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Heterogeneous Bifunctional Catalysts for Catalyzing Conversion of Levulinic Acid to γ-Valerolactone

Yuewen Shao , Qingyang Li , Xinyi Dong , Mengjiao Fan , Lijun Zhang , Xun Hu

Progress in Chemistry ›› 2023, Vol. 35 ›› Issue (4) : 593 -605.

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Progress in Chemistry ›› 2023, Vol. 35 ›› Issue (4) : 593-605 DOI: 10.7536/PC220928
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Heterogeneous Bifunctional Catalysts for Catalyzing Conversion of Levulinic Acid to γ-Valerolactone
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Abstract

Levulinic acid is important biomass-derived compounds, and catalytic conversion of them to γ-valerolactone (GVL) over heterogeneous bifunctional catalysts has become a hot focus in the field of biorefining. In this paper, the direct hydrogenation of levulinic acid and its esters to GVL catalyzed by noble and non-noble metal bifunctional catalysts, and the transfer hydrogenation of levulinic acid and its esters to GVL catalyzed by the bifunctional catalysts, such as metal-supported catalysts, modified zeolite, and mixed metal oxides, are reviewed. Conversion of levulinic acid and its esters to GVL over bifunctional catalysts involves two steps, including hydrogenation of carbonyl group and subsequent lactonization reaction. In addition, the importance of active sites of various bifunctional catalysts in conversion of levulinic acid and its esters is studied in this paper, and the advantages and problems of different catalysts during the conversion of levulinic acid/esters are discussed. Finally, the development of bifunctional catalysts and the synthesis of GVL in the future are prospected.

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levulinic acid / γ-valerolactone / heterogeneous bifunctional catalysts / hydrogenation / lactonization

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Yuewen Shao, Qingyang Li, Xinyi Dong, Mengjiao Fan, Lijun Zhang, Xun Hu. Heterogeneous Bifunctional Catalysts for Catalyzing Conversion of Levulinic Acid to γ-Valerolactone. Progress in Chemistry, 2023, 35(4): 593-605 DOI:10.7536/PC220928

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Contents

1 Introduction
2 Heterogeneous bifunctional catalysts for catalyzing conversion of levulinic acid and its esters toγ-valerolactone
2.1 Direct hydrogenation of levulinic acid and its esters toγ-valerolactone
2.2 Catalytic transfer hydrogenation of levulinic acid and its esters toγ-valerolactone
3 Importance of active sites for hydrogenation of levulinic acid and its esters toγ-valerolactone
4 Conclusion and outlook

1 Introduction

With the shortage of fossil fuels, biomass, as an important renewable resource, can replace fossil resources, and the development and utilization of biomass resources have attracted great attention. Lignocellulosic biomass is the most abundant biomass resource, which mainly contains cellulose, hemicellulose and lignin, as shown in Figure 1[1]. Cellulose is a polymer mainly composed of D-glucose linked by β-1,4 glycosidic bonds. Hemicellulose is an amorphous polymer molecule composed of a variety of monosaccharides as monomers, and xylose is the main component. Lignin is an aromatic polymer composed of different structural units containing phenylpropanols connected by C — O — C and C — C bonds. Lignocellulosic biomass and its derivatives can be further converted for the production of fuel additives as well as high value-added compounds[2,3].
Levulinic acid is an important biomass-based platform compound, which is mainly produced from cellulose and hemicellulose[4,5]. As shown in fig. 1, under the action of a Bronsted acid catalyst, cellulose is hydrolyzed to obtain hexose glucose, a Lewis acid catalyzes the isomerization of glucose to obtain fructose, the Bronsted acid catalyzes the dehydration of fructose to produce 5-hydroxymethylfurfural, and the Bronsted acid subsequently catalyzes the hydrolysis of 5-hydroxymethylfurfural to produce levulinic acid or alcoholysis to obtain levulinate[6⇓~8]. In addition, hemicellulose is hydrolyzed under the action of Bronsted acid to generate pentose xylose, the Bronsted acid further catalyzes the dehydration of the xylose to generate furfural, the furfural is hydrogenated to obtain furfuryl alcohol, and the Bronsted acid catalyzes the hydrolysis of the furfuryl alcohol to generate levulinic acid or alcoholysis to obtain levulinate[9]. Levulinic acid and its esters can be further upgraded into value-added chemicals such as γ-valerolactone (GVL), 1,4-pentanediol, 2-methyltetrahydrofuran, and valeric acid and its esters[10][11][12][13]. Among them, GVL can be used as a fuel, a fuel additive, and a green solvent[14,15]. Therefore, it is of great research significance to use biomass-derived levulinic acid and its esters to prepare GVL.
The conversion pathway of levulinic acid and its ester to produce GVL is shown in Figure 1: (1) First, the carbonyl group in levulinic acid and its ester is hydrogenated to produce 4-hydroxypentanoic acid or 4-hydroxypentanoic acid ester, and these intermediates are subsequently lactonized to produce GVL[13]. (2) that levulinic acid is dehydrate under the action of an acid catalyst to generate angelica lactone, and then the angelica lactone is further hydrogenate to obtain GVL[13]. In order to realize the hydrogenation conversion of levulinic acid and its esters to produce GVL, a series of hydrogenation catalysis and acid catalysis reactions are needed[15]. Bifunctional catalysts as well as catalytic systems were developed for the hydroconversion of levulinic acid and its esters to obtain GVL in higher yields. A number of noble metal or non-noble metal supported bifunctional catalysts have been reported, which contain metal species for hydrogen activation and acid sites for dehydration reaction to achieve lactonization, and the synergistic catalysis of metal species and acid sites realizes the hydrogenation of levulinic acid to produce GVL[16,17]. In addition, bifunctional catalysts containing Bronsted acid and Lewis acid sites have been reported for the transfer hydrogenation of levulinic acid to GVL, thus avoiding the use of external hydrogen and using hydrogen donors such as alcohols and formic acid instead of hydrogen as hydrogen sources[18,19][20,21].
In this paper, the research progress of different types of heterogeneous bifunctional catalysts in the catalytic conversion of levulinic acid and its esters to GVL was reviewed, and the reaction pathway of GVL was given.The correlation between active sites and reaction paths in different bifunctional catalysts was summarized, and the design and future research of bifunctional catalysts were prospected, which provided a favorable theoretical basis for the development of efficient heterogeneous bifunctional catalysts and the design of green and feasible GVL synthesis strategies.

2 Catalytic conversion of levulinic acid and its ester to γ-valerolactone over heterogeneous bifunctional catalyst

2.1 Preparation of γ-valerolactone by direct hydrogenation of levulinic acid and its ester

Levulinic acid and its esters can be used to prepare GVL by direct hydrogenation. Under the action of the hydrogenation site, hydrogen is activated to generate active hydrogen species, and the carbonyl in the levulinic acid and the ester thereof is further hydrogenated to obtain the 4-hydroxypentanoic acid and the ester thereof[22]. Acidic sites include Bronsted and Lewis acid sites, which further promote the lactonization of 4-hydroxypentanoic acid and its esters to GVL (fig. 2)[22]. In addition, under the action of the acid site, levulinic acid is dehydrated to obtain α or β-angelicolactone (path 2 in fig. 2), and this intermediate is further hydrogenated to obtain GVL under the action of the hydrogenation site[23]. In general, the reported literature focuses on the hydrogenation of levulinic acid and its esters to 4-hydroxypentanoic acid and its esters, followed by lactonization of the intermediate to give GVL as the final product (paths 1 and 3 in fig. 2). Metal-supported acidic supports have been synthesized as bifunctional catalysts for the hydroconversion of levulinic acid, which contain a metal hydrogenation site and an acidic site. Among them, metal hydrogenation sites can be divided into noble metal and non-noble metal. Noble metals include Ru, Pd, Pt, etc., and non-noble metals include Ni, Co, Cu, etc. These catalysts show excellent activity in the preparation of GVL by direct hydrogenation of levulinic acid and its esters[22⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓~36][36⇓⇓⇓~40][36,41][42⇓⇓⇓⇓⇓⇓⇓⇓⇓~52][53⇓⇓⇓~57][58⇓~60].

2.1.1 Precious metal catalyst

Noble metal heterogeneous bifunctional catalysts such as Ru, Pd and Pt were reported for the hydrogenation of levulinic acid. Among them, Ru-based bifunctional catalysts have been studied more, as described in Table 1. The development of Ru-based bifunctional catalysts mainly focuses on the selection and design of supports. Different catalyst supports, such as carbon materials, resins, molecular sieves, metal oxides, metal organic frameworks, etc., have been studied for the synthesis of heterogeneous bifunctional catalysts supported on noble metals[22⇓⇓⇓~26][27][28,29][30⇓⇓~33][34].
The preparation of heterogeneous bifunctional catalysts from ruthenium supported carbon materials has attracted great attention. Ruthenium supported reduced sulfonated graphene oxide (Ru/rGO-S) as well as ruthenium supported reduced graphene oxide (Ru/rGO) were synthesized for levulinic acid hydrogenation in aqueous phase (Table 1, Entry 1 and 2)[22]. Using water as solvent, Ru/rGO-S catalyst catalyzed the hydrogenation of levulinic acid to 4-hydroxypentanoic acid intermediate under mild reaction conditions of 50 ℃ and 2 MPa, and the intermediate was further dehydrated under the action of sulfonic acid strong acid sites to obtain GVL with a target product yield of 82.0% (Table 1, Entry 2). Meanwhile, the Ru/rGO-S catalyst exhibits a TOF value of 522 h-1, which is higher than that of ruthenium supported catalysts reported in other studies. However, the catalyst showed a loss of activity in the cycle stability test, and the sulfonic acid function may reversibly poison the ruthenium species and reduce the hydrogenation activity of the ruthenium species. Ru/C combined with cation exchange resins (A70 and A15), niobium phosphate and oxide to form a bifunctional catalytic system[23]. When Ru/C and A70 coexist, the GVL yield was 98.0% at 70 ° C and 0.5 MPa with water as the solvent (Table 1, Entry 3). The coexistence of the hydrogenation site and the acid site not only accelerates the hydrogenation of the carbonyl group in levulinic acid to 4-hydroxypentanoic acid, but also promotes the lactonization reaction to obtain GVL. In addition, ordered mesoporous carbon is prepared, and the carbon material is used as a carrier for loading Ru through functionalization of acidic groups such as P and S[24]. The functional group contained in S leads to the inactivation of Ru species, and the Ru/OMC-P catalyst modified by phosphate group catalyzes levulinic acid with a GVL yield of 92.1% (Table 1, Entry 4). The acid site introduced by the phosphate group promotes the lactonization of the intermediate 4-hydroxypentanoic acid to produce GVL, and Ru/OMC-P can further catalyze the ring opening of GVL to produce valeric acid at 200 ℃. Ru/OMC-P exhibits excellent cycling stability. In addition, N-doped carbon materials have also been used as supports to support Ru for the preparation of hydrogenation catalysts. The N species in the carbon materials further increase the electron density of Ru, and the electron-rich Ru species realize the highly selective hydrogenation of levulinic acid to GVL[23,24]. The N-doped porous carbon was modified by HfO2, and the obtained support was loaded with Ru nanoclusters to prepare Ru/HfO2@CN,Ru clusters, which cooperated with the generated acidic sites to catalyze the hydrogenation of levulinic acid to prepare GVL with a yield of 92.0% (Table 1, Entry 5)[25]. Ru supported on single carbon materials and heteroatom doped carbon materials resulted in highly active ruthenium bifunctional catalysts (Table 1, Entry 6 and 7). Ru particles promoted the hydrogenation reaction, and the acid sites promoted the lactonization of 4-hydroxypentanoic acid and accelerated the hydrogenation reaction. In addition, sulfonated cation exchange resins were reported to be used as acidic supports, which were further impregnated with Ru to prepare bifunctional heterogeneous catalysts[27]. GVL was prepared by LA hydrogenation catalyzed by Ru @ DOWEX at 70 ° C with 98.0% yield (Table 1, Entry 7). In addition to carbon-based materials and resinous supports, molecular sieves have been considered as common acidic supports for the preparation of noble metal bifunctional catalysts.
Ruthenium-supported ordered mesoporous MCM-49 molecular sieve catalyst was prepared by deposition-precipitation method, and was used for the hydrogenation of levulinic acid to GVL[28]. Ru/MCM-49 catalyst was used to catalyze the hydrogenation of levulinic acid to 4-hydroxypentanoic acid, and then 4-hydroxypentanoic acid was further converted to GVL under the action of acid sites in MCM-49 molecular sieve. Among them, the Lewis acid site promotes the lactonization of 4-hydroxypentanoic acid. GVL yield reached 93.4% at 160 ° C, 2.5 MPa, and 0.5 H (Table 1, Entry 8). In addition, the Mn-modified bimetallic Ru-Mn/MCM-49 catalyst was further prepared to promote the activation of hydrogen by adding Mn to increase the electron density of Ru[29]. The introduction of Mn further increased the ratio of Lewis acid to Bronsted acid, resulting in a GVL yield of 98.0% at a reaction temperature of 160 ° C (Table 1, Entry 9). The bifunctional catalyst prepared by loading Ru on the mesoporous molecular sieve as a catalyst carrier can significantly improve the hydrogenation activity of the catalyst for levulinic acid and obtain GVL with higher yield.
In addition, other mesoporous oxide supports were further reported to support Ru to prepare bifunctional catalysts for the hydrogenation of levulinic acid to GVL. Ruthenium confined spherical mesoporous silica or zirconium modified spherical mesoporous silica catalysts (Ru/ZrSMS and Ru/SMS) were synthesized for the hydrogenation of levulinic acid and its esters (Table 1, Entry 10 and 11). Ultra-small Ru nanoparticles promoted the hydrogenation of levulinic acid to 4-hydroxypentanoic acid.The acid sites provided by Zr promote the dehydration lactonization of the intermediate to produce GVL. Under the reaction conditions of 70 ℃, 0.5 MPa hydrogen and 3 H, the Ru/ZrSMS catalyst achieves 94.5% GVL yield (Table 1, Entry 10)[30]. The addition of acidic molecular sieve catalyst (H-Y30,H-beta25 as well as H-ZSM-530) further promoted the production of GVL, and the acidic sites accelerated the dehydration lactonization reaction. Among them, benzene sulfonic acid and heteropolyacid can poison Ru particles, thus reducing the catalytic activity. The type and number of acid sites can affect the activity of metal active sites and the reaction rate of lactonization. Other mesoporous oxides such as (AlO) (ZrO) 0.1, SBA-15, and TiO2 were further used as acidic supports to support ruthenium to prepare Ru-based bifunctional catalysts (Table 1, Entry 12 ~ 14). The cooperation of Ru nanoparticles and acidic sites promoted the hydrogenation of levulinic acid to produce 4-hydroxypentanoic acid under the action of ruthenium species, and then the lactonization of 4-hydroxypentanoic acid under the action of acidic sites produced higher yield of GVL[31][32][33].
In addition, other types of supports, such as other metal-organic frameworks (Ru/MIL-101-Cr), cross-linked sulfonated polyethersulfone (Ru/SPES), and hydroxyapatite (Ru/HAP), have been reported to prepare ruthenium-based bifunctional catalysts (Table 1, Entry 15-17), which efficiently catalyze the hydrogenation of levulinic acid to GVL at 70 ° C in aqueous phase[34][35][36]. Other bifunctional catalysts supported on noble metals such as Pd and Pt have also been reported (Table 1, Entry 18 ~ 20). Ru-based bifunctional catalysts show better catalytic activity than other noble metals. Metal species and acidic sites cooperate to catalyze the hydrogenation and dehydration of levulinic acid, resulting in higher yields of GVL[36⇓⇓⇓~40][36,41].

2.1.2 Non-noble metal catalyst

Non-noble metals were further studied to replace noble metals for the preparation of non-noble bifunctional catalysts for the hydrogenation of levulinic acid and its esters to produce GVL. Monometallic nickel-based, cobalt-based, copper-based, as well as mixed bimetallic bifunctional catalysts were reported for the conversion of levulinic acid and its esters, as described in Table 2[42⇓⇓⇓⇓⇓⇓⇓⇓⇓~52][53⇓⇓⇓~57][58⇓~60][60⇓⇓⇓~64]. Carbon materials, molecular sieves and oxides are commonly used as catalyst supports to impregnate non-precious metals to prepare bifunctional catalysts[42⇓⇓~45][46][47⇓⇓~50].
Nickel-based bifunctional catalysts have been widely studied for the hydrogenation of levulinic acid and its esters to produce GVL. Ni/HZSM-5 bifunctional catalyst was prepared for gas phase hydrogenation of levulinic acid using nickel particles supported on molecular sieve as acidic carrier[46]. The introduction of nickel species promotes the formation of acidic sites, especially Lewis acid sites. Under the reaction condition of 320 ℃, the nickel particles promoted the hydrogenation of carbonyl group in levulinic acid to 4-hydroxypentanoic acid, the Lewis acid sites promoted the anhydrolactonization of 4-hydroxypentanoic acid to GVL (98.6%, Table 2, Entry 5), the Bronsted acid sites in nickel aluminate had synergistic effect with the metal hydrogenation sites in the catalyst, and the Bronsted acid sites stabilized the metal species[46]. Nickel-based bifunctional catalysts can promote the hydrogenation of levulinic acid and its esters to produce GVL at higher reaction temperatures, and the synergistic catalysis of Lewis acid and Bronsted acid sites with nickel species achieves high GVL yields. In addition, other nickel-based bifunctional catalysts were synthesized for the liquid-phase hydrogenation of levulinic acid, and the catalysts showed excellent catalytic activity by selecting organic solvents such as dioxane and isopropanol as reaction media (Table 2, Entry 1 ~ 11). Nickel species can improve the stability of GVL and avoid further ring opening of GVL to produce downstream products, so it is widely used as a non-precious metal active species[50].
Cobalt-based and copper-based bifunctional catalysts have been further studied compared to nickel-based catalysts. Co-supported N-doped carbon material (Co @ NC-700) catalyzed the hydrogenation of levulinic acid in 1,4-dioxane to prepare GVL, and the synergistic effect of metallic cobalt and acidic sites achieved a GVL yield of 100.0% (Table 2, Entry 12). Cobalt supported Y zeolite catalyst was synthesized for the hydrogenation of levulinic acid to produce GVL. Lewis acid sites are beneficial to improve the selectivity of GVL, and Bronsted acid sites can further promote the ring-opening reaction of GVL at higher temperature to produce valeric acid and other products[54]. The Co/Y catalyst was used to catalyze the hydrogenation of levulinic acid to give GVL (80.0%, Table 2, Entry 13) in a fixed bed reactor at 200 ℃. Other inorganic metal oxides such as silica and alumina were used as supports to support cobalt species to prepare heterogeneous bifunctional cobalt-based catalysts (Table 2, Entry 14-17). Co-Al and 2.1 Co-0.9 Mg-Al catalysts with adjustable hydrogenation sites and acid-base sites were used for the hydroconversion of ethyl levulinate in aqueous phase, and the two catalysts achieved 98.0% and 97.0% GVL yields, respectively, at 150 ° C (Table 2, Entry 16 and 17)[57]. The hydrogenation of ethyl levulinate to ethyl 4-hydroxypentanoate is promoted by the synergistic catalysis of the hydrogenation site and the acid site, the lactonization of ethyl 4-hydroxypentanoate is promoted by the Bronsted acid site, and the Lewis acid site can improve the adsorption of the catalyst to the reaction substrate and the intermediate, so that GVL with high yield is obtained. At the same time, the acidic site cooperates with the cobalt active site to further promote the ring opening of GVL in isopropanol to produce 1,4-pentanediol. Therefore, the distribution of acid sites and cobalt particles in cobalt-based bifunctional catalysts needs to be precisely regulated to obtain GVL as the target product.
In addition, copper supported on oxide supports was used as a bifunctional catalyst to catalyze the conversion of levulinic acid and its esters to produce GVL. The Cu/Zr-Al-3 catalyst was synthesized for the conversion of levulinic acid to produce GVL,Cu0 promoted the dissociation of hydrogen to produce active hydrogen species, which further attacked the carbonyl group to give 4-hydroxypentanoic acid, and the acidic site further promoted the dehydration lactonization of the intermediate to give GVL (100.0%, Table 2, Entry 18)[58]. The presence of oxygen deficiency in the Cu/Zr-Al-3 catalyst also promotes the adsorption of levulinic acid as well as intermediates[57]. The layered double hydroxide-derived CuAl catalyst catalytically converted the hydrogenation of levulinic acid at 110 ° C under reaction conditions to give a GVL yield of 95.3% (Table 2, Entry 19), with copper as the active species to produce active hydrogen species by activating hydrogen,This further enables the hydrogenation of the carbonyl group in levulinic acid to give 4-hydroxypentanoic acid, and the Bronsted acid site promotes the lactonization of 4-hydroxypentanoic acid to produce GVL and stabilize GVL, resulting in a higher GVL yield[59]. At the same time, the basic sites generated by magnesium species in the catalyst can further neutralize the acidic sites, improve the stability of copper species, and promote the further ring opening of GVL to obtain 1,4-pentanediol. The copper-based bifunctional catalyst shows high hydrogenation activity and catalyzes the hydrogenation of levulinic acid and its esters to produce GVL (Table 2, Entry 18-20), but the produced GVL can be further converted into compounds such as 1,4-pentanediol or 2-methyltetrahydrofuran through ring opening, thereby reducing the overall yield of GVL[60].
In order to further develop non-noble metal bifunctional catalysts with high activity and stability, the second metal was further introduced to prepare bimetallic bifunctional catalysts. Catalysts such as Ni/Cu/Al/Fe,Ni4.59Cu1Mg1.58Al1.96Fe0.70,Ni2Co1P,Cu-Ni/Al2O3-ZrO2 and Cu-Ni/Al2O3 have been reported (Table 2, Entry 21 – 25). The bimetallic active sites promote the adsorption of levulinic acid and activation hydrogenation to 4-hydroxypentanoic acid. The acidic sites on the catalyst further promote the dehydration reaction to realize the lactonization of the intermediate to produce GVL[61][62][63][64][65]. Compared with the single metal bifunctional catalyst, the binary metal bifunctional catalyst also showed excellent hydrogenation activity of levulinic acid and its esters, and the bimetallic active sites could further promote the adsorption and activation of hydrogen and accelerate the hydrogenation reaction rate.
In the non-noble metal bifunctional catalyst, the non-noble metal active species and the acid site can promote the hydrogenation of levulinic acid and its ester on the metal site and the lactonization of the intermediate on the acid site to obtain a high yield of GVL. Non-noble metal catalysts catalyze the hydrogenation of levulinic acid and its esters to produce GVL in gas phase or liquid phase, but compared with noble metal bifunctional catalysts, non-noble metal bifunctional catalysts have more stringent reaction conditions, requiring higher reaction temperature and hydrogen pressure. At the same time, due to the low stability of non-noble metal bifunctional catalysts in water phase, the reaction solvents are mainly concentrated in organic solvents such as dioxane and alcohols[42⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓~65]. In order to realize the preparation of GVL from levulinic acid and its esters under greener reaction conditions, non-noble metal bifunctional catalysts with high hydrothermal stability need to be further developed. At the same time, bifunctional catalysts were further studied to catalyze levulinic acid transfer hydrogenation to prepare GVL, avoiding the use of external hydrogen, and replacing high-pressure hydrogen in existing studies by using suitable hydrogen donors.

2.2 Catalytic transfer hydrogenation of levulinic acid and its ester to γ-valerolactone

Compared with the traditional catalytic reaction system with the addition of high-pressure hydrogen, the use of alcohols and other hydrogen sources to replace the addition of hydrogen for the catalytic transfer hydrogenation of levulinic acid and its esters has attracted great attention[66⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓~78]. In the process of catalytic transfer hydrogenation of levulinic acid, the properties of the catalyst, such as acidity and basicity, and metal site-acidity and basicity, affect the catalytic transfer hydrogenation ability of the catalyst[74,75]. Different bifunctional catalysts have been reported for the catalytic transfer hydrogenation of levulinic acid and its esters. In order to realize the catalytic transfer hydrogenation of levulinic acid and its esters to produce GVL, it is necessary for the active site to promote the hydrogen transfer from the hydrogen donor to levulinic acid, and then the hydrogenation of levulinate to 4-hydroxypentanoic acid. Second, the active site is also required to catalyze the anhydrolactonization of 4-hydroxypentanoic acid to give GVL, as shown in Fig. 3[77⇓~79]. Therefore, the developed bifunctional catalyst requires the active sites of C — H and O — H bonds in the activated hydrogen donor and the second active site to catalyze the dehydration reaction to achieve lactonization.

2.2.1 Metal supported catalyst

Noble metal or non-noble metal supported acid supports were used to prepare bifunctional catalysts as described in Table 3. Metal species, such as Ru, Ni, and Cu, catalyze hydrogen transfer from hydrogen donors (Table 3, Entry 1-8), and acidic sites in acidic supports promote dehydration reactions to achieve lactonization[66,68⇓~70].
The CuNi-0.4Al/AC bifunctional catalyst was prepared for the catalytic transfer hydrogenation of levulinic acid, and the GVL yield was 97.2% at 220 ° C for 2 H (Table 3, Entry 4)[69]. The CuNi alloy is used as a hydrogenation site to activate isopropanol to generate active hydrogen species, thereby realizing the hydrogenation of carbonyl in levulinic acid to obtain 4-hydroxypentanoic acid, and the subsequent acid site promotes the lactonization reaction of 4-hydroxypentanoic acid to generate GVL. Ni3P-CePO4 catalyst was synthesized for catalytic transfer hydrogenation of levulinic acid to produce GVL, and the distribution of acidic sites and basic sites in the catalyst was controlled by changing the Ce/Ni ratio[70]. Under the reaction conditions of 180 ° C and 2 H, the Ni3P-CePO4(0.1) catalyst achieved 99.9% levulinic acid conversion and 89.9% GVL yield (Table 3, Entry 5). The Lewis acid site activates the carbonyl group in levulinic acid, the Lewis base site catalyzes the dissociation of the hydroxyl group in isopropanol to give an active hydrogen species, isopropanol is converted to acetone, the unsaturated carbonyl group interacts with the metal site and reacts with the adjacent active hydrogen to give 4-hydroxypentanoic acid, and the subsequent acid site further promotes the anhydrolactonization reaction to produce GVL[70]. In the catalytic transfer hydrogenation process of the metal-supported bifunctional catalyst, the metal site or the Lewis base site can promote the hydrogen donation of the hydrogen donor, the active hydrogen species realize the hydrogenation of levulinic acid to obtain 4-hydroxypentanoic acid, and the subsequent acidic site promotes the further lactonization of the intermediate to obtain GVL (fig. 3).

2.2.2 Modified molecular sieve catalyst

Acid site as well as basic site tunable bifunctional catalysts were prepared by metal heteroatom modified molecular sieves (Table 3, Entry 9 and 10). Zr-beta was synthesized for Meerwein-Ponndorf-Verley (MPV) reduction of levulinic acid to prepare GVL. Under the reaction conditions of 118 ℃ and 10 H, the conversion of levulinic acid in isopropanol solvent reached 100.0%, and the yield of GVL reached 96.0% (Table 3, Entry 9)[74]. A Lewis acid site and a basic site in Zr-beta promote MPV reduction reaction of an unsaturated carbonyl group in levulinic acid to generate 4-hydroxypentanoic acid,The subsequent weak acid sites promote the anhydrolactonization of 4-hydroxypentanoic acid to produce GVL, and too many Bronsted acid sites can promote the esterification of levulinic acid with isopropanol, or promote the occurrence of other side reactions, affecting the yield of GVL. There are abundant acid sites in the modified molecular sieve catalyst, among which Lewis acid sites can replace the traditional metal sites to promote the MPV reduction reaction to realize the hydrogenation of unsaturated carbonyl groups in levulinic acid and its esters, and basic sites can promote the MPV reduction together with Lewis acid sites[75]. In addition, 4-hydroxypentanoic acid acts as an intermediate to produce GVL by lactonization at the Bronsted acid site.

2.2.3 Mixed metal oxide catalyst

Different mixed metal oxide bifunctional catalysts have been reported, such as SnO2/SBA-15, GluPC-Zr, ZrO2(10)/SBA-15, ZrFeO (1:3) -300, ZrO3, Zr1Fe1-150, and Mn2CoOx (Table 3, Entry 11 – 17). By regulating the types of oxides, the distribution of acidic sites and basic sites in the catalyst can be changed, and then the MPV reduction of levulinic acid and its esters and the subsequent lactonization of 4-hydroxypentanoic acid can be regulated[76][77][78][79][80][81][82]. The SnO2/SBA-15 was prepared to prepare GVL by catalytic transfer hydrogenation of levulinic acid with isopropanol as solvent at 110 ℃ for 8 H, the conversion of LA was 85. 0%, and the yield of GVL was 80. 8% (Table) The Lewis acid sites in the 3,Entry 11),SnO2/SBA-15 promoted the MPV reduction reaction to realize the hydrogenation of levulinic acid to obtain 4-hydroxypentanoic acid, and the Bronsted acid sites promoted the subsequent dehydration lactonization reaction of 4-hydroxypentanoic acid to obtain GVL[76]. In addition, the FeZrOx catalyst was synthesized to prepare GVL by catalytic transfer hydrogenation of ethyl levulinate, and the conversion of ethyl levulinate was 100.0% and the yield of GVL was 87.2% at 230 ℃ for 3 H with ethanol as solvent (Table 3, Entry 14)[79]. The FeZrOx catalyst has abundant acid sites and basic sites, and the basic sites and Lewis acid sites promote the hydrogen donation of the alcohol, so that the hydrogenation of levulinic acid and levulinic acid ester is realized through MPV reduction reaction to obtain an intermediate, and the acid sites further catalyze the lactonization of the intermediate to obtain GVL. The acidic site and the basic site in the Zr1Fe1-150 catalyst cooperate to catalyze levulinic acid to prepare GVL, and the product yield is 96.7% at 200 ℃ for 1 H (Table 3, Entry 16)[81]. In addition to alcohols, formic acid was used as a hydrogen donor, and a GVL yield of 77.0% was obtained 1 h,Mn2CoOx catalyst at 230 ° C (Table 3, Entry 17)[82]. Therefore, a bifunctional catalyst composed of mixed acidic and basic oxides is used, the basic sites in the catalyst and a Lewis acid promote catalytic transfer hydrogenation, and other Bronsted acid or weak acid sites promote the lactonization reaction of 4-hydroxypentanoic acid and esters thereof, so that different sites cooperate to catalyze the hydrogenation of levulinic acid and esters thereof to prepare GVL. In the process of hydrogen transfer hydrogenation, alcohols, especially isopropanol, are more used as solvents than hydrogen donors such as formic acid to realize the transfer hydrogenation of levulinic acid and its esters to produce GVL.

2.2.4 Other catalyst

In addition, bifunctional catalysts such as metal cation-modified MOF catalysts (ZrF MOFs), cation-modified corrosion acid catalysts (Zr-humic acids), MOF-derived bifunctional catalysts (UiO-66-S60), and heteropolyacid and metal-modified MOF composite catalysts (HPW @ MOF-808) have been further studied (Table 3, Entry 18 – 21)[83][84][85][86]. The bifunctional catalyst is obtained by compounding different acidic materials and modifying an acidic carrier with metal, and has adjustable Lewis acid, Bronsted acid and basic sites. The bifunctional catalyst realizes the hydrogen donation of a hydrogen donor by means of a Lewis acid and a basic site to promote the MPV reduction reaction, promotes the transfer hydrogenation of levulinic acid and esters thereof to obtain intermediates such as 4-hydroxypentanoic acid or amyl ester, and the subsequent Bronsted acid site promotes the lactonization reaction of the intermediates to obtain GVL[84].
Compared with the direct hydrogenation of levulinic acid and its esters to prepare GVL, the catalytic transfer hydrogenation reaction avoids the use of high-pressure hydrogen, and uses hydrogen donors such as alcohols and formic acid to replace high-pressure hydrogen, which is simpler, more feasible and more sustainable. Isopropanol is used more as a hydrogen source than other hydrogen donors, as the hydroxyl groups on the branched chain in isopropanol are more likely to break down to produce active hydrogen species[87,88]. In addition, formic acid is used as a hydrogen source and a solvent, and since formic acid is acidic and can corrode a reaction apparatus, it is more preferable to use an alcohol as a hydrogen source[89]. The reaction rate of catalytic transfer hydrogenation is slower than that of direct hydrogenation, just as the adsorption activation of hydrogenation sites for hydrogen is easier than the hydrogen donation of hydrogen donors. Subsequently, transfer hydrogenation catalysts with higher activity and stability need to be further developed.

3 Importance of Active Sites for Hydrogenation of Levulinic Acid and Its Esters to γ-Valerolactone

Different heterogeneous bifunctional catalysts have been studied for direct hydrogenation and catalytic transfer hydrogenation of levulinic acid and its esters to produce GVL. A large number of studies have focused on noble metal and non-noble metal bifunctional catalysts for the direct hydrogenation of levulinic acid and its esters. These bifunctional catalysts have noble metal or non-noble metal active sites to activate the added hydrogen to active hydrogen species (Figure 4A).The active hydrogen species further attacks the activated unsaturated carbonyl group to realize hydrogenation of levulinic acid and ester thereof to obtain 4-hydroxypentanoic acid and ester thereof, and then further catalyzes the intermediate to realize lactonization under the action of an acidic site to obtain GVL[20]. At the same time, under the action of higher temperature and abundant acidic sites, the acidic sites catalyze the dehydration of levulinic acid to obtain angelica lactone, which is further hydrogenated to obtain GVL (Figure 4A, path 2)[53].
In addition, the development of more green and feasible heterogeneous bifunctional catalysts and the avoidance of the use of added hydrogen have received great attention, and more research has begun to focus on the development of bifunctional catalysts for the catalytic transfer hydrogenation of levulinic acid and its esters to produce GVL. The green and sustainable hydrogenation conversion of levulinic acid and its esters is realized by using hydrogen donors such as alcohols and formic acid to replace the traditional external hydrogen. A series of bifunctional catalysts for hydrogen transfer hydrogenation have been developed, such as metal-supported bifunctional catalysts, modified molecular sieve bifunctional catalysts, mixed metal oxide bifunctional catalyst, and other composite bifunctional catalyst[65,66][69][71][75,76]. These catalysts use the metal site to activate the hydroxyl group and C-H group in the hydrogen donor to obtain the activated hydrogen species, and then realize the transfer hydrogenation of levulinic acid to 4-hydroxypentanoic acid, followed by the lactonization of the acidic site catalytic intermediate to produce GVL (Fig. 4B). In addition, the Lewis acid and the basic site can also promote the MPV reduction reaction to realize the transfer hydrogenation of the unsaturated carbonyl group in the levulinic acid in the hydrogen donor to obtain 4-hydroxypentanoic acid, and then the intermediate is lactonized under the action of the acidic site to obtain GVL[69]. Levulinic acid to GVL involves (1) esterification of levulinic acid to obtain levulinic acid esters, further transfer hydrogenation of levalinic acid and its esters to 4-hydroxypentanoic acid and its esters, and subsequent dehydration and esterification of the intermediate to produce GVL; (2) dehydration of levalinic acid to obtain angelica lactone, and subsequent further hydrogenation of angelica lactone to produce GVL. Among them, in many studies, the main reaction pathway focuses on the hydrogenation of levulinic acid to 4-hydroxypentanoic acid, followed by the dehydration of intermediate lactonization under the action of acidic sites to form GVL. The route of direct dehydration of levulinic acid to angelicolactone has been less reported. Therefore, the design of heterogeneous bifunctional catalysts, which contain both hydrogenation and acid catalytic activity, can efficiently catalyze the continuous conversion of levulinic acid and its esters to GVL.

4 Conclusion and prospect

The preparation of GVL from biomass-derived levulinic acid and its esters is a hot topic in the field of biorefining, and heterogeneous bifunctional catalysts play an important role in this reaction process. The existing research results show that the bifunctional catalysts catalyze levulinic acid and its esters to prepare GVL, including (1) direct hydrogenation of levulinic acid and its esters catalyzed by noble metal and non-noble metal bifunctional catalysts to prepare GVL; (2) transesterification hydrogenation of levulinate and its esters catalyzed by different types of bifunctional catalysts. A bifunctional catalyst is designed, which contains a hydrogenation site and an acid site, and can catalyze the hydrogenation reaction of the carbonyl group in levulinic acid and the ester thereof and the lactonization reaction of 4-hydroxypentanoic acid and the ester thereof respectively, and finally obtain GVL with high yield. At present, there are still some problems in the hydrogenation of levulinic acid and its esters over heterogeneous bifunctional catalysts, such as high separation cost, harsh reaction conditions, and the development of heterogeneous bifunctional catalysts with higher activity and hydrothermal stability. In view of the current research status, in the future, the preparation of GVL from levulinic acid and its esters catalyzed by bifunctional catalysts can be carried out from the following aspects.
(1) The activation energy of different paths in the hydrogenation of levulinic acid and its esters was studied by kinetic analysis. The preparation of GVL by hydrogenation conversion of levulinic acid and its ester involves the hydrogenation of carbonyl in levulinic acid and its ester and the lactonization of intermediate 4-hydroxypentanoic acid or 4-hydroxypentanoic acid ester. Different catalysts show different activities for the hydrogenation of carbonyl and the lactonization of intermediate. It is necessary to analyze the activation energy of catalysts for different reaction paths by means of reaction kinetics to understand the rate-determining step in the hydrogenation of levulinic acid and its esters, so as to establish the correlation between catalyst active sites and reaction paths.
(2) To clarify the catalytic reaction mechanism of bifunctional catalysts in the conversion of levulinic acid and its esters. Metal sites, acidic sites and basic sites have been reported to play a synergistic catalytic role in the hydrogenation of levulinic acid and its esters to produce GVL by bifunctional catalysts. In the direct hydrogenation process, the metal site and the acid site promote the hydrogenation and the dehydration lactonization reaction, respectively. The catalytic reaction mechanism of the active site needs to be further studied to give a more feasible catalytic reaction path. In the process of hydrogen transfer hydrogenation, basic sites and acidic sites cooperate to catalyze the conversion of levulinic acid and its transesterification hydrogenation to produce GVL. The roles of different types of basic sites and acidic sites need to be further studied to establish the relationship between active sites and catalytic reaction pathways, and to give a more convincing catalytic reaction mechanism. Subsequently, the selectivity of products can be precisely regulated by balancing the distribution of active sites.
(3) Develop bifunctional catalysts with hierarchical pore structure. Bifunctional catalysts are mostly concentrated on mesoporous materials. Levulinic acid and its esters, as macromolecular reactants, have mass transfer limitations in the catalytic conversion process. The development of mesoporous materials or even hierarchical porous materials with larger pores as catalyst supports may avoid mass transfer limitations and accelerate the catalytic conversion of reactants to produce high value-added compounds. At the same time, the produced GVL can also be further transformed, and more attention should be paid to how to design bifunctional catalysts with unique pore structure and use shape-selective effect to regulate the selectivity of products.
(4) Develop non-noble metal bifunctional catalysts with high activity and high hydrothermal stability. Noble metal bifunctional catalysts can exhibit excellent catalytic hydrogenation activity under mild reaction conditions and excellent cycling stability in aqueous phase. However, due to the high production and processing costs of precious metal bifunctional catalysts, non-precious metal bifunctional catalysts have been developed to replace precious metal based catalysts. The non-noble metal bifunctional catalysts reported so far show more stringent reaction conditions, and the reaction media are mainly organic solvents such as alcohols and 1,4-dioxane, and the stability of non-noble metal catalysts in aqueous phase is poor. Therefore, one of the future research directions of bifunctional catalysts is to further develop and prepare non-noble metal bifunctional catalysts with high activity and high hydrothermal stability for GVL hydrogenation of levulinic acid and its esters. For example, the surface of bifunctional catalyst is modified to change the hydrophilic-hydrophobic characteristics of the catalyst, thereby regulating the stability of the catalyst in the aqueous phase.
(5) Development of efficient heterogeneous bifunctional catalyst system for catalytic transfer hydrogenation of levulinic acid and its esters. Alcohols and formic acid are used as hydrogen donors instead of external high pressure hydrogen. These bifunctional catalysts have lower catalytic transfer hydrogenation reaction rates, require longer reaction times, and also have harsher reaction conditions. Therefore, it is necessary to further develop heterogeneous bifunctional catalysts to realize the catalytic transfer hydrogenation of levulinic acid and its esters to produce GVL under milder conditions and shorter reaction time.
And (6) selecting levulinic acid upstream biomass and derivatives thereof as raw materials to realize continuous conversion to prepare GVL. At present, bifunctional catalysts are mainly used for the hydrogenation of levulinic acid and its esters to produce GVL. Levulinic acid and its esters, as biomass derivatives, are produced from raw materials such as cellulose and hemicellulose through acid catalysis and hydrogenation. Therefore, the bifunctional catalyst should be further used for the catalytic conversion of upstream products, thus realizing the one-pot conversion of cellulose, hemicellulose, and their derived saccharides to prepare GVL.
And (7) the side reaction in the hydrogenation process of the levulinic acid and the ester thereof is reduced, and the circulation stability of the catalyst is improved. The bifunctional catalyst has hydrogenation active sites and acidic sites. On the one hand, the acidic sites can catalyze the transfer hydrogenation and dehydration reactions in the catalytic reaction process, on the other hand, they can also promote some side reactions leading to carbon deposition, thus causing the deactivation of the catalyst. Therefore, it is necessary to better optimize the catalyst formulation, reasonably regulate the distribution of hydrogenation sites and acid sites in the catalyst, and avoid the deactivation of the catalyst due to carbon deposition. Further green and feasible methods to synthesize heterogeneous bifunctional catalysts and improve the activity and stability of catalysts need to be further concerned in future research.
(8) Increase the production process and scale of levulinic acid and its esters. At present, the development of heterogeneous bifunctional catalysts for the preparation of GVL by hydrogenation of levulinic acid and its esters is mainly concentrated in small-scale laboratory production, and it is necessary to further expand the scale of production and processing, further break through the laboratory small-scale test to achieve pilot test and put into industrial production, so as to achieve large-scale production of GVL by hydrogenation of levulinic acid and its esters.

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Funding

National Natural Science Foundation of China(51906084)

Program for Taishan Scholars of Shandong Province Government

R&D program of Shandong Basan Graphite New Material Plant and Innovation

Entrepreneurship Training Program for College Students of Shandong Province(S202110427093)

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