Applied Surface Science 255 (2008) 33613370

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Applied Surface Science

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Chemical modication of silica-gel with hydroxyl- or amino-terminated polyamine for adsorption of Au(III)
Rongjun Qu *, Minghua Wang, Changmei Sun, Ying Zhang, Chunnuan Ji, Hou Chen, Yanfeng Meng, Ping Yin
School of Chemistry and Materials Science, Ludong University, Yantai 264025, China

A R T I C L E I N F O

A B S T R A C T

Article history: Received 13 July 2008 Received in revised form 20 September 2008 Accepted 20 September 2008 Available online 1 October 2008 Keywords: Chemically modied silica-gel Preparation Characterization Adsorption Au(III)

Silica-gel chemically modied by g-aminopropyltrimethoxysilane (APTS) reacted with methyl acrylate (MA) to form esteried silica-gel SiO2MA, and then SiO2MA reacted with ethanolamine (EA), diethanolamine (DEA), ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA) respectively to obtain ve novel adsorbents, hydroxyl-terminated polyamine functionalized silica-gels (SiO2EA and SiO2DEA) and amino-terminated ones (SiO2EDA, SiO2DETA, and SiO2TETA). Their structures were characterized by FTIR, WAXD, thermal analysis, and elemental analysis. The investigation of adsorption kinetics of the ve adsorbents for Au(III) under different temperatures showed that all the adsorption processes were endothermic in nature. The amino-terminated polyamine grafted silica-gels exhibited higher adsorption rates than the hydroxyl-terminated ones. The Langmuir model was better than Freundlich model to t the adsorption isotherms of the ve products for Au(III). 2008 Published by Elsevier B.V.

1. Introduction In recent years, silica-gel has attracted lot of attention due to its excellent thermal and mechanical stability and applications in catalysis [1,2], ion exchange [3], chromatography [4,5], solid phase extraction and metal ion preconcentration [6,7], and several others [810]. Chemical modication of the skeleton of silica-gel via the covalent coupling of an organic moiety is a promising approach to develop specic surface properties such as immobility, mechanical stability and water insolubility, thereby increasing the efciency and selectivity of the analytical application [11,12]. Therefore, a considerable number of chemically modied silica-gel were synthesized and characterized over the past three decades. Many variations in the behavior of the modied solid adsorbents are mainly dependent on the presence of some active donor atoms or groups such as O, N [1316], and S [17,18] into the incorporated organic modier. It is well known that chelating adsorbents with complex ligands containing nitrogen have excellent sorption selectivity for divalent transition metal cations due to the strong afnity between nitrogen atom and these metal ions. Examples of such complex ligands mainly include ethylenediamine, diethyle-

* Corresponding author. Tel.: +86 535 6673982. E-mail addresses: rongjunqu@sohu.com, qurongjun@eyou.com (R. Qu). 0169-4332/$ see front matter 2008 Published by Elsevier B.V. doi:10.1016/j.apsusc.2008.09.055

netriamine, triethylenetetramine, and polyamines, guanidyl group, aminopyridine [1924]. Generally, the polyamine is immobilized on the surface of silica-gel by reacting with the active CCl [2527] or epoxy group [14,28]. In this paper, we attempted to introduce polyamines such as ethanolamine (EA), diethanolamine (DEA), ethylenediamine (EDA), diethylenetriamine (DETA), and triethylenetetramine (TETA) on the surface of silica-gel through amido bond and expected to obtain some novel adsorbents. The structures of these adsorbents were characterized by FTIR, WAXD, thermal analysis, and elemental analysis. The above-mentioned ve kinds of polyamines were chosen as functional groups due to their different end-groups and varied lengths of chain besides their low cost. Gold, as a global currency, is one of the precious metals and has held an allure for thousands of years. Moreover, the demand for gold has shown an increasing trend due to the increasing uses of gold in industry. Therefore, it is necessary to recover gold from industrial scraps and wastewater. At present, many methods, such as re assay [29], co-precipitation [30], ion exchange [3133] and solvent extraction [34,35], etc. have been used to separate and enrich gold. Among these methods, chelating adsorption is one of promising approaches of solidliquid separation due to its good selectivity for gold [36,37]. The objective of this study is to investigate the relationship between structures of adsorbents and their adsorption properties choosing Au(III) as representative. The factors affecting adsorption

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properties of the above adsorbents for Au(III) as temperatures, contact times, and concentration of solutions were investigated. 2. Experimental 2.1. Materials and methods Silica-gel of chromatographic grade was obtained from Yantai Chemical Institute, Shandong Province of China. It was treated with nitric acid (HNO3:H2O = 1:1) at reuxing temperature for 3 h, 18% hydrochloric acid aqueous solution at room temperature for 6 h, and then calcined in mufe at 200 8C for 10 h, nally dried in vacuum at 110 8C for 48 h before use. g-Aminopropyltrimethoxysilane (APTS) (Shuguang Chemicals Factory, Nanjing, China) was used without further purication. Methyl acrylate (MA) and toluene were redistilled just before use. Ethanolamine, diethanolamine, ethylenediamine, diethylenetriamine, triethlyenetetramine, and other reagents used were of analytical-reagent grade. Au(III) solution was prepared using HAuCl44H2O (Sinopharm Chemical Reagent Co., Ltd., China) dissolved in distilled water and the pH of solution was adjusted to 2.6 with 5% dilute nitric acid or 5% sodium hydroxide aqueous. Infrared spectra were recorded on a Nicolet MAGNA IR 550 (series II) spectrophotometer; test conditions: potassium bromide pellets, scanning 32 times, resolution are 4 cm1. The data were treated with Thermo Nicolet Corporation OMNIC32 software of version 6.0a. Thermogravimetric analysis (TG) was recorded on a NETZSCH STA 409 thermal analyzer. Test conditions: type of crucible, DTA/ TG crucible Al2O3; nitrogen atmosphere, ow rate 30 ml min1; sample mass, 36 mg; heating rate: 25 K/min. Wide-angle X-ray diffractions were determined on a Rigaku-D/ max-2500VPC (Japan). These samples prepared by powder were laid on the glass sample holder (20 mm 15 mm 2 mm) and analyzed under plateau conditions. Ni-ltered Cu Ka radiation (k = 1.54 A) generated at a voltage of 40 kV and current of 40 mA

was utilized, and a scan speed of 0.18/s from 28 to 808 was used. The measured temperature was 25 8C. C, N analysis of all products was subjected to elemental analysis by the Elementar VarioEL III instrument, Elementar Co., Germany. Porous structure parameters were characterized using an automatic physisorption analyzer ASAP 2020 (Micromeritics Instruments Corporation, USA) by BET and BJH methods through N2 adsorption at 77 K. Atomic absorption analysis of Au(III) was performed with a ame atomic absorption spectrophotometer (Model 932A, GBC, Australia). 2.2. Synthetic route of hydroxyl- and amino-terminated polyamine grafted silica-gel The ideal synthetic routes of hydroxyl- and amino-terminated polyamine grafted silica-gel are illustrated in Scheme 1. 2.3. Preparation of SiO2APTS The introduction of amino groups onto the silica surface was achieved by the treatment of surface silanol groups with APTS. A typical procedure is similar to the method described in Ref. [38]. A suspension of 145.0 g of silica-gel and 146 ml of APTS were stirred at 70 8C in the 437 ml of toluene solution for 8 h. The product was then ltered off and transferred to a Soxhlet extraction apparatus for reux-extraction in toluene and methanol for 6 h, respectively. The product was dried under vacuum at 50 8C over 48 h. Elemental analysis: C% 10.21, N% 2.79. 2.4. Preparation of SiO2MA Under a nitrogen atmosphere, a mixture of 166 g of SiO2APTS (approximately 330.7 mmol-NH2) and 129 ml of MA (approximately 3839.0 mmol) was added to a 1000 ml ask with 600 ml of methanol as solvent. The mixture was stirred at 50 8C for 3 days to react

Scheme 1. The ideal synthetic routes of hydroxyl- and amino-terminated polyamine grafted silica-gel.

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sufciently. The solid product was then ltered off and transferred to the Soxhlet extraction apparatus for reux-extraction in methanol and tetrahydrofuran (THF) for 12 h, respectively. After extracting, the product was dried under vacuum at 50 8C over 48 h and SiO2MA was obtained. Elemental analysis: C% 13.71, N% 2.38. 2.5. Preparation of SiO2EA The reaction was carried out under a nitrogen atmosphere, and a suspension of 10 g of SiO2MA and 90 ml of EA (approximately 1.5 mol) was stirred at 50 8C in a ask use 80 ml of methanol as solvent for 5 days. The product was ltered off and transferred to the Soxhlet extraction apparatus for reux-extraction in methanol and THF for 12 h, respectively and then was dried under vacuum at 50 8C over 48 h. The product SiO2EA was obtained. Elemental analysis: C% 13.50, N% 3.42. 2.6. Preparation of SiO2DEA The reaction was carried out under a nitrogen atmosphere, and a suspension of 10 g of SiO2MA and 145 ml of DEA (approximately 1.5 mol) was stirred at 50 8C in a ask using 120 ml of methanol as solvent for 5 days. The product was ltered off and transferred to the Soxhlet extraction apparatus for reux-extraction in methanol and THF for 12 h, respectively and then was dried under vacuum at 50 8C over 48 h. The product SiO2DEA was obtained. Elemental analysis: C% 12.08, N% 3.09. 2.7. Preparation of SiO2EDA The reaction was carried out under a nitrogen atmosphere, and a suspension of 10 g of SiO2MA and 100 ml of EDA (approximately 1.5 mol) was stirred at 50 8C in a ask using 80 ml of methanol as solvent for 5 days. The product was ltered off and transferred to the Soxhlet extraction apparatus for reux-extraction in methanol and THF for 12 h, respectively and then was dried under vacuum at 50 8C over 48 h. The product SiO2EDA was obtained. Elemental analysis: C% 13.33, N% 4.75. 2.8. Preparation of SiO2DETA The reaction was carried out under a nitrogen atmosphere, and a suspension of 10 g of SiO2MA and 162 ml of DETA (approximately 1.5 mol) was stirred at 50 8C in a ask using 150 ml of methanol as solvent for 5 days. The product was ltered off and transferred to the Soxhlet extraction apparatus for reux-extraction in methanol and THF for 12 h, respectively and then was dried under vacuum at 50 8C over 48 h. The product SiO2DETA was obtained. Elemental analysis: C% 15.26, N% 5.50. 2.9. Preparation of SiO2TETA The reaction was carried out under a nitrogen atmosphere, and a suspension of 10 g of SiO2MA and 224 ml of TETA (approximately 1.5 mol) was stirred at 50 8C in a ask using 180 ml of methanol as solvent for 5 days. The product was ltered off and transferred to the Soxhlet extraction apparatus for reux-extraction in methanol and THF for 12 h, respectively and then was dried under vacuum at 50 8C over 48 h. The product SiO2TETA was obtained. Elemental analysis: C% 16.36, N% 5.81. 2.10. Adsorption kinetics In kinetics experiment, 20 mg of adsorbent was added to 20 ml of 2.43 mmol L1 Au(III) solution in a 50 ml of iodine ask

with ground-in glass stopper. The mixture was shaken continuously at desired temperature. At predetermined intervals, aliquots of 1 ml solution were withdrawn for analysis and the concentration of metal ion was determined by atomic absorption spectrometry. 2.11. Adsorption isotherm The isothermal adsorption was investigated also by batch studies. A typical procedure is as follows: a series of 50-ml iodine asks with ground-in glass stopper were employed. Each ask was lled with 10 ml of Au(III) solution of varying concentrations. A known amount of adsorbents (about 20 mg) was added into each ask and agitated intermittently at 25 8C for 20 h. The adsorption capacities were calculated also by using equation Q = (C0 C)V/W, where, Q is the adsorption amount (mmol g1); C0 and C are the initial and the equilibrium concentrations of Au(III) (mmol ml1), respectively; V is the volume of Au(III) solution (ml); and W is the dry weight of adsorbents (g). 3. Results and discussion 3.1. FTIR characterization The FTIR is usually employed to monitor the immobilization process by comparing the precursor and modied surfaces [13]. The infrared spectra of the original and chemically modied silica-gel are presented in Fig. 1. The broad low-frequency band centered at about 3422 cm1, followed by a weak band at 1630 cm1 in Fig. 1 curve 1, which is attributed to OH bond stretching vibration of the adsorbed water, and the surface silanols groups may be overlapped. The peaks around 800 and 473 cm1 are attributed to the typical symmetric stretching and bending vibrations of SiOSi of the mesoporous silica network, respectively [39]. The absorption at 1560 cm1, which is characteristic of primary amino group [40], and some new absorption peaks appeared around 2932 cm1 in Fig. 1 curve 2, which is the characteristic of the asymmetric CH2 bands, suggesting the APTS were successfully introduced onto the surface of silica-gel. Fig. 1 curve 3 shows a new and distinct peak at 1739 cm1 attributed to ester bonds (CO2CH3), which disappeared after reaction with polyamines. As illustrated in curves 4, 5, 6, 7, and 8, the bands located at 1647 and 1560 cm1 are the characteristic absorption of C O of amido group and primary (or secondary) amino groups, respectively [40]. These changes in the spectra corroborate the immobilization process proposed in Scheme 1. Based on the above analysis, it was concluded that corresponding organic moieties were grafted successfully on the silica-gel surface, respectively. 3.2. Thermal stability Thermal stability of silica-gel and its derivatives have been determined by thermogravimetric analysis. The results are shown in Fig. 2. As can be seen from curve 1, for silica-gel in the room temperature (25 8C) to 131 8C interval, an rst loss of 4.1% is attributed to physisorbed water molecules released and a second loss of 2.9% from 131 to 800 8C is attributed to the condensation of silanol groups bonded to the surface [14]. Different from silica-gel, the functionalized silica-gels show multistage thermogravimetric proles. The dehydration losses of physisorbed water are 4.5, 2.7, 2.6, 3.1, 4.4, 5.2, and 4.5% for SiO2APTS, SiO2MA, SiO2EA, SiO2 DEA, SiO2EDA, SiO2DETA, and SiO2TETA, respectively under the temperature below 160180 8C. Between the temperature ranges of 160800 8C, the weight losses beginning at 160180 8C and

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Fig. 1. FTIR spectra of silica-gel and its derivatives. (1) Silica-gel, (2) SiO2APTS, (3) SiO2MA, (4) SiO2EA, (5) SiO2DEA, (6) SiO2EDA, (7) SiO2DETA, and (8) SiO2TETA.

440 8C are mainly attributed to the loss of organic moiety and of water from the condensation of silanol groups bond to the surface of silica-gel, respectively [41]. The total losses at this temperature range of 160800 8C are 19.5, 20.0, 16.6, 18.0, 19.2, 22.4, and 23.1%

for SiO2APTS, SiO2MA, SiO2EA, SiO2DEA, SiO2EDA, SiO2 DETA, and SiO2TETA, respectively. This fact indicated that this series of modied silica-gel should be applied under no more than temperature of 160 8C.

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Fig. 2. Thermogravimetric curves of silica-gel and its derivatives. (1) Silica-gel, (2) SiO2APTS, (3) SiO2MA, (4) SiO2EA, (5) SiO2DEA, (6) SiO2EDA, (7) SiO2DETA, and (8) SiO2TETA.

3.3. Nitrogen adsorptiondesorption isotherms Fig. 3 shows the BJH desorption pore size distributions of silicagel and its derivatives. As illustrated in Fig. 3, the pores between 3 and 14 nm were dominant for all products. With the proceeding of

the reaction, the amount of the pores between 7 and 14 nm became smaller gradually and the pore size distribution moved to the smaller pore size. The porous structure parameters of the products derived from the basis of the nitrogen adsorption data are summarized in Table 1. As shown in Table 1, the values of BET

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R. Qu et al. / Applied Surface Science 255 (2008) 33613370 Table 1 The parameters of porous structure of silica-gel and its derivatives. Samples BET surface area (m2/g) BJH desorption cumulative volume of pores (cm3/g) 0.88 0.70 0.68 0.42 0.36 0.32 0.28 0.25 BJH desorption average pore diameter (nm) 7.85 6.89 6.87 6.18 6.20 5.69 5.42 5.16

Silica-gel SiO2APTS SiO2MA SiO2EA SiO2DEA SiO2EDA SiO2DETA SiO2TETA

349.37 281.45 274.28 192.65 156.50 147.37 127.60 114.91

Fig. 3. BJH desorption pore size distributions of silica-gel and its derivatives.

surface area, BJH desorption average pore diameter and BJH desorption cumulative volume of pores decreased gradually with the functionalization reactions, this result is in accordance with the results reported by the literature [42]. This fact can be interpreted as follows: the molecules of reagent rst diffused into the interior of pores of silica-gel, and then reacted with the active sites. With the formation of grafted pendant organic chains and crosslinking products, the pores size of silica-gel became smaller and smaller and even some pores disappeared. In addition, the presence of pendant organic chains on the surface partially blocked the

adsorption of nitrogen molecules. It should be noted that aminoterminated products show greater pore blockage than the hydroxyl-terminated products of similar size, which can be interpreted by the formation of H-bond between basic amines and unreacted surface silanols [43]. For amino-terminated products of SiO2EDA, SiO2DETA, and SiO2TETA, their values of BET surface area, BJH desorption average pore diameter and BJH desorption cumulative volume of pores decreased with the increase of molecular chain length of polyamines, which could be interpreted by the steric hindrance of grafted functional group to the diffusion of nitrogen into interior of silica-gel. This deduction can be adopted to interpret the performance of hydroxyl-terminated products of SiO2EA and SiO2DEA in the BET surface area, BJH desorption average pore diameter and BJH desorption cumulative volume of pores.

Fig. 4. Nitrogen adsorptiondesorption isotherms of silica-gel and its derivatives.

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Fig. 5. XRD patterns of silica-gel and its derivatives. (1) Silica-gel, (2) SiO2APTS, (3) SiO2MA, (4) SiO2EA, (5) SiO2DEA, (6) SiO2EDA, (7) SiO2DETA, and (8) SiO2TETA.

Fig. 4 shows the nitrogen adsorptiondesorption isotherms for silica-gel and its derivatives. It can be seen that the bare silica-gel and its derivatives are type IV according to the IUPAC classication and have a H1 hysteresis loop that is representative of mesopores. The volume adsorbed for bare silica-gel steeply increases at a relative pressure (P/P0) of approximately 0.6, representing capillary condensation of nitrogen within the uniform mesoporous structure. The inection position shifted toward lower relative pressures and the volume of nitrogen adsorbed decreased with functionalization. 3.4. XRD analysis Fig. 5 shows that all the diffraction peaks of silica-gel and its functionalized derivatives appeared at about 248, which is the amorphous diffraction peak of silica-gel [44]. This result shows that there was no an essential change occurred in topological structure of silica-gel before and after functionalized reactions, implying that silica-gel was stable enough to experience the Michael addition and amidation reactions. It should be noticed that the polarity of grafted organic moieties had an evident effect on the relative intensity of diffraction peak. The introduction of CO2CH3 and OH led to the decrease of intensity of diffraction peak and that of NH led to the slight increase of intensity of diffraction peak. This may be interpreted also by the formation of hydrogen bond between basic amines and unreacted surface silanols. 3.5. Adsorption kinetics The adsorption kinetics of SiO2EA, SiO2DEA, SiO2EDA, SiO2 DETA, and SiO2TETA for Au(III) were investigated at different temperatures to determine the adsorption equilibrium time. The

results are shown in Fig. 6. From Fig. 6, it can be observed that the amino-terminated products required only 2 h to reach adsorption equilibrium and the hydroxyl-terminated ones did at least 46 h. In order to ensure the adsorption completely, the equilibrium time was xed on 20 h in the following experiment. In order to compare the adsorption rates of different products, the data in Fig. 6 were treated by Boyd equation:   Q ln 1 kt Q0 (1)

where Q and Q0 are the adsorption amounts at sorption time t and at equilibrium, respectively; k is the apparent adsorption rate constant. The slope of straight line that was made by plotting ln(1 Q/Q0) versus t, yielded the apparent adsorption rate constant k. The results are listed in Table 2. It can be observed from Table 2 that the orders of adsorption rate constants at 5, 15, 25, and 35 8C are SiO2EDA > SiO2 TETA > SiO2DETA > SiO 2DEA > SiO2EA, SiO 2TETA > SiO 2 EDA > SiO 2 DETA > SiO 2 DEA > SiO 2 EA, SiO 2 TETA > SiO 2 EDA > SiO 2 DETA > SiO 2 DEA > SiO 2 EA, SiO 2 TETA > SiO 2 DETA > SiO 2EDA > SiO2DEA > SiO2 EA, respectively. Some conclusions can be drawn from the above orders: (1) the amino-terminated products have higher adsorption rate constants for Au(III) than the hydroxyl-terminated ones. A possible explanation for this is that the amino groups in the aminoterminated products were protonated at this experimental condition of pH 2.60, and the adsorption of protonated amino groups for AuCl4 through electrostatic attraction is more easily than hydroxyl groups in hydroxyl-terminated products. (2) For the amino-terminated products, the orders of adsorption rate constants do not accord with the order of chain length of polyamine

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Fig. 6. The adsorption kinetics of SiO2EA, SiO2DEA, SiO2EDA, SiO2DETA, and SiO2TETA for Au(III) at different temperatures.

TETA > DETA > EDA. It should be noted that SiO2EDA has the highest adsorption rate constant among the ve products at lower temperature (e.g. 5 8C) and SiO2TETA has the most adsorption rate constant at higher temperature (e.g. 1535 8C). This phenomenon may be because that grafted functional groups with long chain polyamine on the surface of silica-gel are too inexible to capture Au(III) at lower temperature. With the increasing of temperature, the functional groups are extended gradually which made Au(III) ions diffuse more easily into the inside of layer of organic functional groups. Unlike SiO2TETA, SiO2EDA possesses abundant surface amino groups which are easily to capture Au(III) at lower temperature. (3) For the hydroxyl-terminated products, the DEA derived product has a higher adsorption rate constant than EA derived one. This phenomenon can be interpreted as that the former product possesses more abundant surface hydroxyl groups than the latter one, and the end hydroxyl groups in hydroxyl-

terminated products are the major contributor to coordinate with Au(III). (4) The saturated adsorption capacities of the ve adsorbents for Au(III) are very proximate at the same temperatures, implying that increasing the number of amino or OH groups does not obviously affect the saturation adsorption capacity. Temperature is commonly an important factor affecting the adsorption. The results in Fig. 6 clearly indicates the high temperatures favours the adsorption of Au(III) on the ve products. This may be due to the desolvation of Au(III) and the increasing in active surface centers available for adsorption.

Table 2 The apparent adsorption rate constants k and correlation coefcients R2 of SiO2EA, SiO2DEA, SiO2EDA, SiO2DETA, and SiO2TETA for Au(III) at different temperatures. Parameters Temperatures (8C) SiO2EA SiO2DEA SiO2EDA SiO2DETA SiO2TETA k 5 0.82 1.61 3.92 3.49 3.78 15 0.68 0.90 3.35 3.00 3.48 25 0.67 0.76 2.69 2.60 3.13 35 0.55 0.72 2.08 2.16 3.05 R2 5 0.9792 0.9714 0.9960 0.9887 0.9983 15 0.9752 0.9973 1.0000 0.9875 0.9765 25 0.9881 0.9759 0.9951 0.9634 0.9968 35 0.9821 0.9711 0.9871 0.9910 0.9980

Fig. 7. Adsorption isotherms of Au(III) on SiO2EA, SiO2DEA, SiO2EDA, SiO2DETA, and SiO2TETA.

R. Qu et al. / Applied Surface Science 255 (2008) 33613370 Table 3 The Langmuir and Freundelich parameters of SiO2EA, SiO2DEA, SiO2EDA, SiO2 DETA, and SiO2TETA for Au(III) at 25 8C. Samples Freundlich parameters KF SiO2EA SiO2DEA SiO2EDA SiO2DETA SiO2TETA 6.31 6.36 10.20 7.67 3.45 1/n 0.43 0.42 0.50 0.48 0.35 R2 F 0.9005 0.9030 0.9806 0.9856 0.8111 Langmuir parameters Q0 0.68 0.71 0.86 0.74 0.54 b 1118.40 1192.03 633.86 657.28 1857.60 R2 L 0.9838 0.9849 0.9943 0.9981 0.9849

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bonds between the basic amines and unreacted surface silanols of silica-gel. (4) The investigation of adsorption kinetics of the ve adsorbents for Au(III) showed that the all the adsorption processes are endothermic in nature under different temperatures. The amino-terminated polyamine grafted silica-gel exhibited higher adsorption rates than the hydroxyl-terminated ones. The amino-terminated products required only 2 h to reach adsorption equilibrium and the hydroxyl-terminated ones did at least 46 h. The Langmuir model are better than Freundlich model to t the adsorption isotherm of the ve products for Au(III). Increasing the number of amino or OH groups does not obviously affect the saturation adsorption capacity.

3.6. Adsorption isotherms The adsorption isotherms were studied and the data in Fig. 7 were analyzed with Langmuir (2) and Freundlich (3) equations, respectively. C 1 C Q bQ 0 Q 0 1 ln C ln K F n (2) Acknowledgements The authors are grateful for the nancial support by the Nature Science Foundation of Shandong Province (Nos. Y2005F11 and Y2007B19), the Nature Science Foundation of Ludong University (Nos. 032912, 20052901, and 042920); Educational Project for Postgraduate of Ludong University (Nos. YD05001 and Ycx0612). References
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ln Q

(3)

where Q is the adsorption capacity (mmol g1), C the equilibrium concentration of Au(III) ions (mmol ml1), Q0 the saturated adsorption capacity (mmol g1), b an empirical parameter, n the Freundlich constant, and KF the binding energy constant reecting the afnity of adsorbents to metal ions. As we know, the Langmuir equation is applicable to homogeneous adsorption, where the adsorption of each sorbate molecule onto the surface had equal adsorption activation energy. While, the Freundlich equation is employed to describe heterogeneous system and reversible adsorption, but it is not restricted to the formation of monolayer. The parameters for the isotherms obtained from Fig. 7 are presented in Table 3. It can be seen that the regression coefcients (R2 ) obtained from Langmuir model are much closer to 1 than L those (R2 ) from Freundlich model, suggesting the Langmuir model F are better than Freundlich model to t the adsorption isotherm of the ve products for Au(III). The above fact shows that hydroxyolterminated products have similar adsorption mechanism as the amino-terminated ones and all of them are attributed to monolayer adsorption. 4. Conclusions (1) FTIR and elemental analysis demonstrated that hydroxyl- and amino-terminated polyamines were grafted successfully on the surface of silica gel through amido bond. (2) Thermal analysis reveled that this series of chemical modied silica-gels can be applied in the case of no more than 160 8C of temperature. (3) The BET surface area, BJH desorption average pore diameter and BJH desorption cumulative volume of pores of silica-gel decreased after chemical modication. For amino-terminated products of SiO2EDA, SiO2DETA, and SiO2TETA, their values of BET surface area, BJH desorption average pore diameter and BJH desorption cumulative volume of pores decreased with the increase of molecular chain length of polyamines due to the steric hindrance of grafted functional group to the diffusion of nitrogen into interior of silica-gel. The amino-terminated products showed greater pore blockage than the hydroxylterminated products of similar size due to the presence of H-

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