CN115304812A - 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. In-situ synthesis hydrofluoric acid etching method for preparing Ti 3 C 2 T x And preparing A-Ti by modifying TAT polypeptide 3 C 2 T x /Ti 3 C 2 T x Nanosheets. By amination treatment of bacterial cellulose toLiquid phase spraying and vacuum filtering to obtain the TAT polypeptide modified MXene/aminated bacterial cellulose composite material. A-Ti 3 C 2 T x Having a large positive charge capable of reacting with Ti 3 C 2 T x Through electrostatic bonding, the bonding force between MXene nanosheets is enhanced, and the density 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 endless emergence of various electronic products, which bring convenience to people and also generate a great amount of electromagnetic radiation. When the electromagnetic radiation exceeds a certain limit, electromagnetic pollution can be caused, and adverse effects are brought to daily production and life and body health of people. Electromagnetic waves can be divided into two types according to radiation sources, wherein one type is from nature, such as cosmic rays, lightning phenomena, strong ultraviolet rays of the sun and the like; the other is artificial, such as radar, base station signal, and wireless devices such as communication, which are intentionally transmitted, and in addition, household appliances, electronic devices, etc. can radiate unnecessary electromagnetic waves to harm human health. Therefore, the development of high-performance electromagnetic shielding materials is of great significance for reducing or eliminating electromagnetic radiation pollution. For a long time, metals have been widely used in electromagnetic shielding due to their high electrical conductivity and good shielding effect. However, due to the miniaturization and intellectualization of modern electronic devices, it is desired to develop an electromagnetic shielding material having both high electromagnetic shielding efficiency and excellent mechanical properties. It is clear that metallic materials have limited their practical application 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 from 2011 (such as Ti) 3 C 2 T x ) Has attracted the attention of people in the past. In general, MXene is produced by selective etching of Al element from a MAX phase and ultimately forms a film of the 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, and Tx is a surface functional group (e.g., -OH, -F, -O, etc.). In view of MXene's low resistance, unique layered structure, abundant surface functional groups, and excellent physicochemical properties, it has attracted considerable interest to researchers in batteries, capacitors, catalysts, and electromagnetic shielding. However, although MXene exhibits excellent electromagnetic shielding performance compared to most existing shielding materials, poor interaction between the original MXene nanosheets results in applications that are not satisfactory in terms of ductility and tensile strength, which also hinders further applications of MXene in high performance electromagnetic shielding.
As a small molecule polypeptide that is hydrophilic and has a large number of positive charges, TAT has been applied to drug carriers and tumor therapy, among other things. 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 guanidyl in the arginine structure can be combined with substances with negative charges on the surface, the small-molecule TAT polypeptide can be used for changing the surface potential of MXene to increase the binding force between MXene sheets and improve the transmission process of electrons between layers.
Bacterial Cellulose (BC) is a natural organic material produced by bacteria. Has the characteristics of rich sources, high mechanical strength, no environmental pollution and the like, thereby being an ideal substrate material. In addition, the bacterial cellulose has abundant surface hydroxyl groups, and can be combined with MXene in a hydrogen bond form to make up for the defect of poor mechanical property. However, only a few studies to date use bacterial cellulose as a substrate of the MXene composite material, and the problems of long preparation process cycle, single preparation method, lack of innovation and the like exist. Therefore, the development of an innovative bacterial cellulose-based MXene composite material remains a significant challenge.
The invention takes bacterial cellulose as a substrate and uses TAT polypeptide to Ti 3 C 2 T x The modification generates a large amount of positive charges on the surface. Modified A-Ti 3 C 2 T x Capable of reacting with unmodified Ti 3 C 2 T x Combined together by electrostatic adsorption to form A-Ti 3 C 2 T x /Ti 3 C 2 T x Nanosheets. With Ti 3 C 2 T x In contrast, 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 promotion of electron transmission and electric conductivity. In addition, after the bacterial cellulose is subjected to amination treatment, 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 Combination of nanosheet on bacterial cellulose surface and increase of A-Ti 3 C 2 T x /Ti 3 C 2 T x The 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 property and poor electromagnetic shielding effect of the conventional 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 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) In-situ generated hydrofluoric acid etching method for preparing Ti 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 for 48h at 40 ℃, centrifuging, washing, collecting lower layer clay-like substance, performing ultrasonic treatment for 120min, centrifuging again for 20min at 7000 r/min, collecting upper layer solution, and freeze drying to obtain Ti 3 C 2 T x A powder;
(2) TAT polypeptide modified A-Ti prepared by adopting electrostatic self-assembly method 3 C 2 T x /Ti 3 C 2 T x : firstly, 2.5 mg/mL Ti is prepared 3 C 2 T x Into solution and adding Ti 3 C 2 T x Adding 20ml of ethanol solution into the solution, then adjusting the pH value of the solution to be below 6 by acetic acid and uniformly stirring the solution; adding 3 to 15 ml of TAT polypeptide to obtain TAT polypeptide modified Ti 3 C 2 T x Nanosheets, namely A-Ti 3 C 2 T x Then adding A-Ti 3 C 2 T x The solution was added to an equal amount 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 the electrostatically self-assembled A-Ti 3 C 2 T x /Ti 3 C 2 T x Nanosheets;
(3) Preparing the aminated bacterial cellulose by a water bath method: putting 105mg of blocky bacterial cellulose (the length and the width are both 4cm, and the thickness is 5 mm) into deionized water, heating to 30-60 ℃, and continuously introducing argon to remove dissolved O in the water 2 Adding 20mL of ammonium ceric nitrate solution with the concentration of 0.1 mol/L for reaction for 20 to 50min, then dropwise adding 5mL of glycerol methacrylate within 30min, reacting for 2h, and then addingWashing to obtain the treated massive bacterial cellulose; then putting the treated blocky bacterial cellulose into a mixed solution prepared from 75ml of ethylenediamine and 50ml of deionized water, stirring for 2 hours at 353K, and washing to obtain aminated bacterial cellulose;
(4) Preparing the MXene/aminated bacterial cellulose electromagnetic shielding composite material modified by TAT polypeptide by adopting a liquid phase spraying-vacuum filtering method: taking 10 to 100mg of A-Ti prepared in the step (2) 3 C 2 T x /Ti 3 C 2 T x Dissolving the nanosheets in deionized water to prepare a coating, spraying the coating onto the aminated bacterial cellulose prepared in the step (3), and finally performing vacuum filtration and heating curing to obtain the MXene/aminated bacterial cellulose composite material.
Spraying 10 to 100 milligrams of A-Ti each time 3 C 2 T x /Ti 3 C 2 T x And (4) nanosheets, and carrying out multiple compounding by changing the spraying amount.
Further, in-situ generation of hydrofluoric acid for preparing 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 3 AlC 2 The particle size of the powder was 200 mesh.
Further, in-situ generation of hydrofluoric acid for preparing Ti 3 C 2 T x In the process, stirring for 48h, after etching is completed, repeatedly cleaning with deionized water, and repeatedly centrifuging at 3500 rpm/min for multiple times until the pH is more than or equal to 6.
Further, in-situ generation of hydrofluoric acid for preparing Ti 3 C 2 T x In the process, the ultrasound is carried out in an 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 in an electrostatic self-assembly method 3 C 2 T x /Ti 3 C 2 T x In the process, 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 amination bacterial cellulose by a water bath method, the time for introducing argon is more than or equal to 30min to completely remove dissolved oxygen in water, and water and alcohol are alternately used for washing.
Further, in the process of preparing the aminated bacterial cellulose by a water bath method, a freeze dryer is finally used for drying treatment to prevent the massive bacterial cellulose from deforming.
Further, in the process of preparing the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, the specific spraying process parameters are as follows: the pressure of compressed air is 0.4-0.7MPa, the electrostatic spraying voltage is 70KV, and the distance between a spray gun and the small steel sheet is 150nm.
Further, in the preparation process of the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, the heating and curing conditions are that the material is heated for 2 hours in a heating box at 70 ℃. .
The invention has the remarkable advantages that:
1. the invention is achieved by using TAT polypeptide to Ti 3 C 2 T x Modified A-Ti 3 C 2 T x Having a positive zeta potential and being able to interact electrostatically with Ti 3 C 2 T x And the combination improves the weak interaction and low density between MXene adjacent nanosheets, and improves the conductivity and mechanical properties. The preparation process has the advantages of simplicity, low cost and large-scale preparation.
2. The invention makes the surface of the bacterial cellulose generate a large amount of active groups (-OH, -NH) by carrying out amination modification on the bacterial cellulose 2 And the like) are added, bonding sites between the bacterial cellulose and the MXene are increased, and the adhesion of the MXene nanosheet 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 composite film is prepared by using a liquid-phase electrostatic spraying-vacuum filtering method, which is different from the traditional preparation methods of composite films such as vacuum filtration and coating, the coating obtained by the method is more uniform, the spraying efficiency is higher, the sample density is higher, and the method is suitable for large-scale production.
Drawings
FIG. 1 is a schematic flow diagram of a method for preparing a TAT polypeptide modified MXene/aminated bacterial cellulose composite material in accordance with the present invention;
FIG. 2 is an SEM picture of an MXene/aminated bacterial cellulose composite material modified with a TAT polypeptide in example 3;
FIG. 3 is a partially enlarged SEM picture of an MXene/aminated bacterial cellulose composite material modified by TAT polypeptide in example 3;
FIG. 4 shows Ti in comparative example 1 3 C 2 T x SEM picture of bacterial cellulose composite material;
FIG. 5 shows Ti in comparative example 2 3 C 2 T x SEM picture of/amination bacterial cellulose composite material;
fig. 6 is a graph showing electromagnetic shielding effectiveness of the embodiments and the comparative example.
Detailed Description
The invention provides a preparation method of a TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit 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 preparation by in-situ generated 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 for 48h at 40 ℃, centrifuging, washing, collecting lower layer clay-like substance, performing ultrasonic treatment for 120min, centrifuging again for 20min at 7000 r/min, collecting upper layer solution, and freeze drying to obtain Ti 3 C 2 T x Powder;
(2) TAT polypeptide modified A-Ti prepared by adopting electrostatic self-assembly method 3 C 2 T x /Ti 3 C 2 T x : first, 2.5 mg/mL Ti is prepared 3 C 2 T x Into solution and to Ti 3 C 2 T x Adding 20ml of ethanol solution into the solution, then adjusting the pH value of the solution to be below 6 by acetic acid and uniformly stirring the solution; adding 3 to 15 ml of TAT polypeptide to obtain TAT polypeptide modified Ti 3 C 2 T x Nanosheets, namely A-Ti 3 C 2 T x Then adding A-Ti 3 C 2 T x The solution was added to an equal amount 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 the A-Ti after electrostatic self-assembly 3 C 2 T x /Ti 3 C 2 T x Nanosheets;
(3) Preparing the aminated bacterial cellulose by a water bath method: putting 105mg of blocky bacterial cellulose into deionized water, heating to 30-60 ℃, and continuously introducing argon to remove dissolved O in the water 2 Adding 20ml of 0.1 mol/L ammonium ceric nitrate solution to react for 20 to 50min, then dropwise adding 5ml of glycerol methacrylate within 30min, reacting for 2h, and washing to obtain the treated blocky bacterial cellulose; then putting the treated blocky bacterial cellulose into a mixed solution prepared from 75ml of ethylenediamine and 50ml of deionized water, stirring for 2 hours at 353K, and washing to obtain aminated bacterial cellulose;
(4) Preparing the MXene/aminated bacterial cellulose electromagnetic shielding composite material modified by TAT polypeptide by adopting a liquid phase spraying-vacuum filtering method: taking 10mg of A-Ti prepared in the step (2) 3 C 2 T x /Ti 3 C 2 T x Dissolving the nanosheets in deionized water to prepare a coating, spraying the coating onto the aminated bacterial cellulose prepared in the step (3), and finally performing vacuum filtration and heating curing to obtain the MXene/aminated bacterial cellulose composite material.
In-situ generation of hydrofluoric acid for preparing 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 (titanium) 3 AlC 2 The particle size of the powder was 200 mesh.
In-situ generation of hydrofluoric acid for preparing Ti 3 C 2 T x In the process, after the etching is finished, stirring for 48 hours, repeatedly cleaning with deionized water, and repeatedly centrifuging at 3500 r/min for multiple times until the pH value is more than or equal to 6.
In-situ generation of hydrofluoric acid for preparing Ti 3 C 2 T x In the process, the ultrasound is carried out in an 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, 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 amination bacterial cellulose by a water bath method, the time for introducing argon is more than or equal to 30min to completely remove dissolved oxygen in water, and water and alcohol are alternately used for washing.
In the process of preparing the amination bacterial cellulose by a water bath method, a freeze dryer is finally used for drying treatment to prevent the massive bacterial cellulose from deforming.
In the preparation process of the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, the specific spraying process parameters are as follows: the pressure of compressed air is 0.4-0.7MPa, the electrostatic spraying voltage is 70KV, and the distance between a spray gun and the small steel sheet is 150nm.
In the preparation process of the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, the heating and curing conditions are that the composite material is heated for 2 hours in a heating box at 70 ℃.
Example 2
A preparation method of 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) Using in situ generationPreparation of Ti by 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 for 48h at 40 ℃, centrifuging, washing, collecting lower layer clay-like substance, performing ultrasonic treatment for 120min, centrifuging again for 20min at 7000 r/min, collecting upper layer solution, and freeze drying to obtain Ti 3 C 2 T x A powder;
(2) TAT polypeptide modified A-Ti prepared by adopting electrostatic self-assembly method 3 C 2 T x /Ti 3 C 2 T x : firstly, 2.5 mg/mL Ti is prepared 3 C 2 T x Into solution and adding Ti 3 C 2 T x Adding 20ml of ethanol solution into the solution, adjusting the pH value of the solution to be below 6 by acetic acid, and uniformly stirring the solution; adding 3 to 15 ml of TAT polypeptide to obtain TAT polypeptide modified Ti 3 C 2 T x Nanosheets, i.e., A-Ti 3 C 2 T x Then A-Ti 3 C 2 T x The solution was added to an equal amount 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 the A-Ti after electrostatic self-assembly 3 C 2 T x /Ti 3 C 2 T x A nanosheet;
(3) Preparing the aminated bacterial cellulose by a water bath method: putting 105mg of blocky bacterial cellulose into deionized water, heating to 30-60 ℃, and continuously introducing argon to remove dissolved O in the water 2 Adding 20ml of ammonium ceric nitrate solution with the concentration of 0.1 mol/L to react for 20-50min, then dropwise adding 5ml of glycerol methacrylate within 30min, reacting for 2h, and then washing to obtain treated massive bacterial cellulose; then putting the treated blocky bacterial cellulose into a mixed solution prepared from 75ml of ethylenediamine and 50ml of deionized water, stirring for 2 hours at 353K, and washing to obtain aminated bacterial cellulose;
(4) Using a liquidPreparing the MXene/aminated bacterial cellulose electromagnetic shielding composite material modified by TAT polypeptide by a 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 nanosheets in deionized water to prepare a coating, spraying the coating onto the aminated bacterial cellulose prepared in the step (3), and finally performing vacuum filtration and heating curing to obtain the MXene/aminated bacterial cellulose composite material.
In-situ generation of hydrofluoric acid for preparing 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 3 AlC 2 The particle size of the powder was 200 mesh.
In-situ generation of hydrofluoric acid for preparing Ti 3 C 2 T x In the process, stirring for 48h, after etching is completed, repeatedly cleaning with deionized water, and repeatedly centrifuging at 3500 rpm/min for multiple times until the pH is more than or equal to 6.
In-situ generation of hydrofluoric acid for preparing Ti 3 C 2 T x In the process, the ultrasound is carried out in an 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, 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 amination bacterial cellulose by a water bath method, the time for introducing argon is more than or equal to 30min to completely remove dissolved oxygen in water, and water and alcohol are alternately used for washing.
In the process of preparing the amination bacterial cellulose by a water bath method, a freeze dryer is finally used for drying treatment to prevent the massive bacterial cellulose from deforming.
In the preparation process of the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, the specific spraying process parameters are as follows: the pressure of compressed air is 0.4-0.7MPa, the electrostatic spraying voltage is 70KV, and the distance between a spray gun and the small steel sheet is 150nm.
In the preparation process of the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, the heating and curing conditions are that the composite material is heated for 2 hours in a heating box at 70 ℃.
Example 3
A preparation method of 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) In-situ generated hydrofluoric acid etching method for preparing Ti 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 for 48h at 40 ℃, centrifuging, washing, collecting lower layer clay-like substance, performing ultrasonic treatment for 120min, centrifuging again for 20min at 7000 r/min, collecting upper layer solution, and freeze drying to obtain Ti 3 C 2 T x Powder;
(2) TAT polypeptide modified A-Ti prepared by adopting electrostatic self-assembly method 3 C 2 T x /Ti 3 C 2 T x : firstly, 2.5 mg/mL Ti is prepared 3 C 2 T x Into solution and adding Ti 3 C 2 T x Adding 20ml of ethanol solution into the solution, then adjusting the pH value of the solution to be below 6 by acetic acid and uniformly stirring the solution; adding 3 to 15 ml of TAT polypeptide to obtain TAT polypeptide modified Ti 3 C 2 T x Nanosheets, i.e., A-Ti 3 C 2 T x Then adding A-Ti 3 C 2 T x The solution was added to an equal amount 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 the electrostatically self-assembled A-Ti 3 C 2 T x /Ti 3 C 2 T x Nanosheets;
(3) Preparing the aminated bacterial cellulose by a water bath method: 105mg of the bulk bacteriaPutting the cellulose into deionized water, heating to 30-60 ℃, and continuously introducing argon to remove dissolved O in the water 2 Adding 20ml of 0.1 mol/L ammonium ceric nitrate solution to react for 20 to 50min, then dropwise adding 5ml of glycerol methacrylate within 30min, reacting for 2h, and washing to obtain the treated blocky bacterial cellulose; then putting the treated blocky bacterial cellulose into a mixed solution prepared from 75ml of ethylenediamine and 50ml of deionized water, stirring for 2 hours at 353K, and washing to obtain aminated bacterial cellulose;
(4) Preparing the MXene/aminated bacterial cellulose electromagnetic shielding composite material modified by TAT polypeptide by adopting a liquid phase spraying-vacuum filtering method: 50mg of A-Ti prepared in the step (2) 3 C 2 T x / Ti 3 C 2 T x Dissolving the nanosheets in deionized water to prepare a coating, spraying the coating on the aminated bacterial cellulose prepared in the step (3), and finally carrying out vacuum filtration and heating curing to obtain the MXene/aminated bacterial cellulose composite material.
In-situ generation of hydrofluoric acid for preparing 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 (titanium) 3 AlC 2 The particle size of the powder was 200 mesh.
In-situ generation of hydrofluoric acid for preparing Ti 3 C 2 T x In the process, stirring for 48h, after etching is completed, repeatedly cleaning with deionized water, and repeatedly centrifuging at 3500 rpm/min for multiple times until the pH is more than or equal to 6.
In-situ generation of hydrofluoric acid for preparing Ti 3 C 2 T x In the process, the ultrasound is carried out in an 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, 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 amination bacterial cellulose by a water bath method, the time for introducing argon is more than or equal to 30min to completely remove dissolved oxygen in water, and water and alcohol are alternately used for washing.
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 massive bacterial cellulose from deforming.
In the preparation process of the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, the specific spraying process parameters are as follows: the pressure of compressed air is 0.4-0.7MPa, the electrostatic spraying voltage is 70KV, and the distance between a spray gun and the small steel sheet is 150nm.
In the preparation process of the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, the heating and curing conditions are that the composite material is heated for 2 hours in a heating box at 70 ℃.
Example 4
A preparation method of 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 preparation by in-situ generated 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 for 48h at 40 ℃, centrifuging, washing, collecting lower layer clay-like substance, performing ultrasonic treatment for 120min, centrifuging again for 20min at 7000 r/min, collecting upper layer solution, and freeze drying to obtain Ti 3 C 2 T x A powder;
(2) TAT polypeptide modified A-Ti prepared by adopting electrostatic self-assembly method 3 C 2 T x /Ti 3 C 2 T x : first, 2.5 mg/mL Ti is prepared 3 C 2 T x Into solution and to Ti 3 C 2 T x Adding 20ml of ethanol solution into the solution, then adjusting the pH value of the solution to be below 6 by acetic acid and uniformly stirring the solution; adding 3 to 15 ml of TAT polypeptide to obtain TAT polypeptide modified Ti 3 C 2 T x Nanosheets, i.e., A-Ti 3 C 2 T x Then will beA-Ti 3 C 2 T x The solution is added to an equal amount 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 the A-Ti after electrostatic self-assembly 3 C 2 T x /Ti 3 C 2 T x A nanosheet;
(3) Preparing the aminated bacterial cellulose by a water bath method: putting 105mg of blocky bacterial cellulose into deionized water, heating to 30-60 ℃, and continuously introducing argon to remove dissolved O in the water 2 Adding 20ml of 0.1 mol/L ammonium ceric nitrate solution to react for 20 to 50min, then dropwise adding 5ml of glycerol methacrylate within 30min, reacting for 2h, and washing to obtain the treated blocky bacterial cellulose; then putting the treated blocky bacterial cellulose into a mixed solution prepared from 75ml of ethylenediamine and 50ml of deionized water, stirring for 2 hours at 353K, and washing to obtain aminated bacterial cellulose;
(4) Preparing the MXene/aminated bacterial cellulose electromagnetic shielding composite material modified by TAT polypeptide by adopting a liquid phase spraying-vacuum filtering method: 70mg of A-Ti prepared in the step (2) 3 C 2 T x / Ti 3 C 2 T x Dissolving the nanosheets in deionized water to prepare a coating, spraying the coating onto the aminated bacterial cellulose prepared in the step (3), and finally performing vacuum filtration and heating curing to obtain the MXene/aminated bacterial cellulose composite material.
In-situ generation of hydrofluoric acid for preparing 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 (titanium) 3 AlC 2 The particle size of the powder was 200 mesh.
In-situ generation of hydrofluoric acid for preparing Ti 3 C 2 T x In the process, stirring for 48h, after etching is completed, repeatedly cleaning with deionized water, and repeatedly centrifuging at 3500 rpm/min for multiple times until the pH is more than or equal to 6.
In-situ generation of hydrofluoric acid for preparing Ti 3 C 2 T x In the process, the ultrasound is needed to be 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, 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 amination bacterial cellulose by a water bath method, the time for introducing argon is more than or equal to 30min to completely remove dissolved oxygen in water, and water and alcohol are alternately used for washing.
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 massive bacterial cellulose from deforming.
In the preparation process of the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, the specific spraying process parameters are as follows: the pressure of compressed air is 0.4-0.7MPa, the electrostatic spraying voltage is 70KV, and the distance between a spray gun and the small steel sheet is 150nm.
In the preparation process of the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, the heating and curing conditions are that the composite material is heated for 2 hours in a heating box at 70 ℃.
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 preparation by in-situ generated 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 for 48h at 40 ℃, centrifuging, washing, collecting lower layer clay-like substance, performing ultrasonic treatment for 120min, centrifuging again for 20min at 7000 r/min, collecting upper layer solution, and freeze drying to obtain Ti 3 C 2 T x Powder;
(2) Is prepared by adopting an electrostatic self-assembly methodTAT polypeptide modified A-Ti 3 C 2 T x /Ti 3 C 2 T x : firstly, 2.5 mg/mL Ti is prepared 3 C 2 T x Into solution and adding Ti 3 C 2 T x Adding 20ml of ethanol solution into the solution, adjusting the pH value of the solution to be below 6 by acetic acid, and uniformly stirring the solution; adding 3 to 15 ml of TAT polypeptide to obtain TAT polypeptide modified Ti 3 C 2 T x Nanosheets, namely A-Ti 3 C 2 T x Then A-Ti 3 C 2 T x The solution is added to an equal amount 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 the A-Ti after electrostatic self-assembly 3 C 2 T x /Ti 3 C 2 T x Nanosheets;
(3) Preparing the aminated bacterial cellulose by a water bath method: putting 105mg of blocky bacterial cellulose into deionized water, heating to 30-60 ℃, and continuously introducing argon to remove dissolved O in the water 2 Adding 20ml of 0.1 mol/L ammonium ceric nitrate solution to react for 20 to 50min, then dropwise adding 5ml of glycerol methacrylate within 30min, reacting for 2h, and washing to obtain the treated blocky bacterial cellulose; then putting the treated blocky bacterial cellulose into a mixed solution prepared from 75ml of ethylenediamine and 50ml of deionized water, stirring for 2 hours at 353K, and washing to obtain aminated bacterial cellulose;
(4) Preparing the MXene/aminated bacterial cellulose electromagnetic shielding composite material modified by TAT polypeptide by adopting a liquid phase spraying-vacuum filtering method: 90mg of A-Ti prepared in the step (2) 3 C 2 T x / Ti 3 C 2 T x Dissolving the nanosheets in deionized water to prepare a coating, spraying the coating on the aminated bacterial cellulose prepared in the step (3), and finally carrying out vacuum filtration and heating curing to obtain the MXene/aminated bacterial cellulose composite material.
In situ generationPreparation of Ti from 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 (titanium) 3 AlC 2 The particle size of the powder was 200 mesh.
In-situ generation of hydrofluoric acid for preparing Ti 3 C 2 T x In the process, stirring for 48h, after etching is completed, repeatedly cleaning with deionized water, and repeatedly centrifuging at 3500 rpm/min for multiple times until the pH is more than or equal to 6.
In-situ generation of hydrofluoric acid for preparing Ti 3 C 2 T x In the process, the ultrasound is carried out in an 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, 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 amination bacterial cellulose by a water bath method, the time for introducing argon is more than or equal to 30min to completely remove dissolved oxygen in water, and water and alcohol are alternately used for washing.
In the process of preparing the amination bacterial cellulose by a water bath method, a freeze dryer is finally used for drying treatment to prevent the massive bacterial cellulose from deforming.
In the preparation process of the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, the specific spraying process parameters are as follows: the pressure of compressed air is 0.4-0.7MPa, the electrostatic spraying voltage is 70KV, and the distance between a spray gun and the small steel sheet is 150nm.
In the preparation process of the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, the heating and curing conditions are that the composite material is heated for 2 hours in a heating box at 70 ℃.
Comparative example 1
Ti 3 C 2 T x The preparation method of the bacterial cellulose composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) In-situ generated hydrofluoric acid etching method for preparing Ti 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 for 48h at 40 ℃, centrifuging, washing, collecting lower layer clay-like substance, performing ultrasonic treatment for 120min, centrifuging again for 20min at 7000 r/min, collecting upper layer solution, and freeze drying to obtain Ti 3 C 2 T x A powder;
(2) Preparation of Ti by liquid phase spraying-vacuum filtration method 3 C 2 T x Bacterial cellulose composite material: taking 50mg of Ti 3 C 2 T x Dissolving the nanosheets in deionized water to prepare a coating, spraying the coating on 105mg of blocky bacterial cellulose, and finally carrying out vacuum filtration and heating curing to obtain Ti 3 C 2 T x Bacterial cellulose composite material.
Comparative example 2
Ti 3 C 2 T x The preparation method of the amination bacterial cellulose composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) Ti preparation by in-situ generated 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 for 48h at 40 ℃, centrifuging, washing, collecting lower layer clay-like substance, performing ultrasonic treatment for 120min, centrifuging again for 20min at 7000 r/min, collecting upper layer solution, and freeze drying to obtain Ti 3 C 2 T x Powder;
(2) Preparing the aminated bacterial cellulose by a water bath method: putting 105mg of blocky bacterial cellulose into deionized water, heating to 30-60 ℃, and continuously introducing argon to remove dissolved O in the water 2 Adding 20ml of ammonium ceric nitrate solution with the concentration of 0.1 mol/L to react for 20-50min, then dropwise adding 5ml of glycerol methacrylate within 30min, reacting for 2h, and then washing to obtain treated massive bacterial cellulose; then putting the treated blocky bacterial cellulose into a solution prepared from 75ml of ethylenediamine and 50ml of deionized waterStirring the mixture for 2 hours at 353K in a mixed solution prepared by water, and washing to obtain the aminated bacterial cellulose;
(3) Preparing Ti by adopting a liquid phase spraying-vacuum filtering method 3 C 2 T x Aminated bacterial cellulose composite material: taking 50mg of Ti 3 C 2 T x Dissolving the nanosheets in deionized water to prepare a coating, spraying the coating on the aminated bacterial cellulose prepared in the step (2), and finally carrying out vacuum filtration and heating curing to obtain Ti 3 C 2 T x Amino bacterial cellulose composite material.
As can be seen from figures 2-3, no layering phenomenon occurs between MXene nanosheets and bacterial cellulose substrates in the TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material, and excellent compactness is shown. In comparative example 1, ti without any modification treatment 3 C 2 T x The density of MXene nano-sheets in the bacterial cellulose electromagnetic shielding composite material is lower, and the MXene nano-sheets and a bacterial cellulose substrate have obvious layering phenomenon (figure 4). As shown in FIG. 5, ti is added to the bacterial cellulose by amination 3 C 2 T x The nanoplatelets can be tightly bound to the aminated bacterial cellulose substrate. Compared with the TAT polypeptide modified MXene/aminated bacteria cellulose composite material, ti 3 C 2 T x Adjacent Ti in amination bacterial cellulose composite material 3 C 2 T x The nano-sheet has more porous structure, which indicates that Ti 3 C 2 T x The van der waals force between the nanoplatelets is weak, which is disadvantageous for the transmission of electrons between the layers, 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.
Use of TAT Polypeptides for the study of the invention 3 C 2 T x Modification Effect of (1), we applied to the prepared Ti 3 C 2 T x 9ml TAT polypeptide modified A-Ti 3 C 2 T x And A-Ti 3 C 2 T x /Ti 3 C 2 T x The zeta potential value of (A) was investigated. As can be seen by comparing the zeta potential values in Table 1, untreated Ti 3 C 2 T x Has a potential value of-40, indicating that Ti is present 3 C 2 T x The functional groups of the surface contain a large number of negative charges. After TAT modification, the potential value of MXene is changed to +34, which indicates that TAT polypeptide is successfully modified to MXene. A-Ti 3 C 2 T x /Ti 3 C 2 T x Zeta potential value of (A) indicates Ti 3 C 2 T x And A-Ti 3 C 2 T x Successfully joined 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
In order to research the mechanical property and the electromagnetic shielding property of the material prepared by the invention, a universal material testing machine and an Agilent vector network analyzer are used for testing the stress and the electromagnetic shielding effect of a sample. From the examples in Table 2, it can be found that the tensile stress of the TAT polypeptide modified MXene/aminated bacterial cellulose composite material in the examples 1 to 5 is increased and then decreased, and the tensile stress is A-Ti in the example 3 3 C 2 T x /Ti 3 C 2 T x The maximum content of the nano-sheets reaches 50mg, and the maximum content is 182MPa. In comparative example 1 and comparative example 2, the tensile stress of the composite material is 128MPa and 135MPa respectively, while example 1 can still show 158MPa of tensile stress under the condition of less MXene loading, which shows that the modified amino bacterial cellulose and TAT polypeptide modified MXene generate mechanical properties of the composite filmAnd (4) synergistic effect. And, the composite material showed an excellent electromagnetic shielding effectiveness of 49.7 dB.
TABLE 2 mechanical and electromagnetic shielding Properties of examples and comparative examples
The invention adopts an in-situ synthesis hydrofluoric acid etching method to prepare Ti 3 C 2 T x Followed by modification of Ti with TAT polypeptides 3 C 2 T x Preparing A-Ti 3 C 2 T x /Ti 3 C 2 T x Nanosheets. Performing amination treatment on the bacterial cellulose by adopting a water bath method, and performing liquid phase spraying and vacuum filtration to obtain the TAT polypeptide modified MXene/aminated bacterial cellulose composite material. TAT polypeptide modified A-Ti 3 C 2 T x Having a large positive charge capable of reacting with Ti 3 C 2 T x The (containing-OH, -F and the like) are combined together through electrostatic interaction, so that the binding force between the MXene nanosheets 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 158MPa tensile stress and 49.7dB electromagnetic shielding effectiveness under the condition of small MXene content. Has the tensile stress of up to 182MPa at the optimal content of MXene of 50mg and shows high electromagnetic shielding effect of 61.0 decibels. The method has the advantages of strong controllability, simplicity, high efficiency and low cost, and has great industrialization and application prospects in the field of electromagnetic shielding. It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of 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 preparation by in-situ generated hydrofluoric acid etching method 3 C 2 T x : dissolving LiF in hydrochloric acid solution, and adding Ti 3 AlC 2 Continuously stirring for 48h at 40 ℃, centrifuging, washing, collecting lower layer clay-like substance, performing ultrasonic treatment for 120min, centrifuging again, collecting upper layer solution, and freeze drying to obtain Ti 3 C 2 T x A powder;
(2) Preparing TAT polypeptide modified A-Ti by adopting electrostatic self-assembly method 3 C 2 T x /Ti 3 C 2 T x : first, ti is prepared 3 C 2 T x Into solution and to Ti 3 C 2 T x Adding an ethanol solution into the solution, then adjusting the pH value of the solution to be below 6 by using acetic acid, and uniformly stirring the solution; adding TAT polypeptide to obtain TAT polypeptide modified Ti 3 C 2 T x Nanosheets, i.e., A-Ti 3 C 2 T x Then A-Ti 3 C 2 T x The solution was added to an equal amount 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 the A-Ti after electrostatic self-assembly 3 C 2 T x /Ti 3 C 2 T x Nanosheets;
(3) Preparing the aminated bacterial cellulose by a water bath method: putting the blocky bacterial cellulose into deionized water, heating to 30-60 ℃, and continuously introducing argon to remove dissolved O in the water 2 Adding a ceric ammonium nitrate solution for reaction for 20 to 50min, then dropwise adding methacrylic glyceride within 30min, reacting for 2h, and washing to obtain treated blocky bacterial cellulose; then the treatedPutting the massive bacterial cellulose into a mixed solution prepared from ethylenediamine and deionized water, stirring for 2 hours at 353K, and washing to obtain aminated bacterial cellulose;
(4) Preparing the MXene/aminated bacterial cellulose electromagnetic shielding composite material modified by TAT polypeptide by adopting a liquid phase spraying-vacuum filtering method: the A-Ti prepared in the step (2) 3 C 2 T x /Ti 3 C 2 T x Dissolving the nanosheets in deionized water to prepare a coating, spraying the coating onto the aminated bacterial cellulose prepared in the step (3), and finally performing vacuum filtration and heating curing to obtain the MXene/aminated bacterial cellulose composite material.
2. The method according to claim 1, wherein in the step (1), ti is slowly added within 5min 3 AlC 2 The powder is prevented from local overheating, and the stirring speed is 550 revolutions per minute; ti 3 AlC 2 The particle size of the powder was 200 mesh.
3. The method of claim 1, wherein: in the step (1), stirring is carried out for 48 hours, after etching is finished, deionized water is used for repeated washing, and repeated centrifugation is carried out for many times at 3500 revolutions per minute until the pH value is more than or equal to 6.
4. The method of claim 1, wherein: in the step (1), the ultrasonic treatment needs to be carried out in an ice bath, argon is introduced to reduce oxidation, the ultrasonic power is 600 watts, and the frequency is 40 kilohertz.
5. The method of claim 1, wherein: in the step (2), TAT polypeptide needs to be slowly added within 10min and fully stirred for more than or equal to 12h.
6. The production method according to claim 1, characterized in that: in the step (3), the time for introducing argon is more than or equal to 30min to completely remove dissolved oxygen in water, and water and alcohol are alternately used for washing.
7. The production method according to claim 1, characterized in that: in the step (3), freeze drying is adopted for final drying.
8. The method of claim 1, wherein: in the step (4), the specific spraying process parameters are as follows: the pressure of compressed air is 0.4-0.7MPa, the electrostatic spraying voltage is 70KV, and the distance between a spray gun and the small steel sheet is 150nm.
9. The production method according to claim 1, characterized in that: in the step (4), the heating and curing conditions are heating for 2 hours in a heating box at 70 ℃.
10. A TAT polypeptide modified MXene/aminated bacterial cellulose electromagnetic shielding composite material prepared by the preparation method of any one of claims 1-9.
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