Cu1-Cu0 bicomponent CuNPs@ZIF-8 for highly selective hydrogenation of biomass derived 5-hydroxymethylfurfural

Article abstract of DOI:10.1039/c9gc01331h

99% yield of 2,5-dihydroxymethylfuran (DHMF) was achieved from biomass derived 5-hydroxymethylfurfural (HMF) with novel CuNPs@ZIF-8 using a relatively low hydrogen pressure and short reaction time. The activation energy of transformation of HMF to DHMF is only 39 kJ mol^-1 and the TOF value reached is 21 h^-1. The coexistence of Cu¹ and Cu⁰ in Cu species is demonstrated to contribute to the high activity for the hydrogenation of HMF to DHMF.

Full text of DOI:10.1039/c9gc01331h

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DOI: 10.1039/C9GC01331H
Green Chemistry
COMMUNICATION
1
0
Cu -Cu bicomponent CuNPs@ZIF-8 for high-selective
hydrogenation of biomass derived 5-hydroxymethylfurfural
a
a
a
a
abc
d
Yunchao Feng, Guihua Yan, Ting Wang, Wenlong Jia, Xianhai Zeng, * Jonathan Sperry, Yong
Received 00th January 20xx,
Accepted 00th January 20xx
abc
abc
e
abc
Sun, Xing Tang, Tingzhou Lei and Lu Lin
DOI: 10.1039/x0xx00000x
www.rsc.org/
9
9% yield of 2,5-dihydroxymethylfuran (DHMF) was achieved from methylfurfural (MF), 5-methylfurfuryl alcohol (MFA) and other
biomass derived 5-hydroxymethylfurfural (HMF) with a novel chemicals could be formed as by-products (Scheme 1).
CuNPs@ZIF-8 using a relative lower hydrogen pressure and shorter To achieve an efficient conversion of HMF to DHMF,
reaction time. The activation energy of transformation of HMF to considerable catalyst systems have been investigated with
-1
5-7
DHMF is only 39 kJ/mol and TOF valve reached 21 h . The various hydrogen sources, for example, alcohols, formic
coexistence of Cu and Cu in Cu species is demonstrated to be high acid, silanes and molecular hydrogen (H
active for the hydrogenation of HMF to DHMF. them, catalytic hydrogenation with H obviously represents an
1
0
8, 9
10
).2, 11, 12 Among
2
2
attractive alternative with more atom-economic. So far
effective catalysts for the selective hydrogenation of HMF to
5
-Hydroxymethylfurfural (HMF) is widely regarded as a key
platform intermediate for the conversion of lignocellulosic
biomass into valuable chemicals and fuels as the presence of –
OH, -C=O and furan ring functional group. In particular, the
selective hydrogenation of HMF to 2, 5-dihydroxymethylfuran
DHMF) is highly desired for that DHMF is an essential precursor
applied in the synthesis of resins, pharmaceuticals, artificial
fibers and functional polymers. The conversion of HMF to
DHMF can be regarded as the hydrogenation of
heteroaromatic aldehyde, thus a series of derivatives such as 5-
2
DHMF with H are typically rare and high-cost noble metal ones
13, 14
15
16
17, 18
19, 20
(e.g., Au,
Pt, Pd, Ru
and Ir
. Unremitting efforts
1
-3
have been devoted to design and synthesis of high-performance
noble metal free catalysts for DHMF production, among which
copper-based materials show the highest activity and
(
21
2
selectivity. However, high H pressure ( ≥ 5Mpa) and long
4
reaction time (≥5h) are required in most cases (Table S1). Thus,
to develop high-efficiency Cu-based catalysts could improve the
reaction rate via controlling the particle size and increasing the
surface area of acquired catalysts such as Cu-nanoparticle (Cu-
a
HO
OH
NP) catalysts, which does not rely on high H
desirable.
2
pressure, is highly
O
O
OH
HO
O
DHMF
O
HMF
O
MFA
O
MF
Scheme 1. Reaction path for the hydrogenation of HMF to DHMF
a.
b.
College of Energy, Xiamen University, Xiamen 361102, China.
Fujian Engineering and Research Centre of Clean and High-valued Technologies
for Biomass, Xiamen 361102, China.
c.
d.
e.
Xiamen Key Laboratory of Clean and High-valued Utilization for Biomass, Xiamen
3
61102, China.
Centre for Green Chemical Science, University of Auckland, Auckland 1142, New
Zealand
Henan Key Lab of Biomass Energy, Huayuan Road 29, Zhengzhou, Henan 450008,
Scheme 2. Schemetic illustration of the synthesis of CuNPs@ZIF-8
China
E-mail: xianhai.zeng@xmu.edu.cn (Xianhai Zeng); Tel./Fax: +86 592-2880701
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
On the other hand, the small metal nanoparticles (NPs) are
prone to aggregate and thermodynamically unstable during the
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reaction, resulting in the decline of activity.22, 23 The catalytic CuNPs@ZIF-8 (11.5wt% Cu as determined by ICP-VOieEwSA)rtsichleoOwnleinde
performance of metal was known to be significantly affected that the framework structure of ZIF-8 DwOaIs: 10u.n10c3h9a/nC9gGedC0u13p3o1Hn
and/or eventually determined by the nature of supporters. In introduction of Cu NPs (Figure 1a, Figure S2). No visible
this context, metal organic frameworks (MOFs) could be a ideal diffraction peaks were detected for Cu NPs, which indicated
candidate because (1) they posses large surface area and that ZIF-8 encapsulated Cu NPs were small. N sorption studies
2
tunable pore sizes, which are desirable for hosting NPs and of CuNPs@ZIF-8 showed appreciable decreases in BET surface
ensuring high NP dispersion; (2) their permanent pore structure areas compared to parent supporters, revealing that Cu NPs
allows the accessibility of substrates into the NP active sites; (3) were dispersed in ZIF-8 framework (Figure 1b, Table S2). H
their framework can stabilize NPs and prevent sorption experiments evidently demonstrated the
2
H
2
agglomeration/growth of NPs; and especially, (4) their unique enrichment capability of CuNPs@ZIF-8, which favoured the
property of H adsorption is beneficial to the catalytic catalytic hydrogenation (Figure 1c).
2
hydrogenation.24 In view of the high chemical and thermal
stability, ZIF-8, a zeolite-type MOF, has been widely studied as
an effective matrix to encapsulate various metal NPs (e.g., Au,
Pt, Pd,Ru, Ni) and improve their catalytic performance in recent
years.2
5-29
In our recent work, effective catalysts have been
3
, 30-32
applied for HMF production, achieving high HMF yields.
In
this work, we report excellent ZIF-8 encapsulated Cu NPs
(
(
CuNPs@ZIF-8) catalysts for the conversion of HMF to DHMF
>99% conversion and 99% yield), which presents the first
successful example of MOF-supported noble metal free
catalysts for the hydrogenation of HMF.
The three-step synthesis of CuNPs@ZIF-8 was shown in
Scheme 2 (also see Supporting Information for more details).
Briefly, ZIF-67 was first synthesized using the modified room-
3
3
2+
temperature precipitation method. Subsequently, Cu were
incorporated and dispersed in ZIF-8 framework. Finally,
4
CuNPs@ZIF-8 was obtained by the fast reduction with NaBH .
Figure 2. (a)TEM image of ZIF-8. (b,c)TEM image of CuNPs@ZIF-8.
(d)HRTEM image of CuNPs@ZIF-8.
The chemical nature of the CuNPs@ZIF-8 was characterized
by X-Ray photoelectron spectroscopy (XPS). Cu 2p3/2 peak
0
1
around 932.4 could be assigned to Cu /Cu (indistinguishable),
while no obvious shake up peak was observed, excluding the
3
4
presence of CuO (Figure 1d). Cu LMM Auger spectra
1
0
corresponded to the typical Cu (916.5) and Cu (918.4) peaks,
1
0
demonstrating that Cu and Cu coexisted in the Cu species
3
5
(Figure 1e).
The size and distribution of ZIF-8 immobilized Cu NPs were
characterized by transmission electron microscopy (TEM)
subsequently. As shown clearly in the Figure 2a, synthetic ZIF-8
was composed of microcrystals with uniform morphology. After
Figure 1. (a) XRD patters for ZIF-8 and CuNPs@ZIF-8. (b)
N sorption isotherms for ZIF-8 and CuNPs@ZIF-8. (c) H
2 2
sorption isotherms for ZIF-8 and CuNPs@ZIF-8. (d) XPS
spectra for CuNPs@ZIF-8. (e) Cu LMM Auger spectra of
CuNPs@ZIF-8
2
+
in-situ fast reduction of Cu , highly dispersed nano Cu species
with size around 2~4nm were observed (Figure 2b, 2c). And
obviously crystalline interplanar spacings in Cu NPs can be
0
1
corresponded to Cu /Cu (Figure 2d).
The catalytic activity on the selectivity hydrogenation of HMF
The powder X-ray diffraction (XRD) pattern of synthetic ZIF-8 for the resulting composites was evaluated in ethanol. As shown
o
was consistent with a simulated analogue, proving the in Figure 3a, around 99% DHMF yield was achieved at 140 C for
formation of pure phase of ZIF-8 (Figure S1). XRD pattern of 3h with 2MPa H , suggesting that CuNPs@ZIF-8 was enable to
2
2
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0
0
1
0
0
1
effectively catalyze HMF to DHMF. Detailed reaction condition Cu @MCM-41, Cu /Cu @MCM-41, Cu @/C and Cu /Cu @C
View Article Online
DOI: 10.1039/C9GC01331H
inverstigations showed that the DHMF production rate can be were prepared to understand if the synergistic effect between
1
0
2
improved by incresing H pressure, reaction temperature and Cu and Cu exists without or with other common supports (see
catalysts dosages without visible side reactions (Figure S3-S5), supporting information for preparation details, see Figure S6-S7
which further proved the high selectivity of CuNPs@ZIF in for XRD pattren). As shown in figure 3f, the TOF values of
1
0
hydrogenation.
Cu /Cu with/without supports were much higher than that of
0
1
0
The kinetic studies HMF conversion to DHMF were Cu , directly proving that the doping of Cu in Cu species can
investigated to further assess the catalytic activity of the Cu promote the hydrogenation of HMF.
NPs@ZIF-8. Due to the high selectivity of DHMF, pseudo-first-
order kinetics is assumed in the investigated conditions using
the equation of ln c
HMF after a reaction time of t, c
HMF, and k is the rate constant. As shown in figure 3b, the linear
relationship between lnc and t supported the hypothesis of
t
/c
0
t
= -kt, where c is the concentration of
0
is the initial concentration of
t
pseudo-first order for HMF to DHMF transformation. The rate
constant (k) increased with the increase of reaction
temperature, proving that higher reaction temperature can
notably promote the conversion reaction. According to the
Arrhenius equation of ln k = ln A −Ea/RT, The apparent
activation energy (Ea) of the conversion of HMF over
CuNPs@ZIF-8 is about 39 kJ/mol (Figure 3c), which is lower than
3
6
that of 104.9 kJ/mol for Ru/C catalyst.
Figure 4. (a) leaching experiment of CuNPs@ZIF-8. (b) catalyst
recycling studies for CuNPs@ZIF-8. (c) XRD patters of CuNPs@ZIF-8
before and after 4 catalytic runs. And (d) TEM images of CuNPs@ZIF-
8
after 4 runs.
The heterogeneous nature of the CuNPs@ZIF-8 was checked
by removing catalysts from the solution after 1h of reaction,
and heating the filtrate for another 2 hours (Figure 4a). ICP-OES
analysis of the reaction solution conformed that the content of
Cu was below the detection limit, suggesting no obvious Cu
leaching during the reaction. The reusability/stability of the
nanocatalyst CuNPs@ZIF-8 is important for further practical
applications. Our prepared Cu-NPs could be recycled and
reused for up to four runs without significant loss of catalytic
activity and selectivity (Figure 4b), suggesting that the highly
dispersed Cu-NPs have been effectively immobilized by the
frameworks of ZIF-8.
Figure 3. (a) Hydrogenation of HMF to DHMF by CuNPs@ZIF-8.
(b) The kinetics profiles for the conversion of HMF to DHMF
(fitted by first-order assumption) with CuNPs@ZIF-8 as catalyst.
(c) Arrhenius plots for the conversion of HMF to DHMF. (d) The
The crystallinity of CuNPs@ZIF-8 was well maintained after
the reaction as demonstrated by XRD (Figure 4c), and two
TOF values in various catalyst dosages. (e) The TOF values in
various H pressure. (f) Hydrogenation of HMF to DHMF in
o
o
2
obvious peaks of 36.5 (Cu O, PDF# 77-0199) and 43.3 (Cu,
2
PDF#85-1326) were observed, which should be due to (1) the
increase of Cu-NP size or (2) the shifting of Cu-NP from the
framework of ZIF-8 into the surface of ZIF-8. As shown in TEM
images (Figure 4d), only ignorable Cu species existed in the
outline of ZIF-8, while a slight aggregation was observed, which
was consistent with the XRD analysis. Thus, the slight decrease
in the activity is ascribed to the increase of CuNP size as
evienced by TEM. For comparison, NiNPs@ZIF-8 and
CoNPs@ZIF-8 were also prepared, and exhibited lower
various catalyst.
On the other hand, there is a large rise in the TOF value from
8
to 16 and 21 upon increasing the H
respectively (Figure 3d and 3e). Besides the ultrasmall size of Cu
NPs and H enrichment capability of ZIF-8, these high TOF values
may be determined by the coexistence of Cu and Cu in Cu
2
pressure and Cu dosages,
2
1
0
0
0
1
species. To remove the supporter effect of ZIF-8, Cu , Cu /Cu ,
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selectivity than CuNPs@ZIF-8 (Figure S8), further encapsulated Cu NPs for the selective hydrogenation of
View Article Online
DOI: 10.1039/C9GC01331H
demonstrating the key role of the Cu particles in hydrogenation. unsaturated aldehydes to alcohols. Furthermore, the
1
0
Selective hydrogenation of various unsaturated aldehydes coexistence of Cu and Cu in Cu species is demonstrated to be
over CuNPs@ZIF-8 were also investigated subsequently (Table high active for the hydrogenation of HMF to DHMF.
1
). Biomass-derived furanic aldehydes such as furfural and 5-
We thank for the financial support from the National Natural
methylfurfural, which are also very important platform Science Foundation of China (Grant Nos. 21506177; 21676223),
chemicals, gave high yields to the correponding alcohol the special fund for Fujian Ocean High-Tech Industry
products. With unsaturated aromatic aldehydes and pyridine Development (No. FJHJF-L-2018-1), China, the Natural Science
aldehydes as substrates, the desired products were also Foundation of Fujian Province of China (Grant No.
obtained in satisfying yields, indicating that CuNPs@ZIF-8 has 2019J0131653), the Energy Development Foundation of the
high selectivities and activities for the transformation of College of Energy, Xiamen University (No. 2017NYFZ02). We
unsaturated aldehydes to alcohols.
also thank the New Zealand Ministry of Business, Innovation
and Employment (MBIE) for support through the Catalyst Fund
(16-UOA-049-CSG).
Table 1. Selective hydrogenation of various unsaturated aldehydes
over CuNPs@ZIF-8
R'
CuNPs@ZIF-8 (7.2mol% Cu)
R'
o
Conflicts of interest
1
40 C, 2MPa H2, 3h
R
O
OH
R
There are no conflicts to declare.
OH
O
OH
OH
O
O
OH
HO
Notes and references
9
9%
99%
99%
94%
1
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2
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1
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pair electrons of oxygen and the strong electron-deficient Cu
center. Meanwhile, hydrogen molecules dissociate at the Cu
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2
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Table of contents
1
0
Cu -Cu bicomponent CuNPs@ZIF-8 is a high selective and active catalyst for the
hydrogenation of HMF to DHMF