Faculty of Resources Science and Technology

Properties of Carbon Microtubes @ Nitrogen-Doped Reduced Graphene Oxide Hybrid

NURIQMALLIA BINTI MAHMUT (65120)

Bachelor of Science with Honours

Resources Chemistry

2021
DECLARATION

I barely declare that the project report entitled ‘Properties of Carbon Microtubes @

Nitrogen-Doped Reduced Graphene Oxide Hybrid’ is being submitted by me, Nuriqmallia

Binti Mahmut (65120) in partial fulfilment of the Final Year Project 2 (STF3015) course.

I further declare that this report is my original work conducted under the supervision

of Dr Rafeah Binti Wahi from Faculty of Resources Science and Technology, University

Malaysia Sarawak (UNIMAS). It has not been submitted for examination to any other

university.
ACKNOWLEDGEMENT

First of all, I would like to thank God for leading all the way in my life and your blessings

had given me strengths that enable me to complete this project smoothly. Online learning is a

system that been used as part of my final year project due to pandemic covid-19 since March

2020. This project would not have been possible without supporting and contribution of

related individuals. Hence, I would like to all people who had helped me during my project

especially my supervisor, Dr Rafeah Binti Wahi for her guidance, advice, encouragement,

expertise, help and patience in supervising my work. I am grateful to cooperate with my team

members in completing this project and I want to express my sincere thanks to all of them for

their help and tolerance. I would like to thank UNIMAS lectures who willing to become

evaluators and gave valuable comments and suggestion during evaluation phase of this

project. Last but not least, my deepest gratitude goes to my family members and my friends

for their encouragement and prayers.

ABSTRACT

In this modern era, the concept on of improving a resource-conserving and environment-

friendly society the developing of green, sustainable, and multifunctional materials has become very

important. Therefore, there are many steps taking by researchers to come out on more possible ways

on these projects. One of them is the production of carbon microtube @ nitrogen-doped reduced

graphene oxide (CMT@N-RGO) hybrid as an excellent carbonaceous scaffold for energy storage and

electrolysis. The objective of the studies is to prepare the (CMT@N-RGO) hybrid, to determine the

properties of (CMT@N-RGO) hybrid and to study the application of (CMT@N-RGO) hybrid. The

methodology approached in order to produce CMT@N-RGO hybrid is fabricated by combining

dipping and chemical vapor deposition methods. In short, the fabricated hybrid served as electrodes of

supercapacitor present fast charge/discharge rate, excellent rate performance, and outstanding

capacitance retention of 95% (93%) and high energy efficiency of 65–77% (61–72%) for both. The

CMT@N-RGO hybrid chemically and physically approve to be function as sustainable high

capacitance energy storage.

ABSTRAK

Di era moden ini, konsep untuk meningkatkan masyarakat yang memulihara

sumber daya dan mesra alam membangun bahan hijau, lestari, dan pelbagai fungsi menjadi

sangat penting. Oleh itu, terdapat banyak langkah yang diambil oleh penyelidik untuk

mencari jalan yang lebih mungkin dalam projek-projek ini. Salah satunya ialah penghasilan

hibrida karbon mikrotube @ nitrogen-doped graphene oxide (CMT @ N-RGO) sebagai

perancah karbonat yang sangat baik untuk penyimpanan tenaga dan elektrolisis. Objektif

kajian adalah untuk menyiapkan hibrid (CMT @ N-RGO), untuk menentukan sifat hibrid

(CMT @ N-RGO) dan mengkaji penerapan hibrid (CMT @ N-RGO). Metodologi yang

didekati untuk menghasilkan hibrid CMT @ N-RGO dibuat dengan menggabungkan kaedah

pemendapan dan pemendapan wap kimia. Ringkasnya, hibrid fabrikasi berfungsi sebagai

elektrod supercapacitor dengan kadar cas / pelepasan yang cepat, prestasi kadar yang

sangat baik, dan pengekalan kapasitansi yang luar biasa sebanyak 95% (93%) dan

kecekapan tenaga yang tinggi 65-77% (61-72%) . Hibrid CMT @ N-RGO secara kimia dan

fizikal disetujui untuk berfungsi sebagai simpanan tenaga berkapasiti tinggi yang lestari.
 CONTENT
DECLARATION................................................................................................................................... 2

ACKNOWLEDGEMENT .................................................................................................................... 3

ABSTRACT ........................................................................................................................................... 4

ABSTRAK ............................................................................................................................................. 5

1. INTRODUCTION............................................................................................................................. 8

1.1 Research Background ................................................................................................................... 8

1.2 Problem Statement ........................................................................................................................ 9

1.3 Objective ....................................................................................................................................... 9

2. LITERATURE REVIEW .............................................................................................................. 10

2.1 Reduced Graphene Oxide ..................................................................................................... 10

2.1.1 Definition, structure, and source. .................................................................................. 10

2.1.2 Reduction of graphene oxide. ....................................................................................... 11

2.2 Properties of reduced graphene oxide. .................................................................................. 12

2.2.1 Mechanical properties ................................................................................................... 12

2.2.2 Electrochemical properties ............................................................................................ 15

2.3 Application of reduced graphene oxide ...................................................................................... 17

2.3.1 Electronic devices .............................................................................................................. 17

2.3.2 Energy storage devices.................................................................................................. 17

3.METHODOLOGY .......................................................................................................................... 18

3.1 Materials ............................................................................................................................... 18

3.2 Fabrication of CMT@N-RGO hybrid................................................................................... 18

 3.3 Fabrication of pure CMT ...................................................................................................... 18

3.4 Characterization of materials ................................................................................................ 19

3.4.1 Material Characterization..................................................................................................... 19

3.4.2 Electrochemical Characterization ........................................................................................ 19

3.5 Preparation of CMT@N-RGO and pure CMT electrode ............................................................ 20

4.RESULT AND DISCUSSION......................................................................................................... 21

4.1 Structure and morphology........................................................................................................... 21

4.2 Electrochemical performance in supercapacitors........................................................................ 24

4.3 Catalytic properties in oxygen reduction reaction ...................................................................... 26

4.3 Reduced Graphene Oxide Preparation ........................................................................................ 28

CONCLUSION ................................................................................................................................... 29

REFERENCES .................................................................................................................................... 30
1. INTRODUCTION

1.1 Research Background

Reduced graphene oxide is the form of graphene oxide that is processed by chemical,

thermal and other methods in order to reduce the oxygen content. Graphene oxide can be

converted into valuable nanoscale products for high performance electronic device and

energy storage that has gain interest among scientist and industry as an effort to produce an

affordable commercial manufacture of graphene-type product (Perrozzi et al., 2015).

Other than that, reduced graphene oxide also used as a supercapacitor or electrode. In

the used of electrodes, the nickel will be applied as positive electrode and reduce graphene

oxide that coated on nickel foam will be the negative electrode to produce a great

electrochemical performance (Saeed et al., 2018).

The mechanical properties of reduced graphene oxide that have been studied is the

monolayer of graphene oxide that produced by a modified Hummer's method with a Young's

modulus of 207.6 ± 23.4 GPa, an order-of-magnitude drop but still notably high (Suk et al,

2010). Meanwhile, the electrochemical properties was researchers reduced a colloidal

suspension of graphene oxide exfoliated in water with hydrazine hydrate which exhibited an

electrical conductivity and improving the conductivity of the graphene oxide by 5 orders of

magnitude (Stankovich et al, 2007).

In this study, modified Hummers’ method with the presence of 𝑁𝐻3 under 800°C was

the process on preparing the fabrication of CMT@N-RGO hybrid and pure CMT. The chinar

seeds which in dried or ripe condition was separated until become fluff where it was used as a

raw material on producing CMT@N-RGO hybrid and pure CMT in chemical vapor

decomposition.
1.2 Problem Statement

Previously, there was a limitation on the properties of reduced graphene oxide as a

fully functioning reduced graphene oxide. There was a study on reduced graphene oxide that

produce by biochar and the result was sustainable enough to be use as supercapacitors but

CMT@N-RGO hybrid as an improvement. In comparison, the CMT@N-RGO hybrid can be

used as bifunctional material that used in high performance supercapacitor and oxygen

reduction catalyst. Therefore, in this paper, the properties of CMT@N-RGO hybrid was

discuss in order for it function excellently.

1.3 Objective

1. To prepare the carbon microtubes @ nitrogen-doped reduced graphene oxide hybrid.

2. To determine the properties of carbon microtubes @ nitrogen-doped reduced

graphene oxide hybrid.

3. To study the application of carbon microtubes @ nitrogen-doped reduced graphene

oxide hybrid.
2. LITERATURE REVIEW

2.1 Reduced Graphene Oxide

2.1.1 Definition, structure, and source.

Reduced graphene oxide can be defined as the form of graphene oxide that

was processed by chemical, thermal and other methods to reduce the oxygen content

in the graphene oxide compound (Dimitrios et al., 2015). Functionalized graphene,

chemically modified graphene or chemically converted graphene also considered as

the other names of reduced graphene oxide (Eda et al., 2010).

Graphene is an atomically thin, 2-dimensional (2D) sheet of sp2 carbon atoms

in a honeycomb structure. It has been shown to have many desirable properties.

Graphene oxide has a similar hexagonal carbon structure to graphene but also

contains hydroxyl (-OH), alkoxy (C-O-C), carbonyl (C=O), carboxylic acid (-COOH)

and other oxygen-based functional groups (Pendolino et al, 2017). Graphene

derivatives such as graphene oxide, reduced graphene oxide and graphene quantum

dots have proven to be effective fillers in polymer nanocomposite materials thanks to

their ideal material properties and dispersibility in polymer matrices (Yoo et al, 2014).

Graphene oxide is one of those materials and it is a single-atomic layered

material that made by the powerful oxidation of graphite, which is cheap and

abundant. Graphene oxide is an oxidized form of graphene, laced with oxygen-

containing groups. Reduced graphene oxide can be gain by the synthesis of graphene

oxide in several processes such as modified Hummers’ method.

2.1.2 Reduction of graphene oxide.

In order to produce reduced graphene oxide, the exhaustive research has been

done to remove the oxygen functional groups of graphene oxide (Silva et al, 2017).

This reduction can be accomplished by a number of means, from thermal to chemical

to electrochemical, each of which leads to differences in morphology.

Reduction of graphene oxide by thermal treatment relies on the decomposition

of oxygen groups into CO and CO2 gases at elevated temperatures (Pei et al, 2012).

The fast evolution of these gases has also been shown to exfoliate individual graphene

oxide nanosheets. A thermal reduction can be done by thermal annealing at elevated

temperatures in an oxygen-free environment or by less-conventional methods such as

microwaving graphene oxide powders or flash reduction of graphene oxide films by

high-intensity light. The addition of chemical reducing agents to graphene oxide

solutions is common and many techniques are well-supported by the literature (Chua

et al, 2014), these can include hydrazine metal hydrides or hydrohalic acids

(Stankovich et al, 2007). Reduced graphene oxide can also be synthesized through

photocatalyzed reactions.

Reduced graphene oxide also able gain by using ultraviolet light in the

presence of a TiO2 catalyst (William et al, 2008). Electrochemical reduction is also

possible and does not require the use of chemical agents where this reduction is

exclusively driven by electron exchange between graphene oxide and the electrodes

of a typical electrochemical cell (Yang et al, 2016). In recent years, a number of

“green” reducing agents have been reported to be effective at synthesizing reduced

graphene oxide, such as ascorbic acid, sugars, amino acids, and even microorganisms

(Silva et al, 2016).

2.2 Properties of reduced graphene oxide.

2.2.1 Mechanical properties

Mechanical properties of pristine monolayer graphene are well-reported as

recorded on having a break strength of 42 N m−1, a Young's modulus of 1.0 TPa, and

an intrinsic tensile strength of 130.5 GPa (Lee et al, 2007). The fracture toughness of

graphene has reported to be as low as 4.0 ± 0.6 MPa m1/2, confirming the low fracture

of graphene sheets (Zhang et al, 2014). Graphene oxide and reduced graphene oxide

blends are produced in an attempt to achieve these properties, with values ranging

depending on the number of surface groups and defects leftover from oxidation or

other treatment processes. The studied was reported monolayer of graphene oxide that

produced by a modified Hummer's method with a Young's modulus of

207.6 ± 23.4 GPa, an order-of-magnitude drop but still notably high (Suk et al, 2010).

Polymer nanocomposites benefit greatly from the use of graphene oxide and

its derivatives as fillers (Kim et al, 2010). For example, the investigation on the effect

of graphene oxide in polyvinyl alcohol films produced by solution casting and

founded that a 20% graphene oxide filler content was able to increase the tensile

strength of the nanocomposite to 59.6 MPa which is more than five times the strength

of the pure PVA film (Cheng-An et al, 2017). The huge improvement in mechanical

properties can be attributed not only to the strength of the graphene oxide filler but the

strength of the matrix/filler interface such as the hydroxyl groups of polyvinyl alcohol

and the oxygen functionalities of the graphene oxide led to a high degree of hydrogen

bonding. Moreover, there was reported on a unique combination of polyurethane with

graphene oxide and graphene oxide reinforced carbon fibres (CF-GO) as shown in

Figure 1(A) (Jiang et al, 2018). By incorporating only 0.1 wt. % graphene oxide
nanosheets into polyurethane before moulding in a vulcanizing press, the tensile

strength of polyurethane elastomer was increased from 42.4 to 49.3 MPa which is

16.4% improvement as show in Figure 1(B). In addition, by incorporating 0.1 wt. %

graphene oxide as well as 1% CF-GO, the tensile strength improved to 62.1 MPa

which is 46.4% higher. The carbon fibres had graphene oxide grafted onto their

surfaces by electrophoretic deposition at 3 V of applied voltage to improve the

interfacial adhesion of graphene oxide and polyurethane.

As a result, the elongation at break also improved for the CF-GO/PU

nanocomposites which improved stress transfer from the matrix to the fillers shown in

Figure 1(C). The preparation on reduced graphene oxide/polylactic acid (PLA)

nanocomposites by melt blending on a twin-roller mill (Bao et al, 2012). Then, after

preparing graphene oxide from graphite under pressurized oxidation conditions and

chemically reducing it into reduced graphene oxide with hydrazine and ammonia and

the reduced graphene oxide included in their nanocomposite had an average thickness

of 0.4–0.6 nm and an average lateral dimension of 0.1–0.5 μm. Inclusion of these

nanosheets into melt-blended PLA which give the result in a storage modulus increase

from 2.56 GPa to 4.04 GPa at 2 wt. %.

 Figure 1: (A) Schematic illustration of the CF-GO multiscale reinforcements for PU

elastomer nanocomposites. (B) Tensile strength of PU-based materials at room temperature

and its retentivity at 80 °C. (C) Stress-strain curves of PU-based materials (Jiang et al, 2018).
2.2.2 Electrochemical properties

Graphene is an electrically conductive material with high electron mobility

and electrical conductivity consisting of 2D layers of sp2 carbon one atom thick

(Novoselov et al, 2012). Graphene has been shown to greatly improve the electrical

conductivity of polymers at low filler contents example as 0.1 S m−1 at 1 vol% in

polystyrene (Stankovich et al, 2006). In the general fabrication of graphene oxide, the

process results in disruption of the sp2 bonding orbitals of graphene and the addition

of abundant surface groups that inhibit its electrical conductivity, making graphene

oxide electrically resistive (Wang et al, 2012). As the properties in high resistivity,

researchers have explored reduction techniques of graphene oxide into reduced

graphene oxide. In the reduction, the electrical conductivity of graphene oxide can be

greatly improved and can be tuned over several orders of magnitude with

conductivities (Pei et al, 2010). The reduced graphene oxide still contains residual sp3

bonded carbon to oxygen even after the reduction which it will disturbs the movement

of charge carriers through the rest of the sp2 clusters. Electrical transport in reduced

graphene oxide occurs primarily by hopping, which differs from that of mechanically

exfoliated graphene (Bagri et al, 2010).

Researchers have been exploring various techniques to improve the synthesis

of electrically conductive of reduce graphene oxide. For example, researchers reduced

a colloidal suspension of graphene oxide exfoliated in water with hydrazine hydrate

which exhibited an electrical conductivity and improving the conductivity of the

graphene oxide by 5 orders of magnitude (Stankovich et al, 2007). Researchers also

used a conventional microwave at 1000 W for 1–2 s to form reduced graphene oxide

which improved the electron mobility of graphene oxide in field effect transistors
(Voiry et al, 2016). Other methods have also been shown effective in synthesizing

highly conductive reduced graphene oxide, including immersion in hydroiodic acid

and activation with KOH (Zhang et al, 2012).

The enhanced electrical properties of reduced graphene oxide have made it a

promising material as a conductive filler to add to polymer matrices for uses in a wide

array of materials. For example, the development of a highly flexible supercapacitor

of polyaniline with reduced graphene oxide (Kim et al, 2014). This material had a

maximum electrical conductivity at a 24 wt. % reduced graphene oxide of

9.06 × 104 S m−1 which its making an improvement from the individual components

which only had electrical conductivities of 5.80 × 104 S m−1 and 4.65 × 103 S m−1 for

polyaniline and reduced graphene oxide, respectively (Kim et al, 2014). The improved

performance was a result of forming a more compact packing of the polyaniline

chains by inducing an expanded conformation of the polyaniline chains with π- π

interactions between reduced graphene oxide and polyaniline.

On the other hand, there was a development of reduced graphene oxide and

cellulose nanofiber paper with an electrical conductivity using a novel sandwich

structure of cellulose nanofiber covered on top and bottom with reduced graphene

oxide (Hou et al, 2018). The composite only contains 4 wt. % reduced graphene

oxides, and it showed a superior conductivity over blending of the reduced graphene

oxide in cellulose nanofiber.

2.3 Application of reduced graphene oxide

2.3.1 Electronic devices

Almost all electronic devices are using graphene oxide for at least one of the

components. For example, graphene-based field effect transistors where it uses reduced

graphene oxide as chemical sensors and biosensors (Lu et al., 2011). In field effect

transistors, to detect hormonal catecholamine molecules, avidin and DNA, reduced graphene

oxide is use as semi-conductor in respective biosensor (He et al., 2010). Other than that,

reduced graphene oxide also used in electrochemical glucose sensor after being deposited on

an electrode (Liu et al., 2010). Furthermore, reduced graphene oxide also produces in form of

transparent electrode that been used as a hole transport layer in polymer solar cells and LEDs

(Saha et al., 2014).

2.3.2 Energy storage devices

Due to larger surface area, reduced graphene oxide is classified as electrode in

batteries and double layered capacitor including fuel cells and solar cells (Zhu et al., 2010). In

this modern world era, hybrid cars may be one of the most used cars. As graphene oxide has

the capability to store hydrogen, it might be possible to be useful for the storge of hydrogen

in this type of modern cars. Lithium-ion batteries is the rechargeable invention that give big

impact to our world. In lithium-ion batteries, electrically will insulate the metal oxide

nanoparticles that will be adsorbed onto reduced graphene oxide to increase the performance

of these materials in batteries (Wang et al., 2010). The anode material such as iron oxide

found that the energy storage fabricated in lithium-ion battery device using reduce graphene

oxide coated will made high surface area using microwave-assisted exfoliation and reducing

graphene oxide fabrication of supercapacitors as energy storage device (Zhou et al., 2010).
3.METHODOLOGY

3.1 Materials

The raw materials used is the fluff from the ripe seed of chinar tree or in scientific

name is Platanus Orientalis. The other materials used in ordered to produce CMT@N-RGO

hybrid were graphene oxide with 2mg m𝐿−1 concertation and chemical vapor decomposition

furnace with certain flow of 𝑁𝐻3 under 800°C.

3.2 Fabrication of CMT@N-RGO hybrid

To produce CMT@N-RGO hybrid, the chinar fluff was dipped into the graphene

oxide with 2mg m𝐿−1 concertation for 2 days. After 2 days, the colours of the chinar fluff

were changed from white to yellow as the result of a complete graphene solution absorbed.

The fluff with the complete loaded of graphene solution was placed into a chemical vapor

decomposition furnace with certain flow of 𝑁𝐻3 under 800°C. In addition, chemical vapor

decomposition is a vacuum deposition method that used to produce high quality, high-

performance, solid materials. Therefore, at the end of the process there were a solid

compound of CMT@N-RGO which in form of powder as a product (Xiong et al., 2020).

3.3 Fabrication of pure CMT

Pure CMT also produced as a comparison of the results. To produce pure CMT, the

pure chinar fluffs were placed into a chemical vapor decomposition furnace with certain flow

of 𝑁𝐻3 under 800°C. As same as CMT@N-RGO, the products were in form of powder

(Xiong et al., 2020).

3.4 Characterization of materials

3.4.1 Material Characterization

The structural characterization based on method describe by Ramasamy et al., 2019

which the carbonized materials will be performed by using X-ray diffraction (XDR) analysis.

The morphology of the sample produce will be analysed by using the scanning electron

microscopy (SEM) and transmission electron microscopy (TEM). Fourier transform infrared

(FT-IR) will be used to collect of functional group that over the range from 4000 to 500

〖cm〗^ (-1). The UV-vis absorption spectra will be recorded in the wavelength ranging

from 200 to 1100 nm.

3.4.2 Electrochemical Characterization

The electrochemical measurement will be conducted in a standard multichannel

potentiates as describe in Ramasamy et al. The cyclic voltammetry (CV) will be analysed

various scan rates ranging from 10 to 500 mV/s. The galvanostatic charge-discharge analysis

will be performed at different current density ranging from 0.025 to 1 mA and the

electrochemical impedance spectroscopy (EIS) studied will be using an electrochemical

workstation which is Biologic (VSP). The capacitive behaviour of the materials will be

examined by three-electrode system in a 2M potassium hydroxide (KOH) aqueous

electrolyte. A platinum rod, a saturated calomel electrode and reduced graphene oxide

electrode will use the counter electrode, reference electrode and working electrode,

respectively. The specific capacitance (𝐶𝑠 ) will be derived from a galvanostatic curve

(Ramasamy et al., 2019).

3.5 Preparation of CMT@N-RGO and pure CMT electrode

As the production of CMT@N-RGO and pure CMT electrode, the reagent that will be

used is acetylene black, polytetrafluoroethylene (PTFE) emulsion, and ethanol. As shown in

Figure 3, there was nickel foam act as a current collector and PTFE as a binder. In this

experiment, nickel will be used as it helps in higher energy density delivery with large

capacity at lower cost (Saeed et al., 2018). Respectively, PTFE used as binder as it provides

high reproducible performance of electrode also cheaper compared to Nafion (Hawaiah et la.,

2017)

The first step in the process of preparation CMT@N-RGO or CMT electrode will be

cutting the nickel with about 1 cm diameter and the respective mass will be weighed (𝑚0 ).

After that, 90mg of the sample should be CMT@N-RGO, 24mg of acetylene black, and 6mg

of PTFE will be weighed, respectively. Then, all the weighed reagents will be mixed in agate

shelter and ethanol will be added into the mixture. The mixture will be grinded until become

into paste and the paste will be CMT@N-RGO hybrid or pure CMT. Back to the nickel foam,

the CMT@N-RGO hybrid or pure CMT paste will be smeared on the one side of it evenly

then dried in vacuum drying chamber under 80°C for 15 hours. After dry, the sample will be

weight (M) and the CMT@N-RGO hybrid or pure CMT electrode will be calculated as the

following equation:

m = (M-𝑚0 )75% m: weigh of CMT@N-RGO hybrid or pure CMT electrode.

In the use of supercapacitor, nickel will be applied as positive electrode and reduce

graphene oxide that coated on nickel foam will be the negative electrode to produce a great

electrochemical performance (Saeed et al., 2018).

4.RESULT AND DISCUSSION

4.1 Structure and morphology

The pure CMT and CMT@N-RGO can be evince by scanning electron microscope

(SEM) which shown in Figure 2. In Figure 2(a), there are shown the cross-linked CMT which after

the carbonization of the chinar tree fluff. As in further amplification by local area, CMT are present in

long hollow tubes that have approximately 3µm diameter which can be seen clearly as in Figure 2(b).

After the introduction of N-RGO, there are a transparent film that covered a cross-linked which can be

shown in comparison of Figure 2 (a) and Figure 2(b).

Figure 2: The SEM image of (a), (b) CMT and (c), (d) CMT@N-RGO under different magnification. The inset

shown in Figure 2 (d) is the EDS of the CMT@N-RGO hybrid.

The present of CMT is as a spacer that can prevent the staking of N-RGO effectively

to maximize the use of specific surface area to get large capacitance. Moreover, from the data

in EDS spectra that attached on Figure 2(d) it clearly shows the presence of C, N and O

element which mean the nitrogen is successfully doped into reduced graphene oxide.
(A)

CMT CMT/N-RGO

300

250
VOLUME ADSORBED/CM³G¯¹

200

150

100

50
0.0 0.2 0.4 0.6 0.8 1.0
RELATIVE PRESSURE/ (P/P˳)

(B)

CMT/N-RGO

0.10
0.09
0.08
PORE VOLUME / CM³G¯¹

0.07
0.06
0.05
0.04
0.03
0.02
0.01
0.00
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
PORE SIZE (NM)

Figure 3: (A) The 𝑁2 adsorption/desorption isotherms of the CMT and CMT@RGO hybrid. (B) The pore size

distributions of the CMT@RGO hybrid.

 The specific surface area and pore size distribution of electrode material are the main

factors that affecting the electrochemical performance of the materials, as shown in Figure 3.

In Figure 3(A), it shows the comparison between the 𝑁2 adsorption/desorption isotherm of

CMT and CMT@N-RGO hybrid. As the specific surface area of the CMT@N-RGO hybrid,

the demonstrating of specific surface area of CMT also increase to show it will function as

charge storage. The reason of increasing specific surface area in CMT@N-RGO hybrid are

usually cause by the porous structure that formed among the cross-linked of CMT and the

introduction of graphene oxide. Moreover, the curve belongs to type IV with characteristic

𝐻3 hysteresis loop, implying its mesoporous characteristics (Xiong et al, 2017), which

matches well with the curve of the pore size distribution of the CMT@N-RGO hybrid

presented in Figure 3(B) where the range of the pore size from 2nm to 8nm.
4.2 Electrochemical performance in supercapacitors

Figure 4: The comparison of the (a) CV curves, (b) GCD curves, (c) The capacitance

retention of and (d) The specific capacitances and energy efficiency of the CMT@N-

RGO/MnO2 and CMT@N-RGO/PANI hybrid under different scan rates and current densities

(Xiong et al, 2020)

The CMT@N-RGO/MnO2 and CMT@N-RGO/PANI hybrid electrochemical

performance was studied based on aqueous Li2SO4 electrolyte as shown in Figure 4. The

electrochemical of pure CMT and CMT@N-RGO was detected under the same carbonization

condition as a comparison. In Figure 4 (a) and (b), it shows the cyclic voltammetry (CV) and

galvanostatic charge/discharge (GCD) curves which the pure CMT and CMT@N-RGO were

come out with an ideal rectangular shape and symmetrical triangle shape at the scan rate of

100mV/s and current density of 8A g/1, respectively. In order to functional as good

capacitive performance and electrochemical reversibility, which demonstrates that the as-

obtained carbonaceous material has a great potential in serving as a highly efficient scaffold

to construct hierarchical hybrid for high-performance supercapacitor.

 Moreover, by comparison, it can be seen clearly that the CV curves of the CMT@N-

RGO/Mn𝑂2and CMT@N-RGO/PANI present obvious redox peaks from Mn𝑂2 or PANI,

especially for the PANI, which matches well with a typical pseudocapacitive characteristic of

PANI (Cheng et al, 2013). Additionally, the GCD curves of the CMT@N-RGO/Mn𝑂2 and

CMT@N-RGO/PANI display were most symmetrical triangle shapes with a little deviation

to linearity indicating a pseudocapacitive contribution from Mn𝑂2or PANI, which is

consistent with the results of the CV curves. Other than that, the area of the CV curve and the

discharge time of the CMT@N-RGO/Mn𝑂2 and CMT@N-RGO/PANI hybrid at the same

condition are obviously larger and longer than that of the pure CMT and CMT@N-RGO,

which demonstrates that the CMT@N-RGO/Mn𝑂2 and CMT@N-RGO/PANI hybrid have

improved specific capacitance after introduction of Mn𝑂2 or PANI. This is mainly due to the

good synergistic effect of the CMT and N-RGO/Mn𝑂2 or N-RGO/Mn𝑂2 as analysed in SEM.

The capacitance retention of the CMT@N-RGO/Mn𝑂2 and CMT@N-RGO/PANI

hybrid under various scan rates were also compared as shown in Figure 4(c). Apparently,

both present higher capacitance retention of 91% and 95%, respectively when the scan rates

increase from 10 to 200 mV/s to show an excellent capacitive performance. Furthermore, the

relationship between the specific capacitance, energy efficiency and current densities for the

CMT@N-RGO/Mn𝑂2 and CMT@N-RGO/PANI hybrid are also investigated to check the

comprehensive electrochemical properties that been detect in Figure 4(d). Apparently, the

specific capacitance of both decreases from 612 to 475 to 420 and 306 F g/1 respectively

when the current densities increase from 10 to 40 A g/1 implying excellent rate performance.

The high energy efficiencies of 65–77% and 61–72% are also obtained for both to indicate a

high degree of reversible Faraday reaction of the hybrid during the process charging and

discharging.
4.3 Catalytic properties in oxygen reduction reaction

On the other hands, to prepare a friendly CMT@N-RGO/PANI material is an

improvement to serve as an efficient electrocatalyst in the oxygen reduction reaction (ORR).

The CV curves are determined to check the ORR activity of the hybrid as material as shown

in Figure 5(a), where an obvious peak from the reduction of 𝑂2 with the assistance of the

hybrid at a potential of ~ - 0.35 V in 𝑂2-saturated KOH solution (0.1 M) is shown to compare

with the result tested in 𝑁2 -saturated KOH solution, indicating that the effective ORR

catalytic property of the CMT@N-RGO/PANI hybrid is obtained. As a comparison, the

polarization curves of commercialized Pt/C, CMT and CMT@N-RGO/PANI hybrid are

displayed in Figure 5 (b), respectively. The CMT@N-RGO/PANI hybrid displays a larger

positive onset potential of 0.12 V and half-wave potential of 0.21 V, which is much higher

than that of pure CMT, and can be comparable to that of commercial Pt/C electrode (0.05 V

and 0.1 V). In addition, to further study the electrocatalytic kinetics of the CMT@N-

RGO/PANI hybrid in ORR, polarization curves under different rotation speed are also

measured as shown in Figure 5(c). It can be seen clearly that diffusion-limiting current

densities increase along with the increase of speed due to the shorter 𝑂2 diffusion length. The

above results indicate that the friendly CMT@N-RGO/PANI material has a great potential in

acting as an efficient ORR catalyst.

Figure 5: Oxygen reduction reaction properties of the CMT@N-RGO/PANI hybrid (a) CV

curves tested in N2- and O2-saturated KOH solution (0.1 M). (b) The comparison of

polarization curves of Pt/C, CMT and CMT@N-RGO/PANI. (c) Polarization curves of the

CMT@N-RGO/PANI hybrid tested with various rotation speed (Xiong et al, 2020).
4.3 Reduced Graphene Oxide Preparation

The procedure for the synthesis of reduced graphene oxide derived from coconut shell

waster will involves of direct carbonization in muffled furnace. The raw material of coconut

shell obtain will be crushed and grounded to produce a powder coconut shell sample. Then,

0.5g of the powder sample will be mixed with 0.1g of ferrocene and placed in a muffle

furnace for 15 minutes at 300°C under atmospheric conditions before it allow to be cool in

room temperature. Carbonization at temperature 300°C will be chosen due as it will allow

full oxidation of coconut shell powder sample into graphene oxide that will be produced a

well graphite 2-dimensional structure of graphene oxide sheets. Optimization of the reduced

synthesis process will be confirmed using X-ray diffraction analysis (Ramasamy et al., 2019).
CONCLUSION

In conclusion, the previous study on reduced graphene oxide that produce by biochar

was enough capacitance to be use as high-performance supercapacitors compared to

CMT@N-RGO hybrid. As a preparation to produce CMT@N-RGO hybrid was fabricated by

combining dipping the chinar fluff into graphene solution and chemical vapor deposition

methods. The properties of CMT@N-RGO hybrid was divided into two which were

mechanical properties and electrochemical properties. The main used of reduced graphene

oxide that important to technology were in electric devices and energy storage. The

advantage of this study was improving the production of reduced graphene oxide as an

excellent carbonaceous scaffold for energy storage and electrolysis. The limitation in this study was

the sources of raw materials which were from chinar tree that mostly found in southern Asia. The

recommendation on this limitation is to planting chinar trees as ornamental plants in every country to

get sufficient resources in the future.

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