Y. Zhong, et al.
MolecularCatalysis493(2020)111056
Table 3
Comparison of catalytic performance of Fe/FeOx@LDH with other catalytic systems containing homogeneous base in reaction of furfural with n-PrOH.
.
Entry
Catalysts
Reaction conditions
Conv.(%)
Sel.(%)
Ref.
1
2
3
4
5
6
7
8
Fe/FeOx@LDH
Fe/FeOx@LDH
Pt/FH + K2CO3
Fe@C + K2CO3
[Co(tia)(H2O)2]n + Cs2CO3
CoxOy-N@K-10+Cs2CO3
Au/FH + K2CO3
Catalyst: 50 mg; furfural: 1 mmol, n-PrOH: 5 mL, 140 °C, 4 h, 5 MPa (Ar).
Catalyst: 50 mg; furfural: 1 mmol, n-PrOH: 5 mL, 140 °C, 4 h, 5 MPa (O2).
Catalyst: 50 mg; furfural: 0.2 g, n-PrOH: 15 mL, 140 °C, 4 h, 0.3 MPa (O2), K2CO3: 50 mg.
71.3
20.8
90.1
86.7
84.9
75.1
94
87.1
99.8
90
96.2
99.7
92.8
97
This work
This work
−
Catalyst: 25 mg; furfural: 0.1 g, n-PrOH: 15 mL, 140 °C, 4 h, 0.3 MPa (O2), Cs2CO3: 25 mg.
Catalyst: 50 mg; furfural: 0.2 g, n-PrOH: 15 mL, 140 °C, 4 h, 0.3 MPa (O2), Cs2CO3: 50 mg.
−
−
CuO-CeO2 + K2CO3
85.4
95.3
a
The reaction conditions are the same as in Entry 3.
anion intercalated LDH for catalyzing the one-pot two-step CeC band
forming reaction of furfural with n-propanol in the absence of a
homogeneous base. The irregularly shaped Fe/FeOx NPs (a passivation
layer of oxidized iron species of Fe2+ and Fe3+ on the surface of Fe
NPs) with diameters less than 10 nm together with the support LDH as a
whole proved to be effective in catalyzing the transfer hydrogenation of
furfural with n-propanol to prepare furfuryl alcohol and n-propanal,
while only acetal reaction occurred when using the sole Fe nano-
particles and the sole LDH as catalysts; the support LDH imparted basic
catalytic function to the composite realizing the second-step aldol re-
action of furfural with the intermediate n-propanal to produce the main
product 3-(furan-2-yl-)-2-methylacrylaldehyde (C8). Both high con-
version of furfural and high selectivity to the main product (C8) can be
obtained in a non-oxidizing atmosphere of Ar or H2/Ar mixed gas, re-
action temperature of 140 °C and reaction time of 4 h. This catalyst is
also applicable for the CeC bond forming reaction of other short-chain
alcohols such as ethanol and n-Butanol with furfural to prepare the
corresponding C7 and C9 products. The catalyst was easily deactivated
during cycle experiments, probably due to the oxidation of Fe/FeOx in
the used catalyst during the drying process. By soaking Fe/FeOx@LDH
in a solution of nickel nitrate, the cyclic catalytic stability of the catalyst
can be effectively improved, but at the cost of reducing partial catalytic
activity. In addition, in some batches of reactions, the yields of the
byproduct furfuryl alcohol were lower (or much lower) than those of
the main product 3-(furan-2-yl-)-2-methylacrylaldehyde, indicating
other unknown reaction paths are involved in this catalytic system,
which needs to be explored further in the following research.
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CRediT authorship contribution statement
Yang Zhong: Conceptualization, Methodology, Investigation,
Writing - original draft. Bo Zhou: Investigation, Methodology. Lijun
Wang: Conceptualization, Resources, Writing – review & editing,
Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
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We greatly acknowledge the financial support from the National
Natural Science Foundation of China (Grant No. 51402195) and
Natural Science Foundation of Zhejiang Province (Grant Y20B070011).
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Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
7