Synthesis of Various Carbon Nanomaterials (CNMs) on Powdered

Activated Carbon.

Mohammed A. AlSaadi1,, Abdullah Al-Mamun1*, Suleyman Aremu Muyibi1, Md Zahangir Alam1, Iis
Sopyan1, Muataz Ali Atieh12, Yehya M. Ahmed1.
1
Nanoscince and Nanotechnology research group (NANORG), Faculty of Engineering, International Islamic
University Malaysia (IIUM), Jalan Gombak 53100, Kuala Lumpur, Malaysia
2
Department of Chemical Engineering, Head of Nanocarbon Research Unit Centre of Research Excellent in
Nanotechnology, King Fahd University of Petroleum and Minerals (KFUPM), P.O. Box 5050, Dhahran-31261,
Saudi Arabia.
*corresponding author: E-mail: mamun@iium.edu.my, Tel: +60361965760, Fax: +60361964442

ABSTRACT

Carbon Nanomaterials CNMs are promising in many potential applications for its attractive

physical and chemical properties. Chemical vapor deposition technique CVD is used to

synthesize CNMs on fixed substrate. PAC was used as a successful substrate for CNMs growth

in CVD reaction process. Iron clustered nano particles Fe3+ was impregnated successfully on

PAC surface under sonication. EDX characterization results showed the evidence on

impregnation and growth of CNMs on PAC surface. The optimum weight percentage of Fe3+

impregnation on PAC was found 5%. The CVD reactor used in this investigation was locally

fabricated and modified to reduce the process time and cost. CNMs were synthesized at deferent

temperatures (850, 750, 650 and 550 oC) the maximum yield was obtained at 550 oC with

majority of CNFs. Various types of CNMs were grown: CNTs, CNFs, CN spheres and CN-

coils. FESEM and TEM images were studied for all the samples to investigate the nanostructures

for CNMs.

1
Keywords: Carbon nanomaterials, Carbon nanotube, Carbon nanofibers, Nanotechnology,

Chemical vapor deposition, Catalyst impregnation, Activated carbon

……………………………………………………

Introduction

Nano science and Nanotechnology promises to unleash enormous potential for diverse

applications and innovations ranging from new materials for textiles, packaging, and food, to

sophisticated medical procedures and treatments(Delgado, 2010; Trojanowicz, 2006).nanoscale

Materials can show different properties compared to what they exhibit on a macroscale, enabling

unique applications(Deck, Flowers, McKee, & Vecchio, 2007). For instance, opaque substances

become transparent (copper); stable materials turn combustible (aluminum); insoluble materials

become soluble (gold). A material such as gold, which is chemically inert at normal scales, can

serve as a potent chemical catalyst at nanoscales. Quantum and surface phenomena that matter

exhibits at the nanoscale are responsible of these fascinating change in the behavior of matter at

this scale.

Carbon nonmaterials, such as carbon Nanotubes (CNTs) or carbon nanofibers (CNFs) have

attracted the attention in the recent decades for its exceptional electrical, structural and

mechanical properties that make them highly promising novel materials for application in many

nanotechnology related fields such as: nanobiosensors nanoparticles and powders; nanolayers

and coats; electrical, optic and mechanical nanodevices; chemical analysis devises based on

carbon Nanotubes (Trojanowicz, 2006) and nanostructured (Chen, Wang, Xu, & Yu, 2004)

biological materials(Du et al., 2008),(Ruparelia, Duttagupta, Chatterjee, & Mukherji, 2008).

2
Carbon nanotubes (CNTs) are among the most eminent materials in the first rank of revolution

nanotechnology. The most eye-catching features of these structures are their electronic,

mechanical, optical and chemical characteristics, which open a way to future applications. These

properties can even be measured on single Nanotubes (CNTs) and nanofiber. For commercial

application (Dresselhaus, Dresselhaus, & Avouris, 2001).

Several methods of production of (CNMs) have been reported (Ashby, Ferreira, & Schodek,

2009; Danafar, Fakhru'l-Razi, Salleh, & Biak, 2009; Kim & Min; Kukovecz, Méhn, Nemes-

Nagy, Szabَ, & Kiricsi, 2005; Merchan-Merchan, Saveliev, & Kennedy, 2004; Morançais et al.,

2007; Qiu et al., 2003; Tang et al., 2009; Xi et al., 2006; Xie, Huang, & Huang; Xu, Deng, &

Chen, 2003; H. M. Zhang, Wan, & Liming, 2006; Y. Zhang & Zhu, 2002). , The most common

techniques used nowadays are: arc discharge, laser ablation and chemical vapour deposition.

Chemical vapor deposition (CVD) is a versatile process suitable for the manufacturing of

coatings, powders, fibers, and monolithic components. Chemical vapor deposition may be

defined as the deposition of a solid on a heated surface from a chemical reaction in the vapor

phase. It belongs to the class of vapor-transfer processes, which is atomistic in nature that is the

deposition species are atoms or molecules or a combination of these (Pierson, 1999).

In the CVD-method different hydrocarbons such as benzene (C6H6), pentane (C5H12), acetylene

(C2H2), methane (CH4) and carbon monoxide are decomposed over different metallic catalysts

(Fe, Co, Ni) at temperatures between 500 and 1200°C. This method was used for a long time for

the synthesis of carbon fibers and nanofiber (Ci et al., 2001; YY Li, Bae, Sakoda, & Suzuki,

2001; Y Li et al., 2003) , (Ci et al., 2000); (Lee, Lyu, Kim, Park, & Yang, 2002) (Lee, et al.,

2002) (Sun et al., 2001) but there were no indications that it could also be used for the synthesis

3
of carbon Nanotubes until Yacamán et al., (1993) reported this method for the first time for the

production of Nanotubes.(José Yacamán, Miki Yoshida, Rendon, & Santiesteban, 1993)

The CVD method deposits hydrocarbon molecules on top of heated catalyst material. Metal catalysts

dissociate the hydrocarbon molecules. The CVD process uses hydrocarbons as the carbon source.

Hydrocarbons flow through the quartz tube where it is heated at a high temperature (Sinnott et al., 1999).

The energy source is used to “crack” the molecule into reactive atomic carbon. Then, the carbon diffuses

towards the substrate, which is heated and coated with a catalyst (usually a first row transition metal such

as Ni, Fe or Co) where it will bind. Carbon nanotubes will be formed if the proper parameters are

maintained,(Ren et al., 1999; Rinaldi et al., 2009).

In CVD methods the catalyst particle should be supported on a substrate such as Silica, or

Alumina. As a support, activated carbon (AC) has attracted much interest because it offers

advantages such as high thermal stability, high surface area, and cheap and easy recovery of the

metal catalyst by simple combustion. Carbon–carbon composites may represent combinations of

carbons having different dimensions (nano with micro) and/or different orderings (graphitic or

disordered)(Rinaldi, et al., 2009)

The reported methods of catalyst support on the substrate are impregnation, deposition of

catalyst particles on the substrate and sputtering. (Kong, Soh, Cassell, Quate, & Dai, 1998). In

this research powdered activated carbon (PAC) derived from palm crenel waste is used as a

novel substrate to support the metallic catalyst (Fe3+) for Growth of CNMs.

The resulting nano material can be used in many applications such as gas storage , removal of

heavy metals and organic contaminants from water treatment, protein immobilization or catalytic

carbon supported reactions,.

4
Methodology

To produce CNT on powdered activated carbon PAC the metallic catalyst (Iron III) was

impregnated on PAC. The metallic catalyst was dispersed on the surface of PAC by the method

of incipient wetness impregnation. Iron nitrate Fe (NO3)3·9H2O was dissolved in a solvent

(Acetone). The substrate PAC suspended in the same solvent in a (2 cm dia) glass bottles and

placed in a sonication bath for 1 hr. then the temperature of the sonication bath was raised to 60
o
C. The mixture was dried under sonication until all the solvent was evaporated. The dried cake

was grinded. Deferent percentages of Fe3+/PAC was studied (1, 3, 5 and 7 wt%) .The catalyst –

substrate powder was subjected to tow heat treatment steps. Firstly it was calcinated in N2

atmosphere at 350 oC for 1 hr to remove moisture secondly it was reduced in presence of H2 at

350 oC for 1 hr. Both of these two processes were carried out in a tubular reactor consist of

ceramic tube ( 50 mm OD, 40 mm ID, 1500 mm L).

Heat treated (Fe3+/PAC) was placed in a ceramic boat inside the CVD reactor and heated to 750
o
C under N2 atmosphere then the N2flow was stopped and the reaction gases H2 (300 ml/min)

andC2H2 (30ml/min) or C6H6 vapor (50 ml/min) are injected for various periods. After the

reaction was completed and reaction gases were stopped, N2 stream was delivered to prevent air

leak in during reactor cooling down to room temperature. Cooling system and closing system

for reactor was locally modified to reduce production time from 8 hours to 2 hours per run. The

optimum catalyst impregnation percentage was selected depending on the yield of carbon nano

material and 5% w/w Fe3+/PAC ratio produced the optimum yield. Therefore this impregnation

percentage was used to study the effect of temperature (850, 750, 650 and 550 oC), carbon

source- hydrogen gas ratio (0.05, 0.1 and 0.15) and growth reaction time(20, 30, 60 and 90 min)

5
Characterization of the produced samples was carried to identify the nature of nano materials.

Field emission scanning electron microscopy (FESEM) was used for the morphology analysis of

the samples. FESEM images were obtained by a JEOL JSM-6700F electron microscope using an

accelerating voltage of 10 kV. In order to enhance their conductivity, samples were placed in

aluminum stubs and coated with a platinum layer by sputtering. Transmission electron

microscopy (TEM) observations were made with a JEOL JEM-1200CX Π microscope that

operated at 120 keV to observe the dispersion of active site on support surface. The samples

were suspended in acetone. After ultrasonic dispersion, a droplet was deposited on a copper grid

supporting a perforated carbon film.

6
 Quality coverage of
Average
Sample ID Fe % PAC surface with Yield
Diameter(nm)
CNT %

F01 1% 30 0.21 59

F03 3% 75 0.29 56

F05 5% 90 0.39 54

F07 7% 58 0.36 49

Conditions

N2 Flow 400 ml/min 30min

Heating to 300oC under N2 Atmosphere for 2 hr.( Calcinations )

H2 flow for 2 hr 400 ml /min ( Reduction)

Benzene Flow 50 ml/min + H2 400ml /min for 30 min (Growth)

N2 flow ( Cooling)

Weight of sample (500 mg) in a ceramic boat

Table1: The coverage percentage of CNT on the PAC surface Iron impregnation percentage (Fe wet %)

. and The yield of CNT grown on the PAC surface

7
(a) (b)
Figure 1 FESEM image for PAC impregnated with Fe3+ before growth, PAC with 3 % Fe3+(a)

and PAC with 7 % Fe3+ (b)

Figre (2): FESEM image for CNT/PAC 1%Fe3+, 50 Benz 400 H2. 750C , 30 min

8
Figure 3 PAC-3%Fe3+after growth using C2H2

9
Figure 4 CNMs grown under conditions of Fe3+ 5%, Benzene 50 ml/ min and temperature 750
o
C TEM images revealing the multi wall CNTs(a) FESEM image shows the deferent diameter

CNTs with CNFs (b)

10
Figure 5 FESEM for PAC 7 % Fe3+ after growth of CNMs under C2H2 the Y-branched CNTs

are clear observed in the top image.

11
 (b)
(a)

hollow core

Figure 6 FESEM image for CNM1 growth temperature is 550 oC (a).The hollow core confirms

the CNT growth in the TEM image (b).

Figure 7 FESEM image for CNM2 growth temperature is 650 oCA7

12
Figure 8 FESEM image for CNM3, growth temperature is 650C

13
Figure 9 TEM image for the sample CNM4 confirms the CNT presence with CNFs (a). TEM

image for the same sample CNTs with top view for the multi wall structured nano tube

surrounded by CNFs (b) and FESEM image for CNM4 growth temperature is 650 oC (c)

14
 Figure 10 FESEM image for CNM5 growth temperature is 750 oC (a). TEM image revealing
(b)
(a) CNT structur surrounded by amorphous carbon and encapsulated metal nano particles (b).

15
Figure11 FESEM image for CNM6 growth temperature is 750 oC

Figure 12 FESEM image for CNM7 growth temperature is 850 oC

16
 C2H2/H2 Mean Diameter
Sample ID Temp. oC Time min Yield Type of CNMs
Ratio nm

CNM1 550 90 0.15 1.7 Long CNFs + CNTs + CNT coils 104

CNM2 650 60 0.1 0.4 CN spheres + CNTs 165

CNM3 650 60 0.1 1 Y-type branched CNTs 175

CNM4 650 90 0.1 0.75 CNTs + CNFs + CN coils 110

CNM5 750 60 0.1 0.045 CNTs + CNFs 120

CNM6 750 90 0.05 0.1 CNFs + CN coils 150

CNM7 850 20 0.1 0.3 CNTs + CNFs 93

Table 2 various CNMs samples with deferent production conditions.

17
 0.45

0.4
yield of CNMs grown on PAC
0.35

0.3

0.25

0.2

0.15

0.1 y = 1695.x3 - 304.7x2 + 17.93x + 0.02

R² = 0.948
0.05

0
0 0.02 0.04 0.06 0.08

percentage of impregnated Fe3+

Figure 13 yield of CNMs growth on PAC versus weight percentage of Fe3+ impregnation.

18
 2400 1500
2100 1350
1800 1200 C (a)
1500 1050 C
1200 900
900
Counts

750
600 Pt
600
300 Si
0
450
O Al
Mg
Pt
Ca
300 O Pt K K Ca
Pt Pt
150

0
2400
2400 0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00
2100 2100 keV
1800 1800 (b)
1500
Counts

C
1200 1500
Counts

900 1200
600
900 Pt
300 Fe
Fe Zr Pt Fe
0 600 N Fe Si Zr Fe
Pt FeKesc Fe Pt Pt
300

0
2400 2400
0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00
2100 2100
keV
1800
1800
(b)
1500
1200 1500
Counts

900 1200 C
600
300 900 Pt Zr

0
Fe
Fe Zr
600 N Fe Si Pt Fe
Pt FeKesc Fe Pt Pt
300

0
2400
2400 0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00
2100 2100 C keV
1800
1800 (c)
1500
C
1200 1500
900
Counts

600 1200
300 900
0 Pt
600 Fe
Si Pt Fe
Fe Pt Pt
FeKesc Fe Pt
300

0
0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00
0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00
keV

keV

Figure 14 EDX pattern for: raw PAC before impregnation with Fe3+ (a), after impregnation (b)

and after CNMs growth(c).

19
 PAC Sample

Furnace
Reaction
gases Flue gases and water traps
Cooling system

Figure 15 schematic diagram for the CVD reactor.

Results and Discussion

Optimization of catalyst

CNT were grown on Iron -impregnated PAC with deferent compositions as shown in Table 1.

The produced samples were characterize by measuring its weight and determining the yield of

decomposed carbonatious nano materials on it. The samples were tested by FESEM and the

images were analyzed to determine the coverage quality of its surfases with CNTs and the

diameter distribution of the nanotubes . As shown in Table 1 . these data were studied by plotting

yield versus Fe3+ percentage . Figure 2 shows images of CNTs of PAC impregnated with 1% of

Fe3+. the quality of coverage was poor comparing with that of 3% and 5% and 7% figures (3,4,5)

respectively . FESEM images revealed the sizes of tubes diameter which was determined from

measuring and accounting the number of tubes in each image. Table 1shows the average

diameter data collected from images . The yield increase with the increase of % Fe3+ until it

reach the maximum at 5% Fe3+ as shown in Figure 13 which represents the polynomial function

20
curve of Yield against % Fe3+ . the produced regression equation was successfully representing

the yield as function of Fe3+ percentage in this specific conditions of production with a

correlation coefficient (R2 ) of 0.948 .The conclusion of this optimization process is that the

percentage of 5% Fe3+ is the optimum percentage in terms of CNTs yield , diameter and

coverage quality.

EDX characterization gave the evidence of the successful impregnation and growth on PAC

surface. figure 14 shows the EDX patterns of three deferent cases: PAC before impregnation of

Fe3+ showed no Fe atoms on the surface, PAC after impregnation with Fe3+ the iron atoms are

detected on the surface consisting about 25% of the surface atoms and PAC surface after growth

of CNMs the majority of surface atoms are carbon more than 94% and Fe atoms disappeared

under the grown CNMs.

FESEM images show distribution of the metallic clusters on the surface of for the Fe3+

impregnated PAC after heat treatment. Figure (1a) shows the surface of Catalyst-substrate

distribution for the sample of PAC impregnated with 3% Fe3+ while Figue1b shows that of 7%

Fe3+. The bright objects dispersed on the black carbon surface are the metallic clusters with

average size of 20 to 50 nm and taking spherical like shape. These clusters are the platforms for

CNTs and CNFs growth where the carbon atoms cracked from the carbon precursor are adsorbed

on the metallic catalyst clusters surfaces and form the cap of CNTs then the growth starts.

Figure 1 shows the catalyst metal clusters formed in deferent sizes. The size of metallic clusters

affects the size of CNT grown on it as shown in Figure (3) where the deferent CNT sizes.

Figures4,5 show dense growth with uniform distribution of CNT on PAC surface

21
Nanostructure

Figures (4, 6, 9 & 10) show the TEM images revealing the internal structure of multiwall CNTs

and CNFs attached to amorphous carbon of the PAC surface , the internal hollow structure is

clear revealing the CNT formation, while the solid structure is for other forms of CNMs , the

dark spots in the TEM images represents the metallic catalyst clusters where the carbon atoms

build up to form the CNTs and other CNMs structure around it.

In this investigation various types of nanostructured carbon materials were obtained at deferent

production conditions. The majority of the grown CNMs are the multi walled carbon Nanotubes

CNTs and carbon nano fibers CNFs. CNTs are grown at wide range of temperature starting from

550 oC to 850 oC but with various characteristics . However, the average diameter of CNTs

grown at high temperature 850 oC is less than that of relatively low temperatures. As illustrated

in Table 2 coiled structure carbon nano tubes CN-coils were obtained at deferent temperatures

550 oC ( Figure 6) and 750 oC ( Figure11) . Y-branched CNTs were obtained at temperature 650
o
C (Figure 8). Carbon nano spheres appeared at temperature 650 oC (Figure 7).

Conclusion

PAC was used as a successful substrate for CNMs growth in CVD reaction process. Fe3+ was

impregnated successfully on PAC surface under sonication . EDX characterization results

showed the evidence on impregnation and growth of CNMs on PAC surface. The optimum

weight percentage of Fe3+ impregnation on PAC was found 5%. The CVD reactor used in this

investigation was locally fabricated and modified to reduce the process time and cost. CNMs

were synthesized at deferent temperatures (850, 750, 650 and 550 oC) the maximum yield was

obtained at 550 oC with majority of CNFs. Various types of CNMs were grown: CNTs, CNFs,

22
CN-spheres and CN-coils. FESEM and TEM images were studied for all the samples to

investigate the nanostructures for CNMs.

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