CN113000056A - MXene doping-based composite material and preparation method thereof - Google Patents
MXene doping-based composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 36
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 15
- 239000012065 filter cake Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000001338 self-assembly Methods 0.000 claims abstract description 8
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000007789 sealing Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000005530 etching Methods 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000002135 nanosheet Substances 0.000 claims description 25
- 239000011941 photocatalyst Substances 0.000 claims description 23
- 239000013078 crystal Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 241000446313 Lamella Species 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 229910015419 Mo2GaC Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 4
- 230000006798 recombination Effects 0.000 abstract description 3
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- 239000000243 solution Substances 0.000 description 73
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 18
- -1 polytetrafluoroethylene Polymers 0.000 description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 10
- 229960000907 methylthioninium chloride Drugs 0.000 description 10
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
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- 239000004065 semiconductor Substances 0.000 description 6
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- 238000005119 centrifugation Methods 0.000 description 4
- 238000004042 decolorization Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- 238000003760 magnetic stirring Methods 0.000 description 3
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- 239000006228 supernatant Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides an MXene doping-based composite material and a preparation method thereof, wherein MAX phase materials are used as raw materials, and MXene colloidal solution is prepared through etching and stripping; centrifuging, washing and ultrasonically resuspending the MXene colloidal solution for several times, then carrying out self-assembly under vacuum filtration, and carrying out vacuum drying on the obtained filter cake to obtain MXene paper; dissolving MXene paper in isopropanol solution, adding tetrabutyl titanate, uniformly mixing, dropwise adding hydrofluoric acid solution, sealing and performing hydrothermal treatment after dropwise adding is completed, and cooling, washing and drying to obtain the target product. The composite material based on MXene doping and the preparation thereofThe method has simple preparation process and lower requirements on instruments and equipment, can effectively improve the photon-generated carrier recombination efficiency and promote TiO2The photocatalytic activity of the base composite catalyst.
Description
Technical Field
The invention belongs to the field of composite photocatalysts, and particularly relates to a composite material based on MXene doping and a preparation method thereof.
Background
Photocatalysis is a potential energy conversion and environmental treatment technology, has the characteristics of directly utilizing sunlight and converting light energy into electric energy or chemical energy, and is widely concerned by people. In recent years, scientists have made abundant results in research on hydrogen production by decomposing water and pollutant degradation by using photocatalytic materials.
It has now been found that the materials with photocatalytic activity are mainly semiconductors, including ZnO, TiO2、WO3、SnO2Etc. of which TiO2The semiconductor is very much concerned in the research of photocatalytic materials due to the advantages of easy availability, no toxicity, no harm, low cost, stable chemical properties and the like. But nano TiO2The forbidden bandwidth of the semiconductor is about 3.2eV, and the longest wavelength of excited electrons which are transited from a valence band to a conduction band is directly determined to be 387.5nm, namely, the excited electrons can only be excited by ultraviolet light; on the other hand, nano TiO2The photo-generated carriers of the semiconductor are heavily phase-recombined, so that the proportion of effective carriers that can reach the surface of the catalyst and participate in the reaction is very low, which greatly influences the photocatalytic activity. In order to improve the defects, researchers utilize semiconductor compounding, precious metal deposition, surface photosensitization, ion doping and other means to carry out nano TiO2Is adjusted to try to improve the TiO2Photocatalytic activity of (1). In addition, a means for adjusting the performance of the photocatalytic material by regulating the exposure degree of different crystal faces of the crystal is attracting attention. For anatase TiO2The thermodynamically favored growth usually exposes the {101} crystal face, and theoretical calculation and experiments show that the {001} crystal face has higher photocatalytic activity, so that TiO exposed to the {001} crystal face is synthesized2Provides a new idea for improving the photocatalytic activity of the photocatalyst.
The two-dimensional material has the advantages of unique layered structure, large specific surface area, abundant active sites and the like, and shows excellent performance in the fields of photocatalytic degradation and the like. MXene as a new family of two-dimensional layered metal carbides, with a structure similar to graphene, can provide larger metalsSpecific surface area, ultra-thin thickness, abundant catalytically active sites and a high proportion of coordinately unsaturated surface sites. The advantages enable MXene to be used as a proper cocatalyst to modify a metal oxide semiconductor so as to promote the spatial separation of photogenerated electrons and holes and improve the separation efficiency of photogenerated carriers in the field of photocatalysis. Existing MXene/TiO2The preparation method of the composite material comprises the steps of synthesizing TiO by in-situ hydrothermal and forced air drying oxidation2Underutilization of TiO2High activity {001} crystal plane.
Disclosure of Invention
In view of the above, in order to solve the above problems, the present invention provides a composite material based on MXene doping and a preparation method thereof, so as to effectively improve the recombination efficiency of photo-generated carriers and enhance TiO2The photocatalytic activity of the base composite catalyst.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a composite material based on MXene doping comprises the following steps:
(1) preparing MXene colloidal solution by etching and stripping MAX phase materials serving as raw materials;
(2) repeatedly washing the MXene colloidal solution until the pH value of the solution is more than or equal to 6, taking the precipitate, sequentially performing ultrasonic dispersion in absolute ethyl alcohol and deionized water to obtain a suspension solution, and centrifuging the suspension solution to obtain a blue-black MXene lamella colloidal solution;
(3) carrying out vacuum filtration and self-assembly on the MXene sheet layer colloidal solution to obtain a filter cake as a stacked MXene sheet layer, and carrying out vacuum drying on the filter cake to obtain MXene paper;
(4) dissolving MXene paper in an isopropanol solution, and performing ultrasonic mixing to obtain a uniform MXene nanosheet solution;
(5) adding tetrabutyl titanate serving as a titanium source into the MXene nanosheet solution, and performing ultrasonic mixing uniformly to obtain a solution A;
(6) slowly dropwise adding a hydrofluoric acid solution into the solution A under the stirring condition, and sealing and carrying out hydrothermal treatment after dropwise adding is finished;
(7) after the hydrothermal treatment is finished, cooling, washing and drying to obtain the baseIn MXene-doped composites, i.e. exposing {001} crystallographic plane of anatase TiO2MXene composite photocatalyst is doped in the nanosheet.
Further, in the step (1), the MAX phase material is Mo2GaC、Mo2Ga2One or two of C.
Further, in the step (2), the repeatedly washing of the MXene colloidal solution specifically comprises: and (3) adding deionized water to the MXene colloidal solution for repeatedly washing for 5-10 times under the conditions of 4000-5000 rmp and centrifugation for 10-15 min.
Further, in the step (2), the precipitates are taken and then ultrasonically dispersed in absolute ethyl alcohol and deionized water at the temperature of 4 ℃ for 1-2 hours; and centrifuging the suspension solution for 30-60 min at 8000-9000 rmp to obtain a blue-black MXene lamella colloidal solution.
Further, in the step (3), the MXene lamellar colloidal solution is subjected to vacuum filtration self-assembly by adopting a cellulose carbonate filter membrane with the pore diameter of 0.2 μm.
Further, in the step (3), the temperature for vacuum drying of the filter cake is 50-70 ℃, and the time is 8-10 hours.
Furthermore, in the step (4), the mass percent of the isopropanol solution is 98%, and the mass ratio of MXene paper to isopropanol is 0.14-0.19: 100.
Further, in the step (4), the ultrasonic treatment time is 10-40 min.
Further, in the step (5), the mass ratio of tetrabutyl titanate to isopropanol is 0.15-1.05: 1.
Further, in the step (5), the ultrasonic treatment time is 20-40 min.
Further, in the step (6), the dropping speed of the hydrofluoric acid solution is 1-3 drops per second.
Further, in the step (6), the mass percentage of the hydrofluoric acid solution is 40%, and the volume ratio of the hydrofluoric acid solution to the solution A is 3: 100; the temperature of the hydrothermal treatment is 180-190 ℃, and the time is 12-14 h.
Further, in the step (7), after the hydrothermal treatment is finished, cooling to 20-25 ℃, washing the precipitate for 3 times with anhydrous ethanol and deionized water, and then vacuum-drying the precipitate at 70-90 ℃ for 24-48 h.
The composite material prepared by the preparation method of the MXene doping-based composite material is anatase TiO with exposed {001} crystal face2MXene composite photocatalyst is doped in the nanosheet.
Compared with the prior art, the MXene doping-based composite material and the preparation method thereof have the following advantages:
(1) the preparation method of the composite material based on MXene doping adopts hydrothermal reaction to prepare anatase TiO with exposed {001} crystal face in one step2The nano-sheet doped MXene composite photocatalyst has a simple preparation process and lower requirements on instruments and equipment; the prepared anatase type TiO with exposed {001} crystal face2The nano-sheet is uniformly distributed on the surface of the MXene sheet layer, and the TiO is fully utilized2The {001} crystal face superiority improves the photocatalytic activity of the composite photocatalyst.
(2) The composite material prepared by the MXene doping-based composite material preparation method can effectively adjust the width of TiO due to the doping of the MXene sheet layer2The absorption band has larger specific surface area in the two-dimensional structure, which is beneficial to reducing the recombination rate of photo-generated electrons and holes, thereby improving the TiO2Absorption in the visible light range and its light quantum efficiency, and overcomes TiO at one time2Two major disadvantages of the base photocatalyst are that TiO is oxidized2The base photocatalyst has wider application prospect in the fields of hydrogen production by photocatalytic decomposition of water, organic matter photocatalytic degradation, wastewater treatment and the like.
Drawings
FIG. 1 is a graph of example 1 illustrating the exposure of {001} crystal plane anatase TiO form2A trend graph of the MB (methylene blue) decoloring degradation rate of the nanosheet-doped MXene composite photocatalyst changing along with time;
FIG. 2 is a view showing the exposure of {001} crystal plane anatase type TiO according to examples 1 to 32The effect graph of the nano-sheet doped MXene composite photocatalyst on the 150min decolorization degradation rate of MB (methylene blue) is shown.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to the following examples and accompanying drawings.
Example 1
(1) At room temperature, 2g LiF was added to a polytetrafluoroethylene beaker containing 40mL of 9mol/L hydrochloric acid, stirred for 3min, and 2g Mo was added2Ga2C, stirring uniformly; putting the obtained mixed solution into a magnetic stirring water bath kettle at the constant temperature of 37 ℃, putting a polytetrafluoroethylene rotor, and stirring and reacting for 100 hours to obtain MXene colloidal solution;
(2) repeatedly washing MXene colloidal solution with deionized water for 5 times under the conditions of 4000rmp and centrifugation for 10min until the pH of the solution is more than or equal to 6, pouring out supernatant, ultrasonically dispersing the precipitate in absolute ethyl alcohol and deionized water at 4 ℃ for 2h with 600W power to obtain suspension, and centrifuging the suspension for 60min under 8000rmp to obtain black MXene lamella colloidal solution;
(3) carrying out vacuum filtration and self-assembly on the blue-black MXene sheet layer colloidal solution by adopting a cellulose carbonate filter membrane with the pore diameter of 0.2 mu m to obtain a filter cake which is a stacked MXene sheet layer, and carrying out vacuum drying on the filter cake at 70 ℃ for 8h to obtain MXene paper;
(4) dissolving 33mg of MXene paper in an isopropanol solution with the mass concentration of 98%, wherein the mass ratio of the MXene paper to the isopropanol is 0.19:100, and performing ultrasonic treatment for 30min to obtain a uniform MXene nanosheet solution;
(5) adding tetrabutyl titanate into the MXene nanosheet solution, wherein the mass ratio of the tetrabutyl titanate to isopropanol in the MXene nanosheet solution is 0.35: 1, performing ultrasonic treatment for 30min to obtain a uniform solution A;
(6) putting the solution A into a polytetrafluoroethylene high-pressure autoclave, dropwise adding a 40% hydrofluoric acid solution into the solution A at a speed of 3 drops per second while continuously stirring, wherein the volume ratio of the added hydrofluoric acid solution to the solution A is 3:100, sealing the polytetrafluoroethylene high-pressure autoclave after dropwise adding is finished, and carrying out hydrothermal treatment at the temperature of 180 ℃ for 14 hours;
(7) after the hydrothermal treatment is finished, cooling a hydrothermal reaction system consisting of the mixed solution A and hydrofluoric acid to 25 ℃, washing and precipitating by using absolute ethyl alcohol and deionized water for 3 times respectively, and drying the precipitate in vacuum at the temperature of 70 ℃ for 48 hours to obtain the anatase type TiO with the exposed {001} crystal face2MXene composite photocatalyst is doped in the nanosheet.
Example 2
(1) At room temperature, 2g LiF was added to a polytetrafluoroethylene beaker containing 40mL of 9mol/L hydrochloric acid, stirred for 3min, and 2g Mo was added2Ga2C, stirring uniformly; putting the obtained mixed solution into a magnetic stirring water bath kettle at the constant temperature of 37 ℃, putting a polytetrafluoroethylene rotor, and stirring and reacting for 100 hours to obtain MXene colloidal solution;
(2) repeatedly washing the MXene colloidal solution with deionized water for 7 times under the conditions of 4500rmp and centrifugation for 12min until the pH of the solution is more than or equal to 6, pouring out the supernatant, ultrasonically dispersing the precipitate in absolute ethyl alcohol and deionized water at 4 ℃ for 1.5h with 700W power to obtain a suspension solution, and centrifuging the suspension solution under 8500rmp for 45min to obtain a bluish black MXene lamellar colloidal solution;
(3) carrying out vacuum filtration and self-assembly on the blue-black MXene sheet layer colloidal solution by adopting a cellulose carbonate filter membrane with the pore diameter of 0.2 mu m to obtain a filter cake which is a stacked MXene sheet layer, and carrying out vacuum drying on the filter cake at 65 ℃ for 9h to obtain MXene paper;
(4) dissolving 16mg of MXene paper in an isopropanol solution with the mass concentration of 98%, wherein the mass ratio of the MXene paper to the isopropanol is 0.14:100, and performing ultrasonic treatment for 10min to obtain a uniform MXene nanosheet solution;
(5) adding tetrabutyl titanate into an MXene nanosheet solution, wherein the mass ratio of the tetrabutyl titanate to isopropanol in the MXene nanosheet solution is 1.05:1, performing ultrasonic treatment for 20min to obtain a uniform solution A;
(6) putting the solution A into a polytetrafluoroethylene high-pressure autoclave, dropwise adding a 40% hydrofluoric acid solution into the solution A at a speed of 2 drops per second while continuously stirring, wherein the volume ratio of the added hydrofluoric acid solution to the solution A is 3:100, sealing the polytetrafluoroethylene high-pressure autoclave after dropwise adding is finished, and carrying out hydrothermal treatment at 185 ℃ for 12 hours;
(7) after the hydrothermal treatment is finished, cooling a hydrothermal reaction system consisting of the mixed solution A and hydrofluoric acid to 23 ℃, washing and precipitating by using absolute ethyl alcohol and deionized water for 3 times respectively, and drying the precipitate in vacuum at the temperature of 80 ℃ for 36 hours to obtain the anatase type TiO with the exposed {001} crystal face2MXene composite photocatalyst is doped in the nanosheet.
Example 3
(1) At room temperature, 2g LiF was added to a polytetrafluoroethylene beaker containing 40mL of 9mol/L hydrochloric acid, stirred for 3min, and 2g Mo was added2Ga2C, stirring uniformly; putting the obtained mixed solution into a magnetic stirring water bath kettle at the constant temperature of 37 ℃, putting a polytetrafluoroethylene rotor, and stirring and reacting for 100 hours to obtain MXene colloidal solution;
(2) repeatedly washing the MXene colloidal solution with deionized water for 10 times under the conditions of 5000rmp and centrifugation for 15min until the pH of the solution is more than or equal to 6, pouring out the supernatant, ultrasonically dispersing the precipitate in absolute ethyl alcohol and deionized water at 4 ℃ for 1h with the power of 800W to obtain a suspension solution, and centrifuging the suspension solution at 9000rmp for 30min to obtain a blue-black MXene lamella colloidal solution;
(3) carrying out vacuum filtration and self-assembly on the blue-black MXene sheet layer colloidal solution by adopting a cellulose carbonate filter membrane with the pore diameter of 0.2 mu m to obtain a filter cake which is a stacked MXene sheet layer, and carrying out vacuum drying on the filter cake at 50 ℃ for 10h to obtain MXene paper;
(4) dissolving 65mg of MXene paper in an isopropanol solution with the mass concentration of 98%, wherein the mass ratio of the MXene paper to the isopropanol is 0.165:100, and performing ultrasonic treatment for 40min to obtain a uniform MXene nanosheet solution;
(5) adding tetrabutyl titanate into the MXene nanosheet solution, wherein the mass ratio of the tetrabutyl titanate to isopropanol in the MXene nanosheet solution is 0.15: 1, performing ultrasonic treatment for 40min to obtain a uniform solution A;
(6) putting the solution A into a polytetrafluoroethylene high-pressure autoclave, dropwise adding a 40% hydrofluoric acid solution into the solution A at a speed of 1 drop per second while continuously stirring, wherein the volume ratio of the added hydrofluoric acid solution to the solution A is 3:100, sealing the polytetrafluoroethylene high-pressure autoclave after dropwise adding is finished, and carrying out hydrothermal treatment at 190 ℃ for 13 hours;
(7) after the hydrothermal treatment is finished, cooling a hydrothermal reaction system consisting of the mixed solution A and hydrofluoric acid to 20 ℃, washing and precipitating by using absolute ethyl alcohol and deionized water for 3 times respectively, and drying the precipitate in vacuum at the temperature of 90 ℃ for 24 hours to obtain the anatase type TiO with the exposed {001} crystal face2MXene composite photocatalyst is doped in the nanosheet.
Performance testing
1. Anatase type TiO exposing {001} crystal face prepared in example 12An experiment of photocatalytic degradation of methylene blue under the irradiation of an ultraviolet lamp with the wavelength of 365nm is carried out on the nanosheet doped MXene composite photocatalyst, and the comparative example is a methylene blue solution without added photocatalyst.
As can be seen from FIG. 1, in the comparative example, the decolorization effect of methylene blue degraded by ultraviolet light with a wavelength of 365nm is weak, while the {001} crystal face exposed anatase type TiO prepared in example 1 is added2After the MXene composite photocatalyst is doped into the nanosheets, the decolorization rate is remarkably improved (the degradation rate is shown in fig. 2 when the reaction time is 150min and can be as high as more than 95%). The catalysis under the wavelength can be applied in the processes of water phase, gas phase sterilization and disinfection, and ultraviolet lamps with other wavelengths such as UV254 and UV185 can also be used as excitation light sources to carry out photocatalytic reaction with the catalyst, and the application is expanded.
2. Anatase TiO exposing {001} crystal planes prepared in examples 2 and 32An experiment of photocatalytic degradation of methylene blue under the irradiation of an ultraviolet lamp with the wavelength of 365nm is carried out on the nanosheet-doped MXene composite photocatalyst.
As shown in FIG. 2, example 2 prepared anatase type TiO with exposed {001} crystal plane2The decolorization experiment of photocatalytic degradation of methylene blue under the irradiation of an ultraviolet lamp with the wavelength of 365nm is carried out on the nanosheet-doped MXene composite photocatalyst, and the degradation rate of the nanosheet-doped MXene composite photocatalyst is 90.7% when the reaction time is 150 min.
As shown in FIG. 2, the exposed 001 crystal plane prepared in example 3 is sharpTitanium ore type TiO2A decoloring experiment for photocatalytic degradation of methylene blue under the irradiation of an ultraviolet lamp with the wavelength of 365nm is carried out on the nanosheet-doped MXene composite photocatalyst, and the degradation rate of the nanosheet-doped MXene composite photocatalyst is 82.3% when the reaction time is 150 min.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a composite material based on MXene doping is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing MXene colloidal solution by etching and stripping MAX phase materials serving as raw materials;
(2) repeatedly washing the MXene colloidal solution until the pH value of the solution is more than or equal to 6, taking the precipitate, sequentially performing ultrasonic dispersion in absolute ethyl alcohol and deionized water to obtain a suspension solution, and centrifuging the suspension solution to obtain a blue-black MXene lamella colloidal solution;
(3) carrying out vacuum filtration and self-assembly on the MXene sheet layer colloidal solution to obtain a filter cake as a stacked MXene sheet layer, and carrying out vacuum drying on the filter cake to obtain MXene paper;
(4) dissolving MXene paper in an isopropanol solution, and performing ultrasonic mixing to obtain a uniform MXene nanosheet solution;
(5) adding tetrabutyl titanate serving as a titanium source into the MXene nanosheet solution, and performing ultrasonic mixing uniformly to obtain a solution A;
(6) slowly dropwise adding a hydrofluoric acid solution into the solution A under the stirring condition, and sealing and carrying out hydrothermal treatment after dropwise adding is finished;
(7) after the hydrothermal treatment is finished, cooling, washing and drying are carried out to obtain the MXene doping-based composite material, namely the anatase TiO with the {001} crystal face exposed2MXene composite photocatalyst is doped in the nanosheet.
2. The method for preparing a composite material based on MXene doping according to claim 1, characterized by: in the step (1), the MAX phase material is Mo2GaC、Mo2Ga2One or two of C.
3. The method for preparing a composite material based on MXene doping according to claim 1, characterized by: in the step (2), the precipitates are taken and then ultrasonically dispersed in absolute ethyl alcohol and deionized water at the temperature of 4 ℃ for 1-2 h; centrifuging the suspension solution for 30-60 min at 8000-9000 rmp.
4. The method for preparing a composite material based on MXene doping according to claim 1, characterized by: in the step (3), the MXene lamellar colloidal solution is subjected to vacuum filtration and self-assembly by adopting a cellulose carbonate filter membrane with the pore diameter of 0.2 mu m.
5. The method for preparing the MXene doping-based composite material according to claim 4, wherein: in the step (3), the temperature for vacuum drying of the filter cake is 50-70 ℃, and the time is 8-10 hours.
6. The method for preparing a composite material based on MXene doping according to claim 1, characterized by: in the step (4), the mass percent of the isopropanol solution is 98%, and the mass ratio of the MXene paper to the isopropanol is 0.14-0.19: 100.
7. The method for preparing a composite material based on MXene doping according to claim 1, characterized by: in the step (5), the mass ratio of tetrabutyl titanate to isopropanol is 0.15-1.05: 1.
8. The method for preparing a composite material based on MXene doping according to claim 1, characterized by: in the step (6), the mass percent of the hydrofluoric acid solution is 40%, and the volume ratio of the hydrofluoric acid solution to the solution A is 3: 100; the temperature of the hydrothermal treatment is 180-190 ℃, and the time is 12-14 h.
9. The method for preparing a composite material based on MXene doping according to claim 1, characterized by: in the step (7), after the hydrothermal treatment is finished, cooling to 20-25 ℃, washing the precipitate for 3 times by using absolute ethyl alcohol and deionized water respectively, and then drying the precipitate for 24-48 hours in vacuum at the temperature of 70-90 ℃.
10. A composite material prepared by the method for preparing a composite material based on MXene doping according to any one of claims 1 to 9, wherein: the composite material is anatase type TiO with exposed {001} crystal face2MXene composite photocatalyst is doped in the nanosheet.
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| CN114377706A (en) * | 2022-01-04 | 2022-04-22 | 上海第二工业大学 | MXene/TiO loaded by glass fiber ball bundle2Aerogel composite material and preparation method thereof |
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| CN114849497A (en) * | 2022-04-11 | 2022-08-05 | 华南理工大学 | Fibril-like self-repairing anti-pollution ZnO/MXene base membrane and preparation method and application thereof |
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| CN116026195B (en) * | 2023-03-02 | 2023-11-21 | 中国工程物理研究院激光聚变研究中心 | MXene composite film flying piece and preparation method thereof |
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