CARBON 6 2 ( 2 0 1 3 ) 4 1 3 –4 2 1

Available at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/carbon

Synthesis and explosive decomposition

of polynitro[60]fullerene
a,b,*
Franco Cataldo , Ornella Ursini c, Giancarlo Angelini c

a
Tor Vergata University, Via della Ricerca Scientifica, 00133 Rome, Italy
b
Lupi Chemical Research srl, Via Casilina 1626A, 00133 Rome, Italy
c
Istituto di Metodologie Chimiche, CNR, Via Salaria Km 29,300, Monterotondo Stazione, 00016 Rome, Italy

A R T I C L E I N F O A B S T R A C T

Article history:
Received 22 February 2013
Accepted 12 June 2013
Available online 20 June 2013
Prolonged treatment of C60 in benzene with very high concentrations of N2O4 leads to a new
polynitro[60]fullerene whose composition was determined as C60(NO2)14 by thermogravi-
metric analysis. The compound is unstable and deflagrates above 170 C when heated
under nitrogen or in air with the release of a considerable amount of heat as observed
by the differential thermal analysis and as measured by differential scanning calorimetry.
The decomposition steps of C60(NO2)14 were followed by the thermogravimetric analysis
coupled with Fourier-transform infrared spectroscopy analytical technique. At the deflagra-
tion point C60(NO2)14 releases a mixture of nitrogen oxides: NO2 and NO with minor
amounts of N2O. The deflagration leaves a residue of oxidized carbon which by heating
releases CO2 and CO and at 700 C is reduced to a carbonaceous matter free from residual
oxygenated groups showing also the presence of small amounts (610%) of C60 fullerene.
 2013 Elsevier Ltd. All rights reserved.

1. Introduction molecule for the synthesis of other fullerene derivatives tak-

The chemistry of fullerenes has been widely expanded since
their discovery at the end of last century [1]. A series of books
and reviews [2–9] (cited without the presumption of being
exhaustive) testify how deep is our knowledge on the chemi-
cal behavior of C60 and C70 and also about their potential
applications and impact in very different fields of science.
In the current paper we wish to report about a novel fullerene
derivative, the tetradecanitro[60]fullerene and about the evi-
dences of its explosive properties.
One of the first attempts to produce a nitrofullerene deriv-
ative involved the use of nitric acid resulting in the formation
of a nitro-oxidized C60 [10]. Instead, the use of NO2 [11] or
N2O4 in CS2 [12] as nitrating agent was a successful approach
in the synthesis of polynitrofullerene. The synthesis of hexa-
nitrofullerene was achieved using NO2 in benzene solutions
of C60 [13–17]. The resulting C60(NO2)6 was used as starting
ing advantage from the fact that NO2 moieties are very good
leaving groups in nitrofullerene. Therefore, arylamino-deriva-
tives of C60 [14,15], fullerenols [16] and other more complex
derivatives [17] were prepared using C60(NO2)6 as starting mol-
ecule for further synthesis.
The interest on nitrofullerenes does not regard only their
potential use as precursors for the synthesis of more complex
fullerene derivatives but regards also the potential properties
as explosives and propellants additives [18] and the relative
thermochemical aspects [19–23]. The interest in nitrated ful-
lerene is enforced also by the discovery that another nitrated
cage compound: octanitrocubane (ONC) [23–25] which is char-
acterized by a series of unique properties as explosive in
terms of high density, favorable oxygen balance, very high
detonation velocity and very high detonation pressure which
has permitted the classification of ONC as one of the most
powerful explosive [24] with a relative effective factor (RE

* Corresponding author at: Tor Vergata University, Via della Ricerca Scientifica, 00133 Rome, Italy. Fax: +39 0694368230.
E-mail address: franco.cataldo@fastwebnet.it (F. Cataldo).
0008-6223/$ - see front matter  2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.carbon.2013.06.026
414 CARBON 6 2 ( 2 0 1 3 ) 4 1 3 –4 2 1
factor) against trinitrotoluene (TNT) of 2.38, which means
that 2.38 kg of TNT have the equivalent effect of 1 kg of
ONC [25,26].
2. Experimental
2.1. Materials and equipment
Fullerene C60 was a high purity grade (99.9%) from MTR Ltd.
Company, USA. Benzene, concentrated nitric acid (>65%)
and copper turnings were obtained from Sigma–Aldrich,
USA. Thermogravimetric analysis was made on a Linseis
apparatus model L81 + DTA at a heating rate of 10 C/min un-
der N2 flow of 20 L/h or under a air flow of 40 L/h. Differential
scanning calorimetry (DSC) was performed on a Mettler-Tole-
do DSC-1 Star System using heating rates of 10 C/min or
20 C/min (see Section 3) under a nitrogen or air flow of 5 L/
h. The DSC on polynitrofullerene samples were performed
under N2 flow using stainless steel hermetically sealed med-
ium pressure crucibles on samples size of 5–9 mg instead,
the DSC under air flow were made using opened stainless
steel crucibles. The FT-IR spectra of polynitrofullerenes and
their decomposition products were recorded on a Nicolet
6700 spectrometer from Thermo-Scientific with samples
embedded in KBr pellets.
2.2. Synthesis of polynitro[60]fullerene
C60 fullerene (114 mg) was mixed with 110 ml of benzene and
sonicated for 3 h in a stoppered conical flask in an ultrasonic
bath. The resulting solution was transferred in a gas washing
bottle and then an abundant stream of NO2 was passed into
the solution which was cooled externally at +10 C. Nitrogen
dioxide was produced in a separate apparatus by dropping
concentrated nitric acid 64% over abundant copper turnings.
NO2 was dried over anhydrous calcium chloride prior to bub-
bling into the benzene solution of C60 as suggested in Ref.
[11,13]. Because of the large amount of NO2 employed and
the low temperature adopted, a brown mixture of benzene
and N2O4 was obtained and left stoppered at 10 C for 24 h.
Afterwards the benzene/N2O4 solution was found with a dark-
green color with an abundant red precipitate. The benzene/
N2O4 was decanted and the red precipitate was dried at room
temperature in vacuum. On drying it turned its color from red
to orange-red. The yield of the collected precipitate was
122 mg. The distillation of the benzene/N2O4 yielded other
58 mg of nitrofullerene.
2.3. Synthesis of polynitro[60]fullerene with pre-saturated
benzene/N2O4 mixture
About 90 ml of benzene recovered from the previous batch
were treated with NO2 until a brown solution was obtained.
Then, C60 fullerene (104 mg) was added to the solution which
was sonicated for 30 min in an ultrasonic bath. The C60 disso-
lution was rapid and complete. The solution appeared red-
dish. The reaction mixture kept at +10 C was saturated
with dry NO2 until it has assumed a dark-green color. After
24 h on standing at +10 C the mixture showed a red precipi-
tate at the bottom while the benzene solution remained dark-
green. The red precipitate was collected by decantation and
dried in vacuum to yield 104 mg. Other 50 mg of polynitro-
fullerene were collected by distillation of the benzene/N2O4
under reduced pressure.
3. Results and discussion
3.1. Aspects of the synthesis of polynitrofullerene
Nitrogen dioxide (NO2) and its dimer dinitrogen tetroxide
(N2O4) are well known nitrating agents either used alone or
dissolved in organic solvents [27–30]. NO2 is prevalent in the
gas phase and it is used in gas phase nitration reactions
[27]. Instead the dimer N2O4 is prevalent in liquid phase and
in organic solvents where it is highly soluble and forms also
charge-transfer complexes [26–30]. When N2O4 is dissolved
in CS2 and reacted with C60 yields on average a tetranitro
derivative [2].
However, it is more convenient to use benzene as reaction
solvent in the nitration of C60 with N2O4 since the reaction
mixture of N2O4/CS2 may be dangerous to handle. Instead,
benzene does not undergo nitration reaction with N2O4 at
ambient and sub-ambient temperature while there is the for-
mation of a charge-transfer complex between benzene and
N2O4 where the former acts as a charge donor [28,29]. The
complex is described as an equimolar ratio of benzene/N2O4
with a melting point at 7 C [28]. The dissociation constant
of the reaction N2O4 ! 2NO2 is reported to be 3.2 · 105 mol/
L in liquid N2O4 against 1.4 · 105 mol/L when N2O4 is dis-
solved in benzene in a wide molar ratio range with solvent
[29]. This implies that the nitration mechanism of the sub-
strate C60 is the same both in liquid N2O4 or in benzene solu-
tion and is due the free radical attack of the NO2 radicals to
the fullerene double bonds.
Some authors [11,13–16] have studied the gradual nitration
of C60 and shown that the nitration stops at the hexani-
tro[60]fullerene derivative after a very long contact time be-
tween the benzene/N2O4 and the fullerene substrate.
However, none of the mentioned authors have used very high
concentration of N2O4 in benzene as we have done and none
of the authors reported the spontaneous precipitation of the
polynitrofullerene from the benzene solution on standing,
as we observed. Consequently, our synthetic approach has
lead to the production of highly nitrated fullerene C60.
3.2. Determination of the composition of
polynitrofullerene and discovery of its explosiveness
To assess the chemical composition of the polynitro[60]fuller-
ene prepared as detailed in Section 2 we have used the ther-
mogravimetric analysis both under nitrogen flow and under
air flow. The TGA curves obtained are shown in Fig. 1. Both
TGA curves show a sudden and explosive decomposition of
the polynitro[60]fullerene suggested by the vertical lines par-
allel to the ordinate axis which show an extremely rapid and
complete weight loss which is not accompanied by further
weight loss at higher temperatures. The sudden and rapid
weight loss corresponds to a deflagration process of the poly-
nitro[60]fullerene with the onset occurring at 171 C under N2
and at 176 C under air (see Fig. 1). The sudden weight loss in
 CARBON 6 2 (2 0 1 3) 4 1 3–42 1 415

Fig. 1 – Thermogravimetric analysis (TGA) of tetradecanitro[60]fullerene recorded at a heating rate of 10 C/min under
nitrogen flow and air flow. The decomposition onset of the former sample under N2 occurs at slightly lower temperature than
the sample tested in air flow. The total weight loss of 47.3% corresponds to the theoretical value of 47.2% which can be
calculated for C60(NO2)14.

the TGA corresponds to the strong exothermal peaks ob-
served in the differential thermal analysis (DTA) recorded
simultaneously with TGA (Fig. 2). In the DTA the peaks of
the deflagration process occur at 175 C under N2 and at
185 C in air flow.
The total weight loss after the deflagration of the polyni-
tro[60]fullerene samples is 47.3% for the sample heated under
N2 and 46.2% for the sample heated under air flow. Both these
values are almost coincident to the theoretical value of 47.2%
which can be calculated for C60(NO2)14, the tetradecani-
tro[60]fullerene which is the composition of the polyni-
tro[60]fullerene prepared in the present work.
Neither the explosive decomposition of polynitrofullerene
nor a so high level of nitration of C60 has ever been reported in
literature till now suggesting that our new synthetic approach
has been fecund.
3.3. Infrared spectroscopy of polynitro[60]fullerene and of
the carbon residue collected after the deflagration
The FT-IR spectrum of the polynitro[60]fullerene prepared in
the present work and having the elemental composition
C60(NO2)14 displays an infrared spectrum dominated by the
asymmetric and symmetric NO2 vibrations at about 1570

Fig. 2 – Differential thermal analysis (DTA) signal recorded simultaneously with the TGA measurement of the previous figure
on tetradecanitro[60]fullerene samples under N2 flow and under air flow. In both cases two strong exothermal transitions
respectively at 175 C and 183 C were observed corresponding to the deflagration of the tetradecanitro[60]fullerene.
416 CARBON 6 2 ( 2 0 1 3 ) 4 1 3 –4 2 1

and 1330 cm1 respectively (see Fig. 3). These bands were also
observed in other nitro[60]fullerenes with lower content of ni-
tro groups [11–15]. In the C–N stretching region of the nitro-
groups [31], the main infrared absorption band at about
805 cm1 is accompanied by a series of sub-bands. The NO2
deformation vibrations which include the scissoring, wagging
and rocking of the NO2 group occurs in the spectrum at low
wavenumbers [31] and in particular the peak at about
685 cm1 in Fig. 3 can be assigned to the NO2 wagging mode
[31]. The weak peaks at 561 and 543 cm1 shown in Fig. 3
are attributable to the NO2 group rocking [31].
When C60(NO2)14 is heated under nitrogen, it deflagrates at
175 C as shown by the TGA and DTA (Figs. 1 and 2 respec-
tively). The decomposition leaves a residue of carbonaceous
matter in the TGA crucible. In Fig. 4 are reported the infrared
spectra of a series of carbonaceous samples obtained from
the thermal decomposition of C60(NO2)14 under nitrogen flow
and heated till 210 C, 300 C, 400 C, 500 C, 650 C and 700 C
and then cooled down to room temperature under nitrogen
flow. The FTIR spectra of the carbonaceous matter obtained
from C60(NO2)14 from 210 C to 400 C show a broad ketone
band with two peaks at 1775 and 1735 cm1 accompanied by
the a,b-unsaturated ketone band stretching at 1617 cm1 hav-
ing approximately the same intensity of the ketone band. At
500 C the broad ketone band shifted at 1774 and 1720 cm1
and has the same intensity as the a,b-unsaturated ketone
band at 1617 cm1. At 650 C the ketone band appears much
weaker and shifted at 1711 cm1 while the a,b-unsaturated
ketone band is now replaced by an aromatic band at
1575 cm1. At 700 C the ketone band is completely removed
remaining only the aromatic band at 1586 cm1. These data
show very clearly that the decomposition of polynitrofulle-
rene produces an highly oxidized carbonaceous matter
resembling polymeric fullerene oxide, the heavy oxidized car-
bon obtained by prolonged ozonization of C60 [32–34]. The
assignments of the ketone band at 1775 cm1 observed up
to 500 C were discussed in previous works [33,34] and are
due to acid anhydride group (–CO–O–CO–), to lactones and
to four-membered cyclic ketone while the band at
1720 cm1 is due to regular ketone or aldehyde group [31].
Fig. 4 shows also two weak features at 551 and 525 cm1 in
the sample prepared at 300 C. Such features become slightly
stronger in the samples obtained at higher temperature than
300 C and at 650–700 C the two bands are clearly located at
576 and 528 cm1 and consequently must be attributed to
C60. This implies that C60(NO2)14 decomposes to amorphous
and oxidized carbon resembling polymeric fullerene oxide
but also back to C60 fullerene especially at higher temperature
(i.e. >650 C) when the oxygenated functional groups are re-
moved. From the infrared spectrum of Fig. 4 recorded on the
carbonaceous matter obtained at 700 C, the C60 fullerene
fraction can be estimated 610% of the total carbon.
The carbonaceous matter obtained at 700 C shows also
the aromatic out-of plane bending modes respectively at
878 cm1 due to isolated C–H in a polycyclic aromatic struc-
ture, 823 cm1 due to two adjacent aromatic C–H groups

1.4 364-37 Nitro[60]fullerene

1.2

1.0
1330
0.8
Abs

0.6
805
683
0.4
786
1266 1115 561
764
0.2 1036 851
978
1566 736 543
-0.0 524
403-37 Nitro[60]fullerene
0.7

0.6

0.5 1332

0.4
Abs

822
0.3 802
685
1118 788
0.2
1034
761
0.1
1570
0.0
2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
Wavenumbers (cm-1)

Fig. 3 – FT-IR spectra of tetradecanitro[60]fullerene having the elemental composition of C60(NO2)14 as determined by the TGA.
The infrared spectrum of the sample prepared as detailed in Section 2.2 (spectrum at the top of the figure) is practically
identical to that prepared as reported in Section 2.3 (spectrum at the bottom of the figure).
 CARBON 6 2 (2 0 1 3) 4 1 3–42 1 417

1.0 382-37 Nitro[60]fullerene heated 210°C N2 1735

1776 1617 1345
Abs

1067
0.5

0.0
1.0 *403-37 Nitro[60]fullerene heated 300°C N2
1774
1735 1619
Abs

0.5 1386 1223

928 751 697 551
525

1.0 411-37 Nitro[60]fullerene heated 400°C N2

1777 1614 1384 1230
1732
Abs

0.5 1853
925 765 547
698
2337 2226 528
1.0 *410-37 Nitro[60]fullerene heated 500°C N2 1774 1240

1720 1614 764 545

Abs

0.5 911 709 528

2336 2225

1.0 *364-37 Nitro[60]fullerene heated 650°C N2 1575 1439

1221 576
525
Abs

1711 768
0.5 883

1.0 *364-37 Nitro[60]fullerene heated 700°C N2

1586 1429
1282
Abs

823 576
878 757
0.5
528

2500 2000 1500 1000 500

Wavenumbers (cm-1)

Fig. 4 – FT-IR spectra of C60(NO2)14 decomposed by deflagration under nitrogen at the following temperatures (from top to
bottom): 210 C, 300 C, 400 C, 500 C, 650 C and 700 C.

and 757 cm1 due to four adjacent aromatic C–H groups [31].
This fact suggests that the removal of oxygenated groups
from the carbonaceous matter obtained from C60(NO2)14 leads
to polycyclic aromatic moieties necessarily formed from the
fullerene cage breakdown although a small fraction of
C60(NO2)14 is transformed back to C60.
3.4. TGA-FTIR of the gases released
polynitro[60]fullerene thermal decomposition
The aspect of the decomposition of hexanitrofullerene yield-
ing oxidized carbon was examined by other authors [32] who
have proposed also a mechanism explaining the formation of
oxidized carbon residue. In this section using the TGA-FTIR
analytical tool (under nitrogen flow) we have analyzed the
gaseous products released by C60(NO2)14 during the thermal
decomposition. In Fig. 5 is reported the infrared spectrum of
the gaseous products released by C60(NO2)14 at 170 C, a tem-
perature corresponding to the onset of the deflagration. Three
gaseuos products were identified: nitric oxide (NO), nitrogen
dioxide (NO2) and even dinitrogen monoxide (N2O). These
gases are firmly identified through the Omnic library of our
spectrometer and in Fig. 5 are shown also the reference spec-
tra of these three gases. The decomposition of nitrocom-
pounds normally produces a mixture of nitrogen oxides.
This has been found in a previous work with TGA-FTIR dedi-
cated to the thermal decomposition of nitro-polyisoprene [35]
and reported also in other reference works [36].
Fig. 6 shows the temporal evolution of the nitrogen oxides
NO2 and NO as function of the temperature of the C60(NO2)14
and the values in the ordinate of the graph are reported as
Ln[(Abs)t/(Abs)0] where (Abs)t is the area measured below
the peak at 1626 cm1 for NO2 and below the peak at
by 1903 cm1 for NO at any temperature t while (Abs)0 is the area
below the mentioned peak at the temperature when the evo-
lution of a given gas starts. Of course, being each TGA-FTIR
experiment conducted at a heating rate of 10 C/min, the tem-
perature scale in abscissa can be converted into a time scale.
Fig. 6 shows that the production of NO2 and NO starts already
at 60 C and the amount of the evolved gases grows with tem-
perature. At 100 C NO2 reaches a first maximum and then
peaks again at the deflagration temperature of C60(NO2)14 be-
tween 170 C and 180 C. Instead NO shows a plateau between
100 C and 140 C and then it the largest amount is released
again at the deflagration temperature between 170 C and
180 C. The trend of N2O is not shown in Fig. 6 because it is
produced exclusively between 170 C and 180 C, during the
deflagration and in considerably smaller amounts than the
other nitrogen oxides. Particularly interesting is the produc-
tion of NO from the decomposition of C60(NO2)14. It has been
suggested [32] that the nitrogroup of a generic nitrofullerene
once is released by thermal treatment as NO2 it reacts with
418 CARBON 6 2 ( 2 0 1 3 ) 4 1 3 –4 2 1

410-37 Nitro[60]fullerene 170°C

1629
1600
Abs 0.04
1902
18751851
0.02 2209
2236
-0.00
1.0 Nitrogen dioxide NO2
1628 1600
Abs

0.5

1.0 Nitric oxide NO

1906 1875
Abs

0.5 1842

1.0 Dinitrogen monoxide N2O

2237 2213
Abs

0.5

2200 2000 1800 1600 1400

Wavenumbers (cm-1)

Fig. 5 – FTIR spectrum of the gaseous products released by C60(NO2)14 at the decomposition temperature of 170–180 C
(spectrum at the top of the figure). The 2nd, 3rd and 4th spectra from top are reference spectra taken from the Omnic library.

Fig. 6 – Amount of gases NO2 and NO produced from the thermal decomposition of C60(NO2)14 as measured through the TGA-
FTIR analysis. The area below the peak at 1626 cm1 for NO2 and below the peak at 1903 cm1 for NO was measured with the
Ominc software of the infrared spectrometer and reported as Ln[(Abs)t/(Abs)0] in the ordinate of the graph.

the surface of the fullerene cage forming a labile nitrito-ad-
duct which, on further heating decomposes to NO leaving
an oxygen atom in the oxidized carbon network:
C  NO2 ! C þ NO2 ! C  ONO ! C  O þ NO
After the deflagration of C60(NO2)14 the release of nitrogen
oxides drops to zero but continuous heating of the residual
carbonaceous matter reveals the release of CO2 and CO. Also
these two gases were revealed by the TGA-FTIR analytical
technique and identified through the Ominc library of our
spectrometer. Fig. 6 shows that the emission of CO2 reaches
ð1Þ its maximum immediately after the deflagration of the sam-
ple, when the carbonaceous residue is brought at about
200 C. Afterwards the CO2 release drops to a certain level
and from 250 C stabilizes and remains constant. On the other
hand, the release of CO starts as well after the deflagration,
 CARBON 6 2 (2 0 1 3) 4 1 3–42 1
Fig. 7 – Amount of gases CO2 (circles) and CO (squares)
produced from the thermal decomposition of C60(NO2)14 as
measured through the TGA-FTIR analysis. The area below
the peaks at 2363 and 2335 cm1 for CO2 and 2172 and
2115 cm1 for CO was measured with the Ominc software of
the infrared spectrometer and reported as Ln[(Abs)t/(Abs)0]
in the ordinate of the graph.
reaches a plateau from 250 C to 340 C and then grows
again at higher temperatures. Of course the production of
CO2 and CO should be considered in the frame of the dis-
cussion of the previous Section 3.3 where it was shown that
the oxidized carbon produced from the deflagration gradu-
ally loses its oxygenated groups with the increase of the
temperature becoming completely free from oxygenated
groups at 700 C (see Fig. 4). Therefore, the release of CO2
and CO as reported in Fig. 7 is a consequence of the car-
bonization process.
Fig. 8 – DSC trace of C60(NO2)14 recorded at a heating rate of 10 C/min under N2 flow in a sealed stainless steel crucible. The
integral heat of decomposition is 2017 J/g.
419
3.5. DSC of polynitro[60]fullerene and determination of
the heat of decomposition
To measure the amount of heat of decomposition released by
C60(NO2)14 a differential scanning calorimetric (DSC) measure-
ment was recorded as shown in Fig. 8. The DSC trace shows
three main exothermal transitions: first of all a minor exo-
thermal peak at 98 C can be observed followed by the defla-
gration peak at 190 C with the onset at 160 C, thus in a
temperature range completely in line with that measured in
the DTA of Fig. 2. After the deflagration peak there is another
broad exothermal transition with a peak at 247 C. From the
TGA-FTIR we know that above the 210 C C60(NO2)14 is com-
pletely decomposed into an oxidized carbon which releases
only CO2 and CO. Consequently, the real decomposition en-
thalpy of C60(NO2)14 should be calculated using only the first
two transitions at 98 C and 190 C. The integration of these
two peaks corresponds to a total released heat of 434 J/g
which, multiplied by the molecular weight of C60(NO2)14
(1364.74 Da) corresponds to a decomposition enthalpy DHr =
592.3 kJ/mol. Assuming that the decomposition reaction of
C60(NO2)14 is essentially of the following type:
C60 ðNO2 Þ14 ! 60Camorphous þ 14NO2 ð2Þ
Then, it is possible to calculate the free enthalpy of forma-
tion as follows:
DHr ¼ 14DHNO2  DHnitro½60fullerene ð3Þ
592:3 ¼ 14ð33:2Þ  DHnitro½60fullerene ð4Þ
DHnitro½60fullerene ¼ þ1057 kJ=mol ð5Þ
This value of free enthalpy of formation of C60(NO2)14 is
considerably lower than the value predicted by Richard and
Ball who expected theoretically DHnitro[60]fullerene = +4617 kJ/
420 CARBON 6 2 ( 2 0 1 3 ) 4 1 3 –4 2 1
Table 1 – Thermodynamic parameters of tetradeca[60]fullerene and octanitrocubane.
Decomposition
enthalpy (J/g)
Tetradeca[60]fullerene up to 200 C 434
Tetradeca[60]fullerene DSC integration 2017
Octanitrocubane Ref. [24,37] 7489
mol [22]. The complete integration of all the exothermal tran-
sitions of the DSC trace including also those occurring at tem-
peratures higher than 210 C leads to total decomposition
enthalpy of 2017 J/g. In this value we are integrating all the
phenomena that from C60(NO2)14 lead to amorphous carbon
and multiplying by the molecular weight of C60(NO2)14 we
get a decomposition enthalpy (DHr) of 2752.7 kJ/mol. Substi-
tuting this value in Eqs. (3) and (4) it leads to a free enthalpy of
formation of C60(NO2)14:
DHnitro½60fullerene ¼ þ3217:5 kJ=mol ð6Þ
a value considerably closer to the theoretical value predicted
by Richard and Ball [22] (DHnitro[60]fullerene = +4617 kJ/mol) [22]
and more reasonable than the former value of +1057 kJ/mol.
In Table 1 are summarized the key parameters of tetra-
deca[60]fullerene in terms of the decomposition enthalpy as
measured by the DSC up to 200 C or integrated on the entire
DSC curve up to 500 C and the resulting free energy of forma-
tion calculated according to reaction (2). These values are
compared with the decomposition enthalpy of octanitrocu-
bane as reported in Ref. [24,37]. Octanitrocubane is by far a
more energetic material than tetradeca[60]fullerene releasing
3.71 times more energy per gram than the latter.
The decomposition reaction of octanitrocubane is admit-
ted to occur under the conventional form [24,37]:
C8 ðNO2 Þ8 ! 8CO2 þ 4N2 ð7Þ
a decomposition path which is completely different from that
we have observed for tetradeca[60]fullerene reported in Eq. (2).
4. Summary
This study has shown that under certain experimental cir-
cumstances a highly nitrated C60 fullerene is obtained which
is insoluble in benzene and precipitates from the solution.
The TGA analysis has shown that the polynitro[60]fullerene
has a elemental composition of the type C60(NO2)14 and the
TGA in combination with the DTA have shown that it decom-
poses exothermally above 170 C with a considerably release
of heat, a process which can be refereed as deflagration.
The FTIR analysis of the carbonaceous product formed
after the deflagration and heated from 200 C to 650 C has re-
vealed which consists of oxidized carbon rich in different
types of oxygenated groups and resembling polymeric fuller-
ene oxide. At 700 C the carbonaceous matter appears com-
pletely free from oxygenated groups and shows also the
signature of C60 fullerene which is present in low amounts
610% in the carbon matrix.
C60(NO2)14 was also analyzed through the TGA-FTIR ana-
lytical technique and it was found that the deflagration oc-
curs with the release of a mixture of nitrogen oxides: NO2,
Decomposition Free energy of
enthalpy (kJ/mol) formation (kJ/mol)
592 1051
2752 3217
3475 594
NO and smaller amounts of N2O. After the deflagration, when
the release of nitrogen oxide mixture is stopped, only CO2 and
CO are released. The former in higher amounts at lower tem-
perature while the latter becomes more abundant at higher
temperatures. The DSC analysis of C60(NO2)14 in sealed cruci-
bles has permitted us to measure the decomposition enthalpy
of this compound. The decomposition enthalpy including the
deflagration point (up to 210 C) corresponds to 434 J/g or
DHr = 592.3 kJ/mol. If instead the entire DSC exotherm is
integrated as shown in Fig. 8, then the decomposition exo-
therm involves the release of 2017 J/g which corresponds to
decomposition enthalpy DHr = 2752.7 kJ/mol.
The decomposition enthalpy of tetradeca[60]fullerene is by
far lower than that of octanitrocubane.
From these values the free energy of formation of
C60(NO2)14 has been calculated and compared with a theoret-
ical value.
R E F E R E N C E S
[1] Kroto HW, Allaf AW, Balm SP. C60 buckminsterfullerene.
Chem Rev 1991;91:1213–35.
[2] Taylor R. Lecture notes on fullerene chemistry. A handbook
for chemists. London: Imperial College Press; 1999.
[3] Birkett PR. Fullerene chemistry. Annu Rep Prog Chem Sect A
Inorg Chem 1999;95:431–51.
[4] Hirsch A, Brettreich M. Fullerenes. Chemistry and
reactions. Weinheim: Wiley-VCH; 2005.
[5] Nierengarten JF, Martin N, Fowler P, editors. Chime des
fullerenes – fullerene chemistry. Comptes Rendus Chimie
2006;9:859–1116.
[6] Troshin PA, Lyubovskaya RN. Organic chemistry of fullerenes:
the major reactions, types of fullerene derivatives and
prospects for practical use. Russ Chem Rev 2008;77:323–69.
[7] Cataldo F, Da Ros T. Medicinal chemistry and
pharmacological potential of fullerenes and carbon
nanotubes. Dordrecht: Springer; 2008.
[8] Cataldo F, Iglesias-Groth S. Fulleranes: the hydrogenated
fullerenes. Dordrecht: Springer; 2010.
[9] Darwish AD. Fullerenes. Annu Rep Prog Chem Sect A Inorg
Chem 2010;106:356–75.
[10] Hamwi A, Marchand V. Oxidized fullerene derivatives
containing hydroxyl, nitro and fluorine groups. Fullerene Sci
Technol 1996;4:835–51.
[11] Chiang LY, Bhonsle JB, Wang L, Shu SF, Chang TM, Hwu JR.
Efficient one-flask synthesis of water-soluble [60]fullerenols.
Tetrahedron 1996;52:4936–72.
[12] Cataldo F. Preparation of polynitrofullerene by the action of
dinitrogen tetroxide on C60. Fullerene Sci Technol
1997;5:257–65.
[13] Anantharaj V, Bhonsle J, Canteenwala T, Chiang LY. Synthesis
and characterization of nitrated [60]fullerene derivatives. J
Chem Soc Perkin Trans 1999;1:31–6.
 CARBON 6 2 (2 0 1 3) 4 1 3–42 1
[14] Anantharaj V, Wang LY, Canteenwala T, Chiang LY. Synthesis
of starburst hexa-oligoanilinated C60 using
hexanitro[60]fullerene as a precursor. J Chem Soc Perkin
Trans 1999;1:3357–66.
[15] Anantharaj V, Wang LY, Chiang LY. Phenylamine analogous
adducts of C60. Fullerene Sci Technol 1999;7:493–504.
[16] Troshin PA, Astakhova AS, Lyubovskaya R. Synthesis of
fullerenols from halofullerenes. Fullerenes Nanot Carbon
Nanostruct 2005;13:331–43.
[17] Franco JU, Ell JR, Hilton AK, Hammons JC, Olmstead MM.
C60Cl6, C60Br8 and C60(NO2)6 as selective tools in organic
synthesis. Fullerenes Nanot Carbon Nanostruct
2009;17:349–60.
[18] Wang N. Review on the nitration of [60]fullerene. Propellants
Explos Pyrotech 2001;26:109–11.
[19] Slanina Z, Sugiki T, Zhao X, Lee S-L, Chiang LY, Osawa E.
C60(NO2)2: quantum-chemical evaluations of structure,
energetics, and vibrational spectra. Fullerene Sci Technol
2000;8:351–867.
[20] Slanina Z, Zhao X, Chiang LY, Osawa E. Biologically active
fullerene derivatives: computations of structures, energetics,
and vibrations of C60(OH)x and C60(NO2)y. Int J Quantum Chem
1999;74:343–9.
[21] Slanina Z, Iida S, Zhao X, Chiang LY, Adamowicz L, Osawa E.
Computation of hexa-nitrated and hexa-anilinated
fullerenes. Synthetic Met 2001;121:1101–2.
[22] Richard RM, Ball DW. Enthalpies of formation of
nitrobuckminsterfullerenes: extrapolation to C60(NO2)60. J
Mol Struct Theochem 2008;858:85–7.
[23] Peköz R, Erkoç S. Structural and thermochemical properties,
and energetics of C8(NO2)8 and C20(NO2)4n (n = 0–4). Comput
Mater Sci 2009;46:849–53.
[24] Eaton PA, Gilardi RL, Zhang MX. Polynitrocubanes: advanced
high-density, high-energy materials. Adv Mater
2000;12:1143–8.
[25] Kubota N. Propellants and explosives. Weinheim: Wiley-
VCH; 2007.
421
[26] Cooper PW. Explosives engineering. Weinheim: Wiley-VCH;
1996.
[27] Gray P, Yoffe AD. The reactivity and structure of nitrogen
dioxide. Chem Rev 1955;55:1069–154.
[28] Waddington TC. Non-aqueous solvents. London: Thomas
Nelson; 1969.
[29] Miaskiewicz MK, Kecki Z. EPR study of the dinitrogen
tetroxide dissociation in organic solvents. J Sol Chem
1985;14:665–73.
[30] Shiri M, Zolfigol MA, Kruger HG, Tanbakouchian Z. Advances
in the application of N2O4/NO2 in organic reactions.
Tetrahedron 2010;66:9077–106.
[31] Lin-Vien D, Colthup NB, Fateley WG, Grasselli JG. The
handbook of infrared and raman characteristic
frequencies of organic molecules. Academic Press; 1991
[chapter 11].
[32] Zhai R-S, Das A, Hsu C-K, Han C-C, Canteenwala T, Chiang LY,
et al. Polymeric fullerene oxide films produced by
decomposition of hexanitro[60]fullerene. Carbon
2004;42:395–403.
[33] Cataldo F, Heymann D. A study of polymeric products formed
by C60 and C70 fullerene ozonation. Polym Degrad Stabil
2000;70:237–43.
[34] Cataldo F. Polymeric fullerene oxide (fullerene ozopolymers)
produced by prolonged ozonation of C60 and C70 fullerenes.
Carbon 2002;40:1457–67.
[35] Cataldo F, Ursini O, Cherubini C, Rocchi S. Synthesis of cis-
and trans-polyisoprene adduct with nitrogen dioxide (NO2/
N2O4 mixture) and a study of the thermal stability of the
adduct. Polym Degrad Stabil 2012;97:1090–100.
[36] Hatakeyama T, Liu Z. Handbook of thermal
analysis. Chichester: John Wiley & Sons; 1998.
p. 337–77.
[37] Sikder AK, Sikder N. A review of advanced high performance,
insensitive and thermally stable energetic materials
emerging from military and space applications. J Hazard
Mater 2004;A112:1–15.