KIT 357 Industrial Practical

Industrial Chemistry
1st Semester of Academic Year
2013/2014

Number of Experiment

Experiment 3

Title of the Experiment : Chitosan Stabilized Cu Catalysts for

the Reduction of p- nitrophenol
Lecturers Name
Bakar.

Prepared by
(112808)

Dr. Noor Hana Hanif Bt. Abu

:

Mizan Sulastri Binti Mawardi

Moi Wei Yun (113773)

Date of the Experiment

16th December 2013

Objective
To prepare chitosan stabilized Cu colloidal catalysts via chemical reduction
technique and to investigate its activity for the reduction of p-nitrophenol .
Introduction
Catalysts play a significant role in numerous industrial process. It has been applied
not only for the synthesis of fine chemicals and hydrogen generation for the
production of energy but also to address environmental purposes. In short , catalyst
are available in practically every aspect of our lives. Hence the synthesis of
catalysts has develop over many years to meet the requirements of a particular era.
Usually, these catalyst have been synthesized with the intention of improving the
reactivity or selectivity of a catalytic reaction , employing greener catalysts and
enhancing its reusability . To date, nanocatalysts has seemed to be able to these
requirements .
Nanocatalysts are materials in which at least one of the components is in the
nanosize range that is, ranging from 1 100 nm. This range of materials has shown
to exhibit properties that differ from their bulk materials For example , they exhibit
unique electronic properties. As such , they have been applied in various fields,
among them as heterogeneous and homogenous catalysis.
As homogeneous catalysis, these materials are generally referred to as colloidal
catalysis. Here, the metal nanoparticles are synthesized from metal salt using a
reducing agent and are stabilized by a stabilizer in the form of a surfactant or
polymer. Depending on the type of stabilizer and its concentration, the morphology
of the nanoparticles in terms or both size and shape can be tailored to suit a
reaction. Generally , the use of stabilizer is advantageous as it can control the
growth of the nanoparticles considering smaller sized nanoparticles can lead to a
higher surface area of the active phase available for a catalytic reaction in terms of
selectivity. Although in comparison to heterogeneous catalysis, enhanced activity
and selectivity can usually be achieved when using colloidal catalysis, this formof
catalysis can be disadvantages when high concentrations of the stabilizer is
employed.
Chitosan is a linear polysaccharide composed of randomly distributed -(1-4)linked D-glucosamine and N-acetyl-D-glucosamine. It is made by treating shrimp
and other crustacean shells with the alkali sodium hydroxide. Chitosan has a
number of commercial and possible biomedical uses. It can be used in agriculture as
a seed treatment and biopesticide, helping plants to fight off fungal infections. In
winemaking it can be used as a fining agent, also helping to prevent spoilage. In

industry, it can be used in a self-healing polyurethane paint coating. In medicine, it

may be useful in bandages to reduce bleeding and as an antibacterial agent; it can
also be used to help deliver drugs through the skin.

Experimental Method
PART 1: PREPARATION OF CHITOSAN STABILIZED COPPER (Chi-Cu) catalyst
Chemicals :

1.5 % v/v chitosan medium MW stock solution in acetic acid

0.02 M Cupric acetatesolution.
0.1 M Potassium borohydride solution
Methanol
0.04 M Chitosan solution

Apparatus

Volumetric flasks (10 ml, 100 ml, 250 ml)

Sample vials
Magnetic bar
Magnetic stirrer
Graduated pipette (1 ml, 5 ml)

Procedure

Pipette chitosan solution into a sample vial and diluted with the addition of
methanol.
Add cupric acetate into the mixture with vigorous stirring for 5 mins.
Add chilled potassium borohydride dropwise to reduce the copper ions. The
solution changes to brown color indicate the formation of copper
nanoparticles.
Take the UV spectra for each prepared sample

Table 1 : Sample compositions

Ratio Cu : Chi

Chitosan (ml)

5:1
1:2
1: 4

0.1
1
2

CuCOOCH3
(ml)
1
1
1

Methanol (ml)

KBH4 (ml)

2.9
2
1

1
1
1

1:6

PART 2: CATALYTIC REDUCTION OF p-NITROPHENOL

Chemicals:

Potassium Borohydride

4.66

102

M p-nitro phenol

Apparatus:

Graduated pipette
Micro pipette
Sample vials
Magnetic stirrer
Magnetic bar
Timer

Instrument:
Type U-2000 spectrophotometer, the settings of the UV vis spectrophotometer are
Mode: wavelength scan
Wavelength: 200-500 nm
Absorbance range: 0-1 Abs
Procedure:
The effect of chitosan to copper ratios
Carefully weigh 25.0 mg of KBH4 in a sample vial and dissolve with 25 ml
distilled water.
Add 100 micro liter catalyst into theKBH4 solution
The reaction starts once 20 micro liter of p-nitro phenol was introduced into
the solution
Record the absorbance of the solution at interval time using a UV-vis
spectrophotometer. Obtain at least 5 readings during which absorbance
decreases.

Repeat steps 6.1.1 to 6.1.4 for catalyst prepared at different chitosan to

copper ratio

The effect of catalyst loading

The as synthesized chitosan stabilized copper catalyst at a ratio of 1 : 4 is used
throughout the PART 2 experiment section 6.2 ,
Repeat the procedure at section 6.1.1
Ad catalyst into the solution according to the stipulated volume
Repeat procedures at section 6.1.3 and 6.1.4

Results and Discussion

PART 1: PREPARATION OF CHITOSAN STABILIZED COPPER (Chi-Cu) CATALYST
Wavelength
(nm)
500
480
460
440
420
400
380
360
340
320
300
280
260
240
220
200

Ratio 5 : 1
1.948
1.936
1.888
1.828
1.724
1.564
1.378
1.457
1.076
1.147
1.213
1.242
1.344
1.412
1.203
0.769

Absorbance
Ratio 1 : 2
Ratio 1 : 4
0.853
0.610
1.028
0.738
1.224
0.886
1.408
1.048
1.509
1.201
1.444
1.274
1.282
1.235
1.364
1.348
0.969
0.981
1.039
1.054
1.101
1.118
1.129
1.146
1.234
1.250
1.301
1.317
1.086
1.097
0.654
0.662

Ratio 1 : 6
0.580
0.698
0.826
0.979
1.131
1.226
1.210
1.334
0.979
1.054
1.118
1.146
1.251
1.316
1.097
0.661

Graph of absorbance vs wavelength

2.5
2

Absorbance Ratio 5 : 1

1.5
Absorbance

Absorbance Ratio 5 : 1
Absorbance Ratio 5 : 1

Absorbance Ratio 5 : 1

0.5
0
0

200

400

600

Wavelength (nm)

In the peak Cu : Chitosan for ratio 5 : 1 has the highest peak among the samples.
The peaks for wavelength is 490 nm. The peak decrease in ratio of 1:2 , followed by
ratio of 1:4 and 1: 6. For the Surface Plasmon Resonance, the appearance of peak at
certain wavelength shows the presence of nano-size particles. Thus ratio for 5 :1
has the most number nanoparticles.
Part 2 : The effect of chitosan to copper ratio
Ratio Cu : Chitosan of 5 : 1

Ratio Cu :
Chitosan
5:1

Time (min)

A max

A 500

0
2
4
6
8

1.024
1.025
1.035
1.045
1.032

0.532
0.667
0.615
0.652
0.617

Ac = Amax
A 500
0.492
0.358
0.42
0.393
0.415

ln Ac
-.0709
-1.027
-0.868
-0.934
-0.879

Graph of ln Ac vs time for Ac

Cu : Chitosan 5 : 1
0
-0.2 0

-0.4
ln Ac -0.6
-0.8

9
Linear ()

f(x) = - 0.08x - 0.45

R = 0.39

-1
-1.2
Time (min)

Ratio Cu :
Chitosan
1:2

Time (min)

A max

A 500

0
2
4
6
8

0.901
0.953
0.982
1.013
0.898

0.381
0.534
0.641
0.654
0.504

Ac = Amax
A 500
0.520
0.419
0.341
0.359
0.394

ln Ac
-0.654
-0.870
-1.076
-1.024
-0.931

Graph of ln Ac vs time for Ac

Cu : Chitosan 1 : 2
0
-0.2 0
1
2
3
4
5
-0.4
ln Ac -0.6
-0.8
-1 f(x) = - 0.01x - 0.85
-1.2 R = 0.06

Linear ()

Wavelength (nm)

Ratio Cu :
Chitosan
1:4

Time (min)

A max

A 500

0
2
4
6

0.735
0.804
0.845
0.879

0.297
0.454
0.576
0.578

Ac = Amax
A 500
0.438
0.350
0.269
0.301

ln Ac
-0.826
-1.049
-1.313
-1.200

0.869

0.540

0.329

-1.112

Graph of ln Ac vs time for Ac

Cu : Chitosan 1 : 4
0
0

-0.5

Linear ()

ln Ac
-1
-1.5

f(x) = - 0.04x - 0.96

R = 0.39
Wavelength (nm)

Ratio Cu :
Chitosan
1:6

Time (min)

A max

A 500

0
2
4
6
8

0.619
0.738
0.614
0.646
0.645

0.151
0.337
0.228
0.274
0.196

Ac = Amax
A 500
0.468
0.401
0.386
0.372
0.449

ln Ac
-0.759
-0.914
-0.952
-0.989
-0.800

Graph of ln Ac vs time for Ac

Cu : Chitosan 1 : 6
0
-0.2 0
1
2
3
4
5
-0.4
ln Ac -0.6
-0.8
-1 f(x) = - 0.01x - 0.85
-1.2 R = 0.06

Linear ()

Wavelength (nm)

The amount of copper was fixed while the amount of chitosan increases. As the
concentration of chitosan increases , the rate of reaction increases. The graph for
ratio 1 : 2 and 1 : 6 has the lower gradient compared to 1 : 4 and 5 : 1 . It has the
same values, which is -0.0078. This is because the copper particles aggregated into
bulk particles which do not facilitate the reaction rate with lower surface area. The
gradient for the graph ratio 1 : 4 and 5 : 1 is 0.0762 and -0.0361. The chitosan has
control the growth of nanoparticle with this ratio. In the graph ratio for Chitosan :
Copper , very small amount of chitosan is added. Thus reaction between chitosan is
lowest compared to other ratio. We can conclude that the higher the ratio of Cu :
Chitosan , the low formation of nanoparticles in the formation.

PART 3 : The effect of catalyst loading

Volume of
Cu :
Chitosan of
1:4
0 uL

50 uL

150 uL

Time (min)

Amax

A500

Ac = A max
A500

ln Ac

0
2
4
6
8
0
2
4
6
8
0
2
4
6
8

1.259
1.191
1.101
1.035
1.043
1.068
1.098
1.121
1.041
1.044
1.131
1.162
1.098
1.074
1.042

0.049
0.069
0.106
0.137
0.175
0.143
0.281
0.310
0.218
0.198
0.270
0.439
0.269
0.322
0.271

1.210
1.122
0.995
0.898
0.868
0.925
0.817
0.811
0.823
0.846
0.861
0.723
0.829
0.752
0.771

0.191
0.115
-0.005
-0.108
-0.142
-0.077
-0.202
-0.209
-0.195
-0.167
-0.149
-0.324
-0.188
-0.285
-0.260

Conclusion
For stabilized the chitosan : copper collodiol catalyst system, the UV-vis
spectrophotometer was used to identify it. The peak at 400 shows the highest and it
its proof that presence of nanoparticles which due to higher the peak. This was
observed through the varying the ratio of Cu : Chitosan and with different amount of
nanocatalyst at sample Cu:Chitosan ratio of 1:4
References
1. KIT357 Industrial Practical Manual, School of Chemical Sciences, Universiti
Sains Malaysia
2. Biological Properties of Chitosan Degreadation by Maria
3. www.google.com