Technology, Virtual University of Pakistan, Lahore, Pakistan
Arif Rahman Department of Chemistry, Faculty of Mathematic and Natural Sciences, Universitas Negeri Jakarta, Jakarta Timur 13220, Indonesia
Yohanes Eko Adi Prasetyanto Faculty of Medicine and Health Sciences, Universitas Katolik Indonesia Atma Jaya, Jalan Pluit Raya 2, Jakarta 14440, Indonesia
Anwar Usman Department of Chemistry, Faculty of Science, Universiti Brunei Darussalam, Jalan Tungku Link, Gadong, BE1410, Negara Brunei Darussalam
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Micro-structured Materials for the Removal of Heavy Metals using a Natural Polymer Composite

In this study, a precipitation method was employed to prepare a synthetic hydroxyapatite (HAP)/chitosan (CHN) composite by the modification of synthetic HAP with CHN. The HAP/CHN composite was characterized by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy equipped with energy-dispersive X-ray spectroscopy (SEM-EDX). Furthermore, the HAP/CHN composite in a 1:1 ratio (wt.%) was investigated as an adsorbent for the removal of heavy metals ions (such as Cr6+, Cd2+ and Zn2+) from simulated wastewater. Adsorption experiments were conducted in batch mode at room temperature. In addition, the effect of process conditions, such as contact time, was evaluated. Kinetic data were well-described by the pseudo-second-order kinetic model, where adsorption was governed by the intraparticle diffusion model. The HAP/CHN composite demonstrated potential utility as an adsorbent for the removal of heavy metals from an aqueous solution, with the highest maximum adsorption capacities of 39.3, 30.8 and 29.9 mg/g for Cr6+, Cd2+ and Zn2+, respectively. The HAP/CHN composite materials with variable structure and composition exhibited remarkably different adsorption properties and potential applicability for industrial applications due to the material cost-effectiveness.

Adsorption; Chitosan; Composite; Micro-structured materials; Simulated wastewater


Heavy-metal contamination poses a serious problem for the environment and human health. Industries such as mining, smelting, batteries, and chemical production release certain heavy metals into surface and groundwater supplies, resulting in negative environmental effects (Duan et al., 2020). In recent years, adsorption-based methods have been employed to investigate the removal of heavy metal ions from wastewater (Gupta et al., 2012; Salah et al., 2014; Zhang et al., 2018; Vieira et al., 2019; Kusrini et al., 2020a; Kusrini et al., 2020b). Adsorption is typically employed in industries due to its high efficiency and cost-effectiveness (Kusrini et al., 2019a; Kusrini et al., 2019b; Kusrini et al., 2019c). Some polymers and synthetic materials, such as chitosan (CHN), hydroxyapatite (HAP), activated carbon and zeolites have been reportedly used as adsorbents to remove heavy metal ions from aqueous media (Gupta et al. 2012; Salah et al., 2014; Zhang et al., 2018; Vieira et al., 2019). HAP has been reported to exhibit high removal capacities for divalent heavy-metal ions (Corami et al., 2007). To improve the HAP adsorption performance for heavy-metal species, a composite of HAP with some polymers can be prepared, including HAP/polyacrylamide (HAP/PAAm), HAP/polyurethane (HAP/PU) and HAP/polyvinyl alcohol (HAP/PVA) (Dong et al., 2010). In addition, the adsorption of Cu2+ and Cr6+ on biopolymers such as CHN was also reported (Schmuhl et al., 2001). HAP-CHN composites have been reported for the removal of Fe3+ (Kousalya et al., (2010), Pb2+, Co2+ and Ni2+ (Gupta et al., 2012), Cd2+ (Salah et al., 2014), Pb2+ (Zhang et al., 2018) and Cr6+, Cd2+ and Zn2+ (Kusrini et al., 2013). Recently, HAP/CHN-layered composites have been reported for the removal of lead ions from continuous-flow wastewater (Zhang et al., 2020); in that study, HAP is extracted from Tilapia fish and then a composite with CHN is prepared to remove Pb2+ from wastewater (Liaw et al., 2020). A CHN/HAP composite nanofiber membrane for the adsorption of Pb, Co and Ni ions from an aqueous solution has been reported (Aliabadi et al., 2014). The presence of amine (-NH2) and hydroxyl (-OH) groups in CHN can serve as active sites for the removal of heavy metals from aqueous media via adsorption (Gupta et al. 2012; Aliabadi et al., 2014; Kusrini et al., 2019a).

Chromium (Cr) is well known to be the main additive in stainless steel that inhibits corrosion. As a result, stainless steel has a high market value due to its corrosion resistance and hardness. Several applications of stainless steel are known as a result of the electroplating industry. Cr3+ is not considered toxic; however, hexavalent chromium (Cr6+) is highly toxic and carcinogenic. Zinc (Zn) is also most commonly used due to its anti-corrosion properties as well as for galvanization, whereas cadmium (Cd) is used for corrosion-resistant plating on steel and to colour glass, as well as to stabilize plastic. Cd is toxic, which is replaced by metal hydride or lithium-ion batteries in the battery industry. Previously, HAP modified with CHN in a 30:70 (wt%) ratio for the removal of heavy-metal ions from aqueous media has been reported (Kusrini et al., 2013). In this study, synthetic HAP was modified with CHN in a 1:1 ratio. In addition, a new material adsorbent was developed as a composite material that contains CHN and synthetic HAP. As well, its synergistic properties were investigated for the removal of heavy-metal ions (such as Cr6+, Cd2+ and Zn2+) from an aqueous solution to evaluate the optimum removal efficiency. Notably, an equal composition of HAP and CHN was investigated to observe the effect of the weight ratio of HAP and CHN and to examine the effect of carboxyl and hydroxyl functional groups from the natural polymer CHN on the composite surface.


    In summary, synthetic composites containing HAP with CHN were prepared by combined precipitation and mixing methods, along with characterization by FTIR and SEM-EDX methods. The adsorption of heavy metals on the 1:1 (wt.%) HAP/CHN composite from aqueous media was studied using a batch adsorption system. The results revealed the benefits of the amine and hydroxyl functional groups of CHN in the composite adsorbent, which provided adequate and versatile adsorption for the removal of heavy-metal ions. The maximum adsorption capacities of Cr6+, Cd2+ and Zn2+ in batch adsorption studies were estimated as 39.3, 30.8 and 29.9 mg/g, respectively. Adsorption of heavy-metal ions using the HAP/CHN composite adsorbent tended to follow the pseudo-second-order and intraparticle diffusion models. The variable structure and composition of the HAP/CHN composite, including contact time for the adsorption process revealed remarkably different adsorption properties. The modified CHN material can enhance the adsorption capacity of heavy-metal ions, along with the effects of parameters, such as temperature, pH and co-existing ions on the adsorption properties. Further studies are underway to gain insight into the role of competitor ions, selectivity and thermodynamics of adsorption of new nano- and micro-structured composites materials, which can be further used for industrial applications.


    The authors greatly acknowledge the Kemenristek/BRIN for a research grant award through the PTUPT grant No. NKB-1733/UN2.R3.1/HKP.05.00/2019. We also thank Mr. Santoso for preparing synthetic HAP and assistance with some materials characterization.


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