Preparation of Mesoporous Silica from Electrolytic Manganese

Research Article pubs.acs.org/journal/ascecg

Cite This: ACS Sustainable Chem. Eng. 2017, 5, 10258-10265

Preparation of Mesoporous Silica from Electrolytic Manganese Slags by Using Amino-Ended Hyperbranched Polyamide as Template Daohong Zhang,*,† Daiyong Xiao,† Qian Yu,† Sufang Chen,*,‡ Shenghui Chen,† and Menghe Miao§ †

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Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission & Ministry of Education, Hubei Province, South-Central University for Nationalities, 182 Minzu Road, Wuhan, Hubei Province 430074, China ‡ Key Laboratory for Green Chemical Process of Ministry of Education, Wuhan Institute of TechnologyLiuFang Campus, No.206, Guanggu First Road, Donghu New & High Technology Development Zone, Wuhan, Hubei Province 430205, China § CSIRO Manufacturing, 75 Pigdons Road, Waurn Ponds, Victoria 3216, Australia ABSTRACT: Large quantities of waste slags are produced during the preparation of electrical manganese, causing serious pollution to the environment. The recycling and utilization of electrolytic manganese slag (EMS) is a serious challenge to the industry. Here, we report the utilization of EMS in preparation of high-performance mesoporous silica using aminoended hyperbranched polyamide (AEHPA) as template. The effects of AEHPA content and molecular weight on properties of mesoporous silica, including the specific surface area, pore diameter, pore volume, size, and distribution, have been investigated. On the basis of 0.3 wt % AEHPA-2 during the preparation of silica, the specific surface area, pore volume, and pore diameter of the produced amorphous mesoporous silica are 451.34 m2 g−1, 0.824 cm3 g−1, and 7.09 nm, respectively, showing remarkable improvements over the silica without AEHPA in specific surface area (271.05 m2 g−1), pore volume (1.167 cm3 g−1), and pore diameter (17.43 nm). The formation mechanism of mesoporous silica has been supposed and substantiated by FT-IR, XRD, XPS spectra, and SEM micrographs. This preparation method of mesoporous silica from EMS may open a new avenue for recycling and utilization of manganese slag. KEYWORDS: Electrolytic manganese slags, Mesoporous silica, Hyperbranched polymers, Recycling and utilizing

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a long period of time. It is thus imperative to find a viable recycling method to end the pollution caused by EMS.14 Mesoporous silica has been widely used in catalysis and chromatography fields because its high surface area, high hydrothermal stability, tunable pore sizes and volumes, and diverse surface functionality.15−17 Mesoporous silica can be used to carry, transport, and protect macromolecules,18 and as a basis for the synthesis of complex porous structures.19,20 Mesoporous silica can also be used as supramolecular aggregates in life science, biomedicine, and catalytic reactions,21 and it is a good nanocarrier of biological macromolecules and polymers.22 Mesoporous silica is usually prepared using template-based methods, including small-molecule and polymer templates. Tetraethyl-orthosilicate, ionic surfactant, and cellulose, are the main small-molecule templates.23,24 Polymer templates include polyethylene glycol, polypyrrole, ultrathin polymer films, polymer microsphere dual-templates, cetyltrimethylammonium bromide, P123, and so on.25−27 It is easy to form a homogeneous reactive system with simple morphology by using a small molecule as template. Polymers, on the other hand, can tune the microstructure of nanomaterials and synthesize more complicated target products using a more

INTRODUCTION

Electrolytic manganese slag (EMS) is a category of acidic filtered byproduct from the extraction of electrolytic manganese. The rapid development of electrolytic manganese brings great benefits. However, simultaneously, about 6−9 tons of the solid waste is produced per ton of electrolytic manganese produced,1 and particularly, some heavy metal elements and compounds in EMS can pollute surrounding soil and receiving water bodies.2 Therefore, the large quantity of byproduct EMS solid waste poses a heavy burden to the environment and an urgent challenge to the industry.3 China has been the top contributor to the production of electrolytic metal manganese, accounting for over 98.5% of the total world capacity in 2014.4,5 The recycling of EMS has become a major problem for the industry. Many scientists and engineers have studied recycling of EMS and have made progress in many approaches, including synthesis of zeolite,6 geopolymers,7 road beds, soil fertilizer, autoclaved bricks, ground granulated blast-furnace slag cement, cementing material, chemical raw materials,8−11 and metal recovery.12,13 These methods are very difficult to be applied industrially because of low efficiency, high cost of production, and low value of the resultant products. The recycling of EMS is still limited to laboratory scales while the increasing quantity of EMS is being stacked near factories, causing potential pollution from the heavy metals of EMS as rain soaks EMS over © 2017 American Chemical Society

Received: July 7, 2017 Revised: September 2, 2017 Published: September 11, 2017 10258

DOI: 10.1021/acssuschemeng.7b02268 ACS Sustainable Chem. Eng. 2017, 5, 10258−10265

Research Article

ACS Sustainable Chemistry & Engineering complex process. During the synthesis of mesoporous silica, both small molecules and polymers have a positive function for stabilizing the material.28 The cavities inside hyperbranched polymers and the large number of reactive end-groups can stabilize and disperse nanoparticles.29,30 Moreover, the cavities can provide a place for reactions between the small molecules. Therefore, hyperbranched polymers are ideal templates for controlling the morphology and properties of nanomaterials.31 Main synthesis methods of silica include hydrothermal reaction,32 chemical vapor deposition, microemulsion, sol− gel, and chemical precipitation.33 Both the chemical vapor deposition method and the sol−gel method involve expensive raw materials and high energy consumption.34 The microemulsion method35 needs a complicated post-treatment process, involving the difficult removal of organics and potential environmental pollution, although it is convenient in controlling the particle size of silica. The chemical precipitation method36 is of large particle size and wide distribution, and the method shows low energy consumption, high extraction efficiency, process simplicity, and easy industrialization. Here, we research recycling and utilization of electrolytic manganese slags by using the chemical precipitation method. Amino-ended hyperbranched polyamide (AEHPA) is used as template to prepare high-performance silica with high quality by taking advantage of its liquidity and availability of functional amino groups.37 The size, distribution, pore property, and specific surface area of the silica particles can be controlled by changing the content and molecular weight of the AEHPA. The obtained mesoporous silica shows a higher surface area and higher content of silicon dioxide than that from the conventional method without AEHPA, indicating the potential industrial value of recycling electrolytic manganese slags.

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Scheme 1. Synthesis Scheme of AEHPA and Ideal Chemical Structure of AEHPA-2

EMS powder. Portions of 20 g of dried EMS powder and 95 g of 40 wt % sodium hydroxide solution were added into a 250 mL three-necked flask equipped with a mechanical stirrer and a condenser. The reaction was conducted at 140 °C for 12 h. The filtrate (sodium silicate solution) was obtained after the resultant solution was filtered. Sodium silicate solution was added into a 250 mL three-necked flask equipped with a mechanical stirrer and heated gradually to about 80 °C. Then, 0.06 g of AEHPA-2 as a template was added to the flask. An appropriate content of 10 wt % sulfuric acid solution was added dropwise into the flask for neutralizing the solution to pH 5−6, and then, the solution was reacted for about 2 h at 80 °C, resulting in the formation of a white emulsion. The white emulsion was filtered to form a white filter cake. Deionized water was used to wash the filter cake several times until the filtrate contains no sulfate ion as tested using barium chloride solution. A 4.13 g portion of mesoporous silica was obtained after the resultant cake was dried at 120 °C for 3 h. The silica quality has been measured according to the standard method (HG/T 3061-2009) for silica, and the results conclude that the SiO2 content is about 93.1 wt % (≥90 wt %), manganese content about 38.5 mg kg−1 (≤40 mg kg−1), ferric content about 479.3 mg kg−1 (≤500 mg kg−1), and copper content about 8.2 mg kg−1 (≤10 mg kg−1), indicating highest quality of mesoporous silica according to HG/T 3061-2009. Characterization of Mesoporous Silica. The particle size distribution was measured by a laser particle analyzer (OMEC, Ltd., Zhuhai, China). The morphology of mesoporous silica was examined by scanning electron microscopy (SEM, Hitachi, Co., SU8010, Japan). The specific surface area, pore volume, and pore size distribution of the mesoporous silica were determined by N2 adsorption−desorption isotherms (BET, Quantachrome, Co., Autosorb-1-C-TCD-MS). X-ray photoelectron spectroscopy (XPS) patterns of mesoporous silica particles were measured on a Multilab 2000 (VG, England) instrument. FT-IR measurements were performed on a Bruker Vector 33 spectrometer using a sealed cell (KBr 0.5 mm). X-ray diffraction (XRD) patterns were obtained using a Bruker-D8 diffractometer with monochromatized Cu Kα radiation (λ = 1.54 Å) at 40 kV and 40 mA.

EXPERIMENTAL SECTION

Materials. Electrolytic manganese slag (EMS) was supplied by Citic Dameng Mining Industries Reagent Co., Ltd., and its overall elemental composition38 is composed of 4.46 wt % Mn, 1.32 wt % Al, 15.06 wt % Si, 6.75 wt % Fe, 9.94 wt % Ca, 1.06 wt % Mg, 0.78 wt % K, 0.14 wt % Na, 0.07 wt % P and 0.02 wt % Zn. Sodium hydroxide, sulfuric acid, hydrofluoric acid, diethylenetriamine (DETA), methyl acrylate (MA), ethylenediamine (EDA), methanol, and ethanol were supplied by Sinopharm Chemical Reagent Co., Ltd. All chemical reagents were of analytical grade and used as received. Preparation of Amino-Ended Hyperbranched Polyamide. Three types of amino-ended hyperbranched polyamides (AEHPA-n, n = 1, 2, and 3) were synthesized using different molar ratios among ethylenediamine, diethylenetriamine, and methyl acrylate according to Scheme 1.37 Portions of 0.25 mol diethylenetriamine and 0.25 mol methyl acrylate were added into a 250 mL three-neck flask equipped with a mechanical stirrer, a nitrogen inlet, and a water trap attached with a condenser. The mixture reacted for about 12 h at 0−5 °C, and then, an appropriate content of ethylenediamine was added dropwise into the flask according to three different molar ratios (2:2:1, 6:6:1, and 14:14:1) among diethylenetriamine, methyl acrylate, and ethylenediamine, respectively. The mixture was heated gradually to about 70 °C to react for 1 h and then heated to about 130 °C to react for 7 h under nitrogen atmosphere. Three types of yellowish liquid products were obtained with yields of about 96%. The three products were named as AEHPA-1, AEHPA-2, and AEHPA-3 in sequence, and their theoretical molecular weights are calculated to be 374, 1002, and 2258 g mol−1 according to their molar ratios; their amino-ended numbers are 4, 8, and 16. The ideal chemical structure of AEHPA-2 is presented in Scheme 1. Preparation of Mesoporous Silica. A 200 g portion of EMS was washed by using 500 mL of deionized water four times followed by filtering. The residue was dried for about 2 h at 120 °C to obtain dried

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RESULTS AND DISCUSSION Effect of AEHPA Molecular Weight on the Properties of Mesoporous Silica. The mesoporous materials were characterized for specific surface area, pore volume, and pore size. The N2 sorption spectra of the mesoporous silica prepared using AEHPA and without using AEHPA are shown in Figure 1. Their properties are presented in Table 1. From Table 1 and Figure 1, the specific surface area, pore volume, and pore diameter of the produced mesoporous silica by using AEHPA-2 as template are 451.34 m2 g−1, 0.824 cm3 10259


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Figure 1. (a) N2 adsorption−desorption isotherms and (b) pore distribution curves of mesoporous silica with different molecular weights of AEHPA-n (n = 1, 2, and 3).

AEHPA molecular weight, the specific surface area of mesoporous silica increases first and then decreases. When the moderate molecular weight AEHPA-2 was used as template for preparing mesoporous silica, the specific surface area was the largest. Presumably, the molecular weight of the AEHPA template has a significant influence on the specific surface area and pore diameter of the mesoporous silica. According to Brunauer−Deming−Deming−Teller (BDDT) and the International Union of Pure and Applied Chemistry (IUPAC) adsorption isotherm system,40,41 all of the samples with AEHPA show type-IV isotherms in Figure 1a. The number of adsorption layers is limited when it reaches the saturated vapor pressure. The N2 isotherms exhibit a capillary condensation step at P/P0 = 0.6−0.9, as indicated by the hysteresis loop. The isotherms rose rapidly and were accompanied by hysteresis in the relative moderate pressure due to the existence of capillary condensation. The hysteresis loop of the mesoporous silica with AEHPA belongs to the H1 type. The pores show an irregular size distribution with a complex structure, showing a typical “wormlike mesoporous channel” and pipe-type hole with an uneven distribution. The hysteresis loops take a flat oval shape, and are typical physical

Table 1. Effect of AEHPA Molecular Weight on the Property of Mesoporous Silica molecular weight

BET surface area (m2 g−1)

pore volume (cm3 g−1)

pore size (nm)

without AEHPA 0.3 wt % AEHPA-1 0.3 wt % AEHPA-2 0.3 wt % AEHPA-3

271.05 352.22 451.34 381.87

1.17 0.88 0.82 0.82

17.43 10.15 7.09 8.60

g−1, and 7.09 nm, respectively, compared with the specific surface area (271.05 m2 g−1), pore volume (1.167 cm3 g−1), and pore diameter (17.43 nm) of the silica prepared without AEHPA. This suggests a significant increase in specific surface area and decreases both in pore volume and in diameter. These distinct changes may be attributed to the cavities inside hyperbranched polymers and the hydrogen-bond interaction between the amino of AEHPA and the hydroxyl group of the silicon precursor.29,30 The mesoporous silica with AEHPA exhibited narrow pore size distributions, which confirms that the mesopores remain accessible by nitrogen even after the polymerization.39 As shown in Table 1, with the increase of

Figure 2. Particle size distribution of silica by using different AEHPA samples as templates: (a) without AEHPA, (b) AEHPA-1, (c) AEHPA-2, and (d) AEHPA-3. 10260


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ACS Sustainable Chemistry & Engineering adsorption curves for mesoporous materials.42 The sample without AEHPA shows type-II isotherms and a type-H3 hysteresis loop, indicating formation of a disordered material. In principle, the preparation of mesoporous silica by using AEHPA-2 as template can increase the specific surface area, which can affect the particle size distribution of the silica particles.43 The particle size distribution of the mesoporous silica is shown in Figure 2. The average diameter (Figure 2a) of the silica without AEHPA is approximately 25.72 μm. However, the average diameters of the mesoporous silica with AEHPA-1, AEHPA-2, and AEHPA-3 are 19.96, 18.60, and 18.89 μm, respectively. With the increase of molecular weight of AEHPA, the particle diameter first decreases and then increases slightly as shown in Figure 2b−d. Because the molecular weight of AEHPA-1 is much smaller than that of AEHPA-2 in the system, the AEHPA is not enough to form a protective film and stabilize the silicon precursor, resulting in a wide distribution of particle size. However, the even larger-molecular-weight AEHPA-3 has higher viscosity than the smaller-molecularweight AEHPA-2, resulting in self-aggregation to form uneven templates with various sizes which leads to some large-diameter silica particles. Effect of AEHPA-2 Content on the Specific Surface Area of Mesoporous Silica. As shown in Table 1, mesoporous silica with high specific surface area can be prepared using the intermediate molecular weight AEHPA-2 as template. The effect of AEHPA-2 content on the properties of mesoporous silica is shown in Table 2 and Figure 3.

AEHPA-2 increases by 66.5%. At the same time, the pore volume and pore diameter of mesoporous silica reached their respective minimum values, corresponding to decreases of 29.4% and 59.3%, respectively. With the further increase of AEHPA-2 content, the specific surface area of the produced mesoporous silica declined slightly. The reason for the decrease is that the high content of AEHPA-2 leads to high viscosity, which is unfavorable for forming mesoporous silica particles with high specific surface area.44 Figure 3 shows the dependence of N2 adsorption− desorption isotherms and pore distribution curves of mesoporous silica on the AEHPA-2 content. When the AEHPA-2 content is less than 0.1 wt %, the BDDT and IUPAC of the mesoporous silica belong to type-II and type-H3 isotherms, respectively (Figure 3a), and the mode of pore size is 12.764 nm (Figure 3b and Table 2), indicating a kind of large-pore-diameter material arising out of such interstitial cavities (textural pores). When the AEHPA-2 content is higher than or equal to 0.3 wt %, the BDDT and IUPAC of the mesoporous silica belong to type-IV and type-H1 isotherms, respectively (Figure 3a), and the mode of pore size is about 7− 8 nm at the maximum probability (Figure 3b and Table 2). The N2 isotherms exhibit a capillary condensation step at P/P0 = 0.6−0.9, and the mesoporous silica prepared by using AEHPA as template is used to maintain the mesoporous structure.45 A 0.3 g sample was dispersed in 40 mL of distilled water and was allowed to undergo a supersonic wave at room temperature. After 2 min, particle size distribution and average particle size of silica in water were measured using a laser particle analyzer. Average particle sizes and particle size distributions of mesoporous silica with different AEHPA-2 contents are shown in Figure 4. With the increase of AEHPA-2 content, the average particle size of mesoporous silica decreases sharply first and then increases slightly, reaching its minimum value when the AEHPA-2 content is 0.3 wt %. Compared with the average particle size (25.72 μm) of the silica without AEHPA-2, the value of 18.60 μm for 0.3 wt % AEHPA-2 represents a decrease of 27.68%. The average diameters of the samples obtained by using 0.1, 0.5, 0.7, and 0.9 wt % AEHPA-2 are 23.70, 21.18, 21.37, and 21.41 μm, respectively. The particle size distribution of mesoporous silica becomes substantially narrow with the addition of AEHPA-2, and its minimum value appears at 0.3 wt % (Figure 4c). The small average particle size and narrow particle size distribution of mesoporous silica may be attributable to a

Table 2. Effect of AEHPA Content on the Property of Mesoporous Silica content

BET surface area (m2 g−1)

pore volume (cm3 g−1)

pore size (nm)

without AEHPA-2 0.1 wt % AEHPA-2 0.3 wt % AEHPA-2 0.5 wt % AEHPA-2 0.7 wt % AEHPA-2 0.9 wt % AEHPA-2

271.05 337.60 451.34 421.79 399.28 404.87

1.167 0.834 0.824 0.797 0.769 0.824

17.428 12.764 7.090 7.147 8.276 8.146

As shown in Table 2, with the increase of AEHPA-2 content, the specific surface area of mesoporous silica increases first and then decreases with the maximum value achieved when the AEHPA-2 content was 0.3 wt %. Compared with that of the silica without AEHPA-2, the specific surface area of 0.3 wt %

Figure 3. (a) N2 adsorption−desorption isotherms and (b) pore distribution curves of mesoporous silica with different contents of AEHPA-2. 10261


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Figure 4. Particle size distribution of silica obtained by different contents of AEHPA-2: (a) without AEHPA-2, and (b) 0.1, (c) 0.3, (d) 0.5, (e) 0.7, and (f) 0.9 wt % AEHPA-2.

surfactant effect of the amino of AEHPA. The hydrogen-bond interaction between the amino of AEHPA and the hydroxyl groups of the silicon precursor29,30 forms a protective film on the surface of the silicon precursor. When the content of AEHPA is lower than 0.3 wt % in the system, the AEHPA is not enough to form a protective film to stabilize the silicon precursor, resulting in aggregation of the silica during acidolysis and thus a wide particle size distribution (Figure 4a,b). Too much AEHPA (0.5−0.9 wt %) in the system may form a thick protective film, resulting in excessive silicon precursor molecules in the film to form large size particles and wide particle size distribution of mesoporous silica (Figure 4d−f). The incorporation of 0.3 wt % AEHPA-2 seemingly reaches a balance that gives the minimum average particle size and particle size distribution in Figure 4c. Formation Mechanism of Mesoporous Silica. The possible formation mechanism of mesoporous silica is presented in Scheme 2. (1) First, both the amino-ended groups of AEHPA-2 (Scheme 2a) and the hydroxyl groups of sodium silicate have strong hydrogen-bonding force and form a protective film (Scheme 2b) on the surface of the silicon precursor (named AEHPA@Na2SiO3 complex). (2) During acidolysis of the complex, dehydration of hydroxyl groups condenses the AEHPA@Na2SiO3 complex and forms silica micelles (Scheme 2c). The protective film on the outer layer of the silica micelles effectively prevents their aggregation. (3) Sufficient water is used to wash the silica micelles for removing Na+ and SO42−, simultaneously; all of the AEHPA template

Scheme 2. Formation Mechanism of Mesoporous Silica

agent on the surface of the silica micelles is also removed and cavities are formed (Scheme 2d). (4) When the silica micelles are dried at about 120 °C, the mesoporous silica (Scheme 2e) is formed after the free water is removed completely. The FT-IR spectra of all samples in Figure 5a appear with similar peaks at 3450 and 1640 (s, OH), 1095 (b, Si−O), 799 (b, OH), and 465 10262


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Figure 5. (a) FT-IR, (b) XRD, (c) XPS, and (d) N 1s XPS spectra of various mesoporous silica.

(s, Si−O−Si) cm−1, and the characteristic peaks of AEHPA-n have not been observed, indicating that the templates AEHPAn have been removed completely after formation of mesoporous silica. This is substantiated by the disappearance of the N 1s peak at a binding energy of about 399 eV in Figure 5c,d. The XRD spectra of all samples in Figure 5b show that there is no obvious diffraction peak in ∼0−5°, suggesting that the prepared silica may be amorphous silica wormlike mesoporous channels, but not ordered mesoporous structures. For an investigation into the microstructure of mesoporous silica obtained by templates AEHPA-n, their SEM micrographs have been shown in Figure 6. Compared with the compact structure of embedded big particles about silica without AEHPA-n in Figure 6a, the size of mesoporous silica particles decreases, and the microstructure becomes loose and porous because of the usage of templates AEHPA-n in Figure 6b−d. With an increase of AEHPA-2, the loose and porous microstructure increases first and then decreases from Figure 6c,e,f, and the mesoporous silica (Figure 6c) obtained by 0.3 wt % AEHPA-2 indicates the highest surface area, in agreement with the result in Table 2 and the formation mechanism of the mesoporous silica in Scheme 2.

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CONCLUSION Electrolytic manganese slag (EMS) could be used to prepare high-performance mesoporous silica by using amino-ended hyperbranched polyamide (AEHPA) as template. The effects of AEHPA content and molecular weight on the properties of resulting amorphous mesoporous silica were investigated, including the specific surface area, pore diameter, and pore volume. When 0.3 wt % AEHPA with intermediate molecular weight was used, the resultant mesoporous silica shows a specific surface area of 451.34 m2 g−1, a pore volume of 0.824 cm3 g−1, and a pore diameter of 7.09 nm, compared with the specific surface area (271.05 m2 g−1), pore volume (1.167 cm3 g−1), and pore diameter (17.43 nm) without the use of AEHPA. These indicate a significant increase in specific surface area and decreases in both pore volume and pore diameter. The

Figure 6. SEM micrograph of mesoporous silica obtained by AEHPA as templates: (a) without AEHPA-n, (b) 0.3 wt % AEHPA-1, (c) 0.3 wt % AEHPA-2, (d) 0.3 wt % AEHPA-3, (e) 0.1 wt % AEHPA-2, and (f) 0.5 wt % AEHPA-2.

reported preparation method of mesoporous silica from EMS may open an avenue of recycling and utilizing manganese slags, and the mesoporous silica with high specific surface area may be used as catalyst supports.

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. (Daohong Zhang). *E-mail: [email protected]. (Sufang Chen). 10263


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Daohong Zhang: 0000-0002-1640-0805 Menghe Miao: 0000-0003-1799-1704 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We gratefully acknowledge the financial support of the National Natural Science Foundation of China (21403158, 51573210, and 51373200) and Key Project in the National Science & Technology Pillar Program during the Twelfth Five-year Plan Period (2015BAB01B03).

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Preparation of Mesoporous Silica from Electrolytic Manganese

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