CN114989448A - System for regulating and controlling different lignin morphologies and regulating and controlling method thereof - Google Patents

System for regulating and controlling different lignin morphologies and regulating and controlling method thereof Download PDF

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CN114989448A
CN114989448A CN202210637054.3A CN202210637054A CN114989448A CN 114989448 A CN114989448 A CN 114989448A CN 202210637054 A CN202210637054 A CN 202210637054A CN 114989448 A CN114989448 A CN 114989448A
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lignin
regulating
electrolyte
controlling
cosolvent
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CN114989448B (en
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姜曼
胡翔洲
徐汪杰
王峰
周昱帆
陆远
潘宇
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Southwest Jiaotong University
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Abstract

The invention discloses a system for regulating and controlling different lignin morphologies and a regulating and controlling method thereof, wherein the system comprises: independently dispensed co-solvent and/or electrolyte. The regulation and control method comprises the following steps: adding lignin into water, adding cosolvent, mixing, and dialyzing; or adding lignin into water, adding cosolvent, adding electrolyte, mixing, and dialyzing. The invention provides a system and a method for regulating and controlling lignin to form nanotubes, nanowires, nanocapsules and other different shapes, the system and the method are simple and low in cost, the lignin is regulated and controlled to form different nanometer shapes by regulating and controlling co-solvent, electrolyte and dialysis parameters, and the obtained lignin nanotube is a lignin nanotube with a new shape and has a branch structure and an end-capping structure.

Description

System for regulating and controlling different lignin morphologies and regulating and controlling method thereof
Technical Field
The invention relates to the technical field of lignin, in particular to a system for regulating and controlling the shapes of different lignin and a regulating and controlling method thereof.
Background
The lignin is the only renewable natural aromatic macromolecule in the nature, the source of the lignin is wide, the lignin accounts for more than 15-30% of various agriculture and forestry biomass resources, in addition, the pulping and papermaking industry can also generate a large amount of lignin wastes, and the lignin wastes are mostly consumed as low-value fuels or fillers, so that the resource waste is caused. The lignin has the functions of antibiosis, antioxidation, ultraviolet absorption and the like, contains a large number of phenolic hydroxyl functional groups, and can be assembled into a stable nano structure by means of pi-pi interaction and hydrogen bond interaction of benzene rings of the lignin. The existing common lignin nanostructures are as follows: nanospheres and nanoparticles, but no system for regulating and controlling lignin molecules to assemble into different nano shapes is found.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a system for regulating and controlling the shapes of different lignins and a regulating and controlling method thereof, wherein the system can regulate and control the lignins to form nanotubes, nanowires, nanocapsules and other shapes.
The technical scheme for solving the technical problems is as follows: providing a system for regulating and controlling different lignin morphologies, comprising: independently dispensed co-solvents and/or electrolytes; the electrolyte is formed by the following anions and cations:
the cation being H + 、Na + 、K + 、Ca 2+ 、Mg 2+ 、Cu 2+ 、Fe 2+ 、Fe 3+ 、Zn 2+ 、Ag + And Al 3+ Any one of the above;
the anion being Cl - 、Br - 、I - 、NO 3 - 、SO 4 2- 、HSO 4 - 、PO 4 3- 、HPO 4 2- 、HPO 3 2- 、OH - 、CO 3 2- And HCO 3 - Any one of them.
The invention has the beneficial effects that: the cosolvent is used for promoting the dissolution of lignin in water, and the electrolyte can be combined with the lignin to promote the self-assembly of the lignin to form the lignin nano-tubes or nano-wires. The formation of lignin nanotubes is based on the combination of lignin with electrolytes with weak complexing power, while the formation of lignin nanowires is based on the combination of lignin with electrolytes with strong complexing power.
On the basis of the technical scheme, the invention can be further improved as follows:
further, when the electrolyte is formed by the following anions and cations, the lignin can be regulated to form the lignin nanotube:
the cation being H + 、Na + 、K + 、Ca 2+ 、Mg 2+ 、Cu 2+ 、Fe 2+ 、Fe 3+ 、Zn 2+ And Ag + Any one of the above;
the anion being Cl - 、Br - 、I - 、NO 3 - 、SO 4 2- 、HSO 4 - 、PO 4 3- 、HPO 4 2- 、HPO 3 2- 、OH - 、CO 3 2- And HCO 3 - Any one of them.
The beneficial effects of adopting the further technical scheme are as follows: the electrolyte used for forming the lignin nanotubes is the above-mentioned cation-forming substance, and the electrolyte is an electrolyte with weak complexing ability, and the inventors guess that the formation of the lignin nanotubes by the electrolyte may be because the cations in the electrolyte, in particular, may complex with lignin, and may promote the formation of the lignin nanotubes.
Further, lignin can be regulated to form lignin nanowires when the electrolyte is formed by the following anions and cations:
the cation being Fe 3+ Or Al 3+ ；
The anion being Cl - 、Br - 、I - 、NO 3 - 、SO 4 2- 、HSO 4 - 、PO 4 3- 、HPO 4 2- And HPO 3 2- Any one of them.
The beneficial effect of adopting the further technical scheme is as follows: the electrolyte species plays a very critical role in the formation of lignin nanowires when strong electrolytes such as those containing Fe as described above are added 3+ 、Al 3+ The cationic substance can effectively promote the formation of lignin nanowires, and the added electrolyte does not have strong complexing ability, for example, the electrolyte with weak complexing ability such as Fe-containing electrolyte is added 2+ The cationic species do not form lignin nanowires.
Further, lignin can be manipulated to form lignin nanocapsules when no electrolyte is added.
Furthermore, the cosolvent is alcohol, an aprotic solvent, a protic solvent, a deep eutectic solvent or ionic liquid.
Further, the alcohol is methanol, ethanol or ethylene glycol; the aprotic solvent is tetrahydrofuran or dioxane; the protic solvent is N, N-dimethylformamide; the deep eutectic solvent is choline chloride/citric acid, choline chloride/acetic acid; the ionic liquid is [ Amim ] Cl, [ Bmim ] Cl and DMSO/TBAH.
The beneficial effect of adopting the further technical scheme is as follows: the cosolvent can be a pure substance or an aqueous solution of the substance, can enable lignin to be quickly dissolved in water, and enables the lignin to be self-assembled to form nanocapsules through dialysis, or can be combined with an electrolyte to promote the formation of lignin nanotubes or nanowires. The above-mentioned partial cosolvents are only listed, for example, the alcohol substance as the cosolvent can be not only methanol, ethanol or ethylene glycol as the cosolvent in the technical scheme, but also other alcohol substances as long as the alcohol substance can play the same solubilizing role, which is not listed here.
The method for regulating and controlling the lignin to form different morphologies by adopting the system comprises the following steps:
adding lignin into water, adding cosolvent, mixing, and dialyzing; or
Adding lignin into water, adding cosolvent, adding electrolyte, mixing, and dialyzing.
The invention has the beneficial effects that: the lignin is added into water, then the cosolvent is added, the dissolving speed of the lignin in the water can be accelerated, the lignin is uniformly dispersed in the water, and then the lignin can be self-assembled to form the lignin nanocapsule in the dialysis process through the dialysis process.
When electrolyte with weak complexing ability is added before dialysis, the electrolyte can be complexed with groups in lignin, and the lignin can be effectively promoted to be self-assembled to form a nano tube in the dialysis process. In the preparation process of the lignin nanotube, the size can be influenced by electrolyte, cosolvent and dialysis factors, and the diameter and the length-diameter ratio of the lignin nanotube can be regulated and controlled by regulating the parameters.
When electrolyte with strong complexing ability is added before dialysis, the electrolyte can form strong complexing with groups in lignin, and the formation of lignin nanowires can be effectively promoted in the dialysis process. The size of the lignin nanowire can be regulated and controlled by factors such as electrolyte, cosolvent and dialysis. Electrolyte Fe with strong complexing power 3+ ，Al 3+ The diameter of the nanotube is reduced, the length is not changed, the length-diameter ratio is increased, and the nanowire is formed; the dialysis temperature is increased, the diameter of the nanotube is unchanged, the length is reduced, and the length-diameter ratio is reduced.
The electrolyte species plays a very crucial role in the formation of lignin nanowires or lignin nanotubes when strong electrolytes are added, such as those containing Fe as described above 3+ 、Al 3+ The cationic substance can effectively promote the formation of lignin nanowires, and the added electrolyte does not have strong complexing ability, for example, the electrolyte with weak complexing ability such as Fe-containing electrolyte is added 2+ The cationic species do not form lignin nanowires but nanotubes, when strongly complexed electrolytes such as Fe are present 3+ Cations, which form nanotubes only at low concentrations when an electrolyte containing the ions is added, and at too high concentrationsNanowires are formed.
Further, the lignin is a pure lignin reagent such as dealkalized lignin, sodium lignosulfonate and the like.
Further, the mass concentration of the lignin in the cosolvent aqueous solution is 1-20%, that is, the lignin is added into water, and then the cosolvent is added, and the mass concentration of the lignin in the reaction system reaches 1-20%.
Furthermore, after the cosolvent is added, the volume concentration of the cosolvent in the reaction system is 10-90%.
The beneficial effect of adopting the further technical scheme is as follows: the lignin is added into water, and then the cosolvent is added to promote the lignin to be dissolved quickly, the mass concentration of the lignin is 1-20%, and the lignin can be dissolved quickly under the cosolvent condition at the concentration, so that the lignin with different shapes in the later period is formed.
Further, the concentration of the electrolyte in the reaction system is 0.01-1mol/L after the electrolyte is added.
The beneficial effect of adopting the further technical scheme is as follows: only when the concentration of the added electrolyte in the reaction system is 0.01-1mol/L, the added electrolyte can be effectively combined with lignin to form lignin nanotubes or lignin nanowires, namely, only when the specific electrolyte is at a specific concentration, the lignin with a specific shape can be effectively formed.
Further, the dialysis temperature is 20-60 deg.C, and the dialysis time is 2-4 days.
The beneficial effect of adopting the further technical scheme is as follows: during the dialysis process, lignin can be self-assembled to form lignin nanotubes, nanowires or nanocapsules, and the dialysis temperature and the dialysis time can be used for determining parameters such as the aspect ratio of the shapes. As in the above dialysis temperature range, the dialysis temperature is increased and the aspect ratio of the nanotubes is decreased.
The invention has the following beneficial effects:
the invention provides a system and a method for regulating and controlling lignin to form nanotubes, nanowires, nanocapsules and other different shapes, the system and the method are simple and low in cost, the lignin is regulated and controlled to form different nanometer shapes by regulating and controlling co-solvent, electrolyte and dialysis parameters, and the obtained lignin nanotube is a lignin nanotube with a new shape and has a branch structure and an end-capping structure.
Drawings
FIG. 1 is an SEM image of a lignin nanotube prepared in example 1 with NaCl as electrolyte.
FIG. 2 is a perspective view of a lignin nanotube prepared in example 1 using NaCl as electrolyte.
FIG. 3 is a second perspective view of the lignin nanotubes prepared in example 1 using NaCl as electrolyte.
FIG. 4 is an SEM topography of lignin raw material and the lignin nanotubes prepared in example 1.
FIG. 5 is an SEM image of the lignin nanotubes prepared in example 2 using sodium bromide as the electrolyte.
FIG. 6 is an SEM image of the lignin nanotubes prepared in example 3 using sodium sulfate as electrolyte.
FIG. 7 is an SEM image of the lignin nanotubes prepared in example 4 using sodium nitrate as electrolyte.
FIG. 8 is an SEM image of the lignin nanotubes prepared in example 5 using copper chloride as electrolyte.
FIG. 9 is an SEM image of the lignin nanotubes prepared in example 6 using ferric chloride as electrolyte.
FIG. 10 is an SEM topography of lignin nanowires prepared in example 7 using ferric chloride as an electrolyte.
FIG. 11 is an SEM topography of lignin nanocapsules prepared in example 8.
FIG. 12 is an SEM topography of the lignin nanotubes prepared in example 10.
Fig. 13 is an SEM topography of lignin nanowires prepared in example 19.
FIG. 14 is an SEM topography of lignin nanocapsules prepared in example 23.
FIG. 15 is a photograph of a feedstock dealkalized lignin.
Fig. 16 is a picture of the raw material sodium lignosulfonate.
FIG. 17 is a photograph of the lignin nanotubes prepared in example 1 after freeze-drying.
Fig. 18 is a photograph of the lignin nanocapsule prepared in example 8 after freeze-drying.
Fig. 19 is a photograph of freeze-dried lignin nanocapsules prepared by replacing the dealkalized lignin as the raw material in example 8 with sodium lignin sulfonate.
Fig. 20 is a photograph of lignin nanowires prepared in example 19 after freeze-drying.
Detailed Description
The following examples are given for the purpose of illustration only and are not intended to limit the scope of the invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
Example 1:
a system for manipulating different lignin morphologies, comprising: tetrahydrofuran (THF) and sodium chloride.
The system is adopted to regulate and control lignin to form the nanotube, and the specific regulation and control method comprises the following steps:
adding dealkalized lignin into water, then adding Tetrahydrofuran (THF), wherein the mass concentration of the lignin in the system is 1%, the volume concentration of the THF is 20%, then adding sodium chloride to enable the concentration to be 0.05mol/L, fully dissolving the lignin and the sodium chloride, and dialyzing for 48h at 30 ℃ to obtain the lignin nanotube.
As can be seen from FIGS. 1 to 3, the morphology of the lignin nanotubes has a branched structure and a capped structure.
In FIG. 4, the figures a-a "are SEM topography of the dealkalized lignin of the lignin raw material, and the figures b-b" are SEM topography of the lignin nano-tube. As can be seen from FIG. 4, the dealkalized lignin is aggregated into large particles, and the lignin nanotubes having a length of about 500 μm and a diameter of about 500nm are obtained by nanocrystallization.
Example 2:
a system for regulating and controlling different lignin morphologies, comprising: tetrahydrofuran (THF) and sodium bromide.
The system is adopted to regulate and control lignin to form the nanotube, and the specific regulation and control method comprises the following steps:
adding dealkalized lignin into water, then adding Tetrahydrofuran (THF), wherein the mass concentration of the lignin in the system is 1%, the volume concentration of the THF is 20%, then adding sodium bromide to enable the concentration to be 0.05mol/L, fully dissolving the lignin and the sodium bromide, and dialyzing for 48h at 30 ℃ to obtain the lignin nanotube.
As can be seen from fig. 5, the lignin nanotubes obtained by the control all have a branched structure and a capped structure.
Example 3:
a system for manipulating different lignin morphologies, comprising: tetrahydrofuran (THF) and sodium sulfate.
The system is adopted to regulate and control lignin to form the nanotube, and the specific regulation and control method comprises the following steps:
adding dealkalized lignin into water, then adding Tetrahydrofuran (THF), wherein the mass concentration of the lignin in the system is 1%, the volume concentration of the tetrahydrofuran is 20%, then adding sodium sulfate to enable the concentration to be 0.05mol/L, fully dissolving the lignin and the sodium sulfate, and dialyzing for 48h at 30 ℃ to obtain the lignin nanotube.
As can be seen from FIG. 6, the lignin nanotubes obtained by the adjustment have both branched structures and end-capped structures.
Example 4:
a system for manipulating different lignin morphologies, comprising: tetrahydrofuran (THF) and sodium nitrate.
The system is adopted to regulate and control lignin to form the nanotube, and the specific regulation and control method comprises the following steps:
adding dealkalized lignin into water, then adding Tetrahydrofuran (THF), wherein the mass concentration of the lignin in the system is 1%, the volume concentration of the THF is 20%, then adding sodium nitrate to enable the concentration to be 0.05mol/L, fully dissolving the lignin and the sodium nitrate, and dialyzing for 48h at 30 ℃ to obtain the lignin nanotube.
As can be seen from fig. 7, the lignin nanotubes obtained by the control all have a branched structure and a capped structure.
Example 5:
a system for regulating and controlling different lignin morphologies, comprising: tetrahydrofuran (THF) and copper chloride.
The system is adopted to regulate and control lignin to form the nanotube, and the specific regulation and control method comprises the following steps:
adding dealkalized lignin into water, then adding Tetrahydrofuran (THF), wherein the mass concentration of the lignin in the system is 1%, the volume concentration of the tetrahydrofuran is 20%, then adding copper chloride to enable the concentration to be 0.05mol/L, fully dissolving the lignin and the copper chloride, and dialyzing for 48h at 30 ℃ to obtain the lignin nanotube.
As can be seen from fig. 8, the lignin nanotubes obtained by the control all have a branched structure and a capped structure.
Example 6:
a system for manipulating different lignin morphologies, comprising: tetrahydrofuran (THF) and ferric chloride.
The system is adopted to regulate and control lignin to form the nanotube, and the specific regulation and control method comprises the following steps:
adding dealkalized lignin into water, then adding Tetrahydrofuran (THF), wherein the mass concentration of the lignin in the system is 1%, the volume concentration of the tetrahydrofuran is 50%, then adding ferric chloride to enable the concentration to be 0.05mol/L, fully dissolving the lignin and the ferric chloride, and dialyzing for 48h at 30 ℃ to obtain the lignin nanotube.
As can be seen from fig. 9, the lignin nanotubes obtained by the control all have a branched structure and a capped structure.
Example 7:
a system for manipulating different lignin morphologies, comprising: tetrahydrofuran (THF) and ferric chloride.
The system is adopted to regulate and control lignin to form the nanowire, and the specific regulation and control method comprises the following steps:
adding dealkalized lignin into water, then adding a cosolvent Tetrahydrofuran (THF), wherein the mass concentration of the lignin in the system is 1%, the volume concentration of the THF is 20%, then adding ferric chloride to enable the concentration of ferric chloride to be 0.05mol/L, and dialyzing for 48h at 30 ℃ after fully dissolving the dealkalized lignin and the ferric chloride to obtain the lignin nanowire.
Example 8:
a system for manipulating different lignin morphologies, comprising: tetrahydrofuran.
The system is adopted to regulate and control lignin to form the nanocapsule, and the specific regulation and control method comprises the following steps:
adding dealkalized lignin into water, then adding Tetrahydrofuran (THF), wherein the mass concentration of the lignin in the system is 1%, and the volume concentration of the THF is 20%, and dialyzing at 30 ℃ for 48h to prepare the lignin nanocapsule.
As can be seen from fig. 11, the lignin self-assembles to form nanocapsules without adding electrolyte.
Example 9:
a system for manipulating different lignin morphologies, comprising: n, N-Dimethylformamide (DMF).
The system is adopted to regulate and control lignin to form the nanocapsule, and the specific regulation and control method comprises the following steps:
adding dealkalized lignin into water, then adding N, N-dimethylformamide, wherein the mass concentration of the lignin in the system is 1 percent, and the volume concentration of the N, N-dimethylformamide is 20 percent, and dialyzing at 30 ℃ for 48 hours to prepare the lignin nanocapsule.
After the lignin is dissolved in water and a cosolvent, the lignin and the cosolvent with specific concentrations are formed, then self-assembly is carried out under the dialysis condition, and the lignin is self-assembled to form the nanocapsule under the condition of not adding electrolyte.
Example 10:
a system for manipulating different lignin morphologies, comprising: tetrahydrofuran (THF) and sodium chloride.
The system is adopted to regulate and control lignin to form the nanotube, and the specific regulation and control method comprises the following steps:
adding dealkalized lignin into water, then adding Tetrahydrofuran (THF), wherein the mass concentration of the lignin in the system is 1%, the volume concentration of the THF is 20%, then adding sodium chloride to ensure that the concentration is 0.05mol/L, fully dissolving the lignin and the sodium chloride, and dialyzing at 60 ℃ for 2 days to prepare the lignin nanotube.
As can be seen from fig. 12, when the dialysis temperature was increased, the length of the lignin nanotubes produced was shortened. Comparing fig. 12 with fig. 1, it is evident that the length of the lignin nanotubes is significantly affected when the dialysis temperature is changed.
Example 11:
a system for manipulating different lignin morphologies, comprising: tetrahydrofuran (THF) and calcium chloride.
The system is adopted to regulate and control lignin to form the nanotube, and the specific regulation and control method comprises the following steps:
adding dealkalized lignin into water, then adding Tetrahydrofuran (THF), wherein the mass concentration of the lignin in the system is 1%, the volume concentration of the THF is 10%, then adding calcium chloride to enable the concentration to be 0.01mol/L, fully dissolving the lignin and the calcium chloride, and dialyzing at 60 ℃ for 2 days to obtain the lignin nanotube.
Example 12:
a system for manipulating different lignin morphologies, comprising: n, N-Dimethylformamide (DMF) and sodium chloride.
The system is adopted to regulate and control lignin to form the nanotube, and the specific regulation and control method comprises the following steps:
adding dealkalized lignin into water, then adding N, N-Dimethylformamide (DMF), wherein the mass concentration of the lignin in the system is 1 percent, the volume concentration of the N, N-dimethylformamide is 10 percent, then adding sodium chloride to ensure that the concentration is 0.01mol/L, and dialyzing for 2 days at 60 ℃ after the lignin and the sodium chloride are fully dissolved to prepare the lignin nanotube.
Example 13:
a system for regulating and controlling different lignin morphologies, comprising: n, N-Dimethylformamide (DMF) and calcium chloride.
The system is adopted to regulate and control lignin to form the nanotube, and the specific regulation and control method comprises the following steps:
adding dealkalized lignin into water, then adding N, N-Dimethylformamide (DMF), wherein the mass concentration of the lignin in the system is 1%, the volume concentration of the N, N-dimethylformamide is 10%, then adding calcium chloride to enable the concentration to be 0.01mol/L, fully dissolving the lignin and the calcium chloride, and dialyzing at 60 ℃ for 2 days to obtain the lignin nanotube.
Example 14:
a system for manipulating different lignin morphologies, comprising: tetrahydrofuran (THF) and potassium carbonate.
The system is adopted to regulate and control lignin to form the nanotube, and the specific regulation and control method comprises the following steps:
adding dealkalized lignin into water, then adding Tetrahydrofuran (THF), wherein the mass concentration of the lignin in the system is 10%, the volume concentration of the tetrahydrofuran is 20%, then adding potassium carbonate to enable the concentration to be 0.05mol/L, fully dissolving the lignin and the potassium carbonate, and dialyzing at 60 ℃ for 2 days to obtain the lignin nanotube.
Example 15:
a system for regulating and controlling different lignin morphologies, comprising: n, N-Dimethylformamide (DMF) and ferric chloride.
The system is adopted to regulate and control lignin to form the nanowire, and the specific regulation and control method comprises the following steps:
adding dealkalized lignin into water, then adding a cosolvent N, N-Dimethylformamide (DMF), wherein the mass concentration of the lignin in the system is 1%, the volume concentration of the N, N-dimethylformamide is 20%, then adding ferric chloride to enable the concentration of the ferric chloride to be 0.2mol/L, and dialyzing for 48h at 30 ℃ after fully dissolving the dealkalized lignin and the ferric chloride to obtain the lignin nanowire.
Example 16:
a system for manipulating different lignin morphologies, comprising: n, N-Dimethylformamide (DMF) and ferric chloride.
The system is adopted to regulate and control lignin to form the nanowire, and the specific regulation and control method comprises the following steps:
adding dealkalized lignin into water, then adding a cosolvent N, N-Dimethylformamide (DMF), wherein the mass concentration of the lignin in the system is 1%, the volume concentration of the N, N-dimethylformamide is 20%, then adding ferric chloride to enable the concentration of the ferric chloride to be 0.1mol/L, and dialyzing for 48h at 30 ℃ after fully dissolving the dealkalized lignin and the ferric chloride to obtain the lignin nanowire.
Example 17:
a system for manipulating different lignin morphologies, comprising: ethanol and ferric chloride.
The system is adopted to regulate and control lignin to form the nanowire, and the specific regulation and control method comprises the following steps:
adding dealkalized lignin into water, then adding cosolvent ethanol, wherein the mass concentration of the lignin in the system is 1%, the volume concentration of the ethanol is 20%, then adding ferric chloride to enable the concentration of the ferric chloride to be 0.1mol/L, fully dissolving the dealkalized lignin and the ferric chloride, and dialyzing for 48h at 30 ℃ to obtain the lignin nanowire.
Example 18:
a system for manipulating different lignin morphologies, comprising: ethanol and ferric chloride.
The system is adopted to regulate and control lignin to form the nanowire, and the specific regulation and control method comprises the following steps:
adding dealkalized lignin into water, then adding cosolvent ethanol, wherein the mass concentration of the lignin in the system is 1%, the volume concentration of the ethanol is 20%, then adding ferric chloride to enable the concentration of the ferric chloride to be 0.2mol/L, fully dissolving the dealkalized lignin and the ferric chloride, and dialyzing for 48h at 30 ℃ to obtain the lignin nanowire.
Example 19:
a system for manipulating different lignin morphologies, comprising: tetrahydrofuran (THF) and ferric chloride.
The system is adopted to regulate and control lignin to form the nanowire, and the specific regulation and control method comprises the following steps:
adding dealkalized lignin into water, then adding a cosolvent Tetrahydrofuran (THF), wherein the mass concentration of the lignin in the system is 1%, the volume concentration of N, N-dimethylformamide is 20%, then adding ferric chloride to enable the concentration of ferric chloride to be 0.1mol/L, and dialyzing for 48h at 30 ℃ after fully dissolving the dealkalized lignin and the ferric chloride to obtain the lignin nanowire.
As can be seen from FIG. 13, the lignin nanowires can be prepared by the above-mentioned regulation system and regulation method, and the diameter of the nanowires is less than 100nm, and the length of the nanowires is greater than 100 μm.
Example 20:
a system for regulating and controlling different lignin morphologies, comprising: tetrahydrofuran (THF) and ferric chloride.
The system is adopted to regulate and control lignin to form the nanowire, and the specific regulation and control method comprises the following steps:
adding dealkalized lignin into water, then adding a cosolvent Tetrahydrofuran (THF), wherein the mass concentration of the lignin in the system is 1%, the volume concentration of N, N-dimethylformamide is 20%, then adding ferric chloride to enable the concentration of ferric chloride to be 0.2mol/L, and dialyzing for 48h at 30 ℃ after fully dissolving the dealkalized lignin and the ferric chloride to obtain the lignin nanowire.
Example 21:
a system for manipulating different lignin morphologies, comprising: tetrahydrofuran and aluminum chloride.
The system is adopted to regulate and control lignin to form the nanowire, and the specific regulation and control method comprises the following steps:
adding dealkalized lignin into water, then adding a cosolvent Tetrahydrofuran (THF), wherein the mass concentration of the lignin in the system is 1%, the volume concentration of the THF is 20%, then adding aluminum chloride to enable the concentration of the aluminum chloride to be 0.05mol/L, and dialyzing for 48h at 30 ℃ after fully dissolving the dealkalized lignin and the aluminum chloride to obtain the lignin nanowire.
Example 22:
a system for manipulating different lignin morphologies, comprising: n, N-dimethylformamide and aluminium chloride.
The system is adopted to regulate and control lignin to form the nanowire, and the specific regulation and control method comprises the following steps:
adding dealkalized lignin into water, then adding a cosolvent N, N-dimethylformamide, wherein the mass concentration of the lignin in a system is 1%, the volume concentration of the N, N-dimethylformamide is 20%, then adding aluminum chloride to ensure that the concentration of the aluminum chloride is 0.05mol/L, and dialyzing for 48h at 30 ℃ after the dealkalized lignin and the aluminum chloride are fully dissolved to prepare the lignin nanowire.
Example 23:
a system for regulating and controlling different lignin morphologies, comprising: and (3) ethanol.
The system is adopted to regulate and control lignin to form the nanocapsule, and the specific regulation and control method comprises the following steps:
adding dealkalized lignin into water, then adding ethanol, wherein the mass concentration of the lignin in the system is 1%, and the volume concentration of the ethanol is 20%, and dialyzing at 30 ℃ for 48h to prepare the lignin nanocapsule.
As shown in fig. 14, the lignin self-assembles to form nanocapsules without adding electrolyte and using ethanol as a cosolvent.
In conclusion, the lignin is added into the water and the cosolvent, or the lignin is directly added into the cosolvent water solution, and the lignin can be self-assembled to form the nanocapsule shape through dialysis under the condition of not adding the electrolyte. The formed lignin nanocapsules are spherical with a diameter of 100-1000 nm.
And after different electrolytes are added, lignin can be regulated to form different appearances, such as lignin nanotubes and lignin nanowires with branch structures (branches can be generated at equal positions in the middle of one nanotube to form a plurality of nanotubes) and end-capping structures (protrusions are arranged at branch positions or at the end parts of the nanotubes). The diameter of the nanowire is less than 100nm, the length of the nanowire is more than 100 mu m, the diameter of the nanotube is 100-600nm, and the length of the nanotube is more than 100 nm.
The invention regulates and controls the lignin to form different nano-morphologies through a regulation and control system, and expands the application of the lignin.
The pictures of the raw material dealkalized lignin and sodium lignosulfonate adopted in the invention are shown in figures 15 and 16. The picture of the lignin nanotube prepared in example 1 after freeze-drying is shown in fig. 17; the picture of the lignin nanocapsule prepared in example 8 after freeze-drying is shown in fig. 18; a picture of the lignin nanocapsule freeze-dried obtained by replacing the dealkalized lignin as the raw material in example 8 with sodium lignosulfonate is shown in fig. 19; the picture of the lignin nanowires prepared in example 19 after freeze-drying is shown in fig. 20.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A system for regulating and controlling different lignin morphologies, comprising: co-solvents and/or electrolytes; the electrolyte is formed by the following anions and cations:
the cation being H + 、Na + 、K + 、Ca 2+ 、Mg 2+ 、Cu 2+ 、Fe 2+ 、Fe 3+ 、Zn 2+ 、Ag + And Al 3+ Any one of the above;
the anion being Cl - 、Br - 、I - 、NO 3 - 、SO 4 2- 、HSO 4 - 、PO 4 3- 、HPO 4 2- 、HPO 3 2- 、OH - 、CO 3 2- And HCO 3 - Any one of them.
2. The system for regulating and controlling the morphology of different lignins according to claim 1, wherein the lignin can be regulated and controlled to form lignin nanotubes when the electrolyte is a substance formed by the following anions and cations:
the cation being H + 、Na + 、K + 、Ca 2+ 、Mg 2+ 、Cu 2+ 、Fe 2+ 、Fe 3+ 、Zn 2+ And Ag + Any one of the above;
the anion being Cl - 、Br - 、I - 、NO 3 - 、SO 4 2- 、HSO 4 - 、PO 4 3- 、HPO 4 2- 、HPO 3 2- 、OH - 、CO 3 2- And HCO 3 - Any one of them.
3. The system for regulating and controlling the morphology of different lignins according to claim 1, wherein the lignin can be regulated and controlled to form lignin nanowires when the electrolyte is formed by the following anions and cations:
the cation being Fe 3+ Or Al 3+ ；
The anion being Cl - 、Br - 、I - 、NO 3 - 、SO 4 2- 、HSO 4 - 、PO 4 3- 、HPO 4 2- And HPO 3 2- Any one of them.
4. The system for regulating and controlling morphology of lignin according to claim 1, wherein the lignin can be regulated and controlled to form lignin nanocapsules without the addition of electrolyte.
5. The system for regulating and controlling morphology of different lignins according to any one of claims 1-3, wherein the co-solvent is an alcohol, an aprotic solvent, a protic solvent, a deep eutectic solvent or an ionic liquid.
6. The method for regulating and controlling lignin to form different shapes by adopting the system of any one of claims 1 to 5 is characterized in that lignin is added into water, then added with cosolvent, mixed evenly and dialyzed; or
Adding lignin into water, adding cosolvent, adding electrolyte, mixing, and dialyzing.
7. The method for regulating and controlling the formation of different morphologies by lignin according to claim 6, wherein the mass concentration of lignin in the cosolvent aqueous solution is 1-20%.
8. The method for regulating and controlling the formation of different morphologies by lignin according to claim 6, wherein the cosolvent is added so that the volume concentration of the cosolvent in the reaction system is 10-90%.
9. The method for regulating and controlling the formation of different morphologies of lignin according to claim 6, wherein the electrolyte is added so that the concentration of the electrolyte in the reaction system is 0.01 to 1 mol/L.
10. The method for regulating and controlling the formation of different morphologies of lignin according to claim 6, wherein the dialysis temperature is 20-60 ℃ and the dialysis time is 2-4 days.
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