Synthesis and properties of Polypyrrole (PPy)-ZnO-ZnS composite:

Application as photocatalyst for drug and dye degradation from waste

water.

Name: Suzon Kumar Paul

Student at Dept. of Chemistry
SUST
Session: 2017-18

Department of Chemistry
Shahjalal University of Science & Technology, Sylhet-3114, Bangladesh

1
 Introduction

Conducting polymers : An organic based polymer that can act as a semiconductor or a

conductor. The most widely studied organic polymers are polyaniline
(PANI), Polypyrroles(PPy), polythiophenes, and polyphenylene. They
are conjugated, that is, they have π electron delocalization along
their polymer backbone, hence giving them unique optical and
electrical properties .

Polypyrrole(PPy) Polyaniline(PANI)
Goals of composite formation:
The polymer based composites are formed to increase-
 Solubility
 Conductivity
 Thermal stability
 Sensor activity
 Photocatalytic activity
 Rigidity
 Charging capability
 Photoconductivity
 Enhance antibacterial activity

3
 General consideration on
ZnO and ZnS

Zinc Oxide (ZnO) Zinc Sulfide (ZnS)

 A very well known semiconductor.
 Optimum Band gap 3.37 eV.
 Photocatalyst.
 Anti corrosive agent.
 Antifungal agent.
 A famous semiconductor.
 Optimum band gap 3.54 eV.
 Uses in drug delivery, ultra sensitive
diseases detector.
 Efficient photocatalyst.

4
 Objectives
The objectives of the research are:

 To synthesize PPy-ZnO-ZnS composites through insitu chemical oxidative

polymerization method.
 To observe possible incorporation of ZnO and ZnS in PPy in the PPy-ZnO-ZnS
composites.
 To identify the morphological behavior of PPy-ZnO-ZnS composites.
 To study the applications (Drug degradation property, Dye removal property) of PPy-
ZnO-ZnS composites.

5
 Synthesis procedure

Synthesis of ZnS :
Addition of Na2S solution dropwise
ZnCl2
solution
Stirring 15 min. separately
Milky white
ZnCl2 solution
product
Na2S
solution Centrifuge 20 min in test
tubes at 2000 rpm.

Drying the
ZnS particles product.
Collected
residue

Figure: Scheme for Synthesis of ZnS.

6
 *A. Batool, F. Kanwal, M. Imran, T. Jamil, S. A. Siddiqi, Synth. Met. 161, (2012) 2753.
Synthesis of PPy-ZnO-ZnS composite:
Dropwise addition
of pyrrole
FeCl3, ZnO and ZnS

Table: Synthesis composition of Pyrrole, ZnO and ZnS.

Amount Amount of Amount of
Wt% of ZnO ZnS
i) 1.5 hr. sonication Pyrrole (mg) (mg)
20 min. stirring
ii) Transfer in RBF (g)
15 mL H2O Mixed soln Dispersed soln
3 0.241 3.72 3.72
5 0.241 6.34 6.34
7 0.241 9.06 9.06
Stirring for 3 hr. 10 0.241 13.38 13.38
at 1000 rpm.

Drying in oven Washing with excess

at 60 °C for 4 hr. dist.water
followed by ethanol
Dry product
wet product Filtered composite

Figure: Schematic representation of synthesis of PPy-ZnO-ZnS composites.

7
 Characterization

Characterization of ZnS: FTIR spectra exhibited the characteristic peaks at 630 cm-1 , 3431 cm-1 and 1624 cm-1 .
Also, UV-Visible absortion at 314 nm which confirmed the formation of ZnS.
ZnS
0.8
(a) (b)
100
0.6
%T

75 314 nm
630

Abs.
0.4
50
1624

25 0.2

3431
-0
3750 3000 2250 1500 750
1/cm
0.0
250 300 350 400 450 500
ZnS cm -1
Wavelength(nm)

  Figure: (a) FTIR and (b) UV-Visible spectra of ZnS

 
 

  8
 FTIR characterization of PPy-ZnO-ZnS composites.

100
100
%T

1446.61
1485.19
%T

680.87

669.30
3433.29
3471.87

1309.67

1298.09
90

781.17
90

918.12
921.97
1045.42
1193.94

1170.79
1554.63

1544.98

1037.70
80
80

70

70
60
3750 3000 2250 1500 750 3750 3000 2250 1500 750
PPy-ZnO-ZnS – 7 wt% 1/cm
cm-1
Polypyrrole 4
Polypyrrole (PPy)
1/cm
cm-1
.
 
 Table: FTIR peaks for synthesized PPy and PPy-ZnO-ZnS composites:
Sample N-H C=C C-C C–H =C-N C-H in plane Out of plane ZnO ,ZnS
  3471 PPy
stretchin stretching stretching in-plane stretching bending ring stretching
 
 
g deformatio deformation v(N-H)
(cm ) -1
(cm ) -1
(cm ) -1
n (cm )-1
(cm ) -1
(cm ) -1
(cm-1) (cm-1) 3448 3 wt%
 

Transmittance (%)
PPy 3471 1554 1485 1309 1193 1045 921   3456 5 wt%
                 
ZnO               876
3433 7 wt%
                 
ZnS               630
3444 10 wt%
                 
3 wt% 3448 1543 1458 1298 1172 1037 912 779, 671
3500 3000 2500 2000 1500 1000 500
                 
Wavenumber (1/cm)
5 wt% 3456 1546 1475 1294 1178 1037 914 785, 671
                  All basic vibrational frequencies of
7 wt% 3433 1544 1446 1298 1170 1037 918 781, 669 PPy were showed significant shifting
                  in lower wavenumbers which means
10 wt% 3444 1541 1456 1298 1172 1037 910 779, 669 that the effective interaction of ZnO
  and ZnS in PPy matrix.

10
 UV-Visible spectroscopy characterization of PPy-ZnO-ZnS composites.
π-π* transition wavelength shifted from 273 nm to around 292-298 nm.
DMF used as solvent. Peak intensities of composites lower than PPy.
Which means little solubility of composites than PPy alone as similar amount of samples and solvent used.

PPy
3 wt%
5 wt%
7 wt% Table : UV-Visible absorption data for PPy and PPy-ZnO-ZnS composites.
10 wt%
Samples Λmax (nm)
Absorbance

PPy 273
3 wt% 292
5 wt% 296
7 wt% 298
10 wt% 296

300 400 500 600

Wavelength (nm)

Figure : UV-Visible absorption spectra of PPy and PPy-ZnO-ZnS composites.

11
 FESEM and EDX measurements of PPy-ZnO-ZnS composites:
SEM image of composites demonstrates spherical structure and the surface is found smooth and regular.
Elemental composition measurements of PPy-ZnO-ZnS by EDX confirms the presence of all expected
elements.

Table: Elemental composition of PPy-ZnO-ZnS composites.

 
Elements Percent contribution, %
C 60.52
N 28.56
O 10.79
S 0.01
Zn 0.04
Total 100

Fig. SEM image of the synthesized PPy-ZnO-ZnS composites.

Figure : Energy dispersive X-ray spectra of PPy-ZnO-ZnS composites.

 Applications
Photocatalytic experiment using these composites:* D. A. Reddy, S. Lee, J. Choi, S. Park, R. Ma, H. Yang, T. K. Kim, Appl. Surf. Sci. 341, (2015) 175.

100 mL analytes, Sun

10 mg photocatalyst

Sample collection

(about 5 mL)

Sample collection in
stirring 1 hr in
magnetic stirrer specific time interval
magnetic stirrer dark.
(In sunlight)
(in dark)
Collected
samples

UV- measurement of Centrifuge

samples
15 min.

Figure: Scheme for Photocatalytic degradation.

13
 Dye degradation using PPy-ZnO-ZnS composites as photocatalyst:
Composites performed better than PPy alone . Among the composites 7 wt% performed best
which removes 92% dye in 570 minutes whereas PPy alone 72% in the same time interval.
100
PPy
PPy
1.00
Blank 80 3wt%
7wt%
Dark 1.00
Blank
5wt%
30 min Dark 7wt%
0.75 60 min 30min
60min 60 10wt%

% of dye removal
120 min 0.75
120min
Absorbance

180 min
180min
240 min

Absorbance
240min
0.50 300 min 300min
360 min 0.50 360min 40
420 min 420min
480 min 480min
0.25 570min
570 min
0.25 20

0.00
500 600 700 800 0.00
500 600 700 800 0
Wavelength (nm)
Figure: Dye (MB) degradation. Wavelength (nm)
0 100 200 300 400 500 600
Time (min.)
Figure: Dye degradation efficiency measurements of PPy and PPy-ZnO-ZnS composites.

14
 Drug degradation using PPy-ZnO-ZnS composites as photocatalyst:
Here also composites performed better than PPy alone and also 7 wt% performed best which
removes 94% drug (MNZ) in 420 minutes whereas PPy alone 82% in the same time interval.

0.4 0.4
PPy
7wt% 100
Blank
Dark Blank
Dark PPy
30min
0.3 0.3 30min 3wt%
60min
90min 60min 75 5wt%
120min 90min 7wt%
120min 10wt%
Absorbance

Absorbance
180min

% of drug removal
0.2 240min 180min
0.2 240min
300min 50
360min 300min
420min 360min
420min
0.1
0.1 25

0.0
300 400 500 0.0 0
300 400 500
Wavelength (nm) 0 100 200 300 400 500
Wavelength (nm)
Time (min.)
Figure: Drug, Metronidazole (MNZ) degradation.

Figure: Drug degradation efficiency measurements of PPy and PPy-ZnO-ZnS composites.

15
 Conclusion
 PPy-ZnO-ZnS (3-10 wt%) composites were synthesized via insitu chemical oxidative polymerization by
varying the amount of ZnO-ZnS keeping PPy amount fixed.
 The synthesized composites were characterized by FTIR, UV-Visible spectroscopy, and FESEM/EDX
measurements.
 All spectral data confirmed the significant incorporation of ZnO-ZnS in PPy-ZnO-ZnS composites.
 Morphological behavior and elemental composition measured by integrated FESEM/EDX system.
 Synthesized composites were applied as photocatalyst in Dye (MB) and Drug (MNZ) in direct solar
irradiation where all the composites were performed better than PPy alone.

16
 I solemnly express my Gratitude to
 My Supervisor: Prof. Dr. Mohammad Mizanur Rahman Khan.
 My all Respected Teachers of Department of Chemistry, SUST