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One-pot cascade production of 2,5-diformylfuran

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Cite this: DOI: 10.1039/d2cy02017c

from glucose over catalysts from renewable
resources†
Mei Hong, * Yuxiang Liu, Haidi Sun, Liping He, Junkai Zhu, Huixian Wang,
Shifa Wang and Licheng Li*

Lignocellulosic biomass is a potential sustainable feedstock to replace fossil fuels. Utilization of

lignocellulosic biomass in a green and effective way is of great significance for sustainable development.
The direct, one-pot, one-step catalytic conversion of glucose to 2,5-diformylfuran is a challenging task. In
this work, Al(NO3)3 has been heterogeneously supported on porous carbon derived from Na-
lignosulfonate or a mixture of Na-lignosulfonate and Na-polystyrene sulfonate via ice-templating, mild
pyrolysis (350 and 450 °C) and H+ exchange techniques to obtain bifunctional carbocatalysts (Al(NO3)3@LH
or Al(NO3)3@LH–PH). The catalysts were characterized by Fourier transform infrared (FT-IR), pyridine
adsorption infrared (Py-IR), X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), field emission
scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDS) and Brunauer–
Received 25th November 2022, Emmett–Teller (BET) analyses. A novel one-step cascade method of producing DFF directly from glucose
Accepted 18th January 2023
through the binary catalyst Al(NO3)3@LH or Al(NO3)3@LH–PH with AlBr3 in 99% DFF yield without the need
for a strong oxidant is described. Mechanistic studies show that the cascade conversion of glucose involves
DOI: 10.1039/d2cy02017c
isomerization, dehydration and successive Kornblum-type oxidation. Moreover, the catalysts could be
rsc.li/catalysis reused in consecutive runs, exhibiting a slightly lower activity in the synthesis of DFF from glucose.

1. Introduction ring and two formyl groups. Thus, this compound is widely
used to produce fungicides, macrocyclic ligands, furan resins
The use of renewables for the production of energy and and novel polymers.7 A great deal of research work has been
chemicals (biorefining) has gained considerable attention in contributed to the one-pot direct conversion of fructose to
recent years due to the shrinking petroleum reserves, their 2,5-diformylfuran (DFF) in recent years.8,9 Compared with
unstable market fluctuations and environmental concerns.1 fructose, glucose is a more promising feedstock for the
Lignocellulosic biomass (lignin, hemicellulose and cellulose) production of DFF owing to its abundance and cheapness.
represents a natural renewable chemical feedstock that can However, despite great efforts only limited progress has been
be used to produce high value-added products.2–4 Substantial reported using glucose as a substrate for DFF production.10
interest is now focused on converting cellulosic sugars into Hu et al. reported the synthesis of DFF directly from glucose
furan and furan derivatives, due to their essential role in the by using a two-step procedure involving the dehydration of
degradation of lignocellulosic biomass and the possibilities of glucose by CrCl3·6H2O/NaBr under a nitrogen atmosphere
developing industrial production of valuable platform followed by filtration of CrCl3·6H2O/NaBr and air oxidation of
molecules in biorefinery engineering.5 Specifically, the the resulting HMF by NaVO3·2H2O. Thus, DFF is obtained
conversion of carbohydrates to 2,5-diformylfuran (DFF) is with an overall yield of 55%, which is the best result so far.11
considered as one of the most promising routes to the Jadhav et al. have utilized a CC–SO3H–NH2 catalyst to
synthesis of valuable chemicals from renewable biomass, synthesize DFF from glucose in 51% yield in DMSO by
because of the wide range of applications for DFF.6 As an stepwise bubbling N2 for 15 h and air for 22 h at 140 °C.12
example, DFF is a multipurpose intermediate in the synthesis Wang et al. have synthesized a multi-functional PMoV2@CP-
of high value-added chemicals because it contains one furan 5.5-400 catalyst for the one-step cascade conversion of glucose
in 51.2% DFF yield.13 Notably, these one-pot syntheses of DFF
from glucose usually require two steps and the yields are low.
College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037,
China. E-mail: [email protected]
This limitation remains a major challenge for the economic
† Electronic supplementary information (ESI) available. See DOI: https://doi.org/ feasibility of the process scale-up. The one-pot transformation
10.1039/d2cy02017c of glucose to DFF involves a three-step process including the

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isomerization of glucose to fructose by basic or Lewis acidic for one-pot, one-step synthesis of 2,5-diformylfuran (DFF)
sites, the dehydration of fructose to 5-hydroxymethylfurfural from glucose; when AlBr3 was used as a co-catalyst, they
(HMF) by acidic sites, and the oxidation of HMF to DFF by exhibited remarkable DFF yields (99%), good
redox active sites.14 During these processes, glucose rings are chemoselectivity, and good recyclability (Scheme 1).
relatively more stable than fructose rings and thereby a lower
amount of the reactive open-chain form is available for the 2. Experimental section
further dehydration reaction, so the isomerization of glucose 2.1 Materials and reagents
to fructose becomes the key intermediate and rate-limiting
step.15 Moreover, to obtain relatively high yields of DFF, the Chemicals were all of analytical grade and mostly purchased
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reactions often take place in two steps avoiding fructose from Sigma Aldrich such as: Al(NO3)3·9H2O, AlCl3·6H2O, AlBr3,
oxidation reactions into undesired products.10 There are few glucose and DMSO. Na-Lignosulfonate (Aladdin) and Na-
examples of a simplified one-pot, one-step conversion of polystyrene sulfonate (M.W. 80 000, Shanghai Macklin
glucose to DFF. Therefore, novel catalysts with well-designed Biochemical Co., Ltd) were obtained from commercial sources.
compositions and structures tailored to the requirements of a All the reagents were utilized without further pretreatment.
particular application are essential to producing DFF from
glucose efficiently and economically. 2.2 Preparation of lignosulfonate-derived carbon-supported
Recently, there has been great interest in exploiting and catalysts
developing heterogeneous catalysts derived from high-volume LH and LH–PH were prepared from Na-lignosulfonate
renewable resources to enhance the overall sustainability of according to modified Konwar's work,18 which were used as
catalytic processes because of the high production cost of the support for the immobilization of Al(NO3)3, AlBr3 or
traditional catalysts.16 Apart from their high activity during Al(NO3)3–AlBr3 to obtain the samples Al(NO3)3@LH,
reactions, the heterogeneous catalysts derived from Al(NO3)3@LH–PH, AlBr3@LH, and Al(NO3)3–AlBr3@LH. In a
renewable resources especially solid wastes could be typical process, 5 g Na-lignosulfonate was dissolved in a
synthesized cheaply, which further reduces the cost of DFF mixture of 10 mL deionized water/acetonitrile (3 : 1, v : v),
production.17 Lignosulfonate is a derived product of lignin transferred to a 40 mL freeze drying flask and submerged in
via the sulfite process and contains sulfonic acid groups at a dry ice/acetone cooling bath (−78 °C) for 30 min. The frozen
aliphatic carbons. In the current market, the scope of samples were freeze-dried for 24 h using a freeze dryer to give
lignosulfonate is limited to a handful of applications (cement dry Na-lignosulfonate. In another instance, Na-lignosulfonate
industry, animal husbandry, mineral processing) and sold in was substituted with 20% Na-polystyrene sulfonate. In the
bulk, at low margins. The high level of S content renders the next step, the freeze-dried Na-lignosulfonate was subjected to
chemical processing of lignosulfonate challenging, mild pyrolysis at a temperature of 350 °C and Na-
nonetheless, it has been chemically processed into useful lignosulfonate/Na-polystyrene sulfonate at a temperature of
products such as dimethyl sulfide, dimethyl sulfoxide and 450 °C; the heating rate, holding time and N2 flow rate were
vanillin.18 On the other hand, the presence of naturally fixed at 30 °C min−1, 1 h and 50 mL min−1, respectively. The
occurring –SO3Na groups makes lignosulfonate an excellent solid products (designated as LS and LS–PS) from pyrolysis
raw material for the synthesis of acidic catalysts and/or acid experiments were ground to powder and protonated by ion-
exchange materials through ion/H+ exchange. H+ exchanged exchange with 2 M H2SO4 (100 mL acid per g solid) at room
lignosulfonate has been heterogenized by phenol- temperature for 24 h. The protonated products (designated
formaldehyde type condensation reactions.19–23 However, as LH and LH–PH) were filtered and thoroughly washed with
irrespective of their excellent properties as an acidic catalyst a mixture of deionized water and acetone (8 : 1, v : v) at 80 °C
material, the aforementioned lignosulfonate or (until the pH of the filter liquor was neutral) and dried at 100
lignosulfonate-based materials have several drawbacks such °C overnight. Supported aluminum catalysts were prepared
as poor thermal and mechanical stability, thus limiting their by using the impregnation method. The unprotonated or
applicability as solid catalysts. Also, they do not possess protonated solid was slowly stirred in an ethanol solution of
textural properties of an ideal heterogeneous catalyst such as Al(NO3)3, AlBr3 or Al(NO3)3–AlBr3 mixture (molar ratio 1 : 1)
high specific surface area, well defined porosity, etc. for 12 hours, followed by rotary evaporation. The obtained
Commercial ion exchange sulfonic resins, such as Amberlyst solid was further washed several times with absolute ethanol
and Amberlite IR 120, are cost ineffective and thermally and freeze-dried for 12 hours to obtain Al(NO3)3@LS,
unstable under harsh conditions.24 These factors render the
scale-up of an ion exchange resin-based process from the
laboratory to industrial scale difficult.
Keeping the above in mind, Al(NO3)3 supported on Na-
lignosulfonate derived meso/macroporous solid sulfonic
carbon materials by ice-templating,25 mild pyrolysis (350 and
450 °C) and H+ exchange named Al(NO3)3@LH–PH and
Al(NO3)3@LH were studied as bifunctional solid acid catalysts Scheme 1 Conversion of glucose to 2,5-diformylfuran.

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AlBr3@LS, Al(NO3)3@LH, AlBr3@LH, Al(NO3)3–AlBr3@LH and by HPLC or DFF was isolated from flash chromatography
Al(NO3)3@LH–PH. (SiO2, petroleum ether/EtOAc, 5 : 1).

2.3 Catalyst characterization 2.6 Product analysis

FT-IR spectra were recorded with a Nicolet 380 FT-IR HMF and DFF were analyzed with HPLC (Agilent 1200) using
instrument. TGA and differential thermal analyses were a reversed-phase C18 column (250 × 4.6 mm) at 30 °C with a
carried out with a TG 209F1 thermal analyzer under a detection wavelength of 280 nm. The mobile phase was
nitrogen atmosphere at a heating rate of 10 °C min−1. FE- acetonitrile and 0.1 wt% acetic acid aqueous solution (65 : 35,
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SEM was conducted using a Regulus 8100. The FE-SEM was v : v) at 0.5 mL min−1. The conversions of glucose were
equipped with an EDS instrument (Oxford Ultim Max 170). analyzed with HPLC (Agilent 1260 Infinity) using a
Powder XRD patterns of Al(NO3)3@LH and Al(NO3)3@LH–PH ChromCore Sugar-10H column (Nano Chrom Technologies
were recorded with a Rigaku D/Max 2400 X-ray diffractometer Co., Ltd. Suzhou) and a refractive index detector. 0.005 M
using Cu Kα (λ = 0.15406 nm) radiation. XPS spectra were H2SO4 solution was used as the mobile phase at a flow rate
recorded with a Kratos Axis Ultra DLD spectrometer, and the of 0.6 mL min−1, and the temperatures of the column and
binding energy was calibrated using the C 1s peak. The the detector were 60 °C and 35 °C, respectively. The amounts
contents of aluminum in Al(NO3)3@LH and Al(NO3)3@LH– of HMF and DFF in the samples were calculated by
PH were quantitatively determined using inductively coupled interpolation from calibration curves. Calibration curves for
plasma mass spectrometry (ICP-MS) on a Perkin-Elmer the observed products were constructed by injecting known
Instruments Optima 2000 DV spectrometer and the loading concentrations of commercial reference products. The yields
was found to be 3.12 and 3.56 mmol g−1, respectively. The of products are defined as follows:
specific surface area (SBET) values of the samples were
measured on an Autosorb-iQ instrument through N2 Yield of HMF (mol%)
adsorption–desorption isotherms at 77 K using the = (mole of HMF produced)/(mole of starting glucose) × 100%
Brunauer–Emmett–Teller (BET) method. Pyridine adsorption
infrared (Py-IR) measurements were performed on a Nicolet Yield of DFF (mol%)
6700 spectrometer device equipped with a diffuse reflectance = (mole of DFF produced)/(mole of starting glucose) × 100%
attachment and an MCT detector. The tested powders were
placed into an in situ chamber and smoothed. Initially, the Conversion of glucose (mol%)
powders were pretreated with He (30 mL min−1) at 300 °C for = (1‐mole of unreacted glucose/mole of starting glucose) × 100%
1 h, cooled down to room temperature and scanned for the
background. Thereafter, gaseous pyridine was adsorbed on 3. Results and discussion
the powders until adsorption saturation. He was injected into
the in situ chamber and purged the powders for 1 h. Finally, 3.1 Catalyst characterization
the infrared spectrum in the region from 1600 cm−1 to 1400 The catalysts were systematically characterized by Fourier
cm−1 could be recorded. The amounts of acid groups on the transform infrared spectroscopy (FT-IR), X-ray diffraction
catalyst surface were measured using a titration method as (XRD), field emission scanning electron microscopy (FE-
described in previous work26 (see section 1 in the ESI†). SEM), energy dispersive X-ray spectroscopy (EDS), X-ray
photoelectron spectroscopy (XPS), thermogravimetric analysis
2.4 General procedure for the synthesis of HMF from glucose (TGA), Brunauer–Emmett–Teller isotherms (BET), inductively
coupled plasma optical emission spectroscopy (ICP-MS) and
The synthesis of HMF from glucose was carried out in a 25 pyridine adsorption infrared (Py-IR). The FT-IR spectra
mL test tube. Typically, glucose (1 mmol), DMSO (2 mL) and (Fig. 1) showed characteristic peaks at around 1147 and 1090
the catalyst were added into the reactor and the reaction cm−1 for SO3− stretching vibration.27 The samples also had a
mixture was heated (oil bath 140 °C) for 5 h. The products
were quantitatively analyzed by HPLC.

2.5 General procedure for the synthesis of DFF from glucose

The synthesis of DFF from glucose was carried out using the
same procedure with the addition of AlBr3 and the reaction
time was extended to 24 h. After cooling to room
temperature, the mixture was diluted with EtOAc (50 mL).
The organic phase was washed with H2O (3 × 20 mL). The
combined aqueous phases were extracted with EtOAc (20
mL). The combined organic phases were dried over Na2SO4, Fig. 1 FT-IR spectra of various (a) LS and (b) LS–PS monolith derived
and then filtered. The products were quantitatively analyzed carbon samples.

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Fig. 2 XRD patterns of Al(NO3)3@LH and Al(NO3)3@LH–PH.

Fig. 4 Representative TGA patterns showing the thermal stability of
Al(NO3)3@LH and Al(NO3)3@LH–PH.
band at about 530 cm−1, which arose from the C–S bond
vibration of the sulfonic group, due to the presence of
sodium sulfite or sodium bisulfite in the sulfite pulping Thermogravimetric analysis (TGA) of Al(NO3)3@LH and
process.28 They indicated the presence of sulfonic acid Al(NO3)3@LH–PH was performed to evaluate the stability of
groups on the surface of the catalysts. The typical absorption the catalysts. High temperature stability is necessary to utilize
peaks in the range of 1400 to 1621 cm−1 are assigned to the the catalysts, because the conversion of glucose to DFF
aromatic skeletal vibrations.22 requires heating, and catalysts are required to remain stable
The XRD patterns (Fig. 2) of the Al(NO3)3@LH and in the range of the reaction temperature to ensure catalyst
Al(NO3)3@LH–PH catalysts displayed a very weak (101) graphitic activity and recyclability. The TGA curves in Fig. 4 exhibit that
structure peak near 2θ = 35–50° and two broadened (002) all the lignosulfonate samples started decomposition over
diffraction peaks centered at 2θ = 10° and 23°, corresponding to 200 °C, which guaranteed the stability of the lignin-based
an amorphous carbon structure composed of aromatic carbon catalysts under our reaction conditions. These findings
sheets oriented in a considerably random fashion.8 suggested that our prepared catalysts were quite suitable for
From XPS analysis of the Al(NO3)3@LH catalyst, S 2p the catalytic research.
(Fig. 3a) can be deconvoluted into two adjacent peaks S 2p1/2 The Brunauer–Emmett–Teller (BET) surface areas were
(163.5 eV) and S 2p3/2 (164.9 eV), which reveals the presence determined by N2 adsorption to be 106.7 m2 g−1, 131.8
of C–S bonds in the material.29 Also, based on the S 2p m2 g−1, 15.6 m2 g−1 and 32.8 m2 g−1 for LH, LH–PH,
spectrum (Fig. 3b), the peak at 164.2 eV belongs to the C–S–C Al(NO3)3@LH and Al(NO3)3@LH–PH, respectively. After
bond.30 The signal at approximately 169 eV in the XPS loading Al(NO3)3, both the BET surface areas of Al(NO3)3@LH
spectra for S 2p evidently can indicate the presence of and Al(NO3)3@LH–PH decreased sharply. From the acidity
sulfonic acid groups in both Al(NO3)3@LH and measurement results compiled in Table 1, it can be seen that
Al(NO3)3@LH–PH.31 The Al 2p spectra (Fig. 3c and d) have a these carbon materials exhibit acidity (total acidity) in the
signal at 74.8 eV, which supports the presence of Al3+.32 range of 3.12–4.31 mmol g−1. The gravimetric density of the
–SO3H groups in Al(NO3)3@LH and Al(NO3)3@LH–PH was
calculated through acid–base titrations. Table 1 presents that
the sulfonic acid groups determined using NaCl were 1.07
and 2.51 mmol g−1 for the Al(NO3)3@LH and Al(NO3)3@LH–
PH catalysts, respectively.
Further investigation of the Al(NO3)3@LH and
Al(NO3)3@LH–PH samples by FE-SEM images revealed that
the carbon materials as catalyst supports possessed a smooth
surface structure made up of pores and there were depositing
particles on the carbon support after supporting Al(NO3)3
(Fig. 5). The energy dispersive spectroscopy (EDS) elemental
(Al and S) mapping analysis showed that the Al metal and
–SO3H were evenly distributed on the catalyst surface (Fig. 6).
To gain more insights into the Lewis and Brønsted acidic
sites of the catalysts, pyridine-adsorbed FT-IR spectra were
obtained at a desorption temperature of 200 °C under
vacuum conditions. As can be seen from Fig. 7, both
Al(NO3)3@LH and Al(NO3)3@LH–PH exhibited bands at 1540
cm−1 due to the pyridine that has been adsorbed on the
Fig. 3 XPS spectra of the S 2p and Al 2p regions for the (a and c) Brønsted acid sites, at 1445 cm−1 and 1597 cm−1 due to the
Al(NO3)3@LH and (b and d) Al(NO3)3@LH–PH catalysts. pyridine that has been adsorbed on the Lewis acid sites, and

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Table 1 The surface properties of the catalysts

Samples –SO3H (mmol gcat−1) –COOH (mmol gcat−1) –OH (mmol gcat−1) Total (mmol gcat−1) BET (m2 g−1)
Al(NO3)3@LH 1.07 0.78 1.27 3.12 15.6
Al(NO3)3@LH–PH 2.51 0.83 0.97 4.31 32.8

at 1490 cm−1 attributed to the pyridine that has been glucose to HMF. Then tests were conducted to study the
adsorbed on both the Lewis and Brønsted acid sites. The catalytic performance of other aluminum salts and metal
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Lewis acid sites should originate from the Al centers and the nitrates (Table 2, entries 3–9). In the presence of metal
Brønsted acid sites should arise from the –SO3H in the nitrates, such as Fe(NO3)3·9H2O and Zn(NO3)2·6H2O, HMF
molecular structure of Na-lignosulfonate or Na-polystyrene was obtained in yields of less than 16.1%. The reaction yield
sulfonate. reached 68% and 56.8% using AlCl3·6H2O and Al2(SO4)3 as
catalysts, respectively. No DFF was produced using the above-
mentioned metal salts as catalysts. When AlBr3 was used as a
3.2 One-step synthesis of DFF from glucose catalyst, HMF and DFF were obtained in 45 and 11.2% yields,
Before the catalysis of the conversion of glucose into DFF, the respectively, under identical conditions (Table 2, entry 7).
conversion of glucose into HMF was tested. Initial Reducing the reaction time to 3 h resulted in an increase in
experimentation was undertaken in DMSO by using glucose the HMF yield of 54.2% with a 2% DFF yield. As the reaction
and 5 mol% of Al(NO3)3·9H2O, the mixture being heated at time was further reduced to 1 h, an HMF yield of 40.5% with
140 °C for 5 h. As shown in Table 2, an HMF yield of 78.7% no DFF was achieved. It seems that the Br anion was active
was achieved under the initial conditions. A control in targeted oxidation of HMF to DFF.
experiment without a catalyst revealed that only 3% yield of After the above studies on the conversion of glucose to
HMF was achieved. These results imply that the added HMF, various metal nitrates and bromide salts were further
Al(NO3)3·9H2O can act as a catalyst in the conversion of evaluated as catalysts for the one-pot synthesis of DFF from
glucose in DMSO. When the reaction time was extended to
24 h, the blank run without a catalyst showed that an HMF
yield of 34.1% and a DFF yield of 5.9% were obtained,
indicating the dominating reaction of isomerization and
dehydration induced by DMSO. The formation of a small
amount of DFF was deemed to mainly result from the aerobic
oxidation of HMF at atmospheric pressure. In contrast,
Al(NO3)3·9H2O (10 mol%) provided a 60.6% HMF yield along
with a 3.6% DFF yield and AlBr3 (10 mol%) provided a DFF
yield of 64.5%. The results further suggest that AlBr3 is active
in the oxidation of HMF to DFF. Thus it is reasonable to
speculate that the conjunction of Al(NO3)3·9H2O and AlBr3
would fabricate an effective catalytic system for the
conversion of glucose into DFF. Table 2 shows the
performance of the binary catalyst Al(NO3)3·9H2O with AlBr3
in the one-pot and one-step conversion of glucose into DFF
Fig. 5 FE-SEM images of (a) LH, (b) Al(NO3)3@LH, (c) LH–PH and (d) under different conditions. The reaction temperature
Al(NO3)3@LH–PH. demonstrated a remarkable effect on the catalytic

Fig. 6 EDS elemental (Al and S) mapping of (a) Al(NO3)3@LH and (b)
Al(NO3)3@LH–PH. Fig. 7 Py-IR spectra of Al(NO3)3@LH and Al(NO3)3@LH–PH.

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Table 2 One-step synthesis of HMF or DFF from glucosea

Yieldb (%)
Entry Catalyst (mol%) T (°C) Solvent t (h) HMF DFF
1 Blank 140 DMSO 5 3 n.d.
2 Al(NO3)3·9H2O(5) 140 DMSO 5 78.7 n.d.
3 Fe(NO3)3·9H2O(5) 140 DMSO 5 2 n.d.
4 Zn(NO3)2·6H2O(5) 140 DMSO 5 16.1 n.d.
5 AlCl3·6H2O(5) 140 DMSO 5 68 n.d.
6 Al2(SO4)3(5) 140 DMSO 5 56.8 n.d.
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7 AlBr3(5) 140 DMSO 5 45 11.2

8 AlBr3(5) 140 DMSO 3 54.2 2
9 AlBr3(5) 140 DMSO 1 40.5 n.d.
10 Blank 140 DMSO 24 34.1 5.9
11 Al(NO3)3·9H2O(10) 140 DMSO 24 60.6 3.6
12 AlBr3(10) 140 DMSO 24 n.d. 64.5
13 Al(NO3)3·9H2O(5) + AlBr3(5) 140 DMSO 24 2.3 57.1
14 Al(NO3)3·9H2O(5) + AlBr3(5) 130 DMSO 24 37.7 22.8
15 Al(NO3)3·9H2O(5) + AlBr3(5) 150 DMSO 24 0 85.9
16 Al(NO3)3·9H2O(5) + AlBr3(8) 140 DMSO 24 2.5 63.8
17 Al(NO3)3·9H2O(5) + AlBr3(10) 140 DMSO 24 n.d. 81.3
18 Al(NO3)3·9H2O(8) + AlBr3(5) 140 DMSO 24 7.5 56
19 Al(NO3)3·9H2O(10) + AlBr3(5) 140 DMSO 24 14.9 57.4
20 Al(NO3)3·9H2O(10) + AlBr3(10) 140 DMSO 24 n.d. 99
21 AlCl3·6H2O(10) + AlBr3(10) 140 DMSO 24 1 82.7
22 Al2(SO4)3(10) + AlBr3(10) 140 DMSO 24 5.8 32.8
23 Fe(NO3)3·9H2O(10) + AlBr3(10) 140 DMSO 24 1.8 46.8
24 Cu(NO3)2·3H2O(10) + AlBr3(10) 140 DMSO 24 1.2 58.1
25 Zn(NO3)3·6H2O(10) + AlBr3(10) 140 DMSO 24 9.7 37.6
26 Bi(NO3)3·5H2O(10) + AlBr3(10) 140 DMSO 24 22.1 3.5
27 Al(NO3)3·9H2O(10) + NaBr(10) 140 DMSO 24 10 41.1
28 Al(NO3)3·9H2O(10) + KBr(10) 140 DMSO 24 10 63
29 Al(NO3)3·9H2O(10) + CuBr2(10) 140 DMSO 24 2.3 35.4
30 Al(NO3)3·9H2O(10) + HBr(10) 140 DMSO 24 9.7 43.1
31 Al(NO3)3·9H2O(10) + Et4NBr(10) 140 DMSO 24 17 46
a
Reaction conditions: glucose 180 mg. n.d.: not detected. b Yields determined by HPLC analysis.

performance of Al(NO3)3·9H2O and AlBr3 for the conversion 3.3 Heterogenization of Al(NO3)3
of glucose to DFF from 130 to 150 °C (Table 2, entries 13–15).
When the reaction was performed at 130 °C for 24 h, a low Having demonstrated that the Al(NO3)3–AlBr3 catalytic
yield (22.8%) of DFF was obtained. The yield of DFF system was very convenient for the one-pot one-step
dramatically increased to 85.9% as the reaction temperature conversion of glucose to DFF, we next investigated the
was increased to 150 °C. Since DMSO disproportionation catalytic ability of lignosulfonate-based catalysts for the
occurs at 150 °C,33 yielding Me2S and Me2SO2, the formation tandem reaction. The presence of sulfonic acid groups in
of these impurities complicates the DFF purification. lignosulfonate derived acidic carbon (LH) prompted us to
Considering the increasing energy consumption and the explore LH-supported Al(NO3)3 as a solid acid catalyst for
difficulties in the product isolation, 140 °C was chosen as the glucose dehydration. Lignosulfonate-derived acidic carbon-
optimum reaction temperature. The results indicate that the supported Al(NO3)3 samples were synthesized through ice-
dosage of the two catalyst components also affects the templating, mild pyrolysis (350 and 450 °C), H+ exchange
reaction (Table 2, entries 16–20). The excellent DFF yield of and impregnation methods. HMF was obtained in 46.1%
99% is superior to all the previous catalytic systems in a one- yield at 140 °C in 5 h with Al(NO3)3@LS as the catalyst
pot and one-step conversion of glucose into DFF. (Table 3, entry 1). The HMF yield increased to 52.4% in the
In order to confirm whether the synergistic effect between presence of Al(NO3)3@LH. Apparently, the enhanced
aluminum salts (or metal nitrates) and bromides contributes catalytic activity of Al(NO3)3@LH may originate from the
to the direct synthesis of DFF from glucose, a series of acidity of sulfonic acid groups. LH and LH–PH afforded a
parallel experiments were conducted and the results are given very low HMF yield of 6.8% and 8.3%, respectively, because
in Table 2. The presence of a synergistic promoting of the lack of Lewis acid sites in their structures. The
interaction between Al(NO3)3·9H2O and AlBr3 was of vital dehydration of glucose into HMF is regarded as a two-step
importance in affecting the catalytic performance in the tandem reaction, and the isomerization of glucose into
conversion of glucose to DFF. The mixture of AlCl3·6H2O and fructose is the vital step. Al(NO3)3, an aluminum salt, can
AlBr3 was less efficient. act as a Lewis acid, which plays an important role in this

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Table 3 One-step synthesis of HMF and DFF from glucose using heterogeneous Al(NO3)3 catalystsa

Yield (%)
Entry Catalyst t (h) Solvent HMFb DFF
1 Al(NO3)3@LS (20 mg) 5 DMSO 46.1 n.d.
2 Al(NO3)3@LH (20 mg) 5 DMSO 52.4 n.d.
3 LH (20 mg) 5 DMSO 6.8 n.d.
4 LH–PH (20 mg) 5 DMSO 8.3 n.d.
5 Al(NO3)3@LH (30 mg) 5 DMSO 57 n.d.
6 Al(NO3)3@LH (40 mg) 5 DMSO 67.3 n.d.
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7 Al(NO3)3@LH–PH (20 mg) 5 DMSO 63.2 n.d.

8 Al(NO3)3–AlBr3@LH (60 mg) 24 DMSO 13.8 22.8
9 Al(NO3)3@LH (30 mg) + AlBr3@LS (30 mg) 24 DMSO 55.3 20
10 AlBr3@LH (30 mg) 24 DMSO 2.3 45.8
11 AlBr3@LH (80 mg) 24 DMSO 1.2 53.7
12 Al(NO3)3@LH (40 mg) + AlBr3 (8 mol%) 24 DMSO n.d. 99(89)c
13 Al(NO3)3@LH–PH (25 mg) + AlBr3 (8 mol%) 24 DMSO n.d. 99
14 Al(NO3)3@LH (40 mg) + AlBr3 (5 mol%) 24 DMSO 24.8 53.0
15 Al(NO3)3@LH (35 mg) + AlBr3 (8 mol%) 24 DMSO 1.3 86.6
16 Al(NO3)3@LH–PH (20 mg) + AlBr3 (8 mol%) 24 DMSO n.d. 87.8
17d Al(NO3)3@LH–PH (20 mg) + AlBr3 (8 mol%) 24 DMSO n.d. 89.5
18e Al(NO3)3@LH (40 mg) + AlBr3 (8 mol%) 24 DMSO 7.8 62
19 f Al(NO3)3@LH (40 mg) + AlBr3 (8 mol%) 24 DMSO 3.4 62.9
20e Al(NO3)3@LH–PH (25 mg) + AlBr3 (8 mol%) 24 DMSO 4.4 69.5
21 f Al(NO3)3@LH–PH (25 mg) + AlBr3 (8 mol%) 24 DMSO 9.6 63.8
22 Al(NO3)3@LH (40 mg) + AlBr3 (8 mol%) 16 DMSO 10.1 49.9
23 Al(NO3)3@LH (40 mg) + AlBr3 (8 mol%) 18 DMSO 6.7 68.5
24 Al(NO3)3@LH (40 mg) + AlBr3 (8 mol%) 20 DMSO 2.1 85.2
25 Al(NO3)3@LH (40 mg) + AlBr3 (8 mol%) 22 DMSO 0.7 93.8
26 Al(NO3)3@LH (40 mg) + AlBr3 (8 mol%) 23 DMSO n.d. 97
27 Al(NO3)3@LH–PH (25 mg) + AlBr3 (8 mol%) 3 DMSO 68.2 (87.1) 5.8
28 Al(NO3)3@LH–PH (25 mg) + AlBr3 (8 mol%) 5 DMSO 72.6 (90.6) 11.4
29 Al(NO3)3@LH–PH (25 mg) + AlBr3 (8 mol%) 10 DMSO 60.9 (95.3) 29.3
30 Al(NO3)3@LH–PH (25 mg) + AlBr3 (8 mol%) 12 DMSO 18.4 57.8
31 Al(NO3)3@LH–PH (25 mg) + AlBr3 (8 mol%) 15 DMSO 36.6 (96.1) 53.3
32 Al(NO3)3@LH–PH (25 mg) + AlBr3 (8 mol%) 18 DMSO 10 81.2
33 Al(NO3)3@LH–PH (25 mg) + AlBr3 (8 mol%) 20 DMSO 6.8 87
34 Al(NO3)3@LH–PH (25 mg) + AlBr3 (8 mol%) 21 DMSO 7.7 89.9
35 Al(NO3)3@LH–PH (25 mg) + AlBr3 (8 mol%) 22 DMSO 4.9 (100) 93.2
36 Amberlite IR 120 H (25 mg) + AlBr3 (8 mol%) 24 DMSO 2 43
37 Al(NO3)3@Amberlite IR 120 H (25 mg) + AlBr3 (8 mol%) 24 DMSO 2 27
38 Al(NO3)3@LH–PH (25 mg) + AlBr3 (8 mol%) 24 GVL 1 3.5
39 Al(NO3)3@LH–PH (25 mg) + AlBr3 (8 mol%) 24 GBL 2 3
40 Al(NO3)3@LH–PH (25 mg) + AlBr3 (8 mol%) 24 MIBK n.d. n.d.
a
Reaction conditions: glucose 180 mg, 140 °C, solvent (2 mL). b Conversions of glucose are given in parentheses. c
Yield of the isolated
product is given in parentheses. d An oxygen balloon. e Glucose 270 mg. f Glucose 360 mg. n.d.: not detected.

step. 57% and 67.3% HMF yields were achieved when the optimizing the catalytic system, the effect of catalyst loading
Al(NO3)3@LH catalyst was 30 mg and 40 mg, respectively. was studied. Upon using Al(NO3)3@LH (40 mg) in
20 mg of the Al(NO3)3@LH–PH used resulted in an HMF conjunction with AlBr3 (8 mol%), DFF was obtained in 99%.
yield of 63.2%, suggesting that the supports significantly The same result was achieved by using a mixture of
affect the activity. The superior activity shown by Al(NO3)3@LH–PH (25 mg) and AlBr3 (8 mol%). Next, the
Al(NO3)3@LH–PH in terms of the yield of HMF may be amount of catalyst was reduced to check the impact on the
ascribed to the fact that it has a larger surface area and yield of DFF. The reduction of Al(NO3)3@LH, Al(NO3)3@LH–
higher contents of –SO3H and Al3+. PH and AlBr3 amounts to 35 mg, 20 mg and 5 mol%,
Next, lignosulfonate derived carbon-supported catalysts respectively, obviously resulted in a decrease of the yield of
were used as the catalysts in the one-pot and one-step DFF (Table 3, entries 14–16). It seems that 40 mg of
synthesis of DFF from glucose. The reaction was performed Al(NO3)3@LH or 25 mg of Al(NO3)3@LH–PH with 8 mol%
over Al(NO3)3–AlBr3@LH, mixed Al(NO3)3@LH and AlBr3@LS, AlBr3 is a favorable catalyst loading for such a sequential or
and AlBr3@LH systems, where DFF was obtained in yields of tandem reaction. The tolerance for the concentration of
less than 53.7%. Thus the one-step conversion of glucose to feedstock is an important aspect to evaluate a catalytic
DFF was conducted with a mixture of Al(NO3)3@LH or conversion process from an economical point of view. Thus
Al(NO3)3@LH–PH and AlBr3 as catalysts. With the aim of the effect of initial glucose concentrations including 7.6 wt%,

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10.9 wt% and 14.1 wt% on the conversion of glucose to DFF

was investigated. Increasing the concentration of glucose
from 7.6 to 10.9 wt% had a negative impact on the yield of
DFF, whereas a further increase of the concentration to
14.1% had no clear influence on the DFF yield (Table 3,
entries 18–21). The reaction time was varied to find the
Fig. 8 Proposed mechanisms for the oxidation step.
optimal reaction conditions for the conversion of glucose to
DFF. As shown in Table 3, with Al(NO3)3@LH as the catalyst,
the DFF yield increased from 49.9% to 97% when the
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reaction time increased from 16 to 23 h (Table 3, entries 22– 5-methylsulfanylmethyl-furan-2-carbaldehyde (MSMFC) was the
26), respectively. A kinetic study was performed over the intermediate,35,36 therefore, we prepared MSMFC according to
Al(NO3)3@LH–PH catalyst by monitoring glucose conversion the method by Rode37 (see section 4 in the ESI†) and
and HMF/DFF yields as functions of time (Fig. S1†). The DFF investigated its reactivity in DMSO. However, under identical
yield increased from 5.8% to 93.2% when the reaction time conditions, MSMFC led to no production of DFF (Scheme 2b).
increased from 3 to 22 h (Table 3, entries 27–35), respectively. Thus, based on the findings, a mechanism was proposed for
In the case of glucose, the conversion increases sharply in the oxidation step.33 Initially, protonation of the alcohol group
the first 3 h. After 3 h of reaction, 87.1% glucose conversion of HMF by HBr led to the formation of the neutral intermediate
was achieved, and this parameter seems to increase slowly (BMF), which would undergo nucleophilic addition of DMSO.
(Table 3, entries 27–29, 31 and 35). Intramolecular deprotonation of a hydrogen atom led to DFF
For comparison, Al(NO3)3 supported on Amberlite IR 120 and Me2S (Fig. 8).
H (Al(NO3)3@Amberlite IR 120 H) via electrostatic
interactions was prepared by the same impregnation method
as in the preparation of Al(NO3)3@LH–PH. We explored the 3.4 Recycling of the catalysts
activity of the commercial resin Amberlite IR 120 H and In the final set of experiments, we further assessed the
Al(NO3)3@Amberlite IR 120 H for the conversion of glucose stability and reusability of the Al(NO3)3@LH and
into DFF (Table 3, entries 36 and 37), and they displayed Al(NO3)3@LH–PH catalysts in the one-pot, one-step
inferior catalytic performance. conversion of glucose to DFF, because it is crucial to confirm
Finally, to collect information on the role of DMSO, other that the highly active catalysts are recyclable. As shown in
solvents such as gamma-valerolactone (GVL), gamma Fig. 9, there was a drop in the DFF yield to about 10% in the
butyrolactone (GBL), and methyl isobutyl ketone (MIBK) were second run. However, the decrease in activity loss becomes
tested in the presence of Al(NO3)3@LH–PH and AlBr3, but they smaller with the number of runs. The ICP analysis of the
all led to only trace amounts (<4%) of HMF and DFF (Table 3, filtrate after the catalytic reaction showed a 9% and 7% loss
entries 38–40). Moreover, there was a minimal impact on the of Al in the catalysts Al(NO3)3@LH and Al(NO3)3@LH–PH,
DFF yield when this transformation was conducted under an respectively. These losses could be caused by the leaching of
oxygen atmosphere (Table 3, entries 16 and 17). Therefore, we Al from the catalysts and the losses of the very fine particles
speculated that this transformation should occur through the of Al(NO3)3@LH and Al(NO3)3@LH–PH due to the stirring
formation of 5-(bromomethyl)furan-2-carbaldehyde (BMF), during the recycling reaction. At the same time, the inevitable
followed by a Kornblum-type reaction.34 To test the hypothesis, loss of some catalysts during the recycling operation was
we isolated the intermediate, and the corresponding NMR another reason behind the decrease of the DFF yield. In spite
analysis (Fig. S2 and S3†) further confirmed the structure.
Furthermore, to understand the role of BMF as the
intermediate in the reaction mechanism, we performed a
reaction of BMF under the established protocol. Surprisingly,
we obtained DFF up to 99% yield (Scheme 2a) which clearly
indicated that BMF was the intermediate for the DFF
formation. In some of the documented results,

Fig. 9 Reusability of Al(NO3)3@LH and Al(NO3)3@LH–PH for the one-

pot, one-step synthesis of DFF from glucose (40 mg Al(NO3)3@LH or
25 mg Al(NO3)3@LH–PH, 8 mol% AlBr3, 140 °C reaction temperature,
Scheme 2 Reactions of (a) BMF and (b) MSMFC in DMSO. and 2 mL DMSO).

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