Catalysis Communications 114 (2018) 42–45

Contents lists available at ScienceDirect

Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom

Short communication

Catalytic conversion of furfural-acetone condensation products into bio- T

derived C8 linear alcohols over NieCu/Al-SBA-15
Rubén Ramosa, José M. Hidalgoa, Michael Göpela, Zdeněk Tišlera, Francine Bertellab,
⁎
Agustín Martínezb, Oleg Kikhtyanina,c, David Kubičkac,
a
Unipetrol Centre of Research and Education (UNICRE), Chempark Litvínov, Záluží-Litvínov 436 70, Czechia
b
Instituto de Tecnología Química, Universitat Politècnica de Valencia (UPV-CSIC) - Consejo Superior de Investigaciones Científicas, Avda. de los Naranjos, s/n, 46022
Valencia, Spain
c
Technopark Kralupy, University of Chemistry and Technology Prague, Žižkova 7, 27801 Kralupy nad Vltavou, Czechia

A R T I C LE I N FO A B S T R A C T

Keywords: The production of C8 linear diols from a furfural-acetone condensation product has been achieved for the first
Furfural time using a non-noble metal based catalyst. In particular, SBA-15 supported NieCu bimetallic catalyst showed
Aldol condensation the best hydrogenating activity reaching an outstanding yield (ca. 63%) of the fully saturated product. The
Hydrogenation incorporation of acidity by the preparation of NieCu/Al-SBA-15 resulted in the promotion of ring-opening steps,
SBA-15
which led to a remarkable yield of C8 linear diols (28%). These results establish a competitive catalytic route for
Ni-Cu catalysts
the production of bio-based diols over cost-efficient 3d transition metal-based catalysts.

1. Introduction phase(s) is required to promote the hydrogenation steps, whereas acid

Within the context of future biorefineries, furanic compounds, such
as furfural (C5) and 5-hydroxymethylfurfural (C6), are expected to play
an essential role as bio-platform molecules for the production of che-
micals and fuels. These compounds can be obtained by acid-catalysed
hydrolysis and dehydration of C5-C6 carbohydrates, which constitute
the main building blocks of lignocellulosic biomass [1, 2]. To obtain
larger organic molecules, more suitable for the upgrading to biofuels,
furan derivatives can be transformed by aldol condensation with other
carbonyl-containing molecules forming CeC bonds [3–5]. This ap-
proach has been successfully applied for the condensation of furfural
with acetone, yielding as main product: 4-(2-furyl)-3-buten-2-one
(FeAc) [6, 7]. The subsequent hydrogenation and CeO hydrogenolysis
of this over-functionalized adduct leads to the production of versatile C8
linear diols suitable for the synthesis of both biofuels and bio-derived
polyesters (Fig. 1) [8]. This challenging transformation involves several
chemical reactions, which require the use of high temperatures
(170–300 °C), hydrogen pressures (20–80 bar) and the participation of
heterogeneous catalysts capable of reducing the number of separate
catalytic steps by allowing transformation of a wide variety of func-
tionalities; i.e. furan rings, olefins and carbonyl groups [9].
Porous materials with easy accessibility of bulky reactants to surface
acid and supported metal sites have attracted much attention in the
conversion of furfural-acetone adducts. The presence of reduced metal
sites have been proved to be necessary for CeO hydrogenolysis reac-
tions. Hence, Pd has shown a significant performance over supports
such as: NbOPO4 [10], cobalt aluminate [11], HZSM-5 [12], MgO-ZrO2
[13] and Beta zeolite [14]. Equally, Pt has been extensively studied
using as carriers: CoAl2O4 and NbOPO4 [15], SiO2-Al2O3, zeolites, MgZr
mixed oxide and activated carbons [16]. Likewise, promising results
were obtained using Ru/C and Ru nanoparticles supported onto an
ionic liquid phase [17].
Opposed to the use of noble-metal-based catalysts, the catalytic
conversion of furfural-acetone adducts with readily available 3d transi-
tion metals has been scarcely studied. Likewise, to the best of our
knowledge, the use of SBA-15 based catalysts has not been reported in
the literature yet. This ordered mesoporous material exhibits excellent
support properties advantageous for the aimed transformation, e.g.; high
(hydro)thermal stability, large specific surface area (> 700 m2 g−1) and
a well-defined mesoporous system (4–30 nm) [18]. Furthermore, the
variable framework composition allows the incorporation of species such
as Al or Zr [19], which provide the required surface acidity for further
conversion towards the targeted alcohols.
In this work, we address further catalyst development in the con-
version of furfural-acetone adducts using SBA-15 supported Ni and Cu
catalysts. The obtained product distributions were correlated with
physico-chemical properties of the catalysts. This study aims to estab-
lish a rational design of more efficient heterogeneous catalysts for the

⁎
Corresponding author.
E-mail address: David.Kubicka@vscht.cz (D. Kubička).

https://doi.org/10.1016/j.catcom.2018.06.006
Received 12 February 2018; Received in revised form 29 May 2018; Accepted 6 June 2018
Available online 08 June 2018
1566-7367/ © 2018 Elsevier B.V. All rights reserved.
R. Ramos et al. Catalysis Communications 114 (2018) 42–45

Fig. 1. Reaction pathway for the transformation of FeAc into C8 linear diols.

Table 1
FeAc conversion over SBA-15 supported metal catalystsa.
Yield (%)

Catalyst Metalb (wt%) dMc (nm) Conv. (%) A B C D E C8 diols

Cu/SBA-15 3.4 – 59 59 – – – – –
Ni/SBA-15 10.2 39.4 100 0 3 52 25 9 –
Ni-Cu/SBA-15 10–3.1 41.9 100 – – 8 63 16 –
Ni-Cu/Al-SBA-15 7–2.5 44.7 100 1 4 13 7 10 17
Pt/SBA-15 1 20.7 100 7 1 68 5 2 –
Pd/SBA-15 0.7 10.2 100 5 2 87 1 1 –
Ru/SBA-15 1.3 20.2 100 – – 28 57 6 –

a
Reaction conditions: 1 g(FeAc), 150 ml acetone, 0.25 gcat, T = 200 °C, P = 50 bar H2, 1000 rpm, t = 8 h.
b
Metal content calculated from ICP/TEM-EDX measurements.
c
Mean metal crystallite size based on TEM images.

production of C8+ linear alcohols from lignocellulose-derived furanic
compounds.
2. Experimental
2.1. Catalysts synthesis and preparation
Mesoporous all-silica SBA-15 and Al-containing (Si/Al = 30) SBA-
15 materials were synthesised according to the method reported by
Zukal et al. [20]. The incorporation of metal phases was carried out by
incipient wetness impregnation. After impregnation, the samples were
dried at 120 °C overnight and calcined in air at 550 °C for 6 h. Further
details related to the synthesis and preparation methods are given in the
ESI.
2.2. Catalysts characterization
The prepared catalysts were characterized for their chemical com-
position (ICP-OES, FESEM-EDX), BET area and pore size distribution
(N2 physisorption isotherms), surface acidity (NH3-TPD) and mor-
phology (HAADF-STEM), as described in the ESI.
2.3. Catalytic experiments
All reactions were performed in a high-pressure autoclave reactor
system. Prior to the reaction, the catalyst was reduced in a flow of H2.
Afterwards, the reactor was cooled to room temperature and loaded
with a solution of FeAc (1 g) in acetone or 2-propanol (150 ml).
Subsequently, the reactor was heated to 200 °C and the reaction started
by pressuring the autoclave to 50 bar of hydrogen. The identification
and quantification of the products were done using standard reference
compounds and chromatographic methods (see ESI).
3. Results and discussion
Table 1 shows the product distributions obtained from the conversion of
FeAc over different SBA-15 supported metal catalysts using acetone as sol-
vent. The reaction conditions (T = 200 °C, PH2 = 50 bar and 1000 rpm) were
based on our previous findings regarding the conversion of FeAc with dif-
ferent supported Pt catalysts [9]. In addition to the products listed in Table 1,
other compounds, like 2-methyl-1,6-dioxaspiro[4,4]nonane and 2-propyl-
tetrahydropyran were also identified with yields < 3%.
The Cu/SBA-15 sample showed an incomplete conversion of the
FeAc reactant after 8 h (59%) forming 4-(2-furyl)-butan-2-one (A) as
the only product. The hydrogenation of the furan ring and the ketone
group was completely impeded, in accordance with the poor catalytic
performance of similar Cu-containing catalysts in hydrogenation of
furfural [21, 22] and ketone-containing reactants [23, 24]. On the other
hand, the Ni/SBA-15 catalyst exhibited a remarkable hydrogenation of
FeAc, affording a significant yield of the fully hydrogenated 4-(2-tet-
rahydrofuryl)-butan-2-ol (D = 25%). These differences can be attrib-
uted to the different in structure and nature preferential adsorption
sites over Cu and Ni. Thus, while Cu metal surfaces have very weak
affinity for the C]C bonds of the furan ring, the stronger adsorption of
these bonds over Ni metal surfaces promotes the hydrogenation of the
furan ring and the C]O group, which is in the same plane [22]. These
results highlight the good performance of the Ni loaded catalyst
showing a higher hydrogenation activity than SBA-15 supported Pt and
Pd catalysts (D = 1–5%). On the other hand, the Ru/SBA-15 catalyst
showed a higher production of D (57%), consistent with the reported
high selectivity of this metal for furan ring hydrogenation [25]. Like-
wise, a noticeable production of 2-butyl-furan and 2-butyl-tetra-
hydrofuran (E = 6–9%) was observed when using supported Ni and Ru
catalysts, indicating that CeOH hydrogenolysis reactions occurred to
some extent on these supported metals.
The NieCu/SBA-15 bimetallic catalyst exhibited a significantly
different catalytic activity compared to Ni and Cu monometallic cata-
lysts. Particularly, the NieCu/SBA-15 sample showed the highest yield
of D (63%) and E (16%) among the tested materials. Similar synergetic
catalytic effects from the combination of Ni and Cu were previously
proven in ethanol steam reforming [26, 27], glycerol hydrogenolysis
[28] and hydrogenation of furfural and aromatics [29, 30]. According

43
R. Ramos et al.
100 (a)
90
80
70
60
Yield (%)
50
40
30
20
10
0 0
0 60 120 180 240 300
Time (min)
Fig. 2. Time evolution of FeAc conversion and yield of products over the NieCu/Al-SBA-15 catalyst in (a) acetone and (b) 2-propanol. T = 200 °C and P = 50 bar H2.
to these studies, the improved performance was due to an active NieCu
binary phase exhibiting electronic properties different from the mono-
metallic counterparts [31]. Because of the fewer d-band holes in the
NieCu bimetallic phase compared to Ni, the adsorption strength of
active hydrogen is weakened, enhancing its diffusion on the catalyst
surface and facilitating hydrogenation reactions [32]. Hence, the
NieCu bimetallic catalyst enhanced the hydrogenation rate of FeAc,
along with a higher promotion of C-OH hydrogenolysis reactions.
Despite the superior hydrogenation activity shown by the NieCu/
SBA-15 catalyst, no linear compounds were detected in the product
mixture, suggesting the inhibition of ring-opening steps over this ma-
terial. This behaviour can be related to the absence of surface acid sites,
since those are usually required to promote the CeO hydrogenolysis of
furanic rings [9]. Thus, the purely siliceous SBA-15 support was mod-
ified by incorporating Al during the synthesis procedure to introduce
mild surface acidity (Al-SBA-15, Si/Al = 30). The subsequent impreg-
nation with Ni and Cu metal phases resulted in a bifunctional NieCu/
Al-SBA-15 catalyst, which combined surface acid sites and the hydro-
genating metal phase (see characterization of this catalyst by N2 phy-
sisorption, NH3-TPD and electron microscopy in Figs. 1–3 of the ESI).
The obtained product distribution using NieCu/Al-SBA-15 showed
a significant yield of 2,5-octanediol and 1,7-octanediol (C8
diols = 17%), together with a low yield of D (7%). The formation of
further deoxygenated octanols was not observed, suggesting that CeO
hydrogenolysis/dehydration of the produced diols are limited under the
reaction conditions. However, the main fraction of products corre-
sponded to longer carbon chain compounds C8+ ≈ 44% (not listed in
Table 1). The formation of these heavier by-products is likely due to the
aldol condensation between ketone-containing compounds (mostly A)
and acetone (Fig. 5 of the ESI). This reaction has been reported to
prevail in the presence of acid sites and at moderate temperatures [9,
33]. Accordingly, despite yielding linear compounds through CeO hy-
drogenolysis, the extent of aldol condensation as side reaction over the
NieCu/Al-SBA-15 catalyst reduced the selectivity towards the targeted
C8 diols.
In order to prevent the formation of the heavier by-products, we
tested the performance of the NieCu/Al-SBA-15 catalyst using 2-pro-
panol instead of acetone as a solvent to limit condensation reactions. In
this sense, 2-propanol has been revealed as an excellent solvent in the
conversion of FeAc due to its protic nature, intermediate polarity
(εr = 18.3) and secondary alcohol character [34]. Fig. 2 depicts the
reaction progress profiles over NieCu/Al-SBA-15 in acetone (Fig. 2a)
and 2-propanol (Fig. 2b). In both experiments, A was the first inter-
mediate due to the favoured hydrogenation of the C]C aliphatic bond,
reaching a maximum at short reaction times (30–120 min). The fol-
lowing hydrogenation of A formed products like B, C and D. The yield
Catalysis Communications 114 (2018) 42–45
F-Ac 100 (b) F-Ac
A A
B 90 B
C C
D 80 D
E E
70 C8 diols
C8 diols
C8+ condensates 60
Yield (%)
50
40
30
20
10
360 420 480 0 60 120 180 240 300 360 420 480
Time (min)
of the latter was considerably different in acetone (7%) and 2-propanol
(53%) after 480 min of reaction. This fact could be related with the
formation of condensate products when using acetone and with the
promotion of catalytic hydrogen transfer reactions (based on the
Meerwein-Ponndorf-Verley reduction) in 2-propanol (Fig. 2a). On the
contrary, aldol condensation reactions did not take place in 2-propanol
(C8+ compounds were not detected), showing a higher selectivity to-
wards the fully hydrogenated product D. Both C8+ condensates (in
Fig. 2a) and D (in Fig. 2b) exhibited a similar yield over time behaviour,
showing a continuous increase in the interval 60–240 min and no sig-
nificant change at reaction times > 240 min. The latter trend is likely
associated with the total consumption of their main precursors after
240 min, i.e. FeAc, A and B. On the other hand, the lack of further
conversion of D suggests that the CeO hydrogenolysis of this compound
is not favoured under the reaction conditions applied. Thus, the no-
ticeable production of C8diols reached in 2-propanol (28%) likely oc-
curs via ring opening of other intermediates like A or C. This observa-
tion agrees with previous studies which report that CeO hydrogenolysis
of furanic compounds preferentially takes place through non-saturated
rings (such as hydrofuranic) due to the higher activation energy re-
quired for tetrahydrofuran intermediates [35–37].
4. Conclusions
A direct catalytic process for the partial defunctionalisation of furfural-
acetone adducts using non-noble metal-based catalysts under mild reaction
conditions has been reported. A bimetallic NieCu phase supported on Al-
SBA-15 has been demonstrated as an effective catalyst to produce C8 linear
diols. The combination of a highly redox-active metal phase and acid sites
promotes the required hydrogenation and CeO hydrogenolysis reactions.
Likewise, the noticeable differences between acetone and 2-propanol reveal
the great impact of the solvent on the obtained product distribution, af-
fecting both activity and selectivity. Nevertheless, more studies of the non-
precious NieCu/Al-SBA-15 catalysts are required for deeper understanding,
mainly of the catalytic chemistry and stability. Equally, the use of alter-
native solvents with lower H2 solubility and slower hydrogenation kinetics
could be explored in order to promote acid-ring opening over furan hy-
drogenation reactions. This work improves the understanding of the con-
version of furfural-acetone adducts, and may enable the design of 3d
transition metals-based catalysts for the transformation of furanic com-
pounds to fuels and commodity chemicals.
Acknowledgements
This work was supported by the Czech Science Foundation (project
No. P106/12/G015).
44
R. Ramos et al.
References
[1] J.N. Chheda, Y. Román-Leshkov, J.A. Dumesic, Green Chem. 9 (2007) 342–350.
[2] I. Agirrezabal-Telleria, I. Gandarias, P.L. Arias, Catal. Today 234 (2014) 4–58.
[3] A. Bohre, S. Dutta, B. Saha, M.M. Abu-Omar, ACS Sustain. Chem. Eng. 3 (2015)
1263–1277.
[4] M.I. Alam, S. Gupta, A. Bohre, E. Ahmad, T.S. Khan, B. Saha, M.A. Haider, Green
Chem. 18 (2016) 6431–6435.
[5] S. Dutta, A. Bohre, W. Zheng, G.R. Jenness, M. Núñez, B. Saha, D.G. Vlachos, ACS
Catal. 7 (2017) 3905–3915.
[6] L. Faba, E. Díaz, S. Ordóñez, Appl. Catal. B Environ. 113 (2012) 201–211.
[7] L. Hora, V. Kelbichová, O. Kikhtyanin, O. Bortnovskiy, D. Kubička, Catal. Today 223
(2014) 138–147.
[8] X. Tang, J. Wei, N. Ding, Y. Sun, X. Zeng, L. Hu, L. Lin, Renew. Sustain. Energy Rev.
77 (2017) 287–296.
[9] R. Ramos, Z. Tišler, O. Kikhtyanin, D. Kubička, Catal. Sci. Technol. 6 (2016)
1829–1841.
[10] Q.N. Xia, Q. Cuan, X.H. Liu, X.Q. Gong, G.Z. Lu, Y.Q. Wang, Angew. Chem. Int. Ed.
53 (2014) 9755–9760.
[11] W. Xu, X. Liu, J. Ren, P. Zhang, Y. Wang, Y. Guo, G. Lu, Catal. Commun. 11 (2010)
721–726.
[12] J. Yang, N. Li, S. Li, W. Wang, L. Li, A. Wang, X. Wang, Y. Cong, T. Zhang, Green
Chem. 16 (2014) 4879–4884.
[13] J.N. Chheda, J.A. Dumesic, Catal. Today 123 (2007) 5970.
[14] A. Bohre, B. Saha, M.M. Abu-Omar, ChemSusChem 8 (2015) 4022–4029.
[15] W. Xu, Q. Xia, Y. Zhang, Y. Guo, Y. Wang, G. Lu, ChemSusChem 4 (2011)
1758–1761.
[16] L. Faba, E. Díaz, S. Ordóñez, Catal. Sci. Technol. 5 (2015) 1473–1484.
[17] K.L. Luska, J. Julis, E. Stavitski, D.N. Zakharov, A. Adams, W. Leitner, Chem. Sci. 5
(2014) 4895–4905.
[18] Y. Yang, C. Ochoa-Hernández, V.A. de la Peña, J.M. O'Shea, D.P. Serrano Coronado,
45
Catalysis Communications 114 (2018) 42–45
ACS Catal. 2 (2012) 592–598.
[19] J.A. Melero, L.F. Bautista, J. Iglesias, G. Morales, R. Sánchez-Vázquez, Catal. Today
195 (2012) 44–53.
[20] A. Zukal, J. Pastva, J. Čejka, Microporous Mesoporous Mater. 167 (2013) 44–50.
[21] S. Sitthisa, D.E. Resasco, Catal. Lett. 141 (2011) 784–791.
[22] R.S. Rao, R.T.K. Baker, M.A. Vannice, Catal. Lett. 60 (1999) 51–57.
[23] R. Ramos, A. Grigoropoulos, N. Perret, M. Zanella, A.P. Katsoulidis, T.D. Manning,
J.B. Claridge, M.J. Rosseinsky, Green Chem. 19 (2017) 1701–1713.
[24] X.L. Li, J. Deng, J. Shi, T. Pan, C.G. Yu, H.J. Xu, Y. Fu, Green Chem. 17 (2015)
1038–1046.
[25] R. Alamillo, M. Tucker, M. Chia, Y. Pagán-Torres, J.A. Dumesic, Green Chem. 14
(2012) 1413–1419.
[26] A.J. Vizcaíno, A. Carrero, J.A. Calles, Int. J. Hydrog. Energy 32 (2007) 1450–1461.
[27] A. Carrero, J.A. Calles, A.J. Vizcaíno, Appl. Catal. A Gen. 327 (2007) 82–94.
[28] I. Gandarias, J. Requies, P.L. Arias, U. Armbruster, A. Martin, J. Catal. 290 (2012)
79–89.
[29] R.M. Lukes, C.L. Wilson, J. Am. Chem. Soc. 73 (1951) 4790–4794.
[30] A.G. Boudjahem, W. Bouderbala, M. Bettahar, Fuel Process. Technol. 92 (2011)
500–506.
[31] S.D. Robertson, B.D. McNicol, J.H. De Baas, S.C. Kloet, J.W. Jenkins, J. Catal. 37
(1975) 424–431.
[32] Y. Yao, D.W. Goodman, J. Mol. Catal. A Chem. 383 (2014) 239–242.
[33] O. Kikhtyanin, V. Kelbichová, D. Vitvarová, M. Kubů, D. Kubička, Catal. Today 227
(2014) 154–162.
[34] R. Ramos, Z. Tišler, O. Kikhtyanin, D. Kubička, Appl. Catal. A Gen. 530 (2017)
174–183.
[35] S. Wang, V. Vorotnikov, D.G. Vlachos, Green Chem. 16 (2014) 736–747.
[36] A.D. Sutton, F.D. Waldie, R. Wu, M. Schlaf, A. Louis III, J.C. Gordon, Nature 5
(2013) 428–432.
[37] S. Yao, X. Wang, Y. Jiang, F. Wu, X. Chen, X. Mu, A.C.S. Sustain, Chem. Eng. 2
(2013) 173–180.