b i o m a s s a n d b i o e n e r g y 5 5 ( 2 0 1 3 ) 3 5 5 e3 6 9

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http://www.elsevier.com/locate/biombioe

Review

Advances in biomass transformation to

5-hydroxymethylfurfural and mechanistic aspects

Saikat Dutta a,**, Sudipta De b, Basudeb Saha b,*

a
Department of Chemistry, University of Florida, Gainesville, FL 32611, USA
b
Laboratory of Catalysis, Department of Chemistry, University of Delhi, Delhi 110 007, India

article info abstract

Article history: Biomass-derived 5-hydroxymethylfurfural (HMF) has been emerged as a key platform
Received 25 October 2011 chemical for the production of fine chemicals and liquid fuels. The direct transformation of
Received in revised form cellulose and lignocellulosic biomass into HMF in ionic liquids and organic solvents is most
30 January 2013 desired in terms of process economics and sustainability. The focus of this review is purely
Accepted 3 February 2013 on the HMF production from cellulose and lignocelluloses and mechanistic aspects of HMF
Available online 26 March 2013 formation in order to bridge the gap in understanding the factors responsible for selective
conversion and selection of catalyst. Additionally, present review is devoted exclusively to
Keywords: the latest developments, namely microwave-assisted degradation of cellulose to HMF,
Biomass application of solid acid and ionic-liquid catalysis to address their effectiveness for HMF
Cellulose production. Approaches for the cellulose transformation into HMF are especially empha-
Lignocellulosics sized in order to explore newer avenues of biomass as renewable feedstock for energy and
Dehydration mechanism chemicals.
Sustainable chemistry ª 2013 Elsevier Ltd. All rights reserved.

1. Introduction and hydrocarbons [5]. In this context, biomass-derived bio-

The ever increasing global demand for energy coupled with a
finite oil supply not only dramatically volatilizes the oil prices
but also challenges economic and industrial security world-
wide [1,2]. Continued reliance on petroleum feedstock will
lead to an unacceptable amount of greenhouse gas emissions
which has been the major concern [3]. Since the global con-
sumption of the liquid petroleum tripled in the ensuing years
[4], researchers and policy-makers have given priority to
explore alternative feedstock to avoid the most unfortunate
scenarios of energy crisis in future. Much of this attention has
been directed at liquid biofuels and in particular, biomass
feedstock which has been utilized as source for liquid biofuels
fuels feature tremendous potentials as renewable energy.
Biomass represents an abundant carbon-neutral renewable
resource and its enhanced use would address several chal-
lenges. Advances in process chemistry leading to a new
manufacturing concept for converting renewable biomass-
derived carbohydrates and biomasses into valuable chem-
icals and liquid fuels, offers the total sustainability that will
lead to a new manufacturing paradigm [6].
It is estimated that after about 15 years, up to 30% of raw
materials for the chemical industry will be produced from
renewable biomass [7]. The products from renewable resources
(fiber composite materials, starch- and protein-derived prod-
ucts) are already available in the market [8]. Current chemical

* Corresponding author. Tel.: þ91 011 2766 6646; fax: þ91 011 2766 7794.
** Corresponding author.
E-mail address: bsaha@chemistry.du.ac.in (B. Saha).
0961-9534/$ e see front matter ª 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.biombioe.2013.02.008
356 b i o m a s s a n d b i o e n e r g y 5 5 ( 2 0 1 3 ) 3 5 5 e3 6 9

research is focused on the production of scalable quantity of
platform chemicals to convert them into chemical building
blocks [9]. The platform chemicals can be produced from car-
bohydrates and biomass chemically or biologically. The
building-block chemicals can subsequently be converted into
multitude of high-value added bio-based chemicals (molecules
with multiple functional groups). HMF is an aromatic aldehyde
that exists naturally in coffee, honey, dried fruits, fruit juices
and flavoring agents. The concentration of HMF in food prod-
ucts varies widely, for example levels of HMF in wine, spirits
and fruit juices have been found to be as high as 200 mg dm3
[10]. HMF has been considered as feedstock of bioenergy,
building-block chemical, and medicine. Among the burgeoning
chemical technologies for alternatives, controlled elimination
of water from biomass-derived carbohydrates (catalytic dehy-
dration) has been extensively studied in the recent years to
access HMF [11]. In the past, HMF was produced preferentially
from a biopolymer, inulin by acid-catalyzed intramolecular
dehydration [12]. HMF holds special promise since the carbon
skeletons are identical to those obtained in cellulose and
hemicelluloses and can serve as a sustainable feedstock for
liquid fuels and chemicals as shown in Fig. 1. Common poly-
ester building-block 2,5-furandicarboxylic acid (FDCA) (1) can
be derived from HMF [13,14]. FDCA can be used as a replace-
ment for terephthalic acid in the production of poly-
ethyleneterephthalate and polybutyleneterephthalate [15].
Furthermore, the reduction of HMF can lead to products such as
2,5-bis(hydroxymethyl)furan (2), and 2,5-bis(hydroxymethyl)
tetrahydrofuran (3) (Fig. 1) which serve as alcohol components
in the production of polyesters, providing completely biomass-
derived polymers when combined with FDCA.
In addition, HMF is a precursor for the 2,5-dimethylfuran
(4) and 2-methylfuran (5) (Fig. 1) which are promising liquid
transportation fuels [16e18]. Moreover, HMF can serve as a
precursor in the synthesis of liquid alkanes for their use in
diesel fuel [19]. Moreover, HMF also successfully functions as
an anti-sickling agent that specifically binds to intracellular
sickle hemoglobin (Hbs) without inhibition by plasma and
tissue proteins or other undesirable sequences [20]. Deriving
HMF from biomass (cellulose, lignocellulose) would bridge the
growing gap between the supply and demand of energy and
chemicals. Doing so requires efficient chemical catalysts to
directly convert biomass into HMF selectively. In the produc-
tion process of HMF, degradation is associated and evidences
in support of both the open-chain and the cyclic fructofur-
anosyl intermediate pathways suggest that HMF degradation
occurs by fragmentation, condensation, rehydration, rever-
sion, and/or additional dehydration processes (Fig. 2) [21,22].
Unfortunately, the industrial use of HMF as a chemical inter-
mediate is currently impeded by high production costs [12].
HMF could be produced in high yields from sugars using high-
boiling organic solvents including DMSO, DMF, and mixture
of polyethyleneglycol with water over various catalysts,
including sulfuric acid and sulfonic acid resins which make
the process energy-intensive including tedious isolation pro-
cedures [23e26]. In pure water, biomass conversion is gener-
ally nonselective, leading to many by-products such as
levulinic acid, formic acid, and humins [27]. Application of
biphasic water-immiscible organic solvent to extract HMF
continuously from the aqueous phase resulted poor HMF
partitioning into the organic streams which consumes large
volume of solvents leading to high expenditure to purify the
HMF product [21,28].
Dumesic et al. introduced a modified biphasic system to
address limitations of HMF production by the acid-catalyzed
dehydration of 30e50% fructose (by mass fraction) feed with

OH
O OH
O HO OH
HO O O
n
OH Building Block Chemicals
Cellulose OH O O
HO OH HO OH
Hydrolysis
OH
OH (2) (3)
O O O
O O O
HO O
OH HO OH HO OH
OH
Cellobiose (1)
Hydrolysis O
OH
HO H
O Isomerization O Dehydration O (4)
HO H OH
OH HO O O
OH H
OH OH
Glucose OH H
Fructose (5)
Enzyme Inhibition Liquid Fuels
Hydrolysis
OH HO H
O O
HO H OH
O
OH OH
OH
Sucrose OH H

Fig. 1 e Production of HMF, from cellulose and carbohydrates, serves as feedstock for a range of chemicals and liquid fuels.
 b i o m a s s a n d b i o e n e r g y 5 5 ( 2 0 1 3 ) 3 5 5 e3 6 9
Rehydration Products
O Fragmentation
O
+ H
HO
formic Acid
O
levulinic Acid +2 H2O
O O
HO O HO
HMForg HMFaq
soluble polymers and
insoluble humins
Condensation Products
Fig. 2 e Schematic representation of reaction pathways for catalytic dehydration of fructose and by-product formation.
the addition of modifiers in both phases. The reactive aqueous
phase containing the catalyst and sugar was modified with
polar aprotic DMSO or NMP and hydrophilic polymer (PVP).
The water-immiscible (methylisobutylketone (MIBK)) phase
was used during the reaction to extract HMF and was modified
with 2-butanol in a batch process with simulated counter
current extraction and evaporation steps [15]. A microreactor
based continuous process has been introduced to perform the
HCl-catalyzed dehydration of fructose in aqueous medium at
high-temperature and -pressure (185  C, 1.7 MPa) in only 1 min
which produces maximum 540 mmol HMF per mol of fructose
[29]. The most promising part of this area is the application of
HMF as a platform chemical to produce liquid fuels like 2,5-
dimethylfural (DMF) [16] and HMF-ether (EMF) [30] for trans-
portation fuel. DMF, is a potential blendstock for gasoline and
diesel engines and has been derived from sugars by using solid
catalysts and H2 via the hydrogenationehydrogenolysis of
intermediate HMF product [31]. A major success in environ-
mentally sustainable HMF production process would provide
easy access to scalable production of DMF which would
enhance the application of biofuels. For the efficient and
economic production of promising biofuels, HMF must be
utilized as renewable feedstock.
2. Scope
In contrast to the facile HMF synthesis from food-biomass
including sugars using ionic liquids (ILs) [32], heterogenous
catalysts [33], so far only limited success has been achieved in
cellulose and lignocellulosic biomass conversion to HMF
perhaps due to the strong 3D network of polymeric sugar units
present in biomass. It is anticipated that an update on the recent
approaches of HMF synthesis from cellulose would be essential.
Thus, the present review will focus on various issues related to
the biomass transformations to HMF with a descriptive illus-
tration on results obtained by using new catalysts. Limited
studies on the direct conversion of lignocellulosic biomass and
algal biomass into HMF will be discussed. Attention is also paid
357
Products
O O
OH
O O O
H H
H2O fructofuranosyl
O and acyclic
intermediates
O
O
O OH
HO OH
O
Additional Dehydration
products
in discussing the mechanistic aspects of HMF formation, espe-
cially from glucose which includes very important step of
isomerization of glucopyranose to fructofuranose under mild
condition. Essentially, the review attempts to bridge the gap
between the mechanistic aspect of biomass transformation to
HMF and catalyst design by the discussion on the some poten-
tially important work at the intersection of sustainability and
ionic-liquid chemistry. This survey on recently research out-
comes is believed to be of interest to a broad readership.
3. Direct conversion of biomass into HMF
Transformation of abundant and inexpensive cellulosic
biomass through a non-fermentative process into biofuels
and bio-based products is extremely attractive target for
sustainable energy. In the recent years, research initiatives to
develop chemical catalyst for direct conversion of lignocellu-
losic biomass to valuable products including HMF have been
witnessed [16,34e37]. However, the hydrolysis of cellulose is
catalyzed either by enzymes or by inorganic proton-acids and
none of the present methods are yet cost-effective for large-
scale applications. Biomass is the most abundant renewable
resource, with an estimated global production of around
1.1  1011 t per year [38]. Lignocellulosic biomass (e.g. corn
stalk, wheat straw, switch grass, sugarcane bagasse) as well as
microalgae are being considered as a most promising feed-
stock for the production of fuels and chemicals [39]. The mass
fractions of major constituents of lignocellulosic biomass are:
cellulose (40e50%), hemicellulose (25%) and lignin (25%)
[40e42]. Structurally, cellulose is a linear polymer which is
formed from the anhydroglucose units into glucan chains.
These units are bound together by glycosidic linkages. Unlike
cellulose, hemicelluloses consist of different monosaccharide
units, and contain shorter and amorphous branches. It is due
to the amorphous nature, hemicelluloses are partially soluble
in water. On the other hand, lignin is a cross-linked racemic
macromolecule with molecular masses excess of 10,000 with
hydrophobic and aromatic nature.
358 b i o m a s s a n d b i o e n e r g y 5 5 ( 2 0 1 3 ) 3 5 5 e3 6 9
The depolymerization or hydrolysis of lignocellulosics into
intermediates that are more susceptible for chemical or bio-
logical transformations is a prerequisite “first-step” for the
production of biofuels and chemicals [43]. Under mild condi-
tions, the conversion of lignocellulose to low-molecular weight
intermediates such as HMF, furfural and levulinic acid is diffi-
cult because of its compact structure and chemical complexity.
The multiple hydroxyl groups of cellulose that form hydrogen
bonds between adjacent polymers, and create crystalline
structures (giving structural strength to plants), make cellulose
particularly difficult to digest and limit access to b-1,4-
glycosidic bonds or other functional groups for the enzymes
[44]. The breaking of this resistance is therefore an important
priority for the development of the lignocellulosic biorefinery
concept [45]. In this regard, biomass pretreatment is believed to
have a great potential for the efficiency and reduction of
expense of hydrolysis of carbohydrates to fermentable sugars
[46]. Low melting point ILs are however attracting attention as
solvents for the dissolution and homogenous processing of
cellulose [47]. It has been shown that crystallinity of cellulose
decreases during hydrolysis and becomes more accessible to
catalytic transformation [44]. The structural change results in
3e30 times faster hydrolysis rates, for amorphous cellulose
than for the high-crystalline cellulose [48]. It is a prerequisite
for achieving a successful conversion of cellulose to HMF is that
the catalytic system can induce facile transformation of
resulting glucose into HMF. Pioneering studies indicated that
the IL, 1-butyl-3-methylimidazolium chloride [C4MIM]Cl, has
been a powerful solvent for solubilizing cellulose as revealed by
NMR spectroscopy [49]. Since then, it has attracted much
attention and subsequent chemical hydrolysis and hydro-
genolysis of cellulose in ILs were reported [50].
3.1. Cellulose and lignocellulose to HMF
It is well-established that Lewis acidic metal salts in IL act as
efficient catalyst for the conversion of cellulose into furan
derivatives [30]. However, considering the toxicity of the metal
salts and environmental pollution, replacements were also
investigated with promising results. The strikingly impressive
yields of HMF obtained from untreated biomass and purified
cellulose fibers in DMAeLiCl solvent in the presence of chro-
mium chloride and IL were promising probably due to the use
of mineral acid, HCl, as co-catalyst since mineral acids are
powerful for cellulose hydrolysis to yield hexose sugar [51].
This was supported by the fact that HMF yields obtained by
Binder and Raines, were comparable with that obtained from
cellulose catalyzed by aqueous acid in ILs reported in the
patent literature [52]. Results of HMF obtained from direct
conversion of cellulose and lignocellulosic biomass are pre-
sented in Table 1 which points out the fact that for an opti-
mum concentration of IL additive [EMIM]Cl, HMF yield
considerably improves.
In 2009, Su and Zhang et al. reported a single-step conver-
sion of cellulose to HMF catalyzed by combination of metal
chlorides (CuCl2 and CrCl2) in [EMIM]Cl [37]. In this process,
combination of CuCl2 with CrCl2 (total loading 37 mmol/g) was
used which provided maximum 575 mmol HMF per mol of
cellulose at 120  C in 8 h. In this case, after separation of HMF
product by extraction using methylisobutylketone (MIBK) at
100  C, the performance of recovered [EMIM]Cl and the cata-
lysts was maintained for at least three repeated reaction cycles.
Chen and Qian et al. [53] found that ILewater mixtures
enhance the water dissociation constant (Kw) which resulted
efficient cellulosic biomass conversion. In this case, CrCl2 was
used as a catalyst in a mixture of [EMIM]Clewater, under
relatively mild conditions (140  C, 0.1 MPa pressure).
Consequently, in the absence of added acid catalyst, cellulose
in IL has been converted into water-soluble reducing sugars
resulting high total reducing sugar yield (up to 970 mmol per
mol of cellulose), or directly into the biomass platform
chemical HMF in high conversion (up to 890 mmol per mol of
the starting substrate) when CrCl2 was added to catalyze
aldoseeketose isomerization process (Fig. 3). Authors have
shown by using combination of experimental methods and ab
initio calculations that a significant increase in water dissoci-
ation constant Kw in the ILewater mixture and the dissociated
water appears to catalyze hydrolysis of biomass without
the need of CrCl2 or added acids. It was found that under the
same condition, water in IL can exhibit high Kw values (up to
three orders of magnitude higher that the pure water under
ambient conditions) which would be achievable only at high-
temperature or subcritical water conditions. Undoubtedly,
this remarkable enhancement of Kw promises for the future
technology development for the efficient conversion of cellu-
losic biomass.
Lewis acidic metal halide catalyzed biomass trans-
formation was further explored by Zhao and Li et al. [54] in
2009 when they reported an effective direct conversion of
cellulose into HMF using CrCl3 as a catalyst in [EMIM]Cl under
microwave irradiation by technically escaping a sugar sepa-
ration step. From different cellulose samples that they have
used for the transformation produced highest 620 mmol iso-
lated yield of HMF per mol of cellulose when irradiated at
400 W for 2 min (Table 2). Author’s results claim that this
method worked equally well regardless of cellulose type and
degree of polymerization.
Qi et al. [55] had explored the potential of CrCl3 as a catalyst
for the direct conversion of cellulose into HMF in [BMIM]Cl at
150  C under conventional water bath heating. A maximum
yield of 540 mmol HMF per mol of cellulose was obtained in
10 min reaction time. IL ([BMIM]Cl) solvent was recycled for six
consecutive cycles without a significant loss in catalytic ac-
tivity. Additionally, results also revealed that, neutral ILs with
Cl counter ion, such as [BMIM]Cl with CrCl3 was effective for
conversion, but the acidic ionic liquids with HSO4  as anion
had a negative influence on HMF formation.
More recently, Niktin and Mascal [56] have reported an
excellent method for the conversion of cellulose or lignocel-
lulosic biomass feedstocks into HMF via the solvolysis of 5-
chlorimethylfurfural (CMF). Since, CMF can be derived in
high yield (700e900 mmol CMF per mol of cellulose), this
process of producing maximum 860 mmol HMF from 1 mol of
CMF via hydrolysis presents an efficient entry into the value-
added product synthesis from biomass feedstock. In this
process, along with HMF, 100 mmol levulinic acid was also
obtained as a by-product. When using cellulose and corn
stover as substrates, the yields of HMF were 720 mmol and
691 mmol per mol of the respective substrates through the
conversion of biomass feedstocks into CMF with aqueous HCl
 b i o m a s s a n d b i o e n e r g y 5 5 ( 2 0 1 3 ) 3 5 5 e3 6 9 359

Table 1 e Synthesis of HMF from cellulose and lignocellulosic biomass.a

Biomass Solvent Catalyst, mmol Additive, mass fraction, % t (h) HMF (mmol mol1)b

Cellulose DMA-LiCl (10%) [EMIM]Cl, 40 2 40

Cellulose DMA-LiCl (10%) CrCl2, 250 6 150
Cellulose DMA-LiCl (15%) CrCl3, 360 6 170
Cellulose DMA-LiCl (10%) CrCl2, 250:HCl 100 2 220
Cellulose DMA-LiCl (10%) CrCl2, 250:HCl 100 2 330
Cellulose DMA-LiCl (10%) CrCl2, 250:HCl 60 [EMIM]Cl, 20 4 330
Cellulose DMA-LiCl (10%) CrCl2, 250:HCl 60 [EMIM]Cl, 40 1 430
Cellulose DMA-LiCl (10%) CrCl2, 250:HCl 60 [EMIM]Cl, 60 2 540
Cellulose DMA-LiCl (10%) CrCl2, 250:HCl 60 [EMIM]Cl, 80 2 470
Cellulose DMA-LiCl (10%) CrCl2, 250:HCl 60 [EMIM]Cl, 40 4 380
Cellulose [EMIM]Cl CrCl2, 250:HCl 60 1 530
Cellulose DMA CrCl2, 250:HCl 100 LiI, 10 3 <10
Cellulose DMA CrCl2, 250:HCl 100 LiBr, 10 3 <10
Cellulose DMA-LiCl (10%) CrCl2, 250:HCl 100 LiBr, 3 2 370
Corn stover DMA-LiCl (10%) CrCl2, 380 [EMIM]Cl, 10 6 160
Corn stover DMA-LiCl (10%) CrCl2, 380 [EMIM]Cl, 10 6 160
Pine sawdust DMA-LiCl (10%) CrCl2, 330 [EMIM]Cl, 15 5 190
Corn stover DMA-LiCl (10%) CrCl2, 100:HCl 100 [EMIM]Cl, 20 3 230
Corn stover DMA-LiCl (10%) CrCl2, 100:HCl 100 [EMIM]Cl, 40 3 240
Corn stover DMA-LiCl (10%) CrCl2, 100:HCl 100 [EMIM]Cl, 60 3 360
Corn stover DMA-LiCl (10%) CrCl2, 100:HCl 100 [EMIM]Cl, 80 3 310
Corn stover [EMIM]Cl CrCl2, 100:HCl 100 3 290
Corn stover DMA-LiCl (10%) CrCl2, 100:HCl 100 [EMIM]Cl, 20 3 260
Corn stover DMA-LiCl (10%) CrCl2, 100:HCl 100 [EMIM]Cl, 40 1 390
Corn stover DMA-LiCl (10%) CrCl2, 100:HCl 100 [EMIM]Cl, 60 2 480
Corn stover DMA-LiCl (10%) CrCl2, 100:HCl 100 [EMIM]Cl, 80 2 470
Corn stover [EMIM]Cl CrCl2, 100:HCl 100 1 420

a Cellulose was reacted at a concentration of 4 wt% relative to the total mass of the reaction mixture. Biomass was reacted at a concentration of
10 wt% relative to the total mass of the reaction mixture. Solvent composition is indicated by weight percent of LiCl relative to DMA with
additive concentrations relative to the total mass of the reaction mixture. Catalyst loading and molar yield are relative to moles of glucose
monomers contained in the cellulose in the starting material. Yields are based on HPLC analysis.
b Molar yield from pine sawdust assumes a typical cellulose content of 40%; yields from corn stover are based on cellulose analysis of 34.4%.

at 80e100  C in 3 h followed by a rapid hydrolysis of CMF in It was found that zeolite HeY is very efficient for the
boiling water in 30 s and extraction of HMF product with ethyl hydrolysis of cellulose into mono- and di-saccharide products
acetate. Very recently, Zhang and Tan et al. [57] have devel- in 1 h which supports the utility of Zeolite HeY (HeY, CVB 400).
oped a unique route for the direct conversion of cellulose into CrCl2 catalyst containing bulky N-heterocyclic carbene (NHC)
HMF using a combined CrCl2/zeolite/[BMIM]Cl catalytic sys-
tem at 120  C in which solid acid zeolite with moderate acidity
was employed to promote the cellulose hydrolysis and to
slowdown the decomposition process of HMF product (Fig. 4). Table 2 e Results of HMF production from cellulose in
[EMIM]Cl under microwave irradiation.a
Entry Substrate Time HMFb TRSc
OH OH
OH (min) (mmol mol1) (mmol mol1)
O HO O
HO O O
HO 1 Avicel 2 610 160
O HO OH
OH HO n-2 OH 2 Spruce 2 530 260
3 Sigmacell 2 550 230
Cellulose
4 a-Cellulose 2 620 200
Cl or Cl 5d Avicel 240 170e 450
120-140 oC N N N N
R R 6d,f Avicel 240 20 150
Me 7 Avicel 2 16 97
H2O CrCl2
OH a Unless otherwise specified, reaction condition: cellulose
O O (100 mg), and CrCl3$6H2O (10 mg) in [C4MIM]Cl (2.0 g) under 400 W
O HO O MI.
HO OX
OH b Isolated yield unless otherwise specified.
HMF c Determined by the DNS method.
X = H or glucosidic unit (1-15) d Heated by oil-bath at 100  C.
TRS = 97% (R = Et) 89% (R = Et)
e Determined by spectrophotometrically at 282 nm.
f Three equiv of 2,20 -bipyridine (17.5 mg) were introduced there-
Fig. 3 e Conversion of cellulose substrates with and
after the addition of CrCl3$6H2O (10 mg).
without CrCl2 catalyst.
360 b i o m a s s a n d b i o e n e r g y 5 5 ( 2 0 1 3 ) 3 5 5 e3 6 9

OH OH O
OH Zeolite NHC-CrCl2 O
O HO HO O
O O HO HO H
HO O IL [BMIM]Cl
OH n OH OH
OH
Cellulose Glucose HMF

Fig. 4 e Conversion of cellulose to HMF over zeolite containing NHCeCrCl2 catalyst.

(1,3-bis(2,6-diisopropylphenyl)imidazolylidene) and saturated
NHC (1,3-bis(2,6-diisopropyl)phenylimidazolinylidene) origi-
nally introduced by Ying et al. [58]. Out of these NHC based
catalysts, IpreCrCl2 catalyzed reaction produced maximum
47.5 mol% HMF yield at 120  C in 12 h (Table 3).
Heteropolyacids and heteropolytungstate salts were
known as effective catalysts for the hydrolysis of microcrys-
talline cellulose that produces sugar alcohols selectively and
in carbon-efficient way [59e61]. Since heteropolyacids are
important catalyst in biomass transformation, certain modi-
fications of the heteropolyacids may result selective formation
of targeted chemicals from cellulose-biomass. Remarkably
high HMF yield (527 mmol HMF per mol of substrate) was
obtained by Wang et al. from a one-pot conversion of cellulose
by using a BrønstedeLewis-surfactant-combined hetero-
polyacid Cr[(DS)H2PW12O40]3 (DS ¼ OSO3C12H25 dodecyl sul-
fate) as heterogenous catalyst at 150  C in 2 h [62]. This dual
acidic (Brønsted and Lewis) material overcomes the diffusion
problem in the solidesolid interaction and promotes the re-
action rate by providing a hydrophobic environment, suffi-
cient for protecting HMF from further decomposition and
decreases by-products formation (Fig. 5).
Using micellar catalyst Cr[(DS)H2PW12O40]3, untreated
lignocellulosic biomass such as corn stover and husk of Xan-
thoceras sorbifolia Bunge was converted to HMF in 308 mmol
and 355 mmol yields for 1 mol of the respective substrates at
150  C in 2 h. The major advantage of this micellar catalyst
was the easy separation process, in which after HMF extrac-
tion with MIBK, catalyst Cr[(DS)H2PW12O40]3 exists between
the water phase and organic phase as an emulsion could be
easily separated. Want et al. also suggested that higher cata-
lytic activity of this catalyst was due to the dual Brønsted
Table 3 e Conversion of cellulose to HMF by chromium
catalysts in [BMIM]Cl.a
Entry Catalyst Additives Time (h) HMF
(mM) (mmol mol1)b
1 IpreCrCl2 6 370
2 IpreCrCl2 H2O (20 6 134
3 IpreCrCl2 HCl (20) 6 520
4 IpreCrCl2 6 þ 3c 430
5 IpreCrCl2 6 þ 3c 475
6 SIpreCrCl2 6 210
7 IpreCrCl3 6 240
8 CrCl2 6 340
a Reaction conditions 1.5 g of [BMIM]Cl, 100 mg of cellulose, 100 mg
of zeolite, 0.24 mmol of catalyst, 120  C in air.
b Isolated yield.
c The reaction system was extracted two times.
and Lewis acidities and micellar structure with hydrophobic
groups.
Direct conversion of cellulose to HMF using acidic ILs cat-
alysts, such as [EMIM]HSO4, has been reported in the recent
years. 13C NMR spectroscopic results confirmed that cellulose
conversion to HMF at a temperature range of 80e120  C is
progressed via the formation of glucose as intermediate [63].
Cho et al. have adopted a high throughput method for
screening several combination of metal chlorides catalysts in
[EMIM]Cl solvent for direct transformation of cellulose into
HMF. The authors demonstrated that CrCl2eRuCl3 combina-
tion in 4:1 molar ratio which was most effective, giving nearly
600 mmol HMF yield per mol of cellulose at 120  C in 2 h [64].
This method was also successful for the scale-up process of
HMF production from cellulose. The same synthetic strategy
was applied for the conversion of lignocellulosic raw materials
such as Reed (Phragmites communts, Trin.) as a model ligno-
cellulosic raw materials which produced 410 mmol HMF and
260 mmol furfural from 1 mol of the starting substrate in 2 h at
120  C by using CrCl2/RuCl3 catalyst (4:1) in [EMIM]Cl solvent.
More recently, HMF was produced from cellulose with
maximum 619 mmol yield per mol of the substrate using CrCl3
and LiCl in 1:1 molar ratio in [BMIM]Cl at 140  C under mi-
crowave irradiation for 40 min [65]. Investigation on the effect
of the catalyst dosage on the HMF yield revealed that increase
in catalyst loading led to improve HMF yields. In this case,
more catalyst (R ¼ 1.5:1) accelerated the formation of HMF
from cellulose, while it also favored the rehydration of HMF
product into levulinic acid, which offset increased in HMF
yield. With an advantage of easily recyclable CrCl3/LiCl cata-
lyst, HMF was also produced from wheat straw as feedstock
with maximum 614 mmol yield per mol of the substrate in
15 min at 160  C in [BMIM]Cl which is comparable to that ob-
tained from pure cellulose.
Microwave-assisted degradation of cellulose to HMF has
gained significant attention in the recent years. Microwave
dielectric heating has not only become a popular tool in
common organic laboratories ever since Gedye [66] and
Giguere [67], have adopted this method, it has been shown
Cr[(DS)H2PW12O40]3
miceller catalyst
OH
OH
O HO O
O O O OH
HO O 0
OH n Water, 150 C
2h HMF
cellulose OH
52.7%
Fig. 5 e Direct conversion of cellulose into HMF by miceller
BrønstedeLewis acidic CreHPA catalyst.
 b i o m a s s a n d b i o e n e r g y 5 5 ( 2 0 1 3 ) 3 5 5 e3 6 9
that controlled microwave heating dramatically decreases
reaction time, increases product yield, and enhances product
purity by reducing unwanted side reactions mainly due to the
flash heating effect [68]. This method has shown to be more
effective for hydrolysis and transformation of glycans into
small organic platform molecules and degradation of carbo-
hydrates into chemicals over conventional heating. Most
recent literature report also evidenced similar observation
that microwave-assisted heating reactions offered higher
yield of the desired platform chemicals in shorter time as
compared to the conventional heating experiments [69].
3.2. Biomass to HMF in biphasic media without IL
Apart from using ILs as a catalyst or solvent or both, a signif-
icant progress has been made for direct conversion of cellu-
losic biomass to HMF and furfural using Lewis and Brønsted
acidic catalysts in mixed aqueous medium containing lignin
derived solvents, such as alkylphenols (2-sec-butylphenol, 4-n-
hexylphenol, 4-propylguaiacol, etc.) [70]. A new biorefining
strategy for converting hemicellulose fraction of lignocellu-
losic biomass to furfural by utilizing mineral acids in biphasic
solvent systems consisting 2-sec-butylphenol as an organic
phase and water as an aqueous phase has been demonstrated
by Dumesic and co-workers [71]. This method of furfural
production is also applicable for efficient production of HMF.
Reasons for alkylphenols being preferred solvents over
expensive ILs are as follows: (i) high partition coefficients of
alkylphenols for extraction of furanics; (ii) alkylphenols do not
extract mineral acids from aqueous phase; (iii) higher boiling
points of alkylphenols than the desired furanics product; and
(iv) alkylphenols are derived from biomass (i.e., lignin). Apart
from using biomass-derived solvents in biphasic media for
efficient production of platform chemicals, use of pure tetra-
hydrofuran (THF) and water as a single phase solvent has been
effective when ordered porous silicas (one inorganic SBA-15
type silica, two ethane-bridged SBA-15 type organosilicas)
were used as catalysts [72]. Under similar reaction conditions,
catalysts containing ordered pore structures improved HMF
selectivity in the product from 60 to 75% in comparison to
the non-ordered catalyst. Complete analysis of the recovered
silica catalysts suggests the hydrolytic cleavage of the acid
sites, which can be partially recaptured by the free surface
hydroxyl groups of the silica surface. 2-sec-butylphenolewater
biphasic solvent system has also been demonstrated as an
effective alternative for expensive ILs-based solvent for com-
bined Lewis acid (AlCl3) and Brønsted acid (HCl) catalyzed
conversion of biomass to HMF, in which both the acid cata-
lysts remained in the aqueous phase [73]. Lanthanide-based
Lewis acids (YbCl3, DyCl3 and LaCl3) were also effective cata-
lysts for the conversion of glucose to HMF in aqueous-sec-
butylphenol solvent [74]. Recently, biphasic aqueous-THF has
also been successfully used for the production of HMF in the
presence of AlCl3,6H2O as a catalyst [75,76].
3.3. Algal biomass to HMF
Compositions of lignocellulosic biomass, which contains
lignin (w26%), cellulose (w44%), and hemicelluloses (w30%),
vary with plant cell type, geography or environment. The
361
components are intertwined in a complex composite matrix
[77]. Investigations suggest that it is rather difficult to trans-
form cellulose biologically and/or chemically. Unlike cellu-
lose, hemicellulose consists of different monosaccharide
units, and contained shorter and amorphous branches. In this
context, marine carbohydrate biomass can be preferable from
several points of views: First, carbohydrate content is high
with no lignin and the major carbohydrate component, called
galactan, can be readily extracted from the original feedstock.
For example, Gelidium amansii, a red algae species commonly
found in the shallow coast of many East and Southeast Asian
countries contains a large portion of carbohydrates (approxi-
mately 75e80% of total dried mass, agar/cellulose ca. 4:1).
Second, it grows well naturally; thus, multiple cropping is
possible without feeding additional fertilizer. Third, CO2
remediation is much more effective than for land plants, thus
reduces greenhouse gases.
Algal biofuels may be a sustainable alternative to petro-
leum energy, yet far from the production on a commercial
scale [78]. However, considerable investment has been made
to these technologies [79]. There have been only limited ef-
forts to study the fermentation of algal biomass to produce
ethanol [80], but otherwise applications of polymeric carbo-
hydrates from algal biomass have barely reflected the US DOE
“TOP 10” lists of value-added chemicals from biomass. Algal
polysaccharides would be depolymerized to recover C5 and C6
sugars that could lead to several of the DOE “Top 10” chem-
icals that are more readily obtained from algae than plants.
Unique potential of algal polysaccharides as source of chem-
ical building block was illuminated by Kim et al. on macro-
algae-derived agar transformation to HMF with yield mass
fraction of 10% of the agar feed (Fig. 6) [81]. The single-step
transformation of agar primarily from red microalgae into
HMF in the presence of solid Brønsted catalyst (Dowex 50WX
(50% by mass fraction)) in DMSO at 110  C for 5 h was reported.
Most recently, microalgae derived agar has been effectively
converted to promising biofuel 2,5-dimethylfuran with
maximum 270 mmol yield per mol of the substrate [82]. This
one-pot process using a catalytic system comprising formic
acid and Ru/C progressed through the formation of HMF as
intermediate. Although the yield of HMF was not quantita-
tively measured, the yield can estimated to be more than 60%
based on measured DMF and unconverted intermediates in
the final product [82].
From a structural point of view, agarose is a major
component of agar that has two features distinguishable from
starch or cellulose. First, agarose has a highly strained addi-
tional cyclic unit corresponding to 3,6-anhydrogalactose that
can lead to higher reactivity under acidic conditions. Second,
agarose has a different linkage pattern between repeating
units. Unlike amylose (a linear polysaccharide part of starch)
and cellulose, the repeating units of which are linked by
OH O SO3H O
OH O OH
O
HO O
O
O DMSO HMF
OH n
110 0C, 5h
Agar 10%
Fig. 6 e Single-step conversion of macroalgae-derived agar
into HMF in the presence of a solid Brønsted acid.
362 b i o m a s s a n d b i o e n e r g y 5 5 ( 2 0 1 3 ) 3 5 5 e3 6 9

C1/C4 bonds, the repeating unit of agarose, agarobiose, is OH OH

linked by C1/C3. Therefore, it can be assumed that agarose Mutarotation
O O
HO HO OH
would be cleaved under acidic conditions to form a carboca- HO HO
tion at the C3 position (1) and then 3-deoxy-2-keto galactose OH OH
α GlucoseOH β Glucose
(2) consequently; 5-membered-ring closure would give a
furanose-type intermediate as a precursor of HMF. +[EMIM]MClx -[EMIM]MClx
Besides chemical methods for biomass conversions, bio-
OH OH H
logical transformations may also benefit from the presence of Cl Im
O Cl O
relatively exotic C5 and C6 monomers in algae. For example, HO HO M Cl
HO Im HO
the fermentation of fructose and rhamnose can lead to a M Cl
OH OH O Cl
higher production of 1,2-propanediol compared to starting O Cl
H
from glucose [83]. Therefore, algal polysaccharides rich in
OH Isomerization
sugar units could be more easily accessible for commodity HO O
O O
chemical production. Given the diversity of algal species and HO OH H
their biochemical compositions, as well as varying cultivation HO
OH
conditions, it will be important for carbohydrate processing β Glucose HMF
and recovery methods to be robust. A recent report describes a
+[EMIM]MClx
cellulose hydrolysis technique that is effective in concen- Cl Im
Cl O
trated sea water, which might be useful in the treatment of OH O Cr Cl -EMIM]MClx HO H OH OH
biomass from marine algae [84]. O H H OH
HO OH H
OH OH H Fructose
4. Mechanism of HMF formation
Fig. 7 e Proposed metal halide interaction with glucose in
[EMIM]Cl. CrCl2 catalyzed mutarotation leading to the
In-depth understanding of biomass transformation process
interconversion of a- and b-glucopyranose anomer.
remains highly important to attain more insights on the fac-
tors control the transformation. Until now, most of the
mechanistic studies on HMF formation are focused towards
transformation of sugar derivatives to HMF in ILs and aqueous Zhang and co-workers reported dehydration of glucose into
medium based on the 1H and 13C NMR spectroscopic evi- HMF under microwave-assisted heating. It is proposed that
dences. Zhang et al., in their pioneering work of glucose to CrCl3 in [BMIM]Cl forms complexes [BMIM]m[CrCl3þn] (n ¼ 1e3)
HMF transformation, using various combinations of ILemetal [54]. A mechanism was proposed in which bonding of Cr to
salts, showed that glucose, when dissolved in the [EMIM]Cl, an enediol intermediate results from the ring-opening of the
predominantly exists as a-anomer [85]. The interaction of the a-glucopyranose anomer resulting from cellulose hydrolysis.
metal chloride and eOH group of carbohydrate proceeds Additionally, it is proposed that CrCl3  anion coordinates to
through hydrogen bonding and surprisingly, the same inter- enediolate intermediate, which subsequently undergoes the
action is unable to cause mutarotation (a-anomer to b-anomer hydrogen transfer (H-shift) for the isomerization of glucose to
conversion). 1H NMR chemical shift of the six eOH resonances fructose (Fig. 8). It was assumed that the role of the IL media is
is sharp in case of the pure glucose however, in the presence to provide a noncoordinating polar environment to stabilize
of catalytic amounts of CuCl2 the eOH resonances shift upfield catalytically active low-coordinate metal species.
and broadened which indicates exchange through interaction Hensen et al. recently unraveled the molecular-level de-
with the metal. NMR spectroscopic investigations on the tails of the unique reactivity of chromium(II) chloride towards
bonding motif of the sugaremetal interaction by adding stoi- selective glucose dehydration at 100  C in [EMIM]Cl by using
chiometric glycerol or glyceraldehyde to the glucose solution combined kinetic experiment results, in-situ X-ray absorption
revealed that the glyceraldehydes exist as a hemiacetal dimer spectroscopy (XAS), and density functional theory (DFT) [86].
in [EMIM]Cl, thus representing an effective mimic for gluco- The reaction proceeds through glucose isomerization to
pyranose. Glyceraldehyde affected the inhibition by reducing fructose, followed by the dehydration to HMF in 620 mmol
the HMF yield to less than 200 mmol per mol of the substrate. yield per mol of the substrate in 3 h. XAS study at 100  C in
In the presence of the 2,20 -bipyridine, reaction essentially 10 min and 180 min time intervals suggested that Crþ2 is co-
stops resulting recovery of 90% starting glucose. The results of ordinated by Cl. DFT calculations confirmed the structure of
the glycerol and glyceraldehyde competition studies showed
that the metal interacts with the hemiacetal portion of glu-
OH OH OH
copyranose. Zhang et al. disclosed the efficiency of the CrCl2 in
comparison to the CuCl2 and FeCl2 and their different bonding HO HO HO
OH OH OH
motif with glucose. To explain the results with CrCl2 catalytic
H H H H H
system, participation of a CrCl3  anion in proton transfer HO HO HO H
facilitated the mutarotation of glucose in [EMIM]Cl. Based on O O O O O O
this understanding, it can be argued that the presence of
CrCl3  is to facilitate a formal hydride transfer, leading to Fig. 8 e Scheme showing the H-shift that takes place
isomerization of glucose to fructose (Fig. 7). during glucose isomerization.
 b i o m a s s a n d b i o e n e r g y 5 5 ( 2 0 1 3 ) 3 5 5 e3 6 9 363

OH
open-Glu-CrCl3-
OHH

HO H O
Cl CrCl2
+H+ HO O Cr
Cl Cl
deprot-O1-Glu-CrCl3-2
HO -H+
HO OH OH deprot-O2-open-Glu-Cr2Cl5-2

O OHH
O Cl
Cl O 2- HO H O Cr
Cl Cr Cl Cl
HO O Cr Cl
Cl Cl
-H+ H-shift
OH
-
D-GP-CrCl3
OHH deprot-O1-open-Fru-Cr2Cl5-2
HO
HO OH H Cl
HO O Cr
O O Cl
HO O Cr Cl
Cl OH Cl Cl
Cl Cr Cl
OH OH
OH CH2OH +H+
OHH
glucose O OH H Cl
fructose OH HO OH Cr
Cl Cl
Cl Cr HO O Cr Cl
Cl
Cl Cl
CrCl2
D-FF-CrCl3-

Fig. 9 e Catalytic cycle for the isomerization of glucose in presence of CrCl2 in a model MMIM ionic-liquid medium. D-FF [ D-
fructofuranose, D-GP [ D-glycopyranose.

chromium(II) chloride in [EMIM]Cl in which geometry opti- typical four-coordinate geometry of CrII. The DFT based free-
mization of a cluster model containing two CrCl2 units and energy calculations suggested the involvement of mono and
five ion pairs of the ionic liquid led to the formation of two binuclear Cr complexes. The free-energy barrier to the for-
noninteracting square-planar CrCl4 2 units by supporting mation of open form of D-glucose is low and does not depend

OH OH
HO O O
[EMim][BF4] HO
HO HO
HO HO
OH OH
Glucopyranose
1
Path A
[EMim][BF4] RT
SnCl4
OH OH OH
HO O O HO OH
HO
HO Heating HO HO
H O O H O Cl O H O Cl O
Im H H H
Cl Cl Cl Sn Cl Sn
Sn Cl Cl
Cl Cl Cl Cl
Im 4
2 3
Part B

HO
HO O O OH OH OH
O OH HO
H H
OH Cl O
OH OH O Sn Cl
HMF Fructosefuranose 5 H Cl Cl

Fig. 10 e Proposed process of glucose conversion to produce HMF catalyzed by SnCl4 in [EMIM]BF4.
364 b i o m a s s a n d b i o e n e r g y 5 5 ( 2 0 1 3 ) 3 5 5 e3 6 9

HO HO HO O
O O +GeCl4
HO HO HO
HO OH HO HO
OH O
1 OH 2 OH H O
Ge
Cl Cl
3 Cl Cl

HO H Cl Cl Cl HO
O OH -GeCl4 OH
OH OH O Ge Cl HO
HO
OH O H O
HO H O
OH Ge
OH OH Cl Cl
H2O Cl Cl
5 4
HO OH
HO O
O OH X- OH
OH
Base O
OH HO O
X- H
OH HO
Furanosyl Nucleophile O OH HMF
oxocarbenium ion OH
X
OH

Fig. 11 e Proposed mechanism of HMF formation from glucose catalyzed by GeCl4.

on the nuclearity of the Cr complex. The free-energy change
for the ring-opening of D-glucose coordinated to a single Cr
center compares favorably to that of the noncatalytic ring-
opening. The isomerization of glucose to fructose requires
an H-shift between C2 and C1 of the open form of the sugar
(Fig. 9) involving an enediol intermediate. Open form
when stabilized by a Cr center, endothermic H-shift step
(þ68 kJ mol1) with an overall free-energy barrier is calculated
to be 120 kJ mol1. Glucose intermediate is stabilized by a
second Cr center (Fig. 9). However, the energy barrier to the
direct H-shift from C2 to C1 in this complex is negligible
(9 kJ mol1). The product Cr dimer which contains the open
form of D-fructose deprotonated at O1 (Fig. 9) and the resulting
complex is more stable than its mononuclear counterpart.
The overall activation free-energy barrier 63 kJ mol1 for the
binuclear pathway compares favorably with the barrier for the
mononuclear pathway.
A recent report on the mannose and other unutilized sugars
(e.g. galactose, lactose, tagatose, psicose and sorbose) conver-
sion to HMF in organic and IL media using Cr catalyst reveals
that mannose and glucose share a common intermediate
fructose in the key step of aldose-to-ketose conversion, via 1,2-
hydride shift during the transformation as revealed by the
isotope labeling studies [87]. This investigation disclosed the
mechanistic insights into the role of chromium and hexose
structure in HMF formation. Reactivity of psicose, the C-3
epimer of fructose and exists as 50% furanose tautomers in
DMSO, and sorbose also revealed that aldose-to-ketose con-
version occurs via a 1,2-hydride shift, which is followed by
dehydration of the furanose tautomer.
Hu et al. studied the mechanism of SnCl4 catalyzed glucose
to HMF conversion in ionic liquid [EMIM]BF4 [88]. It was pro-
posed that when interacting with Snþ4 center, acyclic and five-
or six-membered-ring intermediates form. Addition of alco-
hols like ethanol, ethylene glycol and 1,3-propanediol in 1:1
molar ratio resulted poor glucose conversion (less than
50 mmol per mol of glucose) suggests that the alcohol can
form a five-membered-ring-chelate with Sn, resulting signifi-
cant inhibition of the glucose conversion, whereas ethanol or
1,3-propanediol, which can form acyclic or six-membered-
ring-chelate complex with Sn. This suggests more stability
of the five-membered-ring-chelate with the SnCl4 [88]. 1H NMR
spectroscopic investigation revealed that both a-glucose and
b-glucose exist in pyranose form in [EMIM]BF4 and when SnCl4

H3C H3C
S O S O OH
H3C H3C
OH OH H O CHO
OH H OH O OH
O H
O -H2O O -H2O -H2O O CHO
HO OH HO OH
OH HO HO
CH3 O H C A
CH3 3
HO O S HO S O
HO O S
CH3 H3C
CH3
-f/ -f 2 3

Fig. 12 e Proposed mechanism for the dehydration of D-fructouranose forms (a-f/b-f) to HMF in DMSO at 150  C.
 b i o m a s s a n d b i o e n e r g y 5 5 ( 2 0 1 3 ) 3 5 5 e3 6 9
H
Cl
HO OH a HO OH HO
O O
HO HO
HO OH
H2O HO
fructose
Fig. 13 e Putative mechanism for the dehydration of fructose in imidazolium chloride with boric acid as promoter.
interacts with glucose at room temperature, the signals cor-
responding to the eOH of glucose (HOH) disappeared due to the
formation of intermediate 2 (Fig. 10). At higher temperatures
(80e100  C), a new signal at d 4.90 ppm was identified which
showed an increased intensity with the increase in tempera-
ture suggests a new interaction between glucose and SnCl4
which corresponds to intermediate 2 (Fig. 10). The proposed
intermediate 2 could induce the formation of the intermediate
4, that consisted of glucose in straight-chain. Intermediate 4
was further converted into b-glucopyranose and enediol in-
termediates 5 which then transformed to HMF. Authors
claimed the formation of fructose based on their HPLC data
when the reaction was run at 80  C for 3 h.
In the case of GeCl4 catalyzed conversion of glucose to HMF
in [BMIM]Cl reported by Zhao et al., 13C NMR evidence suggests
that the starting glucose exists in a-pyranose and b-pyranose
in [BMIM]Cl at room temperature [89]. Upon addition of GeCl4,
new signal at d 76.4 ppm was observed in 13C NMR. This sug-
gests the formation of a hypervalent germanium compound. It
is proposed that GeIV can interact with the two O atom of 1,2-
dihydroxy group of a-glucose to result a stable intermediate 3
(Fig. 11). As proposed by Zhao et al., fructose resulted as an
intermediate from glucose through an enediol intermediate
catalyzed by GeCl4 (Fig. 11). The fructose then eliminates one
water molecule to form the fructofuranosyl oxocarbenium
ion. Due to the basicity and nucleophilicity of the halide ion
(X), oxocarbenium ion loses HX to form the enolic species
through the nucleophile or the base assisted pathway, fol-
lowed by loss of two water molecules to result HMF.
The mechanism of HMF formation from fructose has been
a topic of debate over the years, in which case both pathways
involving cyclic intermediates as well as an open-chain
mechanism have been proposed. It was several years ago,
Antal et al. concluded that the cyclic mechanism is the more
plausible of the two [22]. A cyclic intermediate formation was
confirmed by NMR spectroscopic investigation of the D-fruc-
tose dehydration in pure DMSO-d6 at 150  C [90]. The key in-
termediate in the reaction was identified as (4R,5R)-4-
hydroxy-5-hydroxymethyl-4,5-dihydrofuran-2-carbaldehyde
from 1H and 13C NMR spectrums in which case DMSO acts as a
potential catalyst for the conversion (Fig. 12). In a recent study,
Riisager et al. showed that the isomerization of glucose to
fructose occurs via two different routes when using boric acid
365
tautomerization
OH H Cl HO
HO
O O OH O
HO H O
HO HO
Cl
HO
HO
HO
H2O
HO
HO O O
O O
H2O HO A
as a promoter in IL [91]. Based on the computational modeling
with DFT calculations at B3LYP level using basis sets LACVP*
and 6-31G*, the formation of a 1:1 glucoseeborate complex
suggests that the process involves an enediol mechanism
(Fig. 13). Raines et al. [51] proposed that Cl ion, obtained from
imidazolium IL, functions as “base” and “nucleophile”. Simi-
larly Cl acts as nucleophile in the boric acid catalyzed process
via intermediate A (Fig. 13).
In the case of AlCl3 catalyzed transformation of glucose to
HMF, the dehydration is believed to occur by the hydrolysis
AlCl3 in water resulting a cationic species [Al(OH)(H2O)5]þ2
which acts as a potential electrophile when reacting with a-
glucopyranose and form Al(OH2)5-glucose intermediate [92].
The intermediate is then possibly converted to ketohexoses by
a hydride transfer process resulting fructofuranose through
cyclization. This step is similar to the mechanism described
by Davis et al. using SnCl4 catalyst [93]. It has been proposed
that the transformation of fructofuranose to cyclic interme-
diate occurs via a cyclic mechanism assisted by proton that
generates during AlCl3 hydrolysis. It is to note that possibil-
ities of Cl to act as a base was accounted for abstraction of
proton from the oxonium ion.
5. Future directions and conclusions
Biomass conversion to value-added chemicals is the current
challenges. In this regard, solid catalysts have played a crucial
role due to their superior selectivity and cost-effectiveness
[94e96]. The development of bio-products at a large indus-
trial scale requires that their quality and cost meet consumer
demand. The final cost of bio-products includes the price of
the starting feedstock, but it also depends heavily upon the
processing cost. A judicious choice of biomass conversion
strategy could be essential to achieve a cost-effective devel-
opment of biomass utilization towards bio-products.
There are cases in which biomass conversion to chemicals
and fuels fulfills the green chemistry principles. Thus, the
conversion of starch to isosorbide via glucose and sorbitol or
the aerobic oxidation of glucose could be achieved with 100%
atom economy in aqueous solutions over heterogenous cata-
lysts that can be recycled repeatedly. On the other hand the
sustainable nature of some biomass conversion processes is
366 b i o m a s s a n d b i o e n e r g y 5 5 ( 2 0 1 3 ) 3 5 5 e3 6 9
impaired by the use of toxic reagents and solvents, generates a
lot of waste and has a modest atom economy. One would like
to rely on simple metrics such as those based on E-factor and
atom efficiency that could be used as a decision making tool at
an early stage of product synthesis, but as outlined by Sheldon
[97]. In the recent years, many biomass feedstocks have
been explored for developing biomass-based technology for
chemicals and fuel production of which the most inexpensive
feedstocks are naturally occurring biopolymers, weeds etc.
which holds the promise of a successful sustainable economy
[98,99].
Significant role may be played by the ILs and super-critical
fluid for the transformation of raw biomass into platform
chemicals. Post-reaction extraction of HMF by the use of
super-critical fluid in a cellulose conversion process would be
interesting to study both for the academic interest and com-
mercial scale application. Until now, attempts were not made
toward this direction, except the one [94] in which six vari-
ables that affected extraction of HMF from raisins were
studied. Based on one feature, i.e., affinity toward CO2 of each
compounds present in a mixture which can influence the
solubility of the required compounds (e.g. HMF). Raw biomass
conversion must be investigated more extensively due to the
high polymeric sugars contents or scaling up the process. In
this respect, multifunctional catalysts that follow both ho-
mogenous and heterogenous route would be desirable can-
didates. New developments on using biphasic media without
the need for ILs and with complete recycling of the Lewis acid
catalysts also holds outstanding promise for efficient HMF
production from lignocellulose. Cost-effective and scalability
of using biphasic media with superior extracting solvent such
as alkylphenol has been found to be highly successful.
Recently developed multi-component catalyst Cr[(DS)
H2PW12O40]3 containing strong BrønstedeLewis acid sites
coupled with an anionic surfactant (DS) functions as an acid
catalyst for the hydrolysis of cellulose followed by the con-
version of resulting reducible sugars into HMF with high
selectivity [62]. In this process, Crþ3/þ2 plays a significant role
in isomerization of glucopyranose to fructofuranose. In such
role, Snþ4 can also be effective as observed in the case of SnCl4
catalyzed glucose conversion by Hu et al. resulting maximum
610 mmol HMF yield per mol of the substrate [88]. To this far,
application of Brønsted acids containing eSO3H functional
groups in homogenous and heterogenous catalytic processes
has been limited to Dowex and Amberlyst resins. Toward this
direction, sulfonic acid functionalized mesoporous silica
(SBA-SO3H) by incorporating Cr or Sn in the walls of the nano-
reactor would receive great interest for both applications and
academic purpose. Multifunctional catalyst would help in
accumulation of more concentration of cellulose on the sur-
face of the catalysts for high conversion. The application of
mesoporous nanoparticulate catalyst [100] with surface acid-
ity would also be useful for a scalable biomass transformation.
An analysis of often studied algal species, Neochloris oleoa-
bundans, says it contains 33% carbohydrates, 29% protein, and
37% lipids [101]. Incentives to make the conversions of algal
biomass into HMF would attract considerable attention and
investment. Kim et al. have first studied the potentials of
Brønsted acidic ILs as catalysts in which they showed that
highly acidic [NMP]þ[HSO4] catalyzed the conversion of
fructose to HMF in organic solvents [102]. We have initiated
chemical conversions of plant biomass including weeds,
non-edible mushrooms to chemicals and liquid fuels based
on the effectiveness of unconventional, less-expensive
Brønsted acidic ILs of DMA (N,N-dimethylacetamide) and
NMP (N-methylpyrollidone). The effective recycling, recovery
and reuse of ILs is indeed critical to reduce the costs, as well as
to emphasize the environmental benefits. The choice of
regeneration solvent is considered a key factor that affects
yield of the regenerated product, as well as the cost of the
pretreatment process.
Although recent advancement has shown some exciting
results, in order to speed up this process, some specific points
should be important in the future studies as follows: (1)
investigation of the reaction mechanisms and kinetics for the
dehydration of biomass-derived carbohydrates using nuclear
magnetic resonance, density functional theory, molecular
dynamics and energetics; (2) design and preparation of the
lower viscous and biodegradable ionic liquids; (3) an effective
combination of solid catalysts, solvents and microwave
irradiation for the rapid production of furanics; (4) one-pot
synthesis of biofuels directly from biomass-derived carbohy-
drates or lignocellulosics; (5) the establishment of high-
efficiency and energy-efficient separation and purification
technologies such as membrane separation and super-critical
carbon dioxide extraction; (6) a complete techno-economic
evaluation of the complexity processes for the production of
furanics. The present status of large scale HMF and DMF, a
promising liquid fuel-component, production can be realized
from a techno-economic analysis reported recently which
describes that installed equipment costs are estimated as
102.4 million $ for HMF and 121.9 million $ for the DMF process
with considering a minimum selling price for HMF and DMF
are estimated as 1.33 $ l1 and 2.02 $ l1 [103].
Over a decade, HMF has been examined for its potential as
platform chemical for the production of fine chemicals and
liquid fuels. The literature report suggests that HMF yield and
selectivity depend on the starting carbohydrate concentrations.
Humin is one of the side reaction products of carbohydrate
dehydration process. The percentage of humin formation in-
creases with an increase in acid concentration during the
degradation of cellulose, and thereby lowers the desired HMF
yield [104]. To avoid the formation of side-products and loss of
HMF, efforts are taken towards the unconventional synthetic
strategies including ILs, biomass-derived Me-THF, alkylphenols
as solvents and efficient catalysts, biphasic aqueouseorganic
medium for HMF extraction, microwave-assisted rapid syn-
thesis, sub- and super-critical water for efficient HMF recovery,
and efficient catalyst recovery by using solid acid catalysts.
Among several unresolved problems, the high cost of the pro-
duction is the toughest challenge to be solved. Initial analysis of
the recent results suggest that the weeds, switch grass, and
unutilized sugars such as inulin etc. are attracting more
attention as feedstock with the evolution of more promising
separation technique by using biomass-derived alkylphenols as
extracting solvents. This opens more cost-effective process
that might meet the target for scale-up. Odds-of-success
involved in the application of biomass-derived solvent based
processes is the large-scale production of solvents for HMF
production. Nevertheless, studies on the direct transformation
 b i o m a s s a n d b i o e n e r g y 5 5 ( 2 0 1 3 ) 3 5 5 e3 6 9
of cellulose into HMF are paving the way towards an environ-
mentally sustainable route.
Acknowledgment
The authors gratefully acknowledge the financial support by
the University Grant Commission (UGC), Council of Scientific
and industrial Research (CSIR), India and the University of
Delhi. S. Dutta thanks United States-India Educational Foun-
dation (USIEF) for a Fulbright scholarship and UGC, India for a
DS Kothari Postdoctoral Research Fellowship. S. De thanks
UGC, India for a Senior Research Fellowship.
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