Efficient Concentration of Indium(III) from Aqueous Solution Using

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Efficient concentration of indium(III) from aqueous solution using layered silicates Natthawut Homhuan, Sareeya Bureekaew, and Makoto Ogawa Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.7b01575 • Publication Date (Web): 17 Aug 2017 Downloaded from http://pubs.acs.org on August 19, 2017

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Efficient concentration of indium(III) from aqueous solution using layered silicates Natthawut Homhuan,1 Sareeya Bureekaew2 and Makoto Ogawa2* 1. School of Molecular Science and Engineering, Vidyasirimedhi Institute of Science and Technology (VISTEC), 555 Moo 1 Payupnai, Wangchan, Rayong 21210, Thailand 2. School of Energy Science and Engineering, Vidyasirimedhi Institute of Science and Technology (VISTEC), 555 Moo 1 Payupnai, Wangchan, Rayong 21210, Thailand

ABSTRACT: A synthetic layered alkali silicate, magadiite, and a natural montmorillite were found to concentrate indium(III) ion from aqueous solution by ion exchange reactions. The adsorption was examined by the reaction between silicates and aqueous solution of indium(III) chloride of different concentration at room temperature for 10 min.

The

adsorption isotherms were H type, indicating strong interactions between the silicates and indium(III) ion. The maximum adsorbed indium(III) amount for magadiite was quite high, ca. 0.70 mmol/g silicate, which corresponded to 96 % of the ideal cation exchange capacity of magadiite derived from the chemical formula (Na2Si14O29). In addition, the selectivity of the indium was very high, efficient adsorption of indium was observed from the sodium chloride solutions and the solutions containing zinc, nickel and copper. The large adsorption capacity, high selectivity of indium and the short reaction time (10 min at room temperature) make the adsorption on magadiite useful for the concentration of indium(III) ion from aqueous environments.

ACS Paragon Plus Environment

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Introduction Concentration of metal ions from water on solid surfaces is a topic of scientific and practical interests. The removal of toxic elements such as heavy metals and radioactive metals for water purification and the collection of noble elements from environments are important and general issues. The adsorption (ion exchange) onto solids is a way for them and the adsorption of metal ions onto ion exchangers has been reported to examine the adsorbent-adsorbate interactions, adsorption capacity, and selectivity for specific target ions. Ion exchangeable inorganic layered solids are characterized by the chemical and thermal stabilities of the structures, large and variety of cation exchange capacity, and the welldefined structures, which make it possible to design the functions of the resulting ion exchange solids.1

Accordingly, the adsorption (or ion exchange) of ionic species from

aqueous solutions to ion exchangeable layered solids has extensively and systematically been investigated2-6 from the viewpoints of the concentration of ions. A wide variety of ion exchangeable layered solids are available and the mechanisms of the ion exchange is not fully elucidated, therefore, the selection of the ion exchangers for the concentration of specific target ion are still not straightforward. Therefore, the adsorption of various ions onto layered solids is further worth investigating to achieve efficient, selective and practical ion exchange reactions. Efficient concentration of radioactive ions onto a mica is a known example7-9 and, more recently, a layered double hydroxide was shown to concentrate dichromate anion from acidic solution.10 In the present study, the adsorption of indium(III) onto layered silicates is reported. Indium is a rare element and the application of indium as metal, its alloys and oxides are versatile from on-going liquid crystal display (LCD) manufacture and electrical components to future advanced materials application of indium complexes and nanoparticles of indium


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compounds.11 In addition to the elemental importance, the potential toxicity of indium12 motivated the research on the concentration of indium from various aqueous environments, and such methods as chemical precipitation,13 solvent extraction,14 membrane filtration,15 electrochemical method,16 biosorption17 and adsorption18 have been proposed so far for the indium concentration. Magadiite is a layered sodium silicate with the chemical formula of Na2Si14O29. Magadiite was found in nature and, later on, synthesized in laboratory by hydrothermal reactions.19-22 Besides the structural characterization, the materials application of magadiite has been examined through various host-guest reactions based on the cation exchange,23-26 grafting,27-31 and pillaring.32,33 nanocomposite.34,35

The application includes the adsorbent28,29 and polymer

Cation exchange properties of magadiite toward various inorganic

cations have been investigated so far36-41 and, recently, were summarized in a review.42 The nature of the cation exchange sites of magadiite has been discussed by careful spectroscopic characterization using IR and NMR.43,44 The cation exchange with alkali and alkaline earth ions has been studied. The ion exchange with rare earth ions and the photoluminescent behavior of the resulting ion exchanged layered silicates has been investigated.45,46 Not only the efficient cation exchange, there are few examples of selectivity of such metal ions as Zn(II), Cu(II), and Cd(II) for the ion exchange on magadiite, however, the sequence (selectivity) of the ion exchange from aqueous mixture is still controversial and experimental conditions need to be optimized/unified for common understanding.37-41,47,48 In addition, it has been reported that the interlayer ion formed nanoparticles of oxides48,49 and metals50,51 to give hybrids with silica after the thermal treatments.

These reports motivated us to

investigate the preparation and the properties of magadiite ion exchanged with other cations as a precursor of novel types of metal containing silica/silicates. Accordingly, the adsorption of various ions on magadiite is worth investigating from the viewpoints of the construction of


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the hybrid materials based on the layered silicate structure in addition to the collection of the noble or toxic elements from aqueous environments. The adsorption of indium(III) onto magadiite has not been reported so far, therefore, in the present study, the adsorption of indium(III) onto magadiite from aqueous solution was investigated to find the efficient and selective indium(III) adsorption.

Experimental Materials Magadiite (Na2Si14O29.xH2O) was synthesized hydrothermally from colloidal silica and sodium hydroxide according to the method described previously52 and was characterized by XRD, IR and SEM before the adsorption experiment as described previously to confirm high purity aggregated platy particle. A Na-montmorillonite (Kunipia-F, which is a purified sodium-type bentonite and contains only a small amount of quartz) was kindly donated by Kunimine Industries Co., Ltd and used after the characterization. Typical SEM images of the silicates will be given in the Results and Discussion section. The chemical composition was analyzed to be (Na0.53Ca0.09)0.71+((Al3.28Fe0.31Mg0.43) (Si7.65Al0.35)O20(OH)4))0.71− and CEC was determined to be 1.07 meq/ g clay in our previous study.53 Indium(III) chloride (Alfa Aesar), zinc chloride (Sigma-Aldrich), nickel chloride hexahydrate (Daejung) and copper chloride dihydrate (QREC) were used without further purification.

In3+ adsorption from aqueous solution Adsorption of indium(III) onto ion exchangers (magadiite and montmorillonite) was examined by the following procedure; silicate (0.10 g) was mixed with an aqueous solution 50 mL (0.20, 0.60, 1.0, 1.4, 1.8 mM) of indium(III) chloride and the mixture was allowed to react for 10 min at room temperature. After the centrifugation at 4,000 rpm for 5 min, the


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resulting precipitate was dried at room temperature in a vacuum oven for 1 day.

The

concentration of indium(III) in the supernatant was determined by ICP. Adsorption of indium(III) onto magadiite from aqueous NaCl solution was examined by the following procedure, indium(III) chloride was dissolved in a 0.468 M aqueous NaCl solution 50 mL(0.20, 0.60, 1.0, 1.4, 1.8 mM). Magadiite (0.10 g) was mixed with the solution and the mixture was allowed to react for 10 min at room temperature. After the centrifugation at 4,000 rpm for 5 min, the resulting precipitate was dried at room temperature in vacuum oven for 1 day. The concentration of indium(III) in the supernatant was determined by ICP. Competitive adsorption of indium(III) with zinc, nickel, and copper was examined by the same procedure from the mixed solution of indium(III) chloride, zinc(II) chloride, nickel(II) chloride hexahydrate and copper(II) chloride dihydrate. The mixture was allowed to react with magadiite for 24 h at room temperature. In order to examine the possible collection of the adsorbed indium from magadiite, a sample after the adsorption of indium(III) (15 mg) was allowed to react with an aqueous HCl solution (0.1 M, 50 mL, pH=1.13) or an aqueous NH4Cl solution (0.1 M, 50 mL, pH=5.17) for 4 h at room temperature. After the centrifugation, the concentration of indium(III) in the supernatant was determined by ICP.

Characterization X-ray powder diffraction patterns were obtained on a Bruker (NEW D8 ADVANCE) X-ray powder diffractometer using monochromatic Cu Kα radiation operated at 40 kV and 40 mA. The amount of indium(III) in the supernatant was determined by ICP analysis (Agilent Technologies 700 Series ICP-OES). Calibration curves (R factor > 0.999) were made for each measurement using standard indium(III) chloride solutions.


Scanning electron

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micrographs were obtained on a JEOL (JSM-7610F) scanning electron microscope for the samples coated with Pt. Elemental mapping was obtained by an Oxford energy dispersive Xray fluorescence spectrometer (X-MaxN). Langmuir plot The Langmuir model assumes which adsorption isotherm behaves a homogeneous surface as monolayer of adsorbate on surface of adsorbent. 1 = +

Ce

=

the equilibrium concentration (mmol/L)

qe

=

amount of adsorption (mmol/g)

qm

=

the maximum adsorption capacity of the adsorbent (mmol/g)

KL

=

Langmuir constant (L/mmol)

The values of qm and KL are calculated from the slope and intercept of the linear plot of Ce/qe (y-axis) against Ce (x-axis).

Results and discussion The adsorption isotherms of In(III) onto magadiite and montmorillonite from aqueous solutions are shown in Figure 1A. The isotherms were classified as type H according to the classification by Giles et al.54 showing the high affinity between In(III) and the silicates surface. The loaded In(III) cations were almost quantitatively adsorbed on magadiite, more than 90 % of the theoretical cation exchange capacity (CEC) value (2.22 meq/ g silicate), which was determined from the ideal formula of magadiite (Na2Si14O29). The shape of the adsorption isotherm is consistent with the previous papers on the ion exchange of magadiite with several metal ions including monovalent and divalent ions.36-41 The maximum adsorbed amount vary to some extent, partly due to the pH during the reactions, and completely quantitative cation exchange has been difficult even for the cation exchange with cationic


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surfactant.28,29 In order to avoid the precipitation of basic salts of metals ions, the solution has been maintained in slightly acidic during the ion exchange reactions in the previous studies. It is known that CEC of magadiite depends on pH.44 In the present study, the pH of the initial indium chloride solution was in the range of 3.5 – 4.0 (depend on the concentration), and it became 4.0 – 6.5 (lower pH starting from the higher concentration of indium(III)) during the reaction as a result of the ion exchange of In(III) with sodium. The pH values were not high enough to precipitate indium(III) hydroxides. The adsorbed In(III) amount of 0.70 mmol/ g silicate, which is slightly smaller than the ideal cation exchange capacity (2.22 meq/ g silicate). The adsorption of In(III) onto montmorillonite was examined as comparison, because the origin of the cation exchange site for montmorillonite (permanent charge coming from the isomorphous substitution in the silicate layer) are different from that of magadiite (pH dependent charge). The adsorption of In(III) cations on montmorillonite was also efficient, while magadiite adsorbed larger amount of In(III) (0.70 mmol/g silicate) than the montmorillonite (0.48 mmol/g clay), confirming the advantage of the high CEC of magadiite. The adsorbed In(III) amount of 0.48 mmol/g observed for the montmorillonite was significantly higher (ca.35% higher) than the CEC (1.07 meq/g clay) of the montmorillonite used.53 The indium hydroxide precipitation during the ion exchange may be concerned, while precipitation of hydroxide particle was not observed in the SEM image of the In(III) adsorbed montmorillonite.(Figure 2) The ion exchange was also evaluated from the viewpoint of the recovery (removal) of In(III) by the adsorption onto magadiite. The recovery of In(III) from 50 mL of In(III) chloride solution (the concentration of 100 ppm) by using different amount of magadiite(50, 100, 150 and 200 mg) was examined and the results are shown in Figure 1B.

The

concentration of 100 ppm was determined from the concentration of In(III) solution from LCD leaching solution.55 As expected, the increased magadiite amount contributed to


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improve the recovery, and the complete removal was achieved by 100 mg of magadiite for the present solution (100 ppm, 50mL).

Figure 1. (A) The adsorption isotherms of In (III) onto magadiite (red) and montmorillonite (blue) from aqueous solutions and (B) removal % of In(III) from aqueous solution (100 ppm) by the adsorption on magadiite with different amounts.

Figure 2. SEM images of montmorillonite before (a) and after (b) the ion exchange with In(III) from the aqueous In(III) chloride solution of 1.8 mM.


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The XRD patterns of magadiite after the adsorption of In(III) are shown in Figure 3, together with that of the original magadiite. The basal spacing (1.56 nm) of magadiite decreased after the ion exchange with In (III) to be ca. 1.37 nm. Since the thickness of the silicate layer is 1.12 nm as estimated from the basal spacing of the dehydrated H-magadiite,43 the gallery height of the products obtained by the reaction with higher concentration indium chloride solution was derived from the observed basal spacing to be 0.25 nm. The ionic radius of In(III), which is smaller than that of Na, and the difference in the hydration were possible reasons for the change in the basal spacing (from 1.56 to 1.37 nm by the ion exchange with In(III)) and the change in the hydration was confirmed by the TG. In addition to the change in the basal spacing, the diffraction pattern became broad after the ion exchange.

Similar broadening has been observed previously for the ion exchange of

magadiite, while the sharpening of the diffraction has been observed for the ion exchange with cationic surfactant. The arrangement of hydrated ion in the interlayer space may be concerned, though further careful examination is required to explain the broadening. The XRD patterns of montmorillonite after the adsorption of In(III) are also shown in Figure 4, together with that of the original montmorillonite. Different from the magadiite system, montmorillonite gave the increase basal spacing after the ion exchange (ca. 1.5 nm), which is often observed for montmorillonite with bidentate and tridentate ion in the interlayer space.53 The change reflected the monolayer hydration (1.25 nm for Na-montmorillinite) to bilayer hydration for In(III) montmorillonite.


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Figure 3. X-ray powder diffraction patterns of magadiite before (a) and after (b-f) the reactions with indium chloride (using the indium(III) chloride solutions of the concentration of 0.2 (b), 0.6 (c), 0.10 (d), 0.14 (e) and 0.18 mM (f)).

Figure 4. X-ray powder diffraction patterns of the montmorillonite before (a) and after (b-f) the reactions with indium chloride (using the indium(III) chloride solutions of the concentrations of 0.2 (b), 0.6 (c), 0.10 (d), 0.14 (e) and 0.18 mM (f)).

Scanning electron micrographs of the original magadiite and the magadiite after the ion exchange reaction with the solution of 0.6 and 1.8 mM are shown in Figures 5a, 5b and 5c, respectively. The rosette morphology composed of aggregated platy particles, observed


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for the original magadiite, was retained after the ion exchange with In(III) from aqueous solutions. Elemental mapping of magadiite and magadiite after the ion exchange with indium chloride solutions of the concentration of 0.6 and 1.8 mM are shown in Figures 5a, 5b and 5c, respectively.

Magadiite after the ion-exchange with indium chloride solution of the

concentration of 1.8 mM showed homogeneously distributed In(III). For the samples after the ion exchange with indium chloride, homogeneous distribution of Na and In(III) in each particle was seen (Figure 5b and c), although the elemental mapping data were obtained for the aggregated platy particles (characteristic to magadiite). Taking the single phase XRD pattern into account (Figure 3c), it was thought that In(III) was not segregated and co-existed with sodium in the interlayer space. The segregation of two different ions is an important issue for the ion exchange mechanisms and the functional design of the intercalation compounds.3, 46-51 The present finding suggests a possible functional design of the In(III)magadiite intercalation compounds with different In(III) content.


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Figures 5. SEM images and elemental mapping of magadiite (a) and magadiite after the ion exchange with indium chloride solution of the concentration of (b) 0.60 and (c) 1.8 mM. The element was presented by Si (blue), Na (yellow) and In (pink). In addition to the efficient and the high capacity of the ion exchange mentioned above, the selective adsorption of In(III) from the solution containing other metal ions is also necessary. The adsorption isotherm of In(III) onto magadiite from aqueous NaCl solutions containing In(III), where the amount of sodium is 260-2340 times excess of In(III), are shown in Figure 6A. The isotherm was also classified as type H, indicating the efficient adsorption. The loaded In(III) cations were almost quantitatively adsorbed on magadiite, the maximum adsorbed amount was over 0.80 mmol/ g silicate, which was higher than the value (0.70 mmol/ g silicate) obtained for the adsorption of In(III) from aqueous solution (in the absence of NaCl). The adsorbed In(III) amount from aqueous solution (in the absence of NaCl) was 0.70 mmol/ g silicate and a partial proton exchange during the reaction can be a reason for the smaller value than the ideal cation exchange capacity of magadiite. The proton exchange is less plausible for the In(III) adsorption from the aqueous NaCl solution, to lead the larger In(III) amount, which is very close to the ideal cation exchange capacity of magadiite. Since the crystal structure is not solved yet and the purity of the magadiite is not determined experimentally, detailed quantitative discussion based on the structural characterization and the purification will be fruitful. The adsorption of In(III) onto magadiite and montmorillonite was evaluated by Langmuir plot as shown in Figures 6B, 6C and 6D.56 The Langmuir plots fitted very well with the high correlation coefficients for the adsorption of In(III) examined in the present study. The Langmuir isotherm confirmed the interactions between In(III) cation and negative charge of layered silicate to form an ordered monolayer. The Langmuir parameters of the adsorption of In(III) onto magadiite are summarized in Table 1. The parameters were qm =


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0.70 mmol/g and KL = 75 L/mmol for the adsorption onto magadiite, and qm = 0.87 mmol/g and KL = 76 L/mmol for the adsorption of In(III) onto magadiite from aqueous NaCl solutions. The parameters were qm = 0.48 mmol/g and KL = 61 L/mmol for the adsorption onto montmorillonite.

These values strongly suggested the adsorption of In(III) onto

magadiite from NaCl solutions is very efficient for the recovery of In(III).

Figures 6. (A) The adsorption isotherm of In (III) onto magadiite from aqueous NaCl solutions and the Langmuir plots of the adsorption of In(III) onto magadiite from (B) aqueous solutions, (C) NaCl solutions and (D) that onto montmorillonite.

Table 1. Langmuir parameters for the adsorption of indium onto layered silicates.


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Ion exchangers

qm (mmol/g)

KL (L/mmol)

R2

Magadiite

0.70

75

0.9995

Magadiite (from NaCl solution)

0.87

76

0.9926

Montmorillonite

0.48

61

0.9994

The adsorption capacity (derived from the Langmuir plot) of In(III) achieved in the present study and those reported for typical ion exchangers are summarized in Table 2. The In(III) adsorption capacity of magadiite (0.70 and 0.87 mmol/g silicate) was comparable or superior to the values observed for ion exchange resins.57-60 This advantage motivates further study on the In(III) adsorption using other layered solids with varied cation exchange capacity.1-3 The adsorption is being investigated in our laboratory and the results will be reported subsequently.

Table 2. Examples of the adsorption capacity of In(III) reported for various ion exchangers.

Condition

Adsorbed In(III) amount (mmol/g)

Ref.

Magadiite

Stirring, 10 m

0.70

This study

Magadiite (from NaCl solution)

Stirring, 10 m

0.87

This study

Montmorillonite

Stirring, 10 m

0.48

This study

PVA–boric acid coated solvent impregnated resins containing 2ethylhexyl phosphoric acid mono (2-ethylhexyl) ester

Shaking, 12 h

0.21

[57]

Impregnated sec-octylphenoxy acetic acid on styrene–divinyl benzene copolymer support

Shaking, 12 h

0.34

[58]

Poly(glycidyl methacrylate-copoly(ethylene glycol) diacrylate) microbead modified with

Shaking, 4 h

0.61

[59]

Ion exchanger


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iminodiacetic acid Poly(vinylphosphonic acid-comethacrylic acid) microbead

Shaking, 4 h

0.70

[60]

In nature, indium is found in minerals associated with other metals including zinc and copper.11 When sphalerite (ZnS ore) was smelted in zinc mining, Zn(II), In(III) and other metals are released into environment. Therefore, the adsorption of In(III) onto magadiite from mixed In(III), Zn(II), Ni(II) and Cu(II) solutions (1.35, 2.04, 2.04 and 2.04 mM, respectively) was examined and the results are shown in Figure 7. As shown in Figure 7, magadiite adsorbed In(III) with high selectivity among the four co-existed metal ions probably due to the stronger interactions between trivalent ion, In(III), and the negative charge of the magadiite surface if compared with those for divalent ions. This selectivity is an important advantage of the ion exchange over co-precipitation as a mean of the metal ion recovery.

Figure 7. Removal of In, Zn, Ni and Cu by the adsorption onto magadiite from the mixed metal solutions. The collection of the adsorbed In(III) from magadiite was examined by the reaction of the In(III) adsorbed magadiite with 0.1 M of HCl (pH = 1.17) or 0.1 M of NH4Cl solution


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(pH = 5.05). All the adsorbed In(III) was released from the magadiite to both solutions as confirmed by the amount of the released In(III) determined by ICP, suggesting possible In(III) recovery from the adsorbents. On the other hand, the leaching of the adsorbed ion to the solution can be a problem for the materials application of the In(III) intercalated magadiites. In order to find the application of the resulting In(III) adsorbed silicates, the post synthetic treatments to stabilize the materials and to convert the structures are being done in our laboratory and the results will be reported subsequently.

Conclusions Magadiite concentrated indium(III) ions from aqueous solutions efficiently (high capacity and selectivity) and easily (10 min at room temperature). The adsorption capacity achieved was very high (over 0.7 mmol/ g silicate), thanks to the high cation exchange capacity of magadiite. The adsorption was selective as shown by the efficient adsorption of indium(III) from the solution containing large excess of Na with higher adsorption capacity (0.87 mmol/ g silicate). Selective indium(III) adsorption was also found from the solution containing similar amount of Zn, Ni, and Cu ions. Eco-friendly and non-toxic nature of magadiite and the simple adsorption process, short reaction time and easy sample collection by centrifugation or filtration, make the practical application of magadiite for the indium(III) adsorption plausible.

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TOC Graphic

Magadiite adsorbed In(III) from aqueous environments efficiently and with high capacity


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Efficient Concentration of Indium(III) from Aqueous Solution Using

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