Conversion Of Lignin Model Compounds Research Articles

Crystalline porous materials for catalytic conversion of lignin‐related substances

AbstractThe conversion of the biomass into eco‐friendly fuels and chemicals has been extensively recognized as the essential pathway to achieve the sustainable economy and carbon neutral society. Lignin, as a kind of promising biomass energy, has been certified to produce the high‐valued chemicals and fuels. Numerous efforts have been made to develop various catalysts for lignin catalytic conversion. Both metal‐organic frameworks (MOFs) and covalent organic frameworks (COFs) belong to very important heterogeneous porous catalysts due to their regular porous structures, high specific surface area, and precisely tailored diversities. In the review, the first part focused on the catalytic conversion of lignin, lignin model compounds, and lignin derivatives using the pristine MOFs, functional MOF composites, and MOF‐derived materials. The second part summarized the catalytic conversion of lignin model compounds using pristine COFs and functional COF composites. The review here mainly concentrated on the design of the materials, screening of catalytic conditions, and explorations of the corresponded mechanisms. Specifically, (1) we summarized the MOF‐ and COF‐based materials for the effects on the catalytic transformation of lignin‐related substances; (2) we emphasized the catalytic mechanism of C–C and C–O bonds cleavage together with the structure–activity relationships; (3) we in‐depth realized the relationship between the chemical/electronic/structural properties of the MOF‐ and COF‐based catalysts and their catalytic performance for lignin‐related substances. Finally, the challenges and future perspectives were also discussed on the catalytic conversion of lignin‐related substances by MOF‐ and COF‐based catalysts.

Hydrodeoxygenation of Lignin-Based Compounds over Ruthenium Catalysts Based on Sulfonated Porous Aromatic Frameworks.

Bifunctional catalysts are a major type of heterogeneous catalytic systems that have been widely investigated for biomass upgrading. In this work, Ru-catalysts based on sulfonated porous aromatic frameworks (PAFs) were used in the hydrodeoxygenation (HDO) of lignin-derived compounds: guaiacol, veratrole, and catechol. The relationship between the activity of metal nanoparticles and the content of acid sites in synthesized catalysts was studied. Herein, their synergy was demonstrated in the Ru-PAF-30-SO3H/5-COD catalyst. The results revealed that this catalytic system promoted partial hydrogenation of lignin-based compounds to ketones without any further transformations. The design of the Ru-PAF-30-SO3H/5-COD catalytic system opens a promising route to the selective conversion of lignin model compounds to cyclohexanone.

Hierarchical Porous Activated Carbon-Supported Ruthenium Catalysts for Catalytic Cleavage of Lignin Model Compounds

The catalytic conversion of lignin model compounds was performed using Ru/C catalysts and an autoclave reactor. The Ru/C catalysts were prepared by the impregnation method using highly porous homemade activated carbon and characterized by XRD, SEM, and specific surface area. The catalytic reactions were performed in a high pressure/temperature reactor at different temperatures and with different solvents. The results showed that the novel Ru/C catalysts prepared from carbon supports activated by the KOH agent showed higher catalytic activity than the commercial catalyst. Ethanol and 2-propanol were suitable solvents for the cleavage of the β–O–4 ether bond of 2-phenoxy-1-phenyl ethanol (~65–70% conversion) over a Ru/C-KOH-2 catalyst at 220 °C in comparison to tert-butanol and 1-propanol solvents (~43–47% conversion of 2-phenoxy-1-phenyl ethanol). Also, the increase in reaction temperature from 200 °C to 240 °C enhanced the cleavage of the ether bond with an increase in phenol selectivity from 9.4% to 19.5% and improved the catalytic conversion of 2-phenoxy-1-phenyl ethanol from 46.6% to 98.5% over the Ru/C-KOH-2 catalyst and ethanol solvent. The Ru/C-KOH-2 catalyst showed outstanding conversion (98.5%) of 2-phenoxy-1-phenylethanol at 240 °C, 1h, ethanol solvent. This novel hierarchical porous activated carbon-supported ruthenium catalyst (Ru/C-KOH-2) can be applied for the further conversion of the lignin compound.

Water promoted photocatalytic Cβ-O bonds hydrogenolysis in lignin model compounds and lignin biomass conversion to aromatic monomers

Photocatalysis has proved its potential in cleaving the Cβ-O linkages between the natural aromatic units in lignin biomass and converting abundant lignin biomass to valuable aromatic monomer products. However, the slow reaction rate and low selectivity for aromatic monomers still hinder its future industrial implementation. To address these challenges in photocatalytic Cβ-O bond fragmentation, a Zn/S rich phase zinc indium sulfide photocatalyst was developed to promote hydrogenolysis of Cβ-O linkages in lignin. In this work, water is for the first time, used as the hydrogen donor and can significantly promote the photocatalytic process by eliminating the limitation of protons supply. The reaction selectivity for aromatic monomers increased by 170% and PP-ol conversion rate raised by 58% comparing to the reaction condition without water. Notably, complete conversion of lignin model compounds with an expectational improved reaction rate and over 90% selectivity for aromatic monomers have been achieved in this study. The isotopic labeling experiments and kinetic isotope effects (KIE) measurements also indicate that the dissociation of the O–H bond in water which provides protons to the Cβ-O bond hydrogenolysis process is a critical step to this reaction. Mechanistic studies reveal that the dehydrogenated radical intermediates are initially generated by the oxidation of photogenerated holes, and the protons generated from photocatalytic water splitting are superior in facilitating the subsequently hydrogenolysis process of Cβ-O bonds. This study provides a new and effective strategy to promote the cleavage of Cβ-O linkages and is helpful for the future development of photocatalytic lignin valorization.

Analysis of Electrochemical Conversion of Lignin Model Compounds

Electrochemical conversion of biomass like lignin to generate value-added products is interesting, but has not been commercialized to date. One barrier to a viable industrial process is understanding the reaction mechanism. The mechanism is difficult to elucidate because lignin is a complex biopolymer, and conversion results in a wide range of products. Simpler compounds that have similar bonds to lignin have been used to better understand the mechanism controlling electrochemical conversion. In this seminar, we will present results from our efforts investigating electrochemical conversion of lignin model compounds on NiCo electrocatalysts. As part of this effort, we have employed statistical analysis to understand the changes imposed on the lignin model compound during electrochemical oxidation. We will present our analytical results and discuss the implications for understanding the primary electrochemical conversion mechanism.

Electrochemical Conversion of Lignin Model Compounds

Electrochemical conversion of biomass, including lignin, is one possible means of generating industrial chemicals like aromatic compounds from a renewable raw material. The complexity of much of this raw material, however, makes controlling the major product classes difficult. To complicate matters, in many cases the primary reaction mechanism is not clear. Indeed, there may be several competing reaction pathways. It may be that during early-stage research efforts, clearer information can be achieved by investigating electrochemical conversion of smaller, more simple model compounds that share some common features with the larger biomass polymer. In this study, we investigate electrochemical conversion of lignin model compounds on non-precious metal electrocatalysts with subsequent analysis using techniques including GC-MS. We investigate possible electrochemical oxidation mechanisms, including whether the dominant mechanism may be driven by hydroxyl radical mediation. The focus of this talk will be on the electrochemical process and analysis of the products leading to identification of the most likely reaction pathways.

Microwave-assisted chemistry: parametric optimization for catalytic degradation of lignin model compounds in imidazolium-based ILs

Lignin, a readily available form of biomass with a potential source of aromatic chemical compounds, has not been fully utilized due to its complex structure. Hence, this study aims to elaborate and optimize the effects of parametric microwave conditions for the catalytic degradation of lignin model compounds. In addition to that, 41 types of imidazolium-based Ionic liquids were employed for the conversion of lignin model compounds such as guaiacol and benzyl phenyl ether. The microwave-assisted conversion of lignin model compounds in imidazolium-based ionic liquids was performed at optimum applied microwave power 700 W and 30-min irradiation time. The percentages conversion and yield were quantified using high-performance liquid chromatography (HPLC) analysis. Results revealed that the chloride anion-based ionic liquids exhibited better nucleophilic behavior and catalyzed the cleavage of ether-based compounds efficiently under microwave irradiation. Among the imidazolium-based ionic liquids, 1H-methylimidazolium chloride ([1H-MIM][Cl]) exhibited better performance with guaiacol conversion and catechol yield of 99% and 81%, respectively. Therefore, the microwave-assisted technique was found to be more promising than conventional methods for the ionic liquid-based catalytic degradation of lignin model compounds.

Selective conversion of lignin model veratryl alcohol by photosynthetic pigment via photo-generated reactive oxygen species

Abstract The selective conversion of veratryl alcohol (VA), a model compound of lignin, to produce veratraldehyde was investigated in a simple light-driven system consisting of photosynthetic pigment chlorophyllin and VA. Irradiation experiments and liquid chromatography tandem mass spectrometry analysis indicated that light in the wavelength range of 310–420 nm induced the efficient conversion of veratryl alcohol to veratraldehyde (76% in 4 h). Results from differential pulse voltammetry and linear sweep voltammetry indicated that light enhanced the two reduction peaks of chlorophyllin and boosted the photocurrent from 2.7 to 3.8 μA/cm2 at 0.8 V between excited chlorophyllin and electrodes, confirming the occurrence of photoelectrons transferring between excited chlorophyllin and oxygen in the presence of light. Quenching experiments further demonstrated that superoxide anion radicals, produced via one-electron reduction reaction between triplet chlorophyllin and oxygen, were responsible for the efficiently selective conversion of veratryl alcohol to veratraldehyde. Our results not only contribute to revealing the role of reactive oxygen species and excited photosynthetic pigment chlorophyllin in the photochemical conversion of lignin model compounds, but also provide ideas for applications of chemical processing in lignin utilization for valuable chemical production.

Heterogeneous Catalyzed Thermochemical Conversion of Lignin Model Compounds: An Overview.

Thermochemical lignin conversion processes can be described as complex reaction networks involving not only de-polymerization and re-polymerization reactions, but also chemical transformations of the depolymerized mono-, di-, and oligomeric compounds. They typically result in a product mixture consisting of a gaseous, liquid (i.e., mono-, di-, and oligomeric products), and solid phase. Consequently, researchers have developed a common strategy to simplify this issue by replacing lignin with simpler, but still representative, lignin model compounds. This strategy is typically applied to the elucidation of reaction mechanisms and the exploration of novel lignin conversion approaches. In this review, we present a general overview of the latest advances in the principal thermochemical processes applied for the conversion of lignin model compounds using heterogeneous catalysts. This review focuses on the most representative lignin conversion methods, i.e., reductive, oxidative, pyrolytic, and hydrolytic processes. An additional subchapter on the reforming of pyrolysis oil model compounds has also been included. Special attention will be given to those research papers using "green" reactants (i.e., H2 or renewable hydrogen donor molecules in reductive processes or air/O2 in oxidative processes) and solvents, although less environmentally friendly chemicals will be also considered. Moreover, the scope of the review is limited to those most representative lignin model compounds and to those reaction products that are typically targeted in lignin valorization.

Activating molecular oxygen with Au/CeO2 for the conversion of lignin model compounds and organosolv lignin.

Au/CeO2 was demonstrated to be a high efficiency catalyst for the conversion of 2-phenoxyacetophenol (PP-ol) employing O2 as an oxidant and methyl alcohol as the solvent without using an erosive strong base or acid. Mechanistic investigations, including emission quenching experiments, electron spin-resonance (ESR) and intermediate verification experiments, were carried out. The results verified that the superoxide anion activated by Au/CeO2 from molecular oxygen plays a vital role in the oxidation of lignin model compounds, and the cleavage of both the β-O-4 and Cα–Cβ linkages was involved. Au/CeO2 also performed well in the oxidative conversion of organosolv lignin under mild conditions (453 K), producing vanillin (10.5 wt%), methyl vanillate (6.8 wt%), methylene syringate (3.4 wt%) and a ring-opened product. Based on the detailed characterization data and mechanistic results, Au/CeO2 was confirmed to be a promising catalytic system.

Spectroscopic Investigation of Thermochemical Depolymerization of Lignin Model Compounds in the Presence of Novel Liquidlike Nanoparticle Organic Hybrid Solvents for Efficient Biomass Valorization

This study reports the thermochemical transformation of lignin model compounds using nanoparticle organic hybrid materials (NOHMs). NOHMs have recently been developed as an emerging class of self-suspended nanoparticle solvent systems created by ionically or covalently grafting organic oligomers or polymers (canopy) onto surface-modified inorganic nanoparticles (core). Because NOHMs exhibit negligible vapor pressure with the ability to tailor physicochemical properties, they could be a promising catalytic solvent for the lignin thermochemical conversion process. The thermochemical conversion of lignin model compounds was achieved with the synthesized NOHM at an elevated temperature of 473 K, and the results were compared with the case of the ionic liquid [EMIM][ESO4]. The fractured moieties of the lignin model compounds were qualitatively identified by ATR FT-IR and 2D COSY NMR spectroscopies. The results indicated that the NOHM decomposed the C–O and/or C–C bonds of lignin model chemicals more efficientl...

Effects of HZSM-5 on volatile products obtained from the fast pyrolysis of lignin and model compounds

This study aimed to experimentally investigate the effect of HZSM-5 on the distribution of volatile products, especially carbon monoxide (CO), C1–C5 hydrocarbons and aromatic hydrocarbons (AHs) during catalytic pyrolysis of lignin and lignin model compounds. Catechol was pyrolyzed using a two-stage tubular reactor (TS-TR) connected to a gas chromatography system over HZSM-5 at 550–950 °C. Forty-three products, including four inorganic gases, twenty C1–C5 hydrocarbons, and nine AHs were quantified using three GC-columns. Results indicated that HZSM-5 accelerated the catechol conversion with a large amount of CO and AHs produced. C1–C5 hydrocarbons were formed during non-catalytic pyrolysis of model compounds, and consumed quickly during HZSM-5 catalytic pyrolysis of catechol. Catalytic pyrolysis of phenol, guaiacol and syringol was carried out at 650 °C in the TS-TR over HZSM-5. HZSM-5 obviously promoted the conversion of lignin model compounds, and largely increased the yield of volatile products especially CO and AHs. Three lignin samples were also catalytically pyrolyzed over HZSM-5 in the TS-TR at 650 °C. HZSM-5 increased the yield of C2-C3 hydrocarbons and AHs, and reduced the yield of oxygenated compounds. HZSM-5 could promote the formation of AHs (lower than 10 wt%) during lignin pyrolysis, but not as obviously as during model compounds pyrolysis (higher than 19 wt%). High yields of char and tar would account for the low catalytic efficiency of HZSM-5 during lignin pyrolysis.

Rapid microwave-hydrothermal conversion of lignin model compounds to value-added products via catalytic oxidation using metal organic frameworks

Microwave irradiation is an effective method for faster heating to shorten reaction time of oxidative valorization of lignin. However, studies using microwave irradiation for lignin oxidation all employ homogeneous catalysis. Thus, this study aims to investigate heterogeneous catalytic oxidation of lignin under microwave irradiation. Especially, metal organic frameworks (MOFs) are adopted as transition metal-containing heterogeneous catalysts for lignin oxidation. In particularly, MOFs (MIL-101 (Cr), MIL-101 (Fe), UiO-66, HKUST-1, and MOF-801) are also prepared using microwave irradiation and used as for oxidative conversion of a model lignin compound, vanillyl alcohol (VAL), to the valuable products, vanillin (VN) and vanillic acid (VAC), using H2O2 as an oxidant. While the tested MOFs all exhibit catalytic activities for VAL conversion to VN/VAC, MIL-101 and MOF-801 appear to be relatively effective. Through investigating the effect of temperature, VAL conversion to VN/VAC is less favorable at higher temperature possibly due to degradation of H2O2 at high temperatures. While a higher dosage of H2O2 increases VAL conversion, the additionally added H2O2 seems to further oxidize VN to VAC instead of converting more VAL to VN. Through the EPR analyses, the mechanism of VAL conversion to VN/VAC may be attributed to both the OH-based and non-OH• routes. The most effective MOF, MOF-801, also exhibited very similar catalytic activities over several cycles. The results indicate that MOFs can convert VAL to valuable products of VN and VAC within a very short time (10 min) under microwave irradiation. MOF-801 was also validated as a promising MOF for VAL conversion.

Transition-metal-free conversion of lignin model compounds to high-value aromatics: scope and chemoselectivity

A simple transition-metal-free base-promoted oxidative dehomologation of dilignol model compounds to the corresponding aromatic alcohols and acids was demonstrated.

Hydrogenolysis of lignin model compounds into aromatics with bimetallic Ru-Ni supported onto nitrogen-doped activated carbon catalyst

Lignin is the most abundant and renewable resources for production of natural aromatics. In this paper, new bimetallic catalytic system of Ru and Ni supported onto nitrogen-doped activated carbon (Ru-Ni-AC/N) was developed and its performances on hydrogenolysis of lignin model compounds under mild reaction conditions (1.0MPa, 230°C, in aqueous) were investigated. The results indicate that Ru-Ni-AC/N was a highly active, selective and stable catalyst for the conversion of lignin model compounds into aromatics, e.g. phenol, benzene and their derivatives. As verified by BET, XRD, HRTEM, XPS, H2-TPR and ICP-MS, the strong synergistic effects between i) Ru and Ni and ii) metals and N-groups were contributed to its excellent aromatics selectivity. What’s more, the introduction of electron rich N atoms on AC was beneficial to the stabilization of metal particles, which greatly enhanced the durability of the catalyst.

Engineering Towards Catalytic Use of Fungal Class-II Peroxidases for Dye-Decolorizing and Conversion of Lignin Model Compounds

Engineering Towards Catalytic Use of Fungal Class-II Peroxidases for Dye-Decolorizing and Conversion of Lignin Model Compounds

Conversion of lignin model compounds by Pseudomonas putida KT2440 and isolates from compost

Starting from mature vegetable compost, four bacterial strains were selected using a lignin-rich medium. 16S ribosomal RNA identification of the isolates showed high score similarity with Pseudomonas spp. for three out of four isolates. Further characterization of growth on mixtures of six selected lignin model compounds (vanillin, vanillate, 4-hydroxybenzoate, p-coumarate, benzoate, and ferulate) was carried out with three of the Pseudomonas isolates and in addition with the strain Pseudomonas putida KT2440 from a culture collection. The specific growth rates on benzoate, p-coumarate, and 4-hydroxybenzoate were considerably higher (0.26–0.27 h−1) than those on ferulate and vanillate (0.21 and 0.22 h−1), as were the uptake rates. There was no direct growth of P. putida KT2440 on vanillin, but instead, vanillin was rapidly converted into vanillate at a rate of 4.87 mmol (gCDW h)−1 after which the accumulated vanillate was taken up. The growth curve reflected a diauxic growth when mixtures of the model compounds were used as carbon source. Vanillin, 4-hydroxybenzoate, and benzoate were preferentially consumed first, whereas ferulate was always the last substrate to be taken in. These results contribute to a better understanding of the aromatic metabolism of P. putida in terms of growth and uptake rates, which will be helpful for the utilization of these bacteria as cell factories for upgrading lignin-derived mixtures of aromatic molecules.

Conversion of lignin model compounds under mild conditions in pseudo-homogeneous systems

A novel pseudo-homogeneous catalyst system consisting of noble metal nanoparticles and ionic liquids is developed for the selective reductive cleavage of C–O and hydrodeoxygenation under mild conditions.

Microwave-assisted fast conversion of lignin model compounds and organosolv lignin over methyltrioxorhenium in ionic liquids

Fast depolymerization of β-O-4 model compounds and organosolv lignin to aromatic chemicals over methyltrioxorhenium in ionic liquids without oxidant/reducing agent under microwave irradiation is developed.

Catalytic decomposition of phenethyl phenyl ether and benzyl phenyl ether to aromatics over Pd/Cs xH 3.0− xPW 12O 40 ( x = 2.0, 2.3, 2.5, 2.8, and 3.0)

Palladium catalysts supported on cesium-exchanged heteropolyacid (Pd/Cs x H 3.0− x PW 12O 40, x = 2.0–3.0) were prepared and applied to the decomposition of lignin model compounds. Phenethyl phenyl ether and benzyl phenyl ether were employed as lignin model compounds for representing β-O-4 and α-O-4 bonds in lignin, respectively. Phenol, ethylbenzene, benzene, and toluene were mainly produced by the decomposition of phenethyl phenyl ether. On the other hand, phenol, benzene, and toluene were mainly produced by the decomposition of benzyl phenyl ether. Conversion of lignin model compounds (phenethyl phenyl ether and benzyl phenyl ether) and total yield for main products were closely related to the surface acidity of Cs x H 3.0− x PW 12O 40. Conversion of lignin model compounds and total yield for main products increased with increasing surface acidity of Cs x H 3.0− x PW 12O 40. Among the catalysts tested, Pd/Cs 2.5H 0.5PW 12O 40 with the largest surface acidity of Cs 2.5H 0.5PW 12O 40 showed the highest conversion of lignin model compounds and total yield for main products.