CN115487872A - Preparation method and application of composite photocatalyst with good performance - Google Patents

Preparation method and application of composite photocatalyst with good performance Download PDF

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CN115487872A
CN115487872A CN202210344281.7A CN202210344281A CN115487872A CN 115487872 A CN115487872 A CN 115487872A CN 202210344281 A CN202210344281 A CN 202210344281A CN 115487872 A CN115487872 A CN 115487872A
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composite photocatalyst
titanium dioxide
btc
graphene oxide
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CN115487872B (en
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唐波
谈伟
李森
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Changzhou University
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Abstract

The invention belongs to the technical field of photocatalysts, and particularly discloses a preparation method and application of a composite photocatalyst with good performance. According to the invention, the graphene sheet, the Cu-BTC and the titanium dioxide are selected as photocatalyst materials, the three materials are modified, and the three materials are combined through a hydrothermal method after modification to prepare the titanium dioxide-graphene-Cu-BTC composite material.

Description

Preparation method and application of composite photocatalyst with good performance
Technical Field
The invention belongs to the technical field of environmental pollution treatment, and particularly relates to a composite photocatalyst with visible light activity and application thereof in degradation of organic matters.
Background
In recent years, the protection and purification of water resources have become global issues, and the realization of human sustainable development has attracted strong attention from countries around the world. The discovery that titanium dioxide irradiated by solar light can continuously carry out oxidation-reduction reaction on water by Japanese scientists Fujishima and Honda in the early 70 th of the last century starts the research of semiconductor photocatalysis technology initiated by solar energy, and the research is one of the initial marks of heterogeneous photocatalysis research. After that, frank et al found that titanium dioxide could degrade cyanide in water by photocatalysis, and became a pioneer for purifying sewage by using photocatalyst. In subsequent studies, scientists have continued to find that titanium dioxide is effective in degrading and mineralizing a wide variety of organic pollutants including halogenated hydrocarbons, dyes, polycyclic aromatic hydrocarbons, phenols, surfactants, pesticides, and the like. To date, a great deal of research on titanium dioxide photocatalysts is carried out by scholars at home and abroad, so that the titanium dioxide photocatalyst becomes the most active research field in photocatalytic pollutant degradation, and a series of breakthrough progresses are obtained.
However, there are two current bottlenecks that prevent the widespread use of titanium dioxide. The first bottleneck is that titanium dioxide has a wide band gap such that it responds only to incident light in the ultraviolet range and is not active in visible light. Only light with a wavelength shorter than 390nm can excite electron-hole pairs in the titanium dioxide. However, the main energy in sunlight is distributed in the visible wavelength range, and the proportion of ultraviolet light only accounts for about 4% of the total energy. This inevitably results in low utilization rate of sunlight, and affects the popularization of titanium dioxide in practical use. In addition, the photo-generated electron-hole pair has a high recombination rate in titanium dioxide, and becomes a second bottleneck of the application. Because the photogenerated electrons and holes are constantly moving in titanium dioxide, only those electrons and holes that migrate to the surface of the sample and react with organic matter are significant fractions. In fact, most of the photo-generated electron-hole pairs are mutually compounded in the process of surface migration of the photo-generated electron-hole pairs, so that the utilization rate of the electron-hole pairs is low, and the photocatalysis effect of the electron-hole pairs is seriously influenced.
In order to solve the above two bottlenecks, a great deal of research is being conducted by researchers at home and abroad. Researchers adopt a method of doping other elements in titanium dioxide or hybridizing the titanium dioxide with other substances to prepare the titanium dioxide photocatalyst with visible light activity. Other metal or nonmetal elements are doped into the titanium dioxide to form a recombination center of the photo-generated electron-hole pair, so that the utilization efficiency of the photo-generated electron-hole pair is greatly reduced. Therefore, the titanium dioxide is hybridized with other materials to prepare the composite photocatalyst, which is the best method for endowing the titanium dioxide with visible light activity. The graphene has zero band gap, has semimetal characteristics and good electrical characteristics, and can be used as a photosensitizer to endow titanium dioxide with visible light activity. It is prone to curling during the bonding process, which severely affects its specific surface area and its corresponding ability to adsorb contaminants. The titanium dioxide-graphene composite material is prepared in the prior art of synthesis and performance research of titanium dioxide and graphene composite materials, and the like, wherein titanium dioxide nanoparticles wrap graphene to improve the catalyst degradation efficiency of the graphene, but the structure is not beneficial to improving the catalytic stability, and the equivalent degradation efficiency is difficult to maintain after the titanium dioxide-graphene composite material is repeatedly used. How to further improve the photocatalytic performance and catalytic stability of the titanium dioxide-graphene composite material is a technical problem to be solved by the invention.
Disclosure of Invention
The invention aims to prepare a composite photocatalyst with good performance. The composite photocatalyst is prepared from nano titanium dioxide particles, cu-BTC and graphene sheets serving as raw materials by a hydrothermal method. Graphene in the compound can realize rapid separation of photo-generated electron hole pairs, and the capability of photocatalyst in decomposing pollutants is enhanced. The Cu-BTC endows the composite photocatalyst with a larger specific surface area, improves the pollutant adsorption capacity of the composite photocatalyst, and improves the activity of the visible light photocatalyst. The graphene sheet, the Cu-BTC and the titanium dioxide are subjected to a hydrothermal method, and conditions are adjusted, so that the obtained composite material structure is beneficial to improving the stability of the catalyst, and the service life of the catalyst is long.
The composite photocatalyst is prepared from the following raw materials in parts by weight: 3-5 parts of graphene oxide sheets, 80-95 parts of nano titanium dioxide particles, 1-2 parts of Cu-BTC powder, 2-3 parts of a surfactant and 77-80 parts of water, and the titanium dioxide composite photocatalyst jointly modified by graphene-Cu-BTC is prepared by a hydrothermal method.
According to the composite photocatalyst, the graphene oxide is subjected to amino surface modification, so that main functional groups on the surface of the graphene oxide are amino and carboxyl, and the graphene oxide is oxidizedThe graphene sheet has a size of 100-200nm and a thickness of 1-3nm. Can be prepared by conventional method or purchased from Changzhou Kongting nanometer materials science and technology company (trade name is Graphene-NH) 3 -200). After the surface of the amino group of the graphene oxide is modified, the surface functional groups of the graphene oxide are the amino group and the carboxyl group, and the two groups can promote the combination of the graphene oxide nanosheet and the titanium dioxide particles, so that the closer interface contact level of the graphene oxide nanosheet and the titanium dioxide particles is realized, and the rapid transportation and the high utilization rate of photo-generated electrons are facilitated. If the size of the graphene oxide nanosheet (black) is too large, part of incident light can be absorbed, so that the performance of the composite photocatalyst is influenced, and if the size is too small, the titanium dioxide nanoparticles cannot be effectively loaded, so that the function of the photosensitizer cannot be fully exerted. The smaller the thickness, the better, the more sufficient contact with the titanium dioxide is, but the thinner the thickness, the higher the cost.
The composite photocatalyst has rutile type nanometer titania and N atom doped, where the N atom is substitutional atom in 0.1 wt% and the doped matter is 20-30nm in size. Can be prepared by conventional method or purchased from Ningxia Weitai New Material science and technology Limited (brand: tiO) 2 -N10). Rutile titanium dioxide has a larger specific surface area and higher stability than anatase and brookite crystal types, and too large a size reduces the specific surface area and is not beneficial to absorption of pollutant molecules, and too small a size results in too high cost. In addition, N atom doping is carried out in titanium dioxide, a donor level is introduced into an energy band structure, the band gap width is reduced, the titanium dioxide has higher activity on visible light, the surface chemical activity of the titanium dioxide is improved by the doped N atom, the binding capacity of the titanium dioxide with graphene oxide nanosheets and Cu-BTC is improved, and the self-clustering behavior is inhibited.
The Cu-BTC specific surface area of the composite photocatalyst is 800-1000m 2 The size is 200-300nm. And the Cu-BTC sample is activated for 24 hours in an oxidation environment, so that the surface activity of the sample is enhanced, the number of surface dangling bonds is increased, and the binding capacity of the sample with the graphene oxide nanosheets and the titanium dioxide nanoparticles is improved. The samples were purchased from Heizhou Honghui nanometer materials science and technology Inc. (under the designation Cu-BTC-B1000). The specific surface area of Cu-BTC is related to the size thereof and is 800-1000m 2 The size is moderate, and the graphene/titanium dioxide composite material can be well combined with graphene sheets and titanium dioxide particles
In the composite photocatalyst, the surfactant is sodium dodecyl benzene sulfonate or stearic acid. Purchased from Shanghai reagent works. The surfactant realizes the combination of the graphene sheet, the Cu-BTC and the nano titanium dioxide in the hydrothermal reaction process.
The temperature of the composite photocatalyst is 100-120 ℃ in the hydrothermal process, and the reaction time is 6 hours.
The composite photocatalyst is prepared by adding 3-5 parts of graphene oxide sheets into 2-3 parts of sodium dodecyl benzene sulfonate solution, and slowly adding 37-40 parts of water. And (3) carrying out ultrasonic treatment on the mixed solution for 2 hours to uniformly disperse the graphene oxide sheets in the sodium dodecyl benzene sulfonate. And then adding 80-95 parts of nano titanium dioxide into the solution, stirring for 30 minutes, slowly adding 40 parts of water, and adding 1-2 parts of Cu-BTC. The mixture was then transferred to a hydrothermal reactor having a capacity of 100 mL. Putting the reactor into a vacuum drying oven to maintain the temperature of the reactor at 100-120 DEG C ℃ Hydrothermal reaction was carried out for 6h. After hydrothermal reaction, transferring the product into a beaker, washing with water for three times, carrying out vacuum filtration on the solution, and finally obtaining a substance at 80% ℃ The obtained product is dried in a vacuum drying oven for 24 hours and then ground into powder to obtain the composite photocatalyst. Compared with the prior art, the invention has the advantages that:
(1) The method has the characteristics of simple and rapid process, simultaneously exerts the graphene to effectively promote the separation of photo-generated electrons and hole pairs, provides a large specific surface area and pollutant adsorption capacity by Cu-BTC, and is a novel composite photocatalyst with visible light activity.
(2) The specific surface area of the composite photocatalyst obtained by the invention reaches 200m 3 g -1 The specific surface area of the graphene/titanium dioxide particle composite photocatalyst is about 4 times that of the graphene/titanium dioxide particle composite photocatalyst, and the pollutant adsorption capacity is greatly improved.
(3) The composite photocatalyst prepared by the invention has high stability, and can rapidly decompose common pollutants in sewage at the temperature of 3-50 ℃.
(4) The composite photocatalyst prepared by the invention has longer service life, and the capability of degrading pollutants is not obviously changed after the composite photocatalyst is repeatedly used for 10 times.
Detailed Description
Example 1
Taking 4g of amino surface modified Graphene oxide sheet (Graphene-NH) 3 200, size 100-200nm, thickness 1-3 nm) was added to 2g of sodium dodecylbenzenesulfonate solution, followed by slow addition of 37g of water. And carrying out ultrasonic treatment on the mixed solution for 2 hours to uniformly disperse the amino surface modified graphene oxide sheets in the sodium dodecyl benzene sulfonate. Then 85g of N-doped nano titanium dioxide (doping amount 0.1%, tiO) was added to the solution 2 -N10, 20-30 nm), stirring for 30 minutes, slowly adding 40mL of water, and then adding 2g of activated Cu-BTC (Cu-BTC-B1000, specific surface area 800-1000 m) 2 And the size is 200-300 nm). The mixture was then transferred to a hydrothermal reactor having a capacity of 100 mL. The reactor was placed in a vacuum oven at 120 ℃ for 6h hydrothermal reaction. And after hydrothermal reaction, transferring the product into a beaker, washing for three times, carrying out vacuum filtration on the solution, finally drying the obtained substance in a vacuum drying oven at the temperature of 80 ℃ for 24 hours, and then grinding the substance into powder to obtain the composite photocatalyst.
Example 2
Taking 1g of amino surface modified Graphene oxide sheet (Graphene-NH) 3 -200) to a solution of 2g of sodium dodecylbenzenesulfonate, then 37g of water are slowly added. The mixed solution is subjected to ultrasonic treatment for 2 hours to ensure that the amino surface modified graphene oxide sheets are uniformly dispersed in the sodium dodecyl benzene sulfonate. Then 85g of N atom-doped nano titanium dioxide (doping amount of 0.1%, tiO) was added to the solution 2 -N10), stirring for 30 minutes, slowly adding 40mL of water, and then adding 2g of activated Cu-BTC (Cu-BTC-B1000). The mixture was then transferred to a hydrothermal reactor having a capacity of 100 mL. The reactor was placed in a vacuum oven at 120 ℃ for 6h hydrothermal reaction. After hydrothermal reaction, transferring the product into a beaker, washing with water for three times, carrying out vacuum filtration on the solution,and finally, drying the obtained substance in a vacuum drying oven at 80 ℃ for 24 hours, and then grinding the dried substance into powder to obtain the composite photocatalyst.
Example 3
Taking 7g of amino surface modified Graphene oxide sheet (Graphene-NH) 3 -200) to a solution of 2g of sodium dodecylbenzenesulfonate, then 37g of water are slowly added. The mixed solution is subjected to ultrasonic treatment for 2 hours to ensure that the graphene oxide sheets on the surface of the amino group are uniformly dispersed in the sodium dodecyl benzene sulfonate. Then 85g of N atom-doped nano titanium dioxide (doping amount of 0.1%, tiO) was added to the solution 2 -N10), stirring for 30 minutes, slowly adding 40mL of water, and then adding 2g of activated Cu-BTC (Cu-BTC-B1000). The mixture was then transferred to a hydrothermal reactor having a capacity of 100 mL. The reactor was placed in a vacuum oven at 120 ℃ for 6h hydrothermal reaction. After hydrothermal reaction, transferring the product into a beaker, washing with water for three times, carrying out vacuum filtration on the solution, finally drying the obtained substance in a vacuum drying oven at 80 ℃ for 24 hours, and then grinding the substance into powder to obtain the composite photocatalyst.
Example 4
Taking 4g of amino surface Graphene oxide sheet (Graphene-NH) 3 200) slowly add 37g of water. And carrying out ultrasonic treatment on the mixed solution for 2h to uniformly disperse the graphene oxide sheets on the surface of the amino group in water. Then 85g of N atom-doped nano titanium dioxide (doping amount of 0.1%, tiO) was added to the solution 2 -N10), stirring for 30 minutes, slowly adding 40mL of water, and then adding 2g (Cu-BTC-B1000). The mixture was then transferred to a hydrothermal reactor having a capacity of 100 mL. The reactor was placed in a vacuum oven at 120 ℃ for 6h hydrothermal reaction. After hydrothermal reaction, transferring the product into a beaker, washing the product with water for three times, carrying out vacuum filtration on the solution, and finally, putting the obtained substance into a vacuum pump for 80 minutes ℃ The obtained product is dried in a vacuum drying oven for 24 hours and then ground into powder to obtain the composite photocatalyst.
Example 5
Taking 4g of amino surface modified Graphene oxide sheet (Graphene-NH) 3 -200) to a solution of 2g of sodium dodecylbenzenesulfonate, then 37g of water are slowly added. Subjecting the mixed solution to ultrasonic treatment for 2hThe graphene oxide sheets are uniformly dispersed in the sodium dodecylbenzenesulfonate. Then 85g of N atom-doped nano titanium dioxide (doping amount of 0.1%, tiO) was added to the solution 2 -N10), stirring for 30 minutes, then slowly adding 40mL of water, and then 2g of activated Cu-BTC (Cu-BTC-B1000). The mixture was then transferred to a hydrothermal reactor having a capacity of 100 mL. The reactor was placed in a vacuum oven at 120 ℃ for 6h hydrothermal reaction. After hydrothermal reaction, transferring the product into a beaker, washing with water for three times, carrying out vacuum filtration on the solution, finally drying the obtained substance in a vacuum drying oven at 80 ℃ for 24 hours, and then grinding the substance into powder to obtain the composite photocatalyst.
Example 6
Taking 4g of amino surface modified Graphene oxide sheet (Graphene-NH) 3 -200) to a solution of 2g of sodium dodecylbenzenesulfonate, then 37g of water are slowly added. The mixed solution is subjected to ultrasonic treatment for 2 hours to uniformly disperse graphene oxide sheets in sodium dodecyl benzene sulfonate. 70g of N atom-doped nano-titanium dioxide (doping amount of 0.1%, tiO) was then added to the solution 2 -N10), stirring for 30 minutes, slowly adding 40mL of water, and then adding 2g of activated Cu-BTC (Cu-BTC-B1000). The mixture was then transferred to a hydrothermal reactor having a capacity of 100 mL. The reactor was placed in a vacuum oven at 120 ℃ for 6h hydrothermal reaction. And after hydrothermal reaction, transferring the product into a beaker, washing for three times, carrying out vacuum filtration on the solution, finally drying the obtained substance in a vacuum drying oven at the temperature of 80 ℃ for 24 hours, and then grinding the substance into powder to obtain the composite photocatalyst.
Example 7
Taking 4g of amino surface modified Graphene oxide sheet (Graphene-NH) 3 -200) to a solution of 2g of sodium dodecylbenzenesulfonate, then 37g of water are slowly added. And (3) carrying out ultrasonic treatment on the mixed solution for 2 hours to uniformly disperse the graphene oxide sheets in the sodium dodecyl benzene sulfonate. Then 110g of N atom-doped nano-titanium dioxide (doping amount of 0.1%, tiO) was added to the solution 2 -N10), stirring for 30 minutes, slowly adding 40mL of water, and then adding 2g of activated Cu-BTC (Cu-BTC-B1000). The mixture was then transferred to a hydrothermal reactor having a capacity of 100mL. The reactor was placed in a vacuum oven to maintain 120 ℃ Hydrothermal reaction was carried out for 6h. After hydrothermal reaction, transferring the product into a beaker, washing with water for three times, carrying out vacuum filtration on the solution, and finally obtaining a substance at 80% ℃ The obtained product is dried in a vacuum drying oven for 24 hours and then ground into powder to obtain the composite photocatalyst.
Example 8
Taking 4g of amino surface modified Graphene oxide sheet (Graphene-NH) 3 -200) to a solution of 2g of sodium dodecylbenzenesulfonate, then 37g of water are slowly added. The mixed solution is subjected to ultrasonic treatment for 2 hours to uniformly disperse graphene oxide sheets in sodium dodecyl benzene sulfonate. Then 85g of N-doped nano titanium dioxide (doping amount 0.1%, tiO) was added to the solution 2 -N10), stirring for 30 minutes and slowly adding 40mL of water. The mixture was then transferred to a hydrothermal reactor having a capacity of 100 mL. The reactor was placed in a vacuum oven at 120 ℃ for 6h hydrothermal reaction. After hydrothermal reaction, transferring the product into a beaker, washing with water for three times, carrying out vacuum filtration on the solution, finally drying the obtained substance in a vacuum drying oven at 80 ℃ for 24 hours, and then grinding the substance into powder to obtain the composite photocatalyst.
Example 9
Taking 4g of amino surface modified Graphene oxide sheet (Graphene-NH) 3 -200) to a solution of 2g of sodium dodecylbenzenesulfonate, then 37g of water are slowly added. And (3) carrying out ultrasonic treatment on the mixed solution for 2 hours to uniformly disperse the graphene oxide sheets in the sodium dodecyl benzene sulfonate. Then 85g of N-doped nano titanium dioxide (doping amount 0.1%, tiO) was added to the solution 2 -N10), stirring for 30 minutes, slowly adding 40mL of water, and then adding 5g of activated Cu-BTC (Cu-BTC-B1000). The mixture was then transferred to a hydrothermal reactor having a capacity of 100 mL. The reactor was placed in a vacuum oven at 120 ℃ for 6h hydrothermal reaction. After hydrothermal reaction, transferring the product into a beaker, washing with water for three times, carrying out vacuum filtration on the solution, finally drying the obtained substance in a vacuum drying oven at 80 ℃ for 24 hours, and then grinding the substance into powder to obtain the composite photocatalyst.
Example 10
Taking 4g of amino surface modified Graphene oxide sheet (Graphene-NH) 3 -200) to a solution of 2g of sodium dodecylbenzenesulfonate, then 37g of water are slowly added. The mixed solution is subjected to ultrasonic treatment for 2 hours to uniformly disperse graphene oxide sheets in sodium dodecyl benzene sulfonate. Then 85g of nano-titania was added to the solution, and after stirring for 30 minutes, 40mL of water was slowly added, followed by 2g of activated Cu-BTC (Cu-BTC-B1000). The mixture was then transferred to a hydrothermal reactor having a capacity of 100 mL. Placing the reactor into a vacuum drying oven to maintain the temperature of the reactor at 100-120 DEG C ℃ Hydrothermal reaction was carried out for 6h. After hydrothermal reaction, transferring the product into a beaker, washing with water for three times, carrying out vacuum filtration on the solution, finally drying the obtained substance in a vacuum drying oven at 80 ℃ for 24 hours, and then grinding the substance into powder to obtain the composite photocatalyst.
This example was prepared in the same amount and procedure as example 1, but using titanium dioxide which was not doped with N atoms.
Example 11
4g of graphene oxide sheets were added to 2g of sodium dodecylbenzenesulfonate solution, and then 37g of water was slowly added. And (3) carrying out ultrasonic treatment on the mixed solution for 2 hours to uniformly disperse the graphene oxide sheets in the sodium dodecyl benzene sulfonate. Then 85g of N-doped nano titanium dioxide (doping amount 0.1%, tiO) was added to the solution 2 -N10), stirring for 30 minutes, slowly adding 40mL of water, and then adding 2g of activated Cu-BTC (Cu-BTC-B1000). The mixture was then transferred to a hydrothermal reactor having a capacity of 100 mL. The reactor is put into a vacuum drying oven to keep 100-120 ℃ for 6h of hydrothermal reaction. After hydrothermal reaction, transferring the product into a beaker, washing with water for three times, carrying out vacuum filtration on the solution, finally drying the obtained substance in a vacuum drying oven at 80 ℃ for 24 hours, and then grinding the substance into powder to obtain the composite photocatalyst.
This example was carried out using the same amount and procedure as example 1, but using graphene oxide which was not surface-modified with amino groups.
Example 12
Taking 4g of amino surface modified oxidized stoneGraphene sheet (Graphene-NH) 3 -200) to a solution of 2g of sodium dodecylbenzenesulfonate, then 37g of water are slowly added. The mixed solution is subjected to ultrasonic treatment for 2 hours to uniformly disperse graphene oxide sheets in sodium dodecyl benzene sulfonate. Then 85g of N atom-doped nano titanium dioxide (doping amount of 0.1%, tiO) was added to the solution 2 -N10), stirring for 30 minutes, slowly adding 40mL of water, and then adding 2g of Cu-BTC. The mixture was then transferred to a hydrothermal reactor having a capacity of 100 mL. The reactor is put into a vacuum drying oven to keep 100-120 ℃ for 6h of hydrothermal reaction. After hydrothermal reaction, transferring the product into a beaker, washing with water for three times, carrying out vacuum filtration on the solution, finally drying the obtained substance in a vacuum drying oven at 80 ℃ for 24 hours, and then grinding the substance into powder to obtain the composite photocatalyst.
This example was carried out in the same amount and procedure as example 1, but using Cu-BTC which had not undergone the activation process.
Photocatalytic test
In order to test the degradation capability of the graphene/titanic acid nanotube composite photocatalyst prepared by the invention on various pollutants, methyl blue is selected as a simulated pollutant. The catalytic lamp used a 500W xenon lamp (Shanghai Lansheng device Co., ltd.) and a filter device. The filtering adopts self-made packaging 1mol L when the wavelength of 400nm is cut-off wavelength -1 A quartz sealed container (simulating visible light) of sodium nitrite solution. The degradation of methyl blue was used as a simulated source of contaminated water to evaluate the catalytic performance of the photocatalyst. A typical catalytic experiment is as follows: 15mg of photocatalyst was added to 50mL (10 mgL) -1 ) The solution of methyl blue is firstly sonicated for 5 minutes and then stirred in the dark for 100 minutes to reach the adsorption and desorption equilibrium. The mixed solution was then placed under a catalytic lamp, with moderate agitation during irradiation. At regular intervals, 2mL of the solution was removed, centrifuged at 5000 rpm for 10 minutes, and the supernatant was removed to test the concentration of methyl blue remaining. The concentration of methyl blue was measured by integrating the area of the peak at 553nm using an ultraviolet spectrophotometer (model UV-721, mingbo environmental protection technologies, inc., qingdao).
TABLE 1 residual concentration of methyl blue and apparent properties of samples after 20 minutes of irradiation with catalytic lamps of different samples
Figure BDA0003580452000000081
From the above photocatalytic performance and appearance of the sample, too high or too low graphene content is not good for high catalytic performance of the product, because too low graphene content cannot fully exert the function of the photosensitizer, and too high graphene content absorbs too much visible light and is used for heat generation. The surfactant must be added, otherwise, graphene and titanium dioxide are difficult to combine, titanium dioxide particles have a serious agglomeration phenomenon, and the excessive surfactant cannot continuously improve the catalytic performance of the photocatalyst. Insufficient amount of titanium dioxide cannot sufficiently exert its photocatalytic effect, and excessive amount of titanium dioxide causes serious agglomeration. The addition of Cu-BTC can avoid the agglomeration phenomenon of titanium dioxide, ensure larger specific surface area and higher photocatalytic performance, and the same excessive Cu-BTC can not continuously improve the photocatalytic performance because the main function of Cu-BTC is to provide larger specific surface area, and the material playing the catalytic action is still titanium dioxide.
In addition, as can be seen from examples 10 to 12, if the titanium oxide used is not doped with an N atom, there occurs a decrease in the photoactivity thereof because the donor ability is lost, which is active only to ultraviolet light; the specific surface area is also significantly reduced because the binding ability to graphene oxide sheets is reduced, and the agglomeration phenomenon occurs. If the graphene oxide is not subjected to surface amino modification, the photoactivity of the graphene oxide is reduced, because the binding capacity of the graphene oxide and titanium dioxide nanoparticles is reduced, uniform distribution of titanium dioxide cannot be effectively realized, the photocatalytic performance is reduced, and the specific surface area is also remarkably reduced. If the surface of the Cu-BTC is not activated, the surface of the Cu-BTC also has a certain negative influence on the photoactivity of the composite photocatalyst. Therefore, the modification of the three raw materials has important influence on the photoactivity of a sample, and the three modified raw materials have a synergistic effect, so that the photocatalytic performance of the three raw materials can be obviously improved.
The above description is only a random embodiment of the present invention, and all changes and modifications made according to the claims of the present invention should fall within the scope of the present invention.

Claims (8)

1. A preparation method of a composite photocatalyst with good performance is characterized by comprising the following steps: the composite photocatalyst is prepared from the following raw materials in parts by weight: 3-5 parts of graphene oxide sheets, 80-95 parts of nano titanium dioxide particles, 1-2 parts of Cu-BTC powder, 2-3 parts of surfactant and 77-80 parts of water, and preparing a graphene-Cu-BTC co-modified titanium dioxide composite photocatalyst by adopting a hydrothermal method;
the preparation method of the composite photocatalyst comprises the following steps:
adding graphene oxide sheets into a surfactant solution, slowly adding a part of water to obtain a mixed solution, performing ultrasonic treatment to uniformly disperse the graphene oxide sheets in the surfactant, then adding nano titanium dioxide into the mixed solution, slowly adding the other part of water, then adding Cu-BTC, transferring the mixture into a hydrothermal reactor, performing hydrothermal reaction at 100-120 ℃, washing and drying a product after the hydrothermal reaction, and grinding the product into powder to obtain the composite photocatalyst.
2. The method for preparing the composite photocatalyst with good performance as claimed in claim 1, wherein the method comprises the following steps: the graphene oxide sheet has a size of 100-200nm and a thickness of 1-3nm.
3. The method for preparing the composite photocatalyst with good performance as claimed in claim 1, wherein: and carrying out amino modification on the surface of the graphene oxide.
4. The method for preparing the composite photocatalyst with good performance as claimed in claim 1, wherein: the nanometer titanium dioxide is nitrogen-doped nanometer titanium dioxide with the size of 20-30nm and is rutile type.
5. The method of claim 1The preparation method of the composite photocatalyst with good performance is characterized by comprising the following steps: the Cu-BTC is obtained by oxygen activation treatment, and has a specific surface area of 800-1000m 2 The size is 200-300nm.
6. The method for preparing the composite photocatalyst with good performance as claimed in claim 1, wherein: the surfactant is sodium dodecyl benzene sulfonate or stearic acid.
7. The method for preparing the composite photocatalyst with good performance as claimed in claim 1, wherein: the temperature in the hydrothermal process is 100-120 ℃, and the reaction time is 6h.
8. Use of a composite photocatalyst prepared by the method of any one of claims 1 to 7 to catalyze organic pollutants under visible light.
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