Conversion of 5-Hydroxymethylfurfural To Chemicals-A Review of Catalytic - Reference For HMF Conversion To Chemicals and Production Applications

Fuel Processing Technology 209 (2020) 106528
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Fuel Processing Technology

journal homepage: www.elsevier.com/locate/fuproc
Invited review article
Conversion of 5-hydroxymethylfurfural to chemicals: A review of catalytic T

routes and product applications
⁎ ⁎
Qing-Shan Konga,b, Xing-Long Lia, Hua-Jian Xub, , Yao Fua,
a
Hefei National Laboratory for Physical Sciences at the Microscale, iChEM, CAS Key Laboratory of Urban Pollutant Conversion, Anhui Province Key Laboratory of
Biomass Clean Energy, Institute of Energy, Hefei Comprehensive National Science Center, Department of Chemistry, University of Science and Technology of China, Hefei
230026, China
b
School of Food and Biological Engineering, Hefei University of Technology, Hefei 230009, China
A R T I C LE I N FO A B S T R A C T
Keywords: Biomass is the sole renewable organic carbon resource in nature. Conversion of Biomass can produce a series of
5-Hydroxymethylfurfural platform molecules. As an essential multi-purpose bioderived furanic platform compound, 5-hydro-
Platform chemicals xymethylfurfural (HMF) can be effectively transformed into a variety of value-added derivatives due to its rich
Hydrogenation chemistry and potential availability, which is an ideal renewable alternative to fossil fuels. This review high-
Catalytic conversion
lights recent advances in the development of efficient catalytic systems for the conversion of HMF, especially
Furan derivatives
Material monomers
heterogeneous catalysts. Heterogeneous catalysts have advantages in facile separation and recovery, tunable
performance by adjusting catalyst structures. Simultaneously, we mainly focus on the application of downstream
products in material monomers, pharmaceutical intermediates, and fuels. Furthermore, a few potential research
trends are also proposed, in order to provide some useful ideas for the further exploration of the utilization and
conversion of HMF in a much simple, efficient, and economical way.
1. Introduction substance that exist in foods such as honey, vegetables, coffee, and
other beverages in small amounts. It is also an ingredient of aroma in
Energy and consumer goods produced by the petrochemical in- liqueurs. The earliest publication of HMF can be dates back to 1895.
dustry are vital to our modern life. The study predicts that human de- Dull et al. reported for the first time that HMF was obtained by heating
mand for these resources will double by 2035 [1–4]. It also means inulin in an oxalic acid solution under certain pressure [5]. In the same
carbon dioxide emissions will continue to increase over the next year, HMF was also synthesized from sugarcane by Kiermayer et al. [6].
15 years, definitely leading to increased global warming, endangering And since then, both academia and industry have shown great interest
the balance of natural ecosystems and the human living environment. in the preparation and utilization of HMF. The global industry market
Therefore, the exploitation of renewable resources and the development for HMF is expected to grow at a CAGR of roughly 1.4% over the next
of sustainable technology have become an inevitable trend. five years, will reach 61 million USD in 2024, from 56 million USD in
Biomass, as a unique renewable carbon resource, can be obtained 2019. In the future eight years, researchers predict the CAGR of global
directly from plant raw materials, crop wastes, and industrial residues. revenue is 1.45%. The major players profiled in this report include:
The efficient utilization of biomass resources is a promising way to AVA Biochem, Robinson Brothers, Penta Manufacturer, NBB Company,
overcome the dependence on fossil hydrocarbons (oil, coal, and natural Treatt, Beijing Lys Chemicals, Xuzhou Ruisai Technology, and Wutong
gas). Biomass raw materials can be converted to numerous platform Aroma Chemicals [7]. Meanwhile the number of publications on the
compounds through chemical catalysis or biocatalytic processes. U.S. production and conversion of HMF has increased significantly over the
Department of Energy has selected 12 most representative biomass past decade (Fig. 1a). In particular, the number of published reviews
platform molecules. 5-hydroxymethylfurfural (HMF), an essential also illustrates its significance from another perspective (Fig. 1b).
furan-based platform molecule, known as the “sleeping giant”, is re- Currently, the price range of HMF is about 500 to 1500 USD/kg,
garded as a bridge between petrochemical resources and biomass re- which is three orders of magnitude higher than fossil-based chemicals.
sources. Therefore, only when the cost of HMF is less than 1 USD/kg in the
5-hydroxymethylfurfural (HMF) [CAS: 67-47-0] is a natural industrial-scale production, the competitiveness of HMF and its
⁎
Corresponding authors.
E-mail addresses: [email protected] (H.-J. Xu), [email protected] (Y. Fu).
https://doi.org/10.1016/j.fuproc.2020.106528
Received 11 January 2020; Received in revised form 3 June 2020; Accepted 3 July 2020
Available online 28 July 2020
0378-3820/ © 2020 Elsevier B.V. All rights reserved.
Q.-S. Kong, et al. Fuel Processing Technology 209 (2020) 106528
Fig. 1. Number of publications on HMF annually from 2010 to 2019. (a) Number of publications. (b) Number of reviews. Source: Web of Science (keyword: 5-
hydroxymethylfurfural).
Scheme 1. The conversion pathway from cellulose to HMF.
downstream chemicals can be effectively improved. Multistep acid- Researchers have reported the chemical conversion reaction to gain
catalyzed dehydration of hexoses can prepare HMF, for example, cel- stable HMF derivatives without isolating HMF in recent years [220]. In
lulose, glucose, fructose, sucrose, starch, inulin, and some raw biomass short, to gradually realize the wide industrial applications of HMF,
such as wheat straw are all active substrates. Carbohydrates (cellulose) more ideas should be discussed and optimized around the stability of
can be converted to HMF through a three-step reaction, including hy- HMF and the optimization of separation and purification steps.
drolysis of cellulose to glucose, isomerization reaction of glucose to Extensive research and development in chemical utilization of HMF,
obtain fructose, and fructose removes three molecules of water to ob- a large number of high value-added derivatives of HMF, were dis-
tain HMF (Scheme 1). Different kinds of hexoses can be converted into covered. These downstream products have significant value in material
HMF but with varying selectivity. The best selectivity of HMF formation monomers, pharmaceutical intermediates, and fuels. (Fig. 2). Our group
was obtained from fructose and other ketoses, while the selectivity of has been devoted to the preparation and utilization of HMF for a long
glucose and other aldoses is poor. time. Therefore, based on the usage of biomass resources and green
Researchers have developed a variety of catalytic systems to achieve synthesis concept, we tried to summarize the catalytic routes of HMF,
high yields of HMF from different biomass substrates. There have been and introduce the application fields of downstream derivatives of HMF
many reviews on the HMF preparation process from different per- through broad classification. In addition, we investigated the applica-
spectives: mechanistic and process chemistry [8,9], catalytic systems tion of niche chemicals (e.g., glucose, fructose) to synthesize HMF de-
[10–13], ionic liquid [14], biphasic solvents [15,14]. rivatives in one step [16].
However, at present, preparation methods of HMF are not suitable This review evaluates recent advances in the development of effi-
for a wide range of industrial applications. Carbohydrates are highly cient catalytic systems for the conversion of HMF. We emphasized the
hydrophilic, so the choice of reaction medium usually selects polar various routes of HMF transformation, focus on the advantages of
solvents, such as water, alcohols, dipolar aprotic solvents, or ionic li- heterogeneous catalytic systems. Besides, one-pot synthesis of HMF
quids. The use of a large number of organic solvents or ionic liquids will derivatives from raw biomass has also been summarized. Since the
cause expensive costs, requiring the design of complex solvent recovery present review focuses mainly on the conversion of HMF, the produc-
systems. In aqueous systems, regardless of the type of substrate and acid tion of HMF is only briefly described here. Research on sustainable
catalyst used, HMF yields are typically below 50%. Lower yield is be- catalysts in the production of HMF is worthy of attention. For example,
cause HMF is easily soluble in water. In an acidic aqueous solution, a biochar, served as a green synthesis of biomass-derived catalyst, played
considerable amount of HMF will undergo rapid and irreversible oli- a vital role in the production of HMF. Many researchers have shown
gomerization to form humins. As a result, the separation and purifica- interest and carried out various reports [17–23]. Notably, development
tion steps of HMF become more complicated, and the selectivity of HMF of more sustainable catalysts to promote the transformation of HMF is
is poor. In summary, the relatively high cost of the reaction medium important for biomass field. For complete catalytic systems and un-
and complex post-treatment process reduces the commercial attrac- derlying mechanisms for biomass to HMF, readers can refer to the re-
tiveness of HMF. views mentioned above.
Researchers have proposed that the water/organic solvent two-
phase system shows high efficiency in the conversion process of HMF, 2. Material monomer
which reduces the occurrence of side reactions, irreversible oligomer-
ization, and carbonization. However, the ability of HMF extraction from 2.1. 2,5-Diformylfuran (DFF)
the aqueous phase in this system is the main factor affecting the final
yield of HMF, and more process optimization is needed. Therefore, DFF can be transformed into monomers of biomass-based polymers,
these approaches are still not used in commercial applications. Besides, drug intermediates, and other high value-added chemicals. Several
there is another possible solution to avoid the problem of HMF in- studies have reported the selective oxidation of HMF to DFF using
stability. Stable additives were used to prepare C6-modified carbohy- various oxidants, such as Pb(OAc)2, (K2Cr2O7), trimethylammonium
drates, leading to appropriate and stable O-modified HMF derivatives. chloromate (TMACC), and pyridinium chlorochromate (PCC).
2
Fig. 2. Application of HMF derivatives.
Scheme 2. The main conversion pathways of HMF in material monomer applications.
However, the use of equivalent oxidants and a large amount of the three and VOHPO4 [39], Amberlyst-15 and polyaniline-VO(acac)2 [40],
wastes emissions do not conform to the concept of green chemical in- WO3HO-VO-@Fe3O4 [41], Fe3O4-SBA-SO3H and K-OMS-2 [42]. In
dustrial development (Scheme 2). contrast, the yield of DFF obtained by the one-step method is relatively
Heterogeneous catalysts have been widely used for the oxidation of low. Fructose may be oxidized to undesired by-products during this
HMF into DFF including supported manganese (Mn) [24–29], vana- process. At relatively high reaction temperatures, graphene oxide (GO)
dium (V) [30–33], iron (Fe) [34,35], and molybdenum (Mo) [36,37] [43] and Cs0.5H2.5PMo12 [44] as a catalyst can obtain DFF with a yield
(Table 1). Mn catalysts showed the best catalytic performance over of 53% and 69%, respectively.
others, which may be attributed to the rich valence of manganese. However, in current preparation methods of DFF, the use of organic
Besides, Mn-based catalysts have good stability and low price. Thus, Mn solvents such as Dimethyl Sulfoxide (DMSO) and N,N-dimethylforma-
catalysts show great potential in the large-scale production of DFF from mide (DMF) is inevitable. These solvents are difficult to recover,
HMF. making separation of DFF difficult. Aqueous systems are more acces-
The concept of green synthesis is expected to integrate multistep sible to industrial applications due to their lower cost, while the DFF
reactions in one pot. Huber and Zhang [38] reviewed relevant reports can be purified through simple filtration, extraction, etc. Therefore, it is
on the direct conversion of fructose to DFF in a one-pot method. Spe- particularly important to strengthen the research on the catalytic
cifically, the process can be divided into a one-step approach and a two- system of the water phase. In particular, we need to pay attention to the
step method. In the two-step process, the catalytic systems can achieve extraction process, because DFF is easily oxidized and deteriorated
a DFF yield of more than 70%, such as H-form cation-exchange resin when exposed to air for a long time, so it is necessary to shorten the
3
Table 1
Oxidation of HMF to DFF under various heterogeneous catalysts.
Entry Catalyst Solvent Reaction conditions HMF conversion [%] DFF yield [%] Ref.
1 OMS-2 N,N-dimethylformamide 110 °C, 5 bar O2, 1 h 100 97.2 [24]

2 15 wt% Ag-OMS-2 Isopropanol 165 °C, 15 bar air, 4 h 90.0 99.0 [25]
3 Mn3O4 N,N-dimethylformamide 120 °C, 20 mL min−1O2, 4 h 100 83.2 [26]
4 Fe3O4/Mn3O4 Dimethyl sulfoxide 120 °C, 20 mL min−1O2, 4 h 84–99.8 51–82 [27]
5 Meso 5% Mn/CoOx N,N-dimethylformamide 100–130 °C, 4 h, air 70.0–80.0 70.0–77.0 [28]
6 Mn0.7Cu0.05Al0.2 Water 90 °C, 8 bar, 24 h 90.0 78.0 [29]
7 VO2-PANI/CNT Dimethyl sulfoxide 120 °C, 10 bar O2, 11 h > 99 96.0 [30]
8 V2O5/H-Beta (1 wt% V) Dimethyl sulfoxide 125 °C, 10 bar O2, 3 h 84 84 [31]
9 VSi-Beta(100), H2SO4 Dimethyl sulfoxide 130 °C, O2 balloon, 3 h > 99.9 93 [33]
10 V2O5/AC Methyl isobutyl ketone 100 °C, 2.8 bar O2, 4 h 95.2 91.8 [32]
11 FeCo/C Toluene 100 °C, 10 bar O2, 6 h > 99.9 > 99.9 [34]
12 FeOx/C Toluene 150 °C, 1 MPa O2, 12 h > 99 99 [35]
13 Mo-HNC Dimethyl sulfoxide 140 °C, 20 mL min−1 O2, 12 h 97.0 96.0 [36]
14 CsH4PMo10V2O40 Dimethyl sulfoxide 120 °C, 1 bar O2, 6 h > 99.9 > 99.9 [37]
extraction time or set up additional protective measures as soon as nanosized Fe3O4-CoOx catalyst by the impregnation method. However,
possible. In addition, clean oxidation methods such as photocatalytic an excess of t-BuOOH was used in the reaction to generate a large
and electrocatalytic systems are also worthy of attention and expecta- amount of tert-butanol, which was challenging to scale up industrially
tion. [63]. In ionic liquid [BMIM] Cl, Fe0.6Zr0.4O2 can catalyze HMF to FDCA
in the absence of alkali and oxygen, but the ionic liquid is relatively
expensive [64].
2.2. Furan-2,5-dicarboxylic acid (FDCA) Electrochemical oxidation is considered as a clean synthetic method
(Table 2, entries 19–21) [65]. Choi et al. prepared FDCA by electro-
FDCA is one of the 12 most valuable biomass-derived platform chemical oxidation in acid medium with MnOx anode, and the yield of
compounds identified by the U.S. Department of Energy. FDCA can be FDCA was 53.8% [66]. Recently, Taitt et al. used a NiOOH electrode to
used as a replacement for terephthalic acid, in various polyesters. FDCA convert HMF to FDCA, achieving up to 96.0% yield of FDCA in 0.1 m
also has essential applications in metal-organic framework materials, KOH (pH = 13) solution [67]. Gao et al. synthesized Nise@niox core-
chemical synthesis, and plasticizers, etc. The mechanism of oxidation of shell nanowire electrocatalyst. The catalyst achieved the highly effi-
HMF to FDCA can be divided into two pathways (Scheme 3). cient conversion of HMF to FDCA (with a yield of about 99%) and
Based on the difficulty in the separation and recycling of homo- showed stability for continuous electrolysis [68].
geneous catalysts [45,46], researchers paid extensive attention to de- Photocatalysis has excellent potential in the field of biomass con-
veloping heterogeneous catalytic systems. Noble heterogeneous metal version [69]. Au nanoparticles (AuNPs) supported on TiO2 can effec-
catalysts are widely used, such as palladium (Pd) (Table 2, entries 1–4) tively catalyze the oxidation of HMF to FDCA in Na2CO3 aqueous so-
[47–51], gold (Au) (Table 2, entries 5–8) [52–54], ruthenium (Ru) lution. Under the optimal conditions, the selectivity of the products is
(Table 2, entry 9) [55], and platinum (Pt) (Table 2, entries 10–14) higher than 95%. The authors suggest that Na2CO3 acts as an active
[56–60]. Under optimal reaction conditions, the yield of FDCA is more promoter of the reaction.
than 85%. Given the needs for industrial-scale production, the devel- We also pay attention to the conversion of carbohydrates to FDCA.
opment of non-noble metal catalytic systems has become particularly Researchers still mainly use fructose as a substrate. Kroger et al. first
important. However, its low catalytic activity and poor stability often reported the conversion of fructose to FDCA through a two-step reac-
require the reaction to be performed in the presence of an organic tion in 2000. However, the yield of FDCA is relatively low [70]. Sub-
solvent and a strong oxidant. At the same time, most heterogeneous sequently, the same multi-step reactions were also reported. Re-
catalytic systems require additional bases to promote oxidation. The searchers usually used an acid catalyst to hydrolyze fructose to HMF,
resulting FDCA salt cannot be used directly in the production of poly- and then utilize a heterogeneous catalyst to oxidize HMF to FDCA, such
mers, and it is often necessary to release FDCA by adding a large as Au/HT [71], Au–Pd/HT [72], Ru/C [73], and Fe3O4–CoOx [63]. In
number of inorganic acids such as hydrochloric acid or sulfuric acid. particular, Ribeiro and Schuchardt reported the one-pot transformation
Therefore, it is necessary to improve the activity and stability of non- of fructose into FDCA. Cobalt acetylacetonate encapsulated in sol–gel
noble metal catalysts and to choose more environmentally friendly re- silica was shown to be an efficient bifunctional catalyst. The authors
action systems. Saha's group developed a Fe-POP catalyst formed by also revealed the reaction process. Fructose was dehydrated into HMF
combining Fe3+ with a porphyrin-based porous organic polymer, and on a silica catalyst, and then HMF was oxidized to FDCA by the metal
100% HMF conversion and 79% FDCA yield can be obtained under mild active site [74].
conditions [61]. Jain et al. synthesized a new type of metal oxide cat- In summary, there have been many reports about FDCA production,
alyst Li2CoMn3O8, and the yield of FDCA was 80% under the optimal but these methods are less green and less cost-effective. So much effort
conditions. The addition of acetic acid and NaBr to the catalyst system is still needed to develop new catalytic systems that are mild, cheap,
caused difficulties in product purification [62]. Wang et al. prepared a
Scheme 3. The conversion path from HMF

to FDCA.
4
Table 2
Oxidation of HMF to FDCA with various catalytic system.
Entry Catalyst Solvent Reaction conditions Gas source FDCA yield [%] Ref.
1 Pd-Bi-Te/C H2O–methanol 50 °C, 6 h, KOH O2 95 [47,48]

2 Pd/P,N-codoped graphene Water 50 °C, 6 h, NaOH, 0.1 MPa O2 83 [49]
3 Pd/CC Water 140 °C, 30 h, K2CO3, 0.1 MPa O2 85 [50]
4 Ni-Pd alloy Water 80 °C, 4 h, Na2CO3 Air 70 [51]
5 Au-Pd alloy NPs on anion-exchange resin Water 100 °C, 4 h, Na2CO3, 1 MPa O2 93 [52]
6 Au-Pd alloy NPs on anion-exchange resin Water 100 °C, 4 h, Na2CO3, 4 MPa Air 83 [52]
7 Au-Pd alloy NPs on poly(ionic liquid) Water 90 °C, 12 h, K2CO3 O2 99 [53]
8 AuPd/La-CaMgAl-LDH Water 100 °C, 6 h, 0.5 MPa O2 86 [54]
9 Ru/MnCo2O4 Water 120 °C, 10 h, 2.4 MPa Air 99 [55]
10 Pt/CeO2 Water 70 °C, 12 h, NaOH O2 96 [56]
11 Pt/SiO2 H2O/dioxane 90 °C, 20 h, 1.48 MPa O2 91 [57]
12 Pt/ZrO2 Water 100 °C, 12 h, 0.4 MPa O2 99 [58]
13 Pt-Ni/AC-xALD Water 100 °C, 15 h, 1.0 MPa O2 98 [59]
14 Pt/C NMP/water 80 °C, 0.5 h, NaOH, 2.2 MPa Air 74 [60]
15 Fe-POP Water 100 °C, 10 h, 1 MPa Air 79 [61]
16 Li2CoMn3O8 NaOH(aq) 150 °C, 10 h, NaBr, ~5.5 MPa Air 80 [62]
17 Fe3O4–CoOx DMSO 80 °C, 12 h, t-BuOOH O2 68.6 [63]
18 Fe0.6Zr0.4O2 [Bmim]Cl 160 °C, 24 h, 2 MPa O2 60.6 [64]
19 Cu-foam-coated electrode 1,4-Dioxane Water, KOH, electrolysis – 64 [65]
20 NiSe@NiOx electrode 0.1 M KOH Electrolysis – ~99 [68]
21 NiOOH 0.1 M KOH Electrolysis – 96.0 [67]
22 Au/TiO2 Water Illumination, Na2CO3, 30 °C – 95 [69]
and environmentally friendly. Table 3

Reduction of HMF to BHMF.
2.3. 2,5-Bishydroxymethylfuran (BHMF) Entry Catalyst Solvent Reaction Gas source BHMF Ref.
conditions yield [%]
BHMF is a vital polymer monomer and intermediate of drug
1 Shvo's Toluene 90 °C, 1 h H2 99.0 [75]
synthesis, which can be used to synthesize polyester, polyurethane 2 Ni/MCM-41 H2O 35 °C, 2 h H2 89.0 [76]
foam, crown ether, medicine, and so on. In the presence of molecular 3 MgO CH3OH 160 °C, 3 h – 100 [77]
hydrogen and noble metal catalysts, HMF is easy to be over-hydro- 4 Au/Al2O3 H2O 120 °C, 2 h H2 96 [78]
genated. Thus, there is a difficult problem to prepare BHMF by selective 5 Pd/Al2O3 H2O 140 °C, 4 h H2 20 [78]
6 Ru/CeOx H2O, 1- 130 °C, 2 h H2 81 [79]
hydrogenation of HMF: how to ensure the priority hydrogenation of the Butanol
aldehyde group on HMF molecule and avoid the hydrogenation of the 7 Cu/AlOx BDO 220 °C, 6 h – 93 [80]
hydroxymethyl group and carbon-carbon double bond on furan ring 8 Cu-ZnO 1,4- 100 °C, 2 h H2 99.1 [83]
(Scheme 4) [75–80,85]. Dioxane
9 Ir/TiO2 Ionic 50 °C, 3 h H2 95.4 [85]
Noble metal catalysts are widely used in the production of BHMF,
liquid/
such as Ruthenium (Ru), gold (Au), palladium (Pd). Compared with Pd/ water
Al2O3 catalyst, Au/Al2O3 significantly improved the selectivity of
BHMF, which shows that Au has a high selectivity for the hydrogena-
tion of HMF to BHMF. Recently, new methods to gain these two compounds by selective oxi-
Non-precious metal catalysts have been widely developed and uti- dation of biomass-derived platform molecules such as HMF and furfural
lized due to economic applicability. Cu-based catalysts show good re- have drawn increasing attention [88] (Scheme 5).
ducing activity [81]. Zhu et al. reported the bifunctional catalyst Cu- Up to now, researchers have found that vanadium-based catalysts
ZnO, showed that the reaction temperature has a great effect on the are the most effective catalysts in the preparation of MA [89–91], in-
product selectivity. At 100 °C, the main product is BHMF, along with cluding VO(acac)2, vanadium-containing heteropolyacid catalysts,
the reaction temperature increases to 220 °C, DMF was the main pro- VOHPO4, (VO)2P2O7, and V2O5. Considering the reduced ability of the
duct [82]. Using Cu/SiO2 [83] and Cu-PMO [84] catalysts also obtained supported transition metal oxide catalyst to recycle, Li et al. developed
a similar conclusion. It is found that temperature plays an important a catalyst-free system for the conversion of furfural to maleic acid by
role in the selective hydrogenation of HMF. At lower temperatures, using H2O2 as oxidant [92], MA was obtained in a good yield. Then, the
aldehydes are easily reduced to hydroxyl groups, while at higher tem- researchers made some improvements to this catalytic system [93,94].
peratures, carbon-oxygen bonds are broken (Table 3). The usage of HMF as a substrate provides a new and sustainable way
to produce MA, which will reduce dependence on petroleum-based raw
2.4. Maleic anhydride (MA) and maleic acid (MAC) materials.
MA and its derivative MAC are widely used in the synthesis of un-
2.5. 3-Hydroxymethylcyclopentanone (HCPN) and 1-hydroxyhexane-2,5-
saturated polyester resins, pesticides, food additives, lubricant ad-
dione (HHD)
ditives, drugs, etc. [86] [87] These two chemicals are currently pro-
duced mainly by selective oxidation of petroleum-based products.
With the deepening of research, new methods of converting bio-
mass-derived raw materials into useful chemicals through ring-opening
and rearrangement reactions of furan rings have also attracted more
attention. 3-Hydroxymethylcyclopentanone (HCPN) is an essential in-
termediate for the manufacture of perfume, pesticides, polymers, drugs,
Scheme 4. The conversion of HMF to BHMF. and solvents. Reaction of HCPN from HMF undergoes three stages:
5
Scheme 5. The conversion of HMF to MA and MAC.
Scheme 6. The conversion of HMF to HHD and HCPN.
selective hydrogenation of aldehyde group, ring-opening, and ring PE, rubber, and PTFE is relatively weak. HMVF has also demonstrated
closure reaction. During the reaction, it is necessary to suppress the cell-adhesive properties [108].
occurrence of side reactions such as excessive hydrogenation of the HMVF was synthesized in a yield of 67% by using methyl triphe-
furan ring to the tetrahydrofuran ring, deep hydrolysis of HMF to le- nylphosphonium bromide and potassium carbonate as catalysts [110].
vulinic acid (LA), and oligomerization of the reaction intermediate to HMVF can be effectively polymerized by AIBN initiated free radical
form humins (Scheme 6). polymerization (Scheme 8). Recently, Ji et al. demonstrated that HMVF
Ohyama et al. studied the catalytic effect of various Au supported exhibits strong adhesion to metals through in situ polymerization and
metal oxide catalysts, and screened the most reactive catalyst Au/ crosslinking after heating or acid treatment, suggesting that HMVF can
Nb2O5 with a yield of 86% [95]. Throughout the reaction, the acidity of be used as a biomass-derived adhesive [109]. Studies have also shown
the carrier significantly promoted the ring-opening reaction, aldol that HMVF can be prepared by polymerization to obtain polymers and
condensation, and subsequent dehydration reaction. Au/Nb2O5 cata- glasses with high adhesion to steel, copper, and aluminum.
lyzes the polymerization of HMF and reduces the response yield due to
the relatively strong acidic sites on the support. While because of weak 2.7. HMF alkynylation products
Lewis acidity, Au/TiO2 showed excellent ring-opening rearrangement
reaction performance. Ohyama et al. studied the catalytic activity of 2-Hydroxymethyl-5-ethynylfuran (HMEF) could be obtained from
heterogeneous Pt-based catalysts by using different supports [96,97]. HMF with a high yield of 97% by Ohira-Bestmann reaction [111],
Ramos et al. investigated the effect of pH on the production distribution which can be used as a polymer monomer to prepare various valuable
and found that a pH of 5–7 was most suitable for the ring rearrange- materials (Scheme 9). HMEF can continue to be used as an alkyne
ment reaction [98,99]. substrate for further characteristic reactions to obtain high value-added
In summary, the ring rearrangement reaction of HMF is greatly af- products (Scheme 10), such as the Sonogoshira coupling reaction,
fected by the support of the catalyst and the pH of the aqueous solution. Glaser oxidation reaction, and Ru-catalyzed polymerization.
Thus, the prospect of designing metal-acid bifunctional catalysts for the
preparation of HCPN is promising, but the synergistic effect of metal 2.8. 1,6-Hexanediol (1,6-HD)
and acid sites needs further investigation.
It can be seen from the above reaction description that HHD is an 1,6-Hexanediol (1,6-HD) is an essential precursor for the production
important intermediate for HCPN formation. HHD is also an important of polyurethanes, coatings, adhesives, and polymer plasticizers.
diol for the synthesis of caprolactam/caprolactam and polymers (e.g., Polyester made of 1,6-HD has excellent flexibility due to its long carbon
polyester, polyurethane, various adhesives) [100]. Pd/Nb2O5 [101], chain. 1,6-HD is mainly obtained by hydrogenation of adipic acid or its
Pd/C [102], Au/Nb2O5 [95], Pt/C [104], and Amberlyst-15 [105] ester on various homogeneous or heterogeneous catalysts [112].
catalyst systems have been successfully applied to this reaction. Our In a pioneering study by Buntara et al., a mixture of Pd/C and
group also reported a homogeneous Cp*Ir (III) semi-sandwich compo- copper chromite was used, but only a 4% 1,6-HD yield was obtained
site catalysts for the conversion of HMF to HHD [106]. It was recently under severe reaction conditions [113]. Buntara et al. found that the
reported that HMF was catalyzed by bifunctional Pd/MIL-101 to obtain addition of trifluoromethylsulfonic acid can achieve high selectivity of
HHD with a yield of 82% [107]. 1,6-HD (96%). However, direct hydrogenolysis of 1,2,6-hexanol can
For further research, it is important to prepare bifunctional catalysts form 1,5-hexanediol with 73% selectivity at the total conversion [114].
with balanced metal acid centers, which directly catalyze the cleavage Zhang et al. studied the translation of HMF to 1,6-HD in a fixed bed
of the C-O bond in the furan ring while avoiding its excessive hydro- reactor [103]. They showed that DHMTHF and 1,2,6-hexanol were the
genation. critical intermediates in the formation of 1,6-HD. Chen et al. used Rh-
ReOx/C catalyst to convert tetrahydrofuran methanol [115], due to the
synergistic effect between ReOx and Rh, 1,6-HD (84%) with high yield
2.6. HMF alkenylation products
was obtained. Tuteja et al. developed a Pd/ZrP catalyst and received
43% 1,6-HD yield [116]. The high Brønsted acid on ZrP accelerated the
2-Hydroxymethyl-5-vinylfuran (HMVF), a biomass-based solvent-
C-O cracking to form 1,3,5-triene-1,6-diol, which was further converted
free adhesive, was synthesized from HMF through a Wittig reaction
into 1,6-hexadiol by hydrogen in formic acid.
(Scheme 7). HMVF was polymerized giving a polymer with high ad-
In conclusion, 1,6-HD can be obtained from two ways: ring-opening
hesiveness to steel, copper, aluminum, and glass, but the adhesion to
of DHMTHF intermediate or direct ring-opening of HMF. In the first
route, the selectivity and activity need to be further improved, and Rh/
Re-based catalysts are reported to be promising catalysts for the ring-
opening of DHMTHF. Compared with tetrahydrofuran ring-opening of
DHMTHF intermediate, HMF can directly hydrogenate ring-opening
under mild conditions. Further research is needed to prepare a bi-
Scheme 7. The conversion of HMF to HMVF. functional catalyst with the metal acid center, which can directly
6
Scheme 8. Cross-linking mechanism of HMVF to poly-HMVF.
halogenation reaction of HMF to obtain a medium or higher yield

[118]. Sanda et al. have done much research on the halogenation re-
action of 5-HMF. They used chlorotrimethylsilane or bromo-
trimethylsilane to increase the yield of 5-CMF and 5-BMF to more than
90% and found that CHCl3 was the best solvent [119–121]. Besides, the
synthesis of 5-CMF and 5-BMF catalyzed by Vilsmeier reagent was
studied in great detail, and DMF was found to be the best solvent for
Scheme 9. The conversion of HMF to HMEF.
this reaction.
catalyze the cleavage of the C-O bond in the furan ring and avoid its
3.2. Reductive amination product of HMF
over hydrogenation.
HMF can be converted into valuable N-containing furanyl com-
3. Pharmaceutical intermediates pounds through the reductive amination of aldehyde groups. 2-(hy-
droxymethyl)-5-(aminomethyl)-furan could be obtained in 72% yield
Oxygen heterocyclic compounds are the second most common het- from the reductive amination reaction of HMF and liquid ammonia
erocyclic compounds among the structural components of drugs ap- catalyzing by the Raney nickel catalyst. The latter can be used as an
proved by the US Food and Drug Administration (FDA). 311 different intermediate of transformant (Scheme 13). After changing liquid am-
drugs contain at least one oxygen heterocycle (as of 2017) and have a monia to methylamine, 2-(hydroxymethyl)-5-(methylaminomethyl)
significant impact in treating a wide variety of diseases. As a typical furan can be obtained in a yield of 91% [122].
oxygen heterocyclic compound, furyl compounds have high research Stevens et al. reported that HMF and aromatic or aliphatic primary
value in drug synthesis [117] (Scheme 11). amines were used to synthesize 5-aminomethyl-2-furfuryl alcohol with
higher yields [123]. Liu et al. reported the use of abundant and in-
3.1. HMF halogenated products expensive CO and water as reducing agents and Au/TiO2-R as catalysts
to catalyze the reduction amination of 5-HMF with primary amines and
The hydroxyl group of 5-HMF is relatively easy to be replaced by secondary amines to prepare a series of N-containing biomass com-
chlorine and bromine, forming 5-chloromethylfurfural (5-CMF) and 5- pounds [124]. In particular, the synthetic method can also conveniently
bromomethylfurfural (5-BMF), which are valuable pharmaceutical in- obtain bis (hydroxymethylfurfuryl)-amine, which is a new group of
termediates (Scheme 12). For example, 5-CMF can be used as a raw furan-based monomers and has great potential to form functional bio-
material to synthesize the critical drug ranitidine gradually. Traditional polymers with adjustable properties (Scheme 14).
halogenation reaction conditions can be directly used for the The use of heterogeneous catalysts to catalyze such reactions has
Scheme 10. Multiple transformation pathways of HMEF.
7
Scheme 11. The conversion of HMF to pharmaceutical intermediates.
attracted researchers' interest. Beller et al. reported that cobalt nano-

particles coated with graphite shell catalysts have sufficient ability for
reductive amination. Under the optimal conditions, the yield of 5-
aminomethyl-2-furfuryl alcohol can reach 89% [125]. Hara et al. used a
Ru/Nb2O3 catalyst for the reduction amination and obtained a yield of
Scheme 13. The conversion of HMF to reductive amination product.
96% [126]. Therefore, heterogeneous catalysts are very active for re-
ductive amination reactions, but the hydrogen pressure in the currently
reported catalytic systems is relatively high (4 MPa), which is not
conducive to industrial production. Therefore, it is necessary to develop
a safer and more efficient catalytic system.
3.3. Products of HMF condensation with various reagents
3.3.1. Benzoin condensation reaction Scheme 14. The conversion of HMF to bis (hydroxymethylfurfuryl)-amine.
Alpha-diketone is a crucial structural molecule and has been widely
used in fine chemical and pharmaceutical synthesis. Traditional
synthesis methods of α-diketones are mainly olefin oxides, alkynes,
sulfoxides, dihydroxy compounds, but the reaction conditions are
harsh, and the product yield is low. Das et al. reported the benzoin
condensation reaction of HMF by using the NHC catalyst in the DMSO
solvent with a yield of 74% [127] (Scheme 15).
Scheme 15. The benzoin condensation reaction of HMF.
3.3.2. The aldol condensation reaction
Suryawanshi et al. reported that potassium hydroxide catalyzed the the 5-hydroxymethylfurfural acetone with a yield of 99% [129]. Then,
reaction of hydroxymethylfurfural and acetophenone to produce 5-hy- 5-hydroxymethyl-furfuryl-ethanone can be continuously oxidized to
droxymethylfurfural acetone in a methanol solution with a yield of 82% prepare different 5-hydroxymethyl-furancarboxylic acids, which can be
[128]. Arias et al. used an Mg-Al mixed oxide (HTc) catalyst to obtain used as phosphatase inhibitors or synergistic antifungals. Under
Scheme 12. The conversion of HMF to 5-CMF

and 5-BMF.
8
Scheme 16. The aldol condensation reaction of HMF.
microwave radiation, KF/Al2O3 was used as a catalyst for the conver- products [132]. Biomass platform molecule cyclopentanone can also
sion of 5-hydroxymethylfurfural to chalcone with a yield of 76% [128]. effectively double-condense with HMF to synthesize molecules. The
Anti-diuretic activity is also studied. Suryawanshi et al. found that li- latter can be used as synergistic antifungal compounds [133] and also
thium hydroxide is the beneficial catalyst for the condensation of HMF an essential intermediate for the preparation of long-chain naphthenes
with 1-C-(β-D-galactopyranosyl) propan-2-one to prepare galactose- [134].
derived. The yield was 65% and the product proved to be an active The authors report studies on the synthesis and cytotoxicity of 5-
antimycobacterial agent (Scheme 16). hydroxymethyl furfural curcumin analogs [135]. They first formed a
In an alcohol solution, HMF and cyclooctanone can undergo con- complex of boric anhydride with 2,4-pentanedione from the Knoeve-
densation reaction to form an intermediate product (Scheme 17). The nagel reaction, and the aldol condensation reaction occurred only on
intermediate product can be further converted into thio [2,3-b] pyr- the terminal carbon. The target compounds were obtained in yields of
idine, which is active against elongation factor-2 kinase (eEF2-K) [130]. 12% and 32%, respectively (Scheme 18). The authors also investigated
Dihydroxybenzofuran and HMF can undergo aldol condensation reac- its cytotoxicity.
tion by the catalysis of KOH, and the product can be used as an im- Through the three-component condensation reaction of HMF, a
portant pesticide or pharmaceutical intermediate [131]. derivative of HMF that can be used as an adenosine receptor antagonist
Witczak et al. reported the condensation reaction between dihydro- (A2A) was obtained [136] (Scheme 19).
l-glucosone and HMF under base catalysis and obtained a yield of 86% The synthesis of α, β-unsaturated carboxylic acids from aldehydes,
Scheme 17. The aldol condensation reaction of HMF and cyclic ketones.
9
Scheme 18. The synthesis of 5-hydroxymethyl furfural curcumin analogs.
is a widespread carbon-carbon double bond-forming reaction that is Dow et al. found a Mitsunobu-type reaction between HMF and
profoundly meaningful in organic chemistry [137]. The α, β-un- diethyl azodicarboxylate (DEAD) in the absence of other nucleophiles
saturated carboxylic acids represent a relatively large family of organic (Scheme 25). 5-HMF hydrazine derivative was obtained, but un-
acids, which are essential reagents in organic synthesis both as inter- fortunately, the yield was only 12% [147].
mediates and final products. For instance, they have been used to
prepare bioactive compounds such as the antibacterial reutericyclin 3.5. HMF esterification products
[138] or tetrahydromyricoid [139]. Due to their extensive applications,
the α,β-unsaturated carboxylic acids are synthesized on a commercial The esterification of HMF can prepare some important pharma-
scale. ceutical intermediates (Scheme 26). Jogia et al. reported that in a
5-Hydroxymethyl-2-furanoic acid is a critical furan-based polymer pyridine solvent, HMF reacted with an aryl acid chloride in a medium
monomer. Meanwhile, it is used in the pharmaceutical industry to yield (30–66%) to form HMF ester derivatives [148]. Cottier et al. re-
synthesize furanylamine, a derivative of esters of which is an essential ported that under the catalysis of NaOAc, acetic anhydride and HMF
fragrance and is widely used in food, cosmetics, and flavors. were esterified to produce 5-acetoxymethylfurfural with a yield of 81%
Knoevenagel-Doebner reaction is widely recognized as the primary [149]. DCC can promote the coupling reaction of HMF and coumarin-
method to construct the carbon-carbon double bond, which is necessary derived acid to prepare ester, which has inhibitory activity on protein
to provide the α, β-unsaturated carboxylic acids. However, tyrosine phosphatase 1B [150]. HMF can prepare mumefural through a
Knoevenagel-Doebner reactions often require severe refluxing condi- two-step reaction. Mumefural can improve human blood flow [151].
tions. Recently a simple method was reported for the synthesis of ac- First, in the presence of DCC, HMF was reacted with malic acid with a
rylic compounds. Hydroxymethyl furfural and malonic acid were re- protective group to obtain intermediate with a yield of 91%, and then
fluxed in a pyridine solvent to obtain furan acrylic acid with a yield of the protective group was removed to obtain mumefural with a yield of
88% [140,141] (Scheme 20). 68%.
3.4. HMF amidation products 4. Fuels
It is well known that amides are important polymer monomers. With the global consumption of fossil resources, the growth of en-
Under oxidation conditions in the presence of ammonia, 5-HMF can be ergy demand, and a large amount of greenhouse gas (GHG) emissions,
converted into a series of nitrile-amide derivatives (Scheme 21). The the living environment of human beings is facing severe challenges.
process of the amidation reaction mainly depends on the type of cata- Biomass resources have the advantages of sustainability and not in-
lyst. 2,5-furancarboxamide was obtained by using an aluminum-doped crease the net content of CO2 in the process of use. Therefore, using
manganese ore catalyst with a yield of 97% [142]. them as raw materials to obtain liquid fuel through bio-refining has
Yu et al. reported the Baylis-Hillman reaction of HMF with methyl become the current research front in the field of energy and chemical
acrylate in 2001 [143] (Scheme 22). Using 1,4-diazabicyclo [2.2.2] engineering.
octane (DABCO) as the catalyst, the identical product was obtained
after 36 h with a yield of 62% (Scheme 20). One year later, Yu et al. 4.1. 2,5-Dimethyl-fura (DMF)
reported that under the Baylis-Hillman reaction of 5-HMF and acryla-
mide with a yield of 61% [144]. 2,5-dimethylfuran (DMF) can be obtained by hydrogenolysis of
Goodman et al. reported the Horner-Wadsworth-Emmons reaction formyl and hydroxyl groups in HMF. DMF is an ideal liquid fuel with an
of 5-HMF with phosphonic imide catalyzed by DBU (Scheme 23). The ideal boiling point (92–94 °C), high energy density (30 kJ·cm−3), and
reaction was performed in THF to obtain N-[3-(5-hydroxymethylfuran- high octane number (RON = 119). DMF is also an essential raw ma-
2-yl) acryloyl] benzamide in a yield of 87% [145]. terial for biomass-derived para-xylene. Biomass-derived para-xylene
Lewis et al. reported the Mitsunobu reaction of HMF with N, O can be prepared by D-A cyclization of DMF and ethylene [152].
(bisphenoxycarbonyl) hydroxylamine to give a hydroxyurea derivative The conversion of HMF to DMF generally requires the combined
(Scheme 24) [146]. action of a hydrogenation catalyst and an acid catalyst. The
Scheme 19. The synthesis of adenosine receptor antagonist (A2A) from HMF.
10
Scheme 20. The conversion of HMF to 5-hydroxymethyl-2-furanoic acid and subsequent derivatization.
of HMF in supercritical methanol to obtain a DMF yield of 48% [167].

Noble metal catalyst has high activity and good catalytic effect, but
its price is high, which limits its application in industrial production.
Therefore, non-precious metal catalysts such as Ni-based, Cu-based, and
Scheme 21. The synthesis of furan-2,5-dicarboxamide from HMF. Fe-based catalysts have become research hotspots. Gorte et al. obtained
100% conversion of HMF and about 80% yield of DMF by using Ni/C
hydrogenation catalyst is responsible for the hydrogenation of the al- catalyst instead of noble metal catalyst at 453 K in 2-MTHF solvent for
dehyde group and the hydrogenation reaction after the fracture of the HMF HDO reaction [168]. Besides, due to the excellent catalytic ac-
C-O bond. The acid catalyst is mainly used to break the C-O bond on the tivity of the bifunctional group catalyst, it has also attracted people's
hydroxymethyl group. Various hydrogenolysis catalysts have been re- attention. Our research group used Ni-W2C/AC as a catalyst for the
ported for the conversion of HMF to DMF, such as Pd-based (Table 4, conversion of HMF to DFF in the THF solvent, and the yield of DMF is
entries 1–4) [153–155], Ru-based (Table 4, entries 5–8) [156–159], and 96% [169]. The synergy between Ni and W2C gives the catalyst the
Pt-based catalysts (Table 4, entries 9–13) [160–162]. ability to hydrogenate and deoxidize. In addition, in this catalyst, W2C
Among them, under the optimal conditions, the conversion of 100% contains both acidic sites and metal sites, which can catalyze deox-
HMF and the yield of more than 90% DMF can be obtained by the noble ygenation and hydrogenation reactions, thereby providing higher DMF
metal catalysts such as Pd-based and Pt-based catalysts. Nevertheless, yields. In addition, CoCu@C [170], NiZnAl [171], Ni2-Fe/CNTs [172],
the reaction is usually carried out at higher hydrogen pressure and Fe-N/C [173], CuZn nanoalloy [81], CuCo/NGr/αAl2O3 [174] and
temperature. The newly developed supercritical carbon dioxide water other base metal catalysts can also obtain DMF in higher yields. How-
solvent system combined with the Pd/C catalyst can significantly im- ever, the required system conditions are relatively harsh.
prove the mass transfer and heat transfer in the reaction process, and It is worth noting that Kwon et al. reported the electrocatalytic HMF
the yield of DMF is 100%. The newly developed supercritical carbon to DMF [175,176]. Although the reaction has poor selectivity and low
dioxide water solvent system combined with the Pd/C catalyst can yield, making electrocatalytic hydrogenation a potential method to
significantly improve the mass transfer and heat transfer in the reaction convert HMF to DMF requires more attention to new electrode mate-
process, and the yield of DMF is 100%. Schuth's group reported that a rials with catalytic effect.
DMF yield of 98% was obtained using a PtCo/HCS catalyst in n-butanol So far, the direct one-pot transformation of monosaccharides (glu-
at 180 °C. Rauchfuss et al. used formic acid as a hydrogen source and cose and fructose) into 2,5-DMF with a high-yield is still a great chal-
Pd/C as a catalyst to convert HMF to DMF in a yield of more than 95% lenge. The process of producing DMF from a monosaccharide goes
[153]. through two steps. First, the acid catalyzes the dehydration of the
However, in order to obtain DMF with high yield, acid catalysts monosaccharide to HMF, and then hydrogenates the HMF to DMF
such as formic acid and sulfuric acid must be used simultaneously, through a heterogeneous catalyst. Researchers have reported many
which will place higher requirements on the stability of the reaction examples of homogeneous and heterogeneous acid catalysts, such as
equipment and catalyst. Therefore, the development of an acid-free HCl/CrCl3 [177], SO42−/ZrO2-TiO2 [156], Ru/C [165], Cu-Ru/C [152],
catalyst system for the hydrogenation of HMF to DMF is a significant HT-Cu/ZnO/Al2O3 [171], and 4.8 PD/UiO-66@SGO [155]. However,
challenge. In the absence of formic acid, Chidambaram and Bell et al. the yield of DMF is relatively low. Therefore, it is very urgent to develop
used Pd/C catalysts in ionic liquids to obtain 47% HMF conversion and more efficient and cheap heterogeneous catalysts.
32% DMF yield, which avoided the use of unfriendly additives [163]. In short, noble metal catalysts have excellent catalytic performance
The low solubility of hydrogen in ionic liquids leads to a decrease in the but are difficult to scale up industrially. Therefore, there is a need to
conversion efficiency of the raw materials and an increase in the re- develop effective and stable base metal catalysts, and a milder reaction
action time. system compatible with them.
Cu and Ru-based catalysts have been shown to significantly promote
the C-O bond hydrogenolysis of HMF [164]. Román-Leshkov et al. de- 4.2. Liquid alkanes
veloped a catalytic method for preparing DMF using fructose as raw
material and catalytic conversion of HMF using a bimetallic CuRu/C Five-carbon liquid alkane is the main component of transportation
catalyst, yielding a yield of 70% DMF. However, the CuRu/C catalyst fuels such as gasoline, diesel, aviation fuel, etc. Currently, it can only be
has poor stability in the presence of chloride ions, and the reaction loss obtained from non-renewable fossil resources (coal, oil, natural gas). It
is severe. The Cu-Co/CeO2 (or ZrO2, Al2O3) bimetal catalyst can be used is of considerable significance to realize the catalytic conversion of
to achieve a 78% DMF yield [165]. The Ru/Co3O4 catalyst prepared by biomass-derived platform chemicals into more than seven carbon liquid
Wang et al. still retains high reactivity after five cycles, and can obtain alkanes.
94% DMF yield under mild reaction conditions [158]. Nagpure et al. Using HMF as a substrate, C8–C16 alkane compounds can be pre-
used a Ru-doped hydrotalcite (HT) catalyst Ru/HT to hydrolyze HMF to pared through reactions such as aldol condensation, hydroxyalkylation,
DMF to obtain a moderate product yield of 58% [166]. Hansen et al. or self-coupling. These compounds have high oxygen content, resulting
used copper-containing mixed metal oxides for catalytic hydrogenolysis in low thermal stability and energy density of the compounds.
Scheme 22. The reaction of HMF and ac-

rylamide.
11
Scheme 23. The reaction of HMF and phosphonic imide.
Continued hydrodeoxygenation (HDO) of condensation products can ring can undergo ring-opening reaction under acidic conditions to ob-
convert these oxygenates into aviation fuel. Products can be prepared tain polyketone compounds, which avoids the formation of tetra-
by the aldol condensation reaction of HMF with α-H ketone compounds hydrofuran intermediates and reduces the reaction conditions for sub-
(including acetone, methyl ethyl ketone, methyl isobutyl ketone, le- sequent hydrodeoxygenation. The obtained polyketone compound was
vulinic acid, etc.), and then long-chain alkanes can be obtained by HDO co-catalyzed by Pd/C and La(OTf)3 in glacial acetic acid to obtain linear
reaction [178,179]. and branched alkanes [187]. Chen et al. used N-heterocyclic carbene as
In 2005, Huber et al. reported the preparation of long-chain alkanes a catalyst to catalyze the benzoin condensation reaction of 5-hydro-
through a two-step reaction: a) In the presence of a MgO-Al2O3 catalyst, xymethylfurfural. The condensation product is converted into a C10–C12
a carbon chain length of 9 to 15 was obtained through the aldol con- alkane mixture under the catalytic system of Pt/C and TaOPO4 [188].
densation of 5-hydroxymethylfurfural and acetone.; b) the hydro- In addition, Abu-Omar et al. synthesized a water-resistant hetero-
deoxygenation reaction is then performed in the presence of Pd/Al2O3 geneous catalyst, zirconium carbonate Zr(CO3)x, and studied its cata-
and Pt/SiO2-Al2O3 catalysts to obtain long-chain alkanes (Scheme 27). lytic effect in the aldol condensation reaction of HMF and acetone.
The obtained alkanes can be used directly as aviation kerosene or diesel Under mild reaction conditions, the catalyst showed excellent activity,
oil, or as their additive components [180]. The research work of Huber capable of quantitatively converting HMF and obtaining a C9 con-
et al. has led to a large number of researches on the preparation of long- densation product yield of 92%, which is a precursor of C9 hydrocarbon
chain alkanes from biomass resources through the two-step reaction of fuel. HDO reaction of aldol condensation products with Pd/β molecular
aldol condensation and hydrodeoxygenation. Cueto, Dumesic, Hu et al. sieve catalysts yielded a total yield of n-nonane and 1-ethoxynonane in
studied the effects of alkali metals, alkaline earth metal oxides, and 96% [189].
basic zeolites on the aldol condensation reaction of HMF with acetone Alkylation is another way to achieve carbon chain growth. Studies
[181–183]. on the alkylation of many aldehydes (such as HMF or methylbenzal-
At the same time, bifunctional catalysts such as Pd, Pt, Ru, Ni-based dehyde) with levulinic acid or ketones have been reported [190–192].
catalysts were developed. Due to their aldol condensation reaction and HMF can undergo an F-C alkylation reaction with a benzene ring
hydrodeoxygenation reaction activity, they have also been used for the compound, thereby obtaining a condensation product with a growing
condensation of HMF and ketone compounds and Subsequent hydrocarbon chain. Condensation products can be further hydro-
deoxygenation to medium and long-chain alkanes. Barrett et al. used a deoxygenated to obtain long-chain alkanes (Scheme 28).
bifunctional catalyst Pd/MgO-ZrO2 to catalyze the aldol condensation Zhou et al. used HCl and chlorine salts (CrCl3, FeCl3) as catalyst
reaction and hydrodeoxygenation reaction of acetone and HMF in a systems to catalyze the alkylation reaction of mesitylene and HMF in a
one-pot method [184]. The aldol condensation reaction was performed formic acid/water/CH2Cl2/MeNO2 solvent, and 94% alkylated con-
at 80 ° C, and the hydrodeoxygenation reaction was performed at 120 ° densation products were obtained. These alkylation products can be
C and 5 MPa hydrogen, and 63% of water-soluble long-chain oxygen- used to prepare cyclic liquid alkanes [193].
containing organic compounds were finally obtained. Studies have Subsequently, Arias et al. reported a method for preparing long-
found that the catalyst exhibits weak acidity and can only convert the chain naphthenes using toluene and 5-hydroxymethylfurfural as raw
condensation products into water-soluble intermediates (containing materials through alkylation reaction and hydrodeoxygenation [194]
tetrahydrofurfuryl rings) instead of the final linear alkanes. Palkovits (Scheme 29). Zeolites such as USY-1, ITQ-2, MCM-41, and PTSA are
et al. used a Cu/MgAl2O4 bifunctional catalyst for aldol condensation used to catalyze the F-C alkylation of toluene with 5-hydro-
reaction of HMF and acetone and subsequent hydrodeoxygenation re- xymethylfurfural. 91% of the alkylated product was obtained. Subse-
action. However, the Cu/MgAl2O4 catalyst is effective only for the C-O quently, Pt/C and Pt/TiO2 are used to hydrodeoxygenate the alkylated
bond hydrocracking of primary and secondary alcohols. It is not valid products in a fixed-bed reactor to obtain a C8 to C13 long-chain
for hydrogenation and ring-opening of furan rings. The final product naphthene mixture, which can be directly used as aviation fuel. In
was 3-hydroxybutyl-5-methylfuran instead of a linear alkane, with a addition, zeolite catalysts are also used in the F-C alkylation of other
selectivity of 84% [185]. Wang et al. used sodium hydroxide as a cat- benzenes such as o-xylene, mesitylene, and anisole with 5-hydro-
alyst to promote the condensation reaction of HMF and acetone while xymethylfurfural, which can also obtain long-chain oxygen-containing
using a Pd/NbOPO4 catalyst to hydrodeoxygenate the condensation intermediates.
products to obtain nonane products. The reaction system is also ap-
plicable to the process of preparing octane by the condensation of 4.3. HMF etherification products
furfural and acetone [186].
Although Huber's work has adequately demonstrated that alkanes Alkoxymethylfurfural (such as MMF and EMF) and 2,5-bis (alkox-
can be prepared from tetrahydrofuran-containing intermediates by ymethyl) furan (BXMF) obtained by etherification and hydro-
hydrodeoxygenation, it should be noted that the reaction conditions are etherification reaction of fatty alcohol and HMF have been proved to be
harsh (300 °C, 5.5 MPa). This issue has attracted the attention of many used Diesel fuel additives and oxygenated fuels (Scheme 30).
researchers. Gordon et al. studied the hydrodeoxygenation reaction of According to Avantium, EMF is an excellent additive for diesel with
HMF and acetone aldol condensation products. It is found that the furan a high energy density of 8.7 kWh·L−1, which is similar to regular
Scheme 24. The synthesis of hydroxyurea deri-

vative from HMF.
12
Scheme 25. The synthesis of hydrazine derivative from HMF.
Scheme 26. The synthesis of HMF esterification products.
Table 4
The conversion of HMF to DMF.
Entry Catalyst Solvent Reaction conditions HMF conversion [%] DMF yield [%] Ref.
1 Pd/C Water 80 °C, 2 h, PH2 = 1 MPa, PCO2 = 10 MPa 100 100 [153]
2 Pd/C THF 60 °C, 6 h, 0.1 MPa 99 99 [154]
3 PdAu/C THF 60 °C, 6 h, 0.1 MPa 99 99 [154]
4 4.8 wt% Pd/UiO-66@SGO THF 160 °C, 3 h, 1 MPa 99.9 99.2 [155]
5 Ru/C THF 180 °C, 2 h, 2 MPa 100 95 [156]
6 Ru/Cu/Fe3O4/rGO DMSO 150 °C, 0.3 h, 0.8 MPa 100 91 [157]
7 40 wt% Ru/Co3O4 THF 130 °C, 24 h, 0.7 MPa 99.9 93.4 [158]
8 Ru/CoFe-LDO THF 180 °C,6 h, 1 MPa 95.2 91.8 [159]
9 Pt3Co2/C 1-Propanol 16 0 °C, 3.3 MPa, W/F = 1.0 g min/g 100 98 [160]
10 Pt3Ni/C 1-Propanol 200 °C, 3.3 MPa, W/F = 1.0 g min/g 100 98 [161]
11 Pt2Zn/C 1-Propanol 200 °C, 3.3 MPa, W/F = 1.0 g min/g 100 98 [161]
12 PtCu/C 1-Propanol 200 °C, 3.3 MPa, W/F = 1.0 g min/g 100 96 [161]
13 PtCo@HCS 2 1-Butanol 180 °C, 2 h, 1 MPa 100 98 [162]
14 CuZn nanoalloy CPME 200 °C, 6 h, 2 MPa 100 89.1 [83]
15 CuCo/NGr/αAl2O3 THF 180 °C, 16 h, 2 MPa > 99 > 99 [174]
16 Ni-W2C/AC THF 180 °C, 3 h, 3 MPa > 99 > 99 [169]
17 NiZnAl 1,4-Dioxane 180 °C, 7 h, 1.5 MPa 100 93.6 [171]
18 Ni2-Fe1/CNTs n-Butanol 200 °C, 3 h, 3 MPa 100 91.3 [172]
19 CoCu@C Ethanol 180 °C, 8 h, 5 MPa 100 99.4 [170]
20 20 wt% Fe-N/C n-Butanol 240 °C, 6 h, 4 MPa 100 86 [173]
Scheme 27. The preparation of liquid alkanes from HMF and acetone.
13
Scheme 28. The preparation of liquid alkanes from HMF and cyclic ketone.
Scheme 29. The preparation of liquid alkanes from HMF and toluene.
Scheme 30. The preparation of etherification products

from HMF.
gasoline (8.8 kWh·L−1) and almost as good as diesel (9.7 kWh·L−1) and system to achieve the one-pot reduction of HMF to 2,5-bis(ethox-
significantly higher than ethanol (6.1 kWh·L−1). The company has also ymethyl)furan and 5-(ethoxymethyl)furfuryl alcohol, respectively
successfully tested EMF applications in engines to demonstrate the [217]. In the study of Gruter et al., HMF was first hydrogenated to
potential of this new biofuel [195]. At present, a variety of catalytic BHMF in the presence of a Pt/C catalyst, and then BHMF was cataly-
systems have been reported for the conversion of HMF to EMF. The tically etherified to produce BXMF in a yield of 75% [218]. Mu et al.
separation, recovery, and reuse of homogeneous catalysts are difficult, used a Cu/SiO2 and HZSM-5 co-catalyst system to obtain a 70% BMMF
resulting in a large number of waste salts [196]. Correspondingly, the yield through a two-step catalytic conversion of HMF [83].
recovery of heterogeneous catalysts is simple, and the equipment is less At present, the reductive etherification of HMF to prepare BMMF
corrosive. Therefore, many researchers have tried to find suitable solid generally uses a co-catalyst system composed of a hydrogenation cat-
acid catalysts [197–199]. Researchers have successively reported the alyst and an acid catalyst. However, it is still challenging to obtain
reaction effects of Zr-SBA-15, Al-MCM-41 [200], k-10 clay-HPW [201], reductive etherification products with high yields under mild condi-
SiO2-SO3H [202], Fe3O4@SiO2-HPW [203], Fe3O4@SiO2-SO3H [204], tions using bifunctional catalysts that have both hydrogenation activity
Fe3O4@C-SO3H [205], Fe3O4@ SiO2-SH-Im-HSO4 [206], and found that and etherification activity. Our group has developed the efficient re-
the yield of EMF has improved slightly, but none have exceeded 90%. In ductive etherification of HMF to BMMF by using the simple reduced
addition, ionic liquids have also been reported as catalysts or additives metallic Co catalyst [219]. HMF was converted completely, and 98.5%
for the conversion of HMF to EMF [207]. Due to the difficulty in se- yield of etherified product BMMF was obtained by using the Co-400
parating HMF, ionic liquids are limited by practical applications. catalyst. According to XRD analysis, we found that only the diffraction
Many efforts have also been made in the one-pot synthesis of EMF peaks arising from Co0 species were present, indicating that Co3O4
from fructose and glucose. For example, the use of a sulfonic acid- species were in an amorphous state in the Co catalyst. The catalyst
functionalized ionic liquid to catalyze the hydrolysis-etherification of became more porous and rougher after reduction at a high temperature,
fructose can yield an EMF yield of 55% [208]. Heteropoly acid according to the TEM and SEM analyses. This may be more beneficial
H3PW12O40 was used as a catalyst for the production of EMF from for enhancing the selectivity of the etherification product and the mass
fructose, sucrose, and inulin [209]. The K-10 clay-supported transfer of reaction species. Finally, 66.5% isolated yield of BMMF was
H3PW12O40 catalyst showed high activity for the synthesis of EMF. A obtained from fructose in two-steps.
yield of 61.5% was obtained from fructose through a one-pot reaction.
The catalyst also showed high stability [201]. The method of EMF
5. Summary and outlook
synthesis from glucose is complicated, where the isomerization of glu-
cose to fructose is a crucial step [210].
With the constant consumption of resources, undoubtedly, the in-
In short, the EMF synthesis of HMF, fructose, or glucose all involves
evitable increase in the price of fossil resources will give an impetus to
acid-catalyzed reactions. Proper adjustment of the catalyst acidity and
development for broader industrial utilization of biomass-based re-
acid species can achieve high yields of EMF [211].
sources. As an essential biomass platform molecule, 5-hydro-
The synthesis of 2,5-bis (alkoxymethyl) furan (BXMF) first requires
xymethylfurfural is a vital bridge to connecting petroleum-based re-
hydrogenation of HMF to BHMF, and then it is obtained by catalytic
sources and biomass-based resources. The catalytic conversion of HMF
etherification with an acid catalyst. Reductive etherification is gen-
can produce a variety of high value-added fuels and chemicals, and they
erally carried out by transition metal catalysts [212], Lewis acids [213],
have critical applications in the fields of medicine, pesticides, materials,
Brønsted acid [214], and organic thiourea catalysts catalyzed [215].
and fuel. The significant increase in the number of publications over the
According to current reports, the yield of reductive etherification of
years can see the related fiery research of HMF. Redox reaction and
HMF is generally low, which may be due to the formation of deep
ring-opening reactions are important ways of HMF conversion, which
hydrolysis product levulinic acid, the acetal reaction of aldehyde
can prepare a series of high value-added chemicals and fuels. We added
groups on HMF and the formation of oligomeric humins, resulting in
a comprehensive table to briefly summarize the derivatives of HMF
lower yields of reduced etherification [216].
mentioned in this review as well as their catalyst systems and yield
Balakrishnan et al. used a Pt/Al2O3 and Amberlyst-15 co-catalyst
ranges for better comparison (Table 5).
14
Table 5
The conversion of HMF to derivatives.
Yield
Substrate Derivative Catalyst system Ref.
[%]
HMF DFF Mn-based catalyst, certain oxygen pressure 77–99 [24–29]
Fructose DFF V-based catalyst, two-step method 42–77 [30–33]
Fructose DFF GO, one-step method 53 [43]
Fructose DFF Cs0.5H2.5PMo12, one-step method 69 [44]
HMF FDCA Pd-based catalyst, add base 70–99 [47–54]
HMF FDCA Pt-based catalyst, add base 74–96 [56–60]
HMF FDCA Fe-based catalyst, add base 60.6–79 [61,63,64]
HMF FDCA Electrolysis 96–99 [67,68]
HMF FDCA Illumination, add base 95 [69]
Glucose FDCA Amberlyst-15, CrCl3·6H2O, Au–Pd/HT 50 [72]
Fructose FDCA HCl, Au–Pd/HT 41 [72]
Fructose FDCA Ru/C 53 [73]
Fructose FDCA Fe3O4–CoOx 59.8 [88]
HMF BHMF Ni/MCM-41, H2 89.0 [76]
HMF BHMF Au/Al2O3 96 [78]
HMF BHMF Au/Al2O3 96 [78]
HMF BHMF Cu-ZnO 99.1 [83]
HMF MA V-based catalyst, 59–75 [89–91]
HMF MA H2O2 89 [92]
HMF HCPN Au/Nb2O5, certain hydrogen pressure 86 [95]
HMF HCPN Au/TiO2, certain hydrogen pressure 54 [95]
HMF HHD Pd/Nb2O5, certain hydrogen pressure 85 [101–103]
HMF HHD Au/Nb2O5, certain hydrogen pressure 86 [95]
HMF HHD Cp*Ir (III) semi-sandwich composite catalysts 98 [106]
HMF HHD Pd/MIL-101, certain hydrogen pressure 85 [107]
Triphenylphosphonium bromide and potassium

HMF HMVF 67 [109]
carbonate
HMF HMEF Ohira-Bestmann reagent, Cs2CO3 97 [111]
HMF 1,6-HD Rh-ReOx/SiO2, certain hydrogen pressure 100 [115]
HMF 1,6-HD Pd/ZrP 42.5 [116]
(continued on next page)
15
Table 5 (continued)
HMF 5-CMF Me3SiCl 92 [119–121]
HMF 5-BMF Me3SiBr >98 [119–121]
2-(Hydroxymethyl)-5-
HMF Raney nickel 91 [122]
(aminomethyl)-furan
5-Aminomethyl-2-furfuryl
HMF NaBH4 >70 [123]
alcohol
HMF N-containing biomass compounds Au/TiO2-R >80 [124]
HMF Co-DABCO-TPA@C-800 89 [125]
alcohol
HMF Ru/Nb2O3, certain hydrogen pressure 96 [126]
alcohol
2-Hydroxy-1,2-bis(5-
HMF (hydroxymethyl)furan-2-yl)ethan- NHC, K2CO3 74 [127]
1-one
HMF Chalcone KF/Al2O3, MW 76 [128]
HMF Furan-2,5-dicarboxamide [Al]-KOM-2 97 [142]
2-(Hydroxy(5-
HMF (hydroxymethyl)furan-2- DABCO 62 [143]
yl)methyl)acrylamide
HMF DMF Pd-based catalyst, certain hydrogen pressure 99–100 [153–155]
HMF DMF Ru-based catalyst, certain hydrogen pressure 91–95 [156–159]
HMF DMF Pt-based catalyst, certain hydrogen pressure 96–98 [160–162]
HMF DMF Cu-based catalyst, certain hydrogen pressure 89.1–99 [170,81]
HMF DMF 20 wt% Fe-N/C 86 [173]
HMF DMF Ni2-Fe/CNTs 91.3 [172]
Fructose DMF Ru/C 50 [165]
Fructose DMF Cu-Ru/C 73 [152]
Fructose DMF HT-Cu/ZnO/Al2O3 40.6 [171]
Glucose DMF PD/UiO-66@SGO 45.3 [155]
Furyl
C10–C12 alkane compounds Pt/C, TaOPO4 [188]
compounds
HMF EMF MCM-41-HPW 83.4 [200]
HMF EMF k-10 clay-HPW 91.5 [201]
HMF EMF [BmimSO3H]3PW12O40 90.7 [207]
Fructose EMF k-10 clay-HPW 61.5 [201]
(continued on next page)
16
Table 5 (continued)
Fructose EMF [BmimSO3H]3PW12O40 90.5 [207]
Fructose EMF H3PW12O40, MW 65 [209]
Sucrose EMF H3PW12O40, MW 33 [209]
Inulin EMF H3PW12O40, MW 62 [209]
HMF 2,5-Bis(ethoxymethyl)furan Pt/Al2O3, Amberlyst-15 59 [218]
HMF 2,5-Bis(ethoxymethyl)furan Co-400, certain hydrogen pressure 84.1 [220]
5-(Ethoxymethyl)furfurylalcohol
HMF Pt/Al2O3, Amberlyst-15 26 [218]
alcohol
5-Methoxymethyl-furfuryl
HMF Co-400, certain hydrogen pressure 40.7 [220]
alcohol
HMF 2,5-Bis(methoxymethyl)furan Co-400, certain hydrogen pressure 66.7 [220]
For the crucial downstream material monomers of HMF, such as of the CAS (XDA21060101), the National Key Research and
furandicarboxylic acid and furan dimethanol, researchers have devel- Development Program of China (2018YFB1501604), the National
oped a variety of catalytic systems and achieved good product yields. Natural Science Foundation of China (21572212, 51821006,
However, there are still problems such as low reaction substrate con- 51961135104), the Major Science and Technology Projects of Anhui
centration, short catalyst life, and high product preparation costs. This Province (18030701157), and the Local Innovative and Research
is still a certain distance from the further industrial production of Teams Project of Guangdong Pearl River Talents Program
monomers and materials. Therefore, it is still an important subject for (2017BT01N092).
researchers to develop a cheaper and more efficient catalyst system and
achieve highly selective preparation of monomers downstream of HMF. References
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lyzed reductions of carbonyl compounds and their derivatives, Tetrahedron 44
21

Conversion of 5-Hydroxymethylfurfural To Chemicals-A Review of Catalytic - Reference For HMF Conversion To Chemicals and Production Applications

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Fuel Processing Technology 209 (2020) 106528

Contents lists available at ScienceDirect

Fuel Processing Technology

Invited review article

Conversion of 5-hydroxymethylfurfural to chemicals: A review of catalytic T

Scheme 1. The conversion pathway from cellulose to HMF.

Fig. 2. Application of HMF derivatives.

Scheme 2. The main conversion pathways of HMF in material monomer applications.

1 OMS-2 N,N-dimethylformamide 110 °C, 5 bar O2, 1 h 100 97.2 [24]

Scheme 3. The conversion path from HMF

1 Pd-Bi-Te/C H2O–methanol 50 °C, 6 h, KOH O2 95 [47,48]

and environmentally friendly. Table 3

Scheme 5. The conversion of HMF to MA and MAC.

Scheme 6. The conversion of HMF to HHD and HCPN.

Scheme 8. Cross-linking mechanism of HMVF to poly-HMVF.

halogenation reaction of HMF to obtain a medium or higher yield

Scheme 10. Multiple transformation pathways of HMEF.

Scheme 11. The conversion of HMF to pharmaceutical intermediates.

attracted researchers' interest. Beller et al. reported that cobalt nano-

3.3. Products of HMF condensation with various reagents

Scheme 12. The conversion of HMF to 5-CMF

Scheme 16. The aldol condensation reaction of HMF.

Scheme 18. The synthesis of 5-hydroxymethyl furfural curcumin analogs.

3.4. HMF amidation products 4. Fuels

of HMF in supercritical methanol to obtain a DMF yield of 48% [167].

Scheme 22. The reaction of HMF and ac-

Scheme 23. The reaction of HMF and phosphonic imide.

Scheme 24. The synthesis of hydroxyurea deri-

Scheme 25. The synthesis of hydrazine derivative from HMF.

Scheme 26. The synthesis of HMF esteriﬁcation products.

Scheme 30. The preparation of etheriﬁcation products

HMF DFF Mn-based catalyst, certain oxygen pressure 77–99 [24–29]

Fructose DFF V-based catalyst, two-step method 42–77 [30–33]

Fructose DFF GO, one-step method 53 [43]

Fructose DFF Cs0.5H2.5PMo12, one-step method 69 [44]

HMF FDCA Pd-based catalyst, add base 70–99 [47–54]

HMF FDCA Pt-based catalyst, add base 74–96 [56–60]

HMF FDCA Fe-based catalyst, add base 60.6–79 [61,63,64]

HMF FDCA Electrolysis 96–99 [67,68]

HMF FDCA Illumination, add base 95 [69]

Glucose FDCA Amberlyst-15, CrCl3·6H2O, Au–Pd/HT 50 [72]

Fructose FDCA HCl, Au–Pd/HT 41 [72]

Fructose FDCA Ru/C 53 [73]

Fructose FDCA Fe3O4–CoOx 59.8 [88]

HMF BHMF Ni/MCM-41, H2 89.0 [76]

HMF BHMF Au/Al2O3 96 [78]

HMF BHMF Au/Al2O3 96 [78]

HMF BHMF Cu-ZnO 99.1 [83]

HMF MA V-based catalyst, 59–75 [89–91]

HMF MA H2O2 89 [92]

HMF HCPN Au/Nb2O5, certain hydrogen pressure 86 [95]

HMF HCPN Au/TiO2, certain hydrogen pressure 54 [95]

HMF HHD Pd/Nb2O5, certain hydrogen pressure 85 [101–103]

HMF HHD Au/Nb2O5, certain hydrogen pressure 86 [95]

HMF HHD Cp*Ir (III) semi-sandwich composite catalysts 98 [106]

HMF HHD Pd/MIL-101, certain hydrogen pressure 85 [107]

Triphenylphosphonium bromide and potassium

HMF HMEF Ohira-Bestmann reagent, Cs2CO3 97 [111]

HMF 1,6-HD Rh-ReOx/SiO2, certain hydrogen pressure 100 [115]