INDUSTRIAL CROPS AND PRODUCTS
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2023
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IF 5.9
Shuyang He,Feng Shu,Xianglin Liu,Ke Yan,Shijie Lei,Yupeng Liu,Mingu Zhou,Hang Yu,Junhua Zhang,Fangxia Yang
Pretreatment method is one of the key factors to improve the quality of nanocellulose (NC) production. As a green novel solvent, ternary deep eutectic solvent (TDES) plays an important role in production of lignin-containing nanocellulose (LNC), however, higher reaction temperature would limit its industrial application. Herein, a novel strategy of FeCl 3 -catalyzed TDES (F-TDES) pretreatment combined microfluidization was proposed to produce LNC from poplar ( PopulusL. ) at lower temperature (80 °C). The TDES was composed of choline chloride, lactic acid, and p -toluenesulfonic acid in a molar ratio of 2:10:1. When the optimum dose of FeCl 3 in per gram TDES system was 0.15 mmol (i.e. about 3.9% based on the weight of F-TDES), ribbon-like LNCs about 28.68 nm wide and 3.46 nm thick were obtained, which were smaller than that of lignin-free nanocellulose attained from the same preparation conditions. The LNC, lignin content 18.93%, displayed good dispersion stability in water and higher cellulose I crystallinity (57.8%) and thermal stability (T max =376 °C). Especially, the LNC exhibited more excellent emulsification performance and emulsion stability than NC, which was closely associated with its good amphiphilicity. Within the studied LNC concentration (0.1–0.4%) and oil/water mass ratio (20:80–50:50), increasing LNC concentration and/or oil/water mass ratio was beneficial for the stability of Pickering emulsions. The findings not only provide a milder route for producing LNC from lignocellulose , but also prove LNC would have promising prospects in emulsion systems.
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CHEMICAL ENGINEERING JOURNAL
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2023
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IF 15.1
Zhongwei Wang,Xiangqian Chen,Yisheng Sun,Dongliang Hua,Shuangxia Yang,Laizhi Sun,Tianjin Li,Lei Chen
Designing highly active and stable catalysts for the selective cleavage of the C-O bond of lignin is important to convert it into high-valued aromatic compounds. Herein, a facile synthetic strategy was developed using melamine as a soft template to prepare a highly active catalyst consisting of highly dispersed Ni nanoparticles on defective N-doped carbon support. The results indicated that the decomposition of melamine during the pyrolysis process induced the nitrogen atoms into aromatic carbon. The introduction of N-doped carbon support acted as anchor points for the Ni nanoparticles, strengthening the metal-support interaction. Approximately 100 conversion of the representative lignin model compounds, including 2-phenylethyl phenyl ether, were converted into their aromatic monomers under mild conditions. The as-prepared catalyst was stable and reusable after five cycles with no apparent signs of deactivation. Moreover, the theoretical calculation revealed that N-doped carbon supported Ni-based catalyst possessed a lower activation energy of C-O bond than only carbon supported Ni-based catalyst for the C-O bond cleavage in hydrogenolysis of lignin and its model compounds.
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INDUSTRIAL CROPS AND PRODUCTS
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2023
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IF 5.9
Xiaoyan Zeng,Yongfa Huang,Tingzhen Li,Zheng Lian,Ren Zou,Xinwen Peng
As a wood containing many ordered cell cavities and blood vessels, eucalyptus is an ideal precursor material in preparing hierarchical porous carbon electrodes for Zn-air batteries. However, insufficient micro-mesoporous and minor active sites inhibit the application of wood-directly derived carbon materials in Zn-air batteries. Hence, a simple and cost-effective formic acid pretreatment method was proposed to prepare nitrogen-doped bulk phase catalysts with abundant micro-mesoporous and enough high active sites from eucalyptus. Formic acid pretreatment selectively removed part of lignin and hemicelluloses , thus generating abundant nanopores and contributing to the introduction of more nitrogen active sites. Moreover, the obtained bulk carbon had high mechanical strength and wonderful electrical conductivity, containing cross-linked networks and natural ion transport channels. Benefiting from the above advantages, the bulk carbon catalyst could be directly used as self-supported cathode, and the resulting Zn-air batteries achieved a long cycle life of more than 300 h. This work provides a simple and feasible method for the development of biomass-derived hierarchical bulk-phase porous carbons for energy-related applications.
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2023
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IF 4.2
Erhu Li,Xuliang Lin,Shirong Sun,Xueqing Qiu
The highly selective conversion of technical lignin to low-oxygen-content compounds is still challenging due to the presence of methoxy and ether bonds in natural lignin. Herein, tunable ternary deep eutectic solvents (DESs) containing choline chloride, oxalic acid, and another bifunctional reagent with a hydrogen-bond donor and nucleophilic function were used for the β-aryl ether bond cleavage or Cα-etherification of lignin followed by pyrolysis to improve the yield of methoxy-free lignin monomers. The relationship between the lignin structure and pyrolysis behavior was investigated by 2D-NMR, FTIR, GPC, XPS, TGA, TG-FTIR, EPR, etc. The DES pretreatment changed the pathway of lignin pyrolysis toward a higher yield of bio-oil and methoxy-free products. Compared with technical lignin, the yield of phenolic products after Cα-etherification with ethanol and ethylene glycol as nucleophilic reagents increased from 0.73 × 1011 to 4.10 × 1011 and 5.56 × 1011 area/mg, respectively. Besides, the introduction of ethanol and ethylene glycol is more conducive to the demethoxylation of pyrolysis products and the formation of methoxy-free phenols during pyrolysis. This work realizes the conversion of lignin to high-value phenolic products with low-oxygen-content compounds without adding catalysts by a pyrolysis strategy.
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BIOMASS & BIOENERGY
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2023
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IF 6
Jiubing Zhang,Bo Chen,Yuanyuan Ge,Zhili Li
The efficient depolymerization of lignin for the production of high-value chemicals is essential for the development of a sustainable and competitive biorefinery . In this study, we report the preparation of homologous biochar-supported inlaid Cu–Ni catalysts (Cu x Ni y /BC) using a one-step method, and their application for lignin depolymerization in mild water without the need for external hydrogen, additives, or co-catalysts. The Cu 1 Ni 3 /BC (0.05 g catalyst, 8 h, 280 °C, and 18 mL water) showed exceptional catalytic activity , with a monophenol yield of 94.35 ± 2.92 mg/g, bio-oil yield of 68.98 ± 1.42%, and a lignin conversion rate of 92.36 ± 1.99%, which outperformed both the biochar support and monometallic catalysts. The outstanding catalytic performance of Cu 1 Ni 3 /BC was attributed to its strong metal-support interaction, alloy sites, and well-dispersed nanoparticles . Reusability experiments demonstrated that the Cu 1 Ni 3 /BC exhibited relatively good stability for up to four reuses, with only a 2.32% reduction in catalytic activity per cycle. Mechanism investigation revealed that the Cu 1 Ni 3 /BC, with its abundant mesoporous structure and enhanced acid sites, displayed excellent deoxygenation ability, enabling effective cleavage of C–O/C–C bonds and the production of G-type phenols . This approach provides new insights into the large-scale utilization of lignin for the production of high-value chemicals.
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Green Energy & Environment
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2022
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IF 12.781
Jiahui Mu,Cuihuan Li,Jiankang Zhang,Xianliang Song,Sheng Chen,Feng Xu
Lignin waste from the papermaking and biorefineries industry is a significantly promising renewable resource to prepare advanced carbon materials for diverse applications, such as the electrodes of supercapacitors; however, the improvement of their energy density remains a challenge. Here, we design a green and universal approach to prepare the composite electrode material, which is composed of lignin-phenol-formaldehyde resins derived hierarchical porous carbon (LR-HPC) as conductive skeletons and the self-assembly manganese cobaltite (MnCo 2 O 4 ) nanocrystals as active sites. The synthesized C@MnCo 2 O 4 composite has an abundant porous structure and superior electronic conductivity, allowing for more charge/electron mass transfer channels and active sites for the redox reactions. The composite shows excellent electrochemical performance, such as the maximum specific capacitance of ∼726 mF cm −2 at 0.5 mV s −1 , due to the significantly enhanced interactive interface between LR-HPC and MnCo 2 O 4 crystals. The assembled all-solid-state asymmetric supercapacitor, with the LR-HPC and C@MnCo 2 O 4 as cathode and anode, respectively, exhibits the highest volumetric energy density of 0.68 mWh cm −3 at a power density of 8.2 mW cm −3 . Moreover, this device shows a high capacity retention ratio of ∼87.6% at 5 mA cm −2 after 5000 cycles.
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CHEMICAL ENGINEERING JOURNAL
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2022
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IF 16.744
Yilu Wu,Jieyi Wen,Changsheng Su,Chenhang Jiang,Changwei Zhang,Yankun Wang,Yongjie Jiang,Wenqiang Ren,Peiyong Qin,Di Cai
Reductive catalytic fractionation (RCF) is an emerging biomass valorization strategy with high atom economy, which primarily outputting extensively depolymerized reductive lignin oil and highly delignified pulp. In downstream processes, the polysaccharide rich pulp can be potentially transferred into various value-added biochemicals through fermentation. In this study, the negative influences of the residual lignin oil that remaining on the surface of the RCF pulp towards different industrial microbes (total 9 species, categorized into eukaryotes, Gram-negative, and Gram-positive strains) was investigated. Results indicated the reduced lignin fractions were the key inhibitors in the RCF lignin oil, whilst the polarities, molecular weight, and the substitution groups of lignin possessed significant impacts on the growth of strains. Meanwhile, the resistance to RCF lignin oil by different category of industrial strains was analyzed. Generally, eukaryotes exhibited better resistance than the Gram-negative and Gram-positive strains. Took bioethanol and acetone-butanol-ethanol fermentation as examples, the negative influence of the lignin oil on biochemicals production using the RCF pulp as substrate was explored. Batch fermentation results revealed that the RCF lignin oil limited both the sugars (glucose and xylose) metabolism and the pathways toward bio-alcohols production of the microorganism. Therefore, it is vital to take continuous technical improvement in order to minimize the negative influences of the residual lignin oil on downstream biotransformation of the RCF pulps.
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FUEL PROCESSING TECHNOLOGY
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2022
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IF 8.129
Dongpo He,Jingyu Xu,Yanzhu Guo,Mengtian Yu,Qingyu Wang,Jinghui Zhou,Xing Wang
Peanut shell, as a widespread agricultural waste, is a biomass resource rich in lignin that has not been fully utilized. Herein, a novel and efficient hydrogenolysis process was provided for the selective decomposition of peanut shell lignin. Ru and Ni nanoparticles embedded within N-doped nanofibers were synthesized by a simple electrospinning technique and carbonized to obtain a bimetallic catalyst (Ru x Ni y -NCNFs). With the optimized catalyst of Ru 2 Ni 1 -NCNFs, 74.46 wt% of lignin oil was obtained with a char formation rate lower than 2.44 wt% at 300 °C for 3 h without an external hydrogen source . 2D-HSQC-NMR demonstrated that representative interunit linkages, such as β-O-4, β-5, and β-β, were considerably degraded during the depolymerization process. The obtained lignin oil has a narrow molecular weight distribution, low molecular weight and high burning value, indicating that it has great potential to become a high-quality aromatic fuel through subsequent upgrade processing. This study opens a novel avenue toward the exploration of highly efficient but low-cost bimetallic catalysts for lignin hydrogenolysis.
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FOOD HYDROCOLLOIDS
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2022
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IF 11.504
Zhipeng Zou,Balarabe B. Ismail,Xinhui Zhang,Zhehao Yang,Donghong Liu,Mingming Guo
Chitosan (CS) films have demonstrated strong antibacterial properties, excellent biocompatibility and biodegradability, but poor UV blocking, oxygen and water barrier and mechanical properties limit their application in antimicrobial food packaging. In this study, CS films were incorporated with nanofillers, including lignin nanoparticles (LNP, 1–5 wt %) and acylated soy protein isolate nanogel (ASPNG, 3–7 wt %) to improve their tensile strength, oxygen and water barrier, UV blocking and antibacterial properties. SEM images illustrated that the addition of LNP and ASPNG significantly affected the surface morphology of the CS film. Meanwhile, LNP incorporation improved UV blocking property of composite film, while an improved sustained antibacterial property was achieved with ASPNG incorporation. Interestingly, CS composite film incorporated with 3% LNP and 5% ASPNG showed a remarkable increase in tensile strength (37.29–54.29 MPa) and decreased oxygen barrier property (5.73–2.83 cm 3 /m 2 ·24 h MPa) relative to pure CS film. It is worth mentioning that the bacterial counts in samples treated by 3% LNP/5% ASPNG-CS composite film decreased approximately 2.37 log CFU/mL, which exhibited higher antibacterial activity than other composite films. However, this study also demonstrated that incorporation of LNP and ASPNG slightly decreased the light transmission and increased surface roughness of CS film. All in all, the CS composite film with enhanced mechanical, barriers, antibacterial properties were obtained by incorporating an appropriate proportion of LNP and ASPNG and could further be utilized as a promising antibacterial food packaging material.
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
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2022
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IF 8.025
Hong-jia Xiang,Ai-ling Zhong,Hong Wang,Ling Xiao,Tian-ren Deng,Teng-gen Hu,Peng Wen
For the greater utilization of β -carotene in antioxidant material, β -carotene-loaded emulsion stabilized by alkali lignin (AL) was successfully electrospinning with poly (vinyl alcohol) (PVA) (PVA/AL/ β -carotene nanofiber). Transmission electron microscopy demonstrated the core-shell structure of nanofiber with the average diameter being 356.31 nm, and 85.7 % of β -carotene was effectively encapsulated into the core section. Fourier transform infrared spectra and differential scanning calorimetry revealed the good compatibility and decreased crystallinity of β -carotene, favoring its stability and solubility, respectively. As expected, the PVA/AL/ β -carotene nanofiber exhibited higher antioxidant activity than free β -carotene due to the protection of AL matrix and the special structure of nanofiber, as the DPPH free radical scavenging rate being 90.7 % at 7th day. The sustained release behavior of β -carotene and AL from fiber followed Fickian diffusion model, contributing to the greater protection for fish oil than that of emulsion. Thus, this study provides an approach to develop hydrophobic compounds-loaded emulsion electrospun antioxidant material with controlled release property and enhanced activity.
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PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2022
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IF 16.744
Junxian Xie,Jun Xu,Zhaohui Zhang,Bin Wang,Shiyun Zhu,Jun Li,Kefu Chen
Ternary deep eutectic solvents (TDESs) as a new class of solvents play a key role in fabrication of lignin containing cellulose nanofibrils (LCNF), however, current work requires a considerable time and thus limits industrial application of TDES. Herein, a novel strategy was proposed to produce lignin containing cellulose nanofibrils (LCNF) by TDESs based on benzyltrimethylammonium chloride (BTMAC), formic acid (FA), and maleic acid (MA). The TDESs could remove 87.80% of lignin and 89.15% of hemicellulose from Radiata Pine while most of the cellulose reserved under optimum pretreatment conditions (TDES = 100 wt%, T = 130 °C, t = 1.5 h). Benefiting from the increase in cellulase accessibility, desired sugar yield of 98.9% was obtained. Moreover, the proposed TDESs could be regarded as a green medium for the production of containing cellulose nanofibrils (LCNF) in which lignin has been esterified. The LCNF displayed a well-individualized structure with a wide size distribution (32.3–146.9 nm), which was closely associated with lignin content. 13 C− 1 H HSQC 2D NMR test was performed to illustrate the molecular − structural features of lignin and polysaccharide in LCNF. In addition, the self-standing LCNF films exhibited excellent UV-blocking, higher thermal stability, and mechanical strength. Most importantly, LCNF films showed strong barrier property to oil and air owing to lower surface free energy and smaller pore structure. Briefly, this work highlights the pretreatment performance of TDESs for cascade utilization of lignocellulosic biomass to high-value products.
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ACS Applied Materials & Interfaces
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2022
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IF 10.383
Ganggang Zhang,Chenru Tian,Jinwei Shi,Xi Zhang,Jun Liu,Tianwei Tan,Liqun Zhang
Lignin, the most abundant aromatic polymer in nature, is one of the most promising renewable feedstocks for value-added polymer products. However, it is challenging to prepare high-performance and multifunctional polymer materials with renewable lignin because of its poor compatibility with the elastomer matrix. In fact, lignin often requires solvent fractionation, chemical modification, or prohibitively expensive additives. This work develops a cost-effective strategy to prepare ionomeric elastomer composites based on a commercial carboxyl elastomer and a high content of lignin without purification or chemical modification. The compatibility between the elastomer and lignin is improved by the incorporation of zinc oxide which creates metal–ligand coordination at the interfaces between the carboxyl groups of the elastomer and the oxygen-bearing groups of the lignin. This results in fine dispersion of the lignin in the elastomer matrix, even when its content reaches 50 wt %. The lignin/elastomer composites show excellent mechanical properties, which are attributed to the reinforcing effect of the lignin domains and the presence of abundant sacrificial coordination bonds. Moreover, ionic bonds and ionic aggregates created by the neutralization of the zinc ions with the carboxyl groups of the elastomer behave as physical crosslinks which endow the composites with excellent recyclability; namely, their mechanical properties are retained or even improved after multiple reprocessing cycles. They also show good self-repairability and shape memory. Hence, this work may open up new avenues to utilize lignin as a renewable alternative to petroleum derivatives for designing and fabricating high-performance and multifunctional elastomer materials.
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