CN113101957A - Preparation method of three-phase composite photocatalytic material - Google Patents

Preparation method of three-phase composite photocatalytic material Download PDF

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CN113101957A
CN113101957A CN202110231935.0A CN202110231935A CN113101957A CN 113101957 A CN113101957 A CN 113101957A CN 202110231935 A CN202110231935 A CN 202110231935A CN 113101957 A CN113101957 A CN 113101957A
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sntcpp
tio
phase composite
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photocatalytic material
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何仰清
马占营
杨谦
曹凯
姚秉华
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Xian University of Technology
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    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts

Abstract

The invention discloses a preparation method of a three-phase composite photocatalytic material, which comprises the following steps: step 1: mixing melamine and thioureaPreparation of g-C by high temperature calcination3N4(ii) a Step 2: synthesizing SnTCPP by using carboxybenzaldehyde, pyrrole and anhydrous tin chloride as raw materials; and step 3: hydrothermal preparation of TiO2/g‑C3N4A two-phase composite material; and 4, step 4: by carboxyl groups of SnTCPP with g-C3N4The amino group is condensed to prepare the three-phase composite photocatalyst SnTCPP/TiO2/g‑C3N4. The preparation process has low requirement on equipment, mild reaction conditions and simple and easily realized synthesis process; the prepared three-phase composite photocatalytic material has high visible light capturing capacity, electron and hole separation and good transmission effect, has higher photocatalytic degradation performance under the condition of visible light irradiation, and provides a reliable reference basis for preparing other multi-phase photocatalytic materials.

Description

Preparation method of three-phase composite photocatalytic material
Technical Field
The invention belongs to the field of photocatalytic materials, and particularly relates to a preparation method of a three-phase composite photocatalytic material.
Background
With the rapid growth of economy and the rapid development of industrialization, environmental pollution becomes a great problem to be solved at present. Among these contaminants, water contamination is the most serious. The water pollution is mainly from domestic sewage, industrial wastewater, medicine, chemical industry, agriculture and other aspects. These waste waters contain various organic or inorganic substances, and the long-term accumulation thereof results in increasingly poor water quality. The traditional sewage treatment methods mainly comprise a precipitation method, an adsorption method, a microbiological method and the like. Although the method has high purification efficiency, the used chemical reagents can change phases to pollute the environment. Adsorption also simply converts the contaminant from one phase to another and does not achieve complete degradation. Among all the methods, the method for treating sewage by using microorganisms has the highest degradation rate and causes less environmental impact, and the degradation rate of organic pollutants can reach 90 percent[. However, for some non-degradable contaminants, prolonged use can render the microorganisms biologically inert. Many catalysts have been developed to accelerate the degradation rate of pollutants, and titanium dioxide and carbon nitride are the most interesting catalysts, but these two catalyst monomers have poor catalytic effect in the visible light region. Various sensitivities have been presentedThe porphyrin sensitization is one of the main groups, and the properties of the monomer catalyst are changed by utilizing the sensitization of the porphyrin, so that the aim of improving the photocatalytic activity is fulfilled. Two catalysts of metalloporphyrin-titanium dioxide, titanium dioxide-carbon nitride and metalloporphyrin-carbon nitride have been made, but the modification effect of the combination of the three products has not been tried.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a composite photocatalytic material which has simple preparation process, high visible light response performance and high photocatalytic capacity.
In order to solve the technical problems, the invention adopts the technical scheme that:
a preparation method of a three-phase composite photocatalytic material specifically comprises the following steps:
step 1, adding C3H3N6And CH4N2Preparation of g-C from S mixture by high temperature calcination3N4；
Step 2, preparing SnTCPP by using carboxybenzaldehyde, pyrrole and anhydrous stannic chloride as raw materials;
step 3, preparing the two-phase composite material SnTCPP-TiO by a hydrothermal method2；
Step 4, using C3N4The amino group reacts with the carboxyl group on SnTCPP, and g-C prepared in the step 1 is reacted3N4SnTCPP-TiO prepared in step 32Combining to prepare three composite photocatalysts SnTCPP/TiO2/g-C3N4。
Further, g to C in step 13N4The preparation method specifically comprises the following steps:
step 1.1, weighing an appropriate amount of C3H3N6And CH4N2S, uniformly mixing in a mortar;
step 1.2, placing the mixture obtained in the step 1.1 in a semi-closed alumina crucible, covering the crucible, placing the crucible in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, firing for 4 hours, and cooling to room temperature to obtain a light yellow powder solidDrying and grinding to obtain g-C3N4。
Further, C3H3N6And CH4N2The weight ratio of S is 5: 1-8: 1.
Further, the preparation method of SnTCPP in step 2 specifically comprises:
step 2.1, weighing 2.16g of 4-formylbenzoic acid, adding the 4-formylbenzoic acid into a three-necked flask, pouring 150mL of propionic acid, heating the mixture to 135 ℃ in an oil bath, slowly dropwise adding 1mL of mixed solution of pyrrole and 20mL of propionic acid for 60min, and refluxing for 2h at 140 ℃ after dropwise adding is finished;
step 2.2, cooling the reaction product obtained in the step 2.1 to room temperature, adding 50mL of ethanol, placing the mixture into a refrigerator for 12h for crystallization, removing reaction liquid by suction filtration, washing the reaction liquid with propionic acid for three times, washing the reaction liquid with deionized water and acetone for three times respectively, and drying and recovering to obtain TCPP;
step 2.3, weighing 1.0g of TCPP and SnCl obtained in step 2.22.6H2Dissolving O2.5 g in 100ml of DMF, refluxing for 1h in a 250ml round-bottom flask at 120 ℃, cooling to room temperature, performing suction filtration to remove reaction liquid, and washing the rest solid with DMF and deionized water for three times respectively;
and 2.4, drying the product obtained in the step 2.3 in a constant-temperature reaction drying oven at the temperature of 80 ℃ to obtain black solid SnTCPP.
Further, the step 3 of preparing the two-phase composite material SnTCPP-TiO2The method specifically comprises the following steps:
step 3.1, 20mg of SnTCPP was dissolved in 100mL of ethanol, followed by 2.0mg of TiO2Adding the solution into SnTCPP solution, performing ultrasonic dispersion for 30min, and transferring the dispersion solution into a three-neck flask;
step 3.2, refluxing the reaction mixture obtained in step 3.1 at 80 ℃ in an oil bath for 120min with stirring, then removing the solvent under vacuum, drying the solid residue to obtain SnTCPP-TiO2。
Further, the SnTCPP and TiO2The mass ratio of (A) to (B) is 10: 1.
Further, the step 4 utilizes C3N4The amino group on the SnTCPP reacts with the carboxyl group on the SnTCPP, C3N4With SnTCPP-TiO2Combining to prepare the three composite photocatalysts SnTCPP-TiO2-g-C3N4The method specifically comprises the following steps:
step 4.1: SnTCPP-TiO is weighed respectively2PyBOP, DIEA, weighing SnTCPP-TiO2PyBOP and DIEA were dissolved in 35mL of anhydrous DMF and sonicated for 1.5 h;
at the same time, 20mg of g-C3N4Putting the mixture into 15mL of DMF for ultrasonic treatment for 1.5 h;
step 4.2: dispersing the two ultrasonic processed powders, mixing, stirring at 60 deg.C for 6h, and drying to obtain SnTCPP/TiO2/g-C3N4。
Further, the SnTCPP-TiO2PyBOP, DIEA in a ratio of 1:1: 2.5.
The invention has the beneficial effects that:
1. in g-C3N4As a support, TiO2And SnTCPP is taken as a sensitizer to successfully synthesize SnTCPP/TiO2/g-C3N4A composite material.
2. The preparation process has low requirement on equipment, mild reaction conditions and simple and easily realized synthesis process.
3. The three-phase composite photocatalytic material prepared by the method is g-C3N4SnTCPP and TiO2When the mass ratio of (1) to (10: 10: 1) is higher, the visible light capture capability is higher, the electron and hole separation effect is better, and the photocatalytic degradation performance is higher.
4. Provides reliable reference for preparing other heterogeneous photocatalytic materials.
Drawings
FIG. 1 shows TiO starting material used in example 12And g-C of preparation3N4，SnTCPP，SnTCPP/TiO2/g-C3N4Ultraviolet diffuse reflectance spectrum.
FIG. 2 shows SnTCPP/TiO prepared in example 12/g-C3N4Scanning electron micrograph (c).
FIG. 3 shows Ti as a raw material used in example 1O2And g-C of preparation3N4，SnTCPP，SnTCPP/TiO2/g-C3N4X-ray diffraction (XRD) pattern of (a).
FIG. 4 is g-C prepared in example 13N4，SnTCPP，SnTCPP/TiO2/g-C3N4An infrared spectrum of (1).
FIG. 5 shows the composite photocatalytic material SnTCPP/TiO prepared in example 12/g-C3N4Graph of photocatalytic efficiency for methylene blue.
Detailed Description
The following embodiments are described in detail with reference to the accompanying drawings, so that how to implement the technical features of the present invention to solve the technical problems and achieve the technical effects can be fully understood and implemented.
A preparation method of a three-phase composite photocatalytic material specifically comprises the following steps:
step 1: c is to be3H3N6And CH4N2The mixture of S is applied to a high-temperature calcination method to prepare graphite-phase carbon nitride g-C3N4The method specifically comprises the following steps:
step 1.1, weighing a proper amount of melamine C3H3N6With thiourea CH4N2S is mixed evenly in a mortar, C3H3N6And CH4N2The weight ratio of S is 5: 1-8: 1;
step 1.2, placing the mixture obtained in the step 1.1 in a semi-closed alumina crucible, covering and placing in a muffle furnace, raising the temperature to 550-600 ℃ at the heating rate of 2 ℃/min, firing for 4h, cooling to room temperature to obtain a light yellow powdery solid, drying and grinding to obtain g-C3N4。
Step 2, using carboxybenzaldehyde, pyrrole and anhydrous stannic chloride as raw materials to prepare tetracarboxyphenyl stannic porphyrin SnTCPP, which specifically comprises the following steps:
step 2.1, weighing 2.16g of 4-formylbenzoic acid, adding the 4-formylbenzoic acid into a three-necked flask, pouring 150mL of propionic acid, heating the mixture to 135 ℃ in an oil bath, slowly dropwise adding 1mL of mixed solution of pyrrole and 20mL of propionic acid for 60min, and refluxing for 2h at 140 ℃ after dropwise adding is finished;
step 2.2, cooling the reaction product obtained in the step 2.1 to room temperature, adding 50mL of ethanol, placing the mixture into a refrigerator for 12h for crystallization, removing the reaction liquid by suction filtration, washing the reaction liquid for three times by propionic acid, washing the reaction liquid for three times by deionized water and acetone respectively, and drying and recovering the washing liquid for three times to obtain tetracarboxylphenylporphyrin TCPP;
step 2.3, weigh 1.0g of Tetracarboxyphenylporphyrin (TCPP) and 2.5g of cobalt dichloride hexahydrate (SnCl)2.6H2O), dissolving in 100ml of N, N-Dimethylformamide (DMF), refluxing for 1h in a 250ml round-bottom flask at 120 ℃, cooling to room temperature, performing suction filtration to remove reaction liquid, and washing the residual solid with DMF and deionized water for three times respectively;
and 2.4, drying the product obtained in the step 2.3 in a constant-temperature reaction drying oven at the temperature of 80 ℃ to obtain black solid SnTCPP.
Step 3, preparing the two-phase composite material SnTCPP-TiO by a hydrothermal method2The method specifically comprises the following steps:
step 3.1, 20mg of SnTCPP was dissolved in 100mL of ethanol, and then 2.0mg of TiO was added2Adding into SnTCPP solution, ultrasonic dispersing for 30min, transferring into three-neck flask, and mixing with the above SnTCPP and TiO2The mass ratio of (A) to (B) is 10: 1;
step 3.2, refluxing the reaction mixture obtained in step 3.1 at 80 ℃ in an oil bath for 120min with stirring, then removing the solvent under vacuum, drying the solid residue to obtain SnTCPP-TiO2。
Step 4, reacting amino on the carbon nitride with carboxyl on the SnTCPP to react the carbon nitride with the SnTCPP-TiO2Combining to prepare the three composite photocatalysts SnTCPP-TiO2-g-C3N4The method specifically comprises the following steps:
step 4.1: according to the mol ratio SnTCPP-TiO2Benzotriazole-1-yl-oxy tripyrrolidinyl phosphorus hexafluorophosphate (PyBOP) and N, N-Diisopropylethylamine (DIEA) are weighed according to the proportion of 1:1:2.5, and the weighed SnTCPP-TiO is2PyBOP and DIEA were dissolved in 35mL of anhydrous DMF and sonicated for 1.5 h;
at the same time, 20mg of g-C3N4Sonicate in 15mL DMFTreating for 1.5 h;
step 4.2: dispersing the two ultrasonic processed powders, mixing, stirring at 60 deg.C for 6h, and drying to obtain SnTCPP/TiO2/g-C3N4。
Example 1
Step 1: c is to be3H3N6And CH4N2Preparation of g-C from S mixture by high temperature calcination3N4The method specifically comprises the following steps:
step 1.1: weighing C in a weight ratio of 5:13H3N6And CH4N2Mixing in mortar;
step 1.2: placing the mixture obtained in the step 1.1 into a semi-closed alumina crucible, covering the crucible, placing the crucible into a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, firing for 4 hours, cooling to room temperature to obtain a light yellow powdery solid, drying and grinding to obtain g-C3N4。
Step 2: the method for preparing the tetracarboxyphenyl stannum porphyrin SnTCPP by using carboxybenzaldehyde, pyrrole and anhydrous stannic chloride as raw materials comprises the following steps:
step 2.1: weighing 2.16g of 4-formylbenzoic acid, adding into a three-necked flask, pouring 150mL of propionic acid, heating to 135 ℃ in an oil bath, slowly dropwise adding mixed solution of 1mL of pyrrole and 20mL of propionic acid within 60min, and refluxing for 2h at 140 ℃ after dropwise adding;
step 2.2: cooling the reaction product obtained in the step 2.1 to room temperature, adding 50mL of ethanol, putting the mixture into a refrigerator for 12h for crystallization, removing the reaction liquid by suction filtration, washing the reaction liquid with propionic acid for three times, washing the reaction liquid with deionized water and acetone for three times respectively, and drying and recovering to obtain tetracarboxyphenylporphyrin TCPP;
step 2.3: 1.0g of TCPP and 2.5g of SnCl obtained in step 2.2 are weighed2.6H2Dissolving O in 100mL of DMF, refluxing for 1h in a 250mL round-bottom flask at 120 ℃, cooling to room temperature, performing suction filtration to remove reaction liquid, and washing the residual solid with DMF and deionized water for three times respectively;
step 2.4: and (3) putting the product obtained in the step 2.3 into a constant-temperature reaction drying oven for drying at the temperature of 80 ℃ to obtain black solid SnTCPP.
And step 3: preparation of two-phase composite material SnTCPP-TiO by hydrothermal method2The method specifically comprises the following steps:
step 3.1: 20mg of SnTCPP was dissolved in 100mL of ethanol, and then 2.0mg of TiO was added2Adding the solution into SnTCPP solution for ultrasonic dispersion for 30 minutes, and transferring the dispersion solution into a three-neck flask;
step 3.2: the reaction mixture obtained in step 3.1 is refluxed in an oil bath at 80 ℃ for 120min with stirring, then the solvent is removed under vacuum and the solid residue is dried to obtain SnTCPP-TiO2。
Step 4, reacting amino on the carbon nitride with carboxyl on the SnTCPP to react the carbon nitride with the SnTCPP-TiO2Combining to prepare three composite catalysts SnTCPP/TiO2/g-C3N4The method specifically comprises the following steps:
step 4.1: according to the mol ratio SnTCPP-TiO2Weighing the reagent according to the proportion of PyBOP to DIEA being 1:1:2.5, and weighing SnTCPP-TiO2PyBOP and DIEA were dissolved in 35mL of anhydrous DMF and sonicated for 1.5 h;
20mg of g-C3N4Putting the mixture into 15mL of DMF for ultrasonic treatment for 1.5 h;
step 4.2: dispersing the two ultrasonic processed powders, mixing, stirring at 60 deg.C for 6h, and drying to obtain SnTCPP/TiO2/g-C3N4。
FIG. 1 is TiO2，g-C3N4SnTCPP and SnTCPP/TiO2/g-C3N4Ultraviolet diffuse reflectance spectrum (UV-vis DRS). As can be seen from the figure, TiO2The absorption is only in the ultraviolet region below 400nm, and no absorption peak appears in the visible region. g-C3N4The absorption peak of (2) is also mainly concentrated in the ultraviolet region, and the absorption in the visible region is less. The SnTCPP has strong absorption peaks in ultraviolet and visible light regions. And use of TiO2And SnTCPP to g-C3N4After sensitization, g-C3N4Obvious red shift occurs from an ultraviolet region to a visible light region, and further proves that the three-phase composite photocatalyst SnTCPP/TiO prepared by the method2/g-C3N4Has stronger response performance to visible light. Therefore, the material has obviously improved photocatalytic activity in the visible light region.
FIG. 2 shows SnTCPP/TiO2/g-C3N4Scanning electron micrograph (c). As can be seen from FIG. 2, g-C3N4The material in the form of sheet porous particles is such that the rod-like or spherical particles adhered thereto are SnTCPP and TiO2. Thus, SnTCPP and TiO can be obtained from electron micrographs2Successfully loaded to g-C3N4A surface.
FIG. 3 comparison of the individual terms with the final synthesized product SnTCPP/TiO2/g-C3N4XRD pattern of (a). As can be seen from FIG. 3, in the composite material SnTCPP/TiO2/g-C3N4In the middle, obvious SnTCPP and TiO are present2Characteristic diffraction peak of (1). In addition, g-C3N4The characteristic diffraction peak of the compound has no obvious change, and further shows that SnTCPP and TiO2Without changing its crystal form.
FIG. 4 shows g-C prepared in example 13N4SnTCPP and composite material SnTCPP/TiO2/g-C3N4An infrared spectrum of (1). As can be seen from FIG. 4, in the composite material SnTCPP/TiO2/g-C3N4In the infrared spectrum of (1), 3159-3281 cm-1The broad peak of (A) can be attributed to g-C3N4Medium N-H telescopic vibration, 1637cm-1Is due to the stretching vibration of C ═ O bond, 1243cm-1,1320cm-1,1403cm-1The peak at (A) is due to aromatic C-N stretching vibration, 807cm-1The peak at (A) is a characteristic peak of a typical s-triazine ring. In addition, the signal is 889cm-1Is the stretching vibration of Sn-N in SnTCPP. Therefore, the three-phase composite material SnTCPP/TiO synthesized by the method2/g-C3N4In the middle, g-C is apparently contained3N4And the characteristic peak of SnTCPP, further proves the successful synthesis of the composite material.
FIG. 5 shows a three-phase composite SnTCPP/TiO synthesized by the method prepared in example 12/g-C3N4Under the irradiation condition of visible light, the ultraviolet absorption spectrum of methylene blue of the organic dye changes. As can be seen from FIG. 5, SnTCPP/TiO2/g-C3N4Has better adsorption effect on methylene blue. Meanwhile, the degradation rate of the photocatalyst on methylene can reach 97.80% within 100min, the photocatalyst is an excellent photocatalyst, and the photocatalyst has good capability of removing organic dyes in a water environment.
Example 2
Step 1: preparation of g-C3N4The method specifically comprises the following steps:
step 1.1: weighing C in a weight ratio of 6:13H3N6And CH4N2Mixing in mortar;
step 1.2: placing the mixture obtained in the step 1.1 into a semi-closed alumina crucible, covering the crucible, placing the crucible into a muffle furnace, heating to 600 ℃ at a heating rate of 2 ℃/min, firing for 4 hours, cooling to room temperature to obtain a light yellow powdery solid, drying and grinding to obtain g-C3N4。
Step 2: preparing tetra-carboxyl phenyl stannin SnTCPP, which comprises the following steps:
step 2.1: weighing 2.16g of 4-formylbenzoic acid, adding into a three-necked flask, pouring 150mL of propionic acid, heating to 135 ℃ in an oil bath, slowly dropwise adding mixed solution of 1mL of pyrrole and 20mL of propionic acid within 60min, and refluxing for 2h at 140 ℃ after dropwise adding;
step 2.2: cooling the reaction product obtained in the step 2.1 to room temperature, adding 50mL of ethanol, putting the mixture into a refrigerator for 12h for crystallization, removing the reaction liquid by suction filtration, washing the reaction liquid with propionic acid for three times, washing the reaction liquid with deionized water and acetone for three times respectively, and drying and recovering to obtain tetracarboxyphenylporphyrin TCPP;
step 2.3: 1.0g of TCPP and 2.5g of SnCl obtained in step 2.2 are weighed2.6H2Dissolving O in 100mL of DMF, refluxing for 1h in a 250mL round-bottom flask at 120 ℃, cooling to room temperature, performing suction filtration to remove reaction liquid, and washing the residual solid with DMF and deionized water for three times respectively;
step 2.4: and (3) putting the product obtained in the step 2.3 into a constant-temperature reaction drying oven for drying at the temperature of 80 ℃ to obtain black solid SnTCPP.
And step 3: preparation of two-phase composite SnTCPP-TiO2The method specifically comprises the following steps:
step 3.1: 20mg of SnTCPP was dissolved in 100mL of ethanol, and then 2.0mg of TiO was added2Adding the solution into SnTCPP solution for ultrasonic dispersion for 30 minutes, and transferring the dispersion solution into a three-neck flask;
step 3.2: the reaction mixture obtained in step 3.1 is refluxed in an oil bath at 80 ℃ for 120min with stirring, then the solvent is removed under vacuum and the solid residue is dried to obtain SnTCPP-TiO2。
Step 4, reacting amino on the carbon nitride with carboxyl on the SnTCPP to react the carbon nitride with the SnTCPP-TiO2Combining to prepare three composite catalysts SnTCPP/TiO2/g-C3N4The method specifically comprises the following steps:
step 4.1: according to the mol ratio SnTCPP-TiO2Benzotriazole-1-yl-oxy tripyrrolidinyl phosphorus hexafluorophosphate (PyBOP) and N, N-Diisopropylethylamine (DIEA) are weighed according to the proportion of 1:1:2.5, and the weighed SnTCPP-TiO is2PyBOP and DIEA were dissolved in 35mL of anhydrous DMF and sonicated for 1.5 h;
20mg of g-C3N4Putting the mixture into 15mL of DMF for ultrasonic treatment for 1.5 h;
step 4.2: dispersing the two ultrasonic processed powders, mixing, stirring at 60 deg.C for 6h, and drying to obtain SnTCPP/TiO2/g-C3N4。
Example 3
Step 1: c is to be3H3N6And CH4N2Preparation of g-C from S mixture by high temperature calcination3N4The method specifically comprises the following steps:
step 1.1: weighing C in a weight ratio of 8:13H3N6And CH4N2Mixing in mortar;
step 1.2: placing the mixture obtained in the step 1.1 into a semi-closed alumina crucible, covering the crucible, placing the crucible into a muffle furnace, heating to 580 ℃ at a heating rate of 2 ℃/min, firing for 4 hours, and cooling to room temperature to obtain the pale yellow powderThe solid in the form of a powder is dried and ground to give g-C3N4。
Step 2: the method for preparing the tetracarboxyphenyl stannum porphyrin SnTCPP by using carboxybenzaldehyde, pyrrole and anhydrous stannic chloride as raw materials comprises the following steps:
step 2.1: weighing 2.16g of 4-formylbenzoic acid, adding into a three-necked flask, pouring 150mL of propionic acid, heating to 135 ℃ in an oil bath, slowly dropwise adding mixed solution of 1mL of pyrrole and 20mL of propionic acid within 60min, and refluxing for 2h at 140 ℃ after dropwise adding;
step 2.2: cooling the reaction product obtained in the step 2.1 to room temperature, adding 50mL of ethanol, putting the mixture into a refrigerator for 12h for crystallization, removing the reaction liquid by suction filtration, washing the reaction liquid with propionic acid for three times, washing the reaction liquid with deionized water and acetone for three times respectively, and drying and recovering to obtain tetracarboxyphenylporphyrin TCPP;
step 2.3: 1.0g of the tetracarboxyphenylporphyrin TCPP obtained in step 2.2 and 2.5g of SnCl, cobalt dichloride hexahydrate2.6H2Dissolving O in 100mL of DMF, refluxing for 1h in a 250mL round-bottom flask at 120 ℃, cooling to room temperature, performing suction filtration to remove reaction liquid, and washing the residual solid with DMF and deionized water for three times respectively;
step 2.4: and (3) putting the product obtained in the step 2.3 into a constant-temperature reaction drying oven for drying at the temperature of 80 ℃ to obtain black solid SnTCPP.
And step 3: preparation of two-phase composite material SnTCPP-TiO by hydrothermal method2The method specifically comprises the following steps:
step 3.1: 20mg of SnTCPP was dissolved in 100mL of ethanol, and then 2.0mg of TiO was added2Adding the solution into SnTCPP solution for ultrasonic dispersion for 30 minutes, and transferring the dispersion solution into a three-neck flask;
step 3.2: the reaction mixture obtained in step 3.1 was refluxed at 80 ℃ for 120min in an oil bath with stirring, and then the solvent was removed under vacuum. Drying the solid residue to obtain SnTCPP-TiO2。
Step 4, reacting amino on the carbon nitride with carboxyl on the SnTCPP to react the carbon nitride with the SnTCPP-TiO2Combining to prepare three composite catalysts SnTCPP/TiO2/g-C3N4The method specifically comprises the following steps:
step 4.1: according to the mol ratio SnTCPP-TiO2Benzotriazole-1-yl-oxy tripyrrolidinyl phosphorus hexafluorophosphate (PyBOP) and N, N-Diisopropylethylamine (DIEA) are weighed according to the proportion of 1:1:2.5, and the weighed SnTCPP-TiO is2PyBOP and DIEA were dissolved in 35mL of anhydrous DMF and sonicated for 1.5 h;
20mg of g-C3N4Putting the mixture into 15mL of DMF for ultrasonic treatment for 1.5 h;
step 4.2: dispersing the two ultrasonic processed powders, mixing, stirring at 60 deg.C for 6h, and drying to obtain SnTCPP/TiO2/g-C3N4。
The above-mentioned embodiments only express the specific embodiments of the present invention, and the description thereof is specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (8)

1. The preparation method of the three-phase composite photocatalytic material is characterized by comprising the following steps:
step 1, adding C3H3N6And CH4N2Preparation of g-C from S mixture by high temperature calcination3N4；
Step 2, preparing SnTCPP by using carboxybenzaldehyde, pyrrole and anhydrous stannic chloride as raw materials;
step 3, preparing the two-phase composite material SnTCPP-TiO by a hydrothermal method2；
Step 4, using C3N4The amino group reacts with the carboxyl group on SnTCPP, and g-C prepared in the step 1 is reacted3N4SnTCPP-TiO prepared in step 32Combining to prepare three composite photocatalysts SnTCPP/TiO2/g-C3N4。
2. Root of herbaceous plantThe method for preparing the three-phase composite photocatalytic material as recited in claim 1, wherein g-C in step 13N4The preparation method specifically comprises the following steps:
step 1.1, weighing an appropriate amount of C3H3N6And CH4N2S, uniformly mixing in a mortar;
step 1.2, placing the mixture obtained in the step 1.1 in a semi-closed alumina crucible, covering the crucible, placing the crucible in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, firing for 4 hours, cooling to room temperature to obtain a light yellow powdery solid, drying and grinding to obtain g-C3N4。
3. The method for preparing the three-phase composite photocatalytic material as recited in claim 2, wherein C is3H3N6And CH4N2The weight ratio of S is 5: 1-8: 1.
4. The preparation method of the three-phase composite photocatalytic material according to claim 1, wherein the preparation method of SnTCPP in step 2 specifically comprises the following steps:
step 2.1, weighing 2.16g of 4-formylbenzoic acid, adding the 4-formylbenzoic acid into a three-necked flask, pouring 150mL of propionic acid, heating the mixture to 135 ℃ in an oil bath, slowly dropwise adding 1mL of mixed solution of pyrrole and 20mL of propionic acid for 60min, and refluxing for 2h at 140 ℃ after dropwise adding is finished;
step 2.2, cooling the reaction product obtained in the step 2.1 to room temperature, adding 50mL of ethanol, placing the mixture into a refrigerator for 12h for crystallization, removing reaction liquid by suction filtration, washing the reaction liquid with propionic acid for three times, washing the reaction liquid with deionized water and acetone for three times respectively, and drying and recovering to obtain TCPP;
step 2.3, weighing 1.0g of TCPP and SnCl obtained in step 2.22.6H2Dissolving O2.5 g in 100ml of DMF, refluxing for 1h in a 250ml round-bottom flask at 120 ℃, cooling to room temperature, performing suction filtration to remove reaction liquid, and washing the rest solid with DMF and deionized water for three times respectively;
and 2.4, drying the product obtained in the step 2.3 in a constant-temperature reaction drying oven at the temperature of 80 ℃ to obtain black solid SnTCPP.
5. The method for preparing the three-phase composite photocatalytic material according to claim 1, wherein the two-phase composite material SnTCPP-TiO prepared in the step 3 is SnTCPP-TiO2The method specifically comprises the following steps:
step 3.1, 20mg of SnTCPP was dissolved in 100mL of ethanol, followed by 2.0mg of TiO2Adding the solution into SnTCPP solution, performing ultrasonic dispersion for 30min, and transferring the dispersion solution into a three-neck flask;
step 3.2, refluxing the reaction mixture obtained in step 3.1 at 80 ℃ in an oil bath for 120min with stirring, then removing the solvent under vacuum, drying the solid residue to obtain SnTCPP-TiO2。
6. The method for preparing the three-phase composite photocatalytic material according to claim 5, wherein the SnTCPP and the TiO are2The mass ratio of (A) to (B) is 10: 1.
7. The method for preparing the three-phase composite photocatalytic material according to claim 1, wherein the step 4 utilizes C3N4The amino group on the SnTCPP reacts with the carboxyl group on the SnTCPP, C3N4With SnTCPP-TiO2Combining to prepare the three composite photocatalysts SnTCPP-TiO2-g-C3N4The method specifically comprises the following steps:
step 4.1: SnTCPP-TiO is weighed respectively2PyBOP, DIEA, weighing SnTCPP-TiO2PyBOP and DIEA were dissolved in 35mL of anhydrous DMF and sonicated for 1.5 h;
at the same time, 20mg of g-C3N4Putting the mixture into 15mL of DMF for ultrasonic treatment for 1.5 h;
step 4.2: dispersing the two ultrasonic processed powders, mixing, stirring at 60 deg.C for 6h, and drying to obtain SnTCPP/TiO2/g-C3N4。
8. The method for preparing the three-phase composite photocatalytic material as recited in claim 7, wherein the three-phase composite photocatalytic material is prepared by a method comprisingSnTCPP-TiO2PyBOP, DIEA in a ratio of 1:1: 2.5.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108579820A (en) * 2018-04-09 2018-09-28 西北师范大学 A kind of copper（Ⅱ）The preparation and application of tetracarboxylic phenyl porphyrin/composite titania material
CN109482238A (en) * 2018-11-23 2019-03-19 华南理工大学 A kind of titanous-titanium dioxide-porphyrin/nitridation carbon composite photocatalyst and preparation method thereof
CN110404590A (en) * 2019-08-19 2019-11-05 王世扬 A kind of Ir load g-C of organic salt dopping3N4Close TiO2Photocatalytic semiconductor material
CN111974454A (en) * 2019-05-23 2020-11-24 西安建筑科技大学 D35-TiO2/g-C3N4Dye-sensitized composite photocatalyst and preparation method and application thereof
AU2020102640A4 (en) * 2020-09-18 2020-11-26 Qilu University Of Technology PREPARATION METHOD AND APPLICATION OF g-C3N4/(101)-(001)-TiO2 COMPOSITE MATERIAL

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108579820A (en) * 2018-04-09 2018-09-28 西北师范大学 A kind of copper（Ⅱ）The preparation and application of tetracarboxylic phenyl porphyrin/composite titania material
CN109482238A (en) * 2018-11-23 2019-03-19 华南理工大学 A kind of titanous-titanium dioxide-porphyrin/nitridation carbon composite photocatalyst and preparation method thereof
CN111974454A (en) * 2019-05-23 2020-11-24 西安建筑科技大学 D35-TiO2/g-C3N4Dye-sensitized composite photocatalyst and preparation method and application thereof
CN110404590A (en) * 2019-08-19 2019-11-05 王世扬 A kind of Ir load g-C of organic salt dopping3N4Close TiO2Photocatalytic semiconductor material
AU2020102640A4 (en) * 2020-09-18 2020-11-26 Qilu University Of Technology PREPARATION METHOD AND APPLICATION OF g-C3N4/(101)-(001)-TiO2 COMPOSITE MATERIAL

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
郑锰锰: "半导体异质结光催化剂的制备及其可见光催化性能研究", 《中国优秀博硕士学位论文全文数据库》 *
霍添: "卟啉MOFs敏化TiO2催化剂的合成及其可见光催化性能研究", 《中国优秀博硕士学位论文全文数据库》 *

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