CN112121855B - Preparation method of photocatalytic thiourea modified two-dimensional MXene material - Google Patents
Preparation method of photocatalytic thiourea modified two-dimensional MXene material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 92
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 40
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 24
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 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 description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 8
- ICXYINJACKJQQV-UHFFFAOYSA-N 2-(isothiocyanatomethyl)furan Chemical compound S=C=NCC1=CC=CO1 ICXYINJACKJQQV-UHFFFAOYSA-N 0.000 claims description 7
- BYIMSFXYUSZVLI-UHFFFAOYSA-N 3-methoxysilylpropan-1-amine Chemical compound CO[SiH2]CCCN BYIMSFXYUSZVLI-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000010306 acid treatment Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000004729 solvothermal method Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 11
- 239000011259 mixed solution Substances 0.000 claims 2
- 238000001704 evaporation Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 14
- 150000002500 ions Chemical class 0.000 abstract description 10
- 230000001360 synchronised effect Effects 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 239000007777 multifunctional material Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000011191 terminal modification Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 9
- 239000003344 environmental pollutant Substances 0.000 description 8
- 231100000719 pollutant Toxicity 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000004043 responsiveness Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
The invention relates to a preparation method of a photocatalytic thiourea modified two-dimensional MXene material, which comprises the steps of synthesizing the MXene material and then preparing TiO2The method comprises the following steps of @ MXene composite material, and finally preparing the thiourea modified two-dimensional MXene material, namely the magnetic multifunctional material, through terminal modification. The preparation method provided by the invention is simple to operate, low in cost, wide in application range and has practical application value. The invention also provides application of the multifunctional adsorbing material in synchronous adsorption of phenol and lead ions in wastewater and photocatalytic phenol reduction.
Description
Technical Field
The invention belongs to the technical field of environmental sewage treatment, and particularly relates to a preparation method of a photocatalytic thiourea modified two-dimensional MXene material.
Background
The pollution of water environment directly threatens the growth of animals and plants and the health of human bodies, and is increasingly and widely concerned, and the sewage treatment is paid much attention. Organic pollutants and heavy metal ions are the main harmful components in sewage, and the combined pollution of the organic pollutants and the heavy metal ions is a difficult point for controlling environmental pollution. At present, the classical methods for treating the pollutants comprise ion exchange, membrane separation, oxidation reduction, adsorption and the like, most of the methods can only treat single pollutants, and the identification efficiency and range of various pollutants are limited. Therefore, the development of a degradable and efficient sewage treatment technology for recycling treatment becomes a current focus of attention.
In the treatment technology of degrading pollutants and recycling, the method for removing complex pollution by using functional materials is an effective and convenient method, and can be used for research by using the existing equipment. Wherein the key point is to synthesize and prepare a practical novel magnetic multifunctional material. The magnetic adsorption composite material has magnetism, adsorptivity, reproducibility and high efficiency, and is a good environment-friendly adsorption material. There are many patents relating to the study of magnetic adsorption composites to adsorb contaminants. For example, patent No. CN109317089A discloses a method for treating thallium-containing wastewater with a magnetic adsorbing material. The patent with the patent number of CN107570116A discloses a method for removing antibiotics in water by adsorbing magnetic MOFs adsorbing materials. From the existing patents, most of the existing magnetic adsorption materials have single functions and small application range. Therefore, it is necessary to develop a novel magnetic multifunctional composite material capable of degrading and efficiently adsorbing various pollutants.
Disclosure of Invention
In order to solve the problem that most of adsorption materials are only limited to adsorbing pollutants, the invention provides a preparation method of a magnetic, photocatalytic degradation and dual-adsorption multifunctional thiourea modified two-dimensional MXene material, and the preparation method has the characteristics of wide application range, low production cost and environmental protection.
The invention also provides application of the method for synchronously adsorbing phenol and lead ions in the wastewater and degrading phenol through photocatalysis.
The invention is realized by the following technical scheme:
the preparation method of the photocatalytic thiourea modified two-dimensional MXene material comprises the following steps:
(1) pretreatment of MAX phase materials
Grinding and sieving MAX phase materials; carrying out ultrasonic treatment on the ethanol solution for 30-60 min; acid treatment: and soaking the MAX phase material subjected to ethanol ultrasonic treatment in an acid solution for 2-4 hours, wherein the aim is to remove possible metal and metal alloy impurities. Alkali treatment: and soaking the MAX phase material subjected to acid treatment in an alkali solution for 1.5-3.0 h, wherein the aim is to remove Al possibly existing and impurities which are soluble in an alkali solution.
The MAX phase material is Ti3AlC2、Ti2One of AlC;
the acid solution can be one or two of hydrochloric acid and sulfuric acid;
the mass-volume ratio of the MAX phase precursor material to the acid solution is 1 g: 100-150 mL;
preferably, the molar concentration of the acid solution is 0.3-1.0 mol/L;
preferably, the grinding and sieving are 800-1000 meshes;
preferably, the mass fraction of the ethanol solution is 95-99%;
preferably, the frequency of ultrasonic treatment is 30-50 KHz;
the alkali solution can be one of sodium hydroxide and ammonia water;
the mass-volume ratio of the MAX phase material to the alkali solution is 1 g: 100-150 mL;
preferably, the molar concentration of the alkali solution is 0.5-1.5 mol/L;
(2) preparation of MXene material
NH4F, etching method: slowly adding NH into the MAX phase material treated in the step (1) at 40-60 DEG C4Stirring and reacting the solution F and the HCl solution for 10-15 hours, and then cleaning the solution with secondary distilled water; and carrying out vacuum filtration and drying to obtain the MXene material.
The preparation reaction formula is as follows
The MAX phase material and NH4F. The mass ratio of HCl is 1: 1.5-2.5: 2-6;
(3)TiO2preparation of @ MXene composite material
Measuring tetrabutyl titanate and hydrofluoric acid solution, sequentially adding the tetrabutyl titanate and the hydrofluoric acid solution into the MXene powder prepared in the step (2), adding an organic solvent, carrying out a solvothermal reaction at 50-70 ℃, washing and drying after 24-36 hours to obtain TiO2@ MXene composite material.
The preparation route is as follows:
the mass volume ratio of the tetrabutyl titanate to the hydrofluoric acid to the MXene to the anhydrous solvent is 2.0-3.5 g: 0.4-0.6 g: 1 g: 40-50 mL;
the mass fraction of the hydrofluoric acid solution is 35-50%;
the organic solvent can be one of absolute ethyl alcohol, methanol and acetone.
(4) Photocatalytic thiourea modified two-dimensional MXene material (L-TiO)2@ MXene) preparation
TiO prepared in the step (3)2Dispersing the @ MXene composite material in an acetone solution, performing ultrasonic reaction for 30-60 min, then sequentially dropwise adding 3-aminopropyl-methoxysilane and 2-furfuryl isothiocyanate into the solution, refluxing at 70-90 ℃ for 36-48 h, then cooling to room temperature, performing rotary evaporation on the solvent, adding ice water into the residue, stirring, performing suction filtration, recrystallizing the crude product with absolute ethyl alcohol to obtain the photocatalytic thiourea modified MXene material (L-TiO)2@MXene)。
The preparation route is as follows:
the TiO is2The mass volume ratio of the @ MXene composite material to the 3-aminopropyl-methoxysilane to the 2-furfuryl isothiocyanate is 1 g: 10-15 mL: 5.0-7.0 mL;
the TiO is2The mass-volume ratio of the @ MXene composite material to the acetone solution is 1 g: 100-200 mL.
The invention provides a preparation method of a photocatalytic thiourea modified two-dimensional MXene material, which has a synchronous adsorption function, can effectively adsorb heavy metal ions and organic pollutants, has good magnetic responsiveness and is convenient for recycling and reusing the material; supported TiO2The performance of the two-dimensional lamellar material for degrading phenolic pollutants by photocatalysis can be enhanced.
Compared with the prior art, the invention has the beneficial effects that: has the characteristics of low cost, wide application range, high adsorption efficiency and environmental protection. Can synchronously adsorb organic phenol pollutants and heavy metal ions in the wastewater and has the functions of magnetic response and photocatalytic degradation.
Drawings
FIG. 1 shows a photocatalytic thiourea modified two-dimensional MXene material (L-TiO) prepared in example 12@ MXene) nuclear magnetism1H, spectrogram;
FIG. 2 shows MXene and TiO compounds prepared in example 12Transmission electron micrograph of @ MXene;
FIG. 3 shows the photocatalytic thiourea modified two-dimensional MXene material (L-TiO) prepared in example 12@ MXene) magnetic response performance test chart;
FIG. 4 shows the photocatalytic thiourea modified two-dimensional MXene material (L-TiO) prepared in example 12@ MXene) for synchronously adsorbing heavy metal ions and phenol;
FIG. 5 shows the photocatalytic thiourea modified two-dimensional MXene material (L-TiO) prepared in example 12@ MXene) photocatalytic degradation of phenol.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
example 1:
a preparation method of a photocatalytic thiourea modified two-dimensional MXene material.
(1) Pretreatment of MAX phase materials
Mixing 1g of Ti3AlC2The phase material is ground and sieved (800 meshes); carrying out ultrasonic treatment on 95% 100mL ethanol solution for 60 min; acid treatment: subjecting ethanol to ultrasonic treatment to obtain Ti3AlC2The phase material was soaked in 0.8 mol/L100 mL hydrochloric acid solution for 4 h. Alkali treatment: subjecting the acid-treated Ti3AlC2The phase material was soaked in 1 mol/L100 mL NaOH solution for 2.0 h.
(2) Preparation of MXene material
NH4F, etching method: 1g of Ti as the material treated in the step (1) was added at 60 ℃3AlC2Slowly add a solution containing 2.0g of solute NH4F and 4.0g of solute HCl, stirring and reacting for 12 hours, and then cleaning with secondary distilled water; and carrying out vacuum filtration and drying to obtain the MXene material.
(3)TiO2Preparation of @ MXene composite material
Weighing 2.5g of tetrabutyl titanate and 1.5mL of 40% hydrofluoric acid solution, sequentially adding into 1g of MXene powder, adding 50mL of methanol, carrying out a solvothermal reaction at 70 ℃, washing and drying after 36h to obtain TiO2@Ti3AlC2A composite material.
(4) Thiourea modified two-dimensional lamellar material L-TiO2Preparation of @ MXene
1g of TiO2@Ti3AlC2Dispersing the composite material in 150mL of acetone solution, performing ultrasonic reaction for 45min, then sequentially dropwise adding 10mL of 3-aminopropyl-methoxysilane and 5mL of 2-furfuryl isothiocyanate into the solution, refluxing at 70 ℃ for 36h, then cooling to room temperature, performing rotary evaporation on the solvent, adding 500mL of ice water into the residue, stirring, performing suction filtration, and recrystallizing the crude product with absolute ethyl alcohol to obtain the photocatalytic thiourea modified two-dimensional MXene material (L-TiO)2@Ti3AlC2)。
Example 2:
a preparation method of a photocatalytic thiourea modified two-dimensional MXene material.
(1) Pretreatment of MAX phase materials
Mixing 1g of Ti3AlC2The phase precursor material was ground and sieved (900 mesh); performing ultrasonic treatment on 99% 100mL ethanol solution for 60 min; acid treatment: subjecting ethanol to ultrasonic treatment to obtain Ti3AlC2The phase precursor material was soaked in 5.5 mol/L100 mL hydrochloric acid solution for 3 h. Alkali treatment: subjecting the acid-treated Ti3AlC2The phase precursor material was soaked in 1.5 mol/L100 mL NaOH solution for 2 h.
(2) Preparation of MXene material
NH4F, etching method: 1g of Ti as the precursor material treated in the step (1) was added at 55 deg.C3AlC2Slowly add 2.2g NH4F and 5.5 mol/L100 mL HCl solution, stirring for reaction for 12h, and then cleaning with secondary distilled water; and carrying out vacuum filtration and drying to obtain the MXene material.
(3)TiO2Preparation of @ MXene composite material
Weighing 2.0g of tetrabutyl titanate and 1mL of 40% hydrofluoric acid solution, sequentially adding into 1g of MXene powder, adding 50mL of absolute ethyl alcohol, carrying out solvothermal reaction at 70 ℃, washing and drying after 36h to obtain TiO2@ MXene composite material.
(4) Photocatalytic thiourea modified two-dimensional MXene material (L-TiO)2@ MXene) preparation
1g of TiO2Dispersing the @ MXene composite material in 150mL of acetone solution, performing ultrasonic reaction for 60min, then sequentially dropwise adding 15mL of 3-aminopropyl-methoxysilane and 7mL of 2-furfuryl isothiocyanate into the solution, refluxing at 70 ℃ for 48h, then cooling to room temperature, performing rotary evaporation on the solvent, adding 500mL of ice water into the residue, stirring, performing suction filtration, recrystallizing the crude product with absolute ethyl alcohol to obtain the photocatalytic thiourea modified two-dimensional MXene material (L-TiO)2@MXene)。
Example 3:
a preparation method of a photocatalytic thiourea modified two-dimensional MXene material.
(1) Pretreatment of MAX phase materials
Mixing 1g of Ti2Grinding and sieving the AlC phase material (900 meshes); performing ultrasonic treatment on 99% 100mL ethanol solution for 60 min; acid treatment: subjecting ethanol to ultrasonic treatment to obtain Ti2The AlC phase material is soaked in 5.5 mol/L100 mL hydrochloric acid solution for 3 h. Alkali treatment: subjecting the acid-treated Ti2The AlC phase material was soaked in 1.5 mol/L100 mL NaOH solution for 2 h.
(2) Preparation of MXene material
NH4F, etching method: 1g of Ti as the material treated in the step (1) was added at 55 deg.C2Slowly adding 2.2g NH into AlC4F and 5.5 mol/L100 mL HCl solution, stirring for reaction for 12h, and then cleaning with secondary distilled water; and carrying out vacuum filtration and drying to obtain the MXene material.
(3)TiO2Preparation of @ MXene composite material
Weighing 2.0g of tetrabutyl titanate and 1mL of 40% hydrofluoric acid solution, sequentially adding into 1g of MXene powder, adding 50mL of absolute ethyl alcohol, carrying out solvothermal reaction at 70 ℃, washing and drying after 36h to obtain TiO2@Ti2AlC composite material.
(4) Photocatalytic thiourea modified two-dimensional MXene material (L-TiO)2@ MXene) preparation
1g of TiO2Dispersing the @ MXene composite material in 150mL of acetone solution, carrying out ultrasonic reaction for 60min, then sequentially dropwise adding 15mL of 3-aminopropyl-methoxysilane and 7mL of 2-furfuryl isothiocyanate into the solution, refluxing at 70 ℃ for 48h, and carrying out ultrasonic reaction on the mixtureCooling to room temperature, performing rotary evaporation on the solvent, adding 500mL of ice water into the residue, stirring, performing suction filtration, and recrystallizing the crude product with absolute ethyl alcohol to obtain the photocatalytic thiourea modified two-dimensional MXene material (L-TiO)2@MXene)。
Test example 1:
photocatalytic thiourea modified two-dimensional MXene material (L-TiO)2@ MXene) was tested for structure and performance.
Test samples: photocatalytic thiourea modified two-dimensional MXene material (L-TiO) prepared in example 12@MXene)。
1. Nuclear magnetism (1H NMR) analysis: grinding and crushing a sample, and testing the sample by using a solid nuclear magnetic resonance spectrometer1The H NMR spectrum is shown in figure 1. L-TiO 22Of @ MXene1H NMR spectrum of the product shows-CH chemical shifts at δ 6.06, 6.27 and 7.28 and-CH chemical shifts at δ 0.58, 3.45 and 4.562Chemical shift, δ -2.0 is-NH chemical shift. Proving that L-TiO2Successful preparation of @ MXene.
2. Transmission Electron Microscopy (TEM) analysis: 0.5mg of the sample was placed in absolute ethanol and tested against a copper mesh background. After the test, a transmission electron micrograph is obtained, as shown in fig. 2. MXene (FIG. 2A) was seen to be lamellar after treatment; two-dimensional lamellar material L-TiO2TiO is seen in the electron micrograph of @ MXene (FIG. 2B)2Loaded on the layered surface to prove that the two-dimensional lamellar material L-TiO2Successful preparation of @ MXene.
3. Magnetic responsiveness (VSM) analysis: the magnetization curve was measured with a vibrating sample magnetometer (0 to. + -. 1T) under the test condition of 273K, and the results are shown in FIG. 3. Can see the two-dimensional lamellar material L-TiO2The @ MXene has good magnetic responsiveness, the magnetization value is 6.8emu/g, and the @ MXene is easy to recycle.
Test example 2:
photocatalytic thiourea modified two-dimensional MXene material L-TiO2Testing the synchronous adsorption performance of @ MXene and the performance of degrading phenol by photocatalysis.
Test samples: example 1 photocatalytic thiourea modified two-dimensional MXene material L-TiO2@MXene。
1. Synchronous adsorption performance analysis:taking 1g L-TiO2@ MXene was placed in 50mL of a solution of 300 mg. L-1The pH of the solution was adjusted to 7 in the lead ion and phenol solutions, and the solutions were adsorbed by shaking at 25 ℃ and the concentrations of lead ions and phenol in the filtrates were measured at 5, 10, 20, 30, 50, 60, 80, 100, and 120min, respectively. A graph of the adsorption time versus the amount of adsorption was plotted as shown in FIG. 4. The graph shows that L-TiO2The adsorption capacity of @ MXene to lead ions and phenol reaches 171.2mg g-1、88.4mg·g-1. Proving that L-TiO2The @ MXene has good performance of synchronously adsorbing heavy metal ions and organic pollutants.
2. Photocatalytic degradation performance analysis: under the condition of visible light irradiation, the change of the content of phenol in the solution is measured at time intervals of 1, 2, 3 and 4h, and a graph is made, as shown in the attached figure 5. It can be seen that the longer the exposure to visible light, the lower the phenol concentration in the solution, as the time passed, demonstrating the addition of TiO2Can effectively improve the photodegradability of MXene.
Claims (10)
1. The preparation method of the photocatalytic thiourea modified two-dimensional MXene material is characterized by comprising the following steps:
(1) pretreatment of MAX phase materials
Grinding and sieving the MAX phase material, and performing ultrasonic treatment for 30-60 min by using an ethanol solution; soaking the MAX phase material subjected to ethanol ultrasonic treatment in an acid solution for 2-4 h, and then soaking the MAX phase material subjected to acid treatment in an alkali solution for 1.5-3.0 h;
(2) preparation of MXene material
By NH4F etching method, namely slowly adding NH into the MAX phase material treated in the step (1) at 40-60 DEG C4Stirring and reacting the solution F and the HCl solution for 10-15 hours, and then cleaning the solution with secondary distilled water; carrying out vacuum filtration and drying to obtain MXene material;
(3)TiO2preparation of @ MXene composite material
Measuring tetrabutyl titanate and hydrofluoric acid solution, sequentially adding the tetrabutyl titanate and the hydrofluoric acid solution into the MXene powder prepared in the step (2), adding an organic solvent, and carrying out solvothermal reaction at 50-70℃ to 24EWashing and drying after 36h to obtain TiO2@ MXene composite;
(4) photocatalytic thiourea modified two-dimensional MXene material (L-TiO)2@ MXene) preparation
TiO prepared in the step (3)2Dispersing the MXene composite material in acetone to form a mixed solution 1, performing ultrasonic reaction for 30-60 min, then sequentially dropwise adding 3-aminopropyl-methoxysilane and 2-furfuryl isothiocyanate into the mixed solution 1, refluxing at 70-90 ℃ for 36-48 h, rotationally evaporating the solvent, adding ice water into the residue, stirring, performing suction filtration, recrystallizing the crude product with 95% ethanol to obtain the photocatalytic thiourea modified two-dimensional MXene material (L-TiO)2@MXene)。
2. The method for preparing the photocatalytic thiourea modified two-dimensional MXene material as claimed in claim 1, wherein the MAX phase material in step (1) is Ti3AlC2、Ti2One kind of AlC.
3. The preparation method of the photocatalytic thiourea modified two-dimensional MXene material as claimed in claim 1, wherein the acid solution in step (1) is one or two of hydrochloric acid and sulfuric acid, and the concentration is 0.3-1.0 mol/L.
4. The preparation method of the photocatalytic thiourea modified two-dimensional MXene material as claimed in claim 1, wherein the alkali solution in step (1) is one of sodium hydroxide and ammonia water, and the concentration is 0.5-1.5 mol/L.
5. The preparation method of the photocatalytic thiourea modified two-dimensional MXene material as claimed in claim 1, wherein in step (2), MAX phase material and solute NH are adopted4F. The mass ratio of solute HCl is 1: 1.5-2.5: 2 to 6.
6. The preparation method of the photocatalytic thiourea modified two-dimensional MXene material as claimed in claim 1, wherein the mass volume ratio of tetrabutyl titanate, solute HF, MXene and organic solvent in step (3) is 2.0-3.5 g: 0.4-0.6 g: 1 g: 40-50 mL.
7. The preparation method of the photocatalytic thiourea modified two-dimensional MXene material as claimed in claim 1, wherein the mass fraction of the hydrofluoric acid solution in step (3) is 35-50%.
8. The method for preparing the photocatalytic thiourea modified two-dimensional MXene material as claimed in claim 1, wherein the organic solvent in step (3) is one of absolute ethanol, methanol and acetone.
9. The preparation method of the photocatalytic thiourea modified two-dimensional MXene material as claimed in claim 1, wherein the TiO in step (4) is2The mass volume ratio of the @ MXene composite material to the 3-aminopropyl-methoxysilane to the 2-furfuryl isothiocyanate is 1 g: 10-15 mL: 5.0-7.0 mL.
10. The method for preparing the photocatalytic thiourea modified two-dimensional MXene material as claimed in claim 1, wherein the TiO in step (4) is2The mass-volume ratio of the @ MXene composite material to the acetone is 1 g: 100-200 mL.
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