Heteropoly Acid-Based Catalysts for Hydrolytic Depolymerization of Cellulosic Biomass

Introduction

With the continuous exploitation of human beings, the amount of fossil energy that is the most main energy consumed in the world is decreasing gradually. Therefore, developing a sustainable renewable energy source that can provide valuable chemicals and biofuels is of great importance (Zhang et al., 2015). To furnish the desired bioproducts, some resources are needed which can provide us with basic elements such as C, H, and O in luxuriant amounts (Dhepe and Fukuoka, 2008). Compared with other energy sources (e.g., coal, oil, and natural gas), biomass energy has incomparable advantages as a renewable energy source with little pollution. Moreover, biomass has become the focus of development because of its universality, abundance, and low pollution. In some biorefinery typically using biomass instead of oil, biomass can be converted into energy and relevant bioproducts through multifarious platforms (Chang et al., 2013; Hu et al., 2015; Li et al., 2016; Liu et al., 2016). Especially, biorefinery combines the key technologies of transforming biological raw materials into industrial intermediates and final products (Scheme 1; Kamm and Kamm, 2004; Dhepe and Fukuoka, 2008; Li et al., 2015; Liu and Zhang, 2015; Zhang et al., 2018). Therefore, the utilization of biomass is a wonderful choice to develop sustainable and renewable energy.

SCHEME 1

Scheme 1. Biorefinery for the development of industrially relevant products.

As the most abundant source of biomass and one of the most widely distributed and abundant polysaccharides in nature, cellulose provides more possibilities for sustainable chemicals and fuels in the future (Huber et al., 2006; Climent et al., 2014; Sheldon, 2014; To et al., 2015). Hence, the conversion of cellulose could become a significant part of biomass utilization, which plays an important role in the development of chemicals and fuels in the future. However, cellulose is a homopolymer of D-glucose made up of β-1,4 glycosidic bonds (Scheme 2A). Its intramolecular and intermolecular hydrogen bonds are formed (Scheme 2B), resulting in its water insolubility (Geboers et al., 2011; Wang et al., 2012; Harada et al., 2014; Yabushita et al., 2014). Therefore, the processes of cellulose conversion are complicated because this biopolymer is insoluble in water, and most organic solvents (Klemm et al., 2005; Albert et al., 2014).

SCHEME 2

Scheme 2. (A) Molecular structure of cellulose. (B) Intermolecular and intramolecular hydrogen bond interactions in cellulose (n = DP, degree of polymerization).

Many homogeneous and heterogeneous acid catalysts were found to be capable of converting cellulose into glucose, a monosaccharide which is an important component for synthesizing different kinds of chemicals and fuels (Scheme 3), such as furans (Li et al., 2014), ethanol (Chheda et al., 2007), polyhydric alcohol (Geboers et al., 2010; de Op Beeck et al., 2013; Xie et al., 2014; He et al., 2018), furfural (Yu et al., 2009b; Feng et al., 2011; Li et al., 2013; Pan et al., 2013), organic acid (Yan et al., 2014; Zhang et al., 2014; Ren et al., 2015), and so on. Several excellent review literature on the conversion of cellulose have been reported, with focus on the discussion of different solid acid catalysts (e.g., Amberlyst-15, PCPs–SO₃H, BC–SO₃H, CMK-3-SO₃H, Zn–Ca–Fe, CsH₂PW₁₂O₄₀, Ru/CMK-3, Fe₃O₄-SBA–SO₃H, CaFe₂O₄, H₃PW₁₂O₄₀, H₅BW₁₂O₄₀, H₅AlW₁₂O₄₀, H₅GaW₁₂O₄₀, and H₆CoW₁₂O₄₀) for hydrolysis of cellulose (Table 1; Kobayashi et al., 2010; Pang et al., 2010; Rinaldi et al., 2010; Tian et al., 2010, 2011; Wu et al., 2010; Akiyama et al., 2011; Komanoya et al., 2011; Lai et al., 2011; Ogasawara et al., 2011; Zhang et al., 2011).

SCHEME 3

Scheme 3. The main reaction network of glucose hydrogenation and oxidation.

TABLE 1

Table 1. Cellulose hydrolysis over different solid acid catalysts.

Compared with other solid acids, HPA catalysts are more favorable for hydrolysis of cellulose, considering that they have some unique properties such as stronger acidity compared to other mineral acids (e.g., H₂SO₄, HCl), high redox properties, good thermal stability, easy separation, good reusability, fewer side products, less waste generation, non-toxicity, and easy handling, as illustrated in Figure 1 (Kozhevnikov, 1987, 1998; Mizuno and Misono, 1994; Kaur and Kozhevnikov, 2002; Yu et al., 2009a; Yang et al., 2011; Deng et al., 2012; Reddy et al., 2012; de Op Beeck et al., 2013). Furthermore, HPA catalysts can be used in both homogeneous and heterogeneous systems. The most significant advantage of the heterogeneous system is that the HPA catalysts can be easily separated from the reaction products, thus improving the catalyst reusability. The most common HPAs are Keggin-type HPAs, which have the anions of [XM₁₂O₄₀]ⁿ⁻, where X is a heteroatom (e.g., P, Si) and M is a metal ion (e.g., W⁶⁺, Mo⁶⁺). Among them, H₃PW₁₂O₄₀ is the most common Keggin-type HPA. Moreover, H₃PW₁₂O₄₀ with strong acidity is highly soluble in water and can completely dissociate protons, which facilitates contact with the heterogeneous substrates, thus endowing enhanced reaction rates (Tian et al., 2010). Besides, the basic structural units of Keggin-type HPAs are oxygen-containing tetrahedron and octahedron anions in good symmetry and low charge density (Figure 2).

FIGURE 1

Figure 1. Some unique properties of heteropoly acids (HPAs).

FIGURE 2

Figure 2. The structure of common Keggin-type HPA.

Given the unique features and rapid development of HPAs-based catalysts in the preliminary degradation of cellulosic biomass with high efficiency, this review mainly reports the design and structural characterization of different types of HPAs employed for hydrolytic depolymerization of cellulosic biomass. In addition, the properties and preparation methods of HPAs as well as their advantages in the hydrolysis of cellulose are discussed. Also, possible research trends of HPAs in the future are forecasted.

HPAs-Based Catalysts

HPA Properties and Classification

HPA catalysts have attracted people's attention, and are known as effective, environmentally friendly and economically viable acid catalysts (Kozhevnikov, 1998), which can be used in either homogeneous or heterogeneous state (Izumi et al., 1983; Nowinska et al., 1996; Song and Lee, 2004; Bennardi et al., 2010; Zhao et al., 2013). Compared with a homogeneous system, the heterogeneous system has the advantage that the catalyst is easy to separate from the reaction products. Due to these special features, HPA catalysts are more beneficial to the degradation of cellulosic biomass than other catalysts.

HPA catalysts can be classified into the following categories: (1) Keggin-type HPAs, the most common HAPs with the anions of [XM₁₂O₄₀]ⁿ⁻, where X is a heteroatom (e.g., P, Si) and M is a metal ion (e.g., W⁶⁺, Mo⁶⁺). (2) Substituted HPAs, the H⁺ ions on conventional HPAs are substituted by monovalent cations, such as Cs⁺ ions. (3) Supported HPAs, the heteropoly compounds are supported on suitable supporters, such as silica. (4) Assembled HPAs, the new catalysts with higher activity are synthesized by self-assembly of HPAs with other substances, such as ionic liquids. (5) Other types, new types of heterogeneous catalysts formed by an effective combination of HPAs with other substances.

Catalyst Preparation Methods

Up to the present, many patents and literature on the preparation of HPAs were published, including e.g., traditional acidification method incorporated with an ether extraction, ion exchange method, impregnation method, and sol-gel method (Bechtold and Square, 1950; Laferty and John, 1966; Chiola and Lawrence, 1969; Chiola et al., 1969; Izumi et al., 1995; Vázquez et al., 2000; Mrowiec-Białoń et al., 2002; Cardoso et al., 2004; Yang et al., 2005; Ahmed et al., 2011). The traditional synthesis method of conventional HPAs is an acidification process coupled with an ether extraction, which is commonly used for the synthesis of phosphotungstate HPA catalysts. In this method, the HPA is prepared by mixing heteroatom oxygen-containing acid and ligand oxide in a certain proportion, heating, refluxing, and then acidifying to obtain HPA. The HPA is dissolved in ether, and the solid HPA is obtained after ether volatilization (Chiola and Lawrence, 1969; Chiola et al., 1969). However, the acidification procedure coupled with an ether extraction has the disadvantages of low safety due to the use of toxic substances and low yield of some HPAs. In connection with this, the ion-exchange method has been developed, which first obtains the corresponding ammonium salt, and then obtains HPA through hydrogen ion-exchange resin. This method avoids the use of ether and improves process safety, but the production cycle is relatively long (Bechtold and Square, 1950; Laferty and John, 1966). For some supported HPAs, the impregnation method is commonly used. The method is to add the carrier into the solution of HPA with a certain concentration, stir for a long time at a certain temperature, stand still, and then remove the excess solvent to obtain the catalyst. The method is simple and safe, but there are some problems such as the loss of catalyst activity and limited recycling ability. Therefore, the support should be screened and optimized (Vázquez et al., 2000; Cardoso et al., 2004; Liu et al., 2004). The sol-gel method is to add raw materials to the HPA colloid and obtain the HPA catalyst through a series of specific processes, such as drying and heat treatment. This method can be used to prepare catalysts at a low temperature or mild condition, which is widely used in manufacturing nanomaterials catalysts. Likewise, this method has the disadvantages of low security and long cycle (Izumi et al., 1995; Mrowiec-Białoń et al., 2002; Yang et al., 2005). Some examples of catalysts for the preparation of HPAs are as follows:

1. Keggin-type Mo-V-P heteropoly acid catalysts (Scheme 4; Zhizhina and Odyakov, 2008; Odyakov and Zhizhina, 2009): Firstly, V₂O₅ was dissolved in cold diluted H₂O₂ solution to form peroxy complexes, which was gradually decomposed with oxygen to give H₆O₁₀V₂₈. Then, by adding excess H₃PO₄, H₆O₁₀V₂₈ acid produced was immediately stabilized to give H₉PV₁₄O₄₂, following by addition into the boiling suspension of MoO₃ and H₃PO₄ to form the catalyst.

2. Substituted heteropoly tungstic acid catalyst Cs_xH_3−xPW₁₂O₄₀ (x = 1–3): It is usually prepared by titration method (Okuhara et al., 1992, 1996, 2000; Tian et al., 2011). At room temperature, dropping 0.10 mol dm⁻³ Cs₂CO₃ aqueous solution into 0.8 mol dm⁻³ of H₃PW₁₂O₄₀ aqueous solution at a constant rate was stirred continuously. Then the resulting solution was aged overnight at room temperature and heated at 50°C to obtain the catalyst.

3. The synthesis of catalyst (HOCH₂CH₂N(CH₃)₃)_x H_3−xPW₁₂O₄₀ (abbreviated as Ch_xH_3−xPW₁₂O₄₀) is shown in Scheme 5 (Duan et al., 2013; Zhang et al., 2016): choline chloride (ChCl, HOCH₂CH₂N(CH₃)₃Cl) (3.34 mmol) was added to H₃PW₁₂O₄₀ (3.34 mmol) solution and the white precipitate was formed after stirring in 20 mL distilled water for 8 h at room temperature. Then the white precipitate was washed with distilled water, followed by recrystallization twice with CH₃CN, drying at 60°C, and finally getting the white product ChH₂PW₁₂O₄₀ (HOCH₂CH₂N(CH₃)₃H₂PW₁₂O₄₀).

4. The self-assembled HPA ionic liquid catalyst [C₄H₆N₂(CH₂)₃SO₃H]₃PW₁₂O₄₀ (Scheme 6; Leng et al., 2010): 0.11 mol methyl imidazole and 0.10 mol 1,3-propane sulfone were dissolved in 20 mL toluene under nitrogen and stirred for 24 h at 50°C. The resulting white precipitate is filtered and washed three times with ether and then dried in a vacuum. Then it was added to the aqueous solution of H₃PW₁₂O₄₀ (0.02 mol) and stirred for 24 h at room temperature. Then water was removed in vacuum to obtain solid products, washed with water and ethanol, and dried at 100°C for 3 h.

SCHEME 4

Scheme 4. The overall scheme for the synthesis of Mo-V-P HPA catalysts.

SCHEME 5

Scheme 5. The synthetic procedure of Ch_xH_3−xPW₁₂O₄₀ catalyst.

SCHEME 6

Scheme 6. The synthetic routes to [C₄H₆N₂(CH₂)₃SO₃H]₃PW₁₂O₄₀.

Hydrolytic Depolymerization of Biomass With HPAS-Based Catalysts

Keggin-Type HPAs

Keggin-type HPAs are the most common HPA catalysts, which have great application prospects for biomass degradation. The potential of HPAs for catalyzing the hydrolysis of cellulose to glucose has been explored.

Cellulose Conversion to Glucose

Tian et al. developed the heteropoly acid H₃PW₁₂O₄₀ for selective conversion of cellulose (Scheme 7). The heteropoly acid catalyst can promote cellulose hydrolysis, achieving the glucose selectivity and yield of 92.3 and 50.5%, respectively at 180°C for 2 h with 0.10 g cellulose amount. The authors also studied and optimized reaction parameters influencing the hydrolysis of cellulose and determined the most optimizing reaction conditions. Compared with HCl, H₃PW₁₂O₄₀ had greater catalytic activity and glucose selectivity under identical reaction conditions with the same acid concentration (Table 2: 0.2 mmol HCl is equivalent to 0.06 mmol H₃PW₁₂O₄₀, and 0.06 mmol H₃PW₁₂O₄₀ had higher catalytic activity). After testing the catalytic activity of H₃PW₁₂O₄₀ in six consecutive reaction cycles, the total loss of H₃PW₁₂O₄₀ was 8.8% of its initial loss (Figure 3; Tian et al., 2010). It was found that the acid catalyst H₃PW₁₂O₄₀ was generally stable and could be recycled by extraction using diethyl ether. However, there was still a little loss of catalyst activity, which led to a slight decrease in the yield of TRS and glucose.

SCHEME 7

Scheme 7. Main products and by-products of cellulose conversion by an acid catalyst H₃PW₁₂O₄₀.

TABLE 2

Table 2. Hydrolysis of cellulose with different acid catalysts (Tian et al., 2010).

FIGURE 3

Figure 3. The recyclability of H₃PW₁₂O₄₀ in six consecutive reaction cycles. Reaction conditions: 0.1 g cellulose, 0.08 mmol catalyst, 5 mL water at 180°C for 2 h. Reproduced with permission from Tian et al. (2010).

In 2009, Shimizu et al. studied the effects of Brønsted and Lewis acidities on the activity and selectivity of HPA catalysts for hydrolysis of cellulose (Furukawa et al., 2009). The authors also reported that HPAs (i.e., H₃PW₁₂O₄₀ and H₄SiW₁₂O₄₀) could catalyze the hydrolysis of cellulose with high selectivity to glucose. It was concluded that for Brønsted acid catalysts, the activity increases with the decrease in the deprotonation enthalpies (DPE, for the description of the acid strength of HPAs) (Macht et al., 2008; Shimizu and Satsuma, 2011), indicating that stronger Brønsted acidity is more beneficial to the hydrolysis of cellulose (The effect of DPE on catalysts activity shown in Figure 4). In other words, stronger Brønsted acid is more beneficial to the hydrolysis of β-1,4 glucosidic bonds of cellulose. More interestingly, the obtained catalyst rates are higher for moderate Lewis acidity, while the catalysts with moderate Lewis acidity have higher TOFs for glucose production than H₃PW₁₂O₄₀ (Figure 5). Therefore, the Brønsted and Lewis acidities of HPA catalysts can influence the hydrolysis of cellulose. Moreover, with the increase of the catalyst dosage, the yield of glucose increased, which is due to the increase in the number of catalytic active sites. As shown in Figure 4, the lower DPE corresponds to stronger acidity of the catalysts, which is responsible for higher catalytic activity, with the TRS yield in the order of H₄SiW₁₂O₄₀ > H₃PW₁₂O₄₀ > HClO₄ > H₂SO₄ > H₃PO₄.

FIGURE 4

Figure 4. The effect of deprotonation enthalpy (DPE) of acid catalysts on catalysts activity (∘, TRS yield; •, cellulose conversion; Δ, TRS selectivity of cellulose hydrolysis). Reaction conditions: 0.58 mmol cellulose, 6 mL H₂O, 6 mol catalyst (M_n/3PW₁₂O₄₀) at 150°C for 2 h. Reproduced with permission from Macht et al. (2008) and Shimizu and Satsuma (2011).

FIGURE 5

Figure 5. The effect of Lewis acid on the catalytic rate of catalysts (∘, TRS yield; •, cellulose conversion; Δ, TRS selectivity of cellulose hydrolysis). Reaction conditions: 0.58 mmol cellulose, 6 mL H₂O, 6 mol catalyst (M_n/3PW₁₂O₄₀) at 150°C for 2 h. Reproduced with permission from Shimizu and Satsuma (2011).

Ogasawara et al. found that the highly negatively charged HPAs (e.g., H₅BW₁₂O₄₀, H₅AlW₁₂O₄₀, and H₅GaW₁₂O₄₀) could efficiently promote the hydrolysis of crystalline cellulose into glucose in concentrated aqueous solutions (Ogasawara et al., 2011). In particular, H₅BW₁₂O₄₀ showed a superior yield of glucose (77%) for 48 h in 0.7 mol/L cellulose solution at a lower reaction temperature (60°C), which avoided the formation of undesirable byproducts such as humic substances and dehydration products. And its performance is much better than the commonly utilized mineral acids and HPAs, such as H₂SO₄, HCl, H₃PW₁₂O₄₀, and H₄SiW₁₂O₄₀ (Table 3). Procedures for saccharification contains two important points: turning the acidity of catalysts and decreasing the crystallinity of cellulose by breaking intermolecular hydrogen bonding that can be achieved by concentrated H₅BW₁₂O₄₀ aqueous solutions (0.70 mol/L). Besides crystalline cellulose, the present system was suitable for the selective transformation of cellobiose and starch into glucose with a good yield of 82 and 85%, respectively (Scheme 8). Also, H₅BW₁₂O₄₀ and saccharide can be completely separated from aqueous reaction solutions by extraction using alcoholic solvents due to their different solubility. And the retrieved highly negatively charged HPA H₅BW₁₂O₄₀ can be used repeatedly at least ten times without significant performance loss (Figure 6; Ogasawara et al., 2011).

TABLE 3

Table 3. Hydrolysis of cellulose using different concentrations of aqueous acidic solutions (Ogasawara et al., 2011).

SCHEME 8

Scheme 8. Transformation of cellobiose and starch in concentrated H₅BW₁₂O₄₀ aqueous solutions (0.70 mol/L, 2 mL).

FIGURE 6

Figure 6. Recyclability of H₅BW₁₂O₄₀ for the conversion of pretreated cellulose. Reaction conditions: 100 mg pretreated cellulose (the cellulose was mercerized and then ball-milled), 0.70 mol/L, 2 mL H₅BW₁₂O₄₀ solution, 60°C for 24 h. Reproduced with permission from Ogasawara et al. (2011).

For the conversion pathways, the HPAs can initially hydrolyze cellulose into glucose that can be further converted into other substance in the assistance of their bifunctional properties (i.e., acidity and redox property), such as catalytic oxidation of cellulose to formic acid (Wölfel et al., 2011; Albert et al., 2012, 2014; Gromov et al., 2016; Lu et al., 2016), direct conversion of cellulose to glycolic acid (Zhang et al., 2012), and cellulose transformation into methyl glucosides (Scheme 9; Zheng et al., 2018).

SCHEME 9

Scheme 9. Conversion of cellulose to other substance with an HPA catalyst (H⁺, HPA catalyst).

Cellulose Conversion to Formic Acid

Conversion of cellulose to formic acid using HPAs as catalysts is an efficient and environmentally friendly catalytic system (Lu et al., 2016). This conversion system involves two stages (Scheme 10): (1) acid-catalyzed the hydrolysis of cellulose into glucose, and (2) oxidation of glucose to formic acid with an oxidizer (C-C bond in glucose is oxidized and cracked by HPA catalysts) (Albert et al., 2014; Gromov et al., 2016).

SCHEME 10

Scheme 10. The stages of converting cellulose into formic acid.

In 2014, different Keggin-type HPAs H_3+n[PVnMo_12−nO₄₀] (n = 0–6) were synthesized, and the optimized HPA catalyst system H₈[PV₅Mo₇O₄₀] could selectively oxidize biomass to formic acid (Albert et al., 2014). The whole reaction mechanism was divided into three steps: acid-assisted hydrolysis of the insoluble substrate, oxidative cleavage of C–C bonds in the substrate, and re-oxidation of the in situ reduced HPA catalyst by molecular oxygen. The acid catalyst redox cycle is shown in Scheme 11. Albert et al. also confirmed that the HPA catalysts screened with glucose as substrate had general reactivity, and the higher V-substituted catalysts (n = 2–6) showed better activities than the lower V-substituted catalysts (n = 0–1) (Albert et al., 2014). The comparison of the yields of glucose to formic acid under different HPA catalysts is shown in Table 4. Moreover, when H₅PV₂Mo₁₀O₄₀ and p-toluenesulfonic acid (TSA) are used as a catalyst and an additive, respectively, the conversion of cellulose was explained as a two-stage process that acid-catalyzed both cellulose hydrolysis and glucose oxidation to formic acid (Wölfel et al., 2011; Albert et al., 2014). In the system, TAS was used for the hydrolysis of cellulose, while H₅PV₂Mo₁₀O₄₀ was used for the oxidant of glucose. It is worth noting that H₈[PV₅Mo₇O₄₀] catalyst has pronounced activity for the conversion of cellulose to formic acid, but with the disadvantage of low selectivity toward formic acid.

SCHEME 11

Scheme 11. The redox cycle of the catalyst H₅PV₂Mo₁₀O_40.

TABLE 4

Table 4. The comparison of the yields of glucose to formic acid with different HPA catalysts (Albert et al., 2014).

In 2016, Lu et al. found that a Keggin-type heteropoly acid catalyst H₅PV₂Mo₁₀O₄₀ with H₂SO₄ was efficient for catalytic oxidation of cellulose to formic acid with oxygen as an oxidant (Lu et al., 2016). The authors discussed the effects of the pH on the catalyst and reaction pathway by adding H₂SO₄ with variable amounts (Table 5). It was shown in Figure 7 that when 1.6 wt% H₂SO₄ was added (equivalent to a significant reduction in pH), the conversion of cellulose increased from 60 to 100%, and the yield of formic acid increased from 28 to 61% in a reaction time of 5 min. It can be concluded that adding H₂SO₄ to the solution promotes the protonation of H₅PV₂Mo₁₀O₄₀. Decreasing the pH from 1.87 to 0.56 is beneficial for the catalyst protonation and can increase the oxidation potential. In summary, the H₅PV₂Mo₁₀O₄₀ + H₂SO₄ system shows a stronger catalytic impact by reducing pH than the direct use of H₅PV₂Mo₁₀O₄₀ (Lu et al., 2016).

TABLE 5

Table 5. Synthesis of formic acid (FA) from cellulose at different pH (Lu et al., 2016).

FIGURE 7

Figure 7. Conversion of cellulose to formic acid (FA) and acetic acid (AA) under different concentration of H₂SO₄. Reaction conditions: 0.16 g cellulose, 0.10 g catalyst, 6 mL H₂O, 3 MPa O₂, 180°C for 0.25 h. Reproduced with permission from Lu et al. (2016).

Likewise, Gromov et al. reported the one-pot catalytic process which was applied to hydrolytic oxidation of cellulose to formic acid (Gromov et al., 2016). In their work, Mo-V-P heteropoly acid catalysts were found to be beneficial for hydrolytic oxidation of cellulose to formic acid because of their bifunctional (i.e., oxidizing and acidic) catalytic properties. The oxidizing and acidic catalytic properties correspond to the conversion process of cellulose to formic acid which involves two stages: Step 1: hydrolysis of cellulose to glucose via acidic HPA sites; Step 2: The oxidation of glucose to formic acid taking place at the oxidation sites of Mo-V-P HPA (V⁵⁺) (Scheme 12). Therefore, cellulose was hydrolyzed and then oxidized to formic acid using the low-cost Mo-V-P HPA catalysts. Cascade hydrolysis and oxidation of cellulose to formic acid with high yields (65–66 mol%) were achieved by the single-step catalytic process in the presence of Mo-V-P HPA catalysts. In addition, the temperature of 150–160°C and air pressure of 10–20 Mpa (20% O₂ and 80% N₂) were found to be the optimal reaction conditions.

SCHEME 12

Scheme 12. The overall scheme of the hydrolysis-oxidation of cellulose.

The Keggin-type (Mo-V-P)-HPAs were used to catalyze the hydrolysis of hemicellulose in a diluted aqueous solution that was reported by Shatalov (2019). HPAs of series H_(n+3)[PMo_(12−n)VnO₄₀] used as the bifunctional catalysts were studied. For example (Mo-V-P)-HPAs-catalyzed hydrolysis of model xylan, which confirmed the established order of HPAs catalytic activity in hydrolysis reaction (H₃PMo₁₂O₄₀ > H₆[PMo_8.9V_3.1O₄₀] > H₇[PMo_7.9V_4.2O₄₀] >> H₂SO₄). In addition (Mo-V-P)-HPAs, showed remarkable activity in both the acid-catalyzed reactions and the oxidative degradation of lignin. Therefore (Mo-V-P)-HPAs, as the green bifunctional catalysts have the potential to be an alternative to common mineral acids for selective hydrolysis and oxidative degradation of a variety of polysaccharides.

Cellulose Conversion to Other Substances

In the oxygen environment, HPAs can also catalyze cellulose being converted to glycolic acid. In 2019, Zhang et al. reported the conversion of cellulose to glycolic acid by phosphomolybdic acid catalyst (Zhang et al., 2012). In this reaction system, the heteromolybdic acid acted as multifunctional catalysts that first hydrolyzed cellulose to glucose, followed by oxidation to glycolic acid in a water medium, which combines the advantages of homogeneous and heterogeneous catalysts. The proposed reaction pathways for the conversion of cellulose to glycolic acid are shown in Scheme 13. Cellulose was hydrolyzed to glucose, which was converted to glycolaldehyde by the continuous retro-aldol reaction, and then to glyoxal by oxidation. Simultaneously, the isomerization of glucose produced fructose, which was converted to glycolaldehyde and formaldehyde via the retro-aldol reaction, which was then oxidized to glycolic acid and formic acid, respectively. In addition, the authors investigated the reusability of the phosphomolybdic acid catalyst in cellulose conversion (Figure 8). The results indicated that the catalyst exhibited constant catalytic performance. X-ray photoelectron spectroscopy (XPS) showed that the oxidation state of Mo in the heteromolybdic acid catalyst was unchanged after successive reactions (Figure 9). It can be concluded that Mo-containing HPAs can effectively promote the conversion of various kinds of cellulosic biomass materials to glycolic acid.

SCHEME 13

Scheme 13. The proposed reaction pathways for the conversion of cellulose to glycolic acid.

FIGURE 8

Figure 8. The yield of glycolic acid in the continuous reaction of cellulose conversion with HPM (H₃PMo₁₂O₄₀) as the catalyst. Reproduced with permission from Zhang et al. (2012). Reaction conditions: 200 mg cellulose, 0.025 mmol catalyst, 20 mL H₂O, 0.6 MPa O₂, 180°C for 1 h. Reproduced with permission from Zhang et al. (2012).

FIGURE 9

Figure 9. XPS spectra of Mo 3d in the fresh (A) and used (B) HPM (H₃PMo₁₂O₄₀) catalyst. Reproduced with permission from Zhang et al. (2012).

The effective alcoholysis of cellulose to monosaccharide is of great significance for fuel production. The H₃PW₁₂O₄₀ catalyst can promote cellulose transformation into methyl glucosides after pretreatment of microcrystalline cellulose by the ionic liquid 1-allyl-3-methylimidazolium chloride, as reported by Zheng et al. (2018). In their work, cellulose was firstly obtained by pretreatment with the ionic liquid 1-allyl-3-methylimidazolium chloride, followed by cellulose alcoholysis using H₃PW₁₂O₄₀ as the bifunctional catalyst. It was found that cellulose was easier to be saccharified after pretreatment by the ionic liquid. Meanwhile, prolonging the pretreatment time with the increased temperature is beneficial to the succedent alcoholysis reaction. Whereafter, the authors investigated the effects of various parameters on the alcoholysis reaction, including the alcoholizing time, the alcoholizing temperature, and different concentrations of H₃PW₁₂O₄₀ catalyst. It was observed that under the optimum conditions (110°C, 60 min), the yield of methyl glucosides could be up to 70.2% with this system. Therefore, using some processes such as pretreatment of cellulose with ionic liquid can make it easier to saccharify, thus better-promoting HPA catalytic conversion of cellulose into the desired products. However, the reusability of the catalyst is not satisfactory. As shown in Figure 10, the activity of the H₃PW₁₂O₄₀ catalyst decreased gradually in the repeated experiment, indicating the low catalyst stability.

FIGURE 10

Figure 10. Recyclability of H₃PW₁₂O₄₀ in alcoholysis of cellulose to methyl α-D-glucoside (M-α-G) and methyl β-D-glucoside (M-β-G). Reaction conditions: 0.3 g cellulose, 8.7 mmol/L catalyst H₃PW₁₂O₄₀, 170°C for 2.75 h. Reproduced with permission from Zheng et al. (2018).

In addition, the HPA is also an important catalyst for the formation of glucose from other saccharides. In 2015, Klein et al. found that HPA can catalyze the hydrolysis of glycogen to glucose (Klein et al., 2015). Through a series of experiments, it can be concluded that glycogen could be completely converted to glucose by using H₃PW₁₂O₄₀·nH₂O and H₄SiW₁₂O₄₀·nH₂O as the catalyst, respectively, and the optimized hydrothermal conditions are a mass fraction of catalyst 2.4%, 100°C temperature, and 2 h reaction time. In addition to hydrolysis in an autoclave, the authors also investigated microwave irradiation and sonication heating mode for glucose synthesis (Table 6). The results showed that using H₄SiW₁₂O₄₀ as a catalyst, glycogen could be completely converted into glucose by the autoclave method and sonication method without other by-products, so relatively high selectivity toward glucose (>99%) was obtained using these two methods. On the other hand, when glycogen was hydrolyzed by microwave method, glycogen was completely transformed in 0.25 h, but giving by-products like levulinic acid and formic acid, which showed lower selectivity of glucose than the other two methods. More importantly, under microwave irradiation, the formation of glucose was the result of the increase of reaction temperature in the process of microwave irradiation (Klein et al., 2012). In the process of sonochemical irradiation, the acoustic bubble collapsed at a faster speed, causing local high temperatures, thus promoting the hydrolysis of glycogen to glucose (Klein et al., 2012). Therefore, high temperature is the key factor of glycogen hydrolysis, and the HPAs are highly efficient, environmentally friendly, and reusable catalysts that can catalyze the hydrolysis of glycogen to glucose.

TABLE 6

Table 6. Effect of H₄SiW₁₂O₄₀ on glycogen hydrolysis using different methods (Klein et al., 2012).

Substituted HPAs

Substituted HPAs are formed when H⁺ ions on conventional HPSs are substituted by monovalent cations, such as Cs⁺ ions. One of the typical substitutional HPAs, Cs_xH_3−xPW₁₂O₄₀ has the advantages of super acidity, microporous structure, shape selectivity, and hydrophobicity, which is conducive to the hydrolysis of cellulose (Okuhara, 2002).

Cellulose Conversion to Glucose

In 2010, Tian et al. reported hydrolysis of cellulose over the Cs_xH_3−xPW₁₂O₄₀ (x = 1–3) catalysts, which were active in the hydrolysis of cellulose into glucose. Notably, cellulose can be hydrolyzed to glucose in the presence of Cs_xH_3−xPW₁₂O₄₀ catalysts due to the breaking of β-1,4-glycoside bond (Scheme 14).

SCHEME 14

Scheme 14. The pathways of cellulose hydrolysis into glucose over Cs_xH_3−xPW₁₂O₄₀.

After a series of catalyst tests, it was found that Cs₁H₂PW₁₂O₄₀ showed the best catalytic performance in terms of cellulose conversion (54.0%) and glucose yield (27.2%), while Cs_2.2H_0.8PW₁₂O₄₀ showed the highest selectivity toward glucose (83.9%). The test results are shown in Figures 11A–C. In the meantime, they also studied the effect of Cs_xH_3−xPW₁₂O₄₀'s properties on cellulose hydrolysis. Cs₁H₂PW₁₂O₄₀ with the strongest protonic acid site was found to have the best catalytic performance for the hydrolysis and transformation of cellulose. However, the catalyst surface area and porous structure have little effect on the conversion of cellulose (Tian et al., 2010). Stronger Brønsted acid is more beneficial to the hydrolysis of β-1,4-glycoside bond in cellulose (Furukawa et al., 2009). It is further proved that Cs₁H₂PW₁₂O₄₀ with the strongest acidity is more conducive to the degradation of cellulose. When the catalyst and the unreacted cellulose were in the same reaction, the catalyst kept high activity during the hydrolysis of cellulose to TRS and glucose with the yields was 30.1 and 27.2%, respectively. Therefore, the tested acid catalyst is stable and can be reused.

FIGURE 11

Figure 11. (A) The relationship between cellulose conversion and cesium content in Cs_xH_3−xPW₁₂O₄₀, (B) the relationship between the yield of TRS and glucose and cesium content in Cs_xH_3−xPW₁₂O₄₀, and (C) the relationship between the selectivity of TRS and glucose and cesium content in Cs_xH_3−xPW₁₂O₄₀. Reaction conditions: 0.1 g microcrystalline cellulose, 0.06 mmol Cs_xH_3−−xPW₁₂O₄₀, 5 mL distilled water, at 160°C for 6 h (stirring 30 rpm). Reproduced with permission from (Okuhara, 2002).

Cellulose Conversion to Other Products

In 2011, Geboers et al. studied the hydrotreated cesium salts of HPAs in combination with Ru/C which can be used to degrade cellulose for the synthesis of hexitol (Geboers et al., 2011). The authors discussed the effects of calcination temperature and cesium HPAs hydrotreating conditions on cellulose conversion. The catalytic properties of several cesium HPAs were discussed and compared with conventional HPAs (Table 7). The synthesized cesium salts of HPAs were more active than the natural HPA salts, and their hydrolysis activity was further improved by increasing the calcination and hydrotreating temperature in the synthesis process.

TABLE 7

Table 7. Hydrolysis and hydrogenation of cellulose with Ru/C and different HPAs at 190°C and 5 MPa H₂ (Geboers et al., 2011).

As compared with their fully protonated counterparts (Cs_2.5PW and Ru/C or Cs_3.5SiW and Ru/C), the cesium HPAs have higher proton activity due to their higher surface acidity and hydrophobicity. After a hydrotreatment of cesium HPAs catalysts in water at 190°C was performed, the activity and selectivity of the catalysts were improved obviously due to the increase of crystallinity and hydrophobicity of samples. Finally, they found that these cesium HPAs could be completely recovered under certain conditions by a simple recrystallization method (Geboers et al., 2011). In 2011, they had studied the catalysts formed by natural HPAs in combination with Ru/C for cellulose degradation to hexitols (90%). These catalysts also had extraordinary catalytic performance, but they were difficult to recovery and reuse because of the limitation of reaction temperature (Geboers et al., 2010). Therefore, the hydrotreated cesium salts of HPAs in combination with Ru/C are more ideal for cellulose degradation.

In 2014, Zhang et al. synthesized a series of HPA catalysts (HOCH₂CH₂N(CH₃)₃)_xH_3xPW₁₂O₄₀ (HOCH₂CH₂N(CH₃)₃ abbreviated as Ch), which could be used as heterogeneous catalysts for degradation of cellulose to 5-hydroxymethylfurfural (HMF) (Zhang et al., 2016). By comparing several different types of acid catalysts (Figure 12), they found that the conversion of cellulose with Brønsted acid in HCl and H₃PW₁₂O₄₀ was 41.5 and 89.2%, respectively, while that of ChCl and Ch₃PW₁₂O₄₀ without Brønsted acid was 2.0 and 12.2%, respectively. So the strong Brønsted acidity of the catalyst was the necessary condition for cellulose hydrolysis. And (HOCH₂CH₂N(CH₃)₂)H₂PW₁₂O₄₀ had the highest catalytic activity among the previous catalysts. The yield of HMF can reach 75% when cellulose was catalyzed by (HOCH₂CH₂N(CH₃)₂)H₂PW₁₂O₄₀ within 8 h at 140°C. Besides, the temperature-responsive property and high stability of the catalyst made the recovery and reuse benefit reach 10 times without obvious activity loss (Figure 13).

FIGURE 12

Figure 12. Hydrolysis of cellulose under different catalysts. Reaction conditions: 0.1 g cellulose, 0.11 mmol catalyst, 0.5 ml water, 5 mL methyl isobutyl ketone, 140°C for 8 h. Reproduced with permission from Zhang et al. (2016).

FIGURE 13

Figure 13. The recycle reaction test of catalyst. Reaction conditions: 0.1 g cellulose, 0.11 mmol ChH₂PW₁₂O₄₀, 0.5 mL water, 5 ml methyl isobutyl ketone, 140°C for 8 h. Reproduced with permission from Zhang et al. (2016).

Overall, it can be seen that the substituted HPA catalysts showed high activity in the conversion of cellulose and they were stable and reusable. Therefore, the substituted HPA catalysts have good application prospects in cellulose degradation. However, the substituted HPA catalysts still suffer the disadvantage of low target product yield or selectivity, possibly due to the resistance of mass transfer.

Supported HPAs

So far, more and more attention has been paid to the supported acid catalysts, especially the supported HPAs. The dispersion of these catalysts on the support material increases the specific surface area, thus improving the catalytic activity. Some supported HPAs have been used in the degradation of cellulose. In 1981, Yusuke and Urabe found that activated carbon can encapsulate a certain amount of HPA, thus producing solid acid catalysts, which provided a convenient method for liquid phase etherification and gas-phase selective esterification of alcohols (Yusuke and Urabe, 1981). In 1989, the nuclear magnetic resonance (NMR) technology had been used in the structural research of HPAs and H₃PW₁₂O₄₀ supported on SiO₂ (Mastikhin et al., 1990).

HPAs are usually used as soluble catalysts in the liquid phase and as supported catalysts in the gas phase. From a practical point of view, it is useful to develop those supported HPA catalysts, which can be applied to a variety of reactions through fixed catalysts without leakage of HPA in the liquid, such as acylation of anisole with acetic anhydride (Bachillerbaeza and Anderson, 2004), the electrophilic substitution of phenols and aldehydes with HPA/MCM-41 (Udayakumar et al., 2007), and dehydration of aldehydes to nitriles catalyzed by silica-supported HPAs (Scheme 15; Parghi et al., 2011), and so on.

SCHEME 15

Scheme 15. Dehydration of aldehydes to nitriles catalyzed by HPA-SiO₂.

In 2007, Guo et al. studied a sol-gel co-condensation technology that can be used to prepare the green supported heteropoly acid catalysts (H₃PW₁₂O₄₀-silica), which was an efficient and reusable solid acid catalyst for the catalytic esterification of levulinic acid (LA) with phenol (Guo et al., 2007). The SBA-15 silica-supported H₃PW₁₂O₄₀ catalysts exhibited unique surface physicochemical properties, such as high porosity, larger pore size, and larger surface area (Table 8) that is attractive for the study of acid-catalyzed reactions. Figure 14 shows the nitrogen adsorption-desorption isotherms of the H₃PW₁₂O₄₀/SBA-15 catalyst, indicating a clear mesoporous structure and relatively narrow pore size distribution. It is shown in Figure 14 that all isotherms are type IV and the results show that the capillary condensation occurs at high relative pressure (P/P₀ = 0.45−0.85), indicating that the mesoporous structure is clear and the pore size distribution is relatively good.

TABLE 8

Table 8. Comparison of surface properties and catalytic activities of different catalysts in the esterification of levulinic acid (LA) with phenol (Guo et al., 2007).

FIGURE 14

Figure 14. Nitrogen adsorption-desorption isotherms and pore size distribution profiles (inset) of H₃PW₁₂O₄₀/SBA-15 materials. (A) Removal of H₃PW₁₂O₄₀/SBA-15 by extraction with acidic ethanol, and (B) removal of H₃PW₁₂O₄₀/SBA-15 by calcination at 400°C. Reproduced with permission from Guo et al. (2007).

In 2011, silica-supported HPA, a heterogeneous and environmentally benign catalyst was found by Parghi et al. (2011). And it was characterized by many analytical techniques. The effect of catalysts on aldosterone dehydration is shown in Table 9. The results showed that the silica-supported phosphotungstic acid catalyst was the most favorable catalyst for the aldosterone dehydration reaction they studied. The reusability of the catalyst was investigated, and it was found that the catalyst was stable in five consecutive recycles with benzonitrile yield slightly decreasing from 85 to 79%.

TABLE 9

Table 9. Aldosterone dehydration with different catalysts (Parghi et al., 2011).

In 2012, An et al. reported on the conversion of cellulose and cellobiose by polyoxometalate-supported gold nanoparticles (An et al., 2012). The catalysts, Cs_xH_3xPW₁₂O₄₀ supported Au nanoparticles can convert cellulose and cellobiose into gluconic acid that is widely used in the pharmaceutical and food industry. The reaction pathways of cellulose to gluconic acid are shown in Scheme 16. Cellulose was first hydrolyzed to glucose, which was then oxidized to gluconic acid by oxygen. The selectivity of Au/Cs_xH_3xPW₁₂O₄₀ to gluconic acid was significantly higher than that of Au catalysts supported on typical metal oxides, carbon nanotubes, and zeolites (Table 10; An et al., 2012). The possible reasons were the acidity of polyoxometalates and the average particle size of Au nanoparticles. The strong acidity of polyoxometalates not only benefited the conversion of cellobiose but also promoted desorption to improve the selectivity of gluconic acid. And smaller Au nanoparticles expedited the oxidation of glucose to gluconic acid, thus increasing the conversion of cellobiose (Figure 15).

SCHEME 16

Scheme 16. Catalytic conversion of cellulose to gluconic acid with Au/Cs_xH_3xPW₁₂O₄₀.

TABLE 10

Table 10. Transformation of cellobiose with different supported catalysts (An et al., 2012).

FIGURE 15

Figure 15. The effect of Au/Cs_2.2H_0.8PW₁₂O₄₀ catalysts with different average particle sizes of Au on TOFs of glucose oxidation to gluconic acid. Reaction conditions: 24 mmol/L glucose, 25 mL H₂O, 0.5 MPa O₂, 145°C for 3 h. Reproduced with permission from An et al. (2012).

In 2012, Lanzafame et al. reported that some solid acid catalysts can convert cellulose into glucose, HMF, and other soluble by-products in 190°C aqueous solution for 5 h or <5 h (Lanzafame et al., 2012). They mainly studied supported solid acid catalysts, including sulphated zirconia supported over HPAs, which were found to effectively transform cellulose at a reaction temperature of 190°C (Figure 16). It can be seen that all the catalysts were active in the hydrolysis of cellulose to glucose. However, a significant disadvantage is that the conversion of cellulose with a solid acid catalyst produces more by-products, resulting in low glucose selectivity.

FIGURE 16

Figure 16. Activity comparison of different solid acid catalysts for cellulose conversion. Reaction conditions: 2 g cellulose, 0.2 g catalyst, 55 mL distilled water, 190°C for 5 h. Reproduced with permission from Lanzafame et al. (2012).

In 2014, Hafizi et al. found a unique heterogeneous silica-supported Preyssler heteropoly acid catalyst (H₁₄NaP₅W₃₀O₁₂₀), which can be used for alkylation of benzene (Hafizi et al., 2014). Preyssler HPA has the advantages of high thermal stability, high hydrolysis stability, regeneration, safety, easy separation, and so on (Bamoharram et al., 2004; Heravi et al., 2007, 2008). It combines with silica to form a supported heteropoly acid catalyst, which is active for the alkylation of benzene. In 2019, Zhang et al. developed a series of highly efficient heterogeneous catalysts with good stability and reusability for the catalytic conversion of cellulose to glucose. A typical Keggin type HPA (H₃PW₁₂O₄₀) was immobilized on the surface and pore of carbon foam (CF) to prepare supported HPA catalyst (H₃PW₁₂O₄₀/CF) for cellulose conversion to glucose (Zhang et al., 2019). After comparing with different CFs that were prepared from damaged starch and gluten protein (s is the percentage of gluten protein), it was found that CF30 was considered as the best porous support material for fixing the HPW catalyst because of its higher specific surface area (Table 11). In addition, H₃PW₁₂O₄₀/CF30 catalyst had good reusability and was easy to separate and recover from the reaction system (Figure 17). It was shown that the supported catalyst could effectively catalyze the conversion of cellulose to glucose, and the supported technology could improve the catalytic performance and high-efficiency reusability of the catalyst.

TABLE 11

Table 11. Selected properties of different catalysts (Zhang et al., 2019).

FIGURE 17

Figure 17. Reusability test of the HPW/CF30 catalyst for cellulose hydrolysis. Reaction conditions: 0.1 g MAMCC (mechanical activation microcrystalline cellulose), 1.0 g HPW/CF30, 10 mL H₂O, 170°C for 9 h. Reproduced with permission from Zhang et al. (2019).

Based on the studies of these supported HPA catalysts, it can be seen that the supported HPAs have a higher specific surface area than conventional HPAs. Also, the supported HPAs can be used in the heterogeneous reaction, which is more convenient for product separation and can be reused. It is worth noting that there are still some shortcomings of the catalysts, such as low selectivity of the target product and gradual decline of stability of the catalysts in recycles.

Assembled HPAs

In recent years, people began to explore new efficient catalysts for cellulose conversion. The assembled HPA catalysts have also become one of the research directions. It is noteworthy that the assembled HPA catalysts were studied for the degradation of cellulose in biomass and other valuable catalytic reactions. For example, in 2010, Wee et al. proposed a simple and highly repetitive synthesis method for the assembly of nanomaterial catalyst H₃PW₁₂O₄₀/Cu₃(BTC)₂ (BTC = benzene tricarboxylic acid). Cu₃(BTC)₂ was encapsulated into Keggin HPA H₃PW₁₂O₄₀ for application in catalysis (Wee et al., 2010). And this assembled HPA nanomaterial catalyst can be used in acid-catalyzed esterification (Figure 18).

FIGURE 18

Figure 18. Effect of catalysts on conversion of acetic acid in esterification. Catalysts: (A) without catalyst, (B) micron-sized HPW/Cu₃(BTC)₂, (C) ultrastable Y zeolite (CBV 720), (D) 65 nm HPW/Cu₃(BTC)₂, and (E) 50 nm HPW/Cu₃(BTC)_2. Reaction conditions: 1 mol acetic acid, 40 mol 1-propanol, 2.23 wt% catalyst, 60°C. Reproduced with permission from Wee et al. (2010).

In 2011, Cheng et al. reported that a micellar HPA catalyst [C₁₆H₃₃N(CH₃)₃]H₂PW₁₂O₄₀ (C₁₆H₂PW) was designed to hydrolyze cellulose and starch into glucose. The micellar HPA catalyst can allow cellulose molecules to enter into the catalytic sites, so as to improve the reaction rate and cellulose conversion rate (Dwars et al., 2005; Cheng et al., 2011). As a heterogeneous catalyst [C₁₆H₃₃N(CH₃)₃]H₂PW₁₂O₄₀ exhibited remarkable catalytic performance for cellulose degradation, and the yield and selectivity of glucose were 39.3 and 89.1% respectively (Table 12). In addition, the catalyst was easily recovered by centrifuge and had good reusability (Figure 19). Therefore, the heterogeneous micelle HPA catalyst is a clean, economical and environmentally friendly catalyst for hydrolysis of cellulose.

TABLE 12

Table 12. Hydrolysis of cellulose over different catalysts (Cheng et al., 2011).

FIGURE 19

Figure 19. Recycling test of the [C₁₆H₃₃N(CH₃)₃]H₂PW₁₂O₄₀ catalyst. Reaction conditions: 0.1 g cellulose, 0.07 mmol catalyst, 7 mL water, 170°C for 8 h. Reproduced with permission from Cheng et al. (2011).

In 2012, Sun et al. investigated a kind of HPA-ionic liquid catalysts [C₄H₆N₂(CH₂)₃SO₃H]_3−nH_nPW₁₂O₄₀ (n = 1, 2, 3) (abbreviated as [MIMPSH]_nH_32nPW), which can be used to degrade cellulose into water-soluble products such as glucose and levulinic acid (Sun et al., 2012). Glucose was the main product of hydrolysis of cellulose by the HPA-based on the ionic liquid catalyst, and the conversion of cellulose and the yield of glucose was 55.1 and 36.0%, respectively at 140°C for 5 h in a biphasic system (water–MIBK). Compared with the previously reported HPA catalysts, such as H₃PW₁₂O₄₀ and Cs_2.5H_0.5PW₁₁₂O₄₀, the assembled catalyst showed much better catalytic performance because of its better solubility in water (Table 13). Moreover, the HPA-ionic liquids catalyst can also depolymerize other polysaccharides, from which high yields of glucose can be obtained (Scheme 17). More importantly, the HPA-ionic liquids catalyst can be completely recovered and reused six times without significant performance loss (Figure 20).

TABLE 13

Table 13. Hydrolysis of cellulose with different catalysts^a (Sun et al., 2012).

SCHEME 17

Scheme 17. Conversion of other polysaccharides over the [MIMPSH]H₂PW catalyst. Reaction conditions: 0.077 mmol catalyst, 0.5 mL water, and 5.0 mL MIBK.

FIGURE 20

Figure 20. Reusability test of the [MIMPSH]H₂PW catalyst. Reaction conditions: 0.1 g cellulose, 0.07 mmol catalyst, 0.5 mL H₂O, 5 mL MIBK, 140°C for 5 h. Reproduced with permission from Sun et al. (2012).

In 2013, Chen et al. synthesized the polyvinylpyrrolidone-stabilized heteropolyacids (PVP–HPAs), a kind of reusable self-assembling catalysts for conversion of cellulose (Chen et al., 2013). A model for the synthesis of PVP-HPAs is shown in Scheme 18 and the alcoholysis diagram of cellulose is shown in Scheme 19. First, cellobiose alcoholysis, then dehydration between glucose and alcohol molecules, and final interconversion between β-alkylglucoside and α-alkylglucoside gives the product. The authors used a variety of characteristic techniques (e.g., FT-IR and Solid MAS ¹H-NMR) to study the structure of the self-assembling catalysts (Figures 21A,B), and they found that HPAs can protonate PVP and the protonated PVP can form the structure similar to the ionic liquid and interact with heteropolyanion (Chen et al., 2013). Moreover, the structure of PVP assembled with HPA contributes to the easy separation and reuse of catalysts. After optimizing the content of PVP and HPA, the results showed that the self-assembling catalyst PVP–H₄SiW₁₂O₄0.5H₂O (1/5:3/4) had excellent catalytic performance for the alcoholization of cellulose, and the conversion of cellulose was more than 60% (Chen et al., 2013). The application of the self-assembled catalyst is expected to expand to other reactions.

SCHEME 18

Scheme 18. Synthetic routes to PVP-HPAs model.

SCHEME 19

Scheme 19. The conversion pathways and mechanism for the alcoholysis of cellulose.

FIGURE 21

Figure 21. (A) The FT-IR spectra of PVP, HPAs, and PVP–HPAs, and (B) solid MAS ¹H-NMR spectra of PVP–HPW catalysts. Reproduced with permission from Chen et al. (2013).

In 2015, Sun et al. synthesized an assembled HPA catalyst [C₁₆H₃₃N(CH₃)₃]_xH_6−xP₂W₁₈O₆₂ (abbreviated as (C₁₆TA)_nH_6−nP₂W₁₈O₆₂). Wells–Dawson heteropolyacid H₆P₂W₁₈O₆₂ was used to synthesize the micellar assembly catalyst, which can catalyze the hydrolysis of cellulose to glucose (Sun et al., 2015). The mechanism of cellulose conversion by (C₁₆TA)_nH_6−nP₂W₁₈O₆₂ catalysts is shown in Scheme 20. The micelle catalyst first partially hydrolyzes cellulose to the oligomer, and then further degrades cellulose to glucose. Meanwhile, this catalyst can also promote the conversion of other polysaccharides, such as starch and cellobiose (Sun et al., 2015). The (C₁₆TA)H₅P₂W₁₈O₆₂ (n = 1) catalyst exhibited higher catalytic activity than ordinary Keggin heteropoly acid catalyst H₃PW₁₂O₄₀ (Table 14).

SCHEME 20

Scheme 20. The mechanism of cellulose conversion by (C₁₆TA)_nH_6−nP₂W₁₈O₆₂ catalyst.

TABLE 14

Table 14. Conversion of cellulose over different catalysts (Sun et al., 2015).

Sun et al. found that the high catalytic activity of the catalyst was due to the interaction of a high concentration of acid sites, which provided more opportunities for the substrate to enter the catalytic sites and the oxidation ability of (C₁₆TA)_nH_6−nP₂W₁₈O₆₂ (Sun et al., 2015). Moreover, this micellar assembled HPA catalyst was used as a heterogeneous catalyst and recycled by simple centrifuge (Figure 22).

FIGURE 22

Figure 22. The circulation reaction test of the [C₁₆H₃₃N(CH₃)₃]H₅P₂W₁₈O₆₂ catalyst in conversion of cellulose to glucose. Reaction conditions: 100 mg cellulose, 0.08 mmol catalyst, 5 mL H₂O, 160°C for 9 h. Reproduced with permission from Sun et al. (2015).

Lu et al. prepared heterogeneous catalysts (C_nH_2n+1N(CH₃)₃)H₄PW₁₁TiO₄₀ (n = 4, 8, 12, 14, 16, and 18) composed of HPAs and amphiphilic quaternary ammonium salt by self-assembly method (Lu et al., 2015). The results showed that the heterogeneous catalyst (C₁₆H₃₃N(CH₃)₃)H₄PW₁₁TiO₄₀ had the strongest acidity and exhibited excellent activity in the conversion of saccharides to other useful substances, with HMF yield of 53.7 and 50.8% from fructose and glucose, respectively (Figure 23). Meanwhile, the self-assembled structure of (C₁₆H₃₃N(CH₃)₃)H₄PW₁₁TiO₄₀ in water could make cellulose and other polysaccharides gather to the catalytic sites, thus improving the catalytic efficiency. Also, the catalyst can be easily separated from the reactant, and the activity was almost no loss after recycling for many times (Figure 24).

FIGURE 23

Figure 23. The efficiency of different catalysts for fructose transformation. Reaction conditions: 0.6 g fructose, 0.01 mmol catalyst, 2 mL H₂O, 130°C for 1.5 h. Reproduced with permission from Lu et al. (2015).

FIGURE 24

Figure 24. Recycling test of the (C₁₆H₃₃N(CH₃)₃)H₄PW₁₁TiO₄₀ catalyst in the conversion of fructose to HMF. Reaction conditions: 0.6 g fructose, 0.01 mmol catalyst, 2 mL H₂O, 130°C for 1.5 h. Reproduced with permission from Lu et al. (2015).

It can be seen that the assembled HPA catalysts can convert cellulose into glucose or other substances. Their unique structure can make cellulose aggregate to the catalytic sites, thus improving the catalytic efficiency. And almost all of them can be recycled by simple instruments. These advantages make their research more meaningful. However, it can not be ignored that some supported catalysts have low selectivity and yield for glucose, such as (C₁₆TA)H₅P₂W₁₈O₆₂ and [MIMPSH]H₂PW. Moreover, the stability of some HPA catalysts decreased after reuse, which should be improved by the exploration of novel preparation methods.

Other HPA Catalysts

In addition to the HPA catalysts mentioned above, many other HPAcatalysts have also been developed and utilized for cellulose degradation. For example, HPAs can be combined with other catalysts to facilitate cellulose conversion. Palkovits et al. proved that the combination of HPAs and supported Ru catalysts can directly convert cellulose into glycols with a yield of 81% (Palkovits et al., 2011). And the catalyst is very easy to recycle. In 2014, Xie et al. used HPA to synthesize a new catalyst Ru/[Bmim]₃PW₁₂O₄₀, which can selectively convert microcrystalline cellulose to hexanol under mild conditions (Xie et al., 2014). The catalyst was synthesized by supporting Ru on ionic liquid (BmimPF₆)-heteropoly acid (H₃PW₁₂O₄₀·nH₂O), which resulted in the formation of Brønsted acid sites. It improves the performance of the catalyst and is an important reason for the remarkable activity of the catalyst in the conversion of cellulose. Su et al. used HPA and ZrO₂ to synthesize a kind of dual-functional heterogeneous catalyst (H₃PW₁₂O₄₀/ZrO₂-Et-HNS), which was composed of organosilicon hollow nanospheres and can be used in esterification (Su et al., 2014). The unique hollow nanospherical morphology of the catalyst increases its surface acidity and thus improves its catalytic activity. Basahel et al. (2016) synthesized a heterogeneous catalyst Al_xH_3xPW₁₂O₄₀ by ion-exchange method. The HPA catalysts formed by the exchange of hydrogen and aluminum ions showed higher activity because of the increase of Lewis acid sites on the surface of the catalysts. These catalysts proved to be able to synthesize bioactive pyrido[1,2-a]pyrimidines with yields above 90%. In 2017, Wu et al. synthesized a new luryamine-modified

phosphotungstic acid catalyst. They used several characterization instruments to characterize the catalyst and found that the modified heteropoly acid was still the Keggin structure (Wu et al., 2017). As compared with conventional phosphotungstic acid, the luryamine-modified HPA catalyst showed more stable and higher catalytic activity. It's worth mentioning that the yield of glucose reached 100% by hydrolysis of sucrose with the modified catalyst which can provide a way to study cellulose hydrolysis in the future. All the HPA catalysts reported above are heterogeneous. They have a common feature that they are easy to separate from reactants and can be reused with almost no loss of catalytic activity.

Comparison of Different HPA-Based Catalysts

As discussed above, it can be concluded that the Keggin HPA-based catalysts are one of the most common cellulose degradation catalysts. Due to their dual functional properties, the HPA-based catalysts can further promote the oxidation of hydrolysates into valuable compounds. However, their specific surface areas are relatively low, which is not conducive to the catalytic activity. To solve this deficiency, some substituted and supported heteropoly acid catalysts were developed, which are demonstrated to have higher specific surface areas, higher reactivity, and better thermal stability, and are more conducive to the separation because they are commonly used in the heterogeneous systems. It is worth noting that the preparation of these catalysts is complicated and the synthesis cycle is long. In order to further improve the catalytic activity of HPAs, the assembled HPAs and other modified HPA catalysts have been developed. With unique structures, these catalysts exhibit high catalytic performance in cellulose conversion. More importantly, they are all heterogeneous catalysts, providing convenience for the catalyst separation and recycling processes. Therefore, different HPA catalysts have their own characteristics, advantages and disadvantages, and the catalytic upgrading of cellulosic biomass can be effectively enabled with these HPA-based catalysts as long as their properties are properly switched.

Conclusions and Outlook

With the rapid development and utilization of chemical fuels, depolymerization of cellulosic biomass has become one of the ways to provide organic carbon sources. It is reported that cellulose can be converted into a variety of useful platform molecules that can be applied in various fields. In this review, the focus is placed on finding homogeneous and heterogeneous HPA catalysts for cellulose degradation.

HPAs, as a king of efficient, environmentally friendly, and safe catalysts, show high catalytic activity for cellulose degradation. HPA catalysts have higher catalytic activity than conventional solid acid catalysts, which are more conducive to the degradation of cellulose into valuable platform molecules, such as glucose. Meanwhile, due to its unique physical and chemical properties, HPAs can be used in homogeneous and heterogeneous systems. And they can all be reused after separation in the reactor with almost no loss of catalytic activity.

Several methods have been developed to synthesize HPA catalysts. (1) The acidification process coupled with an ether extraction is the most commonly used method, which is mainly used for the synthesis of common HPAs (e.g., H₃PW₁₂O₄₀, H₃SiW₁₂O₄₀), but its safety is low due to the use of some toxic substances. (2) The ion-exchange method has high safety, but it has the disadvantage of a long production cycle. (3) The impregnation method is simple and safe but suffers the disadvantage of the loss of catalyst activity and limited recycling ability. (4) The sol-gel method can prepare HPA catalysts at low temperatures or mild conditions, which is widely used in the synthesis of HPA-based nanomaterial catalysts. However, this method has the disadvantages of low security and long cycle. Therefore, it is very important and urgent to develop more efficient methods for the preparation of HPA-based catalysts.

As depicted in previous studies, typical Keggin-type HPA catalysts are the most common ones for cellulose degradation, and they can further catalyze the oxidation of the hydrolysates to valuable substances due to their dual functional properties. Then, the supported and substituted HPA catalysts always exist in heterogeneous form. After supporting and substituting disposal, the acid site number, the acid strength, and the specific surface area of the HPA catalysts increase, which improves the catalytic properties of the catalysts. In addition, the assembled HPA catalysts and other modified HPA catalysts show good catalytic performance in cellulose conversion because of their unique structure. Therefore, HPA-based catalysts provide convenience for cellulose degradation and more possibilities for the development of chemical fuels in the future. But it cannot be neglected that some of HPAs have the disadvantages of high catalyst dosage and relatively low catalytic activity with respect to the reaction conversion, product selectivity, and catalyst stability. For example, the selectivity of substituted and supported HPAs toward target products is lower than that of Keggin-type HPAs. Also, the stability of the supported HPAs is lower than that of common HPAs.

Although HPAs-based catalysts in either homogeneous or heterogeneous state have made great progress in the degradation of biomass cellulose, there are still many deficiencies to be improved:

(1) Study on the relationship between the properties of HPA catalysts and the degradation of cellulose to further improve the catalytic activity.

(2) Design of a cleaner, safer, and more effective HPA catalyst with simple preparation methods to promote cellulose degradation.

(3) Development of more new HPA catalysts with special structure, and ensure no or fewer side reactions in the reaction process, with the focus on the improvement of the HPA catalyst disadvantages especially unsatisfactory conversion, selectivity, and stability.

(4) Further understanding the structural characteristics of HPAs, study of the reaction mechanism catalyzed by HPAs, and promotional completion of the target reaction by linking the relationship between them.

(5) Extension of HPA catalysts to other biomass feedstocks, providing more help for the future development of fuels and HPAs in the field of catalysis.

In summary, this review mainly summarizes some examples of the degradation of cellulose by some kinds of HPA catalysts. The HPA catalysts are considered to have great application prospects in the degradation of cellulose and the conversion of other relevant research fields.

Author Contributions

XL and HL initiated the project. XL, HW, CL, ZL, HL, HZ, YL, YS, and SY searched the data and wrote, revised, and completed the manuscript. All authors contributed to the article and approved the submitted version.

Funding

The authors thank the financial support from the National Natural Science Foundation of China (21666008, 21908033, and 21576059), Fok Ying-Tong Education Foundation (161030), Guizhou Science & Technology Foundation ([2018]1037), and Program of Introducing Talents of Discipline to Universities of China (111 Program, D20023).

Conflict of Interest

The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

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