SURFACE CHARACTERIZATION OF GREEN SYNTHESIZED ZINC OXIDE

NANOPARTICLES USING Hibiscus rosa-sinensis (GUMAMELA) AQUEOUS

EXTRACT EMBEDDED ON CARBON NANOTUBES FOR ADSORPTION OF
CHROMIUM WATER EFFLUENTS

PHYSICAL SCIENCE – TEAM

Franc Roger Glason P. Aguitez

Gracie Lou R. Lanting
Johann Clarence L. Pasamba
Proponents

Franz Kevin B. Manalo

Research Adviser

Prof. Emmanuel A. Florido

Research Supervisor

San Pablo City Science Integrated High School

Brgy. San Jose, San Pablo City

University of the Philippines Los Baños

Institute of Mathematical Sciences and Physics
Physics Division
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SURFACE CHARACTERIZATION OF GREEN SYNTHESIZED ZINC OXIDE

NANOPARTICLES USING Hibiscus rosa-sinensis (GUMAMELA) AQUEOUS
EXTRACT EMBEDDED ON CARBON NANOTUBES FOR ADSORPTION OF
CHROMIUM WATER EFFLUENTS

Franc Roger Glason P. Aguitez, Gracie Lou R. Lanting, Johann Clarence L. Pasamba
San Pablo City Science Integrated High School, San Pablo City, Laguna, Philippines

ABSTRACT

Chromium is a waste product of many industrial applications and can enter the water
supplies when chromium waste is dumped near public water supplies. The most common forms
are Chromium (0), Chromium (III), and Chromium (VI). At short-term exposure, Chromium (VI)
may already cause headaches, dizziness, and nausea. If exposure is above the maximum
contaminant level, chromium causes skin and stomach irritation or ulceration, dermatitis, damage
to liver, kidney circulation, nerve tissue damage, mood changes, impaired thinking, and death in
large doses. The study aimed to green synthesize zinc oxide nanoparticles (ZnO NPs) from
Hibiscus rosa-sinensis and embed it on carbon nanotubes (CNTs) using chemical evaporation
method. Also, it determined its adsorption capacity against hexavalent chromium. Varying ratios
(0:100, 75:25, 50:50, 25:75, 100:0) of 100mg CNT-ZnO NPs nanocomposites were evaluated on
1L simulated contaminated water containing 30ppm of chromium. The samples were then
analyzed using colorimetric method, UV-VIS spectrophotometry after 2 hours of contact time.
Results showed that the 75:25 and 50:50 ratio yielded the highest adsorption percentage of 30.32%
and 30.34%, comparable to the ratios 25:75 and 100:0 of 18.58% and 14.50% respectively, while
significantly different to the ratio 0:100 of 12.00% (p<0.05). This implied that zinc oxide
nanoparticles enhanced the adsorption capacity of carbon nanotubes.

Keywords: Chromium, green synthesis, zinc oxide nanoparticles, carbon nanotubes, adsorption
 iii

TABLE OF CONTENTS

Title Page…………………………………………………………….……………………………i
Abstract……………………….………………………………………………………………….ii
Table of Contents……………………………………………………………………………......iii
Introduction………………………………………………………………………………………1
Background of the Study……………………………………………………………………...1
Statement of Objectives……………………………………………………………………….2
Hypotheses…………………………………………………………………………………….3
Significance of the Study……………………………………………………………………...3
Scope and Limitations…………………………………………………………………………4
Definition of Terms………………………………………………………………………………4
Review of Related Literature………………………………………………………………….....5
Water pollution…………………………………………………………………………….......5
Heavy Metals………………………………………………………………………………….6
Chromium…………………………………………………………………………………......7
Nanotechnology……………………………………………………………………………….8
Hibiscus rosa-sinensis…………………………………………………………………………9
Green Synthesis……………………………………………………………………….……….9
Zinc Oxide Nanoparticles……………………………………………………………………10
X-ray Diffraction…………………………………………………………………………….11
Carbon Nanotubes……………………………………………………………………………11
Scanning Electron Microscope………………………………………………………………12
Methodology…………………………………………………………………………………….14
Materials and Methods…………………………………………………………………………15
Gathering of Materials……………………………………………………………………………15
Preparation of Hibiscus rosa-sinensis Aqueous Extract………………………………….………15
Green Synthesis of Zinc Oxide Nanoparticles using Hibiscus rosa-sinensis Leaf Extracts……..15
Characterization of Collected Zinc Oxide Nanoparticles………………………………………..16
Fabrication of Carbon Nanotubes embedded with Zinc Oxide Nanoparticles…………………..16
Characterization of the Carbon Nabotubes embedded with Zinc Oxide Nanoparticles…………17
 iv

Preparation of the Chromium-contaminated Water Set Ups…………………………………….18

Adsorption Test…………………………………………………………………………………..18
Data Analysis…………………………………………………………………………………….18
Waste Disposal…………………………………………………………………………………...19
Risk Assessment…………………………………………………………………………………19
Results and Discussion………………………………………………………………………….20
Conclusion………………………………………………………………………………………29
Recommendations………………………………………………………………………………29
Acknowledgement………………………………………………………………………………31
References……………………………………………………………………………………….32
Appendices………………………………………………………………………………………39
Experimental Design Diagram…………………………………………………………………...39
Raw Data…………………………………………………………………………………………41
Statistical Data…………………………………………………………………………………...42
Photo Documentation……………………………………………………………………………44
 1

INTRODUCTION
Background of the Study

Water pollution is one of the most serious ecological threats that people face today. Water

pollution happens when toxic substances enter water bodies such as lakes, rivers, oceans and so

on, getting dissolved in them, lying suspended in the water or depositing on the bed. Unsafe water

kills more people each year than war and all other forms of violence combined. Moreover,

contaminants have common origin solely from industrial effluents, municipal wastes and

agricultural inputs (Bhuyan, et al. 2017). Meanwhile, our drinkable water sources are finite: less

than 1 percent of the Earth’s freshwater is actually accessible to us (Denchak, 2018). As of 2016,

the Philippines’ 421 rivers, as many as 50 are considered dead and unable to support any but the

most robust life (Marrone, 2016). An eighth of the country’s rivers are considered too toxic for

human and animal ingestion or contact and are unable to support most forms of life. Fewer than

half of the total number of rivers in the Philippines have water safe enough for consumption. In

recent years, contaminants found in large and small bodies of water contributed to one third of the

reported illnesses in the Philippines (Andrews, 2018).

Heavy metals are naturally occurring elements that have a high atomic weight and a density

at least 5 times greater than that of water. Their multiple industrial, domestic, agricultural, medical

and technological applications have led to their wide distribution in the environment; raising

concerns over their potential effects on human health and the environment. Their toxicity depends

on several factors including the dose, route of exposure, and chemical species, as well as the age,

gender, genetics, and nutritional status of exposed individuals. (Tchounwou, et al. 2012). The

distribution, mobility and availability of metals in the environment depend not only on their total

concentration but also on their formations and bounds with the soil (Akratos, et al. 2014).
 2

chromium, lead, arsenic, cadmium, and mercury are the most common heavy metals found in water

nowadays.

Chromium is a waste product of many industrial applications and can enter the water

supplies when chromium waste is dumped near public water supplies. One form of chromium,

chromium 6, can cause cancer and serious health problems. A study showed that chromium can

also be found in Laguna Lake. 16 samples were taken consisting of 8 wastewaters, 6 sediments

and 2 soils. These were collected from various industries discharging wastewaters into

watercourses which ultimately drain into Laguna Lake. (Labunska, et al. 2018). Chromium

contamination in water can also affect fishes living in polluted waters. These contaminated fishes,

if eaten, will also give the same "effect" to the person that consumed it. One study proves that

fishes sold in public markets in Metro Manila, sells fish that has been contaminated with lead (Pb),

cadmium (Cd) and chromium (Cr). All of which exceeded the standard limits set by US-EPA and

FDA (Solidum, et al. 2013).

Zinc oxide or ZnO, when exposed to UV rays, has the ability to reduce heavy metal’s

toxicity. ZnO nanoparticles will be obtained from Hibiscus rosa-sinensis leaf extract by green

synthesis. Embedding ZnO Nps to carbon nanotubes will be done in order to test if this will be

more effective in filtering out chromium from polluted water. This study is only limited to

removing chromium from polluted waters.

Statement of Objectives

This study was conducted to investigate the potential of embedded zinc oxide on carbon

nanotubes in degrading hexavalent chromium in simulated contaminated water.

Specifically, this aimed to achieve the following objectives:

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1. Green synthesize zinc oxide nanoparticles using Hibiscus rosa-sinensis aqueous extract

2. Characterize the green synthesized zinc oxide nanoparticles and carbon nanotubes by using

XRPD Analysis

3. Fabricate the zinc oxide nanoparticles embedded on carbon nanotubes by using the

chemical evaporation method

4. Characterize the surface morphology of zinc oxide nanoparticles embedded on carbon

nanotubes by SEM analysis

5. Determine if there is a significant difference in the chromium content of water using

different ratios of zinc oxide nanoparticles and carbon nanotubes

Hypotheses

H0: There is no significant difference between the amount of hexavalent chromium adsorbed by

the different ratios of zinc oxide nanoparticles embedded on carbon nanotubes.

H1: There is a significant difference between the amount of hexavalent chromium adsorbed by the

different ratios of zinc oxide nanoparticles embedded on carbon nanotubes

Significance of the Study

Chromium is mined in different countries around the world as the naturally occurring form,

chromate ore. It is a multifunctional metal with many uses. It is an important component of various

metal alloys and stainless steels. Chromium is mainly used in chrome planting, leather tanning,

paint pigments, and wood treatment in the chemical industry (Owlad et al. 2013). However, it is

one toxic pollutant. It can affect air quality by producing coal, which can eventually lead to

contamination of water or soil. Water contaminated with chromium will accumulate on the head,
 4

meat, and internals of most fishes, which will have a negative effect on the health of aquatic

animals and to those who will consume them (Solidum et al. 2013). Thus, this study aims to help

lessen water contamination in an eco-friendly manner. Zinc oxide nanoparticles will be green

synthesized from Hibiscus rosa-sinensis aqueous extracts, meaning that all chemicals to be used

during the synthesis will not be harmful. The synthesized nanoparticles will then be embedded in

carbon nanotubes, and the said nanocomposite will be tested for adsorption of hexavalent

chromium from contaminated water.

Scope and Limitations

The study aimed to fabricate a carbon nanotube-zinc oxide nanoparticles nanocomposite

and investigate its potential in removing and/or reducing chromium (VI) from contaminated water.

The said nanoparticles were synthesized from Hibiscus rosa-sinensis crude ethanolic extract. The

synthesis of zinc oxide nanoparticles was conducted in the laboratory of the Institute of

Mathematical Sciences and Physics (IMSP) in University of the Philippines Los Baños. The

procedure was accomplished under the supervision of Prof. Emmanuel A. Florido. The carbon

nanotubes were already available and readily obtained in the IMSP laboratory. However, this study

was only focused on adsorbing one type chromium, which is hexavalent chromium. The analysis

of water samples was conducted in external laboratory services.

DEFINITION OF TERMS

Adsorption. Adhesion of atoms to a surface.

ANOVA. Analysis of variance; statistical technique that assesses potential differences

across different groups.

 5

Bioaccumulation. The build-up of harmful chemicals inside a living organism.

Carbon nanotubes. Allotrope of carbon which may be single-walled or multi-walled.

Chromium. Usually added to iron or nickel to make an alloy that is highly resistant to

corrosion and oxidation; may cause skin burns, pneumonia, and other health complications.

Green synthesis. Production processing that tries to release less or completely no

hazardous materials into the environment; using eco-friendly materials and processes for the

synthesis of a product.

Heavy metals. Elements that have a high atomic weight; 5 times the density of water.

Nanoparticles. Particles whose size is between 1 and 100 nanometers.

Nanotechnology. Manipulating or manufacturing of materials and instruments on the

atomic scale.

SEM. Scanning Electron Microscope; an instrument that uses electron beams in a vacuum

to detect the signals produced from the sample and presents it in an image.

XRPD. X-Ray Powder Diffraction; a rapid analytical technique primarily used for phase

identification of a crystalline material.

REVIEW OF RELATED LITERATURE

Water Pollution

Hundreds of living creatures are found in the aquatic environment which can majorly

benefit humans. However, due to the continuous rise in the development of industries, many of

these water creatures are killed because of contamination. Water pollution is of great concern since

water is the inevitable requisite for the survival of all living organisms (Inyinbor et al., 2018).
 6

Water pollution has become a continuous increasing problem on the earth which is danger for

living things.

The Philippines is a developing country which is also rapidly becoming urbanized and

industrialized. Many people rely on unsafe supplies of water. In addition, access to adequate

sanitation facilities has been a problem to approximately 30 million Filipinos. Literature review

provided evidences that consumption of contaminated water may be implicated in the occurrences

of several diseases.

Heavy Metals

The environment and its compartments have been severely polluted by heavy metals

(Masindi & Muedu, 2018). Among the various water pollutants, heavy metals require special

attention because of their toxic effect on humans and the environment (Anusa, Sivakumar &

Ravichandran, 2017). Heavy metals are considered as a major pollutant causing environmental

cytotoxic, mutagenic and carcinogenic effects in animals and aquatic organisms. Pollution caused

by these substances can arise from many sources and the major problem associated with its

persistence is its potential for bioaccumulation. The removal of heavy metals from water and

wastewater is a matter of concern worldwide. These heavy metals are of serious health and

environmental concern and there is a need to discover new and effective methods for their removal

from industrial effluents (Mahdavi, Jalali & Afkhami, 2012).

Laguna de Bay is the Philippines’ largest lake, and supplies Metro Manila’s approximately

16 million people with a third of their fish. However, its importance has caused problems including

pollution from untreated sewage and industrial waste, too much fishing, and the sedimentation and

illegal repossession that are destroying its capacity. An assessment of the Laguna Lake showed
 7

the risk factors to human health associated with the exposure to heavy metals since the study results

showed that most of the fish, especially the Tilapia, from Laguna de Bay is not fit enough for

consumption because of contamination.

Heavy metal contamination was also present in Iloilo City. Cadmium, chromium, and lead

exceeded the allowed value set by DENR AO No. 34 (1990). As stated by Sarinas et al., the highest

amount of dissolved chromium and lead found in the seawater were 0.545 mg/L and 0.771 mg/L,

respectively.

Chromium

Chromium is one such toxic pollutant due to its carcinogenic effects on human health,

especially in its hexavalent form. Chromium is a well-known highly toxic metal present in the

environment in several different forms. The most common forms are Chromium (0), Chromium

(III), and Chromium (VI). It is a common pollutant introduced into natural waters due to the

discharge of a variety of industrial wastewaters (Aroua et al., 2008). On the other hand, chromium-

based catalysts are also usually employed in various chemical processes.

According to the World Health Organization or WHO, the maximum allowable limit for

total chromium in drinking water is 0.05 mg l−1. The physiological effects of the ingestion of

chromium ions on human health have been studied intensively. Chromium can easily penetrate the

cell wall and exert its toxic influence on the cell itself. Chromium compounds can be irritants due

to their high solubility and diffusivity in tissue, allowing them to cross biological membranes

easily. At short-term exposure, Chromium (VI) may already cause headaches, dizziness, and

nausea. If exposure is above the maximum contaminant level, chromium causes skin and stomach
 8

irritation or ulceration, dermatitis, damage to liver, kidney circulation, nerve tissue damage, mood

changes, impaired thinking, and death in large doses.

Nanotechnology

In modern science, Nanotechnology is an ablaze field for the researchers which play a

dominant role in day to day life aspects and it is making an impact in all spheres of human life and

creating a growing sense of excitement in the life sciences especially biomedical devices and in

other field (Parthasarathy et al., 2016). Nanotechnology refers broadly to a field of applied science

and technology whose unifying theme is the control of matter on the molecular level in scales

smaller than 1 micrometer. It can be seen as an extension of existing sciences into the nanoscale,

or as a recasting of existing sciences using a newer, more modern term. Nanomaterials can show

atom-like behaviors which result from higher surface energy due to their large surface area, while

a bulk material has constant physical properties regardless of its size, at the nanoscale, this is often

not the case (Sorbiun et al., 2018).

Nanoparticles present an extremely attractive platform for a diverse range of applications.

Nanoparticles are used immensely due to its small size, orientation, physical properties, which are

reportedly shown to change the performance of any other material which is in contact with these

tiny particles and having a size of 1-100 nm in one dimension, is used significantly concerning

medical chemistry, atomic physics and all other known fields. These particles can be prepared

easily by different chemical, physical, and biological approaches.

According to a study conducted by Azizi et al. (2017), biosynthesized nanoparticles

exhibited a great adsorption for the Lead ions that followed an adsorption model and pseudo
 9

second-order equation. These also provide an efficient technique for the removal of contaminants

from wastewater.

Hibiscus rosa-sinensis

Hibiscus rosa-sinensis, commonly known as gumamela, is an evergreen shrub growing at

a fast rate. It is endemic to south east Asia since it does not tolerate cold weather conditions. It

grows in well-drained soils in sunny areas. Hibiscus rosa-sinensis is usually cultivated for

ornamental uses, but it is used in various fields since its parts are considered as anti-infectious,

anthelmentic, anti-inflammatory, diuretic, and antipyretic. Its flowers yield polyphenols,

flavonoids, and anthocyanins, that is why it is one of the most common plants used in laboratories.

Hibiscus rosa-sinensis provides an environmentally friendly sample and an efficient route

for the synthesis of nanoparticles due to its plenteous presence and its natural capping and reducing

agents (Devi & Gayathri, 2014).

Green Synthesis

Using plants in synthesizing nanoparticles are promising because of their ability to produce

these nanoparticles in a large scale. Green synthesis of nanoparticles is an approach that connects

nanotechnology with plants (Parveen, Banse and Ledwani, 2016). Green synthesis is known to be

an alternative synthesis process with reduced negative impacts on the environment. It is currently

gaining importance for there is a growing need to develop an environmentally friendly process for

the synthesis of nanoparticles that does not employ toxic chemicals, and the use of plants extracts

in synthesis of nanoparticles is said to be relatively novel for it is ecofriendly, low cost, and timely

process.
 10

In green synthesis, the formation of nanoparticles is due to the reduction and oxidation of

the ions. Plant leaves usually contain a high level of poly-phenols. Phenolic compound has

hydroxyl and ketonic groups which are able to bind to metals and reduce the metal salt and provide

stability. Plant extracts then give protein and enzyme to the solution in which the ions combine

with the enzyme to form enzyme substrate complex. The enzyme released from the plant extract

act on the ions and there is a release of nanoparticle from enzyme (Agarwal et al., 2017).

Zinc Oxide Nanoparticles

Zinc oxide (ZnO) is a coarse-grained mineral (zincite) in nature. It is technically obtained

by oxidation of zinc or zinc vapor with atmospheric oxygen or calcination of various components

such as zinc hydroxide, zinc carbonate or zinc nitrate. It has an excellent thermal and chemical

stability.

Zinc oxide (ZnO) nanoparticles exhibit various properties. Besides their excellent

biocompatibility, economic and low toxicity, these nanoparticles have gathered interest because

of its diverse application in solar energy conversion, sensors, catalysis, cosmetics, paints, fibers,

drug-delivery, and antibacterial properties. That is why in the recent years, zinc oxide

nanoparticles are utilized in completely different industrial sectors such as medication, cosmetic

materials and concrete, opposed microorganism, textile and automotive industries (Manokari and

Shekhawat, 2017). Its microcrystals are very efficient light absorbers in the UVA and UVB region

of spectra (Siddiqi, Rahman and Husen, 2018). These were also investigated for its antimicrobial

effect against multiple pathogens and food contaminants. Zinc oxide nanoparticles are generally

less toxic than silver nanoparticles in a broad range of concentrations (20 to 100 mg/l) with average

particle size of 480 nm.

 11

X-Ray Diffraction

X-Ray diffraction acted as the pivot or turning point of 20th century science. Its

development sparked the developments of solid-state sciences and our understanding of chemical

bonding. X-ray powder diffraction (XPRD) plays a critical role in materials research and

development, the quality and quantity of the phases present in a specimen can be obtained through

it (Misture & Synder, 2001). It is a rapid analytical technique wherein x-rays are generated in a

cathode ray tube by heating a filament to produce electrons, accelerating the electrons toward a

target by applying a voltage, and bombarding the target material with electrons. In order to identify

an unknown substance, the powder diffraction pattern is recorded. These data are compared with

the standard line patterns available for various compounds, found in the Powder Diffraction File

(PDF) database (Chatterjee, 2001).

Carbon Nanotubes

Carbon nanostructures with different morphologies, especially carbon nanotubes are

assumed to be one of the major elements in nanotechnology. Carbon nanotubes (CNTs) are

cylindrical molecules that consist of rolled-up sheets of single-layer carbon atoms. They can be

single walled (SWCNT) with a diameter of less than 1 nanometer (nm) or multi-walled (MWCNT),

composed of several nanotubes which are interlinked, with diameters reaching more than 100 nm.

Their length can reach several micrometers or even millimeters. Carbon nanotubes are composed

of carbon atoms linked in hexagonal shapes, with each carbon atom covalently bonded to three

other carbon atoms.

One study showed that carbon nanotubes supported by activated carbon are capable for the

removing of pollutants from water source and thus, provides high expectations on the development
 12

of wastewater treatment and environmental contamination reduction. However, activated carbon

is not really good at removing chemicals that are not attracted to carbon and has a short service

life. The effectiveness of filtration by using activated carbon is determined by factors such as the

time water stays in contact with the filter media, and it decreases if water does not stay in contact

long enough with the carbon filter media. Investigations have also been carried out on the

adsorption of heavy metals and hazardous organic materials (Goering et al., 2008).

Scanning Electron Microscopy

Surface Characterization provides an authoritative guide to the wide range of powerful

techniques that are used to characterize the surfaces of materials (Vogler, 2013). These techniques

enable us to clarify the alteration of the structure, electronic states, physical properties,

functionalities and reactions at surface due to the methods used to process the materials. This

usually focuses on the topography, composition and distribution of elements, geometrical

arrangement of atoms, and chemical bonding. Surface Characterization not only describes the

major analytical techniques but emphasizes how they can be used to solve a multitude of chemical

and physical problems as it is a practical approach. This might be a combination of numbers of

techniques like microscopies, spectroscopies, and spectrometries that are based on reflection,

adsorption, or emission of particles.

A scanning electron microscope allows characterization of particles, nanoparticles,

composites and their constituents, fracture surfaces, and surface morphologies. Scanning electron

microscopy is a useful technique for the analysis of surfaces since it involves a collimated beam

of electrons that sweeps across the surface of the specimen being analyzed. A huge depth of field
 13

is delivered by using this technique, which means the area of the sample that can be viewed in

focus at once is seemingly large.

 14

METHODOLOGY

Green synthesis of
Preparation of
Zinc oxide
Gathering of Hibiscus rosa- nanoparticles using
materials sinensis aqueous Hibiscus rosa-
extract sinensis aqueous
extract

Characterization of Fabrication of
the Carbon Characterization
Carbon nanotubes
nanotubes of the collected
embedded with
embedded with Zinc oxide
Zinc oxide
Zinc oxide nanoparticles nanoparticles
nanoparticles

Preparation of
the Chromium- Adsorption
contaminated
Data analysis
test
water Set-Ups

Risk Water
assessment disposal

Figure 1. Flow chart of methods

 15

MATERIALS AND METHODS

Gathering of Materials

Most of the equipment were acquired at the Institute of Mathematical Sciences and Physics

(IMSP), University of the Philippines Los Baños. These include stirrer-heaters, magnetic stirrers,

analytical balance, spatulas, beakers, stirring rods, iron stand, iron clamp, thermometers, and

graduated cylinders. Hibiscus rosa-sinensis leaves were collected from Brgy. Salac, Lumban,

Laguna. Twenty-three liters of distilled water was bought from a convenience store. Gloves,

masks, air-tight containers, tweezers, one liter of ethanol, and five hundred grams of Potassium

Dichromate (K2Cr2O7) were bought from Nicolie Enterprises, UPLB. Two packs of plastic

containers, two packs of coffee stirrers, and one yard of cheese cloth were bought in a nearby

market.

Preparation of Hibiscus rosa-sinensis Aqueous Extract

All the materials used in the experiment were of analytical grade. 500g of Hibiscus rosa-

sinensis leaves were washed thoroughly in clean water and then grinded using a mortar and pestle.

The collected extracts were filtered using a cheese cloth, stored in plastic containers and were

taken up for further investigations.

Green Synthesis of Zinc Oxide Nanoparticles using Hibiscus rosa-sinensis Leaf Extracts

Different concentrations of the aqueous extract were prepared with 27.2ml of distilled

water by dilution. Each solution was stirred using a magnetic stirrer at 70ºC using a stirrer-heater.

2.72 grams of zinc acetate dihydrate was added to the solution as the temperature reached 70ºC.
 16

The mixture was then boiled until it is reduced into a deep yellow-colored paste. This paste was

collected into a ceramic crucible and was annealed at 400ºC for 2 hours. A white colored powder

was obtained and was carefully collected. The table below shows the various concentrations of the

aqueous extract prepared with distilled water.

Table 1. Concentrations of the Hibiscus rosa-sinensis extract in each treatment

Concentration of
Treatment
Aqueous Extract (g)
1 5
2 2.5
3 1.25
4 0.625

The procedure was repeated for other replicates. The concentration which produced the

greatest amount of the white colored powder was treatment 3 in the second replicate. The collected

powder from the said variation of concentration were used for further experiments.

Characterization of the Collected Zinc Oxide Nanoparticles

The collected powder from each treatment in each replicate were transferred in vials. The

sample with the greatest amount of powder collected was sent to UPLB NanoScience and

Technology Facility Analytical and Instrumentation Service Laboratory for X-ray Diffraction

(XRD) Analysis to determine if the powder formed was zinc oxide nanoparticles.

Fabrication of Carbon Nanotubes embedded with Zinc Oxide Nanoparticles

Multi-walled carbon nanotubes and zinc oxide nanoparticles were weighed in the plastic

containers using analytical balance. The zinc oxide nanoparticles synthesized from the Hibiscus

rosa-sinensis leaf extracts were then embedded inside the carbon nanotubes by the chemical
 17

evaporation method. 50ml of ethanol was mixed with the different concentrations of the carbon

nanotubes with zinc oxide nanoparticles. Each mixture was stirred using a magnetic stirrer at a

stirrer-heater for 1 hour at 100ºC and then sonicated for 45 minutes at room temperature. Each

mixture was stirred again for an hour at 150ºC and was evaporated at 100ºC. The table below

shows the different ratios of carbon nanotubes to zinc oxide nanoparticles.

Table 2. Different ratios of carbon nanotubes to zinc oxide nanoparticles

Ratio of Carbon
Nanotubes to Zinc Amount of Carbon Amount of Zinc Oxide
Oxide Nanoparticles Nanotubes (mg) Nanoparticles (mg)
(100%)
0:100 0 100
25:75 25 75
50:50 50 50
75:25 75 25
100:0 100 0

The procedure was repeatedly done for other trials and set-ups.

Characterization of the Carbon Nanotubes Embedded with Zinc Oxide Nanoparticles

The nanocomposite fabricated was sent for Scanning Electron Microscope (SEM) Analysis

at the Nanotech Analytical Services and Training Corporation (NASAT) Laboratory, Muntinlupa

City, Alabang. The surface of the sample was scanned with a finely converged electron beam in

vacuum. The information and signals produced images of the sample surface on the monitor

screen.
 18

Preparation of the Chromium-Contaminated Water Set-Ups

To obtain approximately 30ppm of the chromium content present in water, potassium

dichromate was used to create the chromium stock solution. All required solutions were prepared

with analytical reagents and distilled water. 0.71g of potassium dichromate was first dissolved in

250ml of distilled water to gain a 3000ppm of stock solution. Then 29.9mL of chromium stock

solution was diluted into distilled water until the volume reaches 1000mL. This procedure was

repeated for another 15 times to satisfy the amount needed for the trials and replicates. The water

bottles were then sealed and stored properly.

Adsorption Test

The nanocomposite fabricated was then put into the chromium-contaminated water and

shaken until the nanocomposite is evenly distributed within the solution. The carbon nanotubes

embedded with zinc oxide nanoparticles was removed from each solution after 2 hours using a

vacuum filter. The chromium content present in the contaminated water after the removal of the

nanocomposite was measured at the Nanotech Analytical Services and Training Corporation

(NASAT) Laboratory, Cabuyao, Laguna using the colorimetric method, UV-VIS

spectrophotometry. The procedure measures only hexavalent chromium. The amount of chromium

present was determined colorimetrically by reaction with diphenylcarbazide in acid solution.

Data Analysis

One-way Analysis of Variance (ANOVA) was employed to determine the significant

difference in the mean concentration (mg/L) of Hexavalent Chromium at 95% confidence level.
 19

Pairs of treatments that are significantly different were further analyzed using Duncan Multiple

Range Test. SPSS statistical software was utilized.

Waste Disposal

The excess chemicals were stored in its appropriate containers and residues were disposed

properly. All laboratory equipment which were used were washed thoroughly with distilled water

and were then disposed or stored properly.

Risk Assessment

High risk was expected from potassium dichromate as it was a used for the preparation of

hexavalent chromium in water. Hexavalent chromium has been shown to be carcinogenic by

inhalation and corrosive to tissue. All experimental procedures were conducted in laboratories

under the supervision of the designated supervisor/s. The use of laboratory gowns, masks, and

gloves was strictly observed. Familiarity with the procedures and awareness to possible risks were

established prior to experimentation.

 20

RESULTS AND DISCUSSIONS

X-Ray Diffraction (XRD) Analysis of Green Synthesized Zinc Oxide Nanoparticles using

Hibiscus rosa-sinensis Aqueous Extract

XRD analysis is a versatile and non-destructive analytical method used for characterization

of the structure of different crystalline forms. This was conducted to identify the mineral content

of the powder synthesized from the leaf extracts and determine if it was zinc oxide nanoparticles.

Figure 2 represents the x-ray diffraction pattern of the powder. The peaks located at 31.737º,

34.420º, 36.225º, 47.515º, 56.536º, 62.836º, 66.304º, 67.893º, 69.015º, 72.561º, 76.891º, 81.364º,

and 89.544º indicate that the prepared material consists of particles in nanoscale range. From this

analysis, peak intensity, position and width, and full width at half maximum (FWHM) data were

identified. The table below shows the summary diffraction pattern of peaks and analysis of the size

of the crystallites. XRD results revealed a hexagonal structure of the zinc oxide nanoparticles with

an average crystallite size of 75.04 ± 0.44. It also shows that the peaks of the powder analyzed are

in a good agreement with that of the structure of the zincite which is shown in figure 3, and with

that of the peaks of commercially available zinc oxide nanoparticles shown in figure 4.

Table 3. Summary diffraction pattern peaks and crystallite size analysis

Crystalline
Nearness
Position, Average Phase of
FWHM Crystallite score of
Intensity 2θ Crystallite %RSD first three
(degrees) size, nm material
(degrees) size, nm database
pattern
hit

670.16 36.27 0.9600 75.45 81

Zincite,
75.04 ±
412.36 34.66 0.9600 75.11 0.59 Hexagonal, 80
0.44
ZnO
390.74 31.82 0.9600 74.57 78
 21

Counts
07182019_EFlorido_ZnO_SPC_1

2000

1000

0
10 20 30 40 50 60 70 80 90

Position [°2Theta] (Copper (Cu))

Counts
07182019_EFlorido_ZnO_SPC_1
800

600

400

200

10 20 30 40 50 60 70 80 90

Position [°2Theta] (Copper (Cu))

Figure 2. (A) XRD pattern of the green synthesized zinc oxide nanoparticles, (B) Diffraction
pattern of zincite
 22

Figure 3. Comparison of the powder diffraction file of zincite

Figure 4. XRD pattern of commercially available zinc oxide nanoparticles

 23

Scanning Electron Microscope-Energy Dispersive X-Ray (SEM-EDX) Analysis of the

Carbon Nanotubes embedded with Zinc Oxide Nanoparticles

SEM-EDX is a widely used analytical technique for characterization and elemental

analysis of a sample. The surface morphology of the carbon nanotubes embedded with zinc oxide

nanoparticles was analyzed using a scanning electron microscope (Hitachi TM4000Plus). Figure

5 represents the SEM pictures of zinc oxide nanoparticles embedded in carbon nanotubes at

different magnifications. The white particles observed represents the zinc oxide nanoparticles.

Table 3 shows the elemental analysis of the nanocomposite which revealed the presence of Zn, C,

and O as also depicted in the spectra in Figure 6. Based on the following images and the data

gathered, the successful fabrication of the zinc oxide nanoparticles embedded in carbon nanotubes

was emphasized.

Table 3. Elemental analysis of the carbon nanotubes embedded with zinc oxide nanoparticles

Mass
Element At. No. Atom [%]
Norm. [%]
Zn 30 36.51 10.33
Si 14 0.51 0.34
O 8 8.82 10.20
Ni 28 0.86 0.27
Ca 20 1.35 0.62
C 6 49.88 76.82
Al 13 2.07 1.42
100.00 100.00
 24

Figure 5. SEM images of zinc oxide nanoparticles embedded in carbon nanotubes at different
magnifications. (A) 500x magnification power, (B) 600x magnification power, (C) 1000x
magnification power, (D) 2000x magnification power
 25

Figure 6. SEM-EDX spectra of the surface of the nanocomposite. The region lined out (A)
indicates the area analyzed with EDX spectra
 26

Hexavalent Chromium Adsorption Test using the Colorimetric Method, UV-VIS

Spectrophotometry

Adsorption test results of hexavalent chromium can be seen in Table 4. One-way ANOVA

showed that there is a significant difference among the mean concentration (mg/L) of hexavalent

chromium in water filtrates using different ratios of the carbon nanotubes to zinc oxide

nanoparticles. The table revealed that the ratios of carbon nanotubes to zinc oxide nanoparticles

that exhibited the greatest amount of adsorption were 50:50 and 75:25. It also showed that the ratio

that poorly performed was the pure zinc oxide nanoparticles while the ratios that performed fairly

were 25:75 and 100:0.

It is apparent that the amount of adsorbent used in the removal of a solute from water is

critical for its practical application. The initial concentration of hexavalent chromium provides an

importance to overcome all mass transfer. Figure 7 shows that the adsorbance of hexavalent

chromium is directly proportional to its concentration.

Table 4. Mean concentration of hexavalent chromium after adsorption and percent adsorption

Ratio of Carbon Nanotubes

Mean Concentration (mg/L) Percent Adsorption (%)
to Zinc Oxide Nanoparticles
0:100 27.5467b, c 12.00

25:75 24.7300b 18.58

50:50 21.0000a 30.34

75:25 19.1800a 30.32

100:0 25.6500b 14.50

Control 29.5900c 0
*Data are means of three replicates
*Means of the same letter are not significantly different. Statistical differences were determined
using one-way ANOVA (p<0.05) followed by Duncan’s test.
 27

Figure 7. Regression analysis of the relation between adsorption and concentration

Chromium is one of the most common heavy metals found in water. Its hexavalent form is

considered as a human carcinogen because of its carcinogenic and mutagenic properties.

Adsorption is the adhesion of ions or molecules to the surfaces of the bodies with which they are

in contact. It is now recognized as an effective and economic method for wastewater treatment

because its process offers flexibility hence producing high-quality treatments (Rodriguez, 2015).

Figure 8 shows adsorption processes and adsorption types. Adsorbents are widely used as a

medium for separation of pollutants from water, thus, it is important that an adsorbent has good

mechanical properties such as strength and resistance to destruction. Adsorbate is the substance

which is adsorbed.
 28

Figure 8. Adsorption process and adsorption types (Rodriguez, 2015)

Nanotechnology enables novel applications since nanomaterials possesses different

properties such as high surface area, pore size distribution, superparamagnetism for particle

separation, and electronic properties that are used in water quality monitoring. A variety of

nanomaterials are currently used in stages of research and development. Recently, carbon

nanotubes (CNTs) have gained interest because of their superior electrical, thermal, and

mechanical properties. Moreover, metal oxide nanoparticles are also classified as promising

materials for removal of heavy metals because of their shape, structure, and unique physical and

chemical properties.

Numerous studies have revealed that nanomaterials are used in adsorption of heavy metals.

A study conducted by Taman et al. (2015) showed that metal oxide nanoparticles are effective in

removing heavy metals such as cadmium, iron, and lead from water. Asadi (2012) revealed that

zinc oxide nanoparticles were able to degrade hexavalent chromium to trivalent chromium in
 29

water. Atieh (2011) and Parlayici et al. (2015) revealed that carbon nanotubes supported with

activated carbon can also be employed efficiently in removal of hexavalent chromium in

contaminated water. However, in Parlayici’s study, the amount of the adsorbent they used was

fixed, thus, the active adsorption sites of the nanocomposites became saturated and the adsorption

capacity was reduced. Thus, in line with these studies, carbon nanotubes embedded with zinc oxide

nanoparticles should be capable in adsorption of hexavalent chromium.

CONCLUSIONS

The XRD analysis of the green synthesized zinc oxide nanoparticles (ZnO-Nps) showed

hexagonal shape. The peaks also showed that the mineral content of the green synthesized ZnO-

Nps were almost identical to those of zincite which proves that green synthesis is also an effective

method of producing ZnO-Nps. The SEM results showed that the green synthesized ZnO-Nps

succesfully embedded on the surface of the CNT. The colorimetric method, UV-VIS

spectrophotometry shows that The 75:25 and 50:50 ratio of CnT:ZnO yielded the highest

adsorption percentage of chromium compared to the ratios 25:75 and 100:0 CnO:ZnO, while

significantly different to the ratio of 0:100 (p<0.05).

RECOMMENDATIONS

Based on the results and findings gathered and analyzed by the researchers, the following

recommendations are hereby proposed for further improvement of the study:

1. Characterization and analysis of the Hibiscus rosa-sinensis aqueous extract

 30

2. Increase the amount of the adsorbent used in each trial

3. Study lower concentrations of the chromium present in water

4. Adjust the pH level of water

5. Create more trials and replicates for more accurate results

6. Utilization of the available time productively

 31

ACKNOWLEDGEMENT

First of all, we would like to thank God for giving us the strength, knowledge, wisdom,

and skills that we needed to pursue this project. We would also like to express our gratitude and

appreciation to the following groups and individuals who supported us from the very start.

To Prof. Allan L. Alinea, Head of the Physics Division, University of the Philippines Los

Baños, for allowing us to use their laboratory and equipment in conducting the experiment.

To our consultant, Prof. Emmanuel A. Florido, MSc, Assistant Professor at the Institute

of Mathematical Sciences and Physics, University of the Philippines Los Baños, thank you very

much for supervising us in doing our study. For being very patient with us despite our errors, for

all the advice, ideas, and time, thank you. Under your supervision, it has truly been an honor.

To our dearest principal, Ma’am Neliza P. Cuasay, for letting us gain more knowledge

through research and for allowing us to leave the school during our experimentations, thank you.

To our beloved research adviser, Sir Franz Kevin B. Manalo, who guided and helped us

in all aspects of our project. Thank you for the undying support and encouragement you have given

us since day one. You have inspired and motivated us to do the best that we can do.

To Sir Jeffrey D. Magtibay, faculty member of San Pablo City Science Integrated High

School, for helping us in our computations and preparation of our stock solution. To our dearest

teachers, for being considerate and excusing us on their classes.

To our friends and classmates who never forgot to remind us about the activities that we

have missed during our conduct of experimentation.

Last but not the least, to our beloved parents, for their continuous support. Thank you for

providing us everything we need accomplish this project. Again, thank you for all those who have

helped us throughout this journey.

 32

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 39

EXPERIMENTAL DESIGN DIAGRAM

Independent Variable: Different Concentrations of Hibiscus rosa-sinensis Aqueous Extract in

each treatment

Green Synthesis of Zinc Oxide Nanoparticles

0.625g of 1.25g of
2.5g of Aqueous 5g of Aqueous
Treatment Aqueous Aqueous
Extract Extract
Extract Extract

Trials 1 1 1 1

Replicates 2 2 2 2

Dependent Variables: Amount of powder produced

Constant Variables: Source of leaves, Amount of water, Amount of zinc acetate dihydrate used

per treatment, No. of trials, No. of replicates

Independent Variable: Different Ratios of Carbon Nanotubes (CNT) to Zinc Oxide (ZnO)

Nanoparticles

Fabrication of CNTs embedded with ZnO Nps

100:0 CNT- 75:25 CNT- 50:50 CNT- 25:75 CNT- 0:100 CNT-
Treatment
ZnO NPs ZnO NPs ZnO NPs ZnO NPs ZnO NPs

Trials 1 1 1 1 1

Replicates 3 3 3 3 3
 40

Chromium (VI) Adsorption

100:0 CNT- 75:25 CNT- 50:50 CNT- 25:75 CNT- 0:100 CNT-
Treatment
ZnO NPs ZnO NPs ZnO NPs ZnO NPs ZnO NPs

Trials 1 1 1 1 1

Replicates 3 3 3 3 3

Dependent Variables: Amount of hexavalent chromium adsorbed

Constant Variables: Amount of potassium dichromate, Amount of water, No. of trials, No. of

replicates
 41

RAW DATA

Trial Treatment Adsorbance Results Initial ppm %

0:100 1.482 23.19 30 22.7
1 CNT-ZnO 1.791 29.45 30 1.833333
Nps 1.818 30 30 0
25:75 1.471 22.96 30 23.46667
2 CNT-ZnO 1.621 26 30 13.33333
Nps 1.583 25.23 30 15.9
50:50 1.498 23.51 30 21.63333
3 CNT-ZnO 1.338 20.27 30 32.43333
Nps 1.286 19.22 30 35.93333
75:25 1.354 20.59 30 31.36667
4 CNT-ZnO 1.252 18.53 30 38.23333
Nps 1.247 18.42 30 38.6
100:0 1.625 26.08 30 13.06667
5 CNT-ZnO 1.614 25.86 30 13.8
Nps 1.572 25.01 30 16.63333
Negative
29.59 30
Control
 42

STATISTICAL DATA

Sum of Squares df Mean Square F Sig.

Between Groups 231.112 5 46.222 11.740 .000

Within Groups 47.246 12 3.937

Total 278.358 17

95% Confidence
Mean
Std. Interval
(I) Ratio Difference Sig.
Error Lower Upper
(I-J)
Bound Bound
25CNT-
2.81667 1.62012 .108 -.7133 6.3466
75ZnO
50CNT-
6.54667* 1.62012 .002 3.0167 10.0766
50ZnO
0CNT-
75CNT-
100ZnO 8.36667* 1.62012 .000 4.8367 11.8966
25ZnO
100CNT-
1.89667 1.62012 .264 -1.6333 5.4266
0ZnO
Control -2.04333 1.62012 .231 -5.5733 1.4866
0CNT-
-2.81667 1.62012 .108 -6.3466 .7133
100ZnO
50CNT-
3.73000* 1.62012 .040 .2001 7.2599
50ZnO
25CNT-
LSD 75CNT-
75ZnO 5.55000* 1.62012 .005 2.0201 9.0799
25ZnO
100CNT-
-.92000 1.62012 .581 -4.4499 2.6099
0ZnO
Control -4.86000* 1.62012 .011 -8.3899 -1.3301
0CNT-
-6.54667* 1.62012 .002 -10.0766 -3.0167
100ZnO
25CNT-
-3.73000* 1.62012 .040 -7.2599 -.2001
75ZnO
50CNT-
75CNT-
50ZnO 1.82000 1.62012 .283 -1.7099 5.3499
25ZnO
100CNT-
-4.65000* 1.62012 .014 -8.1799 -1.1201
0ZnO
Control -8.59000* 1.62012 .000 -12.1199 -5.0601
 43

0CNT-
-8.36667* 1.62012 .000 -11.8966 -4.8367
100ZnO
25CNT-
-5.55000* 1.62012 .005 -9.0799 -2.0201
75ZnO
75CNT-
50CNT-
25ZnO -1.82000 1.62012 .283 -5.3499 1.7099
50ZnO
100CNT-
-6.47000* 1.62012 .002 -9.9999 -2.9401
0ZnO
Control -10.41000* 1.62012 .000 -13.9399 -6.8801
0CNT-
-1.89667 1.62012 .264 -5.4266 1.6333
100ZnO
25CNT-
.92000 1.62012 .581 -2.6099 4.4499
75ZnO
100CNT-
50CNT-
0ZnO 4.65000* 1.62012 .014 1.1201 8.1799
50ZnO
75CNT-
6.47000* 1.62012 .002 2.9401 9.9999
25ZnO
Control -3.94000* 1.62012 .032 -7.4699 -.4101
0CNT-
2.04333 1.62012 .231 -1.4866 5.5733
100ZnO
25CNT-
4.86000* 1.62012 .011 1.3301 8.3899
75ZnO
50CNT-
Control 8.59000* 1.62012 .000 5.0601 12.1199
50ZnO
75CNT-
10.41000* 1.62012 .000 6.8801 13.9399
25ZnO
100CNT-
3.94000* 1.62012 .032 .4101 7.4699
0ZnO
*The mean difference is significant at the 0.05 level.

Subset for alpha = 0.05

Ratio N
1 2 3
75CNT-25ZnO 3 19.1800
50CNT-50ZnO 3 21.0000
25CNT-75ZnO 3 24.7300
Duncana 100CNT-0ZnO 3 25.6500
0CNT-100ZnO 3 27.5467 27.5467
Control 3 29.5900
Sig. .283 .123 .231
*Means for groups in homogenous subsets are displayed.
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PHOTO DOCUMENTATION

Figure 9.1 Gathering of Hibiscus rosa-sinensis leaves

Figure 9.2 Maceration of Hibiscus rosa-sinensis leaves using mortar and pestle
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Figure 9.3 Filtration of the macerated Hibiscus rosa-sinensis leaves to obtain aqueous extract

Figure 9.4 Stirring and heating Hibiscus rosa-sinensis aqueous extract dissolved in a zinc acetate
dihydrate solution
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Figure 9.5 Crucible containing the Hibiscus rosa-sinensis and zinc acetate dihydrate

Figure 10.1 Preparation of crucibles to be used for furnacing

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Figure 10.2 Electric furnace used to heat the solution to 400 ̊C

Figure 10.3 Some of the solutions to be furnaced

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Figure 10.4 White powder obtained after annealing the solution

Figure 10.5 White powder obtained by annealing different concentrations of solution (upper
right) and their corresponding weight (middle) first replicate (A) & second replicate (B)
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Picture 2.6 Powder sample used for XRD anaylsis

Figure 10.6 Powder sample used for XRD analysis

Figure 10.7.1 Raw diffraction pattern of the powder sample

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Figure 10.7.2 Treated diffraction pattern

Figure 10.7.3 Comparison of the diffraction file of zincite and diffraction pattern of powder
sample
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Figure 11.1 Zinc oxide nanoparticles (ZnO Nps) to be used for embedding

Figure 11.2 Carbon nanotubes to be embedded with ZnO Nps

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Figure 11.3 Zno-CnT dispersed in ethanolic solution after sonication

Figure 11.4 ZnO-CnT nanocomposite after chemical evaporation process

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Figure 12.1 Equipment used for the SEM analysis of the nanocomposite

Figure 12.2 Microscopic view of the nanocomposite

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Figure 13.1 Potassium dichromate used for the preparation of chromium stock solution

Figure 13.2 3000ppm chromium stock solution

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Figure 13.3 Diluting 29.9mL of chromium stock solution on distilled water

Figure 13.4 500mL chromium solution

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Figure 13.5 Shaking the solution with nanocomposite