Efficient Synthesis of Sugar Alcohols over a Synergistic and Sustainable Catalyst

Article abstract of DOI:10.1002/cjoc.202100140

A series of catalysts were prepared for sugar alcohols production to overcome the deficiencies of the previous reported catalysts, such as low yield of sugar alcohols, single function, instability, and controversial role of active sites. The role of each metal and their synergistic-cooperation was discussed in detail with a combination of conditional experiments and characterizations. The results indicated that bifunctional Ni_6.66Fe₁Al_1.55 catalyst has unique structure with superparamagnetism and excellent activity. The (111) and (200) planes of metallic Ni are the hydrogenation active phases and preferentially exposed on Ni-Al-O_x spinel. The desired arabitol or mannitol was obtained by tuning the ratio of Br?nsted and Lewis acid sites. The recycling tests indicated that the unique structure of the prepared Ni-based catalyst can suppress leaching and poisoning, which has high textural stability and activity.

Full text of DOI:10.1002/cjoc.202100140

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Title: Efficiently Synthesis of Sugar Alcohols over a Synergistic and Sustainable
Catalyst
Authors: Liangqing Zhang, Jiarong Qiu, Xing Tang, Yong Sun, Xianhai Zeng,* Lu Lin*
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Cite this paper: Chin. J. Chem. 2021, 39, XXX—XXX. DOI: 10.1002/cjoc.202100XXX
Efficiently Synthesis of Sugar Alcohols over a Synergistic and
Sustainable Catalyst
Liangqing Zhang, a, b Jiarong Qiu, Xing Tang, Yong Sun,b, c Xianhai Zeng,*, b, c Lu Lin*, b, c
a
b, c
a
School of Advanced Manufacturing, Fuzhou University, Jinjiang 362251, China
College of Energy, Xiamen University, Xiamen 361102, China
Fujian Engineering and Research Center of Clean and High-valued Technologies for Biomass, Xiamen Key Laboratory of High-valued
b
c
Conversion Technology of Agricultural Biomass, Xiamen University, Xiamen 361102, China
Keywords
Biomass | Heterogeneous catalysis | Magnetic properties | Brønsted to Lewis acids | Sugar alcohols
Main observation and conclusion
A series of catalysts were prepared for sugar alcohols production to overcome the deficiencies of the previous reported
catalysts, such as low yield of sugar alcohols, single function, instability, and controversial role of active sites. The role of
each metal and their synergistic-cooperation was detail discussion with a combination of conditional experiments and
characterizations. The results indicated that bifunctional Ni6.66Fe
netism and excellent activity. The (111) and (200) planes of metallic Ni are the hydrogenation active phases and preferen-
tially exposed on Ni-Al-O spinel. The desired arabitol or mannitol was obtained basing by tuned the ratio of Brønsted and
1
Al1.55 catalyst has unique structure with superparamag-
x
Lewis acid sites. The recycling tests indicated that the unique structure of the prepared Ni-based catalyst can suppress
leaching and poisoning, which has high textural stability and activity.
Comprehensive Graphic Content
*E-mail: xianhai.zeng@xmu.edu.cn; lulin@xmu.edu.cn
View HTML Article
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differences between this version and the Version of Record. Please cite this article as doi:
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Zhang et al.
studies applied non-noble metal catalysts for hydrogenation of
lignocellulosic-derived sugars, but most studies only yield a single
xylitol or sorbitol, but did not obtain or study high value-added
[
19, 24-26]
arabitol or mannitol.
The following side reactions are one
of the main reasons for the low yield of sugar alcohols (especially
arabitol) in the reported literatures. It is well known that sugar
alcohols can be produced by hydrogenation or isomeriza-
tion/hydrogenation of lignocellulosic-derived sugars. Some studies
reported that overmuch Brønsted and Lewis acid sites, the ligno-
cellulosic-derived sugars tend to dehydrated to yield furfural or
5
1
-hydroxymethyl furfural (5-HMF) at low temperatures (100–
[27-30]
45°C),
5 6
while the aldehyde groups of C and C sugars are
Background and Originality Content
prone to cleave and then hydrogenate to form diols at high tem-
peratures (over 160°C). Therefore, synthesizing proper catalyst
and detail conditional experiments for efficient sugar alcohols
production are necessary.
With the diminishing fossil resources and global warming, the
utilization of renewable biomass to produce fuels, value-added
chemicals, biomaterials, and prebiotics has attracted great atten-
[1-7]
tion.
Sugar alcohols—xylitol, arabitol, and sorbitol, are derived
In addition, to the best of our knowledge, many researchers
focused on improving single sugar alcohol production and the
discussion of the active sites and catalyst structure are insuffi-
from lignocellulose, which listed as the 12 most important target
[
8]
chemicals that selected by the US Department of Energy. Sugar
alcohols are the components that widespread applied in sweets,
ice cream fillings, hard candies, sugar-free chewing gum, moistur-
[9, 31, 32]
cient.
Due to insufficient study, the role of active sites in
[
9, 31, 32]
[
9, 10]
the conversion of sugar alcohols is still controversial.
izer, softener, and texturizer in food and medical industries.
Hence, understanding the role of active sites in the conversion of
sugar alcohols is novel and essential. Besides, the preparation of
economic, environmental-friendly, and easy recover catalysts with
high performance and stability is the main focus in the field of
catalysis. Therefore, the development of bifunctional non-noble
metal catalysts with excellent performance and understanding the
role of each metal and their synergistic effect, which embody the
aforementioned deficiencies, are urgent need and main challenge
for sugar alcohols production.
Sugar alcohols as functional sweeteners also have prebiotic effects
which can reduce triglyceride, cholesterol level, and blood glu-
[11]
cose. In addition, sugar alcohols are crucial versatile intermedi-
ates, for conversion to high-value chemicals such as ethylene gly-
col, propylene glycol, pentane, bio-hydrogen, 1,3- pentadiene, and
[33]
[12, 13]
lactic acid.
The traditionary production of sugar alcohols was conducted
in a three-phase slurry batch reactor over Raney nickel cata-
[14-16]
lyst.
Although Raney nickel catalyst is low price, high activity
In this work, a series of catalysts were synthesized for the
production of sugar alcohols and the role of each metal and their
synergistic-cooperation were detailed investigate with a combina-
tion of catalytic evaluation experiments and catalyst characteriza-
tions. Some new perspectives of the study may provide a feasible
approach and good inspiration for both industrial and academic
fields in production of sugar alcohols.
and selectivity, the easily poisoned and relatively fast deactivation
[
15, 17]
hinder its wide application.
The conventional expensive no-
[18]
[19]
ble-metal catalysts, such as Ru/C, Pt/MWCNT,
Ru/MWCNT, Ru/(NiO–TiO ), Ru/PSN, Pt/γ-Al2O
Ru/HZY catalysts were extensively used for the production of
sugar alcohols, and most of them are poor stability, single func-
tion, low product yield, and difficult recovery during recycling,
which impede their practical application. In recent years, several
[20]
[15]
[21]
,[22] and
2
3
[23]
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© 2018 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2018, XX, 1－X

Synthesis Sugar Alcohols over Synergistic-Cooperation Catalyst
Chin. J. Chem.
peak center of Ni6.66Fe
Al1.55 hydrotalcite precursor was around
1
Results and Discussion
XRD analysis
The chemical components of the prepared catalysts were
listed as Table S1. XRD profiles of the catalysts were shown in
4
03°C. The addition ofAl species for co-precipitation obvious
changed the reduction characteristic of the precursors, and a
huge difference reduced peaks verified the intimate interaction of
Ni and Al species and may existence of Ni-Al-O spinel in the
x
[
33, 36]
Ni Fe Al catalyst.
6.66
1
1.55
Figure 1a. For the Ni6.59Fe
Ni6.89Fe Cu1.01, and Ni catalysts, the peaks corresponding to planes
111), (200), (220) at around 2θ of 44.3°, 51.7°, and 76.1° could be
indexed to the face-centered cubic (fcc) nickel (JCPDS No.
1 1 1 1
, Ni13.19Fe , Ni19.48Fe , Ni13.70Fe Cr0.14,
1
(
2+
8
9-7128). Ni phase which observed in XPS (Figure 2a) did not
2
+
detect in XRD, suggesting that Ni were highly dispersed on the
catalyst surface and lying below the detection limits of XRD.
[33]
The XRD profiles of the Ni6.98Fe Al1.69 (physical mixture),
1
Ni6.66Fe
1
Al1.55, Ni6.73Al
1
, and recycle catalyst (Ni6.66Fe Al1.55) were
1
shown in Figure 1b. As indicated by XRD patterns, all the catalysts
were indexed to fcc nickel. The difference is that the diffraction
peak of the Ni6.98Fe
suggesting the presence of Fe
, and recycle catalyst at 2θ of 37.1° and 63.8° indicating
1
Al1.69 catalysts was observed at 2θ of 35.5°,
2
O
3
; the peaks of the Ni6.66Fe Al1.55,
1
Ni6.73Al
1
[33, 34]
spinel phases of the catalyst may existence.
As proved by
Morales-Marín et al., the existence of spinel-like structure could
significant increase the accessible metallic nickel surface, which
favor dispersion of the metallic nickel phase formed upon reduc-
[33]
tion. It may be high dispersion over the surface of
co-precipitation catalysts as no detected Fe of the
2 3
O
[35]
1 1
Ni6.66Fe Al1.55, Ni6.73Al , and recycle catalyst.
Figure 2 (a) XPS profile of Ni 2p of Ni6.66Fe
Al 2p and Ni 3p of Ni6.66Fe Al1.55 catalyst; (c) XPS profile of Fe 2p of the
Ni6.66Fe Al1.55 catalyst; (d) XPS profile of Al 2p of Ni6.98Fe Al1.69 catalyst; (e)
Magnetization curves of the Ni6.59Fe , Ni19.48Fe , and Ni6.66Fe Al1.55 catalysts;
f) Infrared spectra of pyridine adsorbed at 350°C on the Ni6.53Fe
Al3.63 catalysts.
1
Al1.55 catalyst; (b) XPS profile of
1
1
1
1
1
1
(
1
Al0.38,
1 1
Ni6.66Fe Al1.55, Ni6.48Fe Al2.13, Ni6.61Fe
1
Al3.06, and Ni6.55Fe
1
XPS analysis
The XPS profiles of Ni 2p, Al 2p, Ni 3p, and Fe 2p of the
Ni6.66Fe Al were shown in Figure 2a–d. The binding energies of
1
1.55
Ni 2p3/2 and 2p1/2 at 853.2 and 872.3 eV indicated the presence
0
[33]
of Ni state, and 879.4 eV is the satellite of the binding energy
of 872.3 eV. Two obvious peaks at 855.2 and 860.7 eV were similar
to XPS profiles of Ni-Al-Ox spinel, which attributed to the spectral
Figure 1 (a) and (b) XRD profiles of the catalysts; (c) H
Al1.69 precursor, and hydrotalcite precursors; (d) N
tion-desorption isotherm of the Ni6.66Fe Al1.55 catalyst and pore size distri-
2
-TPR profiles of the
NiO, Ni6.98Fe
1
2
adsorp-
1
2+
[37-39]
peaks of Ni and its satellite.
was ascribedto spin-orbit doublets Ni 2p1/2 of Ni 2p, which also
indicated the presence of Ni state.
The binding energy at 873.6 eV
bution curve (inset) generated by the BJH method from the N
isotherms.
2
desorption
2+
[40]
2
H -TPR analysis
The Al 2p spectrum of the Ni6.66Fe Al catalyst resembling
1
1.55
with the report of Garbarino and co-workers, as the binding ener-
gy ofAl 2p of the Ni6.66Fe Al catalyst was 73.6 eV (Figure 2b),
The H -TPR profiles of the NiO, Ni Fe Al precursor, and
2
6.98
1
1.69
1
1.55
hydrotalcite precursors were shown in Figure 1c. The hydrotalcite
precursors (Ni Fe , Ni Fe ), Ni Fe Al precursor, and NiO
which significantly deviated from the binding energy of Al 2p
of
6.59
1
13.19
1
6.98
1
1.69
Al2O3 at 74.2 eV. The Al 2p peak of the Ni Fe Al catalyst
6.66 1 1.55
[41]
showed narrow reduction peaks within the range between 175–
shifted toward the lower binding energy by ~0.6 eV as compared
to Al 2p peak of Al O , which was
4
2
(
69°C, the reduction peak centers were around 325°C, 328°C,
94°C, and 378°C. The addition of Al species for co-precipitation
2
3
attributed to a higher density of
[39] The binding
energy of Al 2p (Ni Fe Al1.55) decreased significantly that indi-
the phase or a decreased ionicity of the Al-O bond.
e.g. Ni6.66Fe Al1.55 hydrotalcite precursor) exhibited broad reduc-
1
6
.66
1
tion peaks within range between 166–844°C, and the reduction
3+
cated surface Al preparing by co-precipitation has a strong inter-
Chin. J. Chem. 2021, 39, XXX－XXX
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Report
Zhang et al.
action of other species.[39] As compared to the Ni6.66Fe
Al1.55 cata-
1
1
2
3
4
5
Ni6.53Fe Al
0.24 0.43 0.56
1.10 0.27 4.07
1.41 0.24 5.88
87.62
100
100
100
100
n.d
n.d
n.d
n.d
1
1
1
0.38
1.55
2.13
lyst that prepared by co-precipitation, the binding energy of Al 2p
that prepared by physical mixture was slightly decreased (74.0 eV,
as shown in Figure 2d), which indicated week metals interaction of
the physical mixed Ni Fe Al catalyst.
Ni6.66Fe Al
6.98
1
1.69
Ni6.48Fe Al
n.d
n.d
In addition, as shown in Figure 2b, the peak at the range from
3.0 to 71.0 eV was attributed to the Ni 3p core level spectra of
Ni state. Two split peaks at the binding energies of 67.0 and
6
2+
[39]
1
Ni6.61Fe Al3.06 2.05 0.17 12.06
7.27
12.68
7.27
12.68
6
9.1 eV were additional Ni-containing species, indicating the for-
[39, 42]
mation of Ni-Al-Ox spinel.
Ni6.55Fe Al
1
3.63
2.38 0.14 17.00
The binding energies at 708.8 and 711.8 eV suggested the
2
+
3+
presence of Fe 2p3/2 and Fe 2p3/2, accompanying with a
a
b
B: Brønsted acidity, m mol/g.
L: Lewis acidity, m mol/g.
[
43-45]
satellite at 718.5 eV (Figure 2c).
p1/2 was owning to the binding energy of Fe .
The peak at 724.8 eV of Fe
3
+ [45-47]
2
The
2+
3+
existence Fe and Fe in catalyst may modulate the magnetic
[
47-49]
behaviors.
c
Reaction conditions: 2 g xylose, 0.4 g catalyst, 40 mL H
2
O, 3 MPa H ,
2
1
20°C, and 600 rpm; n.d: not detected.
Magnetic properties
1 1
The magnetization curves of the Ni6.59Fe , Ni19.48Fe , and
Ni6.66Fe Al1.55 catalysts were shown in Figure 2e. The catalysts have
1
TEM and SEM analysis
Al1.55 catalyst was analyzed by TEM and SEM for
further understand the morphology of catalyst. The TEM images
were shown in Figure 3. The wormhole-like ordered and internal
The Ni6.66Fe
1
superparamagnetism as the curves exhibiting perfect sigmoidal
shapes and zero coercivity, which indicated the catalysts have no
magnetic attraction for aggregation that affect the catalytic
mesoscopic void space were clearly observed in the Ni6.66Fe
Figure 3). The TEM images revealed that the Ni6.66Fe Al1.55 cata-
lyst is nanocomposites with average particle size of 14.12 nm
1
Al1.55
[
50]
activity during the reaction. The specific saturation
1 1
magnetization of the Ni6.59Fe , Ni19.48Fe , and Ni6.66Fe Al1.55 cata-
(
1
1
lysts were 85.25, 70.34, and 20.52 emu/g, and loading Fe species
is the main reason for increasing saturation magnetization. As
(
(
Figure 3c inset) and coexistence of two different lattice fringes
Figure 3a and b inset). The inter-planar distance d was around
compared to the Ni6.59Fe
magnetization of the Ni19.48Fe
attributed to the low magnetic Ni and non-magnetic Al doping
1
catalyst, the decrease of saturation
0
.2041ꢀnm and 0.1732 nm, corresponding to the (111) and (200)
1
1
and Ni6.66Fe Al1.55 catalysts were
[58, 59]
planes of metallic Ni (Figure 3a and b inset),
which were ba-
sically consistent with the results that calculated from the XRD
data (0.2045 nm and 0.1773 nm). Numerous well-dispersed white
dots were also observed, which were attributed to the stronger
[
51]
that reduced the number of spins aligning. Nevertheless, the
Al1.55 catalyst is still very responsive to an external mag-
netic field that can quickly isolate from the reaction system and
Ni6.66Fe
1
[
59, 60]
scattering of ultrafine Fe species.
The Al atoms may exist as
[
52, 53]
convenient for catalyst recycling.
nanoclusters that was too small as no crystalline phase of Al spe-
[
61]
cies was found. The observed (111) and (200) planes of metallic
Ni were the main catalytically active phases that preferentially
Py-FTIR analysis
Py-FTIR analysis was applied for insights into the acidic species
of the catalysts to understand the effect of acidic types on the
yield of sugar alcohols. Figure 2f exhibited the Py-FTIR spectra of
pyridine adsorbed on the catalysts by evacuation at 350ꢀ°C, which
x
exposed on the Ni-Al-O spinel.
The SEM image, EDS element analysis, and EDX elemental
mapping were shown in Figure S1. EDS elemental analysis showed
that metal species (Ni, Fe, and Al) were existence in the surface of
[
54]
is defined as strong acid sites. The peak centers at around 1456
Ni6.66Fe
1
Al1.55 catalyst (Figure S1b inset), in which the weight per-
centage of Ni species accounts for the largest proportion, up to
0.71%. As reported by Morales-Marín et al., a major fraction of
−
1
and 1540 cm can be assigned to the pyridine adsorption at the
Lewis and Brønsted acid sites, respectively. The IR band at around
8
−
1
[55]
1
489 cm is attributed to the Lewis-Brønsted acid complex.
nickel metal particles forming on the surface due to the oxygen
vacancies move through to the spinel particle surface and thus
The amount of Brønsted and Lewis acid sites was quantitated
according to fitting deconvolution, which were summarized in
Table 1. The ratio of the density of Brønsted and Lewis acidic sites
changes in the surface microstructure during the reduction pro-
[23, 33]
cess of spinel.
EDX elemental mapping showed that the Ni,
[55]
is defined as B/L value. The results indicated that increasing Al
ratio of Ni Fe Al catalyst can reduce Lewis acidity and strengthen
Fe, and Al species were homogeneous distribution on the catalyst
surface (Figure S1c–e). The textural properties observed by TEM
x
y
z
Brønsted acidity, and thus enhance B/L value, which is in agree-
ment with the reports that loading Al species can increase
and SEM also indicated the unique structure of Ni6.66Fe
alyst.
1
Al1.55 cat-
[56, 57]
Brønsted acidity.
Therefore, we can conclude that B/Lvalue
can be tuned via adjusting the ratio of metal species.
Table 1 Composition of acid sites for the co-precipitation Ni
x
Fe
y
Al cata-
z
lysts by Py-FTIR and effect of Brønsted and Lewis acids on arabitol produc-
c
tion.
Xylose
Arabitol
selectivity
(%)
Arabitol
yield (%)
Entry Catalyst
B
L
B/L conversion
(%)
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. J. Chem. 2021, 39, XXX－XXX

Synthesis Sugar Alcohols over Synergistic-Cooperation Catalyst
Chin. J. Chem.
[36]
C=N bonds. Nevertheless, xylitol yield is still lower than that
reported in literature as applied Ni Fe catalysts for the reaction.
x
y
Table 2 Effect of catalyst types on xylose hydrogenation.a
Xylose conver-
sion (%)
Xylitol
Xylitol selec-
tivity (%)
Entry
Catalyst
Ni
yield (%)
1
2
20.12
50.56
89.63
58.74
49.60
100
14.02
38.37
87.13
38.76
4.75
69.07
75.89
97.21
65.99
9.58
Ni6.59Fe
1
3
Ni13.19Fe
1
1
4
Ni19.48Fe
5
Fe
1
Al1.46
Ni6.73Al
Ni13.70Fe Cr0.14
Ni7.05Fe Mg1.84
Cu1.01
6
1
90.85
95.92
14.87
92.44
99.78
70.74
90.85
95.92
14.87
98.67
99.78
83.88
Figure 3 TEM images of the Ni6.66Fe Al1.55 catalyst. The inset of (a) and (b)
1
7
1
100
indicated the interplanar distance measured, (c) the particle size distribu-
tion.
8
1
100
BET surface area and pore size
9
Ni6.89Fe
Ni6.66Fe
Ni6.98Fe
1
93.69
100
The N
distribution of the Ni6.66Fe
The Ni6.66Fe Al1.55 catalyst exhibited type IV isotherm typical of
2
adsorption-desorption isotherm and pore size
1
Al1.55 catalyst were shown in Figure 1d.
10
1
Al1.55
Al1.69
1
1
1
1
84.33
mesoporous material. The pore size distribution curve shown that
the average pore size is around 8 nm (Figure 1d inset). A few large
pores were observed in the Ni6.66Fe Al1.55 catalyst, which may
1
cause by the collapse of the pores during preparation process of
the catalyst (Figure 1d inset). As shown in Table S1, the surface
a
Reaction conditions: 2 g xylose, 0.4 g catalyst, 40 mL H
20°C, 600 rpm, and 3 h.
2
O, 3 MPa H ,
2
1
To our delight, the best performance was observed, as 100%
xylose conversion with 99.78% xylitol yield could be obtained in
the presence of the N Fe Al catalyst; whereas 84.33% xylose
conversion with 70.74% xylitol yield were obtained as applied
physical mixed Ni6.98Fe Al1.69 catalyst (similar composition as
compared with Ni Fe Al catalyst) for the reaction. This phe-
nomenon is very interesting. To the best of our knowledge, the
unique structure of catalyst and the main catalytic activephase of
xylose hydrogenation did not discuss in the reported literatures.
area of the representative catalyst, such as Ni6.59Fe
1
, Ni13.19Fe
1
,
Ni6.53Fe
1
Al0.38, Ni6.66Fe
1
Al1.55, Ni6.48Fe
1
Al2.13, and Ni6.61Fe Al3.06 cata-
1
i
6.66
1
1.55
2
lysts were 3, 4, 18, 90, 126, and 171 m /g. Catalysts with
incorporating Al species by co-precipitation have larger surface
1
area and smaller pore size, which was attributed to the high dis-
persion of Al species on the surface of the catalysts.[
62]
6.66
1
1.55
2
N adsorp-
1
tion-desorption isotherm indicated that the Ni6.66Fe Al1.55 catalyst
was mesoporous material with high surface area, which has great
potential application in the catalytic field.
As indicated by XRD, H
SEM analysis, the well-dispersedAl species in the Ni Fe Al
1.55
-TPR, XPS, N physisorption, TEM, and
2
2
Effect of catalyst types on xylitol production
6.66
1
The catalytic activity of xylose hydrogenation was evaluated
and the results were shown in Table 2. No sugar alcohols were
catalyst prepared by co-precipitation method facilitated the for-
mation of nanoparticles (Ni species), and Ni species interacted
detected as not introduced catalyst or H for the reaction, indi-
species and thus formed Ni-Al-O spinel, while no
x
2
closely with Al
detected the formation of spinel by physical mixed Ni Fe Al
1.69
cated that catalyst and H are essential for the sugar alcohols
2
6.98
1
production (results not shown). It is well known that Ni is primary
catalyst. The (111) and (200) planes of metallic Ni preferentially
[19, 33, 63]
species for the hydrogenation reaction,
demonstrated inour study. For instance, 49.60% xylose conversion
with 9.58% xylitol selectivity were obtained when applied Fe
Table 2, Enter 5) catalyst for the reaction, whichare significantly
lower than Ni-based catalyst, such as Ni and Ni6.73Al catalysts
as it is also
exposed on the Ni-Al-O spinel with high specific surface area,
x
which would be the main catalytically active phase with superior
A
l1.46
1
hydrogenation performance. To the best of our knowledge, we
obtained highest xylitol yield among the reported non-noble met-
al catalysts, and the xylitol yield can be comparable to that re-
ported by noble metal catalysts. For instance, the reported cata-
lysts, such as Raney Ni, Ru/C, Rt/C, and Ru (1.0%)/NiO (5.0%)–
TiO2, the selectivity to xylitol is 96.7% (96.9% xylose conversion),
(
1
(
Table 2, Enter 1 and 6).
However, single Ni catalyst without promoter is not good for
xylitol production. For example, as employed Ni catalyst for the
reaction (Table 2, Entry 1), the xylose conversion (20.12%) and
98.1% (75.2% xylose conversion), and 100% (97.3% xylose con-
xylitol yield (14.02%) were still low. However, as applied Ni6.59Fe
,
version), and 99.8% (99.9% xylose conversion), respectively.
[
15, 19,
1
Ni
Fe , and Ni
Fe for the reaction (Table 2, Entry2, 3, and 4),
64] Therefore, the magnetic Ni Fe Al catalyst
6.66 1 1.55
with excellent
13.19
1
19.48
1
the xylose conversion and xylitol yield increased at least 151.29%
and 173.68%, indicating the introduced Fe species for
catalytic performance show great potential in commercial applica-
tion.
co-precipitation in Ni-based catalyst could beneficial to the hy-
drogenation of aldose. The results were also similar with the re-
In addition, the experiments for the loading of Mg, Cr, or Cu
species in Ni Fe based catalyst were also carried out for catalyst
2+
3+
x
y
port of Raso et al. that addition of Fe species (Fe and Fe ) in
Ni-based catalyst can improve the hydrogenation of C=C, C=O, and
screening of xylitol production. The loading of Mg species in Ni Fe
x y
based catalyst had an adverse effect on the xylose hydrogenation;
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Zhang et al.
while the proper amount loading of Cr or Cu species as promoters
had a positiveeffect on xylose hydrogenation (Table 2, Enter 7–9),
and the order of activity species was: Cr > Cu > Mg. Combined with
the hydrogenation performance of the aforementioned Fe species,
we can conclude that Cr, Cu, and Fe are effective promoters for
xylose hydrogenation, and the results are consistent with the re-
port of Mikkola and co-workers. In addition to hydrogenation
promoter, Fe species have superior magnetic properties and can quickly
separate the catalyst and the reaction liquid under an external magnetic
field with economic and environmentally friendly, which was prefer
promoter for the co-precipitation. Therefore, Ni, Fe, and Alspecies
were combined for co-precipitation to study the effect of condi-
tional experiments on the yield of sugar alcohols.
the reaction, which exhibited to improve arabitol selectivity, as
compared with Table 3, Enter 2 that did not addition of H PO for
the reaction (applied Ni6.66Fe Al1.55 catalyst for the reaction). In
conclusion, the proper B/L value could promote the yield of
arabitol.
3
4
1
[65]
Reaction mechanisms for xylose to xylitol and arabitol
Plausible mechanism for hydrogenation of xylose to xylitol was
proposed, as shown in Scheme 1. The hydrogen mole-
cules undergo dissolution and dissociation, and generate active
0
hydrogens on the surface of Ni (main catalytically active phase,
with (111) and (200) planes), then active hydrogens move to the
Ni-Al-O support via the so-called ‘hydrogen spillover’ effect, in
x
which hydrogen atoms incorporating in pairs to organic molecule
The main by-product of the catalysts in Table 2 was deter-
mined, and the test processes were as follows. Initially, the sub-
stances in reaction solutions were examined by HPLC, the HPLC
spectrum indicated that only the xylose and xylitol were detected
and nearly no other substances were produced (Figure S2). Then,
the reaction solutions were investigated by GC-MS, and no sub-
stances were detected. Further, the gas was collected and exam-
[10, 23, 31, 70, 71]
is the principle for hydrogenation.
species (Fe and Fe ) as an effective promoter, together with Ni
adsorb the aldehyde group of the sugar molecule.
Meanwhile, Fe
2+
3+
0
[10, 36, 71]
A nu-
cleophile is formed after the decomposition of the hydrogen mol-
ecules, in which the pair of electrons of it attack the carbon of the
[31]
carbonyl group. The protonation resulting from the addition of
hydrogen with appearance of an alcohol group, thus xylitol is
produced and finally dissociated from the surface of the cata-
2
ined by GC after the reaction, only the purged H in the reaction
gas as well as O and N from the air were detected, which clearly
2
2
[10, 23, 31]
lyst.
indicated that no C-C breaking products (such as CH4 or CO2)
were formed (Figure S3). Interestingly, the color of reaction solu-
tions changed from colorless to yellow (Figure S4), indicating that
the xylose was over-hydrogenated, and formed the undetectable
humins. Therefore, the humins were the main by-products in the
reaction solutions (The main substances of reaction solutions for
various catalysts in Table 2 are consistent. The HPLC and GC re-
sults and yellow color of reaction solution with employed Ni as the
catalyst were shown in the Figure S2–4.).
Scheme 1 Plausible mechanism for hydrogenation of xylose to
xylitol.
Effect of acidic types on arabitol production
In general, arabitol is high value-added product that mainly
[
66, 67]
produced by microorganism,
chemical conversion is still low.
while arabitol that produced by
For instance, Mishral ap-
Plausible mechanism for conversion of xylose to arabitol was
proposed, as shown in Scheme 2. The formation of xylulose was
[15, 19, 23]
[
28,
plied Ru/HYZ catalyst to produce sugar alcohols and 46% xylose
detected duo to exist the certain Brønsted to Lewis acids (B/L),
[
23]
31, 64, 71, 72]
conversion and 22% arabitol selectivity were obtained, and
Yadav et al. reported that 1% arabitol selectivity as employed
Raney Ni catalyst for the reaction.[15] It is well known that xylulose
are isomerized by xylose through a certain amount of B/L, and
and the isomerization mechanism involves a complex in
which the reactant is coordinated to an acid medium center,and
the reaction requires hydrogen transforms directly through an
intramolecular hydride shift between the carbonyl-containing C
1
[
23, 27, 65, 68, 69]
[28, 31, 72-74]
xylulose could further hydrogenate to obtain arabitol.
As reported by Mishra, xylose hydrogenation/isomerization are
and the hydroxyl-bearing C
2
of xylose.
The mechanism
for hydrogenation of xylulose to arabitol is similar with that of
[23]
competing reactions. For example, Brønsted and Lewis acid
sites were affected by the ratio of Al/Si of Zeolite Y, and high ratio
xylose to xylitol, the only difference is the active sites did not ad-
sorb the aldehyde group but ketone group, and the hydrogens
[
23]
[10,
ofAl/Si could promote xylose isomerization over hydrogenation.
Besides, Saravanamurugan et al. applied glucoseas asubstrate to
attack the carbon of the carbonyl in ketone group (Scheme 2).
2
3, 31, 36, 70, 71]
[68]
study the effect of Al/Si ratio on glucose isomerization. As the
ratio of Al/Si of H-USY catalyst was 0.17, the product distribution
of glucose and fructose is 28 and55 mol%, while the Al/Si ratio
was reduced to 0.033, the product distribution of glucose and
[68]
fructose is 63 and 24 mol%.
Several co-precipitation Ni Fe Al catalysts were prepared to
x
y
z
study the effect of acidic types on arabitol production. The results
were shown in Table 1. As applied Ni6.53Fe
Al2.13 catalysts for the reaction, not arabitol was detected
Table 1, Entry 1, 2, and 3); while employed Ni6.61Fe
Al3.63 catalysts for the reaction, i.e. 7.27%and 12.68%
1 1
Al0.38, Ni6.66Fe Al1.55, and
Ni6.48Fe
(
1
Al3.06 and
1
Ni6.55Fe
1
arabitol yield were obtained (Table 1, Entry 4 and 5), respectively.
According to the reports, Py-FTIR analysis, and conditional exper-
iments, increasing B/L value contributes to xylose
Scheme 2 Plausible mechanism for conversion of xylose to arabi-
tol.
[23, 27, 65, 68, 69]
isomerization,
thus favor arabitol production. This
was further proved upon addition of H PO (Table 3, Enter 6) for
3
4
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Synthesis Sugar Alcohols over Synergistic-Cooperation Catalyst
Chin. J. Chem.
Conditional experiments for xylose conversion
large apparent activation energy (i.e. high reaction temperature)
should be carried out for xylose isomerization to obtain desired
arabitol yield as applied Ni Fe Al catalyst for the reaction,
The effect of reaction temperature, hydrogen pressure, reac-
tion time, andreaction medium on product distribution for xylose
conversion was shown in Table 3 (applied Ni6.66Fe Al1.55 catalyst for
1
6.66
1
1.55
30, 65]
[
which is consistent with the reports.
furfural and diols were detected during the reaction, which indi-
cated that the B/L value of the Ni6.66Fe Al1.55 catalyst is appropri-
No side reactions such as
the reaction). The xylitol yield increased 136.84% when the reac-
tion temperature rose from 100 to 120°C (Table 3, Enter 1 and 2),
which is agreement with the report of Zhang et al. that reaction
rate and conversion efficiency could enhance by elevated tem-
1
ate, as no dehydration or Retro-Aldol occurred at low or high reac-
tion temperature, respectively. For instance, Choudhary reported
that the coordination of proper amount of B/L value favors xylu-
[75]
perature. As mentioned the section 3.2.1, the best perfor-
mance, 100% xylose conversion and 99.78% xylitol yield were
obtained at 120°C, i.e. obtaining high yield for single product (Ta-
ble 3, Entry 2). The yield remained constant (99.69–99.86%)as the
reaction time ranging from 0.5 to 5 h (reaction temperature
[27, 28]
lose dehydration to furfural at low reaction temperatures;
Liu et al. reported that the presence of Lewis acid sites and hy-
drogenation sites on a Cu/γ-Al2O3 catalyst had high glycol selec-
tivity (66.6%) for glucose conversion at high reaction tempera-
[
76]
tures, and the results were also agreement with those
maintained at 120°C), suggesting that the Ni6.66Fe
has high efficiency and product stability for xylose hydrogenation
Table 3, Entry 8–12).
Al1.55 catalyst
1
[
77-79]
reports.
(
An adverse effect on xylitol yield was observed when the reac-
tion was performed in a soluble acidic or alkaline medium (Table
Table 3 Effect of temperature, reaction medium, H
2
pressure, and reaction
3
, Enter 6 and 7). A small amount of furfural was detected as addi-
time on product distribution for xylose conversion.a
tion of strong Brønsted acid—H PO , thus the dehydration reac-
tion of xylose was occurred. Due to reaction temperature be-
3
4
[80]
Xylitol
Arabitol
Arabitol
Xylose
Xylitol
T
low 160°C, no formation of diols was observed as addition soluble
Entry
conversion yield
selectivity
selectivity
%)
yield
(%)
(%)
[77, 81]
(°C)
alkaline medium for the reaction.
However, the light yellow
(%)
(%)
(
color of reaction solution was observed after the reaction, indi-
[
68]
cating that a small amount of humins was formed. These results
indicated that side reactions were occurred in overmuch Brønsted
acidity or alkaline medium, thus decreased xylitol yield. Therefore,
an aqueous medium was chosen for production of sugar alcohols.
1
2
3
4
5
100
120
140
160
180
120
120
120
120
120
120
120
43.12
42.13
99.78
96.83
90.35
76.97
88.67
68.36
99.69
99.82
99.8
97.72
n.d
n.d
n.d
n.d
100
100
100
100
100
90.43
100
100
100
100
100
99.78
96.83
90.35
76.97
88.67
75.59
99.69
99.82
99.80
99.86
99.76
2.94
9.50
20.73
5.83
n.d
2.94
9.50
20.73
5.83
n.d
Catalytic performance on glucose conversion
Given the outstanding performance of the Ni6.66Fe Al cata-
1
1.55
lyst in xylose conversion, another important biomass-based plat-
form chemical—glucose, was also subjected for the synthesis of
sorbitol and mannitol. The effect of product distribution for glu-
cose conversion was shown in Table 4. The results of glucose con-
version under conditional experiments were similar with those of
xylose conversion. A proper amount of promoters such as Fe (Ta-
ble 4, Entry 2 and 3) and Cr (Table 4, Entry 5) species loading with
Ni-based catalysts could improve the sorbitol yield. To our delight,
6b
7c
8d
9e
n.d
n.d
9
9% glucose conversion and 99.88% arabitol selectivity were ob-
tained under the reaction conditions of 3 MPa H , 130°C and 5 h, as
n.d
n.d
2
applied the Ni Fe Al catalyst for the reaction (Table 4, Entry
6.66
1
1.55
0f
10)
. High yield of sorbitol can be obtained by proper reaction
1
n.d
n.d
temperature (Table 4, Entry 10–12). Besides, a higher yield of
1
1g
2h
99.86
99.76
n.d
n.d
mannitol was observed when applied catalyst with high ratio of Al
for the reaction (Table 4, Entry 10,13–16), as similar with the
results of acidic types on arabitol production. The results of condi-
tional experiments and characterizations shown that the unique
structure (Ni-Al-O spinel) of bifunctional Ni6.66Fe Al1.55 catalyst
x 1
with proper B/L value and reaction conditions contribute to sugar
alcohols production.
1
n.d
n.d
a
1
Reaction conditions: 2 g xylose, 0.4 g Ni6.66Fe Al1.55, 40 mL H
2
O, 3 MPa H ,
2
6
00 rpm; n.d: not detected.
The main advantages of the Ni6.66Fe Al1.55 catalyst were that
1
xylose or glucose hydrogenation was occurred at low tempera-
tures, while conversion to high value-added chemicals like arabitol
or mannitol was viable at high temperatures, and both are edible
sugar alcohols with high selectivity. To the best of our knowledge,
it is the highest yield for the conversion of xylose to arabitol in the
b
5
mmol/L H
3
PO .
4
c
5
mmol/L NaOH.
[
22, 82, 83]
reported catalysts.
The original data curve of mixed
solution of sorbitol and mannitol by HPLC was shown in Figure S5.
d–h
Reaction time is 0.5, 1, 1.5, 2, and 5 h, respectively.
Table 4 Effect of reaction conditions on product distribution for glucose
a
conversion.
The arabitol yield increased as the temperature over 120°C,
and the yield is as high as 20.73% while the reaction temperature
is 180°C (Table 3, Entry 5). The results could be explained that the
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Zhang et al.
Man-
nitol
yield
3
4
100
100
99.45
99.32
99.45
99.32
Glucose
Sorbitol
yield
Sorbitol
selectiv-
ity (%)
Mannitol
selectivity
(%)
Entry
1
Catalyst
Ni
conversion
(
%)
(%)
(
%)
a
Reaction conditions: 2 g xylose, 0.4 g Ni6.66Fe
MPa H , 120°C, 600 rpm, and 3 h; n.d: not detected.
1
Al1.55 catalyst, 40 mL H O, 3
2
37.42
98.77
99.65
55.19
99.00
98.74
62.49
99.41
95.79
99.00
94.92
99.65
99.16
99.25
99.62
99.25
10.49
86.49
87.76
18.11
98.14
37.04
61.74
92.19
84.68
98.89
94.69
84.57
92.93
93.61
70.48
64.80
28.05
87.57
88.07
32.82
99.13
37.52
98.79
92.74
88.40
99.88
99.76
84.88
93.72
94.32
70.75
65.29
n.d
n.d
n.d
n.d
n.d
n.d
n.d
n.d
n.d
n.d
n.d
n.d
n.d
2
2
3
4
5
6
7
8
9
Ni6.59Fe
1
Thereusabilityofthe Ni6.66Fe Al was studied afterbeingre-
1 1.55
coveredbymagnetic separation and drying. Recycling experiments
showed that xylitol yield remained stable after successive used for
Ni13.19Fe
1
1
n.d
4
times (Table 5). After 4 th recycled, no new phase was generated as
Ni19.48Fe
n.d
indicated the XRD patterns of fresh and recycled catalyst (Figure 1b).
Besides, N adsorption-desorption isotherm (Table S1) proved that
2
Ni13.70Fe
1
Cr0.14
n.d
recycled catalyst still maintained pore size (7.41 nm) and specific
surface area (87 m /g). Metal sintering basically not occurred due
to the creation of a nickel aluminate layer between the metallic Ni
particles and thealumina duringthe reductionprocess ofspinel,
2
Ni7.05Fe
1
Mg1.84
n.d
Ni6.89Fe
1
Cu1.01
n.d
[
33]
thus suppress sintering. In addition, as detected by ICP-OES,
only 1.20%, 2.31%, and 1.34% of Ni, Fe, and Al species leaching
were detected after 4 th recycled (the species leaching decreases
as the number of cycles increases), indicating high stability of the
catalyst. The particle size distribution of 4th run catalyst (Figure
S6) is similar with the fresh catalyst (Figure 3c). The results indi-
cated that the catalytic active phases and textural properties of
recycled catalyst were practically no changes as compared with
the fresh catalyst, which show the promising use of spinel-based
Ni6.73Al
1
n.d
Ni6.98Fe
Ni6.66Fe
Ni6.66Fe
Ni6.66Fe
Ni6.53Fe
Ni6.48Fe
Ni6.61Fe
Ni6.55Fe
1
1
1
1
1
1
1
1
Al1.69
n.d
10
Al1.55
Al1.55
Al1.55
Al0.38
Al2.13
Al3.06
Al3.63
n.d
1
1b
n.d
1
2c
12.9
n.d
12.95 catalyst for aqueous-phase to produce sugar alcohols.
1
3
4
5
6
n.d
Conclusions
1
4.82
15.24
25.21
O, 3 MPa H
4.86
In summary, the novel and bifunctional Ni6.66Fe Al catalyst
was synthesized with outstanding performance. The (111) and
200) planes of metallic Ni are the main catalytic active phases and
1
1.55
1
1
15.30
25.40
(
preferentially exposed on Ni-Al-Ox spinel with high hydrogenation
activity. This work proved that Fe species is hydrogenation pro-
moter and the main donor of magnetic properties. The proper ratio
of Brønsted and Lewis acid sites could promote the yield of arabi-
tol or mannitol, which could be tuned by theratio of metal spe-
cies. The catalyst has superparamagnetism without magnetic at-
traction for aggregation to affect the catalytic performance and
can quickly isolate from the reaction system and convenient for
a
Reaction conditions: 2 g glucose, 0.4 g catalyst, 40 mL H
30°C, 600 rpm, and 5 h; n.d: not detected.
2
2
,
1
b
Reaction temperature is 120°C.
Reaction temperature is 140°C.
c
catalyst recycling. The main advantages of the Ni6.66Fe Al1.55 cata-
1
lyst were that hydrogenation of xylose or glucose was occurred at
Recycling of the catalyst
In addition to high activity and selectivity, stability is also an
important index for catalytic performance. As we know, except for
conventional noble-metal catalysts, Ni-based catalysts are also
widespread applied for hydrogenation. However, the major
drawbacks of the Ni-based catalysts are Ni leaching, poisoning, and
low temperatures, while conversion to high value-added chemi-
cals like arabitol or mannitol was viable at higher temperatures,
and both are edible sugar alcohols with high selectivity. As em-
ployed xylose as the substrate, the yield of xylitol and arabitol up
to 99.78% (nearly 100% selectivity) and 20.73% under proper con-
ditions, while sorbitol yield up to 98.89% and nearly 100% selec-
tivity as applied glucose as the substrate. To the best of our
knowledge, it is the highest yield for the conversion of xylose to
arabitol in the reported catalysts. Recycledexperiments indicated
that the prepared Ni Fe Al catalyst with Ni-Al-O spinelstruc-
turecan suppress leaching, poisoning, and sintering, which over-
come the drawbacks of the Ni-based catalysts and have outstand-
ing activity and textural stability. In addition to the unique struc-
ture and excellent performance that the reported catalysts did not
have, we also provided some new cognitive perspectives through
systematic studies of catalytic evaluation experiments and char-
acterizations.
[19, 33, 63]
sintering.
Therefore, the preparation of non-noble metal
Ni-based catalysts with high stable performance is of great signifi-
cance for sugar alcohols production.
Table 5 Successive use of the Ni6.66Fe Al1.55 catalyst on xylose hydrogena-
1
6.66
1
1.55
x
tion.a
Xylose
Xylitol
Xylitol
Recycle times
conversion (%)
yield (%)
selectivity (%)
1
2
100
100
99.65
99.36
99.65
99.36
Experimental
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. J. Chem. 2021, 39, XXX－XXX

Synthesis Sugar Alcohols over Synergistic-Cooperation Catalyst
Chin. J. Chem.
Materials
of the catalyst were evaluated by a Squid-VSM. FEI Tecnai G2 F20
transmission electron microscopy (TEM) microscope, operating at
Cu(NO
Cr(NO ·9H
fructose, ethylene glycol, 1,2-propanediol,
-hydroxymethylfurfural, and furfural were purchased from Alad-
3
)
2
2
·6H
O, Ni, Na
2
O, Fe(NO
3
)
3
·9H
2 3 2 2 3 3 2
O, Ni(NO ) ·6H O, Al(NO ) ·9H O,
100 kV, was used to investigate the morphology and microstruc-
3
)
3
2
CO
3
, NaOH, xylose, xylitol, arabitol, glucose,
ture of the catalysts.
5
Catalysts test
din Reagent Co. Ltd. Mg(NO
Chemical Reagent Co. Ltd.
3 2 2
) ·6H O was supplied by Sinopharm
All reaction tests were carried out in a 100 mL of stain-
less-steel high-pressure reactor (PARR instrument company, USA).
A typical experimental procedure was as follows: 2.0 g xylose, 0.4
g catalyst, and 40 mL distilled water were added to the reactor,
Catalysts preparation
The Ni/Al/Fe/Cu/Mg/Cr catalysts were synthesized by a modi-
fied co-precipitation procedure, according to Velu and
2
and then purged with H five times before pressurized, and heat-
[
84]
ed to the predetermined pressure and temperature for a desired
reaction time with stirring at 600 rpm. After the reaction, the re-
actor was cooled to room temperature, and solid-liquid separation
was performed with a magnet to recover the catalyst. The recov-
ered catalyst was washed with water and then dried at 105°C for
co-workers. Typical magnetic catalyst was synthesized as fol-
lows: 350 mL aqueous solutions containing 76.48 g Ni(NO ·6H
5.20 g Fe(NO ·9H O, and 18.35 g Al(NO ·9H O with 1 mol/L
cationic concentration was dropwise with vigorous stirring and
added into 350 mL NaOH (29.64 g) and Na CO (3.18 g) solution,
3
)
2
2
O,
1
3
)
3
2
3
)
3
2
2
3
1
2 h.
with the pH kept between 8.5 to 10. The resulting slurry was aged
at 60°C for 12 h, then filtrated precipitate and washed thoroughly
with distilled water until the pH value of filtrate was around 7. The
filtrated residue was dried at 105°C for 10 h and ground into
powder before passed through a 100-mesh sieve. Prior to the
experiment, the precursor was reduced at 500°C for 4 h (the se-
lected reduction temperature of precursors based on the experi-
Samples analysis
Quantitative analysis of the products was performed using
Waters e2695 (Waters, USA) high performance liquid chromatog-
raphy (HPLC), which equipped with a Shodex sugar KS-802 column
(
0.8ꢁ×ꢁ30ꢁcm, Showa Denko, Japan), on elution with distilled water
at a flow rate of 0.6 mL/min at 60°C. The following formulas (1–
1) were used to calculate reactant conversion, product yield and
mental results of H
2
-TPR). The reduced catalyst was denoted as
1
Ni6.66Fe
1
Al1.55 by inductively coupled plasma optical emission
selectivity:
spectrometry (ICP-OES).
Other catalysts were synthesized by introducing corresponded
nitrates, based on the modified co-precipitation procedure.
(
Mole of initial xylose − mole of xylose after reaction)
(1)
Xylose conversion (%) =
´ 100%
Mole of initial xylose
Among them, the catalyst precursors, Ni
Ni Fe Cu , and Fe Al were reduced at 400°C for 4 h, and the re-
duced catalysts were denoted as Ni6.59Fe
Cu1.01, and Fe
x
Fe
y
, Ni
x
Fe
y
Cr
z
, Ni
x
Fe
y
Mg
z
,
x
y
z
y
z
1
, Ni13.19Fe
1
, Ni19.48Fe
Al1.46; Ni
1
,
Mole of xylitol in the product
×100%
(2)
Xylitol yield (%) =
Mole of initial xylose
Ni13.70Fe
1
Cr0.14, Ni7.05Fe
1
Mg1.84, Ni6.89Fe
1
1
x
Al
y
and Ni
alysts were donated as Ni6.73Al
Al3.06, and Ni6.55Fe Al3.63 by ICP-OES. Physical mixed cata-
lyst was prepared for experimental comparison, as following
steps: 76.48 g Ni(NO ·6H O, 15.20 g Fe(NO ·9H O, and 18.35 g
Al(NO ·9H O were dissolved in a small amount of water, and
x y z
Fe Al were reduced at 500°C for 4 h, and the reduced cat-
1 1 1
, Ni6.53Fe Al0.38, Ni6.48Fe Al2.13,
Xylitol yield
Xylose conversion
(3)
Ni6.61Fe
1
1
Xylitol selectivity (%) =
×100%
3
)
2
2
3
)
3
2
3
)
3
2
Mole of arabitol in the product
Mole of initial xylose
(4)
(5)
Arabitol yield (%) =
×100%
then dried at 105°C for 8 h and ground into powder before passed
through a 100-mesh sieve, and reduced at 400°C for 4 h, and the
reduced catalysts were donated as Ni6.98Fe
by calcining Ni(NO ·6H O at 400°C and its reduced Ni was also
used for experimental comparison. All the prepared catalysts were
reduced under the H flow.
1
Al1.69. The NiO formed
3
)
2
2
Arabitol yield
Xylose conversion
Arabitol selectivity (%) =
×100%
2
Catalysts characterizations methods
(Mole of initial glucose − mole of glucose after reaction)
Glucose conversion (%) =
×100%
Mole of initial glucose
(
6)
ICP-OES with equipped an Agilent 7700 spectrometer was car-
ried out to analyze chemical composition of the catalysts. The
surface morphology, energy-dispersive X-ray (EDX) element map-
ping images, and energy dispersive X-ray spectrometer (EDS) were
obtained by using a Supra 55 Sapphire field emission scanning
electron microscope (SEM). Brunauer-Emmett-Teller (BET) surface
Mole of fructose in the product
Mole of initial glucose
(7)
(8)
Fructose yield (%) =
×100%
2
area and pore size were detected by N physisorption using a Mi-
Mole of sorbitol in the product
Mole of initial glucose
Sorbitol yield (%) =
×100%
crometrics ASAP 2020 HD sorption analyzer, and BET–BJH meth-
ods were applied to evaluate the pore size distribution and sur-
face area. X-ray diffraction (XRD) data were obtained by using a
Rigaku Ultima IV diffractometer with Cu-Kα radiation at 2θ from 5
to 90° with a scanning speed of 10°/min. X-ray photoelectron
spectroscopy (XPS) profiles were obtained by using a Thermo Sci-
entific ESCALAB 250Xi photoelectron spectrometer with mono-
chromated X-ray irradiation Al Kα. Fourier Transform Infrared
Spectrometer of pyridine (Py-FTIR) spectra were recorded on
Bruker Tensor 27 IR spectrometer to detect surface Brønsted acid
sites and Lewis acid sites of the catalysts. The magnetic properties
Sorbitol yield
Glucose conversion
(9)
Sorbitol selectivity (%) =
×100%
Mole of mannitol in the product
Mole of initial glucose
(10)
Mannitol yield (%) =
×100%
Chin. J. Chem. 2021, 39, XXX－XXX
© 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
www.cjc.wiley-vch.de

Report
Zhang et al.
rous Carbon from Mixed Leaves for High-Performance Superca-
Mannitol yield
Glucose conversion
(11)
Mannitol selectivity (%) =
×100%
pacitors. Chin. J. Chem. 2020.
Supporting Information
8.
Bozell, J. J.; Petersen, G. R. Technology development for the
production of biobased products from biorefinery carbohy-
drates—the US Department of Energy’s “Top 10” revisited. Green
Chem. 2010, 12, 539-554.
The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.2021xxxxx.
Acknowledgement
9
.
Zada, B.; Chen, M.; Chen, C.; Yan, L.; Xu, Q.; Li, W.; Guo, Q.;
This work was supported by National Key Research and De-
velopment Program of China (Nos. 2019YFB1503903,
Fu, Y. Recent advances in catalytic production of sugar alcohols
2
019YFB1503904), National Natural Science Foundation of China
(
Nos. 21676223, 21978248), and Natural Science Foundation of
and their applications. Sci. China-Chem. 2017, 60, 853-869.
Fujian Province of China (No. 2019J06005, 2019J01246).
1
0. Zhang, X.-J.; Li, H.-W.; Bin, W.; Dou, B.-J.; Chen, D.-S.; Cheng,
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Manuscript accepted: XXXX, 2021
Accepted manuscript online: XXXX, 2021
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Synthesis Sugar Alcohols over Synergistic-Cooperation Catalyst
Chin. J. Chem.
Table of Contents
Efficiently Synthesis of Sugar Alcohols over a Synergistic and Sustainable Catalyst
Liangqing Zhang, Jiarong Qiu, Xing Tang, Yong Sun, Xianhai Zeng,* Lu Lin*
Chin. J. Chem. 2021, 39, XXX—XXX. DOI: 10.1002/cjoc.202100XXX
1
A novel inexpensive superparamagnetic Ni6.66Fe Al1.55 catalyst with high activity and stability was synthesized for sugar alcohols production. In addi-
tion to the unique structure and excellent performances that reported catalysts did not have, we also provided some new cognitive perspectives
through systematic studies of conditional experiments and characterizations.
Chin. J. Chem. 2021, 39, XXX－XXX
© 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
www.cjc.wiley-vch.de