A nonmetal catalyst for molecular hydrogen activation with comparable catalytic hydrogenation capability to noble metal catalyst

Article abstract of DOI:10.1021/ja9061097

(Chemical Equation Presented) Fullerene can activate molecular hydrogen and is a novel nonmetal hydrogenation catalyst. The hydrogenation of aromatic nitro compounds to amino aromatics is achieved on this catalyst with high conversion and selectivity under 1 atmospheric pressure of H₂ and light irradiation at room temperature or under conditions of 120-160°C and 4-5 MPa H₂ pressure without light irradiation, which is comparable to the case with a noble metal catalyst.

Full text of DOI:10.1021/ja9061097

Published on Web 10/21/2009
A Nonmetal Catalyst for Molecular Hydrogen Activation with Comparable
Catalytic Hydrogenation Capability to Noble Metal Catalyst
Baojun Li and Zheng Xu*
State Key Laboratory of Coordination Chemistry and Nanjing National Laboratory of Microstructure, Department
of Chemistry and Chemical Engineering, Nanjing UniVersity, Nanjing, 210093, PR China
Received August 5, 2009; E-mail: zhengxu@netra.nju.edu.cn
Table 1. Hydrogenation of Nitrobenzene to Aniline under Light
Molecular hydrogen not only is a bright future fuel but also is
widely used today in fundamental chemical transformations. For
example, all crude oil is treated with H2 and 108 tons of ammonia
fertilizer is produced annually via catalytic hydrogenation. Any
small improvement of the performance and cost of the catalysts
would help to cut the cost of these important processes. But such
improvements are hard to achieve because the H2 is held together
in a strong marriage. It can be split apart only by using a transition
metal in most of the catalytic systems known.1 Although a few of
nontransition metal catalysts for hydrogenation reactions have been
reported such as KOtBu2,3 and organocatalyst,4,5 such systems
require serious reaction conditions or do not employ H2 directly
but a surrogate as the stoichiometric source of hydrogen. The only
nonmetallic systems reported to split apart H2 under mild experi-
mental conditions are phosphine-borane species,6-10 a stable
digermyne,11 and selected carbenes.12,13 The key issue for develop-
ing nonmetal hydrogenation systems is to search out an effective
system that reacts cleanly with H2, but few are known.
Irradiation with Various Fullerene Catalysts at Room Temperaturea
entry
catalyst
light radiation
t, h
conv. %
select. %
1
2
3
4
5
6
7
8
9
absence
C60
C60
UV
1.0
4.0
1.0
1.0
4.0
4.0
4.0
4.0
4.0
0
0
0
∼
absence
absence
UV
UV
UV
UV
UV
visible
∼
-
∼
C60
C60
C60
82.6
100
98.2
89.9
84.0
39.1
78.9
92.4
72.5
92.9
87.6
74.8
-
C70
C70
-
C60
a Reaction conditions: 1.0 g of substrate, 0.036 g of catalyst, and 250
mL of THF solvent under 1 atmospheric pressure of H2 and light
irradiation (300 W high pressure Hg lamp or 350 W Xe lamp) in a
cylinder quartz reactor.
The control experiments showed that the H2 molecule cannot
react with nitrobenzene to form aniline in the absence of light
irradiation or C60 catalyst (Table 1, entries 1-3). In a typical
reaction, 0.036 g of C60 and 1.0 g of nitrobenzene were added
in a quartz reactor containing 250 mL of tetrahydrofuran (THF)
with stirring and bubbled with N2 and H2 in succession to remove
air and to saturate the reactor with H2 respectively, and the high-
pressure-mercury lamp was turned on and illuminated for 1 h
with bubbled H2; the reacted solution was then filtered to separate
the solid C60 catalyst. The filtrate was analyzed by GC-MS.
The results show that the main product is aniline with 21.1%
azoxybenzene and azobenzene. The yield of aniline is 78.9%
with 82.6% conversion of nitrobenzene (Table 1, entry 4).
Prolonging the time to 4 h gives aniline in 92.4% yield with
∼100% conversion of nitrobenzene and the yield of azoxyben-
zene and azobenzene further decreases to 7.6%. The results
showed that the C70 molecule as well as C70 and C60 anions also
can catalyze the hydrogenation of nitrobenzene with similar
conversion and selectivity under the same conditions as in the
case of C60 catalyst (Table 1, entries 6-8). The conversion and
Here we demonstrate that fullerene14 can activate molecular
hydrogen and is a novel nonmetal hydrogenation catalyst. The
hydrogenation of aromatic nitro compounds to amino aromatics is
achieved on this catalyst with high yield and selectivity under 1
atmospheric pressure of H2 and light irradiation at room temperature.
More interestingly, there exists a cooperation effect between C60
-
and C60-. At C60:C60 ) 2:1, ∼100% conversion and ∼100%
selectivity are achieved under conditions of 120-160 °C and 4-5
MPa of H2 pressure without light irradiation. The catalytic
performance is comparable with that of the noble metal catalyst.
Also, it exclusively catalyzes the reduction of a nitro group without
the need to add metal salts and avoids the accumulation of the
corresponding hydroxylamine and the formation of azoxy and azo
compounds and is a highly selective and environmentally friendly
catalyst. These findings foreshadow a new catalytic system available
for applications both in academic laboratories and in industry,
allowing stoichiometric reductions mediated by Fe or Na2S to be
performed in a catalytic fashion and greatly reducing subsequent
waste production. Moreover, the catalyst developed here could
replace expensive precious metal catalysts, therefore offering the
potential benefit of lowering cost and diminishing the environmental
impact from heavy-metal pollutants.
-
selectivity are 98.2% and 72.5% for C60 catalyst; 89.9% and
-
92.9% for C70 catalyst, and 84.0% and 87.6% for C70 catalyst.
MALDI TOF MS data show that the fullerene catalyst after
reaction still is fullerene itself without fullerene hydride, which
rules out the possibility of fullerene hydride as an active
hydrogen intermediate (Figure S4). The experiments under
visible light irradiation were conducted. The result (Table 1,
entry 9) indicates that it also works, but the efficiency is less
than that of UV irradiation; a possible reason is that there is
insufficient overlap between the emission spectra of the Xe lamp
and the absorption of one C60. Various C60 produced by different
companies exhibit a similar catalytic performance with ∼96%
conversion and ∼88% selectivity under UV irradiation and
∼94% conversion and ∼73% selectivity under dark. The detailed
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16380 J. AM. CHEM. SOC. 2009, 131, 16380–16382
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C O M M U N I C A T I O N S
results are listed in Tables S1 and S2. Recently, the catalysis of
a trace amount of metal contaminates in the coupling reactions
has been reported.15 To rule out the possibility of catalysis by
a trace amount of metal contaminates in the fullerene, the metal
contaminates in fullerene were determined by an inductively
coupled plasma (ICP) emission spectrometer. A trace amount
(ppm) of Co, Cr, Cu, Fe, and Ag was found in C60 samples,
others are below the detecting limit (Table S3). The control
experiments of catalytic hydrogenation of nitrobenzene by
various metal ions alone (absence of fullerenes) and by the blank
-
solution of preparation C60 (that is, absence of C60, see SI for
details) were completed, and the results showed that no aniline
could be detected and the influence of a trace amount of metal
contaminates on the catalytic hydrogenation of nitrobenzene may
be neglected (see SI).
Figure 2. Catalytic hydrogenation of 4-nitrobenzonitrile on C60 catalyst
under light irradiation. Reaction conditions: 1.0 g of substrate, 0.036 g of
catalyst, and 250 mL of THF solvent under 1 atmospheric pressure of H2
and room temperature.
the reactivity of the electronically excited state of C60 and C70 is
all but unknown. Further studies including kinetic and theory
calculation are underway.
Table 2. Hydrogenation of Nitrobenzene to Aniline with Various
C60 Catalysts under Dark Conditiona
entry
catalyst
H2, MPa
T, °C
conv. %
select. %
1
2
3
4
5
6
7
8
C60
C60
C60
C60
C60
C60
C60
C60
C60
5.0
absence
2.0
3.0
3.0
3.0
3.0
5.0
5.0
5.0
5.0
5.0
5.0
140
140
100
100
120
140
140
140
160
140
140
160
140
140
3.8
0
87.8
∼
-
-
-
-
-
-
-
-
21.4
45.0
92.4
96.0
71.2c
99.7
>99.9
99.9
99.8
>99.9
45.5
37.3
46.4
40.4
74.1b
70.9
61.1
73.2
88.9
91.3
99.0
>99.9
27.4
84.7
Figure 1. Catalytic hydrogenation of nitrobenzene on C60 catalyst under
light irradiation. Reaction conditions: 1.0 g of substrate, 0.036 g of catalyst,
and 250 mL of THF solvent under 1 atmospheric pressure of H2 and room
temperature.
9
-
10
11
12
13
14
C60/C60 (1:1)
C60/C60 (2:1)
C60/C60 (2:1)
C60
-
-
To determine if the azoxybenzene and azobenzene are intermedi-
ates of the consecutive reactions, we carried out hydrogenation of
nitrobenzene on the C60 catalyst in a batch reactor by following
the reaction with time. The plots of reaction products against time
are depicted in Figure 1. In the case of C70 or the C70 anion as a
catalyst, similar curves were obtained (Figures S9, S10). These
results show that the yields of azoxybenzene and azobenzene are
quite low and are almost constant within 240 min, which are out
of accordance with the character of the consecutive reactions.
It seems that azoxybenzene and azobenzene were not an inter-
mediate in the reaction sequence nitrobenzenefnitrosobenzenef
azoxybenenefazobenzenefaniline16 but rather products from a
side reaction. The hydrogenation of nitrobenzene is more like to
occur mainly through the direct route, that is, nitrobenzenefnitro-
sobenzenefphenyl hydroxylaminefaniline.16 The exact mecha-
nism is unknown; a further study is underway.
Fullerene is excellent in hydrogenation not only for nitroben-
zene but also for aromatic nitro compounds such as 4-nitroben-
zonitrile, 4-nitroacetophenone, and 4-chloronitrobenzene. The
plots of products vs time are shown in Figures 2, S7, and S8,
respectively. From Figure 2, we can see that the hydrogenation
reaction proceeds very rapidly, and ∼100% conversion of
nitrobenzonitrile with ∼100% selectivity was achieved within
only 1 h. There is no bis(cyano)azoxybenzene in the reaction
products after reacting for 1 h.
2-
-
C70
5.0
a Reaction conditions: 1.0 g of substrate, 0.036 g of catalyst, and 40
mL of THF solvent for 4.0 h; the different components in the product
are listed in Table 3. b Azoxybenzene as main product. c Reaction
conditions: 4.0 g of substrate, 0.036 g of catalyst, and 40 mL of THF
solvent for 12 h.
Although catalytic hydrogenation of aromatic nitro compounds
cannot occur without light irradiation at ambient conditions, it takes
place well under forcing conditions of 120-160 °C and 4-5 MPa
of H2 pressure (Table 2). In this case, the catalytic performance of
the C60 anion is better than that of neutral C60. The reason for that
is inclear; it seems that the solubility of C60 anion in THF is better
than that of neutral C60, and the charge on the C60 anion is of benefit
to the formation of a synergistic complex. The experimental results
exhibit that conversion of nitrobenzene increases with increasing
H2 pressure or reaction temperature (Table 2, entries 3-9). At the
optimum conditions (160 °C, 5 MPa of H2), 99.9% conversion of
nitrobenzene with 88.9% selectivity of aniline are achieved (Table
2, entry 9). The results show that the catalytic performance of the
-
C60 catalyst has no remarkable degradation after increasing the
amount of substrate and prolonging the reaction time by 4 and 3
times respectively (Table 2, entry 7), which is equivalent to that of
the catalyst after reuse ∼4 times. It is interesting that there was a
cooperative effect between the C60 anion and neutral C60 (Table 2,
Based on these results, we might conjecture that electronically
excited C60 or C70, H2, and nitrobenzene form a synergistic exciplex,
which makes the H2 molecule active and achieves transfer of
hydrogen atoms to the nitro group to form aniline. Unfortunately,
-
entries 10-12). At the optimum ratio of C60/C60 () 2:1), the
selectivity of aniline significantly increases from 73.2% (C60- alone,
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C O M M U N I C A T I O N S
-
140 °C) to 99% (C60:C60- ) 2:1, 140 °C) and to ∼100% (C60:C60
and 1 atmospheric pressure of H2 at room temperature. There was
a cooperative effect between C60 and C60- and at an optimum ratio
(2:1); ∼100% conversion and ∼100% selectivity are achieved under
dark conditions at 5 MPa of H2 and 160 °C. The results are
comparable with those of the noble metal catalyst, which are being
reported for the first time. The reaction mechanism might involve
a synergistic exciplex (under light irradiation) or an active complex
(under dark conditions). We anticipate our discovery to be a starting
point for more effective all carbon molecular-based nonmetal
catalyst systems for molecular hydrogen activation and will promote
the development of electronically excited state reactions and novel
molecular H2 activation and storage systems. The exact mechanism
is not clearly understood at this moment, and a further study is
underway.
) 2:1, 160 °C), while the conversion of nitrobenzene is maintained
at ∼100%. It is an excellent nonmetal hydrogenation catalyst for
hydrogenation of aromatic nitro compounds, and the catalytic
performance is comparable to that of the noble metal counterpart,
which has never been reported before.
Table 3. Product Distribution of Hydrogenation Reactions Listed in
Table 2
entry in Table 2
nitro-
azoxy-
azo-
aniline
1 (C60, 5 MPa of H2, 140 °C)
3 (C60-, 2 MPa of H2, 100 °C)
4 (C60-, 3 MPa of H2, 100 °C)
5 (C60-, 3 MPa of H2, 120 °C)
6 (C60-, 3 MPa of H2, 140 °C)
8 (C60-, 5 MPa of H2, 140 °C)
96.2
78.7
55.0
7.6
4.1
0.3
0.5
11.5
26.1
68.5
0
0
0
0.7
7.5
27.9
21.7
3.4
9.8
18.2
16.4
68.0
73.2
5.0
Acknowledgment. Financial support from the National Natural
Science Foundation of China under the major research project (No.
90606005) and the Jiangsu Province Foundation of Natural Science
(No. BK2006717) are acknowledged.
The distribution of different products of hydrogenation reactions
is listed in Table 3. The catalytic activity of the neutral C60 solid is
quite poor and the conversion of nitrobenzene and selectivity of
aniline are only 3.8% and 87.8% respectively with 0.5% azoxy-
benzene (Table 3, entry 1), whereas the catalytic performance of
the C60 anion is quite good with the conversion and selectivity at
99.7% and 73.2% respectively; the byproducts are azobenzene
(21.7%) and azoxybenzene (5%)(Table 3, entry 8). As the reaction
temperature and H2 pressure increase, the conversion of nitroben-
zene increases and the product compositions change significantly.
For example, the yield of azoxybenzene increases remarkably from
11.5% to 26.1% with increasing H2 pressure from 2 to 3 MPa (Table
3, entry 4) and further increases to 68.5% with increasing reaction
temperature to 120 °C (Table 3, entry 5). Upon further increase in
temperature to 140 °C, aniline becomes a main product with 68.0%
yield (Table 3, entry 6). It seems that increasing the reaction
temperature and H2 pressure is of benefit to the formation of aniline
and azobenzene.
Supporting Information Available: Experimental details and
analytical results of fullerene catalysts. This material is available free
of charge via the Internet at http://pubs.acs.org.
References
(1) For general reviews on the hydrogenation, see: (a) Chen, B.; Dingerdissen,
U.; Krauter, J. G. E.; Lansink Rotgerink, H. G. J.; Mo¨bus, K.; Ostgard,
D. J.; Panster, P.; Riermeier, T. H.; Seebald, S.; Tacke, T.; Trauthwein, H.
Appl. Catal., A 2005, 280, 17–46. (b) Ma¨ki-Arvela, P.; Ha´jek, J.; Salmi,
T.; Murzin, D. Y. Appl. Catal., A 2005, 292, 1–49.
(2) (a) Walling, C.; Bollyky, L. J. Am. Chem. Soc. 1961, 83, 2968–2969. (b)
Walling, C.; Bollyky, L. J. Am. Chem. Soc. 1964, 86, 3750–3752.
(3) Berkessel, A.; Schubert, T. J. S.; Mller, T. N. J. Am. Chem. Soc. 2002,
124, 8693–8698.
(4) Barbe, G.; Charette, A. B. J. Am. Chem. Soc. 2008, 130, 18–19.
(5) Magnus, R.; Antonchick, A. P.; Theissmann, T. Angew. Chem., Int. Ed.
2006, 45, 3683–3686.
(6) (a) Welch, G. C.; San Juan, R. R.; Masuda, J. D.; Stephan, D. W. Science
2006, 314, 1124–1126. (b) Stephan, D. W. Dalton Trans. 2009, 3129–
3136.
(7) (a) Welch, G. C.; Cabrera, L.; Chase, P. A.; Hollink, E.; Masuda, J. D.;
Wei, P.; Stephan, D. W. Dalton Trans. 2007, 3407–3414. (b) Spies, P.;
Erker, G.; Kehr, G.; Bergander, K.; Fro¨hlich, R.; Grimme, S.; Stephan,
D. W. Chem. Commun. 2007, 5072–5074.
-
Table 4. Hydrogenation of Various Substrates with C60 and C60
Catalysta
(8) (a) Welch, G. C.; Stephan, D. W. J. Am. Chem. Soc. 2007, 129, 1880–
1881. (b) Geier, S. J.; Gilbert, T. M.; Stephan, D. W. J. Am. Chem. Soc.
2008, 130, 16232–16233. (c) Kenward, A. L.; Piers, W. E. Angew. Chem.,
Int. Ed. 2008, 47, 38–41. (d) Holschumacher, D.; Bannenberg, T.; Hrib,
C. G.; Jones, P. G.; Tamm, M. Angew. Chem., Int. Ed. 2008, 47, 7428–
7432. (e) Chase, P. A.; Stephan, D. W. Angew. Chem., Int. Ed. 2008, 47,
7433–7437.
(9) (a) Ullrich, M.; Lough, A. J.; Stephan, D. W. J. Am. Chem. Soc. 2009,
131, 52–53. (b) Geier, S. J.; Stephan, D. W. J. Am. Chem. Soc. 2009, 131,
3476–3477. (c) Ramos, A.; Lough, A. J.; Stephan, D. W. Chem. Commun.
2009, 1118–1120.
entry
substrate
catalyst
product
conv. %
select. %
-
1
2
3
4
azobenzene
azoxybenzene
azobenzene
C60
aniline
azobenzene
aniline
34.6
82.7
2.9
100
91.6
100
80.2
-
C60
C60
C60
azoxybenzene
azobenzene
3.4
a Reaction conditions: 0.5 g of substrate, 0.036 g of catalyst, 40 mL
of THF solvent, under 5.0 MPa of H2 and 140 °C for 4 h.
(10) (a) Chase, P. A.; Welch, G. C.; Jurca, T.; Stephan, D. W. Angew. Chem.,
Int. Ed. 2007, 46, 8050–8053. (b) Chase, P. A.; Jurca, T.; Stephan, D. W.
Chem. Commun. 2008, 1701–1703. (c) Rokob, T. A.; Hamza, A.; Stirling,
A.; Pa´pai, I. J. Am. Chem. Soc. 2009, 131, 2029–2036.
(11) (a) Spikes, G. H.; Fettinger, J. C.; Power, P. J. Am. Chem. Soc. 2005, 127,
12232–12233. (b) Peng, Y.; Brynda, M.; Ellis, B. D.; Fettinger, J. C.;
Rivard, E.; Power, P. P. Chem. Commun. 2008, 6042–6044.
(12) Ko1tting, C.; Sander, W. J. Am. Chem. Soc. 1999, 121, 8891–8897.
(13) Frey, G. D.; Lavallo, V.; Donnadieu, B.; Schoeller, W. W.; Bertrand, G.
Science 2007, 316, 439–441.
(14) (a) Wu, M.; Wei, X.; Qi, L.; Xu, Z. Tetrahedron Lett. 1996, 37, 7409–
7412. (b) Wei, X.; Wu, M.; Qi, L.; Xu, Z. J. Chem. Soc., Perkin Trans. 2
1997, 1389–1393.
(15) (a) Arvela, R. K.; Leadbeater, N. E.; Sangi, M. S.; Williams, V. A.;
Granados, P.; Singer, R. D. J. Org. Chem. 2005, 70, 168–168. (b) Buchwald,
S. L.; Bolm, C. Angew. Chem., Int. Ed. 2009, 48, 5586–5587.
(16) Corma, A.; Concepcio´n, P.; Serna, P. Angew. Chem., Int. Ed. 2007, 46,
7266–7269.
To gain insight into the reaction mechanism, the catalytic
hydrogenations of azoxybenzene and azobenzene were studied
(Table 4). We can see clearly that their conversion is quite low
under the same conditions as those for hydrogenation of nitroben-
zene. If they are the intermediates of the reaction sequence, their
conversion and the yield of aniline should be similar with those
for the hydrogenation of nitrobenzene. It seems that the hydrogena-
tion reaction under dark conditions occurs mainly through a direct
route but also condensation route.16
In summary, the results reported here show that neutral fullerene,
the fullerene anion, and their combination are excellent nonmetal
hydrogenation catalysts for aromatic nitro compounds to amino
aromatics with high conversion and selectivity under UV irradiation
JA9061097
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