RSC - Li/greenchem: As Featured in

A critical review article presented by Mr Muhammad Sajid, As featured in:
Dr. Xuebing Zhao and Prof. Dr Dehua Liu of Department of

Chemical Engineering, Tsinghua University, China. Volume 20 Number 24 21 December 2018 Pages 5407–5552
Production of 2,5-furandicarboxylic acid (FDCA) from

Green
5-hydroxymethylfurfural (HMF): recent progress focusing on the
Chemistry
Cutting-edge research for a greener sustainable future
rsc.li/greenchem
chemical-catalytic routes
The research progress on the production of 2,5-furandicarboxylic

acid (FDCA) from bio-based platform chemical
5-hydroxymethylfurfural (HMF) has been comprehensively
reviewed. Various oxidation routes and corresponding chemical
mechanisms have been discussed in depth, focusing on the
catalytic oxidation of HMF to FDCA under the catalysis of
ISSN 1463-9262
COMMUNICATION
Baochun Guo, Liqun Zhang et al.
metal-based catalysts. However, although FDCA is an attractive A real recycling loop of sulfur-cured rubber through transalkylation
exchange of C–S bonds
chemical for bio-based polymer production, efforts have to be

made with regards to the reaction kinetics and mechanisms as See Xuebing Zhao, Dehua Liu et al.,
Green Chem., 2018, 20, 5427.
well as development of industrially-feasible processes.
rsc.li/greenchem
Registered charity number: 207890
Green Chemistry
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CRITICAL REVIEW View Journal | View Issue
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Production of 2,5-furandicarboxylic acid (FDCA)

Cite this: Green Chem., 2018, 20,
from 5-hydroxymethylfurfural (HMF): recent
5427 progress focusing on the chemical-catalytic routes
a,b
Muhammad Sajid, Xuebing Zhao *a and Dehua Liu*a
Furandicarboxylic acid (FDCA) has been considered as a good precursor, instead of petroleum-derived tere-
phthalate acid (TPA), for producing green polymers such as polyethylene 2,5-furandicarboxylate (PEF). The
production of FDCA from biomass or its derived sugars or platform chemicals generally involves chemical,
biological and electrochemical methods, while the chemical-catalytic way seems to be the most promising
in terms of the yield, reaction rate and product purity. The oxidative production of FDCA from bio-based
5-hydroxymethylfurfural (HMF) has attracted the most attention; it can be carried out by electrochemical,
catalytic and non-catalytic processes. In the present work, we have comprehensively reviewed the current
progress on the production of FDCA from HMF, primarily focusing on the chemical-catalytic approaches.
The most frequently used catalysts for the chemical-catalytic methods are oxides of noble metals but their
high cost, poor availability and recycling are the major hindrances to their commercial acceptance. Transition
metal oxides are good alternatives but they suffer from relatively low FDCA yield. Electrochemical oxidation
of HMF can be a good alternative route for FDCA production with simultaneous H2 production but the yield
and product recovery have to be further improved. Biocatalytic processes can produce FDCA with compara-
tive yields under mild conditions but they can only be operated at low concentrations of HMF with much
Received 23rd August 2018, lower productivity. It is recommended that future works should be focused on, but not limited to, the com-
Accepted 23rd October 2018
prehensive evaluation of different routes in terms of catalyst development and characterizations, process
DOI: 10.1039/c8gc02680g parameters, product yield and purity, as well as economic feasibility. The kinetics and reaction mechanisms
rsc.li/greenchem of the process also need to be more deeply investigated to guide further process intensification.
Introduction produce green bio-based chemicals.9,10 The U.S. Department

of Energy in collaboration with the U.S. Department of
The scale of the global economy has expanded many-fold to Agriculture have indicated that there will be an increase in the
meet the continuously growing demands of energy, chemicals commodities of biochemicals and bio-materials to 25% in
and materials. The chemical industry has also seen tremen- 2030.11 This goal has settled on the use of LCB as a renewable
dous growth in the use of chemical intermediates, polymeric (in term of CO2 balance) and sustainable resource of pet-
materials and integrated derivatives.1,2 Conventionally, chemi- roleum carbon for the production of commodity chemi-
cal industries rely heavily on fossil fuel-derived petrochem- cals.12,13 This vision will shift the entire scope of the chemical
icals.3,4 However, these petrochemicals are non-sustainable in industry from the prevailing petroleum refinery to LCB biore-
terms of their supply, price and they cause global warming finery.14,15 LCB is usually available in the forms of crop resi-
and environmental pollution.5,6 These features of fossil fuel- dues, forest leftovers, waste paper etc.16 The use of LCB as a
derived chemicals have forced humans to search for more feedstock for the biorefinery will reorient the global chemical
renewable and sustainable feedstocks.7,8 Lignocellulosic industry and boost rural economy.17,18
biomass (LCB) is quite abundant in the natural world with a LCB is primarily composed of cellulose (40–50%), hemicel-
wide geographical distribution and can thus be explored to luloses (20–40%), lignin (20–30%) and other trivial constitu-
ents such as protein, silica, and waxes.19,20 Cellulose is a
water-insoluble biopolymer derived from β-1,4 glycosidic
a
Key Laboratory for Industrial Biocatalysis, Ministry of Education of China, Institute bonds of anhydrous glucose units.21,22 Irrespective of its
of Applied Chemistry, Department of Chemical Engineering, Tsinghua University,
robust structure, cellulose preferably needs to be depolymer-
Beijing 100084, China. E-mail: [email protected],
[email protected] ized to glucose, which is in turn converted to platform bio-
b
Department of Chemical Engineering, University of Gujrat, Gujrat 50700, Pakistan chemicals such as 5-hydroxymethylfurfural (HMF),23,24 levuli-
This journal is © The Royal Society of Chemistry 2018 Green Chem., 2018, 20, 5427–5453 | 5427
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Critical Review Green Chemistry
nic acid,25,26 lactic acid,27 formic acid,2 sorbitol,28 bio-alco- Polymeric materials such as polyethylene terephthalate,
hols,29 and biofuels.30,31 Hemicelluloses are polysaccharides polyamides, and polyurethanes have played vital roles in the
that are composed of various C5 and C6 monosaccharide units modern economy.36,37 Several industries have started consider-
such as xylose, arabinose, mannose, glucose, etc.32,33 Lignin is ing using bio-based chemicals to produce bioplastics.13,38
a conjugate complex polymer consisting of basic phenylpro- Technically, bioplastics can be produced by different routes
pane units including guaiacylpropane (G), syringylpropane (S), starting from LCB as described in Fig. 1. Of these routes, the
and 4-hydroxyphenylpropane (H).34,35 chemical or biological conversion of LCB into monomers, fol-
Fig. 1 Typical production routes of bio-based polymers from lignocellulosic biomass.
Mr. Muhammad Sajid is a Dr. Xuebing Zhao is an Associate

Lecturer of Department of Professor in Department of
Chemical Engineering at Chemical Engineering, Tsinghua
University of Gujrat, Pakistan. University, China. He received
He received his Bachelor degree his PhD degree in Department
and Master degree in Chemical of Chemical Engineering at
Engineering at University of Tsinghua University in 2009,
Punjab, Lahore, Pakistan in and performed his post-doctoral
2008 and 2012 respectively. He research work at Tsinghua
is now a PhD scholar at University (2009–2011) and
Institute of Applied Chemistry, University of Wisconsin-Madison
Department of Chemical (2014–2015), respectively. His
Muhammad Sajid Engineering, Tsinghua University, Xuebing Zhao current research field include the
China. His research interests biorefining of lignocellulosic
include advanced catalytic process for the production of platform biomass to produce biofuels and chemicals via chemical and bio-
biochemicals from biomass-derived sugars. logical approaches. He has published about 100 academic papers
and book chapters. He was awarded Hou De-Bang Chemical
Engineering Science and Technology Youth Award by the Chemical
Industry and Engineering Society of China (CIESC) in the year of
2017.
5428 | Green Chem., 2018, 20, 5427–5453 This journal is © The Royal Society of Chemistry 2018
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Green Chemistry Critical Review
lowed by polymerization, is the most important way to produce furan-2,5-dicarboxylate,58 isononyl furan-2,5-dicarboxylate,59
bio-based polymers.39,40 In a recent attempt, bioplastics have dipentyl furan-2,5-dicarboxylate,60 diheptyl furan-2,5-dicarboxy-
been successfully produced from bio-based ethylene glycol late,61 thiolene films,62 poly(ethylene dodecanedioate-2,5-fur-
(EG) and furandicarboxylic acid (FDCA).41,42 FDCA synthesis is andicarboxylate) (PEDF),15 2-(1-oxopropoxy) and hexanedioic
considered as a precursor for the production of these green acid (PEA).63 It is also applied as a corrosion inhibitor,
polymers, especially polyethylene 2,5-furandicarboxylate pharmaceutical intermediate and crosslinking agent for polyvi-
(PEF).43,44 FDCA derived PEF is a real alternative to the fossil- nyl alcohols.64 The selective reduction of FDCA produces par-
based terephthalic acid (TPA) derived polyethylene tere- tially hydrogenated (2,5-dihydroxymethylfuran etc.), and fully
phthalate (PET).45,46 PEF will not only serve as a novel replace- hydrogenated (2,5-bis(hydroxymethyl) tetrahydrofuran) pro-
ment but will also improve salient features like excellent gas ducts that can be used as alcohol components in the pro-
barrier performance, recyclability and extended mechanical duction of new polyesters. A combination of these alcoholic
properties.47 Despite all the efforts and scientific research, the components with FDCA would lead to a new family of comple-
worldwide production of bioplastics is only a fraction of the tely biomass-derived products. The extension of these concepts
total market supply.48,49 Varieties of processes have been devel- to the production of new nylons, either through reactions of
oped for the production of FDCA from biomass or biomass- FDCA with diamines or through the conversion of FDCA to 2,5-
derived sugars. There are generally four methods to produce bis(aminomethyl)tetrahydrofuran, could lead to future market
FDCA:50,51 (1) biological and chemical conversion of HMF; (2) bio-derivatives with multiple applications.65 Hence, in view of
catalytic transformation of numerous furan derivatives; (3) oxi- the polymer process industry, FDCA is a highly demanding
dation of 2,5 di-substituted furans; (4) dehydration of hexose monomer because of its tremendous utilization in the pro-
derivatives. The objective of this work is to comprehensively duction of different monomers like dichloride- (FDCDCl),
review and discuss the catalytic conversion of HMF to produce dimethyl- (DMFDC), diethyl-, or bis(hydroxyethyl)- (BHEFDC)
FDCA, particularly focusing on the chemical-catalytic routes in derivatives (Scheme 1),65 for the production of polyesters, poly-
terms of the process, kinetics and reaction mechanisms. amides, and plasticizers. The carboxyl groups attached at the
para positions of the furan rings are analogous to fossil-
derived TPA,66 and thus FDCA is an eco-friendly alternative for
FDCA as a chemical building block producing bioplastics.67 Additionally, FDCA is also used for
polyesters like polybutylene terephthalate (PBT) and polyethyl-
FDCA is one of the most important and promising candidates ene terephthalate (PET, Scheme 2),68 which in turn are utilized
of the furan family due to its multi-functionality based on the in film and fiber production, packing materials and soft drink
cyclic structure and di-acidic side chains.52,53 FDCA is found bottles.69,70 Polyesters from FDCA are so appealing that just
naturally in human urine54 and blood plasma,55 and has been five years after the 1st FDCA patent, the Celanese Corporation
utilized for the production of a variety of biochemicals such as of America (1946) filed a patent application for FDCA-derived
succinic acid,16 macrocyclic ligands,56 fungicides,57 isodecyl PEF41 followed by a patent by Mitsubishi for PEF and PBF syn-
thesis.71 PEF has excellent thermochemical properties with
biodegradability that makes it a better choice in comparison
to PET.46,72 The synthesis of PEF has actually been investigated
Dr. Dehua Liu is a Professor and for more than 70 years73 but its production has failed to
Director of Institute of Applied conquer commercialization due to the relatively poor purity,
Chemistry, Department of process difficulties and sustainable availability of FDCA. The
Chemical Engineering, Tsinghua inclusion of FDCA in 12 platform biochemicals highlighted
University, China. He received the extensive research for the sustainable commercial pro-
his PhD degree in Department of duction of FDCA.11 In 2011, Avantium revolutionized FDCA
Chemical Engineering, Tsinghua
University in 1991. His research
field of interest includes pro-
duction of biofuels and bio-
chemicals from natural renew-
able biomass, especially focusing
Dehua Liu on biodiesel production from oil
feedstock and microbial pro-
duction of 1,3-propanediol from biodiesel by-product glycerol. He
has published more than 250 academic papers. He has been
awarded the First Award of the S&T Progress of China Petroleum
and Chemical Industry Federation (CPCIF)(2006), “BlueSky
Awards” for World’s Leading Technology of Renewable Energy
with Best Value of Investment (2016, 2018) and so on. Scheme 1 FDCA derived monomers.65
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Scheme 3 Reaction pathway of HMF oxidation to produce FDCA.
derived intermediates. The chemical conversion requires high

reaction conditions (temperature and pressure) and addi-
tives,77 while bioconversion proceeds via a mild process
environment using biological catalysts.78 The stepwise pro-
Scheme 2 Comparison of the PEF and PET production processes. A: duction of FDCA from biomass typically includes the following
Production of PET from TPA; (B) production of PEF from FDCA. steps: (1) hydrolysis of lignocellulosic cellulose to glucose; (2)
chemical and thermochemical conversion of glucose to plat-
form biochemicals, i.e. dehydration of glucose to HMF; (3)
production through the successful operation of its first pilot catalytic-oxidation of HMF to FDCA. In this process, cellulose
plant with production capacity of 40 tons per year;74 this is usually firstly separated from hemicellulose and lignin by
project unwrapped the industrialization of FDCA. pretreatment, then converted to glucose by chemical or bio-
FDCA also has potential applications in medicine. The logical approaches, followed by isomerization of the obtained
diethyl ester of FDCA has anesthetic properties similar to glucose to form fructose.79 Direct utilization of glucose as feed-
cocaine. Dicalcium 2,5-furandicarboxylate inhibits the growth stock proceeds via the in situ isomerization of glucose to fruc-
of Bacillus megatorium.75 FDCA-derived anilides demonstrate tose followed by dehydration to produce HMF, and oxidation
anti-bacterial actions and FDCA itself is a strong complexing of HMF further yields FDCA.
agent; chelating with ions (Ca2+, Cu2+ and Pb2+) has increased Depending on the system applied, the conversion of HMF to
its utilization in medicine for the removal of kidney stones.75 FDCA can proceed through the preferred aldehyde group oxi-
Interestingly, HMF is metabolized via FDCA in mammals dation to 5-hydroxymethyl-2-furan carboxylic acid (Scheme 3,
including humans. Manufacturing artificial veins for trans- route A), or the alcoholic group oxidation to 2,5-furan dicar-
plantation, via a dilute solution of FDCA in tetrahydrofuran, boxaldehyde (Scheme 3, route B). These process intermediates
and many other medical utilizations are under investigation. are then oxidized to FFCA, which is in turn transformed into
FDCA as the final product.80
Chemical oxidative production of 2,5- Historical methods
FDCA from HMF The production of FDCA was conducted as early as 1876 when
Fittig et al. catalytically produced FDCA from mucic acid in
HMF came out as a promising feedstock for the production of 48% aqueous solution of hydrogen bromide (HBr) as indicated
FDCA in the 19th century. Different reaction systems have been in Scheme 4.81
used for the oxidation of HMF with air, oxygen or other oxidiz- Mucic acid dehydration proceeds with different dehydrating
ing agents (H2O2, KMnO4 etc.).76 Fig. 2 illustrates the diverse agents for the efficient formation of FDCA. However, the
FDCA production processes from biomass and biomass- mucic acid process failed to achieve scientific progress due to
Fig. 2 Schematic generalization of FDCA production processes from cellulose.
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applied as oxidants. t-BuOOH with only CuCl2 resulted in an

FDCA yield of 45% and the addition of LiBr to this system
reduced the yield to 43%.91
The practical utilization of homogeneous catalysts in the
oxidative production of FDCA from HMF mainly suffers from
FDCA production through the dehydration of mucic acid.81
Scheme 4 two discrete drawbacks, i.e. lower FDCA yield and the for-
mation of byproducts.88 The separation of the catalysts and
purification of the product are also major hurdles along with
recycling deficiencies. In contrast, heterogeneous catalysis
demonstrates several merits, with the facile separation and re-
cycling due to the heterogeneous nature.92 Therefore, hetero-
geneous catalysis has attracted more interest for practical
application and potential commercialization as compared to
homogeneous catalysis.
Heterogeneous catalytic methods

The oxidative production of FDCA from HMF over different
heterogeneous catalysts has been studied extensively in
various process environments. Mostly, the oxidation proceeds
with either pure oxygen or air as an oxidizing agent; hydrogen
peroxide (H2O2) and potassium permanganate (KMnO4) have
Scheme 5 FDCA synthesis from furfural.83 also been used but researchers mostly prefer molecular oxygen
considering its higher oxidation potential, eco-friendly impact
and low cost. Different metal supported heterogeneous cata-
its high cost, long reaction time (>20 hours) and relatively high lysts, such as platinum (Pt), gold (Au), ruthenium (Ru) and pal-
reaction temperature (120 °C).82 Following this, FDCA syn- ladium (Pd), with good catalytic activity, recyclability and stabi-
thesis utilizing different starting materials in different lity, have also been developed and successfully applied in HMF
mediums has been investigated.83 Xylose-derived furfural oxidation to FDCA.88 Noble metal oxides occupy the major
could be an alternative raw material for FDCA production. In portion of the heterogeneous catalysis scheme in the current
this process, inorganic oxidants (e.g. HNO3) can be initially FDCA research regime.
used for furfural oxidation, followed by esterification of the HMF oxidation to FDCA over Pt supported catalysts.
formed 2-furoic acid with methanol to form an intermediate, Supported platinum (Pt) catalysts are dynamic for the aerobic
which is finally converted to FDCA by several subsequent steps oxidation of HMF as compared to other noble metal cata-
(Scheme 5).82,83 As indicated by Scheme 5, the production of lysts.88 When applied to HMF oxidation, carbon supported Pt
FDCA from furfural is complex with many intermediates, thus catalysts (Pt/C and Pt–Pb/C) can give 81% yield of FDCA with
reducing the overall yield and selectivity, which has compelled lead (Pb)–free Pt/C and 99% with Pt–Pb/C catalyst under 1 bar
researchers to search for alternative technologies for the O2 pressure (Table 1).93 The detection of HFCA as an inter-
efficient and economical production of FDCA. HMF oxidation mediate proves the preferred oxidation of the formyl group
to FDCA is advantageous because the oxidation process can be over the hydroxymethyl group with the lead-doped Pt catalyst
conducted with homogeneous catalysts,84 heterogeneous cata- (Scheme 3, route A). Yield increment with Pb-doping stimu-
lysts,85 biocatalysts,86 or by electrochemical oxidation,87 as well lated the development of bimetallic catalysts for HMF oxi-
as without any catalyst,88 or in an aqueous–organic biphasic dation. Following this, the bismuth (Bi)-incorporated Pt cata-
system89 that can facilitate the efficient separation of the lyst (Pt–Bi/C) having a Pt–Bi molar ratio of 0.2 was developed
product from the solution mixture.90 and applied in FDCA synthesis.94 A 29% increase in FDCA
yield by Bi addition proved the improvement in the activity of
Homogenous catalytic methods the bimetallic catalyst with identical parameters.95 Pressure
Catalytic oxidation of HMF, either by a homogeneous or reduction negatively affected the yield and an increase in
heterogeneous catalyst, is still the most promising and exten- pressure did not exhibit appreciable effects (Table 1).96 As
sively researched FDCA production pathway. However, the util- such, 1 bar oxygen pressure is the optimum pressure for the
ization of homogeneous catalysts is less attractive as compared Pt/C catalyst that is easy to maintain without any potential
to heterogeneous catalysts, due to the separation and recycling hazard. The rapid oxidation of process intermediates, HFCA
problems.88 High-pressure air oxidation of HMF with Co and DFF, produces FFCA. FFCA oxidation to FDCA is the rate-
(OAc)2, Mn(OAc)2, and HBr could produce FDCA with a yield of controlling step. Bi incorporation to produce Pt–Bi/C catalyst
60.9%. Using Co(OAc)2/Zn(OAc)2/NaBr can only produce DFF can exceptionally stabilize the catalyst by eliminating the
and the addition of trifluoroacetic acid can promote the FDCA oxygen poisoning and Pt leaching tendency, resulting in
production (60% yield).91 Pure oxygen and t-BuOOH have been increased catalyst life and stability.
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Table 1 Some recently reported works on the oxidation of HMF for the production of FDCA over Pt supported catalysts
Catalyst Base Oxidant Time (h) T (°C) FDCA yield (%) HMF con. (%) Ref.
Pt–Pb/C 1.25 M NaOH 1 Bar O2 2 25 99 100 93

Pt/C 1.25 M NaOH 1 Bar O2 2 25 81 100 93
Pt–Bi/C 2 equiv. Na2CO3 40 Bar air 6 100 >99 100 94
Pt/C 2 equiv. Na2CO3 40 Bar air 6 100 69 99 94

Pt–Bi/TiO2 2 equiv. Na2CO3 40 Bar air 6 100 99 >99 97
Pt/TiO2 2 equiv. Na2CO3 40 Bar air 6 100 84 90 97
Pt/RGO 5 equiv. NaOH 1.01325 Bar O2 24 25 84 100 98
Pt/C 2 equiv. NaOH 6.90 Bar O2 6 22 79 100 95
Pt/C pH = 13 10 Bar O2 4 50 80 100 96
Pt/Al2O3 pH = 9 0.2 Bar O2 6 60 99 100 99
Pt/Al2O3 1 equiv. Na2CO3 1 Bar O2 12 75 96 96 100
Pt/ZrO2 1 equiv. Na2CO3 1 Bar O2 12 75 94 100 100
Pt/ZrO2 Base free 4 Bar O2 12 100 97.3 100 101
Pt/C 1 equiv. Na2CO3 1 Bar O2 12 75 89 100 100
Pt/TiO2 1 equiv. Na2CO3 1 Bar O2 12 75 2 96 100
Pt/CeO2 1 equiv. Na2CO3 1 Bar O2 12 75 8 100 100
Pt/Ce0.8Bi0.2O2−δ 4 equiv. NaOH 10 Bar O2 0.5 23 98 100 102
Pt/CeO2 4 equiv. NaOH 10 Bar O2 0.5 23 20 100 102
Pt/PVP Base free 1 Bar O2 24 80 94 100 103
Pt/IP Base free 1 Bar O2 24 80 99 100 103
Fe3O4@C/Pt 1.67 equiv. Na2CO3 1 Bar O2 4 90 84 100 104
Pt-NP5 Base free 1 Bar O2 6 80 60 100 105
Pt-NP-Cl Base free 1 Bar O2 6 80 65 100 105
The effects of the supports have been investigated by produ-

cing Pt–Bi/TiO2 and Pt/TiO2 catalysts and replacing the C
support with TiO2. The TiO2 effectively and selectively
increased the FDCA yield (Table 1). Reduced graphene oxides
(RGOs) with their abundant surface functional groups are also
promising catalyst supports and are now being applied exten-
sively. When the support was changed to RGO (Pt/RGO), quan-
titative FDCA yield was observed (84%) in 24 hours but the
RGO support did not work efficiently with other noble metal Scheme 6 The proposed HMF oxidation mechanism in aqueous alka-
catalysts such as Pd/RGO, Rh/RGO and Ru/RGO. This demon- line solution; CeBi* denotes oxygen opening accompanied by Bi.102
strates the catalytic superiority of Pt over other noble metals
(Table 1).98 However, an increase in the process intermediate
(HFCA) and a decrease in the final product (FDCA) was HMF, substituting β-H with hydroxide ions (OH−). Bi-
observed during the recycling experiments. Containing ceria accelerates the oxygen reduction due to the
The substantial aim of low-pressure oxidation can be availability of more oxygen vacancies and the breakup of tran-
achieved by applying relatively cheap metal oxide-supported Pt sitional peroxides (Scheme 6).102 This smooth catalytic cycle
catalysts. Exceptionally high yield (>99%) was recorded with continues to consume surface electrons in oxygen reduction,
very low oxygen pressure (0.2 bar) in alkaline medium.99,106 which safeguards the catalytic efficiency and the Pt/
Oxygen chemisorption on the active sites of the Pt/γ-A12O3 Ce0.8Bi0.2O2−δ catalyst can work efficiently even in the fifth
catalyst negatively affected and deactivated the catalytic cycle. It has been reported that the observed yield of FDCA was
ability.100 Changing the metal oxide support resolved the 97% in the fifth cycle, which was appreciably close to the
problem of catalyst deactivation. Pt/Zr2O3, Pt/C and Pt/γ-A12O3 recorded yield in the first batch (98%).102
all performed well and Pt/TiO2 and Pt/CeO2 showed poor cata- Alkaline medium oxidation of HMF is kinetically favorable
lytic efficiency under similar conditions (Table 1).100 Bi-Added and gives higher FDCA yield but the separation of inorganic
bimetallic catalyst could improve the yield to 98% over Pt/ salt and neutralization of the product solution are major pro-
Ce0.8Bi0.2O2−δ (Table 1).102 These results suggest that non-redu- blems.107 To overcome this, base-free oxidation has been inves-
cible oxide (γ-A12O3, ZrO2, and C)-supported Pt catalysts have tigated.103 The observed yield can be high enough (95%) over
higher catalytic performance than reducible oxide (TiO2 and PVP-stabilized Pt nanoparticles (Pt/PVP) with low oxygen
CeO2)-supported Pt catalysts due to the low oxygen storage pressure, but long reaction time (24 hours), low feed rate
capacity. (0.29 m mole), and high catalyst loading (5 moles%) are the
Reaction kinetics have shown that HMF oxidation proceeds major disadvantages of this system.103 Hence, at this stage, the
through the Pt-alkoxide intermediate.102 Pt-Nanoparticles yield Pt/PVP catalyst is uneconomical for mass production although
Pt-alkoxides by reacting with the hydroxyl groups present in it has high stability and recyclability with confirmation of the
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green environment protocol. Platinum nanoparticles (Pt-NPs) nation in Pd/ZrO2/La2O3 catalyst increases the yield (90%) and
dispersed in water have been widely employed as oxidation cat- stability over other oxides (Table 2).110 There is rare Pd-NPs
alysts due to their strong oxidizing ability and diverse stabi- aggregation in contrast to other catalysts (Pd–metal oxide) as
lity.108 Pt-NPs-doped polymeric catalysts can not only stabilize analyzed by TEM. Separation and recycling using external mag-
the Pt-NPs by steric and electrosteric interactions but also netic can be further improved by introducing magnetized Pd
catalysts.111,112 Similarly, bimetallic catalyst (Pd–Au/HT)
boost the catalytic activity. Among the different counteranions

explored so far, the Tf2N− anion has exhibited the highest cata- results in higher yield and stability in recycling experiments
lytic activity, presumably because it may be displaced from the without reducing its reactivity.113
NP surface in a facile manner, generating catalytically active A magnetized Pd catalyst (γ-Fe2O3@HAP-Pd) has been
surface sites where the substrates can bind and react, while developed by coating hydroxyapatite [HAP = Ca10(PO4)6(OH)2]
simultaneously offering sufficient electronic and steric protec- on γ-Fe2O3 and Pd2+ was replaced by the Ca2+ in the HAP
tion to stabilize the NPs during reaction.105 macromolecule and was then reduced to Pd(0)-NPs.77 The cata-
HMF oxidation to FDCA over Pd supported catalysts. lyst showed higher FDCA yield with complete HMF conversion
Palladium (Pd) promotes HMF oxidation in a similar manner (Table 2). Magnetism eases the separation of heterogeneous
to Pt but the FDCA yield is relatively low in comparative combi- catalyst from the reaction mixture with the help of an external
nations.95 Numerous Pd catalysts have been developed by magnet, increasing the recyclability without reducing catalytic
doping palladium nanoparticles (Pd-NPs) with C, PVP and activity.77 Recently developed graphene oxides (GO) are suc-
metal oxides as support materials. Stabilized Pd (Pd/PVP) cata- cessfully replacing carbon as a catalyst supporting material
lyst gives a quantitative yield as with Pt.103,109 PD-NPs size can because both retain higher surface area with oxygen functional
be controlled by alkali dosing (NaOH) during the alcoholic groups. Separation and recycling difficulties of C-based nano-
preparation of the Pd/PVP catalyst. The size of Pd-NPs in the particles can be easily overcome by replacing them with gra-
catalyst cluster inversely affects the FDCA yield. Reduced FDCA phene oxide supported NPs and magnetized catalysts. A mag-
yield (81%) was observed when particle diameter increased netically separable catalyst (C–Fe3O4–Pd) prepared using a one-
from 1.8 nm to 2 nm as shown in Table 2.109 The increased step solvothermal process by simultaneously doping Pd and
amount of surface atoms and unsaturated active metal sites Fe3O4 nanoparticles demonstrated an upgraded product yield
have been recognized as a possible reason for the increased (91.8%) under mild process parameters (Table 2).111 A carbon-
reactivity of Pd/PVP nanoparticles with reduced particle size. supported magnetic catalyst (Pd/C@Fe3O4), prepared by in situ
Interestingly, oxygen flow rate also affects the catalytic activity; glucose carbonization on Fe3O4 microspheres, provided high
hence, precise control of the optimum flow rate is highly rec- yield and cyclic stability.112 Low alkali requirements, atmos-
ommended for economical yield. Oxygen chemisorption due pheric pressure (oxygen), ease of separation and recycling,
to excessive availability might cause deactivation of the cata- good recycling efficiency and constant reactivity are the pro-
lyst.88 At low reaction temperature (<70 °C), the rate of reaction found advantages associated with the use of heterogeneous
from FFCA to FDCA is higher than the rate of HFCA to FFCA magnetic Pd catalysts.
and the products exhibit a maximum HFCA, whereas at a HMF oxidation to FDCA over Au supported catalysts.
higher temperature (>90 °C) both oxidation rates are nearly Initially, gold (Au) was considered inactive as a catalyst for
equal and the key product will be exclusively FDCA.109 In alka- chemical transformations till the 1980s and the discovery of its
line medium, the Pd/PVP catalyst suffers from recycling and catalytic ability was a stunning breakthrough for research and
stability problems, but the stability can be improved by metal development.117,118 Recently, many Au catalysts were devel-
oxide impregnation. Assimilation of different metal-oxides oped and applied successfully for a wide range of potential
such as TiO2, γ-Al2O3, KF/Al2O3, and ZrO2/La2O3 usually applications.119,120 Au catalysts display encouraging perform-
expands the efficiency of the catalysts. Pd metal oxide combi- ance for HMF oxidation and their catalytic efficiency is strongly
Table 2 Some recently reported works on the oxidative production of FDCA from HMF over Pd supported catalysts
Catalyst Base Oxidant Time (h) T (°C) FDCA yield (%) HMF con. (%) Ref.
Pd/C 2 equiv. NaOH 6.9 Bar O2 6 23 71 100 95

Pd/PVP 1.25 equiv. NaOH 1.01325 Bar O2 6 90 90 >99 109
Pd/ZrO2/La2O3 1.25 equiv. NaOH 1.01325 Bar O2 6 90 90 >99 110
Pd/Al2O3 1.25 equiv. NaOH 1.01325 Bar O2 6 90 78 >99 110
Pd/Ti2O3 1.25 equiv. NaOH 1.01325 Bar O2 6 90 53 >99 110
γ-Fe2O3@HAP-PD 0.5 equiv. K2CO3 1.01325 Bar O2 6 100 92.9 97 77
C–Fe3O4–Pd 0.5 equiv. K2CO3 1.01325 Bar O2 4 80 91.8 98.1 111
Pd/C@Fe3O4 0.5 equiv. K2CO3 1.01325 Bar O2 6 80 86.7 98.4 112
Pd/TiO2 2 equiv. NaOH 10 Bar O2 4 90 9 100 114
Pd/HT Base free 1 Bar O2 7 100 >99 >99 115
Pd/CC 0.5 equiv. K2CO3 O2 @20 ml min−1 30 140 85 100 116
Pd–Au/HT 2 equiv. NaOH O2 @60 ml min−1 6 60 90 100 113
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conditions.121,123 Increased FDCA yield was observed with an

increase in reaction time over Au/Ce0.9Bi0.1O2−δ catalyst
(Table 3).123 The catalyst can be easily separated and recycled
with an acceptable decrease in catalytic activity. The catalytic
support dependency of Au catalysts has also been investigated
by developing HY-zeolite catalysts.124 The FDCA yield in alka-
line medium is selectively high (>99%) over the Au/HY catalyst

in comparison to channel-type zeolites (ZSM-5 & H-MOR),
TiO2, Mg(OH)2 and CeO2 catalysts (Table 3).124 The efficiency
enrichment is due to the uniform dispersion of Au nano-
clusters in the HY zeolite super-cage structure. The developed
cage structure eradicates the NP agglomeration, which thus
increases the recycling efficiency and performance of the cata-
Scheme 7 Aerobic oxidation reaction mechanisms for aqueous HMF
over the Au/CeO2 catalyst.121 lyst.125 The addition of 1,3 propanediol further improves the
process efficiency by suppressing the self-polymerization and
humin formation over Au metal oxide catalysts.126
Numerous bimetallic Au catalysts with extended physico-
influenced by supporting materials, being similar to other chemical properties were prepared and tested for the aerobic
noble metal (Pt and Pd) catalysts.121 Metal oxide supports play oxidation of HMF. These bimetallic catalysts further improved
a vibrant role and gold nanoparticles (Au-NPs) doped on CeO2 the process efficiency and catalyst stability.127 The physico-
and TiO2 could obtain higher FDCA yield (>99%) than Fe2O3 chemical properties of the developed catalyst can be altered by
and C.122 Although the yield is superior (96%) over the Au/ composition, extent and equality of mixing.127,128 The Au–Cu/
CeO2 catalyst as compared to the Au/TiO2 catalyst with higher TiO2 (bimetallic) catalyst is very stable and more efficient than
HMF/Au ratio (640), the high oxygen pressure and activity the Au/TiO2 catalyst due to strong synergistic effects.129 It not
reduction in the recycling experiments are paramount indus- only eliminates the PVP-stabilized Au post-deposition but also
trial barriers.121 The reactions proceed with HFCA and hemi- accelerates the FDCA yield, reducing competitive reactions. It
acetal intermediates following the same route as illustrated in also improves the efficient recycling without significant
Scheme 7. agglomeration and leaching of metallic nanoparticles in the
The catalytic activity of Au/CeO2 can be further improved by catalyst arrangement. Similar findings have also been recorded
Bi3+ incorporation into the CeO2 support nanostructure.123 with Au–Cu/CeO2, Au–Cu/TiO2 and Au–Pd/AC catalysts
The modified catalyst not only expands O2 activation but also (Table 3).123,130,131 Au–Pd/AC is stable but with decreased re-
increases the hydride transferability of nano-CeO2, due to the cycling efficiency. Extraordinarily superior stability and yield
availability of lone pair electrons (Bi3+). The Bi combined cata- were observed (99% in the fifth cycle) when the modified Au8–
lyst, [Au/Ce1−xBixO2−δ (0.08 ≤ x ≤ 0.5)], can increase the FDCA Pd2/AC catalyst was applied.131 Hence, the deactivation of
yield to 75% from 39% over unaided Au/CeO2 under the same monometallic Au catalysts by the adsorption of reaction inter-
Table 3 Oxidative production of FDCA from HMF over Au support catalysts
Catalyst Base Oxygen pressure Time (h) T (°C) FDCA yield (%) HMF conc. (%) Ref.
Au/C 2 equiv. NaOH 6.9 Bar O2 6 23 7 100 95

Au/CeO2 2 equiv. NaOH 10 Bar air 5 130 96 100 121
Au/TiO2 4 equiv. NaOH 10 Bar air 8 130 84 100 121
Au/Ce0.9Bi0.1O2−δ 5 equiv. NaOH 1 Bar O2 2 65 >99 100 123
Au/HY 5 equiv. NaOH 0.3 Bar O2 6 60 >99 >99 124
Au/CeO2 5 equiv. NaOH 0.3 Bar O2 6 60 73 >99 124
Au/TiO2 5 equiv. NaOH 0.3 Bar O2 6 60 85 >99 124
Au/Mg(OH)2 5 equiv. NaOH 0.3 Bar O2 6 60 76 >99 124
Au/H-MOR 5 equiv. NaOH 0.3 Bar O2 6 60 15 96 124
Au/Na-ZSM5-25 5 equiv. NaOH 0.3 Bar O2 6 60 1 92 124
Au/TiO2 20 equiv. NaOH 20 Bar O2 18 30 71 100 125
Au/TiO2 pH = 13 10 Bar O2 4 50 80 100 96
Au–Cu/TiO2 4 equiv. NaOH 10 Bar O2 4 95 99 100 129
Au8–Pd2/C 2 equiv. NaOH 30 Bar O2 2 60 >99 >99 131
Au/HT Base-free 1 Bar O2 7 95 >99 >99 133
Au–Pd/CNT Base-free 5 Bar O2 12 100 94 100 132
Au–Pd/CNT Base-free 10 Bar air 12 100 96 100 132
Au/TiO2 4 equiv. NaOH 10 Bar O2 4 70 19 100 114
Au/m-CeO2 4 equiv. NaOH 10 Bar O2 4 70 92 100 135
Au/CeO2 0.2 equiv. Na2CO3 5 Bar O2 15 140 91 >99 126
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mediates as compared to bimetallic catalysts verifies that bi- with air under moderately high pressure (Table 3).132 The CNT
metallic Au catalysts are superior in activity and stability. supported reactant adsorption with improved exposed sites
Environmental concerns associated with the use of alkaline and strong synergistic Au–Pd effects can contribute efficiently
solution, salt separation, recycling and product solution neu- to the catalyst performance. Evidence of FFCA and DFF as reac-
tralization can be addressed by employing base-free HMF oxi- tion intermediates indicate the preferred oxidation of the
dation over a hydrotalcite-supported (Au/HT) catalyst.133 The
hydroxyl group, as compared to the aldehyde group, using the

elimination of the acid requirement for product solution neu- Au–Pd/CNT catalyst [Scheme 8(a)].132 The monometallic Au/
tralization caused the base-free process to be more cost com- CNT catalyst, as compared with the bimetallic Au–Pd/CNT
petitive and selective as compared to other alkaline medium catalyst, preferentially oxidizes the aldehyde group, producing
oxidation processes. Some reported base-free processes can be the HFCA intermediate and conforming to the same proces-
performed with high FDCA yield (99%) and complete HMF sing scheme as over Au/CeO2 and Au/TiO2 catalysts in an alka-
conversion under low oxygen pressure (Table 3). Au/MgO, Au/ line environment.121 Unfortunately, HFCA initiates competitive
Al2O3, Au/SiO2 and Au/C either remain unreactive or exhibit reactions by furan ring opening and degradation
very low reactivity, whereas Au/HT unveils exceptional catalytic [Scheme 8(b)].132 The monometallic Pd/CNT and bimetallic
activity in a base-free environment; however, the recycling per- Au–Pd/CNT catalysts propagate the reaction through identical
formance decreases.133 Mg2+ leaching from the HT support pathways. However, Pd addition in the Au–CNT structure mod-
was observed due to the HT-FDCA chemical interaction, which ifies the reaction pathway to DFF from HFCA conversion and
limits the base-free conditions.134 The development of carbon accelerates the FFCA to FDCA oxidation.
nanotubes (CNT) supported Au–Pd catalyst (CNT–Au–Pd) revo- HMF oxidation to FDCA over Ru supported catalysts. Being
lutionarily accelerated the base-free FDCA production.132 The similar to Pt, Ruthenium (Ru)-based catalysts can also be used
CNT–Au–Pd catalyst is more efficient when oxygen is replaced to catalyze the oxidation of HMF.136 Initially, Ru based cata-
lysts were mostly applied to the oxidation of HMF to DFF
rather than to FDCA production.137–139 The mechanism of oxi-
dation, the potential of Ru-oxide catalysts [Ru(OH)x] and the
effects of the base material (La2O3, MgO, and HT) have already
been discussed in detail.140,141 Keeping in mind the perform-
ance of the C-support (as Pd/C and Au/C) in alkaline medium,
the Ru/C catalyst was developed and applied in the HMF oxi-
dation to FDCA. The practical FDCA yield is terribly low even at
high oxygen pressure (Table 4).96 An increasing trend was
observed by using different bases and the highest yield was
obtained with CaCO3.142 Strong alkali (NaOH) not only affords
lower yields but also degrades the HMF. This phenomenon
Scheme 8 Reaction path for the aerobic oxidation of HMF to FDCA: (a) indicates the instability of HMF at higher pH and suggests the
Pd/CNT and Au–Pd/CNT catalysts, (b) Au/CNT catalyst.132 use of weak bases. On the other hand, FDCA was recovered as
Table 4 Recent reported works on the oxidative production of FDCA from HMF over Ru supported catalysts
Catalyst Base Oxygen pressure Time (h) T (°C) FDCA yield (%) HMF conv. (%) Ref.
Ru/C pH = 13 10 Bar O2 4 50 6.48 98.05 96

Ru/C 1 equiv. NaOH 2 Bar O2 5 120 69 100 142
Ru/C 1 equiv. K2CO3 2 Bar O2 5 120 80 100 142
Ru/C 1 equiv. Na2CO3 2 Bar O2 5 120 93 100 142
Ru/C 1 equiv. HT 2 Bar O2 5 120 90 100 142
Ru/C 1 equiv. CaCO3 2 Bar O2 5 120 95 100 142
Ru/C Base free 2 Bar O2 10 120 88 100 142
Ru(OH)x/MgO Base free 2.5 Bar O2 20 140 96 100 143
Ru(OH)x/MgAl2O4 Base free 2.5 Bar O2 42 140 60 100 143
Ru(OH)x/HT Base free 2.5 Bar O2 6 140 100 100 143
Ru(OH)x/HT Base free 1 Bar O2 38 140 >98 100 143
Ru/MnCo2O4 Base free 24 Bar air 10 120 99.1 100 144
Ru/CoMn2O4 Base free 24 Bar air 10 120 82.2 100 144
Ru/MnCo2CO3 Base free 24 Bar air 10 120 69.9 99.9 144
Ru/ZrO2 Base free 10 Bar O2 16 120 71 100 145
Ru/AC 1 equiv. Na2CO3 35% H2O2 6 75 91.3 100 89
Ru/AC 4 equiv. NaHCO3 40 Bar air 2 100 75 100 148
Ru/AC-NaOCl 4 Equiv. NaHCO3 40 Bar air 4 100 55 100 148
Ru/HAP Base free 10 Bar O2 24 120 99.6 100 146
Ru/HAP Base free 10 Bar O2 24 140 99.9 100 146
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Scheme 9 The reaction mechanism for FDCA production from HMF over Ru/C catalyst.142
its calcium salt because of the presence of unreacted calcium required to reduce the process time by either changing the
carbonate for the lower dissolution rate of CaCO3,142 which metal proportion or altering the structure. The catalyst struc-
acts as a neutralizer rather than a promoter of oxidation. This ture strongly demonstrates that the catalytic efficiency and
difficulty compels researchers to use base-free oxidation over cubic spinel structure are responsible for the effective for-
Ru/C catalyst. Astonishingly, the quantitative FDCA yield (88%) mation of FDCA from HMF over the Ru/MnCo2O4 catalyst.144
was observed as a white precipitate, indicating a pure product The reduced yield was observed in the non-cubic spinel struc-
without any competitive soluble byproduct. The Ru/C catalyst tured oxygen deficient Ru/MnCo2CO3 catalyst. The importance
is highly stable in recycling experiments with just a slight of such a structure was further confirmed by the oxygen-
decrease in catalytic activity, which is easy to regenerate by H2/ deficient catalyst (Ru/MnCo2O3), which obtained only 69.9%
Ar. FDCA production proceeds through the DFF route over Ru/ FDCA yield under the same process conditions (Table 4).144
C catalyst (Scheme 9). Process intermediates, DFF and FFCA The recycling of Ru/MnCo2O4 was found to be economical
can be well oxidized to FDCA over the Ru/C catalyst.142 without any significant loss. TEM analysis of the spent catalyst
HMF oxidation to produce FDCA was also investigated by showed no discernible change in the structural stability and
employing diverse combinations of Ru-metal oxides catalysts there was no Ru metal leaching.144 Moreover, the utilization of
in ionic liquids (ILs).143 Ru(OH)x/HT gives the highest yield in the heterogeneous Ru/MnCo2O4 catalyst in the base-free
a base-free environment with 100% conversion of HMF environment is in favor of the green environment protocol.
(Table 4).143 Nevertheless, despite all the efforts, ILs were However, the use of CaCO3 as a cheap base still needs further
unsuccessful for use in large-scale FDCA production because exploration after the development of FDCA salt recovery
of the high cost, relatively low FDCA yield (48%), inefficient methods.147
separation from the product mixture and unsatisfactory cata- HMF oxidation to FDCA over Rh-supported catalysts.
lytic stability.88 These problems shifted the reaction medium Rhodium (Rh) has similar catalytic potential to Au, Pt, and Pd,
to base-free aqueous phase oxidation over MnCo2O4 supported but this metal has been rarely studied for HMF oxidation to
Ru catalyst.144 An exceptionally high yield of FDCA (99.1%) was produce FDCA. Only Strasser’s group has investigated the role
reported under moderate conditions with very small impurities of the Rh/C catalyst for HMF oxidation.96 The authors com-
of FFCA (5-formylfuran-2-carboxylic acid) (Table 4).144 The pared the performance of different metals supported on C for
active sites of Brønsted and Lewis acids on the catalyst (Ru/ FDCA formation under high pressure and low temperature.
MnCo2O4) surface can increase the yield. Supporting material Using the temperature of 50 °C and a higher oxygen pressure
(MnCo2O4) present in the catalyst structure plays a significant of 10 bar resulted in only 12.62% FDCA yield with 82% HMF
role and promotes HMF oxidation. Replacing this material conversion in 4 hours over Rh/C catalyst. Due to the very low
(MnCo2O4) with CoMn2O4 adversely affects the FDCA yield and FDCA yield and HMF conversion, there has not been any
reduces the conversion of FFCA to FDCA. The system perform- further research on utilizing Rh-supported metal catalysts in
ance was found to be affected by the distorted spinel structures FDCA production.
of the CoMn2O4 body-centered tetragonal crystalline structure HMF oxidation to FDCA over non-noble metal supported cat-
in comparison to the cubic structure of MnCo2O4, with low alysts. Noble-metal catalysts are superior in stability, catalytic
surface area (CoMn2O4 = 89.5 m2 g−1 vs. MnCo2O4 = 151 m2 activity, recyclability and performance, but the large-scale util-
g−1) and low adsorption affinity towards oxygen.144 The effect ization of these catalysts seems to be improvident due to their
of surface area was further optimized by developing high high cost and poor availability. Research on inexpensive non-
surface area ZrO2 and Ru/ZrO2 catalysts (surface area = 256 m2 noble metal catalysts has progressed through the development
g−1) through the evaporation-induced self-assembly (EISA) of stable and active transition metal catalysts for industrial
method but there was no further improvement in the catalyst applications.88 The stable iron(III)-porous organic polymer, (Fe-
performance.145 Ru nanoparticles dispersed over HAP (Ru/ POP), was developed and applied in the aerobic oxidation of
HAP) gave the best results with higher stability and recyclabil- HMF.149 High HMF conversion and FDCA yield further
ity.146 Although the conversion and yield are selective, the inspired the development of non-noble metal catalysts.
lengthy reaction time (24 h) is the major disadvantage of this Merrifield resin-supported Co(II)-meso-tetra(4-pyridyl)-por-
process. An increase in catalytic activity and efficiency is phyrin (abbreviated as Merrifield Resin-Co-Py) catalyst was
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Table 5 Oxidative production of FDCA from HMF over non-noble metal heterogeneous catalysts
Catalyst Oxidizing agent Oxidation environment Temp. (°C) Time (h) HMF. Conv. (%) FDCA yield (%) Ref.
Fe-POP 10 Bar O2 100 10 100 79 149

Merrifield resin-Co-Py t-BuOOH Acetonitrile 100 24 95.6 90.4 150
Li2CoMn3O8/NaBr 55 Bar air Acetic acid 150 8 100 80 151
nano-Fe3O4–CoOx — — 80 12 97.2 68.6 152

Fe0.6Zr0.4O2 20 Bar O2 [Bmim]Cl 160 24 99.7 60.6 67
Ce0.5Fe0.5O2 20 Bar O2 [Bmim]Cl 140 24 98.4 13.8 154
Ce0.5Zr0.5O2 20 Bar O2 [Bmim]Cl 140 24 96.1 23.2 154
Ce0.5Fe0.15Zr0.35O2 20 Bar O2 [Bmim]Cl 140 24 99.9 44.2 154
MnCo2O4 20 Bar O2 8.34 m KHCO3 100 24 99.5 70.9 155
developed and applied, and it demonstrated a higher FDCA combinations reveal the scope for further process and catalyst
yield (90.4%) with complete HMF conversion (Table 5).150 development.156,157 Researchers are continuously investigating
Kinetically, HMF oxidation proceeds through the DFF route the development of novel inexpensive transition metal catalysts
(Scheme 3, route B) and the recycling experiments produced and green solvents for quantitative yields of FDCA with green
pleasing results. Spinel mixed metal oxide catalyst properties.158,159
(Li2CoMn3O8), with sodium bromide (NaBr) and acetic acid as Mechanism of HMF oxidation over metal catalysts. All the
additives, gave adequate yield but high temperature, pressure discussed mechanisms for HMF oxidation are based on the
and additive (NaBr and acetic acid) requirements have made stepwise oxidation of aldehyde and alcohol functional groups.
this process less competitive for industrial application.151 The reactions proceed by either the preferred oxidation of alco-
Large-scale production processes always prefer low tempera- holic functional groups (Scheme 3, route A) or aldehyde
ture and pressure due to safety, energy and economic groups (Scheme 3, route B). Many researchers have discussed
concerns. the reaction mechanisms for the catalyst used and have pri-
The recovery and recycling ability of the catalyst were marily agreed on the formation of FFCA in the second step
further addressed by producing the magnetic nano-Fe3O4– and DFF and HFCA as competitive process intermediates in
CoOx catalyst.152 In spite of the higher HMF conversion the first step (Scheme 3).
(97.2%), the obtained yield of FDCA is only 68.6% (Table 5). Davis et al. applied the isotope labeling technique to evalu-
Although the yield is low, this method initiates the utilization ate the exact HMF oxidation mechanism over noble metal cata-
of transition metal catalysts instead of the highly expensive lysts.160,161 The Au/TiO2 catalyzed oxidation of HMF in alkaline
noble metal catalysts with the added advantages of magnetic medium can produce HFCA with higher selectivity (≥98%)
separation. Experiments have proved that HMF oxidation to under 3.45 bar oxygen pressure at 22 °C. The oxygen isotope
18
FFCA, the first step of oxidation, is initiated by the Brönsted O2 has been used as an oxidant to investigate the role of
base even in the absence of a catalyst, while FFCA oxidation to oxygen. Alkaline medium reaction products were analyzed for
FDCA only takes place over the catalyst. The inexpensive the oxygen isotope and the results surprisingly elucidated that
heterogeneous catalyst (Mn0.75/Fe0.25) works efficiently at high there was no 18O2 isotope in the HFCA molecule. This discre-
pressure (8 bar air) and the observed yield can be as high as pancy indicates that oxygen is incorporated from solvent water
99% of FFCA at moderate temperature (90 °C).153 Hence, it was rather than the available oxidant (oxygen). These findings were
elucidated that the two-step oxidation, HMF to FFCA and FFCA then further confirmed by employing labeled water (H218O) as
to FDCA, may generate better conversion and selectivity with a solvent.161 On analysis, two isotopes of oxygen (18O) were
no catalyst deactivation. found to be integrated into Na-HFCA and HFCA structures,
Ionic liquids (ILs) have also been investigated as a reaction hence, O2 is not essential as an oxidant for the oxidation of
medium along with inexpensive mixed oxide catalysts.154 Pure the aldehyde functional group. Aldehyde side groups present
metal oxides (Fe2O3, ZrO2) and their numerous combinations in the HMF molecule are rapidly oxidized to the geminal diol
(Fe/Zr ratio) are in use for catalyst development. The FDCA through reversible nucleophilic addition. The nucleophilic
yield is low irrespective of higher HMF conversion with all pro- addition of OH− to carbonyl radicals and the simultaneous
portions and changing process parameters seems not to proton transfer from water molecules produces unstable inter-
improve the catalyst performance (Table 5).154 Other catalysts mediates (Scheme 10, step 1);161 hence, two oxygen atoms
were developed with different combinations of Mn and Co from water molecules are incorporated into the HMF proces-
oxides.155 Highly selective results have been obtained by apply- sing intermediates, which can be confirmed by the presence of
18
ing the nanoscale center-hollowed hexagon MnCo2O4 spinel to O when H218O is applied as a solvent. Geminal diol dehydro-
catalyze the oxidation of HMF because of its efficient reducibil- genation promoted by the adsorbed OH− on the catalyst
ity and oxygen mobility (Table 5). surface results in the formation of COOH in the second step
The ILs and non-noble metal catalyst combination is less (Scheme 10, step 2), and the aldehyde functional group of
attractive due to low FDCA yield and environmental concerns HMF is successfully oxidized to carboxylic acid. This proves
at this stage. However, increases in performance with changed that the reaction mechanism follows route A of Scheme 3,
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Scheme 10 elucidates that the reaction mechanism of HMF

oxidation is facilitated by the presence of the base-provided
hydroxyl ion (OH−). However, this suggested mechanism
works only in the presence of a base, while base-free HMF oxi-
dation proceeds with a different mechanism. The base-free oxi-
dation mechanism was investigated by Yan’s group over a poly

[bvbim]Cl-stabilized Pd (PVP) catalyst using similar isotope
labeling technology (Scheme 11).103 Isotope labeling con-
firmed the presence of DFF and FFCA as process intermediates
rather than HFCA in base-free oxidation.103 The same mecha-
nism has also been confirmed by others using low pH or base-
free environments.132,161 Similarly, the isotope labeling tech-
nique (H218O) has been utilized to interpret the reaction
mechanisms of HMF oxidation over Pt/PVP catalyst. FFCA and
FDCA were recorded as oxidation end products and the pres-
ence of 18O atoms was confirmed by mass spectra.103 The
peaks with m/z 161 and 163 relate to the 18O-labelled FDCA,
Scheme 10 Reaction mechanism of the aqueous phase oxidation of
HMF in alkaline medium over metal (Pt/Au) catalyst.160,161
while peaks with m/z 143 and 145 relate to the 18O labeled
FFCA. Being analogous to the base-promoted oxidation step 1
(Scheme 10, step 1), nucleophilic addition of H2O to carbonyl
being similar to that found in previous studies.162,163 rapidly produces the geminal diol via the reversible hydration
Furthermore, the oxidation of alcoholic groups present in of the aldehyde groups (Scheme 11).103 In the end, the car-
HFCA is required to obtain FDCA. The presence of a base is boxylic groups are regenerated by the migration of two protons
vital for the oxidation of the alcoholic group, regardless of to the metal surface and water by reactions between molecular
what catalyst is applied. The base-initiated deprotonation of oxygen and surface hydrides; therefore, the base-free oxidation
alcoholic groups produces alkoxy intermediates.164 Base- of HMF takes place completely.103
donated hydroxide ions adsorbed on the catalyst surface then Even though the reaction mechanism for the oxidative pro-
activate the O–H bonds of alcoholic side chains to produce the duction of FDCA from HMF can be well interpreted by the
aldehyde intermediate (FFCA) (Scheme 10, step 3). The next isotope labeling technique, extensive work is still required to
steps are the oxidation of the aldehyde groups (Scheme 10, study the chemical kinetics and reaction mechanism in depth.
steps 4 and 5), which proceeds quite similarly to those in the The utilization of modern techniques for determining the
previous discussion. Again, two oxygen atoms are fused when comprehensive intrinsic kinetic mechanism will help with the
water, having the oxygen isotope (H218O), is used for the syn- understanding of the synthesis process. This solid insight into
thesis of the geminal diol from the reversible hydration of the the reaction pathway will help researchers with the develop-
aldehyde group. The complete oxidation of HMF to produce ment of new, efficient and stable green catalysts and solvent
FDCA can be well explained, indicating that oxygen is incor- systems, which are necessary for the rational design of the cat-
porated from water molecules instead of the freely available alysts and the production process.
molecular oxygen (the oxidant). However, the presence of HMF oxidation to FDCA over metal-free nano-porous graphi-
molecular oxygen or any other oxidizing agent is necessary for tic carbon catalysts. Initially, metal-free catalysts were con-
the oxidative production of FDCA from HMF to indirectly sidered inactive for HMF oxidation and were not applied till
facilitate the oxidation process by removing electrons de- the development of the non-metallic zeolitic-imidazole struc-
posited on the catalyst surface.160,161 ture (ZIF-8), which is imitative of nitrogen-incapacitated nano-
Scheme 11 Integration of 18O into the reaction steps. (18O) is shown in blue and the observed units are in dashed ellipses.103
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porous carbon (denoted as NNC).165 Catalysts were named

NNC-X (X-represents the carbonization temperature) after car-
bonization and calcination under an inert atmosphere. The
catalyst properties such as the graphite-carbon framework,
specific surface area, and porosity are controlled by calcination
and the carbonization mechanism.165 NNC-900 gave the
highest yield of FDCA (80%) with complete conversion of HMF

at 80 °C using pure oxygen under atmospheric pressure in
alkaline medium. The oxidation reaction proceeds via the
HFCA and FFCA route (Scheme 3, route A) over NNC-900 cata-
lyst with the first step being a fast step.165 Increasing tempera-
ture accelerates the HMF conversion, signifying the tempera- Fig. 3 Membrane reactor processing scheme: (1) water phase HMF syn-
ture dependency of the fast step, whereas, the conversion of thesis; (2) HMF diffusion in the MIBK phase; (3) HMF oxidation to FDCA.
HFCA and FFCA to FDCA are recognized as the rate determin- (Adapted from ref. 172).
ing steps (slow steps). These findings are in good agreement
with previously published results indicating the same route
and kinetics.94,165
One of the most important selective aspects of hetero- conversion in MIBK only produces DFF so the presence of
geneous catalysts is that the catalyst can be easily separated water is necessary for the conversion of the alkoxy group to
and recycled for multiple runs. The quaternary nitrogen (N-Q) FDCA.172 A higher yield (25%) of levulinic acid and its
configured NNC-900 catalyst was separated using centrifu- diffusion through the membrane leads to lower FDCA yield.172
gation, washed with deionized water and methanol, dried at Although this one-pot yield is very low and challenging,
150 °C for 5 hours prior to each run. The recorded decrease in together with purification difficulties, it unwraps a new
FDCA yield was 12.5% in the fourth run (1st 80% and 4th about research arena.
70%).165 There was no significant structural change except for A bifunctional catalyst (encapsulation of Co(acac)3 in sol–
a minor change in the N-Q amount. This result indicates the gel silica) increased the fructose conversion and product
selective separation and recycling efficiency of the catalyst selectivity, which was further improved by a one-pot two-step
applied. A long reaction time and low HMF/base ratio make it process.174,175 Fructose was dehydrated to HMF in the HCl-
less competitive for industrial applications but, further catalyzed isopropanol mixture and was then oxidized to FDCA
research can improve the potential of this green and economi- in the second step.175 This particular process has the benefits
cal heterogeneous catalyst system for HMF oxidation. of high overall yield (83%) and efficient solvent (isopropanol)
recovery. The water extraction of FDCA from the product
One-pot production of FDCA from biomass mixture quantitatively affects the product yield, and water
Direct conversion of biomass and biomass fractions into the extraction followed by oxidation over Au/HT catalyst is the
required products is always a fascinating and economical most economical purification methodology with the maximum
alternative for industrial application.166,167 The conversion of yield (98%).175 In contrast, the replacement of the catalyst with
HMF to FDCA is technically feasible but faces problems of solid polybenzylic ammonium chloride decreases the overall
cost, stability and availability.168 There are also many other yield.176 The biphasic system was then modified to the tripha-
potential and more economical uses of HMF that barricade its sic system by introducing tetraethylammonium bromide
oxidation to produce FDCA.169,170 HMF is a biomass-derived (TEAB) as phase I, MIBK as phase II and water as phase III.177
product so the direct synthesis of FDCA from carbohydrates In this triphasic system, phase I eases the dehydration of
such as fructose, glucose, cellulose and lignocellulosic sugars (fructose or glucose) to HMF which is then extracted,
biomass has been researched for a long time.171 This conver- refined, and transported to phase III through a channel
sion process is termed a one-pot synthesis (Fig. 2) and is gen- ( phase II). The Au/HT catalyst used in phase III improved the
erally carried out with combined acidic and metal site multi- HMF oxidation. When fructose was used as feedstock, the
functional catalysts. The competitive oxidation of carbo- FDCA yield was high (78%) but was reduced to 50% with
hydrates is a major hurdle for the direct production of FDCA glucose.177 The one-pot one-step process can be developed
from carbohydrates but it can be partially resolved by applying into a one-pot two-step process to improve the yield and
molecular sieves or polymeric membranes in biphasic selectivity.178 This process facilitates the catalyst recovery and
systems.172,173 The preferred oxidation of carbohydrate is recycling for economic expansion to mass production. The
vetoed by using polytetrafluoroethylene membrane ( pore size = nanocatalyst (Fe3O4–CoOx) efficiently oxidizes HMF to FDCA
0.45 µm and exchange area = 70 cm2) as a reactor divider in utilizing t-BuOOH as an oxidant.178 HMF was produced from
the water and MIBK system (Fig. 3).172 HMF is produced on a fructose over an acid catalyst (Fe3O4@SiO2–SO3H in DMSO) fol-
solid acid catalyst (Lewatit SPC 108) by the dehydration of fruc- lowed by the oxidation to FDCA with t-BuOOH over the nano-
tose passed through the membrane toward the MIBK solution Fe3O4–CoOx catalyst.178 An external magnet can separate the
and oxidized to FDCA over metal base catalysts. Single phase catalyst before HMF oxidation. Although the observed FDCA
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hydrophilic acidic sites for the preferred adsorption of carbo-

hydrate. This will promote the dehydration of carbohydrate to
HMF and then release this product to the reaction mixture.
Active oxidative sites present in a hydrophobic environment
can improve the adsorption of the available HMF that will
intensify its conversion to FDCA. This simultaneous process

will enhance the process yield and selectivity to make the one-
pot process more feasible, selective, reliable and cost
competitive.
Biocatalytic production of FDCA from HMF

Biochemical transformation is more advantageous in terms of
Fig. 4 Schematic representation of the Pd/CC catalyst (adapted from process parameters than chemical conversions as these pro-
ref. 116). cesses are usually performed under mild conditions. There is
also the tendency for relatively non-toxic intermediates and by-
product formation in biocatalytic processes. Therefore, the use
of biologically active catalysts and biological cell sequencing
yield is low (59.8%), the ease of separation and efficient re- technology is needed for the production of biochemicals in
cycling are the added advantages.178 Glucose dehydration with current environment sensitive scenarios.180 Similarly, the pro-
FDCA over iPrOH/H2O or THF/H2O produces quantitative yield duction of FDCA from HMF and other biochemical intermedi-
in comparatively less time.179 The green Pd/CC catalyst (Fig. 4) ates on bioactive catalysts is always interesting but challenging
developed by the carbonization of biomass-derived glucose for the research community.181 In spite of all these associated
works efficiently in the one-pot two-step synthesis of FDCA incentives, the biocatalytic routes for FDCA production has not
from glucose. A more efficient, green, and commercial process yet been well established.
has been reported to produce FDCA with a yield of 64% The biocatalytic conversion of DFF to FDCA is usually con-
without any separation and purification requirements.116 The ducted by pouring an aqueous solution of hydrogen peroxide
developed catalyst showed profound separation and recycling (30%) into the mixture of alkyl esters (alkyl donor) and lipases
efficiency with extended stability. The Pt/C catalyst worked (biocatalyst), which produces peracid and subsequently oxi-
efficiently (91% FDCA yield) with high initial fructose concen- dizes DFF to FDCA.182 High FDCA yield (>99%) and selectivity
trations (15 W%) in a co-solvent system of γ-valerolactone (∼100%) has been observed in the DFF oxidation process
(GVL) in water (GVL/H2O).107 Fructose can be dehydrated to (Scheme 12) but this biocatalytic system is inactive for HMF
HMF in 50% aqueous solution of GVL using the separated oxidation. The use of DFF for the production of FDCA is une-
FDCA product solution as the acid catalyst, followed by oxi- conomical as HMF conversion to DFF is an additional step in
dation over Pt/C catalyst. This process has industrial potential this model.182 A chloroperoxidase from Caldariomyces fumago
as the produced FDCA is easy to separate by crystallization. has been found to have the potential of HMF bio-oxidation but
The clean solution can be recycled to the fructose dehydration this process is also uneconomical due to the low FDCA yield
step for economical reasons.107 This efficient recycling of the (60–75%) and the higher competitive yield of HFCA
spent liquor reduces the need for external acid catalyst (25–40%).183 FDCA produced with HFCA cannot be purified to
together with the elimination of the separation step and mini- such a degree for polymerization so C. fumago-derived chloro-
mizes waste, thus conforming to the green chemistry. peroxidase is not yet good enough for the biosynthesis of
So far, the one-pot production of FDCA is mostly focused FDCA from HMF.183
on the utilization of fructose as feedstock. The FDCA yield by A fermentative synthesis process of HMF to FDCA with
the one-pot process with glucose as the feedstock is usually Pseudomonas putida S12 biocatalyst to facilitate the oxidoreduc-
lower than with fructose because the isomerization of glucose tase from Cupriavidus basilensis HMF14 has been investigated
to fructose is involved in the process. Much lower yield is using glycerol as a carbon source.184 FDCA yield of 97% (from
achieved for one-pot processing of the lignocellulosic biomass
primarily due to the difficulty of releasing glucose from the
cell wall matrix. Although the one-pot process is a new trend
in the research arena, it has the obstacles of low FDCA yield
with less competitive and economic constraints.88 Further
development of the one-pot process is needed in terms of
yield, selectivity and economics. Therefore, the development of
new transition metal catalysts is necessary for the economical
utilization of this concept. Side reaction elimination and FDCA
yield enhancement can be accelerated by the isolation of mul- Scheme 12 DFF oxidation to FDCA through in situ lipase-catalyzed
tiple catalytic sites. Thus, the developed catalyst must have peracid formation.88,182
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HMF feedstock) with 99.4% solid recovery was obtained from benefits of the simultaneous oxidation of the aldehyde and
the culture broth. This model proceeds via the activities of alcoholic group.188 ROBF60-H (expressing HmfH), ROBF60-O
both dehydrogenases and oxidases.184 Usually, enzymes are (expressing HMFO) and ROBF60-HO (expressing both HmfH
either aldehyde oxidant or alcohol oxidant, whereas complete and HMFO) have been applied successfully in analogous
oxidation of HMF requires an enzyme reactive enough to environments and strain ROBF60-HO could provide maximum
HMF conversion (93.6%).188 HMF toxicity could be reduced by
oxidize both the aldehyde and alcohol groups. Hexamethyl fur-

fural oxidase (HMFO) from glucose-methanol-choline oxido- increasing the biomass concentration to keep the catalyst bio-
reductase (GMC) has been identified as having superior oxi- logically active and alive.189 During biotransformation, strain
dation potential at ambient conditions, satisfying this require- ROBF60-H initially converted HMF into HMF-alcohol in
ment.185 Although the yield is very high (95%), the low feed- 24 hours then oxidized it to FDCA. The cultured strain
stock concentration (2 mM) and long reaction time (24 hours) (ROBF60-H) behaved similarly to the wild strain, and HMF-
make this strain less attractive.88 Catalytically active and stable alcohol and HMF concentrations diminished quickly after
strains, Methylobacterium radiotolerans (G-2) and Burkholderia 24 hours.188 Strain ROBF60-O also followed the same route
cepacia (H-2) have been applied in the biotransformation of with a faster rate and converted HMF to the HMF-alcohol
HMF to FDCA.186 Under the optimal conditions with 3% cell complex in 12 hours. Similarly, strain ROBF60-HO also used a
biomass, the isolated strain B. cepacia could produce FDCA of pattern analogous to ROBF60-H with little accumulation of
1276 mg L−1 from 2000 mg L−1 of HMF.186 An increase in HMF and HMF-acid.188 The maximum yield of FDCA was
temperature accelerates the biotransformation rate, while the obtained by R. ornithinolytica BF60.188 Although this biocataly-
optimal temperature (28 °C) is used for the biotransformation tic process is simple and eco-friendly, the low yield makes it
of HMF to FDCA.186 Increasing the concentration of HMF can less attractive for larger scale production. Catalytic perform-
increase the FDCA yield but the recovery is inefficient at higher ance and stability of the newly developed HMFO from
concentration. A lower concentration (<1500 mg L−1) can Methylovorus sp. were further exploited by using the recently-
support minimal cell growth, while higher concentrations developed FRESCO method (a computational approach to
(>2000 mg L−1) reduce the cell density due to the increased identifying thermostabilizing mutations in a protein struc-
HMF toxicity at higher concentration. The produced FDCA also ture).188 HMFO developed with FRESCO in combination with
results in reduced pH, which is also unfavorable for cell the gene shuffling approach can tolerate the presence of co-
growth. Hence, 2000 mg L−1 is the optimum HMF concen- solvents and additional mutants. Due to its stability and cata-
tration for maximum FDCA yield when using B. cepacia. More lytic efficiency, the final HMFO variant appears to be a promis-
concentrated FDCA (11.3 g L−1) can be obtained by the strain ing catalyst for the industrial-scale production of FDCA from
R. ornithinolytica BF60 (@45 g L−1) with HMF conversion of HMF. Quantitative FDCA yield can be obtained using the
89% at 30 °C in a slightly basic medium ( pH = 8, with 50 mM 8BxHMFO variant (Scheme 13).190 Another substrate, methoxy-
phosphate buffer).187 These biocatalysts are very sensitive to methylfurfural (MMF) can be oxidized to FDCA using the
the feed concentration and pH of the medium, so precise enzyme cascade of aryl-alcohol oxidase (AAO), unspecific per-
process control is mandatory for efficient production. oxygenase (UPO) and methanol oxidase (MOX).191 AAO con-
With the approach of a robust biocatalyst, genetically modi- verts MMF to MMFA, slowly releasing 1 equivalent of H2O2
fied strains incorporating HMFO and HmfH with (Scheme 14, step 1), and UPO selectively cleaves the ether
R. ornithinolytica BF60 have been developed to achieve the linkage of MMFA to produce FFCA (Scheme 14, step 2), con-
Scheme 13 Oxidation reaction of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) by HMFO.190
Scheme 14 Oxidation pathways of MMF into FDCA with cascade enzymatic catalysts.191
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suming the H2O2 present in the system. HFCA was observed

in very low proportions, indicating that the FFC route (step
2–5) is the main reaction pathway.191 MOX catalyzes the cano-
nical reaction and produces H2O2 from O2 by the concomitant
catalytic oxidation of methanol to methanal, thus increasing
the FDCA yield to 70%.191 HmfH and HMFO potentially cata-
lyze the oxidation of aldehyde and alcoholic groups, respect-

ively, and can work well for a wide substrate spectrum.191,192
Although the biocatalytic yield of FDCA is low and the
process is uneconomical at this stage, this process still con-
Scheme 15 Proposed reaction route for the oxidative production of
forms to green environment protocols. Further research in this FDCA from HMF using Au/C and Pd/C electrocatalysts in alkaline
field with the development of robust biocatalysts can make medium.80
this route more attractive. Biocatalysis is usually depressed by
harsh process environments so ambient temperature and
atmospheric pressure are generally enough to proceed. all its benefits, this process has not yet been thoroughly inves-
Currently, the biotransformation of HMF to FDCA is per- tigated. The Pt electrode was once used with current density of
formed with lower feedstock concentration for long processing +0.44 mA cm−2 but the recorded FDCA yield was very low
time and the need for sophisticated control. Genetic engineer- (18%) with only 70% HMF conversion, and the competitive
ing and gene sequencing for the production of biocatalysts electrolysis of H2O to parent oxygen and hydrogen was recog-
with enhanced catalytic activity, stability at fluctuating process nized as a limiting reaction.96 Li et al. subsequently reported
conditions and the ability to digest high HMF concentration the electrochemical production of FDCA using carbon black-
will increase the industrial potential of this process. The ‘con- supported noble metal catalyst in alkaline medium.80
struction’ of microorganisms with multiple enzymatic func- Aldehyde oxidation was faster than alcohol oxidation over
tionalities, especially the direct conversion of carbohydrates to Au/C catalyst. Higher electrochemical potential is required for
FDCA, is now an exciting but challenging topic for researchers. preferred alcohol oxidation; hence, the intermediate FFCA pro-
It will not only make the FDCA cost competitive but will also duced with DFF or HFCA depends on the electrode and elec-
increase the production level for sustainable market supply. trode potential (Scheme 15).80 Au/C produces HFCA under
lower electrode potential and further oxidation to FDCA
Electrolytic production of FDCA from HMF requires higher potential, whereas Pd/C-catalyzed reactions
Electrochemical transformation is always considered impor- follow two different routes with changed electrode potential.80
tant as a clean and green technology because the process is At low electrode potential, the oxidation rate of the aldehyde
driven only by the electrochemical potential. Electrochemical group is lower on Pd/C than Au/C but significantly enhanced
oxidation of HMF to produce FDCA under mild conditions pro- with increased potential. Bimetallic (Pd–Au) produces higher
ceeds through electron migration thus eliminating the need FFCA and FDCA than monometallic catalysts at lower electrode
for any external oxidant. This conversion methodology is now potential. Further, the PdAu2/C bimetallic catalyst yields 83%
gaining scientific interest due to environment and energy sen- FDCA with 100% HMF conversion at the electrode potential of
sitivity.193 Control of the faradaic efficiency and oxidation 0.9 V, showing the effect of alloying metals on the enhance-
potential are added advantages of this process, which can ment of the FDCA yield. However, this process produces FDCA
facilitate monitoring of the thermodynamic properties, surface in a mixture with other oxidative products and purification is
chemistry of the reaction and ultimately the rate of reaction.194 very difficult and uneconomical.
Primarily, H-shaped electrochemical cells were used for the The use of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) as
first time (1995) for HMF oxidation to FDCA (Fig. 3) using a mediator greatly reduces the over potential requirements for
nickel oxide/hydroxide as the anode and NaOH solution as the HMF oxidation by suppressing water oxidation.96,193 The
alkaline media.193 The electrochemical oxidation of HMF electrochemical cell used by Choi is shown in Fig. 5a and the
could take place at the anode, yielding 71% of FDCA in reaction pathway over TEMPO is shown in Scheme 16.193 The
4 hours at a current density of 0.016 A cm−2. However, further Au electrode oxidized TEMPO to TEMPO+, which served as an
extensive research on the electrochemical oxidation of HMF oxidizing catalyst and achieved high FDCA yield (⩾99%) with
has not been conducted. Perhaps the importance of FDCA as a ⩾93% faradaic efficiency in alkaline solution ( pH 9.2). In the
green building block has not been explored and the potential electrochemical oxidation of HMF, a photoelectrochemical cell
of this process has not been thoroughly considered. Now, after (PEC) with nanoporous n-type BiVO4 electrode ( photo-anode)
the aggressive enforcement of green environment protocols and Pt-electrode (cathode) was fabricated (Fig. 5b).193 The
and the utilization of green polymer production processes, photoanode generates and separates electron–hole pairs by
researchers are expansively searching for eco-friendly and absorbing photons, then the electron–hole pairs are trans-
economical models for FDCA synthesis. This shift elaborates mitted to the Pt-cathode. At the Pt-cathode, water is reduced to
the importance of the electrochemical process as a green hydrogen gas (eqn (I)), whereas holes, after reaching the BiVO4
technology, especially for polymer production. Regardless of surface, proceed with the HMF oxidation through TEMPO
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Fig. 5 Electrochemical and photoelectrochemical cell comparison: (a) photoelectrochemical TEMPO facilitated FDCA production from HMF;
(b) electrochemical TEMPO facilitated FDCA production from HMF. EF, Femi energy; CB, conduction band (adapted from ref. 193).
Cathode reaction:
6H2 O þ 6e ! 3H2 þ 6OH ðIÞ
Anode reaction:
HMF þ 6OH ! FDCA þ 6H2 O þ 6e ðIIÞ
Inclusive reaction:
Scheme 16 The TEMPO pathway facilitated the electrolytic synthesis of HMF þ 2H2 O ! FDCA þ 3H2 : ðIIIÞ
FDCA from HMF.193
During the electrochemical production of FDCA, the
process intermediate, FFCA, produced either by the DFF or
(eqn (II)). Eqn (III) illustrates the overall cell reaction for FDCA HFCA route, can be oxidized to FDCA. However, all these
production.193 This production process has the advantages of process intermediates (DFF, HFCA and FFCA) remain at
higher yield and better faradaic efficiency without any in- very low concentrations throughout the process (Table 6).196
process pH adjustment. Additionally, H2 gas produced separ- Negligible amounts of HFCA present in the final product solu-
ately by water splitting on the cathode can serve as a clean and tion indicate that the production proceeds through the DFF
green source of energy. A greater proportion of TEMPO (1.5 intermediate (Scheme 3, route B) and the final product FDCA
equivalent) is required for higher FDCA yield, making the is obtained as a white precipitate at pH 0 (addition of H2SO4).
process highly expensive.193 Moreover, the separation and puri- The stability and performance of electrodes can be tested
fication of FDCA from TEMPO, electrolyte and process bypro- through chronoamperometry. These results have elucidated
ducts are difficult.88 Additionally, high FDCA yield can be that Co–P electrodeposited copper foam (Co–P/CF) is an excel-
obtained only by using a low initial concentration of HMF, so lent and stable electrocatalyst for the production of FDCA in
the design of more robust electro-catalysts with efficient HMF an alkaline medium. This system simultaneously produces H2
conversion and high FDCA selectivity is critical. The newly by water splitting at low voltage (1.44 V and current density
developed Co–P as electrocatalyst and the Co–P/CF electrode 20 mA cm−2), whereas independent water splitting and H2 pro-
can achieve a 99% yield of FDCA with 100% faradaic duction require 1.54 V.196 The simultaneous production of
efficiency.193 Similarly, the Ni–Fe layered double hydroxide FDCA and H2 is quite inspiring in the current green energy
(LDH) nanosheets grown on carbon fiber paper produced a and environment sensitive scenario.197 A novel continuous
quantitative yield (98%) with 99.4% faradaic efficiency.195 electrochemical process of HMF oxidation and integrated
These processes have the advantages of separating FDCA pro- product (FDCA) separation using non-noble metal Ni/NiOOH
duction at the anode and clean H2 at the cathode, similar to foam electrodes seems to have solved the problem of yield and
Choi’s finding.193,196 This process was then modified and continuity.198 Prospective scale-up can be achieved using the
patented by Wisconsin alumni research foundation (WARF) filter press type flow reactor with Na2SO4 buffer ( pH = 12) and
Madison, US.197 Ni–Fe-LDH promotes HMF oxidation under the Ni/NiOOH foam anode, which can achieve 90% FDCA yield
lower potential (1.23 V) compared to water electrolysis and is, with 80% faradaic efficiency and 95% product separation
therefore, more efficient and sustainable.195 efficiency.198 This process has been successfully applied to
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Table 6 Oxidation of HMF and product analysis in the AEM-electrolysis flow cell80
Catalyst Potential [V vs. RHE] SDFF [%] CHMF [%] SFDCA [%] SFFCA [%] SHFCA [%]
Pd/C 0.6 <1 75 11 64 25

Pd2Au1/C 0.6 <1 87 8 62 30
Pd1Au2/C 0.6 — 100 25 16 59
Au/C 0.6 — 100 1 <1 98

Pd/C 0.9 — 97 29 <1 70
Pd2Au1/C 0.9 100 64 <1 35
Pd1Au2/C 0.9 — 100 83 <1 16
Au/C 0.9 — 100 1 <1 98
Pd/C 1.2 — 32 3 26 71
Pd2Au1/C 1.2 — 82 22 17 61
Pd1Au2/C 1.2 — 100 36 4 60
Au/C 1.2 — 99 14 5 81
bench-scale production. However, delicate control due to nascent oxygen promotes the FCA formation through the dehy-
higher pH and construction material are the limitations of this drogenation of HFCA. The aldehyde group present in FCA is
process. Scientists are focusing on elucidating detailed mecha- further oxidized to intermediate II with a mechanism similar
nisms and developing robust electrocatalysts to work in a to that of the first step. The dehydration of intermediate II
neutral medium ( pH = 7). finally yields FDCA. No DFF was detected during the process,
which confirms the HFCA route (Scheme 3, route A).
Non-catalytic production of FDCA form HMF Scheme 17 outlines the detailed mechanism.199
It is always scientifically desirable to shift the conversion pro- H2 O2 þ OH $ HOO þ H2 O ðIVÞ
cesses from catalytic to non-catalytic without disturbing the
yield and selectivity, due to financial concerns and availability. H2 O2 þ HOO ! O2 þ OH þ H2 O ðVÞ
Along with the catalyzed production of FDCA, researchers are Considering the advantage of HMF extraction in organic
also continuously struggling to develop a catalyst-free model solvent, catalyst-free oxidation was further investigated using
employing strong oxidizing agents (e.g. H2O2 etc.).88 The FDCA NaOH in dimethylformamide (DMF), which produced high
yield was optimized in an alkaline medium using different FDCA yield (91%) at normal temperature and pressure.201 The
process parameters in a semi-batch reactor. The optimized selected system (NaOH in DMF at 25 °C) is the most pro-
production of pure FDCA was recorded in 55.6% yield by apply- ductive, while changing base (e.g. NaOH with t-BuONa or
ing H2O2 as an oxidizing agent.199 H2O2 decomposes to form NaH), solvent or any other parameters negatively affects the
nascent oxygen (O2) and H2O in the alkaline environment yield. NaOH-promoted oxidation mechanism of HMF in DMF
through HOO− (eqn (IV) & (V)), which plays a vital role in is outlined in Scheme 18.201 The influence of the Cannizzaro
oxidation.200 reaction was observed in the reaction kinetics, which was
HOO− was produced by the reversible attack of hydroxyl initiated by a NaOH nucleophilic attack on the aldehyde
ions (OH−) on H2O2 as shown in eqn (IV). Hence, an increase group, producing the tetrahedral intermediate 2. Intermediate
in OH− concentration favors the process in the forward direc- 3 (BHMF) and intermediate 4 (HFCA) were simultaneously
tion and produces more attacking species (HOO−) for the
second step. In alkaline medium, the decomposition of hydro-
gen peroxide (H2O2) to HOO− in the first step initiates the con-
version of the aldehyde group to the carboxylic group present
in the HMF structure (Scheme 17, intermediate I). Dehydration
of the intermediate I gives HFCA. The in situ production of
Scheme 17 Reaction pathway for catalyst-free alkaline medium oxi- Scheme 18 The reaction mechanism for HMF oxidation promoted by
dation of HMF to FDCA using H2O2.199 NaOH in DMF.201
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produced by the migration of the hydride ion from intermedi- filtered for catalyst separation, and the separated catalyst is
ate 2 to another HMF molecule. Intermediate 3 can be quickly washed with water and recycled for subsequent processing.203
oxidized back to HMF. The alcohol group of intermediate 4 During the oxidation, HMF has the tendency to polymerize,
was oxidized to the sodium salt of FFCA (intermediate 7) after resulting in lower FDCA yield, and this problem can be solved
deprotonation. The aldehyde group present in the sodium salt by developing di-HMF oxidation similar to HMF oxidation by
of FFCA may undergo the Cannizzaro reaction with release of BASF. The HMF to di-HMF mass ratio of 1 : 0.5 produced
the sodium salt of FDCA (intermediate 8). Due to the solubility 78.3% of FDCA with complete conversion.204 The solid catalyst
difference, FDCA-sodium can be separated via acidulation.201 was filtered out from the alkaline solution, washed and
recycled.204 In contrast to the Synvina process, the Corbion
Industrial process development of FDCA production process used the microbial route for FDCA production from
The development of the commercial production of FDCA and HMF (Scheme 20).205 Corbion used highly efficient and selec-
its derivatives by various industrial ventures in the 21st century tive microbes to develop an industrial process for the large-
has indeed been a real breakthrough in the development of scale production of FDCA like Succinity® (a joint product of
biodegradable polymers. The industrial production of FDCA Corbion and BASF), which has efficaciously replaced pet-
was initiated by Avantium, named the Avantium YXY® process, roleum-derived succinic acid.206
at the Chemelot campus in Geleen, Holland. The YXY® Origin Materials (formerly known as Micromidas) designed
technology consists of the catalytic dehydration of carbo- the commercial process for the production of FDCA in collab-
hydrates to alkoxymethylfurfural (RMF) or methoxymethyl- oration with Eastman Chemical Company (Eastman) in
furfural (MMF), which is then oxidized to FDCA (Scheme 19). 2017.207 Eastman patented the FDCA production process by
PEF is produced by the catalytic polymerization of FDCA and the catalytic oxidation of HMF over Co/Mn/Br catalyst with
EG in the last step.202 The pilot plant started its production in >90% purity (99.2% FDCA yield) in a titanium autoclave
December 2011 with a capacity of 40 tons of FDCA per year. (Table 7).208 The catalyst proportion was maintained using
This is the first reported commercial unit for FDCA pro- manganese(II) acetate, cobalt(II) acetate tetrahydrate and hydro-
duction.74 After the successful operation of an FDCA pilot bromic acid and/or sodium bromide respectively. This pro-
plant, Avantium established a joint venture with BASF duction unit will start its operation in the end of 2018 at
(Synvina) and designed a new unit for FDCA production with Western Sarnia-Lambton Research Park.209
an extended capacity of 50 000 tons per year with the onsite DuPont Industrial Biosciences (DuPont) in collaboration
production of PEF using the same technology.202 This plant is with Archer Daniels Midland Company (ADM) presented their
projected to run in 2023–2024.74,202 BASF has developed a innovative process to produce 2,5-furandicarboxylic acid
process using HMF and di-HMF as the substrate for FDCA pro- dimethyl ester (FDME) in 2016.210 HMF was oxidized in an
duction in an autoclave over a heterogeneous catalyst.203,204 aqueous solution of metal salt passing through a high-
Deuterated water (D2O) was used for the preparation of an pressure oxidizer at 115 °C.211 The pressure increased from 20
aqueous solution of HMF and heterogeneous catalyst (Pt) in a bar to 42 bar after 50 minutes of charge. The temperature was
molar ratio of 100 : 1 respectively.203 The autoclave is heated to maintained at 100 °C for half an hour and then increased to
185 °C for 20 hours and then cooled to atmospheric tempera- 115–117 °C for 90 minutes (Table 7).211 The system remained
ture for the separation of FDCA solution. Product solution is at that pressure for about 15 hours at reduced temperature.
Scheme 19 Process scheme of the Avantium YXY® process for FDCA production.202
Scheme 20 The Corbion and Synvina approaches to PEF production.204,205
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Table 7 Reported commercial production of FDCA
Resarch center/ Oxidation Temp. Time Conv. FDCA

company Substrate Catalyst Oxidant environment (°C) (h) (%) yield (%) Ref.
BASF HMF Pt/C (STREM78-1611 100 Bar air D2O 100 20 100 95.2 203
Escat2431)
Synvina HMF and Pt/C 100 Bar air D2O 100 18 100a 78.3 204
(BASF/Avantium) di-HMF
Eastman/origin materials HMF Mn/Co/Br (0.9 : 2 : 3) 8.96 Bar air Acetic acid 132 2 100 89.4 208
ADM/DuPont HMF Metal salt CoBr2 42 Bar O2 Water solution 115 15 100 40 211
Braskem Furfural Au/TiO2; metal 3 Bar O2 1.02 equiv. NaOH 265 4 94.9 89 216
salt (Cdl2/FeCl2)
NOVAMONT HMF Pt/C 5 Bar O2 NaHCO3 100 4 100 95 218 219
Petrobras HMF Metal catalyst 124 Bar air NaOH (pH 10–14) 300 — >90 90 220 221
(Pt/Pd/Au)
VTT Galactaric Methyl trioxo 1 Bar air/5 Bar H2 MeOH 200 2 60 1.7 224, 225
acid rhenium
WARF HMF TEMPO Electrochemical Aqueous boric acid 40 — 99 >90 193, 197
(Pt & BiVO4 electrode) oxidation (pH = 9.2)
a
HMF and di-HMF independently.
The produced FDCA was then esterified to produce FDME with water and reused, can give 95% FDCA yield in the first
using an alcoholic mixture under carbon dioxide (CO2) atmo- two cycles, which is then reduced to 90% in successive
sphere.212 This process produces a more stable FDME, which cycles.218,219
can be then used to produce polytrimethylene furandicarboxy- The two-step FDCA production process was developed by
late (PTF) with FDCA.212 The production facility established at Petrobras.220,221 HMF produced from C6 sugars (sucrose,
Decatur (Illinois, USA) will start production in 2018. glucose, fructose) in the first step was separated using an ion
AVA Biochem, a subsidiary of AVA-CO2 founded in 2012, suc- exchange resin and then converted to FDCA in the second
cessfully started its first manufacturing unit for HMF in 2014 step.220,221 Utilization of sub-critical water effectively catalyzed
with the hydrothermal processing of biomass and then the the process and eliminated the additional catalyst requirement
production of downstream chemicals from HMF.213,214 AVA (Table 7). A high-pressure oxygen-rich source (air, oxygen etc.)
Biochem has set out to produce FDCA and the first phase will was used with a space velocity of 0.2–4 per hour to achieve the
start its production in 2019 with the capacity of 30 000 tons higher yield of FDCA with the maximum conversion of HMF in
per year, which will be then increased to 120 000 tons per an integrated process.220
year.215 This produced FDCA will be used in PEF production by VTT Technical Research Centre of Finland Ltd developed an
the AVA-CO2.214 industrial biological process for the production of FDCA from
Braskem has developed a process for the catalyzed pro- hexaric acid using modified enzymes.222,223 The environmen-
duction of FDCA (2,5-FDCA & 2,4-FDCA) using furfural instead tally friendly process used uronate dehydrogenase enzyme (EC
of HMF.216 Furfural was oxidized to sodium furoate over Au/ 1.1. 1.203) for the conversion of D-galacturonic acid into meso-
TiO2 catalyst in alkaline solution under oxygen pressure galactaric acid (mucic acid).224 Typically, galactaric acid was
(Table 7). Temperature (50 °C) and pressure (3 bar) were main- pressurized with hydrogen along with methanol and heated
tained overnight with constant stirring.216 Sodium furoate, for the production of FDCA over methyl trioxo rhenium cata-
after complete mixing with metal salt, was heated to 265 °C for lyst.225 The production of different furans and muconic acids
four hours and hydrochloric acid (HCl) was added ( pH = 1) for was dependent upon the process temperature, and 200 °C was
FDCA precipitation. A mixture of 2,5-FDCA & 2,4-FDCA in optimized for FDCA synthesis (Table 7). The VTT process is
the proportion of 0.68 : 0.32 was obtained and purified differentiated from others by first oxidizing C6 sugars to C6
using the acetone/chloroform extraction technique.216 aldaric acid and then dehydration to FDCA (Scheme 21).224,225
NOVAMONT developed the process for the production of Hexaric acid production has been commercialized with econ-
HMF and FDCA for the captive use of polymer production omic conversion but the furan production is still under devel-
based on the roots of the cardoon crop (the 5th generation opment for commercial production.222 This method is green,
MATER-BI®).217 An aqueous solution of HMF (2% W), cata- energy efficient and environmentally friendly but has low pro-
lyst (Pt/C) and sodium bicarbonate (NaHCO3) was heated duction volume.
(100 °C) in an autoclave for four hours (Table 7).218 The The electrochemical oxidation of HMF using the TEMPO
required pressure (5 bar) was maintained, regulating the mediator investigated by Choi was further developed by
oxygen flow rate (20 l h−1). The product mixture was filtered Wisconsin alumni research foundation (WARF) for the indus-
for catalyst recovery and the filtrate was acidified for FDCA trial production of FDCA (Fig. 3 & Scheme 16).193,197 This
precipitation at lower pH.218 The recovered catalyst, washed process has the advantages of high yield, a low-cost electrode
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Scheme 21 The VTT process for the production of FDCA.224,225
acting as the catalyst, ambient process parameters and higher suffer from low FDCA yield. However, these catalysts are associ-
faradaic efficiency and the utility of photoelectrochemical cells ated with the benefits of heterogeneous catalysis together with
(PECs).197 Due to these added benefits, WARF is now designing low cost and availability, and hence are good candidates for
a continuous process for the industrialization of this process industrialization.
with efficient product purification.226 Molecular oxygen is the most promising oxidant for oxi-
The industrial production of FDCA is being developed and dation of HMF to FDCA because of its availability and relatively
has been patented since 2000. Many research and develop- low cost, but high-pressure is usually required. Researchers
ment (R&D) organizations such as Corbion Purac, Mercurius have devoted their efforts to the commercial design of the cata-
Biorefining,74,205 and UC Davis, have also developed their pro- lytic aerobic oxidative production of FDCA from HMF utilizing
cesses and are now in the commercial design phase. A noble metal catalysts. Particle size, support, and the active
summary and comparison of the processes developed and phase play vital roles in the catalytic activity, together with
under development are presented in Table 7. As can be seen, process conditions such as temperature, pressure, flow rate
early success has been achieved for the commercial production and oxygen pressure. In term of the stability, Au-based cata-
of FDCA with good HMF conversion and FDCA yield; however, lysts are more selective than Pd and Pt-based catalysts due to
the processes are still facing various challenges in terms of their stability in the oxidizing environment. Deactivation of
product recovery, catalyst recycling, system integration and pro- the metal-based catalysts with process intermediates and by-
duction cost. products results in reduced catalytic activity in successive
cycles. Alloying of Pd, Cu or Pt with a Au-based catalyst to
produce a bimetallic catalyst can impressively upgrade the
Conclusion catalytic activity and selectivity. HFCA was detected as a
process intermediate during the Au metal-based alkaline
Biomass-derived FDCA is a promising feedstock for the pro- medium oxidation, whereas base-free oxidation proceeded via
duction of a variety of downstream chemicals. Its most impor- the DFF route. This phenomenon strongly suggests that alde-
tant application is in the production of polymers replacing hyde group oxidation in HMF is faster than alcohol group oxi-
fossil-derived terephthalic acid (TPA). Therefore, the economi- dation in basic medium. Isotope labeling technology has
cal manufacturing of FDCA and its commercialization will not revealed that the reaction mechanism is the same both in
only play a vital role in the production of biodegradable poly- basic and base-free environments. The oxygen that is merged
mers but also reward enormous financial advantages. into the HMF structure to yield FDCA is incorporated from
Numerous processes for the production of FDCA from HMF water molecules rather than the oxidizing agent (molecular
or directly from biomass-derived carbohydrates (one-pot syn- oxygen) available in the system. Molecular oxygen only plays a
thesis) have been investigated comprehensively in labs and role in catalyst reimbursement by replacing electron depo-
some processes are now growing industrially. These processes sition in the supported metal particles.
include catalytic (both chemical and biological), non-catalytic Fructose is mostly used for the direct conversion of carbo-
and electrochemical processes. Due to the high conversion hydrates to FDCA in a one-pot process, but the one-pot one-
rate and FDCA yield, the chemical-catalytic process emanates step process just gives a low FDCA yield, and the development
as the major FDCA synthesis route. The catalytic processes of the one-pot two-step process has increased the yield to
usually produce a higher yield than non-catalytic processes. some extent but the yield is not yet competitive. The one-pot
Heterogeneous catalytic processes seem to be more promising process is more encouraging for FDCA synthesis due to HMF
than homogenous catalytic processes because of the associ- instability, poor availability and potential economics.
ated merits such as easy separation of product and good recycl- Improvement in technology can make this process more cost-
ability of the catalyst. The most used catalysts are oxides of effective and feasible by excluding the barrier of HMF extrac-
noble metals; however, their high cost, poor availability and tion and purification.
recyclability are the major hindrances to their commercial Different electrochemical processes have been investigated
acceptance. Transition metal oxides are good alternatives but for the production of FDCA with the additional advantage of
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clean H2 production but the yield is very low. The yield can be trimetallic) will further improve the catalytic activity and stabi-
improved by employing more stable and active electrocatalysts. lity. However, the design of the catalyst and supports, com-
Electrochemical oxidation of HMF can be a good alternative bined with molecular simulation, may provide new insights to
route for FDCA production with simultaneous H2 production, guide the process.
which will serve as a green source of energy. Biocatalytic pro- (3) Experiments performed in alkaline solution make the
cesses can produce FDCA with comparative yields under mild process expensive and less green. Additionally, FDCA salt neu-
conditions. However, low HMF concentration in comparison tralization increases the operating cost and time with
to that of metal oxide catalysis is the primary barrier for the additional by-product formation. Base-free systems suffer from
practical application of the biological route. low yield and selectivity and, therefore, have not been
Industrial production of FDCA is being vigorously devel- researched extensively. As such extensive work is required to
oped, and early success has been made with good HMF conver- develop a catalyst focusing on base-free conversion systems
sion and FDCA yield. Most of the developed processes with with extended reactivity.
commercial potential are based on chemical-catalytic routes (4) The utilization of LCB fractions (cellulose, glucose, and
with metal catalysts; however, there are still various challenges fructose) for the one-pot production of FDCA can eliminate the
in terms of product recovery, catalyst recycling, system inte- HMF separation and instability problems. Direct utilization of
gration and production cost. these fractions will improve the economic feasibility with opti-
mized production technologies, as these are cheaply and abun-
dantly available. Designing a multifunctional catalyst with the
Future prospective combined effect of acid, base and metal sites will definitely
achieve this goal. The placement of acid/base sites in the
Substantial work has been done for the production of FDCA hydrophilic environment for carbohydrate dehydration to
from different bioresources with numerous catalysts, tech- HMF, and metal sites in the hydrophobic environment for oxi-
niques and environments. However, in spite of numerous lab- dation of HMF to FDCA are suggested. This will improve carbo-
scale processes, there is still no well-established market share hydrate absorbance on acid/base sites and HMF will desorb
of FDCA in the polymer market. Actually, HMF has an equal or quickly toward hydrophobic metal sites for oxidation. This
sometimes even higher price than FDCA, so the question scheme will improve the overall yield and selectivity. However,
arises as to why produce FDCA. Further developments are still how to efficiently and economically release glucose from LCB
required in oxidation methodologies for mass production in should be considered.
view of industrialization and commercial economics. Based (5) Ionic liquids and deep eutectic solvents with their multi-
upon this review, the following directions for future research functionalities and acid–base properties are in continuous
and development are recommended: development. The merger of the reaction chemistry of direct
(1) Extensive evaluation and correlation of different cata- conversions of fructose to FDCA with the solvents having cata-
lysts for the catalyzed oxidation of HMF to FDCA will help in lytic behavior will extend their utilization in one-pot synthesis.
process selection. Heterogeneous catalysts in comparison to These systems have reactive solvent properties but environ-
homogeneous catalysts and catalyst-free models are more mental concerns need to be addressed for their commercial
promising due to separation and recycling efficiencies. Non- utilization.
noble metal catalysts in contrast to noble metal catalysts are (6) The chemical kinetics and reaction mechanism of FDCA
not widely focused on. Transition metal catalysts are an econ- production either from HMF oxidation or directly from sugars
omical industrial alternative because of their cost, availability, have not been extensively studied. An in-depth understanding
and stability. Bimetallic catalysts (a combination of noble and of the reaction mechanism will facilitate the rational design of
non-noble metals) are also promising substitutes with robust, economical and efficient catalysts with extended life
improved catalytic ability and stability as compared to a mono- and efficient recycling.
metallic catalyst. Alloying with other metals such as copper or (7) Last but not least, the mass production of FDCA is
palladium boosts FDCA selectivity with extended recyclability exceptionally important for the establishment of a green
and stability. A comprehensive comparison of catalytic environment. Many developed methods are technologically
efficiency, stability, and the cost of these catalysts for appli- viable but financially exorbitant. Optimized process design is a
cation in FDCA production will increase the catalyst selectivity long-lasting challenge for researchers. The approach of inter-
and catalyst development methodologies. Further work in tran- disciplinary research, involving material engineering, chem-
sition metal catalyst and bimetallic catalysts will be more istry, and process design, may achieve this objective and
imperative. improve the process.
(2) Noble metal heterogeneous catalysts still suffer from
instability and degradation problems. Different techniques
such as cage encapsulated nanoparticles, CNT structure and
increased interaction between metallic particles and support Conflicts of interest
can avoid agglomeration, thus improving the catalyst stability
and reactivity. Using alloying techniques (either bimetallic or There are no conflicts to declare.
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Acknowledgements 23 W. Li, T. Zhang, H. Xin, M. Su, L. Ma, H. Jameel,

H. Chang and G. Pei, RSC Adv., 2017, 7, 27682–27688.
Authors are grateful to the supports of this work by National 24 S. Zhu, J. Wang and W. Fan, Catal. Sci. Technol., 2015, 5,
Natural Science Foundation of China (No. 21878176) and 3845–3858.
National Energy Administration Project of China (No. 25 B. Girisuta and H. J. Heeres, Levulinic Acid from Biomass:
NY20130402). Synthesis and Applications, Springer, Singapore, 2017,

pp. 143–169.
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A critical review article presented by Mr Muhammad Sajid, As featured in:

Dr. Xuebing Zhao and Prof. Dr Dehua Liu of Department of

Production of 2,5-furandicarboxylic acid (FDCA) from

The research progress on the production of 2,5-furandicarboxylic

chemical for bio-based polymer production, efforts have to be

Production of 2,5-furandicarboxylic acid (FDCA)

Introduction produce green bio-based chemicals.9,10 The U.S. Department

Critical Review Green Chemistry

Fig. 1 Typical production routes of bio-based polymers from lignocellulosic biomass.

Mr. Muhammad Sajid is a Dr. Xuebing Zhao is an Associate

Green Chemistry Critical Review

Critical Review Green Chemistry

Scheme 3 Reaction pathway of HMF oxidation to produce FDCA.

derived intermediates. The chemical conversion requires high

Chemical oxidative production of 2,5- Historical methods

Fig. 2 Schematic generalization of FDCA production processes from cellulose.

Green Chemistry Critical Review

applied as oxidants. t-BuOOH with only CuCl2 resulted in an

Heterogeneous catalytic methods

Critical Review Green Chemistry

Pt–Pb/C 1.25 M NaOH 1 Bar O2 2 25 99 100 93

Pt/C 2 equiv. Na2CO3 40 Bar air 6 100 69 99 94

The eﬀects of the supports have been investigated by produ-

Green Chemistry Critical Review

boost the catalytic activity. Among the diﬀerent counteranions

Pd/C 2 equiv. NaOH 6.9 Bar O2 6 23 71 100 95

Critical Review Green Chemistry

conditions.121,123 Increased FDCA yield was observed with an

line medium is selectively high (>99%) over the Au/HY catalyst

Table 3 Oxidative production of FDCA from HMF over Au support catalysts

Au/C 2 equiv. NaOH 6.9 Bar O2 6 23 7 100 95

Green Chemistry Critical Review

hydroxyl group, as compared to the aldehyde group, using the

Ru/C pH = 13 10 Bar O2 4 50 6.48 98.05 96

Critical Review Green Chemistry

Green Chemistry Critical Review

Fe-POP 10 Bar O2 100 10 100 79 149

nano-Fe3O4–CoOx — — 80 12 97.2 68.6 152

Critical Review Green Chemistry

Scheme 10 elucidates that the reaction mechanism of HMF

dation mechanism was investigated by Yan’s group over a poly

Green Chemistry Critical Review

porous carbon (denoted as NNC).165 Catalysts were named

highest yield of FDCA (80%) with complete conversion of HMF

Critical Review Green Chemistry

hydrophilic acidic sites for the preferred adsorption of carbo-

intensify its conversion to FDCA. This simultaneous process

Biocatalytic production of FDCA from HMF

Green Chemistry Critical Review

oxidize both the aldehyde and alcohol groups. Hexamethyl fur-

Scheme 13 Oxidation reaction of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) by HMFO.190

Critical Review Green Chemistry

suming the H2O2 present in the system. HFCA was observed

lyze the oxidation of aldehyde and alcoholic groups, respect-

Green Chemistry Critical Review

6H2 O þ 6e ! 3H2 þ 6OH ðIÞ

HMF þ 6OH ! FDCA þ 6H2 O þ 6e ðIIÞ

Critical Review Green Chemistry

Pd/C 0.6 <1 75 11 64 25

Au/C 0.6 — 100 1 <1 98

Green Chemistry Critical Review

Scheme 20 The Corbion and Synvina approaches to PEF production.204,205

Critical Review Green Chemistry