334
J. A. Delgado and C. Godard
more dramatic for highly diluted active phases by a second metal, where large site
isolation additionally occur.
While the semi-hydrogenation of alkynes has generally evidenced structure sensitivity, the utilization of sub-nanometer entities such as small metal clusters and single
atoms accessible by current synthetic methodologies have uncovered a new type
of potential catalysts of special value for demanding reactions such as the semihydrogenation of acetylene. In this line, modern unconventional catalytic systems
such as cationic nickel or palladium single sites (with unusual oxidation states such
as Pd(I)), as well as hybrid systems comprised by metal-oxide entities, (with potential to display synergistic reactivities at the metal interface) have demonstrated a
huge potential in selective hydrogenation reactions, but are still at early stages of
exploitation and therefore there is plenty of room for future developments.
References
1. Marteel-Parrish AE, Abraham MA (2013) Understanding the issues. In: Green chemistry and
engineering. Wiley, pp 1–19. https://doi.org/10.1002/9781118720011.ch1
2. Descorme C, Gallezot P, Geantet C, George C (2012) Heterogeneous catalysis: a key
tool toward sustainability. ChemCatChem 4(12):1897–1906. https://doi.org/10.1002/cctc.201
200483
3. Carenco S, Leyva-Pérez A, Concepción P, Boissière C, Mézailles N, Sanchez C, Corma
A (2012) Nickel phosphide nanocatalysts for the chemoselective hydrogenation of alkynes.
Nano Today 7(1):21–28. https://doi.org/10.1016/j.nantod.2011.12.003
4. Carenco S, Le Goff XF, Shi J, Roiban L, Ersen O, Boissière C, Sanchez C, Mézailles N (2011)
Magnetic core–shell nanoparticles from nanoscale-induced phase segregation. Chem Mater
23(8):2270–2277. https://doi.org/10.1021/cm200575g
5. Planken KL, Kuipers BWM, Philipse AP (2008) Anal Chem 80:8871
6. Hori J, Murata K, Sugai T, Shinohara H, Noyori R, Arai N, Kurono N, Ohkuma T (2009)
Highly active and selective semihydrogenation of alkynes with the palladium nanoparticlestetrabutylammonium borohydride catalyst system. Adv Synth Catal 351(18):3143–3149.
https://doi.org/10.1002/adsc.200900721
7. Yarulin A, Yuranov I, Cárdenas-Lizana F, Abdulkin P, Kiwi-Minsker L (2013) Size-effect
of Pd-(Poly(N-vinyl-2-pyrrolidone)) nanocatalysts on selective hydrogenation of alkynols
with different alkyl chains. J Phys Chem C 117(26):13424–13434. https://doi.org/10.1021/
jp402258s
8. Vilé G, Baudouin D, Remediakis IN, Copéret C, López N, Pérez-Ramírez J (2013) Silver
nanoparticles for olefin production: new insights into the mechanistic description of propyne
hydrogenation. ChemCatChem 5(12):3750–3759. https://doi.org/10.1002/cctc.201300569
9. Lopez N, Vargas-Fuentes C (2012) Promoters in the hydrogenation of alkynes in mixtures:
insights from density functional theory. Chem Commun 48(10):1379–1391. https://doi.org/
10.1039/c1cc14922a
10. Crespo-Quesada M, Cárdenas-Lizana F, Dessimoz A-L, Kiwi-Minsker L (2012) Modern
trends in catalyst and process design for alkyne hydrogenations. ACS Catal 2(8):1773–1786.
https://doi.org/10.1021/cs300284r
11. Odom TW, Pileni M-P (2008) Nanoscience. Acc Chem Res 41(12):1565–1565. https://doi.
org/10.1021/ar800253n
12. Beaumont SK (2014) Recent developments in the application of nanomaterials to understanding molecular level processes in cobalt catalysed Fischer-Tropsch synthesis. Phys Chem
Chem Phys 16(11):5034–5043. https://doi.org/10.1039/c3cp55030c
J. A. Delgado and C. Godard
more dramatic for highly diluted active phases by a second metal, where large site
isolation additionally occur.
While the semi-hydrogenation of alkynes has generally evidenced structure sensitivity, the utilization of sub-nanometer entities such as small metal clusters and single
atoms accessible by current synthetic methodologies have uncovered a new type
of potential catalysts of special value for demanding reactions such as the semihydrogenation of acetylene. In this line, modern unconventional catalytic systems
such as cationic nickel or palladium single sites (with unusual oxidation states such
as Pd(I)), as well as hybrid systems comprised by metal-oxide entities, (with potential to display synergistic reactivities at the metal interface) have demonstrated a
huge potential in selective hydrogenation reactions, but are still at early stages of
exploitation and therefore there is plenty of room for future developments.
References
1. Marteel-Parrish AE, Abraham MA (2013) Understanding the issues. In: Green chemistry and
engineering. Wiley, pp 1–19. https://doi.org/10.1002/9781118720011.ch1
2. Descorme C, Gallezot P, Geantet C, George C (2012) Heterogeneous catalysis: a key
tool toward sustainability. ChemCatChem 4(12):1897–1906. https://doi.org/10.1002/cctc.201
200483
3. Carenco S, Leyva-Pérez A, Concepción P, Boissière C, Mézailles N, Sanchez C, Corma
A (2012) Nickel phosphide nanocatalysts for the chemoselective hydrogenation of alkynes.
Nano Today 7(1):21–28. https://doi.org/10.1016/j.nantod.2011.12.003
4. Carenco S, Le Goff XF, Shi J, Roiban L, Ersen O, Boissière C, Sanchez C, Mézailles N (2011)
Magnetic core–shell nanoparticles from nanoscale-induced phase segregation. Chem Mater
23(8):2270–2277. https://doi.org/10.1021/cm200575g
5. Planken KL, Kuipers BWM, Philipse AP (2008) Anal Chem 80:8871
6. Hori J, Murata K, Sugai T, Shinohara H, Noyori R, Arai N, Kurono N, Ohkuma T (2009)
Highly active and selective semihydrogenation of alkynes with the palladium nanoparticlestetrabutylammonium borohydride catalyst system. Adv Synth Catal 351(18):3143–3149.
https://doi.org/10.1002/adsc.200900721
7. Yarulin A, Yuranov I, Cárdenas-Lizana F, Abdulkin P, Kiwi-Minsker L (2013) Size-effect
of Pd-(Poly(N-vinyl-2-pyrrolidone)) nanocatalysts on selective hydrogenation of alkynols
with different alkyl chains. J Phys Chem C 117(26):13424–13434. https://doi.org/10.1021/
jp402258s
8. Vilé G, Baudouin D, Remediakis IN, Copéret C, López N, Pérez-Ramírez J (2013) Silver
nanoparticles for olefin production: new insights into the mechanistic description of propyne
hydrogenation. ChemCatChem 5(12):3750–3759. https://doi.org/10.1002/cctc.201300569
9. Lopez N, Vargas-Fuentes C (2012) Promoters in the hydrogenation of alkynes in mixtures:
insights from density functional theory. Chem Commun 48(10):1379–1391. https://doi.org/
10.1039/c1cc14922a
10. Crespo-Quesada M, Cárdenas-Lizana F, Dessimoz A-L, Kiwi-Minsker L (2012) Modern
trends in catalyst and process design for alkyne hydrogenations. ACS Catal 2(8):1773–1786.
https://doi.org/10.1021/cs300284r
11. Odom TW, Pileni M-P (2008) Nanoscience. Acc Chem Res 41(12):1565–1565. https://doi.
org/10.1021/ar800253n
12. Beaumont SK (2014) Recent developments in the application of nanomaterials to understanding molecular level processes in cobalt catalysed Fischer-Tropsch synthesis. Phys Chem
Chem Phys 16(11):5034–5043. https://doi.org/10.1039/c3cp55030c