Hydrogenated Nanostructured Carbons: Fullerenes & SWNTs

Jeremy Kintigh and Glen P. Miller Department of Chemistry and Materials Science Program

University of New Hampshire

American Chemical Society Meeting, Wash. DC Aug 19, 2009

Hydrogenation of Fullerenes

Proposed Mechanism of Fullerene Hydroamination/ Hydrogenation

+

H

+ RH2C NHC60

HNH

CH2R

(a)

(b)

H

+

HH

+

Aminated [60]fullerene

Hydrogenated[60]fullerene

RH2C NH2

RH2C NH2

RH2C NH2

RH2C NH2RH2C NH.

.

....

.

..

..

.

.

.

..

..

(a) Kintigh, J., Briggs, J., Letourneau, K., and Miller, G. P., Journal of Materials Chemistry, 2007, 17, 4647 – 4651; (b) G. P. Miller, Comptes Rendus Chimie, 2006, 9, 952

Polyamine Hydrogenation of C60 Gives C3v Symmetric C60H18

C60H18 First Isolated and Identified by Roger Taylor and co-workers:J. Chem. Soc., Perkin Trans. 2, 1996, 2051-2054.

J. B. Briggs, M. N. Montgomery, L. Silva and G. P. Miller, Organic Letters 2005, 7, 5553

Spectroscopic Evidence for C3v C60H18

0

10

20

30

40

50

60

70

80

90

100

%Int.

300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500Mass/Charge

738

LDI Mass spectrum

UV-vis trace

J. B. Briggs, M. N. Montgomery, L. Silva and G. P. Miller, Organic Letters 2005, 7, 5553

Spectroscopic Evidence for C3v C60H18

1H NMR Spectrum

*

*

J. B. Briggs, M. N. Montgomery, L. Silva and G. P. Miller, Organic Letters 2005, 7, 5553

Spectroscopic Evidence for C3v C60H18

*

*

*

*

A

BC

DB'

D'

A

BC

DB'

D'

J. B. Briggs, M. N. Montgomery, L. Silva and G. P. Miller, Organic Letters 2005, 7, 5553

A B C D

DET Hydrogenations of C60 are Both High Yielding and Scalable

mass C60 (g) mL DET time (h) mass C60H18 (g) % yield

0.10 7 14 0.083 81

1.0 50 16 0.919 90

5.0 100 20 4.674 91

J. B. Briggs, M. N. Montgomery, L. Silva and G. P. Miller, Organic Letters 2005, 7, 5553

DET Hydrogenation of C60

Total reaction time is reduced to 5-10 minutes using microwave reactor

Kintigh, J., Briggs, J., Letoutneau, K., and Miller, G. P., Journal of Materials Chemistry, 2007, 17, 4647 - 4651. 

DET Hydrogenation of C70 Using Standard Conditions: 200 oC, 15 h

0

10

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30

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50

60

70

80

90

100

%Int.

800 820 840 860 880 900 920 940 960 980 1000 1020 1040Mass/Charge

Data: jb094901_C70Hx_aminehydrog0001.L22 2 Nov 2005 9:55 Cal: Briggs 26 Oct 2005 9:36 Kratos PC Axima CFRplus V2.3.4: Mode reflectron, Power: 100, P.Ext. @ 688 (bin 90)

868.3

~ 26-28 hydrogensper C70

0.01.02.03.04.0

* Diethylene Triamine

* Water

1H NMRspectrum

Lack of Regioselectivity as compared to reaction with C60

Mass spectrum

Kintigh, J., Briggs, J., Letourneau, K., and Miller, G. P., “Fulleranes produced via efficient polyamine hydrogenation of [60]fullerene, [70]fullerene and giant fullerenes,” J. Mater.Chem. 2007, 17, 4647 - 4651.

0

10

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30

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50

60

70

80

90

100

%Int.

800 820 840 860 880 900 920 940 960 980 1000 1020 1040Mass/Charge

Data: jb095401_C70Hydrog_DaBOMB0001.P19 15 Nov 2005 10:28 Cal: Briggs 26 Oct 2005 9:36 Kratos PC Axima CFRplus V2.3.4: Mode reflectron, Power: 105, P.Ext. @ 840 (bin 99)

866.5

DET Hydrogenation of C70 Using More Severe Conditions: 300 oC, 15 h

~ 24-28 hydrogensper C70

2.03.04.0

* Diethylene triamine

1H NMRspectrum

C70 allowed to react with DET at 300 oC for 15 hours

Mass spectrum

Kintigh, J., Briggs, J., Letourneau, K., and Miller, G. P., “Fulleranes produced via efficient polyamine hydrogenation of [60]fullerene, [70]fullerene and giant fullerenes,” J. Mater.Chem. 2007, 17, 4647 - 4651.

DET Hydrogenation of Large Fullerenes

0

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50

60

70

80

90

100

%Int.

1000 1500 2000 2500 3000 3500 4000Mass/Charge

Data: jb095201_PhenylNaphthaleneExtract_SWNT_highmassrange0001.J21 18 Nov 2005 9:59 Cal: Briggs 26 Oct 2005 9:36 Kratos PC Axima CFRplus V2.3.4: Mode reflectron, Power: 92, P.Ext. @ 720 (bin 92)

LDI-MS of large fullerenes prior to DET hydrogenation

1-phenylnaphthalene extract

C78 m/z=936

C84 m/z=1008

C96 m/z=1152

C200 m/z=2400

Kintigh, J., Briggs, J., Letourneau, K., and Miller, G. P., “Fulleranes produced via efficient polyamine hydrogenation of [60]fullerene, [70]fullerene and giant fullerenes,” J. Mater.Chem. 2007, 17, 4647 - 4651.

0

10

20

30

40

50

60

70

80

90

100

%Int.

1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 2100 2200Mass/Charge

Data: jb095502_GF_CH2Cl2_Sol0001.J18 18 Nov 2005 10:28 Cal: Briggs 26 Oct 2005 9:36 Kratos PC Axima CFRplus V2.3.4: Mode reflectron, Power: 97, P.Ext. @ 720 (bin 92)

LDI-MS of large fullerenes after DET

hydrogenation

DET Hydrogenation of Large Fullerenes

C78H26-32

C84H22-30

C96H26-32

Kintigh, J., Briggs, J., Letourneau, K., and Miller, G. P., “Fulleranes produced via efficient polyamine hydrogenation of [60]fullerene, [70]fullerene and giant fullerenes,” J. Mater.Chem. 2007, 17, 4647 - 4651.

Polyamine Hydrogenations of Large Fullerenes

Fullerene Approx. no. of H’s added

[76] 21-28

[78] 26-32

[80] 24

[82] 28

[84] 22-30

[86] 28

[88] 28

[90] 30

[92] 28

[94] 30

[96] 26-32

Polyamine Hydrogenation of

SWNTs

Before Hydrogenation After Hydrogenation

DET Hydrogenation of SWNTs Results in Highly Dispersed Species

“Hydrogenation of Single-Wall Carbon Nanotubes Using Polyamine Reagents: Combined Experimental and Theoretical Study,” J. Amer. Chem. Soc. 2008, 130, 2296-2303.

0

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10000

0 500 1000 1500 2000 2500

1/cm

Inte

nsity

Raman Spectrum of H-SWNTs

D-band~1300 cm-1

G-band~1584 cm-1

Before Hydrogenation

After Hydrogenation

“Hydrogenation of Single-Wall Carbon Nanotubes Using Polyamine Reagents: Combined Experimental and Theoretical Study,” J. Amer. Chem. Soc. 2008, 130, 2296-2303.

30 Seconds 5 Minutes

1 Hour 2 Days

Hydrogenated SWNTs Stay Well Dispersed Without Added Surfactant

H-SWNTs SWNTs H-SWNTs SWNTs

H-SWNTs SWNTs H-SWNTs SWNTs

“Hydrogenation of Single-Wall Carbon Nanotubes Using Polyamine Reagents: Combined Experimental and Theoretical Study,” J. Amer. Chem. Soc. 2008, 130, 2296-2303.

Hydrogenation Weakens SWNTs Making Them Prone to Fracture

Under TEM Irradiation

“Hydrogenation of Single-Wall Carbon Nanotubes Using Polyamine Reagents: Combined Experimental and Theoretical Study,” J. Amer. Chem. Soc. 2008, 130, 2296-2303.

Thermal Annealing at 800 oC Restores Original Structure

BEFORE AFTER

“Hydrogenation of Single-Wall Carbon Nanotubes Using Polyamine Reagents: Combined Experimental and Theoretical Study,” J. Amer. Chem. Soc. 2008, 130, 2296-2303.

Acknowledgements

National Science Foundation: Nanoscale Science & Engineering Center for High-rate Nanomanufacturing (Award # NSF-0425826)

National Science Foundation: Nanoscale Exploratory Research (Award # NSF-0403954)

Army Smart Materiel Command

Mikael JazdzykWenling JiaIrvinder KaurJeremy KintighJonathan BriggsRyan KopreskiChandrani PramanikYi Xu

Nathan SteinPolina PrushevichElizabeth StairsGillian LiuYushu LiShunfu HuJianhua Gao

The Miller Group at UNH Collaborators

Mehmet Dokmeci (NEU)David Tomanek (MSU)Ahmed Busnaina (NEU)Luis Echegoyen (Clemson)Howard Mayne (UNH)Nicholas McGruer (NEU)Joey Mead (UML)