Вы находитесь на странице: 1из 14




Synopsis submitted to




Taiba Naseem
Reg. No. 2009-Gmdg -5085

Session: 2017-19

Department of Chemistry
Faculty of Science

Synopsis Submitted for M.Phil. Degree in Chemistry



Name of Student: Taiba Naseem

Registration No: 2009-Gmdg -5085
Date of Admission: 09-10-2017
Date of Initiation: 26-10-2017
Probable duration: 02 Years


Supervisor: Dr. Zain-ul-Abdin ...…………………….……

Co-supervisor: Dr. Salah-ud-Din …………………………....

Department of Chemistry

Dean Director
Faculty of Sciences Advanced Studies & Research
1. Introduction

Water is human life's most valuable asset, and drinking water is a basic human

requirement. However, we are far from global requirements; this issue will grow over time

(Hillie & Hlophe, 2007). The demand of pure water is rising as water quality, population growth,

and global climate change deteriorate (Tchobanoglous et al., 1991).

Wastewater is a waste product containing pollutants such as microorganisms, organic

materials, soluble inorganic compounds and toxic heavy metals from municipal, industrial and

agricultural activities. These pollutants change cleanwater's physical, chemical and biological

properties (Adams et al., 2006). It can be classified by waste sources in municipal and industrial

wastewater, where municipal waste sources are homes and commercial activities; often

containing feces and urine, but industrial wastewater sources are industrial and agricultural

activities; containing in addition to household compositions; organic and inorganic chemicals

(Adams et al., 2006). Wastewater contains high concentrations of microorganisms like viruses,

bacteria, protozoa, and toxic chemicals like trace elements, heavy metals, and radionuclides.

Thus, wastewater is one of the major sources of waterborne diseases, some of which are fatal,

such as typhoid and cholera. The polluted water caused the death of about 1.6 million people

under 5 in 2004 (AL-Thabaiti et al., 2008).

Wastewater treatment is one of the most important issues today due to its toxic effects on

humans, agriculture and animals from pathogens and hazardous wastewater pollution. Treatment

of wastewater should be considered at the personal and governmental level of investigations to

protect the environment from pollution. Wastewater treatment can involve physical, chemical

and biological processes to clear water from various contaminants (Bartram, 1996: Bitton, 2005).

Wastewater treatment is one of today's most important issues due to its toxic effects of

pathogens and hazardous wastewater pollution on humans, agriculture, and animals. Wastewater

treatment should be considered for pollution protection at the personal and governmental level of

investigations. Treating wastewater can involve physical, chemical and biological processes.

Pollutant removal by environmentally friendly, efficient methods is crucial

(Mendonça2019) Different strategies such as solvent extraction, ultrafiltration, wastewater

evaporation and reverse osmosis are used for treating wastewater. These techniques however

remove impurities from water without making them harmless (Anjaneyulu, 2018). Full

decomposition, whether chemically or photochemically, may be easily achieved with oxidation

(Forgacs et al., 2004).

Graphene oxide (GO) or reduced graphene oxide (rGO) indicates significant removal

ability in the recovery of heavy metal ions (Cd2 +, Pd2 +, Hg2 +, Cr6 +, As3 +, etc.). Due to the

positive charge, these ions alternate with oxygen and negative functional groups on the GO to

improve cation capture. Tan et al. (2015) reported the successful adsorption of Cu2 +, Cd2 + and

Ni2 + on GO / PVA films. The balance is reached in a short time and the membrane is reused

more than six times. Zhang et al. (2016) studies a composite membrane for nanofiltration of GO

for use in the low layer (LbL) method of Torlon support. The film was removed with over 95%

of Ni2 +, Pd2 +, Zn2 + in an aqueous system and exhibited long-term stability in the 150-hour NF


The use of ZnO for water and wastewater disinfection shows promise. It is beneficial to

address the constraints of conventional water treatment methods, most of which are DBP

formation. The physical chemical properties of ZnO contribute to the antibacterial activity.

Nanoscale materials can exhibit different improved properties compared to what they show on

the microscale, mainly due to the increased surface area, thereby increasing the rate of chemical

reactions. Because of the small size compared to large scale, nanoparticles can enter the bacterial

cell wall, eventually leading to cell death. In addition, reactive oxygen species (ROS) can be

produced on the surface of nanomaterials, attacking the bacterial cell wall. As the surface grows,

antimicrobial activity increases. Another feature is the presence of surface disorders, such as

edges and angles, leading to the abrasive action of ZnO in bacterial cell wall destruction

(Stoimenov, et al., 2002).

Despite its brief period of growth, GO-metal oxide nanocomposites have drawn much

interest from researchers owing to their successful environmental and energy-related

implementations. GO / Reduced Graphene Oxide (RGO) composites have been effectively

implemented to handle distinct kinds of organic dyes and heavy metal particles (Al Nafiey, et al.,

2017). Because of its distinctive characteristics such as elevated specific surface area and

chemical stability, researchers have paid much attention to RGO. The distinctive characteristics

of RGO coupled with other nanomaterials have been used for various prospective apps such as

energy storage, antibacterial, electrochemical detector and biosensors, gas sensors, etc.

(Karuppiah, et al., 2015). Due to their increased efficiency in removing toxic heavy metal ions

and other pollutants present in water, metal and metal-oxide functionalized graphene surfaces

have received great interest. RGO nanocomposites and metal oxides have been used to

successfully remove Hg (II) and disinfect wastewater (Lee, et al., 2015).

Photocatalyst layout using low-cost and earth-abundant fabrics with simple recyclability

is an important and enduring feature for practical application solar energy conversion Xu, et al.,

2017). Rapid development of technologies and materials to purify water from pollutants over a

long period of time. One of the main goals is to develop treatment methods that do not have a

great impact on the environment and are cheap. Photocatalysis can satisfy this application,

offering an alternative that is comparatively simple and low cost. Usually, photocatalysts are

photo-stable and non-toxic semiconductors capable of absorbing ultraviolet and visible light.

2. Literature Review

The removal of commercial nanoparticles by water treatment methods has not been fully

investigated. Zhang, et al., 2008) tested commercial metal oxide nanoparticles, Fe2O3, ZnO, NiO

and SiO2 to test their properties, dispersibility and stability in water, and to remove them by

water treatment. In addition to silica, nanoparticles are rapidly combined in tap water and are not

destroyed by ultrasonic or chemical dispersants. The amount of alcoholate material removed is

less than 80% of the total mass of the nanoparticles. It has been reported that the behavior of

metal oxide nanoparticles in water depends on their physical properties and their interaction with

other components in the water.

The organic dye is in the form of ions (cationic or anionic) in water, and GO / rGO is

negatively charged, so it is considered that the adsorption of GO / rGO is determined by

electrostatic interaction. However, other interactions, such as H-bonding and accumulation (Al

Nafiey, et al., 2017), did not exclude the adsorption of organic dyes in GO/rGO-based

composites. On the other hand, the negatively charged graphene oxide (GO) has several oxygen-

containing groups such as OH and COOH. Therefore, it has high adsorption capacity for basic

compounds and metal cations. On the other hand, reduced graphene oxide (rGO) has a

hydrophobic surface, which leads to high adsorption capacity of the dye by intense packing and

hydrophobic interaction (Acharya, et al., 2018). Increased adsorption capacity can be achieved

by changing GO or RGO with metal oxides or organic materials.

The great dispersibility of GO in water has been studied well, while the dispersibility of

RGO in water has attracted little attention in the literature. Based on the above considerations,

we have improved the dispersibility of the less dispersible reduced graphene oxide in dispersible

RGO by functionalizing metals and metal oxides on the surface of graphene sheets (Dubey, et

al., 2015). Our research showed that the dispersibility improved with the metal and metal oxide

nanoparticle coatings on the RGO surface. In this study, the water contact angle and water

content of GO, RGO and RGO composites are correlated.

Single (Ag, Cu2O and Fe3O4) and bimetallic (Ag-Cu2O, Ag-Fe3O4 and Cu2O-Fe3O4)

nanoparticles-RGO composites were synthesized by hydrothermal method. Sodium borohydride

and sodium sorbate are used as reducing agents and stabilizers. We evaluated the potential of

synthetic GMO composites to remove impurities from water. Since metal nanoparticles are

known to have excellent catalytic properties, the RGO complex has also been studied to reduce

4-nitrophenol (4-NP) to 4-aminophenol (4-AP). In addition, the adsorption capacity of As (V)

materials in intermittent isotherm studies was investigated and compared with commercially

available powdered carbon activated carbon (PAC).

There are several possible processing techniques that use different available zinc-

containing materials as raw materials. The synthesis of ZnO can also be a large number of

industrial processes (pyrometallurgy and hydrometallurgical synthesis) or laboratory / test plant

scale processes. The main technical differences between the different processing methods relate

to zinc precursors, process conditions, unit operations and production scale (Moezzi, et al.,


Various laboratory techniques for ZnO synthesis have been reported, including

precipitation, hydrothermal, solvothermal and sol-gel methods (Kolodziejczak, et al., 2014). The

application of ZnO nanoparticles as antibacterial agents depends on process control of particle

size, particle size distribution, shape, surface area and distribution properties (Djurisic, et al.,

2012). However, it may be difficult to control all of the variables in ZnO synthesis, and different

methods and process variables will result in different nanoparticle shapes and sizes (Espitia, et

al., 2012).

In El Saeed et al. (El Saeed, et al., 2015) method for synthesizing ZnO by direct

deposition with Zn (NO3)2·6H2O and (NH4)2CO3 at 40AC. The precipitate was calcined at 550

AC for 2 hours. Transmission electron microscopy (TEM) analysis providing nanoparticle

morphology revealed that the ZnO nanoparticles were non-agglomerated with an average particle

size of 20 nm.

Motshekga, et al., 2015) has developed a nanocomposite in which silver and ZnO

nanoparticles supported on bentonite are synthesized and distributed on chitosan. Gram-negative

E. coli and Gram-positive E. faecalis bacteria were used to test antibacterial activity. Both silver-

containing and ZnO-containing bentonite-chitosan nanocomposites showed good antibacterial

activity. However, Silver ZnO bentonite chitosan nanocomposites exhibit the best antibacterial

activity with a removal efficiency of at least 78%. It has also been suggested that the

antibacterial activity of nanocomposites is also affected by the concentration of bacteria.

Adams et al. reported that ZnO nanoparticles have antibacterial activity on B. subtilis and

E. coli, the study reported that antibacterial activity is not affected by different particle sizes and

its activity is the same under dark and light activity on B. subtilis bacteria, but more activity

under light on E. coli (Adams, Lyon & Alvarez, 2006). Li et al. reported that the toxicity of ZnO

nanoparticles to E. coli increases with decreasing pH (Li2013). Premanathan, et al., reported that

the bacterial activity of ZnO NPs on Gram-positive bacteria such as S. aureus is more effective

than on Gram-negative bacteria such as E. coli (Premanathan, 2011). It reported that the bacterial

activity of ZnO nanoparticles stabilized with tetraoctylammonium bromide (TOAB) surfactant is

higher than that without surface activity against E. coli, S. aureus and B. subtilis (Qasem, 2013)

Sondos et al. reported that ZnO nanoparticles show good antibacterial agents. All activity against

E. coli under sunlight, while the antibacterial activity of ZnO nanoparticles increased as the

anthocyanin dye was used as a sensitizer for (Ateeq, 2012).

3. Justification

Both Graphene Oxide and Zinc Oxide are excellent adsorbent and plays an important role

in wastewater treatment. No research recorded on Zinc Oxide, Graphene, Graphene oxide,

reduced Graphene Oxide and their composites in AJK. Efficient manners to purify water using

graphene and its composites are required to explore. Moreover, it is a cost-effective adsorbent

that can play a vital role in a country's economy for water purification. It will also offer insights

into further study requirements and this technique will be used further to eliminate heavy metals

in water. The composite can be re-use or regenerated.

4. Aims and Objectives

The main objective of this study is wastewater disinfection using environmentally friendly and

inexpensive Graphene Oxide Zinc Oxide nanocomposites monitored by bacterial wastewater

indicators. Other specific goals include:

1. Preparation of Graphene Oxide from graphite powder by improved Hummers method

2. Preparation of reduced Graphene Oxide and Zinc Oxide nanocomposites

3. Characterization of reduced Graphene Oxide Zinc Oxide nanocomposites by UVm SEM,

XRD and FT-IT to determine the structural properties of nanocomposite

4. The antimicrobial activity of the synthesized rGO- ZnO will be performed against the

selected bacterial species.

5. Reduction of 4 nitrophenol by using reduce Graphene Oxide Zinc Oxide nanocomposite.

6. Photocatalytic activities of the synthesized rGO- ZnO nanocomposite.

5. Methodology

Graphene will be Synthesized from graphite using modified Hummers method then
synthesis of graphene oxide, reduced graphene oxide by reduction process will be carried out by
treating graphene oxide with some reducing agents such as sodiumborohydrate or some other
reducing agent. For the analysis of prepared GO, we will used different characterization
techniques such as UV, FTIR, SEM and XRD.

In the literature, different methods have been used for the synthesis of rGO-ZnO
nanocomposites. In this thesis, rGO-ZnO nanocomposite will prepared by simultaneous chemical
reduction of GO and Zn(NO3)2.6H2O with sodium borohydride. Typically, to 5 mL of 1 mg/mL
GO suspension in DIW, will added 50 mg of Zn(NO3)2.6H2O.

The resulting mixture will be sonicated for ten minutes. Then 5 mL of 0.1 M sodium borohydride
aqueous solution will add to the mixture at room temperature. A light purple precipitate will be
formed spontaneously. For separation centrifugation and washing will be performed repeatedly
with water.

Different characterization techniques (SEM, XRD and FTIR) will be used to analyze
rGO/ZnO nanocomposites. By using these nanocomposites, highly efficient reduction of 4-
nitrophenol into 4-amino phenol will be carried out. The progress of the reaction will be
monitored by using ultraviolet-visible spectroscopy. Antimicrobial activity of synthesized
composites will be performed.


Abou El-Nour, K. M., Eftaiha, A., Al-Warthan, A., & Ammar, R. A. (2010). Synthesis and
applications of silver nanoparticles. Arabian Journal of Chemistry, 3(3), 135-140.

Adams, L. K., Lyon, D. Y., & Alvarez, P. J. (2006). Comparative eco-toxicity of nanoscale
TiO2, SiO2, and ZnO water suspensions. Water Research, 40(19), 3527-3532.

AL-Thabaiti, S. A., Al-Nowaiser, F. M., Obaid, A. Y., Al-Youbi, A. O., & Khan, Z. (2008).
Formation and characterization of surfactant stabilized silver nanoparticles: A kinetic
study. Journal of Colloid and Interface Science, 67(2), 230-237.

Al Nafiey, A., Addad, A., Sieber, B., Chastanet, G., Barras, A., Szunerits, S., & Boukherroub, R.
(2017). Reduced graphene oxide decorated with Co3O4 nanoparticles (rGO-Co3O4)
nanocomposite: A reusable catalyst for highly efficient reduction of 4-nitrophenol, and
Cr(VI) and dye removal from aqueous solutions. Chemical Engineering Journal,
322(15), 375-384.

Anjaneyulu, R. B., Mohan, B. S., Naidu, G. P., & Muralikrishna, R. (2018). Visible light
enhanced photocatalytic degradation of methylene blue by ternary nanocomposite,
MoO3/Fe2O3/rGO. Journal of Asian Ceramic Societies, 6(3), 183-195.

Acharya, D., Singh, J. K., Adhikari, M., Gautam, S., Pandey, P., & Dayal, V. (2018). Association
of water handling and child feeding practice with childhood diarrhoea in rural community
of Southern Nepal. Journal of Infection and Public Health, 11(1), 69-74.

Ateeq, S. O.Abed-Alhadi (2012). Water Disinfection by Photo-Degradation of Microorganisms

Using Natural Dye-Sensitized ZnO Catalyst. 1. (Unpublished master’s thesis). An-Najah
National University.

Barndõk, H., Hermosilla, D., Han, C., Dionysiou, D. D., Negro, C., & Blanco, Á. (2016).
Degradation of 1,4-dioxane from industrial wastewater by solar photocatalysis using
immobilized NF-TiO 2 composite with monodisperse TiO 2 nanoparticles. Applied
Catalysis B: Environmental, 180, 44-52

Bartram, J. (1996). Water quality monitoring: a practical guide to the design and implementation
of freshwater quality studies and monitoring programmes. Taylor & Francis.

Bitton, G. (2005). Wastewater microbiology. Wiley-Liss.

Djurišić, A. B., Chen, X., Leung, Y. H., & Man Ching Ng, A. (2012). ZnO nanostructures:
growth, properties and applications. Journal of Materials Chemistry, 22, 6526-6535.

Dubey, S. P., Nguyen, T. T., Kwon, Y.-N., & Lee, C. (2015). Synthesis and characterization of
metal-doped reduced graphene oxide composites, and their application in removal of
Escherichia coli, arsenic and 4-nitrophenol. Journal of Industrial and Engineering
Chemistry, 29, 282-288.

El Saeed, A. M., El-Fattah, M. A., & Azzam, A. M. (2015, 10). Synthesis of ZnO nanoparticles
and studying its influence on the antimicrobial, anticorrosion and mechanical behavior of
polyurethane composite for surface coating. Dyes and Pigments, 121, 282-289.

Espitia, P. J., Soares, N. d., Coimbra, J. S., Andrade, N. J., Cruz, R. S., & Medeiros, E. A.
(2012). Zinc Oxide Nanoparticles: Synthesis, Antimicrobial Activity and Food Packaging
Applications. Food and Bioprocess Technology, 5, 1447-1464.

Forgacs, E., Cserháti, T., & Oros, G. (2004). Removal of synthetic dyes from wastewaters: a
review. Environment International, 30, 953-971.

Hillie, T., & Hlophe, M. (2007). Nanotechnology and the challenge of clean water. Nature
Nanotechnology, 2, 663.

Karuppiah, C., Muthupandi, K., Chen, S. M., Ali, M. A., Palanisamy, S., Rajan, A., … Lou, B. S.
(2015). Green synthesized silver nanoparticles decorated on reduced graphene oxide for
enhanced electrochemical sensing of nitrobenzene in waste water samples. Royal Society
of Chemistry Advances, 5(39), 31139–31146.

Kolodziejczak-Radzimska, A., & T. Jesionowski, T. (2014). Zinc oxide e from synthesis to

application: a review. Materials, 7, 2833-2881.

Li, M., Lin, D., & Zhu, L. (2013). Effects of water chemistry on the dissolution of ZnO
nanoparticles and their toxicity to Escherichia coli. Environmental Pollution, 173, 97-

Mendonça, V. R., Mourão, H. A., Malagutti, A. R., & Ribeiro, C. (2019). The Role of the
Relative Dye/Photocatalyst Concentration in TiO2 Assisted Photodegradation Process.
Photochem Photobiol, 90, 66-72. doi:10.1111/php.12175

Moezzi, A., McDonagh, A. M., & Cortie, M. B. (2012, 3). Zinc oxide particles: Synthesis,
properties and applications. Chemical Engineering Journal, 185-186, 1-22.

Motshekga, S. C., Ray, S. S., Onyango, M. S., & Momba, M. N. (2015). Preparation and
antibacterial activity of chitosan-based nanocomposites containing bentonite-supported
silver and zinc oxide nanoparticles for water disinfection. Applied Clay Science, 114,
330-339. From

Premanathan, M., Karthikeyan, K., Jeyasubramanian, K., & Manivannan, G. (2011). Selective
toxicity of ZnO nanoparticles toward Gram-positive bacteria and cancer cells by
apoptosis through lipid peroxidation. Nanomedicine: Nanotechnology, Biology and
Medicine, 7, 184-192.

Qasem, A. (2013). Synthesis of zinc oxide and cobalt oxide nanoparticles in surfactant /
antibiotics shell and investigating their anti-bacterial activities. (Unpublished master’s
thesis). An-Najah National University.

Stoimenov, P. K., Klinger, R. L., Marchin, G. L., & Klabunde, K. J. (2002). Metal Oxide
Nanoparticles as Bactericidal Agents. Langmuir, 18, 6679-6686.

Tan, P., Sun, J., Hu, Y., Fang, Z., Bi, Q., Chen, Y., & Cheng, J. (2015). Adsorption of Cu 2+,
Cd2+ and Ni2+ from aqueous single metal solutions on graphene oxide membranes.
Journal of Hazardous Materials, 297, 251-260.

Tchobanoglous, G., Burton, F. L., Metcalf, & Eddy. (1991). Wastewater engineering: Treatment,
disposal, and reuse.

Yang, M., Zhang, N., Wang, Y., & Xu, Y. (2017). Metal-free , robust , and regenerable 3D
graphene – organics aerogel with high and stable photosensitization efficiency. Journal of
Catalysis, 346, 21–29.

Zhang, Y., Zhang, S., Gao, J., & Chung, T.-S. (2016). Layer-by-layer construction of graphene
oxide (GO) framework composite membranes for highly efficient heavy metal removal.
Journal of Membrane Science, 515, 230-237.

Zhang, Y., Chen, Y., Westerhoff, P., Hristovski, K., & Crittenden, J. C. (2008). Stability of
commercial metal oxide nanoparticles in water. Water Research, 42, 2204-2212.