Hydroconversion of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran and 2,5-Dimethyltetrahydrofuran over Non-promoted Ni/SBA-15

Article abstract of DOI:10.1002/cctc.201902028

The selective hydroconversion of 5-hydroxymethylfurfural (HMF) to biofuels is currently highly sought-for. While the literature has demonstrated that this reaction is possible on promoted Ni catalysts, we show here that a monometallic, non-promoted Ni/SBA-15 catalyst, prepared by incipient wetness impregnation, can convert HMF to 2,5-dimethylfuran (DMF) and to 2,5-dimethyltetrahydrofuran (DMTHF) at 180 °C, in a consecutive way. Through a control over reaction time, high yields to DMF (71 %, at conversion of 93 %) or DMTHF (97 %, at conversion of 100 %) can be achieved. Kinetic modelling suggests a preferential route to DMF via 5-methylfurfural (MFFR) as intermediate, though the route via 2,5-bis(hydroxylmethyl)furan (BHMF) is also present. The favored route in the experimental conditions involves the hydrogenolysis of the hydroxyl group of HMF as first step, followed by the hydrogenation of the aldehyde function, to methylfurfuryl alcohol (MFOL). It is suggested a higher reaction rate of hydrogenation or hydrogenolysis of the side group is linked to the presence of a methyl group in the molecule. No hydrogenation of the furan ring is detected on the intermediates.

Full text of DOI:10.1002/cctc.201902028

Accepted Article
Title: Hydroconversion of 5-hydroxymethylfurfural to 2,5-dimethylfuran
and 2,5-dihydroxymethyltetrahydrofuran over non-promoted Ni/
SBA-15
Authors: Shuo Chen, Carmen Ciotonea, Karine Vigier, François
Jérôme, Robert Wojcieszak, Franck Dumeignil, Eric Marceau,
and Sébastien Royer
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: ChemCatChem 10.1002/cctc.201902028
Link to VoR: http://dx.doi.org/10.1002/cctc.201902028
A Journal of
www.chemcatchem.org

10.1002/cctc.201902028
ChemCatChem
FULL PAPER
Hydroconversion of 5-hydroxymethylfurfural to 2,5-dimethylfuran
and 2,5-dihydroxymethyltetrahydrofuran over non-promoted
Ni/SBA-15
Shuo Chen,[a] Carmen Ciotonea,[a] Karine De Oliveira Vigier,[b] François Jérôme,[b] Robert
Wojcieszak,[a] Franck Dumeignil,[a] Eric Marceau,*,[a] Sebastien Royer*,[a]
Abstract: The selective hydroconversion of 5-hydroxymethylfurfural
(HMF) to biofuels is currently highly sought-for. While the literature
has demonstrated that this reaction is possible on promoted Ni
catalysts, we show here that a monometallic, non-promoted Ni/SBA-
15 catalyst, prepared by incipient wetness impregnation, can convert
HMF to 2,5-dimethylfuran (DMF) and to 2,5-dimethyltetrahydrofuran
(DMTHF) at 180°C, in a consecutive way. Through a control over
reaction time, high yields to DMF (71%, at conversion of 93%) or
DMTHF (97%, at conversion of 100%) can be achieved. Kinetic
modelling suggests a preferential route to DMF via 5-methylfurfural
(MFFR) as intermediate, though the route via 2,5-
bis(hydroxylmethyl)furan (BHMF) is also present. The favoured route
in the experimental conditions involves the hydrogenolysis of the
hydroxyl group of HMF as first step, followed by the hydrogenation of
the aldehyde function, to methylfurfuryl alcohol (MFOL). It is
suggested a higher reaction rate of hydrogenation or hydrogenolysis
of the side group is linked to the presence of a methyl group in the
molecule. No hydrogenation of the furan ring is detected on the
intermediates.
DMF furan ring hydrogenation, rather than from the
hydrogenolysis of hydroxymethyl tetrahydrofurans.[4] Finally,
competing polymerization and ring opening reactions may also
occur.
HMF being a multifunctional compound, one challenge for its
upgrading is thus to increase selectivity to the valuable desired
products, as several undesired reactions can occur in such a
network of parallel and consecutive reactions. Catalysts based
on noble metals such as Pt, Pd, and Ru have proved highly
active and selective in the reductive transformation of HMF to
DMF and DMTHF. For the production of DMF, a CuRu/C
catalyst was first proposed, giving a yield of 76-79%.[5] The best
performance was then obtained with a Pd/C catalyst under
supercritical conditions, achieving a total conversion of HMF to
DMF in water at 80 °C, under 100 bar CO2 and 10 bar H2 after 2
h. For the synthesis of DMTHF, it is a sulfur-modified Pt/C
catalyst that was first proposed, giving a yield of 50%.[6]
However, noble metal-based catalysts suffer from the limited
availability and high cost of the metals, which may hinder their
commercial applications on a large scale.[7]
Introduction
Selective production of biofuels with high octane number and
high energy density, such as 2,5-dimethylfuran (DMF) and 2,5-
dimethyltetrahydrofuran (DMTHF), is currently highly sought for
in the context of sustainable development. These two molecules
derive from 5-hydroxymethylfurfural (HMF), a platform molecule
produced by dehydration of hexoses.[1] HMF contains a furan
ring bearing both a pending aldehyde function at the C2-position,
and a hydroxymethyl group at the C5-position.[2] Transformation
of HMF to DMF may go through two routes, both involving
hydrogenolysis of the side-groups, either starting with the
hydrogenation reaction of the aldehyde function, thus giving 2,5-
bis(hydroxylmethyl)furan (BHMF) as an intermediate, or with the
hydrogenolysis of the hydroxyl group, giving 5-methylfurfural
(MFFR) as an intermediate (Scheme 1).[3] The formation of
DMTHF is usually supposed to take place in a second stage, via
Scheme 1. Hydrogenation of HMF to DMF and DMTHF and possible side
reactions (dotted arrows represent side reactions).
Alternative solutions should be found in non-noble transition
metals (e.g., Cu, Co or Ni), which are more abundant but
generally less active. High yields of DMF and/or DMTHF
generally require bimetallic combinations (Ni-Cu, Ni-Fe, Cu-Co,
Cu-Zn, etc.), bifunctional catalysts containing both metallic and
acidic active sites, and/or the use of supports that participate in
the reaction directly or indirectly via their specific surface
properties (TiO2, ZnO).[8,9] For example, Seemala et al. used
TiO2 as support to selectively form strong Ni-TiO2 interactions in
Cu-Ni/TiO2. This resulted in a deficit of Ni at the particle surface
and in a promotion of the hydrogenation activity of Cu without
[a]
[b]
Dr. Shuo Chen, Dr. Carmen Ciotonea, Dr. Robert Wojcieszak,
Dr. Eric Marceau, Prof. Franck Dumeignil, Prof. Sebastien Royer
Univ. Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, UMR 8181 -
UCCS - Unité de Catalyse et Chimie du Solide, F-59000 Lille,
France ; Corresponding author : eric.marceau@univ-lille.fr;
sebastien.royer@univ-lille.fr
Prof. Karine Vigier De Oliveira
IC2MP – UMR CNRS 7285, University de Poitiers, F-86000 Poitiers,
France
This article is protected by copyright. All rights reserved.

10.1002/cctc.201902028
ChemCatChem
FULL PAPER
compromising selectivity.[10] The DMF yield was then 84% at
complete conversion at 200 °C, under 2.5 bar in 1,4-dioxane
after 8 h. Luo et al. showed that bimetallic carbon-supported
NiCu3 nanocrystals prepared by a solvothermal method, and
consisting of a Cu-rich core and a 1:1 molar Ni:Cu shell, led to
an excellent DMF yield of 99% at complete conversion at 180 °C
under 33 bar in a continuous flow reactor.[11]
Catalyst characterization
Since emphasis was early put on the need for an auxiliary metal
or for surface acidic sites to obtain a selective catalyst, the
catalytic properties of monometallic catalysts based on non-
noble metals have been paradoxically less explored.[12,13] Ni-
based catalysts are known for their hydrogenation ability,[14] but
successes in the selective conversion of HMF have mostly been
achieved with bimetallic or multifunctional catalysts, e.g., Ni-
W2C/C, Ni-Fe/CNTs (carbon nanotubes), Ni/LaFeO3 and
others.[15-18]
Figure 1. Low angle XRD patterns recorded for SBA-15 and NiO/SBA-15.
Kong et al. have published a series of papers in which the
reactivity of monometallic Ni catalysts was investigated.[14,19-20]
Raney Ni was shown to be active in the hydrogenation of the
aldehyde function and of the furan ring of HMF to BHMTHF at
100°C in dioxane, while hydrogenation and hydrogenolysis of
the side-groups to DMF was favored at a higher temperature of
180°C.[19] Unexpectedly, the hydrogenation of the furan ring was
not as predominant at 180°C as it was at 100°C, with DMTHF
building only slowly from DMF at that temperature. It was
concluded by the authors that the methyl groups of DMF
inhibited its adsorption on the Raney Ni surface. The presence
of acidic groups on the catalyst surface was thus considered as
critical to promote both hydrogenolysis reactions and the
hydrogenation of the furan ring on Ni. In later works by the same
team,[20] Lewis acidic sites were introduced through the
incomplete reduction of Ni2+ ions from a phyllosilicate precursor,
or from an aluminic support derived from the decomposition of a
hydrotalcite. The production of DMTHF was almost quantitative
at 150°C in the first case, and at 180°C in the second case. In
contrast, the hydrogenolysis properties of 20 and 36 Ni wt.%
catalysts supported on pure silica - a support that lacks of acidic
groups - and prepared by impregnation, were quite poor, even at
180°C, and a wide slate of products was obtained. Finally, DMF
Figure 1 depicts the low angle X-ray diffraction domain for SBA-
15 and NiO/SBA-15. Both the support and the calcined
NiO/SBA-15 catalysts exhibit one intense diffraction peak and
four less intense diffraction peaks, indexed to the (100), (110),
(200), (210) and (300) planes: the ordered hexagonal 2D
structure of p6mm symmetry in SBA-15 is well preserved after
the formation of nickel oxide, as formerly reported.[21] The
intensity decrease and the position shifts of the diffraction peaks
of NiO/SBA-15 as compared to SBA-15 could be explained by
the localization of NiO nanoparticles (NPs) inside the support
pores. Filling of pores reduces the electron density contrast
between the pores and silica walls, affecting reflections positions
and their intensities.[21,22]
and DMTHF were formed in
a parallel manner on the
hydrotalcite-derived catalyst at 180°C, and not consecutively as
would be expected, and as was indeed found on Raney Ni.[14,20]
In view of these apparent contradictions, we propose to re-
examine herein the catalytic properties of the non-promoted
monometallic Ni/SiO2 system, by using a Ni/SBA-15 catalyst
prepared by incipient wetness impregnation followed by mild
drying. The SBA-15 support was chosen for its high surface area.
Reaction conditions were screened for the production of DMF
and DMTHF from HMF, and a kinetic profile evidencing the
reaction intermediates was obtained. The results of this study
not only prove that monometallic non-promoted Ni catalysts are
potent systems for the selective hydroconversion of HMF to
biofuel products, but also provide an understanding of the
processes leading to the production both of DMF and DMTHF.
Figure 2. N2 physisorption isotherms and BJH pore size distribution (inset)
obtained for SBA-15, calcined NiO/SBA-15 and reduced Ni/SBA-15 catalyst
(vertical shift of 500 cm3/g between isotherms for better clarity).
N2 adsorption/desorption isotherms obtained for SBA-15,
NiO/SBA-15 (calcined material) and Ni/SBA-15 (reduced
material) are presented in Figure 2, and the calculated textural
properties are listed in Table 1. An isotherm shape of Type IV
according to the IUPAC classification is obtained in all cases,
confirming the retaining of a well ordered mesopore structure
after the impregnation step and the thermal treatments. However,
the change of the hysteresis shape for the catalysts, with a two-
Results and Discussion
This article is protected by copyright. All rights reserved.

10.1002/cctc.201902028
ChemCatChem
FULL PAPER
step desorption and a delayed closure at lower relative pressure
(P/P0 = 0.46 vs. 0.61 for the support) is indicative of the
confinement of NiO NPs in the main mesopores of SBA-15.[23]
The B.J.H. pore size distribution (Figure 2, inset) shows two
maxima: a first maximum located at 6.6 nm, close to the
diameter of the primary mesopores measured for the bare SBA-
15 support; a second maximum located at 5.2 nm which is
associated to the pores filled by the NiO particles. Both open
and NPs-filled cylindrical mesopores are thus present in the
material. Surface area and pore volume are observed to
decrease after introduction of nickel (>30% of decrease), which
is consistent with the pore plugging phenomenon and the
increase in material weight density after deposition. Only a slight
additional decrease in the surface area (-9%) and the pore
volume (-6%) are observed after nickel reduction, while the pore
size distribution remains almost unchanged.
The reducibility of NiO species was investigated by H2-TPR
(Figure 3(A)). The H2-TPR profile of NiO/SBA-15 presents two
main hydrogen consumption peaks, located at 389°C and 495°C,
respectively, with a small H2 consumption also visible at 300°C.
According to the literature, the reduction of bulk NiO generally
takes place at temperatures below 420°C.[24] The main hydrogen
consumption (300 - 389°C) is then associated to NiO NPs
behaving like bulk NiO: NiO NPs confined in the mesopores or
large NiO particles located at the external surface of the silica
grains. Finally, the consumption observed at 495°C is
associated to the reduction of smaller NiO particles, in stronger
interaction with the silica surface. Indeed, small NiO particles are
reported to be less reducible than larger particles behaving like
bulk unsupported particles.[25] Quantification leads to a value of
14.3 mmol H2/gcat, confirming the complete reduction of Ni(II)
into Ni(0).
Figure 3. (A) H2-TPR profile for calcined NiO/SBA-15; (B) XRD pattern of
reduced Ni/SBA-15 (vertical bars: JCPDS file n° 04-0850).
Table 1. Physico-chemical properties of SBA-15, NiO/SBA-15
(calcined), Ni/SBA-15 (reduced) and Ni/SBA-15-used (after reaction).
[a]
Catalyst
SBET
,
Vt,[a]
cm3/g
Dp,[a]
nm
dNi. nm
m2/g
SBA-15
841
519
1.10
0.70
6.8
-
NiO/SBA-15
5.2,
6.6
16.5 [b], 15.9 [c]
Ni/SBA-15
468
242
0.66
0.50
5.2,
6.6
15.5 [b], 14.7 [c]
14.5 [b], n.a.[d]
Figure 4. XPS high resolution spectra of the Ni 2p core levels recorded for
NiO/SBA-15 and Ni/SBA-15 catalysts.
Ni/SBA-15-
used
4.9,
7.0
The speciation of nickel after reduction at 550°C for 2 h was first
determined using XRD analysis (Figure 3(B)). Diffraction peaks
at 52.2° and 61.0°, as well as the corresponding interplanar
spacing values (d111 = 0.20 nm, d200 = 0.18 nm), indicate the
presence of the cubic Ni(0) phase (JCPDS 04-0850). The broad
onset of the otherwise narrow peaks suggests the formation of
crystalline domains of both small and large sizes, with a crystal
domain size, calculated by applying the Scherrer equation to the
narrower part of the peaks, of 15.5 nm (Table 1).
[a] B.E.T. surface area, total pore volume, and B.J.H. pore size obtained
from N2 physisorption; [b] Average crystal size measured for NiO or Ni using
the Scherrer equation; [c] Average size measured from statistical analysis
on TEM images. [d] n.a.: not analysed.
XPS spectra of the Ni 2p core levels were recorded for
NiO/SBA-15 and Ni/SBA-15 (Figure 4). Only Ni2+ species
This article is protected by copyright. All rights reserved.

10.1002/cctc.201902028
ChemCatChem
FULL PAPER
(binding energy of 854.7 eV) are identified on the NiO/SBA-15
catalyst calcined at 550°C.[26] After reduction at 550°C, the Ni
2p3/2 signal shifted to 852.5 eV, which indicates the formation of
metallic Ni(0),[27] and, in line with TPR and XRD, the absence of
residual oxidized nickel after reductive treatment.
hydrogenolysis of the C-O bond (the reaction affording
DMF/DMTHF) has been reported to become slow.[19] On the
other hand, the selectivity to DMF/DMTHF generally decreases
above 240°C, owing to the formation of by-products such as
humins.[10,29] Hence, the reaction temperature was set in the
range of 180-240°C. As maximum DMF/DMTHF yields were
obtained below 50 bar of hydrogen,[1] 45 bar was selected as the
maximum pressure level. The hydrogen pressure was thus
chosen in the range 15-45 bar, considering that increasing
hydrogen pressure increases the concentration of hydrogen in
the solvent, which may benefit to the conversion rate. Finally,
the HMF/Ni molar ratio was varied in the range of 3-30 at
constant concentration of HMF, covering the range of the
HMF/Ni molar ratios mentioned in the literature.[1]
The dispersion of the nickel phase in Ni/SBA-15 was further
evaluated by TEM (Figure 5). After activation of the catalyst
under reducing conditions, the regular hexagonal arrangement
of pores was seen to be maintained, in agreement with the
conclusions issued form low angle XRD. In line with N2
physisorption, both empty and full mesopores exist in the
structure. Two types of nickel particles are observed: in minority,
large nickel particles (20-50 nm) on the external surface of the
silica grains (Figure 5A); in majority, small oblong-shaped nickel
NPs confined within the support channels, and having a size of
8 nm (width) - 15 nm (length) (Figure 5B,C). As shown in the
particle size distribution (Figure 5D), most of the Ni particles
belong to the 5-15 nm range, these particles being located within
the main mesopores of the support. The population of external
NPs with larger sizes amounts to 14% of the whole distribution.
Table 2. Conversions and product distributions obtained under
screening conditions[a]
yield/%
HMF/
Ni
T
P
conv.
/%
C.B.
/%[b]
No.
/°C
/bar
mol.
ratio
DMT
MFF
R
MF
OL
DMF
HF
1
2
3
4
5
6
7
8
9
180
180
180
210
210
210
240
240
240
15
30
45
15
30
45
15
30
45
30
3
7
1
0
1
1
2
1
2
1
8
1
1
2
97
100
34
1
81
0
1
85
15
3
12
1
10
1
90
100
44
72
1
76
15
30
15
30
3
41
17
21
7
0
100
100
100
100
58
21
1
2
32
3
0
11
1
2
100
0
55
1
[a] Catalytic tests were performed in batch-pressurized reactors, using a
Autoplant-Chemspeed instrument, with 0.15 mmol/mL HMF in 25 mL 1,4-
dioxane solution for 8 h. [b] Carbon balance.
Reaction parameters, HMF conversion, main products’ yields
and carbon balances are summarized in Table 2. The
parameters screening showed that:
(1) DMF and DMTHF were the major products, but MFFR and
MFOL were also detected after 8 h of reaction. These results
indicate that the hydrogenolysis of the C-OH bond and the furan
ring hydrogenation are favored over the Ni/SBA-15 catalyst;
(2) low HMF/Ni molar ratios (≤ 15) or large catalyst quantity (≥
0.052 g) are required for an efficient conversion of HMF;
(3) hydrogen pressure in the selected range (15-45 bar) has a
weaker influence on the catalytic results than the HMF/Ni molar
ratio and the reaction temperature;
(4) lower carbon balances (decreasing down to 58%) are
obtained when the HMF/Ni molar ratio decreases, an effect
more visible at high reaction temperatures (Table 2, Entry 4 and
9), due to possible polymerization reaction with BHMF and
MFOL.[30]
Figure 5. (A) Representative TEM images recorded for Ni/SBA-15; (B) Ni(0)
particle size distribution obtained by statistical analysis of TEM images.
Catalytic properties
Dioxane was chosen as the solvent, considering its stability in
reaction, the solubility of HMF in this solvent, the better yields to
the target products than when other solvents are used,[10] and
the possibility of comparison with the results from Kong et al.[19]
In order to determine which reaction parameters would lead to
high DMF/DMTHF yields over Ni/SBA-15, a L9 set of orthogonal
experiments (3 (levels) ^ 3 (factors)) was constructed according
to the Taguchi method using software Minitab 17. Three process
parameters (i.e., reaction temperature, H2 pressure and HMF/Ni
molar ratio) were selected on the basis of the available
literature.[28] When the temperature is lower than 180°C, the
Two of these nine tests stand out. In Entry 5, a DMF yield of
40.6% at 43.8% HMF conversion was obtained at 210°C under
30 bar H2 with a HMF/Ni molar ratio of 15, giving a maximum
DMF selectivity (93%). However, the conversion of HMF is
limited under these reaction conditions and duration because of
This article is protected by copyright. All rights reserved.

10.1002/cctc.201902028
ChemCatChem
FULL PAPER
the low catalyst loading. In Entry 2, a DMTHF yield of 81.4%
(100% HMF conversion) was obtained at 180 °C under 30 bar
H2 with a HMF/Ni molar ratio of 3, suggesting that these
conditions are suitable for the selective production of DMTHF
over Ni/SBA-15: DMTHF yield and carbon balance decrease at
210°C (Entry 4). This result is quite interesting considering that
only one report in the literature reported similarly high DMTHF
yield obtained with Ni-based catalysts.[28] It can be wondered if
the DMF yield can also be high under these reaction conditions,
according to the HMF  DMF  DMTHF pathway depicted in
Scheme 1.
way. When the reaction time was prolonged above 1 h, the yield
of DMTHF continuously increased, reaching 96.6% at complete
HMF conversion after 10 h. The DMF yield was negligible after
10 h (0.6%).
In summary, HMF was first and rapidly converted into DMF by
hydrogenolysis, BHMF, MFFR and MFOL being intermediates
products detected. The furan ring hydrogenation of DMF to
DMTHF occurred in a second stage, at a slower rate, explaining
the need for a longer reaction time to maximize its yield. As
compared to the reports available in the literature (Table 3,
Entries 8-11), the DMTHF yield obtained in this work is among
the highest reported. Only Kong et al. reported comparable
results, but using a bifunctional Ni/Al2O3 catalyst derived from a
hydrotalcite-like precursor (Table 3, Entry 11), after 20 h of
reaction at 180°C under 12 bar and with a higher HMF/Ni molar
ratio of 11.[20] The parallel productions of DMF and DMTHF in
their work let one suppose that sites presenting different types of
reactivity were active on this catalyst.
Figure 6. Evolution of HMF conversion and product yields with reaction time
over Ni/SBA-15. Reaction conditions: 0.144 mmol/mL HMF in 25 mL 1,4-
dioxane, P(H2) = 30 bar, T = 180˚C, HMF/Ni molar ratio of 3.
Scheme 2. Kinetic scheme proposed for the DMTHF production from HMF
The evolution of HMF conversion and products yields in these
reaction conditions (180°C, 30 bar H2, HMF/Ni molar ratio of 3)
was next followed as a function of reaction time (Figure 6). At
short reaction time (30 min), HMF was primarily and rapidly
converted into DMF (70.5% yield), and the yield of DMTHF was
limited (12.2% yield). BHMF and MFOL were also detected at
low concentrations (4.9 and 4.0% yields, respectively), indicating
the existence of a hydrogenation-hydrogenolysis pathway to
DMF (Scheme 1). Only a low amount of MFFR, the intermediate
(kapp: apparent rate constant)
Kinetics of the reaction
Based on these measurements, it was attempted to build a
simplified kinetic model to describe the catalyst properties, lying
on the hypotheses described in the Supporting Information file.
The transformation of HMF to DMF and DMTHF supposes the
formation of MFOL as intermediate (Scheme 2). MFOL itself can
be produced following two routes:
in
the
hydrogenolysis-hydrogenation
pathway,
was
comparatively detected (0.8% yield). The DMF yield obtained
after 30 min is quite comparable to the results obtained over
monometallic Ni-based catalysts reported in the literature (Table
3), especially considering that most catalytic performances have
relied on the use of supports bearing other chemical functions
(Entries 4-5). The results reported in the present work then show
that, in contradiction with former results obtained on Ni/SiO2
catalysts in similar conditions [28], a non-promoted monometallic
Ni catalyst can afford a high hydrogenolysis ability to form a
major amount of DMF under adequate reaction conditions, even
when the support presents no specific chemical function and, in
particular, no acidity.
Prolonging the reaction time to 1 h led to complete HMF
conversion, with a significant decrease of the DMF yield (57.0%)
at the expense of the DMTHF yield (32.1%). The concentrations
of BHMF and MFOL also decreased to negligible levels (yields
<2%). During this period, the main reaction occurring is the furan
ring hydrogenation of DMF to DMTHF, appearing in a sequential
(1) Hydrogenolysis of HMF to MFFR, followed by the
hydrogenation of the aldehyde function of MFFR to MFOL.
(2) Hydrogenation of the aldehyde function of HMF to BHMF,
followed by the hydrogenolysis of BHMF to MFOL.
When reaction is performed at 180°C, both MFFR and BHMF
are detected in small amounts at short reaction times. As will be
seen below, MFOL appears in parallel to BHMF, and not in a
second stage as would be the case if it was produced from
BHMF only. It is thus not possible to eliminate one of these two
routes a priori. Furthermore, as DMTHF appears in the last
stage, once DMF has been produced and accumulated, and
other hydrogenation products have not been detected, we will
suppose that the hydrogenation of the furan ring does not take
place to a large extent on the minor intermediate products.[31]
A fitting of the apparent rate constants was performed by least-
square minimization, according to a mechanism based on the
following steps:[31,32]
This article is protected by copyright. All rights reserved.

10.1002/cctc.201902028
ChemCatChem
FULL PAPER
- HMF being consumed by paths 1 and 2, its consumption was
fitted using a first-rate law of rate constant (k1,app + k2,app):
- As a primary intermediate product, BHMF neat production rate
was defined as the difference between the production rate k2 app
[HMF] and the consumption rate k4 app [BHMF], leading to Eq. (3):
[HMF] = [HMF]0 exp (-((k1,app + k2,app)t))
(1)
k
[HMF]
2,app
- (k
0
- As a primary intermediate product, MFFR neat production rate
was defined as the difference between the production rate k1,app
[HMF] and the consumption rate k3,app [MFFR], leading to Eq. (2):
[
]
BHMF =k
) [ exp (-(k1,app+k2,app)t) -exp(-k4,appt) ] (3)
+k
4,app
1,app
2,app
A first fitting of HMF consumption, and of MFFR and BHMF neat
productions, led to the first evaluation of the four first apparent
rate constants, k1,app to k4,app, and to the calculation of r1 to r4. It
appeared that r1 was approximatively 10 times higher than r2,
and that r3 was larger than r4 by a factor of 20 to 40. The main
production path to MFOL was thus identified as the one
involving MFFR (Scheme 3).
k
[HMF]
1,app
- (k
0
[
]
MFFR =k
) [ exp (-(k1,app+k2,app)t) -exp(-k3,appt) ] (2)
+k
3,app
1,app
2,app
Table 3. Catalytic performances of Ni-based catalysts for the conversion
of HMF to DMF and DMTHF.
- The neat production of the secondary intermediate, MFOL, was
then based on the HMF → MFFR → MFOL pathway, of rate
constants k1,app and k3,app, for the production side, and k5,app for
the consumption rate (Eq. 4):
P
(bar)
T
(˚C)
t
X
(%)
Y
(%)
No.
Catalyst
Feed conditions
ref
(h)
HMF to DMF
12 mmol HMF;
35 mL 1,4-
dioxane;
0.5 g catalyst
12 mmol HMF;
38 mL 1,4-
Raney
Ni
1
15
15
180
130
15
3
100
100
89
73
[19]
[14]
exp(-k1,appt)
[
]
MFOL =(k1,appk3,app)[HMF] [
0 (k3,app-k1,app)(k5,app-k1,app
exp(-k5,appt)
(k1,app-k5,app)(k3,app-k5app
)
Ni/Ni2+
-
2
silicate[a]
dioxane;
exp(-k3appt)
−
+
]
0.08 g catalyst
2 mmol HMF; 20
mL water;
0.05 g catalyst
1 mmol HMF; 12
mL ethanol;
0.1 g catalyst
8 mmol HMF;
100 mL 1-
propanol;
W/F = 2
g.min/mL
12 mmol HMF,
35 mL 1,4-
dioxane,0.1 g
catalyst
1.8 mmol HMF;
12.5 mL 1,4-
dioxane; 0.261 g
catalyst
)
(k1,app-k3,app)(k5,app-k3,app
)
3
4
Ni/CN[b]
30
50
200
230
6
6
100
99
99
98
[13]
[17]
(4)
allowing the fitting of constant k5,app along with k1,app – k4,app
.
Ni/LaFe
O3
- As DMF is not the final product of reaction, it is not possible to
model its production just by subtracting the concentrations of
HMF, BHMF, MFFR and MFOL from [HMF]0. However, BHMF,
MFFR and MFOL being formed in very low amounts with respect
to DMF and DMTHF, it can be attempted to apply the steady
state approximation to these intermediates, and consider that
the production rate of DMF is close to the consumption rate of
HMF. DMF thus becomes an intermediate between HMF and
DMTHF, and its concentration follows the law:
5
Ni/C
33
180
-
92
53
[12]
[20]
6
7
Ni/Al2O3
12
30
180
180
4
100
93
92
71
Ni/SBA-
15
0.
5
this
work
(k
+k
)[HMF]
1,app
2,app
- (k
[
]
DMF = k
0) [exp (-(k1,app+k2,app)t) -exp(-k6,appt) ] (5)
+k
1,app
6,app
HMF to DMTHF
2,app
8 mmol HMF,
100 mL 1-
propanol
making it possible to fit k6,app with the other constants.
8
9
Pd/C
CuZn
33
20
180
220
-
100
100
55
25
[12]
[9]
(6) Finally, DMTHF is calculated as the difference between
[HMF]0, and the concentrations of all the other products,
including the unknown ones completing the carbon balance at
100% (which implicitly supposes that these unknown products
derive from the last stages of the global reaction and not from
the consumption of intermediates).
4 mmol HMF, 20
mL CPME, 0.1 g
catalyst
6
12 mmol HMF,
38 mL 1,4-
dioxane,0.08 g
catalyst
10
11
12
Ni/SiO2
15
12
30
150
180
180
3
100
100
100
26
97
97
[14]
[20]
12 mmol HMF,
35 mL 1,4-
dioxane,0.1 g
catalyst
Ni/Al2O3
20
10
1.8 mmol HMF;
12.5 mL 1,4-
dioxane; 0.261 g
catalyst
Ni/SBA-
15
this
work
[a] Ni(0)/Ni(+II) catalyst from nickel phyllosilicate; [b]: Ni/CN, Ni supported on
mesoporous nitrogen-rich carbon.
Scheme 3. Apparent rate constants for each reaction step of HMF conversion
to DMTHF
This article is protected by copyright. All rights reserved.

10.1002/cctc.201902028
ChemCatChem
FULL PAPER
catalyst for the hydrogenolysis reaction. The apparent rate
constants of the hydrogenation and hydrogenolysis steps
involving intermediates containing a methyl group (MFFR, MFOL)
are found to be much larger than in the others steps, suggesting
a fast adsorption/reaction of these molecules on the catalyst
surface. However, one should recall that the model built here is
very simple and perhaps too simplified, and uncertainties remain
large concerning these intermediates, which one should
remember are detected in quite low amounts at very short
reaction times.
Stability of Ni/SBA-15
The recyclability of the SBA-15 supported Ni catalyst was finally
evaluated (Figure 8). Between each reaction cycle, the catalyst
was recovered by centrifugation and washed with acetone. The
catalyst was re-calcined at 500°C for 6 h and re-reduced at
550°C for 2 h before the next test in order to avoid the presence
of Ni oxidized species that can negatively affect the activity.
Each test was performed for 3 h at 180°C under 30 bar H2. In
the first run, the HMF conversion was 100% with a DMF yield of
45% and a DMTHF yield of 48% (Figure 8). After 3 cycles, the
HMF conversion had decreased to 75%, with an increasing
amount of unreacted BHMF, while the DMF yield and DMTHF
yield had been reduced to 37 and 10%, respectively.
Progressive deactivation is thus a source of concern for this
nickel catalyst.
Figure 7. Kinetic patterns of HMF conversion over Ni/SBA-15 simulated after
least-square minimization of the apparent rate constants (A); enlargement of
the kinetic patterns during the first hour (B). Reaction conditions: 0.144
mmol/mL HMF in 12.5 mL 1,4-dioxane, P(H2) = 30 bar, T = 180˚C, HMF/Ni
molar ratio of 3, data points and solid lines represent experimental data and
model, respectively.
The values of the six apparent rate constants found after least-
square minimization are presented in Scheme 3. A graphical
comparison between the experimental and the modelled
concentrations (Figure 7) raises the following comments:
(1) HMF consumption, MFFR production and BHMF production
are correctly modelled, in particular the position of the maximum
of production of MFFR and BHMF.
(2) In contrast, the production of MFOL is poorly reproduced, as
its consumption starts too early. Decreasing k5,app shifts the
maximum of production to longer times, but also increases
considerably the amount of MFOL formed, which means that
k3,app would also need to be better adjusted. There is thus an
uncertainty on the values of k3,app and k5,app obtained by this
model. A new fitting based only on the concentrations of the
minor species led to a decrease of the two rate constants, but at
the expense of the quality of the fitting for BHMF. In any case,
Figure 8. Recyclability of the Ni/SBA-15 catalyst for the HMF hydrogenation
reaction. Reaction conditions: 0.15 mmol/mL HMF in 20 mL 1,4-dioxane, P(H2)
= 30 bar, T = 180˚C, HMF/Ni molar ratio of 3, 3 h.
After the reaction, the spent catalyst was analyzed by XRD,
TEM, IR spectroscopy and C-content analysis, and the Ni
content in the reaction solution was analyzed by ICP in order to
identify the main cause of the catalyst deactivation. No increase
of the Ni crystal size was measured applying the Scherrer
equation to the XRD pattern (Table 1). The absence of
significant sintering and mesostructured degradation during
reaction was confirmed by microscopy (Figure 9A-F). The
majority of the particles were again found to be confined in the
well-defined mesopores of SBA-15, with a few aggregated Ni
particles outside the channels (Figure 9A,B). Besides, according
to the ICP analysis, the Ni content in the reaction solution after
the recycling tests is of 1.53 ppm. Considering the quantity of Ni
k3,app and k5,app were still large compared to k2,app and k4,app
.
(3) The fits for DMF and DMTHF follow the same tendency as
the experimental data, though at longer times the consumption
of DMF and the production of DMTHF are overestimated. Some
inhibition phenomena not taken into account here can be
postulated.
In summary, on the tested Ni catalyst, both C=O hydrogenation
and hydrogenolysis steps are fast compared to the
hydrogenation of the furan ring. C-O hydrogenolysis and C=O
hydrogenation reactions are in competition. The MFFR route
seems to be predominant, confirming the capability of the Ni
This article is protected by copyright. All rights reserved.

10.1002/cctc.201902028
ChemCatChem
FULL PAPER
(E)
(F)
Figure 9. HRTEM HAADF images (A,C,E) and Ni (B,F) and Si (D) mapping of the Ni/SBA-15-used sample; (G) FT-IR spectra of the fresh and used Ni/SBA-15
catalysts.
from the catalyst presents in the reactor, it corresponds to 0.055
wt.% of the total Ni content. Such result is indicating that the Ni
leaching is negligible, as it could be awaited considering that the
reaction is performed in organic solvent. Consequently, the
deactivation is not associated to modifications of the support
characteristics, Ni dispersion change or Ni leaching. Another
possible way of deactivation is the adsorption of high molecular
weight compounds on the active sites during the reaction.[33]
The FT-IR spectrum, shown in Figure 9E for the used catalyst,
exhibits bands at:
any case faster than the furan ring hydrogenation, which is the
reason behind the high yields of DMF as an intermediate
product toward DMTHF. The stability upon recycling of a non-
promoted Ni catalyst can however be questioned, as
deactivation seems to occur because of carbon deposition,
rather than because of Ni nanoparticles sintering.
Experimental Section
- 880 cm-1 (adsorption of furan compounds)[34]
Synthesis of Ni/SBA-15 catalyst
- 890 and 1254 cm-1 (vibrations involving the C-H groups)[35]
- 1111, 1369 and 1430 cm-1 (C-O stretching vibration)[36]
- 1521, 1566, 1616, 1674 and 1712 cm-1 (assigned to C=O
groups[36]
These results, added to C-content analysis results
demonstrating a 9.2 wt.% carbon content in the used catalyst,
after the three cycles of reaction, indicate that the adsorption of
organic compounds on the catalyst surface,[37] that are not
efficiently removed by oxidative regeneration at 500°C, is the
main reason behind the progressive deactivation during
recycling tests.
The SBA-15 support was synthesized according to
a classical
procedure.[38] In a typical synthesis, 4.0 g of Pluronic P123 was dissolved
in a 1.6 M solution of HCl at 40 °C. Thereafter, 8.5 g of TEOS were
added dropwise to the solution, and this solution was submitted to
magnetic stirring for 24 h. The resulting gel was submitted for 48 h to
hydrothermal ageing at 100 °C. After recovery by filtration, the SBA-15
sample was washed with water, and dried at 100 °C for 24 h. The dried
SBA-15 sample was calcined at 550 °C for 6 h in a muffle furnace, using
a heating ramp of 1.5 °C min-1.
The nickel catalyst was prepared using the incipient wetness
impregnation – mild drying method.[21] To prepare 10 g of 15 wt.%
Ni/SBA-15 catalyst, 9.4 mL of an aqueous solution of nickel nitrate (2.8
mmol/mL; Ni(NO3)2·6H2O, 98% purity, Sigma-Aldrich) was dropped onto
8.5 g of SBA-15 powder (pore volume = 1.1 mL/g). The wet mixture was
placed in an oven set at 25 °C and aged under static conditions for five
days. A calcination under static air was finally performed at 500 °C for 6 h
with a ramp of 1.5 °C/min. The calcined sample is denoted NiO/SBA-15,
the reduced sample is denoted Ni/SBA-15 and the spent catalyst is
denoted Ni/SBA-15-used.
Conclusions
A non-promoted, monometallic Ni/SBA-15 catalyst prepared by
incipient wetness impregnation appears to be an active system
for the hydroconversion of 5-hydroxymethylfurfural (HMF) to 2,5-
dimethylfuran (DMF) and 2,5-dimethyltetrahydrofuran (DMTHF).
High yields of DMF and DMTHF are achieved in dioxane at
180°C under 30 bar H2, 70.5% and 96.6% respectively, by
simply modifying the reaction time. Despite the absence of
acidic sites, the catalyst exhibits both a high hydrogenolysis
ability and a high ability for the furan ring hydrogenation. The
kinetic study suggests that HMF is converted via the route
involving MFFR as an intermediate product. Competitive
reactions of C-O hydrogenolysis and C=O hydrogenation are in
Characterization
X-ray diffraction patterns were recorded on a Bruker D8 Advance X-ray
diffractometer in Bragg-Brentano configuration, with a Cu Kα radiation (γ
= 1.54184 Å). N2 physisorption experiments were performed at -196 °C,
on a Micromeritics Tristar II Plus instrument. The particle size and shape
were analysed by transmission electron microscopy. For fresh catalysts,
experiments were conducted on a JEOL 2100 UHR, operated at 200 kV
This article is protected by copyright. All rights reserved.

10.1002/cctc.201902028
ChemCatChem
FULL PAPER
with a LaB6 source and equipped with a Gatan 832 CCD camera. For the
used catalyst, experiment was conducted on a TITAN Themis 300
S/TEM. The high angle annular dark field (HAADF) images were
collected at angles between 50 and 200 mrad. Ni content in the reaction
solution after recycling tests was evaluated by inductively coupled
plasma optical emission spectrometry (ICP-OES) over an ICP-OES
authors thank technical support from the Lille University: Martine
Trentesaux and Pardis Simon for XPS analysis, Olivier Gardoll
for physical and redox characterization, Laurence Burylo for
XRD experiment, Maya Marinova for HRTEM analysis and
Svetlana Heyte from the REALCAT platform for high throughput
catalytic tests. Stéphane Pronier, from University of Poitiers, is
acknowledged for TEM analysis over fresh catalyst. The
spectrometer (720-ES Agilent) with an axially viewing and
a
simultaneous CCD detection. H2-temperature programmed reduction
(TPR) was performed on an Autochem analyzer (Micromeritics) equipped
with a quartz U-shaped microreactor. Quantification of H2 consumed is
performed using a TCD after trapping of the produced water. The FT-IR
spectra were recorded on an infrared spectrometer in the attenuated total
reflectance mode (IR-ATR) from Thermo Scientific (IS50).
Thermogravimetry experiments were conducted on a system from Mettler
Toledo (TGA/SDTA 851 model). The experiment was conducted under
20%O2 in N2 flow at the rate of 50 mL/min, with a temperature increase
from 50 to 900°C at a rate of 5 °C/min. X-ray photoelectron spectroscopy
analyses were performed on a AXIS Ultra DLD Kratos spectrometer
equipped with a monochromatized aluminium source (Al Kα = 1486.7 eV)
and a charge compensation gun. The spectra were obtained after the
samples were purged at room temperature under vacuum. The data were
collected at a step length of 0.1 eV. For the Ni/SBA-15 catalyst, the
sample was in situ reduced at 550°C for 2 h before XPS analysis.
REALCAT platform is benefiting from
a
state subsidy
administrated by the French National Research Agency (ANR)
within the frame of the ‘Future Investments’ program (PIA), with
the contractual reference ‘ANR-11-EQPX-0037’.
Keywords: HMF • hydroconversion • nickel • biofuels • incipient
wetness impregnation
[1]
[2]
[3]
S. Chen, R. Wojcieszak, F. Dumeignil, E. Marceau, S. Royer, Chem.
Rev. 2018, 118, 11023–11117.
R. J. van Putten, J. C. van der Waal, E. de Jong, C. B. Rasrendra, H.
J. Heeres, J. G. de Vries, Chem. Rev. 2013, 113, 1499–1597.
a) P. Gallezot, Chem. Soc. Rev. 2012, 41, 1538–1558; b) J. P. Lange,
E. Van der Heide, J. Van Buijtenen, R. Price, ChemSusChem. 2012, 5,
150–166; c) G. Dautzenberg, M. Gerhardt, B. Kamm, Holzforschung.
2011, 65, 439–451.
[4]
[5]
[6]
[7]
T. S. Hansen, K. Barta, P. T. Anastas, P. C. Ford, A. Riisager, Green
Chem. 2012, 14, 2457–2461.
Y. Román-Leshkov, C. J. Barrett, Z. Y. Liu, J. A. Dumesic, Nature.
2007, 447, 982–985.
M. A. Jackson, M. Appell, J. A. Blackburn, Ind. Eng. Chem. Res. 2015,
54, 7059–7066.
Hydroconversion of 5-Hydroxymethylfurfural
Preliminary catalytic tests were performed in an 8-parallel automated
autoclave system equipped with 8 high-pressure batch reactors (100 mL).
Prior to the catalytic tests, the catalysts were reduced at 550 °C for 2 h
(heating ramp of 10 °C/min) under 5 vol.% H2 in Ar flow (50 mL/min). The
reactor was loaded under inert atmosphere (glove box) with 0.15
mmol/mL HMF in 25 mL 1,4-dioxane as a solvent and 0.16 g of catalyst,
sealed and purged with H2. Then, the reactor was pressurized with the
required H2 pressure (15–45 bar), heated at the required temperature
(180-240 °C) and stirred at a speed of 700 rpm for 8h. The kinetics of the
reaction was followed using a 45 mL Parr reactor. The pre-reduced
catalyst (550°C, 2 h, pure H2 flow) was inserted in the reactor together
with 12.5 mL of 0.15 mmol/mL HMF solution in 1,4-dioxane. The reactor
was closed, purged with hydrogen several times, and pressurized with H2
up to 30 bar at 180 °C. The pressure was monitored using a gauge
connected to the reactor. The reaction was stirred magnetically. Samples
of reaction medium were collected at selected reaction times: 5 min, 10
min, 20 min, 30 min, 1 h, 2 h, 4 h, 6 h, 8 h and 10 h. For each selected
time, the reactor was placed into ice water for rapid cooling and the
pressure was released. After the sample collection, the reactor was put
back for the reaction at next reaction time and these steps were repeated
until the reaction time of 10 h. The catalyst is recovered by filtration and
the products were analysed by GC (Shimadzu 2010 Plus) equipped with
a ZB-WAX Plus capillary column (30.0 m × 0.25 mm × 0.25 µm) and a
flame ionization detector (FID), and by GC-MS (Shimadzu QP2010 Ultra
EI) equipped with a ZB-1XT capillary column (15.0 m × 0.53 mm × 0.25
µm) and an FID detector.
a) J. Luo, H. Yun, A.V. Mironenko, K. Goulas, J. D. Lee, M. Monai, C.
Wang, V. Vorotnikov, C. B. Murray, D. G. Vlachos, P. Fornasiero, R. J.
Gorte, ACS Catal. 2016, 4095–4104; b) L. Hu, X. Tang, J. Xu, Z. Wu,
L. Lin, S. Liu, Ind. Eng. Chem. Res. 2014, 53, 3056–3064; c) Q. Li, P.
Man, L. Yuan, P. Zhang, Y. Li, S. Ai, Molecular Catalysis. 2017, 431,
32–38; d) S. Nishimura, N. Ikeda, K. Ebitani, Catal. Today. 2014, 232,
89–98; e) M. Chatterjee, T. Ishizaka, H. Kawanami, Green Chem.
2014, 16, 1543–1551; f) J. Luo, J.D. Lee, H. Yun, C. Wang, M. Monai,
C. B. Murray, P. Fornasiero, R. J. Gorte, Appl. Catal. B. 2016, 199,
439–446.
a) B. Chen, F. Li, Z. Huang, G. Yuan, Appl. Catal. B-Environ. 2017,
200, 192–199; b) W. Guo, H. Liu, S. Zhang, H. Han, H. Liu, T. Jiang, B.
Han, T. Wu, Green Chem. 2016, 18, 6222-6228; c) Y. Zhu, X. Kong, H.
Zheng, G. Ding, Y. Zhu, Y.-W. Li, Catal. Sci. Technol. 2015, 5, 4208–
4217; d) S. Srivastava, G.C. Jadeja, J. Parikh, J Mol Catal A-Chem.
2017, 426, 244–256; e) A.J. Kumalaputri, G. Bottari, P.M. Erne, H.J.
Heeres, K. Barta, ChemSusChem. 2014, 7, 2266–2275; f) X. Kong, Y.
Zhu, H. Zheng, Y. Zhu, Z. Fang, ACS Sustain. Chem. Eng. 2017, 5,
11280–11289.
G. Bottari, A. J. Kumalaputri, K.K. Krawczyk, B. L. Feringa, H. J.
Heeres, K. Barta, ChemSusChem. 2015, 8, 1323–1327.
B. Seemala, C. M. Cai, C. E. Wyman, P. Christopher, ACS Catal.
2017, 4070–4082.
J. Luo, M. Monai, C. Wang, J. D. Lee, T. Duchoň, F. Dvořák, V.
Matolín, C. B. Murray, P. Fornasiero, R.J. Gorte, Catal. Sci. Technol.
2017, 7, 1735–1743.
J. Luo, L. Arroyo-Ramírez, J. Wei, H. Yun, C.B. Murray, R. J. Gorte,
Appl Catal A-Gen. 2015, 508, 86–93.
R. Goyal, B. Sarkar, A. Bag, N. Siddiqui, D. Dumbre, N. Lucas, S.K.
Bhargava, A. Bordoloi, J. Catal. 2016, 340, 248–260.
X. Kong, Y. Zhu, H. Zheng, X. Li, Y. Zhu, Y.-W. Li, ACS Catal. 2015, 5,
5914–5920.
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
P. Yang, Q. Xia, X. Liu, Y. Wang, Fuel. 2017, 187, 159–166.
Y. B. Huang, M. Y. Chen, L. Yan, Q.-X. Guo, Y. Fu, ChemSusChem.
2014, 7, 1068–1072.
Acknowledgements
[17]
[18]
[19]
[20]
[21]
M. Y. Chen, C. B. Chen, B. Zada, Y. Fu, Green Chem. 2016, 18,
3858–3866.
P. Yang, Q. Xia, X. Liu, Y. Wang, J. Energy Chem. 2016, 25, 1015-
Chevreul Institute (FR 2638), Ministère de l’Enseignement
Supérieur et de la Recherche and Région Hauts-de-France are
also acknowledged for supporting this work. This work has
benefited from the support of the CSC PhD scholarship program
(S. C.) and of the French National Research Agency (ANR),
through the NobleFreeCat project (ANR-17-CE07-0022). The
1020.
X. Kong, Y. Zhu, H. Zheng, F. Dong, Y. Zhu, Y. W. Li, RSC Adv. 2014,
4, 60467–60472.
X. Kong, R. Zheng, Y. Zhu, G. Ding, Y. Zhu, Y. W. Li, Green Chem.
2015, 17, 2504–2514.
A. Ungureanu, B. Dragoi, A. Chirieac, S. Royer, D. Duprez, E.
Dumitriu, J. Mater. Chem. 2011, 21, 12529–12541.
This article is protected by copyright. All rights reserved.

10.1002/cctc.201902028
ChemCatChem
FULL PAPER
[22]
[23]
S. Chen, C. Ciotonea, A. Ungureanu, E. Dumitriu, C. Catrinescu, R.
Wojcieszak, F. Dumeignil, S. Royer, Catal. Today. 2019, 334, 48–58.
a) J. P Thielemann, F. Girgsdies, R. Schlögl, C. Hess, Beilstein J
Nanotech. 2011, 2, 110–8; b) P.V.D. Voort, P.I. Ravikovitch, K.P.D.
Jong, A.V. Neimark, A.H. Janssen, M. Benjelloun, E.V. Bavel, P. Cool,
B.M. Weckhuysen, E.F. Vansant, Chem. Commun. 2002, 0, 1010–
1011.
[24]
[25]
a) S.D. Robertson, B.D. McNicol, J.H. De Baas, S.C. Kloet, J.W.
Jenkins, J. Catal. 1975, 37, 424–431; b) R. Brown, M.E. Cooper, D.A.
Whan, Appl Catal. 1982, 3, 177–186.
a) C. Louis, Z.X. Cheng, M. Che, J. Phys. Chem. 1993, 97, 5703–
5712; b) S. Sitthisa, A. Wei, D. E. Resasco, J. Catal. 2011, 284, 90-
101; c) P. Burattin, M. Che, C. Louis, J. Phys. Chem. B. 1999, 103,
6171-6178; d) H. H. Kung, In Studies in Surface Science and
Catalysis; Elsevier, 1989; Vol. 45, pp 91–109.
[26]
A.A. Lemonidou, M.A. Goula, I.A. Vasalos, Catal. Today. 1998, 46,
175–183.
[27]
[28]
X.-P. Yu, W. Chu, N. Wang, F. Ma, Catal Lett. 2011, 141, 1228–1236.
a) L. Hu, L. Lin, S. Liu, Ind. Eng. Chem. Res. 2014, 53, 9969–9978; b)
L. Hu, G. Zhao, W. Hao, X. Tang, Y. Sun, L. Lin, S. Liu, RSC Adv.
2012, 2, 11184–11206.
[29]
[30]
[31]
[32]
[33]
[34]
A.S. Nagpure, N. Lucas, S.V. Chilukuri, ACS Sustain. Chem. Eng.
2015, 3, 2909–2916.
Y. Nakagawa, M. Tamura, K. Tomishige, ACS Catal. 2013, 3, 2655–
2668.
A.B. Gawade, M.S. Tiwari, G.D. Yadav, ACS Sustain. Chem. Eng.
2016, 4, 4113–4123.
Y. Liu, M.A. Mellmer, D.M. Alonso, J.A. Dumesic, ChemSusChem.
2015, 8, 3983–3986.
J. Chen, F. Lu, J. Zhang, W. Yu, F. Wang, J. Gao, J. Xu,
ChemCatChem. 2013, 5, 2822–2826.
a) Y. L. Liu, C. Y. Hsieh, J. Polym. Sci. Pol. Chem. 2006, 44, 905–913;
b) A. Gandini, D. Coelho, M. Gomes, B. Reis, A. Silvestre, J. Mater.
Chem. 2009, 19, 8656–8664.
[35]
[36]
[37]
[38]
C. Moreno-castilla, F. Carrasco-marín, F.J. Maldonado-hódar, J.
Rivera-utrilla, Carbon. 1998, 36, 145–151.
U.J. Kim, C.A. Furtado, X. Liu, G. Chen, P.C. Eklund, J. Am. Chem.
Soc. 2005, 127, 15437–15445.
L. Yu, L. He, J. Chen, J. Zheng, L. Ye, H. Lin, Y. Yuan,
ChemCatChem. 2015, 7, 1701–1707.
D. Zhao, J. Feng, Q. Huo, N. Melosh, G.H. Fredrickson, B.F. Chmelka,
G.D. Stucky, Science. 1998, 279, 548–552.
This article is protected by copyright. All rights reserved.

10.1002/cctc.201902028
ChemCatChem
FULL PAPER
Entry for the Table of Contents (Please choose one layout)
Layout 1:
FULL PAPER
Non-promoted monometallic Ni/SBA-
15 catalyst, prepared by Incipient
Wetness Impregnation can convert
HMF to 2,5-dimethylfuran (DMF) or to
2,5-dimethyltetrahydrofuran (DMTHF)
Through the control over reaction
time, high yields to DMF (71%, at
conversion of 93%) and to DMTHF
(97%, at conversion of 100%) can be
achieved. The kinetic study affords the
determination of a preferential
Shuo Chen, Carmen Ciotonea, Karine
Vigier De Oliveira, François Jérôme,
Robert Wojcieszak, Franck Dumeignil,
Eric Marceau,* Sebastien Royer*
Page No. – Page No.
Hydroconversion of 5-
hydroxymethylfurfural to 2,5-
dimethylfuran and 2,5-
dihydroxymethyltetrahydrofuran over
non-promoted Ni/SBA-15
reaction route from HMF to DMTHF
through 5-methylfurfural (MFFR).
This article is protected by copyright. All rights reserved.