Summary of NC200 work

Imran & NorliUpdated: 2/8/2007

Objectives

To get high dispersion of nanocarbon on AC.

To get homogeneous nanocarbon.

Experimental Route Diagram

Washing(removes impurities;

eg: Al, Si, Fe, K)

Washing(removes impurities;

eg: Al, Si, Fe, K)

Catalyst Development

Catalyst Development

Nanocarbon Growth

(Thermal-CVD)

Nanocarbon Growth

(Thermal-CVD)

CharacterizationCharacterization• Monometallic (Iron)

• Bimetallic

• Monometallic (Iron)

• Bimetallic

• Compositional analysis (EDX,XRF)

• Morphology/Structure analysis (SEM, HRTEM)

• Texture/Surface Area analysis (BET)

• Mechanical & Electrical Properties Analysis

• Compositional analysis (EDX,XRF)

• Morphology/Structure analysis (SEM, HRTEM)

• Texture/Surface Area analysis (BET)

• Mechanical & Electrical Properties Analysis

• Carbon source (C2H4)

• Carrier gas (H2, N2)

• Carbon source (C2H4)

• Carrier gas (H2, N2)

Substrate (AC)

Substrate (AC)

ImpregnationImpregnation

CNT/FCNT/F

CNT/F Applicatio

n

CNT/F Applicatio

n

• treat with 5M HNO3, T=30oC, 24 hr

• wash with deionized water, dried T=200oC, 2 hr

• treat with 5M HNO3, T=30oC, 24 hr

• wash with deionized water, dried T=200oC, 2 hr

• Cat. + acetic acid/ ethanol

• under ultrasonic, 30 min, 25oC (water bath)

• aging 45hr/12hr, RT, Drynoza

• Cat. + acetic acid/ ethanol

• under ultrasonic, 30 min, 25oC (water bath)

• aging 45hr/12hr, RT, Drynoza

• Acid Base Titration• Iodine Number• Butane Activity

• Acid Base Titration• Iodine Number• Butane Activity

Working Summary

Drying method: Previous: Oven Current: Drynoza

UTP Temperature Programme: Previous: Calcination: 250oC, 5% O2 in

N2, 1hr, Reduction: 300oC, 5% H2 in N2, 1hr, Growth: 700oC, 30mL C2H4, 200mL H2, 2 hrs

Current: Calcination: 250oC, 5% O2 in N2, 1hr, Reduction: 500oC/700oC, 5% H2 in N2, 1hr, Growth: 700oC, 30mL C2H4, 200mL H2, 2 hrs

Parameters

SampleImpregnati

onDrying Calcination Reduction Growth

Weight of product

NC2FA1

Iron(II)Acetate 1wt%, Acetic Acid

Pure concentratio

n

60oC, Oven, 12hr

250oC, 5% O2 in N2, 1hr

300oC, 5% H2 in N2, 1hr

700oC, 30mL C2H4, 200mL H2, 2

hrs

3.85g

3.93g

3.68g

3.20g

NC2FA2

Iron(II)Acetate 1wt%, Acetic Acid

1M

60oC, Oven, 15hr

NC2FA360oC,

Furnace, 48hr 700oC, 5%

H2 in N2, 1hr

NC2FA4RT, Drynoza, 45hr

Iron (II) Acetate

SampleImpregnati

onDrying Calcination Reduction Growth

Weight of product

E087Iron (II) Nitrate 1 wt%, Ethanol

RT, Drynoza, 12hr

250oC, 5% O2 in N2, 1hr

500oC, 5% H2 in N2, 1hr 700oC,

30mL C2H4, 200mL H2, 2 hrs

2.16g

E090Iron (II) Nitrate 1 wt%, Ethanol

RT, Drynoza, 12hr

700oC, 5% H2 in N2, 1hr 1.20g

Iron (II) Nitrate

Temperature Programme (New)

Temperature Programme for CNF/CNT Growth using UTP

30 30

700700

200

250

0

100

200

300

400

500

600

700

0 100 200 300 400 500 600

Time (min)

Tem

p (

oC

)

Calcination Reduction Growth Cooling

30 min

44 min

60 min

10 min60 min

100 min

60 min 120 min

134 min

SEM images for CNT/AC

NC2FA1(B4)

SEM images for CNT/AC

NC2FA1(Growth)

CNT diameter: 6-11nm.Some CNT growth from the pore.Dispersion was not very good.High concentration of solution.

Try to use 1M acetic acid solution

SEM images for CNT/AC

NC2FA2(B4) with 1M acetic acid solution

SEM images for CNT/AC

NC2FA2(Growth)

No/less CNT growth (most probably because of the drying factor/solution concentration.

Try to use different drying method

SEM images for CNT/AC

NC2FA4(B4) DRYNOZA+new temp. programme

SEM images for CNT/AC

NC2FA4(Growth)

CNT diameter: 5-12 nmDrynoza+new temp. programmeDispersion still not very good.

Check the catalyst dispersion after reduction process (in progress)

SEM images for CNT/AC

E084 (500oC)

• Less growth, most probably Fe is not fully reduce

• not cover all AC substrate

• diameter 8nm – 15nm

SEM images for CNT/AC

E090 (700oC)stick

SEM images for CNT/AC

E090 (700oC)loos

e

BET

Sample

Pore Volume(mesopore)

Surface Area

(m2/g)

Pore volume(cc/g)

Average pore

width (nm)

Total PoreVolume

(cc/g)

Growth

Before

AGBefor

eAG

Before

AGBefor

eAG

Before

AG

NC2FA1

0.0501

0.0635

1205 10190.517

30.444

53.489

3.798

0.5674

0.5080

NC2FA2

0.0345

0.0522

1074962.

70.457

30.416

63.328

3.695

0.4918

0.4688

BET data for NC2FA3 & NC2FA4 still in progress.

BET Isoterm & DFT

0,0 0,2 0,4 0,6 0,8 1,0100

150

200

250

300

350

400

Vol

ume (c

c/g)

Relative Pressure (P/P0)

NC2FA1 NC2FA1(AG) NC2FA2 NC2FA2(AG)

0 10 20 30 40 50 60

0,00

0,02

0,04

0,06

0,08

0,10

Pore

Vol

ume (c

c/A/g

)

Pore Width (A)

NC2FA1 NC2FA1 (AG) NC2FA2 NC2FA2 (AG)

Isoterm DFT

All samples show isoterm type I (micropore) and hysteresis H3 (inuniform slit type). DFT proved that this sample are micropore which diameter between 3-20 A.

Iron (II) Acetate

Thermal AnalysisThermal Analysis condition = air, 32oC – 900oC, rate 5oC/min

• less 200oC loss of water molecules, moisture and nitrate

• 500oC – 750oC – removal of SOFG

• 350oC – 600oC – reduction of Fe nitrate. The width and density of the endothermic peak refers to the contact between the metal and carbon surface in other words it shows the characteristic of metal dispersion of the iron / nickel on AC. (prove from TG of sample Ni/AC 1wt%/2wt%)

• some literature mention, the 4th peak in TGA refers to the second activation of the Fe after being covered by coke and/or the Fe is in a different position in AC matrix, AC raw dont have this peak maybe probably because they present in a different state (Fe silicates etc).

0 100 200 300 400 500 600 700 800 900 1000

0

20

40

60

80

100

we

igh

t lo

ss (

%)

Temperature (ToC)

AC raw-wash impreg. CNF-loose CNF-stick

0 100 200 300 400 500 600 700 800 900 1000

-0.7

-0.6

-0.5

-0.4

-0.3

-0.2

-0.1

0.0

A009 impreg CNF-loose CNF-stick

TG

ATemperature (ToC)

Iron (II) Nitrate

Thermal Analysis

Thermal Analysis condition = air, 32oC – 900oC, rate 5oC/min

0 100 200 300 400 500 600 700 800 900-2.0

-1.8

-1.6

-1.4

-1.2

-1.0

-0.8

-0.6

-0.4

-0.2

0.0

AC raw Fresh Catalyst 500oC reduce 700oC reduce

surface oxygen functional group (SOFG) removal

TG

A

Temperature (oC)

* App. Catal A. 192 (2000) 29-42

Species released Temp. oC (based on TPD exp ref *)

CO2 (carboxylic) 237

CO2 (lactone) 667

CO (Phenol) 632

CO (carbonyl) 807

CO + CO2 (anhydride) 547

CO (ether) 700

CO (quinone) 807

Iron (II) Nitrate

FTIR – Surface Oxygen functional group

4000 3800 3600 3400 3200 3000 2800 26000.000

0.002

0.004

0.006

0.008

0.010

0.012

0.014

0.016

0.018

29

19

29

53

28

84

34

41

Ab

sorb

an

ce

wavenumber [cm-1]

Fresh catalyst 500oC reduce 700oC reduce - stick 700oC reduce - loose

2500 2000 1500 1000 500

0.00

0.02

0.04

0.06

0.08

0.10

0.12

0.14

0.16

76

8

10

99

13

85

Ab

sorb

an

ce

wavenumber [cm-1]

fresh catalyst 500oC reduce 700oC reduce -stick 700oC reduce- loose

17

36

Absorption band [cm-1]

assignment

3417 O-H stretching vibrations, existence of surface hydroxylic groups and chemisorb water, asymmetric of

this band indicates strong hydrogen bonds2916, 2850 Aliphatic species, -CH3 –CH2-

1731 Aromatic rings and double bond vibrations

1579 Conjugated system such as ketone, keto-ester, ketol-enol structures

1385 NOx species from HNO3

1102 Symmetrical stretching vibration of ether ; epi-oxide and phenolic structure in different environmental.* Carbon 36 (1998)

1821-1831

Iron (II) Nitrate

XRD Diffractogram

0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 900

50

100

150

200

gra

phite

(00

2)

gra

ph

ite (

002)

700oC reduce, growth 700oC

500oC reduce, growth 700oC

Fe3

C (

121

)

inte

nsi

ty

2-Theta

XRD diffractogram of samples was indexed to Fe3C and graphite.

XRD diffraction patterns recorded after the reactions shows that the pattern of Fe oxide is no longer present after CVD and the phases present were graphite and Fe carbide.

Some literature says that Fe oxide precursor was converted to Fe3C either during or after the CVD process. Fe3C also expected to form at the reaction conditionsa.

Active phase could be iron carbide or some form of iron carbon solid solutiona.* Carbon 44(2006) 2273-2280

Iron (II) Nitrate

XRD

061127X2_NC2FA2_AG

01-1267 (D) - Iron - Fe - Y: 50.00 % - d x by: 1. - WL: 1.5406 - Cubic - a 2.86070 - b 2.86070 - c 2.86070 - alpha 90.000 - beta 90.000 - gamma 90.000 - Body-centred - Im-3m (229) - 2 - 23.4108 - 50-0926 (I) - Carbon - C - Y: 50.00 % - d x by: 1. - WL: 1.5406 - Hexagonal - a 11.92800 - b 11.92800 - c 10.62000 - alpha 90.000 - beta 90.000 - gamma 120.000 - 1308.55 - Operations: Smooth 0.150 | Import061127X2_NC2FA2_AG - File: 061127X2_NC2FA2_AG.raw - Type: 2Th/Th locked - Start: 2.000 ° - End: 90.000 ° - Step: 0.010 ° - Step time: 2. s - Temp.: 25 °C (Room) - Time Started: 6 s - 2-Theta:

Lin

(C

ount

s)

0

100

200

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

1600

1700

2-Theta - Scale

2 10 20 30 40 50 60 70 80 90

(1,1

,0)

(0,0

,2)

(1,2

,0)

(1,0

,3)

(1,1

,3)

(1,2

,3)

(1,1

,0)

(2,0

,0)

(2,1

,1)

061124X3_NC2FA2

06-0696 (*) - Iron, syn - Fe - Y: 50.00 % - d x by: 1. - WL: 1.5406 - Cubic - a 2.86640 - b 2.86640 - c 2.86640 - alpha 90.000 - beta 90.000 - gamma 90.000 - Body-centred - Im-3m (229) - 2 - 23.5511 -50-0926 (I) - Carbon - C - Y: 50.00 % - d x by: 1. - WL: 1.5406 - Hexagonal - a 11.92800 - b 11.92800 - c 10.62000 - alpha 90.000 - beta 90.000 - gamma 120.000 - 1308.55 - Operations: Smooth 0.150 | Import061124X3_NC2FA2 - File: 061124X3_NC2FA2.raw - Type: 2Th/Th locked - Start: 2.000 ° - End: 90.000 ° - Step: 0.010 ° - Step time: 2. s - Temp.: 25 °C (Room) - Time Started: 8 s - 2-Theta: 2.000 ° -

Lin

(C

ount

s)

0

100

200

300

400

500

600

700

800

900

2-Theta - Scale

2 10 20 30 40 50 60 70 80 90

(1,1

,0)

(0,0

,2)

(1,2

,0)

(1,0

,3)

(1,1

,3)

(1,2

,3)

(1,1

,0)

(2,0

,0)

(2,1

,1)

061124X2_NC2FA1_AG

06-0696 (*) - Iron, syn - Fe - Y: 50.00 % - d x by: 1. - WL: 1.5406 - Cubic - a 2.86640 - b 2.86640 - c 2.86640 - alpha 90.000 - beta 90.000 - gamma 90.000 - Body-centred - Im-3m (229) - 2 - 23.5511 -50-0926 (I) - Carbon - C - Y: 50.00 % - d x by: 1. - WL: 1.5406 - Hexagonal - a 11.92800 - b 11.92800 - c 10.62000 - alpha 90.000 - beta 90.000 - gamma 120.000 - 1308.55 - Operations: Smooth 0.150 | Import061124X2_NC2FA1_AG - File: 061124X2_NC2FA1_AG.raw - Type: 2Th/Th locked - Start: 2.000 ° - End: 90.000 ° - Step: 0.010 ° - Step time: 2. s - Temp.: 25 °C (Room) - Time Started: 9 s - 2-Theta:

Lin

(C

ount

s)

0

100

200

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

1600

1700

1800

1900

2-Theta - Scale

2 10 20 30 40 50 60 70 80 90

(1,1

,0)

(0,0

,2)

(1,2

,0)

(1,0

,3)

(1,1

,3)

(1,2

,3)

(1,1

,0)

(2,0

,0) (2,1

,1)

061123X2_NC2FA1

50-0926 (I) - Carbon - C - Y: 50.00 % - d x by: 1. - WL: 1.5406 - Hexagonal - a 11.92800 - b 11.92800 - c 10.62000 - alpha 90.000 - beta 90.000 - gamma 120.000 - 1308.55 - 06-0696 (*) - Iron, syn - Fe - Y: 50.00 % - d x by: 1. - WL: 1.5406 - Cubic - a 2.86640 - b 2.86640 - c 2.86640 - alpha 90.000 - beta 90.000 - gamma 90.000 - Body-centred - Im-3m (229) - 2 - 23.5511 -Operations: Smooth 0.150 | Import061123X2_NC2FA1 - File: 061123X2_NC2FA1.raw - Type: 2Th/Th locked - Start: 2.000 ° - End: 90.000 ° - Step: 0.010 ° - Step time: 2. s - Temp.: 25 °C (Room) - Time Started: 8 s - 2-Theta: 2.000 ° -

Lin

(C

ount

s)

0

100

200

300

400

500

600

700

800

900

1000

1100

2-Theta - Scale

2 10 20 30 40 50 60 70 80 90

(1,1

,0)

(2,0

,0)

(2,1

,1)(1,1

,0)

(0,0

,2) (1

,2,0

)

(1,0

,3)

(1,1

,3)

(1,2

,3)

Iron (II) Acetate

Current & Future Planning

Produce large amount of Fe/AC for iodine number and acid base titration (each experiment require 10gram of sample)

To set-up apparatus to perform n-butane activity.