CN112143001B - Preparation method of holocellulose nano fluid ion conductor membrane material - Google Patents
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Abstract
The invention relates to a method for preparing a holocellulose nano fluid ion conductor membrane material, which comprises the following steps: s1, dissolving a cellulose raw material in a cellulose solvent to form a cellulose solution; s2, centrifuging the cellulose solution, and adding a chemical cross-linking agent for reaction to generate a crude product; s3, centrifuging and shaping the crude product to obtain alkali gel; s4, orienting and soaking the alkali gel in a coagulating bath to form oriented cellulose hydrogel; and S5, carrying out chemical modification and water washing on the oriented cellulose hydrogel, and carrying out limited-range drying to form a film. The invention successfully prepares the holocellulose nano fluid ion conductor membrane with low cost, degradability, reproducibility, biocompatibility, high strength and high conductivity, can be applied to the research and development of an ultra-sensitive humidity sensor for wearable health monitoring, points out the direction for the application of wearable nano ion conductor materials, and has higher academic and economic benefits.
Description
Technical Field
The invention relates to the field of nanofluid, in particular to a preparation method of a holocellulose nanofluid ion conductor membrane material.
Background
Nanofluids refer to the transport of substances (including liquids, gases, ions, etc.) in channels less than 100 nm. In charged nanochannels, transport of nanofluid ions is mainly dependent on the formation of ionic double layers, also known as Debye layers (Debye layers), at the solid-liquid interface. Positive and negative ions may form a differential charge density in the electric double layer. Different gradient charge densities will encourage ion transport within the channel that produces different rates. Nanofluidic ion transport is also an important process in many physiological activities, such as muscle movement and neuronal signal transmission. These properties give nanofluidic devices great potential in biosensing, ionic devices, desalination, and energy storage.
In order to achieve the nanofluidic effect of ions, the interior of the material requires the presence of a large number of fluidic channels spaced less than 100nm apart, which channels moreover need to be charged. The existing preparation method of the nano-channel material has the problems of pollution, complex preparation process, high cost and the like. Most of the previous materials with nanofluidic channels are composed of polymers such as polyethyleneimine, polyvinyl alcohol and polystyrene sulfonate, but all of them are non-renewable and non-degradable materials, which can cause serious environmental problems. Furthermore, despite the great advances in the preparation of nanochannels under laboratory conditions, challenges remain in scalable commercial applications, limited by high cost glass substrates, photolithographic techniques, or time-consuming/complex manufacturing methods (such as atomic layer deposition). Therefore, the design of nanostructured ion membranes with excellent ion transport properties using green, low cost, renewable materials has yet to be developed. At present, some scientific researchers draw materials from the nature, and solve the problems of high cost, environmental pollution and the like by utilizing the advantages of easy acquisition, degradability, reproducibility, biocompatibility and the like of natural materials. Li, T et al (sci. adv.2019,5, u4238) produced wood films with nanofluidic effect "top-down" using the natural oriented nano-microstructure of wood. A church professor at the university of maryland has implemented low heat recovery using nanofluid wood membranes (nat. mater.2019,18,608), salt concentration gradient osmotic power generation (adv. energy mater.2020,10, 1902590). However, the reports of the prior art have the defects that although the wood has a natural oriented structure, the growth process is uncontrollable, and the structure is difficult to form. In addition, the natural wood needs to be matched with a physical method and a chemical method to further eliminate macropores existing in the wood. The macroporous structure of wood greatly limits the rapid selective transport properties of ions in wood-based nanofluidic channels. Therefore, there is a need to find a new method for preparing a material of nano fluid channel to overcome the above performance deficiencies.
Disclosure of Invention
The invention prepares the holocellulose-based nano fluid ionic conductor membrane material with charged surface and highly oriented structure by utilizing a 'bottom-up' strategy, namely, the steps of physically dissolving cellulose, chemically modifying and the like from the molecular chain level of the cellulose.
The invention is realized by the following technical means:
a method for preparing a holocellulose nano fluid ionic conductor membrane material comprises the following steps:
s1, dissolving a cellulose raw material in a cellulose solvent to form a cellulose solution;
s2, centrifuging the cellulose solution, and adding a chemical cross-linking agent for reaction to generate a crude product;
s3, centrifuging and shaping the crude product to obtain alkali gel;
s4, orienting and soaking the alkali gel in a coagulating bath to form oriented cellulose hydrogel;
the molecular chains in the cellulose alkali gel can be coordinately stretched through external force drafting or compression during orientation; the cellulose is soaked in a coagulating bath, and the cellulose is physically crosslinked, so that an oriented structure in the cellulose is fixed, the mechanical property in the orientation direction is improved, and the ion transport rate of the nanofluid is increased;
s5, carrying out chemical modification and water washing on the oriented cellulose hydrogel, and carrying out limited-range drying to form a film;
the chemical modification can improve the charge density in the cellulose nano channel and promote the transport speed of ions in the channel;
wherein the cellulose solvent comprises alkali, urea and water.
Further, the cellulose raw material is selected from one or more of cotton linter pulp, wood pulp, bamboo pulp and straw pulp.
Further, the cellulose solvent comprises the following components in parts by mass:
6-12 parts of alkali; 10-17 parts of urea; 61-84 parts of water.
Further, in the S1, the stirring speed during the reaction is 3000-10000rpm, the reaction temperature is-20-0 ℃, and the reaction time is 1-10 min.
Further, in the S2, the stirring speed during the reaction is 100-800rpm, the reaction temperature is-5-20 ℃, and the reaction time is 0.5-4 h.
Further, the chemical crosslinking agent is selected from one or more of epichlorohydrin, chloroepoxy butane, glutaraldehyde, genipin and polyethylene glycol diglycidyl ether.
The chemical cross-linking agent is added to introduce a large number of chemical cross-linking points into the cellulose solution to form a chemical cross-linking network, so that the toughness and stability of the material are improved.
Further, the coagulation bath is selected from one or more of sulfuric acid, hydrochloric acid, citric acid, phytic acid or acetic acid.
Further, the concentration of the coagulation bath is 0.01-20%.
Further, in S4, the orientation method is external force drawing or external force compression.
Further, in S5, the chemical modification includes one or more of TEMPO oxidation or etherification.
Further, in the S5, the temperature of the limited drying is 5-80 ℃.
The invention has the beneficial effects that:
the invention takes cellulose with the most abundant reserves in the nature as a raw material, and successfully prepares the holocellulose nano fluid ionic conductor membrane material with low cost, degradability, reproducibility, biocompatibility, high strength and high conductivity. And the conductivity of the invention is superior to that of a wood-based nanofluid film prepared by a top-down strategy under the condition of low salt concentration. The prepared holocellulose nano-fluid ionic conductor membrane material can be applied to the research and development of an ultra-sensitive humidity sensor for wearable health monitoring, indicates a direction for the application of the wearable nano-fluid ionic conductor material, and has high academic and economic benefits.
Drawings
FIG. 1 is a flow chart illustrating the preparation of a holocellulose nanofluid ionic conductor membrane material prepared in example 1 of the present invention;
FIG. 2 is an SEM image of a holocellulose nanofluid ionic conductor film material prepared in example 2 of the present invention;
FIG. 3 is a comparison graph of FTIR of holocellulose nanofluid ionic conductor film materials prepared in example 3 of the present invention and comparative example 1.
FIG. 4 is an AFM image of a holocellulose nanofluid ionic conductor film material prepared in example 4 of the present invention;
FIG. 5 is a potassium ion conductivity test chart of the holocellulose nanofluid ion conductor film material prepared in example 1 of the present invention, the non-chemically modified oriented cellulose film prepared in comparative example 1, and the wood-based nanofluid ion conductor film prepared in comparative example 2 in different concentration solutions.
Detailed Description
The following examples further illustrate the present invention but should not be construed as limiting 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.
The preparation of cellulose solutions is described in the prior art (Macromolecules 2008,23, 9345-9351). Placing the cellulose solvent in cold hydrazine for precooling, adding a cellulose raw material into the precooled solvent, violently stirring, and then centrifuging and defoaming to obtain a cellulose solution.
The ingredients referred to in the examples of the present invention are, unless otherwise mentioned, all common ingredients which are commercially available.
Example 1
A preparation method of a negatively charged holocellulose nanofluid ionic conductor membrane material comprises the following steps:
s1, preparing a cellulose solvent from 8 parts by mass of lithium hydroxide, 15 parts by mass of urea and 80 parts by mass of deionized water, precooling the cellulose solvent at a temperature of-20 ℃ under cold hydrazine to obtain the cellulose solvent, then adding cotton linter pulp, stirring the mixture for 6min at 3000rpm, controlling the temperature to be 5 ℃, and performing centrifugal defoaming (4000 rpm; 5min) to obtain a transparent cellulose solution;
fig. 1 is a flow chart of the preparation of the holocellulose nanofluid ionic conductor film material prepared in embodiment 1 of the present invention, and illustrates a green and controllable process for constructing the holocellulose nanofluid ionic conductor film based on a bottom-up strategy, which is different from a bottom-up construction method of a wood substrate and the like in the present invention.
S2, adding 0.5 wt% of chemical cross-linking agent epichlorohydrin, stirring at constant temperature of-5 ℃ and 350rpm for 1h to obtain a chemically cross-linked crude product;
s3.0 ℃, 6000rpm, centrifuging for 5min, pouring into mold gel, standing at-5 ℃ for 5h, and shaping to obtain alkali gel;
s4, drawing the alkali gel by external force (the drawing strain is 200%), and then placing the alkali gel in a 2% sulfuric acid coagulation bath for 1min to fix the orientation to obtain the high-orientation cellulose hydrogel;
s5, mixing 20g of cellulose hydrogel, 90g of deionized water, 0.010g of TEMPO (tetramethylpiperidine), 0.2g of sodium bromide and 6.203g of sodium hypochlorite, maintaining the pH value of the solution at 10, oxidizing for 1h, cleaning, clamping two ends of the solution, and performing limited drying at 25 ℃ to obtain the negative electricity holocellulose nanofluid ionic conductor membrane material.
Example 2
A preparation method of a negatively charged holocellulose nanofluid ionic conductor membrane material comprises the following steps:
s1, preparing a cellulose solvent from 7 parts by mass of sodium hydroxide, 12 parts by mass of urea and 81 parts by mass of deionized water, precooling the mixture at a temperature of-15 ℃ under cold hydrazine, then adding wood pulp, stirring the mixture at 5000rpm for 3min to obtain a cellulose solution, and performing temperature-controlled centrifugal defoaming (5 ℃, 4000 rpm; 5min) to obtain a transparent cellulose solution;
s2, adding 1 wt% of a chemical cross-linking agent of butylene oxide/cellulose solution, and stirring at constant temperature of 0 ℃ and 500rpm for 2h to obtain a chemically cross-linked crude product;
s3.0 ℃, centrifuging at 3000rpm for 10min, pouring into a mold gel, standing for 3h at 10 ℃ for shaping to obtain alkali gel;
s4, drawing the alkali gel by external force (the drawing strain is 170%), and then placing the alkali gel in a 10% phytic acid coagulation bath for 1min for fixed orientation to obtain high-orientation cellulose hydrogel;
s5, mixing 30g of cellulose hydrogel, 100g of deionized water, 0.016g of TEMPO (tetramethylpiperidine), 0.2g of sodium bromide and 6.203g of sodium hypochlorite, maintaining the pH value of the solution at 10, oxidizing for 2 hours, cleaning, clamping two ends of the solution, and performing limited drying at 45 ℃ to obtain the holocellulose nanofluid ionic conductor membrane material with negative electricity.
Fig. 2 is an SEM image of the holocellulose nano-fluid ionic conductor film material prepared in example 2 of the present invention, which illustrates the debye length of the holocellulose nano-fluid ionic conductor with compact and highly ordered nano-structure and high-speed transmission of the composite ionic conductor.
Example 3
A preparation method of a negatively charged holocellulose nanofluid ionic conductor membrane material comprises the following steps:
s1, preparing a cellulose solvent from 7 parts by mass of sodium hydroxide, 12 parts by mass of urea and 81 parts by mass of deionized water, precooling the mixture under-12 ℃ of cold hydrazine, then adding bamboo pulp, stirring the mixture for 3min at 10000rpm to obtain a cellulose solution, and performing controlled-temperature centrifugal defoaming (0 ℃, 5000rpm, 20min) to obtain a transparent cellulose solution;
s2, adding 0.1 wt% of a chemical cross-linking agent of butylene oxide/cellulose solution, stirring at the constant temperature of-10 ℃ and 300rpm for 3h to obtain a chemically cross-linked crude product;
s3.5 ℃, centrifuging at 3000rpm for 4min, pouring the mixture into a mold gel, and standing for 1h at 40 ℃ for shaping to obtain alkali gel;
s4, drawing the alkali gel by external force (the drawing strain is 160%), and then placing the alkali gel in a 20% hydrochloric acid coagulation bath for 1min to fix orientation to obtain the high-orientation cellulose hydrogel;
s5, mixing 30g of cellulose hydrogel, 100g of deionized water, 0.016g of TEMPO (tetramethylpiperidine), 0.2g of sodium bromide and 6.203g of sodium hypochlorite, maintaining the pH value of the solution at 10, oxidizing for 2 hours, cleaning, clamping two ends of the solution, and performing limited drying at 80 ℃ to obtain the holocellulose nanofluid ionic conductor membrane material with negative electricity.
FIG. 3 is a FTIR comparison graph of holocellulose nanofluid ionic conductor membrane materials prepared in example 3 and comparative example 1, which illustrates that CH2-OH at C6 position of cellulose molecular chain is oxidized into-COOH after TEMPO oxidation treatment, so that the cellulose nanofluid ionic conductor successfully introduces negative charges.
Example 4
A preparation method of a positively charged holocellulose nano fluid ionic conductor membrane material comprises the following steps:
s1, preparing a cellulose solvent from 7 parts by mass of sodium hydroxide, 12 parts by mass of urea and 81 parts by mass of deionized water, precooling the mixture at a temperature of-15 ℃ under cold hydrazine, then adding wood pulp, stirring the mixture at 5000rpm for 3min to obtain a cellulose solution, and performing temperature-controlled centrifugal defoaming (5 ℃, 4000 rpm; 5min) to obtain a transparent cellulose solution;
s2, adding 1 wt% of a chemical cross-linking agent of butylene oxide/cellulose solution, and stirring at constant temperature of 0 ℃ and 500rpm for 2h to obtain a chemically cross-linked crude product;
s3.0 ℃, centrifuging at 3000rpm for 10min, pouring the mixture into a mold gel, and standing for 3h at 10 ℃ for shaping to obtain alkali gel;
s4, drawing the alkali gel by external force (the drawing strain is 170%), and then placing the alkali gel in a 10% phytic acid coagulation bath for 5min for fixing orientation to obtain high-orientation cellulose hydrogel;
s5, soaking 10g of gel in 50g of 5 wt% NaOH solution, adding 24g of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride under stirring at 60 ℃, maintaining the pH value of the solution to be 12.5, carrying out etherification reaction for 2 hours, cleaning, clamping two ends of the hydrogel, and carrying out limited drying at 5 ℃ to obtain the holocellulose nanofluid ionic conductor membrane material with positive charges.
Fig. 4 is an AFM image of the holocellulose nano-fluid ionic conductor film material prepared in embodiment 4 of the present invention, and illustrates that the holocellulose nano-fluid ionic conductor film constructed by the bottom-up strategy according to the present invention has a highly ordered nanostructure.
Comparative example 1
A preparation method of a non-chemically modified holocellulose oriented film material comprises the following steps:
s1, preparing a cellulose solvent from 5 parts by mass of lithium hydroxide, 15 parts by mass of urea and 80 parts by mass of deionized water, precooling the cellulose solvent at a temperature of-20 ℃ under cold hydrazine to obtain the cellulose solvent, then adding cotton linter pulp, stirring the mixture for 6min at 3000rpm, controlling the temperature to be 5 ℃, and performing centrifugal defoaming (4000 rpm; 5min) to obtain a transparent cellulose solution;
s2, adding 0.5 wt% of chemical crosslinking agent epichlorohydrin/cellulose solution, stirring at constant temperature of-5 ℃ and 350rpm for 1h to obtain a chemically crosslinked crude product;
s3.0 ℃, 6000rpm, centrifuging for 5min, pouring into mold gel, standing at-5 ℃ for 5h, and shaping to obtain alkali gel;
s4, drawing the alkali gel by external force (the drawing strain is 200%), then placing the alkali gel in a 2% sulfuric acid coagulation bath for 1min for fixed orientation to obtain high-orientation cellulose hydrogel, cleaning, clamping two ends of the high-orientation cellulose hydrogel, and carrying out limited drying at 25 ℃ to obtain the non-chemically-modified holocellulose oriented film.
Comparative example 2
Referring to the technical method in the prior art (Li, T, etc., sci.adv.,2019,5, u4238), firstly, natural wood is cut into the size with the thickness of less than 5mm and the length/width of less than 10cm along the growth direction, the natural wood is soaked in alkali liquor and hydrogen peroxide to remove lignin and hemicellulose in the wood, and the wood is washed clean to obtain the high-content cellulose wood film. Simultaneously, the wood-based cellulose membrane is oxidized by TEMPO, cleaned, dried and compacted by hot pressing, and the cellulose wood membrane with compact structure is obtained. The specific treatment was as follows, cutting the dimensions (typical thickness, 4 mm; length/width, 10cm) in the growth direction. NaOH and Na 2 SO 3 Dissolved in deionized water at concentrations of 2.5 and 0.4M, respectively. The chips were boiled in the solution for 10 hours. Then, the chips were immersed in boiling H 2 O 2 Solution (30%) until complete whitening. The resulting wood film was then rinsed in deionized water to remove residual ions and chemicals. To prepare an undensified film, the samples were subsequently processed by freeze-drying. To make a dense film, the sample was dried in air at ambient temperature while pressing for 5 hours. For a typical TEMPO oxidation, a cellulose membrane (1g) was immersed in 100ml of water containing 0.016g TEMPO and 0.1g NaBr and the pH adjusted to 10 by the addition of 0.5M NaOH solution. About 5mmol of NaClO was added to the solution to initiate the oxidation reaction. The pH of the solution was closely monitored using a pH meter and maintained at 10 by the continuous addition of 0.5M NaOH. After 2.5 hours, the reaction was stopped by lowering the pH to 7 by addition of 0.5M HCl. The membrane was then removed from the solution and washed with 0.5M HCl. And finally, exchanging the cellulose membrane with an acetone solvent, drying, and performing hot pressing to form the membrane.
Bulk solution
Formulation 10 -6 、10 -5 、10 -4 、10 -3 、10 -2 And 10 -1 M potassium chloride solution with six concentrations is used as a bulk solution. The electric conductivity of the above six concentration solutions was measured with a conductivity meter, respectivelyRate, i.e., the value of the bulk solution conductivity.
Test example
(1) Measurement of the Ionic conductivity of negatively charged holocellulose nanofluid Ionic conductor membranes (example 1)
The test method comprises the following steps: formulation 10 -6 、10 -5 、10 -4 、10 -3 、10 -2 And 10 -1 M potassium chloride solutions with six concentrations, and respectively testing the conductivity values of the bulk solutions with the six concentrations. Then, the test was performed by soaking the test pieces in 10 -6 、10 -5 、10 -4 、10 -3 、10 -2 、10 - 1 Conductivity of the whole cellulose membrane of the potassium chloride solution. Two parallel test probes are placed on both ends of a sample to be tested, then a certain potential is applied to both ends of the probes, and then the current passing through the sample is measured. And (5) making an I-V image by using the obtained current and potential, fitting, and then taking the slope as the conductivity. The calculation equation for the conductivity (λ) is as follows:
λ＝G(l/hw)
where G is the measured conductance (i.e., the slope of the I-V curve), l is the length of the composite film being measured, h is the height of the film being measured, and w is the width of the film being measured.
(2) Ion conductivity measurement of non-chemically modified holocellulose oriented film Material (comparative example 1)
The test method comprises the following steps: two parallel test probes are arranged at two ends of a sample to be tested, and the sample is respectively soaked in 10 -6 、10 -5 、10 -4 、10 -3 、10 -2 、10 -1 The M potassium chloride solution was then applied with a certain potential across the probe, followed by measuring the current through the non-chemically modified holocellulose alignment film. And (4) making an I-V image by using the obtained current and potential, fitting, and taking the slope as the conductivity. The calculation equation for the conductivity (λ) is as follows:
λ ═ G (l/hw), where G is the measured conductance (i.e., the slope of the I-V curve), l is the length of the measured non-chemically modified holocellulose alignment film, h is the height of the measured non-chemically modified holocellulose alignment film, and w is the width of the measured non-chemically modified holocellulose alignment film.
(3) Ion conductivity measurement of negatively charged Wood Membrane (comparative example 2)
The test method comprises the following steps: two parallel test probes are arranged at two ends of a sample to be tested, and the sample is respectively soaked in 10 -6 、10 -5 、10 -4 、10 -3 、10 -2 、10 -1 The M potassium chloride solution was then applied to a potential across the probe, followed by measurement of the current through the negatively charged wood membrane. And (5) making an I-V image by using the obtained current and potential, fitting, and then taking the slope as the conductivity. The calculation equation for the conductivity (λ) is as follows:
λ ═ G (l/hw), where G is the measured conductance (i.e., the slope of the I-V curve), l is the length of the measured negatively charged wood film, h is the height of the measured negatively charged wood film, and w is the width of the measured negatively charged wood film.
FIG. 5 is a potassium ion conductivity test chart of the holocellulose nanofluid ion conductor film material prepared in example 1 of the present invention, the non-chemically modified oriented cellulose film prepared in comparative example 1, and the wood-based nanofluid ion conductor film prepared in comparative example 2 in different concentration solutions. Table 1 shows the potassium ion conductivity data of the negatively charged holocellulose nanofluid ionic conductor membrane material subjected to TEMPO oxidation treatment in example 1 of the present invention, compared with the non-chemically modified oriented cellulose membrane of comparative example 1 and the wood-based nanofluid ionic conductor membrane of comparative example 2, in solutions of different concentrations.
Table 1 conductivity data for different samples
As can be seen from the table, example 1 has different degrees of advantage over comparative examples 1-2, as well as the bulk solution, in general, in conductivity at different solution concentrations.
Claims (7)
1. A preparation method of holocellulose nano fluid ionic conductor membrane material is characterized by comprising the following steps:
s1, dissolving a cellulose raw material in a cellulose solvent to form a cellulose solution;
s2, centrifuging the cellulose solution, and adding a chemical cross-linking agent for reaction to generate a crude product;
s3, centrifuging and shaping the crude product to obtain alkali gel;
s4, orienting and soaking the alkali gel in a coagulating bath to form oriented cellulose hydrogel;
s5, carrying out chemical modification and water washing on the oriented cellulose hydrogel, and carrying out limited-range drying to form a film;
wherein the cellulose solvent comprises alkali, urea and water; in the S1, the stirring speed is 3000-10000rpm, the temperature is-20-0 ℃, and the time is 1-10 min; in the S2, the stirring speed during the reaction is 800rpm, the reaction temperature is-5-0 ℃, and the reaction time is 0.5-4 h; in S5, the chemical modification includes one or more of TEMPO oxidation or etherification.
2. The method for preparing the holocellulose nanofluid ionic conductor film material according to claim 1, wherein the cellulose raw material is selected from one or more of cotton linter pulp, wood pulp, bamboo pulp and straw pulp.
3. The preparation method of the holocellulose nanofluid ionic conductor film material as claimed in claim 1, wherein the cellulose solvent comprises the following components in parts by mass:
6-12 parts of alkali; 10-17 parts of urea; 61-84 parts of water.
4. The method for preparing the holocellulose nanofluid ionic conductor membrane material according to claim 1, wherein the chemical cross-linking agent is selected from one or more of epichlorohydrin, chloroepoxy butane, glutaraldehyde, genipin and polyethylene glycol diglycidyl ether.
5. The method for preparing the holocellulose nanofluid ionic conductor film material according to claim 1, wherein the coagulating bath is selected from one or more of citric acid, sulfuric acid, hydrochloric acid, phytic acid or acetic acid.
6. The method for preparing the holocellulose nanofluid ionic conductor film material according to claim 5, wherein the concentration of the coagulating bath is 0.01-20%.
7. The method for preparing the holocellulose nanofluid ionic conductor film material according to claim 1, wherein in the step S4, the orientation method is external force drafting or external force compression.
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