Carbon Nanostructures Production from Waste Materials: A Review

SUHUFA Alfarisa1,2,a*, SURIANI Abu Bakar1,2,b, AZMI Mohamed1,3,c, NORHAYATI Hashim1,3,d, AZLAN Kamari1,3,e, ILLYAS Md Isa1,3,f,

MOHAMAD HAFIZ Mamat4,g, ABDUL Rahman Mohamed5,h and MOHAMAD Rusop Mahmood6,i

1 Nanotechnology Research Centre, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, 35900 Tanjung Malim, Perak, Malaysia

2 Department of Physics, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, 35900 Tanjung Malim, Perak, Malaysia

3 Department of Chemistry, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, 35900 Tanjung Malim, Perak, Malaysia

4 NANO-ElecTronic Centre, Faculty of Electrical Engineering, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia

5 School of Chemical Engineering, Universiti Sains Malaysia, Engineering Campus, Seri Ampangan, 14300 Nibong Tebal, Pulau Pinang, Malaysia

6 NANO-SciTech Centre, Institute of Science, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia

asuhufaalfarisa@ymail.com, babsuriani@yahoo.com, cazmi.mohamed@fsmt.upsi.edu.my, dnorhayati.hashim@fsmt.upsi.edu.my, eazlan.kamari@fsmt.upsi.edu.my, fillyas@fsmt.upsi.edu.my,

gmhmamat@salam.uitm.edu.my, hchrahman@eng.usm.my, irusop8@gmail.com

Keywords: carbon nanostructures, waste materials.

Abstract. Research innovation in finding new carbon sources for carbon nanostructures material

production was intensively done lately. In this review, we present the production of carbon

nanostructures such as carbon fibers, nanotubes, nanowhiskers, microspheres and porous carbon

from several waste materials. The benefit of the use of waste materials such as waste cooking palm

oil, chicken fat, waste natural oil, glycerol, printed circuit board, plastic wastes, waste engine oil,

scrap tyre, heavy oil residue and deoiled asphalt is not only in the term of their environmentally

friendly approach but also the economic value to reduce the high cost of carbon material production

using common sources. On the other hand, these materials are easy access sources and can be

alternative utilization to convert waste materials into high value nanomaterials.

Introduction

Carbon is an easy accessible element and can be formed into many kind of carbon materials such

as carbon nanotubes (CNTs), carbon microspheres (C-µS), carbon fibers (CFs) and porous carbon.

The studies on producing these carbon materials are being widely done lately due to their versatile

applications in various life areas. Conventional sources for carbon materials production are

methane, ethane, acetylene, toluene and another hydrocarbon based fossil fuel. The use of these

common sources has several disadvantages such as their limited availability and expensive. There

have been many studies on alternative precursors for carbon materials production using

biohydrocarbon sources including turpentine [1], eucalyptus [2], neem [3], palm [4], olive, corn and

sesame oil [5]. The use of these biohydrocarbon sources and their synthesis methods has been

reviewed before [6]. These sources offer an environmentally friendly approach and cheaper cost but

they are less in term of effectiveness because these natural hydrocarbons are still very useful in

human life. Therefore the research on other more effective sources was done using waste materials.

Here we review some waste materials such as waste cooking palm oil (WCPO), chicken fat, waste

natural oil, glycerol, printed circuit board (PCB) waste pyrolysis oil, plastic wastes, waste engine oil

Advanced Materials Research Vol. 1109 (2015) pp 25-29 Submitted: 12.07.2014© (2015) Trans Tech Publications, Switzerland Accepted: 17.07.2014doi:10.4028/www.scientific.net/AMR.1109.25

All rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of TTP,www.ttp.net. (ID: 202.45.133.2-27/03/15,10:04:14)

and scrap tyre rubber as starting material for carbon-based materials production. A brief explanation

of their synthesis method is also discussed. Other than that, rich carbon content in aromatic

hydrocarbon such as asphalt and heavy oil residue also can be used as carbon sources to produce

carbon materials. To the best of our knowledge, there was no a review study yet regarding to this

matter. This short review is meant to help the researchers to generally understand the existing works

on the utilization of waste materials for carbon nanostructures production.

Waste Materials as Carbon Sources to Produce Carbon-based Materials

We simplify this review into two subsection based on the phase of waste materials used, whether

they are in a solid or liquid phase. The solid waste materials reviewed here are waste plastics, PCB,

scrap tyre rubber, chicken fat and banana peel. While for the liquid phase waste materials are

WCPO, waste naturals and engine oil, glycerol, heavy oil residue and deoiled asphalt. However,

several solid waste materials such as PCB and waste chicken fat were initially processed into liquid

form before being used.

Solid Waste Materials. The first waste material reported as the source for carbon material

production was waste plastic by Kukovitskii et al. [7, 8]. The widely use of plastic turn it to be one

of the most abundant waste material in the world. Waste polyethylene plastic was used to produce

microsize crooked CFs by catalytic pyrolysis of granular polyethylene on nickel plates as catalyst

substrate under helium atmosphere at 4 atm pressure [7]. The reaction temperature was at 420-450

°C and the synthesis process lasted for 50-60 mins. The generated carbon products were about

3x10-3 g/cm2 per hour with diameter range of 10-40 nm and thickness of about 100 nm. The

oxidation of carbon products occurred at relatively low temperature of about 420 °C and a low

quality product was also shown by the highly defective structure known from micro-Raman spectra

analysis. Under the same condition with different reaction temperature of 800 °C in their second

work [8] resulted in the formation of CNTs with diameter of 20-60 nm. Many other works then

being done on converting waste plastics into high value CNTs such as a simple catalytic pyrolysis

of waste polypropylene plastic at 600-800 °C using nickel catalyst [9]. Unfortunately, many

amorphous and agglomerate structures were seen through the scanning electron microscopy (SEM)

images of the sample produced. Another work was microwave-irradiation of waste plastic bottle at

irradiation power of 1000 W [10]. The utilization of waste plastic bottle was a very great idea and

innovative. But a lower power consumed method need to be reconsidered for the more effective and

efficient technique. Waste plastics which are non-biodegradable sources consist of organic polymer

with hydrocarbon chains that were believed as the source of carbon atoms for the growth of carbon

materials.

Our research group have reported the synthesis of high quality vertically aligned CNTs

(VACNTs) from waste chicken fat [11] using thermal chemical vapor deposition (TCVD) technique

and ferrocene as catalyst. Synthesis process lasted under typical conditions; reaction temperature of

750 °C and 5.33 wt% of catalyst concentration in argon gas atmosphere. The precursor amount of 6

ml was vaporized at 470 °C and the synthesis lasted for 60 mins. CNTs from waste chicken fat have

diameter in the range of 18-78 nm, 35 µm in length and the purity of 88.2% calculated from

thermogravimetric analysis (TGA). Ferrocene as catalyst decomposed into Fe nanoparticles and

deposited in the synthesis region. Next the precursor also decomposed into lighter hydrocarbon and

dissolved on the Fe surfaces. The diffusion of carbon atoms on the Fe surface will led to the growth

of CNTs.

Synthesis of CNTs and porous carbon were also reported by Quan et al. [12] using PCB waste.

PCB waste is easily collected from waste electrical and electronic components. It was firstly

pyrolized to formed oil and then polymerized with formaldehyde solution 6.5 g 37% using

ammonium hydroxide catalyst at 95 °C for 4 h. The resin then heated for 2 h at 60 °C followed by

12 h at 120°C. This process produced PCB waste pyrolysis oil-based resin used as precursor. The

next long pyrolysis process of oil-based resin and ferrocene catalyst at 900 °C obtained 56.82%

26 NANO-SCITECH 2014

CNTs with outer diameter of 338 nm and wall thickness of 86 nm. The porous carbon was produced

from the carbonization of KOH-treated resin at 700 °C. Somehow, the use of PCB waste as

precursor for carbon materials production is too much complicated compared with another materials

explained before. Scrap tyre rubber was also reported as carbon source to produced CNTs [13].

After pyrolized, the lighter hydrocarbons of scrap tyre rubber can be used for the formation of

carbon materials. TCVD method was used for CNTs production in this work. 50 mg of catalyst

powder was heated under H2 atmosphere for 1 h at 650 °C and then the system was changed to

nitrogen atmosphere. Without any initial treatment, 6 g of scrap tyre rubber was then transferred to

the furnace at 400 °C and the reaction lasted for half an hour. From the TGA, about 40 % of CNTs

were produced. SEM image showed that CNTs produced were short, thick and the structure tends to

agglomerate. It can be said that CNTs from scrap tyre rubber were low in quality.

Banana peel can be also used for CNTs production [14]. It was firstly carbonized at 400 °C,

activated with phosphoric acid and then pyrolized at 600 °C to become banana peel activated

carbon powder. The powder was then mixed with 2% mineral oil, placed in stainless steel tube and

pyrolized at 1000-1200 °C for 1 h to obtained CNTs. CNTs produced have outer diameters of 47-10

nm and inner diameters of 12-30 nm. At high temperature conditions, banana peel activated carbon

– mineral oil mixture was decomposed and formed the graphitic structure of carbon. Unfortunately,

high temperature system is needed in this process

Liquid Waste Materials. With similar procedure as mentioned in waste chicken fat part above, our

research group synthesized high quality VACNTs from WCPO [15]. The differences lied in the

amount of precursor, synthesis time and vaporization temperature used. For WCPO, 3 mL of

precursor was used at 450 °C of vaporization temperature and 30 mins of synthesis time. These

were due to the different amount of energy and time that were needed to decompose the precursors.

CNTs with diameter of 20-50 nm and 120 µm in length with calculated purity of 85 % were

obtained from WCPO precursor. Both of waste chicken fat and WCPO are abundant food waste

since they are widely consumed and used in human life. Datta et al. [16] reported the production of

carbon nanowhiskers (CNWs) from waste natural oils namely waste mustard, soybean, sesame and

castor oil using dry autoclaving method. These oils composed of fatty acid such as oleic, linoleic,

palmitic and stearic acid which are crucial for the formation of CNWs. 1.5 ml of oil and

Fe(NO3)3.9H2O as catalyst were mixed and introduced into closed reactor and treated at 500-850 °C

for 4-10 h in autogenic pressure autoclave. The yield product from 1.5 ml oil is about 0.24-0.29 g

(65-68%). Temperature changing and length of synthesis time played an important role for the

growth of CNWs. At 600 °C and below, fatty acid in the oils were not fully decomposed so that the

amorphous carbon or soot growth along with CNWs. Fully conversion of oil to CNWs was obtained

at synthesis temperature of 850 °C for 10 h. The uniform diameter of CNWs from the overall oils

was in the range of 130-160 nm with 1.65-2 µm in length. The similar work done by the same

research group was conducted using waste engine oil as the precursor [17]. Waste engine oil consist

of 18-34 carbon number range [18] which become the carbon atoms source for carbon material

production. There were no CNWs produced but only C-µS were obtained at 600 and 900 °C of

synthesis temperature. Difference structure of waste engine oil with another waste natural oil may

cause this happened. The hydrocarbon molecule of engine oil formed the gaseous carbon which

later solidified to form carbon droplet (nuclei) that lead the growth of C-µS. Unfortunately, this

autoclaving technique required a high pressure condition for the production of carbon materials. Wu

et al. [19] reported on production of CNTs from waste glycerol. Waste glycerol obtained from

biodiesel process contains alkali metal catalyst, salts and excess methanol and fatty acid methyl

esters. Gas-phase catalytic of glycerol at temperature of 700 °C and 10 wt% Ni-Mg-Al catalyst for 1

h synthesis time produced CNTs.

In another work, Li et al. [20] reported the synthesis of single-walled CNTs from heavy oil

residue, by product of petroleum distillation. CVD method was also used to produce CNTs in this

work. The oil was pyrolized at 200-400 °C and catalyst-coated substrates in another furnace region

were heated at 900 °C. Synthesis process lasted for 20 mins under Ar gas flow. CNTs produced

Advanced Materials Research Vol. 1109 27

have various diameters depended on the catalyst usage. High crystallinity of CNTs obtained from

Fe catalyst have diameter of 0.72-0.87 nm while CNTs with diameter of ∼1.47 nm were generated

from Pt catalyst used. It showed that the catalyst affects the grown CNTs especially their size.

Heavy oil residue is an aromatic hydrocarbon compound with high carbon composition of 86.80

wt%. The decomposition of hydrocarbon chains from the oil will lead the growth of CNTs. Another

aromatic compound and heavy hydrocarbon such as deoiled asphalt also have been reported as

carbon source for carbon-based materials production [21-24].

We noted that various methods and waste materials can be used for production of carbon

nanostructures material. However, each method and carbon source has its own advantages and

disadvantages. From our review, the most produced material was CNTs using CVD technique. This

was due to the better properties and many applications of CNTs among others. The research in this

field is still widely open since the optimization and discovery of another new waste carbon sources

are still very necessary.

Conclusions

Various waste materials can be used for carbon nanostructures production using different

techniques. The use of waste materials is not only to find an abundant and cheaper source for

production of carbon materials, but also as an alternative usage of waste material which most of

them are harmful to the environment. The work in this field is still widely open for future research

in order to obtain high value nanomaterial from cheaper sources and simpler method.

Acknowledgement

The authors are thankful to Malaysia Toray Science foundation (MTSF; Grant code: 2012-0137-

102-11), RACE (Grant code: 2012-0147-102-62), PRGS (Grant code: 2013-0097-102-32) and UPSI

for support of this work.

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