A novel preparation method of nisn alloy catalysts supported on aluminium hydroxide: Application to chemoselective hydrogenation of unsaturated carbonyl compounds

Article abstract of DOI:10.1246/cl.2012.769

A novel method was applied for the preparation of NiSn alloy catalysts that were utilized for chemoselective hydrogenation of unsaturated carbonyl compounds, producing unsaturated alcohols almost exclusively. The formation of the NiSn alloy may have played a key role in the enhancement of the chemoselectivity.

Full text of DOI:10.1246/cl.2012.769

doi:10.1246/cl.2012.769
Published on the web July 21, 2012
769
A Novel Preparation Method of Ni­Sn Alloy Catalysts Supported on Aluminium Hydroxide:
Application to Chemoselective Hydrogenation of Unsaturated Carbonyl Compounds
Rodiansono,1,2 Takayoshi Hara, Nobuyuki Ichikuni, and Shogo Shimazu*
Graduate School of Engineering, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522
Department of Chemistry, Lambung Mangkurat University, Jl A. Yani Km 36 Banjarbaru 70714, Indonesia
1
1
1
1
2
(
Received April 2, 2012; CL-120283; E-mail: shimazu@faculty.chiba-u.jp)
A novel method was applied for the preparation of Ni­Sn
alloy catalysts that were utilized for chemoselective hydro-
genation of unsaturated carbonyl compounds, producing unsa-
turated alcohols almost exclusively. The formation of the Ni­Sn
alloy may have played a key role in the enhancement of the
chemoselectivity.
The chemoselective hydrogenation of the C=O bond in ¡,¢-
unsaturated ketones and aldehydes has been extensively studied
because the unsaturated alcohols that it forms are important in the
1
production of a variety of fine chemicals. It is well known that the
group 9 and 10 metals, such as Rh, Ir, Ni, Pd, and Pt, generally
hydrogenate the C=C bond more easily than the C=O bond of
2
¡
,¢-unsaturated aldehydes. After a large number of attempts
3­5
have been made, only Ir-, Os-, and Pt-based catalysts produced
unsaturated alcohols so far.6 To improve the chemoselective
hydrogenation of the C=O group, the modification of the above-
mentioned metals is necessary, i.e., the addition of more electro-
positive metals or the use of oxide supports that strongly interact
with the active metals. While these modified catalyst systems
7
8
have been effective, catalyst preparation critically depends on the
precise control of the amounts of the second metal. Recently, the
Figure 1. XRD patterns of (a) R-Ni/AlOH and Ni­Sn(x)/
AlOH before H2 treatment with Ni/Sn molar ratios of (b) 7.9,
9
(
c) 3.7, (d) 3.0, (e) 1.4, and (f) 1.0, and Ni­Sn(x)/AlOH after H2
treatment at 773 K for 1 h with Ni/Sn molar ratios of (g) 3.0 and
h) 1.4. ( ) Bayerite; ( ) gibbsite; (#) ¢-Sn; ( ) Ni(0), ( )
tin alloying of the platinum group has been extensively studied
and widely applied in various chemical transformations.10 Pt­Sn/
(
SiO showed a higher selectivity toward furfuryl alcohol (FFalc)
2
11
Ni3Sn, ( ) Ni3Sn2, and ( ) Ni3Sn4.
rather than Pt/SiO2 in the hydrogenation of furfural (FFald).
Delbecq et al. suggested that an increase of the charge density of
Pt metal by the addition of hyperelectronic metals or by the
formation of a metal alloy could enhance the affinity toward C=O
rather than the C=C bond to form unsaturated alcohols in the
hydrogenation of ¡,¢-unsaturated aldehydes.12 However, pre-
cious metals, such as Pt, were utilized in these catalyst systems.
Therefore, alternative economical and eco-friendly heterogeneous
catalysts that would ensure the preferred hydrogenation of the
C=O group over C=C are highly desired.
The XRD patterns of R-Ni/AlOH showed sharp diffraction
peaks at 2ª = 44.3, 51.6, and 76.3° which correspond to the
Ni(111), Ni(200), and Ni(220) species, respectively (Figure 1a).
The sharp diffraction peaks were also observed at 2ª = 18.26,
27.8, and 40.54° that were recognized as bayerite and at
2ª = 18.7, 20.36, 36.66, 37.76, 53.18, 63.88, and 70.72° which
1
3,15
were assigned to gibbsite (Figures 1a­1f).
In contrast, the
XRD patterns of Ni­Sn/AlOH exhibited broadened peaks at
2ª = 44.44° due to the formation of Ni­Sn alloys, i.e., Ni3Sn
In the present work, we prepared Ni­Sn alloy catalysts with
different Ni/Sn ratios and applied them in the selective
hydrogenation of FFald to FFalc. The chemoselectivity of
Ni­Sn catalysts in C=O hydrogenation could be controlled by
changing the additive amount of Sn. The selective hydro-
genations of various unsaturated carbonyl compounds by Ni­Sn
catalysts were also studied. Ni­Sn alloy catalysts supported on
aluminium hydroxide (denoted as Ni­Sn(x)/AlOH, x = Ni/Sn
molar ratio) were synthesized by the hydrothermal treatment of a
mixture of Raney Ni supported on aluminium hydroxide (R-Ni/
AlOH) and SnCl2¢H2O in EtOH/H2O. R-Ni/AlOH was
prepared by following Petro’s protocol.13 The details of catalyst
preparation and product analyses are provided in the Supporting
1
5,16
and Ni3Sn2 (Figures 1b­1f).
In fact, the XRD patterns of Ni­
Sn/AlOH after H treatment at 773 K for 1 h showed that Ni Sn,
2
3
Ni3Sn2, and Ni3Sn4 alloy phases were formed for Ni­Sn(3.0)/
AlOH (Figure 1g). On the other hand, Ni3Sn2 alloy and ¢-Sn
1
5
were formed for Ni­Sn(1.4)/AlOH (Figure 1h). The H2
treatment also caused the transformation of bayerite and gibbsite
to amorphous alumina which have no detectable peaks in XRD
1
7
analysis (Figures 1g and 1h).
The results of the chemoselective hydrogenation of FFald
by various catalysts are summarized in Table 1, and the reaction
pathways are shown in Scheme 1.
It can be observed that by using Ni­Sn(7.9)/AlOH and Ni­
Sn(3.7)/AlOH catalysts, FFalc yields were 78% and 80%,
1
4
Information (SI).
Chem. Lett. 2012, 41, 769­771
© 2012 The Chemical Society of Japan
www.csj.jp/journals/chem-lett/

7
70
Table 1. Hydrogenation of FFald by Ni­Sn/AlOH catalysts
of FFald. Moreover, SnO, SnO2, and SnCl2¢2H2O did not
produce the hydrogenated products under the same conditions
(Entries 14­16). The used Ni­Sn(3.0)/AlOH and Ni­Sn(1.0)/
AlOH catalysts were easily separated by either simple centri-
fugation or filtration in air, and then they were utilized
repeatedly without any special treatments. The catalysts were
found to be reusable without any significant loss of activity or
Snb
mmol g
Temp Convnc Yieldd
Entry Catalysta
¹1
/
/K
/%
/%
1
2
3
4
5
6
7
8
9
0
Ni­Sn(7.9)/AlOH
0.45
0.75
1.04
1.04
1.04
1.04
1.04
1.04
2.14
2.14
3.96
3.96
0
453
453
423
453
453
453
453
453
453
453
453
453
453
453
453
453
>99 78(22)
99 80(19)
Ni­Sn(3.7)/AlOH
Ni­Sn(3.0)/AlOH
Ni­Sn(3.0)/AlOH
Ni­Sn(3.0)/AlOH
Ni­Sn(3.0)/AlOH
Ni­Sn(3.0)/AlOH
Ni­Sn(3.0)/AlOHh
Ni­Sn(1.4)/AlOH
Ni­Sn(1.4)/AlOHh
Ni­Sn(1.0)/AlOH
Ni­Sn(1.0)/AlOH
R-Ni/AlOH
72
98
99
97
66
71(1)
94(4)
96(3)
93(4)
59(7)
18
chemoselectivity (Entries 4 and 6, 11 and 12). Furthermore, the
e
f
hydrogenation of FFalc using the Ni­Sn(3.0)/AlOH catalyst
resulted in only an 8.7% THFalc yield at 453 K and 3 MPa of
H2, even after 6 h. These results suggest that the addition of tin to
nickel retards the C=C hydrogenation activity of nickel. Swift
et al. reported that the formation of a Ni­Sn alloy by the addition
of tin to a Ni/SiO2 catalyst remarkably changed the reactivity of
Ni/SiO2 due to the change in the electron density of nickel
g
>99 70(30)
>99 92(8)
>99 100(0)
1
1
1
97
97
91(6)
91(6)
f
19a
1
1
1
1
1
2
3
4
5
6
metal. Delbecq et al. indicated that the C=O hydrogenation
>99 0(100)
selectivity in the hydrogenation of ¡,¢-unsaturated aldehydes
could be enhanced by the formation of a Pt­Sn alloy due to the
higher affinity toward C=O rather than the C=C bond, as noted
SnO
SnO2
SnCl2¢2H2O
®
®
®
4
28
72
0(0)
6(3)
3(1)
1
2
previously. Resasco et al. reported that the selective hydro-
genation of C=O versus C=C in ¡,¢-unsaturated aldehydes by
a Pd­Cu alloy supported on silica was caused by the preferable
aThe value in the parenthesis is Ni/Sn molar ratio. Reaction
conditions: catalyst (0.05 g), FFald (1.1 mmol), i-PrOH (3 mL),
2
19b
b
© -coordination of C=O to Pd. After H treatment at 773 K
2
H2 (3.0 MPa), 1 h. Loading amount of Sn, determined by ICP-
c
for 1 h, Ni­Sn(3.0)/AlOH catalyst gave 70% and 30% yields
of FFalc and THFalc, respectively (Entry 8). In contrast, Ni­
Sn(1.4)/AlOH catalyst gave 100% FFalc without the formation
of THFalc (Entry 10). Therefore, we conclude that the formation
of a Ni­Sn alloy may facilitate in the adsorption mode of the
FFald molecule through the C=O group, giving rise to much
higher yields and selectivity of FFalc rather than THFalc. These
results are consistent with the fact that no tetrahydrofurfuryl
aldehyde (THFald) was observed in all the catalytic results.
Therefore, we speculate that FFald hydrogenation by Ni­Sn/
AlOH catalysts does not proceed via THFald due to the
formation of the Ni­Sn alloy (Scheme 1).
AES. Conversion, determined by GC using an internal
standard. dYield of FFalc. The value in the parenthesis is
yield of tetrahydrofurfuryl alcohol (THFalc), determined by
e
f
GC using an internal standard technique. 3 h. Reuse experi-
g
ment after the second run. Initial H2 pressure was 2.0 MPa.
h
After H2 treatment at 773 K for 1 h.
Tetrahydrofurfuryl
aldehyde (THFald)
O
O
O
O
The scope of the present Ni­Sn/AlOH catalyst in the
hydrogenation of various aldehydes and ketones was examined,
as summarized in Table 2. Hydrogenation of the ¡,¢-unsatu-
rated aldehyde, cinnamaldehyde, over Ni­Sn(3.0)/AlOH yielded
Ni-Sn/AlOH
4
23-453 K, H2 3.0 MPa
OH
O
Tetrahydrofurfuryl
alcohol (THFalc)
Furfural (FFald)
O
9
2% cinnamyl alcohol at 433 K for 15 h (Entry 1). trans-2-
Hexenaldehyde yielded 85% 2-hexene-1-ol at 403 K for 2 h
Entry 2) while crotonaldehyde yielded 45% crotyl alcohol
OH
Furfuryl alcohol (FFalc)
(
under the same conditions (Entry 3). In the case of the
hydrogenation of the ¡,¢-unsaturated ketone, 2-cyclohexene-1-
one, a 91% yield of 2-cyclohexen-1-ol was obtained at 383 K for
Scheme 1. Reaction pathways of FFald hydrogenation by Ni­
Sn/AlOH catalysts.
1
h (Entry 4). In addition, the hydrogenation of 3-cyclohexene-
respectively (Entries 1 and 2). By increasing the loading amount
carbaldehyde yielded 87% 3-cyclohexenemethanol at 403 K
after 6 h (Entry 5).
¹
1
of Sn (up to 1.04 mmol g ), a remarkable increase of FFalc
yield was achieved (Entry 4, 94%). In the case of Ni­Sn(3.0)/
AlOH, an increase of the reaction temperature from 423 to 453 K
gave a notable increase in FFalc yield from 71% to 94%,
Hydrogenation of the aromatic aldehyde, 3-phenylpropanal,
showed a high yield of aromatic alcohol (Entry 6, 96%).
Furthermore, hydrogenation of aromatic ketones, such as
acetophenone and p-methylacetophenone, gave high yields of
1-phenylethanol (95%) and 1-p-tolylethanol (96%), respectively,
at 433 K after 3 h (Entries 7 and 8). Isobutyrophenone yielded
86% 2-methyl-1-phenyl-1-propanol under the same conditions
(Entry 9).
In conclusion, chemoselective hydrogenation of unsaturated
carbonyl compounds was achieved by Ni­Sn alloy catalysts,
providing remarkable chemoselectivity for their corresponding
unsaturated alcohols. The formation of the Ni­Sn alloy possibly
(Entries 3 and 4). After 3 h, the FFalc yield slightly increased to
96% and, in contrast, that of tetrahydrofurfuryl alcohol (THFalc)
decreased to 3% (Entry 5). This result suggests that further
hydrogenation of the C=C furan ring in FFald did not proceed in
the presence of the Ni­Sn(3.0)/AlOH catalyst. Additionally,
FFalc yield decreased significantly when an initial H2 pressure
of 2.0 MPa was applied (Entry 7, 59%). On the other hand,
R-Ni/AlOH converted FFald to give >99% THFalc (Entry 13),
indicating that R-Ni/AlOH hydrogenated both C=C and C=O
Chem. Lett. 2012, 41, 769­771
© 2012 The Chemical Society of Japan
www.csj.jp/journals/chem-lett/

7
71
Table 2. Hydrogenation of various ketones and aldehydes
catalysed by Ni­Sn(3.0)/AlOH catalysta
8
9
a) A. Dandekar, M. A. Vannice, J. Catal. 1999, 183, 344.
b) M. Consonni, D. Jokic, D. Yu. Murzin, R. Touroude,
J. Catal. 1999, 188, 165. c) R. Zanella, C. Louis, S. Giorgio,
R. Touroude, J. Catal. 2004, 223, 328. d) P. Concepción, A.
Corma, J. Silvestre-Albero, V. Franco, J. Y. Chane-Ching,
J. Am. Chem. Soc. 2004, 126, 5523. e) J. Kijeński, P.
Winiarek, T. Paryjczak, A. Lewicki, A. Mikołajska, Appl.
Catal., A 2002, 233, 171.
Temp Time Convn Yield
Entry
Substrate
Product
b
c
/
K
/h
/%
/%
O
O
OH
OH
1
2
3
433
403
423
15
94
>99
60
92
85
45
2
6
a) J. K. A. Clarke, Chem. Rev. 1975, 75, 291. b) R. Ferrando,
J. Jellinek, R. L. Johnston, Chem. Rev. 2008, 108, 845. c)
H.-L. Jiang, Q. Xu, J. Mater. Chem. 2011, 21, 13705.
O
O
OH
OH
4
5
6
383
1
96
91
10 a) J. Araña, P. R. de la Piscina, J. Llorca, J. Sales, N. Homs,
J. L. G. Fierro, Chem. Mater. 1998, 10, 1333. b) G. F.
Santori, M. L. Casella, O. A. Ferretti, J. Mol. Catal. A:
Chem. 2002, 186, 223. c) D. I. Jerdev, A. Olivas, B. E. Koel,
J. Catal. 2002, 205, 278. d) L. Jiang, Z. Zhou, W. Li, W.
Zhou, S. Song, H. Li, G. Sun, Q. Xin, Energy Fuels 2004,
O
OH
403
433
6
6
>99
>99
87
96
O
OH
1
8, 866. e) T. Komatsu, H. Ikenaga, J. Catal. 2006, 241, 426.
f) C. Dupont, Y. Jugnet, F. Delbecq, D. Loffreda, J. Catal.
010, 273, 211. g) F. Vigné, J. Haubrich, D. Loffreda, P.
O
OH
OH
2
4
4
33
33
3
3
>99
98
95
96
Sautet, F. Delbecq, J. Catal. 2010, 275, 129. h) P. D.
Zgolicz, V. I. Rodríguez, I. M. J. Vilella, S. R. de Miguel,
O. A. Scelza, Appl. Catal., A 2011, 392, 208.
7
8
O
1
1 a) A. B. Merlo, V. Vetere, J. F. Ruggera, M. L. Casella,
Catal. Commun. 2009, 10, 1665. b) V. Vetere, A. B. Merlo,
J. F. Ruggera, M. L. Casella, J. Braz. Chem. Soc. 2010, 21,
O
OH
9
14.
4
33
3
88
86
9
1
1
1
2 a) F. Delbecq, P. Sautet, J. Catal. 1995, 152, 217. b) F.
Delbecq, P. Sautet, J. Catal. 2003, 220, 115.
3 J. Petró, A. Bóta, K. László, H. Beyer, E. Kálmán, I.
Dódony, Appl. Catal., A 2000, 190, 73.
4 The molar ratio of Ni/Al, H2- and CO-uptakes, Ni active
a
Reaction conditions: catalyst (0.05 g), substrate (1.1 mmol),
i-PrOH (3 mL), H2 (3 MPa). Conversion. Yield, determined
by GC using an internal standard technique.
b
c
surface area (S ), BET surface area (SBET), and the estimated
Ni
Ni particle sizes were summarized in Table S1. Supporting
Information, which is available electronically on the CSJ-
Journal Web site, http://www.csj.jp/journals/chem-lett/index.
html.
plays a key role in the enhancement of the chemoselectivity.
Further investigations of the alloy structure formed­reactivity
relationship are now in progress.
1
5 Powder diffraction files: JCPDS-International Centre for
Diffraction Data (ICDD), 1997.
References and Notes
1
2
J. Falbe, H. Bahrmann, W. Lipps, D. Meyer, Ullmann’s
Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag
GmbH & Co., 2005. Vol. 11, p. 21.
16 a) S. H. Overbury, Y.-S. Ku, Phys. Rev. B 1992, 46, 7868.
b) A. Onda, T. Komatsu, T. Yashima, J. Catal. 2001, 201,
13. c) J. W. Shabaker, G. W. Huber, J. A. Dumesic, J. Catal.
2004, 222, 180. d) F. Xie, X. Chu, H. Hu, M. Qiao, S. Yan,
Y. Zhu, H. He, K. Fan, H. Li, B. Zong, X. Zhang, J. Catal.
2006, 241, 211.
17 a) T. Tsuchida, N. Ichikawa, React. Solids 1989, 7, 207. b)
S. D. Vaidya, N. V. Thakkar, J. Phys. Chem. Solids 2001, 62,
977. c) Zs. Wittmann, E. Kántor, K. Bélafi, L. Péterfy, L. P.
Farkas, Talanta 1992, 39, 1583.
18 The XRD patterns of the recovered Ni­Sn/AlOH catalysts
are shown in Figure S1 in Supporting Information which is
available electronically on the CSJ-Journal Web site, http://
www.csj.jp/journals/chem-lett/index.html. The reaction solu-
tion of the Entry 6 was analyzed by ICP-AES, and the
amounts of Ni, Sn, and Al were 0.24, 1.2, and 0.51 mol %,
respectively.
19 a) H. E. Swift, J. E. Bozik, J. Catal. 1968, 12, 5. b) S.
Sitthisa, T. Pham, T. Prasomsri, T. Sooknoi, R. G. Mallinson,
D. E. Resasco, J. Catal. 2011, 280, 17.
a) S.-i. Fujita, Y. Sano, B. M. Bhanage, M. Arai, J. Catal.
2
004, 225, 95. b) A. Ghosh, R. Kumar, Microporous
Mesoporous Mater. 2005, 87, 33. c) X. Wang, R. Y. Saleh,
U. S. Ozkan, J. Catal. 2005, 231, 20.
P. Claus, Top. Catal. 1998, 5, 51.
P. Gallezot, D. Richard, Catal. Rev., Sci. Eng. 1998, 40, 81.
P. Mäki-Arvela, J. Hájek, T. Salmi, D. Yu. Murzin, Appl.
Catal., A 2005, 292, 1.
a) C. Bianchini, E. Farnetti, M. Graziani, G. Nardin, A.
Vacca, F. Zanobini, J. Am. Chem. Soc. 1990, 112, 9190. b) J.
Kašpar, M. Graziani, G. P. Escobar, A. Trovarelli, J. Mol.
Catal. 1992, 72, 243. c) M. De bruyn, S. Coman, R. Bota,
V. I. Parvulescu, D. E. De Vos, P. A. Jacobs, Angew. Chem.,
Int. Ed. 2003, 42, 5333. d) D. V. Sokolskii, N. V. Anisimova,
A. K. Zharmagambetova, S. G. Mukhamedzhanova, L. N.
Edygenova, React. Kinet. Catal. Lett. 1987, 33, 399.
W. M. H. Sachtler, R. A. Van Santen, Adv. Catal. 1977, 26,
3
4
5
6
7
6
9.
Chem. Lett. 2012, 41, 769­771
© 2012 The Chemical Society of Japan
www.csj.jp/journals/chem-lett/