Green Approach towards the Synthesis of MCM-41 from ...Green Approach towards the Synthesis of...

International Journal of Applied Chemistry.

ISSN 0973-1792 Volume 13, Number 3 (2017) pp. 497-514

© Research India Publications

http://www.ripublication.com

Green Approach towards the Synthesis of MCM-41

from Siliceous Sugar Industry Waste

Bhavna A. Shah*a, Alpesh V. Patela, Maryam I. Bagiaa , Ajay V. Shahb

aDepartment of Chemistry, Veer Narmad South Gujarat University, Surat,

Gujarat, India. bScience and Humanity Department, BVPIT, Vidyabharti Trust, Umarakh, Bardoli,

Gujarat, India.

Abstract

The Mesoporous material has been given great attention for diverse

application in the different field of chemistry. The synthesis of MCM-41

derived from organo based silicon sources which are more expensive for small

scale industries and toxic for large scale production. The main aim of this

work is to deduct the cost of production of MCM-41 with utilization of

siliceous sugar industry waste bagasse fly ash as silica source. The BFA is

used as silica source by adopting multistep conventional refluxing with

aqueous alkali solution. The extract contains large amount of silicone for

synthesis of MCM-41. The hydrothermal synthesis of MCM-41 was done in

open vessel with molar gel composition of Si: CTAB: Water is 1:0.09738:

408.31. The synthesized material was analyzed by Inductively Coupled

Plasma Atomic-Emission Spectroscopy (ICP-AES), Powder X-ray

Fluorescence (XRF) X-ray diffraction (XRD), Fourier transformation infrared

spectroscopy (FTIR), Scanning electron microscopy (SEM), Transmission

Electron Microscopy (TEM), Energy dispersive spectroscopy (EDS) and N2

adsorption and desorption. The result confirmed that the as synthesized

material exhibits well-ordered structure with hexagonal cell dimension 43.02

Å, surface area 901 m2/g, large pore volume of 0.723 cc/g, and BJH average

pore diameter of 3.21 nm. The results are the same like the MCM-41

http://www.ripublication.com/

498 Bhavna A. Shah, Alpesh V. Patela, Maryam I. Bagia & Ajay V. Shah

synthesized from reagent grade silica sources. Siliceous Sugar industry waste

bagasse fly ash was successfully utilized for getting silicate precursor for

MCM-41 synthesis.

Keywords- Bagasse Fly Ash, Multistep Silicate Dissolution, MCM-41,

Advance analysis.

INTRODUCTION

The mesoporous materials have been given a significant attention by material

scientists of the world after the discovery of MCM (Mobil Composition of Matter) by

scientists of Mobil Oil Corporation in 1992 [1-3]. They named it as new family of

Zeolite: M41S. Some of the representative zeolites of the family are MCM-41, MCM-

48 and MCM-50. These materials have larger pore diameter in nanometer scale, larger

surface area and large pore volume [1- 4]. These distinct properties made them good

candidate for catalysis [5-7], catalytic supports [8], sensors [9,10], adsorbents [11],

host–guest chemistry [12,13], energy [14,15], and drug carrier [16,17].

The MCM-41 is highly studied amongst the zeolites of M41S family because it shows

extraordinary thermal, hydrothermal, and hydrolytic stabilities [18,19]. Researchers

have typically used two sources of silicon: tetraethlyorthosilicate (TEOS) and sodium

silicate (Na2SiO3) to synthesize mesoporous silica [20,21]. 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 [22]. These silicate precursors not only increase the cost of production but also

result in environmental pollution, which restrict their application in large scale

production. Therefore, new synthetic procedures are developed to prepare this kind of

material either by non-hydrothermal or room temperature synthesis routes [23-25].

These new routes tend to be simple, time saving and low-energy consumption. Also it

is now indisputable that the rapid increase in consumption of mesoporous materials

calls for further work seeking cheaper raw materials for their synthesis. Researchers

successfully made the mesoporous silica material MCM-41 from various cheaper

materials such as natural zeolite [26], clay [27,28], ore tailoring [29,30], agriculture

slag waste [31], E-waste [32], wheat husk [33], rice husk [34,35], coal fly ash

[36,37].

Among these alternatives, Bagasse fly ash is favorable candidate for the synthesis of

mesoporous silica material as it contains good amount of amorphous silica. Bagasse

fly ash is generated as waste product after using Bagasse as boiler fuel in sugar

industries. It is of increasing interest to search for possible alternative use before their

final discharge, including adsorbents [38], filler for building materials [39], and high-

purity mesoporous silica gels [40]. Our method for producing high-purity MCM-41

from bagasse ash was based on the unique solubility properties of silica [40]. The

Green Approach towards the Synthesis of MCM-41 from Siliceous Sugar… 499

solubility of amorphous silica is very low at pH bellow 10, but increases sharply

above pH 10 [41]. Therefore, the silica in bagasse ash could be dissolved in a boiling

alkali solution to form sodium silicate. Owing the high contents of useful silica and

dissolvability, it makes perfect economic approach for industrial application. In this

situation, it is a very useful research to utilize bagasse fly ash for synthesis of

mesoporous materials such as MCM-41.

The aim of the present study was to synthesize MCM-41 materials through a green

approach by using bagasse fly ash as silicone source. A green synthesis approach was

designed to reduce the use or generation of hazardous materials associated with the

synthesis of MCM-41. Moreover, recycling of an agricultural sugar industry waste

material has been performed during synthesis of MCM-41. The material was

characterized by various sophisticated analytical techniques such as ICP-AES, XRF,

XRD, FTIR, SEM, TEM, EDS, BET and BJH.

EXPERIMENTAL

Materials

Bagasse fly ash was collected from a local Sugar Mill “Shree Khedut Sahkari Khand

Udhyog Mandali Ltd.”, Bardoli, Gujarat, India as silica source and n-

Hexadecyltrimethylammonium bromide(CTAB:>95% Sigma Aldrich), as the

structure-directing agent were used as the reagents for the synthesis of MCM-41.

Ethyl acetate, sodium hydroxide (NaOH: >99%), aqueous ammonia (25% NH3) and

other chemical were all supplied by Aldrich and Merck and used without further

modification.

Methods

Pretreatment to BFA

The native BFA was thoroughly washed with deionized water to remove foreign

impurities as suspension materials on water surface. Then, the BFA was dried in a hot

air oven at 353 ± 5 K for 5 h. The dried BFA was sieved in mesh size 75-90 µm and

was used for silicon extraction.

Silicon Extraction

Silicon extraction was done by many researchers using fusion with alkali [42] by

refluxing the silicate material with aqueous alkali solution [43] and applying

microwave dissolution of silicate in aqueous alkali solutions [44,45]. These methods

lead to extraction of silicon as aqueous sodium silicate from which pure silica is

precipitated with mineral acid.


In this study, multistep dissolution of silica was adopted with partial modification of

conventional method. The process of multistep dissolution of silica was done by alkali

using conventional heating. Previously washed and sieved 25.0 g of Bagasse fly Ash

was mixed with 100.0 mL 4.0 M NaOH solution and refluxed for 4 h. The hot liquor

was collected by vacuum filtration and the residue was further treated similarly for

multiple extractions. The combine liquor was analyzed by ICP-AES. The composition

was 35157.3ppm silicone 280.18ppm aluminum and 1702.61ppm sodium. The

liquor was further used for MCM-41 synthesis.

Synthesis of BFA-MCM-41

In typical process, appropriate amount of CTAB was dissolved in 100.0 mL of

distilled water at temperature of 80oC with 300 rpm stirring rate to obtain an aqueous

solution. Then 50.0 mL cooled extracted liquor was added drop wise and stirred for 2

h. The temperature was maintained 80oC during addition process. Further, 5.0 mL

ethyl acetate was rapidly added to resultant mixture which promotes the hydrolysis

process of silicate species and condensation of silicates starts with formation of gel.

To the gel, 5 N H2SO4 solutions was added drop wise with stirring till the solution is

reaches at pH 10. The final volume of the mixture was adjusted such that the molar

gel composition attained the ratio Si: CTAB: Water (1:0.09738: 408.3). The resultant

mixture was stirred at 80°C for 12 h while maintain pH 10. Then resultant mix was

cured overnight at room temperature. The solid was then vacuum filtered, flushed

twice with deionized water. The solid was dried at 100°C for 2 h, and finally calcined

at 550°C for 5 h with a heating rate of 5ºC/min in air atmosphere. The material

obtained accordingly was denoted as BFA-MCM-41.

Characterization

The chemical composition of Bagasse fly ash and the MCM-41 was determined by X-

ray fluorescence spectrometer (Rigaku, Japan). Phase analysis by X-ray diffraction

(XRD) (30 kV, 20mA - Rigaku Geiger-miniFlex, Japan) was carried out at room

temperature with Cu K as the radiation source using a scan speed of 0.5omin-1 and a

step scan of 0.02oA scan angle of 2θ = 10o to 80o was used for identifying the phases

present in BFA. The Small angle X-ray diffraction carried out with a PAN analytical

Empyrean X-ray diffractometer using Cu Kα radiation, operating at 40 kV and 40

mA, at a scanning velocity of 0.02omin-1 in the range of 0.5 o to 10o. The porosities of

the material were measured by N2 adsorption-desorption (BET and BJH) at 77 K

using the Quanta chrome Autosorb 1C BET Surface Area & Pore Volume Analyzer.

The sample was previously dehydrated at 323K for 12 h. The surface area was

calculated from the linear part of the plot using the Brunauer-Emmett-Teller (BET)

equation. The pore size distributions were calculated by using the Barrett-Joyner-


Halenda (BJH) model and by Density Function Theory. The surface functional groups

of synthesized sample was analyzed by Fourier transform infrared (FT-IR)

spectroscope (FT-IR-2000, PerkinElmer, USA), where the spectra were performed in

KBr pellets and recorded from 4000 to 400cm−1.

The morphological analysis was examined on a Hitachi S-3400N scanning electron

microscope (SEM), operated at an accelerating voltage of 15kV. The sample was

initially placed in a vacuum chamber for coating with a thin layer (a few nanometers)

of gold (Au). The EDS was simultaneously carried out with SEM using attachment of

Thermo Electron Corporation.

The pore network and long range of ordering of material where analyzed by

Transmission electron microscope (TEM). The images were collected on a Philips

CM 200 Transmission electron microscope with a field emission gun as the source of

electrons operated at an acceleration voltage of 200kV. Samples were prepared by

dispersing the particles in ethanol and placed on a copper coted carbon grid and dried

before loading in the electron beam.

RESULTS AND DISCUSSION

Mechanism of synthesis of BFA-MCM-41

The silica framework can be formed around preformed liquid crystal mesophases but,

in many cases, the organized architectures are obtained via a self-assembly

cooperative process taking place in situ between the templates and the silica network

precursors. The organic template is then removed by calcination or solvent extraction

to give the resulting mesoporous open structure. Cationic surfactants (e.g., long chain

quaternary ammonium) were used at the beginning and are still widely utilized

because of their favourable electrostatic interactions with the silica surface.

Figure 1. Interaction of silicates with CTAB micelles


As illustrated in Figure 1, CTAB molecules arrange themselves forming rod like

micelle self-assembly to form liquid-crystalline phases so as to reach the

concentration level where packing parameter ‘g‘ is between 1/2 to 1/3 [46]. The

temperature of a system is quiet important for preventing shape change of micelles.

The negatively charged silicate species obtained from BFA by dissolution were

electrostatically attracted toward the positive head group of surfactant. As pH sifted to

lower value by addition of acid, condensation begins to form an inorganic network,

with a hexagonal ordering dictated by the interaction between the surfactant and

silicate species. After removal of the surfactant templates by calcination,

mesoporosity is obtained with pore size of 2–10 nm.

In general, the overall LCT (Liquid Cryastal Templating) mechanism is governed by

two factors: (i) the dynamics of surfactant molecules to form assemblies, micelles,

and ultimately crystalline structure, functioning as template; and (ii) the ability of the

inorganic oxide to undergo hydrolysis and polycondensation reactions leading to a

network surrounding the organic template.

Chemical Composition

X-ray Fluorescence Spectrometry (XRF) Characterization of BFA

The chemical compositions of BFA were determined by quantitative XRF analysis as

the result shown in Table 1. The results indicated that it consist large amount of SiO2

as well as some small amount of Fe2O3, K2O, CaO, P2O5, MgO, Al2O3, TiO2 and

Na2O. Thus BFA is best silica source for synthesis of MCM-41.

Table 1. Mineral oxides compositions (in wt. %) of BFA dried at 373K.

Oxides SiO2 K2O Fe2O3 CaO P2O5 MgO Al2O3 TiO2

Other

minute

constituents

%weight

composition 75.96 5.24 5.08 3.85 2.68 2.53 2.24 1.06 1.36


Energy Dispersive Spectrum (EDS) Characterization of BFA-MCM-41

Figure 2. EDS spectrum of BFA-MCM-41.

The energy dispersive spectrum (EDS) of MCM-41-BFA showed that the relative

weight percent of Si, O, Na and Al are 58.35%, 39.45%, 0.80% and 1.39%

respectively. A typical EDS spectrum of BFA-MCM-41 is shown in Figure 2. The

EDS spectrum at different points of the image confirms that the material is almost free

from impurities and it is similar to reagent grade.

FT-IR Spectral analysis of BFA-MCM-41.

The FTIR analysis of calcined BFA-MCM-41 was carried out by KBr pellet method.

The results are shown in Table 2. IR bands are observed for stretching and bending of

hydroxyl group attached to surface silicon atom and for interstitial water molecules.

Symmetric and asymmetric bands for tetrahedral units are also observed. These bands

are typically observed for mesophase silica.[23] There are no bands observed around

2850 to 3000 cm-1 corresponds to stretching of – C - H group, indicates complete

removal of the surfactant molecules form the pores of the synthesised material.


Table 2. FTIR analysis of BFA-MCM-41.

Rang of IR

bands (cm-1)

Observed

bands (cm-1)

Possible assignments

3200-3500 3417.98 Stretching vibration of –OH, Surface silanols

and the adsorbed water molecules. (Si-OH)

1580-1700 1629.9 -OH deformation and bending vibration of

interstitial water

1030-1240 1232.55 Asymmetric stretching of internal tetrahedral

TO4 , Si-O-Si

≈800 796.63 Symmetric stretching of internal tetrahedral TO4

(T = Si, Al)

1250-950 1078.24 Internal and external asymmetric Si–O stretching

vibrations.

1230-860

420–500

962.51 and 478 Stretching and bending vibration of surface Si–

O-groups

X-ray Diffraction (XRD)

XRD of BFA and BFAAE

The mineralogical composition of bagasse fly ash (BFA) before silica extraction and

after extraction (BFAAE) was shown in Figure 3.

Figure 3. X-ray Diffraction Patterns of BFA and BFA after extraction (BFAAE)


The broad hump in the XRD pattern was removed after alkali extraction which shows

that large amount of amorphous silica present in the BFA was extracted in the

aqueous alkali which produces sodium silicate for mesoporous MCM-41 synthesis.

The diffraction of hematite remains intact after extraction which concludes that

hematite phase is stable even though it partially dissolves in alkali extraction process.

The diffraction of stilbite completely disappears in BFAAE as it gets dissolved during

extraction process. There is no extra diffraction observed after extraction which

confirms the efficiency of silicate extraction process.

XRD of BFA-MCM-41

Figure 4. Law angle XRD of BFA-MCM-41.

The Low-angle powder X-ray diffraction (LAXRD) pattern of BFA-MCM-41 is

shown in Figure 4. It exhibits four characteristic peaks that can be indexed on a

hexagonal lattice of a typical mesoporous MCM-41 material as (100), (110), (200)

and (210) planes [47,48]. They indicate a long-range ordered hexagonal mesoporous

structure. The hexagonal unit cell parameter (a0) indicates the sum of the internal pore

diameter and pore wall thickness, which was 43.02 Å for BFA-MCM-41.


Microscopic analysis by SEM and TEM

Scanning Electron Microscopy (SEM) Characterization of BFA

Figure 5. SEM images of BFA and BFAAE.

The microscopic structure is quite important for the silicate species which are formed

by dissolution with aqueous alkali. The SEM images observed in Figure 5 are both for

BFA and BFAAE. Bagasse fly ash (BFA) particles are not spherical in shape and

exhibit irregularly fragmented particles also its morphology is more compact with

fewer pores while BFAAE is fibrous. BFA particles become more fibrous and porous

as the dissolution of amorphous silicate, stilbite and some of quartz content takes

place. The dissolution is also confirmed by weight difference of the residue.

Scanning Electron Microscopy (SEM) Characterization of BFA-MCM-41

Figure 6. SEM images of BFA-MCM-41


The SEM image of BFA-MCM-41 in Figure 6 shows agglomeration of spherical

particles. It also shows that these particles are formed through the aggregation of very

fine homogeneous grains of nano size.

Transmission Electron Microscopy of BFA-MCM-41

Figure 7. TEM images of BFA-MCM-41

The TEM images of the BFA-MCM-41 synthesized from bagasse fly ash is presented

in Figure 7. These images confirm that the material exhibited highly ordered 2-D

hexagonal mesostructure of and streak structural features of typical MCM- 41. In

addition, particles were also observed with agglomeration of 50-60 nm size with

porous structure in the TEM. The obtained pore size is about 2.94 nm which is in

close agreement with the value determined from XRD (3.37 nm) and N2-adsorption

measurements values (3.21 nm), which confirm the formation of high quality MCM-

41 form bagasse fly ash.

Nitrogen Adsorption-Desorption Characterization

The mesoporous structure of synthesised BFA-MCM-41 was also confirmed by N2

adsorption tests. Figure 8 shows the N2 adsorption - desorption isotherms for the

sample. Sample show a typical type IV isotherm according to the IUPAC

classification, which is a characteristic isotherm shape for mesoporous silica MCM-

41[49,50].


Figure 8. N2 adsorption - desorption isotherm of BFA-MCM-41.

The isotherm exhibits three defined stages, with the inflection points at P/ P0=0.29

and P/P0=0.43. The first stage is due to monolayer and multilayer adsorption of

nitrogen to the walls of the mesoporous at low relative pressures (P/P0˂0.25). The

second stage is characterized by a sharp increase in adsorption (0.25˂P/P0˂0.43). As

the relative pressure increases, the isotherms show that adsorption amount increases

abruptly because of the capillary condensation within the uniform pores which

confirms the existence of mesoporous structure of synthesized silica [51]. Third stage

in the adsorption isotherm gradually increases at high P/P0 (0.43-0.99) values due to

multilayer adsorption on the external surface of the particles. The isotherms of

mesoporous materials with high pressure can be attributed to the condensation of

nitrogen within voids formed by crystal aggregates. The BET equation was applied to

the monolayer region of the isotherm to estimate the surface area. The average pore

diameter was calculated by gas desorption measurements. Also DFT was applied for

pore size determination. The surface areas and pore diameters obtained from BET,

BJH, DFT and XRD were given in Table 3, which are in good agreement with values

of reported materials [52-55].

Table 3. Structural data obtained for BFA-MCM-41.

BET Surface

area

Pore

Volume

BJH pore

size

DFT pore

size

XRD

pore size

Pore wall

Thickness

901 m2/g 0.723 cc/g 3.21 nm 3.31 nm 3.37 nm 1.0993 nm


The synthesized BFA-MCM-41 has been structurally characterized and is in good

agreement with the commercial grade MCM-41 mesoporous material [58].

CONCLUSIONS

Sugar industry siliceous detritus can be successfully utilized as raw material for the

synthesis of mesoporous MCM-41. The multistep silicate extraction gives large

silicon content about 35,157 ppm. The synthesis of BFA-MCM-41 is successfully

carried out with relatively low molar surfactant concentration. The synthesized

material has higher surface area, large pore diameter and pore volume. Low angle X-

ray diffraction pattern and nitrogen adsorption desorption obtained for BFA-MCM-41

confirms the successful synthesis of MCM-41. The purity of BFA-MCM-41

confirmed by EDS analysis which is same to that of commercial grade MCM-41. The

material is suitable for further processing into materials for advanced applications

such as the storage of hydrogen and capturing of carbon dioxide.

ACKNOWLEDGEMENTS

The authors gratefully acknowledge UGC, New, Delhi India for the financial support

as National fellowship of OBC. The authors are thankful to Shree Khedut Sahkari

Khand Udhyog Mandali Ltd.”, Bardoli, Gujarat, India for providing Bagasse Fly Ash.

The authors also acknowledge IISER Bhopal, IIT Kanpur, SAIF Bombay and SVNIT

Surat for providing analysis of sample.

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