CN115304812B - TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material and preparation method thereof - Google Patents
TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material and a preparation method thereof. Ti is prepared by adopting an in-situ synthesis hydrofluoric acid etching method 3 C 2 T x And modifying with TAT polypeptide to obtain A-Ti 3 C 2 T x /Ti 3 C 2 T x A nano-sheet. The bacterial cellulose is subjected to amination treatment, and the liquid phase spraying-vacuum filtration is used for obtaining the MXene/aminated bacterial cellulose composite material modified by TAT polypeptide. A-Ti 3 C 2 T x Has a large positive charge and can be combined with Ti 3 C 2 T x Bonding by electrostatic interaction to enhance MXene nanoplateletsThe bonding force between the two components is improved, and the compactness is improved. The aminated bacterial cellulose contains a large amount of-NH 2 and-OH capable of reacting with A-Ti 3 C 2 T x /Ti 3 C 2 T x The nano-sheets are combined in a hydrogen bond mode, so that the composite material has the advantages of high density, high mechanical strength and the like.
Description
Technical Field
The invention belongs to the field of electromagnetic shielding materials, and particularly relates to a TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material and a preparation method thereof.
Background
The rapid development of human science and technology has led to the proliferation of various electronic products which produce a great deal of electromagnetic radiation while bringing convenience to people. When the electromagnetic radiation exceeds a certain limit, electromagnetic pollution is caused, and adverse effects are brought to daily production and life and physical health of people. Electromagnetic waves can be classified into two types according to radiation sources, one type is from nature such as cosmic rays, lightning phenomenon, strong ultraviolet rays of the sun, and the like; the other type is artificially generated, and if the radar, the base station signal, the communication and other wireless devices are transmitted, unnecessary electromagnetic waves can be radiated by household appliances, electronic devices and the like to hurt the health of human bodies. Therefore, the development of high-performance electromagnetic shielding materials is of great importance for reducing or eliminating electromagnetic radiation pollution. For a long time, metals have been widely used in electromagnetic shielding due to high conductivity and good shielding effect. However, due to miniaturization and intellectualization of modern electronic devices, development of an electromagnetic shielding material having both high electromagnetic shielding efficiency and excellent mechanical properties is desired. Clearly, metallic materials limit their practical use due to their inherent high density and susceptibility to corrosion in complex environments.
In order to meet the practical requirements of electromagnetic shielding, efforts have been made to find flexible electromagnetic interference shielding materials. As a novel two-dimensional material, MXene was discovered by Naguib et al since 2011 (e.g., ti 3 C 2 T x ) Has attracted considerable attention. In general, MXene is produced by selectively etching Al element from MAX phase and finally forming a compound of general formula M n+1 X n T x (n=1, 2, 3), wherein M represents an early transition metal element, X represents C or/and N, tx is a surface functional group (e.g., -OH, -F, -O, etc.). In view of the low resistance, unique layered structure, rich surface functional groups, and excellent physicochemical properties of MXene, it has attracted great interest to researchers in batteries, capacitors, catalysts, and electromagnetic shielding. However, although MXene exhibits excellent electromagnetic shielding properties compared to most existing shielding materials, the poor interaction between the original MXene nanoplatelets results in failure to meet the application requirements in terms of ductility and tensile strength, which also hinders further use of MXene in high performance electromagnetic shielding.
TAT has been used as a hydrophilic and highly positively charged small molecule polypeptide in a variety of applications including drug carriers and tumor therapy. TAT polypeptides generally consist of 5 to 30 amino acids, have a short amino acid sequence, and generally contain the basic amino acids arginine, histidine, lysine, and the like. Since the guanidine groups in the arginine structure are able to bind to substances whose surface has a negative charge, this results in that small molecule TAT polypeptides can be used to alter the surface potential of MXene to increase the binding force between MXene sheets and to enhance the electron transport process between layers.
Bacterial Cellulose (BC) is a natural organic material produced by bacteria. Has the characteristics of rich sources, high mechanical strength, no pollution to the environment and the like, thus being an ideal substrate material. In addition, bacterial cellulose has abundant surface hydroxyl groups, and can be combined with MXene in a hydrogen bond mode to compensate the defect of poor mechanical property. However, only a few studies have been conducted so far on using bacterial cellulose as a matrix for MXene composites, and there are problems of long preparation process period, single preparation method, lack of innovation, and the like. Thus, developing an innovative bacterial cellulose-based MXene composite remains a significant challenge.
The invention uses bacterial cellulose as a substrate and TAT polypeptide to process Ti 3 C 2 T x Modified to create a large positive charge on its surface. Modified A-Ti 3 C 2 T x Can be combined with unmodified Ti 3 C 2 T x Bonded together by electrostatic adsorption to form A-Ti 3 C 2 T x /Ti 3 C 2 T x A nano-sheet. With Ti 3 C 2 T x In comparison with A-Ti 3 C 2 T x /Ti 3 C 2 T x The nano-sheet has larger binding force and interlayer density, and is beneficial to the improvement of electron transmission and conductivity. In addition, after the amination treatment of the bacterial cellulose, more active sites are formed on the surface of the bacterial cellulose, which is beneficial to A-Ti 3 C 2 T x /Ti 3 C 2 T x Binding of nanoplatelets to bacterial cellulose surface and increasing A-Ti 3 C 2 T x /Ti 3 C 2 T x Adsorption force on the substrate.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, and aims to solve the problems of poor mechanical properties and poor electromagnetic shielding effect of the current electromagnetic shielding material. The method has the advantages of strong process controllability, simplicity, high efficiency, low cost and the like, and has great industrialization prospect and electromagnetic shielding application value.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the preparation method of the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material comprises the following steps:
(1) Ti is prepared by adopting an in-situ generation hydrofluoric acid etching method 3 C 2 T x : 1g LiF is dissolved in 20ml of 9 mol/L hydrochloric acid solution, and Ti is added 3 AlC 2 Continuously stirring at 40deg.C for 48h, centrifuging, washing, collecting lower layer clay-like substance, performing ultrasonic treatment for 120min, centrifuging again at 7000 rpm for 20min, collecting upper layer solution, and lyophilizing to obtain Ti 3 C 2 T x A powder;
(2) Preparation of TAT polypeptide modified A-Ti by electrostatic self-assembly method 3 C 2 T x /Ti 3 C 2 T x : first, 2.5. 2.5 mg/mL Ti is prepared 3 C 2 T x Solution and go to Ti 3 C 2 T x Adding 20ml ethanol solution into the solution, adjusting the pH value of the solution to be less than 6 by acetic acid, and uniformly stirring the solution; adding 3-15 ml of TAT polypeptide to obtain TAT polypeptide modified Ti 3 C 2 T x Nanoplatelets, i.e. A-Ti 3 C 2 T x Then A-Ti is added 3 C 2 T x The solution is added to equal amounts of Ti 3 C 2 T x In solution and stirring is continued until A-Ti 3 C 2 T x With Ti 3 C 2 T x Completing self-assembly, and freeze-drying to obtain A-Ti after electrostatic self-assembly 3 C 2 T x /Ti 3 C 2 T x A nanosheet;
(3) The preparation method comprises the steps of (1) preparing aminated bacterial cellulose by adopting a water bath method: placing 105mg of massive bacterial cellulose (with the length and width of 4cm and the thickness of 5 mm) into deionized water, heating to 30-60 ℃, and continuously introducing argon to remove dissolved O in the water 2 And adding 20mL of ammonium ceric nitrate solution with the concentration of 0.1 mol/L for reaction for 20-50 min, then adding 5mL of glycerol methacrylate dropwise within 30min, and reacting for 2hWashing to obtain treated blocky bacterial cellulose; then placing the treated blocky bacterial cellulose into a mixed solution prepared from 75ml of ethylenediamine and 50ml of deionized water, stirring for 2 hours under 353 and K, and washing to obtain aminated bacterial cellulose;
(4) Preparing a TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material by adopting a liquid phase spraying-vacuum filtration method: taking 10-100 mg of A-Ti prepared in the step (2) 3 C 2 T x /Ti 3 C 2 T x Dissolving the nano-sheets in deionized water to prepare a coating, spraying the coating onto the aminated bacterial cellulose prepared in the step (3), and finally carrying out vacuum filtration and heating and curing to obtain the MXene/aminated bacterial cellulose composite material.
Each time spraying 10-100 mg of A-Ti 3 C 2 T x /Ti 3 C 2 T x And (3) nano sheets, and changing the spraying amount to perform multiple compounding.
Further, in situ generation of hydrofluoric acid to prepare Ti 3 C 2 T x In the process, ti needs to be slowly added within 5min 3 AlC 2 The powder was stirred at 550 rpm to prevent local overheating. Ti (Ti) 3 AlC 2 The particle size of the powder was 200 mesh.
Further, in situ generation of hydrofluoric acid to prepare Ti 3 C 2 T x In the process, after the stirring is carried out for 48 hours and the etching is finished, deionized water is needed to be used for repeatedly cleaning, and the centrifugal process is repeated for multiple times at 3500 rpm until the pH value is more than or equal to 6.
Further, in situ generation of hydrofluoric acid to prepare Ti 3 C 2 T x In the process, the ultrasonic treatment is carried out under ice bath and argon is introduced to reduce oxidation, the ultrasonic power is 600 watts, and the frequency is 40 kilohertz.
Further, TAT polypeptide modified A-Ti is prepared by an electrostatic self-assembly method 3 C 2 T x /Ti 3 C 2 T x In the process of (2), TAT polypeptide needs to be slowly added within 10min and fully stirred for more than or equal to 12h.
Further, in the process of preparing the aminated bacterial cellulose by the water bath method, the duration of introducing argon is more than or equal to 30min so as to completely remove dissolved oxygen in water, and water and alcohol are used for washing alternately.
Further, in the process of preparing the aminated bacterial cellulose by the water bath method, a freeze dryer is finally used for drying treatment to prevent the bulk bacterial cellulose from deforming.
Further, in the process of preparing the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, specific spraying technological parameters are as follows: the compressed air pressure is 0.4-0.7MPa, the electrostatic spraying voltage is 70KV, and the distance between the spray gun and the small steel sheet is 150nm.
Further, in the process of preparing the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, the condition of heating and solidifying is that heating is carried out in a heating box at 70 ℃ for 2 hours. .
The invention has the remarkable advantages that:
1. the present invention relates to the use of TAT polypeptides for the preparation of Ti 3 C 2 T x Modified A-Ti 3 C 2 T x Has positive zeta potential and can be combined with Ti through electrostatic action 3 C 2 T x The combination improves weak interaction and low density between adjacent MXene nano-sheets, and improves conductivity and mechanical property. The preparation process has the advantages of simplicity, low cost and large-scale preparation.
2. The invention leads the bacterial cellulose to generate a large number of active groups (-OH, -NH) on the surface of the bacterial cellulose by carrying out amination modification on the bacterial cellulose 2 Etc.), the bonding site between bacterial cellulose and MXene is increased, and the adhesion of the MXene nano-sheet on the surface of the sample is improved. The method is favorable for promoting the application of the bacterial cellulose material in the field of electromagnetic shielding.
3. The invention adopts the liquid phase electrostatic spraying-vacuum filtration method to prepare the composite film, is different from the traditional preparation methods of the composite film such as vacuum filtration, coating and the like, has more uniform coating, higher spraying efficiency and higher sample density, and is suitable for large-scale production.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a TAT polypeptide modified MXene/aminated bacterial cellulose composite material of the present invention;
FIG. 2 is an SEM image of a TAT polypeptide-modified MXene/aminated bacterial cellulose composite material of example 3;
FIG. 3 is a partially enlarged SEM image of a TAT polypeptide modified MXene/aminated bacterial cellulose composite material of example 3;
FIG. 4 is Ti of comparative example 1 3 C 2 T x SEM image of bacterial cellulose composite;
FIG. 5 is Ti of comparative example 2 3 C 2 T x SEM image of an aminated bacterial cellulose composite;
fig. 6 shows electromagnetic shielding performance diagrams of the respective embodiments and the comparative examples.
Detailed Description
The invention provides a preparation method of a TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, which is used for making the purposes, technical schemes and effects of the invention clearer and clearer, and is further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
A preparation method of a TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) Ti is prepared by adopting an in-situ generation hydrofluoric acid etching method 3 C 2 T x : 1g LiF is dissolved in 20ml of 9 mol/L hydrochloric acid solution, and Ti is added 3 AlC 2 Continuously stirring at 40deg.C for 48h, centrifuging, washing, collecting lower layer clay-like substance, performing ultrasonic treatment for 120min, centrifuging again at 7000 rpm for 20min, collecting upper layer solution, and lyophilizing to obtain Ti 3 C 2 T x A powder;
(2) By electrostatic self-assemblyA-Ti modified by TAT polypeptide 3 C 2 T x /Ti 3 C 2 T x : first, 2.5. 2.5 mg/mL Ti is prepared 3 C 2 T x Solution and go to Ti 3 C 2 T x Adding 20ml ethanol solution into the solution, adjusting the pH value of the solution to be less than 6 by acetic acid, and uniformly stirring the solution; adding 3-15 ml of TAT polypeptide to obtain TAT polypeptide modified Ti 3 C 2 T x Nanoplatelets, i.e. A-Ti 3 C 2 T x Then A-Ti is added 3 C 2 T x The solution is added to equal amounts of Ti 3 C 2 T x In solution and stirring is continued until A-Ti 3 C 2 T x With Ti 3 C 2 T x Completing self-assembly, and freeze-drying to obtain A-Ti after electrostatic self-assembly 3 C 2 T x /Ti 3 C 2 T x A nanosheet;
(3) The preparation method comprises the steps of (1) preparing aminated bacterial cellulose by adopting a water bath method: 105mg of massive bacterial cellulose is put into deionized water, the temperature is raised to 30-60 ℃, and argon is continuously introduced to remove dissolved O in the water 2 Adding 20ml of ammonium cerium nitrate solution with the concentration of 0.1 mol/L for reaction for 20-50 min, then adding 5ml of glycerol methacrylate dropwise within 30min, reacting for 2h, and washing to obtain treated massive bacterial cellulose; then placing the treated blocky bacterial cellulose into a mixed solution prepared from 75ml of ethylenediamine and 50ml of deionized water, stirring for 2 hours under 353 and K, and washing to obtain aminated bacterial cellulose;
(4) Preparing a TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material by adopting a liquid phase spraying-vacuum filtration method: taking 10mg of A-Ti prepared in the step (2) 3 C 2 T x /Ti 3 C 2 T x Dissolving the nano-sheets in deionized water to prepare a coating, spraying the coating onto the aminated bacterial cellulose prepared in the step (3), and finally carrying out vacuum filtration and heating and curing to obtain the MXene/aminated bacterial cellulose composite material.
Preparation of Ti by in situ generation of hydrofluoric acid 3 C 2 T x In the process, ti needs to be slowly added within 5min 3 AlC 2 The powder was stirred at 550 rpm to prevent local overheating. Ti (Ti) 3 AlC 2 The particle size of the powder was 200 mesh.
Preparation of Ti by in situ generation of hydrofluoric acid 3 C 2 T x In the process, after the stirring is carried out for 48 hours and the etching is finished, deionized water is needed to be used for repeatedly cleaning, and the centrifugal process is repeated for multiple times at 3500 rpm until the pH value is more than or equal to 6.
Preparation of Ti by in situ generation of hydrofluoric acid 3 C 2 T x In the process, the ultrasonic treatment is carried out under ice bath and argon is introduced to reduce oxidation, the ultrasonic power is 600 watts, and the frequency is 40 kilohertz.
Preparation of TAT polypeptide modified A-Ti by electrostatic self-assembly method 3 C 2 T x /Ti 3 C 2 T x In the process of (2), TAT polypeptide needs to be slowly added within 10min and fully stirred for more than or equal to 12h.
In the process of preparing the aminated bacterial cellulose by the water bath method, the duration of introducing argon is more than or equal to 30min so as to completely remove dissolved oxygen in water, and water and alcohol are used for washing alternately.
In the process of preparing the aminated bacterial cellulose by the water bath method, a freeze dryer is used for drying treatment to prevent the massive bacterial cellulose from deforming.
In the process of preparing the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, specific spraying technological parameters are as follows: the compressed air pressure is 0.4-0.7MPa, the electrostatic spraying voltage is 70KV, and the distance between the spray gun and the small steel sheet is 150nm.
In the process of preparing the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, the condition of heating and solidifying is that heating is carried out in a heating box at 70 ℃ for 2 hours.
Example 2
A preparation method of a TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) Ti is prepared by adopting an in-situ generation hydrofluoric acid etching method 3 C 2 T x : 1g LiF is dissolved in 20ml of 9 mol/L hydrochloric acid solution, and Ti is added 3 AlC 2 Continuously stirring at 40deg.C for 48h, centrifuging, washing, collecting lower layer clay-like substance, performing ultrasonic treatment for 120min, centrifuging again at 7000 rpm for 20min, collecting upper layer solution, and lyophilizing to obtain Ti 3 C 2 T x A powder;
(2) Preparation of TAT polypeptide modified A-Ti by electrostatic self-assembly method 3 C 2 T x /Ti 3 C 2 T x : first, 2.5. 2.5 mg/mL Ti is prepared 3 C 2 T x Solution and go to Ti 3 C 2 T x Adding 20ml ethanol solution into the solution, adjusting the pH value of the solution to be less than 6 by acetic acid, and uniformly stirring the solution; adding 3-15 ml of TAT polypeptide to obtain TAT polypeptide modified Ti 3 C 2 T x Nanoplatelets, i.e. A-Ti 3 C 2 T x Then A-Ti is added 3 C 2 T x The solution is added to equal amounts of Ti 3 C 2 T x In solution and stirring is continued until A-Ti 3 C 2 T x With Ti 3 C 2 T x Completing self-assembly, and freeze-drying to obtain A-Ti after electrostatic self-assembly 3 C 2 T x /Ti 3 C 2 T x A nanosheet;
(3) The preparation method comprises the steps of (1) preparing aminated bacterial cellulose by adopting a water bath method: 105mg of massive bacterial cellulose is put into deionized water, the temperature is raised to 30-60 ℃, and argon is continuously introduced to remove dissolved O in the water 2 Adding 20ml of ammonium cerium nitrate solution with the concentration of 0.1 mol/L for reaction for 20-50 min, then adding 5ml of glycerol methacrylate dropwise within 30min, reacting for 2h, and washing to obtain treated massive bacterial cellulose; then the treated blocky bacterial cellulose is put into a mixed solution prepared by 75ml of ethylenediamine and 50ml of deionized water, stirred for 2 hours under 353 and K, and washed to obtain aminoTransforming bacterial cellulose;
(4) Preparing a TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material by adopting a liquid phase spraying-vacuum filtration method: 30mg of A-Ti prepared in the step (2) 3 C 2 T x / Ti 3 C 2 T x Dissolving the nano-sheets in deionized water to prepare a coating, spraying the coating onto the aminated bacterial cellulose prepared in the step (3), and finally carrying out vacuum filtration and heating and curing to obtain the MXene/aminated bacterial cellulose composite material.
Preparation of Ti by in situ generation of hydrofluoric acid 3 C 2 T x In the process, ti needs to be slowly added within 5min 3 AlC 2 The powder was stirred at 550 rpm to prevent local overheating. Ti (Ti) 3 AlC 2 The particle size of the powder was 200 mesh.
Preparation of Ti by in situ generation of hydrofluoric acid 3 C 2 T x In the process, after the stirring is carried out for 48 hours and the etching is finished, deionized water is needed to be used for repeatedly cleaning, and the centrifugal process is repeated for multiple times at 3500 rpm until the pH value is more than or equal to 6.
Preparation of Ti by in situ generation of hydrofluoric acid 3 C 2 T x In the process, the ultrasonic treatment is carried out under ice bath and argon is introduced to reduce oxidation, the ultrasonic power is 600 watts, and the frequency is 40 kilohertz.
Preparation of TAT polypeptide modified A-Ti by electrostatic self-assembly method 3 C 2 T x /Ti 3 C 2 T x In the process of (2), TAT polypeptide needs to be slowly added within 10min and fully stirred for more than or equal to 12h.
In the process of preparing the aminated bacterial cellulose by the water bath method, the duration of introducing argon is more than or equal to 30min so as to completely remove dissolved oxygen in water, and water and alcohol are used for washing alternately.
In the process of preparing the aminated bacterial cellulose by the water bath method, a freeze dryer is used for drying treatment to prevent the massive bacterial cellulose from deforming.
In the process of preparing the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, specific spraying technological parameters are as follows: the compressed air pressure is 0.4-0.7MPa, the electrostatic spraying voltage is 70KV, and the distance between the spray gun and the small steel sheet is 150nm.
In the process of preparing the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, the condition of heating and solidifying is that heating is carried out in a heating box at 70 ℃ for 2 hours.
Example 3
A preparation method of a TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) Ti is prepared by adopting an in-situ generation hydrofluoric acid etching method 3 C 2 T x : 1g LiF is dissolved in 20ml of 9 mol/L hydrochloric acid solution, and Ti is added 3 AlC 2 Continuously stirring at 40deg.C for 48h, centrifuging, washing, collecting lower layer clay-like substance, performing ultrasonic treatment for 120min, centrifuging again at 7000 rpm for 20min, collecting upper layer solution, and lyophilizing to obtain Ti 3 C 2 T x A powder;
(2) Preparation of TAT polypeptide modified A-Ti by electrostatic self-assembly method 3 C 2 T x /Ti 3 C 2 T x : first, 2.5. 2.5 mg/mL Ti is prepared 3 C 2 T x Solution and go to Ti 3 C 2 T x Adding 20ml ethanol solution into the solution, adjusting the pH value of the solution to be less than 6 by acetic acid, and uniformly stirring the solution; adding 3-15 ml of TAT polypeptide to obtain TAT polypeptide modified Ti 3 C 2 T x Nanoplatelets, i.e. A-Ti 3 C 2 T x Then A-Ti is added 3 C 2 T x The solution is added to equal amounts of Ti 3 C 2 T x In solution and stirring is continued until A-Ti 3 C 2 T x With Ti 3 C 2 T x Completing self-assembly, and freeze-drying to obtain A-Ti after electrostatic self-assembly 3 C 2 T x /Ti 3 C 2 T x A nanosheet;
(3) The preparation method comprises the steps of (1) preparing aminated bacterial cellulose by adopting a water bath method: 105mg of massive bacterial cellulose is put into deionized water, the temperature is raised to 30-60 ℃, and argon is continuously introduced to remove dissolved O in the water 2 Adding 20ml of ammonium cerium nitrate solution with the concentration of 0.1 mol/L for reaction for 20-50 min, then adding 5ml of glycerol methacrylate dropwise within 30min, reacting for 2h, and washing to obtain treated massive bacterial cellulose; then placing the treated blocky bacterial cellulose into a mixed solution prepared from 75ml of ethylenediamine and 50ml of deionized water, stirring for 2 hours under 353 and K, and washing to obtain aminated bacterial cellulose;
(4) Preparing a TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material by adopting a liquid phase spraying-vacuum filtration method: 50mg of A-Ti prepared in the step (2) 3 C 2 T x / Ti 3 C 2 T x Dissolving the nano-sheets in deionized water to prepare a coating, spraying the coating onto the aminated bacterial cellulose prepared in the step (3), and finally carrying out vacuum filtration and heating and curing to obtain the MXene/aminated bacterial cellulose composite material.
Preparation of Ti by in situ generation of hydrofluoric acid 3 C 2 T x In the process, ti needs to be slowly added within 5min 3 AlC 2 The powder was stirred at 550 rpm to prevent local overheating. Ti (Ti) 3 AlC 2 The particle size of the powder was 200 mesh.
Preparation of Ti by in situ generation of hydrofluoric acid 3 C 2 T x In the process, after the stirring is carried out for 48 hours and the etching is finished, deionized water is needed to be used for repeatedly cleaning, and the centrifugal process is repeated for multiple times at 3500 rpm until the pH value is more than or equal to 6.
Preparation of Ti by in situ generation of hydrofluoric acid 3 C 2 T x In the process, the ultrasonic treatment is carried out under ice bath and argon is introduced to reduce oxidation, the ultrasonic power is 600 watts, and the frequency is 40 kilohertz.
Preparation of TAT polypeptide modified A-Ti by electrostatic self-assembly method 3 C 2 T x /Ti 3 C 2 T x In the course of (2), it is necessary to slowly add TAT polypeptide within 10min and sufficientlyStirring for more than or equal to 12 hours.
In the process of preparing the aminated bacterial cellulose by the water bath method, the duration of introducing argon is more than or equal to 30min so as to completely remove dissolved oxygen in water, and water and alcohol are used for washing alternately.
In the process of preparing the aminated bacterial cellulose by the water bath method, a freeze dryer is used for drying treatment to prevent the massive bacterial cellulose from deforming.
In the process of preparing the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, specific spraying technological parameters are as follows: the compressed air pressure is 0.4-0.7MPa, the electrostatic spraying voltage is 70KV, and the distance between the spray gun and the small steel sheet is 150nm.
In the process of preparing the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, the condition of heating and solidifying is that heating is carried out in a heating box at 70 ℃ for 2 hours.
Example 4
A preparation method of a TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) Ti is prepared by adopting an in-situ generation hydrofluoric acid etching method 3 C 2 T x : 1g LiF is dissolved in 20ml of 9 mol/L hydrochloric acid solution, and Ti is added 3 AlC 2 Continuously stirring at 40deg.C for 48h, centrifuging, washing, collecting lower layer clay-like substance, performing ultrasonic treatment for 120min, centrifuging again at 7000 rpm for 20min, collecting upper layer solution, and lyophilizing to obtain Ti 3 C 2 T x A powder;
(2) Preparation of TAT polypeptide modified A-Ti by electrostatic self-assembly method 3 C 2 T x /Ti 3 C 2 T x : first, 2.5. 2.5 mg/mL Ti is prepared 3 C 2 T x Solution and go to Ti 3 C 2 T x Adding 20ml ethanol solution into the solution, adjusting the pH value of the solution to be less than 6 by acetic acid, and uniformly stirring the solution; adding 3-15 ml of TAT polypeptide to obtain TAT polypeptide modified Ti 3 C 2 T x Nanoplatelets, i.e. A-Ti 3 C 2 T x Then A-Ti is added 3 C 2 T x The solution is added to equal amounts of Ti 3 C 2 T x In solution and stirring is continued until A-Ti 3 C 2 T x With Ti 3 C 2 T x Completing self-assembly, and freeze-drying to obtain A-Ti after electrostatic self-assembly 3 C 2 T x /Ti 3 C 2 T x A nanosheet;
(3) The preparation method comprises the steps of (1) preparing aminated bacterial cellulose by adopting a water bath method: 105mg of massive bacterial cellulose is put into deionized water, the temperature is raised to 30-60 ℃, and argon is continuously introduced to remove dissolved O in the water 2 Adding 20ml of ammonium cerium nitrate solution with the concentration of 0.1 mol/L for reaction for 20-50 min, then adding 5ml of glycerol methacrylate dropwise within 30min, reacting for 2h, and washing to obtain treated massive bacterial cellulose; then placing the treated blocky bacterial cellulose into a mixed solution prepared from 75ml of ethylenediamine and 50ml of deionized water, stirring for 2 hours under 353 and K, and washing to obtain aminated bacterial cellulose;
(4) Preparing a TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material by adopting a liquid phase spraying-vacuum filtration method: 70mg of A-Ti prepared in the step (2) 3 C 2 T x / Ti 3 C 2 T x Dissolving the nano-sheets in deionized water to prepare a coating, spraying the coating onto the aminated bacterial cellulose prepared in the step (3), and finally carrying out vacuum filtration and heating and curing to obtain the MXene/aminated bacterial cellulose composite material.
Preparation of Ti by in situ generation of hydrofluoric acid 3 C 2 T x In the process, ti needs to be slowly added within 5min 3 AlC 2 The powder was stirred at 550 rpm to prevent local overheating. Ti (Ti) 3 AlC 2 The particle size of the powder was 200 mesh.
Preparation of Ti by in situ generation of hydrofluoric acid 3 C 2 T x In the process, after stirring for 48 hours and etching is completed, the ion is neededRepeatedly cleaning the seed water, and repeatedly centrifuging at 3500 rpm for multiple times until the pH is more than or equal to 6.
Preparation of Ti by in situ generation of hydrofluoric acid 3 C 2 T x In the process, the ultrasonic treatment is carried out under ice bath and argon is introduced to reduce oxidation, the ultrasonic power is 600 watts, and the frequency is 40 kilohertz.
Preparation of TAT polypeptide modified A-Ti by electrostatic self-assembly method 3 C 2 T x /Ti 3 C 2 T x In the process of (2), TAT polypeptide needs to be slowly added within 10min and fully stirred for more than or equal to 12h.
In the process of preparing the aminated bacterial cellulose by the water bath method, the duration of introducing argon is more than or equal to 30min so as to completely remove dissolved oxygen in water, and water and alcohol are used for washing alternately.
In the process of preparing the aminated bacterial cellulose by the water bath method, a freeze dryer is used for drying treatment to prevent the massive bacterial cellulose from deforming.
In the process of preparing the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, specific spraying technological parameters are as follows: the compressed air pressure is 0.4-0.7MPa, the electrostatic spraying voltage is 70KV, and the distance between the spray gun and the small steel sheet is 150nm.
In the process of preparing the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, the condition of heating and solidifying is that heating is carried out in a heating box at 70 ℃ for 2 hours.
Example 5
A preparation method of a TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) Ti is prepared by adopting an in-situ generation hydrofluoric acid etching method 3 C 2 T x : 1g LiF is dissolved in 20ml of 9 mol/L hydrochloric acid solution, and Ti is added 3 AlC 2 Continuously stirring at 40deg.C for 48h, centrifuging, washing, collecting lower layer clay-like substance, performing ultrasonic treatment for 120min, centrifuging again at 7000 rpm for 20min, collecting upper layer solution, and lyophilizing to obtain Ti 3 C 2 T x A powder;
(2) Preparation of TAT polypeptide modified A-Ti by electrostatic self-assembly method 3 C 2 T x /Ti 3 C 2 T x : first, 2.5. 2.5 mg/mL Ti is prepared 3 C 2 T x Solution and go to Ti 3 C 2 T x Adding 20ml ethanol solution into the solution, adjusting the pH value of the solution to be less than 6 by acetic acid, and uniformly stirring the solution; adding 3-15 ml of TAT polypeptide to obtain TAT polypeptide modified Ti 3 C 2 T x Nanoplatelets, i.e. A-Ti 3 C 2 T x Then A-Ti is added 3 C 2 T x The solution is added to equal amounts of Ti 3 C 2 T x In solution and stirring is continued until A-Ti 3 C 2 T x With Ti 3 C 2 T x Completing self-assembly, and freeze-drying to obtain A-Ti after electrostatic self-assembly 3 C 2 T x /Ti 3 C 2 T x A nanosheet;
(3) The preparation method comprises the steps of (1) preparing aminated bacterial cellulose by adopting a water bath method: 105mg of massive bacterial cellulose is put into deionized water, the temperature is raised to 30-60 ℃, and argon is continuously introduced to remove dissolved O in the water 2 Adding 20ml of ammonium cerium nitrate solution with the concentration of 0.1 mol/L for reaction for 20-50 min, then adding 5ml of glycerol methacrylate dropwise within 30min, reacting for 2h, and washing to obtain treated massive bacterial cellulose; then placing the treated blocky bacterial cellulose into a mixed solution prepared from 75ml of ethylenediamine and 50ml of deionized water, stirring for 2 hours under 353 and K, and washing to obtain aminated bacterial cellulose;
(4) Preparing a TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material by adopting a liquid phase spraying-vacuum filtration method: 90mg of A-Ti prepared in the step (2) is reacted with 3 C 2 T x / Ti 3 C 2 T x Dissolving the nano-sheets in deionized water to prepare a coating, spraying the coating onto the aminated bacterial cellulose prepared in the step (3),finally, the MXene/aminated bacterial cellulose composite material is obtained through vacuum filtration and heating solidification.
Preparation of Ti by in situ generation of hydrofluoric acid 3 C 2 T x In the process, ti needs to be slowly added within 5min 3 AlC 2 The powder was stirred at 550 rpm to prevent local overheating. Ti (Ti) 3 AlC 2 The particle size of the powder was 200 mesh.
Preparation of Ti by in situ generation of hydrofluoric acid 3 C 2 T x In the process, after the stirring is carried out for 48 hours and the etching is finished, deionized water is needed to be used for repeatedly cleaning, and the centrifugal process is repeated for multiple times at 3500 rpm until the pH value is more than or equal to 6.
Preparation of Ti by in situ generation of hydrofluoric acid 3 C 2 T x In the process, the ultrasonic treatment is carried out under ice bath and argon is introduced to reduce oxidation, the ultrasonic power is 600 watts, and the frequency is 40 kilohertz.
Preparation of TAT polypeptide modified A-Ti by electrostatic self-assembly method 3 C 2 T x /Ti 3 C 2 T x In the process of (2), TAT polypeptide needs to be slowly added within 10min and fully stirred for more than or equal to 12h.
In the process of preparing the aminated bacterial cellulose by the water bath method, the duration of introducing argon is more than or equal to 30min so as to completely remove dissolved oxygen in water, and water and alcohol are used for washing alternately.
In the process of preparing the aminated bacterial cellulose by the water bath method, a freeze dryer is used for drying treatment to prevent the massive bacterial cellulose from deforming.
In the process of preparing the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, specific spraying technological parameters are as follows: the compressed air pressure is 0.4-0.7MPa, the electrostatic spraying voltage is 70KV, and the distance between the spray gun and the small steel sheet is 150nm.
In the process of preparing the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, the condition of heating and solidifying is that heating is carried out in a heating box at 70 ℃ for 2 hours.
Comparative example 1
Ti (titanium) 3 C 2 T x The preparation method of the bacterial cellulose composite material is characterized by comprising the following steps of: the method comprises the following steps:
(1) Ti is prepared by adopting an in-situ generation hydrofluoric acid etching method 3 C 2 T x : 1g LiF is dissolved in 20ml of 9 mol/L hydrochloric acid solution, and Ti is added 3 AlC 2 Continuously stirring at 40deg.C for 48h, centrifuging, washing, collecting lower layer clay-like substance, performing ultrasonic treatment for 120min, centrifuging again at 7000 rpm for 20min, collecting upper layer solution, and lyophilizing to obtain Ti 3 C 2 T x A powder;
(2) Ti is prepared by adopting a liquid phase spraying-vacuum filtration method 3 C 2 T x Bacterial cellulose composite: 50mg of Ti is taken 3 C 2 T x Dissolving the nano-sheet in deionized water to prepare a coating, spraying the coating onto 105mg of blocky bacterial cellulose, and finally carrying out vacuum filtration, heating and curing to obtain Ti 3 C 2 T x Bacterial cellulose composite.
Comparative example 2
Ti (titanium) 3 C 2 T x The preparation method of the aminated bacterial cellulose composite material is characterized by comprising the following steps of: the method comprises the following steps:
(1) Ti is prepared by adopting an in-situ generation hydrofluoric acid etching method 3 C 2 T x : 1g LiF is dissolved in 20ml of 9 mol/L hydrochloric acid solution, and Ti is added 3 AlC 2 Continuously stirring at 40deg.C for 48h, centrifuging, washing, collecting lower layer clay-like substance, performing ultrasonic treatment for 120min, centrifuging again at 7000 rpm for 20min, collecting upper layer solution, and lyophilizing to obtain Ti 3 C 2 T x A powder;
(2) The preparation method comprises the steps of (1) preparing aminated bacterial cellulose by adopting a water bath method: 105mg of massive bacterial cellulose is put into deionized water, the temperature is raised to 30-60 ℃, and argon is continuously introduced to remove dissolved O in the water 2 And adding 20ml of 0.1 mol/L ceric ammonium nitrate solution to react for 20-50 min, and then dropwise adding 5ml of methacrylic acid within 30minThe glyceride reacts for 2 hours and then is washed to obtain treated blocky bacterial cellulose; then placing the treated blocky bacterial cellulose into a mixed solution prepared from 75ml of ethylenediamine and 50ml of deionized water, stirring for 2 hours under 353 and K, and washing to obtain aminated bacterial cellulose;
(3) Ti is prepared by adopting a liquid phase spraying-vacuum filtration method 3 C 2 T x Amino bacterial cellulose composite: 50mg of Ti is taken 3 C 2 T x Dissolving the nano-sheets in deionized water to prepare a coating, spraying the coating onto the aminated bacterial cellulose prepared in the step (2), and finally carrying out vacuum filtration, heating and curing to obtain Ti 3 C 2 T x An aminated bacterial cellulose composite.
As can be seen from fig. 2 to 3, no delamination phenomenon occurs between the MXene nanoplatelets and the bacterial cellulose substrate in the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, showing excellent compactness. In comparative example 1, ti which has not undergone any modification treatment 3 C 2 T x The density of MXene nanoplatelets in the bacterial cellulose electromagnetic shielding composite was low and there was significant delamination with the bacterial cellulose substrate (fig. 4). As shown in FIG. 5, ti is produced by subjecting bacterial cellulose to amination 3 C 2 T x The nanoplatelets can be tightly bound to the aminated bacterial cellulose substrate. Compared with a TAT polypeptide modified MXene/aminated bacterial cellulose composite material, ti 3 C 2 T x Adjacent Ti in an aminated bacterial cellulose composite material 3 C 2 T x The nano-sheet has more pore structures, which indicates Ti 3 C 2 T x Van der waals forces between nanoplatelets are weak, which is detrimental to interlayer electron transport, resulting in lower electromagnetic shielding effectiveness (fig. 6). Experimental comparison shows that the preparation method of the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material is feasible.
To study the invention using TAT polypeptides for Ti 3 C 2 T x We have modified the Ti prepared 3 C 2 T x 9ml of TAT polypeptide modified A-Ti 3 C 2 T x And A-Ti 3 C 2 T x /Ti 3 C 2 T x Zeta potential values of (c) were studied. As can be seen by comparing the zeta potential values in Table 1, untreated Ti 3 C 2 T x The potential value of (C) is-40, indicating Ti 3 C 2 T x The functional groups on the surface contain a large number of negatively charged groups. The potential value of MXene was changed to +34 after TAT modification, indicating that TAT polypeptide was successfully modified to MXene. A-Ti 3 C 2 T x /Ti 3 C 2 T x Zeta potential value of (C) indicates Ti 3 C 2 T x With A-Ti 3 C 2 T x Successfully bonded together by electrostatic attraction.
Table 1 Ti 3 C 2 T x And A-Ti in example 1 3 C 2 T x 、A-Ti 3 C 2 T x /Ti 3 C 2 T x Zeta potential value of (2)
In order to study the mechanical property and electromagnetic shielding property of the material prepared by the invention, a universal material tester and an Agilent vector network analyzer are used for testing the stress and electromagnetic shielding effect of a sample. As can be seen from the examples of Table 2, the tensile stress of the TAT polypeptide modified MXene/aminated bacterial cellulose composites from examples 1 to 5 increases and decreases, and the tensile stress is A-Ti in example 3 3 C 2 T x /Ti 3 C 2 T x The content of the nano-sheet reaches the maximum at 50mg and the maximum is 182MPa. In comparative examples 1 and 2, the tensile stress of the composite material was 128MPa and 135MPa, respectively, while example 1 was loaded with MXeneThe tensile stress of 158MPa can still be shown under a small amount of conditions, which shows that the modified aminated bacterial cellulose and the MXene modified by TAT polypeptide have a synergistic effect on the mechanical properties of the composite film. And, the composite material exhibits excellent electromagnetic shielding effectiveness of 49.7 dB.
Table 2 mechanical properties and electromagnetic shielding properties of each of examples and comparative examples
The invention adopts an in-situ synthesis hydrofluoric acid etching method to prepare Ti 3 C 2 T x Subsequent modification of Ti with TAT polypeptide 3 C 2 T x Preparing A-Ti 3 C 2 T x /Ti 3 C 2 T x A nano-sheet. And (3) carrying out amination treatment on bacterial cellulose by adopting a water bath method, and obtaining the MXene/aminated bacterial cellulose composite material modified by TAT polypeptide through liquid phase spraying and vacuum filtration. TAT polypeptide modified A-Ti 3 C 2 T x Has a large positive charge and can be combined with Ti 3 C 2 T x (containing-OH, -F, etc.) are combined together through electrostatic action, so that the bonding force between MXene nano-sheets is enhanced, and the compactness is improved. The aminated bacterial cellulose contains a large amount of-NH 2 and-OH capable of reacting with A-Ti 3 C 2 T x /Ti 3 C 2 T x The nano-sheets are combined in a hydrogen bond mode, so that the composite material has the advantages of high density, high mechanical strength and the like. The prepared TAT polypeptide modified MXene/aminated bacterial cellulose composite material shows a tensile stress of 158MPa and an electromagnetic shielding effectiveness of 49.7dB under the condition of smaller MXene content. Has a tensile stress of up to 182MPa at an optimum content of 50mg of MXene and exhibits a high electromagnetic shielding effect of 61.0 dB. The method has strong controllability, simplicity, high efficiency and low cost, and has great industrialization and application prospect in the field of electromagnetic shielding. It is to be understood that the invention is not limited in its application to the examples described aboveModifications and variations will be apparent to those skilled in the art in light of the foregoing description, and it is intended to cover all such modifications and variations as fall within the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) Ti is prepared by adopting an in-situ generation hydrofluoric acid etching method 3 C 2 T x : dissolving LiF in hydrochloric acid solution, and adding Ti 3 AlC 2 Stirring at 40deg.C for 48 hr, centrifuging, washing, collecting lower layer clay, performing ultrasonic treatment for 120min, centrifuging again, collecting upper layer solution, and lyophilizing to obtain Ti 3 C 2 T x A powder;
(2) Preparation of TAT polypeptide modified A-Ti by electrostatic self-assembly method 3 C 2 T x /Ti 3 C 2 T x : first preparing Ti 3 C 2 T x Solution and go to Ti 3 C 2 T x Adding ethanol solution into the solution, adjusting the pH value of the solution to be less than 6 by acetic acid, and uniformly stirring the solution; adding TAT polypeptide to obtain TAT polypeptide modified Ti 3 C 2 T x Nanoplatelets, i.e. A-Ti 3 C 2 T x Then A-Ti is added 3 C 2 T x The solution is added to equal amounts of Ti 3 C 2 T x In solution and stirring is continued until A-Ti 3 C 2 T x With Ti 3 C 2 T x Completing self-assembly, and freeze-drying to obtain A-Ti after electrostatic self-assembly 3 C 2 T x /Ti 3 C 2 T x A nanosheet;
(3) The preparation method comprises the steps of (1) preparing aminated bacterial cellulose by adopting a water bath method: placing blocky bacterial cellulose into deionized water, heating to 30-60 ℃, and continuously introducing argon to remove dissolved O in the water 2 And is combined withAdding ceric ammonium nitrate solution for reaction for 20-50 min, then dropwise adding glycerol methacrylate within 30min, reacting for 2h, and washing to obtain treated massive bacterial cellulose; then the treated blocky bacterial cellulose is put into a mixed solution prepared by ethylenediamine and deionized water, stirred for 2 hours under 353 and K, and then washed to obtain the aminated bacterial cellulose;
(4) Preparing a TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material by adopting a liquid phase spraying-vacuum filtration method: the A-Ti prepared in the step (2) is treated 3 C 2 T x /Ti 3 C 2 T x Dissolving the nano-sheets in deionized water to prepare a coating, spraying the coating onto the aminated bacterial cellulose prepared in the step (3), and finally carrying out vacuum filtration and heating and curing to obtain the MXene/aminated bacterial cellulose composite material.
2. The process according to claim 1, wherein in step (1), ti is slowly added within 5min 3 AlC 2 Powder to prevent local overheating, stirring at 550 rpm; ti (Ti) 3 AlC 2 The particle size of the powder was 200 mesh.
3. The method of manufacturing according to claim 1, characterized in that: in the step (1), stirring is carried out for 48 hours, and deionized water is needed to repeatedly wash after etching is finished, and centrifugation is repeated for many times at 3500 rpm until the pH is more than or equal to 6.
4. The method of manufacturing according to claim 1, characterized in that: in the step (1), the ultrasonic treatment is carried out under ice bath and argon is introduced to reduce oxidation, the ultrasonic power is 600 watts, and the frequency is 40 kilohertz.
5. The method of manufacturing according to claim 1, characterized in that: in the step (2), TAT polypeptide is slowly added within 10min and fully stirred for more than or equal to 12h.
6. The method of manufacturing according to claim 1, characterized in that: in the step (3), the duration of introducing argon is more than or equal to 30min so as to completely remove the dissolved oxygen in the water, and water and alcohol are used for alternately washing.
7. The method of manufacturing according to claim 1, characterized in that: in the step (3), the final drying is freeze drying.
8. The method of manufacturing according to claim 1, characterized in that: in the step (4), specific spraying process parameters are as follows: the compressed air pressure is 0.4-0.7MPa, the electrostatic spraying voltage is 70KV, and the distance between the spray gun and the small steel sheet is 150nm.
9. The method of manufacturing according to claim 1, characterized in that: in the step (4), the condition of heat curing is that the heating is carried out in a heating box at 70 ℃ for 2 hours.
10. An electromagnetic shielding composite of TAT polypeptide modified MXene/aminated bacterial cellulose prepared by the method of any one of claims 1-9.
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