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Glucose Isomerization into Fructose by Chemocatalytic Route

Yiqiang Liu , Yimei Qiu , Xing Tang , Yong Sun , Xianhai Zeng , Lu Lin

Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (11) : 2128 -2137.

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Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (11) : 2128-2137 DOI: 10.7536/PC200859
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Glucose Isomerization into Fructose by Chemocatalytic Route
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Abstract

The biorefinery based on sugar platform can produce various carbon-based chemicals, materials, and fuels. Compared with glucose and cellulose, a facile conversion of fructose into versatile biomass-based platform molecules such as 5-hydroxymethylfurfural with desirable selectivity can be expected, thus the isomerization of glucose into fructose has become one of the vital reactions for biorefinery. In this review, an in-depth discussion on the reaction mechanism of glucose isomerization by chemocatalytic route is provided, and the recent research progress on glucose isomerization into fructose in the view of isomerization catalysts is comprehensively summarized. Based on the discussion on the catalysts for glucose isomerization and their catalysis, the ongoing research on the chemocatalytic isomerization of glucose into fructose is envisaged.

Contents

1 Introduction

2 Mechanism of glucose isomerization into fructose

2.1 Isomerization mechanism over basic catalysts

2.2 Isomerization mechanism over acidic catalysts

3 Homogeneous catalysts

3.1 Base catalysts

3.2 Acid catalysts

4 Heterogeneous catalysts

4.1 Hydrotalcites

4.2 Metal oxides and insoluble salts

4.3 Zeolites

4.4 Alkaline resins

4.5 Metal organic frameworks

5 Conclusion and outlook

Graphical abstract

Keywords

glucose / fructose / isomerization / chemo-catalysts

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Yiqiang Liu, Yimei Qiu, Xing Tang, Yong Sun, Xianhai Zeng, Lu Lin. Glucose Isomerization into Fructose by Chemocatalytic Route. Progress in Chemistry, 2021, 33(11): 2128-2137 DOI:10.7536/PC200859

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1 Introduction

Since the industrial revolution, with the rapid development of social economy, human demand for energy continues to grow. At present, the main energy sources of human beings also depend on non-renewable fossil resources such as oil, coal and natural gas. Although the continuous discovery of new fossil energy such as shale gas and combustible ice has increased the proven reserves of fossil resources, its non-renewability determines that the total reserves of fossil resources will continue to decrease with the exploitation and utilization[1]. More importantly, the extensive use of fossil resources has led to a large number of greenhouse gas emissions and serious environmental pollution[2]. Therefore, all countries in the world attach great importance to the development and utilization of clean and renewable energy and resources. Biomass is considered to be a promising clean and renewable carbon resource because of the huge amount of biomass produced by photosynthesis every year in the world and the use of biomass will not bring additional carbon emissions to the ecosphere[3,4].
In recent years, more and more attention has been paid to the preparation of various carbon-based chemicals, materials and fuels from biomass. Cellulose is the most abundant biomass resource in nature, which can be hydrolyzed into glucose[5]. 5-Hydroxymethylfurfural (5-HMF) is an important platform compound which can be prepared from glucose and fructose. It has high activity because of its furan ring, aldehyde group and hydroxymethyl group.High value-added chemicals such as 2,5-furandicarboxylic acid, 2,5-furanddimethanol and 2,5-dialkoxymethylfuran can be prepared by oxidation, reduction, etherification, esterification and other reactions, and these chemicals can be used as fuel additives and polymer monomers[1]. However, the selectivity of the catalytic conversion of glucose to platform molecules such as 5-hydroxymethylfurfural in conventional solvents is not ideal. For example, glucose is difficult to be efficiently converted into 5-hydroxymethylfurfural in water, N, N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO)[6][7]. Fructose-catalyzed conversion of 5-hydroxymethylfurfural is usually easier than that of glucose, and the product selectivity is also higher because fructose is easier to convert into furan-type structure[8]. For example, fructose can efficiently convert 5-hydroxymethylfurfural in DMF, DMSO and other solvents by acid catalysis[9,10]. Therefore, the isomerization of glucose to fructose has become a key step in the biorefinery process, and cellulose and its hydrolysate glucose can be further efficiently converted into other bio-based products through fructose. In addition, in the food industry, high fructose corn syrup, which is obtained by enzymatic saccharification and isomerization of corn starch, is a common sweetener and is widely used in beverages and processed foods[11].
At present, the enzymatic isomerization of glucose to fructose has been mature in industrial production, and the main product is fructose syrup mixed with glucose and fructose. However, the cost of enzymes is high, and the need for high-purity glucose and buffer solutions further increases the cost of enzymatic production[12]. In addition, the enzyme is very sensitive to process parameters such as pH and temperature, and the enzyme-catalyzed process usually takes a long time and is limited by the equilibrium concentration of fructose (48% at 45 ℃)[13]. In contrast, chemical catalysts can catalyze the isomerization of glucose in a wider temperature and pH range, and the chemical catalytic process is usually more efficient than the enzymatic catalytic process, so more and more researchers have paid attention to the chemical catalytic isomerization of fructose from glucose in recent years. In this paper, the catalytic mechanism of glucose isomerization to fructose by chemical catalysis was introduced in detail, including alkali catalysis mechanism and acid catalysis mechanism. In addition, the recent advances in the isomerization of fructose from glucose catalyzed by homogeneous and heterogeneous catalysts were reviewed.

2 Mechanism of glucose isomerization to fructose

2.1 Mechanism of base catalysis

At the end of the 19th century, de Bruyn and van Ekenstein first reported the base-catalyzed isomerization of glucose to fructose, and the subsequent studies gradually improved the base-catalyzed reaction mechanism[14][15⇓~17]. The base-catalyzed isomerization of glucose is carried out through a proton transfer mechanism, and the reaction mechanism is shown in Figure 1: under the action of a base catalyst, the alpha carbon connected with the carbonyl group in glucose is firstly deprotonated, and then an enol intermediate product is formed between C1 and C2 after electron transfer; Subsequently, the H atom in the hydroxyl group attached to C2 is easily transferred to the O1 atom attached to C1 in the form of proton and forms a hydroxyl group with it, which is the rate-determining step of the base-catalyzed isomerization reaction. Finally, after electron transfer and rearrangement, the enol structure of C1-C2 was transformed into a more stable aldehyde structure at C2 position, and the isomerized product fructose was obtained.
Base-catalyzed glucose isomerization is achieved by proton transfer between O1 and O2 of the enol intermediate. Wolfrom et al. Confirmed the formation of the enol intermediate, and Roman-Leshkov and Yang et al. Further confirmed that base catalysis followed the above reaction mechanism[16][18⇓~20].

2.2 Acid catalysis mechanism

Researchers such as Roman-Leshkov, Nguyen and Li have confirmed the acid-catalyzed intramolecular hydrogen transfer mechanism of glucose by isotope labeling or molecular mechanics calculation[18][21][22]. As shown in fig. 2, firstly, the Lewis acid center is coordinated with the chain end carbonyl of glucose and the hydroxyl oxygen linked by the carbon at the alpha position through chelation to form a five-membered cyclic transition state; Subsequently, the polarization of the Lewis acid sites on the hydroxyl group promotes the intramolecular hydride transfer from C2 to C1, which is the rate-determining step of the isomerization reaction with the highest barrier. Finally, the protonated C2 carbonyl undergoes hydrogen transfer to the C1 oxygen via the Lewis acid site to form fructose.
Choudhary et al studied the isomerization mechanism of aldose and ketose catalyzed by homogeneous and heterogeneous Lewis acids (chromium chloride, aluminum chloride and Sn-beta molecular sieve) in water system. The results showed that the isomerization of glucose catalyzed by homogeneous and heterogeneous Lewis acids was carried out through the hydrogen transfer from C2 to C1, and it was a rate-determining step[23]. For the main active components of glucose isomerization, the active site of Sn-beta is the partially hydrolyzed framework tin center [ (SiO)3Sn(OH)], while the homogeneous Lewis acid catalyst is the hydrated cation formed by partial hydrolysis of the metal[18][23,24].
It should be noted that chemically catalyzed glucose isomerization is usually accompanied by the formation of mannose, which is mainly due to the epimerization of glucose[25]. The formation of mannose from glucose epimerization catalyzed by Lewis acids proceeds via the C1 — C2 carbon transfer pathway[21,23]. In the process of base catalysis, it is converted to mannose through the enol intermediate. However, it should be pointed out that fructose is still the main product even if there is epimerization. De Wit explained this phenomenon from the perspective of activation entropy: the formation of fructose almost does not change the geometric conformation of the enol intermediate, while the formation of mannose needs to change the geometric conformation by rotating around the C2 — C3 bond, so the activation entropy of fructose formation is relatively low[17].

3 Homogeneous catalyst

According to the mechanism of glucose isomerization, homogeneous catalysts can be divided into homogeneous acid catalysts and homogeneous base catalysts. The experimental results of glucose isomerization to fructose catalyzed by a representative homogeneous catalyst are shown in Table 1.

3.1 Homogeneous base catalysis

Since de Bruyn and van Ekenstein discovered the isomerization of glucose, a series of studies have been carried out on the base-catalyzed isomerization of glucose[14]. The early studies of catalysts mainly focused on soluble alkalis, such as Ca(OH)2, potassium hydroxide and so on[27,35]. It has been found that such base catalysts readily form retro-aldol byproducts (e.g., lactic acid) via cation-ketose complexes, which in turn results in reduced fructose yields (typically less than 20%)[36]. Mendicino et al. Found that the addition of borate could significantly improve the yield of fructose, and the highest yield of fructose could reach 90% in the mixed catalytic system of NaOH and Na2B4O7[28]. Further studies showed that borate could form borate ester complexes with monosaccharides to protect monosaccharides from degradation, and the complexes formed by borate and fructose were more stable than those formed by borate and glucose, so the presence of borate could significantly improve the selectivity and yield of fructose[36][37]. However, the above catalyst system requires a high concentration of NaOH, and the subsequent separation of the catalyst and the product is difficult. Despax et al. Found that NaAlO2 could catalyze the isomerization of glucose efficiently, and the yield of fructose isomerized by glucose in water and organic system (dimethyl sulfoxide/propylene glycol/water) could reach 41% and 49% (55 ℃, 3 H), respectively[29]. However, the NaAlO2, which is insoluble in organic solvents, will undergo significant ion leaching due to the moisture introduced by glucose syrup (70 wt%), which significantly reduces the catalytic stability of the catalyst, while the use of anhydrous glucose can not achieve high fructose selectivity (less than 50%).
In contrast to inorganic bases, organic amines do not form cation-ketose complexes in the process of glucose isomerization, thus avoiding side reactions, so the catalytic effect of organic amines is better than that of inorganic bases. For example, Liu et al. Obtained 31% fructose yield (100 ℃, 3 H) using triethylamine as catalyst[30]. In addition, the conversion of glucose and the yield of fructose catalyzed by morpholine, piperazine, ethylenediamine, piperidine and pyrrolidine can reach 39% -56% and 17% -29%, respectively[30]. The obvious advantages of organic amines over inorganic bases or Lewis acids are their relatively low cost and the fact that they can be prepared by alkylation of bioethanol.
In addition to inorganic base and organic amine catalysts, amino acids can also show certain basicity through different side chains, so they can be used as a green organic base catalyst. For example, Yang et al. investigated the performance of basic amino acids such as arginine, lysine, and histidine to catalyze the isomerization of glucose[19]. The results showed that the yield of fructose could reach 31% (120 ℃, 15 min) when glucose was isomerized by arginine. Compared with other catalysts, amino acids such as arginine are non-toxic and harmless, and a small amount of residues in the production of edible fructose do not affect the performance of the product.
Ionic liquid is a widely used solvent and catalyst in the field of biomass conversion, so its application in the isomerization of glucose has also been studied. For example, Li et al. studied the catalytic performance of [Ch] Pro, an ionic liquid composed of choline cation and proline anion, for the isomerization of glucose[32]. The results showed that 37. 6% yield of fructose could be obtained at 70 ℃ for 30 min. It was further found that the catalytic activity of [Ch] Pro was derived from the basicity of the anion, and the isomerization of glucose followed the proton transfer mechanism. Li et al. Also found that the ion-pair effect of cations could also affect the performance of the catalyst[32]. Xiang Xiaoyan et al. added the complexing agent Na2B4O7 to the reaction system to protect fructose, and the choline phenolate ionic liquid was used as the catalyst for glucose isomerization. The fructose yield of 64. 7% and the selectivity of 73. 1% were obtained in 7 min at 70 ℃ in water system. However, the introduction of complexing agent increased the difficulty and complexity of subsequent product separation[33].

3.2 Homogeneous acid catalysis

Since Bronsted acids do not play a catalytic role in glucose isomerization, Lewis acids are used in acid-catalyzed glucose isomerization. Common homogeneous Lewis acids, such as CrCl3, SnCl4 and AlCl3, can catalyze the isomerization of glucose to fructose, and the yield of fructose is usually between 4. 7% and 26. 3%[24,34]. Although the catalytic performance of these homogeneous Lewis acid catalysts is not very ideal, their well-defined structures are suitable for the study of catalytic mechanism. For example, Jia et al studied the isomerization of glucose catalyzed by CrCl3 in water or water/DMSO mixed system, and verified the coordination behavior of metal Lewis acid center with the terminal aldehyde group of glucose, thus catalyzing the isomerization reaction[34]. Mushrif et al. 'S study based on molecular dynamics also confirmed the above conclusion[38]. Tang and Norton also studied the isomerization mechanism of glucose to fructose catalyzed by AlCl3, and the results showed that glucose C1 — O and C2 — O were coordinated with partially hydrolyzed [Al(OH)2(aq)]+ during the reaction, which promoted the hydrogen transfer in glucose molecules (Fig. 3)[24][39].
Loerbroks et al. systematically studied the catalytic performance of various homogeneous Lewis acids such as CrCl3, AlCl3, CuCl2, FeCl3 and MgCl2 for glucose isomerization in water system.It is considered that the metal salt used as a catalyst for isomerization of glucose should have the properties and activities of moderate Bronsted acid and Lewis acidity (pKa=4~6), low energy empty orbital, ability to coordinate with water or weaker σ donors, and complexing with glucose[40].
In a word, the catalytic effect of homogeneous system is not ideal. Although the introduction of complexing agent can significantly improve the catalytic effect, it also increases the difficulty of product separation to a considerable extent, which may bring additional cost in actual production. However, it should be noted that compared with the heterogeneous catalytic system, the homogeneous catalyst structure is more clear, and the homogeneous catalytic system is less limited by mass transfer, which is more conducive to the study of reaction mechanism.

4 Heterogeneous catalyst

Different from homogeneous catalysis, heterogeneous catalysis is more attractive because of its lower separation difficulty and adjustable acid-base active sites. Commonly used solid base catalysts are hydrotalcite, metal oxides and basic metal salts, cation exchange molecular sieves and so on. The solid acid catalyst is generally a catalyst having Lewis acidity or both Lewis acidity and Bronsted acidity. Common solid acid catalysts mainly include molecular sieves and MOF materials.

4.1 Hydrotalcite

Hydrotalcite is a layered double hydroxide with the general formula An-, where An- represents the interlayer anion and can exhibit weak basicity[47⇓~49]. Hydrotalcite can be transformed into MgO-Al2O3 mixed oxides after calcination, and its surface has O2- sites with medium and strong basicity, so it is often used as a basic catalyst[50]. Representative experimental data for the hydrotalcite-catalyzed isomerization of glucose are listed in Table 2. Commercial hydrotalcite DHT-4A2 was calcined and hydroxylated, and the selectivity of glucose isomerization to fructose was higher than 90%, but the conversion of glucose was low (10% ~ 15%)[41]. Delidovich et al. Synthesized hydrotalcite with high surface alkali concentration by coprecipitation in ethanol-water solution at room temperature, and obtained 30% fructose yield (110 ℃, 1.5 H, 89% selectivity)[42]. Delidovich et al. Further studied the effects of structural properties such as molar ratio and dispersity of hydrotalcite on its catalytic performance, and found that the optimal aluminum molar content was 0.23 ~ 0.3, and the hydrotalcite with better dispersity obtained by co-precipitation in ethanol aqueous solution and at isoelectric point was also more conducive to isomerization catalysis. In order to further improve the catalytic effect of the hydrotalcite, Yu et al. And Lee et al. Calcined the hydrotalcite and then carried out the rehydration process of mechanical stirring in water or ultrasonic treatment, so that the vertical fracture and exfoliation of the hydroTalcite layer were achieved, and the concentration of basic centers on the surface of the catalyst was increased, thereby improving the performance of hydrotalcite in catalyzing the isomerization of glucose[44][44]. Upare et al. Studied the solvent effect under the catalysis of hydrotalcite, and found that the use of 1-butanol as a solvent can effectively avoid the ion leaching of hydrotalcite. Density functional theory calculations also showed that the binding energy of glucose molecules on the surface of houghite in 1-butanol was lower than that in other solvents, so it was more conducive to the selective formation of fructose[45][46]. Under the optimized reaction conditions, the conversion of glucose and the yield of fructose could reach 62% and 51% (120 ℃, 5 H), respectively, over hydrotalcite in 1-butanol. It is worth mentioning that glucose and fructose are almost insoluble in 1-butanol below 50 and 40.degree.C., respectively, so that the crystallized unreacted glucose can be separated from fructose by filtration by cooling the solution to 45.degree.C.after the reaction, and fructose crystals of high purity can be precipitated by further cooling to 25.degree.C[46].

4.2 Metal oxides and insoluble salts

The basicity of metal oxides comes from the negatively charged oxygen in the lattice. Amorphous metal oxides also have unsaturated metal cations, which can provide Lewis acidic sites, while surface hydroxyl groups can provide Bronsted acidity. Therefore, metal oxides can be used as multi-functional catalysts with different catalytic domains[51]. In addition, one of the advantages of metal oxides is that they are cheap and easy to recycle. The experimental results of glucose isomerization catalyzed by metal oxides reported in some literatures are shown in Table 3. For example, Rabee et al. and Kitajima et al. respectively prepared a series of metal oxide-doped ZrO2 mixed oxides, and the results showed that doping CaO and MgO could increase the number of basic sites on the surface of the mixed oxides, thereby improving their catalytic performance for glucose isomerization[52][53]. For example, the conversion of glucose and the yield of fructose can reach 51. 1% and 35. 7% (95 ℃, 6 H), respectively, over MgO-doped MgO-ZrO2[52].
In addition to metal oxides, some metal carbonates and silicates also have catalytic activity for glucose isomerization (Table 3). For example, Son et al. Prepared a water-tolerant zirconium carbonate catalyst, which can efficiently catalyze the isomerization of glucose at 120 ℃, with glucose conversion and fructose yield reaching 45% and 34%, respectively, after 20 min of reaction[54]. In addition, it was found that zirconium carbonate could cooperate with solid acid catalysts such as Amberlyst-15 to catalyze the one-pot conversion of glucose to levulinic acid[54]. In order to further improve the yield of fructose, Lima et al. Synthesized a variety of metal silicates and used them to catalyze the isomerization of glucose, and the yield of fructose obtained was between 30% and 40%[55]. However, due to the loss of crystallinity, leaching of metal ions, surface passivation and other factors, these catalysts also have a certain degree of deactivation after use.

4.3 Molecular sieve

Molecular sieves are widely used in the field of catalysis because of their unique and relatively regular pore structure and various modifiable active sites on the surface. Representative experiments of glucose isomerization catalyzed by molecular sieves are shown in Table 4. In recent years, Moliner et al. First used Sn-beta molecular sieve to catalyze the isomerization reaction of glucose, and the conversion rate of glucose and the yield of fructose reached 54% and 31%, respectively, at 110 ℃ for 30 min[57]. Subsequently, the catalytic activity of Sn-beta was further studied, and it was confirmed that its catalytic isomerization activity mainly came from the partially hydrolyzed open Sn center on the surface (Fig. 4), that is, the Sn species with four coordination from — OSi was partially hydrolyzed to (SiO)3Sn(OH), and the adjacent sites of Sn center were also hydrolyzed to form SiOH groups, which directly participated in the hydrogen transfer process[22,58⇓⇓⇓~62]. In addition, mesoporous Sn-MFI and NaY zeolites can also catalyze glucose isomerization in aqueous system[63][64,65]. In 2017, Zhou Yanbin et al. Synthesized a Sn-beta catalyst with hierarchical pore structure by recrystallization method. The conversion rate and fructose yield of the catalyst for glucose isomerization can reach 60.2% and 47.2% respectively under the reaction conditions of 120 ℃ and 2 H[66].
However, in the pure water solvent system, molecular sieves are prone to deactivation under catalytic reaction conditions[67,58]. Therefore, Guo et al. constructed a solvent system with dioxane/water mixture, in which Sn-beta could better maintain its hydrophobicity, so that the catalytic stability of Sn-beta was significantly improved, and the fructose yield could be further increased to 41. 5% (90 ℃, 240 min, 62% selectivity)[69]. Cordon et al. Also found that the decrease of catalytic activity of Sn-beta in water system was related to the decrease of hydrophobicity of catalyst surface[70]. Li et al. Further studied the catalytic activity of beta molecular sieves supported on different metal centers based on theoretical calculations, and found that the molecular sieves containing Sn and Zr had the lowest reaction barrier for glucose isomerization, and the isomerization reaction was mainly affected by the interaction between the metal center and the C2 hydroxyl group of glucose and the metal polarizability[22].
In 2013, Saravanamurugan et al. explored the way to prepare fructose by two-step isomerization of glucose catalyzed by molecular sieve in methanol system, as shown in Figure 5.The acidic molecular sieve in methanol firstly catalyze that isomerization of glucose into fructose, part of the fructose is subjected to ketalization reaction with methanol unde the catalysis of the molecular sieve to form methyl fructoside, and then the methyl fructoside is subjected to hydrolysis to obtain the fructose after a proper amount of wat is added into the methanol[71].
Because fructose is easier to form glycoside with methanol than glucose in methanol, it can effectively promote the equilibrium of isomerization reaction to move to the direction of fructose formation. Through this two-step reaction pathway, the fructose yields of glucose isomerization catalyzed by H-USY and H-beta molecular sieves at 120 ℃ reached 55% and 40%, respectively (selectivity of 76% and 57%, respectively)[71]. Further studies showed that the Lewis acid site of the molecular sieve played a major catalytic role in the isomerization of glucose to fructose, while the Bronsted acid site of the molecular sieve catalyzed the conversion of fructose to methyl fructoside, thus obtaining a relatively high yield of fructose after hydrolysis[72]. Therefore, although the Bronsted acid site alone does not have catalytic isomerization activity, it is still an important factor affecting the yield of fructose in the two-step reaction path. In addition, Saravanamurugan et al. further studied and compared the catalytic properties of H-USY, Sn-beta and homogeneous Lewis acid, and found that they had the same stereoselectivity for glucose isomerization, that is, the isomerization reaction was carried out by transferring the hydrogen anion to the pro-R position, and the R configuration was obtained after the reaction, which was similar to the stereoselectivity of enzymatic isomerization[73].
Ren et al. Designed and synthesized a self-supporting single-cell nanolayer Sn-MFI molecular sieve, and the conversion rate and fructose yield of glucose isomerization catalyzed by the above two-step reaction path can be increased to 85% and 65% (90 ℃), respectively[74]. The excellent catalytic activity of Sn-MFI is mainly attributed to the high intra-crystalline diffusion rate of the substrate and the large specific surface area of the nano-molecular sieve. In addition, the isomerization yield of fructose from glucose catalyzed by Sn-MWW in alcohol system was more than 50%[75]. However, it should be noted that the above two molecular sieves usually require a long reaction time (24 H) to catalyze the hydrolysis of fructoside to fructose, so the catalytic efficiency of the two-step method for glucose isomerization in the above molecular sieve alcohol system needs to be further improved.

4.4 Basic ion exchange resin

Ion exchange resin is an insoluble polymer with functional groups, which is widely used in acid-base catalysis[78]. Langlois et al. Studied the catalytic performance of hydroxyl ion exchange resin for glucose isomerization, and found that the highest glucose conversion and fructose yield reached 38% and 32% (85 ℃, 40 H), respectively, under the optimized reaction conditions[79]. On this basis, Jacob et al. Modified the hydroxyl ion exchange resin with aluminate, which can form a stable complex with fructose, thus improving the selectivity of fructose[80]. It was further found that the yield of fructose could be increased by lowering the reaction temperature, for example, the yield of fructose could be increased to 72% (glucose conversion rate 90%) after 42 days of reaction at 2 ℃[80]. However, the aluminate-modified ion exchange resin lost its application prospect in industrial production because of the long reaction time and more by-products. In order to design more efficient basic ion exchange resin catalytic system, Mun et al. studied the organic catalytic system with commercially available A-26 ion exchange resin as the catalyst and DMF, DMSO, isopropanol, ethanol and dioxane as the solvents, and found that A-26 had better catalytic performance for glucose isomerization in polar protic solvents, for example, the yield of fructose in ethanol could reach 49.7% (80 ℃, 3 H, selectivity 93.6%)[81].

4.5 Metal-organic framework material

metal-organic frameworks (metal organic frameworks, MOF) are a class of coordination polymers developed recently, which are synthesized by coordination polymerization of organic ligands and metal ions. MOF materials usually have three-dimensional pore structure, and its pore structure has flexible controllability, which can endow MOF materials with different catalytic properties by group modification or regulator[82,83]. Therefore, the application of MOF materials in the catalytic isomerization of glucose to fructose has also received a lot of attention.
In 2014, Akiyama et al. studied the isomerization of glucose catalyzed by Cr-based MOF materials MIL-100 and MIL-101[84]. The results show that MIL-101 with larger pore window is beneficial to the diffusion of substrate molecules, so it shows better catalytic activity than MIL-100. They further studied the effect of ligand substituents on the catalytic performance of MIL-101, and found that the interaction between amino groups and hydroxyl groups of glucose in the MIL-101-NH2 could bind glucose in the pores, thus hindering the isomerization of glucose. In addition, the electron-donating substituents such as the amino group increase the electron density of the Cr center, thereby reducing its Lewis acidity. On the contrary, the electron-withdrawing group can increase the Lewis acidity of the Cr center, thereby promoting the catalytic activity of the Cr site for glucose isomerization. Therefore, the fructose yield and selectivity of glucose isomerization catalyzed by MIL-101-SO3H prepared by introducing sulfonic acid group reached 21.6% and 100% (100 ℃, 24 H), respectively[84]. The mechanism of glucose isomerization catalyzed by MIL-101 is shown in Figure 6. In order to further improve the yield of fructose from glucose isomerization, Guo et al. Used alkaline Cr(OH)3 and acidic MIL-101 to catalyze glucose isomerization[85]. The yield and selectivity of fructose were 59. 3% and 77. 5%, respectively, when the reaction was carried out in ethanol at 100 ℃ for 24 H, followed by adding appropriate amount of water and reacting at 100 ℃ for 24 H. Isotope labeling experiments showed that the isomerization of glucose to fructose was mainly carried out through the proton transfer pathway catalyzed by Cr(OH)3, while MIL-101 catalyzed the ketalization of fructose to form fructoside[84].
In addition, the zirconium-based MOF material UiO-66 also showed excellent catalytic activity for glucose isomerization in a similar two-step pathway[86]. de Mello et al. Found that in the presence of formic acid, the regulator can introduce cluster defects on the surface of UiO-66, thereby increasing the pore volume and surface area of UiO-66[86]. They further studied the performance of the above UiO-66 in the two-step catalytic isomerization of glucose in different alcohol systems, and found that UiO-66 had the highest catalytic activity in propanol, with glucose conversion and fructose selectivity reaching 82% and 72% (90 ℃, 24 H + 24 H), respectively.
Compared with homogeneous catalysts, easy separation is one of the greatest advantages of solid catalysts. In addition, solid catalysts can usually have different active sites, which provides the possibility of designing a continuous catalytic conversion path for products. Some porous materials also have shape-selective catalytic properties. All these advantages promote people to study the application of solid catalysts in glucose isomerization reaction. However, the low hydrothermal stability of solid catalysts and the leaching of metal ions are still obstacles for their industrial application.

5 Conclusion and prospect

As glucose isomerization is an important reaction in biorefinery process, a lot of research has been done on the chemical catalysis of glucose isomerization, and a series of new catalysts and catalytic systems have been developed. The new solid catalyst with high efficiency can greatly improve the low selectivity of homogeneous base catalysis, and the two-step isomerization of glucose in alcohol system can significantly improve the conversion of glucose. At the same time, the study of reaction mechanism has been gradually improved with the development of computational chemistry and detection methods.
However, it can not be ignored that there are still many problems to be solved in the research of glucose isomerization fructose. For example, the yield and selectivity of fructose isomerization from glucose still need to be improved. The hydrothermal stability of solid catalysts should be considered in industrial continuous production, so it is necessary to innovate catalysts and catalytic systems, such as exploring suitable reaction solvents to improve the stability and catalytic activity of catalysts. In addition, it should be noted that the mixture of fructose and unreacted glucose is obtained in most catalytic systems at present, so it is also very important to achieve efficient and low-cost separation of products in actual production. In terms of isomerization mechanism, although the mechanism of acid-base catalytic isomerization of glucose has been relatively clear, it is still necessary to further study the transition state structure and chemical kinetics of different catalysts and catalytic systems with the help of advanced theoretical calculation and characterization techniques in order to achieve the purpose of efficient regulation of isomerization reaction.

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Funding

National Key R&D Program of China(2019YFB1503903)

Key-Area Research and Development Program of Guangdong Province(2020B0101070001)

National Natural Science Foundation of China(21706223)

National Natural Science Foundation of China(21506177)

Fundamental Research Funds for the Central Universities(20720190014)

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