MOLECULES
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2020
·Vol. 25
·期 9
·2109
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IF 3.267
Changzhou Chen,Peng Liu,Haihong Xia,Minghao Zhou,Jiaping Zhao,Brajendra K. Sharma,Jianchun Jiang
It is of great importance to explore the selective hydrogenolysis of β-O-4 linkages, which account for 45–60% of all linkages in native lignin, to produce valued-added chemicals and fuels from biomass employing UV light as catalyst. TiO2exhibited satisfactory catalytic performances in various photochemical reactions, due to its versatile advantages involving high catalytic activity, low cost and non-toxicity. In this work, 20 wt.% Ni/TiO2and oxidant PCC (Pyridinium chlorochromate) were employed to promote the cleavage of β-O-4 alcohol to obtain high value chemicals under UV irradiation at room temperature. The Ni/TiO2photocatalyst can be magnetically recovered and efficiently reused in the following four consecutive recycling tests in the cleavage of β-O-4 ether bond in lignin. Mechanism studies suggested that the oxidation of β-O-4 alcohol to β-O-4 ketone by oxidant PCC first occurred during the reaction, and was followed by the photocatalysis of the obtained β-O-4 ketone to corresponding acetophenone and phenol derivates. Furthermore, the system was tested on a variety of lignin model substrates containing β-O-4 linkage for the generation of fragmentation products in good to excellent results.Keywords:lignin;β-O-4;photocatalyst;Ni/TiO2;oxidant PCC
研究领域:
化学工程
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环境科学
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS
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2016
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IF 3.652
Shiliang Wu,Dekui Shen,Jun Hu,Huiyan Zhang,Rui Xiao
The pyrolytic characteristics of cellulose, cellobiose and glucose were examined by TG-FTIR combined with Py-GC–MS, in order to gain the effect of β -O-4 glycosidic bond on the pyrolysis process. In TG-FTIR analysis, two mass loss peaks were observed for cellobiose and glucose, indicating dehydration in low temperature stage and consequently intensive cracking of glycosidic bond and fragments for cellobiose. The samples were tested in Py-GC–MS at the temperature of 300, 500 and 900 °C according to their mass loss characteristics from TG-FTIR. Formation of furans from cellobiose, which involved the cracking of β -O-4 glycosidic bond, was prominent over other products, compared to that of cellulose and glucose. Four possible chemical pathways for the cleavage of β -O-4 glycosidic bond have been proposed with regard to the formation of furans and anhydrosugars from cellulose. Besides, another two reaction pathways leading to the formation of levoglucosan were also suggested.
研究领域:
生物质化学
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热化学转化
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DOI
高影响因子
ACS Sustainable Chemistry & Engineering
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2023
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IF 8.4
Zhenlong Song,Yuzhen Hu,Song Li,Jianguo Liu,Xinghua Zhang,Longlong Ma,Lungang Chen,Qi Zhang
Valorizing lignin into valuable chemicals requires the selective breaking of a large number of C–O bonds found in the β–O–4 structure. In this study, we present a one-pot strategy that utilizes two NiO/TiO2 catalysts for the photocatalytic depolymerization of β–O–4 alcohols. The S-1.6%NiO/TiO2 catalyst is used for the dehydrogenation of β–O–4 alcohols at 450 nm. Then, the L-0.8%NiO/TiO2 catalyst is employed for the hydrogenolysis of β–O–4 ketones at 365 nm. Remarkably, the dehydrogenation–hydrogenolysis tandem reaction can be conducted in one pot, which affords high yields of ketones and phenols (up to 89%) from β–O–4 alcohols. Additionally, the L-0.8%NiO/TiO2 catalyst prepared in this article is the smallest NiO/TiO2 photocatalyst reported to date, and the size of NiO in the S-1.6%NiO/TiO2 catalyst is even small enough to enter the lattice of TiO2. We successfully regulated the reaction selectivity by controlling the loading method and the amount of NiO. Our work offers a promising solution for efficiently cleaving target bonds in lignin and provides insights into the design of efficient photocatalysts.
研究领域:
化学工程
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材料科学
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可再生资源转化
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DOI
高影响因子
ACS Catalysis
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2016
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IF 9.307
Nengchao Luo,Min Wang,Hongji Li,Jian Zhang,Huifang Liu,Feng Wang
One of the challenges of depolymerizing lignin to valuable aromatics lies in the selective cleavage of the abundant C–O bonds of β-O-4 linkages. Herein we report a photocatalytic oxidation–hydrogenolysis tandem method for cleaving C–O bonds of β-O-4 alcohols. The Pd/ZnIn2S4 catalyst is used in the aerobic oxidation of α-C–OH of β-O-4 alcohols to α-C═O with 455 nm light, and then a TiO2–NaOAc system is employed for cleaving C–O bonds neighboring the α-C═O bonds through a hydrogenolysis reaction by switching to 365 nm light. Interestingly, the oxidation–hydrogenolysis tandem reaction can be conducted in one pot to offer ketones and phenols (up to 90% selectivity) via a dual light wavelength switching (DLWS) strategy. EPR and metal loading experiments elucidate that Ti3+ in TiO2 is formed in situ and is responsible for the photocatalytic hydrogenolysis through electron transfer from Ti3+ to the β-O-4 ketones.
研究领域:
化学工程
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材料科学
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环境科学
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产品关联
DOI
高影响因子
PROCEEDINGS OF THE COMBUSTION INSTITUTE
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2024
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IF 5.3
Wen-luan Xie,Bin Hu,Xiao Yang,Ji Liu,Zhi-mo Fang,Kai Li,Yang-wen Wu,Bing Zhang,Qiang Lu
Phosphoric acid is an effective and widely used catalyst for biomass pyrolysis, with significant catalytic impact on the pyrolytic reactions and product distribution. However, its fundamental catalytic mechanism in lignin pyrolysis remains unclear. In this work, we proposed and investigated three possible H 3 PO 4 -assisted pyrolysis mechanisms, i.e., hydrogen-bond-induced decomposition, phosphoric-acid-assisted hydrogen transfer (H 3 PO 4 -AHT), and phosphorolysis, and carefully discussed them through theoretical calculations, electronic structure analyses, catalytic pyrolysis experiments using the β -O-4 linked lignin model. The results indicated that the H 3 PO 4 -AHT mechanism played a dominant role in lignin catalytic pyrolysis, superior to the other two mechanisms. The phosphoric acid molecule could take advantage of its unsaturated P = O and saturated P −OH groups for hydrogen donation and acceptance in concerted H 3 PO 4 -AHT reactions. Alternatively, it could also participate in concerted intermolecular hydrogen transfer with the active hydroxyl group as a mediator. The C β −O bond cleavage could be significantly enhanced by effectively reducing the tension of the transition state ring, leading to the generation of more phenol and styrene in pyrolysis experiments. Due to the inhibition of hydrogen abstraction, C α −C β breakage of β -O-4 linkage, side chain removal of primary products, etc., the formation of other products in phosphoric acid catalytic pyrolysis of β -O-4 linked lignin was restrained. This H 3 PO 4 -AHT catalytic mechanism was also confirmed to be conductive to tautomerism, elimination, dehydration, α -O-4 linkage fracture, β -1 linkage fracture, and other important decomposition reactions in lignin pyrolysis. The understanding of these mechanisms provides valuable insights into the role of phosphoric acid in lignin pyrolysis and may guide the development of effective biomass catalytic conversion methods.
研究领域:
化学工程
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生物质能
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催化科学
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DOI
高影响因子
PROCEEDINGS OF THE COMBUSTION INSTITUTE
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2022
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IF 6.535
Wen-luan Xie,Bin Hu,Ying Liu,Hao Fu,Ji Liu,Bing Zhang,Qiang Lu
Lignin pyrolysis involves complex radical reactions, whereas the radical chain process, especially the influence of aliphatic substituents , has been rarely studied. Herein, the typical β -O-4 lignin dimer, phenethyl phenyl ether (PPE), and three aliphatic substituted derivatives of PPE, namely α -OH substituted, β -CH 2 OH substituted, and α,β -disubstituted PPE ( α PPE, β PPE, and αβ PPE) were employed as model compounds. DFT calculations, electronic analyses, and fast pyrolysis experiments were combined to investigate three core steps of the radical chain mechanism in lignin pyrolysis, i.e., homolysis, hydrogen abstraction , and radical decomposition. The pathway involving successive C β -O homolysis → α -hydrogen abstraction → C β -O breakage of α -dehydrogenated radical is dominated for the pyrolysis of aliphatic substituted β -O-4 linked lignin, with the formation of phenolics . The hydrogen abstraction reactions at the C α site are obviously superior to those at other sites for PPE derivatives, due to the p- π conjugate stability. Notably, α -hydrogen abstraction can be significantly promoted by the π -electron-dispersing α -OH substitution. The decomposition step of dehydrogenated radicals can be facilitated by the electron-donating β -CH 2 OH substitution, where the C β -O breakage of the α -dehydrogenated radical is dominant. Totally, aliphatic substituents can improve the radical growth stage and change the competitiveness of the hydrogen abstraction and radical decomposition reactions. The fast pyrolysis experiments of PPE and α PPE gave direct proof that the generation of characteristic products from the radical chain process, i.e., benzaldehyde and phenylacetaldehyde, was enhanced by the α -OH substitution. The present work offers the potential to give a comprehensive image of the radical chain mechanism in lignin pyrolysis.
研究领域:
化学工程
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能源科学
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DOI
高影响因子
RENEWABLE ENERGY
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2022
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IF 8.634
Wenjing Song,Mengxue Song,Wenqing Cai,Weichu Li,Xingmao Jiang,Weiping Fang,Weikun Lai
Development of highly active and stable catalyst for C–O bonds cracking is important in biomass conversion , in this work, we report a SiO 2 -encapsulated NiPt/HY core-shell catalyst for phenethoxybenzene (PEB) catalytic cracking . The as-grown silica shell with defined pores serves as a ‘storage’ to enhance local concentration of PEB and intermediate isomers and promotes catalytic cracking on NiPt/HY core. With the increase of silica shell thickness from 0 to 40 nm, PEB reaction rate has increased more than five times, and the major cracking product selectivity is raised to above 90%, which is attributed to the continuous conversion of PEB isomers within the shell. This designed structure endows the NiPt/HY@SiO 2 with a high activity and no obvious deactivation in PEB cracking to corresponding phenol and aromatics. The outstanding performance benefit from the enrichment effect on the unique core-shell structure, as well as the moderate acidity originated from silica regulation. This work can be extended to the modulation of microenvironment to promote the catalytic behavior of core-shell catalysts.
研究领域:
催化化学
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材料科学
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生物质能
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产品关联
DOI
高影响因子
GREEN CHEMISTRY
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2024
·
IF 9.3
Jie Li,Pengpeng Shao,Weijie Geng,Peng Lei,Jing Dong,Yingnan Chi,Changwen Hu
The oxidative depolymerization of β-O-4 linkages into value-added aromatic chemicals is of great importance for lignin valorization. However, achieving highly selective and rapid cleavage of β-O-4 linkages under mild conditions remains a challenge. Herein, cobalt–cobalt oxides (Co-CoOx) supported on N-doped carbon (CoMA/C900) combined with a green and recyclable base K7HNb6O19 (KNb6) have shown remarkable activity for the one-step oxidative cleavage of lignin β-O-4 linkages. Under relatively mild conditions (100 °C, 0.2 MPa O2), a lignin β-O-4 alcohol model compound was almost completely converted within 3 h, affording a narrow product distribution of phenol (yield: 99%) and methyl benzoate (yield: 98%). Based on the control experiments, kinetic study, and spectroscopic analysis, a synergistic oxidative cleavage mechanism was proposed: CoMA/C900 activates molecular oxygen to form a superoxide radical, while basic KNb6 promotes deprotonation of secondary alcohol, and they synergistically catalyze the oxidation of β-O-4 alcohol and the rapid cleavage of Cβ–O and Cα–Cβ bonds. During the reaction, the oxidation of β-O-4 alcohol to β-O-4 ketone is the rate-determining step, while the cleavage of PP-one to phenol and methyl benzoate can be completed within 15 min. Moreover, the CoMA/C900–KNb6 catalyst is recyclable at least three times and highly active for the oxidative cleavages of other lignin models and organosolv birch lignin.
研究领域:
化学工程
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材料科学
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生物质转化
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产品关联
DOI
高影响因子
JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS
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2024
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IF 5.8
Shuang Wang,Huihui Zhang,Chunyan Yu,Yue Liu,Yanju Lu,Lu Li
In this study, Co-Corrin/C catalysts with corrin active skeleton were prepared by pyrolysis under anaerobic conditions using vitamin B12 (VB12) as a precursor and activated carbon with rich mesoporous structure as a carrier. The Co-Corrin/C catalyst was applied to the oxidative cleavage reaction of lignin, showing a 92.74 % breakage of β-O-4 bonds. Density functional theory (DFT) calculations indicate that the low energy gap difference of Co-Corrin/C promotes electron transfer between Co and O. Meanwhile, the pyrrole ring in the corrin structure will be adsorbed and bonded to oxygen, which promotes the generation of large amounts of oxygen free radicals. The C α -OH bond in the lignin aliphatic chain is oxidized to C α =O bond under the action of oxygen radicals, which reduces the dissociation energy of the β-O-4 bond and significantly improves the oxidation efficiency. Cycling experiments proved that Co-Corrin/C has good stability.
研究领域:
生物化学
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材料科学
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环境科学
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产品关联
DOI
高影响因子
iScience
·
2023
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IF 5.8
Luxian Guo,Yangming Ding,Hua Wang,Yuxuan Liu,Qian Qiang,Qi Luo,Fei Song,Changzhi Li
The catalytic conversion of lignin into N-containing chemicals is of great significance for the realization of value-added biorefinery concept. In this article, a one-pot strategy was designed for the transformation of lignin β-O-4 model compounds to imidazo[1,2-a]pyridines in yields up to 95% using 2-aminopyridine as a nitrogen source. This transformation involves highly coupled cleavage of C-O bonds, sp 3 C-H bond oxidative activation, and intramolecular dehydrative coupling reaction to construction of N-heterobicyclic ring. With this protocol, a wide range of functionalized imidazo[1,2-a]pyridines sharing the same structure skeleton as those commercial drug molecules, such as Zolimidine, Alpidem, Saripidem, etc., were synthesized from different lignin β-O-4 model compounds and one β-O-4 polymer, emphasizing the application feasibility of lignin derivatives in N-heterobicyclic pharmaceutical synthesis.
研究领域:
有机化学
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生物炼制
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药物化学
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DOI
高影响因子
ACS Omega
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2021
·
IF 3.512
Xu Chen,Xingyu Ouyang,Jiayi Li,Yi-Lei Zhao
Laccase–mediator systems (LMSs) have been intensively investigated in lignin degradation. Although only natural metabolites are available for fungal lignin degradation, mediator molecules from metabolites have received substantially less attention than artificial organic–synthetic compounds. It remains unclear which metabolites can accelerate laccase-catalyzed reactions and how those natural mediators influence lignin degradation. In this work, we evaluated Trametes versicolor laccase-catalyzed reaction kinetics on a lignin guaiacyl subunit model (guaiacylglycerol-β-guaiacyl ether, G-β-GE) in the presence of a group of lignin syringyl subunit molecules: syringaldehyde, acetosyringone, and methyl syringate. We then compare their performance to a well-known synthetic mediator ABTS, 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid). Time-resolved UPLC-TOF-MS revealed that the syringyl mediators were more effective in accelerating the β-O-4 cleavage and Cα-oxidation of G-β-GE than ABTS under laccase-catalysis, despite the syringyl compounds possessing slower individual oxidation rates. In addition, the product profile of polymerization was also promoted dramatically, compared to that of the ABTS/laccase system. The LMS kinetic modeling suggested that mediator–substrate aggregation played a critical role in the laccase–mediator system; in which, the lignin syringyl and guaiacyl subunits likely form a π–π stacking van der Waals complex that can be oxidized faster than the syringyl or guaiacyl monomers by themselves. This syringyl–guaiacyl aggregation hypothesis postulates that the weak interactions in lignin biopolymers are able to accelerate the laccase-catalyzed biodegradation.
研究领域:
生物化学
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环境科学
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产品关联
DOI
PubMed
高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
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2024
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IF 7.7
Yanqing Zheng,Xiheng Kang,Zi You,Yihan Li,Yongheng Huang,Tieguang He,Tianming Su,Arthur J. Ragauskas,Zhenglong Li,Qiong Wang,Xueping Song
As an “upstream” process in biorefinery, biomass dismantling can dismantle the natural stable structure of lignocellulosic biomass and separate its three major components. To increase the value of the entire biomass by fully utilizing the three main components (cellulose, lignin, and hemicellulose), this study proposes a two-step decomposition system combining formic acid (FA) pretreatment and ethylene glycol-NaOH (EGA) dismantling, aiming to effectively convert sugarcane bagasse into xylose, fermentable glucose, and high-value lignin. In the first step, FA pretreatment removed 79.85 % of hemicellulose at 140 °C for 90 min with 3 % FA. Based on the first step, further combination of EGA dismantling can achieve a hemicellulose removal rate of 92.05 % and a lignin removal rate of 95.90 %. In addition, the solid residue was hydrolyzed by enzymes, and the glucose conversion rate was close to 83.29 % when the cellulase dosage was 10 FPU/g. In addition, the lignin recovered by this system retained 83.62 % of the natural β-O-4 structure, which has the potential to catalyze the formation of aromatic monomers. In summary, this gentle two-step system simultaneously improves the efficiency of lignocellulose decomposition and produces different value-added products, demonstrating the potential for industrial-scale production.
研究领域:
生物化学
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生物质能工程
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产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）