Table 2 Catalytic activity of Starbons-supported metals in the hydrogenation of succinic acida
Catalyst
Conv./mol%
SBDO/mol%
SGBL/mol%
TON
TOF/hꢁ1
Blank
—
75
78
60
90
—
70
85
90
10b
—
30
15
10
30b
—
—
7
13
6
5% Pd–Starbons
5% Pt–Starbons
5% Rh–Starbons
5% Ru–Starbons
158
320
143
223
10
a
b
Reaction conditions: 10 mmol SA, 30 mmol EtOH, 50 mmol H2O, 10 bar H2, 100 1C, 0.1 g catalyst, 24 h reaction. The missing 60 mol%
selectivity for 5% Ru–Starbons corresponds to tetrahydrofuran (THF).
We envisage the protocol to be extended to other platform
molecules including fumaric, itaconic, levulinic, pyruvic and
related acids.
Notes and references
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Biomass, John Wiley & Sons, Chichester, 2008.
7 T. Werpy and G. Petersen, Top value added chemicals from biomass,
8 R. Luque, C. S. K. Lin, C. Du, D. J. Macquarrie, A. Koutinas,
R. Wang, C. Webb and J. H. Clark, Green Chem., 2009, 11, 193–200.
9 (a) V. Budarin, J. H. Clark, J. J. E. Hardy, R. Luque,
K. Milkowski, S. J. Tavener and A. J. Wilson, Angew. Chem.,
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10 (a) L. A. Oro, D. Carmona and J. M. Fraile, in Metal Catalysis in
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Royal Society of Chemistry, Cambridge, 2006, pp. 79–113;
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Scheme 1 Reaction pathway for the hydrogenation of SA using
supported metal catalysts.
Furthermore, the reaction conditions could be tuned to
H. B. Pan and C. M. Wai, J. Phys. Chem. C, 2009, 113, 1520–1525.
11 P. Makowski, R. Demir-Cakan, M. Antonietti, F. Goettmann and
M. M. Titirici, Chem. Commun., 2008, 999–1001.
12 (a) J. M. Campelo, T. D. Conesa, M. J. Gracia, M. J. Jurado,
maximise the production of g-butyrolactone (GBL) from
either Pd–Starbons or Ru–Starbons (up to 65% selectivity
at 45% conversion—10 h reaction—using 5% Pd–Starbons).
R. Luque, J. M. Marinas and A. A. Romero, Green Chem., 2008,
10, 853–858; (b) C. Gonzalez-Arellano, J. M. Campelo,
D. J. Macquarrie, J. M. Marinas, A. A. Romero and R. Luque,
ChemSusChem, 2008, 1, 746–750.
GBL is also a high value-added chemical which is normally
employed as solvent, chemical intermediate, raw material
for pharmaceuticals, component of herbicides and rubber
additives.21 Most importantly, the catalysts were found to be
stable and reusable under the reaction conditions, preserving
over 95% of their initial activity after 5 reaction cycles
(Table S2, ESIw). The leaching of the materials into solution
was also checked by ICP/AES of the final reaction mixture.
No detectable metal traces in solution (o0.5 ppm) were
determined by this method, pointing to the strong interaction
between the metal nanoparticles and the Starbons surface
that prevented metal leaching during/after the reaction, in
good agreement with XPS data.
13 C. Gonzalez-Arellano, R. Luque and D. J. Macquarrie, Chem.
Commun., 2009, 1410–1412.
14 V. L. Budarin, J. H. Clark, R. Luque, D. J. Macquarrie and
R. J. White, Green Chem., 2008, 10, 382–387.
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C. T. Campbell, J. Phys. Chem. B, 2006, 110, 24577–24584.
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18 A. Lewera, W. P. Zhou, C. Vericat, J. H. Chung, R. Haasch,
A. Wieckowski and P. S. Bagus, Electrochim. Acta, 2006, 51,
3950–3956 and references therein.
19 S. Miao, Z. Liu, B. Han, J. Huang, Z. Sun, J. Zhang and T. Jiang,
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Chem., 2009, 11, 562–568.
In summary, these outstanding findings are the first report
of direct and efficient production of high value-added
chemicals including GBL, THF and BDO from succinic acid
via hydrogenation under mild and benign reaction conditions
(10 bar H2, 100 1C, aqueous ethanol as solvent) and may pave
the way to the efficient utilisation of highly active, stable and
inexpensive SMNPs in the production of commodity and
speciality chemicals from biomass.
22 C. Delhomme, D. Weuster-Botz and F. E. Kuhn, Green Chem.,
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Chem. Commun., 2009, 5305–5307 | 5307