CN114105130A - Preparation method of graphene oxide/MXene composite material with sea urchin-like structure - Google Patents
Preparation method of graphene oxide/MXene composite material with sea urchin-like structure Download PDFInfo
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- CN114105130A CN114105130A CN202111413769.2A CN202111413769A CN114105130A CN 114105130 A CN114105130 A CN 114105130A CN 202111413769 A CN202111413769 A CN 202111413769A CN 114105130 A CN114105130 A CN 114105130A
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Abstract
A preparation method of a graphene oxide/MXene composite material with a sea urchin-like structure belongs to the technical field of novel materials. The composite material is in a macroscopic scale, is in a loose porous structure as a whole, and is uniformly distributed with micron-sized graphene oxide, MXene and a small amount of reduced graphene oxide sheet layers on the surface, so that the surface of the composite material is in a sea urchin-like structure. The composite material is a self-supporting brittle material and can bear a certain load. The graphene oxide and MXene have the hydrophilic characteristics, and the composite material has the excellent hydrophilic characteristics due to the unique surface micro-nano structure, the water contact angle is 17.5 +/-2 degrees, and more importantly, the composite material can absorb moisture in air and can keep the structure stable. Compared with the common graphene oxide paper, the graphene oxide paper has higher specific surface area and more active sites due to the unique structure, and a flexible and controllable platform is provided for the preparation of graphene-based and MXenes-based composite materials.
Description
Technical Field
The invention belongs to the technical field of novel materials, and particularly relates to a preparation method of a graphene oxide/MXene composite material with a sea urchin-like structure.
Background
The graphene oxide is a product stripped by chemical oxidation of graphite, has a similar conjugated network structure compared with graphene, but rich oxygen-containing functional groups in the surface endow the graphene oxide with hydrophilic middle hydrophobic (oleophilic) amphiphilic characteristics and a large number of active sites at the edge, and is an important intermediate unit for preparing graphene and graphene-based composite materials. MXene material is a kind of metal carbon/nitride with two-dimensional layered structure and its chemical general formula is Mn+1XnTx(where n-1-3, M represents a transition metal), a lamellar structure similar to graphene, hence the name MXene. The unique physicochemical properties of MXene make MXene have attracted extensive attention in the fields of energy storage and conversion, sensors, multifunctional polymer composite materials and the like in recent years. The typical two-dimensional flexible nano material has higher specific surface area and a series of excellent mechanical, optical and electrochemical properties. Unfortunately, at present, the 'flexible' two-dimensional micro-nano structure unit is assembled into a novel and ordered macro device, so that the characteristics of a two-dimensional material are fully exerted, and the multifunctional application of the two-dimensional micro-nano structure unit is still a difficult challenge. At present, the common structures are: two-dimensional stacked structures (e.g., graphene film, MXene film, (oxidized) graphene/MXene paper), and randomly distributed porous structures (e.g., graphene, and MXene second phase randomly dispersed aerogel). The disadvantages are mainly four points: one is as follows: the surface structure is single and uncontrollable; secondly, the dispersion uniformity is not controllable; thirdly, the internal structure of the membrane (gel) is not controllable; fourthly, the increase of the stacking layer number caused by the clusters greatly reduces the single-layer two-dimensional micro-nano single layerMeta-properties.
Disclosure of Invention
Aiming at the defects of the existing graphene and other two-dimensional materials in the aspect of obtaining a novel micro-nano structure through regulating and controlling an experimental process and key parameters thereof to realize functional application, the invention provides a novel independent self-supporting preparation method of a graphene oxide/MXene composite material with a sea urchin-like structure, so that the graphene oxide and MXene are uniformly distributed in the interior, and the surface of the graphene oxide/MXene composite material is dispersed with micron-level sea urchin-like graphene/MXene sheet protrusions. The material has excellent hydrophilic characteristic and water collecting function, and the higher specific surface area is expected to play an important role in the field of sensors. The preparation method is low in cost, simple to operate and capable of realizing large-scale application.
The invention solves the problems of graphene oxide and MXene two-dimensional material clustering, uneven dispersion and single micro-nano structure. The composite material prepared by the invention has micron-sized graphene and MXene sheets uniformly distributed on the surface, has higher specific surface area and wider application potential due to the unique structure, and can play more excellent performances in the fields of biomedicine, catalysis, extraction separation, batteries or supercapacitors and the like. The method is environment-friendly, low in energy consumption and capable of realizing large-scale preparation.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a graphene oxide/MXene composite material with a sea urchin-like structure is characterized by utilizing the amphiphilic characteristic of graphene oxide lamellar layers and the phenomenon that the graphene oxide lamellar layers are easy to curl and cluster in an acidic environment, adding concentrated acid into graphene oxide dispersion liquid, then adding MXene dispersion liquid in a certain proportion, and then carrying out hydrothermal reaction, drying and freeze drying on the mixture to obtain the graphene oxide/MXene composite material. The composite material is integrally in a loose porous structure, and micron-sized graphene oxide, MXene and a small amount of reduced graphene oxide two-dimensional sheets are uniformly distributed on the surface and inside of the composite material, so that the surface of the composite material is in a sea urchin-like structure and shows excellent hydrophilic property; the method comprises the following steps:
s1: preparing graphene oxide dispersion liquid by adopting an improved Hummers method, so that the concentration of graphene oxide in the dispersion liquid reaches 1 mg/mL-2 mg/mL;
s2: carrying out 125-200W power ultrasonic treatment on the dispersion liquid in an ice bath for 10-30 min, taking the obtained graphene oxide dispersion liquid, and adding strong acid to adjust the pH value of the dispersion liquid to 1-2;
s3: preparing MXene aqueous dispersion by adopting a method for selectively etching MAX phase powder by using hydrofluoric acid (HF):
s4: taking the dispersions of S2 and S3, and mixing the dispersions according to the weight ratio of graphene oxide: mixing MXene at the mass ratio of 10:1-20:1, then performing ultrasonic dispersion on the mixed solution for 15-30min in a cell crusher under an ice bath with the power of 180 and 200W, placing the obtained mixed solution in a reaction kettle for hydrothermal reaction at the temperature of 140 and 160 ℃ for 3-4h, and then taking out, filtering and washing with deionized water until the filtered water is neutral;
s5: and (3) drying the mixture obtained in the step S4 in an oven at 50-80 ℃ for 4-10h, then placing in a refrigerator for freezing for 12h, and carrying out freeze drying for 24-32 h. The ice is completely sublimed and removed.
Further, in S1, the strong acid is one of sulfuric acid, hydrochloric acid, and phosphoric acid at equal concentration.
Further, in S4, the mass ratio of the graphene oxide to MXene is 15: 1.
Further, in S4, the hydrothermal reaction temperature is 160 ℃ and the time is 3 h.
Further, in S4, the hydrothermal reaction temperature is 140 ℃ and the time is 4 h.
Compared with the prior art, the invention has the beneficial effects that:
1. the micron-sized graphene oxide and MXene sheets and a small amount of reduced graphene oxide sheet layers are uniformly distributed on the surface of the graphene oxide/MXene composite material prepared by the method, so that the surface of the composite material presents a sea urchin-like structure, and compared with a graphene oxide/MXene film and aerogel with single internal structures, the unique structure endows the graphene oxide/MXene composite material with a higher specific surface area and more active sites compared with common graphene oxide paper. Meanwhile, a flexible and controllable platform is provided for the preparation of the graphene-based and MXenes-based composite material, a plurality of expected target functions can be realized through subsequent physical or functionalization treatment, and the application potential of the material is greatly increased.
2. The graphene oxide/MXene composite material prepared by the method is in a loose porous structure, so that gas and liquid are easy to permeate, and the graphene oxide and MXene have the hydrophilic characteristic and the sensitivity to humidity, so that the composite material has excellent water collection performance while maintaining the hydrophilic characteristic. The characteristics enable the material to have stronger application prospects in the fields of filtration, catalysis, humidity sensors and capacitors.
3. Acid treatment and high-temperature hydrothermal reaction ensure that a part of graphene oxide lamella is reduced into graphene, so that a stable interlocking structure is formed between the graphene oxide lamella and the graphene oxide lamella, and the graphene oxide lamella cannot be curled, deformed or dispersed again in a heating or humid environment to further damage the overall structure of the composite material.
Drawings
Fig. 1 is a schematic structural diagram of a graphene oxide/MXene composite material having a sea urchin-like structure in example 1;
fig. 2 is an SEM image of the surface structure of the graphene oxide/MXene composite material having a sea urchin-like structure in example 2 at 300 times magnification;
FIG. 3 is an SEM image of the surface structure of the graphene oxide/MXene composite material with the echinoid structure in example 2 at 1000 times magnification;
FIG. 4 is an infrared absorption spectrum image of graphene oxide, MXene and a graphene oxide/MXene composite material having a sea urchin-like structure;
FIG. 5 is a Raman test data graph of graphene oxide, MXene and graphene oxide/MXene composite material with a urchin-like structure;
FIG. 6 is a water contact angle test chart of graphene oxide, MXene and graphene oxide/MXene composite material with a sea urchin-like structure;
fig. 7 shows the change of the quality of the graphene oxide/MXene composite material with the sea urchin-like structure in the humid environment along with the time.
Detailed Description
The technical solution of the present invention is further described below with reference to the drawings and the embodiments, but the present invention is not limited thereto, and modifications or equivalent substitutions may be made to the technical solution of the present invention without departing from the spirit of the technical solution of the present invention, and the technical solution of the present invention is covered by the protection scope of the present invention.
According to the invention, by utilizing the amphiphilic property of graphene oxide lamellar layers and the clustering phenomenon of the graphene oxide lamellar layers which are easy to curl in an acidic environment, concentrated sulfuric acid is added into graphene oxide dispersion liquid and fully mixed, MXene dispersion liquid with a certain proportion is added, bubbles are used as a soft template through a hydrothermal reaction to enable the two-dimensional lamellar layers to curl at a gas-liquid interface to form a highly-folded structure, and then the graphene oxide/MXene composite material with the echinoid-like structure is finally prepared through freeze drying and shaping.
The composite material is integrally in macroscopic scale, the size can be adjusted according to the using amount of raw materials to realize expandable preparation, the protruding height of a two-dimensional lamellar of a sea urchin-like structure on the surface of the material is 0-50 mu m, and the thickness of the two-dimensional lamellar is 20-150 nm. The composite material is mixed with graphene sheets, and the whole material is a self-supporting brittle material and can bear a certain load. The graphene oxide and MXene have self hydrophilic characteristics, and the composite material has excellent hydrophilic characteristics due to the unique surface micro-nano structure, the water contact angle is 17.5 +/-2 degrees, the water in the air can be absorbed, and the self structure is kept stable.
Example 1:
a preparation method of a graphene oxide/MXene composite material with a sea urchin-like structure comprises the following steps:
s1: preparing graphene oxide dispersion liquid by adopting an improved Hummers method and carrying out acid pretreatment on the graphene oxide dispersion liquid, wherein the specific method comprises the following steps: preparing graphene oxide dispersion liquid by taking graphite powder as a raw material, measuring 40mL of 1mg/mL graphene oxide aqueous dispersion liquid, and slowly adding 2mL, 98% and H into the graphene oxide aqueous dispersion liquid under ice bath2SO4And stirring was continued.
S2: the preparation method of the MXene aqueous dispersion comprises the following steps:
(1) 55mL of concentrated hydrochloric acid with the concentration of 12M is measured, 3.2g of LiF is slowly added into the concentrated hydrochloric acid, and the mixture is stirred until the LiF is completely dissolved; then 2g of MAX phase powder is added into the mixture, and the mixture is put into an oil bath kettle and stirred for 24 hours under magnetic force at 50 ℃;
(2) centrifuging the mixture at 3500r/min for 5min, pouring out supernatant, and repeatedly centrifuging and washing for 5 times until the supernatant is neutral;
(3) adding deionized water into the mixture obtained in the step (2) until the mass of the mixed solution is about 160-170g, and performing ultrasonic treatment for 30min by using a cell crusher under the condition of continuously introducing nitrogen protective gas and under the power of 250W;
(4) centrifuging the solution in the step (3) at 3500r/min for 30min, taking the upper layer solution which is the MXene aqueous dispersion to be prepared, and carrying out concentration calibration on the MXene aqueous dispersion for later use;
s3: the preparation method of the graphene oxide/MXene composite material with the sea urchin-like structure comprises the following steps:
(1) taking 40mL of the prepared acidified 1mg/mL graphene oxide dispersion liquid, adding 1mL of 4mg/mL MXene dispersion liquid, mixing, performing ultrasonic treatment for 15min by using a cell crusher under the condition of continuously introducing nitrogen protection gas under the power of 180W, and then placing the mixture into a reaction kettle to react for 4h at 140 ℃;
(2) after the reaction is finished, preparing a graphene oxide/MXene spongy object, slowly taking the graphene oxide/MXene spongy object out, carefully filtering and washing the graphene oxide/MXene spongy object, and drying the graphene oxide/MXene spongy object at 50 ℃ for 8-10h (not completely drying the graphene oxide/MXene spongy object);
(3) freezing the above object overnight, and freeze-drying for 24-48h with a freeze-drying machine to obtain graphene oxide/MXene composite material with sea urchin-like structure, wherein the structural schematic diagram is shown in FIG. 1.
Example 2:
the difference between this embodiment and embodiment 1 is that in S1, the concentrated sulfuric acid solution is strong acid such as hydrochloric acid and phosphoric acid with the same amount and concentration of substances, and finally the same sea urchin-like structure can be obtained, and the scanning electron microscope morphology of the surface is shown in fig. 2 and 3.
Example 3:
the difference between the embodiment and the embodiment 1 is that in the step S2, the calibration method for the concentration of the MXene dispersion liquid is to take 5-10mL of the dispersion liquid, select a water-based microporous membrane with a filtration pore size of 0.25 micron, and perform suction filtration, drying, demolding and weighing calculation.
Example 4:
the difference between this embodiment and embodiment 1 is that in S3, the hydrothermal reaction temperature is 160 ℃ and the reaction time is 3 hours, so as to prevent MXene from being oxidized in a high-temperature humid environment and graphene oxide from being mostly reduced to graphene in a high-temperature acidic environment. The reaction time can be prolonged properly by lowering the reaction temperature. And reacting at 160 ℃ for 3h to finally obtain the composite material, wherein the infrared and Raman test characteristics are shown in figures 4 and 5.
Example 5:
this example differs from example 1 in that in S3, the drying time at 80 ℃ is designed according to the content of the components in the dispersion, and is optimized to have micro-pores on the wetted side wall of the block.
Example 6:
the difference between the present embodiment and embodiment 1 is that when 40mL of graphene oxide dispersion liquid with a concentration of 1mg/mL is acidified to a pH value of 1 by using 98% concentrated sulfuric acid, the graphene oxide dispersion liquid is then mixed with a solvent according to a mass ratio of 10:1, mixing 1mL of MXene dispersion liquid and 4mg/mL of MXene dispersion liquid, performing ultrasonic dispersion at 180W for 30min, performing hydrothermal treatment at 160 ℃ for 3h, drying at 80 ℃ for 4h, freezing in a refrigerator for 12h, and drying by a freeze dryer for 30h to obtain a graphene oxide/MXene composite material sample water contact angle and pure graphene oxide/MXene pair as shown in figure 6. The change in mass of the sample when exposed to moisture is shown in figure 7.
Claims (5)
1. A preparation method of a graphene oxide/MXene composite material with a sea urchin-like structure is characterized by comprising the following steps: the method comprises the following steps:
s1: preparing graphene oxide dispersion liquid by adopting an improved Hummers method, so that the concentration of graphene oxide in the dispersion liquid reaches 1 mg/mL-2 mg/mL;
s2: carrying out 125-200W power ultrasonic treatment on the dispersion liquid in an ice bath for 10-30 min, taking the obtained graphene oxide dispersion liquid, and adding strong acid to adjust the pH value of the dispersion liquid to 1-2;
s3: preparing MXene aqueous dispersion by adopting a method for selectively etching MAX phase powder by adopting hydrofluoric acid:
s4: taking the dispersions of S2 and S3, and mixing the dispersions according to the weight ratio of graphene oxide: mixing MXene at the mass ratio of 10:1-20:1, performing ultrasonic dispersion on the mixed solution for 15-30min in a 180-200W power ice bath, performing hydrothermal reaction on the obtained mixed solution at the temperature of 140-160 ℃ for 3-4h, taking out, filtering and washing with deionized water until the filtered water is neutral;
s5: drying the mixture obtained in S4 at 50-80 deg.C for 4-10h, freezing for 12h, and freeze-drying for 24-32 h.
2. The preparation method of the graphene oxide/MXene composite material with the sea urchin-like structure according to claim 1, wherein the graphene oxide/MXene composite material comprises: in S1, the strong acid is one of sulfuric acid, hydrochloric acid, or phosphoric acid.
3. The preparation method of the graphene oxide/MXene composite material with the sea urchin-like structure according to claim 1, wherein the graphene oxide/MXene composite material comprises: in S4, the mass ratio of the graphene oxide to MXene is 15: 1.
4. The preparation method of the graphene oxide/MXene composite material with the sea urchin-like structure according to claim 1, wherein the graphene oxide/MXene composite material comprises: in S4, the hydrothermal reaction temperature is 160 ℃ and the time is 3 h.
5. The preparation method of the graphene oxide/MXene composite material with the sea urchin-like structure according to claim 1, wherein the graphene oxide/MXene composite material comprises: in S4, the hydrothermal reaction temperature is 140 ℃ and the time is 4 h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107633954A (en) * | 2016-07-19 | 2018-01-26 | 中国科学院上海硅酸盐研究所 | A kind of graphene/MXene combination electrode materials and its application |
| CN111453732A (en) * | 2020-04-08 | 2020-07-28 | 北京化工大学 | Three-dimensional porous MXene/rGO composite material and preparation method thereof |
| CN111799464A (en) * | 2020-07-08 | 2020-10-20 | 中国科学院电工研究所 | MXene/graphene composite nanosheet, preparation method and application thereof, electrode plate and application thereof |
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Patent Citations (3)
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| CN107633954A (en) * | 2016-07-19 | 2018-01-26 | 中国科学院上海硅酸盐研究所 | A kind of graphene/MXene combination electrode materials and its application |
| CN111453732A (en) * | 2020-04-08 | 2020-07-28 | 北京化工大学 | Three-dimensional porous MXene/rGO composite material and preparation method thereof |
| CN111799464A (en) * | 2020-07-08 | 2020-10-20 | 中国科学院电工研究所 | MXene/graphene composite nanosheet, preparation method and application thereof, electrode plate and application thereof |
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| JIANJUN SONG等: ""Rational design of free-standing 3D porous MXene/rGO hybrid aerogels as polysulfide reservoirs for high-energy lithium–sulfur batteries"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
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