Journal of Materials Chemistry A
Communication
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Fig. 15 TEM image after the hydrogenation test (magnification ꢃ2000
and ꢃ20k, scale bar: left, 5mm;right, 500 nm).
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quantied before and aer the reaction, conrming a decrease
from 10.9 mg mꢁ2 to 5.76 mg mꢁ2, half of which can be linked to
the active layer degradation. In conclusion, Ru nanoparticles
were added onto the surface of the modied PES membrane
using a UV source.
The catalytic membrane was characterized with different
techniques in order to evaluate the effective presence of the
active layer and the Ru nanoparticles. The membrane with an
initial pore size of 220 nm and 10.9 mg cmꢁ2 of Ru catalyst was
tested for the hydrogenation of furfural under mild conditions
(7 bar, 70 ꢀC) resulting in >99% selectivity towards FOL with
a TOF of 48 000 hꢁ1, when a H2/furfural molar ratio of 1 : 1 was
used. The resulting TOF was considerably higher than those
reported in the literature suggesting that the catalytic
membrane reactor enhances the catalytic activity of Ru in the
selected reaction, while, a >99% selectivity to THF was obtained
by increasing the H2/furfural molar ratio to 4 : 1 under the same
process conditions. The use of the CMR also resulted in a resi-
dence time of the reactants in the membrane layer of less than 2
seconds, compared to a residence time higher than 1 h for
conventional PBRs. Therefore, this work indicates that selective
hydrogenation of furfural to FOL can be successfully performed
using CMRs under mild conditions, but alternative polymeric
support materials need to be developed/tested and the recy-
clability of the catalysts need to be addressed for rendering this
pathway commercially viable.
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13 C. P. Jimenez-Gomez, J. A. Cecilia, I. Marquez-Rodrıguez,
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´
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R. Moreno-Tost, J. Santamarıa-Gonzalez, J. Merida-Robles
and P. Maireles-Torres, Catal. Today, 2017, 279, 327–338.
14 X. Chen, L. Zhang, B. Zhang, X. Guo and X. Mu, Sci. Rep.,
2016, 6, 28558.
15 M. W. Nolte, A. Saraeian and B. H. Shanks, Green Chem.,
2017, 19, 3654–3664.
16 Y. Nakagawa, K. Takada, M. Tamura and K. Tomishige, ACS
Catal., 2014, 4, 2718–2726.
17 S. Liu, Y. Amada, M. Tamura, Y. Nakagawa and
K. Tomishige, Catal. Sci. Technol., 2014, 4, 2535–2549.
18 R. Fang, H. Liu, R. Luque and Y. Li, Green Chem., 2015, 17,
4183–4188.
19 J. Yang, J. Ma, Q. Yuan, P. Zhang and Y. Guan, RSC Adv.,
2016, 6, 92299–92304.
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20 A. O'Driscoll, T. Curtin, W. Y. Hernandez, P. Van Der Voort
and J. J. Leahy, Org. Process Res. Dev., 2016, 20, 1917–1929.
21 J. Llop Castelbou, K. C. Szeto, W. Barakat, N. Merle,
C. Godard, M. Taouk and C. Claver, Chem. Commun.,
2017, 53, 3261–3264.
Conflicts of interest
22 I. Romanenko, M. Lechner, F. Wendler, C. Horenz, C. Streb
and F. H. Schacher, J. Mater. Chem. A, 2017, 5, 15789–15796.
23 L. Meng, M. Kanezashi, X. Yu and T. Tsuru, J. Mater. Chem. A,
2016, 4, 15316–15319.
There are no conicts to declare.
Acknowledgements
24 H. Li, A. Caravella and H. Y. Xu, J. Mater. Chem. A, 2016, 4,
14069–14094.
25 W. J. Koros, Y. H. Ma and T. Shimidzu, Pure Appl. Chem.,
1996, 68(7), 1479–1489.
The authors thank Dr Ida Daniela Perrotta, Department of
Biology, Ecology and Earth Sciences (Di.B.E.S.T.), University of
Calabria-Arcavacata di Rende, (CS), Italy, for the TEM analysis.
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26 G. Bagnato, A. Iulianelli, A. Vita, C. Italiano, M. Lagana,
C. Fabiano, C. Rossi and A. Basile, Int. J. Membr. Sci.
Technol., 2015, 2, 48–56.
27 J. P. Stanford, M. C. Soto, P. H. Pfromm and M. E. Rezac,
Catal. Today, 2016, 268, 19–28.
28 M. Liu, X. Zhu, R. Chen, Q. Liao, H. Feng and L. Li, Chem.
Eng. J., 2016, 301, 35–41.
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