Applied Clay Science 72 (2013) 206210

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Applied Clay Science

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One-pot green hydrothermal synthesis of stearate-intercalated MgAl layered double hydroxides

Zhuang Zhang, Guangming Chen , Kongli Xu
Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, PR China

a r t i c l e

i n f o

a b s t r a c t
A convenient one-pot green hydrothermal synthesis method has been developed to obtain stearate-intercalated layered double hydroxide (LDH-St), an important nanoller for polymer/LDH nanocomposites. Various factors of the hydrothermal synthesis conditions, including reaction time, temperature and solid content, were taken into account. The resulting products were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), inductively coupled plasma (ICP) atomic emission spectrophotometry, CHN elemental analysis, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The increase of reaction time or solid content is helpful to the formation of LDH-St, whereas high reaction temperature had little effect. Deduced from PXRD and the composition analysis results, prolonging of reaction time led to a packing arrangement transformation from a bilayer-like structure with stearate acids co-intercalated to monolayer for the intercalated stearate anions in the interlayer space. In addition the prepared LDH-St crystallites showed ower-like aggregates with a diameter of about 810 m consisting of sheets with irregular shape. 2013 Elsevier B.V. All rights reserved.

Article history: Received 29 November 2011 Received in revised form 23 December 2012 Accepted 5 January 2013 Available online 1 February 2013 Keywords: Layered double hydroxides Stearate-intercalated One-pot hydrothermal synthesis Green chemistry

1. Introduction Layered double hydroxides (LDHs), also known as anionic clays or hydrotalcite-like compounds, are commonly expressed by the general x+ z 2+ 3+ formula [M1Ax/z mH2O, in which M2+ and M3+ are dix Mx (OH)2] valent (Mg2+, Zn2+, Co2+, Fe2+, Ni2+, etc.) and trivalent (Al3+, Cr3+, Fe3+, etc.) cations occupying in the octahedral positions within the hydroxide layers, and Az can be almost any organic or inorganic anion balancing the positive charges on the layers, while x is generally believed to be between 0.2 and 0.33 (Cavani et al., 1991; Evans and Duan, 2006). Due to their unique anion exchange capacity to intercalate anions, LDHs have been widely applied in many elds, such as catalysts (Xu et al., 2011; Zhou et al., 2011), pharmaceuticals (Bugatti et al., 2011), adsorbents (De Martino et al., 2011; Kim et al., 2011; Ulibarri et al., 2001) and polymer nanocomposite materials (Fu et al., 2010; Liu et al., 2008, 2009). Stearate, as a commonly used intercalated anion, has been investigated extensively in the surface modication of LDHs. The stearateintercalated LDHs (LDH-St) are an attractive candidate as nanoller for polymer based nanocomposites. When compared with the corresponding polymer counterparts, the nanocomposites using LDH-St exhibit enhanced mechanical properties, such as for poly(lactic acid) (PLA) (Mahboobeh et al., 2010), poly(vinyl chloride) (PVC) (Gu et al., 2010), poly[(2-hydroxybutyrate)-co-(3-hydroxyvalerate)] (PHBV) (Dagnon et

Corresponding author. Tel.: +86 10 62560722; fax: +86 10 62559373. E-mail address: chengm@iccas.ac.cn (G. Chen). 0169-1317/$ see front matter 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.clay.2013.01.007

al., 2009) and poly(methyl methacrylate) (PMMA) (Nogueira et al., 2011). In addition, the LDH-St nanollers have been found to greatly enhance the thermal stabilities of polymers including PVC (Liu et al., 2008, 2009; Yi et al., 2011), polyurethane (PU) (Kotal et al., 2011), PMMA (Nogueira et al., 2011) and polyethylene (PE) (Costantino et al., 2005). More importantly, the LDH-St has attracted much current interests in green chemistry. For example, besides reinforcing the rubber matrix, the LDH-St nanoller has been designed and employed in rubber vulcanization to obtain environmentally friendly rubber/LDH nanocomposites (Das et al., 2011). Additionally, due to the dramatically enhanced thermal stability of PVC, the LDH-St may become an efcient candidate to replace the toxic heavy metal Pb thermal stabilizer of PVC (Liu et al., 2008, 2009; Yi et al., 2011). So far, the most frequently-used method for preparation of LDH-St is the coprecipitation of metallic salts with an alkaline solution, and the subsequent anion exchange (Costantino et al., 2005; Dagnon et al., 2009; Magagula et al., 2009; Mahboobeh et al., 2010; Nhlapo et al., 2008; Saber and Tagaya, 2007; Toshio et al., 2003). In addition, one-step coprecipitation (Das et al., 2011; Gu et al., 2010; Liu et al., 2009; Nogueira et al., 2011) and reconstruction (Inomata and Ogawa, 2006; Kotal et al., 2011) methods have been developed to prepare LDH-St. However, from a green chemistry perspective, these methods have obvious drawbacks. In all these methods, waste solutions containing high content of alkali and various salt ions, such as K+, Na+, NO3 , Cl, were produced. The washing step inevitably consumed enormous amounts of water. Additionally, a large excess of stearate anions was required to exchange the original anions in the LDH interlayer. Therefore, these methods have the disadvantages not only of

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Fig. 1. A schematic illustration for the one-pot hydrothermal synthesis of MgAl-LDH-St.

environmental pollution but also of waste of raw materials in the viewpoint of atom economy. Recently, one-pot hydrothermal synthesis from metal oxides or metal hydroxides has been reported as a green and convenient method to prepare LDHs (Greenwell et al., 2010). It could avoid the use of alkali and salt ions, which are required for conventional synthesis methods of LDHs. As a result, the residual liquids via the one-pot hydrothermal route were almost neutral. Furthermore, the one-pot hydrothermal method could overcome the low anion selectivity in the coprecipitation or anion exchange procedure, which greatly reduced the dosage of intercalated anions. In this paper, we report an environment-friendly and simple method, i.e. one-pot hydrothermal method, to synthesize stearate-intercalated MgAl LDH (MgAl-LDH-St) from metal hydroxides. The structure and morphology of the obtained MgAl-LDH-St were investigated. In addition the effects of various hydrothermal conditions, including reaction time, solid content and temperature, were also studied. 2. Experimental Aluminum hydroxide (Al(OH)3) and stearic acid were obtained from Xilong Chemical Co., Ltd. Magnesium hydroxide (Mg(OH)2) was purchased from Tianjin Institute of Jinke Fine Chemicals. All of the reagents are of analytical reagent (A.R.) pure grade, and were used without further purication. Distilled water was used in the synthesis procedure. The synthesis procedure was schematically illustrated in Fig. 1. Mg(OH)2, Al(OH)3 and stearic acid were weighted at desired stoichiometry of Mg:Al:St=3:1:1 (mol), containing 0.5 or 5 wt.% solid. First, Mg(OH)2 and Al(OH)3 were added into an aqueous solution of stearic acid under stirring, which was dissolved in distilled water at 70 C. The mixture was stirred vigorously for 1 h, and subsequently treated by ultrasonic for 30 min. Then, the resultant slurry was transferred into a stainless autoclave with inner Teon vessel, and hydrothermally treated at 150 or 180 C for 1, 5 or 10 days (as shown in Table 1). Finally, when the autoclave was cooled to about 70 C, the resulting white solid was ltered without washing, and dried in vacuum oven at 50 C for 24 h. Powder X-ray diffraction (PXRD) patterns were collected on a Rigaku D/max 2400 diffractometer with Cu K radiation ( = 0.15418 nm) measuring at a scanning rate of 4min 1. The Fourier transform infrared
Table 1 Synthetic conditions and PXRD results of the synthesized MgAl-LDH-St. Sample Synthetic conditions PXRD results IAl/ IMg/ ILDH(%)a ILDH(%)a 16.4 34.4 36.1 10.8 10.0

spectroscopy (FTIR) spectra were recorded on a Perkin-Elmer System 2000 FTIR spectrophotometer after 64 scans within 4000400 cm 1. Content analysis of metals was performed by ICP atomic emission spectroscopy on a SPECTRO ARCOS EOP Axial View Inductively Coupled Plasma Spectrometer (SPECTRO Analytical Instruments GmbH) using the solutions prepared by dissolving the samples in dilute nitric acid. CHN elemental analysis was carried out using a Flash EA1112 elemental analysis instrument. Thermogravimetric analysis (TGA) was performed with a NETZSCH STA 449F3 apparatus between 25 and 800 C in N2 atmosphere at a heating rate of 10 C min 1. Scanning electron microscopic (SEM) images were taken on a HITACHI S-4300 scanning electron microscope with an acceleration voltage of 15 kV. 3. Results and discussion 3.1. MgAl-LDH-St structure characterization The crystalline structure of the MgAl-LDH-St was identied by PXRD technique, and the results were shown in Fig. 2. It is apparent that all of the synthesized samples were with well-dened layered structure. The patterns are characteristic of organic anions intercalated LDHs with basal (00l) reections at low 2 angles (from 1.7 to 3.0). The corresponding basal spacings (d(003)) of the obtained MgAl-LDH-St were calculated (in Table 1) using Bragg's equation, n = 2dsin, where n is equal to 1 for the (003) peak, is the wavelength of Cu K radiation, and is the half of the scattering angle. The large basal spacings for the synthesized products demonstrate the intercalation into the LDH interlayer space, and the success of the formation of the MgAl-LDH-St. Besides the PXRD patterns, FTIR spectra also conrm the formation of the MgAl-LDH-St (Fig. 3). For all samples, the characteristic FTIR absorption bands of stearate anions could be clearly observed. The bands

wt.% Temperature(C) Time(d) d(003)(nm) solid 1 2 3 4 5 5 0.5 0.5 0.5 0.5 150 150 150 150 180 1 1 5 10 10

5.32 25.0 4.85 102.5 4.64(w), 2.94(s) 41.9 3.16 8.3 3.07 6.9

w: weak; s: strong. a The PXRD diffraction intensity ratios of Mg(OH)2/LDH and Al(OH)3/LDH were calculated by the peak height (detailed in Section 3.2).

Fig. 2. PXRD patterns of MgAl-LDH-St (samples 15). Characteristic reections of Mg(OH)2 and Al(OH)3 are marked with a triangle () and a square (), respectively.

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With the increase of reaction time, the values of IAl/ILDH and IMg/ILDH decreased signicantly, suggesting that prolonging the reaction time improved the transform to the MgAl-LDH-St phase. In addition, the solid phase content (wt.%) and the hydrothermal reaction temperature were also major factors for the hydrothermal synthesis. High solid phase content helped to the transform of Mg(OH)2 and Al(OH)3 precursors to MgAl-LDH-St phase. However, for the investigated systems, when the reaction time was 10 days, increasing the hydrothermal temperature from 150 C to 180 C had little effect on the improvement of the phase transformation. Besides the PXRD technique, FTIR spectra were employed to study the structure transformation procedure as well. As shown in Fig. 3, with the increase of the hydrothermal reaction time, the intensity ratios of the bands of hydroxyl groups for Mg(OH)2 and Al(OH)3 in the range of 38003000 cm 1, especially the band at 3697 cm 1 of Mg(OH)2, decreased greatly. These FTIR results agreed with the above PXRD results very well. 3.3. Stearate packing arrangement in the interlayer Table 1 shows that the basal spacings (d(003)) for all of the MgAl-LDH-St samples ranged from 2.94 to 5.32 nm, depending on the synthetic conditions, especially the hydrothermal reaction time. An obvious position change of the (003) reection indicated the transformation of interlayer arrangement for stearate anions during the hydrothermal synthesis. After the distances of an individual LDH platelet (0.48 nm) and the interlayer water layer (0.14 nm, Toshio et al., 2003) were deducted, the height occupied by the stearate anions could be obtained. By comparing with the length of a stearate anion along its longest axis (2.36 nm), it could be used to deduced the stearate anion packing arrangement in the interlayer space. For sample 2 with basal spacing of 4.85 nm, the height occupied by stearate anions was 4.23 nm, slightly less than twice of the length of an individual stearate anion (4.72 nm). Thus, the stearate anions were possibly packed as a bilayer interlayer arrangement with 60 inclined angle. Furthermore according to the ICP, CHN elemental analysis and TGA results (shown in Table 2), the amount of stearate anions exceeded the anion exchange capacity of LDH layer. It is very likely that the stearic acid molecules were co-intercalated with stearate anions to form a bilayer-like arrangement, as depicted in Fig. 4(a). It is reasonable to deduce that hydrophobic interaction among the adjacent alkyl chains of the stearate anions existed. In sharp contrast, as for sample 4, the basal spacing of 3.16 nm indicated a monolayer packing arrangement. The long axis of the anions was nearly perpendicular to the LDH platelets, with an inclined angle of only 7 (Fig. 4(b)). This demonstrated that prolonging the reaction time could distinctly change the stearate packing arrangement. As for sample 3 with reaction time of 5 days, two sharp peaks appeared, showing the co-existence of arrangements of both structures. 3.4. Morphological features of MgAl-LDH-St Since there were little morphological differences among the SEM images for all of the ve MgAl-LDH-St samples, the morphology of sample 5 was shown in Fig. 5. Clearly, ower-like aggregates with a diameter of about 810 m (Fig. 5(a)) were prevalent. An enlargement in Fig. 5(a)

Fig. 3. FTIR spectra of stearate acid, MgAl-LDH-St (samples 2, 3, 4), Mg(OH)2 and Al(OH)3.

at 2920 and 2851 cm 1 were related to asymmetric and symmetric stretching vibrations of \CH2\ groups, respectively. The presence of the two bands resulting from the asymmetric (16001550 cm 1) and symmetric stretching (around 1400 cm 1) vibrations of carboxylate anion provided another proof of the intercalation of the stearate anions in the LDH interlayer. Additionally, the bands below 800 cm 1 might be attributed to the M\O and O\M\O (M= Mg or Al) vibration modes in the MgAlLDH frameworks. In addition the absorption band at 1630 cm 1 was associated to bending vibration of the interlayer water molecules. 3.2. Effects of reaction time, temperature and solid content In Fig. 2, the reections at 2 =38.0 and 18.3 could be observed, which were characteristics of Mg(OH)2 and Al(OH)3, respectively. This indicates the presence of unreacted starting reactants in the synthesized products. Moreover, we note that the peak intensity ratios of Mg(OH)2 or Al(OH)3 to MgAl-LDH-St are different. Therefore, the transformation degree could be quantitatively evaluated by the deviances of the intensity ratios. Here, the relative contents of the Mg(OH)2 and Al(OH)3 phases were calculated by the intensities of the characteristic peaks at 2 = 38.0 and 18.3, respectively, and the peak intensity of the (003) reection was assumed as the content of the MgAl-LDH-St. The corresponding intensity ratios of IAl/ILDH and IMg/ILDH were considered as the contents of the unreacted Al(OH)3 and Mg(OH)2 in the synthesized products, respectively. Table 1 summarized the residual contents of Al(OH)3 and Mg(OH)2 in the MgAl-LDH-St products. Obviously, the hydrothermal reaction time was an important factor for the contents of the residues.
Table 2 The contents of each componenta and possible chemical composition. Sample 1 2 3 4 5
a

Mg (wt.%) 12.42 15.10 13.99 12.86 12.53

Al (wt.%) 0.90 0.84 3.30 4.98 4.57

C (wt.%) 41.92 36.82 33.62 37.17 34.68

H (wt.%) 8.26 8.02 7.36 8.08 7.51

H2O (wt.%) 4.91 4.85 8.42 12.92 11.21

Possible chemical composition Mg0.75Al0.25(OH)2(C18H35O2)0.252.31 Mg0.75Al0.25(OH)2(C18H35O2)0.255.39 Mg0.75Al0.25(OH)2(C18H35O2)0.250.97 Mg0.75Al0.25(OH)2(C18H35O2)0.250.45 Mg0.75Al0.25(OH)2(C18H35O2)0.250.42 H2O3.09 Mg(OH)21.21 HSt H2O4.23Mg(OH)21.12 HSt H2O0.43 Mg(OH)20.13 HSt H2O0.02 Mg(OH)20.02 Al(OH)3 H2O0.05 Mg(OH)20.01 Al(OH)3

The Mg, Al, C, H and H2O contents were detected by ICP, elemental analysis and TGA respectively.

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Fig. 4. Packing arrangement transformation of stearate anions in the interlayer space in hydrothermal synthesis.

showed that the ower-like aggregates composed of curved LDH crystallites. The MgAl-LDH-St crystallites were sheet-like with irregular shape, which was in consistent with previous report of organic anion intercalated LDH (Costa et al., 2008; Xu and Braterman, 2010). The curved and irregular shape may be attributed to the exibility of the alkyl chains and their hydrophobic interaction in the interlayer, while the natural character of LDH frameworks kept their sheet-like morphology. Moreover, the LDH crystallites were crossed over and interconnected with one another, thus affording to ower-like aggregates.

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4. Conclusions MgAl-LDH-St was successfully synthesized via a convenient one-pot green hydrothermal method developed herein. Compared with conventional anion exchange or coprecipitation method, this method has advantages of the absence of using a large excess of the stearate anions, and no need to wash and purify the products. Due to the use of metal hydroxides as starting precursors, it also avoids the waste of atoms, such as alkali and salt ions, conforming to the principle of atom economy. Prolonging the hydrothermal reaction time and increasing the solid content were found helpful to the formation of MgAl-LDH-St, whereas increasing the reaction temperature had no obvious effect for the reaction systems studied here. Additionally, with the increase of reaction time, the stearate anions had a tendency to change the packing arrangement in the interlayer space from a bilayer-like with stearate acid co-intercalated to monolayer. The synthesized MgAl-LDH-St showed a ower-like aggregate morphology, composed of curved sheet-like LDH crystallites with irregular shape.

Acknowledgments The authors are grateful to the National Natural Science Foundation of China (51073162).

Fig. 5. SEM images of MgAl-LDH-St (sample 5) with a scale of (a) 10 m or (b) 2 m.

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