CN110606991B - High-thermal-stability amphiphilic g-C3N4 modified CNFs sponge and preparation method thereof - Google Patents

High-thermal-stability amphiphilic g-C3N4 modified CNFs sponge and preparation method thereof Download PDF

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CN110606991B
CN110606991B CN201910922875.XA CN201910922875A CN110606991B CN 110606991 B CN110606991 B CN 110606991B CN 201910922875 A CN201910922875 A CN 201910922875A CN 110606991 B CN110606991 B CN 110606991B
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任衍彪
张立龙
何小武
石铁生
张临财
亓敬波
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Zaozhuang University
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    • C08J2201/00—Foams characterised by the foaming process
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    • C08J2201/0484—Elimination of a frozen liquid phase the liquid phase being aqueous
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    • C08K3/28—Nitrogen-containing compounds

Abstract

The invention takes CNFs sponge prepared by heat treatment of nano-cellulose as a framework, and g-C is doped into the framework3N4The amphiphilic g-C3N4 modified CNFs sponge with high thermal stability is prepared. Wherein g-C3N4From the thermal polycondensation of melamine. The preparation method comprises the following steps: mixing CNFs hydrogel with melamine, performing ultrasonic treatment to prepare a mixed aqueous solution, cooling the mixed aqueous solution in liquid nitrogen, drying the cooled mixed aqueous solution by using a freeze dryer to prepare a CNFs aerogel/melamine mixture, performing heat treatment in a tube furnace, and performing nitrogen protection to prepare the amphiphilic g-C with high thermal stability3N4Modified CNFs sponges. The raw materials of melamine and CNFs are cheap and easily available, and the g-C is ensured by two-step freezing treatment3N4Filling into CNFs aerogel to give g-C3N4The modified partially carbonized CNFs sponge has high thermal stability and amphiphilic property.

Description

High-thermal-stability amphiphilic g-C3N4 modified CNFs sponge and preparation method thereof
Technical Field
The invention belongs to the field of material preparation, and particularly relates to a high-thermal-stability amphiphilic g-C3N4 modified CNFs sponge and a preparation method thereof.
Background
Nanocelluloses (CNFs) are attracting increasing attention due to their biocompatibility, biodegradability and renewability. Many high value-added materials based on CNFs, e.g. thin films and ultra-lightAerogels have been widely developed for use in the fields of optoelectronics, energy storage, and the like. In the natural fiber pretreatment process, a TEMPO oxidation system is used for targeted oxidation of cellulose C6 hydroxyl to carboxyl, the existence of the carboxyl can save energy in the CNFs manufacturing process and improve the colloidal stability of the CNFs solution, and the oxidized cellulose nano-fiber with higher oxidation degree and higher carboxyl molar mass concentration is less prone to sedimentation, so that the sedimentation performance is improved. However, studies have found that the aging problem of CNFs and their related materials is related to their carboxyl content, since carboxyl is the most important intermediate that can be split into CO.，HO.，COO.Free radicals, which attack the C-C and C-O-C bonds on the backbone during fiber oxidation, contribute to poor photothermal stability of CNFs. In optoelectronic device applications, the thermal stability of CNFs materials is an important parameter.
In 2D materials, the graphite phase carbon nitride (g-C)3N4) Because of its excellent thermal, chemical and optical properties, it has been widely used in catalysts, lithium ion storage, photovoltaic devices, etc. In recent years, researchers have found g-C3N4The modified compound can produce excellent flame retardant, heat and mechanical performance. Secondly, g-C3N4Has hydrophobic-lipophilic properties, while the edge groups impart hydrophilic properties, overall g-C3N4Exhibit lipophilic and hydrophilic characteristics. Thus, how to combine g-C3N4Incorporation into CNFs is crucial for the design of amphiphilic and high thermal stability materials.
Disclosure of Invention
In order to solve the problems of easy aging, poor stability and non-ideal hydrophilic and oleophilic effects of CNFs materials in the prior art, the invention provides amphiphilic g-C with high thermal stability3N4Modified CNFs sponges and methods of making the same, the sponges being prepared from inexpensive, readily available raw materials and g-C3N4Filling into CNFs aerogel to give g-C3N4The modified CNFs sponge has high thermal stability and amphiphilic property.
The invention is realized by the following technical scheme:
high thermal stabilityQualitative, amphiphilic g-C3N4The modified CNFs sponge takes the CNFs sponge prepared by heat treatment of nano-cellulose as a framework, and g-C is doped into the framework3N4Preparing to obtain;
said g-C3N4From the thermal polycondensation of melamine.
Preferably, the nanocellulose is prepared by using bamboo pulp with the concentration of 1% (w/v) as a raw material, performing pretreatment by using a TEMPO-NaBr-NaClO oxidation system for 90min, stirring at the speed of 800rpm, and grinding the solution to be CNFs hydrogel by using a homogenizer at high pressure after the pretreatment.
Preferably, the content of carboxyl in the CNFs hydrogel after the homogenizer is used for high-pressure grinding is about 1.02 mmol/g.
In the present invention, the high thermal stability and amphiphilic g-C3N4The preparation method of the modified CNFs sponge is characterized by comprising the following steps:
(1) mixing the CNFs hydrogel with melamine, and performing ultrasonic treatment to prepare a mixed aqueous solution;
(2) placing the mixed aqueous solution obtained in the step (1) in liquid nitrogen for cooling, and drying by using a freeze dryer to prepare a CNFs aerogel/melamine mixture;
(3) carrying out heat treatment on the CNFs aerogel/melamine mixture prepared in the step (2) in a tube furnace, and carrying out nitrogen protection to prepare amphiphilic g-C with high thermal stability3N4Modified CNFs sponges.
Preferably, the mass percentage concentration of the CNFs in the CNFs hydrogel in step (1) is 2%.
Preferably, the mass ratio of the CNFs to the melamine in the step (1) is 1: 0.5-4.
Preferably, the mass ratio of the CNFs hydrogel to melamine in step (1) is 1: 1.
Preferably, the mixed aqueous solution in step (2) is immediately cooled in liquid nitrogen for 10s and then dried for 24h by using a freeze dryer.
Preferably, the heat treatment is carried out for 4h at 350 ℃ in the nitrogen protective atmosphere in the step (3).
Preferably, the ultrasonic treatment of step (1) is 300W ultrasonic treatment for 5 min.
The invention prepares g-C by an in-situ blending synthetic route3N4Modifying the partially carbonized CNFs sponge so as to obtain the novel high-thermal-stability and amphiphilic carbon sponge material. The carbon sponge material comprises g-C obtained by thermal condensation polymerization of Melamine (Melamine)3N4，g-C3N4Display the amphiphilic characteristic and the flame retardant property; preparing carbon sponge as skeleton of 3D network by heat treatment of nano-cellulose prepared from bamboo pulp, g-C3N4The modified carbon sponge shows hydrophile lipophilicity and high thermal stability, and can quickly adsorb water and oil, and the research of the amphiphilic material provides a foundation for developing a new material with a special surface wettability and the application thereof.
Advantageous effects
1) The melamine and the CNFs are cheap and easy to obtain; mixing melamine and CNFs hydrogel, freezing with liquid nitrogen, freeze-drying and heat-treating to ensure g-C3N4Filling into CNFs aerogel to give g-C3N4Modifying the high thermal stability and the amphiphilic property of the partially carbonized CNFs sponge;
2) preparation of g-C by in-situ blending synthetic route3N4The partially carbonized CNFs sponge is modified to obtain a novel high-thermal-stability and amphiphilic CNFs sponge material, and a novel design idea and a novel research method can be provided for the amphiphilic and high-thermal-stability materials through exploration and research.
Drawings
FIG. 1 (a, b, C) shows g-C prepared in comparative example 13N4Digital photographs and SEM pictures of modified CNFs sponges; (d, e, f) is g-C prepared in example 13N4Digital photographs and SEM pictures of modified CNFs sponges.
FIG. 2 shows g-C prepared by freezing with liquid nitrogen and freeze-drying CNFs and cyanamide at different mass ratios3N4Residue yield of @ CNFs complex at different temperatures.
FIG. 3 shows g-C prepared from CNFs and Melamine at a mass ratio of 1:13N4Modified CNFs sponge burn test.
FIG. 4 shows g-C3N4Contact angle test of CNFs sponges carbonized in the modified part.
Detailed Description
In order to make the technical solutions of the present invention better understood, the following description is provided clearly and completely, and other similar embodiments obtained by those skilled in the art without creative efforts shall fall within the protection scope of the present application based on the embodiments in the present application.
Example 1
(1) Pretreating bamboo pulp with the concentration of 1% (w/v) at room temperature by using TEMPO, NaBr and NaClO, wherein the treatment time is 90min, the stirring speed is 800rpm, the pH value of the solution is controlled to be 10, and after pretreatment, preparing CNFs hydrogel by using a homogenizer through high-pressure grinding; the carboxyl content in the CNFs hydrogel is 1.02 mmol/g;
(2) adding water into the CNFs hydrogel in the step (1) to enable the mass percentage concentration of the CNFs to be 2%, and then mixing the CNFs with melamine, wherein the mass ratio of the CNFs to the melamine is 1:1, and performing ultrasonic treatment for 5min under 300W to obtain a mixed aqueous solution;
(3) quickly placing the mixed aqueous solution in the step (2) in liquid nitrogen for cooling for 10s, drying for 24h by using a freeze dryer (vacuum, condensation temperature-50 ℃) to prepare a CNFs aerogel/melamine mixture,
(4) placing the CNFs aerogel/melamine mixture prepared in the step (3) into a tube furnace, and carrying out heat treatment for 4 hours at 350 ℃ under the nitrogen protection atmosphere to obtain g-C3N4Modified CNFs sponges.
Example 2
(1) Pretreating bamboo pulp with the concentration of 1% (w/v) at room temperature by using TEMPO, NaBr and NaClO, wherein the treatment time is 90min, the stirring speed is 800rpm, the pH value of the solution is controlled to be 10, and after pretreatment, preparing CNFs hydrogel by using a homogenizer through high-pressure grinding; the carboxyl content in the CNFs hydrogel is 1.02 mmol/g;
(2) adding water into the CNFs hydrogel in the step (1) to enable the mass percentage concentration of the CNFs to be 2%, and then mixing the CNFs with melamine, wherein the mass ratio of the CNFs to the melamine is 1:2, and performing ultrasonic treatment for 5min under 300W to obtain a mixed aqueous solution;
(3) rapidly placing the mixed aqueous solution in the step (2) in liquid nitrogen for cooling for 10s, and then drying for 24h by using a freeze dryer (set conditions) to prepare a CNFs aerogel/melamine mixture;
(4) placing the CNFs aerogel/melamine mixture prepared in the step (3) into a tube furnace, and carrying out heat treatment for 4 hours at 350 ℃ under the nitrogen protection atmosphere to obtain g-C3N4Modified CNFs sponges.
Example 3
(1) Pretreating bamboo pulp with the concentration of 1% (w/v) at room temperature by using TEMPO, NaBr and NaClO, wherein the treatment time is 90min, the stirring speed is 800rpm, the pH value of the solution is controlled to be 10, and after pretreatment, preparing CNFs hydrogel by using a homogenizer through high-pressure grinding; the carboxyl content in the CNFs hydrogel is 1.02 mmol/g;
(2) adding water into the CNFs hydrogel in the step (1) to enable the mass percentage concentration of the CNFs to be 2%, and then mixing the CNFs with melamine, wherein the mass ratio of the CNFs to the melamine is 1:3, and performing ultrasonic treatment for 5min under 300W to obtain a mixed aqueous solution;
(3) rapidly placing the mixed aqueous solution in the step (2) in liquid nitrogen for cooling for 10s, and then drying for 24h by using a freeze dryer (set conditions) to prepare a CNFs aerogel/melamine mixture;
(4) placing the CNFs aerogel/melamine mixture prepared in the step (3) into a tube furnace, and carrying out heat treatment for 4 hours at 350 ℃ under the nitrogen protection atmosphere to obtain g-C3N4Modified CNFs sponges.
Example 4
(1) Pretreating bamboo pulp with the concentration of 1% (w/v) at room temperature by using TEMPO, NaBr and NaClO, wherein the treatment time is 90min, the stirring speed is 800rpm, the pH value of the solution is controlled to be 10, and after pretreatment, preparing CNFs hydrogel by using a homogenizer through high-pressure grinding; the carboxyl content in the CNFs hydrogel is 1.02 mmol/g;
(2) adding water into the CNFs hydrogel in the step (1) to enable the mass percentage concentration of the CNFs to be 2%, mixing with melamine, and performing ultrasonic treatment for 5min at 300W under the mass ratio of the CNFs to the melamine of 1:4 to obtain a mixed aqueous solution;
(3) rapidly placing the mixed aqueous solution in the step (2) in liquid nitrogen for cooling for 10s, and then drying for 24h by using a freeze dryer (set conditions) to prepare a CNFs aerogel/melamine mixture;
(4) placing the CNFs aerogel/melamine mixture prepared in the step (3) into a tube furnace, and carrying out heat treatment for 4 hours at 350 ℃ under the nitrogen protection atmosphere to obtain g-C3N4Modified CNFs sponges.
Comparative example 1:
(1) pretreating bamboo pulp with the concentration of 1% (w/v) at room temperature by using TEMPO, NaBr and NaClO, wherein the treatment time is 90min, the stirring speed is 800rpm, the pH value of the solution is controlled to be 10, and after pretreatment, preparing CNFs hydrogel by using a homogenizer through high-pressure grinding; the carboxyl content in the CNFs hydrogel is 1.02 mmol/g;
(2) adding water into the CNFs hydrogel in the step (1) to enable the mass percentage concentration of the CNFs to be 2%, quickly placing the CNFs into liquid nitrogen to be cooled for 10s, and drying the CNFs for 24h by using a freeze dryer to prepare the CNFs aerogel;
(3) and (3) placing the CNFs aerogel prepared in the step (2) into a tube furnace, and carrying out heat treatment for 4 hours at 350 ℃ in a nitrogen protective atmosphere to obtain the CNFs sponge.
Comparative example 2
(1) Pretreating bamboo pulp with the concentration of 1% (w/v) at room temperature by using TEMPO, NaBr and NaClO, wherein the treatment time is 90min, the stirring speed is 800rpm, the pH value of the solution is controlled to be 10, and after pretreatment, preparing CNFs hydrogel by using a homogenizer through high-pressure grinding; the carboxyl content in the CNFs hydrogel is 1.02 mmol/g;
(2) adding water into the CNFs hydrogel in the step (1) to enable the mass percentage concentration of the CNFs to be 2%, and then mixing the CNFs with melamine, wherein the mass ratio of the CNFs to the melamine is 1:1, and performing ultrasonic treatment for 5min under 300W to obtain a mixed aqueous solution;
(3) quickly placing the mixed aqueous solution in the step (2) in a freeze dryer (set conditions) for drying treatment for 24 hours to prepare a CNFs aerogel/melamine mixture;
(4) placing the CNFs aerogel/melamine mixture prepared in the step (3) into a tube furnace, and carrying out heat treatment for 4 hours at 350 ℃ under the nitrogen protection atmosphere to obtain g-C3N4Modified CNFs complexes.
Results and data analysis:
（1）g-C3N4microscopic morphology observation of modified CNFs sponges
Observation of two g-C' S using FESEM, model number Hitachi S-4800, classical by Hitachi3N4Samples of CNFs sponges were modified. Wherein the sample 1 is g-C prepared by mixing CNFs and melamine in a mass ratio of 1:1, freeze-drying and then carrying out heat treatment3N4Modified carbonized CNFs (comparative example 2). Sample 2 is g-C prepared by mixing CNFs and melamine at a mass ratio of 1:1, freezing with liquid nitrogen, freeze-drying, and heat-treating3N4The carbonized CNFs sponges were modified (example 1).
From FIGS. 1a, b, C it can be observed that sample 1 (comparative example 2) has no 3D network porous structure, nanocellulose self-assembles into lamellar structure, and melamine is thermally condensed into g-C3N4The modification is in the sheet.
From fig. 1D, e, f it can be observed that sample 2 (example 1), CNFs self-assemble into a 3D network porous structure.
（2） g-C3N4Thermal stability testing of modified CNFs sponges
Mixing CNFs hydrogel with melamine: 5 samples were prepared by formulating a mixed aqueous solution of CNFS and melamine in a mass ratio of 1:0 (comparative example 1), 1:1 (example 1), 1:2 (example 2), 1:3 (example 3) and 1:4 (example 4). Thermogravimetric analysis five samples were tested for thermal stability in nitrogen atmosphere using a Netzsch TGS-2 thermal analyzer at a temperature range of room temperature-500 deg.C and a temperature rise rate of 10 deg.C/min, according to whichThe yield of five sample residues can be calculated from the TEG curve. From fig. 2 it can be found that: the increase of the N element can increase the thermal stability of the whole sample, and the thermal stability of the sample is enhanced along with the increase of the addition amount of the melamine. Wherein g-C is prepared at 350 ℃ when the mass ratio of CNFs to melamine is 1:13N4The modified partially carbonized CNFs sponges have the most excellent thermal stability.
FIG. 3 shows g-C prepared from CNFs and Melamine at a mass ratio of 1:13N4Modified CNFs sponge burn test.
g-C3N4Amphiphilic Performance testing of modified partially carbonized CNFs sponges
Testing g-C prepared from CNFs and melamine at a mass ratio of 1:1 by using a contact angle measuring instrument3N4The contact angle of partially carbonized CNFs sponge samples was modified.
From fig. 4 it can be found that: when a water drop was dropped onto the sample surface, the water spread completely over the sample surface after 1.21s, indicating g-C3N4The modified partially carbonized CNFs sponge sample has super-hydrophilic property; when the silicone oil fell to the surface of the sample, the silicone oil spread completely on the surface of the sample after 1.47s, indicating g-C3N4The modified partially carbonized CNFs sponge samples have super-oleophilic properties.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (9)

1. Amphiphilic g-C with high thermal stability3N4Modified Carbonized Nanocellulose (CNFs) sponges, characterized in that said sponges are of the high thermal stability, amphiphilic g-C type3N4Modified CNFs sponges were prepared by the following method:
(1) mixing the CNFs hydrogel with melamine, and performing ultrasonic treatment to prepare a mixed aqueous solution;
(2) placing the mixed aqueous solution obtained in the step (1) in liquid nitrogen for cooling, and drying by using a freeze dryer to prepare a CNFs aerogel/melamine mixture;
(3) carrying out heat treatment on the CNFs aerogel/melamine mixture prepared in the step (2) in a tube furnace, and carrying out nitrogen protection to prepare amphiphilic g-C with high thermal stability3N4Modified CNFs sponges;
said g-C3N4From the thermal polycondensation of melamine.
2. The high thermal stability, amphiphilic g-C of claim 13N4The modified CNFs sponge is characterized in that the preparation method of the CNFs hydrogel in the step (1) is characterized in that bamboo pulp with the concentration of 1% (w/v) is used as a raw material, a TEMPO-NaBr-NaClO oxidation system is used for pretreatment, the treatment time is 90min, the stirring speed is 800rpm, the pH value of the solution is 10, and after the pretreatment, the solution is ground into the CNFs hydrogel by a homogenizer at high pressure.
3. The high thermal stability, amphiphilic g-C of claim 23N4The modified CNFs sponge is characterized in that the content of carboxyl in the CNFs hydrogel after the CNFs hydrogel is ground by a homogenizer under high pressure is about 1.02 mmol/g.
4. The high thermal stability, amphiphilic g-C of claim 13N4The modified CNFs sponge is characterized in that the mass percentage concentration of CNFs in the CNFs hydrogel in the step (1) is 2%.
5. The high thermal stability, amphiphilic g-C of claim 13N4The modified CNFs sponge is characterized in that the mass ratio of the CNFs to the melamine in the step (1) is 1: 0.5-4.
6. The high thermal stability, amphiphilic g-C of claim 13N4The modified CNFs sponge is characterized in that the mass ratio of the CNFs hydrogel to the melamine in the step (1) is 1: 1.
7. The method of claim 1High thermal stability of amphiphilic g-C3N4The modified CNFs sponge is characterized in that the mixed aqueous solution in the step (2) is rapidly placed in liquid nitrogen for cooling for 10s and then is dried for 24h by using a freeze dryer.
8. The high thermal stability, amphiphilic g-C of claim 13N4The modified CNFs sponge is characterized in that the heat treatment is carried out for 4 hours at 350 ℃ in the nitrogen protective atmosphere in the step (3).
9. The high thermal stability, amphiphilic g-C of claim 13N4Modified CNFs sponge, and the ultrasonic treatment of 300W in the step (1) is carried out for 5 min.
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