C. Ortiz-Cervantes, J.J. García / Inorganica Chimica Acta 397 (2013) 124–128
127
1
1
20
00
by vacuum to yield a brown residue, which was used as the cata-
lyst in the next reaction using the same reagents above quoted.
Catalyst activity is completely lost after 4 cycles.
8
6
4
2
0
0
0
0
0
4
.4. Hg (0) poisoning test
Homogeneity tests were performed following the above de-
scribed procedures while in addition to the reactants, two mercury
drops were added to the mixture. After reaction completion, the
solution was filtered and analyzed by GC–MS.
TEM micrographs were determined on a Jeol-2010 microscope
equipped with a lanthanum hexaboride filament operating at an
accelerating voltage of 200 kV. Samples for TEM observations were
prepared by placing a thin film of the heptanes Ru-NPs solution in
a holey carbon grid. The metal particle size distribution was esti-
mated from the measurement of about 200 particles, assuming a
spherical shape, found in an arbitrary chosen area in enlarged
micrographs.
fresh
1st
2nd
3rd
4th
Fig. 2. Catalyst recycling study in the hydrogenation of levulinic acid to GVL.
4
. Experimental
Conversion and selectivity of the catalytic reactions were deter-
mined via Gas Chromatographic analyses performed on an Agilent
All manipulations were performed using a MBraun glovebox
(
<1 ppm of H
P99.5%), molecular sieves (3 Å) Ru
Å and FA (reagent grade P95%) were purchased from Sigma–Al-
2
O and O
2
). LA (98% purity), triethylamine (purity
5
975C system equipped with a 30 m DB-5MS capillary (0.32 mm
3
(CO)12, molecular sieves of
ID) column.
3
drich and deoxygenated. Tetrahydrofuran (J.T. Baker) was dried
and distilled from dark purple solutions of sodium/benzophenone
ketyl radical. Methanol and ethyl acetate were purchased from
J.T. Baker. Isopropyl alcohol was purchased from Mallinckrodf AR.
Methanol and isopropyl alcohol were dried and distilled from solu-
tions of metallic magnesium with iodine. All water used was dis-
tilled and deoxygenated under argon flow. Ultra high purity
hydrogen (5.0, Praxair) was used.
Acknowledgments
We thank CONACyT 0178265 and DGAPA-UNAM (IN-210613)
for their financial support to this work. We thank Iván Puente-
Lee (USAI-UNAM) for TEM determinations. C.O-C also thanks
CONACYT for a graduate studies grant.
Appendix A. Supplementary material
4
.1. Hydrogenation of LA with molecular hydrogen using Ru-NPs
Catalytic tests were carried out in 100 mL stainless steel Parr
autoclaves. In a typical experiment, the reactor was loaded with
References
1
0
H
g of LA (8.6 mmol), 3 mg of nanoparticles precursor (Ru
.005 mmol) and 15 mL of distilled water, pressurized with 5 bar
at room temperature, and heated at 130 °C for 12 h. The reaction
3
CO12,
[
1] J.J. Bozell, G.R. Petersen, Green Chem. 12 (2010) 539.
2
[2] R.A. Sheldon, Chem. Soc. Rev. 41 (2012).
[
[
3] D.M. Alonso, J.Q. Bond, J.A. Dumesic, Green Chem. 12 (2010) 1493.
4] S. Murat Sen, C.A. Henao, D.J. Braden, J.A. Dumesic, C.T. Maravelias, Chem. Eng.
Sci. 67 (2012) 57.
mixture was extracted with 5 Â 20 mL of ethyl acetate and the sol-
vent was removed with vacuum. Experiments with 3 Å-MS and
THF were carried out in a similar way. Batches of GVL were centri-
fuged after workup without observing deposition of metal
nanoparticles.
[5] E.I. Gürbüz, S.G. Wettstein, J.A. Dumesic, ChemSusChem 5 (2012) 383.
[
6] S.W. Fitzpatrick, in: A.S. Series (Ed.), Feedstocks for the Future, Biofine
Technologies LLC, vol. 921, Waltham, MA, USA, 2006, p. 271.
[
7] H. Mehdi, V. Fábos, R. Tuba, A. Bodor, L. Mika, I. Horváth, Top. Catal. 48 (2008)
49.
[
[
8] L. Deng, J. Li, D.-M. Lai, Y. Fu, Q.-X. Guo, Angew. Chem., Int. Ed. 48 (2009) 6529.
9] J.C. Serrano-Ruiz, R.M. West, J.A. Dumesic, Annu. Rev. Chem. Biomol. Eng. 1
4.2. Hydrogenation of LA with FA using Ru-NPs
(
2010) 79.
[
[
[
10] I.T. Horvath, Green Chem. 10 (2008) 1024.
11] S.W. Baldwin, M.T. Crimmins, P.M. Gross, Tetrahedron Lett. 19 (1978) 4197.
12] D. Fegyverneki, L. Orha, G. Láng, I.T. Horváth, Tetrahedron 66 (2010) 1078.
In a typical experiment, the vessel was loaded with 1 g of LA
(
0
7
8.6 mmol), 3 mg of nanoparticles precursor ([Ru
3
CO12],
.005 mmol) and 5 mL of distilled water. Then were added
00 L of FA (820 mg, 16.92 mmol) and finally 220 L (1.57 mmol)
N. The reactor was heated at 130 °C for 24 h. The reaction
[13] J.Q. Bond, D.M. Alonso, D. Wang, R.M. West, J.A. Dumesic, Science 327 (2010)
110.
[
[
1
l
l
14] I.T. Horvath, H. Mehdi, V. Fabos, L. Boda, L.T. Mika, Green Chem. 10 (2008) 238.
15] F.M.A. Geilen, B. Engendahl, A. Harwardt, W. Marquardt, J. Klankermayer, W.
Leitner, Angew. Chem., Int. Ed. 49 (2010) 5510.
of Et
3
mixture was extracted with 5 Â 20 mL of ethyl acetate and the sol-
vent was removed by vacuum.
[16] A.M.R. Galletti, C. Antonetti, V. De Luise, M. Martinelli, Green Chem. 14 (2012)
88.
6
[
[
[
[
17] L. Deng, Y. Zhao, J. Li, Y. Fu, B. Liao, Q.-X. Guo, ChemSusChem 3 (2010) 1172.
18] M.G. Al-Shaal, W.R.H. Wright, R. Palkovits, Green Chem. 14 (2012) 1260.
19] P. Kluson, L. Cerveny, Appl. Catal. A 128 (1995) 13.
20] H. Heeres, R. Handana, D. Chunai, C. Borromeus Rasrendra, B. Girisuta, H. Jan
Heeres, Green Chem. 11 (2009) 1247.
4
.3. Catalyst recycling experiments
The catalyst recycling was made on a sample prepared as fol-
lows: using 3 mg of [Ru
3
(CO)12], (0.005 mmol), 1 g of LA
[21] F.M.A. Geilen, B. Engendahl, M. Holscher, J.R. Klankermayer, W. Leitner, J. Am.
Chem. Soc. 133 (2011) 14349.
(
8.6 mmol), and 5 mL of distilled water were charged in an auto-
[
[
22] L.E. Manzer, Appl. Catal. A 272 (2004) 249.
23] F.K. Cheung, A.J. Clarke, G.J. Clarkson, D.J. Fox, M.A. Graham, C. Lin, A.L. Criville,
M. Wills, Dalton Trans. 39 (2010) 1395.
clave, then 700
lL of FA (820 mg, 16.92 mmol) were added fol-
lowed by 220
lL (1.57 mmol) of Et N, finally, the components
3
[
[
[
24] S. Enthaler, ChemSusChem 1 (2008) 801.
25] F. Joó, ChemSusChem 1 (2008) 805.
26] A. Boddien, F. Gärtner, R. Jackstell, H. Junge, A. Spannenberg, W. Baumann, R.
Ludwig, M. Beller, Angew. Chem., Int. Ed. 49 (2010) 8993.
were stirred at room temperature in a vessel for a few minutes
and heated at 130 °C for 24 h. The LA was converted to GVL quan-
titatively, determined by GC–MS. Then all volatiles were removed