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Experimental Report (unit 3)

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Unit 3. Preparation and Characterization of Molecular Sieves for


Adsorption of Organic Pollutant
1. Purpose
Grasp hydrothermal synthesis method for microporous and mesoporous
molecular sieve.
Understand the operation principle and grasp the analysis procedures for XRD
and N2 sorption isotherm.
Master the operation principle and analysis procedure for HPLC and UV-Vis
absorption
2. Principle
Mesoporous silica as a kind of white amorphous silica powder, can be used for
adsorption, catalysis and energy storage. Generally, mesoporous silica is synthesized
through the self-assembly of surfactant and silicates, where the electrostatic or
hydrogen bonding interaction is utilized. The surfactant can be removed through
solvent-extraction of high-temperature calcination, producing mesoporous channel
and silicates framework. Mesoporous silica possesses flexible adsorption performance
to inorganics and organics through tuning the pore structure, size and framework
composition.
3. Equipment and Materials
Falsks, mechanical stirrer, glass rod, sand-core funnel, filtration devices,
cetyltrimethylammonium, bromide (CTAB), NaOH, tetraethyl orthosilicate (TEOS), 1,2bis(triethoxysilyl)ethane(BTEE), 2,4-dicholorophenol(2,4-DCP) and water.
4. Experiment:
1Synthesis of mesoporous materials:
200 mg of CTAB was dissolved into 100 mL of ultrapure water, and then 0.7 mL of
NaOH (2M) was added under stirring. The solution was heated to 70 oC after 15 min. then
1.0 mL of silica precursor was added into the mixture. The solution was allowed to stand
at 70oC for 2 h. CTAB were removed by mild extraction with 240 mg of NH 4Ac and 20
mL of ethanol solution under refluxing for 1 h. the sample was dried at 60 oC in the
vacuum after washing by water and ethanol.
2Batch Adsorption:
Organic 2,4-DCP was adopted as the pollutant models. The solution pH was adjusted by
the addition of 0.1 M HNO3. Adsorption kinetic and thermodynamics experiments were
carried out to investigate the adsorption equilibrium time, confirm the adsorption type and
assess the adsorption rate. 60 mg/L of 2,4-DCP. The adsorbent doses for the adsorption of
2,4-DCP was 0.2 g/L. The mixture was put into the gas bath thermostatic oscillator, and
shook at a certain temperature for 4 h. Then the mixture was centrifuged at 12000r/min
for 10 min. The obtained liquid was filtered through syringe filters (cellulose acetate
membranes) with the size of 0.22m to remove the particles after the adsorption, and
diluted 10 times for the characterization by HPLC (flow rate: 1 mL per min, mobile
phase: 60% acetonitrile, column temperature: 40 oC, determine wavelength: 282 nm).

Experimental Report (unit 3)


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5. Requirements:
1) Present the small-angle XRD pattern and N2 sorption isotherm of mesoporous silica.
2) Use HPLC to analyze the influence of temperature and adsorption performance to
2,4-DCP.
6. Analysis:
1) TEM
(a)

(b)

(c)

(d)

Fig. 1 TEM images of the prepared silica from TEOS (a, b)


and BTEE(c, d), respectively.
The TEM results confirms that mesoporous silica can be synthesized from TEOS and
BTEE, both as the silica precursors. While more products can obtained with BTEE as
silicate source. In the images (a, b) is observed the uniformly spherical morphology of
silica with particles size range of 200~300 nm and 200~500 nm, for TEOS and BTEE as
the precursors respectively. Also, this spherical morphology is perfectly appreciated in the
high resolution image by TEM that is displayed in (b) and (d). In this image it can be seen
the uniform pore structure and well-ordered channels that matches well with the images
reported for typical silica indicating that the product has the structural organization of
silica network and it can be successfully obtained through the solution process. In
addition, this image is a clear evidence of that the long-range structural order of mesopore
does not lost after removal of surfactant.

Experimental Report (unit 3)


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2) XRD
The X-ray diffraction (XRD) pattern of the prepared sample from TEOS shows in Fig. 2.
The low-angle XRD pattern of the prepared sample shows a strong diffraction at 2
smaller than 3that confirm the presence of mesoporous product in the prepared sample.

X-ray diffraction patterns of the synthesized Molecular Sieves

Fig.2. XRD patterns of the prepared molecular sieves sample.


3) BET
Table 1. Physical properties of the sample
Sample

Surface Area
(BET Surface Area)

Group-2

1259.2052

Pore Volume(BJH

Pore Size(BJH

Adsorption cumulative

Adsorption average

volume of pores)
0.750498 cm3g-1

pore width)
2.6 nm

m2g-1
The nitrogen adsorption/desorption isotherms and pore size distribution curves of the
prepared molecular sieves are shown in Fig. 3. The nitrogen adsorption/desorption
isotherms show a typical profile of type IV due to the presence of mesopores in the
sample. Little difference is observed between the N 2 sorption curves and desorption
curves of the prepared mesoporous silica, which suggests that the prepared silica has the
uniform mesoporous structure.
The BET surface area of the prepared silica is 771.4 m 2g1 based on the N2
adsorption/desorption isotherm (Fig. 3). The Barrett-Joyner-Halenda (BJH) pore size
distributions indicate the pore diameters of 2.6 nm.

Experimental Report (unit 3)


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Fig. 3. Nitrogen sorption/desorption isotherms and pore size distribution of the sample.

4) Pollutant Adsorption Report


Table 2. Adsorption of the pollutant
Sample

Calibration Curve

Peak of the sample


Corresponding
=276644
Concentration
Sample-1
y = 7464.1x - 992.2
x=37.20
C = 37.20 mg/L
The sorbent performance of the prepared silica was studied through the model
procedure of 2,4-DCP removal from aqueous solutions. The organic molecule uptake
is analyzed by HPLC. Results of the experiments are shown in Table 2. Sorption
capacity of the prepared silica for 2,4-DCP in our work was about 20 mg/L after
mixed with the organic pollutant solution for one night.

Experimental Report (unit 3)


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Calibration Curve of 2, 4-DCP


400000

300000

f(x) = 7464.1x - 992.2


R = 1

Peak 200000

100000

Fig. 4 Calibration Curve of 2, 4-DCP by HPLC