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Bifunctional carbon nanoplatelets as metal-free

Cite this: DOI: 10.1039/d0cy00489h
catalysts for direct conversion of fructose to 2,5-
Received 11th March 2020,
diformylfuran†
Accepted 2nd June 2020
Jun Zhao,ab Yibo Yan,b Zhong-Ting Hu,c Vishal Jose,b
DOI: 10.1039/d0cy00489h Xiaoping Chenb and Jong-Min Lee *b
rsc.li/catalysis

Synthesis of 2,5-diformylfuran (DFF) using a carbohydrate as a DFF can be used to synthesize many useful chemicals and
raw material by dehydration to 5-hydroxymethylfurfural (HMF) polymer materials, such as fluorescent agents,3 macrocyclic
and in situ selective oxidation of HMF is important for the direct ligands,4 organic conductors5 and pharmaceuticals6 through
preparation of high value chemicals from biomass materials, to hydrogenation, oxidation, polymerization, hydrolysis, etc.7 It
avoid the energy consumption process of HMF separation and is generally prepared by the selective oxidation of the
purification. In this study, carbon nanoplatelets were prepared by hydroxyl group in HMF. Traditional oxidants, such as
a facile molten-salt method and functionalized to be the NaOCl,8 BaMnO4 (ref. 9) and pyridinium chlorochromate,10
bifunctional catalysts for the tandem reaction from fructose to have primarily been used in the oxidation process, resulting
DFF. The excellent catalytic performance of the catalysts was in a low atomic utilization rate and formation of toxic waste.
attributed to the rich oxygen-containing groups on the surface of In recent years, green oxidants, such as H2O2,11 oxygen and
the catalysts. A DFF yield of 70.3% can be achieved in a one-pot air, have been used in the synthesis of DFF from HMF in the
and one-step conversion of fructose to DFF with oxygen as the presence of various catalysts, such as Pt/C,12 Ru/C,13 Pd/C,14
only oxidant at atmospheric pressure. V2O5/TiO2,15 Cs/MnOx (ref. 16) and OMS-2.17 The DFF yield
was greatly enhanced by the use of these noble metals or
The development of green and efficient chemical technology transition-metal based catalysts. However, the large-scale
using biomass materials instead of fossil fuels to produce production of DFF was still limited by the high cost of HMF,
bulk chemicals, organic intermediates and polymer materials which is typically obtained from the dehydration of fructose
has attracted wider attention around the world which is by an acid.18 Integration of fructose dehydration with HMF
facing continuous consumption of fossil resources and oxidation in a one-pot reaction has gradually become an
increasing environmental problems. As one of the most important research topic because it can dramatically reduce
important biomass platform compounds, the production cost of DFF by avoiding the separation and
5-hydroxymethylfurfural (HMF) is an ideal intermediate for purification of HMF. An acidic catalyst for fructose
the synthesis of various chemicals due to its rich chemical dehydration and an oxidative catalyst for HMF oxidation
properties.1 The selective oxidation of HMF can produce work synergistically in the one-pot reaction process.
several kinds of furan chemicals, such as 2,5-diformylfuran Amberlyst-15 and Ru/HT,19 Fe3O4–SBA–SO3 and K-OMS-2,20
(DFF), 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), H-form cation-exchange resin and VOHPO4 (ref. 21) are such
5-formyl-2-furancarboxylic acid (FFCA) and 2,5- types of catalyst couples used in the one-pot synthesis of DFF
furandicarboxylic acid, as shown in Scheme S1.†2 from fructose. However, the two catalysts should be added
into the reaction system in phases in order to achieve a high
a DFF yield, which means that the oxidative catalyst should be
Institute of Bioresource and Agriculture, Hong Kong Baptist University, Kowloon
Tong, Hong Kong, China added after most of the fructose is converted to HMF in the
b
School of Chemical and Biomedical Engineering, Nanyang Technological presence of acidic catalysts. Otherwise, premature addition of
University, Singapore, 637459, Singapore. E-mail: [email protected] the oxidative catalyst will lead to the direct oxidation of
c
College of Environment, Zhejiang University of Technology, Hangzhou 310014, fructose, resulting in a low DFF yield. Recently, bifunctional
China
catalysts possessing both acidity and oxidability have been
† Electronic supplementary information (ESI) available: Experimental details
such as material synthesis, characterization, and reaction tests. See DOI: developed to achieve a one-pot and one-step conversion of
10.1039/d0cy00489h fructose to DFF. MOF-derived Fe3O4,22 sulfonated MoO3–

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ZrO2,23 V–g-C3N4 (H+)24 and a series of Mo-containing Keggin

heteropolyacids25–27 were prepared and applied in the one-
pot and one-step synthesis of DFF from fructose. It can be
seen that metal/metal oxides were used in all of these
catalysts, whether in a two-step or one-step process. However,
a recent study showed that graphene oxide can achieve
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metal-free catalytic conversion of fructose to DFF, avoiding

metal leaching which may affect the product quality or make
the product purification difficult.28 Since graphene, carbon
nanotubes and active carbon are well carbonized materials, a
harsh treatment method can be applied in order to enrich
the oxygen-containing functional groups, which are
responsible for the catalytic activity.29 Inspired by the acidic
and oxidative properties of graphene oxide, we herein
synthesized a low cost carbon-based catalyst bearing rich
oxygen-containing groups under relatively mild conditions.
The carbon nanoplatelets showed excellent performance in
the one-pot and one-step synthesis of DFF from fructose. Fig. 1 a) Dehydration of fructose to HMF over GN, GN-S, GN-N, GN-
Carbon nanoplatelets were synthesized by a modified NS and CNT, b) oxidation of HMF to DFF over GN, GN-S, GN-N, and
molten salt method using glucose as a carbon source and GN-NS, c) one-pot synthesis of DFF from fructose over GN, GN-S, GN-
N, GN-NS and CNT, and d) reaction monitoring of one-pot synthesis
functionalized with oxygen-containing groups, such as a of DFF from fructose over GN-NS.
carboxyl group, sulfonic acid group, or nitro group through
nitric/sulfuric acid treatment. The FTIR spectra (Fig. S3†) and
Table S2† show that GN-N treated with nitric acid has rich and HMF yield at the relatively lower reaction temperature
carboxyl groups. Sulfonic acid groups were introduced on suggested that the oxygen-containing groups in GN can
GN-S by sulfuric acid treatment. GN-NS possessed nitro promote the dehydration of fructose to HMF. The fructose
groups in addition to carboxyl groups and sulfonic acid conversion and HMF yield increased to 85.7% and 65.34%,
groups (Fig. S6†). These differences are consistent with the respectively, in the presence of GN-N. The increase can be
element analysis results of the as-synthesized catalysts. In attributed to the increase of the amount of carboxyl groups
Table S1,† it can be seen that all the carbon materials contain in GN-N by the HNO3 treatment. Further enhancement of
rich oxygen-containing groups compared with CNT. The fructose conversion and HMF yield can be achieved by the
oxygen content of the carbon materials increased catalysts treated with H2SO4. All the fructose was converted
significantly after the acid treatment. Sulfur was detected in and a HMF yield as high as 87.38% was obtained when GN-S
GN-S and GN-NS, while nitrogen was detected in GN-N and was used as the catalyst, demonstrating the high activity of
GN-S, indicating that the successful introduction of the sulfonic acid groups towards fructose dehydration to HMF.32
nitrogen group and sulfonic acid group was attributed to the Comparable fructose conversion and HMF yield were
concentrated nitric acid and sulfuric acid treatment, obtained when GN-NS was used as the catalyst. The highest
respectively.30 The increase of oxygen content was mainly HMF yield was achieved by GN-S which contains the highest
attributed to the increase of the amount of carboxyl groups. number of sulfonic acid groups but the lowest number of
The CO/CO2-TPD-MS spectra (Fig. S5†) show that the carboxyl groups (Table S2†), indicating that the sulfonic acid
sulphuric acid treatment could introduce anhydride, phenol, group is much more efficient than the carboxyl group in the
carbonyl, quinone and lactone groups, while the nitric acid fructose dehydration process.
treatment can introduce more carboxyl groups. The aerobic oxidation of HMF to DFF was conducted
The dehydration of fructose to HMF was conducted in a under similar reaction conditions to those for fructose
25 mL flask equipped with a reflux condenser. 200 mg dehydration to HMF. 0.5 mmol HMF was dissolved in 5 mL
fructose was dissolved in 5 mL DMSO to form the reaction DMSO and heated to 140 °C in the presence of 10 mg
solution. The reaction was ran at 110 °C in the presence of catalysts. Oxygen was bubbled into the reaction systems at a
10 mg catalyst. The product was analyzed by HPLC and the flow rate of 20 mL min−1. Reaction results are summarized in
results are shown in Fig. 1. It has been demonstrated in Fig. 1b. It has been reported that the carboxyl group is active
many reports that DMSO can promote the dehydration of in the catalytic oxidation of HMF to DFF,33 which can be
fructose and help to stabilize the produced HMF.31 For proved through the comparison of the catalytic performance
example, 21.6% fructose conversion and 14.7% HMF yield of GN and GN-N. A HMF conversion of 12.37% and a DFF
were obtained in 2 h at 140 °C without any catalyst, as yield of 9.83% were obtained after 19.5 h with GN as the
reported by G. Lv.28 In Fig. 1a, a fructose conversion of catalyst. The HMF conversion and DFF yield increased
73.26% and a HMF yield of 52.14% were obtained at 110 °C significantly to 41.31% and 36.25%, respectively, when GN-N
in 2 h with GN as the catalyst. The higher fructose conversion was used as the catalyst. Comparing the catalytic

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performance of GN-S and GN-N or GN, it can be found that the increase in HMF yield and decrease in DFF yield, when
sulfonic acid groups can also promote the conversion of GN-S was used as the catalyst, suggest that sulfonic acid
HMF,34 but the selectivity to DFF is not as high as that of groups can significantly promote the dehydration of fructose
carboxyl-catalyzed HMF oxidation. The highest HMF to HMF but have very limited catalytic activity in the
conversion and DFF yield were achieved by using GN-NS oxidation of HMF to DFF. A DFF yield of 40.28% was
which bears the highest amount of carboxyl groups. achieved in the presence of GN-N, showing once again the
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Therefore, the carboxyl acid groups are more active than the high catalytic activity of carboxyl groups toward the aerobic
sulfonic acid groups in promoting the conversion of HMF to oxidation of HMF to DFF. The DFF yield increased further to
DFF. 51.36% using GN-NS as the catalyst. The above reaction
It is well known that the carboxyl group and sulfonic acid results reveal that GN-NS with rich oxygen containing groups
group can be introduced in carbon materials through nitric (carboxyl group, nitro group, and sulfonic acid group) is the
acid and sulfuric acid treatment, respectively, and the best catalyst candidate for the one-pot and one-step
additional nitro group could be grafted on the carbon conversion of fructose to DFF. The lowest DFF yield was
material when it is treated with the mixture of sulfuric acid obtained by CNT due to the limited amount of carboxyl
and nitric acid. In order to confirm whether nitro groups groups on it, indicating that the as-synthesized carbon
contribute to the oxidation of HMF to DFF, a series of parallel materials are more active than CNT during the acid
experiments were conducted and the results are given in treatment.
Table 1. CS (carbon sphere) and CNT (carbon nanotube) were The one-pot and one-step reaction process was monitored
used as catalysts, respectively, for HMF oxidation. NaNO2 was by using HPLC to measure the product concentration during
chosen as the additive to the reaction mixtures to mimic the the reaction. It can be seen clearly that the reaction process
nitro groups since nitrite can adsorb on the surface of carbon can be divided into two phases in Fig. 1d. The dehydration of
materials. Both CS and CNT showed low activity toward fructose to HMF is the main reaction within the first 2 hours,
oxidation of HMF to DFF, and the addition of NaNO2 into the which is the first reaction phase. Almost all the fructose was
reaction system in the presence of CS showed no significant converted to HMF after two hours and then the aerobic
improvement, also ruling out the activity of NaNO2 dissolved oxidation of HMF to DFF becomes the main reaction, which
in the solution. However, the HMF conversion and DFF yield is the second reaction phase. The HMF yield peaked at
increased dramatically when NaNO2 was added into the 87.13% after 2 hours, and then decreased as the reaction
reaction mixture with CNT, possibly due to the conductivity progresses due to the oxidation of HMF to DFF. The DFF
difference in the two carbon materials and implying that the concentration in the reaction solution continuously increased
electron transfer in the carbon materials plays an important until the DFF yield reached 70.26% after 25 hours. The long
role in alcohol oxidation. A similar comparison experiment reaction process also led to the formation of FFCA as an over-
was reported by J. Luo et al. using CNT as the catalyst and oxidized product. The dark brown reaction solution and
NaNO2 as the additive for benzyl alcohol aerobic oxidation.35 relatively low carbon balance may be caused by the
The addition of NaNO2 did not enhance the catalytic activity degradation of HMF and fructose, forming by-products, such
in the test. In the study, the CNT was treated with HCl, rather as humic acid, levulinic acid, etc.36
than HNO3. Thus, the amount of carboxyl groups may be Based on the analysis of the reaction results and the
limited. It can be speculated that the conductive graphene reported works on graphene oxide catalyzed alcohol
sheets bearing an adequate amount of carboxyl groups can oxidation,37–39 we propose a mechanism for the direct
activate the nitro groups for the catalytic oxidation of HMF to synthesis of DFF by catalytic conversion of fructose in the
DFF. presence of GN-NS in Fig. 2. The protons ionized from
The one-pot and one-step conversion of fructose to DFF sulfonic acid groups catalyze the dehydration of fructose to
was conducted with the same reflux setup in an oil bath. 200
mg fructose was dissolved in 5 mL DMSO and reacted at 150
°C with 10 mg catalyst for 19 h. The results are summarized
in Fig. 1c. A DFF yield of 34.26% and a HMF yield of 12.77%
were obtained when GN was used as the catalyst. In contrast,

Table 1 Effect of NaNO2 on HMF oxidation

Entry Catalyst HMF conversion/% DFF yield/%

1 CS 21.5 4.8
2 CS + NaNO2 23.64 5.26
3 CNT 25.78 11.43
4 CNT + NaNO2 72.67 44.93

Reaction conditions: HMF (63 mg), catalysts (10 mg), DMSO (5 mL), Fig. 2 Mechanism of GN-NS catalyzed fructose dehydration to HMF
O2 (20 mL min−1), 140 °C, and 18 h. and HMF oxidation to DFF.

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Foundation (NRF), Prime Minister's Office, Singapore under

its Campus for Research Excellence and Technological
Enterprise program, and an AcRF Tier 1 grant (RG105/19),
Ministry of Education, Singapore. Thanks for the support
from the Institute for Advanced Materials, Hong Kong SAR.
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Conflicts of interest
There are no conflicts of interest to declare.

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