CN112537773B - Method for vertically growing MXene on conductive substrate - Google Patents
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Abstract
A method for vertically growing MXene on a conductive substrate comprises the following steps: (1): selecting a conductive substrate and carrying out pretreatment; (2): immersing the conductive substrate treated in the step (1) in MXene dispersion liquid to make the conductive substrate fully contacted with the MXene dispersion liquid; (3): and (3) carrying out freeze-drying treatment on the conductive substrate treated in the step (2), wherein the freeze-drying treatment is carried out as follows: gradient condensation: taking a gradient condensation mold with a structure shown in the figure, partially immersing the gradient condensation mold in a condensation medium to ensure that the whole cuboid module A and part of the wedge-shaped module B are in direct contact with the condensation medium, and the wedge-shaped module C is not in direct contact with the condensation medium, placing the conductive substrate on the wedge-shaped module C, and freezing in the condensation medium for 1-20 min to obtain a frozen conductive substrate; and secondly, transferring the frozen conductive substrate into a freeze dryer, and performing subsequent heating and drying operation to obtain the MXene-based conductive substrate, wherein the MXene grows on the surface of the conductive substrate in a vertical arrangement mode.
Description
Technical Field
The invention belongs to the technical field of nano material preparation and application, and particularly relates to a method for vertically growing MXene on a conductive substrate.
Background
MXene as a novel two-dimensional material following graphene is obtained by etching MAX phase with an etchant to destroy weak bonding force between MX sheet layer and A sheet layer, and has a general formula of Mn+1XnTx. Wherein, the MAX phase is generally a block structure and represents a series of ternary layered compounds, M is generally a transition metal element, A is a group IV element, and X is carbon or nitrogen. Common MAX phase etchants include HF or LiF + HCl solutions. MXene prepared by HF etching has a complete structure and clear layer sheets and is suitable for being used as a base material; MXene prepared by LiF + HCl has a fuzzy layered structure, and MXene chips which are easy to adhere to and fall off from the surface are more suitable for preparing layered MXene. In general, MAX phases are prone to generate functional groups such as-OH, -F, ═ O, etc. during chemical etching. The characteristic leads MXene obtained by etching to have excellent conductivity and hydrophilicity on one hand; on the other hand, compared with a single valence bond between C and C in the classical two-dimensional material graphene, MXene has richer and more adjustable performance due to the covalent bond-ionic bond-metal bond mixed valence bond existing between MX.
In recent years, MXene and its composites have been reported in the literature for applications in various research fields. For example, Yan et al constructs Ti-based MXene nano-material, utilizes niobium doping and alloying treatment to improve the electrocatalytic performance of the Ti-based MXene nano-material, and carefully researches the hydrogen production reaction performance of the Ti-based MXene nano-material in alkaline environment (adv. Sci.2019, 1900116). However, when a two-dimensional material is directly decorated on a substrate, due to the characteristics of the lamellar structure of the two-dimensional material, the material is easily accumulated on the substrate, which greatly affects the conductivity of the decorated substrate and the efficient transmission of substances. The MXene-based modified electrode is constructed by vertically and orderly arranging two-dimensional materials such as MXene on the conductive substrate through regulation and control, and is favorable for developing the application of MXene in the fields of electrocatalysis, sensors and the like. Therefore, the development of a new technology for vertically growing MXene on a conductive substrate is urgently needed.
The freeze drying technology is a heat and mass transfer process at low temperature and low pressure, and can realize dehydration and drying of the nano material at low temperature and in a vacuum state. The freeze drying process is roughly divided into three stages of prefreezing, sublimation drying and desorption drying. Specifically, the nanomaterial dispersion is frozen at a low temperature, and then sublimation-dried in a vacuum state to remove moisture, and further analysis-dried to remove a part of bound water. The technology avoids the change of physical, chemical or biological properties of the nano material to the maximum extent in the drying process, so that the original structure of the nano material is maintained and the nano material is kept in a loose state. However, in the current literature and patent, a method for vertically growing MXene on a conductive substrate based on a freeze-drying technology has not been reported.
Disclosure of Invention
The invention aims to provide a method for vertically growing MXene on a conductive substrate, which is used for regulating and controlling the vertical ordered arrangement growth of MXene on the conductive substrate to obtain the MXene-based conductive substrate.
In order to achieve the purpose, the specific technical scheme of the invention is as follows:
the invention provides a preparation method of MXene vertically growing on a conductive substrate, which comprises the following steps:
step (1): selecting a conductive substrate for pretreatment;
step (2): immersing the conductive substrate treated in the step (1) in MXene dispersion liquid with the concentration of 0.5-20mg/mL to ensure that the conductive substrate is fully contacted with the MXene dispersion liquid;
and (3): and (3) performing freeze drying treatment on the conductive substrate treated in the step (2), wherein the freeze drying treatment is performed as follows:
gradient condensation: taking a gradient condensation mold, wherein the mold consists of a cuboid module A, a wedge-shaped module B and a wedge-shaped module C, the wedge-shaped module B and the wedge-shaped module C are stacked to form a cuboid structure and are arranged on the cuboid module A, the cuboid module A and the wedge-shaped module C are separated through the wedge-shaped module B and are not in direct contact with each other, the heat conductivity coefficient of the material of the cuboid module A and the heat conductivity coefficient of the material of the wedge-shaped module C are not less than 205W/(m.K), and the heat conductivity coefficient of the material of the wedge-shaped module B is not more than 0.024W/(m.K); partially immersing the gradient condensation mould in a condensation medium to ensure that the whole cuboid module A and part of the wedge-shaped module B are in direct contact with the condensation medium and the wedge-shaped module C is not in direct contact with the condensation medium, placing the conductive substrate treated in the step (2) on the wedge-shaped module C of the gradient condensation mould, freezing for 1-20 min in the condensation medium, and realizing gradient condensation operation by using the condensation medium and the wedge-shaped mould to obtain a frozen conductive substrate;
and secondly, transferring the frozen conductive substrate into a freeze dryer, and performing subsequent heating and drying operation to obtain the MXene-based conductive substrate, wherein the MXene grows on the surface of the conductive substrate in a vertical arrangement mode.
In the step (1) of the invention, the conductive substrate is carbon cloth, carbon paper, a nickel net, a copper net or a titanium sheet, preferably the conductive substrate is carbon cloth, and the pretreatment method of the carbon cloth is concentrated nitric acid hydrothermal treatment (preferably, heat preservation is carried out in a hydrothermal reaction kettle at 85-95 ℃ for 3-4 h), and then washing and drying are carried out.
In step (2) of the present invention, MXene dispersion is prepared by the prior art, specifically MAX phase (Ti)3AlC2) Etching by LiF + HCl solution, and then carrying out ultrasonic stripping.
In step (2) of the present invention, the concentration of the MXene dispersion is 0.5-20mg/mL, and the concentration affects the density and arrangement of MXene growing on the conductive substrate, more preferably 10-15 mg/mL.
In the step (2) of the invention, the conductive substrate needs to be fully contacted with the MXene dispersion liquid, and the conductive substrate and the MXene dispersion liquid can be fully contacted by means of hand shaking or ultrasound and the like in the process.
In the step (3), the cuboid module A and the wedge-shaped module C are both preferably made of high-thermal conductivity materials (thermal conductivity is more than or equal to 205W/(m.K)), and are preferably made of aluminum or copper. The material of the wedge-shaped module B is preferably a low-heat-conductivity-coefficient material (the heat conductivity coefficient is less than or equal to 0.024W/(m.K)), and is preferably a polyester polyurethane or TDD vacuum heat-insulation heat-preservation plate. The section view of the wedge-shaped module B is in a right trapezoid shape, and the included angle between the optimal inclined edge and the horizontal plane is 10-45 degrees.
In step (3) of the present invention, the condensing medium is preferably liquid nitrogen or dry ice, and more preferably liquid nitrogen.
In the step (3), the freezing time in the condensing medium is 1-20 min, and more preferably 3-5 min.
In step (3) of the present invention, the temperature-raising drying operation may be performed according to a default temperature-raising program of the freeze dryer, which is not particularly required by the present invention.
The invention constructs a novel MXene-based modified electrode by regulating and controlling the vertical and ordered arrangement of MXene on a conductive substrate. Compared with the conventional preparation method, the method realizes the construction of the modified electrode of the MXene vertically and orderly arranged, effectively avoids the accumulation phenomenon of a two-dimensional material during substrate modification, improves the conductivity and the substance transfer efficiency of the MXene-based modified substrate, and further widens the application prospect of the MXene in the research fields of electro-catalysis, sensors and the like.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention realizes the upward growth of the MXene vertical temperature gradient on the substrate by utilizing the gradient freeze drying technology to obtain the conductive substrate of the MXene with vertical growth.
Drawings
FIG. 1 is a schematic view of a gradient condensing mold, and FIGS. 2 to 5 are SEM images of examples 1 to 4, respectively.
Detailed Description
The following detailed description of the preferred embodiments of the invention is intended to be illustrative of the invention and is not to be construed as limiting the invention. The experimental procedures in the examples, which do not indicate specific conditions, are generally carried out under conventional conditions or under conditions recommended by the manufacturer.
MXene dispersions used in the examples were prepared according to the methods reported in the literature (Nature,2018,557, 409-412).
Example 1:
the preparation method of the MXene vertically grown on the conductive substrate is implemented according to the following steps:
(1) selecting carbon cloth as a conductive substrate, and pretreating the carbon cloth. The specific operation is as follows:
first, a 50mL hydrothermal reaction kettle was selected, 30mL concentrated nitric acid was added to the teflon liner, and 8 x 2cm carbon was placed in it. Then, the reaction kettle is placed in an oven to be heated from room temperature to 90 ℃, and the temperature is kept for 3.5 h. Finally, the carbon cloth after the hydro-thermal treatment is washed by secondary water and dried for standby at 60 ℃.
(2) Immersing the carbon cloth treated in the step (1) in 10mL of a solution having a concentration of 15mg mL-1And (3) shaking the MXene dispersion liquid by hand for 20min to ensure that the conductive substrate is fully contacted with the MXene dispersion liquid.
(3) And (3) taking out the carbon cloth in the step (2), and performing liquid nitrogen gradient condensation operation on the carbon cloth. The specific operation is as follows:
selecting two materials (polyester polyurethane, the thermal conductivity coefficient of 0.024W/(m.K)) and an aluminum block (the thermal conductivity coefficient of 237W/(m.K)) with different thermal conductivities, cutting the materials according to a certain proportion to obtain a cuboid module A (the aluminum block, the size of 12X 4X 1.5cm) and two wedge-shaped modules B, C (B: polyester polyurethane, 9X 3X 3.3 cm; C: the aluminum block, 9X 3cm), splicing the two wedge-shaped modules into a cuboid (9X 3X 3.3cm, the module C is arranged above and the module B is arranged below), integrally arranging the cuboid on the module A to obtain a gradient condensation mould, and finally arranging the carbon cloth in the step (2) on the module C, immersing the whole module A and a part of the module B in liquid nitrogen to ensure that the liquid nitrogen does not contact with the module C, and performing condensation for 3min by using the liquid nitrogen to obtain the frozen carbon cloth.
(4) And (4) transferring the carbon cloth in the step (3) into an LGJ-10E type freeze dryer, and drying according to a default temperature rise program (-40 ℃,2h (-35 ℃,2h (-30 ℃,2h (-20 ℃,2 h), -10 ℃,3h, -0 ℃,3h, -10 ℃,2h, -20 ℃,20h) to obtain a denser carbon cloth substrate with MXene vertically growing.
Example 2:
on the basis of the embodiment 1, the step (2) is changed into the following steps: immersing the carbon cloth treated in the step (1) in 10mg mL of solution-1And (3) shaking the MXene dispersion liquid by hand for 20min to ensure that the conductive substrate is fully contacted with the MXene dispersion liquid. The loose carbon cloth substrate with the vertically grown MXene can be obtained。
Example 3:
on the basis of the embodiment 1, the step (3) is changed into the following steps: and (3) taking out the carbon cloth in the step (2) to a culture dish, pouring liquid nitrogen into the culture dish to ensure that the carbon cloth is completely immersed, and performing rapid condensation operation to obtain the condensed carbon cloth. And obtaining the carbon cloth substrate with MXene arranged in a disordered way.
Example 4:
on the basis of the embodiment 1, the step (3) is changed into the following steps: and (3) taking out the carbon cloth in the step (2) to a culture dish, directly placing the carbon cloth in a cold trap of a freeze dryer, and performing slow condensation operation to obtain the condensed carbon cloth. And obtaining the carbon cloth substrate with the MXene arranged in a disordered way.
SEM images of examples 1-4 are shown in FIGS. 2-5, respectively. As can be seen from fig. 2 and 3, MXene in examples 1 and 2 has a structure of ultrathin flake layer, and is uniformly and orderly vertically arranged on the surface of carbon cloth. In addition, the distribution of MXene on the surface of the carbon cloth is more meticulous in example 2, and the distribution of MXene on the surface of the carbon cloth is looser in example 3. As shown in fig. 4 and 5, MXene in example 3 and example 4 has a lamellar structure and a disordered arrangement on the carbon cloth substrate.
Claims (7)
1. A method for vertically growing MXene on a conductive substrate comprises the following steps:
step (1): selecting a conductive substrate and carrying out pretreatment; the conductive substrate is carbon cloth, and the pretreatment method of the carbon cloth is concentrated nitric acid hydrothermal treatment, and then washing and drying are carried out;
step (2): immersing the conductive substrate treated in the step (1) in MXene dispersion liquid with the concentration of 0.5-20mg/mL to ensure that the conductive substrate is fully contacted with the MXene dispersion liquid;
and (3): and (3) performing freeze drying treatment on the conductive substrate treated in the step (2), wherein the freeze drying treatment is performed as follows:
gradient condensation: taking a gradient condensation mold, wherein the mold consists of a cuboid module A, a wedge-shaped module B and a wedge-shaped module C, the wedge-shaped module B and the wedge-shaped module C are stacked to form a cuboid structure and are arranged on the cuboid module A, the cuboid module A and the wedge-shaped module C are separated through the wedge-shaped module B and are not in direct contact with each other, the heat conductivity coefficient of the material of the cuboid module A and the heat conductivity coefficient of the material of the wedge-shaped module C are not less than 205W/(m.K), and the heat conductivity coefficient of the material of the wedge-shaped module B is not more than 0.024W/(m.K); partially immersing the gradient condensation mould in a condensation medium to ensure that the whole cuboid module A and part of the wedge-shaped module B are in direct contact with the condensation medium and the wedge-shaped module C is not in direct contact with the condensation medium, placing the conductive substrate treated in the step (2) on the wedge-shaped module C of the gradient condensation mould, freezing for 1-20 min in the condensation medium, and realizing gradient condensation operation by using the condensation medium and the wedge-shaped mould to obtain a frozen conductive substrate;
and secondly, transferring the frozen conductive substrate into a freeze dryer, and performing subsequent heating and drying operation to obtain the MXene-based conductive substrate, wherein the MXene grows on the surface of the conductive substrate in a vertical arrangement mode.
2. The method of claim 1, wherein: in the step (2), the concentration of the MXene dispersion liquid is 10-15 mg/mL.
3. The method of claim 1, wherein: in the step (3), the cuboid module A and the wedge-shaped module C are made of aluminum or copper respectively and independently.
4. The method of claim 1, wherein: in the step (3), the wedge-shaped module B is made of polyester polyurethane or a TDD vacuum heat insulation board.
5. The method of claim 1, wherein: the section of the wedge-shaped module B is in a right trapezoid shape, and the included angle between the inclined edge and the horizontal plane is 10-45 degrees.
6. The method of claim 1, wherein: in the step (3), the condensing medium is liquid nitrogen or dry ice.
7. The method of claim 1, wherein: in the step (3), the freezing time in the condensing medium is 3-5 min.
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