CN114989449B - Lignin-anthraquinone electrolyte material and preparation method and application thereof - Google Patents

Lignin-anthraquinone electrolyte material and preparation method and application thereof Download PDF

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CN114989449B
CN114989449B CN202210709369.4A CN202210709369A CN114989449B CN 114989449 B CN114989449 B CN 114989449B CN 202210709369 A CN202210709369 A CN 202210709369A CN 114989449 B CN114989449 B CN 114989449B
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anthraquinone
lignin
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aqueous solution
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CN114989449A (en
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戴红旗
焦亮
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Nanjing Forestry University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
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Abstract

The invention discloses a lignin-anthraquinone electrolyte material and a preparation method and application thereof, belonging to the technical field of battery energy storage. The method comprises the steps of firstly enabling 1,4-dihydroxy anthraquinone to generate conjugation transfer and ionization under an alkaline condition, then adding lignin monomers to enable the lignin monomers to generate cyclization reaction to form lignin-anthraquinone cyclization derivatives, and finally separating the lignin-anthraquinone derivatives through a chromatographic column to obtain the lignin-anthraquinone electrolyte material. The lignin-anthraquinone electrolyte material prepared by the invention overcomes the defect of poor chemical stability of anthraquinone electrolyte materials, and simultaneously improves the electrochemical activity of lignin-based electrolyte materials. The invention has the advantages of simple preparation method, excellent electrochemical performance, low raw material cost and the like, and the obtained electrolyte material has high capacitance and long service life.

Description

Lignin-anthraquinone electrolyte material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of battery energy storage, and particularly relates to a lignin-anthraquinone electrolyte material and a preparation method and application thereof.
Background
Organic Redox Flow Batteries (ORFBs) use electrochemically active organic molecules as electrolyte materials, and are becoming one of the important technologies for realizing green large-scale energy storage under the "dual-carbon" strategy due to their characteristics of high storage capacity, low cost, synthesis adjustability and the like in nature. The organic electrolyte material can avoid energy loss caused by the fact that substances with redox activity penetrate through an ion exchange membrane in the charging and discharging processes, and is a good substitute of an inorganic electrolyte material.
Organic matters with electrochemical active groups such as phenolic hydroxyl, methoxyl, sulfur, nitrogen and the like can realize the transfer and storage of electrons through redox reaction, and are common energy storage electrolyte materials. The lignin is used as an aromatic compound with the largest reserve in nature, is rich in a phenolic hydroxyl structure and has an energy storage characteristic. Compared with the method using metal ions as the electrolyte of the flow battery, the method has the advantages that the cost is obviously reduced, but the defects of poor oxidation-reduction potential symmetry, unsatisfactory cycle stability and the like still exist. Anthraquinone has been widely used as an organic electrolyte material of a flow battery, but anthraquinone has poor chemical stability, and the service life of the flow battery equipped with the anthraquinone is short.
Disclosure of Invention
In view of the above problems in the prior art, the first technical problem to be solved by the present invention is to provide a lignin-anthraquinone electrolyte material; the second technical problem to be solved by the invention is to provide a preparation method of the lignin-anthraquinone electrolyte material; the third technical problem to be solved by the invention is to provide an application of the lignin-anthraquinone electrolyte material as a negative electrode electrolyte material of a flow battery.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a lignin-anthraquinone electrolyte material comprises the following steps:
1) 1,4-dihydroxy anthraquinone, sodium thiosulfate, sodium hydroxide aqueous solution and ethanol aqueous solution are taken and stirred and dissolved in ice water bath, so that 1,4-dihydroxy anthraquinone is subjected to conjugate transfer and ionized into an ionic state;
2) Adding a lignin monomer into the solution obtained in the step 1) to carry out cyclization reaction, and adding hydrochloric acid to carry out acidification treatment after the cyclization reaction is terminated to obtain a reaction product; the molar ratio of the lignin monomer to 1,4-dihydroxy anthraquinone is 1: 2-4: 1;
3) Extracting, drying and concentrating the reaction product obtained in the step 2), and separating the residue by using a rapid chromatographic column to obtain the lignin-anthraquinone cyclic derivative.
Further, in step 1), the ratio of the amounts of 1,4-dihydroxyanthraquinone, sodium thiosulfate, aqueous sodium hydroxide solution and aqueous ethanol solution is 0.1 mmol: 1 mmol: 5 mL: 10mL.
Further, in the step 1), the concentration of the aqueous solution of sodium hydroxide is 3mol/L.
Further, in the step 2), the temperature of the cyclization reaction is-20 to 20 ℃, and the time of the cyclization reaction is 10 to 70 minutes.
Further, in the step 2), 30wt.% of hydrogen peroxide is adopted to terminate the cyclization reaction; in this application, 1ml of 30wt.% hydrogen peroxide was added and stirring was continued for 10 minutes to terminate the cyclization reaction.
Further, in the step 2), the concentration of hydrochloric acid is 3mol/L.
Further, in the step 2), the lignin monomer is coniferyl aldehyde or sinapine aldehyde.
Further, in the step 3), the reaction product obtained in the step 2) is extracted by dichloromethane, dried and concentrated, and the residue is separated by a flash chromatography column on silica gel by taking dichloromethane as a mobile phase to obtain the lignin-anthraquinone cyclized derivative.
Furthermore, the mesh number of the silica gel is 200-300 meshes.
The lignin-anthraquinone electrolyte material prepared by the method.
The lignin-anthraquinone electrolyte material is applied to being used as a negative electrode electrolyte material of a flow battery.
Compared with the prior art, the invention has the beneficial effects that:
the invention obtains the lignin-anthraquinone electrolyte material by cyclization reaction of the lignin monomers (coniferyl aldehyde and sinapinal) and 1,4-dihydroxy anthraquinone, the electrolyte material has simple preparation method and good electrochemical characteristics, improves the electrochemical activity of lignin and the chemical stability of anthraquinone, and controls the yield of cyclization products by adjusting the raw material ratio, the reaction temperature and the reaction time, thereby obtaining the electrolyte material of the liquid flow battery with high electric capacity and long service life.
Drawings
FIG. 1 is a nuclear magnetic map of a lignin-anthraquinone cyclized derivative prepared in example 1; in the figure, G is coniferyl aldehyde, and LAQD (G) is coniferyl aldehyde-anthraquinone cyclized derivative;
FIG. 2 is a nuclear magnetic map of the lignin-anthraquinone cyclized derivative prepared in example 2; in the figure, S is sinapildehyde and LAQD (S) is sinapildehyde-anthraquinone cyclized derivative;
FIG. 3 is a cyclic voltammogram of the lignin-anthraquinone prepared in example 1 at different sweep rates;
FIG. 4 is a cyclic voltammogram of the lignin-anthraquinone prepared in example 2 at different sweep rates;
FIG. 5 is a constant voltage charge and discharge curve and a constant current charge and discharge curve of the lignin-anthraquinone prepared in example 1;
FIG. 6 is a constant voltage charge and discharge curve and a constant current charge and discharge curve for the lignin-anthraquinone prepared in example 2.
Detailed Description
The invention is further described with reference to specific examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Modifications or substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and scope of the invention. In the following examples, unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
Example 1
Putting 0.1mmol of 1, 4-dihydroxyanthraquinone, 1mmol of sodium thiosulfate, 5mL of sodium hydroxide aqueous solution (3 mol/L) and 10mL of ethanol aqueous solution into a four-neck flask, introducing nitrogen for protection, stirring in an ice-water bath at 0 ℃, adding 0.4mmol of coniferyl aldehyde after complete dissolution, reacting at 0 ℃ for 50 minutes, adding 1mL of hydrogen peroxide (30 wt%), continuing stirring for 10 minutes, finishing the reaction, and adding 1mL of hydrochloric acid (3 mol/L) for acidification to obtain a reaction product. Extracting the obtained mixture by using dichloromethane, drying and concentrating, separating residues by using dichloromethane as a mobile phase through flash column chromatography on silica gel (200-300 meshes), and purifying to obtain a cyclization product, wherein the selectivity of the cyclization product reaches 72.3%, the yield of the cyclization product is 71.7%, and the cyclization degree of a lignin monomer is 17.9%.
FIG. 1 shows nuclear magnetic spectra before and after cyclization reaction of coniferyl aldehyde, respectively, and the result shows that the cyclization product retains the characteristic absorption peak of coniferyl aldehyde. In that 1 In the H-NMR spectrum, the absorption peak of hydrogen on the benzene ring is at 6.8-8.7ppmThe strong absorption peak of hydrogen on methoxy at 3.8ppm, whereas the cyclization product has a strong absorption peak at 5.8ppm, compared to coniferyl aldehyde, here the absorption peak of hydrogen on the cyclization structure; in that 13 In the C-NMR spectrum, the cyclized product had an absorption peak at 134 to 136ppm of carbon in the cyclized structure as compared with coniferyl aldehyde, which confirmed that a coniferyl aldehyde-anthraquinone derivative was produced by the cyclization reaction.
Cyclic voltammograms were tested using a CHI 660e electrochemical workstation (660 e, china). Weighing a certain amount of coniferyl aldehyde-anthraquinone cyclized derivative, dissolving the coniferyl aldehyde-anthraquinone cyclized derivative in 40mL of KOH aqueous solution with different pH values to prepare saturated electrolyte, placing the saturated electrolyte in an electrolytic cell, and introducing nitrogen for 20min, thereby avoiding the influence of oxygen on the redox reaction. And (3) performing cyclic voltammetry on the electrolyte by using a three-electrode system to determine the oxidation-reduction potential of the lignin monomer.
FIG. 3 is a cyclic voltammogram of example 1, in which a plurality of oxidation peaks occur in the positive sweep, due to the difference in oxidation potential between the quinone structure on 1,4-dihydroxyanthraquinone and the quinone structure on coniferyl aldehyde, which are-0.58V and 0.16V, respectively; in the reverse scanning process, the quinone structure on 1,4-dihydroxy anthraquinone is more easily reduced, so that a reduction peak appears at-0.67V; compared with coniferyl aldehyde monomer, the 1,4-dihydroxyanthraquinone with stronger electrochemical activity is introduced into the molecular structure, so that the cyclized derivative is easier to be oxidized and reduced, and the energy storage is more favorable.
For the cycle charge and discharge test of the full cell, the electrolyte was assembled in a completely discharged state. And (3) positive electrode electrolyte: weighing 0.683g K 4 Fe(CN) 6 Dissolved in 40mL KOH aqueous solution (1 mol/L) to prepare 0.04mol/L K 4 Fe(CN) 6 A positive electrode electrolyte; and (3) cathode electrolyte: 40mL of KOH aqueous solution (1 mol/L) is respectively dissolved with 0.0712g of coniferyl aldehyde-anthraquinone to prepare 0.01mol/L of lignin anthraquinone cathode electrolyte. Serpertine flow type coke-sealed POCO graphite flow plates are adopted at two sides of the flow battery as collecting electrodes, a Nation-212 membrane is adopted as an ion exchange membrane, and polytetrafluoroethylene sheets are adopted between the graphite plates for sealing. The electrolyte was controlled by a peristaltic pump at a rate of 50 mL/min. Performed using CHI 660e electrochemical workstation (660 e, china)Constant current charge and discharge test and constant voltage charge and discharge test.
FIG. 5 is a constant voltage charge and discharge curve and a constant current charge and discharge curve for the lignin-anthraquinone prepared in example 1. At 40mAcm -2 Under the current density, the capacitance can reach 148.0mAhl -1 The electric capacity of the cyclic derivative is close to that of the coniferyl aldehyde monomer, which shows that the coniferyl aldehyde-anthraquinone cyclic derivative has the same electron number loss as the coniferyl aldehyde in the oxidation-reduction process under the same current density, and the coniferyl aldehyde-anthraquinone cyclic derivative is not completely oxidized and reduced; and a constant voltage cyclic charge and discharge test was carried out at a current density of 40mA cm -2 When the open-circuit voltage is 1.2V, the initial volume capacitance can reach 148.0 mAh.L -1 After 200 cycles of charging and discharging, the volume capacitance is 132.2 mAh.L -1 The capacity retention rate reaches 89.3%, and the coulomb efficiency is always maintained at about 99% in the charging and discharging process.
Example 2
Putting 0.1mmol of 1, 4-dihydroxyanthraquinone, 1mmol of sodium thiosulfate, 5mL of sodium hydroxide aqueous solution (3 mol/L) and 10mL of ethanol aqueous solution into a four-neck flask, introducing nitrogen for protection, stirring in an ice-water bath at 0 ℃, adding 0.4mmol of sinapine after complete dissolution, reacting at 0 ℃, adding 1mL of hydrogen peroxide (30 wt%) after 50 minutes of reaction, continuing stirring for 10 minutes, ending the reaction, and adding 1mL of hydrochloric acid (3 mol/L) for acidification treatment to obtain a reaction product. The resulting mixture was extracted with dichloromethane, dried and concentrated, and the residue was subjected to flash column chromatography on silica gel (200-300 mesh) with dichloromethane as the mobile phase, and purified to give the cyclized product with a selectivity of 20.3%, yield of 69.8%, and degree of cyclization of lignin monomer of 17.0%.
FIG. 2 is a nuclear magnetic diagram of the lignin-anthraquinone cyclized derivative prepared in example 2. The cyclization reaction of sinapinal with 1,4-dihydroxyanthraquinone is the same as coniferyl aldehyde, and FIG. 5 shows nuclear magnetic spectra before and after the reaction of sinapine aldehyde. Compared with sinapinal, in 1 In an H-NMR spectrum, the cyclized product has a strong absorption peak at 5.8ppm, which is an absorption peak of hydrogen on the cyclized structure; in that 13 Absorption of carbon having a cyclized structure at 134-136ppm in a C-NMR spectrumPeak, indicating sinapildehyde forms a cyclized structure with 1,4-dihydroxyanthraquinone.
The cyclic voltammogram was tested as in example 1.
FIG. 4 is a cyclic voltammogram of the lignin-anthraquinone prepared in example 2 at different sweep rates. The oxidation potential is-0.58V.
The cycle charge and discharge test was the same as in example 1.
FIG. 6 is a graph showing permanent charge and discharge and constant current charge and discharge of lignin-anthraquinone prepared in example 2. The potential change was greater with increasing current density, since sinapine was rapidly oxidized with increasing current density, so a current density of 1mAcm was chosen -2 Can realize continuous charge and discharge, so that the voltage is kept on a working platform, and the capacitance can reach 132.1mAhL -1 Compared with sinapine aldehyde monomer, the capacitance is obviously improved, which shows that the quinone structures on the sinapine aldehyde and anthraquinone molecules are simultaneously oxidized and reduced under low current density, the number of lost electrons is increased, and the capacitance is improved; and through constant voltage cyclic charge and discharge test, the current density is 1mAcm -2 When the open-circuit voltage is 1.2V, the initial volume capacitance can reach 132.1mAhL -1 After 200 cycles of charging and discharging, the volume capacitance is 107.3mAhL -1 The capacitance retention rate reaches 81.2%, and is obviously improved compared with the capacitance retention rate of a sinapildehyde monomer, so that the chemical stability is improved, and the oxidation state and the reduction state of the capacitor are stable in the charging and discharging processes; and the coulomb efficiency is always maintained at about 99% in the charging and discharging process.
Example 3
Putting 0.1mmol of 1, 4-dihydroxyanthraquinone, 1mmol of sodium thiosulfate, 5mL of sodium hydroxide aqueous solution (3 mol/L) and 10mL of ethanol aqueous solution into a four-neck flask, introducing nitrogen for protection, stirring in an ice-water bath at 0 ℃, adding 0.05mmol of sinapaldehyde after complete dissolution, reacting at-20 ℃, adding 1mL of hydrogen peroxide (30 wt%) after 70 minutes, continuing stirring for 10 minutes, ending the reaction, and adding 1mL of hydrochloric acid (3 mol/L) for acidification to obtain a reaction product. The resulting mixture was extracted with dichloromethane, dried and concentrated, and the residue was subjected to flash column chromatography on silica gel (200-300 mesh) with dichloromethane as the mobile phase and purified to give the cyclized product.
Example 4
Putting 0.1mmol of 1, 4-dihydroxyanthraquinone, 1mmol of sodium thiosulfate, 5mL of sodium hydroxide aqueous solution (3 mol/L) and 10mL of ethanol aqueous solution into a four-neck flask, introducing nitrogen for protection, stirring in an ice-water bath at 0 ℃, adding 0.4mmol of sinapine after complete dissolution, reacting at 20 ℃, adding 1mL of hydrogen peroxide (30 wt%) after 10 minutes of reaction, continuing stirring for 10 minutes, ending the reaction, and adding 1mL of hydrochloric acid (3 mol/L) for acidification treatment to obtain a reaction product. The resulting mixture was extracted with dichloromethane, dried and concentrated, and the residue was subjected to flash column chromatography on silica gel (200-300 mesh) with dichloromethane as the mobile phase and purified to give the cyclized product.
The lignin monomer can perform cyclization reaction with 1,4-dihydroxy anthraquinone in alkaline environment, and phenolic hydroxyl and methoxyl on the lignin monomer are not damaged. The lignin monomer and the anthraquinone cyclized derivative can be used for preparing organic electrolyte materials, can overcome the defect of poor chemical stability of anthraquinone electrolyte materials, and simultaneously improves the electrochemical activity of lignin-based electrolyte materials.

Claims (10)

1. The preparation method of the lignin-anthraquinone electrolyte material is characterized by comprising the following steps:
1) 1,4-dihydroxy anthraquinone, sodium thiosulfate, sodium hydroxide aqueous solution and ethanol aqueous solution are taken and stirred and dissolved in ice water bath, so that 1,4-dihydroxy anthraquinone is subjected to conjugate transfer and ionized into an ionic state;
2) Adding a lignin monomer into the solution obtained in the step 1) to carry out cyclization reaction, and adding hydrochloric acid to carry out acidification treatment after the cyclization reaction is terminated to obtain a reaction product; the molar ratio of the lignin monomer to 1,4-dihydroxy anthraquinone is 1: 2-4: 1;
3) Extracting, drying and concentrating the reaction product obtained in the step 2), and separating the residue by using a rapid chromatographic column to obtain the lignin-anthraquinone cyclic derivative.
2. The method for preparing the lignin-anthraquinone electrolyte material according to claim 1, wherein in the step 1), the using ratio of 1,4-dihydroxy anthraquinone, sodium thiosulfate, an aqueous solution of sodium hydroxide and an aqueous solution of ethanol is 0.1 mmol: 1 mmol: 5 mL: 10mL.
3. The method for producing a lignin-anthraquinone electrolyte material according to claim 1, wherein in step 1), the concentration of the aqueous solution of sodium hydroxide is 3mol/L.
4. The method for producing a lignin-anthraquinone electrolyte material according to claim 1, wherein in the step 2), the temperature of the cyclization reaction is-20 to 20 ℃, and the time of the cyclization reaction is 10 to 70 minutes.
5. The preparation method of the lignin-anthraquinone electrolyte material according to claim 1, wherein in the step 2), 30wt.% of hydrogen peroxide is adopted to terminate the cyclization reaction; the concentration of hydrochloric acid was 3mol/L.
6. The method for preparing a lignin-anthraquinone electrolyte material according to claim 1, wherein in step 2), the lignin monomer is coniferyl aldehyde or sinapaldehyde.
7. The method for preparing the lignin-anthraquinone electrolyte material according to claim 1, wherein in the step 3), the reaction product obtained in the step 2) is extracted by dichloromethane, dried and concentrated, and the residue is separated by a flash chromatography column on silica gel by taking dichloromethane as a mobile phase to obtain the lignin-anthraquinone cyclic derivative.
8. The method of preparing a lignin-anthraquinone electrolyte material according to claim 7, wherein the mesh number of the silica gel is 200-300 mesh.
9. The lignin-anthraquinone electrolyte material produced by the method of any one of claims 1 to 8.
10. The use of the lignin-anthraquinone electrolyte material of claim 9 as a negative electrolyte material for a flow battery.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5595628A (en) * 1992-05-05 1997-01-21 Grant S.A. Production of pulp by the soda-anthraquinone process (SAP) with recovery of the cooking chemicals
JP2006172921A (en) * 2004-12-16 2006-06-29 Osaka Univ Lead acid storage battery and negative electrode and negative electrode active material used for it
CN109072088A (en) * 2016-04-07 2018-12-21 Cmblu企划股份公司 The method for preparing the aromatic series lignin-derived compounds of low molecular weight

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5595628A (en) * 1992-05-05 1997-01-21 Grant S.A. Production of pulp by the soda-anthraquinone process (SAP) with recovery of the cooking chemicals
JP2006172921A (en) * 2004-12-16 2006-06-29 Osaka Univ Lead acid storage battery and negative electrode and negative electrode active material used for it
CN109072088A (en) * 2016-04-07 2018-12-21 Cmblu企划股份公司 The method for preparing the aromatic series lignin-derived compounds of low molecular weight

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Donald R. Dinmel et al.Electron Transfer Reactions in Pulping Systems (II): Electrochemistry of Anthraquinone/Lignin Model Quinonemethides.Journal of Wood Chemistry and Technology .2007,第5卷(第1期),15-36. *
Maryam Rajabi et al.Green and one-pot electrochemical synthesis of new benzofurans based on an ECC mechanism.Progress in reaction kinetics and mechanism.2015,第40卷(第2期),163-168. *
Tsutomu Ikeda et al.Chemical Properties of Softwood Soda-Anthraquinone Lignin.Journal of Wood Chemistry and Technology .2015,第35卷(第3期),167-177. *

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