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APPLIED CATALYSIS B-ENVIRONMENTAL · 2023 · IF 22.1

A 3D porous Fe-MoS2/CMF catalyst for high-efficient catalytic reforming of lignin vapor by microwave irradiation

Wenliang Wang,Jiale Huang,Yishuai Fu,Weikun Jiang,Yutong Chen,Yujun Ma,Sizhe Han

Improving the yield of target monophenols plays an important role in increasing the economic competitiveness of lignin valorization. In this study, a 3D porous Fe-MoS 2 /CMF catalyst with nanoflower microstructure was successfully fabricated by a simple one-step hydrothermal method. The catalytic depolymerization of the lignin β-O-4 model showed that Fe-doping increased the efficiency of the catalytic conversion reaction and promoted the cleavage of the β-O-4 ether bond, in agreement with theoretical calculations. Reforming of lignin depolymerization vapor revealed that the Fe-MoS 2 /CMF catalysts significantly improved the selectivity of phenol (30.01 wt%) and styrene (16.34 wt%) with the decrease of oligomers . Moreover, finite element simulation showed that the Fe-MoS 2 /CMF catalysts can also enhancing the local thermal effect by creating hot spots on the surface, thereby facilitate the lignin vapor reforming. Consequently, this work provides a promising method for the efficient production of phenol and styrene from lignin using bimetallic nanoarray microwave responsive catalyst.

CAS / MDL: 409-21-2
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2023 · IF 8.2

Efficient preparation of nitrogen-doped lignin-based carbon nanotubes and the selectivity of nitrogen speciation for photothermal therapy

Yuting Peng,Bosen Guo,Wenda Wang,Peng Yu,Zhiping Wu,Lishu Shao,Weihua Luo

In this study, the lignin was pre-modified using small-molecule nitrogen-containing compounds, and then the nitrogen-doped lignin-based carbon nanotubes (L-NCNTs) were fabricated by pyrolysis using the modified lignin as raw materials. The obtained L-NCNTs were multi-walled carbon nanotubes with diameters between 10 and 80 nm. The modification of lignin had an important effect on the nitrogen morphology of L-NCNTs, and promoted the high selectivity of pyridine-N in the L-NCNTs. Defects and pyridinic-N structure were conducive to boosting photothermal properties of the L-NCNTs. The photothermal conversion efficiency of the L-NCNTs after 808 nm laser irradiation for 5 min reached 58.8 %. The L-NCNTs can be used as photothermal agents in drug delivery system to achieve mild photothermal therapy, and it is basically non-toxic to normal cells, indicating good biocompatibility. This work provides new ideas for development of lignin-based high value-added products from biomass.

CAS / MDL: 108-78-1
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ARCHIVES OF ENVIRONMENTAL CONTAMINATION AND TOXICOLOGY · 2023 ·Vol. 84 ·期 3 ·413-425 · IF 4

Dissolved Organic Matter and Lignin Modulate Aquatic Toxicity and Oxidative Stress Response Activated by Layered Double Hydroxides Nanomaterials

Wang Zhuang,Yu Le,Wang De-Gao

Advanced nanomaterials can be released into the environment and can coexist with natural organic matter (NOM). However, evidence on the impacts of NOM on the environmental behavior and toxicity of advanced nanomaterials is still scarce. Here, we investigated the behavior and toxic effects of two layered double hydroxides (LDHs) nanomaterials with different metallic constituents (Mg-Al-LDH and Zn-Al-LDH) at relatively low exposure concentrations on a freshwater green alga ( Chlorella pyrenoidosa ) in the absence and presence of two types of NOM, namely dissolved organic matter (DOM) and dealkaline lignin (DL). The DOM or DL interaction with the LDHs at different mixture levels was shown to be an antagonistic effect on the growth inhibition toxicity to C. pyrenoidosa mainly. The estimation of the index of Integrated Biological Responses version 2 indicated that the joint interaction of the LDHs with DOM or DL occurred in the following order of frequency synergism > antagonism > additivity. Furthermore, the physicochemical characteristics of LDHs were crucial for illuminating the mechanism by which the DOM or DL modified the LDH-induced oxidative stress response. These findings highlighted the important role of NOM in the behavior and effect of LDHs as a representative of a new class of multifunctional nanomaterials in the freshwater environment.

CAS / MDL: 9005-53-2
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Journal of Energy Chemistry · 2023 · IF 13.1

Synthesis of high density and low freezing point jet fuels range cycloalkanes with cyclopentanone and lignin-derived vanillins

Xinghua Zhang,Miaojia Song,Jianguo Liu,Qi Zhang,Lungang Chen,Longlong Ma

In this work, a “cyclopentanone-vanillin” strategy was proposed for the preparation of jet fuel range cycloalkanes from lignocellulose-derived ketones and lignin-derived aldehydes via aldol condensation and hydrodeoxygenation (HDO). Ethanolamine lactate ionic liquid (LAIL) exhibited excellent catalytic activity in the aldol condensation of cyclopentanone and vanillin. Desired mono-condensation and bi-condensation products were obtained with yield of 95.2% at 100 °C. It is found that the synergy effects between amino group of ethanolamine and hydroxyl group of lactic acid play a key role in the aldol condensation. The condensation products were converted into cycloalkanes by HDO over 5%Pd/Nb 2 O 5 catalyst. The density of the obtained HDO products is 0.89 g/cm 3 and the freezing point is lower than −60 °C. These results suggest that the resulted cycloalkanes can be used as additives to improve the density and low-temperature fluidity of the jet fuels.

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CARBOHYDRATE POLYMERS · 2023 · IF 11.2

Fully biobased sustainable elastomers derived from chitin, lignin, and plant oil via grafting strategy and Schiff-base chemistry

Zhiqiang Wang,Pengfei Tang,Shuaishuai Chen,Yuxian Xing,Chuantao Yin,Jiajun Feng,Feng Jiang

With the dramatically increased environmental problems, the rational design of sustainable polymers from renewable feedstocks opens new avenues to reduce the huge pollution impact. The major challenge for sustainable polymers is the decreased mechanical performance compared to that of petroleum-based materials. In this work, fully biobased sustainable elastomers were developed by integrating renewable chitin , lignin, and plant oil into one macromolecule , in which chitin was chosen as the rigid backbone , while a lignin-derived monomer vanillin acrylate (VA) and a plant oil-based monomer lauryl acrylate (LA) were selected as the hard and soft segments for the grafted side chains. A series of Chitin- graft -poly(vanillin acrylate- co -lauryl acrylate) (Chitin- g -P(VA- co -LA)) copolymers with varied feed ratios and chitin contents were synthesized by using reversible addition-fragmentation chain transfer (RAFT) polymerization as an effective grafting strategy. In addition, a dynamic cross-linked network was incorporated via Schiff-base reaction to improve the macroscopic behavior of such kind of chitin graft elastomers. These sustainable elastomers are mechanically strong and show excellent reprocessablity, as well as outstanding UV-blocking property. This strategy is versatile and can inspire the further development of fully biobased sustainable materials from natural resources .

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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY · 2023 · IF 6.1

Producing Lignin and Ethyl Levulinate from Wheat Stalk Using 1-(3-Sulfobutyl) Triethylammonium Hydrogen Sulfate and USY Zeolite

Dingkai Wang,Mingyu Cui,Yanjun Li,Wei Zhao,Shangshang Ma,Zhijie Jiang,Xutang Liu,Chong Liang,Rujuan Li,Long Ma,Yanmin Song,Xian-Yong Wei

The facile, green, and efficient strategy for the separation of lignin from straw and subsequent production of value-added chemicals is crucial to the current utilization of straw. Herein, up to 23.72% of lignin was isolated from wheat stalk over cheap and green 1-(3-sulfobutyl) triethylammonium hydrogen sulfate ([BSTEA]HSO4) in aqueous ethanol (Vethanol: Vwater = 4:1). The acquired lignin was verified as a p-hydroxyphenyl-guaiacyl-syringyl type, which had a narrower molecular weight distribution, better thermal stability, and higher purity compared with those of the lignin obtained using 1-methyl-3-(4-sulfobutyl)-imidazolium hydrogen sulfate and 1-(3-sulfobutyl) pyridinium hydrogen sulfate. Moreover, a carbohydrate-rich liquid containing [BSTEA]HSO4 was obtained by water removal from the waste liquid after lignin separation and further converted to ethyl levulinate (EL) by a one-pot process in the presence of inexpensive and stable USY zeolite. The yield of EL reached 30.23% at 200 °C for 60 min over the presence of 40% [BSTEA]HSO4 and 60% USY zeolite. Under optimal conditions, the yields of lignin and EL can respectively reach 83.89 and 72.28% of those catalyzed by a fresh catalyst after five cycles. In short, the above-mentioned methods present a green, economic, and efficient route for the extraction of lignin and further treatment of the liquid waste generated during the extraction process.

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FUEL · 2023 · IF 7.4

One-pot solvent-free sequential synthesis of high-density polycycloalkanes fuels from lignin-derivatives over laminated NbOPO4 catalyst

Danni Liu,Xiaopo Niu,Zhen Guo,Kaige Zhang,Nan Jiang,Yue Qin,Wenli Zhao,Xiangwen Zhang,Qingfa Wang

Upgrading lignocellulose biomass to renewable fuels is essential to achieve carbon neutrality. However, the multiple synthetic, and purification steps as well as the employment of solvents in the production of renewable fuel inhibit the overall yields and cause the waste of energy and resources. Herein, a new catalytic strategy for one-pot solvent-free sequential synthesis (OSS) of perhydrofluorene and dicyclohexylmethane was developed from lignin-derivatives. A two-dimensional layered nanosheet niobium phosphate (NbOPO 4 -IB) catalyst was fabricated to efficiently integrate the alkylation of phenol and benzyl alcohol and sequential hydrodeoxygenation with a cocatalyst of Ru/C. The high crystalline NbOPO 4 phase and the lamellar morphology contributes to the large specific surface area to expose more active sites, especially more Brønsted acid sites. The NbOPO 4 -IB catalyst with a suitable Brønsted/Lewis acid ratio of 1.49 favors the selectivity of fuel precursors benzyl phenol in the alkylation and also provides the appropriate acid strength to promote hydrodeoxygenation activity. NbOPO 4 -IB also shows good reusability. Excessive phenol plays a vital role in promoting the alkylation reaction by dissolving the intermediates, and then into cyclohexane to enhance the H 2 dissolution in the hydrodeoxygenation. A possible mechanism of OSS from lignin-derivatives into polycycloalkanes over the cocatalysts was proposed.

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Journal of Cleaner Production · 2023 · IF 11.1

Highly wear-resistant and recyclable paper-based self-lubricating material based on lignin-cellulose-graphene layered interwoven structure

Zhiqiang Shan,Xiaohua Jia,Yunfei Bai,Jin Yang,Yunfeng Su,Haojie Song

Conventional paper-based wear-resistant materials employ thermosetting resin as the matrix, which are difficult to recycle, degrade, and reuse after scrapping, causing significant damage to the environment. The discovery of sustainable alternatives has the potential to transform the manufacture of paper-based wear-resistant materials into low-carbon production. Herein, inspired by spider webs sticking to insects, a paper-based self-lubricating material based on lignin-cellulose-graphene layered interwoven structure was prepared by lignin-cellulose assisted in-situ exfoliation of flake graphite strategy. Graphene adheres to the interlaced cellulose network, while lignin serves as a natural binder and matrix, resulting in a 2D interwoven structure. The paper-based film had a 37.4% greater average mechanical strength than pure lignin-cellulose film and a 56% lower toughness loss following heat treatment. The friction coefficient of the film-15% was 173.3% lower than that of the film-10%, and it maintained long-term stability with a low wear rate of 3.9 × 10 −3 mm 3 /(N·m). Furthermore, the end-of-life products were recycled five times and can be degraded by microorganisms in moist soil within 40 days. The degradation products can provide nutrients for plant growth, indicating that it is a potential alternative to non-recyclable wear-resistant materials for light-duty transmission machinery.

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BIORESOURCE TECHNOLOGY · 2023 · IF 11.4

Mechanism of enhanced enzymatic hydrolysis performance by ethanol assisted deep eutectic solvent pretreatment- from the perspective of lignin

Lan Yao,Mengzhen Chai,Pingping Cui,Chang Geun Yoo,Jie Yuan,Xianzhi Meng,Haitao Yang

Valorization of lignocellulose has received a lot of attention due to the abundance of lignocellulosics. It was showed that synergistic carbohydrate conversion and delignification could be achieved via ethanol assisted DES (choline chloride/lactic acid) pretreatment. To explore the reaction mechanism of lignin in the DES, milled wood lignin obtained from Broussonetia papyrifera was subjected to pretreatment at critical temperatures. The results suggested that ethanol assistance could contribute the incorporation of ethyl groups and reduce condensation structures of Hibbert’s ketone. Adding ethanol at 150 °C not only decreased formation of condensed G unit (from 7.23% to 0.87%), but also removed J and S’ substructures, thus effectively reducing the adsorption of lignin on cellulase, and promoting the glucose yield after enzymatic hydrolysis.

CAS / MDL: 9012-54-8
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CHEMICAL ENGINEERING SCIENCE · 2023 · IF 4.7

CoFe-CoxN heterojunction encapsulated by lignin-derived nitrogen-doped biochar as bifunctional oxygen electrocatalysts for zinc-air batteries

Jinhui Zhang,Jianglin Liu,Bowen Liu,Xuliang Lin,Yanlin Qin

The development of low-cost and efficient bi-functional electrocatalysts are still the main challenging for oxygen reduction reactions (ORR) and oxygen evolution reactions (OER) in zinc-air batteries. In this work, CoFe-Co x N heterojunction nanocatalyst encapsulated by N-doped biochar was synthesized by combining carboxylated lignin with metal ions via self-assembly and in situ pyrolysis reduction. The heterojunction endowed the superior oxygen electrocatalytic performance, and the carbon-encapsulated structure improved the stability and corrosion resistance in electrolyte. It exhibited a positive half-wave potential of 0.79 V for ORR and a low overpotential of 404 mV at 10 mA cm −2 for OER. The corresponding zinc-air battery displayed a high-power density of 178 mW·cm −2 and excellent stability. DFT calculation indicated that the existence of CoFe-Co x N and the N-doped carbon layer could improve the electron transfer efficiency. This study demonstrated a viable and eco-friendly design for alloy and nitride heterojunction electrocatalysts for energy conversion by using lignin-metals complex.

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CHINESE JOURNAL OF CHEMICAL ENGINEERING · 2022 · IF 3.898

Effective depolymerization of alkali lignin using an attapulgite-Ce0.75Zr0.25O2(ATP-CZO)-supported cobalt catalyst in ethanol/isopropanol media

Jiajia Chen,Xinyu Lu,Dandan Wang,Pengcheng Xiu,Xiaoli Gu

Lignin is the world's greatest renewable aromatic biofeedstock, and it has promising applications in high value-added chemical products. Herein, N-Co/ATP-CZO was used as a catalyst for the depolymerization of alkali lignin in ethanol and isopropanol systems, and explored the effects of formic acid (FA) amount, reaction time, reaction temperature and other factors on the depolymerization of alkali lignin. Among them, formic acid serves as both catalytic and in situ-hydrogen donor. Ultimately, the highest yield of bio-oil (59.28% (mass)), including 30.05% (mass) of monomer , was obtained after a reaction of FA to alkali lignin mass ratio of 4 and 240 °C for 8 h. Among the monomers, the yield of Guaiacol was the highest (5.94% (mass)), followed by 2-methoxy-4-methylphenol (5.74% (mass)). This study, the modification of attapulgite was carried out to reduce the acidity while enhancing the catalytic activity for depolymerization, and the selection of hydrogen donor was investigated. A feasible pathway for lignin depolymerization research was opened.

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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

Microwave-assisted fractionation of poplar sawdust into high-yield noncondensed lignin and carbohydrates in methanol/p-toluenesulfonic acid

Di Fan,Jian Yang,Xinyi Xie,Meifang Cao,Li Xu,Xueqing Qiu,Qiyu Liu,Xinping Ouyang

Production of noncondensed lignin via lignocellulose fractionation usually shows limited yield. Promoting reaction conditions benefits lignin production but has negative effect on structural condensation and thus inhibits its value-added applications in depolymerization. To address this issue, a unique fractionation method was proposed using p -TsOH ( p -toluenesulfonic acid) in methanol under microwave irradiation to produce high-yield noncondensed lignin. It was found that microwave irradiation efficiently decreased the activation energy of lignin-carbohydrate complex (LCC) bonds cleavage from 102.1 to 63.8 kJ/mol and thereby facilitated lignin exfoliation from carbohydrates. And an effective α-alkoxylation reaction occurred between methanol molecular and C α -OH group in lignin, which protected β -O-4 linkages from condensation. After being fractionated under a relatively mild fractionation condition of 85 ℃ for 30 min, a promising lignin yield of 87.9 % can be obtained from poplar sawdust, with 91.8 % of ether bonds preserved. The obtained lignin can be selectively depolymerized into monophenols with a high yield of 42.0 %, which was 74.9 % to the theoretical yield. Besides, 94.3 % of cellulose was retained in solid part after fractionation, which can be efficiently converted into glucose with a yield of 98.5 % via enzymatic hydrolysis.

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