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Today I would like to share with you an interesting piece of research.

That is Formation of nanostructured graphitic carbon from coconut waste
via low-temperature catalytic graphitization.
And this paper was published with Engineering Science and Technology, an International Journal in
2021

OUTLINE is composed of 4 parts about

Introduction-Experimental-Results and Discussion- and Conclusion
………………………………………………………

INTRODUCTION

Coconut (The name of science is Cocos nucifera)

Coconut is a member of the palm tree family (Arecaceae), and it is vital in the Indonesian economy.

As a tropical country, Indonesia is the world’s largest producer of coconut. And exports coconut
products to countries around the world.

✓ These products include copra

✓ coconut crude oil (CCO) and
✓ CCO derivatives for various applications (cooking, skin, hair, energy)

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Coconut waste

✓ So, that why coconut waste has a large amount of agricultural waste about 62-65%
✓ And 35% of the 6.2 million tons of coconut coir generated as waste in Indonesia each year.

Poor management and improper disposal of coconut waste generates pollution that is socially and
environmentally problematic.

To ensure that coconut production does not adversely affect the environment, efforts should be
made to convert the abundant waste into value-added products.

including food addictive, biofuel, food packaging, ..........

And unsustainable is thrown on the land and water body.

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And next what is Coconut coir

Coconut coir is inside the outer coat of fruit

which is extracted from the fibrous coating of the coconut fruit. Coconut coir is a lignocellulosic
material that is primarily composed of cellulose (32.69%), lignin (42.10%), and hemicellulose
(22.56%).

………………………………………………………

And Lignocellulose compounds

It was degraded at different temperatures through carbonization in oxygen-limited or oxygen-free
environments to produce carbon-rich charcoal and volatile matter products.

The TGA spectra show that Ref The pyrolysis characteristics of three main components
(hemicellulose, cellulose and lignin) of biomass were degraded at different temperatures

From The structure

✓ Hemicellulose is consisted of various saccharides (xylose, mannose, glucose, galactose, etc.),

it appears a random, amorphous structure, rich of branches, which are very easy to degrade
to volatiles evolving out (CO, CO2, and some hydrocarbon, etc.) at low temperatures 220 C–
315 C.
✓ Cellulose consists of a long polymer of glucose without branches, its structure is in a good
order and very strong, and the thermal stability of cellulose is high. So, cellulose begins to
decompose at 315 C–400 C, respectively.
✓ And Lignin is full of aromatic rings with various branches. The activity of the chemical bonds
in lignin covered an extremely wide range, which led to the degradation of lignin occurring in
a wide temperature range about 160-900 C.

……………………………………………………

From literature for example using Coconut coir waste

Show it can be recycled or utilized as a renewable and relatively inexpensive carbon precursor, even
a graphite precursor, with additional treatment.

✓ Lignin-based materials are one of three components of lignocellusic biomass that can
produce porous carbon by direct carbonization without additional activation processes or
templating agents. Owing to its chemical composition and degradation characteristics.

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Graphitic structure

✓ Is A crystalline carbonaceous material.

✓ Composed of a series of stacked parallel planes (see figure). Each layer plane consists of a
series of hexagons where each carbon atom is bonded to three other carbon atoms (see
figure 1).
✓ The carbon atoms are connected through a covalent bond with a short length (approx. 0.141
nm) and high strength (approx. 524 kJ mol-1).
✓ The hybridized fourth valence electron for each carbon atom has a much weaker van der
Waals bond (approx. 7 kJ mol-1) with another delocalized electron from a neighboring plane.
✓ This secondary bond arises from structural polarization and the length between neighboring
planes is large (approx. 0.335 nm)
✓ And can be obtained from pyrolysis coke.

And outstanding properties,

such as excellent electrical conductivity and high thermal and chemical stability.

……………………………………………………

So, the Application of these precursors for example is automobiles [10], batteries [11,12], fuel cells
[13,14], solar cells [15], supercapacitors [16,17] and graphene production [18,19].
Ref Supercapacitor, graphene production: In this study, the symmetric paper supercapacitors with
the structures of graphene electrodes. The results of the symmetric paper supercapacitors based on
the nanomaterials electrode showed excellent performance that could be applied for electrical
energy storage.

Ref Fuel cell: In this study, a thin graphite layer is coated on the carbon/epoxy composite bipolar
plate to decrease the interfacial contact resistance between the bipolar plate and the GDL (Gas
Diffusion Layer).

Ref batteries: They develop a favorable electrode consisting of thin graphite sheets with through-
holes and carbon nanotube. The carbon nanotube can effectively prevent the restack of graphite
sheets. Combining with low desolvation energy electrolyte.

……………………………………………………

In previous studies (GDL),

Gas diffusion layers (GDLs) are one of the main components used in polymer electrolyte membrane
fuel cells (PEMFC). As key components

✓ GDLs have the main function of diffusing reactant gas into the catalyst layer, providing an
electric pathway for electrons, eliminating the water product, removing heat, and providing
mechanical support.

To perform these functions, GDLs should have appropriate

Properties needs for GDLs

✓ High Porosity

✓ High electrical conductivity

✓ Robust and mechanical strength

Proper wetting characteristics
✓

They are typically a porous component from carbon-based materials and available in the form of
carbon paper and carbon cloth.

…………………………………………………

For example

✓ The main objective of this previous study was to investigate the influence of different
carbon material forms on the properties of the two CCPs and their performance as GDLs in a
PEMFC system.

i.e., powder and fiber., namely CCP-1, CCP-2. The GDLs were assembled at both sides of the
membrane.

The required properties of the GDL are being focused on the electrical conductivity and porosity.

So, this work wants to make coconut coir-based carbon material for the gas diffusion layer (GDL)
of the proton exchange membrane fuel cell (PEMFC) in term only Fiber, while using a low energy
consumption graphitization process.

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Catalytic graphitization

Graphitization is a form of heat treatment used to achieve a transformation from disorientated

carbon into graphitic structure. Historically this was achieved at between 2000-3500℃ and required
a very high energy consumption.

Studies in recent years have however shown that with the implementation of a catalyst, the needed
temperature for the graphitization can be lowered while also increasing the degree of graphitization
for the process.

Ref: The graphitization of the carbons thus prepared varies as a function of the carbonization
temperature used and the type of metal employed as catalyst (Fe, Ni or Mn).

✓ The porous characteristics of these materials change greatly with the temperatures used
during the carbonization step. These graphitized carbons exhibit high electrical
conductivities up to two orders larger than those obtained for the non-graphitized samples.

……………………………………………………

In terms of catalysts, minerals and metals have been widely used, where Iron, Nickel and Cobalt are
favored.

Ref: Ni

The synthesis of carbon-based nanomaterials, this work developed a mild one-step hydrothermal
synthesis route for the fabrication of highly dispersed metallic nickel nanoparticles on hydrothermal
carbons derived from waste biomass.

Ref: Fe

Hierarchical micro-/mesoporous graphitic carbon spheres (HGCS) were synthesized by Fe-catalyzed

graphitization of amorphous carbon spheres resultant from hydrothermal carbonization.
…………………………………………………………

Generally, previous work Ref:

Making nickel-based catalytic graphitization process at various temperature of 1000 ◦C to 1300 ◦C,
found that a high graphitic carbon material has been successfully fabricated from renewable
resources of coconut coir waste by simpler and lower energy process than that used for
conventional graphite production.

And from the XRD spectra show %of degree of graphitization that at 1200 ◦C have higher than
1300◦C.

…....................................................

So, this research uses an abundant coconut coir waste as a renewable and inexpensive graphitic
carbon precursor to produce a material with better electrical conductivity. using a low energy
consumption graphitization process.

They selected Ni as a catalyst

because
 ✓ its effectiveness in producing graphitic structures with high crystallinity.
✓ and its corrosion resistance in basic or acidic environments. It was also our objective to
promote the utilization and conversion of coconut coir waste into value-added materials.

…………………………………………………………

So, aim of this study

Graphitic carbon was synthesized by first carbonizing coconut coir at 500 C for an hour to
obtain carbon-rich charcoal.

then impregnated the charcoal with a nickel solution. Pyrolysis at 1300 C transformed the
amorphous charcoal into graphitic structures, and the residual metal was removed with
hydrochloric acid.

……………………………………………………………

EXPERIMENTAL

2.1. Preparation of coconut coir charcoal

The coconut coir used as a carbon source was collected from a local market in Indonesia.

2.2. Preparation of graphitic carbon materials from coconut coir waste

Coconut waste-derived graphitic materials were prepared using a Ni-based catalyst to decrease the
graphitization temperature.

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RESULT AND DISCUSSION

The morphology of carbon material derived from coconut coir was observed by SEM analysis

✓ At low magnification, all samples exhibited the original coconut coir structure (i.e., fibres
with several parallel hollow tube close to each other)
✓ The catalytic graphitization process and HCl treatment of carbon can produce more pores in
the wall of the hollow tube of carbon, respectively.

…………………………………………………………

The porous structure was also confirmed by the BET analysis.

The sample without the catalytic graphitization process and HCl treatment,

✓ The 1300-CC sample exhibited a low surface area and low total pore volume.
✓ The catalytic graphitization process, 1300-Ni-GCM sample, increased surface area and total
pore volume
owing to the etching reaction between the Ni salt catalyst and carbon.
✓ And after treatment of 1300-ANi-GCM using HCl increased surface area, indicating the
removal of Ni particles, which created a more porous carbon.

And next ……………………………………………………………

XRD performed structural changes in the carbon throughout the graphitization process.

The samples treated with Ni each contained a strong peak centered at approximately 26.5.
 ✓ This diffraction peak corresponded to the 002 plane of graphite, and it was also observed in
the XRD pattern of commercial graphite.
✓ In contrast, the sample contained a broad (002) peak shifted in the negative direction.

This indicated that the sample contained large amounts of disordered carbon or an
amorphous phase.

And XRD analysis was also helpful in determining that the HCl treatment was effective for removing
the nickel particles from the sample.

✓ Strong peaks of nickel, there is no clear peaks detection, which indicated the reduction of
nickel particles in the samples.

Eq…………………………………………………

The degree of graphitization was calculated using Eq. (1)

✓ where 3.440 is the interlayer spacing in non-graphitized carbon (Å);

✓ 3.354 is the interlayer spacing in an ideal graphite crystallite (Å);
✓ and d002 is the interlayer spacing in the sample determined from its XRD pattern (Å).

The crystallite size (Lc) was calculated using Eq. (2)

✓ where b is the full width at half maximum (FWHM) peak intensity at 2h (rad),
✓ and K is a dimensionless constant that depends on the plane of reflection.
✓ In this case, K for the (0 02) peak is 0.89.

The number of stacked carbon layer planes (n) was calculated using Eq. (3) ………………………………………

The quantitative analysis in Table. The degree of graphitization is used to quantify the similarity
between a carbon material and a perfect single graphite crystal.

✓ Sample 1300-Ni-GCM had a high degree of graphitization (84.88%) that was slightly lower
than that of commercial graphite (90.23%).
✓ The acid treatment to remove Ni from the graphitic carbon powder shows a lower degree of
graphitization than the sample treat with Ni, because the acid degraded the carbon lattice
This meant that 1300-Ni-GCM had higher graphite content than that of the 1300-ANi-GCM
sample.

…………………………………………………

And The removal of nickel particles by the HCl treatment was confirm by using the EDS data. Can
see that the amount of nickel decreased from 2.72 % to 0.76 % after the HCl treatment.

……………………………………………………

and Raman spectra show that

✓ The sample 1300-CC spectrum contained two broad and overlapping peaks characteristic of
amorphous carbon materials.
✓ The spectra of samples treated with nickel, 1300-Ni-GCM and 1300-Ani-GCM, contained
three peaks. And were similar to that of commercial graphite.
✓ The peak near 2,690 cm1 in each of these spectra was assigned to the 2D band indicates the
presence of graphene layers. But the spectrum of the carbon sample did not contain a 2D
band.
And the fitted peaks are show the IG/ID ratios and peak parameters

✓ The IG/ID ratio of the 1300- Ni-GCM sample was significantly higher than 1300-ANi-GCM and
1300-CC.
✓ These results indicated that the degree of graphitization in 1300-Ni-GCM and 1300-ANi-GCM
samples was higher than it was in the 1300-CC sample.
✓ Moreover, the G and D bands in the spectra of the samples treated with nickel were shaped
differently than the corresponding bands in the 1300-CC spectrum.

…………………………………………………

Next the chemical compositions of sample were analyzed by using XPS.

✓ The Ni signal, which is located at the binding energy of approximately 852.6 eV, does not
appear in the XPS spectra of nickel-treated samples. This result may be caused by the low
detection depth of XPS.
✓ But in TEM analysis can confirm that Ni particles are inside graphene layers with a thickness
of about 15–20 nm

Table shows the XPS quantitative

✓ The catalytic graphitization process causes the increase of surface carbon content from
88.22% to 93 increase in the amount of graphitic carbon from 1300-CC to 1300- Ni-GCM.
✓ And HCl treatment to remove the Ni particles causes a reduction of the carbon content to
decrease to 90.5% and the oxygen content increase to 9.5%.

And same an increase in the surface oxygen content was also observed on 1300-CC after HCl
treatment to 13.08% (Fig. S1) with the same conditions.

…………………………………………………

Next TEM data confirmed that there were structural differences between the samples treated with
nickel and the absence of Ni particles.

✓ The structure in the 1300-CC sample was typical of an amorphous carbonaceous material.
The diffuse halo in the SAED pattern in the inset confirmed that the carbon in the 1300-CC
sample was an amorphous phase.
✓ The image of the 1300-Ni-GCM sample shows spherical projections with Ni nanoparticles in
their cores. The high-resolution TEM (HR-TEM) image shows shells around the Ni
nanoparticles with well-defined lattice fringes.
✓ After acid treatment 1300-ANi-GCM, most of Ni particles were dissolved and removed from
the sample, leaving the ordered carbon nanostructure, which can be clearly seen.

Thus, amorphous carbon, derived from coconut coir waste, was successfully converted into graphitic
materials via catalytic graphitization at a lower temperature than that of conventional graphite
production.

………………………………………………………………………………….

And Electrical conductivity of carbon powder is an important parameter when it is applied as

electrode material. They also investigated the effect of carbon structure from coconut coir on its
electrical conductivity.
 ✓ The powder electrical conductivity measurement of all samples at the pressure of 741 kPa,
the conductivities were determined to be 14.97 S/cm, 25.75 S/cm, and 24.75 S/cm,
respectively.
✓ This confirms the formation of graphitic carbon from amorphous structure in coconut coir
carbon, improved the electrical conductivity.
✓ And proves that the behavior of electron transport measured as electron conductivity is
proportional to the degree of graphitization in carbon material.
✓ But this is still lower than that of commercial graphite powder
✓ The authors are conducting more research on enhancing the structure of coconut coir
carbon to improve electrical conductivity and porosity.

…………………………………………………………………

CONCLUSION

4. Conclusion

✓ They developed a simple method to produce highly graphitic carbon materials from
renewable and abundant coconut coir waste at a lower temperature than that used for
conventional graphite production.
✓ The sample from carbonized coconut coir was successfully transformed into graphitic
structures and samples displayed a remarkably high degree of graphitization, 84.88% and
77.91%, respectively.
✓ Furthermore, the structural change from amorphous to graphitic structure enhances the
electrical conductivity of powder carbon.
✓ So, the simplicity and efficiency of this method for converting biomass waste into graphitic
carbon materials addresses the global challenge of obtaining value-added products without
harming the environment.
✓ And The nanostructures of the carbon materials obtained from coconut coir waste and their
high degree of graphitization also make them potential candidates as gas diffusion layers or
catalyst layers in fuel cells for electrochemical applications.