Photocatalytic depolymerization of lignin into aromatic compounds is of great significance but extremely challenging, hindered by the stable interunit C-C bonds with high dissociation energies. Herein, we developed a phosphorus-doped carbon nitride (P-x-CN) photocatalyst for the selective cleavage of C-alpha-C-beta bonds in lignin model compounds under visible light at room temperature. This approach achieves a nearly complete conversion (> 99.9%) of 2-phenoxy-1-phenylethanol, along with high yields of benzaldehyde dimethyl acetal (91.1%) and benzyl formate (56.3%). Mechanistic investigations reveal that the activation of the C-beta-H bond is crucial for the transformation to occur. Meanwhile, the introduction of phosphorus accelerates the separation efficiency of charge carriers, thereby enhancing the photocatalytic performance of the P-x-CN. This work demonstrates the potential of phosphorus-doped carbon nitride for the high-selectivity photocatalytic cleavage of the C-C bond in lignin to aromatic chemicals.

Im-V/CeO 2 nanorods achieve ~90% conversion and 98% benzaldehyde selectivity in photocatalytic C–C bond cleavage of lignin β -1 model, facilitated by highly dispersed, low-polymerized VO x promoting charge separation and oxygen vacancy formation.

The transformation of aldehydes and ketones into acetals and ketals has garnered significant attention due to their wide applications as fragrances, bio-oil additives, and organic synthetic intermediates. Conventional acetalization methods, however, often rely on corrosive acids or stoichiometric additives, necessitating harsh conditions and increasing production costs. Here, the development of a phosphorus-doped carbon catalyst is presented, that enables the acetalization of aldehydes and ketones into acetals and ketals under mild conditions (e.g., 60 degrees C, atmospheric pressure). This catalyst achieves a high yield of 2-phenyl-1,3-dioxolane (87.1%) from benzaldehyde and exhibits exceptional stability, operating continuously for 120 h in a continuous fixed-bed reactor. In the continuous reaction, the yield of 2-phenyl-1,3-dioxolane remains over 96% in the first 18 h and slightly decreases to 86% after 120 h of continuous operation. Comprehensive physicochemical characterizations reveal that phosphorus acts as a Lewis acid sites and plays a critical role in modulating the Lewis acid sites of the PC catalysts. This work highlights the significance of optimizing acid properties for the efficient acetalization reaction, offering a promising approach to sustainable chemical synthesis.

The oxidation of lignin model compounds to esters via C-C bond cleavage has attracted considerable attention, as esters could be used as important polymer precursors and pharmaceutical intermediates. However, most studies focus on designing homogeneous or noble metal catalysts and conducting the reactions under basic conditions. Here, we report an efficient process for the C-C bond cleavage of lignin model compounds and selectively producing esters over different shaped CeO2 (i.e., nanospheres (S), nanorods (R), nanoparticles (P), and nanocubes (C)) under base-free conditions. Specifically, the yield of methyl anisate from the aerobic oxidation of 1-(4-methoxyphenyl)ethanol reaches 77.6% over CeO2-S in one hour (91% in 9 h), exhibiting higher performance compared to other evaluated CeO2 catalysts (6.4%-40.2%). Extensive characterizations and experimental investigations reveal that the density of weak base sites and oxygen vacancies on the CeO2 surface is positively correlated with the yield of methyl esters. Furthermore, the reaction pathway is investigated, which confirms that 1-(4-methoxyphenyl)ethanol first undergoes two reactions (i.e., etherification and dehydrogenation) to produce intermediates of 1-methoxy-4-(1-methoxy-ethyl)-benzene and 1-(4-methoxyphenyl)ethanone, respectively, followed by a series of functional group transformations to generate the targeted methyl anisate ultimately.

The efficient hydrogenolysis of esters to alkanes is the key protocol for producing advanced biofuels from renewable plant oils or fats. Due to the low reactivity of the carbonyl group in esters, a high reaction temperature (>250 degrees C) is the prerequisite to ensure high conversion of esters. Here, we report a highly dispersed MoOx-Ru/C bimetallic catalyst for the efficient hydrogenolysis of esters to alkanes under 150 degrees C. The optimal catalyst exhibits >99% conversion of methyl stearate and 99% selectivity to diesel-range alkanes, reaching a high rate of up to 2.0 mmol g(cat)(-1) h(-1), 5 times higher than that of Ru/C catalyst (MoOx/C is inert). Integrated experimental and theoretical investigations attribute the high performance to the abundant MoOx-Ru interfacial sites on the catalyst surface, which offers high activity for the C-O cleavage of esters. Furthermore, the dispersed MoOx species significantly weaken the hydrocracking activity of the metallic Ru for C-C bonds, thus yielding alkane products without carbon loss. This study provides a facile and novel strategy for the design of high-performance heterogeneous catalysts for the hydrodeoxygenation of biomass-derived esters to alkane products. (c) 2025, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Lignin and plastics are two of the most extensively used polymeric materials in contemporary industrial systems. As a biomass-derived polymer containing abundant aromatic units, lignin has emerged as a prime candidate for replacing fossil fuels owing to its renewable nature. Paradoxically, as synthetic polymer materials with aromatic structures similar to those of lignin, plastics have become a critical environmental challenge owing to their accumulation over recent decades. The inherent stabilities of lignin and plastics pose significant challenges for their efficient utilization and recycling, making catalytic depolymerization a focal research point in recent years. Innovative catalytic strategies that enable the high-yield production of aromatic compounds through the catalytic hydroprocessing of lignin and plastic waste have recently emerged. These methods offer opportunities for the conversion of recalcitrant polymers into valuable chemicals and sustainable fuels. This paper comprehensively reviews these advancements and emphasizes their potential applications in catalytic hydroprocessing for biofuel production. Additionally, it highlights the latest developments in the high-value upgrading of lignin derivatives and underscores their significance in building a sustainable chemical industry. The review examines the entire value chain from lignin and plastic depolymerization to the production of high-value chemicals to outline the potential for enhancing the efficiency of sustainable processes. This emphasizes the critical role of developing novel cost-effective methodologies for the catalytic depolymerization of lignin and plastic waste. These advancements are expected to play a pivotal role in fostering a sustainable economy and addressing pressing environmental challenges.

Catalytic production of several representative active pharmaceutical ingredients (APIs) from lignin.

储能技术能够将能源以物理或化学的方式储存,直至需要的时候再释放出来.现阶段,储能相关的材料往往都是由不可再生资源制备,并且大多都采用高污染、高成本的方式生产.在当前能源危机加剧和气候变暖的威胁下,使用可再生的生物质资源替代传统的石化资源显得尤为重要.作为含量最丰富的天然高分子材料,木质纤维素和甲壳素在合成电池相关材料(尤其是电极、固态电池、隔膜)和生物燃料方面显示出了举足轻重的作用.文章综述了木质素、纤维素、半纤维素以及甲壳素4 种典型的生物质大分子在合成生物基电极、生物基固态电解液、生物基电池隔膜以及生物燃料方面的研究进展,并展望了未来研究的重点方向.

Dopamine is not only a widely used commodity pharmaceutical for treating neurological diseases but also a highly attractive base for advanced carbon materials. Lignin, the waste from the lignocellulosic biomass industry, is the richest source of renewable aromatics on earth. Efficient production of dopamine direct from lignin is a highly desirable target but extremely challenging. Here, we report an innovative strategy for the sustainable production of dopamine hydrochloride from softwood lignin with a mass yield of 6.4 wt.%. Significantly, the solid dopamine hydrochloride is obtained by a simple filtration process in purity of 98.0%, which avoids the tedious separation and purification steps. The approach begins with the acid-catalyzed depolymerization, followed by deprotection, hydrogen-borrowing amination, and hydrolysis of methoxy group, transforming lignin into dopamine hydrochloride. The technical economic analysis predicts that this process is an economically competitive production process. This study fulfills the unexplored potential of dopamine hydrochloride synthesis from lignin.

High-value utilization of biomass has been driven by increasingly growing industrial demands.Herein, we offer a strategy composed of depolymerization and esterification reaction of lignin to transfer to bio-oil with high liquid yield (79.75~85.25%),which is demonstrated as a high performance lubricant.Overall, the bio-oil has the excellent lubrication properties, where a significant wear reduction of 97.6% was observed as compared with polyethylene glycol 200.Meanwhile, the more ether and less acid in bio-oil could improve the anti-wear properties.This work provides a new application of utilizing lignin in advanced lubrication systems.

In this paper, liquefaction of sodium lignosulfonate (SL) over SO42-/TiO(2)catalyst in methanol/glycerol was investigated. Effects of temperature, time, the ratio of methanol to glycerol and catalyst dosage were also studied. It was indicated that optimal reaction condition (the temperature of 160 degrees C, the time of 1 h, solvent ratio (methanol/glycerol) of 2:1, catalyst dosage of 5 wt % (based on lignin input)) was obtained after sets of experiments. The maximum yields of liquefaction (89.8%) and bio-oil (86.8%) were gained under the optimal reaction conditions. Bio-oil was analyzed by elemental analysis, FT-IR and gas chromatogram and mass spectrometry (GC/MS). It was shown that the functional groups of bio-oil were enriched and calorific value of bio-oil was increased. Finally, it can be seen from GC/MS analysis that the type of products included alcohols, ethers, phenols, ketones, esters and acids. Phenolic compounds mainly consisted of G (guaiacyl)-type phenols.

Enzymatic hydrolysis lignin (EHL) used in this experiment was extracted from the bio-ethanol production residue by enzymatic hydrolysis method. With different modification methods, the purpose of this paper was to investigate the pyrolysis behavior and kinetics of lignin modified products via thermogravimetric analyzer coupled with Fourier transform infrared spectrometry (TG-FTIR). The emergence of specific functional groups detected by FTIR predicted that specific functional groups was grafted onto lignin successfully. Thermogravimetry/derivate thermogravimetry (TG/DTG) results showed that only the pyrolysis process of Lig-F (one of lignin modified products) was similar to that of Lig-C (purified lignin), and pyrolysis processes of other lignin-modified products had changed greatly. Moreover, pyrolysis properties of lignin modified products were different because of different grafting functional groups. In addition, the kinetics of Lig-F was conducted by two kinetic models (FWO: Flynn-Wall-Ozawa and KAS: Kissinger-Akahira-Sunose). Both methods obtained analogous values of activation energy, ranging from 157 kJ mol(-1) to 219 kJ mol(-1). This paper also gave a further evaluation of the application of lignin modified products in the field of flame retardants, which would better promote the multi-functional application of lignin.

In order to improve the thermal property of epoxy resin (EP), a lignin-based flame retardant was prepared. Focusing on the lignin-based flame retardant, this paper investigates its pyrolysis behavior and kinetics via a thermogravimetric analyzer coupled with Fourier transform infrared spectrometry (TG–FTIR). Based on the FTIR result, which showed a peak at 1222 cm−1, it was assigned a syringyl structure. Its absorption peak intensity was enhanced and this meant that the phenolization of the lignin was successful. Thermogravimetry/derivative thermogravimetry (TG/DTG) results showed that the carbon residues of F-lignin and F-lignin@APP were reduced to 33.5% and 37.5%, respectively. In addition, the maximum decomposition rate of F-lignin@APP20/EP is 11.8%/min, which is 8%/min and 4.7%/min lower than for EP and Al-lignin, respectively. The char residue of F-lignin@APP20/EP is 32.5%, which is much higher than for EP. Lower decomposition rate and higher char residue indicate the improvement of thermal stability of EP by F-lignin@APP. Moreover, the kinetics of Al-lignin20/EP and F-lignin@APP20/EP were conducted by two kinetic methods: Flynn-Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS). It was concluded that the pyrolysis process of Al-lignin 20/EP and F-lignin@APP 20/EP could be divided into three stages, while the value and growth rate of the activation energy of F-lignin@APP 20/EP were much higher than that of Al-lignin 20/EP in stage III.

This paper investigated the pyrolytic behaviors of enzymatic hydrolysis lignin (EHL) and EHL treated with steam explosion (EHL-SE) by pyrolysis-gas chromatography/mass spectrometer (Py-GC/MS). It was shown that the main component of the pyrolysis products was phenolic compounds, including G-type, H-type, S-type, and C-type phenols. With different treatment methods, the proportion of units in phenolic products had changed significantly. Meanwhile, proximate, elemental, and FTIR analysis of both lignin substrates were also carried out for a further understanding of the lignin structure and composition with or without steam explosion treatment. FTIR result showed that, after steam explosion treatment, the fundamental structural framework of the lignin substrate was almost unchangeable, but the content of lignin constituent units, e.g., hydroxyl group and alkyl group, evidently changed. It was noticeable that 2-methoxy-4-vinylphenol with 11% relative content was the most predominant pyrolytic product for lignin after steam explosion treatment. Combined with the above analysis, the structural change and pyrolysis product distribution of EHL with or without steam explosion treatment could be better understood, providing more support for the multi-functional utilization of lignin.

In this paper, liquefaction of sodium lignosulfonate (SL) over SO42−/TiO2 catalyst in methanol/glycerol was investigated. Effects of temperature, time, the ratio of methanol to glycerol and catalyst dosage were also studied. It was indicated that optimal reaction condition (the temperature of 160 °C, the time of 1 h, solvent ratio (methanol/glycerol) of 2:1, catalyst dosage of 5 wt % (based on lignin input)) was obtained after sets of experiments. The maximum yields of liquefaction (89.8%) and bio-oil (86.8%) were gained under the optimal reaction conditions. Bio-oil was analyzed by elemental analysis, FT-IR and gas chromatogram and mass spectrometry (GC/MS). It was shown that the functional groups of bio-oil were enriched and calorific value of bio-oil was increased. Finally, it can be seen from GC/MS analysis that the type of products included alcohols, ethers, phenols, ketones, esters and acids. Phenolic compounds mainly consisted of G (guaiacyl)-type phenols.

Three modified 1,2,4-trizaole derivatives were synthesized and compounded in pairs. Their structures were confirmed by 1H NMR and ESI-MS. Antibacterial tests were proceeded to evaluate the fungicidal activity of synthesized compounds. The results of antibacterial tests showed that the synthesized compounds exhibited good antibacterial activities against Coriolus versicolor, Gloeophyllum trabeum, Trichoderma viride, and Aspergillus niger at a ratio of 5:5. In order to improve the water solubility of target products, emulsification experiments were carried out and beta-cypermethrin was added as a pesticide. The appropriate emulsifier types and dosage ratios for the synthesized compounds were finally screened out.

This study aimed to evaluate the preservative ability of modified flutriafol derivatives against decay fungi. The bacteriostatic effect of flutriafol on Trichoderma viride was not efficient as expected. Flutriafol was modified as a parent substrate to improve its broad spectrum performance. Six triazole compounds were synthesized by Friedel-Crafts reaction, oxygen-sulfur-ylide reaction, and ring-opening addition reaction. The structures of the target products were determined by H-1 NMR and MS. Antibacterial and antileakage tests were performed to optimize the most efficient agents among triazole target products.

The thermal decomposition of enzymatic hydrolysis lignin (EHL) was investigated by the thermogravimetric technique (TG/DTG) within the temperature range from room temperature to 920 degrees C at different heating rates (10, 20, 30, 40 and 50 degrees C/min). Little differences in the mass losses as a function of the heating rates were observed from TG analysis. It was established that EHL pyrolysis consisted of three main stages: water evaporation (< 200 degrees C), devolatilization of organic volatiles (200-500 degrees C) and char formation (> 500 degrees C). The evolved gases or volatiles were investigated by Fourier transform infrared spectrometry (FTIR), coupled to a thermo-balance, at the heating rate of 20 degrees C/min, for identifying the gaseous or volatile species and their evolution during EHL thermal degradation. The temperatures corresponding to the maximum evolution rate of H2O, CO2, CO, CH4 and C2H4, as well as the volatile fragments originating from the breaking of covalent chemical bonds, such as C-C, C=O and C-O-C groups, were in agreement with the temperature corresponding to the maximum mass loss rate - of about 385 similar to 400 degrees C. The maximum release rates of H2O, CO2, CO, CH4 and C2H4 took place at 387, 385, 392, 392 and 389 degrees C, respectively. While the maximum rates of evolution of both alkyl groups and oxygen-containing compounds occurred at about 400 degrees C. The kinetic processing of non-isothermal TG/DTG data was performed by the model-free methods proposed by Flynn, Wall, Ozawa (known as FWO method) and Kissing, Akahira and Sunose (KAS method). The average activation energies calculated by the FWO and KAS methods were 191.2 kJ mol(-1) and 191.0 kJ mol(-1), respectively. Experimental results showed that the values of kinetic parameters obtained by both methods were analogous and thus these methods could be successfully applied to understand the complex degradation mechanism of EHL. Also, such an approach is helpful in achieving a better understanding of the devolatilization process of different types of biomass.

Steam exploded lignin (SEL) thermal decomposition was investigated by thermogravimetric technique (TG/DTG) within the temperature range from room temperature to 920 degrees C under different heating rates (10, 20, 30, 40, and 50 degrees C.min(-1)). Little differences in the mass losses with heating rates were observed from TG analysis. It was established that SEL pyrolysis consisted of three main stages: water evaporation (< 200 degrees C); devolatilization of organic volatiles (200-600 degrees C); and char formation (> 600 degrees C). The kinetic processing of non-isothermal TG/DTG data was performed by model-free methods proposed by Flynn-Wall-Ozawa (FWO) and Kissing-Akahira-Sunose (KAS). The average activation energies calculated from FWO and KAS methods are 74.2 kJ.mol(-1) and 173.2 kJ.mol(-1), respectively. Experimental results showed that values of kinetic parameters from both methods were analogous and could be successfully applied to understand the complex degradation mechanism of SEL. It is also helpful to achieve a better understanding of the devolatilization process of different type of biomass.