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VIETNAM NATIONAL UNIVERSITY, HA NOI

VNU UNIVERSITY OF SCIENCE


FACULTY OF CHEMISTRY

Nguyen Bich Ngoc

ADVANCED OXIDATION OF RHODAMINE B


SOLUTION OVER CoOx/SEPIOLITE CATALYSTS

Submitted in partial fulfillment of the requirement for the degree of Bachelor


of Science in Chemistry

(Advanced Program and International Program)

Hanoi – 2019
VIETNAM NATIONAL UNIVERSITY, HA NOI
VNU UNIVERSITY OF SCIENCE
FACULTY OF CHEMISTRY

Nguyen Bich Ngoc

ADVANCED OXIDATION OF RHODAMINE B


SOLUTION OVER CoOx/SEPIOLITE CATALYSTS

Submitted in partial fulfillment of the requirement for the degree of Bachelor


of Science in Chemistry

(Advanced Program and International Program)

Supervisor: Assoc. Prof. Dr. Nguyen Tien Thao

Hanoi – 2019
Acknowledgements

First of all, I am wholeheartedly thankful to my supervisor, Assoc. Prof.


Dr. Nguyen Tien Thao for the enthusiastic instructions and encouragements
throughout this current study.

Secondly, I want to express heartfelt thanks to Dr. Nguyen Thi Nhu for

her support during the process of carrying out my experiments.

Last but not least, I offer my regards and blessings to all of students and

staffs in Faculty of Chemistry for giving permission to do this undergraduate

thesis.

Hanoi, May 2019

Student

Nguyen Bich Ngoc


Contents

Chapter 1: Literature reviews 2


1.1. Dyes and rhodamine B..............................................................................2
1.1.1. Overview of dyes................................................................................2
1.1.2. Rhodamine B.......................................................................................3
1.2. Sepiolite.....................................................................................................4
1.2.1. Structure description...........................................................................4
1.2.2. Chemical and physical properties.......................................................5
1.2.3. Application..........................................................................................5
1.3. Research ability of treatment organic compounds in wastewater by using
CoOx/ sepiolite catalyst in oxidation process.....................................................6
Chapter 2: Experiment and Methodology 8
2.1. Chemicals..................................................................................................8
2.2. Preparation of catalyst...............................................................................8
2.3. Characterization......................................................................................10
2.3.1. X-Ray Diffraction................................................................................10
2.3.2. Energy dispersive X-ray spectroscopy.................................................11
2.3.3. Scanning electron microscope (SEM).................................................12
2.3.4. BET (Brunauer–Emmett–Teller) theory..............................................12
2.4. Catalytic oxidation procedure of Rhodamine B.........................................14
2.5. Calibration curve of rhodamine B..............................................................14
2.5.1. Principle...............................................................................................14
2.5.2. Calibration curve................................................................................15
2.5.3. Calculate the degradation efficiency.......................................................15
Chapter 3: Results and discussions 17
3.1. Characterization of catalysts......................................................................17
3.1.1. X-ray diffraction characteristic............................................................17
3.1.2. EDS spectra.........................................................................................18
3.1.3. Scanning Electron Microscopy (SEM)................................................19
3.1.4. BET Surface Area................................................................................19
3.2. Catalytic performance................................................................................21
3.2.1. Effect of wt.% /sepiolite............................................................21
3.2.2. Effect of oxidant amounts....................................................................22
3.2.3. Effect of mass of catalyst.....................................................................23
3.2.4. Effect of rhodamine B concentration...................................................25
Conclusions 27
Appendices 32
List of figure
Figure 1. 1: Structure of rhodamine B 4
Figure 1.2: Structure of sepiolite 5
Figure 2.1: Progression to synthesize the catalyst 9
Figure 2.2: Diffraction (reflection) of a set of parallel X-rays at the surface
planes of a crystalline material 11
Figure 2.3: Calibration curve of rhodamine B 15
Figure 3.1: XRD patterns for sepiolite, TN03-aCo (a = 3, 5, 7) 17
Figure 3.2: EDS spectra of TN03-5Co catalysts 18
Figure 3.3: SEM images of (a) sepiolite and (b) CoOx/sepiolite 19
Figure 3.4. Nitrogen adsorption/desorption isotherm profiles 20
of sepiolite and CoOx/sepiolite 20
Figure 3.5: Degradation efficiency of rhodamine B aqueous solution 21
after 210 minutes over four samples 21
Figure 3.6: The UV-VIS spectra of rhodamine B aqueous solution 22
over for samples after 210 minutes 22
Figure 3.7: Degradation efficiency of rhodamine B aqueous solution after 210
minutes with different volume of H2O2 23
Figure 3.8: Effect of mass of catalyst on the degradation efficiency of RhB after
210 minutes 24
Figure 3.9: Degradation efficiency of rhodamine B aqueous solution after 210
minutes at different rhodamine B concentration 26
List of table

Table 2.1: The prepared catalyst samples 9


Table 3.1: Specific surface area of sepiolite and CoOx/sepiolite 20
Table 3.2: Degradation efficiency of RhB after 210 minutes with different
amount of catalyst 24
Table 3.3: Degradation efficiency of rhodamine B aqueous solution after 210
minutes at different rhodamine B concentration 25
INTRODUCTION
Recently, the issue of water pollution due to effluents from textile dyeing
industry has received much concern. According to recent statistics, the amount of
dye produced per year increased dramatically to 800,000 tons . The discharge of
these chemical waste resulted in a major challenge for human life as well as a
danger to the environment. For instance, organic dyes such as rhodamine B,
methylene blue, crystal violet, Congo red, and methyl orange have been widely
used in textile industry and their residues are released into water resource in
rivers, lakes, fields...Simultaneously, some traditional craft villages in Vietnam
have been presently used colorant organic dye and contributed to wide-spread
dangerous pollutants in soil and water. International experts have claimed that
some traditional methods such as ultrafiltration, coagulation, adsorption on
activated carbon, and membrane separation can be implemented to remove dyes
from textile wastewater . However, it is difficult to treat dye pollutants
effectively by these processes as they cannot eliminate completely these
pollutants. Consequently, the creation of the adsorbent material and post-
treatment of solid wastes, which requires advanced procedure, are essential .
Thus, the decolorization technologies play an important role in recent
developments of wastewater treatment which result in a considerable
improvement in the oxidative degradation of organic compounds dissolved in
aqueous media . Among these methods, advanced oxidation of dye in the
presence of H2O2 with CoOx/sepiolite catalyst seems to be a very prospective
technique for the reason that CoOx is a transition metal oxide that can be
supported on nanofibrous sepiolite in the oxidation reactions. The objective of
this work is to examine the degradation of rhodamine B (a toxic dye having color
fastness) over CoOx/sepiolite catalysts. In this study, some effects on degree of
decolorization and degradation were studied. The experiment was carried out by
varying one variable at a period of time while other parameters are controlled
constantly .

1
Chapter 1: Literature reviews
1.1. Dyes and rhodamine B
1.1.1. Overview of dyes
Dyes are natural or synthetic compounds having chromophore groups that
can impart color to other materials such as fabrics, papers, plastics and skin [6].
Apart from chromophore groups (OH, NH2, NHR, NR2 and COOH), dyes also
contain auxochrome groups attached to chromophores to enhance the intensity of
absorption (NO2, NO, N=N).
Dyes can be divided into various types according to their solubility and
chemical properties:
- Acid dyes are anionic dyes that dissolve in water. They can connect
to fibers like silk, wool, nylon. The interaction between dye and fiber can be
explained by a formation between negative charge in the dye and positive charge
in the fiber. Most synthetic food colors belong to this group.
- Basic dyes are water-soluble cationic dyes that are mainly related to
acrylic fibers. The addition of acetic acid into the dye bath can help the uptake of
the dye onto the fiber. Basic dyes are also applied in the process of making
colors for paper.
- Mordant dyes need a mordant which prevents the dye from water and
light. The selection of mordant is very important since each mordant can decide
a specific color. Most natural dyes are mordant dyes. Besides, synthetic mordant
dyes are also used extensively in manufacturing process of wool.
- Disperse dyes were originally developed for the dyeing of cellulose
acetate, and are water-insoluble. The dyes are finely ground in the presence of a
dispersing agent and sold as a paste, or spray-dried and sold as a powder. Their
main use is to dye polyester, but they can also be used to dye nylon, cellulose
triacetate, and acrylic fibers. In some cases, a dyeing temperature of 130 °C (266
°F) is required, and a pressurized is used. The very fine particle size gives a large

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surface area that aids dissolution to allow uptake by the fiber. The dyeing rate
can be significantly impacted by the choice of dispersing agent used during the
grinding.
- Azoic dyeing is a method obtained by combining a fiber with both
diazoic and coupling components. The two components react to create the
required insoluble azo dye under suitable conditions. The diazoic and coupling
components play an important role in the formation of final color. Nevertheless,
this technique of dyeing cotton has some restrictions because of the toxic
chemicals used.
- Sulfur dyes are economical dyes that affected by heating the fabric in a
solution of an organic compound, typically a nitrophenol derivative, and sulfide
or polysulfide. The organic compound reacts with the sulfide source to form dark
colors that attach to the fabric.
Textile industry has produced a large amount of dyes since it was born. It
is very difficult to decompose these dyes since they are stable in a normal
condition. Generally, organic dyes are not good for health and for animals.
Some dyes are forbidden to use because they can increase the risk of cancer, for
instance dyes based on benzidine or azo.
1.1.2. Rhodamine B
Rhodamine B (RB, C28H31N2O3 Cl) is a chemical compound that serves as
an important component in industrial dyes. It contains a lot of dark crystals with
red-violet color in powder form. The solubility of this compound is roughly
15 g/L in water [7]. Rhodamine B solution has pink color with maximum
absorbance at wavelength of 553nm.
Moreover, rhodamine B is considered as a toxic compound. If people
contact with rhodamine B for a long time, they may suffer from cancer and
congenital defect [8]. In addition, accumulation of this dye in water system can

3
cause serious environmental problem; some aquatic animals have been on the
brink of extinction.

Figure 1. 1: Structure of rhodamine B


1.2. Sepiolite
1.2.1. Structure description
Sepiolite has been extensively used in many fields; however, the research
of its application in catalytic reaction was mentioned only in a few papers. From
other experiments, it was reported that sepiolite could be used as a wonderful
catalyst support in catalytic reactions because of its special structure.
Sepiolite is a mineral with general formula Mg 8Si12O30(OH)4(H2O)4.8H2O.
Particularly, sepiolite does not belong to a layered phyllosilicate like other clays.
In structure, sepiolite can be described as two layers of SiO4 tetrahedral
surrounding a layer of MgO octahedral. Five objects were well-arranged that
four objects occupy the corners and the fifth was placed in the centre of a square
or rectangle, resulting in the construction of structural channels and tunnels.
Sepiolite is a transition state between the chain structured and layer-structure
silicates [9].

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Figure 1.2: Structure of sepiolite
1.2.2. Chemical and physical properties
- Description: Like palygorskite, sepiolite has an additional tetrahedron at
regular intervals on the chain but the unit cell is 50 % larger than that of
palygorskite [10]; usually clay-like, nodular and fibrous; also compact massive
(meerschaum) or leathery (mountain leather) .
- Color: White with tints of grey-green or red; also light-yellow.
Similar to palygorskite, the structure of sepiolite has open channels that
can trap molecules or ions of certain sizes and charge. Some reports reveal that
its surface areas is varied from 75 to 400 m2/g . This surface contains an inner
surface within which small polar molecules (such as water or ammonia) interact
and a large external area where non-polar organic molecules are adsorbed.
Another important physical property is the long tubular shape, which makes
sepiolite useful as a viscosities and suspending agent.
The high surface area and porosity of sepiolite bring about the remarkable
adsorptive and absorptive properties of this clay. It adsorbs vapors and odors and
can absorb approximately its own weight of water and other liquid [12].

1.2.3. Application

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Sepiolite is considered as a beneficial material. With outstanding sorption
ability, this material brings about various applications due to its pore structure
and its unique particle shape [14].
Sepiolite can be used as a pet litter absorbent thanks to its granular
particles which are an effective litter for absorbing animal waste, especially for
domestic cats [15].
Another function of sepiolite is in drilling mud. When electrolytic content
is changed, the viscosity and gel strength of a sepiolite mud are not influenced.
Thus, sepiolite drilling mud can be applied in salt water. Furthermore, ability of
existence at high temperatures makes this mineral useful in drilling fluids for
geothermal wells. In particular, it is difficult to flocculate sepiolite; therefore, it
is used as a suspending agent in paints, medicines, pharmaceuticals and
cosmetics. One additional application is as a floor sweep compound, for
absorbing oil and grease spills in factories, service stations and others are as
where oil and grease spills are a problem .
Sepiolite is also applied in agriculture as a key component of certain soils
and decision of their characteristics [16]. After mixing the active chemical with
the granular sepiolite particle, the treated particle can then be placed in the
ground with the seed. The pesticide or fertilizer is then released slowly to supply
the crucial protection or nutrient for the growing plant. Meanwhile, finely
pulverized sepiolite that has been loaded with adsorbed chemicals can be dusted
or sprayed onto plants or onto the surface of the ground .
Recently, the test of sepiolite in vitro against human cancer cell lines is
carried out. The results indicated that exposure of cancer human cells to sepiolite
causing growth inhibition that varies with the cell line.

1.3. Research ability of treatment organic compounds in wastewater by


using CoOx/ sepiolite catalyst in oxidation process

6
Many kinds of organic compounds included in the wastewater may cause
a huge damage to human life and environment [1]. Therefore, the issues of
finding effective solutions to treat stable organic compounds have received much
concern. There are various techniques for removing organic compounds such as
oxidation, coagulation, adsorption,… Oxidation process carrying out with many

oxidative reagents like is considered as an effective

method [14]. In case of , the molecular orbital of H2O2 contains 2 pairs of


electrons that have the opposite spins. It has high energy; hence it can easily
oxidize the organic compounds. The decomposition of the peroxide is the reason
for the presence of OH radicals. Thus, the role of strong oxidizing OH· is very
crucial.
Cobalt oxide (CoOx) is a transition metal oxide that decides the catalytic
activity after being loaded on sepiolite carrier. In addition, CoO x/sepiolite
catalyst is a material with large specific surface area [14]. These properties result
in the ability of decomposition of stable organic compounds such as rhodamine
B.

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Chapter 2: Experiment and Methodology
2.1. Chemicals
- Sepiolite (Spain)
- Sodium hydroxide: NaOH (China)
- Cobalt nitrate salt: Co(NO3)2.6H2O (Japan)
- Distilled water
- Rhodamine B (USA)
- Hydrogen peroxide: H2O2 (China)
2.2. Preparation of catalyst
CoOx/sepiolite was synthesized by the precipitation method followed by
calcination. In brief, sepiolite was put into 100mL cobalt nitrate salt solution , and
then precipitated with an excess of sodium hydroxide solution (0.05M) to pH = 8
in 2h. After that, the resultant suspension was separated by filtration, washed
with distilled water until pH = 7, dried at 75 °C for 24h in drying oven. Then the
obtained solid was calcined at 410oC for 4h. The solid gained after calcination is
CoOx/sepiolite catalyst.
The synthesized catalyst samples are denoted as TN03-aCo. Where “a”
indicates the weight content of Co2x+ in the synthesized catalyst. In this study, “a”
was set to be 1, 3, 5, 7, 10, 15 (%).
Relationship between Co2x+ weight and sepiolite weight is described:

8
Figure 2.1: Progression to synthesize the catalyst
The table below shows different catalyst samples with different of wt.%
Co2x+/sepiolite:
Table 2.1: The prepared catalyst samples

Sample wt.% Co2x+/sepiolite

TN03-1Co 1%

TN03-3Co 3%

TN03-5Co 5%

TN03-7Co 7%

TN03-10Co 10%

TN03-15Co 15%

2.3. Characterization
The crystalline structure of prepared samples were investigated by X-Ray
diffraction (XRD) method using D8 Advance-Bruker instrument with CuK α
radiation (λ = 0.1549 nm). The morphological characterization of catalysts was

9
monitored by scanning electron microscope technique (SEM) with Hitachi S-
4500(Japan). Energy-dispersive spectroscopy data were obtained from a Varian
Vista Ax X-ray energy-dispersive spectroscope system. The specific surface area
of catalysts was calculated using Brunauer-Emmett- Teller (BET) theory based
on the physisorption data of nitrogen performed on an Autochem II 2920 (USA).
2.3.1. X-Ray Diffraction
X-ray diffraction (XRD) is an important technique for characterization of
structural materials of a compound. XRD is mainly applied for: identification of
crystalline material; identification of different polymorphic forms
(“fingerprints”); discriminating between amorphous materials and crystalline
material as well as quantification of the percent crystalline of a sample. XRD
analysis is constructed from interaction of monochromatic X-rays and a
crystalline sample. A cathode ray tube generates the X-rays, and then the X-rays
are filtered to produce monochromatic radiation, collocated to concentrate and
directed toward the sample. The interaction of X-rays with the sample creates
constructive interference (and a diffracted ray) according to Bragg’s Law
(nλ=2dsinθ). In this law, the wavelength of electromagnetic radiation is related to
the diffraction angle and the lattice spacing in a crystalline sample.

10
Figure 2.2: Diffraction (reflection) of a set of parallel X-rays at the surface
planes of a crystalline material
The structural phases of prepared CoOx/sepiolite catalysts were
characterized by XRD method in Faculty of Chemistry in VNU University of
Science.
2.3.2. Energy dispersive X-ray spectroscopy
Energy dispersive X-ray spectroscopy (EDS) is a powerful method for
identification of elemental compositions in a tiny amount of material based on
the interaction of some source of X-ray excitation and a sample [18]. Its
characterization abilities are performed due to the standard principle that
characteristic X-rays have specific energy corresponding to each element. The
obtained peak energy is useful for identification of the element; and the quantity
of the element in the sample can be calculated from the integrated intensity of
the peak. To consider the emission of characteristic X-rays from a sample, a
high-energy beam of charged particles or a beam of X-rays, is focused into the
specimen being examined. At rest, an atom in the sample has ground state (or
unexcited) electrons in discrete energy levels or electron shells bound to the
nucleus. The incident beam may excite an electron in an inner shell, ejecting it
from the shell while creating an electron hole where the electron was. An
electron from an outer, higher energy shell then fills the hole, and the change in
energy between the higher-energy shell and the lower energy shell may be
released in the form of an X-ray. The number and energy of the X-rays emitted
from a specimen can be measured by an energy-dispersive spectrometer. As the
energy of the X-rays is characteristic of the difference in energy between the two
shells, and of the atomic structure of the element from which they were emitted,
this allows the elemental composition of the specimen to be measured. The
surface component of catalysts was analyzed by EDS method in Faculty of
Physics at VNU University of Science.

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2.3.3. Scanning electron microscope (SEM)
Scanning electron microscope (SEM) method provides more information
about the morphological characteristics of a sample by scanning the surface with
a focused beam of electrons. Interaction between the electrons with atoms in the
sample creates different signals that supply information about the surface
properties of the sample. In particular, this method needs a raster scan pattern in
order to scan the electron beam, and then the beam's position is associated with
the detected signal to create an image. Resolution in SEM method can be better
than 1 nanometer . SEM technique allows to determine morphological surface of
catalytic material in many forms such as crystal form.
The surface image of the catalyst was determined by using SEM method
in National Institute of Hygiene and Epidemiology.
2.3.4. BET (Brunauer–Emmett–Teller) theory
This technique is very important to calculate the specific surface area, the
pore volume and the pore size distribution of porous materials resulting from the
nonselective physical adsorption of an appropriate adsorbate, typically
dinitrogen (N2), at liquid nitrogen temperature.
Brunauer, Emmett and Teller recommended a model for multilayer
physisorption and derived an equation called the BET equation that allowed the
calculation of monolayer coverage of the adsorbate [20]. This equation was
derived from a model that extended the Langmuir isotherm and included the
following assumptions:
- Each adsorbed molecule in the 1st layer plays a role as a site for the 2nd
layer.
- The rate of adsorption (condensation) on any layer (x) equals the rate of
desorption (evaporation) from the layer above it (x + 1).
- The heat of adsorption of the 2nd layer and all those above it equals the
heat of liquefaction of the adsorbate.

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All layers were summed, and for an infinite number of layers the
following BET equation is obtained:
P   C  1  P 1
  
V  Po  P   Vm C  Po Vm C

C = e(q1qL)/RT

Where V is the total volume adsorbed (STP) at pressure P


Vm is the volume adsorbed (STP) at monolayer coverage
Po is the saturation vapor pressure of the adsorbate gas (or vapor)
ql is the heat of adsorption in the 1st monolayer and q L is the heat
of liquefaction (condensation) of the adsorbate
P P
By plotting V  P  P  versus P , we can obtain a linear plot with a slope
o o

 C  1 1
VmC
and an intercept V C , from which Vm and C can be determined.
m

A specific surface area, A, is calculated from the Vm values:

2.4. Catalytic oxidation procedure of Rhodamine B


Rhodamine B (RhB) has been selected as the degrading pollutants to test
the catalytic activity. The as-prepared catalyst was dispersed in 100.0 mL RhB
aqueous solution which was stirred magnetically. Then the calculated volume of
hydrogen peroxide H2O2 (30 wt. %) solution was added at once. The
decoloration degree of RhB was estimated using the UV-Vis absorption spectra
at a wavelength of 553 nm where RhB obtained the maximum absorption

13
intensity. Approximately 8 mL of reaction mixture was taken out at given time
intervals for the determination of RhB concentration (C).
2.5. Calibration curve of rhodamine B
2.5.1. Principle
Assume that a molecule can absorb the light of a wavelength λ. By
illuminating a source containing light of wavelength λ to a homogeneous
solution, only a small portion of the light will be transmitted through the
solution. Ì the solution is illuminated by the light of intensity I0 (Watts cm-2),
intensity I < I0 will be transmitted. Only the transmitted light can reach the
detector [19].
Without electronics and optics involved, measure transmittance T = I/I0. If
there are no molecules to absorb the light, T = 1. If the solution contains some
absorbing molecules, the values of T is in the range of 0 < T < 1.
The negative base 10 logarithm of transmittance is called absorbance A
A = - log10T
A is a computed quantity, not a directly measured quantity.
According to the Beer-Lambert law:
A = εbC
where A = absorbance
ε = molar absorptivity (L. mole-1 cm-1)
b = path length over which absorbance is observed (cm)
C = concentration of the analyte (mole/L)
If the molar absorptivity and path length are determined, an absorbance
measurement directly gives concentration.

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2.5.2. Calibration curve
- Prepare rhodamine B standard solutions from rhodamine B (powder)
with MW= 479.02 g.mol-1.
- From standard solution, dilute with different concentrations, then
measure UV- VIS at wavelength of 553 nm and construct calibration curve.

Figure 2.3: Calibration curve of rhodamine B


2.5.3. Calculate the degradation efficiency
The degradation efficiency (%) can be withdrawn from the equation:

Efficiency =

Where is the initial concentration of rhodamine B

Ct is the measured concentration of such dye in aqueous solution at a


given time (t).
The concentration of rhodamine B is determined by use of a calibration
curve. The experiment showed that rhodamine B acquired the maximum
absorption at a wavelength of 553 nm. The UV-vis spectrophotometer

15
(Shimazdu, Cary 100 UV-VIS spectrophotometer) with quartz cuvettes was used
for the calculation of degradation efficiency of rhodamine B in the range of 300-
600 nm. Calibration based on the Beer-Lambert law was used to quantify the dye
concentration.

16
Chapter 3: Results and discussions
3.1. Characterization of catalysts
3.1.1. X-ray diffraction characteristic
Phase structure of catalytic material was determined by X-ray diffraction.
Figure 3.1 represents the XRD pattern of as-synthesized CoO x/sepiolite with
different wt.% of cobalt loadings. It can be seen that the characteristic peaks for

sepiolite are shown at 2 = 7.3 7.5 (110). The weak reflection at 2 = 36.8,44.8

, in line with (311),(400) plans for Co3O4, respectively [21]. These signals are
not clear by virtue of a small amount of cobalt oxides dispersed on the high
surface area support or some parts of CoOx may also be in an amorphous form.
The results reveal that Co3O4 has been formed in the sepiolite carrier.
(110)

(311)

2- Theta angle(º)

Figure 3.1: XRD patterns for sepiolite, TN03-aCo (a = 3, 5, 7)

17
3.1.2. EDS spectra
Energy-dispersive X-ray spectrometry (EDS) analysis provides more
information of the composition of different elements in the outermost layers of
the catalyst platelets. EDS patterns of CoOx/sepiolite catalysts are shown in
Figure 3.2. It is clearly to see that EDS patterns display observable signals of
Si, Al, Mg, O as well as the signals of transition metals Co. Furthermore, the
surface composition of recorded spots is quite close to each other, pointing out
that the metal ions have a good dispersion of on the large surface scale of the
sepiolite support. Nevertheless, the chemical composition of the as-synthesized
catalysts is slightly different from the theoretical values because of the
deposition of small particles of metal oxides in the channels and tunnels of the

Figure 3.2: EDS spectra of TN03-5Co catalysts

18
support[22].

19
3.1.3. Scanning Electron Microscopy (SEM)
Scanning Electron Microscopy (SEM) was used to identify the
morphological characteristics of sepiolite and CoOx/sepiolite. From figure 3.3,
sepiolite looks like long tubular crystals. A difference in morphology between
sepiolite and CoOx/sepiolite was observed. When cobalt oxides are added, the
macroscopic structure of sepiolite is not considerably changed and no
agglomeration of metal oxide species is recognized. It is proposed that CoOx
particles can be dispersed both on the external surface and in the tunnels of the
sepiolite. The surface of CoOx/sepiolite became more rough than sepiolite due to
the dispersion of CoOx species on that surface.

(a) Sepiolite (b) CoOx/sepiolite


Figure 3.3: SEM images of (a) sepiolite and (b) CoOx/sepiolite
3.1.4. BET Surface Area
The change in specific surface area between sepiolite and CoO x/sepiolite
was detected with N2 adsorption/desorption technique. The result shows that the
specific surface area of sepiolite was 166.2 m 2/g. After being loaded with CoOx
particle, the specific surface area increases up to 191.1 m2/g which specializes
for the increasing adsorption ability. A rise in the specific area could be
explained by the fact that the preparation process of catalyst removed impurities

20
on the surface of the sepiolite as well as in grooves, increasing gaps in channels
which help the BET surface area rises significantly.
Table 3.1: Specific surface area of sepiolite and CoOx/sepiolite
Catalyst Batch SBET (m2/g)
Sepiolite 166.2
CoOx/sepiolite
191.1

Figure 3.4 draws two isothermal adsorption/desorption plots of the two


representative samples. As observed in Figure 3.4, the shape of the two obeys
type IV according to the IUPAC. Furthermore, desorption line initiates
immediately after completion of the adsorption, leading to the formation of a
narrow hysteresis loop [23-25].

Figure 3.4. Nitrogen adsorption/desorption isotherm profiles


of sepiolite and CoOx/sepiolite

21
3.2. Catalytic performance

3.2.1. Effect of wt.% /sepiolite


In the series of CoOx/sepiolite samples, the activity of catalyst decrease in
the order TN03-1Co, TN03-7Co, TN03-10Co, TN03-15Co. The sample TN03-
1Co with 1% wt.% of Co 2x+ obtained higher decolorization efficiency of
rhodamine B (90.8%) compared to other specimens. The phenomenon that the

catalytic performance is all declined when we increase the ratio of

/sepiolite can be explained by the changing in the number of active sites. On the
other hand, with TN03-7Co, TN03-10Co and TN03-15Co samples, the CoO x
species are not dispersed well over sepiolite, therefore the active site number is
lower than TN03-1Co sample.

Figure 3.5: Degradation efficiency of rhodamine B aqueous solution


after 210 minutes over four samples
(30 mg/L of rhodamine B, 0.10 g of catalyst, 1mL H2O2, room temperature)

22
In order to understand the behavior of oxidation reaction of rhodamine B
in water, UV-vis spectra of rhodamine B were recorded during the reaction
process. As seen in Figure 3.6, the UV-VIS spectra of rhodamine B aqueous
solution over for samples after 210 minutes indicates a steady reduction
absorbance at wavelength of 553nm only, proving that the movement of the main
absorbance is obtained thanks to the de-ethylated reactions in which parts of
chromophore and auxochromes in rhodamine B molecular structure were
destroyed [26,28].

Figure 3.6: The UV-VIS spectra of rhodamine B aqueous solution


over for samples after 210 minutes
(30 mg/L of rhodamine B, 0.10 g of catalyst, 1mL H2O2, room temperature)

3.2.2. Effect of oxidant amounts


Since H2O2 performs a great ability to oxidize rhodamine B aqueous
solution over CoOx/sepiolite catalysts, the addition of different volume of H2O2
into the reaction mixture is carried out in order to investigate the impact of
oxidant amounts on the degradation efficiency of rhodamine B. Figure 3.7

23
illustrates the degradation level of rhodamine B varying with the volume of H2O2
in the range of 0-2mL. The degradation level of rhodamine B changes from 50%
to 94.1 %, determined by on the amount of H2O2 added to the reaction mixture. It
is clear that the decoloration of rhodamine B is proportional to the amount of
additional HO· created by H2O2 dissociation when the H2O2 concentration
increases [29,30].

Figure 3.7: Degradation efficiency of rhodamine B aqueous solution after 210


minutes with different volume of H2O2
(sample TN03-1Co, 30 mg/L of rhodamine B, 0.10 g of catalyst, room
temperature)
3.2.3. Effect of mass of catalyst
Another factor contributing to the degradation efficiency of rhodamine B
is the quantity of catalytic material added to organic dye solution. In this work,
the amount of catalyst is varied from 0 to 0.2 g at reaction condition reported in
Figure 3.8. There is a visible trend that the decoloration of rhodamine B also
increases when the catalyst dosages increase. Meanwhile, the catalyst surface
could have more active sites which would accelerate the degradation rhodamine
B reaction [24]. The highest decolorizaion was discovered in case of 0.2 g of

24
catalyst (96.8%). Therefore, an increase in the amount of catalyst has a marked
influence on degradation efficiency of rhodamine B.
Table 3.2: Degradation efficiency of RhB after 210 minutes with different
Time Degradation efficiency (%)
(min) 0g 0.05 g 0.1 g 0.15 g 0.2 g
0 0 0 0 0 0
30 17.71 60.03 70.14 81.69 83.39
60 12.94 56.8 73.25 86.98 95.68
90 7.86 60.74 79.92 91.83 96.21
120 6.41 62.81 83.02 95.28 97.11
150 5.77 66.33 83.98 95.42 97.21
180 6.89 68.47 84.45 96.07 98.2
210 4.64 69.75 90.84 96.45 96.8

amount of catalyst
(sample TN03-1Co, 30 mg/L of rhodamine B, 1mL H2O2, room temperature)

Figure 3.8: Effect of mass of catalyst on the degradation efficiency of RhB after
210 minutes
(sample TN03-1Co, 30 mg/L of rhodamine B, 1mL H2O2, room temperature)
3.2.4. Effect of rhodamine B concentration

25
The influence of rhodamine B concentration on the efficiency of
degradation was also studied. The outcome of this work is given in Figure 3.9.
By increasing the initial concentration of rhodamine B from 20ppm to 70ppm,
the degradation efficiency of rhodamine B after 210 minutes was 71%, 76%,
91%, 93%, respectively. It is clear that the decolorization decreased because the
amount of H2O2 was constant while rhodamine B concentration increased.
Obviously, when rhodamine B concentration is higher, the rate of reaction is
slower. This can be attributed to the fact that dye molecules have more chance to
collide with others while dye and OH· radicals (comes from H2O2) have lower
probability for collision [31].

Table 3.3: Degradation efficiency of rhodamine B aqueous solution after 210


minutes at different rhodamine B concentration
(sample TN03-1Co, 0.10 g of catalyst, 1mL H2O2, room temperature)

Time Degradation efficiency (%)


(min) 20 mg/l 30 mg/l 40 mg/l 70 mg/l
0 0 0 0 0
30 77.11 70.14 64.9 33.16
60 79.27 73.25 69.67 44.22
90 85.26 79.92 72.62 50.42
120 88.94 83.02 73.57 59.25
150 90.95 83.98 75.22 59.09
180 92.04 84.45 74.69 62.17
210 92.98 90.84 76.3 71.79

26
Figure 3.9: Degradation efficiency of rhodamine B aqueous solution after 210
minutes at different rhodamine B concentration
(sample TN03-1Co, 0.10 g of catalyst,1mL H2O2, room temperature)

27
Conclusions

CoOx/sepiolite catalysts have been synthesized by the precipitation


method and calcinated at 410ºC. These materials were analyzed by XRD, EDS,
SEM, BET. The synthesized catalysts have distribution of Co 3O4 on sepiolite
carrier. The catalysts have been used for the oxidative reaction of rhodamine B
aqueous solution. At the same time, the catalytic activity depends on reaction
conditions (amount of oxidant, catalyst dosages, rhodamine B concentration, wt.
% Co2x+/sepiolite). Since the sepiolite mineral exhibited a good adsorption of
rhodamine B, CoOx/sepiolite catalysts showed both absorbability and catalytic
decomposition activity in the degradation of rhodamine B. At atmospheric
pressure, room temperature, after 210 minutes, the 1 wt.% Co/sepiolite sample
obtained a higher decoloration efficiency of rhodamine B (90.84%) in the
presence of hydrogen peroxide compared to other samples.

28
References
1. Chen X., Z. Xue, Y. Yao , W. Wang, F. Zhu and C. Hong (2012),
"Oxidation Degradation of Rhodamine B in Aqueous by Treatment System",
International Journal of Photoenergy, 2012(5), pp. 1-2.
2. Ertugay N. and F. N. Acar (2017), "Removal of COD and color from
Direct Blue 71 azo dye wastewater by Fenton’s oxidation Kinetic study",
Arabian Journal of Chemistry, 10(1), pp. 1158-1163.
3. Al-Momani F., E. Touraud, J. Degorce-Dumas, J. Roussy and O. Thomas
(2002), "Biodegradability enhancement of textile dyes and textile wastewater by
VUV photolysis", Journal of photochemistry and Photobiology A: Chemistry,
153 (1), pp. 191-197.
4. Georgiou D., P. Melidis, A. Aivasidis and V. Gimouhopoulos (2002),
"Degradation of azo-reactive dyes by ultraviolet radiation in the presence of
hydrogen peroxide", Dyes and Pigments, 52 (2), pp. 69-78.
5. Daneshvar N. and M. Behnajady (2008), "UV/H2O2 treatment of
Rhodamine B in aqueous solution: Influence of operational parameters and
kinetic modeling", Desalination, 230 (1-3), pp. 16-26.
6. Roman P., S. Irina, G. Gonul, T. Oxana, Y. Svetlana, P. Valentin and G.
Vladislav (2011), “Fe-exchanged zeolites as materials for catalytic wet peroxide
oxidation. Degradation of Rodamine G dye”, Applied Catalysis B:
Environmental, 104(1-2), pp. 201–210.
7. Bedmar A. P. and L. Araguas (2002), "Detection and the Prevention of
Leaks from Dams", Taylor & Francis.
8. Lin S., L. Wu, T. Y. Xiu, L. Dian-Yang and W. Zhi (2016), "Rapid and
Sensitive Determination of Rhodamine B in Cosmetics", Analytical Methods, pp.
5289-5294.
9. Youssef H., D. Ibrahim and S. Komarneni (2008), "Microwave-assisted
versus conventional synthesis of zeolite A from metakaolinite", Microporous
Mesoporous Mater, 115, pp. 527–534.
10. Harben P. W. and R. L. Bates (1984), "Geology of the Nonmetallics",
pp.87-125.

29
11. Roberts W. L., G. R. Rapp and J. Weber (1974), "EncycLopedia of
Minerals", pp. 554-555.
12. Alvarez A. (1984), "Palygorskitesepiolite: Occurrences, Genesis and
Uses", pp. 253-287
13. Bish G. D. (1993), " Mineralogy of clay and zeolite dusts (exclusive of 1 :
1, larger silicates)”, pp. 139-184.
14. Thao N. T. , T. T. Huyen, D. T. H. Ly and H. T. P. Nga (2016),
"Characteristics and Rhodamine B Adsorption Ability of Modified Sepiolites",
VNU Journal of Science: Natural Sciences and Technology, 32 (4), pp. 2-3.
15. Cancer IAFRO (2007), "IARC Monographs on the Evaluation of
Carcinogenic Risks to Humans", 91(1), pp. 32-34.
16. Suárez M., J. García-Rivas, E. García-Romero and N. Jara (2016), "
Mineralogical characterisation and surface properties of sepiolite from Polatli
(Turkey)", Applied Clay Science, 131(2), pp.124-130.
17. Cervini-Silva J., A. Nieto-Camacho, M. T. Ramirez-Apan, V. Gomez-
Vidales and J. E. Ronquillo (2015), "Anti-inflammatory, anti-bacterial, and
cytotoxic activity of fibrous clays", Colloids Surf B Biointerfaces, 129(1-6), pp.
1016-1017.
18. Ana V. G. and C. Gianvito (2017), “Application of Scanning Electron
Microscopy-Energy Dispersive X-ray Spectroscopy (SEM-EDS)”.
19. Sanda S.M. (2012), "Spectrophotometric measurements techniques for
Fermentation process", 2(1), pp. 2-4.
20. Brunauer S., P. H. Emmett and E. Teller (1938), “Adsorption of Gases in
multimolecular layers”, Journal of the American Society, 60(2), pp. 309-319.
21. Reis M. C., S. D. T. Barros, E. R. Lachter, J. H. Pais da Silva and T.
Onfroy (2012), “Synthesis, characterization and catalytic activity of meso-
niobium phosphate in the oxidation of benzyl alcohols”, Catalysis Today, 192(1),
p. 117-122.
22. Thao N. T. and N. T. Nhu (2018), "Evaluation of catalytic activity of
MeOx/sepiolite in benzyl alcohol oxidation", Journal of Science: Advanced
Materials and Devices, 3(3), pp. 289-295.

30
23. Belzunce M. M. and J. Haber (1998), “Modification of Sepiolite by
Treatment with Fluorides: Structural and Textural Changes”, Clays and Clay
Minerals, 46, pp. 603-614.
24. Nguyen Tien Thao, Han Thi Phuong Nga, Nguyen Que Vo, Hong Dieu
Khanh Nguyen (2017), “Advanced oxidation of rhodamine B with hydrogen
peroxide over Zn-Cr layered double hydroxide catalysts”, Journal of Science:
Advance materials and devices, pp.317-325.
25. Arizaga G. C., K.G. Satyanarayana, and W. Fernando (2007), “Layered
hydroxide salts: Synthesis, properties and potential applications”, Solid State
Ionics, 178, pp. 1143-1162.
26. Chen F., J. Zhao and H. Hidaka (2003), “Highly selective deethylation of
rhodamine B: Adsorption and photooxidation pathways of the dye on the
TiO2SiO2 composite photocatalyst”, International Journal of Photoenergy, 5(4).
27. Yueying W., H. Bai, J. Zhou and C. Chen (2009), “Thermal and chemical
stability of Cu–Zn–Cr-LDHs prepared by accelerated carbonation”, Applied Clay
Science, 42(3), pp. 591-596.
28. He Z., C. Sun, Y. Ding and Z. Wang (2009), “Photocatalytic degradation
of rhodamine B by Bi2WO6 with electron accepting agent under microwave
irradiation: Mechanism and pathway”, Journal of Hazardous Materials, 162(2),
pp. 1477-1486.
29. Fu H., L. Zhang, W. Yao and Y. Zhu (2006), “Photocatalytic properties of
nanosized Bi2WO6 catalysts synthesized via a hydrothermal process”, Applied
Catalysis B: Environmental, 66(1), pp. 100-110.
30. Chen F. (2017), “Ionothermal synthesis of Fe3O4 magnetic nanoparticles
as efficient heterogeneous Fenton-like catalysts for degradation of organic
pollutants with H2O2”, Journal of Hazardous Materials, 322, pp. 152-162.
31. Abhilasha J. (2009), "A study of catalytic behaviour of aromatic additives
on the photo-Fenton degradation of phenol red", Journal of Chemical Sciences.

31
Appendices:
1. X-ray diffraction of synthesized CoOx/sepiolite catalysts

Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - TNK01-3Co


500

TN03-3Co

400

300
Lin (Cps)

d=12.027

200
d=10.066

d=4.287

100
d=3.170

d=2.602
d=3.737
d=7.943

d=4.461

d=2.550

d=2.436

d=2.303
d=9.215

d=2.401

d=1.835
0

5 10 20 30 40 50 60 70

2-Theta - Scale
File: NhuNCS TNK01-3Co.raw - Type: 2Th/Th locked - Start: 4.990 ° - End: 70.000 ° - Step: 0.030 ° - Step time: 0.3 s - Temp.: 25 °C (Room) - Time Started: 15 s - 2-Theta: 4.990 ° - Theta: 0.500 ° - Chi: 0.00 ° - Phi: 0.00 ° -
1) Left Angle: 5.740 ° - Right Angle: 9.430 ° - Left Int.: 40.0 Cps - Right Int.: 27.6 Cps - Obs. Max: 7.348 ° - d (Obs. Max): 12.020 - Max Int.: 207 Cps - Net Height: 172 Cps - FWHM: 0.698 ° - Chord Mid.: 7.342 ° - Int. Breadt
01-075-1597 (C) - Sepiolite - Mg8(OH)4Si12O30(H2O)12 - Y: 100.00 % - d x by: 1. - WL: 1.5406 - Orthorhombic - a 13.40000 - b 26.80000 - c 5.28000 - alpha 90.000 - beta 90.000 - gamma 90.000 - Primitive - Pncn (52) - 2
00-042-1467 (*) - Cobalt Oxide - Co3O4 - Y: 10.00 % - d x by: 1. - WL: 1.5406 - Cubic - a 8.08370 - b 8.08370 - c 8.08370 - alpha 90.000 - beta 90.000 - gamma 90.000 - Face-centered - Fd-3m (227) - 8 - 528.239 - I/Ic PDF

Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - TNK01-5Co


500

TN03-5Co

400

300
Lin (Cps)

d=11.930

200
d=2.548
d=4.280

100
d=4.472

d=2.433
d=3.199
d=3.741

d=2.263
d=2.824

d=1.514
d=1.544
d=1.650
d=1.717
d=1.819

5 10 20 30 40 50 60 70

2-Theta - Scale
File: NhuNCS TNK01-5Co.raw - Type: 2Th/Th locked - Start: 4.990 ° - End: 70.000 ° - Step: 0.030 ° - Step time: 0.3 s - Temp.: 25 °C (Room) - Time Started: 14 s - 2-Theta: 4.990 ° - Theta: 0.500 ° - Chi: 0.00 ° - Phi: 0.00 ° -
1) Left Angle: 5.800 ° - Right Angle: 9.310 ° - Left Int.: 39.4 Cps - Right Int.: 23.7 Cps - Obs. Max: 7.424 ° - d (Obs. Max): 11.898 - Max Int.: 222 Cps - Net Height: 190 Cps - FWHM: 0.659 ° - Chord Mid.: 7.454 ° - Int. Breadt
01-075-1597 (C) - Sepiolite - Mg8(OH)4Si12O30(H2O)12 - Y: 100.00 % - d x by: 1. - WL: 1.5406 - Orthorhombic - a 13.40000 - b 26.80000 - c 5.28000 - alpha 90.000 - beta 90.000 - gamma 90.000 - Primitive - Pncn (52) - 2
00-042-1467 (*) - Cobalt Oxide - Co3O4 - Y: 10.00 % - d x by: 1. - WL: 1.5406 - Cubic - a 8.08370 - b 8.08370 - c 8.08370 - alpha 90.000 - beta 90.000 - gamma 90.000 - Face-centered - Fd-3m (227) - 8 - 528.239 - I/Ic PDF

32
500
TN03-7Co
Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - TNK01-7Co

400

300
d=11.789
Lin (Cps)

200

100
d=4.287
d=10.035

d=2.552
d=4.472

d=2.428
d=3.318
d=3.174

d=2.252
d=3.725

d=1.740

d=1.542
0

5 10 20 30 40 50 60 70

2-Theta - Scale
File: NhuNCS TNK01-7Co.raw - Type: 2Th/Th locked - Start: 4.990 ° - End: 70.000 ° - Step: 0.030 ° - Step time: 0.3 s - Temp.: 25 °C (Room) - Time Started: 10 s - 2-Theta: 4.990 ° - Theta: 0.500 ° - Chi: 0.00 ° - Phi: 0.00 ° -
1) Left Angle: 6.220 ° - Right Angle: 9.520 ° - Left Int.: 37.2 Cps - Right Int.: 23.6 Cps - Obs. Max: 7.491 ° - d (Obs. Max): 11.792 - Max Int.: 235 Cps - Net Height: 203 Cps - FWHM: 0.580 ° - Chord Mid.: 7.464 ° - Int. Breadt
01-075-1597 (C) - Sepiolite - Mg8(OH)4Si12O30(H2O)12 - Y: 100.00 % - d x by: 1. - WL: 1.5406 - Orthorhombic - a 13.40000 - b 26.80000 - c 5.28000 - alpha 90.000 - beta 90.000 - gamma 90.000 - Primitive - Pncn (52) - 2
00-042-1467 (*) - Cobalt Oxide - Co3O4 - Y: 10.00 % - d x by: 1. - WL: 1.5406 - Cubic - a 8.08370 - b 8.08370 - c 8.08370 - alpha 90.000 - beta 90.000 - gamma 90.000 - Face-centered - Fd-3m (227) - 8 - 528.239 - I/Ic PDF

2. Energy Disperse X-ray analysis of TN03-5Co sample

Element Weight % Atomic %


OK 7.19 12.27
Mg K 4.97 5.59
Al K 0.57 0.58
Si K 78.74 76.56
KK 4.46 3.12
Co K 4.07 1.88
Total 100.00 100.00

33