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Review
Catalytic advances in the production and application of biomass-derived 2,5-dihydroxymethylfuran Lei Hu, Jiaxing Xu, Shouyong Zhou, Aiyong He, Xing Tang, Lu Lin, Jiming Xu, and Yijiang Zhao ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.7b03530 • Publication Date (Web): 28 Feb 2018 Downloaded from http://pubs.acs.org on February 28, 2018
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Catalytic advances in the production and application of biomass-derived 2,5-dihydroxymethylfuran
Lei Hu,*,† Jiaxing Xu,† Shouyong Zhou,† Aiyong He,† Xing Tang,‡ Lu Lin, ‡ Jiming Xu,† and Yijiang Zhao†
†
Jiangsu Key Laboratory for Biomass-based Energy and Enzyme Technology, Jiangsu Collaborative
Innovation Center of Regional Modern Agriculture & Environmental Protection, School of Chemistry and Chemical Engineering, Huaiyin Normal University, Huaian 223300, China ‡
College of Energy, Xiamen University, Xiamen 361102, China
ABSTRACT: In recent years, 2,5-dihydroxymethylfuran (DHMF), which can be produced by the selective hydrogenation of biomass-derived 5-hydroxymethylfurfural (HMF), has attracted great attention and interest of many scientists due to its peculiar symmetrical structure and wide potential applications. At present, studies on the production of DHMF are quickly progressing, with productive approaches being increasingly developed, many crucial achievements have been continually obtained. However, to date, a special and real-time review of this research area is still lacking. To
gain more insight into the current research situation, this review comprehensively summarizes and discusses state-of-the-art advancements of the production of DHMF from HMF via various chemocatalytic pathways, such as conventional hydrogenation, transfer hydrogenation, electrocatalytic hydrogenation, photocatalytic hydrogenation and disproportionation reaction, and biocatalytic pathways. Meanwhile, this review also systematically outlines the latest results of the further transformation of DHMF into value-added derivatives via etherification, polymerization and rearrangement.
KEYWORDS: Biomass; 5-Hydroxymethylfurfural; 2,5-Dihydroxymethylfuran; Selective hydrogenation; Further transformation; Value-added derivatives
1. INTRODUCTION At present, most chemicals and fuels in the world are directly or indirectly produced from the non-renewable fossil resources.1-5 However, as the depletion of fossil resources, exploring appropriate renewable resources has becoming increasingly urgent and necessary.6-10 As the only carbon-based renewable resource in the nature, biomass, possessing many excellent merits such as abundance, diversity, pervasiveness and low cost, is considered to be an optimal and inexhaustible feedstock for the sustainable production of chemicals and fuels.11-16 To make good use of biomass, biorefinery is a very momentous approach.17-20 During the biorefinery process, 5-hydroxymethylfurfural (HMF), which is
obtained by
the
dehydration of
biomass-derived carbohydrates such as fructose,21-26 glucose,27-32 sucrose,33-38 cellobiose,39-43 inulin,44-48 starch49-54 and cellulose,55-60 is hailed as one of the most
important fundamental compounds61-65 because it can be used to synthesize many high-value products via various reactions (Figure 1). For instance, the selective hydrogenation
3-hydroxymethylcyclopetanone (HMCPN).108-110 Among them, DHMF is highly attractive due to its peculiar symmetrical structure and wide potential applications in the production of ethers,111-113 ketones114 and polymers;115-120 hence, it has received much more attention and interest from various scientists. It is generally known that HMF contains C=O, C=C and C−O bonds that cause its very strong reactivity.121-125 Thus, ensuring the hydrogenation of C=O bond and avoiding the further hydrogenolysis of C=C and C−O bonds are the key issues in the selective hydrogenation of HMF into DHMF (Figure 2), which is very similar to the exclusive reduction of α,β-unsaturated aldehydes or ketones into the corresponding unsaturated alcohols.126-131 To solve these issues, many chemocatalytic hydrogenation pathways, such as conventional hydrogenation, transfer hydrogenation, electrocatalytic hydrogenation, photocatalytic hydrogenation and disproportionation reaction, and biocatalytic hydrogenation pathways have been gradually developed in recent years. In 2013 and 2016, Nakagawa et al.121 and Gilkey and Xu132 reviewed some of the available catalytic pathways for the transformation of biomass-derived fundamental compounds,
such as glycerol (GC), furfural (FF) and levulinic acid (LA), in which the selective hydrogenation of HMF into DHMF was partially involved. However, to the best of our knowledge, a special and real-time review of this research area has not been published until now. To gain more insight into the current status of research, state-of-the-art advancements of the catalytic pathways for the selective hydrogenation of HMF into DHMF were comprehensively summarized and discussed in this review. Furthermore, the latest results on the further transformation of DHMF into other valuable derivatives via etherification, polymerization and rearrangement were also systematically outlined. In a word, the main aim of this review is to attract concerns about DHMF and provide some theoretical references and technical supports for the practical production and application of DHMF in the near future.
2. CHEMOCATALYTIC HYDROGENATION OF HMF INTO DHMF In earlier studies, DHMF was mainly prepared by the stoichiometric hydrogenation of HMF in the presence of lithium aluminum hydride (LiAlH4) or sodium borohydride (NaBH4).133-137 However, this pathway has some problems such as the post-treatment of reductive agents and the co-production of equivalent salts. To overcome these problems, substantial efforts have been made to find more proper and greener chemocatalytic pathways that are able to effectively and selectively hydrogenate HMF into DHMF. In the subsequent section, we summarized various chemocatalytic pathways
including
conventional
hydrogenation,
transfer
hydrogenation,
electrocatalytic hydrogenation, photocatalytic hydrogenation and disproportionation
reaction in a comprehensive manner, and we also discussed the effects of various reaction parameters including hydrogen donors, catalysts and solvents on the selective hydrogenation of HMF into DHMF. 2.1. Conventional hydrogenation pathway As is known to all, employing molecular hydrogen (H2) as a hydrogen donor for the selective hydrogenation of HMF is the most common and important pathway to produce DHMF, which has been widely studied over various catalysts in recent years. For example, ruthenium-based dinuclear complex (Ru-based Shvo’s catalyst) was used by Pasini et al. in 2014 for the selective hydrogenation of HMF.138 Under 10 bar H2, an excellent yield of DHMF of 99% was achieved in the presence of toluene at 90 °C for 1 h. Interestingly, the combined experimental and theoretical results indicated that the hydroxyl group moiety in HMF played an important role in the catalytic cycle towards the formation of various intermediates from HMF to DHMF (Figure 3). More surprisingly, a very simple method for separating the target product was developed by directly cooling the reactor to room temperature, which led to the quantitative precipitation of DHMF from the reaction mixture.138 In addition, it should be noted that although a Ru-based Shvo’s catalyst displayed good catalytic performance for the selective hydrogenation of HMF into DHMF, it is a homogeneous catalyst and shows poor recyclability. In this context, heterogeneous catalysts have drawn wide attention (Table 1).
Recently, a series of ruthenium-based heterogeneous catalysts, such as carbon-supported ruthenium (Ru/C),139 zirconia-supported ruthenium (Ru/ZrO2),140 alumina-supported ruthenium (Ru/Al2O3),141 cerium oxide-supported ruthenium (Ru/CeOx),141
zirconia-magnesia-supported
ruthenium
(Ru/ZrO2-MgO)141
and
zirconia-silica-supported ruthenium (Ru/ZrO2-SiO2),142 were designed and prepared. When they were applied for the selective hydrogenation of HMF in water, 1-butanol or 1-butanol/water, DHMF was generated with high yields of 74.5∼100% under moderate reaction conditions. More importantly, these ruthenium-based heterogeneous catalysts could be readily isolated from the corresponding catalytic systems by filtration and then successively used at least five times without an obvious loss in the yield of DHMF,139-142 clearly indicating that they also possessed superior retrievability and reusability.
Unsurprisingly,
like
ruthenium-based
heterogeneous
catalysts,
platinum-based heterogeneous catalysts exhibited parallel catalytic abilities for the selective hydrogenation of HMF. When carbon-supported platinum (Pt/C),143 alumina-supported
platinum
(Pt/Al2O3)112
and
zeolite-supported
platinum
(Pt/MCM-41)144 were used as catalysts, 82∼100% yields of DHMF could be obtained in water or ethanol. Inspired by these satisfactory results, other heterogeneous catalysts such as carbon-supported palladium (Pd/C),145 titania-supported iridium (Ir/TiO2)146 and iron oxide-supported gold (Au/FeOx)147 were subsequently synthesized and employed for the selective hydrogenation of HMF into DHMF. Notably, most heterogeneous catalysts are composed of active metals and auxiliary supports. Apart from the metal properties, such as electron deficiency, particle size and dispersion
degree, the selective hydrogenation of HMF into DHMF may be strongly affected by the natures of supports. To verify this speculation, Ohyama et al. prepared a variety of gold catalysts.148 The experimental results demonstrated that when gold was immobilized on basic supports, such as alumina (Al2O3), lanthana (La2O3) and ceria (CeO2), the corresponding catalysts could effectively catalyze the selective hydrogenation of HMF into DHMF. However, when gold was immobilized on acidic supports, such as titania (TiO2), tantalum pentoxide (Ta2O5) and sulfated zirconia (SO42−/ZrO2), almost no DHMF was formed under the same reaction conditions, suggesting that compared with acidic supports, basic supports were more conducive to the formation of DHMF, which was probably caused by favoring the adsorption of C=O and the dissociation of H2.148 Hence, it can be concluded that the remarkable catalytic performance of heterogeneous catalysts for the selective hydrogenation of HMF into DHMF should be ascribed to the synergistic actions between active metals and auxiliary supports. Among the above heterogeneous catalysts, whether Ru, Pt, Ir or Au, they are precious metals, and therefore, are very expensive. From the viewpoint of economization and industrialization, the development of non-precious metal-based heterogeneous catalysts are highly desirable for the selective hydrogenation of HMF into DHMF. To explore the potential of non-precious metal-based heterogeneous catalysts, Cao et al.,113 Kumalaputri et al.,149 Zhu et al.150 and Lima et al.151 prepared silica-supported copper (Cu/SiO2), copper-doped porous metal oxide (Cu/PMO), zinc oxide-supported copper (Cu/ZnO), RANEYCu and RANEYNi, respectively. When they were employed as catalysts for the selective hydrogenation of HMF in methanol,
ethanol, 1,4-dioxane and water, the yields of DHMF were up to 97, 99, 99.1, 86.5 and 60% under 25, 50, 15, 90 and 90 bar H2 at 100, 100, 100, 90 and 90 °C for 8, 3, 2, 8 and 8 h, respectively, indicating that the non-precious metal-based heterogeneous catalysts, especially the Cu-based heterogeneous catalysts, possessed similar catalytic performance to that of precious metal-based heterogeneous catalysts for the selective hydrogenation of HMF into DHMF. More gratifyingly, by adjusting the hydrogen pressure and reaction temperature, these non-precious metal-based heterogeneous catalysts could also be applied for the synthesis of other products such as DMF and DHMTHF.149-152 In contrast to monometallic heterogeneous catalysts, bimetallic heterogeneous catalysts are thought to be more effective for the selective hydrogenation of HMF into DHMF because of their special geometric structures and electronic environments.152-156 For instance, carbon nanotube-supported nickel and iron (NiFe/CNT) that was developed by Yu et al. provided a 96.1% yield of DHMF at 110 °C for 18 h in the presence of 30 bar H2, whereas DHMF yield was only 76.4% over carbon nanotube-supported
nickel
(Ni/CNT).153
More
interestingly,
when
carbon
nanotube-supported iron (Fe/CNT) was used, DHMF was not produced under the same reaction conditions, evidently demonstrating that the synergy between Ni and Fe was the main reason for the excellent catalytic performance of NiFe/CNT, which could be proved by the calculational results of density functional theory (DFT). To be specific, the addition of oxyphilic Fe on the basis of Ni could form a NiFe alloy that was very beneficial to the stabilization of the surface species of the η2-(C,O)-coordination, which
would further promote the selective hydrogenation of C=O of HMF on the bimetallic alloy due to a strong interaction between the carbonyl O and the oxyphilic Fe.153 Motivated by NiFe/CNT, alumina-supported copper and nickel (CuNi/Al2O3),154 carbon-supported copper and zinc (CuZn/C),152 copper-zinc nanoalloy (CuZn)155 and cobalt-aluminum nanoalloy (CoAl)156 were also prepared for the selective hydrogenation of HMF; the comparable yields of DHMF were achieved under similar reaction conditions to those over NiFe/CNT. Moreover, the bimetallic heterogeneous catalysts containing precious metals could allow more milder reaction conditions for the
selective
hydrogenation of
HMF
into
DHMF.157-159 Particularly, when
silica-supported iridium and rhenium (IrRe/SiO2)158 and graphene oxide-supported platinum and stannum (PtSn/SnO2/RGO)159 were used for the selective hydrogenation of HMF, DHMF could be effectively synthesized in high yields of 99 and 99% at very low temperatures of 30 and 70 °C in 6 and 0.5 h under 8 and 20 bar H2, respectively. In addition to the types of catalysts, the selective hydrogenation of HMF into DHMF is also highly associated with the properties of solvents. Generally, the employed solvents in the selective hydrogenation of HMF into DHMF can be divided into polar protic solvents (such as water, methanol, ethanol, propanol and butanol), polar aprotic solvents (such as acetone and tetrahydrofuran) and nonpolar solvents (such as hexane), and they have various δ values that represent the difference between the acceptor and donor numbers, which are related to a quantitative measure of the Lewis acidity and basicity, respectively. Due to the negative δ values, the protic solvents that are capable of accepting electrons showed better performance than the aprotic
solvents with positive δ values that are the symbol of donating electrons, which could be verified by the results of Chatterjee et al.144 and Han et al.140 Furthermore, with an increase in the value of δ, a declining tendency in the conversion of HMF was also observed in protic solvents (Figure 4), indicating that the δ values of solvents had a great impact on the conversion of substrates.144 Compared with polar solvents, nonpolar solvents exhibited worse performance for the selective hydrogenation of HMF into DHMF under the same conditions, which might be caused by a lower solubility of H2 and a harder polarization of C=O in nonpolar solvents.140 Additionally, the pH values of solutions are also a momentous factor influencing the selective hydrogenation of HMF into DHMF. In contrast to a solution of pH = 7, when this reaction was conducted in a solution of pH < 7, the selectivity of DHMF was unsatisfactory even though HMF could be nearly converted because of the formation of undesirable byproducts, such as 1,2,5-hexanetriol (1,2,5-HT), 1,2,6-hexanetriol (1,2,6-HT) and 1,2,5,6-hexanetetrol (1,2,5,6-HT), resulting from the acid-catalyzed ring-opening and subsequent hydrogenation of DHMF.141 If this reaction was conducted in a solution of pH > 7, DHMF was generated with high selectivity; however, the conversion of HMF was very low.144 Accordingly, it is concluded from the above analysis that neutral water with a smaller δ value and a stronger polarity is regarded as a good solvent, which has been widely used by many researchers for the selective hydrogenation of HMF into DHMF (Table 1). By the conventional catalytic pathway, HMF can be selectively hydrogenated into
DHMF, in which H2 is mostly employed as a hydrogen donor owing to its wide availability and easy activation on many metal surfaces. However, the low solubility of H2 in most solvents requires a high hydrogen pressure to achieve the desired conversion and yield. Apart from the safety issue, handling high pressure hydrogen will incur high infrastructure costs, which introduces an economic barrier to the production of DHMF. To further improve the security and economy of the selective hydrogenation of HMF into DHMF, many novel catalytic pathways without the addition of external molecular H2 have been gradually developed in recent years. 2.2. Transfer hydrogenation pathway The pathway of catalytic transfer hydrogenation (CTH) offers a very promising alternative to the conventional hydrogenation pathway with external molecular H2. In particular, carbonyl compounds including aldehydes and ketones can be exclusively reduced to the corresponding alcohols via the Meerwein-Ponndorf-Verley (MPV) reaction by using formic acid and alcohols as hydrogen donors.160-164 Compared with H2, formic acid and alcohols such as ethanol and isopropanol usually exist in the form of liquid at ambient conditions, and therefore, they are more convenient and secure in the processes of storage, transportation and usage. Furthermore, when they are used as hydrogen donors, additional facilities for the delivery of H2 are unnecessary, leading to a decrease in the number of unit operations. In addition, for alcohols, they can also act as reaction mediums. Hence, when alcohols are used as hydrogen donors, additional reaction mediums are no longer needed, which can also enhance the economy of CTH to some extent. If alcohols are cheap enough, the economy of CTH
will be more obvious. More importantly, after the end of CTH, the unconverted alcohols can be separated from the reaction mixture and then reused as hydrogen donors and reaction mediums, and the converted alcohols, that is, the produced aldehydes or ketones, can also be separated and then integrated into the other reaction steps, such as carbon chain growth reaction via aldol condensation. Based on the above-described advantages, the pathway of CTH has long been extensively employed for the selective reduction of various carbonyl compounds, such as citral (CT),165-168 FF,169-173 benzaldehyde (BA),174-178 crotonaldehyde (CA),179-183 LA184-188 and ethyl levulinate (EL),189-193 via the reaction of MPV. In this respect, it is necessary to emphasize that HMF is also a carbonyl compound with an aldehyde group, and it should be applicable to CTH in theory (Table 2). To verify the feasibility and availability of CTH in the selective hydrogenation of HMF, formic acid, which is an important and renewable co-product in the acid-catalyzed decomposition of biomass-derived carbohydrates into LA,194-198 was firstly adopted as a hydrogen donor by Thananatthanachon and Rauchfuss.199 Surprisingly, the yield of DHMF up to 99% could be achieved in tetrahydrofuran at a very low temperature of 40 °C over various amine-metal complexes, such as Cm∗Ru(HTsDPEN), Cp∗Ir(HTsDPEN), Cp∗Ir(HTsDACH) and Cp∗Ir(NHCPh2C6H4) (Cm, cymene; Cp∗, 1,2,3,4,5-pentamethylcyclopenta-1,3-diene), suggesting that CTH was absolutely workable for the selective hydrogenation of HMF into
DHMF
(Figure
5).
Unsatisfactorily,
homogeneous
catalysts,
especially
Cp∗Ir(HTsDACH) and Cp∗Ir(NHCPh2C6H4), showed poor tolerance to formic acid; half of their initial catalytic performance was lost even in several minutes. In this situation,
Pd/C was found to be capable of tolerating formic acid, and when it was used as a heterogeneous catalyst for the selective hydrogenation of HMF, a comparable yield of DHMF of 94% was obtained under similar reaction conditions.200 More importantly, Pd/C had good recyclability, which could further increase the workability of CTH in the presence of formic acid. However, formic acid has strong acidity and corrosivity, and its adoption requires acid- and corrosion-resistant equipment. Hence, taking this issue into account, the practical application of formic acid as a hydrogen donor may be restricted in the selective hydrogenation of HMF into DHMF.
To avoid the deficiencies of formic acid, ethanol and isopropanol were subsequently investigated as hydrogen donors.201-211 In the selective hydrogenation of HMF into DHMF, alcohol-based CTH is generally slower than H2-based hydrogenation process, but it has still been found to be an effective pathway, which can proceed through the direct hydrogen transfer rather than the metal hydride route.132 To gain more insight into this process, we prepared a low-cost zirconium hydroxide (ZrO(OH)2) for the selective hydrogenation of HMF in the presence of ethanol.203 After 2.5 h at 150 °C, a 83.7% yield of DHMF was obtained. By combining the results of catalyst characterizations and poisoning experiments, the zirconium centers and hydroxyl groups of ZrO(OH)2 as the acidic and basic sites were proved to play a synergistic role in the direct hydrogen transfer (Figure 6). Enlightened by the acid-base bifunctional actions of ZrO(OH)2, a series of zirconium-based organic-inorganic coordination
zirconium-benzylphosphonate nanohybrid (Zr-BPPN) and zirconium-furandicarboxylate nanohybrid (Zr-FDCN) were designed by Li et al. for the selective hydrogenation of HMF.204-206 In the presence of isopropanol, DHMF yields were as high as 98, 93 and 87% at 140, 120 and 140 °C for 2, 2 and 8 h, respectively. Gratifyingly, under similar reaction conditions, other types of catalysts, such as hydroxyapatite-encapsulated ferric oxide (Fe2O3@HAP),207 mesoporous carbon-supported cobaltosic oxide (Co3O4@MC),208 silicon carbide-supported gold (Au/SiC),209 cobaltosic oxide-supported ruthenium (Ru/Co3O4)210 and layered double hydroxide-supported ruthenium (Ru/ZnAlZr-LDH),211 also displayed superior catalytic performance with 72, 97, 83.7, 82 and 94% yields of DHMF, respectively, clearly indicating that isopropanol possessed a broad universality to various catalysts, so it is considered as an excellent hydrogen donor for the selective hydrogenation of HMF into DHMF, which can be mainly ascribed to its lower reduction potential.204-211 According to previous reports,212-214 the reduction potential (∆Hf°) is defined as the difference of the standard molar enthalpy of formation between an alcohol and its corresponding carbonyl compound, and it represents the complexity of hydrogen abstraction. As shown in Table 3, the reduction potentials of various alcohols decrease in the order of methanol > ethanol > 1-butanol > isopropanol ≈ 2-butanol. Compared with primary alcohols, secondary alcohols with lower reduction potentials are more appropriate as hydrogen donors in the process of CTH, and this may be the reason for
that isopropanol is widely used for the selective hydrogenation of HMF into DHMF. Due to similar reduction potential with isopropanol, 2-butanol should also be a superior hydrogen donor. However, to the best of our knowledge, prior to 2017, it had not been employed for the selective hydrogenation of HMF into DHMF. More recently, our group confirmed the capacity of 2-butanol. When it was used as a hydrogen donor over a magnetic zirconium hydroxide (MZH) with a moderate Zr/Fe ratio of 2, a 89.6% yield of DHMF was obtained in 5 h at 150 °C.215 Furthermore, among various alcohols, methanol has the highest reduction potential, and so, it does not easily act as a hydrogen donor in theory. Unexpectedly, Pasini et al. reported very interesting results, in which methanol could be applied as an active hydrogen donor for the selective hydrogenation of HMF over the high surface area of magnesia (MgO).216 After 3 h at 160 °C, almost 100% yield of DHMF was achieved, and more surprisingly, the co-products were exclusively gaseous compounds, such as carbon monoxide (CO), carbon dioxide (CO2) and methane (CH4). From experimental results and theoretical calculations, the further study of reaction mechanism revealed that the resulting formaldehyde could react with the remaining methanol to produce hemiacetal, which could also act as a hydrogen donor for the selective hydrogenation of HMF into DHMF (Figure 7). Meanwhile, its dehydrogenated product, methylformate, would further decompose into the abovementioned gaseous co-products, which were easily removed in the reactor depressurization process.216
In addition to the common alcohols, benzyl alcohol was also tested by Gao et al. in the presence of carbon-supported ruthenium and cobalt (RuCo/C), and the results revealed that it displayed a strong ability to act as a hydrogen donor for the selective hydrogenation of HMF into DHMF, giving an acceptable yield of 86.9% at 150 °C for 10 h.171 More recently, 1,4-butanediol, a renewable diol,217-219 was successfully employed for the selective hydrogenation of HMF. When this reaction was carried out in a continuous flow reactor over alumina-supported copper (Cu/AlOX), a DHMF yield of 93% could be achieved in only 0.6 minute at 220 °C.137 Notably, one molecule of BDO can provide two molecules of H2 and can then be converted into γ-butyrolactone (GBL) by the oxygen-free dehydrogenation and ring-closure reaction, which is also a versatile intermediate for the synthesis of fine chemicals.220-223 2.3. Electrocatalytic hydrogenation pathway The electrocatalytic hydrogenation is considered as a green pathway for the selective hydrogenation of HMF because it can be performed at room temperature and atmospheric pressure in an aqueous solution, in which water and protons generally act as hydrogen donors.224-226 Therefore, the electrocatalytic hydrogenation pathway has been gradually used for the production of DHMF in recent years (Figure 8). In 2013, Kwon et al. firstly studied the selective hydrogenation of HMF via an electrocatalytic pathway in 0.1 M sodium sulfate (Na2SO4).227 By correlating the voltammetry with online product analysis, iron (Fe), nickel (Ni), silver (Ag), zinc (Zn), cadmium (Cd) and indium (In) were verified to be effective for the formation of DHMF. Among these electrodes, Ag showed the best catalytic performance, leading to an 85% selectivity at
−0.81 V. However, if the selective hydrogenation of HMF was conducted in 0.5 M sulfuric acid (H2SO4),228 the most effective electrode was nickel (Ni), indicating that the electrocatalytic hydrogenation of HMF into DHMF was strongly influenced by the types of electrodes and electrolytes, which could be further confirmed by the results of Nilges and Schröder.225 In addition, the onset potentials of the target product formation and hydrogen evolution reaction (HER) in the electrocatalytic hydrogenation of HMF into DHMF are closely correlated to the pH of electrolytes,227-229 which is shown in Figure 9. In a neutral solution (pH = 7),227 the onset potentials of the target product formation on all metal electrodes were −0.5 ± 0.2 V, which were less negative than those of the HER, ranging from −1 to −0.4 V on transition metals and −1.5 to −1 V on post-transition metals. These similar onset potentials implied a weak catalytic effect on the electron transfer reaction, which is the first step in the HER. Namely, the adsorbed hydrogen (Hads) on the metal surface was unlikely to be involved in the formation of the target product, and therefore, this process should occur directly through water molecules from the neutral solution: HMF + 2H2O + 2e− ↔ DHMF + 2OH−.227 However, in an acidic solution (pH < 7),228 the onset potentials of the target product formation shifted to more positive potentials, ranging from −0.4 to 0 V on transiƟon metals and −0.7 to −0.25 V on post-transition metals. Moreover, the onset potentials of the target product formation were also found to be greatly associated with the onset potentials of HER. In both neutral and acidic solutions, the HER could occur via the generation of Hads,
regardless of whether its source was H2O or H+: H+ + e− ↔ Hads or H2O + e− ↔ Hads + OH−. Interestingly, HER in the acidic solution was much more effective than in the neutral solution, suggesting that Hads on the metal surface was involved in the formation of the target product in an acidic solution (HMF + 2Hads ↔ DHMF).228 According to the previous studies, a plausible mechanism for the electrocatalytic hydrogenation of HMF into DHMF on the metal electrodes was proposed by Choi et al.230 As shown in Figure 10, the formation of DHMF could proceed through the transfer of e− to HMF to produce an anionic intermediate that further reacted with H+ or through the simultaneous transfer of e− and H+ to HMF (blue arrows in Figure 10). On the other hand, the HER could result in the formation of Hads on the metal electrode surface, which would further drive the selective hydrogenation of HMF into DHMF (red arrows in Figure 10). Furthermore, Choi et al. also constructed an ideal photoelectrocatalytic pathway by simply replacing a metal anode (such as Pt) in electrocatalytic pathway with a photoanode (such as BiVO4).230 Under illumination, BiVO4 could generate electron-hole pairs. The holes were used for water splitting, while the photoexcited electrons were transferred to the Ag cathode for the selective hydrogenation of HMF (Figure 11), giving satisfactory results with a 95% DHMF selectivity and a 94% faradaic efficiency (FE).230 This photoelectrocatalytic pathway provides a practical, inexpensive and effective approach for decreasing the external voltage necessary for the selective hydrogenation of HMF into DHMF, which is an excellent example of coupling solar energy conversion and biomass conversion.
Note that the electrocatalytic pathway has been deeply studied, but its large-scale application in the selective hydrogenation of HMF into DHMF is currently limited. One of the reasons for this is that the electrocatalytic pathway is a multidisciplinary approach, and for its successful implementation, wonderful cooperation among electrochemistry, electrochemical engineering, organic chemistry, catalysis and process design is indispensable. Unfortunately, this cooperation has not been successfully implemented until now. Furthermore, the electrocatalytic pathway requires a high input of electricity, and considering current electricity prices, this pathway still lacks economic superiority. In this aspect, the photoelectrocatalytic pathway should be more competitive, because it can largely reduce the need for external electricity (Figure 11). If a more effective and inexpensive photoanode with a smaller band gap is developed and a more appropriate cell with a minimum internal resistance drop is designed, the photoelectrocatalytic hydrogenation of HMF into DHMF will probably be achieved with no external electricity input, in which the total energy efficiency should also be considered and compared between the photoelectrocatalytic pathway and the electrocatalytic pathway plus the single solar cell. 2.4. Photocatalytic hydrogenation pathway Inspired by the photoelectrocatalytic pathway, a pure photocatalytic pathway was developed by Guo and Chen in 2016 for the selective hydrogenation of HMF into DHMF,231 in which graphitic carbon nitride-supported platinum (Pt/g-C3N4) was
selected as a multifunctional photocatalyst and triethylamine (TEA) was employed as a sacrificial electron donor in aqueous solution (Figure 12). The experimental results indicated that Pt/g-C3N4 could not only facilitate the photoinduced water splitting to produce hydrogen but also promote the subsequent activation of the produced hydrogen for the selective hydrogenation of HMF, which should be due to the synergistic action of Pt and g-C3N4.231 Under visible light irradiation of a 210 W xenon lamp equipped with a 420 nm cut-off filter, a 6.5% yield of DHMF was observed at 80 °C for 4 h.231 To the best of our knowledge, this is the first time for the direct photocatalytic hydrogenation of HMF into DHMF, and most importantly, this is a sustainable pathway for the conversion of biomass using solar radiation as a driving force. However, it should be emphatically noted that the catalytic performance of this pathway is not ideal, and therefore, is far from large-scale applications. On this occasion, how to design and prepare a more effective photocatalyst and balance the roles of photocatalyst in the production and subsequent activation of hydrogen should be the research priority for the photocatalytic hydrogenation of HMF into DHMF. 2.5. Disproportionation reaction pathway Except for the abovementioned pathways, the selective hydrogenation of HMF into DHMF can also be accomplished by the Cannizzaro reaction,232-234 which is a base-induced disproportionation reaction between the same aldehyde compound lacking a hydrogen atom at the α-position,235-237 where the aldehyde compound serves simultaneously as a hydrogen donor and a hydrogen acceptor. However, for many
decades, only two reports on the Cannizzaro reaction of HMF were published by Blanksma238 and Middendorp239 in 1910 and 1919, respectively. Excitingly, in 2012 and 2013, Kang et al.240 and Subbiah et al.241 restudied the Cannizzaro reaction of HMF, respectively. More importantly, the outstanding yields of DHMF of 100 and 90% could be achieved at 0 °C for 1 and 4 h over sodium hydroxide (NaOH) and sodium hydride (NaH) in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM]TFSI) and tetrahydrofuran, respectively. At the same time, 5-hydroxymethylfuranoic acid (HMFA), a corresponding oxidative product, was also obtained with high yields of 84 and 89%. In theory, the Cannizzaro reaction can form an equimolar mixture of the oxidized and reduced products. If the target product is one of the products, the application of the Cannizzaro reaction will be heavily restrained. However, if the Cannizzaro reaction is applied to HMF (Figure 13), it should be an atom-economic pathway because DHMF and HMFA, the equally important products of HMF, can be simultaneously synthesized. More recently, inspired by the Cannizzaro reaction of HMF, a novel acid-catalyzed disproportionation reaction over trimethylaluminum (AlMe3) was developed in acetonitrile by Li et al. for the selective hydrogenation of HMF into DHMF,242 in which HMF itself acted as both a hydrogen donor and a hydrogen acceptor. Differently, the corresponding oxidative product was 2,5-diformylfuran (DFF) rather than HMFA because the nature of the acid-catalyzed disproportionation reaction is the intermolecular MPV reaction. In addition, although DHMF and DFF were successfully
formed in the presence of AlMe3, HMF conversion was only 26.7% at 80 °C for 1 h. By combining the theoretical and experimental results, the lower conversion of HMF was proved to be due to the redox equilibrium in HMF and DHMF/DFF (Figure 14). Fortunately, DHMF shows a poor solubility in acetonitrile, and therefore, its precipitation from the reaction mixture should shift the redox equilibrium into the desired products. Based on this speculation, a cooling treatment in an ice-water bath at an interval of ten minutes was applied in the acid-catalyzed disproportionation reaction of HMF. Surprisingly, with this strategy, HMF conversion obviously increased by 71.3% under the same reaction conditions, and the relative content of DFF was much higher than that of DHMF in the supernatant liquid. Meanwhile, the relative content of DHMF was much higher than that of DFF in the precipitate,242 indicating that the difference in solubility of DHMF and DFF in acetonitrile not only permitted the redox equilibrium to shift but also provided a promising protocol for the crude separation of DHMF from DFF, which was beneficial to the production and purification of DHMF.
3. BIOCATALYTIC HYDROGENATION OF HMF INTO DHMF As seen from the above descriptions, the chemocatalytic pathway is the main method for the selective hydrogenation of HMF into DHMF, and it has therefore been widely studied in recent years. In contrast to the chemocatalytic pathway, the biocatalytic pathway with a number of advantages, such as excellent selectivity, high efficiency, environmental friendliness and mild reaction conditions, may be a more
attractive option.243-245 Unfortunately, it receives little attention, which may be ascribed to the high cost and vulnerability of enzymes. Compared with isolated enzymes, whole cells are preferable for the selective hydrogenation of HMF into DHMF because they are not only inexpensive and stable but also do not require complex systems for the separation and purification of enzymes.246-248 However, the production of DHMF from HMF using the whole cells is extremely challenging because HMF is a well-known inhibitor and toxic compound to microorganisms.249-251 Hence, searching for a new microbial strain with high tolerance to HMF is essential for the biocatalytic hydrogenation of HMF into DHMF. In 2004, Saccharomyces cerevisiae ATCC 211239 and NRRL Y-12632 and Pichia stipitis NRRL Y-7124 were evaluated by Liu et al. to examine their responses to HMF.252 Surprisingly, among three strains, S. cerevisiae NRRL Y-12632 could not only tolerate 30 mM HMF but also convert it into DHMF. As far as we know, this is the first time that DHMF was identified as the final hydrogenation product of HMF by yeast. Subsequently, Meyerozyma guilliermondi SC1103 was isolated by Li et al. in 2017, and it was proved to be more effective for the biocatalytic hydrogenation of HMF into DHMF.253 When the concentration of HMF was 100 mM, a yield of DHMF of 86% could be achieved at 35 °C for 12 h. Following this exciting result, He et al. found that recombinational Escherichia coli CCZU-K14 also displayed an amazing tolerance and catalytic ability towards HMF (Figure 15).254 When the concentration of HMF was up to 400 mM, a 70.2% yield of DHMF was still obtained at 30 °C for 72 h. If 100 and 200 mM HMF were used as substrates, DHMF yield could even be as high as 100 and 90.2% at the same reaction
temperature, respectively. Obviously, the biocatalytic hydrogenation of HMF into DHMF was successfully realized in the presence of E. coli CCZU-K14. Moreover, reduced nicotinamide adenine dinucleotide (NADH) or reduced nicotinamide adenine dinucleotide phosphate (NADPH) as a co-factor was crucial to the biocatalytic hydrogenation reaction, and its effective regeneration was closely related to the co-substrate glucose and its concentration. Thus, the appropriate concentration of glucose was generally added in the selective hydrogenation of HMF into DHMF via the biocatalytic pathway.252-254 Nevertheless, the reported biocatalytic pathways, although promising, must still be validated in industrial conditions. Considering the industrial production, the immobilized whole cells with excellent reusability and high productivity are highly recommended.
4. FURTHER TRANSFORMATION OF DHMF INTO VALUABLE DERIVATIVES DHMF has a peculiar symmetrical structure containing a furan ring and two hydroxyl groups, determining its wide potential applications. It is well-known that DHMF is an important intermediate in the total hydrogenation and hydrogenolysis of HMF, therefore, by adopting appropriate reaction conditions, it can be further transformed into DMF, DHMTHF, DMTHF, HTO, HDO, HHD or HMCPN, which have been involved in previous reviews.5, 214, 255, 256 Moreover, in the earlier studies, DHMF can also be used for the synthesis of DFF,257 2,5-furandicarboxylic acid (FDCA)258-261 and various crown ethers.111 However, these applications have been rarely reported in the present studies. Thus, in the following section, only a few typical applications of DHMF
will be introduced in detail. 4.1. Through the etherification reaction Due to higher energy density, higher cetane number, higher miscibility and stronger stability, 2,5-bis(alkoxymethyl)furan (BAMF) has been assessed as a more attractive diesel additive than 5-alkoxymethylfurfural (AMF).262-267 Similar to the preparation of AMF from HMF,268-278 BAMF can be synthesized by the etherification of DHMF with the corresponding alcohols in the presence of acid catalysts (Table 4). For instance, Balakrishnan et al. firstly reported the etherification of DHMF with ethanol in 2012.112 The results demonstrated that among various acid catalysts, such as H2SO4, Amberlyst-15, Amberlite IR120, Dowex 50WX8 and Dowex DR2030, Amberlyst-15 showed
an
outstanding
catalytic
performance
with
an
80%
yield
of
2,5-bis(ethoxymethyl)furan (BEMF) at a low reaction temperature of 40 °C for 16 h, which was in accordance with the results of Sacia et al.262 More importantly, Amberlyst-15
could
also
be
employed
for
the
efficient
preparation
of
2,5-bis(propoxymethyl)furan (BPMF)263 and 2,5-bis(butoxymethyl)furan (BBMF)263 via the etherification of DHMF with propanol and 1-butanol, respectively. However, if methanol was applied for the etherification of DHMF, the catalytic performance of Amberlyst-15 was not satisfied, and the yield of 2,5-bis(methoxymethyl)furan (BMMF) was only 57% at 60 °C for 10 h, which might be attributed to the high polarity of methanol, leading to the formation of many byproducts.263 Given this phenomenon, acidic zeolites were selected by Cao et al. to obtain a satisfactory yield of BMMF.113 Among various acidic zeolites, HZSM-5 with a Si/Al ratio of 25 was the most effective
for the etherification of DHMF with methanol. After 3 h at 100 °C, a BMMF yield of 70% could be achieved, which was higher than that over HZSM-5 with a Si/Al ratio of 38 or 300. Note that the smaller ratio of Si/Al of zeolites meant more acidic sites and stronger hydrophilicities, which facilitated the etherification reaction between DHMF and methanol on the surface of catalysts.113 Based on these results, it can be seen that the properties of catalysts and the types of alcohols have a great effect on the etherification of DHMF into BAMF. In addition, it should be specially noted that various BAMF could also be directly produced from HMF in the corresponding alcohols (Table 4),262-267 in which two successive steps were involved in the same reactor: the selective hydrogenation of HMF into DHMF over the hydrogenation catalysts and the subsequent etherification of DHMF into BAMF over the acid catalysts (Figure 16). More gratifyingly, an obvious loss in the yield of BAMF was not observed. Therefore, this one-pot two-step process was more desirable for the preparation of BAMF from the viewpoint of practical production.
4.2. Through the polymerization reaction FDCA has been widely considered as a suitable replacement of terephthalic acid for the synthesis of various polymers.279-283 Correspondingly, it is reasonable to assume that DHMF is also a suitable replacement of terephthalyl alcohol.120 In the early application of DHMF, it was commonly used as a comonomer for the preparation of furan-based polyisocyanurates, polyurethanes, polyacrylonitriles and polyethers, which
were the corresponding components of foams and fibers.284-291 Compared with the benzene ring, the furan ring in DHMF is more reactive and less stable,120 and so, melt polymerization was rarely employed for the polymerization of DHMF with other substrates because it required a very high melt temperature, which was not favorable for the reduced furan nuclei and then led to the occurrence of undesired reactions.284 Therefore, solution polymerization should be more feasible. Recently, Yoshie and co-workers reported a series of studies,292-295 in which poly(2,5-furandimethylene succinate) (PFS) was prepared by the polymerization of DHMF with succinic acid (SA) under basic conditions. Interestingly, this copolymer could be further crosslinked with bismaleimide (M2) by the Diels-Alder reaction to form a network polymer (PFS/M2) (Figure 17), and meanwhile, its mechanical and healing properties could also be correspondingly adjusted by controlling the number and concentration of M2. With this strategy, PFS/M2 displayed an excellent multi-shape memory and recovery behavior (Figure 18). Subsequently, an ultraviolet-induced photopolymerization method was developed by Jang et al. for the preparation of a sequence of novel network polymers from vegetable oils, such as acrylated epoxidized soybean oil (AESO), acrylated castor oil (ACO) and acrylated 7,10-dihydroxy-8(E)-octadecenoic acid (ADOD),118 in which 2,5-furan diacrylate that was synthesized by the acylation of DHMF with acryloyl chloride was used as a difunctional stiffener, and its addition could increase the tensile strength of the network polymers by up to 1.4∼4.2 times relative to those obtained without the addition. It is worth pointing out that photopolymerization was very effective, and
after only 15 min, the gel content in all network polymers was higher than 97%.118 More recently, Jiang et al. explored an enzymatic method for the polymerization of DHMF with various diacid ethyl esters such as diethyl succinate, diethyl glutarate, diethyl adipate, diethyl suberate, diethyl sebacate and diethyl dodecanedioate in the presence of Candida antarctica Lipase B (CALB).296 Through a three-stage process, six polyesters were prepared (Figure 19), and more importantly, they had diverse functions as self-healing materials, biomedical materials and degradable materials. Although enzymatic polymerization has been intensively used for the synthesis of various bio-based polyesters from renewable resources, such as succinic acid, fatty acid, glycerol and 1,4-butanediol,297-303 this method has not received enough attention in the polymerization of DHMF; hence, its application should be reinforced in the future. 4.3. Through the rearrangement reaction In 2016, α-6-hydroxy-6-methyl-4-enyl-2H-pyran-3-one (HMEPO), which is a novel and attractive pyranone for the synthesis of sugar analogues and compounds with excellent biological activities,304-307 was creatively prepared by Gelmini et al. via the ring-rearrangement of DHMF in the presence of water over a heterogeneous acid catalyst of Amberlyst-15.114 Notably, the same treatment in alcohol led to the etherification of hydroxy groups, and no rearrangement reaction was observed. Under the atmospheric pressure of nitrogen (N2), the yield and selectivity of HMEPO could be
achieved to 50 and 70% in 30 min at a moderate reaction temperature of 70 °C, respectively. Furthermore, this ring-rearrangement reaction does not require the addition of oxidants, which is different from the Achmatowicz rearrangement reaction that is a typical oxidative process for the conversion of 2-(α-hydroxyalkyl)furan into 6-hydroxy-3(2H)-pyranones. Based on the previous reports308-312 and the analysis results of gas chromatography mass spectrometry (GC-MS) and proton nuclear magnetic resonance spectroscopy (1H NMR), a plausible reaction mechanism for the ring-rearrangement of DHMF into HMEPO was proposed in Figure 20, which involved hydration, dehydration, ring opening, keto-enol tautomerism and ring closure. In addition, if the proper reaction conditions were adopted, for example, a prolonged reaction time of 5 h or the use of Amberlyst-70 as a catalyst, other interesting products, such as 1,3-dihydroxyhexan-2,5-dione and 1,4-dihydroxyhexan-2,5-dione, could also be preferentially formed from the parallel hydration of the ketonic intermediate or from the consecutive ring opening and hydration of HMEPO. Conclusively, this mechanistic investigation opens an avenue for the development of a general method for the transformation of various dihydroxyfurans.
5. CONCLUSIONS AND PERSPECTIVES As mentioned above, DHMF is a very promising versatile diol, and it can be produced from the selective hydrogenation of biomass-derived HMF via various chemocatalytic pathways and biocatalytic pathways. From the current point of view, among these pathways, the conventional hydrogenation pathway with external
molecular H2 should be the most likely for the industrial production of DHMF. Unfortunately, this process has not yet been realized until now despite the achievement of a series of breakthroughs. Among all the possible bottlenecks, the main one should be attributed to the high cost of HMF. If HMF is prepared in an inexpensive way, greater progress will be readily achieved in this research area; hence, considerable concerns should be persistently focused on the economical synthesis of HMF from carbohydrates or biomass. Moreover, to promote the industrial production and further application of DHMF, the following potential issues should also be further reinforced in future studies: (I) The systematic construction of exclusive catalysts. Because of the special structure and reactivity of DHMF, catalysts must be extremely selective in their production and application. Considering sustainability, recyclability and environmental friendliness, heterogeneous catalysts with non-precious metals, specific sizes, high dispersity and excellent stability are particularly desired. In addition, if DHMF is directly produced and applied via a one-pot reaction from carbohydrates or biomass, the tolerance of catalysts to the complex systems should also be considered. (II) The intensive exploration of appropriate reaction mediums. During the production and application of DHMF, reaction mediums can act not only as solvents but also as hydrogen donors and reactants. From the viewpoint of green chemistry, the development of inexpensive and renewable reaction mediums with strong solvencies and particular functionalities is imminently necessary. (III) The comprehensive optimization of reaction parameters. Once the exclusive catalysts and reaction mediums are chosen in the production and application of DHMF, various reaction
parameters such as reaction temperature, reaction time, catalyst amount and substrate concentration will have a more direct influence on the formation of target products. Thus, to get higher yields, they should be thoroughly optimized. (IV) The strategic establishment of separation methods. It is generally known that DHMF is not very stable especially in high-temperature circumstance and the reaction mixture is quite complicated in its production and application. In this situation, the effective separation of target products from the complicated reaction mixture is the key for their practical uses. Therefore, in addition to getting the higher yields of target products, establishing high-efficiency and energy-efficient separation methods based on the respective physicochemical properties of various target products is urgently needed. (V) The innovative design of continuous reactors. Whether DHMF is produced or applied, multifunctional continuous reactors including catalytic equipment for the production and application of DHMF, recovery equipment for the recycle of catalysts and reaction mediums and separating equipment for the separation of target products should be creatively designed according to the corresponding catalytic systems. Apart from these scientific issues, the in-depth techno-economic analysis of various catalytic pathways should also be intensively performed to appraise their availability for the industrial production and application of DHMF. All in all, we must continue our efforts in the development of appropriate approaches to reduce the synthesis costs of HMF and increase the application economy of DHMF. Despite facing numerous difficulties and challenges, we still believe that the future prospects will be exceptionally bright.
This work was financially supported by the National Natural Science Foundation of China (21506071), the Natural Science Foundation of Jiangsu Province (BK20150413) and the Natural Science Foundation of the Higher Education Institutions of Jiangsu Province (16KJA530001).
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Figure 2. Selective hydrogenation of HMF into DHMF. Note: MF, MFA and HDO are representative of 5-methylfurfural, 5-methylfurfuryl alcohol and 1,6-hexanediol, respectively.
Figure 3. Possible intermediates in the selective hydrogenation of HMF into DHMF over
Ru-based Shvo’s catalyst.138 Adapted with permission from reference 138. Copyright 2014 Royal Chemistry Society.
Figure 4. Relationships between the conversion of HMF and the δ values of solvents over Pt/MCM-41.144 Adapted with permission from reference 144. Copyright 2014 Royal Chemistry Society. H OH
H
O O
H
N
Ph
Ir Cp* N Ts
CO2
Ph
HMF
OH
OH O
H HN
Ir Cp* N Ts
DHMF Ph
HCOO H
Ph
Figure 5. Selective hydrogenation of HMF into DHMF over Cp∗Ir(HTsDPEN) in the presence of formic acid.199 Adapted with permission from reference 199. Copyright 2010 John Wiley and Sons.
Figure 6. Plausible reaction mechanism for the selective hydrogenation of HMF into DHMF over ZrO(OH)2 in the presence of ethanol.203 Adapted with permission from reference 203. Copyright 2016 Royal Chemistry Society.
Figure 7. Simplified reaction pathway for the selective hydrogenation of HMF into DHMF over MgO in the presence of methanol.216 Adapted with permission from
Electrocatalytic hydrogenation H2O or H+ , standard potential = 0.12 V
+ e-
DHMF
H
H2 O + e -
H + OH -
HMF + 2H
DHMF
HMF + 2H +
OH O
+ 2e -
HMF + 2H 2O + 2e
DHMF -
DHMF + 2OH -
Figure 8. Electrocatalytic hydrogenation of HMF into DHMF in an aqueous solution.227-229
Figure 9. Comparison of the onset potentials of the product formation and the HER on transition metals (a) and post-transition metals (b) in neutral and acidic solutions. Note: the onset potentials for the HER are obtained at a current density of −0.5 mA·cm−2.228 Adapted with permission from reference 228. Copyright 2015 John Wiley and Sons.
Figure 10. Plausible reaction mechanism for the selective hydrogenation of HMF into DHMF over a Ag electrode via an electrocatalytic pathway.230 Adapted with permission from reference 230. Copyright 2016 American Chemical Society.
Figure 11. Comparison beween the photoelectrocatalytic pathway (a) and electrocatalytic pathway (b) for the selective hydrogenation of HMF into DHMF.230 Adapted with permission from reference 230. Copyright 2016 American Chemical Society.
Figure 12. Selective hydrogenation of HMF into DHMF via a photocatalytic pathway in water over Pt/g-C3N4 with TEA as a sacrificial electron donor.231 Adapted with permission from reference 231. Copyright 2016 Royal Chemistry Society. OH
O
OH
O
OH
OH
O
O
NaOH or NaH
O
OH
+
Cannizzaro reaction
HMF
DHMF
HMFA
Figure 13. Selective hydrogenation of HMF into DHMF over NaoH or NaH via the Cannizzaro reaction.240 Adapted with permission from reference 240. Copyright 2012 Elsevier. MPV
OH
H
O O
OH
O
2
O
O
HMF
OH
+ DHMF
Al
O O
OH
O
O
O
O
DFF
Reverse MPV
Figure 14. Selective hydrogenation of HMF into DHMF over AlMe3 via the MPV reaction.242 Adapted with permission from reference 242. Copyright 2017 John Wiley and Sons. OH
O O
OH Escherichia coli CCZU-K14
OH O
Buffer, Glucose, 30 °C
HMF
DHMF
Figure 15. Selective hydrogenation of HMF into DHMF via a biocatalytic pathway in the 82
Figure 18. Preparation process (a), shape memory (b) and shape recovery (c) of PFS/M2.295 Adapted with permission from reference 295. Copyright 2014 American Chemical Society. O
Figure 19. Enzymatic polymerization of DHMF with various diacid ethyl esters over CALB.296 Adapted with permission from reference 296. Copyright 2014 American Chemical Society.
Figure 20. Plausible reaction mechanism for the ring-rearrangement of DHMF into HMEPO over Amberlyst-15 in the presence of water.114 Adapted with permission from reference 114. Copyright 2016 Elsevier.
The state-of-the-art advancements of various chemocatalytic pathways and biocatalytic pathways for the production and application of biomass-derived 2,5-dihydroxymethylfuran are comprehensively summarized and discussed.
