Catalytic selective hydrogenation and rearrangement of 5-hydroxymethylfurfural to 3-hydroxymethyl-cyclopentone over a bimetallic nickel-copper catalyst in water

Article abstract of DOI:10.1039/c8gc04009e

The selective hydrogenation and rearrangement of 5-hydroxymethylfurfural (5-HMF) to 3-hydroxymethyl-cyclopentone (HCPN) were studied over a MOF-derived bimetallic nickel-copper catalyst in water. The combination of nickel and copper dramatically improved the efficiency in both the selective hydrogenation of the carbonyl group of 5-HMF and the hydrogenative ring-rearrangement of the C5 ring, affording 70.3% yield for HCPN and 99.8% yield for the rearrangement products. Moreover, it was indicated that water acted as a solvent, reactant, and proton donor by dissociation at an elevated temperature, which supplied slightly acidic conditions and promoted the rearrangement reaction.

Full text of DOI:10.1039/c8gc04009e

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G. Chatel et al.
Heterogeneous catalytic oxidation for lignin valorization into valuable
chemicals: what results? What limitations? What trends?
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DOI: 10.1039/C8GC04009E
Green Chemistry
ARTICLE
Catalytic Selective Hydrogenation and Rearrangement of 5-
Hydroxymethylfurfural to 3-Hydroxymethyl-cyclopentone over
Bimetallic Nickel-Copper Catalyst in Water
Received 00th January 20xx,
Accepted 00th January 20xx
Shujing Zhang,a,b Hong Ma,a* Yuxia Sun,a,b Yang Luo,a,b Xin Liu,a,b Meiyun Zhang,a,b Jin Gaoa and Jie
DOI: 10.1039/x0xx00000x
Xua*
www.rsc.org/
The selective hydrogenation and rearrangement of 5-hydroxymethylfurfural (5-HMF) to 3-hydroxymethyl-cyclopentone
(HCPN) was studied over MOFs-derived bimetallic nickel-copper catalyst in water. The combination of nickel and copper
dramatically improved the efficiency both in the selective hydrogenation of carbonyl group of 5-HMF and hydrogenative
ring-rearrangement of C5 ring, affording 70.3% yield for HCPN and 99.8% yield for rearrangement products. Moreover, it is
indicated that water acts as solvent, reactant, and proton donor by dissociation at elevated temperature, which supplied
slightly acidic conditions and promotes the rearrangement reaction.
Introduction
rearrangement.[24] Despite Lewis acid possessed the
remarkable promotion effect in hydrogenative rearrangement
Production of chemicals and fuels from renewable biomass
resources is an important topic in aspects of chemistry and
chemical engineering.[1,2] Due to the oxygen-rich nature and
excellent water-solubility for lots of biomass-derived
feedstocks, water is recognized as undoubtedly preferred
clean solvent, and thus their corresponding water-phase
transformation has become current research focus.[3-5] As a
representative biomass-derived platform obtained from C6
sugars,[6-8] 5-hydroxymethylfurfural (5-HMF) has been
extensively investigated and upgraded to variety of
downstream chemicals via catalytic dehydration, oxidation,
esterification, hydrogenation, and rearrangement, etc.[9-16] The
initial research on the hydrogenation of 5-HMF mainly focused
of 5-HMF, it simultaneously cause instability of 5-HMF and
leaded to over-dehydration and polymerization by-products in
water. In fact, nonacidic catalysts under acidic additives-free
conditions may be more beneficial, but there have been few
related reports so far.
Particularly, 3-hydroxymethyl-cyclopentone (HCPN), a high
value-added chemical used as an intermediate chemical for
production of fragrances, pesticides, and polymers,[25] is rather
difficult to achieve high selectivity in hydrogenation and
rearrangement of 5-HMF, which still faces great challenge. To
promote the yield of HCPN, two key problems should resolve
as illustrated in Scheme 1. (1) The unsaturated furan ring of 5-
HMF is readily reduced immediately after the initial
hydrogenation of carbonyl group, leading to undesirable by-
product THFDA, which is unable to undergo rearrangement.[26]
Thus, the hydrogenation activity requires to be suppressed in
order to merely reduce the C=O group while retain the furan
achieving
2,5-furandimethanol
(FDA)[17]
and
2,5-
tetrahydrofuran dimethanol (THFDA)[18] via the reduce of C=C
and/or C=O groups. Recently, hydrogenative rearrangement of
5-HMF in water has attracted increasing attention. Water is
recognized to play a crucial role in the rearrangement besides
serving as solvent, although the mechanism is not yet clear
and needs to be clarified. Up to now, precious metal catalysts
(Ru, Pt, Au, and Pd, et al.), have achieved valuable
cyclopentanone derivatives and aliphatic alcohols in water.[19-
21]
In these studies, Lewis acidic supports or additives (Nb2O5,
Al2O3, ZrO2, TiO2, and Ta2O5)[22,23] are generally required for
purpose of promoting rearrangement, via improving the
removal of the hydroxyl group, ring-open, and ring-
a. State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy,
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023,
P. R. China. E-mail: xujie@dicp.ac.cn, mahong@dicp.ac.cn
b. University of Chinese Academy of Sciences, Beijing 100049, P. R. China
Scheme 1 Main and side reactions for hydrogenation and
†Electronic
Supplementary
Information
(ESI)
available:
See
DOI: 10.1039/x0xx00000x
rearrangement of 5-HMF.
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ring. (2) The hydrogenative rearrangement of FDA to HCPN transferred into a Teflon-lined stainless steel autoclave. After
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o
DOI: 10.1039/C8GC04009E
involved ring-rearrangement and dehydration steps, which are solvent-thermal treatment at 120 C for 20 h, the obtained
seriously affected by protons (pH values) and Lewis acids; the sample was centrifuged, thoroughly washed with DMF and
acidic centres need to be accurately regulated to avoid ethanol, and finally dried in oven overnight. Ni-MOF-74, Co-
generating the ring-opening alcohols as well as excessive MOF-74, Cu-MOF-74, Fe-MOF-74, Ni-Fe-MOF-74, and Ni-Co-
dehydration products such as 2-methyl-furural (MF) and 2,5- MOF-74 were prepared using the same method.
dimethylfuran (DMF).[27] Therefore, it is necessary to design
new catalysts with multi-active sites to fulfil these coupled under N2. The typical procedure was described as follows: Ni-
Ni-Cu/C material was prepared by pyrolysis of Ni-Cu-MOF-74
multiple reactions.
Cu-MOF-74 was put in quartz tube and heated at a heating
o
Our group has been dedicated to developing high- rate of 10 C∙min−1 under continuous N2 flow. After the target
o
performance Ni-base catalysts for the catalytic hydrogenation temperature (600 C) reached, the material was held for 2 h
of biomass and its derivatives. Ni/AC that has outstanding and then cooled to room temperature. Ni/C, Co/C, Cu/C, Fe/C,
performances in the fragmentation-hydrogenolysis of lignin, Ni-Fe/C, and Ni-Co/C were prepared using the same method.
was demonstrated incapable to catalyze rearrangement.[29,30]
In addition, Ni-Cu/SBA-15 catalyst that used to efficiently
catalyze another biomass-derived platform furfural to
cyclopentanone via hydrogenation and rearrangement was of
poor selectivity for HCPN.[31] We noticed that the dissociation
Characterization
X-ray powder diffraction (XRD) patterns were obtained using
an Empyrean-100 powder diffraction system with Cu Kα
radiation (λ=0.15406 nm) between 5o and 80o (40 kV, 40 mA).
1H NMR and 13C NMR spectra were recorded on an AVANCE III
of water could be promoted if increasing the reaction
400 MHz spectrometer at room temperature. The acidity of
temperature. Theoretical concentration of proton reached
the samples were measured using temperature programmed
7.37×10-7 mol/L at 100 oC (pH=6.1) for water (pH=7.0 at 25 oC),
desorption of NH3 (NH3-TPD) by a micromeritics autochem Ⅱ
apparatus with mass spectrometer (TPDE-MS) on
micromeritics AutoChem 2910 apparatus. The pH values of
solvents were detected by Sartorius-PB-10 with combination
silver electrode and BNC electrode. The TGA measurements
suggesting water can act as proton donor and create a slightly
a
acidic condition. However, little research has been made on
the proton donor role of water. Herein, nickel was selected as
the active component for hydrogenation, with activity
suppressed through introduction of
a secondary metal
were carried out under nitrogen on
a Mettler Toleso
(copper). Water was selected as solvent, and its role was
studied at adopted temperature by employing carbon as the
carrier to exclude the influence of Lewis acidic sites. According
to the above design, the hydrogenation-rearrangement of 5-
HMF to HCPN could be realized by bimetallic Ni-Cu/C catalyst
in water without any Lewis supports or additives.
TGA/SDTA 851 instrument at a heating rate of 10 oC∙min−1. The
microstructure of the powder was characterized using
scanning electron microscopy (JSM-7800F). The morphology of
the materials was examined by transmission electron
microscopy (TEM) on a HITACHI H7700 electron microscope.
High-angle annular dark field scanning transmission electron
microscope (HAADF-STEM) analysis and the corresponding
energy-dispersive X-ray spectroscopy (EDX) was taken on a
JEM-200F with Mo supporting film for the suspension of
catalysts.
Experimental section
Materials and reagents
Ni(NO3)2, Cu(NO3)2, Co(NO3)2, Fe(NO3)3, ethanol, buffer agents,
Reaction procedures and products analysis
NaOH,
N,N-dimethyl
formamide
(DMF),
dodecane,
The typical catalytic procedure is as follows: 0.126 g (1 mmol)
5-HMF, 5 mL of solvent and specified amount of catalyst were
added into a 50 mL Parr autoclave, and then the autoclave was
sealed. After charging H2, the reaction mixture was stirred and
heated to the specified temperature. The reaction was
stopped after desired hours, and then analyzed by gas
chromatograph (Aligent GC-7890) with internal standard
method. The mass spectrometry was measured by using an
Agilent 6890N GC/5973 MS instrument.
isopropanol, and tetrahydrofuran were obtained from Tianjin
Kermel Chemical Reagent. 2,5-Dihydroxyterephthalic acid, 1,4-
dioxane, and tetrahydrofurfuryl alcohol were obtained from
Aladdin Industrial Inc. 18O-enriched water (97% 18O
abundance) was obtained from Shanghai Research Institute of
Chemical Industry. D2O (99.9% D abundance) was obtained
from Energy Chemical Co., Ltd. FDA and 5-HMF were
purchased from Innochem Co., Ltd. HCPN and HHD were
synthesized in our laboratory. Distilled water was purified in
laboratory.
Synthesis of catalysts
Results and discussion
Ni-Cu-MOF-74 was prepared by the solvent-thermal method
based on a previous literature.[32] In a typical synthesis, 0.35 g
(1.76 mmol) 2,5-dihydroxyterephthalic acid was first dissolved
in 70 mL of N,N-dimethyl formamide (DMF), followed by
addition of 0.79 g (3.29 mmol) Cu(NO3)2, 0.24 g (0.82 mmol)
Ni(NO3)2, 4.7 mL of deionized water, and 4.7 mL of ethanol.
The mixture was stirred and sonicated for 10 min, and then
Characterizations of materials
Ni-Cu/C has been characterized in detail with SEM, TEM, XRD,
and NH3-TPD (Figure 1). SEM and TEM images confirmed that
Ni-Cu/C retained the rod-like morphology of Ni-Cu-MOF-74.
The XRD pattern showed peaks at 43.3o, 50.4o, and 74.2o
assigned to Cu(111), (200), (220) diffraction planes, while
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44.3o, 51.6o, and 76.1o was attributed to Ni (111), (200), and
(220)
(c), and Ni (d), and line-scan (recorded along theVliienweArmticalerOknelidne)
of smaller NPs (e) and bigger NPs (f) ofDNOiI-:C1u0./1C03(9R/eCd8GlCin0e4:00C9uE,
green line: Ni, and grey line: C in e and f ).
while larger ones (around 50-80 nm) were Cu nanoparticles,
due to its facial aggregation during pyrolysis at the high
temperature. Cu nanoparticles are well-dispersed on carbon.
Preliminary comparison of nickel-based catalysts
In the initial study, the as-synthesized MOFs-derived
monometallic catalysts (Ni/C, Cu/C, Fe/C, and Co/C) and
bimetallic catalysts (Ni-Cu/C, Ni-Fe/C, and Ni-Co/C) were
tested in the hydrogenation and rearrangement of 5-HMF. The
o
exploratory experiments were performed at 140 C under 2.0
MPa H2 in water, and the catalytic results were listed in Table
1. As expected, Ni/C achieved >99% conversion with 79.1%
yield to THFDA, suggesting completely hydrogenation of C=O
groups and unsaturated C=C groups in furan ring. As discussed
above, if the intermediate FDA was further hydrogenated to
THFDA, the following hydrogenation rearrangement reaction
could be seriously suppressed. It is noted that Cu/C showed
decreased activity (45.5% conversion) but a certain activity for
rearrangement as detected by 22.7% yield to HHD. In contrast,
Co/C reached nearly completely conversion and showed some
activity for generating rearrangement products, affording yield
of 19.0% to HCPN, 22.8% to HCPEN, and 14.4% to HHD. Fe/C
showed poor activity and achieved only 18.6% conversion
without any hydrogenation and rearrangement products
detected under the same conditions. Considering introduction
of a secondary metal may alter the catalytic performance,
transition metals such as Cu, Co, and Fe were respectively
added to Ni/C. Among them, Ni-Cu/C was screened out as the
best bimetallic catalyst, with 93.8% conversion and 87.2% yield
to rearrangement products. It afforded 50.4% yield to HCPN.
Further decreasing the molar ratio of 5-HMF and metal
contributed to hydrogenative rearrangement (70.3% yield of
HCPN and 99.8% yield for rearrangement products). These
Fig. 1 SEM (a-c), TEM (d), XRD (e), and NH3-TPD (f) of Ni-Cu/C.
face. And diffraction peak at 36.4o was assigned to Cu2O (111).
These indicated pyrolysis of Ni-Cu-MOF-74 at 600 oC in N2
atmosphere leaded to the decomposition of Ni-Cu-MOF-74,
with metal cations reduced to metallic Ni, Cu, and Cu2O
dispersed on carbon. Furthermore, the XRD pattern of Cu/C
displayed Cu0 and Cu2O, and Ni/C possessed Ni0 and NiO.
Afterwards, the chemical compositions within the surface near
region were compared by XPS analysis, and the results were
listed in Tables S2 and S3. It was clear that, for Ni-Cu/C, the
content of Ni0 and Ni2O3 was much lower than that of Ni/C,
while the content of NiO consequently increased. On the other
hand, Cu2O changed to be the major surface metal species for
Ni-Cu/C catalyst, with an obvious decrease in Cu0 and CuO
contents in comparison with Cu/C. Moreover, the absence of
NH3 desorption peaks (Figure 1f) gave evidence that the effect
stems from acidic sites of Ni-Cu/C catalyst could be excluded.
The elemental compositions of the Ni-Cu/C measured by EDX
mapping (Figures 2b-d) and line-scan (Figures 2e,f) confirmed
the smaller particles with average size of 11 nm distributed on
carbon surface and inside were bimetallic Ni-Cu nanoparticles,
results indicated Cu displayed
a remarkable promotion
towards production of unsaturated HCPN, and Ni could endow
the bimetallic catalyst the capacity for hydrogenation of C=O
groups, and simultaneously Cu may contribute to
rearrangement and suppress the activity in C=C
hydrogenation. Then, Cu was replaced with Co or Fe, the
consequent Ni-Co/C and Ni-Fe/C catalysts showed unsatisfied
results, with plenty of humins (brown polymer) generated,
which is consistent with the previous literatures.[33] These
comparative results strongly indicated that the combination of
Cu and Ni guaranteed an excellent activity in the
hydrogenation and rearrangement of 5-HMF to HCPN.
The effect of solvent
Generally, the solvents play an important role in the catalytic
conversion of 5-HMF in term of products distribution. The
effect of solvents was investigated by examining the catalytic
performance of Ni-Cu/C in isopropanol (IPA), tetrahydrofuran
(THF), tetrahydrofurfural alcohol (THFA), ethanol, and 1,4-
Dioxane (Diox). As shown in Figure 3, the solvents remarkably
Fig. 2 HAADF-STEM image of Ni-Cu/C (a), the corresponding
energy-dispersive X-ray spectroscopy (EDX) mappings C (b), Cu
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