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Catalytic oxidation of carbohydrates into organic

acids and furan chemicals
Cite this: Chem. Soc. Rev., 2018,
47, 1351
Zehui Zhang *a and George W. Huber *b

Received 23rd March 2017
DOI: 10.1039/c7cs00213k
rsc.li/chem-soc-rev
A wide variety of commodity chemicals can be produced from the catalytic oxidation of carbohydrates
or carbohydrate derived molecules including formic acid, acetic acid, glycolic acid, gluconic acid,
glucaric acid, malonic acid, oxalic acid, 2,5-diformylfuran (DFF), 5-hydroxymethyl-2-furancarboxylic acid
(HFCA), 5-formyl-2-furancarboxylic acid (FFCA), and 2,5-furandicarboxylic acid (FDCA). This review will
highlight the recent research progress in the development of new routes for the production of organic
acids and furan compounds via catalytic oxidation reactions. Particular attention will be paid to these
one-pot reactions with the requirements of an acidic site and a metal site. For the one-pot
transformation of cellobiose or lignocellulose into gluconic acid, these reactions were performed via a
one-step strategy using a single catalyst containing an acidic site and a metal site. However, a two-step
strategy was adopted for the oxidative transformation of carbohydrates into DFF or FDCA in order
to avoid the oxidation of the carbohydrates. The first step was performed for the dehydration of
carbohydrates into 5-hydroxylmethylfuran (HMF) in the presence of an acid catalyst, and the second
step was performed for the oxidation of HMF into DFF or FDCA with a metal catalyst.

1. Introduction
Biomass typically contains 40–45% weight percent of oxygen.1
a
Key Laboratory of Catalysis and Material Sciences of the State Ethnic Affairs In the petrochemical industry a wide range of commodity
Commission & Ministry of Education, College of Chemistry and Material Sciences,
chemicals are produced via selective oxidation of petroleum
South-Central University for Nationalities, Wuhan, 430074, China.
E-mail: zehuizh@mail.ustc.edu.cn
derived feedstocks. These molecules could potentially be more
b
Department of Chemical and Biological Engineering, University of inexpensively produced from biomass, because it is typically
Wisconsin-Madison, Madison, WI 53706, USA. E-mail: huber@engr.wisc.edu more economical to remove oxygen from a molecule than add

Professor Zehui Zhang obtained his George W. Huber is the Harvey

PhD degree at Dalian Institute of
Chemical Physics (DICP) in 2011,
Chinese Academy of Science. After
that, he joined the Key Laboratory
of Catalysis and Materials Sciences
of the Ministry of Education, South-
Central University for Nationalities
(SCUEC), and started his indepen-
dent research. His current research
interest is the design of new
catalytic materials for the con-
Zehui Zhang version of biomass into chemicals
and liquid fuels and organic
transformations. He is the director of the catalysis and green
chemistry research group at SCUEC. He has published more than
80 papers with a H-Index of 30 and has applied for 10 patents.
Spangler Professor at University of
Wisconsin-Madison. His research
focus is on developing new catalytic
processes for the production
of renewable liquid fuels and
chemicals. He is a co-founder of
Anellotech (www.anellotech.com)
a biochemical company focused
on commercializing catalytic fast
pyrolysis, a technology to produce
renewable aromatics from biomass.
George W. Huber George did a post-doctoral stay with
Avelino Corma at the Polytechnical
University of Valencia, Spain. He obtained his PhD in Chemical
Engineering from University of Wisconsin-Madison (2005) studying
under the direction of James Dumesic. George has published over 138
publications which have been cited over 24 000 times.

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Fig. 1 Chemicals produced by oxidation of glucose and glucose derived molecules.

oxygen via selective oxidization reactions. Many recent papers
have been published on oxidation of carbohydrates or biomass
derived molecules into value-added chemicals.2–5 Fig. 1 shows
that the oxidative transformation of biomass or biomass-derived
molecules can produce a wide range of products including formic
acid, acetic acid, glycolic acid, malonic acid, oxalic acid, gluconic
acid, glucaric acid and furan chemicals. For example, gluconic
acid can be obtained by the direct oxidation of glucose, or the one-
pot transformation of polysaccharides and lignocellulose over
acid–metal bifunctional catalysts. The catalytic oxidative cleavage
of carbon–carbon bonds generates smaller and molecular organic
acids such as formic acid, acetic acid, glycolic acid, malonic acid,
and oxalic acid. 5-Hydroxymethylfurfural (HMF) is a renewable
platform chemical, which is produced from the dehydration of C6
carbohydrates.6 Catalytic oxidation of HMF generates several furan
derivatives including 2,5-diformylfuran (DFF), 5-hydroxymethyl-2-
furancarboxylic acid (HFCA), 5-formyl-2-furancarboxylic acid
(FFCA), and 2,5-furandicarboxylic acid (FDCA).4 The one-pot
conversion of carbohydrates into these furan chemicals has
also been reported using acid–metal bifunctional catalysts.4 As
will be described in detail in this review the above mentioned
biomass-derived oxygenates can be alternatives to fossil resource
derived chemicals as described in Table 1. For example, FDCA
can replace the fossil resource ( p-xylene) for the production of
polyesters.7 Currently, 98% of p-xylene produced commercially
is used as a feedstock for the production of terephthalic acid, an
ingredient for polyethylene terephthalate (PET), which is then
converted to fibers, films, containers, packaging materials, molded
articles, and household consumable goods. However, some of the
biomass-derived chemicals have a high production cost and have
limited annual production ability. For example, the production
cost of FDCA is high and the annual production ability is low
(Table 1). There are very few companies that manufacture and sell
FDCA on demand due to the lack of economic viability. The main
current producers of FDCA are Synbias, V & V Pharma Industries,
Carbone Scientific Tokyo Chemical Industry and Chemsky.

Table 1 Market analysis and applications of commodity chemicals produced by oxidation of carbohydrates

Market price Volume (metric

Chemicals (US $ per metric ton)8 tons per year) Main applications
Formic acid9 400 720 000 Silage and animal feed preservation, leather and tanning, textiles, formate salts,
pharmaceuticals/food chemicals, rubber chemicals, catalysts and plasticizers.
Acetic acid10 450–690 6 500 000 Production of cellulose. Acetate for photographic film and polyvinyl acetate
for wood glue, synthetic fibers and fabrics.
Glycolic acid11 100 000–300 000 15 000 USA12 As a dyeing and tanning agent in the textile industry; as a flavoring agent and
as a preservative in food processing; as a skin care agent in the pharmaceutical
industry; it is also used in adhesives and plastics; a useful intermediate for
organic synthesis, in a range of reactions.
Gluconic acid13 760–830 60 000 Food additive, an ingredient for concrete and raw materials for medicines
and biodegradable polymers.
FDCA14 690 000–720 000 40 Mainly used as a polymer building block as a substitute of terephthalic acid in the
production of polyesters and other current polymers containing an aromatic moiety.

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Aventium is currently running a pilot plant with a 40 ton per
annum capacity in Geelen. However, Aventium has announced
a new technology involving a reactive separation technology
and catalyst which would result in the economic production of
FDCA at USD 1000 per ton from 2016.14
The objective of this review is to document the production of
commodity chemicals that can be produced from carbo-
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hydrates and carbohydrate derived furan compounds by chemical
oxidation routes. In this review, we will highlight the recent
progress in the development of efficient catalytic systems
for the production of formic acid, acetic acid, glycolic acid,
malonic acid, oxalic acid, gluconic acid, glucaric acid, HFCA,
FFCA, DFF and FDCA.
2. Conversion of carbohydrates into
formic acid
Formic acid is a colorless liquid with a pungent odor, which is
completely miscible with water and many polar solvents but
only partially miscible with hydrocarbons.9 Formic acid has
an annual production of 720 000 tons per year.9 Formic acid
is mainly used as a preservative and antibacterial agent in
livestock feed.9 It can also be used in the production of leather
for tanning, dyeing and finishing, and in place of mineral acids
for various cleaning products, such as limescale removers and
toilet bowl cleaners.9 It can also be used in organic synthesis
reactions as a source of formyl groups15 and a hydrogen source
for transfer hydrogenation reactions.16 Recently, formic acid has
been proposed as a feedstock for H2 storage since it contains
4.4 wt% mass fraction of hydrogen and can decompose into
H2 over metal catalysts under mild conditions (o100 1C).17–19
Formic acid has also been proposed to power fuel cells for
electricity generation and automobiles.20 This concept builds
on the 4.4 wt% share of hydrogen in formic acid resulting in
53 g hydrogen per liter of formic acid.17–19 The commercial
production of formic acid from fossil fuel derived methanol occurs
by two steps:21 (1) the carboxylation of methanol with carbon
monoxide to generate formic acid methyl ester (this reaction is
performed in the liquid phase in the presence of 2.5 wt% sodium
methoxide at 353 K and 45 bar CO); and (2) the subsequent
Fig. 2 (a) Overall stoichiometric reaction for oxidation of glucose into formic acid; (b) oxidative conversion of carbohydrates (cellulose as an example)
into formic acid over H3+nPVnMo12 nO40 (HPA) catalysts. HPA-nox: the oxidized state of HPA; HPA-nred: the reduced state of HPA.
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hydrolysis of formic acid methyl ester with water to produce
formic acid (this reaction is performed with excessive water to
shift the equilibrium at 373–413 K and atmospheric pressure).
Recently, there have been some papers on the synthesis
of formic acid by aqueous catalytic partial oxidation of wet
biomass mainly over vanadium catalysts.
2.1 Conversion of carbohydrates into formic acid with O2 as
the oxidant
Oxidation of carbohydrates into formic acid was first reported
in 1954.22 Schöpf and Wild carried out the oxidation of glucose
into formic acid using stoichiometric amounts of periodic acid
(H5IO6).22 Catalytic oxidation of carbohydrates to formic acid with
molecular oxygen (O2) would be preferred over using periodic
acid, as O2 is a clean oxidant. Fig. 2a shows the stoichiometric
reaction of one mole of glucose with three moles of O2 to produce
6 moles of formic acid without any other product. However, a
stoichiometric amount of HI is also produced, when H5IO6 is
used as the oxidant.
The reaction pathway of the catalytic oxidation of cellulose
into formic acid is illustrated in Fig. 2b. It contains two major
steps: the acid-catalyzed hydrolysis of carbohydrates (cellulose
or lignocellulose) into monosaccharides (glucose or xylose) and
the oxidative cleavage of C–C bonds in monosaccharides into
formic acid. Over oxidation of monosaccharides will result in the
complete combustion of biomass to water and CO2, which are
the thermodynamically favored products. Thus, it is of critical
importance that the selected catalyst systems do not oxidize
formic acid to CO2 under the applied reaction conditions.
O2 is usually activated by metal catalysts. Vanadium(V)-
containing catalysts, especially polyoxometalates (POM) with a
formula of H3+nPVnMo12 nO40 (HPA), are effective for formic
acid production from biomass with O2 as an oxidant as shown
in Table 2.23–29 In 2010, Wasserscheid and co-workers first
reported the aqueous transformation of carbohydrates into formic
acid in a batch reactor from 333 to 363 K using H5PV2Mo10O40
(HPA-2) as the catalyst.23 Monosaccharides (glucose, xylose) and
disaccharides (cellobiose, sucrose) produced formic acid in yields
of around 50% at nearly full conversions (498%) at a substrate
concentration of 30 mg mL 1 at 353 K and 30 bar O2 after 26 h
(Table 2, entries 1–4). Fu and co-workers obtained similar results
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Table 2 Oxidation of carbohydrates into formic acida

Feed con. Catalyst

Entry Substrate (mg mL 1) Catalyst ratiob T (K) O2 (bar) Time (h) Con. (%) Yieldc (%) Ref.
1 Glucose 30 H5PV2Mo10O40 22.2 353 30 26 498 47 23
2 Xylose 30 H5PV2Mo10O40 26.7 353 30 26 498 54 23
3 Cellobiose 30 H5PV2Mo10O40 11.7 353 30 26 498 47 23
4 Sucrose 30 H5PV2Mo10O40 11.7 353 30 26 498 48 23
5 Glucose 25 H5PV2Mo10O40 20 373 20 3 100 47 24
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6 Cellulose 30 H5PV2Mo10O40 24.7 353 30 26 n.d. 1 23

7 Cellulose 10 H5PV2Mo10O40 & HCl 20 443 10 9 100 34 24
8 Cellulose 27 H5PV2Mo10O40 & H2SO4 17.5 453 30 0.08 100 61 25
9d Cellulose 27 H5PV2Mo10O40 & TSA 22.2 363 30 24 n.d. 19 26
10 Xylan 27 H5PV2Mo10O40 & TSA 27.3 363 30 24 n.d. 53 26
11 Lignin 27 H5PV2Mo10O40 & TSA — 363 30 24 n.d. 31 26
12 Pomace 33 H5PV2Mo10O40 & TSA — 363 30 24 n.d. 54.6 27
13 Cane trash 33 H5PV2Mo10O40 & TSA — 363 30 24 n.d. 48.9 27
14 Fruit pulp 33 H5PV2Mo10O40 & TSA — 363 30 24 n.d. 45.3 27
15 Spruce chips 33 H5PV2Mo10O40 & TSA — 363 30 24 n.d. 34.6 27
16 Glucose 50 H8PV5Mo7O40 34.8 363 30 8 100 60 28
17 Cellulose 50 H8PV5Mo7O40 & TSA 38.7 363 30 24 100 28 28
18 Cellulose 10 H4PVMo11O40 12.3 453 20 3 100 60.9 29
19 Cellulose 10 H5PV2Mo10O40 12.3 453 20 3 100 44.9 29
20 Cellulose 10 H6PV3Mo9O40 12.3 453 20 3 100 42.0 29
21 Cellulose 67 H4PVMo11O40 40 453 1 1 100 35.5 31
22 Cellulose 67 [MIMPS]3HPMo11VO40 40 453 1 1 93.3 51.3 31
23 Cellulose 67 [BMIM]3HPMo11VO40 40 453 1 1 15.2 5.2 31
24 Glucose 16.7 NaVO3–H2SO4 (0.7 wt%) 3.1 433 30 1 100 68.2 33
25 Xylose 16.7 NaVO3–H2SO4 (0.7 wt%) 3.7 433 30 1 min 100 68.2 33
26 Xylan 16.7 NaVO3–H2SO4 (0.7 wt%) 4.2 433 30 0.5 100 63.5 33
27 Sucrose 83.3 NaVO3–H2SO4 (0.7 wt%) 1.6 433 30 5 min 100 64.2 33
28 Wheat straw 83.3 NaVO3–H2SO4 (0.7 wt%) — 433 30 5 min 100 47 34
29 Cellulose 16.7 NaVO3–H2SO4 (2.0 wt%) 3.8 433 30 10 min — 57.7 37
30 Cellulose 16.7 NaVO3–H2SO4 (2.0 wt%) 3.8 453 30 10 min 37.5 37
31 Cellulose 8.1 VOSO4 10 453 20 1 — 53 38
32 Inulin 8.1 VOSO4 10 453 20 1 — 39 38
33 Starch 8.1 VOSO4 10 453 20 1 — 46 38
34e Glucose 18 H8PV5Mo7O40 20 363 20 48 100 85 39
35 Glucose 18 H8PV5Mo7O40 20 363 20 48 100 53 39
36 Beech wood 16.3 H8PV5Mo7O40 & TSA — 363 20 48 — 61 39
a
All reactions were carried out in water, except for entry 34, in a batch reactor. b The catalyst ratio is the molar ratio of substrates to the catalysts. For
cellulose and xylan as the substrates, the catalyst ratio is calculated as the molar ratio of glucose or xylose to the catalysts. c The yield is reported as a
carbon yield. d TSA is the abbreviation of p-toluenesulfonic acid. e This reaction was performed in a biphasic system of water/1-hexanol (v : v = 1).

(a 47% yield of formic acid) using the same HPA-2 catalyst
(Table 2, entry 5).24 In each case, formic acid was the only
observed product in the liquid solution, and CO2 was the only
other side product. However, the catalytic oxidation treatment
of cellulose over HPA-2 only produced a 1% yield of formic acid
(Table 2, entry 6).23 Fu and co-workers improved the formic acid
yield to 34% from cellulose at a concentration of 10 mg mL 1
after 9 h by the combined use of HPA-2 and 0.01 M HCl (Table 2,
entry 7), due to the higher efficiency of cellulose hydrolysis by
HCl.24 The use of HPA-2 and 1.6 wt% H2SO4 greatly improved the
efficiency of the transformation of cellulose into formic acid,
which produced formic acid in a much higher yield of 61% at
100% cellulose conversion with a high substrate concentration
of 30 mg mL 1 after 5 min at 453 K (Table 2, entry 8).25 The pH of
the reaction system with HPA-2 and 0.01 M HCl was 1.87, while it
was 0.56 for the HPA-2 and 1.6 wt% H2SO4 catalytic system. At
the lower pH of 0.56, the oxidation potential and electron affinity
increased due to the formation of protonated HPA-2 and VO2+
species, favoring the reduction of the catalyst and oxidation of
the substrate, as well as the hydrolysis of cellulose into glucose.
Besides mineral acids, Wasserscheid and co-workers used 0.1 M
p-toluenesulfonic acid (TSA) as the additive to promote the
transformation of water-insoluble biomass into formic acid
over an HPA-2 catalyst.26 Formic acid was produced in a yield
of 19% after 24 h at 363 K at a cellulose concentration of
27 mg mL 1 (Table 2, entry 9). The combined use of HPA-2 and
TSA was also effective at transforming xylan and lignin to formic
acid with yields up to 53% and 31% (Table 2, entries 10 and 11),
respectively. Wasserscheid and co-workers further applied this
method for the oxidative transformation of lignocellulose and
algae feedstocks into formic acid.27 Formic acid was produced
with yields of 34.6–54.6% from pomace, cane trash, fruit
pulp and spruce chips (Table 2, entries 12–15). Subsequently,
Wasserscheid and co-workers prepared an improved heteropoly
acid H8PV5Mo7O40 (HPA-5), which produced formic acid yields of
60% and 28% at 363 K from glucose (8 h) and cellulose (24 h) at a
substrate concentration of 50 mg mL 1, respectively (Table 2,
entries 16 and 17).28 The formic acid yield from cellulose over
HPA-5 was 1.5 times higher than with HPA-2 at a higher cellulose
concentration (Table 2, entries 9 vs. 17).26,28 The higher activity
of the HPA-5 catalyst over the HPA-2 catalyst was due to the
presence of a much higher ratio of pervanadyl species (VO2+) for

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the reaction by the use of the HPA-5 catalyst. VO2+ has a higher
redox potential (0.87 V vs. normal hydrogen electrode) than
HPA-2 (0.68 V vs. normal hydrogen electrode) at pH = 1, and
hence HPA-5 has a higher catalytic activity. Formic acid was the
only product in the liquid solutions for all of the above cases,
and the only byproduct was CO2.
In contrast to the results reported by Wasserscheid and
co-workers,28 Han and co-workers reported that the formic acid
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yield from cellulose increased with the decrease of vanadium
content in the H3+nPVnMo12 nO40 catalysts at 453 K.29 The oxida-
tive conversion of cellulose over H3+nPVnMo12 nO40 catalysts at
453 K did not require additional acid catalysts,29 while it required
TSA to catalyze cellulose hydrolysis at 363 K.26,28 Under the
reaction conditions (453 K and 20 bar O2), cellulose was fully
converted after 3 h, and the formic acid yields from cellulose
followed the order: H4PVMo11O40 (60.9%) 4 H5PV2Mo10O40
(44.9%) 4 H6PV3Mo9O40 (42.0%) (Table 2, entries 18–20). As
cellulose was completely converted after 3 h at 453 K, the yield
of formic acid over H3+nPVnMo12 nO40 catalysts depended on the
selectivity of formic acid. The higher selectivity of H4PVMo11O40
with a single V atom than those of H3+nPVnMo12 nO40 (n = 2, 3)
was possibly due to the synergetic effect of the multiple V atoms in
H3+nPVnMo12 nO40 (n = 2, 3) causing over-oxidation, as implied
by their higher yields of CO2. Besides formic acid, acetic acid
was also obtained with yields around 5% for the three catalysts.29
The decomposition of formic acid can produce CO and CO2 at the
temperature of 410 K. CO2 was the gas byproduct, which was
primarily formed from the intermediates and not formic acid,
similar to what was observed by other authors.23–28
The H+ in the heteropolyacids can be exchanged with other
metal cations or organic group.30 Some modified POM catalysts
were prepared by the exchange of the H+ in POM catalysts with
organic sulfonic acid groups and demonstrated good catalytic
performance for the oxidative transformation of cellulose
into formic acid.31,32 For example, Liu and co-workers studied
the oxidative conversion of cellulose into formic acid over
modified POM catalyst-[MIMPS]3HPMo11VO40, which was pre-
pared by the exchange of three H+ in H4PMo11VO40 with -butyl
sulfonic acid group functionalized imidazole cations.31 Under
the same reaction conditions (453 K, 1 h, 10 bar O2), the parent
H4PMo11VO40 catalyst produced formic acid with a yield 35.5%
at a cellulose concentration of 67 mg mL 1, while the formic
acid yield increased to 51.3% over the [MIMPS]3HPMo11VO40
catalyst (Table 2, entries 21 and 22). Control experiments
indicated that the cations of the [MIMPS]3HPMo11VO40 catalyst
served two important roles. On the one hand, the sulfonic
acid group in [MIMPS]3HPMo11VO40 promoted the hydrolysis
of cellulose. [BMIM]3HPMo11VO40 (1-methyl-3-butyl-imidazole
cation) without the sulfonic acid group produced much lower
cellulose conversion (Table 2, entries 22 vs. 23). On the other
hand, [MIMPS]3HPMo11VO40 suppressed the over oxidation
of the intermediates to CO2 during the oxidation of glucose
into formic acid, as the formic acid yield from glucose over
[MIMPS]3HPMo11VO40 was also higher than that over H4PMo11VO40
(54.7% vs. 44.8%) after 1 h at 453 K and 10 bar O2. Furthermore,
the [MIMPS]3HPMo11VO40 catalyst showed a high stability with
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a slight decrease of formic acid yield (51.3% for the first run vs.
49.5% for the third run).
In addition to the vanadium-containing heteropolyacids,23–29
vanadium salts have also been studied for the oxidative trans-
formation of carbohydrates into formic acid under the strong
acidic conditions.33,34 Sodium metavanadate (NaVO3) with H2SO4
has been reported to have catalytic activity for oxidation of
carbohydrates into formic acid.33,34 As shown in Fig. 3, cellu-
lose conversion and formic acid selectivity increased on
increasing the weight percentage of H2SO4 from 0.1 wt% to
0.7 wt%, which was due to the enhanced hydrolysis of cellulose
at higher weight percentage of H2SO4, and then kept almost
stable beyond 0.7 wt%. The reaction was almost stopped
(cellulose conversion = 3%) without H2SO4. The highest formic
acid yield (64.9%, Fig. 3) was close to that from glucose (68.2%,
Table 2, entry 24), suggesting that the first step of the hydrolysis of
cellulose into glucose was highly efficient. This catalytic system
was also effective at transforming xylose, xylan and sucrose into
formic acid with yields up to 63% (Table 2, entries 25–27),33 and
even wheat straw (Table 2, entry 28).34 Similar to the vanadium-
containing heteropolyacid catalytic systems,23–29 CO2 was also the
sole byproduct over the NaVO3–H2SO4 catalytic system.33,34 The
selectivity of formic acid was dependent on the type of V–O
species in the reaction solution. As shown in Fig. 4, V4O124 is
predominant at pH around 7. V10O286 appears at pH o 6 and
becomes dominant in a pH range of 4.1–3.0. VO2+ appears at
pH o 2 and becomes dominant at pH o 1.35 Among them,
VO2+ showed the highest oxidative potential for selective oxida-
tion reactions.36 In fact, 51V-NMR and X-ray photoelectron
spectra (XPS) analysis confirmed that VO2+ was the only V–O
species by the use of 0.7 wt% H2SO4 with the reaction solution
pH lower than 1. Thus, it is proposed that in the catalytic cycle
VO2+ oxidizes carbohydrates by donating an oxygen atom first
to generate formic acid and VO2+, and VO2+ is then oxidized
by molecular oxygen to generate VO2+. Furthermore, Wu and
Fig. 3 The effect of H2SO4 on the conversion of cellulose into formic
acid. Reaction conditions: initial O2 pressure (30 bar), cellulose (100 mg),
NaVO3 (22 mg), H2O (6 g), 433 K. Conversion was calculated based on the
amount of unconverted carbohydrates. Adapted from ref. 34 with permission
from the Royal Society of Chemistry, copyright 2015.
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Fig. 4 Pourbaix diagram of vanadium at 25 1C and an ionic strength of
1 M. Reproduced from ref. 35 with permission from Elsevier, copyright
2003.
co-workers studied the relationship between oxidation and
hydrolysis in the oxidative conversion of cellulose into formic
acid in NaVO3–H2SO4 aqueous solution.37 They observed that
there were mainly two hydrolysis and two oxidations steps
(Fig. 5): initial hydrolysis of cellulose to glucose and deep
hydrolysis of glucose to levulinic acid; the oxidation of mono-
saccharides to formic acid and the oxidation of levulinic acid to
acetic acid. The reaction temperature, oxygen pressure and the
concentration of H2SO4 all played crucial roles in the control of
the reaction pathways. The increasing rate of deep hydrolysis
was faster than that of catalytic oxidation, when the reaction
temperature was increased. For example, formic acid was produced
in a yield of 57.7% from cellulose at 433 K after 10 min, and
levulinic acid and acetic acid were in low yields of 1.4 and 0.9%,
respectively (Table 2, entry 29). However, the formic acid yield
greatly decreased to 37.5% at 453 K with an increased acetic acid
Fig. 5 Proposed reaction pathways for the transformation of cellulose
into formic acid in NaVO3–H2SO4 catalytic systems. Adapted from ref. 37
with permission from the Royal Society of Chemistry, copyright 2003.
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yield of 9.2% (Table 2, entries 29 vs. 30). The yield of levulinic
acid was almost the same (0.8%) at 453 K. Besides temperature,
the oxidation step to formic acid was accelerated by the increase
of oxygen pressure.
VOSO4 was also used for the oxidative transformation of
cellulose into formic acid in water without acid.38 Formic acid
was produced in a yield of 53% from cellulose after 1 h at 413 K
and 20 bar O2 (Table 2, entry 31). Compared with the NaVO3–
H2SO4 catalytic system,37 it required a longer reaction time to
reach the maximum formic acid yield at lower cellulose concen-
tration (Table 2, entries 29 vs. 31), as this catalytic system did
not use H2SO4 to promote cellulose hydrolysis. This catalytic
system was also effective for the transformation of other
carbohydrates such as inulin into formic acid (Table 2, entries
32 and 33). Mechanism studies revealed that fructose, from the
isomerization of glucose by VOSO4, underwent a retrol-aldol
reaction to give two C3 intermediates (glyceraldehydes and
1,3-dihydroxyacetone, Fig. 6), which were oxidized into formic
acid and CO2. Under a nitrogen atmosphere, lactic acid was
produced with a yield of 54%, which was formed by the
isomerization of C3 intermediates. ESR and NMR spectra of
VOSO4 revealed that the oxidation state of vanadium did not
change during the conversion of cellulose into lactic acid under
a nitrogen atmosphere, suggesting that these steps in Fig. 6 for
the formation of lactic acid were catalyzed by VIV. On the other
hand, the oxidation of VIV to VV by O2 and the subsequent
reduction of VV to VIV by reactants were observed, indicating
that the redox between VIV and VV played key roles in the
oxidative C–C cleavage reactions to form formic acid.
The above examples for the oxidative conversion of biomass
into formic acid were performed in monophasic systems with a
maximum formic acid yield below 70%. Albert and co-workers
used a biphasic system (water/organic solvents) to improve
formic acid yield via the in situ extraction of formic acid.39
The water/1-hexanol (v : v = 1) biphasic system produced formic
acid with a high yield of 85% from glucose over an HPA-5
catalyst at 363 K after 48 h (Table 2, entry 34), while the
oxidation of glucose in water only produced a 53% yield of
formic acid under identical conditions (Table 2, entry 35).
Glucose conversions were 100% either in water or water/
1-hexanol. As formic acid is stable both in water and 1-hexanol,
the higher selectivity of formic acid in the biphasic system is not
caused by the improvement of the stability of formic acid. The
authors claimed that the extraction of formic acid by 1-hexanol
reduced the pH in the aqueous phase during the reaction process
to increase the formic acid selectivity. An additional experiment
confirmed this assumption. Formic acid selectivity from
glucose oxidation over the HPA-5 catalyst decreased sharply from
53% in water to 26% by the addition of 20 wt% formic acid
to the initial reaction solution. Using this biphasic reaction
protocol, raw lignocellulosic biomass (beech wood) could also
be successfully converted into formic acid with a yield of 61%
(Table 2, entry 36).
It is generally accepted that the oxidation of carbohydrates
into formic acid over vanadium-containing POM catalysts
follows an electron-oxygen transfer mechanism (the oxidation
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Fig. 6 Reaction pathways for the conversion of glucose into formic acid over a VOSO4 catalyst. Adapted from ref. 38 with permission from Wiley,
copyright 2014.

Table 3 The oxidation of oxygenated molecules to formic acid using a HPA-2 catalysta

Entry Substrate (g mL 1) Time (h) Temperature (K) Conversion (%) Formic acid yieldb
1 Formic acid (0.05) 6 373 9 —
2 Methanol (0.025) 6 373 0 0
3 Formaldehyde (0.025) 6 373 13 0
4 Ethylene glycol (0.01) 3 373 10 0
5 1,3-Propylene glycol (0.05) 2 398 0 0
6 1,2-Propylene glycol (0.05) 3 398 50 17
7c 2,5-Dihydroxy-1,4-dioxane (0.01) 3 373 90 56
8 Glyoxal (0.01) 3 373 100 65
9 Glyceraldehyde (0.01) 3 373 100 55
a
Reaction conditions: 5 mol% of the HPA-2 catalyst and 20 bar O2 were used. b The yield of formic acid was calculated based on 1 mol of glucose
producing 6 mol of formic acid. c The substrate was the glycolaldehyde dimer. Adapted from ref. 24.

of carbohydrates by high valence (+5) vanadium catalysts, and
the oxidation of reduced vanadium species to the original high
valence state vanadium catalysts, Fig. 6). As shown in Table 3,
Fu and co-workers tried to study the possible mechanism of
glucose oxidation into formic acid by the oxidation of some
intermediates.24 Only formic acid and the feed molecules were
detected in the product solution, for all the reactants used in
Table 3. Firstly, 5 wt% formic acid solution was treated over the
HPA-2 catalyst at 373 K and 20 bar O2, and only 10% of formic
acid was decomposed. As listed in Table 2, entry 5, 48% of CO2
was produced during the oxidation of glucose into formic acid
under the same reaction conditions. Therefore, it suggested
that CO2 was not mainly from the decomposition of formic acid
but the intermediates (Table 3, entry 1). No formic acid was
detected when methanol and formaldehyde were employed as
the substrates (Table 3, entries 2 and 3), indicating that the
reaction mechanism could not be the a-cleavage of glucose to
form methanol or formaldehyde, which would be subsequently
oxidized into formic acid. The conversion of ethylene glycol,
glycolaldehyde dimer, and glyoxal over the same reaction time
showed that the active center of the substrates should be the
aldehyde group (Table 3, entries 4–9). The oxidation of oxalic acid,
glycolic acid, and glyoxylic acid produced very low conversion of
formic acid (less than 5%), suggesting that formic acid could
not be generated from these carboxylic acids.
In the presence of oxygen, the valence of the V and Mo atoms
in the catalysts was the same as that of the fresh catalyst.
However, the peak position of the Mo catalysts remained
basically unchanged in the absence of oxygen, whereas the
change in the peak position of V indicated that the valence of V
changed from five to four. Combining the reaction results for
possible intermediates and the pinacol oxidation mechanism
proposed by Neumann and Khenkin,40,41 Fu and co-workers
proposed that a possible mechanism for glucose oxidation
involved electron and oxygen transfer processes catalyzed by the
HPA-2 catalyst (Fig. 7) and that the reaction intermediates might
be aldehydes. These possible intermediates were also claimed
by Marsh and co-workers for the oxidation of carbohydrates
into formic acid over the NaVO3–H2SO4 catalytic system.35
As mentioned in this section, vanadium catalysts with V5+
are proved to have high rates of electron transfer and moderate
activity for the oxidation of carbohydrates into formic acid.
However, formic acid yields from the current reported methods
are not above 70% (Table 2), which is still far away from the
theoretical value (100%). Selection of the right catalyst is critical
to achieve high formic acid yields. Since complete combustion
of biomass to water and CO2 is always the thermodynamically
Fig. 7 Possible pathway for glucose oxidation catalyzed by H5PV2Mo10O40
(HPA-2) through an electron transfer and oxygen transfer reaction mechanism.
Adapted from ref. 24 with permission from Wiley, copyright 2012.

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favored reaction in biomass oxidation with molecular oxygen,
the applied catalyst should promote fast oxidation of all carbon
in biomass to formic acid, while showing no activity or negli-
gible activity in the further decomposition of formic acid into
CO2 and H2.
2.2 Conversion of carbohydrates into formic acid with H2O2
as the oxidant
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H2O2 can also be used for the hydrothermal oxidation of
carbohydrates into formic acid (Fig. 8). In 2002, Calvo and
Vallejo reported the oxidative conversion of carbohydrates into
organic acids in water with H2O2.42 A formic acid yield of 38%
was obtained in a continuous flow reactor from glucose
at 523 K by the addition of NaOH (55.6 wt% of glucose), and
the glucose conversion was 77%. In addition, acetic acid and
glycolic acid were also detected in yields of 17% and 22%,
respectively. For cellulose transformation, the hydrothermal
oxidation was carried out at a higher temperature of 673 K
with 0.02 wt% H2SO4 and 12 equiv. H2O2 in a continuous flow
reactor, producing formic acid in a low yield of 19.4% with
5.8% yield of acetic acid. Jin and Co-workers first reported the
hydrothermal oxidation of glucose into formic acid in a batch
reactor with a yield of 75% in 1.25 M KOH reaction solution
with 14.4 equiv. mol H2O2 at 523 K.43 The formic acid yield
increased from 24 to 75% with increasing KOH concentration
from 0 to 1.25 M within 1 min. The same authors then
performed the oxidation of monosaccharides (glucose, fructose
and galactose) and disaccharides (cellobiose and maltose) at a
low temperature of 423 K,44 producing high formic acid yields
(80–85%). Compared with previous work,43 a longer reaction
time of 15 min and higher NaOH concentration of 2.0–2.5 M
were required. The alkali played two roles in enhancing the
production of formic acid. One was the inhibition of the formic
acid decomposition. The other role of a base is that the base
was favorable for the selective oxidation at C-1 for aldoses,
which leads to the formation of formic acid via the rupture of
the C1–C2 bond. In addition to formic acid, a few low molecular
weight carboxylic acids including lactic acid, propanoic acid,
acrylic acid and acetic acid were also identified by HPLC. As
shown in Fig. 9, formic acid was proposed to be formed by the
rupture of C1–C2 or C5–C6 (a-scission) and/or the rupture
of C2–C3 (b-scission) or C4–C5 (b-scission) from glucose. The
former directly yields formic acid, but the latter yields formic
acid via oxalic acid. Oxidation of oxalic acid under the same
conditions only produced a low formic acid yield (14%). This
indicates that formic acid is formed from the direct oxidation
of glucose by a-scission.
In contrast to the hydrothermal oxidation methods, the
catalytic oxidation of glucose into formic acid by the use of
Fig. 8 Hydrothermal oxidation of glucose into formic acid by H2O2.
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Fig. 9 Hydrothermal conversion of glucose into formic acid using H2O2
as the oxidant. Adapted from ref. 43 with permission from Royal Society of
Chemistry, copyright 2008.
H2O2 as the oxidant over metal catalysts has been reported to be
performed under mild conditions. Jung and co-workers per-
formed the oxidation of glucose into formic acid over a homo-
genous N-heterocyclic carbenes-amidate Pd(II) complex at room
temperature.45 Formic acid was obtained in a high yield of 91%
after 16 h by the use of a stoichiometric amount of H2O2 and 6
equiv. NaOH. Although formic acid was achieved in a high
yield, it is difficult to recycle the homogeneous Pd(II) complex
catalyst. Ebitani and co-workers prepared a MgO-supported
copper catalyst (denoted as CuCTAB/MgO) for the oxidation
of glucose into formic acid by H2O2, where cetyltrimethyl-
ammonium bromide (CTAB) was used as the capping agent for
Cu nanoparticles.46 Formic acid was produced in a yield of 65%
from glucose after 12 h with 8 equiv. H2O2 at 393 K. In addition,
glyceric acid and glycolic acid were also produced in yields of
29% and 16.6%, respectively. The CuCTAB/MgO catalyst was
stable without any significant loss of activity for three runs.
The one advantage of using H2O2 and O2 as oxidants is that
the reduction product of the oxidants (H2O2 and O2) is H2O. In
contrast to the use of O2 as the oxidant, the hydrothermal
oxidation of carbohydrates into formic acid with H2O2 was
performed under harsh reaction conditions such as at a high
reaction temperature up to 673 K. In addition, it is also difficult
to get a high purity formic acid because other organic acids are
produced as byproducts. Taking all of the above cases for the
oxidative transformation of carbohydrates into formic acid into
consideration, catalytic oxidation with O2 as the oxidant can
overcome the drawbacks caused by the hydrothermal oxidation
method, e.g., the facile availability of O2, wide feedstock scope and
high purity of formic acid. Moreover, hydrothermal treatment can
achieve a highly efficient, rapid conversion and simplify the reaction
procedure, which is key for industrial application. Also, the
selectively of formic acid is high, rather than low. For acetic acid
production, although its selectively was not high, the acetic acid
purity was very high, which is important for separation. Further-
more, the hydrothermal conversion can achieve a continuous-
system, which is also key for industrial application.
3. Conversion of carbohydrates into
acetic acid
Acetic acid is the second simplest carboxylic acid next to formic
acid.10 Its principal use (40%) is in the manufacture of vinyl
acetate.10 Acetic acid can also be converted to ethyl acetate or
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other esters by Fisher esterification.47 Dehydration of acetic
acid can be used to make acetic anhydride, which is used as an
acetylating agent, in the production of cellulose acetate. In the
food industry, acetic acid is used as an acidity regulator and
as a condiment. The global annual demand of acetic acid is
around 6.5 million tones.10 Currently, acetic acid is mainly
produced by methanol carbonylation over rhodium or iridium-
complex catalysts.47 However, this synthetic process requires
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relatively high temperatures (B448 K) and pressures (30 bar),
exotic materials of construction, and extensive safety-related
equipment. Acetic acid can also be produced by fermentation of
ethanol.48 Biological sources of acetic acid are of interest, but
currently uncompetitive with acetic acid produced from metha-
nol carbonylation. Thus, chemical oxidation of renewable bio-
mass would pave a new and effective way for the industrial
production of acetic acid.
The oxidation of biomass into acetic acid typically occurs in
two reactive steps: transformation of the carbohydrates into
intermediates, and the oxidation of the intermediates into acetic
acid. H2O2 is often used as an oxidant for the second step. The
intermediates include HMF, 2-furaldehyde (2-FA), lactic acid and
levulinic acid according to the reaction conditions.
Jin’s group has performed many interesting studies on the
conversion of carbohydrates into acetic acid. A two-step method
was developed by Jin and co-workers to improve the yield of
acetic acid.49 As depicted in Fig. 10a,49 carbohydrates are first
hydrothermally converted into HMF, 2-FA and lactic acid under
Fig. 10 Proposed two-step processes for producing acetic acid via different intermediates.
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an inert atmosphere. The first hydrothermal step produced
lactic acid, HMF and 2-FA, in yields of approximately 16%, 9%
and 6% from cellulose at 573 K for 2 min, respectively. The
second step involves the oxidation of these intermediates into
acetic acid. As shown in Table 4 (entries 1–3), the acetic acid
yields using the two-step method from rice hulls, cellulose, and
starch were nearly double compared with those using the one-
step method. Besides acetic acid, other products were also
produced including formic acid, maleic acid, malonic acid, and
propionic acid. This process was scaled up to a continuous flow
reaction system with a maximum capacity of 2 kg dry starch h 1.50
The highest acetic acid yield (17.5% carbon) in the continuous
flow reaction system was the same as the batch reactor system
(Table 4, entries 3 vs. 4).
The acetic acid yield can be increased by the addition of
mineral acids in the first step.51 In the presence of acid, levulinic
acid is the main intermediate in the first step in Fig. 10b, which
is formed via the dehydration of carbohydrates into HMF and
the subsequent rehydration of HMF. Levulinic acid was then
converted to acetic acid via hydrothermal oxidation. Under
optimal conditions (523 K, pH = 0.5, and a reaction time of
300 s for the first step; 523 K, H2O2 = 12 equiv., and a reaction
time of 60 s for the second step), the yields of acetic acid were as
high as 23% and 26% for glucose and fructose, respectively
(Table 4, entries 5 and 6). The solution pH of the first step was
important for the total yield of acetic acid. The yield of acetic
acid was only approximately 10% for both glucose and fructose
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Table 4 Acetic acid production by oxidation of biomass
Reaction conditions
Substrate First step Second step
1 Rice hulls 573 K, 2 min 573
2 Cellulose 573 K, 2 min 573
3 Starch 573 K, 1 min 573
4d Starch 573 K, 1 min 573
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5 Glucose 523 K, 5 min, pH = 0.5 523
6 Fructose 523 K, 5 min, pH = 0.5 523
7 Corn stover 1 M H2SO4, 463 K, 60 min 463
8 Glucose 573 K, 1 min, 0.64 M Ca(OH)2 573
9 Glucose 548 K, 20 s, glucose/bentonite wt% = 1 548
a
Acetic acid yield was calculated based on carbon of the feedstock. b The purity of acetic acid is defined as the percentage of organic carbon of
acetic acid divided by the total organic carbon (TOC) of the liquid sample after the reaction. c The data are the results using the one-step method.
d
Results obtained by the continuous reactor. The flow rate of H2O2 was 6.5 L h 1.
without the control of acid. However, too strong acidic solution
was also not suitable for the production of acetic acid. The
acetic acid yield from fructose decreased from 26% at pH = 0.5
to 17% at pH = 0.24. Later, Fu and co-workers used this two-step
process for the transformation lignocellulosic biomass into
acetic acid by the use of O2 in the second step.52 Acetic acid
was attained in a yield of 21.3% under the optimal conditions
with a purity up to 84.6% of the total liquid product (Table 4,
entry 7). Other lignocellulosic feedstocks such as corncob, bagasse,
bamboo, poplar and pine could also be transformed into acetic
acid with yields of 15–20%.
Jin and co-workers discovered that oxidation of lactic acid
produced much more acetic acid (about 40%) than furans
(about 15% from HMF and 20% from 2-FA).49 A base promoted
the hydrothermal transformation of biomass into lactic acid.53
Thus alkaline conditions were used to produce acetic acid from
glucose in 27% yield (Fig. 10c and Table 4, entry 8). Later, they
used bentonite as the solid base for the two-step transforma-
tion of glucose into acetic acid.54 The second step just exposed
the reactor to the air for 3 min after the first step. This method
produced acetic acid with a yield of 27% at 548 K with 20 s for
the first step and 90 s for the second step (Table 4, entry 9).
Being different from the above two-step methods, Yan and
co-workers performed one-step transformation of chitin and
waste shrimp shells into acetic acid in 2 M NaOH by the use of
CuO with the molar ratio to carbon = 0.125.55 Acetic acid was
produced in a 32.3% yield from chitin at 573 K and 5 bar O2
after 35 min. The real oxidant was CuO, which was reduced to
Cu2O during the reaction process. The as-formed Cu2O can be
reoxidized to CuO by O2. The use of untreated tiger shrimp
shell powder, consisting of 24.4% chitin, 17.5% protein, and
43.2% calcium carbonate (CaCO3), also produced an acetic acid
yield of 47.9% under the same conditions. The higher acetic
acid yield from raw shrimp shells over purified chitin suggested
that some carbon in proteins may contribute to acetic acid
formation. Glucosamine was firstly formed by hydrolysis from
chitin, which then underwent deamination to produce glucose.
Lactic acid was the main intermediate for the conversion of
glucose into acetic acid.
There is no need for an oxidant for the stoichiometric
conversion of glucose into acetic acid (C6H12O6 - 3CH3COOH).
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Acetic acid yielda Purityb Ref.
c c
K, 1 min, H2O2 = 8.4 equiv. of glucose unit 21.7 (11.7) 75.5 (33.4) 44
K, 1 min, H2O2 = 8.4 equiv. of glucose unit 16.3 (9.0)c 68.5 (26.1)c 44
K, 1 min, H2O2 = 8.4 equiv. of glucose unit 17.5 (9.6)c 70.0 (28.2)c 44
K, 1 min, H2O2 = 8.4 equiv. of glucose unit 17.5 — 45
47c
K, 1 min, H2O2 = 12 equiv. of glucose unit 23 46
K, 1 min, H2O2 = 12 equiv. of fructose 26 52c 46
K, 540 min, 2.0 MPa O2 21.3 84.6 47
K, 3 min, H2O2 = 8.4 equiv. of glucose unit 27 — 49
K, 80 s, in air 27 — 54
The discussed three kinds of two-step methods for the conver-
sion of carbohydrates into acetic acid demonstrate that acetic
acid was produced by the oxidation of the intermediates such
as lactic acid, levulinic acid and furans. The transformation of
lactic acid into acetic acid must cleave one carbon, thus the
theoretical carbon yield of acetic acid should be 66.7%. The
acetic acid yield from lactic acid was reported to be 40% by Jin
and co-workers.49 The relatively low yield of acetic acid also
accompanies another troublesome problem that the purity was
not high because of the byproducts. According to the above
analysis, the current methods for the production of acetic acid
from biomass by catalytic oxidation only produce low yields
of acetic acid. Catalysts may be able to tune this selectively
to produce acetic acid with higher selectivity under milder
conditions.
4. Conversion of carbohydrates into
glycolic acid
Glycolic acid is another important two-carbon carboxylic acid
with a hydroxyl group, which is the smallest a-hydroxy acid. It
has been widely used in organic synthesis, biodegradable
polymer synthesis, skin-care products, industrial rust removal,
and food processing.11 The price for the glycolic acid market in
2011 was $2332 per metric ton, with an expected increase to
$5375 per metric ton in 2018.56 The US annual market size of
glycolic acid was 15 000 per ton in 2011.56 Glycolic acid is mainly
produced from the reaction of formaldehyde with synthesis gas
(carbonylation of formaldehyde). It can also be prepared by the
reaction of chloroacetic acid with sodium hydroxide followed by
re-acidification. The net reaction can be summarized as follows:
ClCH2COOH + NaOH - HOCH2COOH + NaCl. Glycolic acid can
also be produced from cellulose as shown in Fig. 11.
So far, the oxidative conversion of carbohydrates to glycolic
acid has been less studied.57–59 Jin and co-workers performed
the hydrothermal conversion of cellulose into glycolic acid using
commercial CuO as the oxidant under alkaline conditions in a bath
reactor. They achieved a glycolic acid yield of 14.9% with acetic
acid (5.2% yield), formic acid (7.1% yield) and lactic acid (13.8%
yield) as by products (reaction conditions: 573 K for 300 s with
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Fig. 11 Oxidative conversion of carbohydrates (cellulose as an example) into glycolic acid.
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0.035 g of cellulose in 2 mL NaOH (1 M) and 2 mmol CuO).57
Later Han and co-workers studied the oxidative conversion
of cellulose over four kinds of heteropoly acids at 453 K and
6 bar O2.58 H3PMo12O40 and H4SiMo12O40 produced glycolic
acid with yields of 49.3% and 46.5%, respectively, and other
products were formic acid, acetic acid, levulinic acid, glucose
and fructose. Whereas, Mo-free heteropoly acids including
H3PW12O40 and H3SiW12O40 produced only a small amount of
glycolic acid in yields of less than 6%. These results suggested
that the reaction pathway is determined by the type of metal
atom in the heteropoly acids, and that Mo favors a selective
oxidation of cellulose into glycolic acid. Han and co-workers
proposed a reaction pathway for the oxidation of cellulose into
glycol acid (Fig. 12). Cellulose is firstly hydrolyzed to glucose,
which then undergoes successive retro-aldol condensations
to produce glycolaldehyde. In parallel, the isomerization of
glucose gives rise to fructose, which can also be converted by
retro-aldol reactions through dihydroxyacetone and glyceralde-
hydes to glycolaldehyde and formaldehyde. The oxidation of
glycolaldehyde and formaldehyde produces glycolic acid and
formic acid, respectively. As glyceraldehyde and glycolaldehyde
are also intermediates for the oxidation of glucose into formic
acid under similar reaction conditions by Fu and co-workers,24
the difference of the oxidation products should be mainly
due to the use of different catalysts. Vanadium-containing
heteropoly acids such as H5PV2Mo10O40 were effective for the
oxidation of these intermediates into formic acid, while
molybdenum-containing heteropoly acids such as H3PMo12O40
Fig. 12 Proposed pathways for the conversion of cellulose to glycolic acid. Adapted from ref. 58 with permission from American Chemical Society,
copyright 2012.
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and H4SiMo12O40 were effective for the oxidation of these
intermediates into glycolic acid.
The photocatalytic oxidation method was also reported for
the conversion of cellulose into glycolic acid.59 This method
used a UV-Fenton reaction where strong oxidative species such
as hydroxyl radicals ( OH) are produced by H2O2 catalyzed by
FeCl2 under UV irradiation. Glycolic acid was produced in a very
low yield of 4%, and the major products were formic acid (31%)
and CO2 (54%). The addition of ZnCl2 increased the glycolic
acid yield to 33%, and decreased the formic acid and CO2 yields
to 14% and 27%, respectively. The authors proposed that the
Zn2+ enhanced the glycolic acid yield via complexation with
glyconic acid, thus preventing the further oxidative decomposi-
tion of glyconic acid.
5. Conversion of carbohydrates into
malonic acid and oxalic acid
The oxidative conversion of carbohydrates can also generate two
other dicarboxylic acids of malonic acid (propanedioic acid)
and oxalic acid. Malonic acid with a structure of CH2(COOH)2 is
a bulk chemical molecule for the preparation of malonates,
barbituric acid, and meldrum’s acid, and it is also a feedstock to
prepare 1,3-propanediol, which is one of the chemical precursors
of polytrimethylene terephthalate (PTT), an alternative to poly-
ethylene terephthalate (PET) in the future.60 Malonic acid is
mainly prepared by the fermentation of glucose or starch.61
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Fig. 13 Reaction pathways for the conversion of cellulose to malonic acid. Adapted from ref. 62 with permission from American Chemical Society,
copyright 2014.
Yang and Qi reported a hydrothermal method for the oxidative
transformation of cellulose into malonic acid at 573 K with a
high concentration of NaOH.62 Cellulose was firstly dissolved in
an aqueous solution of NaOH and urea. Then the hydrothermal
treatment of the 4 mg mL 1 cellulose solution at 573 K produced
malonic acid in a yield of 39.7% after 1 h at a NaOH concentration
of 100 mg mL 1. At the same time, lactic acid, acetic acid and
formic acid were produced in yields of 9.5%, 7.9% and 6.7%,
respectively. It was proposed that cellulose was firstly hydrolyzed to
glucose, which was subsequently degraded into dihydroxyacetone
and glyceraldehyde, via isomerization and retro-aldol reactions.
In the presence of oxygen, dihydroxyacetone was transformed
to malonic acid (HOOC–CH2–COOH) by a series of oxidation
and dehydration steps (Fig. 13). Meanwhile, lactic acid was
formed from glyceraldehyde through consecutive dehydration
and 1,2-hydride shift reactions.
Oxalic acid (OA) is an industrially important chemical with
various applications, such as the production of celluloid and
rayon, leather manufacture and dressing, and extraction of rare
earths from monazite.63 Oxalic acid was early manufactured by
the oxidation of carbohydrates using nitric acid as the oxidant.63
Obviously, the use of molecular oxygen for the synthesis of oxalic
acid is environmentally-friendly. Han and co-workers reported a
new method for the oxidative conversion of cellulose into oxalic
acid in 2 M NaOH solution catalyzed by CuO.64 Oxalic acid was
produced in a yield of 41.5% with a catalytic amount of CuO at
474 K and 3 bar O2. Formic acid, acetic acid, and lactic acid were
also produced with yields of 20.1%, 6.6% and 3.0%, respectively.
Fig. 14 Reaction pathway for the conversion of cellulose to oxalic acid. Adapted from ref. 64 with permission from American Chemical Society,
copyright 2016.
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As shown in Fig. 14, there are two main degradation pathways
for glucose, namely C3–C4 scission, and C2–C3 scission.65
Glyceraldehyde, an important intermediate formed by the
C3–C4 scission of glucose, has a good selectivity toward lactic
acid in alkali solution. Glycolaldehyde as another intermediate
via C2–C3 scission could be oxidized to glycolic acid, which was
further oxidized to oxalic acid.
6. Conversion of carbohydrates into
gluconic acid and glucaric acid
Gluconic acid is one of the oxidation products of glucose
without the cleavage of the C6 chain.66 Gluconic acid and its
salts are biocompatible and biodegradable chemicals, which
have been widely used as a food additive, an ingredient for
concrete and a raw material for medicines and biodegradable
polymers.13 The current annual worldwide production capacity
for gluconic acid and its derivatives is estimated to be about
60 000 tones per year.13 Current commercial production of
sodium gluconate uses submerged fermentation with A. niger
and is based on the modified process developed by Blom et al.67
It involves fed-batch cultivation with intermittent glucose
feedings and the use of sodium hydroxide as a neutralising
agent. pH is held at 6.0–6.5 and the temperature at about 307 K.
The productivity of this process is very high, since glucose
is converted at a rate of 15 g (L h) 1. The biochemical method
(fermentation) is competitive with chemical techniques
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(such as catalytic methods, and electrolytic methods), and is
at present the method of choice by industry. Although the
biochemical method is used as the industrial method for the
production of gluconic acid, this biochemical process still has a
few drawbacks such as the difficulties in using moulds and free
enzyme separation, waste-water removal, and dead microbes
and accumulated excretory substances of microbes that should
be disposed of.68 In addition, the product of the biochemical
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yield of 99.4% was obtained at a constant pH = 9 with air as the
oxidant after 2.6 h over the Pd–Bi/C catalyst (Table 5, entry 1).
Whereas, a Pd/C catalyst produced gluconic acid with a 78.1%
yield at a glucose conversion of 82.6% after 24 h (Table 5,
entry 2). Bismuth (Bi) was proposed to prevent the oxygen
poisoning of the Pd surface by acting as a co-catalyst in the
oxidative dehydration mechanism (Fig. 16), and the Pd–Bi/C

catalyst could be reused for five runs without any decrease of

process is sodium gluconate, as the fermentation process is
carried out at a relative high pH at 6.0–6.5. Recent developments
have shown the potential of chemical catalytic procedures for
oxidizing glucose with oxygen or air.69,70 The economic viability
of the chemical catalytic processes depend largely on the
activity, selectivity, lifetime and cost of the catalyst as well as
on the measures required for product purification and the
energy demand.
6.1 Oxidation of glucose into gluconic acid with O2 as the
oxidant
Most researchers used supported noble metal catalysts (Pt, Pd
and Au) for the oxidation of glucose into gluconic acid with O2
as the oxidant (Fig. 15). A base is often required in this process.
In 1995, Besson and co-workers studied the aerobic oxidation of
glucose over the Pd/C and Pd–Bi/C catalysts.71 A gluconic acid
gluconic acid yield. A similar phenomenon was also observed by
Karski and co-workers, when they used Pd–Bi/C and Pd–TI/SiO2
catalysts for the oxidation of glucose into gluconic acid.72
In contrast to the Pd–Bi/C and Pd–TI/SiO2 catalysts, Crossley
and co-workers reported that the commercial Pd/C catalyst
(Sigma-Aldrich) was stable for the oxidation of glucose, which
was obtained from the fast pyrolysis of bio-oils, followed by
hydrolysis.73 Crossley obtained a gluconic acid yield of 83% after
24 h at 323 K at and a constant pH = 9.3 (Table 5, entry 3).73 After
the first run, fresh glucose was then added, and the yield of
gluconic acid after 3 h was the same as the first run.
Besides the addition of a second metal to Pd catalysts, the
interaction between metal nanoparticles and a support also
shows some effect on the catalyst activity and stability. Liu and
co-workers studied two kinds of Pd/g-Al2O3 catalysts for glucose
oxidation. The 3.14% Pd/g-Al2O3-(P) catalyst was prepared by

Fig. 15 Catalytic oxidation of glucose into gluconic acid over metal catalysts.

Table 5 Catalytic oxidation of glucose into gluconic acid/salt with O2 as the oxidanta

Entry Catalyst Feed con. (M) Catalyst ratiob T (K) pHc Oxidant Time (h) Con. (%) Yield (%) Ref.
1
1 Pd–Bi/C 1.66 787 313 9 1.5 L min (1 bar air) 2.6 99.6 99.4 71
2 Pd/C 1.66 787 313 9 1.5 L min 1 (1 bar air) 24 82.6 78.1 71
3 Pd/C 0.02 — 323 9.3 60 mL min 1 (1 bar air) 24 83 83 73
4 Pd/g-Al2O3-(P) 0.4 139 323 9 400 mL min 1 (1 bar O2) 6 100 95 74
5 Pd/g-Al2O3-(C) 0.4 139 323 9 400 mL min 1 (1 bar O2) 8 95 90.3 74
6 Pd/HPS — — 353 6.0–7.5 100 mL min 1 (1 bar O2) 20 93.6 93.2 75
7d Pt/C 0.167 — 413 — 50 bar air 1 63 46 77
8d Pt/C 0.167 — 473 — 50 bar air 1 94 22.6 77
9 Pt/HT 0.13 68 323 — 1 bar O2 12 99 83 78
10 Au/C 0.22 1000 323 7 3 bar O2 2.5 100 99 85
11 Au/C 0.22 1000 323 9.5 3 bar O2 0.5 100 99 85
12 Au/C 0.22 1000 373 — 3 bar O2 6 100 99 85
13 Au/CMK-3 0.1 1000 383 — 3 bar O2 2 92 80.5 88
14 Au/TiO2 0.1 4378 313 11 500 mL min 1 (1 bar O2) 2 100 98 89
15 Au/TiO2-SIM 0.06 438 433 — 3 bar O2 1 71.1 67.3 90
16 Au/TiO2-CIM 0.06 438 433 — 3 bar O2 1 30.3 20.0 90
17 Au/TiO2-DP 0.06 438 433 — 3 bar O2 1 61.7 58.0 90
18 Au/TiO2-DP 0.167 140 338 — 2.3 bar O2 2 91 90 91
19 Au/ ZrO2-DP 0.167 140 338 — 2.3 bar O2 2 89 88 91
20 Au/CeO2-DP 0.167 140 338 — 2.3 bar O2 2 89 87 91
21 Au–Pd/MgO 0.5 1225 333 — 1 bar air 24 62 100 114
a
All of the reactions were carried out in water in a batch reactor, except for entries 7 and 8. b The catalyst ratio = the molar ratio of glucose to the
noble metal. c Some reactions were performed without pH control if there was no data in this column. d The reaction was performed in a
continuous flow reactor.

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Fig. 16 Glucose oxidation on the Pd–Bi/C catalyst. Adapted from ref. 71 with permission from Elsevier, copyright 1995.
the argon glow discharge plasma approach, including the
impregnation of g-Al2O3 with PdCl2 and the subsequent treatment
with argon glow discharge plasma.74 The 3.14% Pd/g-Al2O3-(C)
catalyst was also prepared by the conventional impregnation of
g-Al2O3 with PdCl2 followed by calcination in air, and subsequent
reduction with H2. Both catalysts gave the same gluconic acid
selectivity (95%), while the Pd/g-Al2O3-(P) catalyst had higher
activity (Table 5, entries 4 vs. 5). Pd/g-Al2O3-(P) also showed
higher stability than Pd/g-Al2O3-(C), albeit both of them were
not stable. The amount of Pd leaching from the Pd/g-Al2O3-(P)
catalyst was 4.4% in the first run, while it was 17.8% for the
Pd/g-Al2O3-(C) catalyst. The higher activity and stability of
Pd/g-Al2O3-(P) over Pd/g-Al2O3-(C) was attributed to the stronger
interaction between Pd nanoparticles and the support. Diffuse
reflectance Fourier transform infrared (DRIFT) spectra of CO
adsorption indicated that a lower percentage of CO was absorbed
on the surface of Pd/g-Al2O3-(P) than that on the surface of the
Pd/g-Al2O3-(C) catalyst. The lower amount of CO adsorbed over
the Pd/g-Al2O3-(P) catalyst was due to the stronger interaction
between Pd nanoparticles and g-Al2O3. Another example to
enhance the interaction between Pd nanoparticles and a support
involved the deposition of Pd nanoparticles onto hypercrosslinked
polystyrene (HPS) (Pd/HPS).75 HPS contains micropores, meso-
pores and macropores, which have strong interaction with Pd
nanoparticles. The glucose conversion and gluconic acid yield
were 93.6% and 93.2% after 20 h at 353 K (Table 5, entry 6),
respectively. After five runs, the glucose conversion (93.4%) was
almost the same as the first run (93.6%), and the gluconic acid
selectivity was also the same.
Compared with Pd catalysts, Pt catalysts have also been
studied for the aerobic oxidation of glucose, which generally
deactivate and have lower gluconic acid selectivity. In 1981,
Kogelbauer and co-workers studied the oxidation of glucose in
a weakly alkaline medium with a Pt/C catalyst.76 The authors
proposed that the surface of the active Pt was initially covered
with chemisorbed oxygen (Pt–O), and glucose first reacted with
chemisorbed oxygen (Pt–O) to yield gluconic acid. Catalyst
deactivation occurs in this process, due to the formation of
platinum oxide (PtO2). Besides gluconic acid, uronic acid and
glucaric acid were also detected in the reaction solution, and
the selectivity of gluconic acid was only 70% at 323 K at pH = 9.
Later, Koklin and co-workers performed the oxidation of glucose
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over the Pt/C catalyst in a flow reactor without pH control at
higher temperatures (413–473 K). Glucose conversion increased
from 63% at 413 K to 94% at 473 K after 1 h, but gluconic acid
selectivity decreased from 73% at 413 K to 24% at 473 K
(Table 5, entries 7 vs. 8).77 The oxidation of glucose over the
Pt/C catalyst without base required high reaction temperatures
(413–473 K),77 while it could be carried out at a lower tempera-
ture of 323 K at pH = 9.76 Besides the addition of a base to
control a constant pH, a Pt catalyst with a basic support can
also promote glucose oxidation at low temperatures.78 A Pt/HT
catalyst was prepared by adding Pt to hydrotalcite {HT, with a
general formula of Mg6Al2CO3(OH)16
4(H2O)} and produced a
99% conversion of glucose and a 83% yield of gluconic acid
after 12 h at 323 K (Table 5, entry 9).78 Fructose was also
detected in a yield of 8% by the isomerization of glucose, which
was catalyzed by the base support of HT. In addition, other small
molecular weight organic acids such as oxalic acid, malonic acid,
and lactic acid were also observed in minor amounts (4–5%).
Unlike the Pt/C catalyst,76 the Pt/HT catalyst did not suffer
poisoning albeit 10% of the catalyst activity was lost in each
run, which was caused by the leaching of Pt. There was less
research on using Au catalysts for glucose oxidation than Pd and
Pt catalysts for a long time. Since the discovery of the activity of
Au nanoclusters by Haruta in 2003,79 Au catalysts have received
great attention in chemical reactions.80–82 Recently, supported
Au catalysts were found to have catalytic activity towards the
oxidation of glucose into gluconic acid.83,84 The particle size of
Au nanoparticles and the nature of the support were observed to
have an important impact on the catalytic activity, selectivity and
stability.83,84 Supported Au catalysts mainly include Au/C,85–88
Au/TiO2,89–91 Au/g-Al2O3,92–99 Au/CeO2,91,100 Au/ZrO2,91,100,101
Au/SiO2102,103 and polymer supported Au catalysts.104,105 Biella
and co-workers studied a carbon supported Au catalyst (Au/C)
for the oxidation of glucose at pH values from 7.0 to 9.5 and
without pH control (Table 5, entries 10–12).85 The gluconic acid
yield at different pH (7.0 and 9.5) was as high as 99% at 323 K,
but a higher reaction rate was observed at a higher pH (Table 5,
entries 10 and 11). The Au/C catalyst was also active without pH
control, but a higher reaction temperature of 373 K and a
longer reaction time of 6 h were required to get similar results
(Table 5, entry 12). The Au/C catalyst deactivated due to the
leaching and sintering of Au nanoparticles at the pH below 9.5.
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There was no leaching of Au at pH = 9.5, but the size of the Au
nanoparticles increased from 4.4 nm in the fresh catalyst to
5.9 nm after four runs. At pH = 7, 18% of Au was leached into
the solution after 4 runs and the Au size was 5.4 nm. At pH = 7,
gluconic acid can chelate with Au nanoparticles, causing the
leaching of Au from the Au/C catalyst. Later, ordered meso-
porous carbon (OMC) supported Au catalysts were used for
the oxidation of glucose into gluconic acid.86,88 The Au/OMC
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catalyst with an average mesopore size of 5.4 nm and an Au
nanoparticle size of 3.3 nm gave a high TOF of 4.308 mol
glucose molAu 1 s 1 at 313 K and pH = 9 with an O2 flow rate of
100 mL min 1 under atmospheric pressure,86 much higher than
the Au/C catalyst with a TOF of 0.023 mol glucose molAu 1 s 1
at pH = 11 with the same temperature and O2 flow rate.87 The
superior catalyst activity of the Au/OMC catalyst was ascribed to
its mesopore structure that could not be blocked by Au nano-
particles, and the remaining space was enough for molecule
diffusion during the reaction process. Besides, abundant O
and O2 species on the surface of the Au/OMC catalyst also
promoted the oxidation of glucose into gluconic acid. Later,
Yuan and co-workers prepared another ordered mesoporous
carbon (CMK-3)-supported Au catalyst (Au/CMK-3) for the base-
free oxidation of glucose.88 Au nanoparticles were uniformly
dispersed on the surface and in the channels of CMK-3 with an
average size of 3 nm. Glucose conversion reached 92% with a
gluconic acid selectivity of 87.5% after 2 h at 383 K and 3 bar O2
(Table 5, entry 13). Similar to the base-free oxidation of glucose
over the Au/C catalyst,85 the oxidation of glucose over the
Au/CMK-3 catalyst without pH control was also performed at
a relatively high temperature of 383 K.85,86 The Au/CMK-3
catalyst lost its activity, due to the absorption of gluconic acid
molecules. XPS analysis revealed that a peak of O 1s with the
binding energy at 534.1 eV was attributed to the –COOH group,
which increased from 5% in the fresh catalyst to 21% in the
spent catalyst. Two methods were applied to recover the activity of
the spent catalyst. On the one hand, the treatment of Au/CMK-3
with NaOH at 363 K could produce glucose conversion up to 87%
after 2 h at 383 K and 3 bar O2, which was close to the results of a
fresh catalyst. However, the treatment of Au/CMK-3 by calcination
at 773 K only produced glucose conversion of 55% after 2 h
under the same conditions. The authors ascribed the reason to
the growth of Au nanoparticles to 3.5 nm during the calcina-
tions process, while it was kept the same at 3.0 nm with the
treatment by NaOH.
Metal oxide supported Au catalysts were found to be more
stable than the Au/C catalyst under basic conditions. Prüße and
co-workers prepared a TiO2 supported Au (Au/TiO2) catalyst
using the deposition–precipitation method, which produced a
98% yield of gluconic acid within 2 h at 313 K and pH = 11 with
an O2 flow rate at 500 mL min 1 under atmospheric pressure
(Table 5, entry 14).89 The Au/TiO2 catalyst could be reused at
least 17 times without a discernible loss of its activity. ICP
analysis indicated that there was no leaching of Au, and TEM
indicated that there was no change in the Au particle size. Later,
Hutchings and co-workers prepared three kinds of Au/TiO2 catalysts
for the base-free oxidation of glucose.90 Conventional impregnation
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(CIM), deposition–precipitation (DP) and sol-immobilization
methods (SIM) were used for the preparation of the Au/TiO2-
CIM, Au/TiO2-DP and Au/TiO2-SIM catalysts, respectively. The
as-prepared catalysts were further calcined in static air at 250 1C
for 3 h. The Au/TiO2-SIM catalyst showed better catalytic
performance than the other two kinds of catalysts at 433 K
(Table 5, entries 15–17). The Au/TiO2-SIM catalyst not only had
a small size of Au nanoparticles, but also showed the highest
dispersion of Au nanoparticles. Therefore, the Au/TiO2-SIM
catalyst showed the best catalytic activity. Again, the base-free
oxidation of glucose over the Au/TiO2 catalyst was performed at
higher temperature than that with a constant pH = 11.89
Román-Leshkov and co-workers compared the activities of the
three kinds of metal oxide (TiO2, ZrO2, CeO2) supported Au
catalysts for glucose oxidation without pH control, which were
prepared using a deposition–precipitation (DP) method.91 The
three kinds of Au catalysts produced glucose conversion around
90% and gluconic acid selectivity up to 99% after 2 h at 338 K
and 2.3 bar O2 (Table 5, entries 18–20).91 The authors found
that the deactivation of the Au catalysts was caused by the
leaching and hydrothermal sintering of Au nanoparticles, as well
as by the adsorption of reactive species. Lowering the surface
density of Au nanoparticles on metal oxides decreased the
sintering rate of Au nanoparticles and enhanced the stability
and activity of the catalysts. Alumina supported Au catalysts
(Au/g-Al2O3) prepared using different methods were reported to
show high catalytic activity and long-term stability towards the
oxidation of glucose in a continuous flow reactor.92–95,98,99 For
example, the Au/g-Al2O3 catalyst prepared using an incipient wetness
method showed a maximum activity of about 600 mmol g 1 min 1
with 100% yield of sodium gluconate at 313 K and pH = 9 in a
batch reactor with an O2 flow rate of 500 mL min 1 at atmo-
spheric pressure.94 The Au/g-Al2O3 catalyst could be re-used
20 times without any decrease of its activity. Similarly, Thielecke
and co-workers reported that the Au/g-Al2O3 catalyst showed no
loss of its activity and selectivity during 70 days of continuous-
flow glucose oxidation.98,99
Au containing bimetallic and trimetallic catalysts have also
been widely used for glucose oxidation either in the form of
alloys or supported states, including Au–Ag,106–109 Au–Pt,110,111
Au–Pd,112–114 Au–Pt–Pd115 and Au–Pt–Ag,116–118 which have
been documented by Zhang and Toshima in 2013.69 The
bimetallic catalysts generally showed better catalytic perfor-
mance than the monometallic catalysts.69 For example, the
bimetallic Au–Pt/C catalyst showed 6 times higher catalytic
activity (TOF) than the Au/C catalyst without pH control.111
In conclusion, supported Au catalysts typically show
higher activity and stability over supported Pd and Pt catalysts.
Therefore, supported Au catalysts should be promising for the
large-scale production of gluconic acid from glucose oxidation.
High pH is generally required to achieve high activity and
selectivity with supported Au catalysts. Similar to the results
reported by Thielecke and co-workers,99 the Au/g-Al2O3 catalyst
could be used in a continuous reactor for the large scale
oxidation of glucose, but it was performed in an aqueous
solution of NaOH. The product is in the form of sodium
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gluconate and would require acidification to be converted into
gluconic acid.
6.2 Oxidation of glucose into gluconic acid with H2O2 as the
oxidant
The oxidation of glucose into gluconic acid is mostly performed
by the use oxygen as the oxidant rather than H2O2. However,
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there are a handful of studies where they use H2O2 as the
oxidant for glucose oxidation. In addition to O2, H2O2 was also
used for the oxidation of glucose because of its reasonable
price, safe storage, and low environmental impact. Prüße
and co-workers performed the oxidation of glucose with H2O2
using a commercial Au/g-Al2O3 catalyst.119 Under mild reaction
conditions (313 K, pH = 9), quantitative gluconic yields (499%)
were obtained at glucose concentrations ranging from 2–50 wt%
using 1.1 equiv. H2O2. H2O2 was added stepwise in constant
portions during the course of the reaction until the total amount
was reached to avoid the decomposition of H2O2. The apparent
activation energy was 48 kJ mol 1 in the range of 303–333 K,
which was similar to the apparent activation energy (47 kJ mol 1)
of glucose oxidation with O2.94 Later, Repo and co-workers
performed microwave-assisted base-free oxidation of glucose
over the Au/g-Al2O3 catalyst with an average size of 2.4 nm.120
The microwave irradiation could accelerate the reaction rate,
which produced a glucose conversion of 83% with a gluconic
acid selectivity of 87% in 10 min by the use of 2.2 equiv. H2O2
at 393 K. Recycling experiments indicated that the Au/g-Al2O3
catalyst retained constant activity during four consecutive runs,
even though the Au particle size was observed to increase
from 2.4 nm to 3.6 nm. Omri and co-workers also reported a
microwave-assisted oxidation of glucose into gluconic acid over
different metal-oxide supported Au catalysts with H2O2 as the
oxidant.121 Au/g-Al2O3 and Au/CeO2 showed higher catalytic
activity than Au/TiO2 with the same catalyst weight and a similar
average size of around 2–3 nm. High conversions and high
selectivity beyond 90% were produced over the Au/g-Al2O3 and
Au/CeO2 catalysts in 10 min with 1 equiv. of NaOH and 3 equiv.
of H2O2, while the glucose conversion was 46% and a gluconic
acid selectivity of 69% was obtained from the Au/TiO2 catalyst.
The peroxide radical (HO2 ) is supposed to be the active species
for the oxidation of glucose into gluconate. A silica-supported Au
catalyst (Au/SiO2) suspended in 30% H2O2 was also reported for
the oxidation of glucose into gluconic acid.103 100% conversion
of glucose and B80% yield of gluconic acid were attained within
1 h at room temperature and pH = 9.2 by the use of 6 equiv.
H2O2. Besides gluconic acid, glucaric acid was produced with a
selectivity of about 15%. Some catalyst stability problems were
observed using this catalyst system.
Besides supported Au catalysts, the inexpensive and abun-
dant FeSO4 was also used for the oxidation of glucose into
gluconic acid with H2O2 as the oxidant.122 A high gluconic acid
yield up to 97% was obtained after 15 min with ultrasonic
activation at 70 1C by the use of 12 equiv. H2O2. A hydroxyl
radical (HO ) was the oxidative species, which was produced
from the reaction of H2O2 with FeSO4. This catalytic system
demonstrates many challenges including the recycling and
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reuse of the homogeneous FeSO4 catalyst, and the purification
of the product from FeSO4 due to the high affinity of Fe3+ with
gluconic acid. In addition, this system also required the use
of a high amount of H2O2 (12 equiv.) compared with those with
Au catalysts.
6.3 Conversion of polysaccharides and lignocellulose into
gluconic acid
Synthesis of gluconic acid from polysaccharides and ligno-
cellulose basically requires two successive steps: acid-catalyzed
hydrolysis of lignocellulose or polysaccharides into glucose and
the subsequent oxidation of the produced glucose. Therefore,
bifunctional catalysts combining both metal and acidic sites are
essential to integrate the hydrolysis and oxidation steps into a
one-pot reaction for the conversion of cellulose or polysaccharides
into gluconic acid.
In 2009, Wang and co-workers first reported the transforma-
tion of cellobiose into gluconic acid over supported Au catalysts
without pH control.123 Carbon nanotubes (CNTs) pretreated
with 68 wt% HNO3 supported Au catalyst (Au/CNT) produced
the highest gluconic acid yield of 68% at a cellobiose conver-
sion of 81% after 3 h at 418 K and 5 bar O2 (Table 6, entry 1).
The treatment of CNTs with HNO3 created more acidic sites as
measured by NH3-TPD, which were used for the hydrolysis of
cellobiose. Using Al2O3 and MgO as supports also produced
higher cellobiose conversions (93–100%), but the gluconic acid
selectivity was lower (10–20%). The supports showed a great
effect on the degradation of gluconic acid. For example, 14%,
67% and 97% of gluconic acid degraded with CNT, Al2O3 and
MgO, respectively. Similar to the Au/CNT catalyst, the acidic
carbon xerogel (CX) supported Au catalyst (Au/CX) also showed
activity for the one-pot conversion of cellobiose to gluconic
acid.124 The carbon xerogels were prepared by the polyconden-
sation of resorcinol with formaldehyde (molar ration = 1 : 2) in
water, and the subsequent carbonation in a nitrogen atmo-
sphere. Phenolic groups (acidic sites) were introduced on the
surface of the Au/CX catalyst for the hydrolysis of a glycosidic
bond. A selectivity of nearly 80% to gluconic acid and a glucose
conversion of 75% were obtained after 1.25 h at 418 K and 5 bar
O2 (Table 6, entry 2). The partial exchange of H+ in hetero-
polyacids (HPW) with large cations (e.g., Cs+, Ag+) not only
retained their acidity, but also made them not dissolve in water
or organic solvents.125 Zhang and co-workers prepared a bifunc-
tional Au/Cs2HPW12O40 catalyst for the oxidative conversion of
cellobiose with a high gluconic acid yield of 96.5% after 3 h at
418 K and 5 bar O2. (Table 6, entry 3).126 The Au/Cs2HPW12O40
catalyst did not have a high rate of catalyzing gluconic acid
degradation as only 4.5% of gluconic acid was converted into
other byproducts by the use of pure gluconic acid as a feed. The
Au/Cs2HPW12O40 catalyst was more effective than the Au/CNT
and Au/CX catalysts (Table 6, entries 1, 2 vs. 3). The better
catalytic performance of Au/Cs2HPW12O40 was possibly due to
its higher acidity, which catalyzed the hydrolysis of cellobiose
faster. Recycling experiments of the Au/Cs2HPW12O40 catalyst
indicated that cellobiose conversion did not change significantly,
but the selectivity of gluconic acid dropped by approximately 7.8%
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Table 6 One-pot conversion of cellobiose or lignocellulose into gluconic acid and in bath reactorsa

Feed con. Catalyst

Entry Substrates (mg mL 1) Catalyst ratiob T (K) O2 (bar) Time (h) Con. (%) Yield (%) Ref.
1 Cellobiose 5.13 Au/CNT 236 418 5 3 81 68 123
2 Cellobiose 4.1 Au/CXs 118 418 5 1.25 75 B80 124
3 Cellobiose 5.0 Au/Cs2HPW12O40 118 418 5 3 97.5 96.4 126
4 Cellobiose 0.4 Au/Cs1.2H1.8PW12O40 118 418 5 3 97 97 127
5 Cellulose 20 Au/Cs1.2H1.8PW12O40 118 418 10 11 — 60 127
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6 Cellobiose 5 Au/Amberlyst-15 14 373 In air 24 — 44.9 128

7 Cellobiose 5.13 Au/TiO2 118 393 5 3 100 67.4 129
8 Cellobiose 10.3 0.5Cu–0.5Au/TiO2 58 418 10 3 100 88.5 130
9 Cellobiose 10.3 0.5Ru–0.5Au/TiO2 80 418 10 9 100 86.9 130
10 Cellobiose 10.3 0.5Co–0.5Au/TiO2 55 418 10 3 96.8 33.6 130
11 Cellobiose 10.3 0.5Pd–0.5Au/TiO2 83 418 10 3 96.8 35.6 130
12 Starch 9 Pt/AC-SO3H — 393 In air 24 — 40 132
13 Pullulan 9 Pt/AC-SO3H — 393 In air 24 — 35 132
14 Cellobiose 9 Pt/AC-SO3H 13 393 In air 24 — 46 132
a b
All of the reactions were carried out in water. The catalyst ratio = the molar ratio of cellobiose to the noble metals.

in the second run and then stabilized in the following runs.
Similar work was later reported by An and co-workers by the use of
the Au/Cs1.2H1.8PW12O40 catalyst (Table 6, entry 4).127 Meanwhile,
the Au/Cs1.2H1.8PW12O40 catalyst was also effective for the oxidative
conversion of cellulose into gluconic acid with a yield of 60% after
11 h at 418 K and 10 bar O2 (Table 6, entry 5). The yield of gluconic
acid from cellulose increased to 85% by co-feeding H3PO4 with Au/
Cs1.2H1.8PW12O40. H3PO4 promoted the hydrolysis of cellulose into
glucose. A slight decrease of gluconic acid yield was observed over
the H3PO4 and Au/Cs1.2H1.8PW12O40 catalytic system, due to the
growth of Au nanoparticles from 2.7 nm (fresh catalyst) to 3.9 nm
(the spent catalyst after 6 runs). Sakurai and co-workers deposited
Au nanoparticles with an average diameter of 7.3 nm on the surface
of Amberlyst-15 to generate a metal–acid bifunctional catalyst
(Au/Amberlyst-15) for cellobiose conversion to gluconic acid.128
The yield of gluconic acid was low at 44.9% together with a
glucose yield of 6.3% after 24 h at 373 K in air (Table 6, entry 6).
Besides the use of supports with Brønsted acidity, metal-
oxides with Lewis acidity were also used for the construction
of Au–acid bifunctional catalysts for the transformation of
cellobiose into gluconic acid. Yang and co-workers reported
that a TiO2 supported Au catalyst (Au/TiO2) could simultaneously
catalyze cellobiose hydrolysis and the subsequent oxidation of
glucose into gluconic acid.129 NH3-TPD profiles presented two-
peaks with a total acidity up to 354.54 mmol g 1 for the Au/TiO2
catalyst. One weak peak at a low temperature of 534 K was
attributed to the adsorption of NH3 with very weak Brønsted
acid, whereas the strong and conspicuous peak at 648 K was
attributed to the desorption of NH3 on the strong Lewis acid
sites of TiO2. The Au/TiO2 catalyst reduced at 700 1C under a H2
flow produced 100% cellobiose conversion and 67.4% gluconic
acid yield within 3 h at 418 K and 5 bar O2 (Table 6, entry 7). The
byproducts were glycolic acid (14.3% selectivity) and ethylene
glycol (13.2% selectivity). Later, the same authors improved this
method by the use of TiO2 supported bimetallic catalysts.130,131
Complete conversion of cellobiose (100%) and a gluconic acid
selectivity of 88.5% were produced over the 0.5Cu–0.5Au/TiO2
catalyst after 3 h at 418 K and 10 bar O2 (Table 6, entry 8).
Whereas, a longer reaction time of 9 h was required for the
0.5Ru–0.5Au/TiO2 catalyst to get similar results (Table 6, entry 9).
Interestingly, the reaction pathways were affected by the com-
position of the bimetallic catalysts. For the reaction with the
0.5Cu–0.5Au/TiO2 catalyst, it is suggested that cellobiose is
firstly converted to cellobionic acid, followed by the cleavage
of the b-1,4-glycosidic bonds to produce gluconic acid (Fig. 17,
path A). For the reaction over the 0.5Ru–0.5Au/TiO2 catalyst,
glucose was observed as the reaction intermediate and gluconic
acid was formed as a result of glucose oxidation (Fig. 17, path B).
For the reactions over the 0.5Co–0.5Au/TiO2 and 0.5Pd–0.5Au/TiO2
catalysts, low gluconic acid yields were produced under the same
reaction conditions (Table 6, entries 10 and 11), and fructose was
observed as the intermediate from the isomerization of glucose
(Fig. 17, path C). Furthermore, 0.5Co–0.5Au/TiO2 and 0.5Pd–
0.5Au/TiO2 catalysts remarkably promoted the successive retro-aldol
condensation reaction of fructose to produce glyceraldehyde and
glycolaldehyde, which were further oxidized to glycolic acid. For
example, fructose, glyceraldehyde and glycolic acid were also
produced over the 0.5Co–0.5Au/TiO2 catalyst with the selectivity
of 28.6%, 10.6% and 18.1%, respectively. The above discussed
examples all used Au–acid bifunctional catalysts for the oxidative
conversion of cellobiose into gluconic acid. A sulfonated activated-
carbon supported Pt catalyst (Pt/AC-SO3H) was reported to show
catalytic activity towards the oxidative conversion of cellobiose and
even lignocelluloses such as starch and pullulan into gluconic acid.
Gluconic acid was produced with relatively low yields of 35–46%
after 24 h in water at 393 K in air (Table 6, entries 12–14).132
As listed in Table 6, cellobiose can be successfully converted
into gluconic acid over bifunctional catalysts, but it is still not
suitable for the large-scale production of gluconic acid due to the
high cost of cellobiose. The use of cellulose or lignocellulose as the
feedstocks should be encouraged for the production of gluconic
acids. Au catalysts with a strong acidic support are required to
realize the hydrolysis of cellulose into glucose and the in situ
oxidation of glucose into gluconic acid simultaneously. A support
with strong Brønsted acids would be preferred to hydrolyze the
cellulose into glucose and stabilize Au nanoparticles with a
specific size and morphology for the subsequent oxidation of
glucose into gluconic acid.

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Fig. 17 Proposed reaction pathways of cellobiose conversion to gluconic acid and its derivatives. Adapted from ref. 131 with permission from Elsevier,
copyright 2015.
6.4 Conversion of glucose to glucaric acid
Glucaric acid is another important oxidation product of glucose
with the formula of C6H10O8 (Fig. 18). It has been classified by
the United States Department of Energy as a versatile platform
chemical from biomass for making a number of useful products,
such as nylons, plastics, and food additives.133 It serves as an
important precursor for one of the most widely used materials in
industry, adipic acid, which is conventionally obtained from
fossil-fuel-based feedstocks via energy-intensive processes using
expensive catalysts.134
In the past, glucaric acid was produced by the oxidation of
glucose with nitric acid.135 Other methods of glucaric acid synthesis
included either electrochemical or stoichiometric oxidation
using undesirable reagents such as NaBr and NaOCl.136–138
High concentrations of these oxidants in the reaction medium
and the generation of significant amounts of toxic by-products
and inorganic salts are the major issues confronting the
sustainability and environmental compatibility of these current
routes. Catalytic oxidation of carbohydrates into glucaric acid
has become much more attractive in recent years. Unlike the
oxidation of glucose into gluconic acid, the oxidation of glucose
is much more difficult, as it requires the simultaneous oxida-
tion of the hydroxyl group at the C6 position and the aldehyde
group at the C1 position into carboxylic acid groups (Fig. 16).
However, the oxidation of the hydroxyl group necessitates more
severe conditions than that of the aldehyde. Hence, side and
consecutive C–C cleavage reactions generally occur, resulting in
a poor selectivity. Recently, a few kinds of supported Pt catalysts
Fig. 18 Catalytic oxidation of glucose into glucaric acid.
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have been reported for the oxidation of carbohydrates into
glucaric acid with molecular oxygen.139–145
Chaudhari and co-workers prepared a series of supported Pt
catalysts for the oxidation of glucose to glucaric acid with O2 as
the oxidant.139 Initially, the authors screened different kinds of
catalysts for the oxidation of sodium gluconate with bubbles
of oxygen under atmospheric pressure. As shown in Table 7,
TiO2 was a better support than CeO2 (Table 7, entries 1 vs. 2).
Pt catalysts outperformed other monometallic Pd, Cu and Co
catalysts in terms of conversion and glucaric acid selectivity
under the same conditions (Table 7, entries 1 vs. 5, and entries
2 vs. 3 and 4). Other products were tartronic acid, and oxalic
acid, along with monocarboxylic acids such as glyceric, lactic,
glycolic, and formic acids. The PtCu/TiO2 bimetallic catalysts
exhibited much better performance than the Pt/TiO2 and Cu/TiO2
catalysts, suggesting that there was a synergetic effect between
Cu and Pt (Table 7, entries 2, 4 vs. 6). The authors further
studied the different ratios of Pt to Cu for the oxidation of
glucose to glucaric acid, and found that the Pt1Cu3/TiO2 catalyst
gave the highest TOF of 3542 h 1. Kinetic data indicated that the
addition of Cu to Pt altered the possible oxidation pathways,
thus lowering the activation barriers for the formation of
glucaric acids and other acids. The catalytic oxidation of
glucose over the Pt1Cu3/TiO2 catalyst produced glucaric acid
with a yield of 25.4% at full conversion after 24 h at 318 K and
1 bar O2 by the addition of NaOH at a rate of 0.2 mL min 1 for
the initial 2 h. The Pt1Cu3/TiO2 catalyst was stable and could be
reused 3 times without significant loss of its catalytic activity.
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Table 7 Comparison of mono- and bimetallic catalysts for sodium gluconate oxidation

Selectivity (%)
Entry Catalyst Conversion (%) Glucaric Tartronic Oxalic Others Carbon balance (%)
1 Pt/CeO2 28.0 47.0 31.1 6.4 15.6 100.1
2 Pt/TiO2 70.8 38.1 27.7 5.8 11.5 83.1
3 Pd/TiO2 41.1 44.2 28.3 8.3 11.5 92.3
4 Cu/TiO2 2.8 31.2 30.0 9.9 21.1 90.4
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5 Co/CeO2 5.5 21.8 38.9 15.6 15.3 91.6

6 PtCu/TiO2 100 32.3 27.2 19.5 11.1 91.8
Notes: reaction conditions: 3 g sodium gluconate, 1.0 g NaOH, 0.1 g solid catalyst, metal loading 2 wt% or 2–2 wt%, T: 60 1C, others: glyceric,
glycolic, and formic acids. Reaction time: 6 h. Adapted from ref. 139.

Later, the same authors prepared another bimetallic PtPd/TiO2
catalyst for the oxidation of glucose into glucaric acid.140
Similar to the Pt1Cu3/TiO2 catalyst, the PtPd/TiO2 catalyst also
exhibited synergistic activity compared with the monometallic
Pt and Pd ones. Compared with the Pt1Cu3/TiO2 catalyst, the
PtPd/TiO2 catalyst showed higher catalytic performance. The
oxidation of glucose produced glucaric acid with a selectivity
of 44% at full conversion under the same reaction conditions.
Meanwhile, tartronic acid with a selectivity of 15% and oxalic
acid with a selectivity of 6% were also produced. Concentration–
time profiles on the PtPd/TiO2 catalyst showed that no other
products besides gluconic acid were formed before glucose was
completely consumed. These results indicated that glucose
inhibited the second step oxidation of gluconic acid in the reaction
medium, with the secondary oxidation and C–C cleavage occurring
after glucose was consumed. After there was no glucose in the
reaction solution, the gluconic acid concentration gradually
decreased, which was firstly oxidized into glucuronic acid, followed
by oxidation of glucuronic acid into glucaric acid (Fig. 17).
Meanwhile, glucuronic acid easily isomerizes to 5-keto-gluconic
acid in the reaction medium. Direct C–C cleavage of 5-keto-
gluconic acid generated precursors for tartronic acid (Fig. 19).141
C–C cleavage of glucuronic acid generated C2 and C4 inter-
mediates and quickly gave C2 intermediates, which will even-
tually form oxalic acid through further oxidation (Fig. 19).
Furthermore, direct C–C cleavage of gluconic acid can generate
several monocarboxylic acid precursors such as formaldehyde,
glycolic aldehyde, and glyceraldehyde, which undergo further
reaction to form lactic, formic, glycolic, and glyceric acids
(Fig. 19). Recent patents were issued using the base-free oxida-
tion of glucose to glucaric acid over Pt and Pt–Au catalysts.142,143
The glucaric acid yield was reported to be 66% in the presence
of Pt/SiO2 in multiparallel millireactors after 8 h at 363 K and
5 bar O2. The yield reached 71% after 5 h at 393 K and 28 bar
O2 over the Au–Pt/TiO2 catalyst. However, these reactions were
conducted on a micro-liter scale in a 96 well-reactor system,
which was neither reproduced nor conducted on a reasonable
laboratory scale.

Fig. 19 Reaction pathway for the oxdiation of glucose into glucaric acid over the PtPd/TiO2 catalyst. Adapted from ref. 140 with permission from
American Chemical Society, copyright 2016.

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Besides metal-oxide supported Pt catalysts, Pt/C catalysts also
showed catalytic ability for the oxidative conversion of glucose
into glucaric acid. In 1972, Dirkn and co-workers reported that
the oxidation of gluconic acid over the Pt/C catalyst produced a
55% glucaric acid yield (gluconic acid/Pt = 20) at controlled
pH (8–11).144 Later, the oxidation of glucose over the Pt/C catalyst
was also performed at pH = 9. Gluconate was first formed with
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of chemicals. HMF, produced by the dehydration of C6
carbohydrates, is considered to be one of the most important
platform chemicals derived from biomass.149,150 As shown in
Fig. 20, several kinds of furan derivatives can be obtained by the
oxidation of HMF including DFF, HFCA, FFCA, and FDCA.
7.1 Selective oxidation of HMF into HFCA and FFCA

an 80% yield at nearly total conversion of glucose. Then,

HFCA is produced by selective oxidation of the formyl group in
gluconate was further oxidized to glucarate.145 The final selec-
HMF. HFCA is currently only produced on a small scale for the
tivity of glucaric acid was 57% at a 97% glucose conversion.
fine chemical industry ($2.5 per mg, Sigma-Aldrich). It has been
Vlachos and co-workers studied the oxidation of glucose into
used as a monomer in the synthesis of various polyesters,151
glucaric acid over three kinds of commercially available Pt
and as a building block of an interleukin inhibitor.152 HMF can
catalysts (Pt/C, Pt/SiO2 and Pt/Al2O3) with 5 wt% Pt loading.146
be selectively oxidized into HFCA with stoichiometric amounts
Under the same reaction conditions (353 K and 6.2 bar O2),
of silver oxide153 or a mixture of silver and copper(II) oxides154
the catalytic activity of the Pt catalysts decreased in the order of
as oxidants at room temperature. These methods have little
Pt/C 4 Pt/SiO2 4 Pt/Al2O3. The TOFs at 20% conversion
practical application as the cost of the oxidants is high and
of glucose were 879, 195, and 102 h 1 for the Pt/C, Pt/SiO2 and
stoichiometric amounts of metal byproducts are produced. There
Pt/Al2O3 catalysts, respectively, while those for gluconic acid
have been fewer reports on the oxidation of HMF into HFCA with
oxidation, starting from gluconic acid as a substrate, are 285,
O2 as the oxidant. HFCA is an intermediate of the oxidation of
42, and 13 h 1, respectively. These data clearly indicated that the
HMF into FDCA. Gorbanev and co-workers obtained HFCA in a
oxidation rate of the aldehyde group was much faster in glucose
yield of 76% together with a FDCA yield of 20% after 14 h over the
than that of a –CH2OH group in gluconic acid. Gluconic acid is
Au/CeO2 catalyst at 403 K and 10 bar air with NaOH/HMF molar
the major product in an acidic solution, while the selectivity to
ratio = 1.155 Similar work was also reported by Davis and
glucaric acid is poor in a highly basic solution, due to the C–C
co-workers.156 Full HMF conversion with 92–93% selectivity
bond cleavage to low carbon chain carboxylic acids. Thus, the
towards HFCA was attained over the Au/C and Au/TiO2 catalysts
oxidation of glucose into glucaric acid was performed without
after 6 h and 6.9 bar O2 with NaOH/HMF molar ratio = 2.
the addition of a base. A high glucaric acid yield of 74% was
A method was developed for the oxidation of HMF into
produced after 10 h at 353 K and 13.8 bar O2 with glucose/Pt
HFCA using non-noble metal catalysts without a base.157 Bis(acetyl-
ratio = 54. Recently, Besson and co-workers studied the effect of
acetonato)dioxo-molybdenum(VI) [MoO2(acac)2] supported on
the possible impurities in the glucose residues on the oxidation
montmorillonite K-10 clay (K-10 clay-Mo) produced a 86.9%
of glucose.147 The oxidation of glucose produced glucaric acid in
HFCA yield after 3 h at 110 1C with flowing oxygen. DFF was
a 54% yield over the 4.7% Pt/C catalyst after 24 h at 333 K and
identified as the byproduct with a yield of 6.7%. The K-10 clay-Mo
pH = 9 with an air flow rate of 0.5 mL min 1. As regards the
catalyst had a HFCA yield of 86.9% in the first run and 83.9% in
residues in the hydrolysate, sodium salts (acetate and sulfate) or
the sixth run. This catalytic system had three distinct advantages
disaccharides (cellobiose and maltose) showed no significant
over the above examples with Au catalysts: (1) it did not contain
effect on the course of the reaction. The effect of HMF and
any non-precious metal, (2) it did the reaction without a base
furfural (the dehydration products of hexose and pentose sugars,
co-catalyst, and (3) downstream separation and purification of
respectively)148 were also studied, and furfural significantly
HFCA is easy. HFCA was precipitated out from toluene in the
slowed down the reaction rates of glucose oxidation into glucaric
form of needle-like crystals. However, the synthesis of HFCA in
acid over the Pt/C catalyst.
strong alkaline solution over Au catalysts produced HFCA in
its salt form, which makes it difficult to separate and purify
7. Synthesis of furan compounds via the product.
catalytic oxidation reactions The selective oxidation of HMF into FFCA is much more
difficult than the oxidation of HMF into HFCA. Recently,
HMF, furfural and other platform chemicals produced from Dibenedetto and co-workers reported a new method for the
biomass can also be catalytically oxidized into a wide variety oxidation of HMF into FFCA in water by the use of a mixed

Fig. 20 Synthesis of furan chemicals from HMF and carbohydrates.

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oxide CuO
CeO2 as the catalyst.158 FFCA was produced in 90%
yield at 383 K and 9 bar O2. The CuO by itself achieved a
moderate selectivity of FFCA (40%) at a 33% conversion, while
CeO2 showed a higher selectivity towards FFCA (76.6%) at
19.9% conversion of 19.9%. The formation of a CuO
CeO2
mixed oxide increased the basicity of the catalyst.
7.2 Selective oxidation of HMF to DFF with O2
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oxidation of HMF into DFF using Cu(NO3)2/VOSO4 as the
catalyst. A 98% DFF yield was produced after 1.5 h at 353 K
and 1 bar O2 (Table 8, entry 2).166 The oxidation of HMF over
the Cu(NO3)2/VOSO4 catalyst can even produce DFF with a high
yield of 98% at room temperature after 48 h (Table 8, entry 3).
This is the highest reported yield for the oxidation of HMF
into DFF at room temperature. The molar ratio of Cu(NO3)2/
[Cu(NO3)2 + VOSO4] influenced the reactivity and selectivity.167

DFF can be used in the synthesis of polymeric Schiff bases, as an
antifungal agent, in pharmaceuticals, in macro-cyclic ligands, in
fluorescent materials and in resins.159–161 Several reports have
used stoichiometric reagents such as BaMnO4, pyridinium
chlorochromate, NaOCl and 2,2,6,6-tetramethylpiperydine-1-
oxide (TEMPO) for oxidation of HMF into DFF.162–164
As listed in Table 8, there are many reports that use O2 as the
oxidant with both homogeneous and heterogeneous catalysts.
In 2001, Partenheimer and Grushin reported the catalytic
oxidation of HMF into DFF over Co(OAc)2/Mn(OAc)2/Zr(OAc)4/
NaBr catalysts (Table 8, entry 1).165 This method produced a
57% DFF yield after 5.17 h at 348 K. HMF acetate (formed via
the esterification of HMF with acetic acid) and COx were the
side products with a selectivity of 7.2% and 2.1%, respectively.
Xu and co-workers reported an effective method for the
The conversion of HMF goes through a maximum with increased
molar concentration of Cu(NO3)2. The highest DFF yield is
obtained at a molar ratio of Cu(NO3)2 to VOSO4 = 1. The authors
claim that the high DFF selectivity is ascribed to the Cu2+ cation,
which prohibits the oxidative C–C bond cleavage reaction
of HMF and prevents a radical reaction of DFF to humins.
A mechanism was proposed by the authors where the oxidation
of HMF into DFF was catalyzed by V5+ species (Fig. 21).
The V4+ species was then regenerated to V5+ by the NOx,
and NOy was reoxidized to NOx by O2. Tong and co-workers
reported that the combination of CuI and 1-hydroxybenzotriazole
synergistically promoted the oxidation of HMF into DFF in
93% yield in dimethyl sulfoxide (DMSO, Table 8, entry 4).168
1-Hydroxybenzotriazole played a role in the abstraction of hydrogen
from HMF, promoting the formation of DFF. The use of Cu(NO3)2

Table 8 Catalytic oxidation of HMF into DFF in batch reactors

Entry Catalyst Catalyst ratioa Time (h) T (K) Solvent Oxidant Con. (%) Yield (%) Ref.
1 Co/Mn/Zr/Br HMF/Co = 200 5.17 348 Acetic acid 1 bar air 91 57 165
2 Cu(NO3)2/VOSO4 HMF/Cu = 100 1.5 353 Acetonitrile 1 bar O2 99 98 166
HMF/V = 100
3 Cu(NO3)2/VOSO4 HMF/Cu = 100 48 298 Acetonitrile 1 bar O2 99 98 166
HMF/V = 100
4 CuI HMF/Cu = 5 10 403 DMSO 3 bar O2 93.2 92.3 168
5 Cu(NO3)2 HMF/Cu = 50 7 323 Acetonitrile 1 bar O2 — 71 169
6 PVP–VO2+ complex HMF/V = 30 24 403 DMSO 10 bar air 82 81 170
7 SBA–Py–VO2+ HMF/V = 30 24 403 Triflurotoluene 10 bar air 50 49 170
8 SBA–NH2–VO2+ HMF/V = 81; 12 383 4-Chlorotoluene 1 bar O2 98.8 63.4 171
SBA–NH2–Cu2+ HMF/Cu = 154
9 V2O5 HMF/V = 2.8 6 443 Toluene 1 bar air 91 62.7 173
10 V2O5/TiO2 HMF/V = 2.8 4 363 Toluene 16 bar air 100 90 175
11 V2O5/H-beta HMF/V = 72 3 398 DMSO 10 bar O2 84 82 176
12 V2O5/Cu-MOR HMF/V = 3.6 7 373 DMSO 1 bar O2 499.9 91.5 177
13 V2O5/C HMF/V = 20 4 383 MIBK 2.8 bar O2 95.2 88.1 178
14 VO2–PANI/CNT HMF/V = 5.4 11 363 DMSO 10 bar O2 100 96 180
15 VOPO4
2H2O HMF/V = 4.0 6 353 MIBK 1 bar O2 98 49 181
16 VOPO4
2H2O HMF/V = 4.0 6 353 DMF 1 bar O2 56 55 181
17 C14VOPO4 HMF/V = 4.0 6 383 Toluene 1 bar O2 99 82 182
18 C14VOHPO4 HMF/V = 4.0 6 383 Toluene 1 bar O2 99 83 182
19 Ru/HT HMF/Ru = 23 6 393 DMF 1 bar O2 95 92 183
20 Ru/g-Al2O3 HMF/Ru = 56 4 403 Toluene 2.8 bar O2 100 97 184
21 Ru/C HMF/Ru = 80 — 383 Toluene 20 bar O2 100 96 185
22 Ru/CTF HMF/Ru = 40 3 353 MTBE 20 bar air 97.3 72.7 186
23 Ru/mPMF HMF/Ru = 96 12 393 Toluene 20 bar O2 99.6 85 188
24 RuCo(OH)2CeO2 HMF/Ru = 2.3 12 393 MIBK 1 bar O2 96.5 82.6 189
25 Ru3+–PVP/CNT HMF/Ru = 38.3 12 393 DMF 20 bar O2 100 94 191
26 Fe3O4@SiO2–NH2–Ru3+ HMF/Ru = 26.9 4 383 Toluene 1 bar O2 96.1 85.9 192
27 K-OMS-2 HMF/Mn = 0.16 6 383 DMSO 1 bar O2 100 99 193
28 K-OMS-2 HMF/Mn = 2.0 1 383 DMF 20 bar O2 100 99 194
29 Ag-OMS-2 HMF/Mn = 0.13 4 438 Isopropyl alcohol 15 bar air 100 99 195
30 K-OMS-2 HMF/Mn = 0.13 4 438 Isopropyl alcohol 15 bar air 62 51 195
31 Fe3O4/Mn3O4, DMF HMF/Mn = 0.96 4 393 DMF 1 bar O2 99.8 82.1 196
32 Mn0.70Cu0.05Al0.25 — 24 363 H2O 8 bar O2 90 78 197
33 FeCo/C-500 HMF/(Fe + Co) = 20 6 373 Toluene 10 bar O2 100 499 198
a
The catalyst ratio defined as the molar ratio of HMF to the active metals.

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Fig. 21 Promoted role of Cu(NO3)2 in aerobic oxidation of HMF to DFF
catalyzed by VOSO4. Adapted from ref. 116 with permission from Elsevier,
copyright 2011.
and the additive N-hydroxyphthalimide produced DFF with a
yield of 71% in acetonitrile after 7 h (Table 8, entry 5).169
Heterogeneous catalysts have also been used for the oxidation
of HMF into DFF including supported vanadium (V), ruthenium
(Ru) and manganese (Mn). Navarro and co-workers performed the
oxidation of HMF over poly(4-vinylpyridine) supported vanadyl
acetylacetonate [VO(acac)2] (abbreviated as PVP–VO2+).170 They
used pyridine to enhance the catalytic activity. Pyridine acted as
a base to abstract the proton of the hydroxyl group of HMF. An
82% HMF conversion and a DFF selectivity of 99% were obtained
in DMSO after 24 h over the PVP–VO2+ catalyst with pyridine
(0.8 equiv. to HMF) as an additive (Table 8, entry 6). However, 28%
of the PVP–VO2+ catalyst leached after the first run. The catalyst
was then supported on a functionalized mesoporous-silica support
containing trimethyl and g-aminopropyl groups (SBA–Py–VO2+).
When the SBA–Py–VO2+ catalyst was used, only 50% conversion of
HMF was achieved in triflurotoluene but with a 98% DFF selectiv-
ity after 24 h at 403 K and 10 bar air (Table 8, entry 7). No leaching
of the SBA–Py–VO2+ catalyst was observed. The lower catalytic
activity of SBA–Py–VO2+ was attributed to a possible inaccessibility
of the reactants to the active sites owing to the surface capping
with trimethyl groups. Inspired by the results reported by Xu and
co-workers,166 Liu and co-workers used g-aminopropyl group
modified SBA-15 as the carrier to support Cu2+ and VO2+ to
prepare SBA-15–NH2–Cu2+ and SBA-15–NH2–VO2+ catalysts.171,172
However, a lower DFF selectivity of 63.4% was produced at a high
HMF conversion of 98.8% (Table 8, entry 8) compared with the
homogeneous catalytic system.166 The other oxidation product was
FDCA. The combined SBA-15–NH2–Cu2+ and SBA-15–NH2–VO2+
catalysts were stable for the oxidation of HMF into DFF with
high DFF selectivity.
V2O5 and supported V2O5 were also used for the oxidation
of HMF into DFF.173–178 HMF oxidation catalyzed by V2O5 in
toluene produced a 91% HMF conversion and 69% of DFF
selectivity at 443 K and 1 bar air (Table 8, entry 9).173 Moreau
and co-workers performed the oxidation of HMF into DFF in
toluene over the V2O5/TiO2 catalyst with a 90% DFF yield
(Table 8, entry 10).175 V2O5/H-beta produced an 82% yield of
DFF from HMF in DMSO (Table 8, entry 11).176 However, the
V2O5 leached and 45% of the total activity was a result of
the catalytic species dissolved from the solid catalyst. Wang
and co-workers improved the activity and stability of the zeolite
supported V2O5 catalyst using a Cu-containing mordenite
(MOR) zeolite (Cu-MOR) as the support.177 The V2O5/Cu-MOR
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catalyst produced a 91.5% DFF yield after 7 h at 373 K and 1 bar
O2 (Table 8, entry 12). The V2O5/Cu-MOR catalysts showed no
loss of catalytic activity after five runs. The V2O5/C catalyst also
had a high stability and high DFF yield (Table 8, entry 13).178
The V2O5/C catalyst showed no activity loss after 4 recycle runs.
XPS and TEM analysis of the fresh and spent catalysts showed
no change in the catalyst structure. Liu and co-workers system-
atically studied VOx on different supports and tested them for
the aerobic oxidation of HMF into DFF.179 VOx deposited on
acidic supports showed a much higher activity. The structure of
VOx changed from isolated monovanadate to 2D polyvanadate
domains and finally to crystalline V2O5 clusters with an
increased V loading. The activity of the supported VOx catalysts
first increased with the increase of the surface density of VOx,
and then decreased, while the selectivity of DFF continuously
increased with the surface density of VOx and then kept stable.
Vanadium dioxide (VO2) immobilized on polyaniline (PINI)-
functionalized carbon nanotubes (CNTs) (VO2–PANI/CNT) was
also used to produce a DFF yield of 96% (Table 8, entry 14).180
However, the catalyst was not stable and the HMF conversion
decreased from 91% in the initial run to 81% and 62% for the
second and third runs, respectively.
Vanadium phosphate oxide based catalysts showed catalytic
activity towards the oxidation of HMF into DFF. Carlini and
co-workers studied the oxidation of HMF into DFF over a
VOPO4
2H2O catalyst.181 Both the catalytic activity of VOPO4
2H2O
and the selectivity of DFF were greatly affected by the solvents.
A 50% yield of DFF was obtained with this catalyst at a 98%
HMF conversion in MIBK (Table 8, entry 15). The selectivity
increased to 99% using an N,N-dimethylformamide (DMF) solvent,
but the HMF conversion sharply decreased to 56% (Table 8,
entry 16). No reaction was observed in water. Dumeignil and
co-workers improved the catalytic performance of vanadium
phosphate oxides by intercalating long alkyl chain trimethyl-
ammonium into the catalyst structure (C14VOPO4 and C14VOHPO4
catalysts).182 DFF was produced in yields of 82% and 83% after 6 h
over the C14VOPO4 and C14VOHPO4 catalysts, respectively (Table 8,
entries 17 and 18). The authors proposed that this improvement
was ascribed to the reduced oxidative properties of the vanadium
phosphorus oxides, which prevented the deeper oxidation of HMF
into organic acids by intercalating long alkyl chain trimethyl-
ammonium. However, the C14VOPO4 catalyst deactivated with
a 91% yield in the first run and 62% yield in the third run.
As discussed above, the vanadium catalysts were not effective
at effectively converting the HMF into DFF.170,173,181 Some of
the vanadium catalysts were not stable.170,176,181,182
Ru catalysts were also reported to be active for the oxidation
of HMF into DFF. A hydrotalcite-supported ruthenium catalyst
(Ru/HT) produced a 92% DFF yield after 6 h at 393 K (Table 8,
entry 19).183 No leaching of Ru was observed. A Ru/g-Al2O3
catalyst produced a 97% DFF yield after 4 h at 403 K (Table 8,
entry 20).184 However, the Ru/g-Al2O3 catalyst lost its activity
decreasing to 70% and 30% conversions after the second and
third runs, respectively. The decreased activity of the Ru/g-Al2O3
catalyst was due to the deposition of insoluble polymeric furan
compounds, which blocked the Ru sites. Calcination of the
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Chem Soc Rev
catalyst could remove the carbon deposits but produced a
volatile ruthenium oxide phase. Liu and co-workers studied
the oxidation of HMF into DFF over different kinds of Ru
catalysts at 383 K.185 For example, the TOF of Ru/C was 61.2 h 1
at 383 K and 20 bar O2, and 30.1, 22.7, 11.2, 6.9, 2.7 and 7.4 h 1 for
Ru/Al2O3, Ru/ZSM-5, Ru/TiO2, Ru/ZrO2, Ru/CeO2 and Ru/MgO
catalysts, respectively. The DFF selectivity over the Ru/C catalyst
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was 96.2%, and 82.4, 12.4, 57.0, 65.9, 58.4 and 21.4% for Ru/Al2O3,
Ru/ZSM-5, Ru/TiO2, Ru/ZrO2, Ru/CeO2 and Ru/MgO, respectively.
These results suggested that the inert carbon supported Ru catalyst
favored the oxidation of HMF into DFF by avoiding the possible
degradation and polymerization of HMF, which were observed
over other Ru catalysts on the support with different acidity–
basicity and reducibility. A 96% DFF yield was produced over the
Ru/C catalyst (Table 8, entry 21). Ru supported on organic porous
polymers was also used for the oxidation of HMF into DFF.186–188
Palkovits et al. prepared a covalent triazine framework (CTF)
supported Ru catalyst (Ru/CTF) for the oxidation of HMF.186 CTFs
are a class of highly stable polymers formed by the trimeriza-
tion of aromatic dinitriles in molten ZnCl2 that have a surface
area of 2349 m2 g 1. The Ru/CTF catalyst with a high surface
area and a large pore volume showed a high catalytic activity.
A DFF yield of 72.7% was obtained in a methyl t-butyl ether
(MTBE) solvent over the Ru/CTF catalyst (Table 8, entry 22). The
selectivity of the oxidation products was also affected by the
reaction solvents. The reaction in water over the Ru/CTF
catalyst produced FFCA, FDCA and DFF with yields of 35.3%,
37.7% and 8% after 1 h at 413 K and 20 bar air.187 Islam and
co-workers prepared a mesoporous poly-melamine-formaldehyde
material (surface area: 536 m2 g 1) supported Ru catalyst
(Ru@mPMF) for the oxidation of HMF.188 The Ru@mPMF
catalyst gave a 99.6% conversion of HMF and a 85% yield of
DFF after 12 h at 393 K (Table 8, entry 23). The Ru@mPMF
catalyst could be reused without leaching of Ru.
Besides supported metallic Ru catalysts, other kinds of Ru
catalysts were also studied for the oxidation of HMF into DFF.
The trimetallic oxide of RuCo(OH)2CeO2, prepared from RuCl3,
Co(NO3)2, and Ce(NO3)2 under basic conditions, was also
reported to be active for the oxidation of HMF.189 A 96.5%
HMF conversion and a 82.6% DFF yield were produced after
12 h at 393 K (Table 8, entry 24). The HMF conversion was 5.4%
with Co–Ce oxide, suggesting that Ru is the active species for
the oxidation of HMF. Full HMF conversion with low DFF
selectivity (58%) was observed with Ce–Ru oxide, suggesting
that cobalt plays a role in the enhancement of DFF selectivity.
Although there was no leaching of Ru, HMF conversion decreased
from 96.5% in the first run to 88.6% in the fifth run. Similarly,
magnetic ZnFe1.65Ru0.35O4 was also prepared via the alkali-
coprecipitation of the metal salts and used for the oxidation of
HMF.190 A high DFF yield of 93.5% was obtained for the
reaction at 383 K for 4 h in DMSO with an oxygen flow, whereas
the maximum FDCA yield of 91.2% was achieved for the reaction
at 403 K for 16 h in H2O/DMSO. Chen and co-workers anchored
Ru3+ to poly(4-vinylpyridine)-functionalized carbon-nanotubes
(PVP/CNTs), which produced a DFF yield of 94% after 12 h at
393 K (Table 8, entry 25).191 Ru has also been added onto
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magnetic supports to facilitate catalyst recycling.192 A magnetic
Fe3O4@SiO2–NH2–Ru3+ catalyst was prepared by using g-amino-
propyl group functionalized core–shell structured Fe3O4@
SiO2.192 A 99.3% HMF conversion and a 86.4% DFF yield were
produced over the Fe3O4@SiO2–NH2–Ru3+ catalyst after 4 h at
393 K (Table 8, entry 26). After the reaction, the Fe3O4@SiO2–
NH2–Ru3+ catalyst could be readily recovered from the reaction
mixture by a permanent magnet. However, a decrease of the
catalytic activity was observed with DFF yields of 86.4% and
80.8% in the first and the sixth runs, respectively.
Besides V and Ru catalysts, Mn catalysts are also often used for
the oxidation of HMF into DFF. A cryptomelane-type manganese
oxide octahedral molecular sieve (KMn8O16
nH2O; K-OMS-2), which
possesses a 2  2 hollandite structure with one-dimensional pores,
showed a high activity towards the oxidation of HMF.193 A 99% DFF
yield was produced in DMSO after 6 h at 383 K (Table 8, entry 27).
The K-OMS-2 catalyst could be reused five times without a decrease
in DFF yield. However, recycling a catalyst at high conversion does
not demonstrate that the catalyst is stable. As shown in Fig. 22,
HMF is oxidized by Mn4+O2 , and Mn4+O2 is simultaneously
reduced to a Mn3+ ion. The Mn3+ ion is then reoxidized by O2
to produce Mn4+O2 to finish the catalytic cycle. Similar results
were also observed in DMF over the K-OMS-2 catalyst (Table 8,
entry 28).194 Although high DFF yields were obtained in DMSO
and DMF over the K-OMS-2 catalyst, product purification was
difficult due to the high boiling points of DMF and DMSO.
Yadav and Sharma observed that a silver exchanged K-OMS-2
catalyst (Ag-OMS-2) was active for the oxidation of HMF in
isopropyl alcohol.195 A 99% DFF yield was produced after 4 h at
483 K (Table 8, entry 29). The isopropyl alcohol could be easily
removed under reduced pressure, and the purity of DFF was
up to 99%. Compared with Ag-OMS-2, the K-OMS-2 catalyst
produced a lower HMF conversion of 62% and a lower DFF
selectivity of 82% (Table 8, entries 29 vs. 30). NH3-TPD results
indicated that the surface acidity of the Ag-OMS-2 catalyst
decreased, which inhibited the side reactions such as polymeriza-
tion of HMF into humins. HMF conversion and DFF selectivity
were stable during five recycling experiments for the Ag-OMS-2
catalyst. A magnetic Fe3O4 supported Mn3O4 (Fe3O4/Mn3O4)
catalyst was used for the oxidation of HMF.196 This catalyst was
prepared by the solvent-thermal treatment of Mn(OAc)2 in the
presence of Fe3O4 nanoparticles. An 82.1% DFF yield and a full
HMF conversion were produced in DMF after 12 h at 393 K
(Table 8, entry 31). The Fe3O4/Mn3O4 catalyst could be readily
collected by a permanent magnet without a loss of activity. As
listed in Table 8, the oxidation of HMF into DFF was almost
carried out in organic solvents. Recently, Florea and co-workers
reported that a manganese–copper layered double hydroxide
(Mn0.70Cu0.05Al0.25) could promote the oxidation of HMF into
DFF in water,197 which was prepared by the co-precipitation of
these metal salts under basic conditions, followed by calcination
in air. The optimal results were produced at 363 K and 8 bar O2
with a DFF yield of 78% after 24 h (Table 8, entry 32). The catalyst
was stable for 5 runs. The oxidation reaction is initiated by the
reduction of Cu2+ to Cu+ species that is accompanied by a release
of an electron (Fig. 23, step 1). Then a cooperative effect between
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Fig. 22 The mechanism for K-OMS-2-catalyzed conversion of HMF to DFF. Adapted from ref. 193 with permission from Royal Society of Chemistry,
copyright 2012.
Fig. 23 Proposed mechanism for the oxidation of HMF over the Mn0.70Cu0.05Al0.25 catalyst. Adapted from ref. 197 with permission from Elsevier,
copyright 2016.
the two cations results from the oxidation of Mn3+ to Mn4+ by the
released electron (step 2). Furthermore, the oxidation of HMF to
DFF occurs with reduction of Mn4+ to Mn3+. The role of the
increased basicity is to induce the weakening of the hydroxyl
group of HMF, which makes the molecule easier to oxidize.
Other non-noble catalysts have also been reported to be effective
for the oxidation of HMF into DFF. Luque and co-workers reported
that a magnetic Fe–Co/C catalyst was active for the oxidation of
HMF into DFF.198 This catalyst was prepared by the pyrolysis
of bimetallic MOF (MIL-45b) containing Co and Fe with 1,3,5-
benzenetricarboxylate (BTC) as the organic ligand. A quantitative
DFF yield (499%) was produced after 6 h at 373 K (Table 8,
entry 33). The catalytic performance of the FeCo/C catalyst was
attributed to the presence of well-ordered Fe and Co oxides
derived from MIL-45b. The authors claimed that the lattice
1374 | Chem. Soc. Rev., 2018, 47, 1351--1390
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Chem Soc Rev
oxygen of FeCo oxides facilitated HMF oxidation to DFF, which
was later replenished by O2 molecules. The catalyst could be
reused in up to six runs without any significant loss of reactivity.
In summary, Mn catalysts generally showed better catalytic
performance over V and Ru catalysts towards the oxidation of
HMF into DFF in terms of the DFF yield and the catalyst stability.
Some Mn catalysts such as K-OMS-2193 and Ag-OMS-2194 not only
produced quantitative DFF yield, but also showed high stability.
This is because the active species of Mn in K-OMS-2193 and
Ag-OMS-2194 are presented in the form of compounds, which was
unlike the supported vanadium oxides176 or Ru nanoparticles,184
suffering from leaching and the growth of metal nanoparticles.
In addition, Mn based catalysts are cheap. Thus, Mn catalysts
show great potential in the practical production of DFF
from HMF.
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Chem Soc Rev
7.3 TEMPO mediated oxidation of HMF into DFF
2,2,6,6-Tetramethylpiperidine-N-oxide (TEMPO) is a stable radical
with the formula of (CH2)3(CMe2)2NO, which is mainly used as
a co-catalyst for a variety of oxidation reactions.199 There were
some reports on the TEMPO mediated oxidation of HMF into
DFF.200–207 Chung and co-workers studied the oxidation of
HMF into DFF by the use of 4-hydroxy-2,2,6,6-tetramethyl-
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piperidine-1-oxyl (4-hydroxy-TEMPO radical) as the oxidant
with [bis(acetoxy)-iodo]benzene (BAIB) as the co-oxidant and
acetic acid as an additive.200 A 66% DFF yield was obtained
in ethyl acetate after 0.75 h at 303 K over a 4-hydroxy-TEMPO
(0.2 equiv.)/BAIB (1.5 equiv.)/CH3COOH (0.1 equiv.) catalytic
system. As shown in Fig. 24, acetic acid aids in the initial
formation of the oxoammonium form of 4-hydroxy-TEMPO
(compound 2). HMF is then oxidized to DFF, and compound
2 is simultaneously reduced to hydroxylamine (compound 3).
Then, compound 3 is oxidized by BAIB to regenerate the 4-hydroxy-
TEMPO radical to finish the catalytic cycle. Furthermore, TEMPO
was chemically bonded on the surface of SBA-15 (SBA-15-TEMPO).201
SBA-15-TEMPO provided a similar DFF yield (73%) with homo-
geneous TEMPO (78%), which was due to its large surface area
(526 m2 g 1) and large pore size (5.5 nm), facilitating the
diffusive transport of reactants and products. Although SBA-15-
TEMPO is recyclable, this method is still less attractive than the
methods by the use of oxygen as the oxidant because this
approach requires the use of stoichiometric amounts of BAIB
and it produces iodobenzene as a byproduct. Hence, it is desirable
to perform the TEMPO mediated oxidation of HMF by the use of
oxygen as the terminal oxidant.
Riisager and co-workers reported that HMF could be oxidized
to DFF at room temperature in air under atmospheric pressure
over a TEMPO (0.1 equiv.)/2,2-bipyridine (0.3 equiv.)/CuCl
(0.3 equiv.) catalytic system.202 A 92% DFF yield was produced
in acetonitrile after 24 h. Cu(I) was coordinated by 2,2-bipyridin,
which was oxidized to Cu(II) by TEMPO. HMF was then oxidized
by Cu(II) species to give DFF and Cu(I) species. The reduction
state of TEMPO was then reoxidized by O2 to finish the catalytic
cycle. Karimi and co-workers used magnetically separable
TEMPO for the oxidation of HMF.203 TEMPO was chemically
Fig. 24 Proposed reaction pathway for the aerobic oxidation of HMF into
DFF using TEMPO/BAIB/CH3COOH. Adapted from ref. 200 with permis-
sion from springer, copyright 2014.
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Fig. 25 Proposed reaction pathway for the aerobic oxidation of HMF into
DFF using a Fe3O4@SiO2-TEMPO catalyst. Adapted from ref. 203 with
permission from American Chemical Society, copyright 2015.
grafted onto the magnetic support by the reaction of 4-hydroxyl-
TEMPO with the g-aminopropyl functionalized Fe3O4@SiO2–NH2.
Quantitative yield of DFF (499%) was produced in toluene
after 18 h at 323 K and 1 bar O2 using the Fe3O4@SiO2-TEMPO
catalyst (2 mol% TEMPO) with tert-butyl nitrite (5 mol%)
as a co-catalyst and acetic acid (25 mol%) as an additive. As
shown in Fig. 25, the mediation of electron transfer from HMF
to O2 by NO/NO2 couples and the immobilized nitroxyl radical
(Fe3O4@SiO2-TEMPO) through a combination of two redox cycles
is required. The catalyst was successfully recovered by an
external magnet.
Hou and co-workers developed a more sustainable method
for the TEMPO mediated oxidation of HMF into DFF with
graphene oxide (GO) as co-catalysts.204 A 99.6% DFF yield
was produced in acetonitrile after 18 h at 373 K in air in
the presence of GO and TEMPO. Low HMF conversions were
obtained under these same reaction conditions with only
TEMPO or GO, suggesting that GO and TEMPO played syner-
getic roles in the oxidation of HMF into DFF. Electron spin
resonance (ESR) measurements indicated that the edge sites
with unpaired electrons and carboxylic acid groups were the
active catalytic sites on GO. As shown in Fig. 26, TEMPO binds
to the carboxylic acid groups in GO via a hydrogen bond and
forms an electron-donor complex. The unpaired electrons of
porous GO reduce molecular oxygen to form adsorbed super-
oxide radicals ( O2 ), which stabilize the positive charge of the
holes. The anchored TEMPO is oxidized by the positive charge
of the hole to form the oxoammonium cation, and the active
site on GO is regenerated. HMF is oxidized by the oxoammo-
nium cation, producing DFF, and the produced hydroxylamine
is reoxidized by  O2 . The TEMPO molecule is regenerated. The
electronic structure of graphene, and hence catalytic properties,
can be further modified by the introduction of certain hetero-
atoms, such as N, B, and P.205,206 The same authors enhanced
the efficiency of TEMPO mediated oxidation of HMF by the use
of nitrogen-doped graphene.207 A quantitative DFF yield was
reached after 6 h at 383 K under atmospheric air pressure,
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Fig. 26 Proposed mechanism for the aerobic oxidation of HMF into DFF using TEMPO and graphene oxide catalysts. Adapted from ref. 204 with
permission from American Chemical Society, copyright 2015.

while 18 h residence time was required to get 99.6% DFF yield
under the same reaction conditions using unmodified GO.204
7.4 One-pot conversion of carbohydrates into DFF
As shown in Fig. 27 the one-pot conversion of glucose requires
three parallel steps including the isomerization of glucose into
fructose,208 the dehydration of fructose into HMF, and the
oxidation of HMF into DFF. As listed in Table 9, fructose is
mainly used as the feedstock for the one-pot synthesis of DFF
over metal–acid catalysts. In 2002, Halliday and co-workers first
studied the conversion of fructose into DFF using a two-step
method.209,210 Fructose initially dehydrated to HMF in DMSO at
383 K to produce a 85% HMF yield over an acidic ion-exchange
BioRad AG 50W-X8 resin. After the filtration of the acid catalyst,
HMF oxidation was started by the addition of V catalysts at
423 K with a bubble of air. The DFF yields were 52% and 67%
based on the starting fructose over VHPO4
0.5H2O and V2O5
catalysts, respectively (Table 9, entries 1 and 2). However, the
high reaction temperature at 423 K caused the decomposition of
DMSO into Me2SO2 and Me2S, which contaminated the product
of DFF. Therefore, further purification by vacuum sublimation
and Soxhlet extraction was required to obtain pure crystalline
DFF. A polyaniline grafted vanadyl acetylacetonate [polyaniline-
VO(acac)2] catalyst could produce an HMF conversion of 99.2%
and DFF yield of 86.2% after 12 h at 383 K and 1 bar O2.211
The one-pot method by the combined use of Amberlyst 15
and polyaniline-VO(acac)2 catalysts produced DFF with a yield
of 42% after 12 h at 383 K and 1 bar O2 (Table 9, entry 3).

Fig. 27 Synthesis of DFF from glucose and fructose via a one-pot reaction.

Table 9 Catalytic conversion of carbohydrates into DFF in batch reactors

Entry Catalyst Substrates T (K) Solvent Method Con. (%) Yield (%) Ref.
+
1 VOPO4, H -exchange resin Fructose 423 DMSO Two-step — 52 209
2 V2O5, H+-exchange resin Fructose 423 DMSO Two-step — 77 209
3 Amberlyst-15, polyaniline-VO(acac)2 Fructose 383 DMSO One-step 100 42 211
4-Chlorotoluene
4 Amberlyst-15, polyaniline-VO(acac)2 Fructose 383 DMSO Two-step 100 71 211
4-Chlorotoluene
5 V-g-C3N4(H+) Fructose 403 DMSO One-step 99 45 212
6 g-C3N4(H+), V-g-C3N4(H+) Fructose 403 DMSO Two-step 100 63 212
7 Cs2HPMo11VO40 Fructose 383 DMSO Two-step 99 60 213
8 Cs0.5H2.5PMo12 Fructose 433 DMSO One-step — 69 214
9 WO3HO-VO-@Fe3O4 Fructose 353, 298 Isopropanol Two-step 71 215
10 Fe3O4–SBA–SO3H, K-OMS-2 Fructose 373 DMSO Two-step 499 80 192
11 Amberlyst-15, Ru/HT Fructose 373 DMF Two-step 499 49 193
12 Amberlyst-15, HT, Ru/HT Glucose 373 DMF Three-step 98 25 183
13 Amberlyst-15, HT, Ru/HT Raffinose 393 DMF Three-step 100 27 183
14 CrCl3/NaBr//NaVO3 Glucose 383 DMF Two-step — 55 216
15 g-Fe2O3@HAP-Ru; Fe3O4@SiO2–SO3H Fructose 383 DMSO Two-step 100 79 217
4-Chlorotoluene
16 GO Fructose 413 DMSO One-step — 53 220
17 GO Fructose 413 DMSO Two-step — 73 220
18 CC–SO3H–NH2 Glucose 413 DMSO Two-step — 44 222

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A two-step method was then used to further improve the yield. The
dehydration of fructose over the Amberlyst 15 catalyst produced a
91.8% HMF yield after 1.5 h at 383 K. After the removal of the
Amberlyst 15 catalyst, the oxidation of HMF over the [polyaniline-
VO(acac)2] catalyst produced DFF in an overall yield of 71%
after 12 h at 383 K and 1 atm O2 (Table 9, entries 3 vs. 4).
The above two examples required the use of one acid catalyst
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the one-step method produced both HMF and DFF in less than
5% yields at full fructose conversion, which was possibly
caused by the oxidation of fructose. Ebitani and co-workers
performed the conversion of fructose into DFF by the combined
use of Amberlyst-15 and Ru/HT catalysts.183 The one-step
method produced a DFF yield of 13% and HMF yield of 44%
at fructose conversion 499% after 9 h at 373 K and 1 bar O2.

and one metal catalyst. Chen and co-workers prepared proto- The DFF yield increased to 49% using a two-step method
nated vanadium-doped graphitic carbon nitride [V-g-C3N4(H+)] (Table 9, entry 11), including fructose dehydration at 373 K
as a bifunctional catalyst for the oxidative conversion of fructose for 3 h and the subsequent HMF oxidation at 373 K for 6 h. The
into DFF in DMSO.212 The V-g-C3N4(H+) catalyst was prepared by one-pot conversion of glucose into DFF was performed by the
the thermal pyrolysis of dicyandiamide with ammonium meta- use of HT, Amberlyst-15 and Ru/HT catalysts, in which HT
vanadate (NH4VO3) at 813 K for 4 h, followed by treatment with catalyzed the isomerization of glucose into fructose. As shown
HCl. A 99% fructose conversion and a 45% DFF yield were in Fig. 28, the three-step method produced an overall DFF yield
produced after 8 h at 403 K and 1 bar O2 in one-step (Table 9, of 25% (Table 9, entry 12). Furthermore, DFF was produced in a
entry 5). However, the two-step method produced an overall DFF yield of 27% from naturally occurring indigestible trisaccharide
yield of 63%, including the first dehydration step at 393 K for raffinose (galactose, glucose, and fructose units) by the same
2 h and the subsequent oxidation step at 403 K for 6 h (Table 9, method (Table 9, entry 13).216 Hu and co-workers improved the
entry 6). The lower DFF yield by the one-step method was due to DFF yield to 55% from glucose using a two-step method over
the possible oxidation of fructose to undesired byproducts.150 the CrCl3/NaBr/NaVO3 catalysts (Table 9, entry 14).217 Glucose
V-g-C3N4(H+) was not stable due to the leaching of H+, but the was first converted to HMF in DMF with a yield of 65% at 383 K
V-g-C3N4(H+) catalyst could be regenerated by the treatment for 6 h by CrCl3/NaBr, and then the oxidation of HMF was
with HCl. The vanadium-containing heteropolyacids were also performed at 383 K and 1 bar O2 for 10 h over the NaVO3
2H2O
used as bifunctional catalysts for the transformation of fructose catalyst. Similarly, Lin and co-workers also performed the one-
into DFF.213,214 The one-step conversion of fructose over the pot conversion of glucose into DFF in DMF over the AlCl3/NaBr/
Cs2HPMo11VO40 catalyst produced DFF in a yield of 26% in vanadium catalysts, which produced DFF yields of 34–48% with
DMSO after 6 h at 393 K and 1 bar O2.213 The two-step approach
increased the DFF yield to 60% by the first dehydration
of fructose at 383 K for 2 h, followed by oxidation of HMF at
393 K and 1 bar O2 for 6 h (Table 9, entry 7).213 The catalyst
deactivated (60% in the first run vs. 53% in the fourth run),
due to the leaching of vanadium, and the deposition of
insoluble polymeric furan compounds on the catalyst surface.
Cs0.5H2.5PMo12O40 produced a higher DFF yield of 69% from
fructose than Cs2HPMo11VO40 (Table 9, entry 8).214 The DFF
yield declined slightly in the first two runs, then remained
stable after the third cycle. The XRD patterns of the spent
catalyst were the same as the fresh catalyst. To facilitate the
recycling of the bifunctional catalysts, a magnetic bifunctional
WO3HO-VO@Fe3O4 nanocatalyst was prepared and tested for
the synthesis of DFF from fructose.215 An 82% HMF yield was
obtained with the tungstic acid-mediated fructose dehydration
at 353 K within 1 h. After cooling to room temperature, the
oxidation of HMF was performed by the addition of H2O2,
affording 71% DFF yield after 15 h (Table 9, entry 9). The
magnetic WO3HO-VO@Fe3O4 catalyst demonstrated a high
stability with about 5% decrease of DFF yield after the fifth run.
Besides V catalysts, Mn and Ru catalysts were also used
for the oxidative transformation of fructose into DFF. Fu and
co-workers performed the two-step synthesis of DFF from
fructose by the combined use of Fe3O4–SBA–SO3H and K-OMS-2 Fig. 28 Glucose conversion into fructose (’), HMF (n) and DFF (K). HT
catalysts.192 The first step of fructose dehydration of HMF in was initially added into the reactor. The Amberlyst-15 catalyst was then
added after 3 h. The Ru/HT catalyst was further added after 6 h under
DMSO produced HMF with a yield of 80% after 2 h at 383 K over
oxygen flow (20 mL min 1). Reaction conditions: glucose (0.1 g), HT (0.2 g),
the Fe3O4-SBA-SO3H catalyst. The HMF was quantitatively con- Amberlyst-15 (0.1 g), Ru/HT (0.2 g), DMF (3 mL), 373 K. Reproduced with
verted into DFF over the K-OMS-2 catalyst within 6 h at 383 K and permission from ref. 183 with permission from American Chemical Society,
1 bar O2 (Table 9, entry 10). In contrast to the two-step method, copyright 2011.

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almost complete glucose conversion.218 In order to recycle the
catalysts, two magnetic g-Fe2O3@HAP-Ru and Fe3O4@SiO2-SO3H
catalysts were used for the synthesis of DFF from fructose.219
g-Fe2O3 was firstly encapsulated by hydroxyapatite (HAP), and
then Ca2+ in HAP was exchanged with Ru3+ to generate the
g-Fe2O3@HAP-Ru catalyst. Firstly, the dehydration of fructose
produced HMF with a yield of 90.1% after 2.5 h at 383 K over the
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Fe3O4@SiO2–SO3H catalyst. After the removal of the Fe3O4@
SiO2–SO3H catalyst, the oxidation of HMF produced DFF with
an overall yield of 79% after 24 h at 383 K and 1 bar O2 over the
g-Fe2O3@HAP-Ru catalyst (Table 9, entry 15).
Hou and co-workers reported a metal-free transformation of
fructose into FDCA.220 Graphene oxide (GO) was used as a
bifunctional and metal-free catalyst for the transformation of
fructose into DFF. The oxidation of HMF produced a 90%
DFF yield in DMSO after 24 h at 413 K with an O2 flow rate of
20 mL min 1. DMSO was very crucial for this catalytic system,
as the same reaction in DMF could not produce any oxidation
products. The oxidation of HMF was attributed to the in situ
formation of the active component from DMSO at high
temperature, and the reaction pathway involved the proton-
ation of the alcohol group of HMF and a nucleophilic addition
of DMSO, as reported in the literature.221 The reaction under a
N2 atmosphere produced less than 2% HMF conversion indi-
cating that the real oxidant was O2 not DMSO in this catalytic
system. The one-step method produced DFF in a yield of 53%
after 24 h, whereas the two consecutive methods (the first step
under a N2 atmosphere for 2 h and the second step under an O2
atmosphere for 22 h) improved the DFF yield to 73%, based on
fructose (Table 9, entries 16 and 17). Jadhav et al. further
developed a similar catalytic system for the one-pot conversion
of glucose to DFF in DMSO by the use of a carbon material
functionalized with acid–base sites (CC–SO3H–NH2).222 The
base sites acted as the site for the isomerization of glucose
into fructose. The two-step method (the first step under N2
atmosphere for 15 h and the second step under an O2 atmo-
sphere for 27 h) produced a 44% DFF yield from glucose at
413 K (Table 9, entry 18). The CC–SO3H–NH2 catalyst could be
reused five times, maintaining its activity.
7.5 Catalytic oxidation of HMF into FDCA with O2 as the
oxidant
FDCA is another important HMF oxidation product, which is
produced by the simultaneous oxidation of the methylhydroxyl
and formyl group in HMF. It has been identified by the US
Department of Energy as one of 12 priority chemicals for
establishing the ‘‘bridge’’ between fossil fuel resources and
biomass resources.223 FDCA can be used as a replacement for
terephthalic acid, in various polyesters.224,225 Avantium announced
plans to produce 40 ton per year of FDCA monomer at a pilot plant
in 2011 and 30 000 to 50 000 ton per year in 2016.226
Oxidation of HMF into FDCA was first carried out with
stoichiometric oxidants such as KMnO4, N2O4 and HNO3.227–229
The catalytic oxidation of HMF into FDCA with green oxidants
particularly molecular oxygen has been extensively examined with
both homogeneous and heterogeneous catalysts. The homogeneous
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catalytic systems are mainly based on the conventional metal
bromide catalysts (Co/Mn/Br) that are used for the oxidation of
para-xylene to terephthalic acid.230 In 2001, Partenheimer and
Grushin performed the oxidation of HMF in acetic acid over the
Co(OAc)2/HBr/Mn(OAc)2 catalysts, producing 60.9% yield of
FDCA after 3 h at 398 K and 70 bar air pressure.165 Other
byproducts were HMF acetate and the decarbonylation of HMF.
Later, Subramaniam and co-workers improved the FDCA yield
to 90% at a 1/0.015/0.5 molar ratio of Co, Mn, and Br, 7% (v/v)
water, 30 bar (CO2/O2 = 1/1, mol/mol), and 453 K.231 Similar
work was also reported for the oxidation of HMF over the
Co(OAc)2/Zn(OAc)2/NaBr catalysts.232 This method produced
FDCA with a yield of 60% in acetic acid at an HMF conversion
of 90% after 3 h at 363 K and 1 bar O2. Unlike the Co(OAc)2/
HBr/Mn(OAc)2 catalytic system,165 FFCA was also produced in a
yield of 29% over the Co(OAc)2/Zn(OAc)2/NaBr catalysts. Due
to the difficulty in the recycling of homogeneous catalysts,
extensive attention has been paid by researchers to developing
heterogeneous catalytic systems.
As discussed in Section 7.2, the oxidation of HMF into DFF
was mainly catalyzed by V, Ru and Mn catalysts in organic
solvents without a base. In contrast to the oxidation of HMF
into DFF, the oxidation of HMF into FDCA is mainly performed
over noble-metal (Pd, Pt and Au) catalysts in an alkaline
solution (Table 10). In 1983, Verdeguer et al. studied the
oxidation of HMF into FDCA over a Pt/C catalyst.233 FDCA
was produced in a yield of 81% at full HMF conversion after
2 h at 298 K (Table 10, entry 1). The FDCA yield increased to
99% over a Pt–Pb/C catalyst (Table 10, entry 2). Kinetic studies
indicated that the formyl group was oxidized first, followed by
the hydroxymethyl group. The HMF conversions were 100% after
1 h at 373 K and 40 bar air with Na2CO3/HMF molar ratio = 2 over
both the Pt/C and Pt–Bi/C catalysts, but the FDCA yields were
51% and 83% for the Pt/C and Pt–Bi/C catalysts, respectively. Bi
was claimed to increase the resistance of the Pt/C catalyst to
oxygen poisoning. After 4 h, FDCA was produced in a nearly
quantitative yield (499%) over the Pt–Bi/C catalyst (Table 10,
entry 3). Observed initial intermediates were HFCA and DFF,
which were rapidly oxidized to FFCA (the main intermediate).
The FDCA yield slowly decreased from 100% to 90% in the fifth
run with FFCA as the byproduct over the Pt–Bi/C catalyst. Davis
and co-workers studied the catalytic performance of the Pt/C,
Pd/C and Au/C catalysts for HMF oxidation in 0.3 M NaOH
solution at 296 K and 6.90 bar O2 pressure.156 The HMF conver-
sion reached 100% after 6 h for the three catalysts with FDCA
and HFCA as the oxidation products. The FDCA yields were 79%
and 71% for the Pt/C and Pd/C catalysts, respectively (Table 10,
entries 4 and 5), while 92% yield of HFCA was produced for the
Au/C catalyst (Table 10, entry 6), Strasser et al. also observed that
the Pt/C catalyst showed higher catalytic activity than the Pd/C
catalyst.235 Besides the Pt/C catalyst, reduced graphene oxide
(RGO) was also used to stabilize Pt nanoparticles (Pt/RGO) for
the oxidation of HMF at 298 K.236 FDCA was produced in a yield
of 84% with an HFCA yield of 16% over the Pt/RGO catalyst
after 24 h with NaOH/HMF molar ratio = 5 and 1 bar O2
(Table 10, entry 7). The Pt/RGO catalyst could be reused with
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Table 10 Catalytic oxidation of HMF into FDCA in batch reactorsa

Entry Catalyst Catalyst ratioa Oxidant and base T (K) Time (h) Con. (%) Yield (%) Ref.
1 Pt/C 100 1 bar O2, 1.25 M NaOH 298 2 100 81 233
2 Pt–Pb/C 100 1 bar O2, 1.25 M NaOH 298 2 100 99 233
3 Pt–Bi/C 100 40 bar air, 2 equiv. Na2CO3 373 4 100 499 234
4 Pt/C 150 6.9 bar O2, 2 equiv. NaOH 296 6 100 79 156
5 Pd/C 150 6.9 bar O2, 2 equiv. NaOH 296 6 100 71 156
6 Au/C 150 6.9 bar O2, 2 equiv. NaOH 296 6 100 7 156
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7 Pt/RGO 39 1 bar O2, 5 equiv. NaOH 298 24 100 84 236

8 Fe3O4@C/Pt 27 1 bar O2, 1.67 equiv. Na2CO3 363 4 100 84 237
9 Pt/C-EDA-4.1 49 10 bar O2 373 12 100 96 238
10 Pt/ZrO2 100 10 bar air, 8.3 equiv. Na2CO3 373 12 100 98 239
11 Pt–Bi/TiO2 100 40 bar air, 2 equiv. Na2CO3 373 10 100 499 240
12 Pt/Al2O3 100 1 bar O2, 1 equiv. Na2CO3 413 12 96 96 243
13 Pt/PVP 19 1 bar O2 353 24 100 94 244
14 Pt/IP 19 1 bar O2 353 24 100 99 244
15 Pt/C–O–Mg 50 10 bar O2 383 12 100 97 245
16 Pd/PVP 100 1 bar O2, 35 mL min 1, 1.25 equiv. NaOH 363 6 499 90 246
17 Pd/ZrO2/La2O3 100 1 bar O2, 35 mL min 1, 1.25 equiv. NaOH 363 8 499 90 247
18 Pd/Al2O3 100 1 bar O2, 35 mL min 1, 1.25 equiv. NaOH 363 8 499 78 247
19 Pd/TiO2 100 1 bar O2, 35 mL min 1, 1.25 equiv. NaOH 363 8 499 53 247
20 Pd/HT 21.2 1 bar O2, 35 mL min 1 373 7 499 499 248
21 g-Fe2O3@HAP-Pd 43.1 1 bar O2, 0.5 equiv. K2CO3 373 6 97 92.9 249
22 C–Fe3O4–Pd 55 1 bar O2, 0.5 equiv. K2CO3 353 4 98.1 91.8 250
23 Pd/C@Fe3O4 28 1 bar O2, 0.5 equiv. K2CO3 353 6 98.4 86.7 251
24 Au/TiO2 100 20 bar O2, 20 equiv. NaOH 303 18 100 71 155
25 Au/CeO2 150 10 bar Air, 4 equiv. NaOH 403 5 100 96 255
26 Au/TiO2 150 10 bar Air, 4 equiv. NaOH 403 5 100 84 255
27 Au/m-CeO2 100 10 bar O2, 4 equiv. NaOH 343 4 100 92 257
28 Au/Ce0.85Bi0.15O2 d 150 10 bar O2, 4 equiv. NaOH 338 2 100 100 258
29 Au/HT 40 1 bar O2 368 7 499 499 259
30 Au/HY 100 3 bar O2, 5 equiv. NaOH 333 6 499 499 261
31 Au–Cu/TiO2 100 10 bar O2, 4 equiv. NaOH 368 4 100 99 262
32 Au8–Pd2/C 200 10 bar O2, 2 equiv. NaOH 333 6 499 499 263
33 Au/C 200 10 bar O2, 2 equiv. NaOH 333 6 499 80 263
34 Pd/C 200 10 bar O2, 2 equiv. NaOH 333 6 499 9 263
35 Au–Pd/CNT 100 5 bar O2 373 12 100 94 265
36 Pt/CNT 100 5 bar O2 368 14 100 98 267
37 Ru/AC 100 40 bar air, 4 equiv. NaHCO3 373 2 100 75 268
38 Ru/AC-NaOCl 100 40 bar air, 4 equiv. NaHCO3 373 4 100 55 268
39 Ru/MnCo2O4 33.6 24 bar air 393 24 100 99.1 269
40b Mn0.75Fe0.25Ox 50 8 bar O2, 4 equiv. NaOH 363 24 100 90 271
41b NNC-873 317.5 1 bar O2, 100 mL min 1 353 48 100 11 274
3 equiv. K2CO3
42b NNC-973 317.5 1 bar O2, 100 mL min 1 353 48 100 35 274
3 equiv. K2CO3
b
43 NNC-1073 317.5 1 bar O2, 100 mL min 1 353 48 100 72 274
3 equiv. K2CO3
44b NNC-1173 317.5 1 bar O2, 100 mL min 1 353 48 100 80 274
3 equiv. K2CO3
a b
For entries 1 to 39, the catalyst ratio was defined as the molar ratio of HMF to the metals. For entries 40–44, it was defined as the weight ratio of
HMF to the catalyst.

full HMF conversion in each run. However, the FDCA yield
showed a slight decrease with a slight increase in the HFCA yield.
To facilitate catalyst recycling, a magnetic core–shell structured
Fe3O4@C supported Pt catalyst was prepared for HMF oxidation,
producing a quantitative FDCA yield after 4 h at 363 K (Table 10,
entry 8).237 The Fe3O4@C/Pt catalyst could be reused at least three
times without significant performance loss. The above carbon
based Pt catalysts were used in alkaline solution for the oxidation
of HMF into FDCA. A catalyst consisting of Pt supported on a
carbon material with the introduction of nitrogen atoms (basic
sites) (Pt/C-EDA) could promote the base-free oxidation of HMF
into FDCA.238 The Pt/C-EDA catalyst was prepared by first hydro-
thermal treatment of glucose, resorcinol, and ethylenediamine
(EDA), and second pyrolysis. The Pt/C-EDA-4.1 catalyst with
4.1 wt% nitrogen showed the highest activity, producing FDCA
with a yield of 96.0% after 12 h (Table 10, entry 9). XPS
indicated that graphene-type nitrogen, pyrrole-type nitrogen
and pyridine-type nitrogen were present in the catalysts. The
FDCA yields were proportional to the amount of graphene-type
nitrogen. Thus, graphene-type nitrogen played a key role in the
selective oxidation of HMF. However, the Pt/C-EDA-4.1 catalyst
was not stable due to growth of Pt nanoparticles.
Metal oxide supported Pt catalysts were also studied for the
oxidation of HMF into FDCA. The Pt/ZrO2 catalyst produced a
98% FDCA yield at 373 K and 10 bar air (Table 10, entry 10).239
Besson and co-workers compared the catalytic activity of
Pt/TiO2 with Pt/ZrO2.240 Pt/TiO2 showed a higher catalytic activity
than Pt/ZrO2. Moreover, the addition of bismuth (Bi) to Pt/TiO2

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improved the catalyst activity and stability, similar to the
Pt–Bi/C catalyst.234 Quantitative oxidation of HMF into FDCA
was obtained after 10 h at 373 K and 40 bar air over the Pt–Bi/
TiO2 catalyst (Bi/Pt = 0.22) (Table 10, entry 11). The Pt–Bi/TiO2
catalyst was stable for four runs. The Pt/Al2O3 catalyst also showed
good catalytic performance for the oxidation of HMF into
FDCA.241–243 For example, Dhepe and co-workers reported that
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FDCA was produced in a yield of 96% after 12 h at 413 K and 1 bar
O2, but at a high Pt loading (Table 10, entry 12).243 The HMF
conversion remained at 100% for each run by the reduction of the
spent catalyst with H2. However, a small decrease in the FDCA
yield was still observed.
PVP and poly-1,3-bis(4-vinylbenzyl)imidazolium chloride
(abbreviated as IP) stabilized Pt nanoparticles (abbreviated as
Pt/PVP, Pt/IP) were active for the base-free oxidation of HMF
into FDCA.244 DFF and HFCA were the intermediates, and FFCA
was the main intermediate, suggesting that the oxidation of
the hydroxymethyl group was easier than the oxidation of the
formyl group. FDCA was produced in yields of 94% and 99%
after 24 h over the Pt/PVP and Pt/IP catalysts, respectively
(Table 10, entries 13 and 14). The Pt/IP catalyst could be
recycled with a full HMF conversion in each run, but the FDCA
yield decreased to nearly 87% with an FFCA yield of 13% in
the sixth run. The Pt/C–O–Mg catalyst with a basic support
also promoted the base-free oxidation of HMF into FDCA. The
C–O–Mg support was prepared by coating MgO particles with
carbon and then removing the free MgO before loading Pt onto
the carbon surface.245 A 97% FDCA yield was produced after 12 h
at 383 K and 10 bar O2 (Table 10, entry 15). More importantly, the
Pt/C–O–Mg catalyst could be reused ten times. The excellent
activity and stability may come from the formation of a C–O–Mg
bond, which created new, strong and stable basic sites. Further
scaling up the HMF amount to 10 mmol, the isolated FDCA yield
reached 74.9% with very high purity (99.5%).
Several kinds of Pd catalysts were also active for the oxida-
tion of HMF into FDCA. PVP stabilized Pd nanoparticles
(Pd/PVP) with a smaller particle size produced a higher FDCA
yield.246 The Pd/PVP catalyst with a Pd diameter of 1.8 nm pro-
duced a 90% FDCA yield after 6 h at 363 K (Table 10, entry 16),
while it was 81% with a Pd diameter of 2.0 nm. Furthermore, Pd/
PVP deposited on metal oxides (TiO2, g-Al2O3 and ZrO2/La2O3) was
preprared.247 Full HMF conversions (499%) were achieved for
different catalysts after 8 h at 363 K, but Pd/ZrO2/La2O3 produced
the highest FDCA yield of 90% (Table 10, entries 17–19). No
significant aggregation of Pd nanoparticles was observed in the
spent Pd/ZrO2/La2O3 catalyst, while serious aggregation of Pd
nanoparticles was noted in other catalysts. The Pd/ZrO2/La2O3
was recycled for three runs with a full HMF conversion in
each run, but the FDCA yield decrease from 90% in the first run
to 86% in the third run. Similar to the Pt/C–O–Mg catalyst
with a basic support,245 the Pd/HT catalyst with the basic
Mg–Al–hydrotalcite (HT) support was also active for the base-
free oxidation of HMF into FDCA.248 A quantitative FDCA yield
was produced in water after 7 h at 373 K with HFCA and FFCA
as the intermediates (Table 10, entry 20). A slight decrease in
FDCA yield was observed after the 5th run with full HMF
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conversion over the Pd/HT catalyst. Several kinds of magnetic
Pd catalysts were studied for the oxidation of HMF into FDCA
to facilitate catalyst recycling.249–251 Similar to the g-Fe2O3@
HAP-Ru3+ catalyst,219 a magnetic g-Fe2O3@HAP-Pd catalyst was
prepared.249 An HMF conversion of 97% and FDCA yield of
92.9% were produced after 6 h at 373 K and 1 bar O2 over the
g-Fe2O3@HAP-Pd catalyst (Table 10, entry 21). This catalytic
system did not require the use of excessive base (with 0.5 equiv.
of K2CO3 to neutralize FDCA). The catalyst could be reused (a
92.9% FDCA yield in the first run vs. 90.7% in the fifth run)
without the growth of Pd nanoparticles. Graphene oxide with
abundant oxygen functional groups has received great interest
to immobilize nanoparticles.252,253 A magnetically separable
graphene oxide supported Pd catalyst (C-Fe3O4-Pd) was also
used for the oxidation of HMF into FDCA, which was prepared
by the simultaneous deposition of Fe3O4 and Pd nanoparticles
on graphene oxide.250 A 98.1% HMF conversion and a 91.8%
FDCA yield were produced after 4 h at 353 K and 1 bar O2 with
0.5 equiv. K2CO3 (Table 10, entry 22). Similarly, a core–shell
structured C@Fe3O4 supported Pd catalyst was prepared for the
oxidation of HMF into FDCA.251 An HMF conversion of 100%
and FDCA yield of 86.7% were produced over the Pd/C@Fe3O4
catalyst after 6 h at 353 K (Table 10, entry 23). The Pd/C@Fe3O4
catalyst could be reused with a very slight decrease in FDCA
yield (86.7% in the first run vs. 83.7% in the fifth run). XPS
confirmed that metallic Pd(0) was retained, and no aggregation
of Pd nanoparticles was observed in the spent catalyst.
Compared with Pd and Pt catalysts, Au catalysts have
received much more attention for the oxidation of HMF into
FDCA. Riisager and co-workers studied the oxidation of HMF
into FDCA over a commercial Au/TiO2 catalyst.155 HFCA was the
intermediate. A 71% FDCA yield was produced at full HMF
conversion after 18 h at 303 K and 20 bar O2 with 20 equiv. of
NaOH (Table 10, entry 24). Without a base, the deactivation of
the Au/TiO2 catalyst was caused by the absorption of FDCA on
the gold surface. NaOH reacted with FDCA to form a salt in the
reaction solution. Similar phenomena were also observed by
Davis et al. using the same catalyst.254 The activity of the Au
catalysts was greatly affected by the support.255 Under identical
conditions (10 bar air, 403 K, 4 equiv. NaOH), FDCA was produced
in a yield of 84% at full HMF conversion after 8 h over the Au/TiO2
catalyst, while the yield was 100% after 5 h over the Au/CeO2
catalyst (Table 10, entries 25 and 26). The lower selectivity of FDCA
over the Au/TiO2 catalyst was caused by the formation of decar-
boxylated and ring-opening byproducts from HMF. Albonetti et al.
also observed that the Au/CeO2 catalyst showed a better catalytic
performance than the Au/TiO2 catalyst.256 Furthermore, they
prepared an ordered mesoporous CeO2 supported Au catalyst
(Au/mCeO2) for the oxidation of HMF into FDCA.257 HFCA was
the main product within 30 min, and FDCA was produced in a yield
of 92% after 4 h at full HMF conversion at 343 K and 10 bar O2
(Table 10, entry 27). Yang and co-workers found that the catalytic
activity of Au/CeO2 could be enhanced by the addition of Bi into
CeO2.258 Full HMF conversions were attained after 1 h at 338 K and
10 bar O2 over the Au/CeO2 and Au/Ce1 xBixO2 d (0.08 r x r 0.2)
catalysts. The FDCA and HFCA yields were 39% and 57% over
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the Au/CeO2 catalyst, respectively. While FDCA yields around
75% were produced over the Au/Ce1 xBixO2 d catalysts. 100%
yield of FDCA was obtained after 2 h over the Au/Ce0.85Bi0.15O2 d
catalyst (Table 10, entry 28). The higher activity of the Au/
Ce1 xBixO2 d catalysts was attributed to the oxygen activation
and hydride transfer enhanced by Bi doping and the large
amount of oxygen vacancies. The Au/Ce0.85Bi0.15O2 d catalyst
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could be reused with full HMF conversions for four runs.
However, the FDCA yield showed a slight decrease in conjunc-
tion with a slight increase of the HFCA yield. Similar to the
Pd/HT catalyst,248 the 1.92 wt%Au/HT catalyst could also promote
the base-free oxidation of HMF into FDCA.259 A quantitative FDCA
yield was produced with HFCA as the main intermediate after 7 h
at 368 K and 1 bar O2 (Table 10, entry 29). Although HMF
conversion remained 100% for three runs, the FDCA yield showed
a slight decrease in conjunction with a slight increase of the HFCA
and FFCA yields. The spent Au/HT catalyst showed no change in
the oxidation state, morphology and particle size distribution of
Au nanoparticles. Wilson and co-workers260 reported that the
alkali-free HT supported Au catalyst (2.0 wt% Au-HT) produced
80% HMF conversion with HFCA as the product in the absence
of a base. The competitive adsorption between strongly-bound
HMF and reactively-formed oxidation intermediates site-blocks
gold. Aqueous NaOH dramatically promotes solution phase
HMF activation, liberating free gold sites able to activate the
alcohol function within the meta-stable HFCA reactive inter-
mediate. Thus the authors claimed that the base-free oxidation
of HMF into FDCA over the Au/HT catalyst reported by Ebitani
and co-workers259 was caused either by alkali contaminants
leached from Na2CO3/NaOH precipitated hydrotalcites, or par-
tially soluble brucite co-existing with the hydrotalcite. The con-
finement of Au nanoparticles in a rigid cage was an effective way
to prevent Au nanoparticle aggregation. Xu et al. confined Au
nanoparticles of 1 nm into a supercage of Y zeolite (Au/HY) for
HMF oxidation.261 An FDCA yield 499% was produced after 6 h at
333 K (Table 10, entry 28). The HY supercage serves as a natural
nanocage to encapsulate the extremely small Au nanoclusters to
prevent them from aggregation. The particle size of Au was
essentially unaltered in the spent catalyst. However, the FDCA
yield decreased slightly from 99% in the first run to 88% in the
fourth run.
Some Au containing bimetallic catalysts were also studied
for HMF oxidation. Pasini et al. studied the oxidation of HMF
into FDCA over Cu–Au/TiO2 catalysts.262 Au–Cu/TiO2 catalysts
with different Au/Cu ratio showed higher activity by at least a
factor of 2 in each case as compared to the Au/TiO2 catalyst at the
same weight percentage. The enhanced catalytic activity was
attributed to the isolation of Au sites by Cu. The Au–Cu/TiO2
catalyst with the molar ratio Au/Cu = 1 showed the highest
catalytic activity, which afforded a 99% FDCA yield at 368 K and
10 bar O2 (Table 10, entry 31). This catalyst was stable without the
leaching and aggregation of the metal nanoparticles. Supported
bimetallic Pd–Au catalysts also showed better catalytic perfor-
mance than the corresponding Au catalysts.263–266 For example,
an FDCA yield 499% was produced after 4 h at 333 K over the
Au8–Pd2/C catalyst (Table 10, entry 32).263 However, the Au/C
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catalyst produced an 80% FDCA yield together with a 20%
HFCA yield after 6 h (Table 10, entry 33), while HFCA was
produced in a 91% yield over the Pd/C catalyst after 6 h
(Table 10, entry 34). These results indicated that Pd and Au
synergetically promoted the oxidation of HMF into FDCA. The
Au8–Pd2/C catalyst could be reused for five runs with the FDCA
yield remaining 499%. The synergetic effects of Pd and Au
were present in the Au–Pd/TiO2 for the oxidation of HMF into
FDCA.264 For most cases, the oxidation of HMF into FDCA over
Au catalysts was performed by the use of an excessive base.
A carbon nanotube (CNT) supported Au–Pd (Au–Pd/CNT) catalyst
was active for the base-free oxidation of HMF to FDCA.265 A 94%
FDCA yield was produced over the Au–Pd/CNT catalyst after 12 h
at 373 K and 5 bar O2 (Table 10, entry 35). The treatment of CNT
with H2O2 generated carbonyl/quinone and phenol groups on
its surfaces, facilitating the adsorption of HMF and the inter-
mediates on the catalyst surface. The CNT supported Pt catalyst
(Pt/CNT) was also active for the base-free oxidation of HMF into
FDCA.267 A 98% FDCA yield was produced after 14 h at 368 K and
5 bar O2 (Table 10, entry 36). The Pt/CNT catalyst was very stable
without a decrease in FDCA yield.
As listed in Table 8, Ru catalysts were mainly used for
the oxidation of HMF into DFF in organic solvents. Kerdi and
co-workers reported that the active carbon supported Ru
catalyst (Ru/AC) could catalyze the oxidation of HMF into FDCA
in alkaline solution via DFF as the intermediate.268 The intro-
duction of oxygen-functional groups on the surface of active
carbon by NaOCl resulted in a decrease of the catalytic activity.
Full HMF conversion was attained after 2 h over the Ru/AC
catalyst with a 75% FDCA yield, while 4 h was required for the
Ru/AC-NaOCl catalyst to get a full HMF conversion and a 55%
FDCA yield (Table 10, entries 37 vs. 38). The oxygen functional
groups made the catalyst surface more hydrophilic and more
polar, facilitating the preferential adsorption of water compara-
tively to the substrates. A MnCo2O4 spinel supported Ru catalyst
(Ru/MnCo2O4) was reported to be active for the base-free
oxidation of HMF into FDCA, which was due to the presence
of Lewis and Brønsted acids in the support.269 Although a high
FDCA yield of 99.1% was attained in water at 393 K under 24 bar
air, the use of high Ru loading (HMF/Ru molar ratio = 33.6)
makes this method high cost for practical applications (Table 10,
entry 39).269 Some recent progress has been made for the non-
noble metal or metal free oxidation of HMF into FDCA. Amos
Mugweru et al. reported a mixed oxide of Li2CoMn3O8 with NaBr
as the co-catalyst for the oxidation of HMF into FDCA.270 An
isolated FDCA yield of 80% was produced on a gram scale, but
the reaction was performed in acetic acid under harsh condi-
tions (423 K, 55 bar O2). Neatu et al. performed the oxidation of
HMF into FDCA by the use of MnxFey mixed oxides.271 MnxFey
mixed oxides were prepared by the co-precipitation of Fe3+ and
Mn2+ at pH = 9–10, followed by calcination at 773 K in air. The
Mn0.75Fe0.25 mixed oxide (Mn0.75Fe0.25Ox) showed the highest
catalytic activity. The authors found that the oxidation of HMF
into FFCA could be performed without a catalyst. A 79% HMF
conversion and an 88% FFCA selectivity were produced after
12 h at 363 K and 8 bar O2 with NaOH/HMF molar ratio = 1 : 4.
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However, the humins from this step caused the deactivation of
the catalyst. Therefore, a two-step method was adopted. After
the first step, humin species were removed using a simple
precipitation/filtration method by adjusting the pH to 1. Then
the oxidation of the purified FFCA was carried out over the
Mn0.75Fe0.25Ox catalyst, which gave a 90% FDCA yield after 24 h
(Table 10, entry 40). In addition, other kinds of Mn oxides such
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as MnOx–CeO2 and MnO2 were also used for the oxidation of
HMF into FDCA under basic conditions.272,273 More excitingly,
the metal-free oxidation of HMF into FDCA was recently
reported.274 In recent years, nitrogen-doped carbon catalysts
have been discovered to be active for several types of chemical
reactions.275 Wu and co-workers reported a first example on the
metal-free oxidation of HMF into FDCA by the use of nitrogen-
doped carbon catalysts (abbreviated as NNC-X, where X repre-
sents the pyrolysis temperature). NNC catalysts were prepared
by the pyrolysis of ZIF-8 (one-kind of zeolitic imidazole frame-
work), followed by treatment with HCl to remove the zinc
species.274 Full HMF conversions were all observed for the
NNC-X catalysts. FDCA yields of 11%, 35%, 72%, and 80% were
observed in water after 48 h at 353 K over NNC-873, NNC-973,
NNC-1073, and NNC-1173 as the catalysts (Table 10, entries 41–44),
respectively. The FDCA yields were proportional to the amount
of graphene-type nitrogen in the NNC-X catalysts, suggesting
that the graphene-type nitrogen atoms were the active sites for
the activation of O2 to give oxidative species of oxygen radicals.
However, the NNC-1173 catalyst was not stable with a decrease
in FDCA yield from 80% to 70%, due to a decrease in the
amount of graphene-type nitrogen.
Little attention has been paid to the mechanism of oxidation
of HMF into FDCA over supported metal catalysts. Davis et al.
studied the kinetics and mechanism of the oxidation of HMF into
FDCA over Pt/C and Au/C catalysts in alkaline solutions.276,277
According to the isotope labeling technology, a plausible mecha-
nism was proposed for the Pt/C and Au/C catalysts (Fig. 27). The
incorporation of two 18O atoms was observed in HFCA when the
reaction is performed in H218O. The aldehyde side chain is
believed to undergo rapid reversible hydration to a geminal diol
via nucleophilic addition of a hydroxide ion to the carbonyl and
subsequent proton transfer from water to the alkoxy ion inter-
mediate (Fig. 27, step 1). The second step is the dehydrogenation
of the geminal diol intermediate, facilitated by the hydroxide ions
adsorbed on the metal surface, to produce the carboxylic acid
(Fig. 27, step 2). An oxidation experiment performed in the
absence of a base over both Au and Pt catalysts resulted in no
conversion of HMF, indicating the important role of OH in the
oxidation of HMF into FDCA at 295 K. Hydroxide ions on the
catalyst surface then facilitate the activation of the C–H bond
in the alcohol side-chain to form the aldehyde intermediate,
5-formyl-2-furancarboxylic acid (FFCA). Then, FFCA was oxi-
dized to FDCA followed by steps 4 and 5, which were the same
as steps 1 and step 2, respectively. Therefore, this mechanism
in Fig. 29 can explain the incorporation of all 4 18O atoms in
FDCA when the reaction is performed in labeled water. The role
of O2 is used to scavenge electrons from the catalyst surface,
thereby closing the catalytic cycle.
1382 | Chem. Soc. Rev., 2018, 47, 1351--1390
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Chem Soc Rev
Fig. 29 Overall reaction scheme and proposed mechanism for the oxi-
dation of HMF in aqueous solution. Dioxygen (not shown) serves as a
scavenger of electrons that are deposited into the metal particles during
the catalytic cycle. Adapted from ref. 276 with permission from Royal
Society of Chemistry copyright 2012.
7.6 Catalytic oxidation of HMF into FDCA using t-BuOOH and
H2O2 as the oxidant
Besides O2, there are also some reports on the oxidation of HMF
into FDCA with t-BuOOH or H2O2 as the oxidant. Riisager et al.
performed the oxidation of HMF into FDCA in acetonitrile with
t-BuOOH as the oxidant and copper salts as the catalysts.202
A 43% FDCA yield was produced after 48 h at 25 1C with the
CuCl–LiBr catalysts, and that was 45% with CuCl2. Not only are
the FDCA yields lower, but it is also difficult to recycle the
homogeneous catalysts. The merrifield resin supported Co(II)-
meso-tetra(4-pyridyl)-porphyrin catalyst could also promote
the oxidation of HMF into FDCA in acetonitrile by the use of
t-BuOOH, affording a 90.4% FDCA yield after 24 h at 373 K.278
This catalyst could be reused without loss of its catalytic activity.
Although the oxidation of HMF into FDCA with t-BuOOH can be
performed without a base, the large scale production of FDCA is
limited, because of the explosive peroxide. H2O2 is another
environmentally-friendly and green oxidant. Tetra-ethylpyridinium
octamolybdate ([EPy]4Mo8O26) was active for the oxidation of
HMF into FDCA with H2O2 as the oxidant.279 A 99.5% FDCA
yield was produced after 2 h at 373 K with H2O2/NaOH/HMF
molar ratio = 18 : 2 : 1.
7.7 Electrocatalytic oxidation of HMF
The advantage of electrocatalytic oxidation is that it is due to
electron transfer and does not require chemical oxidants.280,281
The first report of electrochemical oxidation of HMF into FDCA
was in 1995 in an H-shaped cell.282 Carbon-black supported
noble metal catalysts were studied for the electrocatalytic oxida-
tion of HMF in alkaline solution.283 In electrocatalytic oxidation
of HMF, a competitive oxidation is the oxidation of water to O2.
Choi and co-workers employed a redox mediator (TEMPO) to
inhibit the oxidation of water over a Pt electrode.284 The use of
TEMPO significantly reduced the necessary overpotential to
initiate HMF oxidation. As shown in Fig. 30, TEMPO was firstly
oxidized to TEMPO+ near the electrode, and TEMPO+ promoted
the HMF oxidation. High FDCA yield (Z99%) and Faradaic
This journal is © The Royal Society of Chemistry 2018

Chem Soc Rev
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Fig. 30 Scheme of electrocatalytic oxidation of HMF into FDCA with
TEMPO as the mediator. Adapted from ref. 284 with permission from
Nature Publishing Group, copyright 2015.
efficiency (Z93%) were obtained in water at pH = 9.2. Kinetic
studies and cyclic voltammetry indicated that DFF was the reaction
intermediate. Similar TEMPO mediated electrocatalytic oxidation
of HMF was performed in a CH2Cl2/H2O biphasic system, produ-
cing an HMF conversion of 92% and DFF yield of 64%.285
Sun and co-workers made great progress in the electrocata-
lytic oxidation of HMF over a noble-metal-free bifunctional
electrocatalyst.286 Ni2P nanoparticles arrayed on nickel foam
(Ni2P/NF) were used as a bifunctional electrocatalyst to couple
HMF oxidation and H2 evolution in alkaline solution. Linear
sweep voltammetry indicated that the oxidation of HMF was
significantly easier than the oxidation of water catalyzed by
Ni2P/NF. The Ni2P/NF catalyst could be employed both as a
cathode and an anode for the HMF oxidation and H2 produc-
tion, respectively, which produced a high current density
(50 mA cm 2) with a voltage at least 200 mV less than that of
pure water splitting electrolysis. In addition, near unity Faradaic
efficiencies were achieved for both H2 (100%) and FDCA (98%)
generation, together with robust stability. HMF oxidation into
FDCA catalyzed by Ni2P/NF likely followed the HMFCA route.
Meanwhile, the same authors also reported similar work by the
use of other kinds of electrocatalysts such as Ni3S2/NF287 and
CoP/copper foam288 for the coupling of HMF oxidation and
H2 evolution. The electrocatalytic methods with the superior
performance for H2 and FDCA production, render the current
catalytic systems very appealing for sustainable energy conver-
sion technologies.
In summary, the oxidation of HMF into FDCA was mainly
carried out over noble metal catalysts with O2 as the oxidant.
Au catalysts have shown encouraging performance for this
reaction over Pt and Pd catalysts. In most cases, the oxidation
reactions were carried out with an excessive amount of base,
Fig. 31 Synthesis of FDCA from glucose via a one-pot reaction.
This journal is © The Royal Society of Chemistry 2018
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Review Article
which made these processes less green and less cost-effective.
Therefore, much effort is still needed to develop new catalytic
methods for the base-free oxidation of HMF into FDCA with
O2 as the oxidant with high activity, selectivity and stability.
Carefully choosing a suitable support and the active metals
seems to be important to realize this aim.
7.8 Conversion of carbohydrates into FDCA
There are a few examples on the oxidative transformation of
carbohydrates into FDCA (Fig. 31). In 2000, Kröger and co-workers
first reported the transformation of fructose into FDCA via a
two-step process using a membrane as shown in Fig. 32.289
Fructose dehydration to HMF was first conducted in water at
353 K with Lewatit SPC 108 (a microporous cationic ion
exchanger in H+ form) as the solid acid catalyst. The HMF
transferred into the MIBK phase through the membrane, followed
by the oxidation of HMF into FDCA over a PtBi/C catalyst at 353 K.
The reaction rate was controlled by the diffusion of HMF through
the membrane. After 7 days, FDCA was produced in an overall
yield of 25% with a selectivity of 50%. Levulinic acid was also
produced in a similar yield of 25%. Ribeiro and Schuchardt
studied the one-pot transformation of fructose into FDCA over a
bifunctional catalyst.290 Cobalt acetylacetonate encapsulated in
sol–gel silica was used as the acid–metal bifunctional catalyst for
the one-step conversion of fructose into FDCA. Fructose conver-
sion of 72% with an FCDA selectivity of 99% was produced at
433 K and 20 bar air in water. Fructose was dehydrated into HMF
on the silica catalyst. The HMF was then oxidized on the metal
sites. No other intermediates were observed. Zhang et al. reported
a two-step method for the synthesis of FDCA from fructose that
Fig. 32 Scheme of the processes in the membrane reactor: 1 – HMF
formation in a water phase, 2 – diffusion of HMF in an MIBK phase and
3 – HMF oxidation. Reproduced with permission from ref. 289 with
permission from springer, copyright 2000.
Chem. Soc. Rev., 2018, 47, 1351--1390 | 1383

Review Article
involved conversion of fructose into HMF in isopropanol with
HCl followed by oxidation of HMF into FDCA over an Au/HT
catalyst.291 Humin impurities decreased the catalyst activity
and stability. The humin impurities could be removed by
evaporating isopropanol from the original solution of HMF at
40 1C under reduced pressure, and then extracting the HMF
from the solids with water. The overall FDCA yield from fructose
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was 83%. Zhang and co-workers then designed a triphasic
approach for the conversion of fructose and glucose into
FDCA.292 HMF was produced in phase I (TEAB or water) from
fructose with Amberlyst-15 or glucose by CrCl3. The HMF in
phase I was extracted into MIBK (phase II) and transferred into
water (phase III), where FDCA was produced with an Au–Pd/HT
catalyst with O2. Overall FDCA yields of 78% and 50% were
obtained from fructose and glucose, respectively. The same
group then used a commercial Ru/C catalyst and FDCA as the
acid catalyst for the two-step transformation of fructose into
FDCA.293 Ru/C catalyzed the base-free oxidation of HMF to FDCA
with a yield of 88% (after 10 h at 293 K and 2 bar O2). The FDCA
could then be used as an acid catalyst for the dehydration of
fructose to HMF in an isopropanol/H2O system, where 64% HMF
yield was produced after 30 min at 443 K. Then the second step
of HMF oxidation to FDCA was demonstrated with an overall
yield of 53% after 15 h (83% yield in the second step). The rate of
oxidation of synthesized HMF (from sugar) was slower than the
rate of oxidation of pure commercial HMF (15 h vs.10 h), which
may be due to some minor water soluble impurities in the
freshly synthesized HMF solution. To facilitate the separation
of the acid–metal catalysts, two magnetic catalysts were used for
the oxidative conversion of fructose into FDCA.294 Fe3O4@SiO2–
SO3H was used as the acid catalyst for the dehydration of
fructose HMF to produce HMF with a yield of 93.1% at 373 K
after 2 h. After the removal of the Fe3O4@SiO2–SO3H catalyst,
HMF was then oxidized into FDCA with t-BuOOH over a nano-
Fe3O4–CoOx catalyst at 353 K. FDCA was obtained in an overall
yield of 59.8% after 15 h based on the starting fructose.
8. Conclusions and perspectives
As listed in Fig. 1, a wide variety of commodity chemicals
including formic acid, acetic acid, glycolic acid, gluconic acid,
glucaric acid, malonic acid, oxalic acid, and furan chemicals
(DFF and FDCA) can be produced from the catalytic oxidation
of carbohydrates and carbohydrate derivative HMF. Polyoxo-
metalates or polyoxometalate based catalysts are mainly used
for the conversion of cellulose or glucose into formic acid with
molecular oxygen as the oxidant. Carbon dioxide is the typical
undesired byproduct from this reaction and is produced
by oxidation of an intermediate. Hydrothermal oxidation by
the use of H2O2 as the oxidant can convert the carbohydrates
into acetic acid or formic acid in low yields as the harsh
hydrothermal reaction conditions (high temperatures and high
pressure) cause other organic acids to be formed. Gluconic acid
can be produced by the oxidation of glucose over supported
metal catalysts under high pH conditions. Au catalysts are more
1384 | Chem. Soc. Rev., 2018, 47, 1351--1390
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Chem Soc Rev
stable for glucose oxidation than Pt and Pd catalysts which
undergo oxidation. Au supported on acidic materials can con-
vert cellobiose into gluconic acid, but is ineffective for cellulose
transformation into gluconic acid. Compared with the oxida-
tion of glucose into gluconic acid, the selective oxidation of
glucose into glucaric acid is much more difficult, which is
currently performed over supported Pt catalysts.
Oxidation of HMF produces DFF and FDCA. Oxidation
of HMF into DFF was mainly carried out in organic solvents
without a base with transition metal (vanadium or manganese)
or ruthenium catalysts. Vanadium catalysts showed low catalytic
performance in terms of activity, DFF selectivity and catalyst
stability, while OMS-2 (KMn8O16
nH2O) based catalysts had
higher activity and stability in the oxidation of HMF into DFF.
The oxidation of HMF into FDCA was mainly performed in water
with an excess of base over supported noble metal catalysts (Pt,
Pd, and Au). Au catalysts had higher selectivity and stability than
Pt and Pd catalysts in the aerobic oxidation of HMF into FDCA.
The one-pot conversion of carbohydrates into DFF or FDCA is
much slower than using HMF as the starting material.
Although great progress has recently been achieved for the
catalytic oxidation of carbohydrates or their derivate HMF into
important organic acids or furanic compounds, further improve-
ments are still necessary in many cases with the aim to realize the
commercial application of these processes for the synthesis of
valuable chemicals through biorefineries. (1) Catalytic oxidation
in a biomass refinery should not be limited to the currently
reported routes, but also should pay special attention to devel-
oping new routes, or even exploring novel strategies to produce
new products; (2) efforts should be devoted to the design of active
and effective catalysts for the transformation of carbohydrates
into the target products under mild reaction conditions with high
conversion and selectivity especially for the production of formic
acid and acetic acid. (3) In order to lower the production cost,
much attention should be directed to the development of none
noble based catalysts for the oxidative transformation of biomass
with high activity, stability and facile catalyst recycling. (4) It is
expected that the design novel multi-functional catalysts will
allow more substrates as the starting materials to produce
chemicals via several steps in a one-pot reaction, thus avoiding
the costly intermediate separation process. (5) It is necessary to
get more insights into the mechanism of the transformation
reactions, and the structure–property relationship of the cata-
lysts, which is of great significance from both scientific and
practical viewpoints. (6) It is extremely important to perform
the large-scale production of chemicals via catalytic oxidation
reactions in a biorefinery. Many current methods are technically
feasible, but not economical. Although these processes still need
to be improved for practical use, we believe that further progress
will realize a biorefinery by heterogeneous catalysis to ensure
sustainable development.
Conflicts of interest
There are no conflicts to declare.
This journal is © The Royal Society of Chemistry 2018

Chem Soc Rev
Acknowledgements
This work was supported by the funding offered by the China
scholarship council (201408420018).
References
Published on 03 January 2018. Downloaded by National University of Kaohsiung on 22/02/2018 10:09:12.
1 G. W. Huber, S. Iborra and A. Corma, Chem. Rev., 2006,
106, 4044–4098.
2 W. P. Deng, Q. H. Zhang and Y. Wang, Catal. Today, 2014,
234, 31–41.
3 T. F. Wang, M. W. Nolte and B. H. Shanks, Green Chem.,
2014, 16, 548–572.
4 X. L. Tong, Y. Ma and Y. D. Li, Appl. Catal., A, 2010, 385,
1–13.
5 Y. Kwon, K. J. P. Schouten, J. C. van der Waal, E. de Jong
and M. T. M. Koper, ACS Catal., 2016, 6, 6704–6717.
6 M. E. Zakrzewska, E. Bogel-Lukasik and R. Bogel-Lukasik,
Chem. Rev., 2011, 111, 397–417.
7 G. Z. Papageorgiou, D. G. Papageorgiou, Z. Terzopoulou
and D. N. Bikiaris, Eur. Polym. J., 2016, 83, 202–229.
8 http://www.alibaba.com/?spm=a2700.7699653.a271qf.40.
APWJep.
9 https://en.wikipedia.org/wiki/Formic_acid.
10 https://en.wikipedia.org/wiki/Acetic_acid.
11 https://en.wikipedia.org/wiki/Glycolic_acid.
12 http://www.transparencymarketresearch.com/glycolic-acid-
market.html.
13 https://en.wikipedia.org/wiki/Gluconic_acid.
14 http://www.grandviewresearch.com/industry-analysis/fdca-
industry.
15 L. F. Fieser and J. E. Jones, Org. Synth., 1955, 3, 590.
16 R. V. Jagadeesh, D. Banerjee, P. B. Arockiam, H. Junge,
K. Junge, M. M. Pohl, J. Radnik, A. Bruckner and M. Beller,
Green Chem., 2015, 17, 898–902.
17 S. Zhang, O. Metin, D. Su and S. H. Sun, Angew. Chem., Int.
Ed., 2013, 52, 3681–3684.
18 Y. Himeda, Green Chem., 2009, 11, 2018–2022.
19 A. Boddien, D. Mellmann, F. Gartner, R. Jackstell, H. Junge,
P. J. Dyson, G. Laurenczy, R. Ludwig and M. Beller, Science,
2011, 333, 1733–1736.
20 L. G. Feng, J. F. Chang, K. Jiang, H. G. Xue, C. P. Liu,
W. B. Cai, W. Xing and J. J. Zhang, Nano Energy, 2016, 30,
355–361.
21 W. Reutemann and H. Kieczka, Formic Acid, Ullmann’s
Encyclopedia of Industrial Chemistry, 2011.
22 C. Schopf and H. Wild, Chem. Ber., 1954, 87, 1571–1575.
23 R. Wolfel, N. Taccardi, A. Bosmann and P. Wasserscheid,
Green Chem., 2011, 13, 2759–2763.
24 J. Li, D. J. Ding, L. Deng, Q. X. Guo and Y. Fu, ChemSusChem,
2012, 5, 1313–1318.
25 T. Lu, M. G. Niu, Y. C. Hou, W. Z. Wu, S. H. Ren and
F. Yang, Green Chem., 2016, 18, 4725–4732.
26 J. Albert, R. Wolfel, A. Bosmann and P. Wasserscheid,
Energy Environ. Sci., 2012, 5, 7956–7962.
This journal is © The Royal Society of Chemistry 2018
View Article Online
Review Article
27 J. Albert and P. Wasserscheid, Green Chem., 2015, 17,
5164–5171.
28 J. Albert, D. Luders, A. Bosmann, D. M. Guldi and
P. Wasserscheid, Green Chem., 2014, 16, 226–237.
29 J. Z. Zhang, M. Sun, X. Liu and Y. Han, Catal. Today, 2014,
233, 77–82.
30 Y. Leng, J. Wang, D. R. Zhu, X. Q. Ren, H. Q. Ge and
L. Shen, Angew. Chem., Int. Ed., 2009, 48, 168–171.
31 J. L. Xu, H. Y. Zhang, Y. F. Zhao, Z. Z. Yang, B. Yu, H. J. Xu
and Z. M. Liu, Green Chem., 2014, 16, 4931–4935.
32 K. X. Li, L. L. Bai, P. N. Amaniampong, X. L. Jia, J. M. Lee
and Y. H. Yang, ChemSusChem, 2014, 7, 2670–2677.
33 W. Wang, M. Niu, Y. Hou, W. Wu, Z. Liu, Q. Liu, S. Ren and
K. N. Marsh, Green Chem., 2014, 16, 2614–2618.
34 M. G. Niu, Y. C. Hou, S. H. Ren, W. Z. Wu and K. N. Marsh,
Green Chem., 2015, 17, 453–459.
35 B. M. Weckhuysen and D. E. Keller, Catal. Today, 2003, 78,
25–46.
36 M. Tani, T. Sakamoto, S. Mita, S. Sakaguchi and Y. Ishii,
Angew. Chem., Int. Ed., 2005, 44, 2586–2588.
37 M. G. Niu, Y. C. Hou, S. H. Ren, W. H. Wang, Q. T. Zheng
and W. Z. Wu, Green Chem., 2015, 17, 335–342.
38 Z. C. Tang, W. P. Deng, Y. L. Wang, E. Z. Zhu, X. Y. Wan,
Q. H. Zhang and Y. Wang, ChemSusChem, 2014, 7, 1557–1567.
39 J. Reichert, B. Bruner, A. Jess, P. Wasserscheid and
J. Albert, Energy Environ. Sci., 2015, 8, 2985–2990.
40 A. M. Khenkin and R. Neumann, J. Am. Chem. Soc., 2008,
130, 14474–14476.
41 A. M. Khenkin, G. Leitus and R. Neumann, J. Am. Chem.
Soc., 2010, 132, 11446–11448.
42 L. Calvo and D. Vallejo, Ind. Eng. Chem. Res., 2002, 41,
6503–6509.
43 F. M. Jin, J. Yun, G. M. Li, A. Kishita, K. Tohji and
H. Enomoto, Green Chem., 2008, 10, 612–615.
44 J. Yun, G. D. Yao, F. M. Jin, H. Zhong, A. Kishita, K. Tohji,
H. Enomoto and L. Wang, AIChE J., 2016, 62, 3657–3663.
45 N. Zargari, Y. Kim and K. W. Jung, Green Chem., 2015, 17,
2736–2740.
46 H. Choudhary, S. Nishimura and K. Ebitani, Appl. Catal., B,
2015, 162, 1–10.
47 B. C. Gates, H. Knozinger and F. C. Jentoft, Adv. Catal.,
2010, 53, 1–45.
48 N. Saichana, K. Matsushita, O. Adachi, I. Frebort and
J. Frebortova, Biotechnol. Adv., 2015, 33, 1260–1271.
49 F. M. Jin, Z. Y. Zhou, T. Moriya, H. Kishida, H. Higashijima
and H. Enomoto, Environ. Sci. Technol., 2005, 39, 1893–1902.
50 F. M. Jin, Z. Y. Zhou, A. Kishita, H. Enomoto, H. Kishida
and T. Moriya, Chem. Eng. Res. Des., 2007, 85, 201–206.
51 Y. Fang, X. Zeng, P. Yan, Z. Z. Jing and F. M. Jin, Ind.
Eng. Chem. Res., 2012, 51, 4759–4763.
52 J. Li, Y. B. Huang, Q. X. Guo and Y. Fu, Acta Chim. Sin.,
2014, 72, 1223–1227.
53 L. Y. Li, F. Shen, R. L. Smith and X. H. Qi, Green Chem.,
2017, 19, 76–81.
54 X. Y. Gao, H. Zhong, G. D. Yao, W. M. Guo and F. M. Jin,
Catal. Today, 2016, 274, 49–54.
Chem. Soc. Rev., 2018, 47, 1351--1390 | 1385

Review Article
55 X. Y. Gao, X. Chen, J. G. Zhang, W. M. Guo, F. M. Jin and
N. Yan, ACS Sustainable Chem. Eng., 2016, 4, 3912–3920.
56 http://www.transparencymarketresearch.com/glycolic-
acid-market.html.
57 F. W. Wang, Y. Q. Wang, F. M. Jin, G. D. Yao, Z. B. Huo,
X. Zeng and Z. Z. Jing, Ind. Eng. Chem. Res., 2014, 53,
7939–7946.
Published on 03 January 2018. Downloaded by National University of Kaohsiung on 22/02/2018 10:09:12.
58 J. Z. Zhang, X. Liu, M. Sun, X. H. Ma and Y. Han, ACS
Catal., 2012, 2, 1698–1702.
59 Z. She, J. G. Wang, J. P. Ni, X. Q. Liu, R. Y. Zhang, H. N. Na
and J. Zhu, RSC Adv., 2015, 5, 5741–5744.
60 A. Corma, S. Iborra and A. Velty, Chem. Rev., 2007, 107,
2411–2502.
61 C. S. K. Lin, L. A. Pfaltzgraff, L. Herrero-Davila,
E. B. Mubofu, S. Abderrahim, J. H. Clark, A. A. Koutinas,
N. Kopsahelis, K. Stamatelatou, F. Dickson, S. Thankappan,
Z. Mohamed, R. Brocklesby and R. Luque, Energy Environ.
Sci., 2013, 6, 426–464.
62 L. Y. Yan and X. Y. Xi, ACS Sustainable Chem. Eng., 2014, 2,
897–901.
63 W. Riemenschneider and M. Tanifuji, Oxalic acid, Ullmann’s
Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag
GmbH & Co. KGaA, 2000.
64 Z. W. Jiang, Z. R. Zhang, J. L. Song, Q. L. Meng, H. C. Zhou,
Z. H. He and B. X. Han, ACS Sustainable Chem. Eng., 2016,
4, 305–311.
65 A. Costine, J. S. C. Loh, F. Busetti, C. A. Joll and A. Heitz,
Ind. Eng. Chem. Res., 2013, 52, 5572–5581.
66 P. N. Amaniampong, Q. T. Trinh, B. Wang, A. Borgna,
Y. H. Yang and S. H. Mushrif, Angew. Chem., Int. Ed., 2015,
54, 8928–8933.
67 R. H. Blom, V. F. Pfeifer, A. J. Moyer, D. H. Traufler and
H. F. Conway, Ind. Eng. Chem., 1952, 44, 435–440.
68 J. Bao, K. Furumoto, K. Fukunaga and K. Nakao, Biochem.
Eng. J., 2001, 8, 91–102.
69 H. J. Zhang and N. Toshima, Catal. Sci. Technol., 2013, 3,
268–278.
70 M. J. Climent, A. Corma and S. Iborra, Green Chem., 2011,
13, 520–540.
71 M. Besson, F. Lahmer, P. Gallezot, P. Fuertes and G. Fleche,
J. Catal., 1995, 152, 116–121.
72 S. Karski, T. Paryjczak and I. Witonska, Kinet. Catal., 2003,
44, 618–622.
73 D. Santhanaraj, M. R. Rover, D. E. Resasco, R. C. Brown
and S. Crossley, ChemSusChem, 2014, 7, 3132–3137.
74 X. Liang, C. J. Liu and P. Kuai, Green Chem., 2008, 12,
1318–1322.
75 V. Y. Doluda, I. B. Tsvetkova, A. V. Bykov, V. G. Matveeva,
A. I. Sidorov, M. G. Sulman, P. M. Valetsky, B. D. Stein,
E. M. Sulman and L. M. Bronstein, Polymer-Protected and
Au-Containing Bi- and Trimetallic Nanoparticles as Novel
Catalysts for Glucose Oxidation, Green Process Synth., 2013,
2, 25–34.
76 J. M. H. Dirkx and H. S. Vanderbaan, J. Catal., 1981, 67, 1–13.
77 A. E. Koklin, T. A. Klimenko, A. V. Kondratyuk, V. V. Lunin
and V. I. Bogdan, Kinet. Catal., 2015, 56, 84–88.
1386 | Chem. Soc. Rev., 2018, 47, 1351--1390
View Article Online
Chem Soc Rev
78 A. Tathod, T. Kane, E. S. Sanil and P. L. Dhepe, J. Mol.
Catal. A: Chem., 2014, 388, 90–99.
79 A. Haruta, Chem. Rec., 2003, 3, 75–87.
80 M. Stratakis and H. Garcia, Chem. Rev., 2012, 112, 4469–4506.
81 M. Pan, A. J. Brush, Z. D. Pozun, H. C. Ham, W. Y. Yu,
G. Henkelman, G. S. Hwang and C. B. Mullins, Chem. Soc.
Rev., 2013, 42, 5002–5013.
82 M. D. Hughes, Y. J. Xu, P. Jenkins, P. McMorn, P. Landon,
D. I. Enache, A. F. Carley, G. A. Attard, G. J. Hutchings,
F. King, E. H. Stitt, P. Johnston, K. Griffin and C. J. Kiely,
Nature, 2005, 437, 1132–1135.
83 B. T. Kusema and D. Y. Murzin, Catal. Sci. Technol., 2013,
3, 297–307.
84 C. D. Pina, E. Falletta and M. Rossi, Chem. Soc. Rev., 2012,
41, 350–369.
85 S. Biella, L. Prati and M. Rossi, J. Catal., 2002, 206, 242–247.
86 C. Y. Ma, W. J. Xue, J. J. Li, W. Xing and Z. P. Hao, Green
Chem., 2013, 15, 1035–1041.
87 M. Comotti, C. D. Pina, E. Falletta and M. Rossi, J. Catal.,
2006, 244, 122–125.
88 P. Y. Qi, S. S. Chen, J. Chen, J. W. Zheng, X. L. Zheng and
Y. Z. Yuan, ACS Catal., 2015, 5, 2659–2670.
89 A. Mirescu, H. Berndt, A. Martin and U. Prusse, Appl.
Catal., A, 2007, 317, 204–209.
90 Y. L. Cao, X. Liu, S. Iqbal, P. J. Miedziak, J. K. Edwards,
R. D. Armstrong, D. J. Morgan, J. W. Wang and
G. J. Hutchings, Catal. Sci. Technol., 2016, 6, 107–117.
91 Y. R. Wang, S. Van de Vyver, K. K. Sharma and Y. Roman-
Leshkov, Green Chem., 2014, 16, 719–726.
92 U. Prusse, M. Herrmann, C. Baatz and N. Decker, Appl.
Catal., A, 2011, 406, 89–93.
93 A. Mirescu and U. Prusse, Appl. Catal., B, 2007, 70, 644–652.
94 C. Baatz and U. Prusse, J. Catal., 2007, 249, 34–40.
95 C. Baatz, N. Thielecke and U. Prusse, Appl. Catal., B, 2007,
70, 653–660.
96 I. V. Delidovich, B. L. Moroz, O. P. Taran, N. V. Gromov,
P. A. Pyrjaev, I. P. Prosvirin, V. I. Bukhtiyarov and V. N. Parmon,
Chem. Eng. J., 2013, 223, 921–931.
97 R. Saliger, N. Decker and U. Prusse, Appl. Catal., B, 2011,
102, 584–589.
98 N. Thielecke, K. D. Vorlop and U. Prusse, Catal. Today,
2007, 122, 266–269.
99 N. Thielecke, M. Ayternir and U. Prusse, Catal. Today, 2007,
121, 115–120.
100 T. Benko, A. Beck, O. Geszti, R. Katona, A. Tungler, K. Frey,
L. Guczi and Z. Schay, Appl. Catal., A, 2010, 388, 31–36.
101 T. Ishida, N. Kinoshita, H. Okatsu, T. Akita, T. Takei and
M. Haruta, Angew. Chem., Int. Ed., 2008, 47, 9265–9268.
102 K. Odrozek, K. Maresz, A. Koreniuk, K. Prusik and
J. Mrowiec-Bialon, Appl. Catal., A, 2014, 475, 203–210.
103 P. Bujak, P. Bartczak and J. Polanski, J. Catal., 2012, 295,
15–21.
104 T. Ishida, S. Okamoto, R. Makiyama and M. Haruta, Appl.
Catal., A, 2009, 353, 243–248.
105 T. Ishida, H. Watanabe, T. Bebeko, T. Akita and M. Haruta,
Appl. Catal., A, 2010, 377, 42–46.
This journal is © The Royal Society of Chemistry 2018

Chem Soc Rev
106 H. J. Zhang and N. Toshima, Appl. Catal., A, 2012, 447, 81–88.
107 H. J. Zhang, N. Toshima, K. Takasaki and M. Okumura,
J. Alloys Compd., 2014, 586, 462–468.
108 H. J. Zhang, M. Haba, M. Okumura, T. Akita, S. Hashimoto
and N. Toshima, Langmuir, 2013, 29, 10330–10339.
109 H. M. Yin, C. Q. Zhou, C. X. Xu, P. P. Liu, X. H. Xu and
Y. Ding, J. Phys. Chem. C, 2008, 112, 9673–9678.
Published on 03 January 2018. Downloaded by National University of Kaohsiung on 22/02/2018 10:09:12.
110 H. J. Zhang and N. Toshima, J. Colloid Interface Sci., 2013,
394, 166–176.
111 M. Comotti, C. D. Pina and M. Rossi, J. Mol. Catal. A:
Chem., 2006, 251, 89–92.
112 E. Smolentseva, B. T. Kusema, S. Beloshapkin, M. Estrada,
E. Vargas, D. Y. Murzin, F. Castillon, S. Fuentes and
A. Simakov, Appl. Catal., A, 2011, 392, 69–79.
113 H. J. Zhang, K. Kawashima, M. Okumura and N. Toshima,
J. Mater. Chem. A, 2014, 2, 13498–13508.
114 P. J. Miedziak, H. Alshammari, S. A. Kondrat, T. J. Clarke,
T. E. Davies, M. Morad, D. J. Morgan, D. J. Willock,
D. W. Knight, S. H. Taylor and G. J. Hutchings, Green
Chem., 2014, 16, 3132–3141.
115 H. J. Zhang, L. L. Lu, Y. N. Cao, S. Du, Z. Cheng and
S. W. Zhang, Mater. Res. Bull., 2014, 49, 393–398.
116 H. J. Zhang and N. Toshima, Appl. Catal., A, 2011, 400, 9–13.
117 H. J. Zhang, M. Okumura and N. Toshima, J. Phys. Chem. C,
2011, 115, 14883–14891.
118 N. Toshima and H. J. Zhang, Macromol. Symp., 2012, 317,
149–159.
119 R. Saliger, N. Decker and U. Prusse, Appl. Catal., B, 2011,
102, 584–589.
120 S. Rautiainen, P. Lehtinen, M. Vehkamaki, K. Niemela,
M. Kemell, M. Heikkila and T. Repo, Catal. Commun., 2016,
74, 115–118.
121 M. Omri, G. Pourceau, M. Becuwe and A. Wadouachi, ACS
Sustainable Chem. Eng., 2016, 4, 2432–2438.
122 D. Rinsant, G. Chatel and F. Jerome, ChemCatChem, 2014,
6, 3355–3359.
123 X. S. Tan, W. P. Deng, M. Liu, Q. H. Zhang and Y. Wang,
Chem. Commun., 2009, 7179–7181.
124 K. M. Eblagon, M. F. R. Pereira and J. L. Figueiredo, Appl.
Catal., B, 2016, 184, 381–396.
125 O. Poole, K. Alharbi, D. Belic, E. F. Kozhevnikova and
I. V. Kozhevnikov, Appl. Catal., B, 2017, 202, 446–453.
126 J. Zhang, X. Liu, M. N. Hedhili, Y. Zhu and Y. Han,
ChemCatChem, 2011, 3, 1294–1298.
127 D. L. An, A. H. Ye, W. P. Deng, Q. H. Zhang and Y. Wang,
Chem. – Eur. J., 2012, 18, 2938–2947.
128 H. Sakurai, K. Koga and M. Kiuchi, Catal. Today, 2015, 251,
96–102.
129 P. N. Amaniampong, K. X. Li, X. L. Jia, B. Wang, A. Borgna
and Y. H. Yang, ChemCatChem, 2014, 6, 2105–2114.
130 P. N. Amaniampong, X. L. Jia, B. Wang, S. H. Mushrif,
A. Borgna and Y. H. Yang, Catal. Sci. Technol., 2015, 5,
2393–2405.
131 P. N. Amaniampong, A. Y. Booshehri, X. L. Jia, Y. Dai,
B. Wang, S. H. Mushrif, A. Borgna and Y. H. Yang, Appl.
Catal., A, 2015, 505, 16–27.
This journal is © The Royal Society of Chemistry 2018
View Article Online
Review Article
132 A. Onda, T. Ochi and K. Yanagisawa, Catal. Commun.,
2011, 12, 421–425.
133 K. Hasegawa, K. Shimidzu, S. Morimoto, Y. Hachino,
K. Hasegawa, Y. Shono, T. Horiuchi, K. Tabuse, Y. Masui,
T. Yamaguchi and Y. Fujita, Yakugaku Zasshi, 2008, 128,
135–140.
134 S. V. de Vyver and Y. Román-Leshkov, Catal. Sci. Technol.,
2013, 3, 1465–1479.
135 I. A. Colon, R. Fernandezgarcia, L. Amoros and H. Blay,
J. Am. Chem. Soc., 1949, 71, 4131–4133.
136 D. S. Bin, H. Wang, J. X. Li, H. Wang, Z. Yin, J. L. Kang,
B. Q. He and Z. H. Li, Electrochim. Acta, 2014, 130, 170–178.
137 M. Ibert, P. Fuertes, N. Merbouh, C. Feasson and
F. Marsais, Carbohydr. Res., 2011, 346, 512–518.
138 M. Ibert, P. Fuertes, N. Merbouh, C. Fiol-Petit, C. Feasson
and F. Marsais, Electrochim. Acta, 2010, 55, 3589–3594.
139 X. Jin, M. Zhao, J. Shen, W. J. Yan, L. M. He, P. S. Thapa,
S. Q. Ren, B. Subramaniam and R. V. Chaudhari, J. Catal.,
2015, 330, 323–329.
140 X. Jin, M. Zhao, M. Vora, J. Shen, C. Zeng, W. J. Yan,
P. S. Thapa, B. Subramaniam and R. V. Chaudhari, Ind.
Eng. Chem. Res., 2016, 55, 2932–2945.
141 I. Matzerath, W. Klaui, R. Klasen and H. Sahm, Inorg.
Chim. Acta, 1995, 237, 203–205.
142 V. J. Murphy, J. Shoemaker, G. Zhu, R. Archer, G. F. Salem
and E. L. Dias, US2011/0306790, 2011.
143 J. Boucher, C. Chirat and D. Lachenal, Cellul. Chem.
Technol., 2015, 49, 303–308.
144 J. M. H. Dirkn, H. S. van der Baan and J. M. A. J. J. van den
Broen, Carbohydr. Res., 1977, 59, 63–72.
145 M. Besson, G. Fleche, P. Fuertes, P. Gallezot and
F. Lahmer, Recl. Trav. Chim. Pays-Bas, 1996, 115, 217–221.
146 J. Lee, B. Saha and D. G. Vlachos, Green Chem., 2016, 18,
3815–3822.
147 E. Derrien, P. Marion, C. Pinel and M. Besson, Org. Process
Res. Dev., 2016, 20, 1265–1275.
148 P. Maki-Arvela, T. Salmi, B. Holmbom, S. Willfor and
D. Y. Murzin, Chem. Rev., 2011, 111, 5638–5666.
149 T. F. Wang, M. W. Nolte and B. H. Shanks, Green Chem.,
2014, 16, 548–572.
150 S. P. Teong, G. S. Yi and Y. G. Zhang, Green Chem., 2014,
16, 2015–2026.
151 H. Hirai, J. Macromol. Sci., Chem., 1984, 21, 1165–1179.
152 A. C. Braisted, J. D. Oslob, W. L. Delano, J. Hyde,
R. S. McDowell, N. Waal, C. Yu, M. R. Arkin and
B. C. Raimundo, J. Am. Chem. Soc., 2003, 125, 3714–3715.
153 T. Elhajj, A. Masroua, J. C. Martin and G. Descotes, Bull.
Soc. Chim. Fr., 1987, 855–860.
154 B. W. Lew, US Pat. 3326944, 1967.
155 Y. Y. Gorbanev, S. K. Klitgaard, J. M. Woodley, C. H.
Christensen and A. Riisager, ChemSusChem, 2009, 2,
672–675.
156 S. E. Davis, L. R. Houk, E. C. Tamargo, A. K. Datye and
R. J. Davis, Catal. Today, 2011, 160, 55–60.
157 Z. H. Zhang, B. Liu, K. L. Lv, J. Sun and K. J. Deng, Green
Chem., 2014, 16, 2762–2770.
Chem. Soc. Rev., 2018, 47, 1351--1390 | 1387

Review Article
158 M. Ventura, M. Aresta and A. Dibenedetto, ChemSusChem,
2016, 9, 1096–1100.
159 P. Vinke, D. de Wit, T. J. W. De Goede and H. Van Bekkum,
New developments in selective oxidation by heterogeneous
catalysis, Elsevier, New York, 1989.
160 A. Gandini and N. M. Belgacem, Polym. Int., 1998, 47,
267–276.
Published on 03 January 2018. Downloaded by National University of Kaohsiung on 22/02/2018 10:09:12.
161 M. Baumgarten and N. Tyutyulkov, Chem. – Eur. J., 1998, 4,
987–989.
162 F. W. Lichtenthaler and S. Mondel, Pure Appl. Chem., 1997,
69, 1853–1866.
163 L. Cottier, G. Descotes, E. Viollet, J. Lewkowski and
R. Skowronski, J. Heterocycl. Chem., 1995, 32, 927–930.
164 A. S. Amarasekata, D. Green and E. McMillan, Catal.
Commun., 2008, 9, 286–288.
165 W. Partenheimer and V. V. Grushin, Adv. Synth. Catal.,
2001, 343, 102–111.
166 J. P. Ma, Z. T. Du, J. Xu, Q. H. Chu and Y. Pang, Chem-
SusChem, 2011, 4, 51–54.
167 X. Q. Jia, J. P. Ma, M. Wang, Z. T. Du, F. Lu, F. Wang and
J. Xu, Appl. Catal., A, 2014, 482, 231–236.
168 X. L. Tong, Y. F. Sun, X. Q. Bai and Y. D. Li, RSC Adv., 2014,
4, 44307–44311.
169 M. O. Kornpanets, O. V. Kushch, Y. E. Litvinov, O. L. Pliekhov,
K. V. Novikova, A. O. Novokhatko, A. N. Shendrik, A. V.
Vasilyev and I. O. Opeida, Catal. Commun., 2014, 57, 60–63.
170 O. C. Navarro, A. C. Canos and S. I. Chornet, Top. Catal.,
2009, 52, 304–314.
171 X. X. Liu, J. F. Xiao, H. Ding, W. Z. Zhong, Q. Xu, S. P. Su
and D. L. Yin, Chem. Eng. J., 2016, 283, 1315–1321.
172 L. F. Liao, Y. Liu, Z. Y. Li, J. P. Zhuang, Y. B. Zhou and
S. Z. Chen, RSC Adv., 2016, 6, 94976–94988.
173 G. Durand, P. Faugeras, F. Laporte, C. Moreau, M. C. Neau,
G. Roux, D. Tichit and C. Toutremepuich, Agrichimie,
WO9617836, 1995.
174 R. Durand, P. Faugeras, F. Laporte, C. Moreau, M. C. Neau,
C. Doutremepuich, G. Roux and D. Tichit, EP0796254,
1997.
175 C. Moreau, R. Durand, C. Pourcheron and D. Tichit, Stud.
Surf. Sci. Catal., 1997, 108, 399–406.
176 I. Sadaba, Y. Y. Gorbanev, S. Kegnaes, S. S. R. Putluru, R. W.
Berg and A. Riisager, ChemCatChem, 2013, 5, 284–293.
177 W. Zhang, J. Y. Xie, W. Hou, Y. Q. Liu, Y. Zhou and J. Wang,
ACS Appl. Mater. Interfaces, 2016, 8, 23122–23132.
178 C. A. Antonyraj, B. Kim, Y. Kim, S. Shin, K. Y. Lee, I. Kim
and J. K. Cho, Catal. Commun., 2014, 57, 64–68.
179 J. F. Nie and H. C. Liu, Pure Appl. Chem., 2012, 84, 765–777.
180 Y. Y. Guo and J. Z. Chen, ChemPlusChem, 2015, 80,
1760–1768.
181 C. Carlini, P. Patrono, A. M. R. Galletti, G. Sbrana and
V. Zima, Appl. Catal., A, 2005, 289, 197–204.
182 F. L. Grasset, B. Katryniok, S. Paul, V. Nardello-Rataj,
M. Pera-Titus, J. M. Clacens, F. De Campo and F. Dumeignil,
RSC Adv., 2013, 3, 9942–9948.
183 A. Takagaki, M. Takahashi, S. Nishimura and K. Ebitani,
ACS Catal., 2011, 1, 1562–1565.
1388 | Chem. Soc. Rev., 2018, 47, 1351--1390
View Article Online
Chem Soc Rev
184 C. A. Antonyraj, J. Jeong, B. Kim, S. Shin, S. Kim, K. Y. Lee
and J. K. Cho, J. Ind. Eng. Chem., 2013, 19, 1056–1059.
185 J. F. Nie, J. H. Xie and H. C. Liu, J. Catal., 2013, 301, 83–91.
186 J. Artz, S. Mallmann and R. Palkovits, ChemSusChem, 2014,
8, 672–679.
187 J. Artz, S. Mallmann and R. Palkovits, ChemSusChem, 2015,
8, 3832–3838.
188 K. Ghosh, R. A. Molla, M. A. Iqubal, S. S. Islam and
S. M. Islam, Appl. Catal., A, 2016, 520, 44–52.
189 Y. Wang, B. Liu, K. Huang and Z. Zhang, Ind. Eng. Chem.
Res., 2014, 53, 1313–1319.
190 Z. Z. Yang, W. Qi, R. X. Su and Z. M. He, Energy Fuels, 2017,
31, 533–541.
191 J. Z. Chen, J. W. Zhong, Y. Y. Guo and L. M. Chen, RSC Adv.,
2015, 5, 5933–5940.
192 S. G. Wang, Z. H. Zhang, B. Liu and J. L. Li, Ind. Eng. Chem.
Res., 2014, 53, 5820–5827.
193 Z. Z. Yang, J. Deng, T. Pan, Q. X. Guo and Y. Fu, Green
Chem., 2012, 14, 2986–2989.
194 J. F. Nie and H. C. Liu, J. Catal., 2014, 316, 57–66.
195 G. D. Yadav and R. V. Sharma, Appl. Catal., B, 2014, 147,
293–301.
196 B. Liu, Z. H. Zhang, K. L. Lv, K. J. Deng and H. M. Duan,
Appl. Catal., A, 2014, 472, 64–71.
197 F. Neatu, N. Petrea, R. Petre, V. Somoghi, M. Florea and
V. I. Parvulescu, Catal. Today, 2016, 278, 66–73.
198 R. Q. Fang, R. Luque and Y. W. Li, Green Chem., 2016, 18,
3152–3157.
199 R. A. Sheldon, Catal. Today, 2015, 247, 4–13.
200 N. Mittal, G. M. Nisola, L. B. Malihan, J. G. Seo, S. P. Lee and
W. J. Chung, Korean J. Chem. Eng., 2014, 31, 1362–1367.
201 N. Mittal, G. M. Nisola, J. G. Seo, S. P. Lee and W. J. Chung,
J. Mol. Catal. A: Chem., 2015, 404, 106–114.
202 T. S. Hansen, I. Sadaba, E. J. Garcia-Suarez and A. Riisager,
Appl. Catal., A, 2013, 456, 44–50.
203 B. Karimi, H. M. Mirzaei and E. Farhangi, ChemCatChem,
2014, 6, 758–762.
204 G. Q. Lv, H. L. Wang, Y. X. Yang, T. S. Deng, C. M. Chen,
Y. L. Zhu and X. L. Hou, ACS Catal., 2015, 5, 5636–5646.
205 X. Wang, X. Li, L. Zhang, Y. Yoon, P. K. Weber, H. Wang,
J. Guo and H. Dai, Science, 2009, 324, 768–771.
206 C. Su and K. P. Lou, Acc. Chem. Res., 2013, 46, 2275–2285.
207 G. Q. Lv, H. L. Wang, Y. X. Yang, X. Li, T. S. Deng,
C. M. Chen, Y. L. Zhu and X. L. Hou, Catal. Sci. Technol.,
2016, 6, 2377–2386.
208 C. Liu, J. M. Carraher, J. L. Swedberg, C. R. Herndon,
C. N. Fleitman and J. P. Tessonnier, ACS Catal., 2014, 4,
4295–4298.
209 V. V. Grushin, N. Herron and G. A. Halliday, WO2003024947,
2003.
210 G. A. Halliday, R. J. Young and V. V. Grushin, Org. Lett.,
2003, 5, 2003–2005.
211 F. H. Xu and Z. H. Zhang, ChemCatChem, 2015, 7,
1470–1477.
212 R. L. Liu, J. Z. Chen, L. M. Chen, Y. Y. Guo and J. W. Zhong,
ChemCatChem, 2014, 6, 3174–3181.
This journal is © The Royal Society of Chemistry 2018

Chem Soc Rev
213 R. L. Liu, J. Z. Chen, L. M. Chen, Y. Y. Guo and J. W. Zhong,
ChemPlusChem, 2014, 79, 1448–1454.
214 Y. Liu, L. F. Zhu, J. Q. Tang, M. Y. Liu, R. Q. Cheng and
C. W. Hu, ChemSusChem, 2014, 7, 3541–3547.
215 N. Mittal, G. M. Nisola, L. B. Malihan, J. G. Seo, H. Kim,
S. P. Lee and W. J. Chung, RSC Adv., 2016, 6, 25678–25688.
216 S. Dabral, S. Nishimura and K. Ebitani, ChemSusChem,
Published on 03 January 2018. Downloaded by National University of Kaohsiung on 22/02/2018 10:09:12.
2014, 7, 260–267.
217 X. Xiang, L. He, Y. Yang, B. Guo, D. Tong and C. Hu, Catal.
Lett., 2011, 141, 735–741.
218 S. Q. Zhang, W. F. Li, X. H. Zeng, Y. Sun and L. Lin,
BioResources, 2014, 9, 4568–4580.
219 Z. H. Zhang, Z. L. Yuan, D. G. Tang, Y. S. Ren, K. L. Lv and
B. Liu, ChemSusChem, 2014, 7, 3496–3504.
220 G. Q. Lv, H. L. Wang, Y. X. Yang, T. S. Deng, C. M. Chen,
Y. L. Zhu and X. L. Hou, Green Chem., 2016, 18, 2302–2307.
221 Q. Girka, B. Estrine, N. Hoffmann, J. Le Bras, S. Marinkovic
and J. Muzart, React. Chem. Eng., 2016, 1, 176–182.
222 P. V. Rathod, S. D. Nale and V. H. Jadhav, ACS Sustainable
Chem. Eng., 2017, 5, 701–707.
223 J. J. Bozell and G. R. Petersen, Green Chem., 2010, 12,
539–554.
224 S. Rajendran, R. Raghunathan, I. Hevus, R. Krishnan,
A. Ugrinov, M. P. Sibi, D. C. Webster and J. Sivaguru,
Angew. Chem., Int. Ed., 2015, 54, 1159–1163.
225 J. Deng, X. Q. Liu, C. Li, Y. H. Jiang and J. Zhu, RSC Adv.,
2015, 5, 15930–15939.
226 https://www.avantium.com/press-releases/avantium-
named-2015-global-cleantech-100/.
227 N. Jacquel, R. Saint-Loup, J. P. Pascault, A. Rousseau and
F. Fenouillot, Polymer, 2015, 59, 234–242.
228 T. Elhajj, A. Masroua, J. C. Martin and G. Descotes, Bull.
Soc. Chim. Fr., 1987, 855–860.
229 M. Toshinari, K. Hirokazu, K. Takenobu and M. Hirohide,
US232815, 2007.
230 Y. W. Cheng, X. Li, L. J. Wang and Q. B. Wang, Ind. Eng.
Chem. Res., 2006, 45, 4156–4162.
231 X. B. Zuo, P. Venkitasubramanian, D. H. Busch and
B. Subramaniam, ACS Sustainable Chem. Eng., 2016, 4,
3659–3668.
232 B. Saha, S. Dutta and M. M. Abu-Omar, Catal. Sci. Technol.,
2012, 2, 79–81.
233 P. Verdeguer, N. Merat and A. Gaset, J. Mol. Catal., 1993,
85, 327–344.
234 H. A. Rass, N. Essayem and M. Besson, Green Chem., 2013,
15, 2240–2251.
235 K. R. Vuyyuru and P. Strasser, Catal. Today, 2012, 195, 144–154.
236 W. Q. Niu, D. Wang, G. H. Yang, J. Sun, M. B. Wu,
Y. Yoneyama and N. Tsubaki, Bull. Chem. Soc. Jpn., 2014,
87, 1124–1129.
237 Y. W. Zhang, Z. M. Xue, J. F. Wang, X. H. Zhao, Y. H. Deng,
W. C. Zhao and T. C. Mu, RSC Adv., 2016, 6, 51229–51237.
238 X. W. Han, C. Q. Li, Y. Guo, X. H. Liu, Y. G. Zhang and
Y. Q. Wang, Appl. Catal., A, 2016, 526, 1–8.
239 M. A. Lilga, R. T. Hallen, J. Hu, J. F. White and M. J. Gray,
US2008103318-A1, 2007.
This journal is © The Royal Society of Chemistry 2018
View Article Online
Review Article
240 H. A. Rass, N. Essayem and M. Besson, ChemSusChem,
2015, 8, 1206–1217.
241 P. Vinke, H. H. van Dam and H. van Bekkum, Stud. Surf.
Sci. Catal., 1990, 55, 147–157.
242 P. Vinke, W. van der Poel and H. van Bekkum, Stud. Surf.
Sci. Catal., 1991, 59, 385–394.
243 R. Sahu and P. L. Dhepe, React. Kinet., Mech. Catal., 2014,
112, 173–187.
244 S. Siankevich, G. Savoglidis, Z. F. Fei, G. Laurenczy, D. T. L.
Alexander, N. Yan and P. J. Dyson, J. Catal., 2014, 315, 67–74.
245 X. W. Han, L. Geng, Y. Guo, R. Jia, X. H. Liu, Y. G. Zhang
and Y. Q. Wang, Green Chem., 2016, 18, 1597–1604.
246 B. Siyo, M. Schneider, M. M. Pohl, P. Langer and
N. Steinfeldt, Catal. Lett., 2014, 144, 498–506.
247 B. Siyo, M. Schneider, J. Radnik, M. M. Pohl, P. Langer and
N. Steinfeldt, Appl. Catal., A, 2014, 478, 107–116.
248 Y. B. Wang, K. Yu, D. Lei, W. Si, Y. J. Feng, L. L. Lou and
S. X. Liu, ACS Sustainable Chem. Eng., 2016, 4, 4752–4761.
249 Z. H. Zhang, J. D. Zhen, B. Liu, K. L. Lv and K. J. Deng,
Green Chem., 2015, 17, 1308–1317.
250 N. Mei, B. Liu and Z. H. Zhang, Catal. Sci. Technol., 2015, 5,
3194–3202.
251 B. Liu, Y. S. Ren and Z. H. Zhang, Green Chem., 2015, 17,
1610–1617.
252 I. Lee, J. B. Joo and M. Shokouhimehr, Chin. J. Catal., 2015,
36, 1799–1810.
253 W. J. Wang, Y. C. Li, Z. W. Kang, F. Wang and J. C. Yu,
Appl. Catal., B, 2016, 182, 184–192.
254 B. N. Zope, S. E. Davis and R. J. Davis, Top. Catal., 2012, 55,
24–32.
255 O. Casanova, S. Iborra and A. Corma, ChemSusChem, 2009,
2, 1138–1144.
256 S. Albonetti, A. Lolli, V. Morandi, A. Migliori, C. Lucarelli
and F. Cavani, Appl. Catal., B, 2015, 163, 520–530.
257 A. Lolli, R. Amadori, C. Lucarelli, M. G. Cutrufello, E. Rombi,
F. Cavani and S. Albonetti, Microporous Mesoporous Mater.,
2016, 226, 466–475.
258 Z. Z. Miao, Y. B. Zhang, X. Q. Pan, T. X. Wu, B. Zhang,
J. W. Li, T. Yi, Z. D. Zhang and X. G. Yang, Catal. Sci.
Technol., 2015, 5, 1314–1322.
259 N. K. Gupta, S. Nishimura, A. Takagaki and K. Ebitani,
Green Chem., 2011, 13, 824–827.
260 L. Ardemani, G. Cibin, A. J. Dent, M. A. Isaacs, G. Kyriakou,
A. F. Lee, C. M. A. Parlett, S. A. Parry and K. Wilson, Chem.
Sci., 2015, 6, 4940–4945.
261 J. Y. Cai, H. Ma, J. J. Zhang, Q. Song, Z. T. Du, Y. Z. Huang
and J. Xu, Chem. – Eur. J., 2013, 19, 14215–14223.
262 T. Pasini, M. Piccinini, M. Blosi, R. Bonelli, S. Albonetti,
N. Dimitratos, J. A. Lopez-Sanchez, M. Sankar, Q. He,
C. J. Kiely, G. J. Hutchings and F. Cavani, Green Chem.,
2011, 13, 2091–2099.
263 A. Villa, M. Schiavoni, S. Campisi, G. M. Veith and L. Prati,
ChemSusChem, 2013, 6, 609–612.
264 A. Lolli, S. Albonetti, L. Utili, R. Amadori, F. Ospitali,
C. Lucarelli and F. Cavani, Appl. Catal., A, 2015, 504,
408–419.
Chem. Soc. Rev., 2018, 47, 1351--1390 | 1389

Review Article
265 X. Y. Wan, C. M. Zhou, J. S. Chen, W. P. Deng, Q. H. Zhang,
Y. H. Yang and Y. Wang, ACS Catal., 2014, 4, 2175–2185.
266 Z. Y. Gui, W. R. Cao, S. Saravanamurugan, A. Riisager,
L. F. Chen and Z. W. Qi, ChemCatChem, 2016, 8, 3636–3643.
267 C. M. Zhou, W. P. Deng, X. Y. Wan, Q. H. Zhang, Y. H. Yang
and Y. Wang, ChemCatChem, 2015, 18, 2853–2863.
268 F. Kerdi, H. A. Rass, C. Pinel, M. Besson, G. Peru, B. Leger,
Published on 03 January 2018. Downloaded by National University of Kaohsiung on 22/02/2018 10:09:12.
S. Rio, E. Monflier and A. Ponchel, Appl. Catal., A, 2015,
506, 206–219.
269 D. K. Mishra, H. J. Lee, J. Kim, H. S. Lee, J. K. Cho, Y. W. Suh,
Y. Yi and Y. J. Kim, Green Chem., 2017, 19, 1619–1623.
270 A. Jain, S. C. Jonnalagadda, K. V. Ramanujachary and
A. Mugweru, Catal. Commun., 2015, 58, 179–182.
271 F. Neatu, R. S. Marin, M. Florea, N. Petrea, O. D. Pavel and
V. I. Parvulescu, Appl. Catal., B, 2016, 180, 751–757.
272 E. Hayashi, T. Komanoya, K. Kamata and M. Hara, Chem-
SusChem, 2017, 10, 654–658.
273 X. W. Han, C. Q. Li, X. H. Liu, Q. N. Xia and Y. Q. Wang,
Green Chem., 2017, 19, 996–1004.
274 C. V. Nguyen, Y. T. Liao, T. C. Kang, J. E. Chen,
T. Yoshikawa, Y. Nakasaka, T. Masuda and K. C. W. Wu,
Green Chem., 2016, 18, 5957–5961.
275 K. S. Lakhi, D. H. Park, K. Al-Bahily, W. Cha,
B. Viswanathan, J. H. Choy and A. Vinu, Chem. Soc. Rev.,
2017, 46, 72–101.
276 S. E. Davis, B. N. Zope and R. J. Davis, Green Chem., 2012,
14, 143–147.
277 S. E. Davis, A. D. Benavidez, R. W. Gosselink, J. H. Bitter,
K. P. de Jong, A. K. Datye and R. J. Davis, J. Mol. Catal. A:
Chem., 2014, 388, 123–132.
278 L. C. Gao, K. J. Deng, J. D. Zheng, B. Liu and Z. H. Zhang,
Chem. Eng. J., 2015, 270, 444–449.
1390 | Chem. Soc. Rev., 2018, 47, 1351--1390
View Article Online
Chem Soc Rev
279 S. Li, K. M. Su, Z. H. Li and B. W. Cheng, Green Chem.,
2016, 18, 2122–2128.
280 B. B. Sarma, I. Efremenko and R. Neumann, J. Am. Chem.
Soc., 2015, 137, 5916–5922.
281 B. Karimi, M. Rafiee, S. Alizadeh and H. Vali, Green Chem.,
2015, 17, 991–1000.
282 G. Grabowski, J. Lewkowski and R. Skowroński, Electro-
chim. Acta, 1991, 36, 1995.
283 D. J. Chadderdon, L. Xin, J. Qi, Y. Qiu, P. Krishna,
K. L. More and W. Z. Li, Green Chem., 2014, 16, 3778–3786.
284 H. G. Cha and K. S. Choi, Nat. Chem., 2015, 7, 328–333.
285 V. P. Kashparova, V. A. Klushin, D. V. Leontyeva,
N. V. Smirnova, V. M. Chernyshev and V. P. Ananikov,
Chem. – Asian J., 2016, 11, 2578–2585.
286 B. You, N. Jiang, X. Liu and Y. J. Sun, Angew. Chem., Int. Ed.,
2016, 55, 9913–9917.
287 B. You, X. Liu, N. Jiang and Y. J. Sun, J. Am. Chem. Soc.,
2016, 138, 13639–13646.
288 N. Jiang, B. You, R. Boonstra, I. M. T. Rodriguez and
Y. J. Sun, ACS Energy Lett., 2016, 1, 386–390.
289 M. Kroger, U. Prusse and K. D. Vorlop, Top. Catal., 2000,
13, 237–242.
290 M. L. Ribeiro and U. Schuchardt, Catal. Commun., 2003, 4,
83–86.
291 G. S. Yi, S. P. Teong, X. K. Li and Y. G. Zhang, ChemSusChem,
2014, 7, 2131–2137.
292 G. S. Yi, S. P. Teong and Y. G. Zhang, ChemSusChem, 2015,
8, 1151–1155.
293 G. S. Yi, S. P. Teong and Y. G. Zhang, Green Chem., 2016,
18, 979–983.
294 S. G. Wang, Z. H. Zhang and B. Liu, ACS Sustainable Chem.
Eng., 2015, 3, 406–412.
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