Title Science and Technology Indonesia e-ISSN:2580-4391 p-ISSN:2580-4405 Vol. 4, No. 2, April 2019 Research Paper Synthesis and Characterization of Zn/Al, Zn/Fe, and Zn/Cr Layered Double Hydroxides: E�ect of M3+ Ions Toward Layer Formation Neza Rahayu Palapa1, Yosi Saria1, Tarmizi Taher2, Risfidian Mohadi3, Aldes Lesbani3* 1Magister of Chemistry, Faculty of Mathematics and Natural Sciences, Sriwijaya University, Jl.. Padang Selasa Bukit Besar Palembang 30139 2Department of Enviromental Science, Graduate School, Sriwijaya University, Jl. Padang Selasa No. 524 Ilir Barat 1, Palembang-South Sumatra, Indonesia 3Department of Chemistry, Faculty of Mathematics and Natural Sciences, Sriwijaya University, Jl. Palembang-Prabumulih, Km. 32, Ogan Ilir, South Sumatra, Indonesia *Corresponding author: aldeslesbani@pps.unsri.ac.id Abstract Layered double hydroxides are composed by substitution of metal cation divalent and trivalent. Metal cation divalent and trivalent can be changed. In this work, e�ect metal cation trivalent (M3+) toward layer formation were studied. Synthesis of LDHs has used co-precipitation methods with molar ratio 3:1 and kept pH at 10. The result of synthesis was characterized by X-ray Di�raction (XRD) and Fourier Transform Infrared (FT-IR) analyses. Keywords layered double hydroxides, LDHs, co-precipitation, Zn/Al LDHs, Zn/Cr LDHs, Zn/Fe LDHs Received: 3 Maret 2019, Accepted: 19 April 2019 https://doi.org/10.26554/sti.2019.4.2.36-39 1. INTRODUCTION Inorganic materials can be classi�ed by layered materials (Ma et al., 2009) and porous materials (Abdelrahman, 2018). Each of these materials has advantages as adsorbents (Taher et al., 2018; Palapa et al., 2018c), catalyst (Jadhav et al., 2007), ion ex- changers (Lins et al., 2018) and sensors (Xu et al., 2018b). One of the most interesting material is layered materials (Mishra et al., 2018). Based on its existence, nature layered materials such as kaolinite and bentonite (Taher et al., 2018, 2017) then synthesized layered material such as layered double hydroxides or hydrotalcite (Jadhav et al., 2007; Lesbani et al., 2018; Palapa et al., 2018b). Nowadays, researchers had been interesting to layered materials especially layered double hydroxides. Layered double hydroxides are more e�ective to be modi�ed because layered double hydroxides have a �exible structure (Takei et al., 2014) and easy to handle (Li et al., 2017). LDHs has many phys- ical and chemical properties which are similar to cationic clay minerals (Zhao et al., 2011). Their layered structure, extensive chemical composition (due to isomorphic variable metal cation substitution), ion exchange properties Chen (2011), reactive in- terlayer space (Xu et al., 2018a), swelling in water, rheological properties and colloids have made LDH like mineral clay (Zhao et al., 2011). Generally, layered double hydroxides have a general formula of M2+ M3+ (OH)2(An-)x/n.yH2O where M3+ and M2+ are repre- sented the trivalent metal and divalent metal, respectively (Tichit et al., 2019; Lins et al., 2018). Formed as 1 − xx layered double Figure 1. Structure of Layered Double Hydroxides was had nitrate anion hydroxides (LDHs) and prepared by two metal salts (divalent and trivalent metal) (Islam and Patel, 2010; Palapa et al., 2018a). In this case, the trivalent metal that essentially can be Al, Fe, Ni, Cr, Ga, and Mn (Elmoubarki et al., 2017). While, the divalent metals cation such as Mg, Mn, Co, Cu, Zn, and Fe. An interlayer anion as counterbalancing the metals cations (Lesbani et al., 2018). The anion can be taken up by layered double hydroxides uses three mechanisms such as anion exchanges in interlayer, surface ad- sorption and reconstruction layered double hydroxides calcined by ‘memory e�ect’ (Gaini et al., 2009). In this research, the e�ect of the comparison of ion M3+ metal cation trivalent from Zn/Al, Zn/Fe, and Zn/Cr layered double hydroxides. The LDHs has been successfully prepared and characterized by XRD and FT-IR analyses. https://doi.org/10.26554/sti.2019.4.2.36-39 Palapa et. al. Science and Technology Indonesia, 4 (2019) 36-39 2. EXPERIMENTAL SECTION 2.1 Chemicals and Instrumentation All chemicals material was used analytical reagents grade such as zinc nitrate, aluminum nitrate, chromium nitrate, iron ni- trate were obtained by Merck. Sodium hydroxide and sodium carbonate were obtained by from Sigma-Aldrich. The solution was prepared by deionized purity water. Then characterized by XRD Di�ractometer Rigaku Mini�ex-600 and Spectrophotometer FT-IR Shimadzu FT-IR Prestige-21. 2.2 Synthesis of Zn/M3+ (M3+: Al, Fe, and Cr) LDHs Zn/Al, Zn/Fe, and Zn/Cr LDHs material have been prepared by co-precipitation method at constant pH. The synthesized of LDHs were used the molar ratio 3:1 was conducted zinc nitrate (100 mL, 0,3 M) and a trivalent metal cation such as aluminum nitrate, iron nitrate, chromium nitrate (100 mL, 0.1 M), respec- tively. This solution was called A solution. Then A solution was stirring for an hour. B solution was prepared by 10 mL of sodium solution 2.5 M and 10 mL of NaOH 3 M. then B solution was added slowly to A solution under vigorous stirring of 2 hours and adjust pH at 10 by addition of NaOH and temperature kept at 60 °C for 24 hours to obtain layered double hydroxides. After that, Layered double hydroxides were washed and kept at room temperature. 3. RESULTS AND DISCUSSION Synthesis of Zn/Al, Zn/Cr, and Zn/Fe layered double hydroxides were obtained from metal cation divalent e.g. zinc nitrate and metal cations trivalent such as aluminum nitrate, iron nitrate, and chromium nitrate. Layered double hydroxides have success- fully prepared by co-precipitation method with molar ratio and adjust pH at 10 by adding NaOH. Co-precipitation method is based on the complex condensation to build the brucite layers with exchanges of metal cation divalent and trivalent and bal- ancing by anion in the interlayer. The result of Zn/Al, Zn/Fe, and Zn/Cr LDHs was shown in Fig. 2. The result has remained white powder, brown powder and grey powder, respectively. Then, Zn/Al, Zn/Fe, and Zn/Cr LDHs were characterized by XRD Di�ractogram. According to Forano et al. (2006) layered double hydroxides (LDHs) has an octahedral-hydroxyl layer which has a positive charge because of substitution of metal cation divalent and metal cation trivalent (Lesbani et al., 2018). This brucite layer described the close packing structure of metal cation and hydroxyl anion. Brucite layers balanced by anion and water molecules namely in- terlayer. X-Ray di�raction is one of the most e�ective methods to determine the synthesis process. The result of X-Ray Di�raction shows in Fig. 3. The pattern of Zn/Al, Zn/Fe, and Zn/Cr LDHs was shown in Fig 3. Fig. 3 shows a similar characteristic of layered double hydroxides has sharp peaks at 2� amount 10°, 22°, 30°, 35°, 49° and overlapping peaks at 60° are responding to (003), (006), (012), (104), (018) and (110) re�ections, respectively. The sharp peak amount 10o for all compounds was indicated interlayer of layered Figure 2. Powder of Zn/AL LDHs (a), Zn/Fe LDHs (b) and Zn/Cr LDHs (c) double hydroxides. The higher value of interlayer is Zn/Cr (7.68 Å) > Zn/Al (7.57 Å) > Zn/Fe (5.80 Å). in this case, the e�ect of ionic radii a�ects the distance between layers (interlayer) due to the di�erence in ionic radii where metal cation trivalent Cr3+ (0.64 Å), Al3+ (0.53 Å) and Fe3+ (0.61 Å). According to Forano et al (2006) the in�uence of the biggest metal ionic radii will be transformed interlayer higher than interlayer of smaller metal ionic radii [24]. However, in this study, the assumption was not answered because Zn/Fe LDHs had the smallest interlayer due to the synthesis of Zn/Fe LDH experiencing impurities and calcite formed due to the temperature that is not kept constant in the synthesis process. According to Parida and Mohapatra (2012), (003), (006) and (110) re�ections are most important characteristic based on a crystallographic parameter. The crystallographic parameter is the �rst re�ection di�raction pattern for layered double hydrox- ides. Based on Braag’s Law, layered double hydroxides have a hexagonal structure, to determining hexagonal structure used unit-cell parameters. However, the hexagonal structure has a rule which a=b≠c parameters, its equation: 1/d2(ℎkl) = ((ℎ2 + k2)/a2) + l2/c2 (1) Data digital of XRD was showed the value of d-spacing (003), (006) and (110) re�ection. (003) and (006) re�ection was used to calculate the ‘c’ parameter. ‘c’ parameter is a parameter that shows the size of the crystal structure using equation c = 3/2 [(d (003)) + (2d (006))] (Benito et al., 2010). Di�raction (110) re�ection were used to calculated ‘a’ parameter using equation a = 2d (110). The data of crystallographic parameter were shown in Table 1. Table 1. Crystallography Parameters of LDHs Parameters Zn/Cr Zn/Al Zn/Fe (003) (Å) 7.68 7.57 5.8 (006) (Å) 3.81 3.79 3.41 (110) (Å) 1.53 1.53 1.49 ’a’ parameter (Å) 3.06 3.06 2.99 ’c’ parameter (Å) 22.962 22.725 18.933 Table 1. were showed the unit cell of parameter crystallo- graphic such a and c parameter. The value of ‘a’ parameters © 2019 The Authors. Page 37 of 39 Palapa et. al. Science and Technology Indonesia, 4 (2019) 36-39 Figure 3. XRD Di�ractograms of LDHs was obtained similar because of the presence of nitrate anion in interlayer for all LDHs. ‘c’ parameter has denoted that size and crystal structure. The value of ‘c’ parameter of Zn/Cr LDHs higher than others its means the basal spacing of Zn/Cr LDHs biggest. Zn/Al, Zn/Cr, and Zn/Fe LDHs have been characterized by FT-IR spectrophotometer analyses. The purpose of character- ized by FT-IR is to determine the functional groups from layered double hydroxides (LDHs). The spectra of Zn/Al, Zn/Cr, and Zn/Fe LDHs was shown in Fig. 4. All compounds had identi- cal spectra where a broadband vibration from -OH stretching amount wavenumber 3400-3600 cm−1 while the weak vibration from water molecules in interlayer at wavenumber 1635 cm−1. Then, the sharp vibration at wavenumber 1380 cm−1 denotes the anion of nitrate as balancing in the interlayer. The M-O bonding vibration was identi�ed at wavenumber under 1000 cm−1. 4. CONCLUSIONS In this research has been successfully prepared Zn/Al, Zn/Cr and Zn/Fe layered double hydroxides (LDHs) by co-precipitation method with ratio molar 3:1 and kept pH at 10. The result has been characterized by X-Ray Di�ractograms and FT-IR spec- trophotometer analyses. XRD data obtained the value of inter- layer Zn/Cr LDHs (7.68 Å) highest than Zn/Al LDHs (7.57 Å) and Zn/Fe (5.80 Å). So, this study can be presented a synthesis of layered double hydroxides and its characterization. Figure 4. FT-IR spectrum of LDHs 5. ACKNOWLEDGEMENT Author thankful to Hibah Tesis Magister form Ministry of Re- search Technology and Higher Education Contract Number 0064.01/UN9/SB3.LP2M.PT/2019 REFERENCES Abdelrahman, E. A. (2018). Synthesis of zeolite nanostructures from waste aluminum cans for e�cient removal of malachite green dye from aqueous media. Journal of Molecular Liquids, 253; 72–82 Benito, P., M. Herrero, F. 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Sheng, J. Hu, C. Chen, and X. Wang (2011). The ad- sorption of Pb II on Mg2Al layered double hydroxide. Chemical Engineering Journal, 171(1); 167–174 © 2019 The Authors. Page 39 of 39 INTRODUCTION EXPERIMENTAL SECTION Chemicals and Instrumentation Synthesis of Zn/M3+ (M3+: Al, Fe, and Cr) LDHs RESULTS AND DISCUSSION CONCLUSIONS ACKNOWLEDGEMENT