Chemical Engineering Journal 171 (2011) 14581468

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Chemical Engineering Journal

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A green route to preparation of MCM-41 silicas with well-ordered mesostructure controlled in acidic and alkaline environments
Tzong-Horng Liou
Department of Chemical Engineering, Ming Chi University of Technology, 84 Gungjuan Rd., Taishan, Taipei 24301, Taiwan

a r t i c l e

i n f o

a b s t r a c t
E-waste is one of the rapidly growing environmental problems of the world. However, the utilization of e-waste to produce economically viable materials such as mesoporous silica molecular sieves has not been well studied to date. Electronic packaging resins have been used widely in semiconductor industry. This study uses resin waste from this packaging process as source of Si and cationic surfactant as a template for the synthesis of highly ordered mesoporous silica with large surface area. This investigation reports the effects of various conditions on the self-assembly process of silica including the duration and temperature of the hydrothermal treatment, the molar ratio of water to surfactant, gelation pH, and calcination temperature. Experimental results conrm that MCM-41 with a well-ordered mesostructure is synthesized in strongly basic conditions. These materials had pore structures ranging from 3 to 10 nm. The produced silica is free of sodium impurities and the purity is as high as 99.8 wt%. SEM reveals that the proposed process can be controlled to produce silica particles with various morphologies under acidic or basic media. TEM images clearly illustrate the hexagonal array of uniform meso-channels in the silica materials. The proposed method for synthesizing mesoporous MCM-41 using resin waste provides a viable alternative for recycling and utilizing silicon-containing industrial waste. 2011 Elsevier B.V. All rights reserved.

Article history: Received 20 January 2011 Received in revised form 3 May 2011 Accepted 18 May 2011 Keywords: Electronic packaging resin Silica MCM-41 Mesostructure Recycling

1. Introduction The synthesis of MCM-41 molecular sieves using an organic template and inorganic silicate species has attracted considerable interest since Mobil Corporation discovered the process in the 1990s [1]. This material features high specic surface area, high pore volume, with large uniform pore size, nding many applications in chemistry [2], biology [3], and material sciences [4]. MCM-41 material has attracted considerable attention for possible application as an adsorbent, because its mesostructure provides the pore size required for adsorbing large molecules of gas and liquid [5]. Researchers have typically used two sources of silicon to synthesize mesoporous silica, tetraethlyorthosilicate (TEOS) and sodium silicate (Na2 SiO3 ) [6,7]. However, expensive TEOS reagents increase the cost of mass production. Commercial fabrication of sodium silicate from quartz sand and sodium carbonate at 1300 C requires a large amount of energy [8]. In contrast, silicon recovered from electronic packaging resin waste using an alkali extraction route is an economically viable source for the industrial scale production of mesoporous silica at relative low temperatures. This resin waste contains a high proportion of silicon (approximately 80 wt%) [9]. Converting packaging resin waste into mesoporous

Tel.: +886 2 29089899x4617; fax: +886 2 29083072. E-mail address: thliou@mail.mcut.edu.tw 1385-8947/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.cej.2011.05.074

materials such as MCM-41 provides another way to eliminate hazardous materials. By the end of 2009, worldwide revenue for semiconductor industry exceeded US 226 billion dollars, and is furthermore expected to grow by 13% in 2010 [10]. However, it is estimated that 2050 million tonnes of electrical and electronic wastes (e-waste) such as old computers, printers, mobile phones, and television sets are generated every year, which could bring human health and environment risks [11]. Taiwans Environmental Protection Administration (EPA) established its Scrap Home Appliances and Computers Recycling Regulation, which is based on the Waste Disposal Act (WDA), to mandate manufacturers and importers to take back their products [12]. Encapsulation of electronic devices such as integrated circuits (IC) consumes considerable quantities of packaging resin materials [13]. Residual resins generated during the process of electronic packaging constitute more than 3050 wt % of the total resin compound produced. With increased production of electronic products, nding efcient disposal methods for this waste is an issue of crucial importance. Typically, the major chemical components in packaging resins are epoxy resin, phenol resin, silica and additives [14]. Because plastic materials are essentially non-biodegradable, putting them in landll is not a viable alternative. Using a cheap source of silicon from packaging resin waste to produce an economically viable MCM-41 material addresses an important environmental concern. This well-organized system of pores makes these materials good candidates for the synthesis of

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novel materials for applications such as the storage of hydrogen [15], silicatitania photocatalysts [16], functionalized biomedical material [17], nano-reactors for the synthesis of nanotubes [18], and capturing CO2 gas [19]. Scientists have employed several procedures to synthesize MCM-41 materials from a silicon precursor. The temperature and duration of hydrothermal treatment, the kind of surfactant template, and calcination temperature all signicantly inuence the surface characteristics of this material. A number of studies have shown that changing the synthesis conditions can alter various morphological characteristics such as sphere-, rod-, and top-like particles of MCM-41 [20,21]. Frasch et al. [22] investigated the precursor system of MCM-41 prior to precipitation and found that the formation of siliceous prepolymers is an important key point in the synthesis of organized mesoporous silica. Angloher et al. [23] synthesized an organic modication of the MCM-41 using a metalorganic route, in which the reaction occurs at a lower temperature compared to traditional techniques. Lelong et al. [6] observed that the silicate/surfactant ratio governs the morphology and texture of MCM-41 particles. Studies have used recycled solid wastes such as coal y ash and rice husk as sources of silicon for the preparation of mesoporous silicas (such as MCM-41, MCM-48, SBA-15, SBA-16) [24,25] and zeolites [26,27]. The potential applications of synthesized zeolite materials from this wastes include the removal of heavy metals or ammonium from wastewater and in supports for catalytic reaction. The proportion of SiO2 in coal y ash and rice husk are 1560 wt% [28] and 1020 wt% [29], respectively. The other chemical components of coal y ash are Al2 O3 (535 wt%), FeO (440 wt%), and trace quantities of impurities. Hui and Chao [30] used coal y ash to prepare MCM-41 material and found that the impurities in the ash were not detrimental to the formation of mesoporous silica. Extracted aluminum species may be tetrahedrally incorporated into the silica framework. On the other hand, a signicant quantity of aluminum embedded in MCM-41 matrix causes moderate acidity, which is useful for applications in acid-catalyzed reactions. However, the existence of aluminum in coal y ash may lead to a reduction in specic surface area (740847 m2 /g) and the pore volume (0.40.7 cm3 /g) of MCM41 samples, compared with that of MCM-41 prepared from pure chemical ingredients (11001393 m2 /g and 0.81.2 cm3 /g) [24,31]. Similarly, the MCM-41 obtained from coal y ash also shows a low silica yield (2032%) due to the relatively low silicon content in the original ash [24,30]. This suggests that resin waste from the packaging of electronics has relatively high silicon content (approximately 80 wt%) and few impurities (3 wt%), which may provide an another way to prepare high quality silica-related materials. Numerous studies on mesoporous materials have focused on MCM-41 molecular sieves. However, relatively few studies have provided detailed investigation of the inuence of reaction parameters on the preparation of this material. Comparing results from these studies is relatively difcult in light of parameters selected. Liou [9] previously recovered high purity silica following the combustion of packaging resin waste. However, there have been no reports concerning the synthesis of MCM-41 material using packaging resin as a raw material. This study synthesized MCM-41 materials using the packaging resin waste at different hydrothermal treatment times and temperatures, molar ratios of water to surfactant, gelation pH, and calcination temperatures. This investigation characterized mesoporous materials using a eld-emission scanning electron microscope, an X-ray diffractometer, a surface area analyzer, an inductivity coupled plasma-mass spectrometer, an element analyzer, and a thermogravimetric analyzer. The results of this study provide a viable method for producing valuable silica nanomaterials and minimizing problems associated with waste disposal.

2. Experimental 2.1. Materials Packaging resin waste was obtained from the electronic packaging mill (Siliconwave Precision Co., Taiwan). Previous studies have illustrated the basic constituents and properties of this material [14]. The commercially available surfactants cetyltrimethylammonium bromide (CTAB, C16 H33 (CH3 )3 NBr, Acros organics) and sulfuric acid (Merck, Germany) were used as a template and precipitate, respectively. Hydrochloric acid and potassium hydroxide, used as acid and base treatments were all analytical grade (Merck, Germany). 2.2. Extraction of silica from resin ash The resin waste was washed well with distilled water to remove any dust. The resin was ground to a powder with a mesh size of less than 45 m using a commercial mixing grinder. This study used Lious method to obtain the ash raw material for mesoporous silica fabrication [9]. Researchers packed a weighed amount of powdered resin into a tubular reactor made of quartz, using highly puried air (Sun Fu Co., 99.999%) as the reaction gas, and heated the resin for 1 h at 800 C. The residual metal impurities in the sample were removed using an acid-leaching process. The ash was reuxed using a hot hydrochloric acid solution. The remaining solid was washed with distilled water until neutralized. This process obtained the packaging resin ash denoted as PRA. This study carried out the dissolution of silica from PRA using an alkali-extraction technique. A known quantity of the PRA sample was mixed with a 4.0 M NaOH solution and boiled at 100 C for 6 h under stirring. The solution was cooled to room temperature and subsequently stirred for 6 days. The silica changed to a sodium silicate solution. The resulting suspension was centrifuged to separate the suspended particles, and then ltered through a glass lter (Whatman plc, Kent, England) to remove any metal and carbon impurities. The solution was ltered several times resulting in a colorless, transparent solution. The solution was diluted with deionized water to 2.0 M and used to synthesize mesoporous silica. 2.3. Synthesis of mesoporous silica molecular sieves In the typical synthesis of mesoporous silica, 2.0 g of CTAB was dissolved in 1.0 M 30 cm3 of sulfuric acid solution and stirred for 25 min at 50 C. The sodium silicate solution was slowly added to the homogeneous acidic solution while being stirred. A S20-K pH meter (Mettler Toledo) monitored the pH of the solution, and standard buffer solutions of pH 4.01, 7.00, and 9.21 served to calibrate the pH meter. The acidity of the mixed solution was adjusted using sulfuric acid or sodium hydroxide, and then violently stirred for 1 h. Gels were loaded into a PTFE-lined stainless steel autoclave and heated from 20 to 140 C for 1168 h. The precipitated products were washed with deionized water followed by ltration and centrifugation, and heated in a drying oven at 60 C. Finally, the as-synthesized samples were calcined in air at 1 C/min heating rate and then maintained at 550 C for 5 h. For further comparison, two other types of silica were synthesized as follows. Silica gel was synthesized from alkali-extracted PRA without the addition of surfactant employing the same titration and water-washing processes. MCM-41 was synthesized using commercial pure sodium silicate, employing the same titration, water-washing, and calcination processes. The yield of the mesoporous silica samples was calculated as: weight of mesoporous silica produced after calcination 100. weight of PRA sample

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Table 1 Metallic ingredients analysis of raw resin, sodium silicate precursor, and mesoporous silica samples prepared at various gelation pH values. Metallic ingredients as oxides, ppm Na Raw resina Sodium silicate solutionb pH = 7c pH = 11d pH = 1e pH = 5e pH = 7e pH =11e
a b c d e

Sb 11,800 81 812 1213 931 1093 883 649

K 8 ND ND ND ND ND ND ND

P 96 2 9 14 6 8 5 9

Au 8 ND ND ND ND ND ND ND

Fe 5780 6 48 501 9 83 85 91

Mg 53 1 4 13 ND ND 11 16

Al 3140 74 888 2896 848 958 842 1001

Cr 1580 ND 2 47 2 4 3 4

Ag 8 ND ND ND ND ND ND ND

Total 22,713 44,964 8944 4954 1830 2339 1927 1839

240 44,800 7181 270 34 193 98 69

Raw resin was un-burnt. PRA was treated with acid-leached process and sodium silicate solution was obtained from alkali-extracted PRA. PRA was treated with acid-leached process and silica was obtained from alkali-extracted PRA without the addition of surfactant. PRA was treated with water-washed process and silica was obtained from alkali-extracted PRA by adding a surfactant. PRA was treated with acid-leached process and silica was obtained from alkali-extracted PRA by adding a surfactant. ND means not detected.

2.4. Characterization of the silica samples The inorganic composition of the produced silica samples was measured using an inductively coupled plasma-mass spectrometer (Kontron Plasmakon, model S-35). The fundamental organic elements in the as-synthesized samples were analyzed using an elemental analyzer (Elementar vario EL III). N2 adsorptiondesorption isotherms were measured using a nitrogen adsorption analyzer (Micrometric, model ASAP 2010). All of the samples were pretreated at 150 C. The specic surface area and pore size of the samples were calculated using the BrunauerEmmettTeller (BET) method and BarrettJoynerHalenda (BJH) method [32], respectively. This study assumed that the cross-sectional area of a nitrogen molecule was 0.162 nm2 . The single point total pore volume was calculated from the volume of adsorbed nitrogen at a relative pressure (P/P0 ) of approximately 0.95. This study assumed that micropores were less than 2 nm wide, mesopores were 250 nm wide, and macropores were more than 50 nm wide. X-ray diffraction (XRD) measurements of samples were performed on an Xpert XRD system (Philip Electronic Instruments) with Cu-K radiation. The acceleration voltage and current were 45 kV and 40 mA, respectively. Field-emission scanning-electron microscopy (FE-SEM) images were observed using a JEOL JSM-6700. The samples were coated with a thin layer of platinum to minimize the charging effects. The porous structure of the synthesized powder materials was observed using a high-resolution transmission electron microscopy (JEOL, JEM 2100). Samples were ultrasonically dispersed in alcohol, and the suspension was pipetted onto a copper microgrid with carbon lm. This experiment analyzed the probable decomposition paths of as-synthesized samples in air using a thermogravimetric analyzer (Perkin-Elmer, model TGA 7). Samples were placed in a platinum pan and heated from 50 to 800 C at a heating rate of 10 C/min in air. This paper denes the remaining mass as W/W0 , where W0 and W, representing the initial and instantaneous mass of the sample, respectively.

[3335], ionic exchange [36], and electrowinning process [37], have been developed. Residual HCl solution can be recovered using ion-exchange separation and membrane electrolysis [38]. After alkali-extracting PRA, the sodium silicate solution shows an obvious increase in Na species. However, a sharp decrease in other metallic impurities is due to dilution effect by aqueous solution. Compare the content of impurities in the two silica samples synthesized at pH 7 with or without surfactant addition. Concentration of Na is relatively higher in the silica sample synthesized without the addition of surfactant. This is because Na salt is comparatively larger than the other metals that may embed in the gel matrix. Therefore, the Na salt is not washed out of the gels [39]. In contrast, a lower proportion of Na is produced by adding a surfactant template, due to the good dispersion characteristics of silica particles in the aqueous solution of surfactant. Na ions easily diffuse out the silica matrix to be removed using a water-washing procedure. To investigate the effects of acid leaching PRA on sample purity, this study prepared MCM-41 from the un-acid leached PRA using the same process as the alkali extraction route forming it at pH 11. The content of impurities in the silica sample prepared from the un-acid leached PRA was noticeably higher than that of the sample prepared from acid-leached PRA. Obviously, acid-leached PRA helps to remove impurities resulting in silica products of high purity. Compare the content of impurities in the mesoporous silica samples synthesized at various pH values. The table shows that the total content of impurities decreased under strongly acidic or strongly basic conditions. The silica obtained at pH 5 had the highest metal content. Gelation pH had a strong inuence on the silica yield of as-synthesized samples in later TGA observations. Silica yields obtained at various pH values are in the order of pH 5 > pH 7 > pH 1 > pH 11. This indicates that a higher degree of poly-condensation forms in silicate species when samples are synthesized in neutral or weakly acidic conditions. A minor amount of metal may remain in the solid silica and water-washing does not remove this. Thus, the content of impurities increases when synthesizing samples at pH 5 and pH 7. The purity of silica samples synthesized at pH 1 and pH 11 was as high as 99.8 wt%.

3. Results and discussion 3.2. Analysis of reaction conditions 3.1. Analysis of metallic impurities This investigation analyzed the metallic impurities of raw resin and mesoporous silica samples obtained from PRA by ICPMS. The results in Table 1 show that Sb, Fe, Al, and Cr were present as major impurities. These metals were dissolved in acidic solution and then collected followed by a ltration process. Recovery of valuable metals from acid-leached e-waste has been well studied, and a number of useful methods including solvent extraction 3.2.1. Effects of hydrothermal treatment duration and temperature Fig. 1(a) illustrates the effects of hydrothermal treatment time on the specic surface area and silica yield of samples synthesized at pH 11. This study found that the surface area of silica decreased with an increase in the duration of hydrothermal treatment and the silica yield increased as the hydrothermal time increased. Researchers have constructed silica with a hexagonally-ordered

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1275 70 1150
70

1461

(a)

Surface area (m2/g)

(a)
65

Surface area (m2/g)

Silica yield (wt %)

1200 BET surface area 1125 Silica yield

60

1100
60

50

1050

BET surface area Silica yield

1050 0 50 100 150

40 1000 300 70

55 900 1200

600

Hydrothermal time (h) H2O/CTAB

1100 1225 (b)

Surface area (m2/g)

Surface area (m2/g)

65 1150 BET surface area Silica yield 1075 55 1000 20 60 100 140 60

Silica yield (wt %)

(b)
70

1050
60

1000
BET surface area Silica yield

50

Hydrothermal temperature (C)

Fig. 1. Effect of (a) hydrothermal treatment time (hydrothermal temperature, 100 C; H2 O/CTAB ratio, 608:1; calcination temperature, 550 C) and (b) hydrothermal treatment temperature (hydrothermal time, 48 h; H2 O/CTAB ratio, 608:1; calcination temperature, 550 C) on the surface area and silica yield of silica powders obtained from PRA at pH of 11.

950
450 550 650 750 850

40

Calcination temperature (C)

Fig. 2. Effect of (a) H2 O/CTAB ratio (hydrothermal time, 48 h; hydrothermal temperature, 100 C; calcination temperature, 550 C) and (b) calcination temperature (hydrothermal time, 48 h; hydrothermal temperature, 100 C; H2 O/CTAB ratio, 608:1) on the surface area and silica yield of silica powders obtained from PRA at pH of 11.

mesostructure from the interaction between silicate species and surfactant micelles [40,41]. At the beginning of the reaction, the pore wall of silica forms much more thinly resulting in samples with a higher surface area and a reduced silica yield. However, when the duration of the hydrothermal treatment continuously increases, the pore walls of the silica gradually thicken. Pore shrinkage decreases the surface area of the sample and increases silica yield. Hydrothermal times higher than 48 h have little inuence on the surface area. This situation indicates that the condensation rate of silicate species in the basic environment is stable. Notably, the silica yield is a reection of the surface area produced through hydrothermal treatment of various durations. The higher the silica yield is, the lower the formation of the sample surface area is. Observation reveals the same trends in all of the following synthesis conditions. Fig. 1(b) shows the inuence of hydrothermal treatment temperature on the specic surface area and silica yield. These results indicate that the surface area of the produced silica is sensitive to temperature of hydrothermal treatment. Surface area decreases with an increase in hydrothermal temperature from 20 to 140 C. Silica yield decreases with a decrease in hydrothermal temperature. Wang et al. [42] studied cubic mesoporous silica MCM-48 materials synthesized using temperature control. They observed that silica synthesized at a high temperature has a larger unit cell parameter and smaller average pore size due to the formation of a thicker silica framework. An increase in hydrothermal temperature accelerates the condensation rate of silicate species on the silica wall, resulting in an increase in silica yield, leading to pores shrinkage, thereby reducing the surface area of the sample. 3.2.2. Effects of the H2 O/CTAB ratio and calcination temperature The molar ratio of H2 O to CTAB plays a key role in the synthesis of ordered arrays of silica and micelles. This study used deionized water as a solvent to regulate the volume of the mixed solution. The surface area of samples decreased considerably with an increase in H2 O/CTAB ratio, as shown in Fig. 2(a). The highest surface area of samples appeared at a molar ratio of 304:1. The initial water content inuenced the pore structure array of silica and surfactant

micelles, as conrmed by XRD patterns. The more highly ordered mesoporous framework of samples formed with a reduced water content led to an increase in surface area. By contrast, an excess of water can destroy the micellar structure, and reduce the degree of order in the pore structure [43]. As a result, sample surface area decreases with a high H2 O/CTAB ratio. A high H2 O/CTAB ratio in a strongly basic environment indicates a greater negative charge covering the surface of the silica. The accelerated accumulation of silicate species on the silica pore wall increased silica yield. Fig. 2(b) shows the BET surface area and silica yield of samples obtained at various calcination temperatures. The largest surface area occurred at a calcination temperature of 650 C. When calcination temperatures were lower than 650 C, the surface area increased slightly and the silica yield decreased with an increase in calcination temperature. This was due to the release of organic substances from the silica/surfactant composite, leaving a porous surface. However, when the calcination temperature exceeded 650 C, the silicas subsequently condensed to form a thicker pore wall in the sample reducing the surface area and increasing silica yield. 3.2.3. Effect of the gelation pH During the process of acid-base titration, silica begins precipitating at pH 1, whereas the formation of solids is slow. Suspended solids become increasingly dense with an increase in gelaton pH, and a large quantity of precipitate is released at approximately pH 57. When the pH exceeds pH 8, the silica solids are partially redissolved. At pH > 12, these solids almost entirely dissolve in water. Fig. 3 shows the effects of gelation pH on the specic surface area and silica yield of the samples. Surface area increases with an increase in pH reaching a maximum of 1033 m2 /g at pH 11. This study recorded the lowest surface area of 193 m2 /g at pH 5. The gelation pH has a considerable inuence on the pore structure of silica samples, as supported by XRD analysis shown below. When the pH was adjusted toward a strongly basic or a strongly acidic environment, the pore structure tended to form an ordered array in the mesoporous framework. The electrostatic interaction between

Silica yield (wt %)

Silica yield (wt %)

1462 Table 2 Elemental content of as-synthesized silica samples.a Composition, wt% C pH = 1 pH = 5 pH = 7 pH = 11

a b

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500

15

Volume adsorbed (mL/g)

(a)
I PRA II pH = 7 (without surfactant addition) 250 II 5 10

H 4.52 3.94 4.96 5.96

Ob 10.07 1.35 3.08 11.45

N 1.29 0.65 1.23 1.83

Ash 62.48 82.01 69.90 49.20

21.64 12.05 20.83 31.56

Silica samples were un-calcined. By difference.

charged silica particles and surfactant templates might explain this action [40]. At a high pH (pH = 11), the surface of the silica takes on a negative electron charge. The silica interacts with positively charged CTA+ templates, leading to the formation of a hexagonal framework. In this situation, the silica comprises an ordered array with a mesoporous structure with a high surface area. With a decrease in pH from 9 to 7, the surface area decreased because the density of the negatively charged silicate decreases in weakly basic conditions. Consequently, an excess of CTA+ covering the surface of the mesostructure restricts the development of the pore structure. When gelation pH decreases to 5, the surface area decreases steeply. This is due to a high degree of poly-condensation occur during the self-assembly process, as indicated in Table 2. As a result, the framework mesopores may be deformed or disappear, leading to the formation of silica with a disordered texture. When pH decreases to 1, the sample surface area reversibly increases. This indicates that a stronger acidic condition reconstructs an ordered mesostructure through counterion-mediated electrostatic binding of cationic silica and surfactant micelles [44]. The mesoporous structure begins transforming into an ordered array when silica is synthesized in a strongly acidic environment, increasing the surface area of the products. Silica yield shows the opposite trend to that of surface area. The highest silica yield occurred at pH 5. To investigate the effects of pH values on sample silica yield, this study performed an additional experiment. Table 2 reports the elemental composition of as-synthesized samples obtained from PRA at various pH values. The content of organics contained in the samples depends on the pH value. Carbon is the most abundant chemical species in all samples.

0 0.0 600

0 0.2 0.4 III II 0.6 0.8 1.0

Volume adsorbed (mL/g)

(b)

400

200

I pH = 7 II pH = 9 III pH = 11

0 0.0 750 0.2 0.4 0.6 0.8 1.0

(c) Volume adsorbed (mL/g)

I pH = 1 500 II pH = 3 III pH = 5 I 250 II III

0 0.0 0.2 0.4 0.6 0.8 1.0

Realative pressure (P/Po)

Fig. 4. Nitrogen adsorptiondesorption isotherms of silica samples: (a) PRA and silica prepared at pH 7 without surfactant addition, and silica prepared with surfactant addition at (b) neutral and basic conditions, and (c) acidic conditions.

90

1000 85

Surface area (m2/g)

80

600 75

Silica yield (wt %)

800

The samples synthesized in stronger basic or acidic condition had a higher content of organics. The silica phase in the as-synthesized sample at pH 5 was approximately 82 wt%, while the silica phase in the pH 1 and pH 11 samples was approximately 62 and 49 wt%, respectively. These results indicate that a higher degree of polycondensation occurred in the silicate species in neutral and weakly acidic samples during the synthesis of sample, yielding higher quantities of silica. 3.3. Analysis of characteristics of silica products 3.3.1. Analysis of pore structure Fig. 4 shows N2 adsorptiondesorption isotherms of PRA and silica samples obtained at various gelation pH values. Fig. 4(a) shows the isotherms of PRA raw material and silica produced at pH 7 without the addition of extra surfactant. After burning the raw resin in air, convexity toward the relative pressure axis characterized the isotherm of the PRA sample (mainly silica) and the isotherm did not appear to contain a hysteresis loop. This adsorption behavior is similar to a type III isotherm, based on IUPAC classication, indicating that the pore structure of the PRA sample included mostly

400 70 BET surface area Silica yield 200 65 1 3 5 7 9 11

Gelation pH
Fig. 3. Effect of gelation pH on the surface area and silica yield of silica powders. Initial conditions: hydrothermal time, 48 h; hydrothermal temperature, 100 C; H2 O/CTAB ratio, 608:1; calcination temperature, 550 C.

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0 4.0

40 II

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(100) (110) (200) (210)

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I PRA 2.0 II pH = 7 (without surfactant addition)

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3E-5

III
I 0.0 0 18.0 5 10 15 20 3E-6
0

2
60

10

(b)
Intensity
30

(b) dVp/dDp, x100

I pH = 7 12.0 I II 6.0 III II pH = 9 III pH = 11

20

40

60

80

Bragg angle (2 Theta)

Fig. 6. X-ray diffraction pattern of silica samples obtained at pH 11: (a) assynthesized silica (I), calcined silica (II), and calcined silica from commercial sodium silicate (III), (b) calcined silica. Initial conditions: hydrothermal time, 48 h; hydrothermal temperature, 100 C; H2 O/CTAB ratio, 608:1; calcination temperature, 550 C.

0.0 2 6.0 3 4 5

(c)
I

dVp/dDp, x100

I pH = 1 4.0 II pH = 3 III pH = 5 2.0 II 0.0 0 10 20 30 III

Dp (nm)
Fig. 5. Differential pore size distribution of silica samples: (a) PRA and silica prepared at pH 7 without surfactant addition, and silica prepared with surfactant addition at (b) neutral and basic conditions, and (c) acidic conditions.

macropores. In the sample prepared using the dissolutionprecipitation method without surfactant, the isotherm was a type IV, as it relates the capillary condensation in the mesopore channels. The isotherm corresponds to a H2 hysteresis loop, indicating the presence of ink-bottle-like pores in the sample [45]. Because the surface of silica charges electrons during gelation, the electrostatic interaction between charged particles forms a three-dimensional silica xerogel porous structure [46]. Fig. 4(b) shows the adsorption isotherms of silica samples obtained in neutral and basic conditions. Adding a surfactant template followed by calcination yields these samples. The isotherm curves at pH 711 were type IV. A gradual increase in the uptake of nitrogen at low relative pressure indicates monolayer/multilayer adsorption in the pores of the sample. A sharp increase at P/P0 = 0.20.3 due to the capillary condensation of nitrogen implies a pore structure of uniform size [47]. When the relative pressure increases by approximately 0.3 < P/P0 < 1.0, a hysteresis loop appears due to the formation of mesoporous structures. This type of isotherm corresponds to a H2 hysteresis loop. A strong hysteresis loop appears in sample synthesized at pH 11 compared to samples synthesized at pH 7 and 9 due to the presence of large mesopores.

Nitrogen adsorption capacity increases with an increase in pH, indicating an increase in pore volume. A low adsorbed volume at pH 7 suggests the presence of a thick silica wall in the shrunk mesostructure. Fig. 4(c) shows the isotherm curves of silica samples obtained in acidic conditions. The isotherm curves of samples at pH 15 were of type IV. The sample at pH 5 shows a hysteresis loop similar to H3. The loop may relate to aggregates of plate-like particles giving rise to slit-shaped pores [48]. The pH 3 sample shows the same curve trend as the curve trend of pH 5; however, the pH 3 sample has a higher nitrogen adsorption capacity, indicating an increase in pore volume. The sample synthesized at pH 1 shows a type H2 hysteresis loop, with an obvious increase in adsorbed volume. In samples at pH 3 and pH 5, a disordered silica texture forms due to the deformation or disappearance of a framework mesostructure during assembly, decreasing the adsorbed volume of the samples. However, we believe the interaction between positively charged silica species and neutral micelles results in mesostuructural silica obtained under strongly acidic conditions (pH 1), increasing the adsorbed volume of the samples. This study obtained pore size distribution from the desorption branch of the nitrogen isotherm using a BJH model. Fig. 5(a) shows the pore size distribution of a PRA sample and silica synthesized at pH 7 without the addition of extra surfactant. The PRA sample shows a very broad pore size distribution ranging from 20 to 160 nm, indicating the formation of a macroporous structure. The silica without additional surfactant shows a peak at a pore diameter of approximately 6.2 nm. Fig. 5(b) shows the pore size distribution of silica samples produced in neutral and basic conditions with the addition of a cationic template. These curves show a bimodal mesostructure, which may be due to mesopores in the silica framework formed by surfactant micelles and textural pores formed in the interparticle space between silica grains [40]. A narrow peak at a pore diameter of approximately 2.52.7 nm increased with an increase in pH, indicating that a decrease in gelation pH thickens the silica wall and decreases mesoporous diameter. A small, broad peak appears at a pore diameter of approximately 3.7 nm. Fig. 5(c) shows the pore size distribution of silica samples produced in acidic conditions. Silica produced at pH 1 shows a narrow pore

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Table 3 Surface area and pore volume of PRA and mesoporous silica samples prepared at various gelation pH values. SBET (m2 /g) PRA pH = 7b pH = 1c pH = 3c pH = 5c pH = 7c pH = 9c pH = 11c
a

Vt (cm3 /g) 0.006 0.730 1.038 1.005 0.470 0.649 0.744 0.887

Vmic (cm3 /g) 0.000 0.001 0.011 0.003 0.004 0.032 0.027 0.028

Vmeso (cm3 /g) 0.001 0.729 1.027 1.002 0.466 0.617 0.717 0.859

Vmeso /Vt (%) 16.67 99.86 98.94 99.70 99.15 95.07 96.37 96.84

2.72 370 732 376 193 696 860 1033

SBET = BET surface area; Vt = total pore volume; Vmic = micropore volume; Vmeso = mesopore volume. a Raw resin was burnt in air at 5 C/min heating rate. b PRA was treated with acid-leached process and silica was obtained from alkali-extracted PRA without the addition of surfactant. c PRA was treated with acid-leached process and silica was obtained from alkali-extracted PRA by adding a surfactant.

distribution with an average size of 4.5 nm. The sample synthesized at pH 3 has a wide pore size distribution and a larger pore diameter, showing that the pore structure is nonuniform. The sample at pH 5 shows a small peak at 4.0 nm. A large peak at 14.5 nm might be due to the deformation and combination of the original pore structure. Table 3 lists the specic surface area and pore volume of samples before and after treatment. The surface area and pore volume of the PRA sample were only 2.72 m2 /g and 0.006 cm3 /g, respectively. Sample results show that using the dissolutionprecipitation

method without surfactant enhances the surface area and pore volume. Comparing silica samples synthesized at pH 7 with and without added surfactant reveals that silica sample with added surfactant had a higher surface area. When synthesizing silica samples at various pH values, the surface area and pore volume of the samples are highly pH dependent. The pore volume increased with an increase in pH in basic conditions. In contrast, the pore volume increased with a decrease in pH in acidic conditions. Experimentation revealed the highest pore volume of 1.038 cm3 /g at pH 1. The

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Fig. 7. X-ray diffraction pattern of silica samples obtained under various reaction conditions: (a) hydrothermal treatment time (hydrothermal temperature, 100 C; H2 O/CTAB ratio, 608:1; calcination temperature, 550 C; gelation pH, 11), (b) hydrothermal treatment temperature (hydrothermal time, 48 h; H2 O/CTAB ratio, 608:1; calcination temperature, 550 C; gelation pH, 11), (c) H2 O/CTAB ratio (hydrothermal time, 48 h; hydrothermal temperature, 100 C; calcination temperature, 550 C; gelation pH, 11), (d) gelation pH (hydrothermal time, 48 h; hydrothermal temperature, 100 C; H2 O/CTAB ratio, 608:1; calcination temperature, 550 C).

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Fig. 8. FE-SEM micrographs of silica samples produced from PRA at various pH values: (a) and (b) pH 1; (c) and (d) pH 3; (e) and (f) pH 5; (g) and (h) pH 7; (i) and (j) pH 9; (k) and (l) pH 11; (m) and (n) pH 11 for sample prepared from commercial sodium silicate.

pH 5 sample shows a lowest pore volume of 0.470 cm3 /g. Table 3 shows that the acid-prepared silica possesses a higher mesopore fraction than base-prepared silica does. To investigate the effects of a silicon precursor on the surface characteristics of samples, this study prepared silica from commercial sodium silicate using the same gelation reaction at pH 11. The BET surface area of this silica was 961 m2 /g, slightly lower than the surface area of the sample produced from PRA. These results reveal that an alkali extraction of packaging resin waste yields high-quality hexagonal MCM-41. 3.3.2. Analysis of crystalline structure and surface morphology Fig. 6(a) shows X-ray diffraction data from the as-synthesized and calcined silica samples obtained from PRA, and the other silica sample obtained from pure commercial sodium silicate. The XRD patterns for every sample show an intense diffraction (1 0 0) peak and three higher order (1 1 0), (2 0 0), and (2 1 0) reections at 2 values below 10 , clearly illustrating the characteristics of MCM41 materials [24]. The as-synthesized and calcined mesoporous materials synthesized at pH 11 have a highly ordered hexagonal mesostructure. The 2 positions of calcined sample shifted to a higher value, indicating a lattice contraction due to the removal of

the template and subsequent condensation of silanol groups [30]. MCM-41 material obtained from PRA (sample II) shows a stronger relative peak intensity than material obtained from pure sodium silicate (sample III). This indicates that the MCM-41 product from PRA has a relatively well-organized silica matrix. Fig. 6(b) shows a wide range scan of XRD patterns of the MCM-41 sample synthesized from PRA with 2 values ranging from 10 to 80 . The sample shows only a broad band centered at 2 angles of 2030 , a typical characteristic of silica, due to the presence of disordered cristobalite. Fig. 7 shows X-ray diffraction data obtained under various reaction conditions, for mesoporous silica. The majority of samples show XRD patterns corresponding to (1 0 0), (1 1 0), (2 0 0), and (2 1 0) reections, characteristic of MCM-41 structures. However, the difference in reaction conditions led to variations in the XRD peaks, suggesting that the initial reaction conditions played an important role in the synthesis of MCM-41. Fig. 7(a) shows the XRD patterns of MCM-41 synthesized with various durations of hydrothermal treatment. The relative intensity between the diffraction peaks increases with hydrothermal treatment time. This suggests an increase in the duration of hydrothermal treatment is favorable for retaining a high degree of mesoscopic ordering with

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Fig. 9. HR-TEM view of silica samples produced from PRA: (a) pH 11 (scale bar: 20 nm), (b) pH 11 (scale bar: 10 nm), (c) pH 11 (scale bar: 10 nm), (d) pH 7 (scale bar: 20 nm).

hexagonal symmetry. The changes in hydrothermal temperature were the same as those from hydrothermal time analysis. Fig. 7(b) shows a poorly ordered MCM-41 sample synthesized at a low temperature of 20 C. Structural order in the sample increased with an increase in hydrothermal temperature. The MCM-41 synthesized at a high temperature of 140 C shows an intense (1 0 0) peak as well as three higher order reections of (1 1 0), (2 0 0), and (2 1 0) planes, indicating hexagonal symmetry. Kim et al. [49] observed the same phenomenon. Fig. 7(c) shows XRD patterns of mesoporous silica synthesized under various molar ratios of H2 O to CTAB. When the molar ratios were 304:1 and 608:1, the patterns exhibited four well-resolved diffraction peaks at (1 0 0), (1 1 0), (2 0 0), and (2 1 0) planes, indicating hexagonal symmetry in the MCM-41 structure. At a molar ratio of 810:1, the four peak intensities obviously weakened. When increasing the molar ratio to 1215:1, the pattern shows only three weak (1 1 0), (2 0 0), and (2 1 0) reections. These observations indicate a more ordered pore structure of samples formed with a decreased ratio of H2 O/CTAB. Excessive water destroys the micellar template, rendering a less ordered pore structure. Fig. 7(d) shows XRD patterns of silica samples synthesized at various pH values. The calcined silica samples are highly pH-dependent. All samples synthesized in basic conditions reveal a pure MCM-41 structure. Increasing the gelation pH further increases the peak intensities, suggesting a strongly basic condition is favorable to the formation

of a highly ordered mesoporous material. Under weakly acidic conditions (pH 5), the four diffraction peaks disappeared, indicating a degradation in the ordered array of the mesoporous structure. An increase in the (1 0 0) reection intensity of approximately 2 = 23 occurred when pH values decreased from 5 to 1. The XRD patterns of the pH 1 sample show an intense (1 0 0) reection is a characteristic of mesophase structure, indicating that increasing the acidity of the precursor solution transfers the textural mesopores into the pores of the ordered framework [50]. Fig. 8 shows FE-SEM images of mesoporous silica synthesized from PRA and pure sodium silicate. Fig. 8(a) and (b) shows the surface morphology of silica obtained at pH 1. The particles in Fig. 8(a) have a uniform spherical morphology with a mean size of 4 m. Fig. 8(b) shows that these particles are formed through the aggregation of very ne, homogeneous grains approximately 1 nm in size. Fig. 8(c) and (d) shows silica particles synthesized at pH 3, revealing aggregates of ower-like silica particles in Fig. 8(c). Each particle consists of several tens of irregular grains (Fig. 8(d)). Fig. 8(e) and (f) shows SEM images of silica synthesized at pH 5, with mainly a sphere-like morphology and particle size of 330 nm (Fig. 8(e)). Enlarging the SEM image in Fig. 8(f) clearly shows uniform growth of porous tissue on the surface of silica particles. Fig. 8(g)(j) shows that SEM images of MCM-41 materials synthesized at pH 7 and pH 9. These particles show a needle-like morphology with a width of 250 nm (Fig. 8(g) and (i)). Silica synthesized at pH 7 shows a

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semi-spherical morphology and the surface of the grains is coarse (Fig. 8(h)). Silica obtained at pH 9 possesses a rectangular morphology with a glossy surface (Fig. 8(j)). Fig. 8(k) and (l) shows that the surface morphology of MCM-41 synthesized at pH 11 possesses high porosity and a needle-like morphology. Observation reveals a number of large cavities in Fig. 8(k), indicating an increase in pore volume. The material comprises irregularly shaped grains and the width of each grain ranges from 200 to 350 nm, as shown in Fig. 8(l). Fig. 8(m) and (n) shows SEM images of the MCM-41 sample obtained from commercial sodium silicate. Particle morphology of the sample in Fig. 8(m) is similar to that of samples prepared using PRA at pH 11, possessing a needle-like morphology. However, silica obtained from pure sodium silicate in Fig. 8(n) shows a smaller grain size, compared with MCM-41 obtained from PRA. This indicates that the mesoporous material produced from PRA grows faster and transforming the material toward an ordered structure. This observation is in agreement with the previous results of XRD analysis. Fig. 9 presents high-resolution transmission electron micrographs of mesoporous silica samples produced from PRA. The MCM-41 obtained at pH 11 (Fig. 9(a)) shows large-scale hexagonal mesostructures (>150 nm). X-ray diffraction analysis conrmed the hexagonal arrangement of the mesopores. The internal morphology observed in Fig. 9(b) and (c) shows a well-ordered array of mesopores with a uniform pore size on the (1 0 0) crystal face, and a uniform tissue of parallel channels on the (1 1 0) crystal face. The material has a mesopore size of 2.5 nm, which is in agreement with the calculated pore size of 2.7 nm using N2 -adsorption measurement (Fig. 5(b)). The self-assembly of anionic silicate species and cationic surfactant micelles through electrostatic interaction constructed the fundamental hexagonal mesostructure. Under a weak basic condition of pH 7, the morphology of the prepared MCM-41 material also shows an ordered mesostructural array (Fig. 9(d)). However, some areas of the samples are not highly ordered. In Fig. 7(d), the XRD conrms a degradation in the order of the array.

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3.3.3. Analysis of thermal decomposition characteristics of as-synthesized silica sample Fig. 10 shows the TG and DTG curves of the as-synthesized silica samples, which are thermal decomposed in air. Fig. 10(a) shows the TG curves of as-synthesized samples obtained under acidic conditions. Four main processes took place when heating the as-synthesized samples. At a constant heating rate, the mass loss caused by specimen decomposition increased as the gelation pH decreased. In the rst stage, the small loss of mass was observed in the TG curves at temperatures below 150 C, due to the removal of physically adsorbed water. The heating curves in the second and third stages ranged from 150 to 300 C and 300 to 400 C. The signicant mass loss during these stages may be associated with the decomposition of organic materials in the raw sample. The mass loss in the second stage was slightly lower than the loss during the third stage. A small mass loss occurred in the fourth stage as the temperature increased from 400 to 600 C, due to the combustion of the remaining organic species, dehydroxylation, and water loss associated with the condensation of the silanol groups [30]. No mass loss occurred when calcination temperature exceeded 600 C, indicating that the decomposition reaction was complete. The DTG curves in Fig. 10 (a) reveal two peaks in each heating curve. The rst peak temperature is 225 C and the second peak temperature is 345 C. The decomposition temperatures of samples at various pH values are very similar. The peak height of the sample synthesized at pH 1 is higher than the peak height of samples synthesized at pH 3 or pH 5. Fig. 10 (b) shows the TGA plots of as-synthesized samples obtained under neutral and basic conditions. The mass loss in these samples occurred in three temperature zones, namely 150, 150350, and 350600 C. This is in agreement with observations by Zhao et al. [51]. Mass loss increases as gelation pH increases. The DTG curves reveal a main peak in the temperature at approximately 250 C and a small peak at 380 C. The temperature of the rst peak increased as the gelation pH decreased. The as-synthesized sample at pH 11 demonstrated a higher thermal decomposition rate than samples synthesized at pH 7 and pH 9 did. A comparison of Fig. 10(a) and (b) shows that the thermal decomposition mechanism of samples synthesized in acidic conditions is different from those synthesized in basic conditions. The sample synthesized in basic conditions had a higher instantaneous rate of thermal decomposition and a higher mass loss than the thermal decomposition and mass loss occurring in acidic conditions. However, the samples synthesized in strong basic (pH = 11) and strong acidic (pH = 1) conditions had the highest weight loss and instantaneous decomposition rate, compared with the weight loss observed in weak basic (pH = 9) and weak acidic (pH = 5) conditions. This is due to the high proportion of organic content in the samples produced in strongly basic or strongly acidic environments. This observation is in agreement with the results of element analysis in Table 2.

4. Conclusions This research used electronic packaging resin waste as a source of silicon for the synthesis of ordered mesoporous arrays via an alkali fusion method with cationic surfactant as a template. This study investigated the evolution of the surface characteristics of silica under various reaction conditions. The MCM-41 tends to produce a well-ordered hexagonal structure when increasing hydrothermal treatment time and temperature while decreasing the molar ratio of H2 O to CTAB. Hydrothermal treatment in weaker acidic conditions led to the formation of disordered pore structures. The electrostatic interaction between charged micelles and the solid silica explains the formation of ordered mesostructures. The increase in the surface area of samples accompanied a decrease

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