• Vol 9, No 6 (2018)
  • Chemical Engineering

Preparation of Layered Double Hydroxides with Different Divalent Metals for the Adsorption of Methyl Orange Dye from Aqueous Solutions

Mazidah Mamat, Mohd Aidil Adhha Abdullah, Maisara Abdul Kadir, Adila Mohamad Jaafar, Eny Kusrini

Cite this article as:
Mamat, M., Abdullah, M.A.A., Kadir, M.A., Jaafar, A.M., Kusrini, E., 2018. Preparation of Layered Double Hydroxides with Different Divalent Metals for the Adsorption of Methyl Orange Dye from Aqueous Solutions. International Journal of Technology. Volume 9(6), pp.1103-1111
Mazidah Mamat Advanced Nano Materials Research Group, School of Fundamental Science, Universiti Malaysia Terengganu, 21030 Kuala Nerus, Malaysia
Mohd Aidil Adhha Abdullah Advanced Nano Materials Research Group, School of Fundamental Science, Universiti Malaysia Terengganu, 21030 Kuala Nerus, Malaysia
Maisara Abdul Kadir Advanced Nano Materials Research Group, School of Fundamental Science, Universiti Malaysia Terengganu, 21030 Kuala Nerus, Malaysia
Adila Mohamad Jaafar Chemistry Department, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor
Eny Kusrini Department of Chemical Engineering, Faculty of Engineering, Universitas Indonesia, Kampus UI Depok, Depok 16424, Indonesia
Email to Corresponding Author


In this study, layered double hydroxides (LDHs) with different divalent metal cations were prepared and then utilized as adsorbent for the removal of dye from aqueous solutions. LDHs are positively charged lamellar solids consisting of divalent and trivalent metallic cations and exchangeable interlayer anions. The potential combinatorial series of M/aluminum (M=Ca, Mn and Zn) LDHs for the removal of methyl orange (MO) dye from aqueous solutions were investigated.  LDHs were synthesized via a co-precipitation method and characterized using powder X-Ray diffraction (PXRD) and Fourier-transform infrared spectrophotometer (FTIR). The LDHs were then used as adsorbent for the removal of MO dye at different LDH dosages. As the LDH dosage increased, the removal percentage of MO dye also increased. CaAl, MnAl and ZnAl LDHs were able to adsorb up to 96.6%, 97.9% and 99.8% of MO dye, respectively, after being put in contact with the LDHs for 24h. Their adsorption ability was further analyzed by using Langmuir and Freundlich isotherm models in which the adsorption mechanism was determined. Adsorption of MO by CaAl, and ZnAl LDHs was governed by the Langmuir isotherm model while the adsorption data for MnAl LDH was found to fit well with the Freundlich isotherm model.

Adsorption; Anionic clay; Methyl orange dye; Layered double hydroxide


Anionic clay, layered double hydroxide (LDH), is a synthetic clay mineral that can be easily synthesized in the laboratory. LDH is a synthetic solid with positive charged brucite-like layers of mixed metal hydroxides separated by interlayer hydrated anions (Lafi et al., 2016). It consists of piles of positively-charged metal cations octahedrally surrounded by oxygen in the form of a hydroxide group (Figure 1). Through edge sharing, this octahedral unit forms infinite sheets and stack of layers which give rise to a positive charge that requires the existence of interlayer anions to retain the overall neutrality charge.

The chemical structure of LDH can be portrayed by the general formula (Peligro et al., 2016)

 Figure 1 Structure of LDH: (a) metal (M) octahedrally surrounded by a hydroxide group; (b) Edge sharing of octahedral units forming infinite sheets


where M2+ is the divalent ion, M3+ is the trivalent ion and An- is the interlayer anion. Due to the high charge density of the sheets and the exchangeability of the interlayer anions, many studies have been conducted on the removal of heavy metals (Peligro et al., 2016), dyes (Saiah et al., 2009) and oil (Wang et al., 2016). Several studies have examined LDHs and their derivatives as low budget adsorbents, which are promising for the remediation of dyes. LDHs are seen as potential adsorbents for wastewater treatment in the future (Zubair et al., 2017). LDHs have relatively weak interlayer bonding, which gives them an outstanding ability to trap organic and inorganic anions (Goh et al., 2008).

Methyl orange (MO) dye is an acid azo dye that is classified as an anionic dye. It may be released into the environment through the discharge of wastewater due to its wide range of applications, such as pH indicator, textile dyestuffs, paper printing, cosmetic dyes and more (Teixeira et al., 2014). MO has moderate mobility in soil due to its ionic nature, which helps it cling to clay particles in soil by ion exchange processes and leads to adsorption on sediment surfaces (Chequer et al., 2013). It is found to be nonvolatile in water due to its ionic nature and aerobic non-biodegradability; hence, it will persist in water for a long period, lead to bioaccumulation (Teixeira et al., 2014) and can cause stress to aquatic organisms (Zaharia et al., 2009). The molecular structure of MO dye is shown in Figure 2.


                                                                                                                      Figure 2 Molecular structure of MO dye


In this study, we report the synthesis of novel LDHs with different divalent metals: Ca, Mn and Zn. Since LDH materials exhibit different stabilities in pH range (Wang & Gao, 2006) and metal ratios, it is difficult to synthesize LDHs with the same pH and ratio. Therefore, the LDHs in this study were prepared at different ratios and pH values. The synthesized LDHs were then used as potential adsorbents for the removal of MO dye from aqueous solutions.


The M/Al LDHs (M=Ca, Mn and Zn) were successfully synthesized via the co-precipitation method and were utilized as an adsorbent for the MO dye. The adsorption data for CaAl and ZnAl fitted well with the Langmuir isotherm model, showing that the process is governed by homogeneous adsorption, while the MnAl data fitted with the Freundlich equation due to the multilayer adsorption of MO by MnAl.


The authors are grateful to the Malaysian government for funding (FRGS 59179) and to the Universiti Malaysia Terengganu for providing research facilities.

Supplementary Material
CE-2379-20180912173620.pdf Reviewer response for i-TREC #190

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