CN113578362A - Preparation method and application of alkynyl-modified semiconductor material - Google Patents
Preparation method and application of alkynyl-modified semiconductor material Download PDFInfo
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- CN113578362A CN113578362A CN202110836193.4A CN202110836193A CN113578362A CN 113578362 A CN113578362 A CN 113578362A CN 202110836193 A CN202110836193 A CN 202110836193A CN 113578362 A CN113578362 A CN 113578362A
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- semiconductor material
- alkynyl
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- ball milling
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 201
- 239000000463 material Substances 0.000 title claims abstract description 191
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
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- 150000001247 metal acetylides Chemical class 0.000 claims abstract description 39
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- 125000000304 alkynyl group Chemical group 0.000 claims description 28
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
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- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical group CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 claims description 6
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- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
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- ARNWQMJQALNBBV-UHFFFAOYSA-N lithium carbide Chemical group [Li+].[Li+].[C-]#[C-] ARNWQMJQALNBBV-UHFFFAOYSA-N 0.000 claims description 3
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 25
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- GSDSWSVVBLHKDQ-JTQLQIEISA-N Levofloxacin Chemical compound C([C@@H](N1C2=C(C(C(C(O)=O)=C1)=O)C=C1F)C)OC2=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-JTQLQIEISA-N 0.000 description 22
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- 238000001069 Raman spectroscopy Methods 0.000 description 1
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- 230000004913 activation Effects 0.000 description 1
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- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
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- B01J27/22—Carbides
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
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Abstract
The invention provides a preparation method and application of an alkynyl-modified semiconductor photocatalyst material, which comprises the steps of placing a semiconductor material and a metal acetylide in a ball milling tank, adding a solvent which does not react with the semiconductor material and the metal acetylide into the ball milling tank, carrying out ball milling under the protection of nitrogen or inert gas after the solvent submerges a steel ball, and carrying out aftertreatment to obtain the alkynyl-modified semiconductor material; the prepared alkynyl-modified semiconductor material is used for degrading organic dyes or antibiotics. The preparation method adopts a ball milling method to prepare the alkynyl-modified semiconductor photocatalyst material, has simple operation, avoids the use of toxic raw materials and the generation of byproducts in the prior art, and the prepared alkynyl-modified semiconductor photocatalyst material has better degradation performance on organic dyes and antibiotics than pure semiconductor materials.
Description
Technical Field
The invention belongs to the technical field of semiconductor materials, and relates to a preparation method and application of an alkynyl-modified semiconductor material.
Background
With the rapid development of industrialization, the problems of energy crisis, environmental pollution and the like in the human society become increasingly serious. The improvement work on environmental pollution is increased in various countries in the world, and the development and utilization of new energy and new energy technology are increased.
The solar energy has great potential, low environmental pollution and sustainable utilization, and is an important energy source for green ecological development. The semiconductor photocatalysis technology can directly utilize solar energy to drive reaction, so the semiconductor photocatalysis technology has important application prospect in the fields of energy and environment. Researchers have made great progress on the research and experimental progress of the theory of photocatalytic materials, and many semiconductor materials have been applied primarily in the field of photocatalysis. However, the performance of the photocatalytic materials that are currently available for industrial use is still to be improved. In g-C3N4For example, the characteristics of simple synthesis, stable physicochemical properties, good biocompatibility, good cycling stability and the like are favored by researchers at home and abroad, and the method is widely applied to the fields of photocatalytic degradation of organic pollutants, photolysis of water and the like. However, g-C3N4The photocatalyst also has defects of weak light absorption capacity, low specific surface area, high efficiency of photo-generated electron-hole recombination and the like, so that the photocatalytic activity is reduced, and the practical application of the photocatalyst is limited.
To overcome these disadvantages, g-C has been treated by various methods3N4The semiconductor material is modified to improve the photocatalytic activity, such as physical/chemical peeling, metal/nonmetal doping, heterojunction preparation and the like, wherein the semiconductor material is modified by some electron-withdrawing functional groups to accelerate the separation and transportation of electron holesEffectively improve g-C3N4And the like. Document 1(adv.mater.2020,32,1904433.) reports a process for the preparation of alkynyl functionalized covalent triazine polymers in a protective atmosphere by triflic acid catalyzed symmetric dicyandiamide organic small molecules, but this process is complicated to operate and involves toxic organic solvents; document 2(Nanotechnology,2018,29(35):355705.) alkynyl functionalization of silicon nanocrystal surface with phenylacetylene adjusts the electronic structure and optical properties of silicon nanocrystals, but the preparation process is complex and harsh, and requires a low temperature of-78 ℃ and an argon atmosphere; document 3(Organic Electronics,2016,28:155-62.) introduces alkynyl groups into an Organic skeleton by Sonogashira coupling reaction, but the post-treatment process is complicated, requires extraction with an Organic solvent and chromatography using a silica gel column.
Therefore, it is necessary to research a preparation method of a novel alkynyl-modified semiconductor material and apply the preparation method to catalytic degradation of pollutants.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method and application of an alkynyl-modified semiconductor material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of alkynyl-modified semiconductor material comprises the steps of putting semiconductor material (as long as the semiconductor material can be reacted with metal acetylide according to the method of the invention) and metal acetylide into a ball milling tank, adding a solvent (such as absolute ethyl alcohol and the like) which does not react with the semiconductor material and the metal acetylide into the ball milling tank, enabling the solvent to submerge a steel ball, carrying out ball milling under the protection of nitrogen or inert gas (preferably argon), and carrying out post-treatment to obtain the alkynyl-modified semiconductor material.
As a preferred technical scheme:
according to the preparation method of the alkynyl-modified semiconductor material, the mass ratio of the semiconductor material to the metal acetylide is 8: 1-2: 1, and if the mass ratio of the semiconductor material to the metal acetylide is not within the range, the metal acetylide and the semiconductor material cannot be fully contacted and reacted, or the metal acetylide can be subjected to self-polymerization.
According to the preparation method of the alkynyl-modified semiconductor material, the mass ratio of the semiconductor material to the metal acetylide is 4: 1.
The preparation method of the alkynyl-modified semiconductor material is that the semiconductor material is g-C3N4、TiO2Semiconductor materials such as poly-3-hexylthiophene, covalent triazine frameworks, and organometallic frameworks; g-C3N4The preparation process of the semiconductor material comprises the following steps: the nitrogen-rich precursor is placed in a muffle furnace and heated to 450-650 ℃ at a heating rate of 5-10 ℃/min (the precursor is decomposed into gas completely when the temperature is higher than the set temperature range, and the precursor cannot be polymerized into a target product because the precursor does not reach the condition of decomposing into an intermediate product when the temperature is lower than the set temperature range), and then the temperature is maintained for 2-6 h to obtain g-C3N4The nitrogen-rich precursor of the semiconductor material is urea, melamine, dicyandiamide or thiourea.
In the preparation method of the alkynyl-modified semiconductor material, the metal acetylide is an alkali metal acetylide or an alkaline earth metal acetylide.
In the preparation method of the alkynyl-modified semiconductor material, the alkali metal acetylide is lithium carbide, sodium carbide or potassium carbide; the alkaline earth metal acetylide is calcium carbide or magnesium carbide.
According to the preparation method of the alkynyl-modified semiconductor material, the ball-milling tank has the volume which can contain steel balls, the semiconductor material, the metal acetylide and the solvent, and a stainless steel tank with the capacity of 50-200 mL can be generally selected to meet the requirement; the ball milling adopts steel balls with the diameters of 2mm, 5mm, 10mm and 20mm in the number ratio of 1:1:1:1, so that the steel balls can fully contact with the semiconductor material and the metal acetylide in the ball milling process; the mass ratio of the steel balls to the semiconductor material is 2400: 1-600: 1, so that enough mechanical force can be obtained for a reaction substrate in the ball milling process to drive the reaction to occur; the ball milling time is 12-24 hours, the rotating speed is 400-700 r/min, if the ball milling time and the rotating speed are too low, the reaction is incomplete, and if the ball milling time and the rotating speed are too high, the defects on the surface of a semiconductor are caused by factors such as shearing force in the ball milling process.
In the preparation method of the alkynyl-modified semiconductor material, the post-treatment process is to sequentially perform the processes of centrifugation, acid washing, deionized water washing, ethanol washing and drying.
According to the preparation method of the alkynyl-modified semiconductor material, dilute nitric acid or dilute sulfuric acid solution with the concentration of 0.1-2.5 mol/L is adopted for acid washing; the drying temperature is 60-80 ℃.
The invention also provides application of the alkynyl-modified semiconductor material prepared by the preparation method of the alkynyl-modified semiconductor material, which is used for degrading organic dye or antibiotic; the alkynyl-modified semiconductor material is obviously superior to unmodified semiconductor materials in the aspect of photocatalytic degradation of organic dyes or antibiotics, such as alkynyl-modified g-C prepared by the invention3N4Is obviously superior to unmodified g-C in the aspect of photocatalytic degradation of rhodamine B and levofloxacin3N4。
The principle of the invention is as follows:
the invention adopts a ball milling method, takes semiconductor materials and metal acetylide as raw materials, and prepares the alkynyl-modified semiconductor. The method is simple and easy to operate, and a hole and a fold structure are introduced on the basis of alkynyl modification in the treatment process, so that the active sites of a sample are increased, and the specific analysis is as follows:
the invention introduces alkynyl in alkali metal acetylide or alkaline earth metal acetylide into semiconductor material by ball milling, and the steel balls strongly impact, grind and stir the raw material by the rotation or vibration of the ball mill, thereby obviously reducing reaction activation energy, refining crystal grains, enhancing powder activity and inducing low-temperature chemical reaction. During the ball milling process, the kinetic energy of the moving steel balls grinds large crystals of the metal acetylide into amorphous nano particles, chemical bonds are broken, a large amount of alkynyl anions are immediately exposed in reactants, and the inherent reactivity of the metal acetylide is activated. Some modifiable surface docking sites in the semiconductor can be chemically bonded with alkynyl anions during ball milling. In the ball milling process, the semiconductor material is bent and deformed due to collision and extrusion between the steel balls, a folded structure is finally formed, and ultraviolet and visible light is subjected to diffuse reflection in the folded structure, so that the utilization efficiency of light is improved. In addition, unreacted metal alkynes are embedded into the semiconductor structure as templates with different sizes, and when the residual metal alkynes are dissolved by dilute acid, a hole structure is generated in situ on the semiconductor, so that active sites are increased. Therefore, the alkynyl-modified semiconductor has better absorption in the visible light range, can effectively degrade dyes (such as rhodamine B and the like) and antibiotics (such as levofloxacin and the like) in a photocatalytic manner, and has the photocatalytic degradation performance equivalent to that of most recently reported semiconductor photocatalytic materials. Meanwhile, the alkynyl modification improves the separation and transmission of the photo-generated electron hole pair of the semiconductor and improves the photocatalytic performance of degrading organic dyes and antibiotics. The invention avoids the generation of toxic raw materials and byproducts in the prior art, has simple operation and low cost, and improves the photocatalytic degradation performance of semiconductor materials.
Has the advantages that:
(1) according to the preparation method, the metal acetylide is used as a template to introduce a hole structure on the semiconductor, so that active sites are increased;
(2) in the preparation method, the semiconductor material is fully stripped into a structure with smaller size in the ball milling process, and a fold structure is formed, so that the specific surface area is increased, and the light absorption capacity and the utilization rate are improved;
(3) in the preparation method, the alkynyl is used as an electron-withdrawing group, so that the separation of a photoproduction electron hole pair can be effectively promoted, and the photocatalytic degradation efficiency is improved;
(4) the degradation performance of the alkynyl-modified semiconductor material prepared by the invention on organic dyes and antibiotics is superior to that of a pure semiconductor material;
(5) the invention adopts a ball milling method, has simple operation, and avoids the use of toxic raw materials and the generation of byproducts in the prior art.
Drawings
FIG. 1 shows alkynyl-modified semiconductor materials and starting materials g to C obtained in examples 1, 2 and 33N4XRD contrast pattern of (a); wherein g-C3N40.125 part of the alkynyl-modified semiconductor material prepared in example 1, g-C3N40.25 part of the alkynyl-modified semiconductor material prepared in example 2, g-C3N4-0.5 is the alkynyl-modified semiconductor material prepared in example 3;
FIG. 2 shows the alkynyl-modified semiconductor material and carbon nitride (g-C) as a raw material obtained in example 23N4) An XPS map of (A);
FIG. 3 is a Raman spectrum of the alkynyl-modified semiconductor material prepared in example 2;
FIG. 4 is an infrared spectrum of the alkynyl-modified semiconductor material and carbon nitride as a raw material obtained in example 2;
FIG. 5 is a scanning electron microscope image and a transmission electron microscope image of the alkynyl-modified semiconductor material prepared in example 2, wherein (a) and (b) are scanning electron microscope images with different magnification, and (c), (d) and (e) are transmission electron microscope images with different positions and different magnification, respectively;
FIG. 6 shows alkynyl-modified semiconductor materials and starting materials g-C obtained in examples 1, 2 and 33N4(ii) an ultraviolet diffuse reflectance absorption spectrum; wherein g-C3N4Is a semiconductor material not modified with alkynyl, g-C3N40.125 part of the alkynyl-modified semiconductor material prepared in example 1, g-C3N40.25 part of the alkynyl-modified semiconductor material prepared in example 2, g-C3N4-0.5 is the alkynyl-modified semiconductor material prepared in example 3;
FIG. 7 shows alkynyl-modified semiconductor materials and starting materials g-C prepared in examples 1, 2 and 33N4Wherein g-C3N4Is a semiconductor material not modified with alkynyl, g-C3N40.125 part of the alkynyl-modified semiconductor material prepared in example 1, g-C3N4-0.25 is the alkynyl modification prepared in example 2Decorated semiconductor material, g-C3N4-0.5 is the alkynyl-modified semiconductor material prepared in example 3;
FIG. 8 shows alkynyl-modified semiconductor material and starting materials g-C prepared in example 23N4(ii) a photoluminescence spectrum of; wherein g-C3N4-0.25 is the alkynyl modified semiconductor material prepared in example 2;
FIG. 9 shows alkynyl-modified semiconductor materials prepared in examples 1, 2 and 3 and starting materials g to C3N4A diagram of degradation performance of rhodamine B under visible light, wherein (a) is a curve of the concentration of the rhodamine B changing along with illumination time, and (B) is degradation rate after 12 minutes of illumination, g-C3N4Is a semiconductor material not modified with alkynyl, g-C3N40.125 part of the alkynyl-modified semiconductor material prepared in example 1, g-C3N40.25 part of the alkynyl-modified semiconductor material prepared in example 2, g-C3N4-0.5 is the alkynyl-modified semiconductor material prepared in example 3;
FIG. 10 shows alkynyl-modified semiconductor materials prepared in examples 1, 2 and 3 and starting materials g to C3N4A plot of degradation performance of levofloxacin under visible light, wherein (a) is a curve of levofloxacin concentration with illumination time, and (b) is degradation rate after 18 minutes of light illumination, g-C3N4Is a semiconductor material not modified with alkynyl, g-C3N40.125 part of the alkynyl-modified semiconductor material prepared in example 1, g-C3N40.25 part of the alkynyl-modified semiconductor material prepared in example 2, g-C3N4-0.5 is the alkynyl-modified semiconductor material prepared in example 3.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The method for testing the degradation rate of rhodamine B in the following embodiments is as follows:
uniformly dispersing a sample into a rhodamine B solution (with the concentration of 25mg/L) according to the mass-volume ratio of 20mg:20mL under magnetic stirring, placing the solution in a dark condition for adsorption and balance for 1h, then placing the solution in a parallel light reaction instrument, carrying out photocatalytic degradation under the irradiation of a visible light source, taking 3mL of liquid every 2min, centrifuging, taking supernatant, measuring the absorbance of the supernatant, and carrying out concentration analysis; according to the Lambert beer law, under the condition that other conditions are kept consistent, the absorbance of a substance at a certain wavelength is in direct proportion to the concentration, so that the ratio of the difference value of the absorbance of rhodamine B before illumination at 553 nm minus the absorbance of rhodamine B at each time interval to the absorbance value of the rhodamine B before illumination is the degradation rate of the rhodamine B at the time interval.
The degradation rate of levofloxacin in the following examples was measured by the following method:
uniformly dispersing a sample into a levofloxacin solution (with the concentration of 25mg/L) according to the mass-volume ratio of 20mg:20mL under the magnetic stirring, placing the solution under a dark condition for adsorption and balance for 1h, then placing the solution into a parallel light reaction instrument, carrying out photocatalytic degradation under the irradiation of a visible light source, taking 3mL of liquid every 2min, centrifuging, taking a supernatant, measuring the absorbance of the supernatant and carrying out concentration analysis; according to the lambert beer law, under the condition that other conditions are consistent, the absorbance of a substance at a certain wavelength is in proportion to the concentration, so that the ratio of the difference of the absorbance of the left ofloxacin at 288 nanometers before illumination minus the absorbance of the left ofloxacin at each time interval to the absorbance value of the left ofloxacin before illumination is the degradation rate of the left ofloxacin at the time interval.
Example 1
A preparation method of an alkynyl-modified semiconductor material comprises the following specific steps:
(1) preparation of raw materials:
semiconductor material: urea was placed in a crucible and then placed in a muffle furnace at 5 ℃/min literHeating to 550 ℃ at a temperature rate, and then preserving heat for 4 hours to obtain g-C3N4A semiconductor material;
metal acetylides: calcium carbide;
(2) placing a semiconductor material and a metal acetylide in a mass ratio of 8:1 into a ball milling tank, adding absolute ethyl alcohol into the ball milling tank, enabling the absolute ethyl alcohol to submerge steel balls, carrying out ball milling under the protection of nitrogen, then sequentially carrying out centrifugation, acid washing by using a dilute nitric acid solution with the concentration of 1mol/L, deionized water washing, ethanol washing and drying (the drying temperature is 60 ℃, and the drying time is 24 hours), and obtaining the alkynyl-modified semiconductor material; wherein, the ball milling adopts steel balls with the diameter of 2mm, 5mm, 10mm and 20mm and the number ratio of 1:1:1:1, and the mass ratio of the steel balls to the semiconductor material is 2400: 1; the ball milling time is 24h, and the rotating speed is 600 r/min.
Example 2
A preparation method of an alkynyl-modified semiconductor material, which is basically the same as that in example 1, except that the mass ratio of the semiconductor material to the metal acetylide is 4: 1.
FIG. 2 is an XPS plot of the alkynyl-modified semiconductor material prepared in example 2, as shown in FIG. 2, except for the starting materials g-C3N4Sp of (A)2And sp3Besides the hybridized peak of C1s, an alkynyl peak is also shown, which indicates that the alkynyl is successfully modified at g-C3N4The above.
Fig. 3 is a raman chart of the alkynyl-modified semiconductor material prepared in example 2, and fig. 4 is an infrared spectrum chart of the alkynyl-modified semiconductor material prepared in example 2, and it can be seen from the chart that a characteristic peak belonging to a C ≡ C bond newly appears in addition to a characteristic peak of carbon nitride, which proves that the alkynyl is successfully modified on the carbon nitride.
Fig. 5 is a scanning electron microscope image and a transmission electron microscope image of the alkynyl-modified semiconductor material prepared in example 2, and it can be seen from the images that the alkynyl-modified semiconductor material prepared in example 2 is in an ultrathin nanosheet shape and has abundant hole structures and wrinkle structures, and the unique structure can endow the material with a large number of active sites, and the wrinkle structures are favorable for diffuse reflection of light on the surface of the material, and increase the utilization rate of photons.
FIG. 8 shows alkynyl-modified semiconductor material and starting materials g-C prepared in example 23N4The intensity of the peak in this figure represents the recombination rate of the photo-generated electrons and holes, and the alkynyl-modified semiconductor material (g-C) obtained in example 23N4Peak of-0.25) is significantly lower than that of the starting material g-C3N4The separation efficiency of the photogenerated electron-hole pairs generated by the alkynyl-modified semiconductor material is higher than that of the original g-C3N4。
Example 3
A preparation method of an alkynyl-modified semiconductor material, which is basically the same as that in example 1, except that the mass ratio of the semiconductor material to the metal acetylide is 2: 1.
FIG. 1 is a comparative XRD diagram of the alkynyl-modified semiconductor materials obtained in examples 1, 2 and 3, as shown by curves (a) and (d) in FIG. 1, and raw materials g to C3N4In contrast, the alkynyl-modified semiconductor material (g-C) prepared in example 13N4In-0.125) there are g-C3N4In addition to the two characteristic peaks of (a), peaks belonging to carbon appear in the XRD spectrum of the alkynyl-modified semiconductor material prepared in example 1; as shown by the curve (b) in FIG. 1, the alkynyl-modified semiconductor material (g-C) obtained in example 23N4-0.25) is stronger than the peak of example 1 belonging to carbon; as shown by the curve (C) in FIG. 1, the alkynyl-modified semiconductor material (g-C) obtained in example 33N4-0.5), which shows that when the amount of the metal acetylide is further increased, the XRD peak of carbon is gradually increased, and the content of the alkynyl in the alkynyl-modified semiconductor is related to the amount of the metal acetylide.
FIG. 6 shows alkynyl-modified semiconductor materials and starting materials g-C obtained in examples 1, 2 and 33N4As can be seen from the ultraviolet diffuse reflection absorption spectrum of (g-C), the alkynyl-modified semiconductor material (g-C) obtained in example 13N4-0.125) has an absorption band edge of 465nm, and the alkynyl-modified semiconductor material (g-C) prepared in example 23N4-0.25) absorption band of 478nm, and the alkynyl-modified semiconductor (g-C) obtained in example 33N4-0.5) has an absorption band edge of 487nm, and the starting materials g-C3N4The absorption band edge of (2) is 452nm, and obviously, after alkynyl modification, the range of a sample to visible light is enhanced, which shows that the utilization rate of the alkynyl-modified semiconductor materials prepared in examples 1, 2 and 3 to visible light is improved, the improvement of the utilization rate of the alkynyl-modified semiconductor to visible light is related to the content of alkynyl, and in a preferred range, the higher the content of alkynyl is, the larger the reaction range of the alkynyl-modified semiconductor to visible light is.
FIG. 7 shows alkynyl-modified semiconductor materials and starting materials g-C prepared in examples 1, 2 and 33N4An optical bandgap diagram of (a); from the figure, the starting materials g-C can be seen3N4The band gap of the alkynyl-modified semiconductor material prepared in examples 1, 2 and 3 is reduced to 2.72eV, 2.65eV and 2.60eV, respectively, compared with the raw material carbon nitride, the band gap of the alkynyl-modified semiconductor material is obviously smaller than that of the raw material, the narrow band gap is easier to excite and generate photo-generated electron-hole pairs, and the visible light response is widened.
FIG. 9 shows alkynyl-modified semiconductor materials prepared in examples 1, 2 and 3 and starting materials g to C3N4The degradation performance diagram of rhodamine B under visible light can be seen, and the removal rate of the alkynyl-modified semiconductor materials prepared in examples 1, 2 and 3 is higher than that of the raw material g-C prepared in examples 1 to 3 within 12min of visible light irradiation3N4. Irradiating with visible light for 12min to obtain g-C3N4Alkynyl-modified semiconductor Material (g-C) prepared in example 13N4-0.125), alkynyl modified semiconductor material (g-C) prepared in example 23N4-0.25) alkynyl-modified semiconductor material (g-C) prepared in example 33N4-0.5) has a degradation rate of 48.5%, 75.1%, 93.7% and 70.9%, respectively. Therefore, when g-C3N4When the proportion of the alkynyl-modified semiconductor material to calcium carbide is 4:1, the prepared alkynyl-modified semiconductor material has the optimal effect of removing pollutants and is a raw material g-C3N41.9 times of the sample.
FIG. 10 shows alkynyl-modified semiconductor materials prepared in examples 1, 2 and 3 and starting materials g to C3N4Degradation performance diagram of levofloxacin under visible light, and as can be seen from the diagram, after the visible light is irradiated for 18min, the alkynyl-modified semiconductor material (g-C) prepared in example 13N4-0.125), alkynyl modified semiconductor material (g-C) prepared in example 23N4-0.25) alkynyl-modified semiconductor material (g-C) prepared in example 33N40.5) the efficiency of removing pollutants is higher than that of raw materials g-C3N4And when g-C3N4When the proportion of the alkynyl-modified semiconductor material to calcium carbide is 4:1, the prepared alkynyl-modified semiconductor material has the optimal effect of removing pollutants, and the removal rate is as high as 80.2%. By alkynylation, g-C3N4The performance of photocatalytic degradation of levofloxacin is improved by 1.52 times.
From the results, the semiconductor material modified by alkynyl can be successfully prepared by taking the semiconductor material and the metal acetylide as raw materials and utilizing a ball milling method, the semiconductor material modified by alkynyl has a wrinkled transparent structure, so that multiple light scattering occurs between nanosheets, the utilization rate of captured photons is further improved, more photogenerated carriers are generated, and the alkynyl-rich group have electron-withdrawing characteristics and can be used as an electron current collector to accept electrons, so that the separation of photogenerated electrons and holes is promoted. In addition, in g-C3N4The abundant alkynyl group grafted on can be beneficial to the formation of a longer pi conjugated system, which solves the problem of g-C3N4The inherent defect of the recombination of the medium and fast photo-generated electron-hole pairs realizes effective charge transfer and separation. Therefore, the obtained sample shows better performance of photocatalytic degradation of pollutants, which has important significance and practical value for researching the modification of semiconductor materials and the improvement of photocatalytic performance.
Example 4
A preparation method of an alkynyl-modified semiconductor material comprises the following specific steps:
(1) preparation of raw materials:
semiconductor material: placing melamine in a crucible and thenPlacing the mixture in a muffle furnace, heating the mixture to 650 ℃ at a heating rate of 10 ℃/min, and then preserving the heat for 2h to obtain g-C3N4A semiconductor material;
metal acetylides: sodium carbide;
(2) placing a semiconductor material and a metal acetylide in a mass ratio of 7:1 into a ball milling tank, adding absolute ethyl alcohol into the ball milling tank, enabling the absolute ethyl alcohol to submerge steel balls, carrying out ball milling under the protection of nitrogen, then sequentially carrying out centrifugation, acid washing by using a dilute nitric acid solution with the concentration of 0.1mol/L, deionized water washing, ethanol washing and drying (the drying temperature is 70 ℃, and the drying time is 24 hours), and obtaining the alkynyl-modified semiconductor material; wherein, the ball milling adopts steel balls with the diameter of 2mm, 5mm, 10mm and 20mm and the number ratio of 1:1:1:1, and the mass ratio of the steel balls to the semiconductor material is 600: 1; the ball milling time is 20h, and the rotating speed is 400 r/min.
The prepared alkynyl-modified semiconductor material is used for degrading rhodamine B, and the degradation rate of the rhodamine B is 92.6% after the rhodamine B is irradiated for 12min by visible light; the prepared alkynyl-modified semiconductor material is used for degrading levofloxacin, and the degradation rate of levofloxacin is 86.2% after the levofloxacin is irradiated for 18min by visible light.
Example 5
A preparation method of an alkynyl-modified semiconductor material comprises the following specific steps:
(1) preparation of raw materials:
semiconductor material: placing dicyandiamide in a crucible, placing the crucible in a muffle furnace, heating the crucible to 450 ℃ at a heating rate of 7 ℃/min, and then preserving heat for 6 hours to obtain g-C3N4A semiconductor material;
metal acetylides: potassium carbide;
(2) placing a semiconductor material and a metal acetylide in a mass ratio of 6:1 into a ball milling tank, adding absolute ethyl alcohol into the ball milling tank, enabling the absolute ethyl alcohol to submerge steel balls, carrying out ball milling under the protection of nitrogen, then sequentially carrying out centrifugation, acid washing by using a dilute nitric acid solution with the concentration of 0.2mol/L, deionized water washing, ethanol washing and drying (the drying temperature is 80 ℃, and the drying time is 24 hours), and obtaining the alkynyl-modified semiconductor material; wherein, the ball milling adopts steel balls with the diameter of 2mm, 5mm, 10mm and 20mm and the number ratio of 1:1:1:1, and the mass ratio of the steel balls to the semiconductor material is 800: 1; the ball milling time is 18h, and the rotating speed is 500 r/min.
The prepared alkynyl-modified semiconductor material is used for degrading rhodamine B, and the degradation rate of the rhodamine B is 91.8% after the rhodamine B is irradiated for 12min by visible light; the prepared alkynyl-modified semiconductor material is used for degrading levofloxacin, and the degradation rate of levofloxacin is 86.4% after the levofloxacin is irradiated for 18min by visible light.
Example 6
A preparation method of an alkynyl-modified semiconductor material comprises the following specific steps:
(1) preparation of raw materials:
semiconductor material: putting thiourea in a crucible, then putting the crucible in a muffle furnace, heating the mixture to 500 ℃ at a heating rate of 8 ℃/min, and then preserving the heat for 5 hours to obtain g-C3N4A semiconductor material;
metal acetylides: lithium carbide;
(2) placing a semiconductor material and a metal acetylide in a mass ratio of 4:1 into a ball milling tank, adding absolute ethyl alcohol into the ball milling tank, enabling the absolute ethyl alcohol to submerge steel balls, carrying out ball milling under the protection of nitrogen, then sequentially carrying out centrifugation, acid washing by using a dilute sulfuric acid solution with the concentration of 0.5mol/L, deionized water washing, ethanol washing and drying (the drying temperature is 65 ℃, and the drying time is 24 hours), and obtaining the alkynyl-modified semiconductor material; wherein, the ball milling adopts steel balls with the diameter of 2mm, 5mm, 10mm and 20mm and the number ratio of 1:1:1:1, and the mass ratio of the steel balls to the semiconductor material is 1000: 1; the ball milling time is 16h, and the rotating speed is 600 r/min.
The prepared alkynyl-modified semiconductor material is used for degrading rhodamine B, and the degradation rate of the rhodamine B is 95.7% after the rhodamine B is irradiated for 12min by visible light; the prepared alkynyl-modified semiconductor material is used for degrading levofloxacin, and the degradation rate of levofloxacin is 88.1% after the levofloxacin is irradiated for 18min by visible light.
Example 7
A preparation method of an alkynyl-modified semiconductor material comprises the following specific steps:
(1) preparation of raw materials:
semiconductor material: TiO 22；
Metal acetylides: magnesium carbide;
(2) placing a semiconductor material and a metal acetylide in a mass ratio of 4:1 into a ball milling tank, adding absolute ethyl alcohol into the ball milling tank, enabling the absolute ethyl alcohol to submerge steel balls, carrying out ball milling under the protection of argon, then sequentially carrying out centrifugation, acid washing by using a dilute sulfuric acid solution with the concentration of 1.5mol/L, deionized water washing, ethanol washing and drying (the drying temperature is 75 ℃, and the drying time is 24 hours), and obtaining the alkynyl-modified semiconductor material; wherein, the ball milling adopts steel balls with the diameter of 2mm, 5mm, 10mm and 20mm and the number ratio of 1:1:1:1, and the mass ratio of the steel balls to the semiconductor material is 1500: 1; the ball milling time is 14h, and the rotating speed is 650 r/min.
The prepared alkynyl-modified semiconductor material is used for degrading rhodamine B, and the degradation rate of the rhodamine B is 89.7% after 12min of visible light irradiation; the prepared alkynyl-modified semiconductor material is used for degrading levofloxacin, and the degradation rate of levofloxacin is 81.5% after the levofloxacin is irradiated for 18min by visible light.
Example 8
A preparation method of an alkynyl-modified semiconductor material comprises the following specific steps:
(1) preparation of raw materials:
semiconductor material: poly-3-hexylthiophene;
metal acetylides: calcium carbide;
(2) placing a semiconductor material and a metal acetylide in a mass ratio of 2:1 into a ball milling tank, adding absolute ethyl alcohol into the ball milling tank, enabling the absolute ethyl alcohol to submerge steel balls, carrying out ball milling under the protection of argon, then sequentially carrying out centrifugation, acid washing by using a dilute sulfuric acid solution with the concentration of 2.5mol/L, deionized water washing, ethanol washing and drying (the drying temperature is 77 ℃, and the drying time is 24 hours), and obtaining the alkynyl-modified semiconductor material; wherein, the ball milling adopts steel balls with the diameter of 2mm, 5mm, 10mm and 20mm and the number ratio of 1:1:1:1, and the mass ratio of the steel balls to the semiconductor material is 1700: 1; the ball milling time is 12h, and the rotating speed is 700 r/min.
The prepared alkynyl-modified semiconductor material is used for degrading rhodamine B, and the degradation rate of the rhodamine B is 92.6% after the rhodamine B is irradiated for 12min by visible light; the prepared alkynyl-modified semiconductor material is used for degrading levofloxacin, and the degradation rate of levofloxacin is 83.5% after the levofloxacin is irradiated for 18min by visible light.
Claims (10)
1. A preparation method of an alkynyl-modified semiconductor material is characterized by placing the semiconductor material and a metal acetylide in a ball milling tank, adding a solvent which does not react with the semiconductor material and the metal acetylide into the ball milling tank, enabling the solvent to submerge a steel ball, carrying out ball milling under the protection of nitrogen or inert gas, and carrying out post-treatment to obtain the alkynyl-modified semiconductor material.
2. The method for preparing an alkynyl-modified semiconductor material according to claim 1, wherein the mass ratio of the semiconductor material to the metal acetylide is 8:1 to 2: 1.
3. The method for preparing an alkynyl-modified semiconductor material according to claim 2, wherein the mass ratio of the semiconductor material to the metal acetylide is 4: 1.
4. The method for preparing an alkynyl-modified semiconductor material according to claim 1, wherein the semiconductor material is g-C3N4、TiO2Poly-3-hexylthiophene, covalent triazine frameworks or organometallic frameworks; g-C3N4The preparation process of the semiconductor material comprises the following steps: placing the nitrogen-rich precursor in a muffle furnace, heating to 450-650 ℃ at a heating rate of 5-10 ℃/min, and then preserving heat for 2-6 h to obtain g-C3N4The nitrogen-rich precursor of the semiconductor material is urea, melamine, dicyandiamide or thiourea.
5. The method according to claim 1, wherein the metal acetylide is an alkali metal acetylide or an alkaline earth metal acetylide.
6. The method for preparing an alkynyl-modified semiconductor material according to claim 5, wherein the alkali metal acetylide is lithium carbide, sodium carbide or potassium carbide; the alkaline earth metal acetylide is calcium carbide or magnesium carbide.
7. The preparation method of the alkynyl-modified semiconductor material as claimed in claim 1, wherein the ball milling is performed by using steel balls with diameters of 2mm, 5mm, 10mm and 20mm in a quantity ratio of 1:1:1:1, and the mass ratio of the steel balls to the semiconductor material is 2400: 1-600: 1; the ball milling time is 12-24 h, and the rotating speed is 400-700 r/min.
8. The method for preparing an alkynyl-modified semiconductor material according to claim 1, wherein the post-treatment comprises sequentially performing centrifugation, acid washing, deionized water washing, ethanol washing, and drying.
9. The method for preparing an alkynyl-modified semiconductor material according to claim 8, wherein dilute nitric acid or dilute sulfuric acid solution with a concentration of 0.1-2.5 mol/L is used for pickling; the drying temperature is 60-80 ℃.
10. Use of an alkynyl modified semiconductor material prepared by a method of preparing an alkynyl modified semiconductor material according to any of claims 1 to 9 for the degradation of organic dyes or antibiotics.
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