2009 acs national meeting wash dc 08-19-09
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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
20
30
40
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
20
30
40
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
10
20
30
40
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
2000
4000
6000
8000
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)
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