2D Heteronuclear Single Quantum Coherence Research Articles

Revealing the structural changes of lignin in Chinese quince (Chaenomeles sinensis) fruit as it matures

Chinese quince fruits (Chaenomeles sinensis) contain substantial amounts of lignin; however, the exact structure of lignin remains to be investigated. In this study, milled wood lignins (Milled wood lignin (MWL)-1, MWL-2, MWL-3, MWL-4, MWL-5, and MWL-6) were extracted from fruits harvested once a month from May to October 2019 to investigate their structural evolution during fruit growth. The samples were characterized via High-performance anion exchange chromatography (HPAEC), Fourier transform–infrared spectroscopy (FT-IR), gel permeation chromatography (GPC), thermogravimetric (TGA), pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS) and NMR (2D-heteronuclear single quantum coherence (HSQC) and 31P). The MWL samples in all fruit growth stages were GS-type lignin and lignin core undergoing minimal alterations during fruit development. The predominant linkage in the lignin structure was β-O-4′, followed by β-β' and β-5′. Galactose and glucose were the main monosaccharides associated with MWL. In MWL-6, the lignin exhibited the highest homogeneity and thermal stability. As the fruit matured, a gradual increase in the β-O-4′ proportion and the ratio of S/G was observed. The results provide comprehensive characterization of the cell wall lignin of quince fruit as it matures. This study could inspire innovative applications of quince fruit lignin and provide the optimal harvest time for lignin utilization.

Advanced NMR Characterization of Aquasolv Omni (AqSO) Biorefinery Lignins/Lignin-Carbohydrate Complexes.

Our recently reported AquaSolv Omni (AqSO) process shows great potential as a parameter-controlled type of biorefinery, which allows tuning of structure and properties of the products towards their optimal use in high-value applications. Herein, a comprehensive NMR (quantitative 13 C, 31 P, and 2D heteronuclear single-quantum coherence) structural characterization of AqSO lignins is reported. The effect of the process severity (P-factor) and liquid-to-solid ratio (L/S) on the structure of the extracted lignins has been investigated and discussed. Low severity (P-factor in the range 400-600) and L/S=1 led to the isolation of less degraded lignin with a higher β-O-4 content up to 34/100 Ar. Harsher processing conditions (P-factor=1000-2500) yielded more condensed lignins with a high degree of condensation up to 66 at P-factor=2000. New types of lignin moieties, such as alkyl-aryl and alkyl-alkyl chemical bonds together with novel furan oxygenated structures have been identified and quantified for the first time. In addition, the formation of lignin carbohydrate complexes bonds has been hypothesized at low severity and L/S. Based on the obtained data we were able to formulate a possible outlook of the occurring reactions during the hydrothermal treatment. Overall, such detailed structural information bridges the gap from process engineering to sustainable product development.

Quantitative Extraction of p-Coumaric Acid and Ferulic Acid in Different Gramineous Materials and Structural Changes of Residual Alkali Lignin

Ferulic acid (FA) and p-coumaric acid (pCA) in bagasse, wheat straw, corn straw, and corncob were extracted by alkaline hydrolysis and characterized by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). It was found that the FA and most of the pCA in gramineous biomass could be dissociated and released after being treated with 1 M NaOH at 100°C for 4 h. The yields of pCA/FA in bagasse, wheat straw, corn straw, and corncob determined by GC-FID are 39.8/11.5, 13.7/11.0, 28.0/11.0, and 35.1/14.5 mg/g, respectively. The raw materials and the treated solid residues were characterized by gel-state 2D Heteronuclear Single Quantum Coherence Nuclear Magnetic Resonance (2D HSQC NMR). It was found that only a small amount of lignin was detected in the residue after alkali treatment, indicating that the alkali treatment conditions can effectively cleave the FA and pCA. Additionally, the lignin in the alkali solution was recovered and characterized by 2D HSQC NMR. The FA was not able to be detected by NMR, whereas a small amount of pCA remained in the alkali lignin. This study reveals the structural change of residual lignins during the quantitative isolation of FA and pCA, which is essential for the selective isolation of pCA/FA and valorization of residual alkali lignin.

Using NMR Titration Experiments to Study E. coli FAS-II- and AcpP-Mediated Protein-Protein Interactions.

Acyl carrier proteins (ACPs) are central to many primary and secondary metabolic pathways. In E. coli fatty acid biosynthesis (FAB), the central ACP, AcpP, transports intermediates to a suite of partner proteins (PP) for iterative modification and elongation. The regulatory protein-protein interactions that occur between AcpP and the PP in FAB are poorly understood due to the dynamic and transient nature of these interactions. Solution-state NMR spectroscopy can reveal information at the atomic level through experiments such as the 2D heteronuclear single quantum coherence (HSQC). The following protocol describes NMR HSQC titration experiments that can elucidate biomolecular recognition events.

Nanolignin-based high internal phase emulsions for efficient protection of curcumin against UV degradation

As an emulsifier, lignin exhibits excellent UV resistance on drug-loaded emulsion systems for drug delivery. However, due to the structural variation and complexity of lignins from various origins, their UV shielding performance varies with the techniques for lignin extraction, which impacts properties and the protection efficiency of lignin-based HIPEs (high internal phase emulsions). In this work, lignin nanoparticles, prepared from three lignin preparations of Eucalyptus, were used in HIPEs delivery systems to protect curcumin from degradation by UV radiation. Structures of the lignin preparations were characterized using 2D HSQC (heteronuclear single-quantum coherence) NMR (nuclear magnetic resonance), 31P NMR, and GPC (gel permeation chromatography). The residual curcumin level after 36 h UV exposure in the nanolignin-based HIPEs was over 72 %, much higher than that (< 10 % after 24 h UV exposure) in the oil phase without lignin, indicating that the nanolignin-based HIPEs with enhanced UV shielding ability protect curcumin better. Of the three lignin preparations, AL (alkali lignin), with the lowest molecular weight, highest contents of phenolic hydroxyl and carboxyl groups, and highest S/G ratio, displayed the best anti-UV radiation ability and the most uniform nanoparticle size.

LigninGraphs: lignin structure determination with multiscale graph modeling

Lignin is an aromatic biopolymer found in ubiquitous sources of woody biomass. Designing and optimizing lignin valorization processes requires a fundamental understanding of lignin structures. Experimental characterization techniques, such as 2D-heteronuclear single quantum coherence (HSQC) nuclear magnetic resonance (NMR) spectra, could elucidate the global properties of the polymer molecules. Computer models could extend the resolution of experiments by representing structures at the molecular and atomistic scales. We introduce a graph-based multiscale modeling framework for lignin structure generation and visualization. The framework employs accelerated rejection-free polymerization and hierarchical Metropolis Monte Carlo optimization algorithms. We obtain structure libraries for various lignin feedstocks based on literature and new experimental NMR data for poplar wood, pinewood, and herbaceous lignin. The framework could guide researchers towards feasible lignin structures, efficient space exploration, and future kinetics modeling. Its software implementation in Python, LigninGraphs, is open-source and available on GitHub.Graphical abstract

Bamboo Lignin Fractions with In Vitro Tyrosinase Inhibition Activity Downregulate Melanogenesis in B16F10 Cells via PKA/CREB Signaling Pathway.

Cosmetic ingredients originating from natural resources have garnered considerable attention, and the demand for whitening ingredients is increasing, particularly in Asian countries. Lignin is a natural phenolic biopolymer significantly effective as a natural sunscreen, as its ultraviolet protection efficacy ranges from 250 to 400 nm. However, using different types of lignin as cosmetic ingredients is difficult owing to the heterogeneity of lignin and the lack of in vitro and in vivo safety and efficacy data. Thus, steam-exploded lignin (SEL) was prepared from bamboo, fractionated via successive organic solvent extraction, and sequentially fractionated using ethyl acetate, methanol, and acetone to investigate its potential as a natural whitening material. Gel permeation chromatography showed that the molecular weight of acetone-soluble and acetone-insoluble SEL fractions were the lowest and the highest, respectively. Monomer structures of the four lignin fractions were elucidated using 1H, 13C, and 2D heteronuclear single quantum coherence nuclear magnetic resonance and pyrolysis gas chromatography/mass spectrometry. The antioxidant and tyrosinase inhibition activities of the four fractions were compared. The methanol-soluble SEL fraction (SEL-F2) showed the highest antioxidant activity (except 2,2-diphenyl-1-picrylhydrazyl scavenging activity), and the enzyme inhibition kinetics were confirmed. In this study, the expression pattern of the anti-melanogenic-related proteins by SEL-F2 was confirmed for the first time via the protein kinase A (PKA)/cAMP-response element-binding (CREB) protein signaling pathway in B16F10 melanoma cells. Thus, SEL may serve as a valuable cosmetic whitening ingredient.

Facile preparation of lignin-containing cellulose nanofibrils from sugarcane bagasse by mild soda-oxygen pulping

Lignin-containing cellulose nanofibrils (LCNFs) with tunable lignin contents from sugarcane bagasse were directly prepared by low-temperature soda‑oxygen pulping combined with simple mechanical treatment. The residual lignin structure, morphology and physical dimensions of LCNFs, and properties of the relevant cellulose nanopapers (CNPs) were investigated. In situ 2D Heteronuclear Single Quantum Coherence (HSQC) NMR spectra showed β–O–4 linkages, ferulate, and para-coumarate were well preserved in the LCNFs. Compared with the cellulose nanofibrils (CNFs), LCNFs displayed a more uniform size and narrow diameter distribution. The corresponding CNPs exhibited outstanding mechanical properties (tensile strength reached 152.9 MPa), and excellent combined optical properties both in the UV blocking and visible light transparency. Moreover, the water contact angles (50.0–80.2°) of LCNFs were much higher than that of CNFs (21.7°). Direct preparation of LCNFs under mild condition would unlock the full potential of cellulosic materials and provide enhanced opportunities for cellulose to fabricate multi-functional and high-value materials.

In‐Depth Identification of Phenolics Fractionated from Eucalyptus Kraft Lignin

AbstractKraft lignin, the principal by‐product of the pulping industry, is an abundant yet highly underutilized aromatic resource. It is useful due to the vast scales involved as a source of fuels, chemicals, and functional materials when suitable postprocessing is applied. It is deemed to be a renewable alternative to fossil sources. Because of the extreme complexity of kraft lignin, in‐depth composition analysis and chemical structural identification are crucial for the development of effective valorization strategies. This work embarks on the characterization and identification of lignin‐derived phenolic compounds in representative hardwood (Eucalyptus) kraft lignin after selective fractionation using a single solvent. Advanced 2D heteronuclear single quantum coherence (HSQC) nuclear magnetic resonance (NMR), 31P NMR, and mass spectrometry in combination with synthetic authentic compounds are used for the structural identification of the low‐molecular‐weight fraction of kraft lignin. A total of 20 phenolic compounds, including several novel monomers (catechols), dimers (diarylethanes, diarylethenes, etc.), and trimers with triphenyl structures are systematically identified in the Eucalyptus kraft lignin. In addition, polysulfide is detected in the low‐molecular‐weight fraction, indicating that the oxidative polymerization of S2−/HS− occurrs during the kraft pulping process. An improved understanding of kraft lignin, especially the low‐Mw fraction, is expected to provide essential information for the selective fractionation and valorization of lignin.

Simultaneous elevation of acid-insoluble lignin and syringyl lignin is the preliminary Cd detoxification strategy in a Cd pollution-safe cultivar (Cd-PSC) of Brassica parachinensis L.

Cadmium (Cd) immobilization in the cell wall is responsible for Cd detoxification in Cd-accumulating cultivars. Lignin is the dominant constituent of the secondary cell wall (SCW), but its role in Cd compartmentalization is poorly understood. The mechanism of Cd compartmentalization by lignin was thus investigated herein. Lignin content and composition, as well as related genes and proteins, were analyzed in the Cd pollution-safe cultivar Brassica parachinensis L. ‘SJ19’. The lignin microstructural regions and Cd affinities were characterized by 2D-heteronuclear single quantum coherence nuclear magnetic resonance (HSQC NMR) and density functional theory (DFT). Lignin combined with 14.2% of the total Cd in SJ19, with a higher Cd distribution in acid-insoluble lignin (AIL). Additionally, the proportion of AIL increased under Cd treatment. The increase in the proportion of the lignin aromatic region syringyl (S) and decrease in the guaiacyl (G) proportion were in accordance with the significant up-regulation of peroxidase P7 and down-regulation of caffeoyl-CoA O-methyltransferase At1g67980 under Cd stress. Moreover, the Cd affinity associating with the lignin aromatic region ranked as S > G> H (p-hydroxyphenyl). Therefore, rather than lignin biosynthesis, the simultaneous elevation of AIL and S lignin was recognized as the preliminary strategy for lignin compartmentalization of Cd in SCW for the first time herein. This is beneficial for Cd detoxification in the Cd pollution-safe cultivar of B. parachinensis.

Monitoring transformation of two tropical lignocellulosics and their lignins after residence in Benin soils

Thermally assisted Hydrolysis and Methylation (THM), and 2D-heteronuclear single quantum coherence nuclear magnetic resonance (2D HSQC NMR) spectroscopy were used to monitor the transformation of ramial chipped wood (RCW) from Gmelina arborea and Sarcocephalus latifolius, together with their organosolv lignins, following soil incubation in Benin (West Africa). Mesh litterbags containing RCW were buried in soils (10 cm depth) and were retrieved after 0, 6, 12 and 18 months of field incubation. Chemical analysis showed that total carbohydrate content decreased, while total lignin content increased as RCW decomposition progressed. Ash and mineral content of RCW increased significantly after 18 months of decomposition in soil. Significant N-enrichment of the RCW was determined following 18 months incubation in soils, reaching 2.6 and 1.9 times the initial N-content for G. arborea and S. latifolius. Results of THM showed that the S + G sum, corresponding to lignins, increased with RCW residence time in the soils, in contrast to the response of compounds derived from carbohydrates, the sum of which decreased. Remarkably, lignin interunit linkages, most notably β-O-4′ aryl ethers, β-β′ resinol, β-5′ phenylcoumaran and p-PCA p-coumarate, survived after 18 months in the soil, despite their gradual decrease over the duration of the experiment.

Demethylation, phenolation, and depolymerization of lignin for the synthesis of lignin-based epoxy resin via a one-pot strategy

A one-pot method to synthesize demethylated-phenolated lignin (DPL) and demethylated-phenolated lignin-based epoxy resin (DPLINP) using phenol as a phenolic reagent and polymerization inhibitor was proposed in this study. This method avoids the occurrence of polycondensation caused by demethylation and simplifies the synthesis of lignin-based epoxy resins. Phenolated lignin (PL)-based epoxy resin (PLINP) and demethylated lignin (DL)-based epoxy resin (DLINP) were prepared to investigate the effects of different modification methods on the resulting lignin and epoxy resin. The results of 1H nuclear magnetic resonance (NMR), Fourier transform infrared, and gel permeation chromatography analyses indicated that the introduction of phenol could significantly reduce the occurrence of polycondensation while also decreasing the molecular weight and increasing the content of phenolic hydroxyl in DPL compared with DL and PL. 2D heteronuclear single quantum coherence NMR analysis was used to further investigate the structural changes of lignin during the modification process. The results obtained via dynamic mechanical analysis, flexural test, and impact test demonstrated that demethylated-phenolated lignin-based epoxy network (DPLIEN) possessed an improved cross-linking density, glass transition temperature, and mechanical performance compared with all other epoxy resins. Moreover, the polycondensation of DL caused by demethylation deteriorated the mechanical performance of demethylated lignin-based epoxy network (DLIEN). The thermal stability of DPLIEN was decreased compared with phenolated lignin-based epoxy network (PLIEN), as the removal of methoxy groups may have reduced the protective char layer formation in DPLIEN. This study provides a novel method for the modification of lignin and synthesis of lignin-based epoxy resins.

Catalytic Hydrogenolysis of Lignin: The Influence of Minor Units and Saccharides.

The precise elucidation of native lignin structures plays a vital role for the development of “lignin first” strategies such as reductive catalytic fractionation. The structure of lignin and composition of the starting material has a major impact on the product yield and distribution. Here, the differences in structure of lignin from birch, pine, reed, and walnut shell were investigated by combining detailed analysis of the whole cell wall material, residual enzyme lignin, and milled wood lignin. The results of the 2D heteronuclear single quantum coherence NMR analysis could be correlated to the product from Ru/C‐catalyzed hydrogenolysis if monomeric products from ferulate and p‐coumaryl and its analogous units were also appropriately considered. Notably, residual polysaccharide constituents seemed to influence the selectivity towards hydroxy‐containing monomers. The results reinforced the importance of adequate structural characterization and compositional analysis of the starting materials as well as distinct (dis)advantages of specific types of structural characterization and isolation methods for guiding valorization potential of different biomass feedstocks.

Chemistry of lignin and hemicellulose structures interacts with hydrothermal pretreatment severity and affects cellulose conversion.

Understanding of how the plant cell walls of different plant species respond to pretreatment can help improve saccharification in bioconversion processes. Here, we studied the chemical and structural modifications in lignin and hemicellulose in hydrothermally pretreated poplar and wheat straw using wet chemistry and 2D heteronuclear single quantum coherence nuclear magnetic resonance (NMR) and their effects on cellulose conversion. Increased pretreatment severity reduced the levels of β─O─4 linkages with concomitant relatively increased levels of β─5 and β─β structures in the NMR spectra. β─5 structures appeared at medium and high severities for wheat straw while only β─β structures were observed at all pretreatment severities for poplar. These structural differences accounted for the differences in cellulose conversion for these biomasses at different severities. Changes in the hemicellulose component include a complete removal of arabinosyl and 4-O-methyl glucuronosyl substituents at low and medium pretreatment severities while acetyl groups were found to be relatively resistant toward hydrothermal pretreatment. This illustrates the importance of these groups, rather than xylan content, in the detrimental role of xylan in cellulose saccharification and helps explain the higher poplar recalcitrance compared to wheat straw. The results point toward the need for both enzyme preparation development and pretreatment technologies to target specific plant species.

Facile adjusting the concentration of siliceous seed to obtain different HZSM-5 zeolite catalysts for effective catalytic depolymerization reaction of lignin

To improve lignin depolymerization reaction performance of HZSM-5 zeolite catalyst, we reported the effective catalytic depolymerization of rice husk lignin (RHL) to lignin phenolic monomer (LP) products over the different Si/Al mole ratios of HZSM-5 zeolite catalyst. Firstly, five samples comprising different Si/Al mole ratio of HZSM-5 zeolite catalyst were prepared by the physical method. The X-ray powder diffraction (XRD), scanning electron microscope (SEM), Brunauer–Emmett–Teller (BET), pyridine adsorption Fourier transform infrared spectroscopy (FT-IR), and temperature-programmed desorption of ammonia (NH3-TPD) were used to characterize various catalysts. Secondly, gas chromatography–mass spectrometry (GC-MS), 2D heteronuclear single quantum coherence (2D-HSQC), and gel permeation chromatography (GPC) were used to characterize various catalytic depolymerization products. The effect of different Si/Al molar ratios on the lignin conversion to LP products and the structural changes of residual lignin were analyzed. Finally, according to the results of LP products, we discovered that after the use of different Si/Al molar ratios of HZSM-5 zeolite catalysts, the content of acid in the different catalysts which increased with decreasing the Si/Al mole ratios. Among them, the A4P PM products (A4P: having a saturated or unsaturated aliphatic side chain in C4 position) increased from 0.58% (SA560, Si/Al: 560) to 1.83% (SA70, Si/Al: 70), the C6P PM products (C6P: having no side chain in C4 position of G, S, and H structure) increased from 1.53% (SA560, Si/Al: 560) to 3.41% (SA70, Si/Al: 70). Finally, the highest 6.05% PM products yield appeared in the SA70 (Si/Al: 70) catalytic system. It is worth noting that PM products produced by this HZSM-5 zeolite catalyst SA70 have great potential to be a promising renewable alternative to fossil resources.

Optimization of Lignin Extraction Variables by Response Surface Methodology from Pine Saw Dust, and Quantification of Major Structural Units in Isolated Lignin Fraction

A synergistic combination of dioxane, acetic acid, and HCl was investigated for lignin extraction from pine wood biomass. After initial screening of reagent combination, response surface methodology (RSM) was used to optimize the lignin yield with respect to the variables of time 24–72 h, solids loading 5–15%, and catalyst dose 5–15 mL. A quadratic model predicted 8.33% of the lignin yield, and it was further confirmed experimentally and through the analysis of variance (ANOVA). Lignin at optimum combination exhibited features in terms of derivatization followed by reductive cleavage (DFRC) with a value of (305 µmol/gm), average molecular weights of 4358 and polydispersity of 1.65, and 2D heteronuclear single quantum coherence nuclear magnetic resonance spectrum (2D-HSQC NMR) analysis showing relative β-O-4 linkages (37.80%). From here it can be suggested that this fractionation can be one option for high quality lignin extraction from lignocellulosic biomass.

Structural characteristics of plant cell wall elucidated by solution-state 2D NMR spectroscopy with an optimized procedure

AbstractA method was developed for rapid qualitative determination of lignocellulose in the tobacco cell wall by utilizing 2D heteronuclear single quantum coherence NMR spectra (2D HSQC NMR). Traditional methods for analyzing the structure of lignocellulose involve many steps of separation and extraction, which is labor-intensive. In this work, the whole cell wall was milled and dissolved in deuterium solvent. The solvent dimethylsulfoxide (DMSO-d6) containing hexamethylphosphoramide (HMPA-d18) enhanced swelling of the sample and gave high-resolution spectra. The tobacco samples are ball milled at different ball milling times, and the state of the particles is observed through an electron microscope, and then the probability of the particles being less than 5 µm is counted. Through the comparison of the abundance and integration of the peak signals in the spectra under different transmittances, it was determined that when the milling time was 6 h, the quality of the NMR spectra was the best. The optimum conditions of characterizing tobacco structure were DMSO-d6/HMPA-d18solution and 6 h milling time. Under these conditions, complete representation of the structure of lignocellulose and simplified process could be achieved.

Unlocking Structure-Reactivity Relationships for Catalytic Hydrogenolysis of Lignin into Phenolic Monomers.

Lignin depolymerization into aromatic monomers with high yields and selectivity is essential for the economic feasibility of biorefinery. However, the relationship between lignin structure and its reactivity for upgradeability is still poorly understood, in large part owing to the difficulty in quantitative characterization of lignin structural properties. To overcome these shortcomings, advanced NMR technologies [2D HSQC (heteronuclear single quantum coherence) and 31 P] were used to accurately quantify lignin functionalities. Diverse lignin samples prepared from Eucalyptus grandis with varying β-O-4 linkages were subjected to Pd/C-catalyzed hydrogenolysis for efficient C-O bond cleavage to achieve theoretical monomer yields. Strong correlations were observed between the yield of monomeric aromatic compounds and the structural features of lignin, including the contents of β-O-4 linkages and phenolic hydroxyl groups. Notably, a combined yield of up to 44.1 wt % was obtained from β-aryl ether rich in native lignin, whereas much lower yields were obtained from technical lignins low in β-aryl ether content. This work quantitatively demonstrates that the lignin reactivity for acquiring aromatic monomer yields varies depending on the lignin fractionation processes.

Mechanistic insights into the thermal deposition of highly thermal-stable jet fuel

Highly thermal-stable jet fuel plays an important role in the advanced supersonic aircrafts, but its oxidation to the insoluble deposits is a serious problem when serving as a coolant. However, there are few reports as to the deep insights of insoluble deposits formation. Here we apply the PetroOxy device to investigate the thermal oxidation and deposition behaviors of highly thermal-stable jet fuel, using decalin as the model jet fuel, in order to explore the formation mechanism of insoluble deposits. All oxidation products (gas, liquid and solid) of fuel at different oxidation stages were separated and carefully characterized. The initial oxidation of fuel produces hydroperoxides, which then decompose rapidly to produce gas products (H2, CO or CO2) as well as large amounts of polar species (soluble oxidized products, e.g., alcohols, ketones, and molecular growth products). Meanwhile, these polar monomer species condense to produce soluble macromolecular oxidatively reactive species (SMORS) and insoluble deposits. The SMORS amount increases during the overall oxidation process, but the amount of insoluble deposits increases only in the presence of oxygen. The characterizations of liquid chromatography/electrospray ionization mass spectrometry and solution-state 2D heteronuclear single quantum coherence NMR confirm that the concentration of highly polar macromolecular species in insoluble deposits is much higher than that in SMORS, which causes the precipitation of the insoluble deposits from the bulk fuel. We further propose the detailed formation process and chemical structures of the insoluble deposits during the autoxidation of highly thermal-stable jet fuel, which would be helpful for a better understanding of the deposition mechanism of jet fuel and the improvement of its thermal stability.

High-quality and phenolic monomer-rich bio-oil production from lignin in supercritical ethanol over synergistic Ru and Mg-Zr-oxide catalysts

The efficient depolymerization of technical lignin to produce high-quality and phenolic monomer-rich bio-oil is challenging owing to the inherent recalcitrant structure of lignin. In addition, the phenolic fragments formed during lignin depolymerization are highly reactive and easily undergo rapid repolymerization to yield undesired heavy oils or char. In the present work, we report a new hybrid catalyst of Ru/C combined with MgO/ZrO2 that is highly effective at depolymerizing lignin to high-quality bio-oil by a cooperative catalysis of Ru-catalyzed reductive depolymerization and MgO/ZrO2-catalyzed stabilization of the reactive phenolic monomers through in-situ capping of the phenol repolymerization initiator, i.e., formaldehyde, by reaction with ethanol. A screening study of various catalyst combinations, including transition metal catalysts such as Pd, Ni, and Ru supported on carbon or Al2O3 as well as basic oxide catalysts such as MgO, MgO/ZrO2, ZrO2, and Mg-Al mixed oxides, revealed that Ru/C–MgO/ZrO2 was the only combination that had a significant positive synergistic catalytic effect on lignin depolymerization, thereby highlighting its unique and exceptional activity. To elucidate the synergistic roles of Ru and MgO/ZrO2 in lignin depolymerization, their individual and integrated catalysis as well as the effect of the Mg/Zr ratio were systematically investigated through a comprehensive analysis of the bio-oil products using several techniques, including 2D heteronuclear single quantum coherence nuclear magnetic resonance spectroscopy (HSQC-NMR). A high bio-oil yield of 76.2 wt% with a low molecular weight of 401 g/mol, large HHV of 34.47 MJ/kg, and high phenolic monomer yield of 31.44 wt% was successfully obtained over the integrated catalyst of Ru/C and MgO/ZrO2 (Mg/Zr = 3) at 350 °C and 30 bar-H2 after 4 h.