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Lignin: A Potential Source of Biomass-Based Catalysts

Xiangyun Chen , Bing Yuan , Fengli Yu , Congxia Xie , Shitao Yu

Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (2) : 303 -317.

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Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (2) : 303-317 DOI: 10.7536/PC200524
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Lignin: A Potential Source of Biomass-Based Catalysts
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Abstract

Lignin is one of the richest natural biomass, and more importantly, it is the only renewable resource containing aromatic structures in nature reserves. However, a large part of this resource are abandoned by far due to the complex structure, which makes the effective utilization of lignin quite difficult. It is well known that lignin can be transformed into a series of substitutes for petrochemical products via some redox processes. Beyond that, not only the oxygen-rich functional groups in lignin structure, but also the sulfur element introduced during the pulping process can provide effective active sites, making lignin resource a promising substrate of various catalysts. In this paper, following a brief summary of the species and structural characteristics of lignin resource, the applications of lignin-based catalysts in acid-base catalytic reactions, such as hydrolysis of biomass platform compounds, electrocatalysis reactions,oxidation-reduction reactions catalyzed by supported metal nanoparticles are summarized according to the catalytic mechanism and modification methods of lignin. The effects of lignin types, preparation or activation conditions on the performance of lignin-based catalytic materials are also discussed in detail. Besides, the current problems and future develop prospects of the development of lignin-based catalysts are also indicated.

Contents

1 Introduction

2 Application of lignin-based catalysts in acid-base catalytic systems

2.1 Lignosulfonic acid and its salts catalysts

2.2 Lignin-based acidic catalysts with hydroxyl groups as active groups

2.3 Lignin-based acidic resin catalysts

2.4 Lignin carbon-based acidic catalysts

2.5 Lignin-based acid-base synergistic catalysts

3 Application of lignin-based catalysts in redox catalytic systems

3.1 Lignin-based redox catalysts with quinone/hydroquinone(Q/HQ)groups as active groups

3.2 Lignin supporting or stable redox catalysts

3.3 Lignin carbon-based redox catalysts

4 Conclusion and outlook

Graphical abstract

Keywords

lignin / catalyst / acid-base catalyzed reaction / redox catalyzed reaction

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Xiangyun Chen, Bing Yuan, Fengli Yu, Congxia Xie, Shitao Yu. Lignin: A Potential Source of Biomass-Based Catalysts. Progress in Chemistry, 2021, 33(2): 303-317 DOI:10.7536/PC200524

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1 Introduction

The production of energy, fuels and chemicals from abundant renewable biomass remains a significant challenge today[1⇓⇓~4]. Natural lignin is an important rigid component of plant cell wall, which is a complex three-dimensional amorphous polymer composed of various types of methoxylated phenylpropane units[5]. Its structure and composition largely depend on the type and even location of plant sources, and it is difficult to process, so the only renewable natural polymer containing aromatic rings, which accounts for about 30% of the total organic carbon in the biosphere, is far from being fully utilized[6][7][8]. Traditionally, lignin is typically a waste stream in most biorefinery processes, with only about 5% being used as a low-grade fuel for heat and electricity or as a concrete additive (lignosulphonate)[6,9][10]. It is only in recent years that there has been a rapid growth in research on the production of high value-added chemicals, alternative fuels or catalytic materials and their substrates from lignin[11⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓~24].
The efficient utilization of natural biomass often requires a clear understanding of its structure. Although the structure of lignin has not yet been fully resolved, its significant structural features, components, and connections have been elucidated by spectroscopy, oxidation/reduction, ozonation, photochemical degradation, thermogravimetric analysis, and computational studies: Lignin is composed of three basic structural units: p-coumarol, coniferyl alcohol, and sinapol (Figure 1).Beta-O-4, beta-5, beta-beta, 5-5, 4-O-5, alpha-O-4, and beta-1 type bond[25][26][27][28][29][30][31][32]. The proportion of each unit varies from plant species to plant species, and it is connected irregularly in various ways, resulting in the complex amorphous structure of lignin.
Black liquor, a byproduct of industrial pulping, is the largest industrial source of lignin. The original structure of lignin is changed due to harsh processing conditions. These typical modified lignins are called kraft lignin, sulfite lignin (SL, also known as lignosulfonate), alkali lignin (AL) and Kelasen lignin (KL) according to different processes[33,34][34,35][36][37,38]. In addition, mild structural modified lignins such as milled wood lignin (MWL), cellulolytic enzyme lignin (CEL), enzymatic mild acid hydrolysis lignin (EMAL), organic solvent lignin (OL) and ionic liquid lignin can also be prepared by grinding and organic solvent extraction (Figure 2)[39,40][41,42][43,44][45,46][47,48].
The molecular weight, solubility, and functional groups of these lignins are quite different from each other, which brings great difficulties to their comprehensive utilization.Current research mainly focuses on the depolymerization of lignin to produce liquid fuels and chemicals based on the high content of phenolic hydroxyl groups and alcoholic hydroxyl groups in lignin structure. At the same time, the high carbon content of lignin itself, the easily modified aromatic ring, and the sulfur-containing groups introduced by various pulping processes also provide abundant structural possibilities and active sites for lignin as a catalyst precursor.The lignin-based catalyst shows excellent performance in proton transfer or electrochemistry of fuel cells, catalytic multi-component reactions, hydrolysis and dehydration of biomass and other processes[49][50,51][52][53,54]. In this paper, the applications of lignin-based catalysts in different mechanism reactions were reviewed, aiming at sorting out the advantages and potential application prospects of lignin-based catalysts from different sources, unit structures, modification methods and active sites, so as to provide reference for further efficient utilization of lignin resources and broadening its application scope.

2 Application of Lignin-Based Catalysts in Acid-Base Catalytic System

2.1 Lignosulfonic acid and its salt catalyst

Lignin sulfonic acid (LSA) with acid catalytic activity was prepared by ion exchange of lignosulfonate.5-hydroxymethylfurfural (5-HMF) was prepared by hydrolysis of sugars with LSA.Under the optimal conditions of 0. 2 G [BMIM] Cl, 0.05 G LSA, 0.5 G fructose, 100 ℃, 10 min, the yield of 5-HMF was 93. 4%, which was 47. 0% when inulin was used as raw material under the same conditions[54]. This process combines renewable raw materials, renewable organic catalysts, ionic liquids and other green solvents to produce high value-added chemicals, presenting an ideal green chemical process (Table 1). The acid strength data of LSA have not been reported, but in the study of the condensation reaction of methoxycresol and formaldehyde in aqueous solution, it was found that the catalytic activity was closely related to the acidity coefficient of the acid catalyst[55]. Under the same reaction conditions, the order of the activity of the catalysts is benzenesulfonic acid (BSA) > p-toluenesulfonic acid BSA(pKa=3.5), and it can be inferred that the acid strength of LSA is close to that of other organic acids with sulfonic groups as active groups, such as BSA(pKa=3.5), PTSA(pKa=1.99) and methane sulfonic acid (pKa=-1.75).
The good ion exchange capacity of lignosulfonate can not only be used to prepare sulfonic acid protonic acid, but also be combined with polyvalent metal cations or organic cations to prepare new catalysts. Heterogeneous catalysts such as LS-Sc, LS-Cu and LS-IL@NH2 (Fig. 3) prepared by Sun et al. From sodium lignosulfonate have shown excellent catalytic performance in organic transformations such as Michael addition/dehydration, electrophilic ring opening, Friedel-Craft, condensation, three-component click, Glaser and Knoevenagel reactions[58].
Sulfonic acid groups introduced into lignin structure by sulfite pulping process can be used as very effective catalytic active sites, which makes lignosulfonate as a cheap waste biomass have good potential as acid catalyst precursors.

2.2 Lignin-Based Acidic Catalysts with Hydroxyl as Active Group

The structure of lignin prepared by different pulping methods contains a large number of hydroxyl groups. For example, the enzymatic hydrolysis lignin of corn straw pretreated by ionic liquid contains 2.96 mmol·g-1 aliphatic hydroxyl groups, which can catalyze the cycloaddition reaction of epoxide and CO2, and the yield of cyclic carbonate reaches 93%[59]. FT-IR and 2D NMR characterization showed that the formation of dimer intermolecular hydrogen bonds in lignin-based catalysts led to higher activity of -H, and the dimer intermolecular hydrogen bonds had higher catalytic activity than the multi-intermolecular hydrogen bond[60]. Hydroxyl, carboxyl and Cα-OH in soda lignin, kraft lignin and enzymatic hydrothermal lignin can activate not only epoxides, but also CO2, which play an important role in the efficiency of the catalytic system. Xiong et al. also modified lignin with deep eutectic solvents (DESs) prepared from choline chloride (ChCl), p-aminobenzoic acid (PABA), or their derivatives, which not only enhanced the catalytic activity of lignin, but also made it easier to recycle in the reaction mixture[61]. A series of cyclic carbonates were obtained in high yields (90% ~ 99%) under the synergistic effect of — OH on the surface of lignin-ChCl-PABA and —NH2 at 110 ℃, 1.0 MPa CO2 and 1. 0 mol% catalyst for 3 H. The above studies show that cheap and renewable lignin can be used as an ideal green "carbon neutralization" catalyst to construct value-added chemicals using CO2 as a carbon source. However, so far, the research of using the hydroxyl groups in lignin as the active center to catalyze the reaction is still relatively scarce, and most of the research focuses on using the hydroxyl groups in lignin structure as the bonding groups to prepare lignin-based polymer functional materials through a series of derivatization reactions.

2.3 Lignin-based acidic resin catalyst

Zhang et al prepared a solid catalyst containing —SO3H, -COOH and -OH groups by condensation of lignosulfonate and formaldehyde, which showed high activity in the hydrolysis of polysaccharides to monosaccharides, and the activity of the catalyst did not change after four times of reuse[62]. Compared with other acid catalysts such as H-ZSM-5 and H-mordenite, cellobiose is more accessible to the -SO3H sites, and the multiple binding of the hydroxyl groups of cellobiose on the — COOH and — OH sites can increase the activity of the response. Li et al. polymerized SLS with formaldehyde under acidic conditions and exchanged it with 2m sulfuric acid to prepare acidic resin (LF), which showed higher catalytic activity and stability than Amberlyst-15 and Amberlyst-36 in the hydroxyalkylation/alkylation (HAA) reaction of 2-methylfuran and 2-furfuraldehyde. By comparing the adsorption heat and NH3 coverage at 353 K, it was found that:The percentage of strong acid sites of LF with ammonia adsorption heat higher than that of 140 kJ·mol-1 is higher than that of Amberlyst-15 and Amberlyst-36, which indicates that LF has higher acid strength. Compared with Amberlyst resins prepared from crosslinked polystyrene, the — COOH and — OH groups adjacent to the —SO3H groups in LF resins can increase the acidity of the —SO3H groups through electron-withdrawing effect[63].
Although AL itself contains almost no sulfonic acid groups, Kumar et AL., after polymerizing AL with formaldehyde, introduced sulfonic acid groups by sulfonation with concentrated sulfuric acid, and also prepared lignin-based solid acid catalysts (LAS)[64]. In the esterification of Tall oil fatty acids (TOFAs) with methanol, the yield of fatty acid esters was as high as 88%, which was higher than that of Amberlyst-15 (80%), although the content of sulfonic acid groups was only (Tall oil fatty acids) and the content of sulfonic acid groups was (4.2±0.1)mmol·g-1), indicating that the — COOH and — OH groups in LAS had synergistic effect with —SO3H groups. Tang et al. compared the activity of acetic acid, Amberlyst-15 or the mixture of acetic acid and Amberlyst-15 to verify the synergistic effect, and found that the fructose conversion and HMF selectivity of the mixture of acetic acid and Amberlyst were significantly higher than those of the other two resins, confirming that there was indeed a synergistic effect between —SO3H and — COOH groups[65]. Further comparison of the activity of glycolic acid, acetic acid, o-hydroxybenzoic acid and benzoic acid showed that there was also a synergistic effect between — COOH and adjacent — OH groups.

2.4 Lignin carbon-based solid acid catalyst

In 2004, Hara et al. Treated naphthalene, anthracene and other polycyclic aromatic hydrocarbons in concentrated sulfuric acid at 250 ℃ for 15 H to obtain a carbon material with incomplete carbonization of sulfoaromatic hydrocarbons. Its total acid content (4.9 mmol·g-1) is much larger than that of Nafion NR50(0.93 mmol·g-1), and its catalytic activity is also higher than that of Nafion NR50 in the esterification of acetic acid (343 K), hydrolysis of cyclohexyl acetate (353 K) and hydration of 2,3-dimethyl-2-butene (343 K)[81]. The sulfonated carbon solid acid catalyst prepared by using glucose and cellulose as raw materials also has good catalytic activity and excellent stability in the synthesis of biodiesel and the hydrolysis reaction of cellulose[82][83][84]. The carbon-rich aromatic ring network of lignin composed of phenol units has a higher carbon yield after pyrolysis treatment, and tends to form a graphite-like structure, while its linear branches are lost as small molecules containing various hydrocarbons. Therefore, lignin, as the only natural renewable raw material containing benzene rings, is more suitable for preparing carbon-based solid acid catalysts (Table 2)[21][85][8,86].
Lignin-based sulfonated carbon (CSC) rich in — OH, — COOH and —SO3H can be prepared by a two-step process of pyrolysis carbonization followed by sulfuric acid sulfonation[66]. The strong oxidizability and dehydrating property of sulfuric acid can also be utilized to prepare the lignosulfonated carbon (SC) by one-step carbonization and sulfonation[67]; SC and CSC have the same functional groups and amorphous structure, but the carbonization degree of SC is lower than that of CSC, resulting in lower —SO3H content and higher oxygen content[49,87]. Our group also found that CSC has better activity and selectivity than SC in the clean benzylation of aromatic compounds. Lee used higher oxidizing oleum (20%), resulting in sulfonated carbon with higher total acid and —SO3H content[68]; When CSC was oxidized by H2O2, the content of —SO3H was the same, but the total acid content of sulfonated carbon was higher[69]. It should be noted that the catalytic activity of LSC is not always proportional to the content of its acidic groups, and the direct pyrolytic carbon of AL has only 0.13 mmol·g-1 total acid content, but it also shows good catalytic activity in the hydrolysis of cellulose and lignocellulosic biomass[70].
TG-MS studies (fig. 4) show that the sulfonate of SLS dissociates into SO2 above 230.d egree. C[88]. The oxygen-containing groups dissociate CO, CO2 and CH4 at further elevated temperatures with a loss of mass. Therefore, in order to ensure that the carbon material contains more oxygen-containing functional groups, the carbonization temperature should be controlled below 500 ℃. In addition, carbonization in air flow is favorable for the formation of more oxygen-containing functional groups and micropores (mesopores/macropores are burned during carbonization), while carbonization in static air atmosphere is favorable for the formation of more sulfonic acid groups and mesopores/macropores. The total amount of these oxygen-containing and sulfonic acid sites was the largest when the catalyst was carbonized in air flow, and there was a positive correlation between the total acid amount and the fructose conversion. The total acid amount of the catalyst prepared in air flow was 13.6 mmol·g-1, the fructose conversion was 100%, and the 5-HMF selectivity was 59.9%. The steric hindrance of the micropores in the catalyst also restricted the formation of humic substances and enhanced the 5-HMF selectivity.
The removal of sulfonic acid groups from the sulfonated carbon under the reaction conditions is also an important factor to consider[68]. It was found that the structure of sulfonated carbon became stable after three times of washing, and the first three times of methanol washing showed certain esterification activity. The characteristic peak of PAHs appeared in the 1H-NMR of methanol washing solution at 7.4 ~ 7.8 ppm, which indicated that acidic PAHs were leached[89]. Chen et al. Used PTSA to simulate the preparation of sulfonated carbon, and used glycine as an internal standard to detect a certain amount of PTSA leaching after heat treatment[90]. Laser scanning found that all catalyst filtrates (glucose and PTSA mixed hydrothermal, glucose and chlorosulfonic acid direct sulfonation) clearly showed laser scattering images, which were attributed to the leaching of nanoscale colloidal carbon moieties rather than the breakage of C — S bonds (Fig. 5A). At the same time, the —SO3H content of the catalyst remained constant when the prepared hydrothermal carbon was refluxed in toluene, while the —SO3H content of the catalyst decreased significantly when acetone and 1-propanol were refluxed, which may be due to the loose bonding of highly polar and hydrophilic sulfonic acid groups, which increased the solubility of the unstable structure in polar solvents[91][89]. Catalyst deactivation after methanol washing was particularly severe, possibly due to strong physical adsorption of methanol via hydrogen bonding to the highly oxidized structure of the catalyst, or due to chemical reaction of methanol with certain acidic groups to form surface methanesulfonates (Fig. 5B).
For glucosyl sulfonated carbon, hydrothermal treatment, low temperature calcination and homogeneous carbonization can be used to effectively reduce the formation of unstable carbon species and improve their stability, but other carbon sources such as lignin require higher treatment conditions[90,92]. Lignin-based hydrothermal carbon was prepared at 265 ℃ (water as solvent) or supercritical conditions (ethanol, 260 ℃, 8.4 MPa, 20 H), and then sulfonated to prepare sulfonated carbon. It was found that high temperature could accelerate the hydrothermal carbonization of lignin, but led to lower yield, volatile matter content and ion exchange capacity[71,72][73][72]. The Lignin-based sulfonated carbons (named as E-260-20-SO3H and E-P400-2-SO3H, respectively) prepared under the above supercritical and subcritical conditions (ethanol, 180 ℃, 7.8 MPa, 1 H),The content of oxygen-containing functional groups (especially the concentration of —SO3H) of the KLC-SO3H of the catalyst obtained by direct pyrolysis carbonization and sulfonation is greatly improved, so that the initial activity of the catalyst in the biodiesel preparation reaction is greatly improved, and more importantly, the repeated use stability of the catalyst is qualitatively improved[93]. Among them, the sulfonated carbon E-260-20-SO3H obtained by supercritical ethanol treatment is more stable than the E-P400-2-SO3H obtained by subcritical ethanol treatment[73].
The specific surface area of the carbon materials prepared by the above methods is low due to the pyrolysis and condensation of lignin, while the preparation method of impregnating lignin with H3PO4, NaOH, KOH, FeCl3, etc. And carbonizing at 400 ~ 600 ℃ is almost the same as pyrolysis and carbonization, and the rigid graphitic amorphous carbon structure with high degree of condensation can be obtained[74,88,94,95][75][76,96][77]. But produce large particles with a large numb of defects/pores during that activation/mild oxidation proces (fig. 6). The solid acid powder prepared by Pua et al by phosphoric acid activation, carbonization and sulfonation of kraft lignin has a round or hemispherical shape with many open volumes on a rough surface[74]. Compared with the raw material and the carbon without phosphoric acid pretreatment, the lignin pyrolytic carbon activated by phosphoric acid is porous, and the specific surface area (654.4 m2·g-1) is greatly increased compared with the carbon without activation (127.6 m2·g-1); However, after sulfonation, the —SO3H is impregnated into the pores, and the specific surface area is reduced to the 54.8 m2·g-1. Under the optimized conditions, the conversion rate of oleic acid reached 96. 1%, and it was still 93. 6% after three cycles. Zhang et al. Used sulfonated carbon prepared from phosphoric acid activated alkali lignin to catalyze the hydrolysis of microcrystalline cellulose (MCC) at 180 ℃ for 3 H, and the yield of total reducing sugar (TRS) reached 50. 8%[94]. Sulfonated carbon (MLC-SO3H) obtained by impregnation with FeCl3 by Hu et al. Has the characteristics of magnetic separation (formation of Fe2O3),FeCl3 at 300 ~ 500 ℃ and decomposition to produce HCl,Volatile substances such as H2O, H2, CO and CO2 increase the specific surface area to 234.61 m2·g-1 after carbonization.The reduction of the particle size enhances the contact between the carbon surface and the H2SO4, which improves the effectiveness of the sulfonation process and increases the fructose conversion from 70.4% to 75.5%[77][97][98]. However, the conversion of fructose catalyzed by Amberlyst-15 with —SO3H content up to 4.7 mmol·g-1 was only 69.7%. Adsorption experiments showed that although —SO3H played a key role in the dehydration of fructose to 5-HMF, the — COOH and — OH groups in MLC-SO3H had strong affinity for fructose, and the synergistic effect of —SO3H, — COOH and — OH groups made the hydrolysis of cellulose catalyzed by MLC-SO3H reach a TRS selectivity of 69. 3%[99].
The above literature shows that although heat treatment can improve the thermal, mechanical and chemical activity and stability, it is difficult for lignin carbon to have ideal heterogeneous catalyst structure properties such as high specific surface area and clear porosity[75,76]. Konwar et al. Used ice templating to introduce aligned macropores to regulate porosity, and introduced 20 wt% sodium polystyrene sulfonate (PS) to promote intermolecular crosslinking during pyrolysis to retain the porous structure of ice templating[78]. It was found that the specific surface area was only 12 m2·g-1,—SO3H 10.7% of the total acid amount without PS carbonization, and the specific surface area increased to 34.7% of the 122 m2·g-1,—SO3H amount with PS carbonization. The carbon samples obtained by pure SLS clearly exhibited less porosity (mainly macropore morphology with no visible mesopores), while the SLS-PS under the same conditions exhibited distinct and uniform mesopores. Gan et AL. Used F123 as a template to pyrolyze and sulfonate AL at high temperature, and the prepared LDMC-SO3H could catalyze the hydrolysis of cellulose to achieve a glucose yield of 42. 5%, which was attributed to its suitable specific surface area (156 m2·g-1), high —SO3H content (1.82 mmol·g-1) and ordered mesoporous structure[79,80]. Compared with hydrothermal activation, KOH-activation can increase the number of oxygen-containing groups in carbon materials[100]. However, the aromatic groups in the sulfonated carbon treated at 450 ℃ are more than those treated at 650 and 850 ℃, and the higher the heat treatment temperature is, the oxygen-containing functional groups will be lost in the form of carbon oxides, so that the number of carboxyl and hydroxyl groups decreases, and the degree of graphitization increases, the number of sulfonic acid groups also decreases, thus the active sites also decrease[101][88].
Proper modification can greatly improve the specific surface area and porosity of lignin-based solid acid, and the introduction degree and distribution of various functional groups on the surface can also be adjusted by the carbonization temperature, atmosphere environment and post-treatment mode in the preparation process of the catalyst[102]. However, special attention should be paid to the fact that the structure and composition of various lignin raw materials may vary with their source sites and seasons, and the potential impact of these factors on the catalytic behavior of lignin-based solid acids should also be considered[58].

2.5 Lignin-based acid-base synergistic catalyst

Qi et al. self-assembled LigS (SLS) with metal chlorides M(HfCl4, ZrCl4, FeCl3, AlCl3 or ZnCl2) under hydrothermal conditions to prepare M-lignosulfonate nanohybrids.The characterization of NH3-TPD, CO2-TPD, Py-FT-IR and XPS showed that there were both acid and base sites in Hf-LigS.The formation of the B acid site (—SO3H) is due to the ion exchange between the H+ generated by the partial hydrolysis of the HfCl4 and the UNa+. The Lewis acid site comes from the Hf center. The functional group of LigS stabilizes the Lewis acid UNHf4+ and acquires the base center site by forming a porous-Ar-O-Hf skeleton structure (fig. 7)[103]. Due to the unique synergistic effect of acid and base sites, Hf-LigS exhibited a high catalytic activity in the reduction of 5-HMF (the conversion of 5-HMF was 85. 1%), while the conversion of 5-HM decreased to 4. 8% and 67. 2% when Hf-LigS was poisoned by benzoic acid and pyridine, respectively. Zr-SLS also showed excellent catalytic performance for a variety of biological platform chemicals, especially furfural (FF), under mild conditions (80 ℃) (the quantitative yield of furfuryl alcohol (FA) reached 96%)[104]. Chen et al. prepared lignosulfonate catalysts with Lewis acid and basic sites by co-precipitation method to fix metal ions. (SLS-M),NH3-TPD and CO2-TPD can detect acidic sites (SLS-Cr:1.2 mmol·g-1,SLS-Sn:1.0 mmol·g-1) and basic sites respectively. (SLS-Cr:0.19 mmol·g-1,LS-Sn:0.22 mmol·g-1),SLS-Cr can catalyze cellulose to achieve the best yield of 46.3% of 5-HMF[105].
The stable structure of the SLS and the chelating property of the sulfonic acid group and the cation provide the possibility of designing a novel acid-base double-center ligno-based catalyst, and the preparation process is simple and non-toxic, so that a new direction is opened up for further exploring a low-cost lignosulfonate used as an environment-friendly and renewable catalytic material for biomass conversion.

3 Application of Lignin-Based Catalysts in Redox Catalytic System

3.1 Lignin-based redox catalysts with quinone/hydroquinone (Q/HQ) groups as active group

Redox active polymers are important materials for chemically modified electrodes in electrochemical and bioelectrochemical sensing, which usually contain intra- or side-chain metal complexes that can undergo reversible redox cycles. Non-metal redox polymers such as pyridazine dyes and catechol (CC) derivatives have also been reported[116][117,118]. The quinone/hydroquinone (Q/HQ) groups obtained from the oxidation of lignin molecules can undergo excellent reversible redox cycles, which is also considered an ideal characteristic of chemically modified electrode materials (Table 3)[109].
Milczarek adsorbed AL as an electrode surface modifier on a polycrystalline gold electrode, and formed an electroactive quinone functional group capable of reversible proton coupling two-electron oxidation/reduction cycle through oxidation reconstruction, and observed efficient electrocatalysis of ascorbic acid oxidation[106]. The sulfonic acid functional group of SLS makes it often used as a proton transfer material in fuel cells or electrochemical processes. Milczarek modified it on a glassy carbon (GC) electrode to prepare a chemically modified electrode with anionic characteristics and redox activity, which showed sustained catalytic activity in the electrochemical reduction of nitrite[51][119][107]. As shown in Scheme 1, the predominant substituted phenylpropane (C9) electroactive subunit in the SLS structure, such as 4-hydroxy-3-methoxy- (guaiacyl-) or 4-hydroxy-3,5-dimethoxy- (syringyl-), produces an ortho-quinone upon anodic polarization, which reversibly cycles between redox States at the mid-peak potential to complete the electrocatalytic process. Sulfonic acid group has little effect on the formal potential of quinone formation, and enhances the catalytic activity in the form of —SO3-|NO+ ion pair. The potentials of the two lignin modified electrodes were + 1.0 V and + 0.8 V, respectively[106][107].
Milczarek also oxidatively deposited SL1 and SL2 on the preactivated GC electrode for the oxidation of NADH. The results showed that in the presence of Mg2+, the quinone group, divalent metal ions and NADH formed a ternary complex, which greatly improved the oxidation rate of the electrode. The sulfonic acid group near the quinone could further enhance this effect[50]. The acid iodate on the electrode surface is electrochemically reduced to form an iodine layer, which can significantly reduce the background current and further improve the detection sensitivity of NADH[108]. It is known that lignosulphonate is a very valuable precursor for electrode redox active deposits, and that the formation of thiol groups after oxidation improves stability[109]. The inorganic/organic composite modified GC electrodes, such as Ni-SL, Mn-SL and ZnO-lignin based carbon fiber, also showed high activity in the electrocatalytic oxidation of methanol, hydrogen peroxide and hydroquinone, respectively, due to the synergistic effect of various redox state metal oxides and quinone functional groups of lignin matrix[112][113][114].
In addition, conductive active polymers (CEP), especially polypyrrole (PPy), which are commonly used in electrocatalytic reactions, have the characteristics of conductivity, oxygen resistance, thermal and environmental stability, easy synthesis and non-toxicity, but their physical and mechanical properties are not good, and they are insoluble in common solvents[120]. In situ doping polymerization of PPy with various sulfonates or organic sulfonic acids can improve its conductivity, solubility and provide special morphology. The structure of SL not only has redox functional groups which can be easily converted into reversible quinones, but also has sulfonic acid groups in the phenylpropane chain segment.The composite prepared by doping SL with PPy can not only be highly dispersed in water, but also has adjustable particle diameter and enhanced charge storage characteristics[120][121,122]. R Rbię et al applied PPy/SL and PEDOT/SL composite materials to the oxidation of hydrazine on the GC electrode by galvanostatic polymerization, and found that the oxidation potential of the electrode modified by SL moved to a negative value, and the sharp increase of the oxidation current at the potential close to and above the E0’ indicated the mediation of quinone groups in the oxidation of hydrazine[111]. In addition, this catalytic behavior was also enhanced by the sharp decrease of the cathodic current of the mediator, indicating that the SL dopant combined with the polymer matrix had better catalytic ability.

3.2 Lignin supported or stabilized redox catalyst

In addition to various potential catalytic active sites in the structure, different types of active centers can be grafted, bonded or stabilized on the lignin structure by various modification means to prepare the lignin supported or stabilized redox catalyst. For example, Yang et al. Have grafted β-cyclodextrin into the structure of alkali lignin, and the prepared β-cyclodextrin polymer phase transfer catalyst can efficiently catalyze the oxidation of cinnamaldehyde to benzaldehyde under mild conditions, and has good recycling stability[123]. The excellent catalytic performance is achieved based on the synergistic effect of hydrogen bonds between the active center and the support, and the hydrophilic and lipophilic properties of the substrate can also be changed during the modification process (Fig. 8)[123⇓⇓~126].
The active components of redox catalysts are more transition metals. Among them, highly dispersed transition metal nanoparticles (NPs) have become a new research hotspot due to their high catalytic activity, and the stability of these high surface energy particles is a key issue in the research and development process. It has been found that cellulose and other natural polymers with electron-rich groups such as hydroxyl and ether groups are good materials for stabilizing metal NPs[127]. Lignin structure, which is also rich in hydroxyl and ether groups, also shows good stability of metal nanoparticles[128]. Lin et al. reduced H2PtCl6 by grinding and suspending wood in aqueous solution, and evaluated the catalytic activity of the prepared Pt NPs by using the reduction of p-nitrophenol by NaBH4 as a model reaction.Spherical Pt NPs (2. 3 ± 0.5 nm) exhibited the highest catalytic activity when the concentration of H2PtCl6 was 0. 1 mM, and the nanoparticles were anchored to the substrate surface by electrostatic interaction with hydroxyl groups, and the phenolic hydroxyl groups of lignin were more reducible than alcoholic hydroxyl groups[129]. Coccia et al. Prepared Pt NPs by reducing natural polymers such as lignin and fulvic acid. When the molar ratio of Pt catalyst prepared from lignin ammonia derivative (Pt AmLig) and fulvic acid (Pt FA) to 4-nitrophenol was 1:183, the selectivity of 4-aminophenol reached 100% after reaction for 0.5 H at 80 ℃, and Pt NPs also showed good catalytic performance in the oxidation of alcohols[130]. SLS can act as both a stabilizer and a reducing agent, and Pd NPs prepared by slow in-situ reduction show good catalytic efficiency in cross-coupling reactions (Heck, Mizoroki-Heck, Suzuki, Sonogashira and Stille reactions)[131][132][131][133][131].
Figure 2 proposes the mechanism of lignin-based raw materials as multi-functional complexing agents, reducing agents and capping agents to prepare stable metal NPs. Phenol-OH in the aromatic chain segment of the skeleton structure and aliphatic-OH in the side chain are dissolved in aqueous metal salts.The guaiacyl and syringyl groups are oxidized to the corresponding quinones, and the aliphatic — OH is oxidized to the corresponding aldehydes or ketones through the binding and complexation of the cation-hydroxyl and cation-π bonds with the metal ions[134,135][134,136][137][138]. To some extent, the morphology and particle size of NPs can be controlled by changing the type of lignin, the pH value of the solution, the type of metal salt and the preparation method (such as laser ablation, hydrothermal method, mechanochemical grinding method)[139][140][141][142][143][144].
However, NPs prepared from the same type of lignin also have some differences in morphology and particle size, and the reproducibility of preparation still needs further discussion. In addition, Coccia et al. Found that although the infrared spectra showed that the methoxyl and aromatic ring vibration bands of lignin residues remained unchanged after the formation of NPs, indicating that the lignin skeleton had not changed significantly.However, the small amounts of acetic acid, formic acid, and methanol detected in the reaction mixture clearly indicate a small amount of oxidation/degradation of the polymer, and the catalyst durability needs to be further improved, especially when used under severe conditions[131]. The condensation of lignosulfonate with formalin under acidic conditions is one of the effective methods to enhance the stability of the catalyst[62]. Xue Man and others used lignin amine prepared by polymerization of lignin and tetraethylenepentamine to support palladium and catalyze Suzuki reaction of sodium tetraphenylborate and iodobenzene, with a yield of 90.2%, which opened up a new way for lignin amine as a carrier[145]. In this study, Mannich reaction and coprecipitation were combined to prepare magnetic lignin amine in alkaline aqueous solution, which was used to stabilize and disperse metal NPs, and obtained excellent catalytic performance in the hydrogenation of α-pinene[146]. Ag/lignin/polyacrylamide hydrogel catalysts prepared by Gao et al. Using polyacrylamide as amine source and bonding agent were used to catalyze the reduction of nitrobenzene under batch and fixed-bed conditions. The introduction of amino groups dispersed silver ions well and restricted the growth of silver nanoparticles[147,148]. Nasrollahzadeh et al. Used Hibiscus Rosasinensis Linn extract to reduce Hibiscus Rosasinensis Linn alone, and then used the combination of calcium lignosulfonate and Fe3O4 as precursors to prepare magnetic lignin-stabilized Pd NPs@Fe3O4-lignin. In the Suzuki-Miyaura reaction of bromobenzene and PhB(OH)2, the yield of biphenyl was as high as 95%, and Cr (Ⅵ) could be reduced at 50 ℃[149]. The introduced Fe3O4 further improves the separability and durability of the catalyst, and the controllability is stronger than that when the lignin is used as a reducing agent and a stabilizing agent alone. Nasrollahzadeh et al. Also bonded 5-aminotetrazole to the Fe3O4- calcium lignosulfonate with 3-chloropropyltrioxysilane to further improve the lignin stabilizing ability, and the catalyst Fe3O4-lignosulfonate@5-amino-1H-tetrazole-Pd(Ⅱ) can be efficiently separated in the aqueous Suzuki-Miyaura reaction and can be continuously reused for seven times under the condition of small yield fluctuation[150].

3.3 Lignin carbon-based redox catalyst

As previously mentioned, lower temperature pyrolytic carbonized lignin can provide a stable precursor for the introduction of sulfonic acid groups; When pyrolysis temperatures, typically above 700.d egree. C., are used, it is difficult for lignin carbon to bind sufficient acidic groups, but sulfur sources, nitrogen sources, or metal active centers can be introduced to form stable lignin carbon-based redox catalysts (Table 4).
He et AL. Used AL as carbon source and sulfur source, urea as nitrogen source, simply mixed and annealed at 900 ℃ to prepare a new nitrogen-sulfur co-doped carbon catalyst N-S-C 900, which had better half-wave potential and diffusion-limited current density in alkaline medium than commercial Pt/C.Its excellent metal-free oxygen reduction (ORR) activity is attributed to its high surface area and micropore-rich structure, as well as the synergistic effect of highly active sites such as ordinary N, graphite N and thiophene S[151]. Similarly, Shen et al. prepared lignin-based 3D mesoporous framework carbon co-doped with nitrogen, sulfur, and chlorine by using eutectic NaCl/ZnCl2 melt as a gas sealing agent and a swelling agent, and the ORR activity and stability in acidic media were superior to those of Pt/C and most non-noble metal catalysts[152]. DFT calculations further demonstrated that the excellent ORR activity and stability of the biocarbon material were attributed to the existence of C-Cl covalent bonds. The lignin-based nitrogen-sulfur CO-doped porous biochar also showed high activity and controllability of the target product in the electrocatalytic CO2 reduction (ECRR).Nitrogen doping was beneficial to the formation of CO, and the chlorine adsorbed on the surface of the biochar after washing with hydrochloric acid could improve the catalytic activity, thus improving the CO yield.The Faraday efficiency of CO at-0. 6 V was 95. 9%[153].
Li et al. prepared Pt/Lg-CDs-800 by carbonizing concentrated acid pulping lignin at 800 ℃, dispersing and loading H2PtCl6 in aqueous solution and reducing with NaBH4, which is superior to commercial Pt/C (40% Pt) and PtRu/C (30% Pt + 15% Ru) catalysts in methanol electro-oxidation reaction[154]. The large specific surface area and abundant oxygen-containing groups of lignocarbon increase the nucleation density of Pt atoms to avoid their aggregation during the reduction process. The kraft lignin carbonized by using H3PO4 as an activating agent contains a large number of oxygen-containing groups and a high mesoporous structure, so that simple substance Pd obtained after loading Pd has high dispersibility and low particle size, and shows high activity, selectivity, stability and reproducibility in hydrogenation reaction and Suzuki reaction[155]. The preparation method utilizes abundant functional groups in the lignin as active or stable sites, and provides a new method for preparing the redox catalyst from natural biological resources.
Hao et al. Used the solid organic residue produced after depolymerization and hydrodeoxygenation of enzymatic lignin as a precursor to prepare carbon materials after activation with KOH[156]. Due to the strong corrosiveness of the depolymerization reaction, 2.94% of Fe element can be obtained from the solid residue in the reaction kettle, and the content rises to 6.40% after carbonization at 800 deg C, and the specific surface area is as high as 2875 m2·g-1. After loading NiMo, the lignin hydrodeoxygenation (HDO) is catalyzed to obtain 72.2 wt% of oil and 21.1 wt% of organic solid products, and a catalyst shows magnetism and is beneficial to recovery[157]. However, the catalyst is easily hindered by the in situ release of sulfur during the reaction of lignosulfonate, which makes the catalyst poisoned. Metal (Co, Ni, Mo, CoMo, NiMo) sulfides supported on carbon formed from lignosulfonate can catalyze the formation of guaiacyl monomers from lignosulfonate[158]. Guan et al. Used dealkalized lignin (DAL) as carbon and sulfur source to prepare MoS2/Mo2C catalyst (Mo-DAL) for hydrogen production from formic acid by impregnation-pyrolysis two-step method. C, S and Na in lignin can form multiple sites (Na-inserted MoS2, MoS2 and β-Mo2C) with the introduced Mo, which can improve the activity of the catalyst and keep the H2 yield unchanged in 50 H cycle[159]. Liu et al. prepared Co-SAs/N @ C and Co-Mn/N @ C catalysts (Fig. 9) by a similar method (impregnation/coordination-pyrolysis), which showed high catalytic activity and stability in the oxidation of HMF and the oxidative esterification of primary alcohols[160,161][162]. Minh et al prepared a series of hierarchical porous catalysts doped with N and S using Co (II) -lignosulfonate. The introduction of cobalt enhanced the polymer crosslinking and thus enhanced the graphitization, resulting in macroporous space and abundant active sites.At the same time, the heteroatom-rich sites and Co-Nx/Sy-C on the conjugated network of the sp2 also greatly improved the catalytic performance of the catalyst for the oxidative degradation of peroxy-sulfate and the reductive amination of several pollutants mediated by borohydride[163].
The biospontaneous assembly of metal-organic complexes using lignin as a macromolecular ligand is a very effective integrated biorefining strategy (Fig. 9), and when the materials obtained from this assembly strategy are not pyrolyzed, they can also provide acid-base synergistic catalytic centers for catalytic systems. Thereby being beneficial to realizing the goal of carbon balance on the one hand and providing a new method for preparing the sustainable and low-cost heterogeneous catalyst on the other hand.

4 Conclusion and prospect

The design and practice of new value chains based on non-fossil carbon sources and renewable resources have marked the beginning of the next industrial evolution in chemistry[1]. Lignin is the most unique renewable carbon-containing resource on the earth, and its structure has abundant available active sites and modification space. Therefore, in addition to being used as raw materials for downstream chemicals and fuels, lignin-based catalytic materials can also be modified by various methods to prepare lignin-based catalytic materials. At present, there are four types of lignin processing methods for the purpose of preparing catalytic materials: (1) depolymerization as a carbon source or cleavage into small fragments containing aromatic rings; (2) introducing a new active site by bonding; (3) carrying out chemical modification on hydroxyl groups, sulfonic acid groups and the like; (4) graft copolymerization. These methods are based on the functional group reactivity and structural characteristics of the lignin feedstock used.
The materials such as lignosulfonic acid, lignosulfonate, lignin carbon, doped lignin carbon, lignosulfonated carbon, amine modified graft copolymerization lignin and the like prepared by the method can realize catalysis through functional groups such as sulfonic acid groups, phenolic hydroxyl groups, alcoholic hydroxyl groups and the like,Or using these functional groups to stabilize other components with catalytic activity, can be applied to a variety of catalytic processes with different reaction mechanisms and under different conditions, and shows the potential to replace expensive and non-renewable conventional catalytic materials. In particular, these alternatives are often aimed at biomass conversion, green process improvement of unit reactions, etc., which reflects the latest twelve principles of green chemistry, and the coordinated promotion of solutions to various sustainability problems will hopefully pave the way for the closed cycle of the non-fossil raw material value chain[1].
However, just as all renewable raw materials need to face the complexity of structure and composition, the diversity of lignin raw materials and their high dependence on sources and processing conditions also increase the complexity of the structure of catalytic materials obtained after modification. On the one hand, we should continue to study the regulation methods and mechanisms of the structure and performance of lignin-based materials, and explore the catalytic structure-activity relationship and regulation methods to solve the basic challenges that must be faced in the development of lignin-based catalysts. On the other hand, challenges and opportunities coexist. Traditional petroleum chemistry also derives a variety of chemical products from limited basic module molecules through the introduction of various functional groups. The complex aromatic ring and other structures in lignin just provide a variety of possibilities for the introduction of functional groups, so the different needs for catalytic materials will also give feedback to the modification methods of lignin-based raw materials.It will greatly stimulate and promote the development of new strategies, theories and practices in the transformation of biodegradable, renewable and low-cost bio-refining by-products into new catalytic materials.

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Funding

National Natural Science Foundation of China(31870554)

National Natural Science Foundation of China(31470595)

Shandong Key R&D Plan(Public Welfare Special Project)(2017GGX40105)

Taishan Scholars Projects of Shandong(ts201511033)

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