Title Science and Technology Indonesia e-ISSN:2580-4391 p-ISSN:2580-4405 Vol. 4, No. 4, October 2019 Research Paper Kinetic Adsorption of Direct Yellow Onto Zn/Al and Zn/Fe Layered Double Hydroxides Neza Rahayu Palapa1, Bakri Rio Rahayu1, Tarmizi Taher2, Risfidian Mohadi1, Aldes Lesbani1 1Department of Chemistry, Faculty of Mathematics and Natural Sciences, Sriwijaya University, Jl. Palembang-Prabumulih, Km. 32, Ogan Ilir, South Sumatra, Indonesia 2Department of Enviromental Science, Graduate School, Sriwijaya University, Jl. Padang Selasa No. 524 Ilir Barat 1, Palembang-South Sumatra, Indonesia *Corresponding author: aldeslesbani@pps.unsri.ac.id Abstract Zn/Al and Zn/Fe layered double hydroxides has successfully synthesized by co-precipitation methods with molar ration 3:1. The samples were characterized using X-Ray Di�raction, Fourier Transform Infrared Spectroscopy and Surface Area using BET method. In this study, Zn/Al and Zn/Fe layered double hydroxides were used to remove direct yellow dye in aqueous solution. The experiments were carried out time variations with the aim of observing the kinetic studies. The results showed that the adsorption of direct yellow onto Zn/Al and Zn/Fe layered double hydroxides based on co-e�icient correlation kinetic models more fit using pseudo-second-order than pseudo-first-order. Keywords Adsorption, Dye, Layered double hydroxides, Kinetic Study, co-precipitation Received: 21 September 2019, Accepted: 19 October 2019 https://doi.org/10.26554/sti.2019.4.4.101-104 1. INTRODUCTION Layered double hydroxides as known as anionic clays with a pos- itive charge excess in their brucite like layers and anion species in interlayer as counter balancing (Gong et al., 2013). In general, layered double hydroxides has formula [M2+(1−x)M 3+x(OH)2](An − )x/nH2O where, M 2+ is divalent metal cation and M3+ is trivalent metal cation (Ke�f et al., 2019; Palapa et al., 2019). Layered double hydroxides is one of most considered attention in recent years with their ability to remediation wastewater were contains dye, toxic metals and organic pollutant in aqueous solution (Meng et al., 2019). Layered double hydroxides were widely used to adsorbent caused their ability. The bene�ts of layered double hydroxides are easy to synthesized, high �exibility structure and easy to modi�ed (Gonçalves et al., 2019). Dyes e�uent contained with wastewater can be bad impact to environment. The remediation technique of wastewater has been studied. The di�erent physical or chemical methods has advantages and disadvantages. The examples of chemical tech- nique such as photocatalysis (Hidayati et al., 2019), and physico- chemical methods such as ion exchange, coagulation, adsorption and membrane �ltration (Kazeem et al., 2019). Many of them are expensive, hard to use and has limitation of dye separation e�ciency (Daud et al., 2019; Hidayati et al., 2019). However, the adsorption method has more advantages which is this method are more useful, low cost, easy to used and have no pollutant (dos Santos et al., 2017; Milagres et al., 2017). In this study, Zn/Al-LDH and Zn/Fe-LDH was applied to re- moval direct yellow dye in wastewater. As known, synthetics dye has bad impact to bodies and environment. According to Kausar et al. (2018) direct dyes are usually used for leather industries, cotton and rayon dyeing and paper industries. The main classes of direct dyes include poly azo and oxazine compounds Palapa et al. (2018a). These dyes have a high a�nity of dyeing process on cellulosic �ber in aqueous solution. In Palembang, these dyes are most popular used for Jumputan home industries. Many of craftsmen assumed that direct dyes have e�ect brighter than other synthetic dyes. In other hand, direct dye was reported that the e�ect health to body is bladder cancer carcinogen Sun et al. (2010); Zhang et al. (2018); Palapa et al. (2018b). This research was removal direct yellow using layered double hydroxides (LDH) by adsorption method. The amount of absorbed were calculated and studied by kinetic models. Kinetic models were �tted are pseudo-�rst-order and pseudo-second-order. 2. EXPERIMENTAL SECTION 2.1 Materials The chemicals all purchased by Merck such as aluminum nitrate nonahydrate, iron nitrate nonahydrate, zinc nitrate hexahydrate, and sodium hydroxide. Nitrogen gas were pro-analytic and The solution was prepared by deionized purity water. Then characterized by XRD Di�ractometer Rigaku Mini�ex-600 and https://doi.org/10.26554/sti.2019.4.4.101-104 Palapa et. al. Science and Technology Indonesia, 4 (2019) 101-104 Spectrophotometer FT-IR Shimadzu FT-IR Prestige-21. 2.2 Synthesis of Layered Double Hydroxides Zn/Al-LDH was synthesized using a co-precipitation method. A mixed-metal nitrate solution (0.25 M Zn2+ and 0.08 M Al3+) was adjusted to the solution pH of 9–10 by adding the required amount of 2 M NaOH. The mixture was �owed nitrogen system and heated to 80 °C for 18 h. The white precipitate was formed. Subsequently, it was �ltered and rinsed with deionized water. After drying at 85 °C, the obtained material was ground gen- tly into a �ne powder. Zn/Fe-LDH was synthesis by Zn(NO3)2 ·6H2O and Fe(NO3)3 ·9H2O salt solution were mixed in a desired Zn (II)/Fe (III) 3:1 molar ratio and titrated slowly with the basic solution of 2M NaOH until the pH reached 10.0 at room tempera- ture maintaining a nitrogen atmosphere. The brown precipitate was formed then the mixed solution was �ltered and rinse with deionized water, drying at 80 °C to obtain powdery LDH. 2.3 E�ect of Contact Time Adsorption Direct Yellow by Zn/Al-LDH and Zn/Fe-LDH The adsorption of direct yellow onto Zn/Al-LDH and Zn/Fe- LDH was performed taking 50 mL from sample solution 100 mg/L. 0.05 g of Zn/Al-LDH and Zn/Fe-LDH were contact to 50 mL direct yellow 100 mg/L. The mixing solution were shake in horizontal shaker 250 rpm by varying times (between 5-180 min). The solution was centrifuged and the �ltrate was analyses using UV-Vis Spectrophotometer at 403 nm. Before analyses, �ve point of standard curve has been examined and coe�cient correlation was linear amount 0.99. The amount of adsorbed were calculated from initial concentration and equilibrium con- centration in supernatant after centrifugation. After that, the data were tested using kinetic models. The kinetic model was used pseudo-�rst-order and pseudo-second-order. The kinetic parameters are calculated using the pseudo-�rst-order: log(qe − qt) = logqe − k1/(2.303)t (1) and pseudo-second-order equations as follows: t/qt = (1/k2qe2) + (1/qe)t (2) where qt is the amount of adsorbate adsorbed at time t (mg.g−1), qe is the adsorption capacity in the equilibrium (mg g−1), k1 is the pseudo-�rst-order rate constant (min−1), k2 is the pseudo-second-order rate (g mg−1min−1) and t is the contact time (min) [6,13]. 3. RESULTS AND DISCUSSION 3.1 Characterization of Layered Double Hydroxides Zn/Al-LDH and Zn/Fe LDH has been successfully prepared and characterized using XRD and FTIR. In Fig. 1. Shows the XRD pat- tern of Zn/Al-LDH and Zn/Fe-LDH. The booth of di�ractograms were shows high crystallinity and speci�c di�raction of LDH was shows at amount 11° about interlayer distance (Taher et al., Figure 1. XRD pattern of Zn/Al-LDH and Zn/Fe-LDH Figure 2. FTIR spectra of Zn/Al-LDH and Zn/Fe-LDH 2019). The distance of interlayer Zn/Al-LDH and Zn/Fe-LDH is 7.57 Å and 5.80 Å, respectively. Fig. 2. shows the spectra of both layered double hydroxides. both spectra have similar spectra. The presence of vibrations at wavenumber about 3400 cm−1 which is OH vibration from hydroxyl group and about 1635 cm−1 a identi�ed the presence of water molecules in interlayer. The sharp peaks at 1381 cm−1 were indicated the vibration of nitrate. The vibration of metal-oxide are shows at 700-900 cm−1. 3.2 E�ect of Adsorption Time Direct Yellow by Zn/Al LDH and Zn/Fe-LDH The comparison of Zn/Al-LDH and Zn/Fe-LDH was showed in Fig. 3. The adsorption e�ciency was increased rapidly at 100 min for Zn/Al-LDH with amount of dye adsorbed is reach 71.93% from 100 mg/L and Zn/Fe-LDH about 51.24% for adsorb direct yellow from 100 mg/L. Layered double hydroxides both are in- creasing rapidly thereafter becomes slow until reach equilibrium. Is caused layered double hydroxides has available active site be- fore equilibrium, so that layered double hydroxides can adsorb rapidly. Dyes sorption of Zn/Al-LDH higher than Zn/Fe-LDH. The di�erence of equilibrium times and e�ciency adsorbed may cause the Zn/Fe-LDH has smaller interlayer than Zn/Al-LDH. © 2019 The Authors. Page 102 of 104 Palapa et. al. Science and Technology Indonesia, 4 (2019) 101-104 According to Ulibarri and Hermosin (2006) that the adsorption of anionic contaminant can be adsorb into surface active site and sometimes exchanges mechanism can be happen in interlayer (Kausar et al., 2018; Palapa et al., 2018b). The schematics of direct yellow adsorption onto layered double hydroxides was shows in Fig. 4. Figure 3. Comparison of the adsorption e�ciency direct yellow by Zn/Al-LDH and Zn/Fe-LDH Figure 4. The schematic adsorption process of direct yellow onto layered double hydroxides Kinetic modeling of the adsorption process provides a pre- diction of adsorption rates, and allows the determination of �tting rate expressions characteristic for possible reaction mech- anisms. In this study, pseudo-�rst-order and pseudo-second- order has been examined. The parameters of pseudo-�rst-order and pseudo-second-order was estimated with the aid of the non- linear regression. the obtained value and coe�cient correlation were showed in Table 1. Based on coe�cient correlation both layered double hydroxides are higher for pseudo-second-order than pseudo-�rst-order. The result indicated that the adsorption Table 1. kinetic parameters of adsorption direct yellow onto layered double hydroxides Kinetic Parameters Layered double hydroxidesmodels Zn-Al-NO3 Zn-Fe-NO3 Pseudo-�rst k1 0.0597 0.0339 order R2 0.9127 0.891 Pseudo-second k2 0.0064 0.0072 order R2 0.9544 0.9176 qe 80.791 54.965 process is chemisorption (Kazeem et al., 2019; Hidayati et al., 2019). 4. CONCLUSIONS In this study, adsorption experiment for removal direct yellow by Zn/Al-LDH and Zn/Fe-LDH. The synthesis of Zn/Al-LDH and Zn/Fe-LDH using co-precipitation method with molar ratio and obtained white and brown powder. Zn/Al-LDH and Zn/Fe- LDH were characterized using XRD and FTIR and applied as adsorbent to removal direct yellow dye in aqueous solution. The adsorption was carried out by varying time and �tted to kinetic models. The result was shows both layered double hydroxides more �tted using pseudo-second-order than pseudo-�rst-order. 5. ACKNOWLEDGEMENT Author thankful to Hibah Tesis Magister form Ministry of Re- search Technology and Higher Education Contract No. 096/SP2H- /LT/DRPM/2019 REFERENCES Daud, M., A. Hai, F. Banat, M. B. Wazir, M. Habib, G. Bharath, and M. A. Al-Harthi (2019). A review on the recent advances, challenges and future aspect of layered double hydroxides (LDH)–Containing hybrids as promising adsorbents for dyes removal. Journal of Molecular Liquids; 110989 dos Santos, R. M. M., R. G. L. Gonçalves, V. R. L. Constantino, C. V. Santilli, P. D. Borges, J. Tronto, and F. G. Pinto (2017). Adsorption of Acid Yellow 42 dye on calcined layered double hydroxide: E�ect of time, concentration, pH and temperature. Applied Clay Science, 140; 132–139 Gonçalves, R. G. L., P. A. Lopes, J. A. Resende, F. G. Pinto, J. Tronto, M. C. Guerreiro, L. C. A. de Oliveira, W. de Cas- tro Nunes, and J. L. Neto (2019). Performance of mag- netite/layered double hydroxide composite for dye removal via adsorption, Fenton and photo-Fenton processes. Applied Clay Science, 179; 105152 Gong, M., Y. Li, H. Wang, Y. Liang, J. Z. Wu, J. Zhou, J. Wang, T. Regier, F. Wei, and H. Dai (2013). An advanced Ni–Fe layered double hydroxide electrocatalyst for water oxidation. Journal of the American Chemical Society, 135(23); 8452–8455 Hidayati, N., D. R. Apriliani, Helda, T. Taher, R. Mohadi, El�ta, and A. Lesbani (2019). Adsorption of congo red using Mg/Fe © 2019 The Authors. Page 103 of 104 Palapa et. al. Science and Technology Indonesia, 4 (2019) 101-104 and Ni/Fe layered double hydroxides. Journal of Physics: Con- ference Series, 1282; 012075 Kausar, A., M. Iqbal, A. Javed, K. Aftab, H. N. Bhatti, S. Nouren, et al. (2018). Dyes adsorption using clay and modi�ed clay: a review. Journal of Molecular Liquids, 256; 395–407 Kazeem, T. S., M. Zubair, M. Daud, N. D. Mu’azu, and M. A. Al- Harthi (2019). Graphene/ternary layered double hydroxide composites: E�cient removal of anionic dye from aqueous phase. Korean Journal of Chemical Engineering, 36(7); 1057– 1068 Ke�f, F., K. Ezziane, A. Bahmani, N. Bettahar, and S. Mayouf (2019). Evans Blue dye removal from contaminated water on calcined and uncalcined Cu-Al-CO3 layered double hydroxide materials prepared by coprecipitation. Bulletin of Materials Science, 42(1); 14 Meng, Z., M. Wu, S. Zhao, R. Jing, S. Li, Y. Shao, X. Liu, F. Lv, A. Liu, and Q. Zhang (2019). Removing anionic dyes from wastewater based on in-situ formation of Fe3O4@ Zn-Al lay- ered double hydroxides by self-assembly. Applied Clay Science, 170; 41–45 Milagres, J. L., C. R. Bellato, R. S. Vieira, S. O. Ferreira, and C. Reis (2017). Preparation and evaluation of the Ca-Al layered double hydroxide for removal of copper (II), nickel (II), zinc (II), chromium (VI) and phosphate from aqueous solutions. Journal of environmental chemical engineering, 5(6); 5469–5480 Palapa, N. R., R. Mohadi, and A. Lesbani (2018a). Adsorption of direct yellow dye from aqueous solution by Ni/Al and Zn/Al layered double hydroxides. In AIP Conference Proceedings, volume 2026. AIP Publishing, page 020018 Palapa, N. R., T. Taher, R. Mohadi, and A. Lesbani (2019). Removal of Anionic Direct Dye Using Zn/Al, Zn/Fe and Zn/Cr Layered Double Hydroxides Toward Interlayer Distance. Science and Technology Indonesia, 4(3); 70–76 Palapa, N. R., T. Taher, R. Mohadi, M. Said, and A. Lesbani (2018b). Synthesis of Ni/Al layered double hydroxides (LDHs) for ad- sorption of malachite green and direct yellow dyes from solu- tions: Kinetic and thermodynamic. In AIP Conference Proceed- ings, volume 2026. AIP Publishing, page 020033 Sun, Z., L. Jin, W. Shi, M. Wei, and X. Duan (2010). Preparation of an anion dye intercalated into layered double hydroxides and its controllable luminescence properties. Chemical Engineering Journal, 161(1-2); 293–300 Taher, T., M. M. Christina, M. Said, N. Hidayati, F. Ferlinahayati, and A. Lesbani (2019). Removal of Iron(II) Using Intercalated Ca/Al Layered Double Hydroxides with [α-SiW12O40]4-. Bul- letin of Chemical Reaction Engineering & Catalysis, 14(2); 260 Zhang, H., H. Chen, S. Azat, Z. A. Mansurov, X. Liu, J. Wang, X. Su, and R. Wu (2018). Super adsorption capability of rhom- bic dodecahedral Ca-Al layered double oxides for Congo red removal. Journal of Alloys and Compounds, 768; 572–581 © 2019 The Authors. Page 104 of 104 INTRODUCTION EXPERIMENTAL SECTION Materials Synthesis of Layered Double Hydroxides Effect of Contact Time Adsorption Direct Yellow by Zn/Al-LDH and Zn/Fe-LDH RESULTS AND DISCUSSION Characterization of Layered Double Hydroxides Effect of Adsorption Time Direct Yellow by Zn/Al LDH and Zn/Fe-LDH CONCLUSIONS ACKNOWLEDGEMENT