CN111250122A - Ag/MXene/TiO modified by nano noble metal2Composite material and preparation method thereof - Google Patents

Ag/MXene/TiO modified by nano noble metal2Composite material and preparation method thereof Download PDF

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Publication number
CN111250122A
CN111250122A CN202010077109.0A CN202010077109A CN111250122A CN 111250122 A CN111250122 A CN 111250122A CN 202010077109 A CN202010077109 A CN 202010077109A CN 111250122 A CN111250122 A CN 111250122A
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mxene
tio
composite material
preparation
nano
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叶晓云
陈龙
黄培金
刘雪华
陈金香
林永南
王乾廷
陈文哲
陈丁桂
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Fujian University of Technology
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Fujian University of Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20Carbon compounds
    • B01J27/22Carbides
    • B01J35/39
    • B01J35/396

Abstract

The invention discloses Ag/MXene/TiO modified by nano noble metal2Composite materials and methods for making the same. The preparation process comprises the steps of firstly preparing a two-dimensional lamellar material MXene with a good lamellar structure, and ultrasonically and uniformly dispersing the MXene to AgNO3To the aqueous solution, followed by addition of a solution containing stannous chloride (SnCl)2) And trifluoroacetic acid (CF)3COOH) in formaldehyde aqueous solution to obtain MXene composite material with nano Ag uniformly distributed, and finally adopting hydrothermal method to precipitate TiO on the MXene surface2Obtaining MXene/TiO modified by nano Ag2A composite material. The nano Ag and TiO in the composite material2The tablets are uniformly dispersed, the contained proportion is adjustable, and the photocatalytic performance is better than that of commercial TiO2(P25) is greatly increased. The addition of the nano Ag enhances the absorption of the composite material in a visible waveband, and the Ag/MXene/TiO2The ternary composite material has potential application in the field of photoelectrocatalysis as a catalyst material.

Description

Ag/MXene/TiO modified by nano noble metal2Composite material and preparation method thereof
Technical Field
The invention relates to Ag/MXene/TiO modified by nano noble metal2Composite materials and methods for making the same.
Background
Environmental pollution and energy shortage are major problems facing mankind today. Therefore, people are constantly striving to find simple, efficient catalysts to purify water resources and obtain clean energy. Such as degrading organic pollutants in water, catalytically decomposing water to obtain clean energy hydrogen, reducing greenhouse gas carbon dioxide and the like. Such as two-dimensional materials (MXene, graphene, MoS)2、TiO2Sheets, etc.) and composites thereof, have been widely studied in the above-mentioned fields of application.
Titanium dioxide (TiO)2) As a common wide bandgap semiconductor (anatase TiO)2The forbidden band width of 3.2 eV), and is widely applied to the field of photocatalysis due to the characteristics of low price, no toxicity, stable chemical property, simple preparation and the like. But leads to TiO due to its wider band gap2The electron-hole pairs are combined quickly, so that the photocatalytic efficiency is influenced, and the application of the electron-hole pairs in the field of photocatalysis is greatly limited. To TiO 22Modification to prolong the electron-hole separation time is a common method for improving the photocatalytic efficiency, such as the combination with carbon materials (MXene, graphene, etc.) and noble metals (Pt, Ag, etc.).
2011 scientists Gogotsi and Barsum et al used hydrofluoric acid (HF) to etch three-dimensional material Ti3AlC2Etching the intermediate layer Al to obtain a two-dimensional lamellar material Ti3C2Also known as MXene. It not only has large specific surface area, many active sites, good hydrophilicity, goldThe graphene material has the advantages of good conductivity, adjustability of chemical composition and the like, belongs to a graphene-like material, has narrow band gap, is easy to excite, has good electronic conduction capability and storage capability, and is widely applied to the field of photoelectrocatalysis in recent years. Ti3C2To build TiO2The combination with the carbonaceous material provides a natural platform. The carbonaceous material can prolong the service life of electron-hole pairs, adjust band gaps and adsorb reactants. Therefore, the research of the precious metal modified MXene-based compound is expanded, and the potential and the prospect in the field of photocatalysis are great. To date, there has been little research on TiO2MXene and noble metal ternary doping system. The Ag/MXene/TiO with good photocatalytic performance, which is simple and easy to obtain, is obtained by the invention2A ternary composite material.
Disclosure of Invention
The invention aims to solve the technical problem of providing Ag/MXene/TiO modified by nano noble metal2Composite material and method for preparing the same, nano Ag particles and TiO2Nanosheet in Ag/MXene/TiO2The ternary compound grows uniformly, and the absorption of the composite material in ultraviolet and visible wave bands is obviously enhanced, so that the high-efficiency separation of electron-hole pairs is facilitated.
In order to achieve the purpose, the invention adopts the following technical scheme:
Ag/MXene/TiO modified by nano noble metal2The preparation method of the composite material comprises the following steps:
step (1) adding Ti3AlC2And etching by using an HF solution at the temperature of 60 ℃ for 24 hours as a precursor. Washing MXene obtained by the reaction with deionized water, and drying in vacuum.
Step (2) appropriate AgNO3Dissolving the powder and MXene in deionized water, and uniformly mixing and performing ultrasonic treatment to obtain a solution A.
Step (3) of adding a proper amount of SnCl2Dispersed in CF3And (4) performing ultrasonic treatment on the COOH in formaldehyde water solution to obtain a solution B.
And (4) slowly dropping the solution B into the solution A, uniformly mixing by ultrasonic waves, centrifugally washing, and drying in vacuum to obtain the MXene composite material modified by the nano Ag, wherein the mass fraction of the Ag is 1-20%.
Step (5) mixing the Ag/MXene composite material with a proper amount of NaBF4Dissolving in hydrochloric acid, and carrying out hydrothermal reaction to obtain Ag/MXene/TiO2A composite material.
Further, in the step (1), the mass fraction of the HF solution is 40-49%, and the mass ratio of MAX to HF is 10.75-5: 1.
further, the etching temperature in the step (1) is 60 ℃, and the time is 24 h.
Further, AgNO in step (3)3、SnCl2And CF3The ratio of the amount of COOH species was 1:1: 2.
Further, the mass fraction of Ag in the Ag/MXene composite material obtained in the step (4) is 1-10%.
Further, the hydrothermal reaction temperature of the step (5) is 120-220 ℃, and the time is 1-36 h.
Further, NaBF in step (5)4The mass ratio of MXene to MXene is 4.95-1.65: 1.
Further, the cleaning process in the step (1) is repeated centrifugal cleaning by a high-speed centrifuge, and the MXene comprises Ti3C2And Ti2C
Further, the concentration of HCl in the step (5) is 1mol/L, and the mass ratio of hydrochloric acid to MXene is 17-5: 1.
The invention has the following advantages: the raw materials required by the preparation are common and easy to obtain, the cost is low, and the environment is protected; the preparation process is simple and convenient, and the two-step synthesis by adopting an aqueous solution method is easy to control; the response is obviously improved, and the method has potential application value in the field of environmental protection.
Drawings
Fig. 1 is an SEM image of a sample: (a) MXene, (b) 5% Ag/MXene compound, (c) MXene/TiO2Composite, (d) 5% Ag/MXene/TiO2And (c) a complex.
FIG. 2 shows 5% Ag/MXene/TiO2EDS mapping profile of the complex.
Fig. 3 is an XRD pattern of the sample: (a)) MXene, (b) 5% Ag/MXene complex; (c) MXene/TiO2A complex; (d) 5% Ag/MXene/TiO2And (c) a complex.
Fig. 4 is a graph of photocatalytic degradation rate of samples: (a) p25, (b) MXene/TiO2A complex; (c) 5% Ag/MXene/TiO2And (c) a complex.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.
Example 1
Weighing 1 g of Ti3AlC2The powder was dispersed in 10 mL of 49% HF solution, and then put into Teflon and reacted at 60 ℃ for 24 hours. The obtained powder is washed with deionized water to pH 7, and is centrifugally washed with ethanol three times, and finally the product is dried in vacuum at 60 ℃ for 24h to finally obtain MXene powder. Weighing 0.25 mmol AgNO3And 3.28 mmol MXene in 50 mL deionized water, mixing, and performing ultrasonic treatment for 30min to obtain solution A. 0.25 mmol of SnCl is weighed2And 0.5 mmol of CF3And dissolving the COOH solution in 3 mL of formaldehyde and 7 mL of deionized water solution, and carrying out ultrasonic treatment for 30min to obtain a B solution. And slowly dripping the prepared solution B into the solution A, uniformly mixing, performing ultrasonic treatment for 30min, centrifuging, washing, and performing vacuum drying to prepare the Ag/MXene compound modified by the nano Ag. 100 mg of Ag/MXene complex and 0.165 g of NaBF were weighed out4Dissolving in 15mL of 1M HCl, and carrying out hydrothermal reaction at 160 ℃ for 4h to obtain 3% Ag/MXene/TiO2A composite photocatalyst is provided.
TABLE 1 Ag/MXene/TiO2Preparation of the formulation Table
Sample name AgNO3 (mmol) SnCl2 (mmol) CF3COOH (mmol) MXene (mmol)
1%Ag/MXene/TiO2 0.09 0.09 0.18 3.61
3%Ag/MXene/TiO2 0.25 0.25 0.5 3.28
5%Ag/MXene/TiO2 0.14 0.14 0.28 1.08
10%Ag/MXene/TiO2 0.17 0.17 0.34 0.62
Examples 2 to 4
Other steps are unchanged, the mass percentage of the added Ag is respectively 1 percent, 5 percent and 10 percent, and the Ag/MXene/TiO is obtained2A composite photocatalyst is provided. The specific formulation is shown in table 2. In addition, the reaction temperature and the reaction time are respectively changed between 120-220 ℃ and 1-36 h.
MXene, Ag/MXene Compound and Ag/MXene/TiO obtained in examples 1 to 42Composition ofThe samples were analyzed using a Field Emission Scanning Electron Microscope (FESEM), X-ray diffractometer (XRD), ultraviolet-visible spectrometer (UV-vis).
FIG. 1 shows MXene, 5% Ag/MXene, MXene/TiO2And 5% Ag/MXene/TiO2SEM image of the sample. As can be seen from FIG. 1a, MXene is in a clear lamellar state and has good layering effect. Fig. 1b can observe that the surface layer of MXene is deposited with more uniform Ag nanoparticles, which grow between the layers of MXene. After the hydrothermal reaction, flaky TiO was precipitated on MXene (FIG. 1 c) and 5% Ag/MXene (FIG. 1 d)2
FIG. 2 shows 5% Ag/MXene/TiO2EDS mapping map of (a). As can be clearly seen from the figure, 5% Ag/MXene/TiO2The paint contains Ti, C, O, F and Ag elements which are uniformly distributed.
FIG. 3 shows MXene, 5% Ag/MXene, MXene/TiO2And 5% Ag/MXene/TiO2XRD pattern of the sample. It can be seen that MXene has characteristic peaks at 8.9 °, 18.2 °, 36.1 °, 41.8 °, 52.5 °, 57.5 °, 60.5 ° and 76.2 °, respectively, corresponding to the (002), (004), (101), (103), (105), (108), (109) and (110) crystal planes. After 5% of Ag is compounded, characteristic peaks of Ag appear at 38.1 degrees, 44.4 degrees, 64.5 degrees and 77.5 degrees of 5% of Ag/MXene, and correspond to (111), (200), (210) and (310) crystal faces of silver respectively, which indicates that the nano Ag is successfully modified on the MXene. After hydrothermal reaction of MXene and Ag/MXene, TiO appears at 25.2 degrees, 36.9 degrees, 47.9 degrees, 54.8 degrees and 62.5 degrees2Characteristic peaks of (a) respectively corresponding to TiO2The (101), (004), (200), (105) and (206) crystal planes of (A) show that TiO is precipitated on the MXene surface2
FIG. 4 shows P25, MXene/TiO2And 5% Ag/MXene/TiO2Graph of the rate of degradation of 20mg/L RhB by 20mg sample under visible light after a dark reaction for 30 min. It can be seen that after dark adsorption for 30min, the adsorption performance of the sample compounded with Ag is increased, and the photodegradation capability is also improved. Ag/MXene/TiO2Compared with P25 and MXene/TiO2The degradation rate of RhB under visible light is faster, which shows that the doping of noble metal Ag can effectively capture wide-bandgap semiconductorBulk TiO2The valence electron inhibits the recombination of electron-hole pairs, thereby improving the Ag/MXene/TiO2Photocatalytic activity of the composite material.
From the above characterization, it can be concluded that: Nano-Ag particles and TiO2Successfully modifying the tablets to Ag/MXene/TiO2On the composite and uniformly distributed. The modified composite material has improved visible light photocatalysis performance, and the composite material has potential application in the field of photoelectrocatalysis.
Although specific embodiments of the invention have been described above, it will be understood by those skilled in the art that the specific embodiments described are illustrative only and are not limiting upon the scope of the invention, and that equivalent modifications and variations can be made by those skilled in the art without departing from the spirit of the invention, which is to be limited only by the appended claims.

Claims (10)

1. Ag/MXene/TiO modified by nano noble metal2The composite material and the preparation method thereof are characterized in that:
step (1) MXene preparation: etching of Ti with HF solution3AlC2Cleaning and drying the powder to obtain MXene;
step (2) dissolving MXene in AgNO3In the water solution, ultrasonic mixing is carried out uniformly to obtain solution A;
step (3) SnCl is weighed2Powder and CF3Dissolving COOH in formaldehyde water solution, and uniformly stirring to obtain a solution B;
slowly dropping the solution B into the solution A, uniformly mixing, centrifugally washing, and drying to obtain the MXene composite material modified by the nano Ag;
step (5) adding the Ag/MXene composite material into NaBF4Carrying out hydrothermal reaction in hydrochloric acid solution to obtain Ag/MXene/TiO2A composite material.
2. The nano noble metal modified Ag/MXene/TiO according to claim 12The preparation method of the composite material is characterized by comprising the following steps:in the step (1), the mass fraction of the HF solution is 40-49%, and the mass ratio of MAX to HF is 10.75-5: 1.
3. the nano noble metal modified Ag/MXene/TiO according to claim 12The preparation method of the composite material is characterized by comprising the following steps: the etching temperature in the step (1) is 60 ℃, and the time is 24 h.
4. The nano noble metal modified Ag/MXene/TiO according to claim 12The preparation method of the composite material is characterized by comprising the following steps: AgNO in the step (3)3、SnCl2And CF3The ratio of the amount of COOH species was 1:1: 2.
5. The nano noble metal modified Ag/MXene/TiO according to claim 12The preparation method of the composite material is characterized by comprising the following steps: the mass fraction of Ag in the Ag/MXene composite material obtained in the step (4) is 1-10%.
6. The nano noble metal modified Ag/MXene/TiO according to claim 12The preparation method of the composite material is characterized by comprising the following steps: the hydrothermal reaction temperature of the step (5) is 120-220 ℃, and the time is 1-36 h.
7. The nano noble metal modified Ag/MXene/TiO according to claim 12The preparation method of the composite material is characterized by comprising the following steps: NaBF of the step (5)4The mass ratio of MXene to MXene is 4.95-1.65: 1.
8. The nano noble metal modified Ag/MXene/TiO according to claim 12The preparation method of the composite material is characterized by comprising the following steps: the cleaning process in the step (1) is repeated centrifugal cleaning by a high-speed centrifuge, and the MXene comprises Ti3C2And Ti2C。
9. According to claim 1 oneAg/MXene/TiO modified by nano noble metal2The preparation method of the composite material is characterized by comprising the following steps: in the step (5), the concentration of HCl is 1mol/L, and the mass ratio of hydrochloric acid to MXene is 17-5: 1.
10. The nano noble metal modified Ag/MXene/TiO prepared by any preparation method of claims 1-92A composite material.
CN202010077109.0A 2020-01-23 2020-01-23 Ag/MXene/TiO modified by nano noble metal2Composite material and preparation method thereof Pending CN111250122A (en)

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CN113198501A (en) * 2021-04-26 2021-08-03 福建工程学院 Novel TiO (titanium dioxide)2Preparation method of/MXene composite material
CN113218296A (en) * 2021-03-23 2021-08-06 上海交通大学 Elastic strain sensor and preparation method thereof
CN113559899A (en) * 2021-07-08 2021-10-29 西南科技大学 Silver-loaded multilayer Ti for uranium reduction separation3C2TxPreparation and application of MXene
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CN114950509A (en) * 2022-05-31 2022-08-30 齐齐哈尔大学 Catalyst for microwave activation persulfate rapid oxidative degradation of PPCPs wastewater and preparation and application methods thereof
CN116328803A (en) * 2023-03-11 2023-06-27 中南民族大学 Preparation method and application of CdS@Ti3C2MXene-MoS 2 ternary composite catalyst
CN116328803B (en) * 2023-03-11 2024-05-10 中南民族大学 Preparation method and application of CdS@Ti3C2MXene-MoS 2 ternary composite catalyst

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CN111921550B (en) * 2020-07-17 2023-06-27 杭州师范大学 MXene/titanium dioxide nanotube composite photocatalyst and preparation method thereof
CN111921550A (en) * 2020-07-17 2020-11-13 杭州师范大学 MXene/titanium dioxide nanotube composite material photocatalyst and preparation method thereof
CN112768259B (en) * 2020-12-30 2022-06-14 郑州轻工业大学 Preparation method and application of MXene derivative/metal nano composite material
CN112768259A (en) * 2020-12-30 2021-05-07 郑州轻工业大学 Preparation method and application of MXene derivative/metal nano composite material
CN113105735A (en) * 2021-02-22 2021-07-13 安徽大学 High-molecular polymer composite heat conduction material with high heat conduction and preparation method thereof
CN113218296A (en) * 2021-03-23 2021-08-06 上海交通大学 Elastic strain sensor and preparation method thereof
CN113218296B (en) * 2021-03-23 2022-05-31 上海交通大学 Elastic strain sensor and preparation method thereof
CN113198501A (en) * 2021-04-26 2021-08-03 福建工程学院 Novel TiO (titanium dioxide)2Preparation method of/MXene composite material
CN113559899A (en) * 2021-07-08 2021-10-29 西南科技大学 Silver-loaded multilayer Ti for uranium reduction separation3C2TxPreparation and application of MXene
CN113559899B (en) * 2021-07-08 2023-11-24 西南科技大学 Uranium reduction separated silver-loaded multilayer Ti 3 C 2 T x Preparation and application of MXene
CN114736680A (en) * 2022-04-22 2022-07-12 东南大学 Preparation method of modified titanium carbide quantum dots based on multi-metal ion coordinated coordination
CN114736680B (en) * 2022-04-22 2023-10-27 东南大学 Preparation method of titanium carbide quantum dot based on multi-metal ion synergistic coordination modification
CN114950509A (en) * 2022-05-31 2022-08-30 齐齐哈尔大学 Catalyst for microwave activation persulfate rapid oxidative degradation of PPCPs wastewater and preparation and application methods thereof
CN114950509B (en) * 2022-05-31 2023-06-20 齐齐哈尔大学 Microwave activated persulfate rapid oxidative degradation PPCPs wastewater catalyst and preparation and application methods thereof
CN116328803A (en) * 2023-03-11 2023-06-27 中南民族大学 Preparation method and application of CdS@Ti3C2MXene-MoS 2 ternary composite catalyst
CN116328803B (en) * 2023-03-11 2024-05-10 中南民族大学 Preparation method and application of CdS@Ti3C2MXene-MoS 2 ternary composite catalyst

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