JOURNAL OF COLLOID AND INTERFACE SCIENCE ARTICLE NO.

200, 121125 (1998)

CS975344

Adsorption Parameters of Cd(II), Pb(II), and Hg(II) on Zirconium(IV) Phosphate Chemically Grafted onto Silica Gel Surface
Noemi Nagata, Lauro T. Kubota, 1 Maria I. M. S. Bueno, and Patricio G. Peralta-Zamora
Instituto de QuB mica, Universidade Estadual de Campinas, P.O. Box 6154, 13083-970 Campinas, SP, Brazil Received July 28, 1997; accepted November 24, 1997

Adsorption properties of metallic ions not essential for human metabolism, such as cadmium, lead, and mercury, on silica chemically modied with zirconium( IV ) phosphate, SiZrP, were investigated using batch systems. The immobilization procedure was efcient and the functionalization degree was 2.82% for zirconium ( 0.31 mol g 01 ) and 2.54% for PO 30 (0.27 mol g 01 ) . These 4 results indicate that phosphate reacted with zirconium in a 1:1 ratio. The equilibrium is reached very quickly ( 15 min ) , indicating that the adsortion sites are well exposed. The best adsorption parameters were evaluated using 50 mL of aqueous phase at pH 4.5, an adsorption time of 15 min, and 0.2000 g of adsorbent. From adsorption isotherms obtained for the metals ions and distribution coefcients the afnity of SiZrP for the metal ions studied increases in the order Cd( II) Pb( II) Hg( II ). Twice as much lead was adsorbed by the SiZrP surface ( Nf 10.0 mmol g 01 ) as cadmium ( Nf 5.0 mmol g 01 ) . For mercury, the capacity was greater ; nevertheless an adsorption plateau was not observed.
1998 Academic Press

Key Words: adsorption; cadmium; lead; mercury; zirconiumphosphate-modied silica.

INTRODUCTION

An important current trend in new materials developments is the modication of classical supports to produce new, more versatile, low-priced materials with well-dened characteristics (1, 2 ). Among the most used is silica gel, a material of well-established particle sizes and well-dened porosity, high surface area, and high mechanical, chemical, and thermal stability (3 ), as well as a low tendency to swell in solvents (4 ). The supercial silanol groups react chemically with distinct species ( 3) . These characteristics allow the preparation of solids with different surface properties, including highly selective materials, which are employed in several adsorption processes (5 ), immobilization ( 6, 7) , chromatography ( 8) , catalysis ( 9) , and other processes ( 10, 11) . The adsorption properties of these functionalized silicas
1

have given rise to great interest for analytical purposes (12), since several evaluations have demonstrated that most of these materials show strong adsorption capacities and mainly selective characteristics, important for speciation (13). Several investigations have demonstrated that modied materials are able to adsorb nonessential metal ions such as cadmium, lead, and mercury, which are potential pollutants. However, more emphasis has been given to silica modied with organic groups that are able to provide a great number of different materials (14) to adsorb metal ions from aqueous (1517) and nonaqueous solvents (1820). For inorganic functionalized silica, few studies of metal ion adsorption properties have been described in the literature (21, 22). However, these materials can present advantages such as stability, adsorption of cations or anions depending on the solution pH (23), and high selectivity (24), giving rise to separation or even speciation (25). Zirconium(IV) phosphate has been studied since the 1950s as a cationic exchange material, due to its strong acid character. To improve the mechanical properties of the material, So (26) proposed its dispersion on silica gel. In a complementary work (27), the author developed selective separation procedures for alkaline and transition metals using this modied matrix. Through a systematic study, the analogy between the exchange properties of this new material and the corresponding free species were demonstrated. The ionic exchange process is represented by the following reaction: 2SiZrP(H) / M 2/ r 2SiZrPM / 2H / . However, the developed methodology promotes high dispersion of the zirconium phosphate on the silica gel, involving not only its surface but its entire solid structure. This effect makes control of the mechanical properties of the material difcult. Therefore, not all phosphate groups are available for the ion exchange process (28). To solve these problems, recent studies have proposed the chemical modication of the silica gel surface with zirconium(IV) phosphate groups (29). The presence of this species denitively
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increases the adsorption capacity of the silica gel toward positive ions because the cationic exchange properties of free zirconium phosphate are conserved in the modied material. In this work the adsorption properties and selectivity of zirconium(IV) phosphate modied silica for cadmium, lead, and mercury ions in the aqueous phase were evaluated in batch systems.
MATERIALS AND METHODS

Adsorption Isotherms and Afnity of Metallic Ion for the Matrix The adsorption isotherm for each metal on SiZrP in aqueous solutions was obtained at room temperature. The afnity of the metal ion to the matrix in aqueous solutions was determined from distribution coefcient (D) values. The solutions of Cd 2/ (0.5200 mg L 01 ), Pb 2/ (0.5116 mg L 01 ) and Hg 2/ (0.5116 mg L 01 ) at pH 4.5 were stirred for 15 min with 0.2000 g of SiZrP. The supernatants were collected to determine the concentrations of cadmium and lead by ame atomic absorption spectrometry (AASPerkin Elmer 5100). The concentration of mercury was determined by spectrophotometry. Aliquots having mercury at concentrations of 0.22.4 mg L 01 were transferred to 5.0 mL volumetric asks, 1.0 mL of 0.05% PAN [1-(2-pyridylazo)-2-naphthol] in ethanol was added, and the volume was completed with 50% ethanol solution at pH 11. The molecular absorption of the reddish HgPAN complex was measured at 550 nm in an optical cell of 1 cm, using a Hitachi U-2000 spectrometer.
RESULTS AND DISCUSSION

Preparation of the Modied Silica The adsorption matrix was prepared according to the methodology already described in the literature (29). In the rst chemical modication step, about 80 g of previously activated silica gel (Fluka), 70230 mesh, with a surface area of 422 m2 g 01 , was used. The amounts of the other reagents used in the reux system were 25 g of pure ZrCl4 (Fluka), dissolved in 400 mL of dried ethanol (Merck). In the second step, 40 g of the obtained material was maintained under stirring in 400 mL of 0.1 mol L 01 aqueous H3PO4 solution at room temperature. Characterization of SiZrP The functionalization degree of the modied matrix was determined through zirconium and phosphorus analysis by energy dispersive X-ray spectrometry (EDXRFTracor Spectrace 5000). The standards were prepared from mixtures of silica gel with controlled particle size (100150 mesh), ZrOCl2r6H2O (Fluka), and Na2HPO4 (Nuclear). The reagents were dried in an oven for 4 h at 100 C before use to prepare the solid standardization mixtures. Standard Solution Preparation Analytical grade reagents were used. Known amounts of Pb(NO3 )2 (Ecibra) and Hg(NO3 )2 (Merck) were dissolved in 0.1 mol L 01 HNO3 to obtain the 2000 mg L 01 stock standard solutions of these metallic ions. The mercury solution was standardized using diphenylcarbazone as indicator according to the Basset method (30), since Hg(NO3 )2 is not considered a primary standard. For cadmium, a standard solution of cadmium was prepared by dissolving a known amount of metallic cadmium (Baker 99.9%) under stirring with 8.0 mL of concentrated HNO3 (Vetec) and diluting to 1000 mL with dionized water. Adsorption Parameters The adsorption of the metallic ions by SiZrP in batch was optimized through the evaluation by EDXRF analysis of the following parameters: pH and volume of aqueous phase, adsorption time, and mass of adsorbent used.

Material Characterization The sample matrices were prepared in duplicate and both samples were analyzed by EDXRF. The mean values were 2.82% for zirconium (0.31 mol g 01 ) and 2.54% for PO 30 4 (0.27 mol g 01 ). These results indicate that phosphate reacted with zirconium in a 1:1 ratio. The small difference between the values may be attributed to the inaccessibility of some zirconium atoms. Taking into account the latter results, the silica gel modication process can be represented as:
SiO Zr SiO OH OH HPO SiO SiO Zr O O P O OH

Furthermore, the x-ray diffraction results indicate that the predominant structure of the zirconium phosphate grafted onto the silica gel surface corresponds to the amorphous form. The acidity of these materials was veried by immersing it in aqueous solution, because the amount of hydrogen ion dissociated in this media can be assigned to the proton of phosphate group (29). Adsorption Parameters As expected, the relative adsorption capacity of SiZrP depends largely of the pH of the aqueous phase. For both metallic species, a characteristic plateau of maximal extrac-

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FIG. 1. The effect of pH on the adsorption of ( ) cadmium and ( ) lead. Aqueous phase volume: 50 mL; [M 2/ ]: 4 mg L 01 ; mass of SiZrP: 0.5 g; temperature: 25 C.

FIG. 2. The effect of aqueous phase volume on the adsorption of ( ) cadmium and ( ) lead. Aqueous phase volume: pH: 3.0; [M 2/ ]: 4 mg L 01 ; mass of SiZrP: 0.5 g; temperature: 25 C.

tion was observed between pH 3 and 5 (Fig. 1). By using pH values located in this extended plateau signicant modications on the adsorption capacity, due to the liberation of hydrogen ion from the matrix, were not observed. Thus, the use of buffer solutions was not necessary. When the aqueous phase volume increase the interaction between the solid phase and the analyte is reduced. However, we observed that generally this dilution effect is not signicant for volumes lower that 300 mL. The behavior of Pb(II) is in agreement with the anterior observation (see Fig. 2). Nevertheless, for Cd(II) a very different comportment was observed. For small aqueous phase volumes (10 to 75 mL) a signicant reduction of the adsorption was observed, in relation to the usual plateau observed for higher volumes. One explication for this anomalous behavior can be presumed from the acid character of the matrix. For small volumes, the liberation of hydrogen ions from the solid phase would cause a signicant decreasing of the solution pH, leaving the system away from the maximal extraction region. That is, the pH of the solution is decreased to values lower than 3. To avoid the inconveniences exposed by the previous study, the subsequent experiments (acquisition of adsorption isotherm and evaluation of the afnity) were carried out with aqueous phase volumes of 50 mL and pH of 4.5. Figure 3 shows that SiZrP has an efcient adsorption property, since a small amount of this species is able to retain a signicant amount of the metals. When a larger amount of SiZrP is used, only a dispersion of the metal ions on the

matrix is observed and the adsorption capacity is similar for both cases. This behavior suggests a great adsorption capacity of the material in adsorption processes. The effect of the time in the absorption process was systematically investigated (Table 1). In this study, we found that the equilibrium condition is reached quickly, probably due to the high dispersion of the sites on the surface of this kind of material. This interesting property of the sorvent,

FIG. 3. The effect of modied silica mass on the adsorption of ( ) cadmium and ( ) lead. Aqueous phase volume: 50 mL; pH: 3.0; [M 2/ ]: 4 mg L 01 ; mass of SiZrP: 0.5 g; temperature: 25 C.

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TABLE 1 The Effect of Time on the Cadmium and Lead Adsorption by the Modied Silica
Time (min) 1 2 5 10 20 25 30 40 % Extraction of cadmium 71.7 71.1 60.8 72.2 72.7 68.0 67.0 67.1 % Extraction of lead 65.4 62.7 59.9 65.4 64.0 65.2 62.9 65.2

permits to reach the maximal extraction quickly, at time lower than 1 min. The extraction time of 15 min was adopted only to increase the homogeneity of the solid phase, which is an essential characteristic for adequate reproducibility of the x-ray measurements. The analytical technique used to optimize the parameters was EDXRF, a technique that is multielemental, simultaneous, rapid, and appropriate to process solid samples. Adsorption Isotherms and Afnity The exchange capacities were evaluated through the determination of Nf, that is, the maximum capacity of adsorption of metal per gram of SiZrP. Equation [1] was used to calculate this parameter. Nf Na 0 Ns w [1]

FIG. 4. Adsorption isotherms of ( ) cadmium, ( ) lead and ( l ) mercury. Aqueous phase volume: 50 mL; pH: 4.5; mass of SiZrP: 0.2 g; temperature: 25 C.

Nf , C

[2]

where C is the equilibrium concentration of the metallic ion in the solution in contact with the solid phase. The distribution coefcients were determined for each point of the isotherms and the D vs [M 2/ ] plots are presented in Fig. 5. For mercury, the distribution coefcient could not be determined because the quantity of mercury in solution was not detectable in the more dilute solutions. However, by observing D

where Na is the initial mol number of the metallic ion in solution, Ns is the mol number of the metallic ion in solution at equilibrium, and w is the weight of modied silica. The exchange capacities values for each concentration permitted to drawing the adsorption isotherms of SiZrP for each metal ion (Fig. 4). Through these proles it is veried that the maximum adsorption capacity is 10 mmol g 01 for lead, and 5 mmol g 01 for cadmium. This parameter could not be calculated for mercury, since a maximum adsorption plateau was not reached. Unfortunately, solutions with higher concentrations than those evaluated here ( 116 mg L 01 ) could not be submitted to the adsorption procedure, due to mercury hydrolysis at the optimized pH 4.5. Considering that the modied silica has 27 mmol g 01 of phosphate groups and the maximum adsorption capacity for cadmium and lead, the ratio of 5 and 3 phosphate groups for each metal ion respectively, indicate that lead presents a higher afnity for modied silica. The afnity of the metallic ions by the adsorption matrix was determined through the calculation of the distribution coefcients according to the equation

FIG. 5. Curve of the distribution coefcients of ( ) cadmium, ( ) lead and ( l ) mercury versus equilibrium concentration in aqueous phase. Aqueous phase volume: 50 mL; pH: 4.5; mass of SiZrP: 0.2 g; temperature: 25 C.

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values for mercury in more concentrated solutions, it is higher than for cadmium and lead. From these proles, it is observed that DHg DPb DCd , when the same initial metallic ion concentration is used for comparison. This observation indicates that SiZrP has a higher afnity for mercury, followed by lead and then cadmium.
CONCLUSION

This work shows adsorption parameters for cadmium, lead, and mercury ions by zirconium(IV) phosphate modied silica. The more representative aspect veried, after optimization of some parameters, was the much higher maximum adsorption capacity for mercury; while lead showed twice the adsorption capacity as cadmium. As for the afnity, represented by the distribution coefcients, the following increasing order was ascribed: Cd 2/ , Pb 2/ , and Hg 2/ . This material has great advantage for adsorption of these non essential ions, due to its great stability, reutilization possibility, rapidity in reaching the equilibrium, high mechanical resistance and surface area.
ACKNOWLEDGMENTS
This work was supported by grants from CNPq, FAPESP, and FAEPUnicamp. The authors thank Professor Carol H. Collins for English revision of the manuscript. NN and LTK are indebted to CNPq for fellowships.

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