CN111111643A - Rare earth doped RGO/titanium dioxide efficient photocatalyst and preparation method thereof - Google Patents

Rare earth doped RGO/titanium dioxide efficient photocatalyst and preparation method thereof Download PDF

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CN111111643A
CN111111643A CN202010057760.1A CN202010057760A CN111111643A CN 111111643 A CN111111643 A CN 111111643A CN 202010057760 A CN202010057760 A CN 202010057760A CN 111111643 A CN111111643 A CN 111111643A
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rare earth
tio
rgo
solution
graphene oxide
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李光照
韩锐
任建
杜发鑫
洋汉军
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Xihua University
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Xihua University
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • B01J35/39—

Abstract

The embodiment of the application provides a rare earth doped RGO/titanium dioxide efficient photocatalyst and a preparation method thereof, relating to the field of photocatalysts. The preparation method of the rare earth-doped RGO/titanium dioxide efficient photocatalyst mainly comprises the steps of mixing and stirring glacial acetic acid, a graphene oxide solution, a rare earth salt solution and absolute ethyl alcohol, wherein a rare earth element is at least one of gadolinium, praseodymium, europium and holmium, and then adjusting the pH value to be less than or equal to 7 to obtain a first solution; dropwise adding a second solution prepared from butyl titanate and absolute ethyl alcohol into the first solution, and stirring for reaction to obtain sol; drying the sol, and carrying out heat treatment at the temperature of 300-480 ℃ for 1.5-5.0 h. The rare earth doped RGO/titanium dioxide efficient photocatalyst and the preparation method thereof disclosed by the embodiment of the application have the advantages of mild reaction conditions, high photocatalytic efficiency of the photocatalyst and good photocatalytic effect under visible light.

Description

Rare earth doped RGO/titanium dioxide efficient photocatalyst and preparation method thereof
Technical Field
The application relates to the field of photocatalysts, in particular to a rare earth doped RGO/titanium dioxide efficient photocatalyst and a preparation method thereof.
Background
TiO2With appropriate energy chargingThe photocatalyst has the advantages of high chemical stability, no toxicity, no harm, higher photoelectric conversion efficiency, low cost, higher activity and the like, and becomes the most important photocatalyst. However, due to TiO2The wide band gap energy (3.2eV) of the photocatalyst not only can be used for low-efficiency utilization of ultraviolet light with a shorter wavelength part in sunlight, but also photogenerated electrons and holes generated in the photocatalysis process are easy to recombine, and the actual photocatalysis performance of the photocatalyst is influenced.
At present, to improve TiO2The researchers improve TiO through various modification methods2The obtained catalyst still has low photocatalytic efficiency, and is difficult to meet the actual use requirement.
Disclosure of Invention
The embodiment of the application aims to provide a rare earth doped RGO/titanium dioxide high-efficiency photocatalyst and a preparation method thereof, the reaction condition is mild, and the photocatalytic efficiency of the photocatalyst is high.
In a first aspect, an embodiment of the present application provides a method for preparing a rare earth-doped RGO/titania high-efficiency photocatalyst, which includes the following steps:
mixing and stirring glacial acetic acid, a graphene oxide solution, a rare earth salt solution and absolute ethyl alcohol, wherein the rare earth element is at least one of gadolinium, praseodymium, europium and holmium, and adjusting the pH value to be less than or equal to 7 to obtain a first solution;
dropwise adding a second solution prepared from butyl titanate and absolute ethyl alcohol into the first solution, stirring at room temperature for reaction for 0.2-1.0h, and then stirring at 30-60 ℃ for reaction for 0.1-1.0h to obtain sol;
drying the sol, and carrying out heat treatment at the temperature of 300-480 ℃ for 1.5-5.0 h.
In the technical scheme, reduced Graphene Oxide/titanium dioxide (RGO/TiO) is prepared in situ by using butyl titanate as a precursor of titanium and Graphene Oxide (GO) as a raw material by a sol-gel method2) The composite material is specifically characterized in that GO is a product containing oxidation functional groups in the interior and at the edge of a GR (Graphene) sheet layer, and a large number of oxygen-containing functional groups exist in GO, so that RGO/TiO is prepared2In the course of the composite material, butyl titanate is oxidized with these oxygenIn-situ hydrolysis of functionalized functional group as site to generate TiO2The particles, after the composite is formed, are heat treated to reduce the remaining oxidized functional groups of GO, thereby forming RGO. More importantly, rare earth elements gadolinium or praseodymium, europium and holmium provided by rare earth salt are doped in the rare earth elements, so that the rare earth doped RGO/titanium dioxide high-efficiency photocatalyst is obtained, and the reaction condition is mild. RGO has similar property with GR, pi electrons can freely move on a two-dimensional plane due to pi bonds in graphene oxide GR, efficient electron transfer is realized on the surface of GR, the conductivity of GR is good, and GR and TiO are connected2And most of the photo-generated electrons are transferred to the GR after recombination, so that the effect of separating the photo-generated electrons from holes is achieved, and the recombination of the photo-generated electron-hole pairs is greatly inhibited. Rare earth elements gadolinium and/or praseodymium and/or europium and/or holmium enter TiO2The crystal lattice can further cause charge imbalance and accelerate catalysis; and GR has higher adsorption performance, can enrich organic macromolecules on the surface of the photocatalyst, and is beneficial to the photocatalytic reaction, thereby improving the photocatalytic efficiency.
In one possible implementation manner, the preparation method of the graphene oxide solution is as follows: dissolving graphene oxide in water, and performing ultrasonic treatment at 40-80 ℃ for 0.5-2.0 h.
In the technical scheme, the graphene oxide is dissolved in water, heated to a certain temperature and subjected to ultrasound for a certain time, the graphene oxide is good in dispersion stripping effect, if the ultrasound condition is too strong (the temperature is too high or the time is too long), the lamellar structure of the graphene oxide is extremely easy to damage, and if the ultrasound condition is too weak (the temperature is too low and the time is too short), the graphene oxide is poor in dispersion effect.
In one possible implementation manner, the preparation method of the graphene oxide comprises the following steps:
uniformly mixing 5-20g of natural graphite powder and 2.5-7.5g of sodium nitrate powder, slowly adding the mixture into 200mL of concentrated sulfuric acid at the temperature of between 115 and 10 ℃, and magnetically stirring for 0-15min to uniformly mix the system;
slowly adding 10-25g of potassium permanganate into the system under the condition of continuous stirring, keeping the reaction temperature lower than 30 ℃, and placing the system in a water bath at 20-55 ℃ for constant-temperature reaction for 20-50min after the addition;
then slowly dripping 150-530mL of distilled water into the system, stopping stirring, and continuously reacting for 10-25min under the oil bath at the temperature of 70-90 ℃;
and after the reaction is finished, adding 435mL of 255-one, 50-70 ℃ distilled water and 20-50mL of 30% hydrogen peroxide, performing suction filtration while the solution is hot, centrifugally washing filter residues to be neutral, drying at 60-100 ℃, and grinding to obtain the graphene oxide.
In the technical scheme, the graphene oxide self-prepared by the method has good conductivity and good adsorption energy absorption, and the prepared rare earth doped RGO/titanium dioxide high-efficiency photocatalyst has high photocatalytic efficiency.
In one possible implementation, the dropping rate is 1-5 ml/min.
In the technical scheme, the RGO/TiO can be formed at a proper dropping speed2The composite material and ensures the doping effect of the rare earth elements.
In one possible implementation, the rare earth salt is a rare earth nitrate, a rare earth sulfate, or a rare earth hydrochloride; optionally, the rare earth salt is a rare earth nitrate, and the mass ratio of the graphene oxide to the rare earth nitrate is 1: 0.5-2.5.
In the technical scheme, the graphene oxide and the rare earth nitrate are mixed according to a certain dosage ratio, the doping amount of the rare earth element is relatively small (about 0.5% -1.5%), the GO content is about 3%, and the prepared photocatalyst has high photocatalytic effect efficiency.
In one possible implementation manner, the mass ratio of the graphene oxide to the butyl titanate is 1: 100-200.
In the technical scheme, the graphene oxide and the butyl titanate are in a certain dosage ratio, so that RGO/TiO with a certain graphene oxide doping amount can be formed2A composite material.
In one possible implementation, the drying temperature is 90-130 ℃.
In the technical scheme, the drying is carried out according to a certain temperature, the drying effect is good, and the frame structure of the photocatalyst can not be damaged.
In a second aspect, embodiments of the present application provide a rare earth doped RGO/titania high efficiency photocatalyst, which is prepared by the method for preparing the rare earth doped RGO/titania high efficiency photocatalyst provided in the first aspect.
In the technical scheme, the photocatalyst has high photocatalytic efficiency, and particularly has good photocatalytic effect under visible light.
In a possible implementation manner, in the high-efficiency photocatalyst, the doping amount of the rare earth element is 0.5% -5%, and the content of the graphene oxide is 0.5% -10%.
In the technical scheme, the doping amount of the rare earth elements and the proper GO is relatively small, the corresponding photocatalyst has high photocatalytic effect efficiency, and particularly has good photocatalytic effect under visible light.
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In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments of the present application will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and that those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
FIGS. 1(a) -1 (j) are scanning electron micrographs of different materials;
FIG. 2 shows GO and TiO2And RGO/TiO2An XRD pattern of (a);
FIG. 3 shows GO and TiO2、1.5％Gd-TiO2And 3% RGO/1.5% Gd-TiO2An XRD pattern of (a);
FIG. 4 shows GO and TiO2、1％Pr-TiO2And 3% RGO/1% Pr-TiO2An XRD pattern of (a);
FIG. 5 shows GO and TiO2And RGO/TiO2(ii) an infrared spectrum;
FIG. 6 shows GO and TiO2、1.5％Gd-TiO2And 3% RGO/1.5% Gd-TiO2(ii) an infrared spectrum;
FIG. 7 shows GO and TiO2、1％Pr-TiO2And 3% RGO/1% Pr-TiO2Red ofAn outer map;
FIG. 8 is TiO2And RGO/TiO2(ii) a diffuse reflectance spectrum of;
FIG. 9 is TiO2、1.5％Gd-TiO2And 3% RGO/1.5% Gd-TiO2(ii) a diffuse reflectance spectrum of;
FIG. 10 is TiO2、1％Pr-TiO2And 3% RGO/1% Pr-TiO2Diffuse reflectance spectrum of (a).
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following is a detailed description of the rare earth doped RGO/titania high efficiency photocatalyst and the preparation method thereof in the examples of the present application.
The embodiment of the application provides a preparation method of a rare earth doped RGO/titanium dioxide efficient photocatalyst, which comprises the following steps:
s1, mixing and stirring glacial acetic acid, a graphene oxide solution, a rare earth salt solution and absolute ethyl alcohol, wherein the rare earth element is at least one of gadolinium, praseodymium, europium and holmium, and specifically, adding the glacial acetic acid, the graphene oxide solution and the rare earth salt solution into the absolute ethyl alcohol, stirring violently, and then adjusting the pH value to be less than or equal to 7 to obtain a first solution. In the embodiment of the application, the rare earth salt solution can be rare earth nitrate, rare earth sulfate or rare earth hydrochloride, and under the normal condition, the rare earth salt is rare earth nitrate; the mass ratio of the graphene oxide to the rare earth nitrate is 1: 0.5-2.5; the rare earth nitrate is selected from at least one of gadolinium nitrate and praseodymium nitrate, and in some embodiments, the rare earth nitrate is gadolinium nitrate, praseodymium nitrate, europium nitrate, or holmium nitrate.
The graphene oxide adopted in the embodiment of the application can be purchased or obtained by self-making. The preparation method of the self-made graphene oxide in the embodiment specifically includes the following steps:
uniformly mixing 5-20g of natural graphite powder and 2.5-7.5g of sodium nitrate powder, slowly adding the mixture into 200mL of concentrated sulfuric acid at the temperature of between 115 and 10 ℃, and magnetically stirring for 0-15min to uniformly mix the system; slowly adding 10-25g of potassium permanganate into the system under the condition of continuous stirring, keeping the reaction temperature lower than 30 ℃, and placing the system in a water bath at 20-55 ℃ for constant-temperature reaction for 20-50min after the addition; then slowly dripping 150-530mL of distilled water into the system, stopping stirring, and continuously reacting for 10-25min under the oil bath at the temperature of 70-90 ℃; and after the reaction is finished, adding 435mL of 255-one, 50-70 ℃ distilled water and 20-50mL of 30% hydrogen peroxide, performing suction filtration while the solution is hot, centrifugally washing filter residues to be neutral, drying at 60-100 ℃, and grinding to obtain the graphene oxide.
In this embodiment, the preparation method of the graphene oxide solution is as follows: dissolving graphene oxide in water, heating and ultrasonically processing at 40-80 ℃ for 0.5-2.0h, optionally heating to 50-70 ℃, and ultrasonically processing for 1-1.5h, as an example, heating to 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃, and ultrasonically dispersing for 0.5h, 1h, 1.5h or 2.0h under the temperature condition.
S2, slowly dropping butyl titanate into the absolute ethyl alcohol, wherein the mass ratio of the graphene oxide to the butyl titanate is 1: 100 and 200, stirring strongly for 5-15min by a magnetic stirrer, and mixing uniformly to form a yellow clear second solution.
It should be noted that, steps S1 and S2 are not sequential, and the first solution may be prepared first, the second solution may be prepared first, or the first solution and the second solution may be prepared simultaneously.
And S3, under the condition of vigorous stirring, dropwise adding the second solution into the first solution, wherein the dropwise adding speed is generally 1-5ml/min, or 2-4ml/min, and the specific dropwise adding speed needs to be correspondingly adjusted according to the concentrations of the first solution and the second solution so as to ensure that the raw materials are reacted completely. After the dropwise addition, the mixture is stirred and reacted for 0.2 to 1.0 hour at room temperature, for example, the mixture is stirred and reacted for 0.2 hour, 0.4 hour, 0.5 hour, 0.7 hour or 1.0 hour at room temperature under the condition of continuous stirring, and then stirred and reacted for 0.1 to 1.0 hour at 30 to 60 ℃ to obtain sol, for example, the mixture is stirred and reacted for 0.1 hour, 0.3 hour, 0.5 hour, 0.7 hour or 1.0 hour at 30 ℃, 40 ℃, 50 ℃ or 60 ℃ under the condition of continuous stirring.
S4, drying the sol, wherein the drying temperature is generally 90-130 ℃, such as 90 ℃, 100 ℃, 105 ℃, 110 ℃, 120 ℃ or 130 ℃, and then performing heat treatment at 300 ℃ and 480 ℃ for 1.5-5.0h, specifically, at 420 ℃ and 460 ℃ for 2-4h, such as at 300 ℃, 350 ℃, 400 ℃, 420 ℃, 450 ℃, 460 ℃ or 480 ℃ for 5h, 4h, 3h, 2h or 1.5h, to obtain the powdered rare earth doped RGO/titanium dioxide high efficiency photocatalyst.
The embodiment of the application also provides a rare earth doped RGO/titanium dioxide efficient photocatalyst, which is prepared by adopting the preparation method of the rare earth doped RGO/titanium dioxide efficient photocatalyst. In the high-efficiency photocatalyst, the doping amount of the rare earth element is 0.5-5%, and can be selected as 0.5-2%; the content of the graphene oxide is 0.5% -10%, and optionally 2% -4%.
The features and properties of the present application are described in further detail below with reference to examples.
The graphene oxide used in the following examples was prepared according to the following preparation process:
uniformly mixing 10g of natural graphite powder and 5g of sodium nitrate powder, slowly adding the mixture into 150mL of concentrated sulfuric acid at 5 ℃, and magnetically stirring for 10min to uniformly mix the system; under the condition of continuous stirring, slowly adding 15g of potassium permanganate into the system, keeping the reaction temperature lower than 30 ℃, and placing the system in a 35 ℃ water bath for constant-temperature reaction for 35min after the addition; then slowly dripping 400mL of distilled water into the system, stopping stirring, and continuously reacting for 20min under the condition of 80 ℃ oil bath; and after the reaction is finished, adding 350mL of distilled water at 60 ℃ and 40mL of 30% hydrogen peroxide, carrying out suction filtration while the solution is hot, centrifugally washing filter residues to be neutral, drying at 80 ℃, and grinding to obtain the graphene oxide.
Example 1
This example provides an RGO/Gd-TiO2The rare earth element is gadolinium, the target doping amount of gadolinium is 0.5%, and the target content of GO is 3% (the doping amount/content in the application refers to the mass percentage of the corresponding substance in the product), namely 3% GO/0.5% Gd-TiO2The preparation method comprises the following steps:
(1) at room temperature, 5ml of glacial acetic acid and 10ml of graphene oxide solution (0.0693 g of graphene oxide is dissolved in 10ml of water, the mixture is heated at 50 ℃ and subjected to ultrasonic treatment for 1h), 10ml of gadolinium nitrate solution (0.03319 g of gadolinium nitrate is dissolved in 10ml of water and stirred uniformly) are added into 40ml of absolute ethyl alcohol, the mixture is stirred vigorously, 1-2 drops of hydrochloric acid are dripped, and the pH is adjusted to be less than or equal to 7, so that a first solution is obtained.
10ml of butyl titanate (9.85g, corresponding to 2.31g of TiO formed) were taken2) Slowly dropping into 40ml of absolute ethyl alcohol, strongly stirring for 10min by using a magnetic stirrer, and uniformly mixing to form a yellow clear second solution.
(2) The second solution was slowly dropped into the first solution with vigorous stirring at a dropping rate of about 3 ml/min.
(3) After the dropwise addition, the reaction is continuously stirred for half an hour, and then the sol is obtained after the constant temperature of a water bath at 50 ℃ for 0.5 h.
(4) Drying the sol at 105 ℃, and carrying out heat treatment at 450 ℃ for 3.0h to obtain the rare earth doped RGO/titanium dioxide efficient photocatalyst powder.
Example 2
This example provides an RGO/Gd-TiO2The photocatalyst comprises gadolinium as rare earth element, gadolinium with target doping amount of 1.0%, and GO with target content of 3%, i.e. 3% GO/1.0% Gd-TiO2The preparation method is substantially the same as that of example 1, except that: the amount of gadolinium nitrate used was 0.06637g, corresponding to a gadolinium doping of 1.0%.
Example 3
This example provides an RGO/Gd-TiO2The photocatalyst comprises gadolinium as rare earth element, target doping amount of gadolinium is 1.5%, and target GO content is 3%, i.e. 3% GO/1.5% Gd-TiO2The preparation method is substantially the same as that of example 1, except that: the amount of gadolinium nitrate used was 0.09956g, corresponding to a gadolinium doping of 1.5%.
Example 4
This example provides an RGO/Gd-TiO2The photocatalyst comprises gadolinium as rare earth element, gadolinium target doping amount of 2.0%, and GO target content of 3%, namely 3% GO/2.0% Gd-TiO2The preparation method is substantially the same as that of example 1, except that: of gadolinium nitrateThe usage amount is 0.1327g, and the corresponding doping amount of gadolinium is 2.0%.
Example 5
This example provides an RGO/Pr-TiO2The rare earth element is praseodymium, the target doping amount of the praseodymium is 0.5%, and the target content of GO is 3%, namely 3% GO/0.5% Pr-TiO2The preparation method comprises the following steps:
(1) at room temperature, 5ml of glacial acetic acid and 10ml of graphene oxide solution (0.0693 g of graphene oxide is dissolved in 10ml of water, the mixture is heated at 50 ℃ and subjected to ultrasound for 1h), 10ml of praseodymium nitrate solution (0.03569 g of praseodymium nitrate is dissolved in 10ml of water and is uniformly stirred) are added into 40ml of absolute ethyl alcohol, the mixture is vigorously stirred, 1-2 drops of hydrochloric acid are dripped, and the pH is adjusted to be less than or equal to 7, so that a first solution is obtained.
10ml of butyl titanate (9.85g, corresponding to 2.31g of TiO formed) were taken2) Slowly dropping into 40ml of absolute ethyl alcohol, strongly stirring for 10min by using a magnetic stirrer, and uniformly mixing to form a yellow clear second solution.
(2) The second solution was slowly dropped into the first solution with vigorous stirring at a dropping rate of about 3 ml/min.
(3) After the dropwise addition, the reaction is continuously stirred for half an hour, and then the sol is obtained after the constant temperature of a water bath at 50 ℃ for 0.5 h.
(4) Drying the sol at 105 ℃, and carrying out heat treatment at 450 ℃ for 3.0h to obtain the rare earth doped RGO/titanium dioxide efficient photocatalyst powder.
Example 6
This example provides an RGO/Pr-TiO2The rare earth element is praseodymium, the target doping amount of the praseodymium is 1.0%, and the target content of GO is 3%, namely 3% GO/1.0% Pr-TiO2The preparation method is substantially the same as that of example 5, except that: the amount of praseodymium nitrate used was 0.07138g, and the amount of praseodymium doped was 1.0%.
Example 7
This example provides an RGO/Pr-TiO2The rare earth element is praseodymium, the target doping amount of the praseodymium is 1.5%, and the target content of GO is 3%, namely 3% GO/1.5% Pr-TiO2Method for the production and implementation thereofThe preparation of example 5 was substantially the same except that: the amount of praseodymium nitrate used was 0.1071g, and the amount of praseodymium doped was 1.5%.
Example 8
This example provides an RGO/Pr-TiO2The rare earth element is praseodymium, the target doping amount of the praseodymium is 2.0 percent, the target content of GO is 3 percent, namely 3 percent GO/2.0 percent Pr-TiO2The preparation method is substantially the same as that of example 5, except that: the amount of praseodymium nitrate used was 0.1428g, and the amount of praseodymium doped was 2.0%.
Example 9
This example provides an RGO/Eu-TiO2The photocatalyst comprises europium as a rare earth element, the target doping amount of the europium is 0.5%, and the target content of GO is 3%, namely 3% GO/0.5% Eu-TiO2The preparation method is substantially the same as that of example 5.
Example 10
This example provides an RGO/Eu-TiO2The photocatalyst comprises europium as a rare earth element, the target doping amount of the europium is 1.0%, and the target content of GO is 3%, namely 3% GO/1.0% Eu-TiO2The preparation method is substantially the same as that of example 5.
Example 11
This example provides an RGO/Eu-TiO2The rare earth element is europium, the target doping amount of the europium is 1.5 percent, and the target content of GO is 3 percent, namely 3 percent GO/1.5 percent Eu-TiO2The preparation method is substantially the same as that of example 5.
Example 12
This example provides an RGO/Eu-TiO2The photocatalyst comprises europium as a rare earth element, the target doping amount of the europium is 2.0%, and the target content of GO is 3%, namely 3% GO/2.0% Eu-TiO2The preparation method is substantially the same as that of example 5.
Example 13
This example provides an RGO/Ho-TiO2The photocatalyst comprises rare earth element holmium, the target doping amount of holmium is 0.5%, and the target content of GO isThe amount is 3%, i.e. 3% GO/0.5% Ho-TiO2The preparation method is substantially the same as that of example 5.
Example 14
This example provides an RGO/Ho-TiO2The rare earth element is holmium, the target doping amount of holmium is 1.0%, and the target content of GO is 3%, namely 3% GO/1.0% Ho-TiO2The preparation method is substantially the same as that of example 5.
Example 15
This example provides an RGO/Ho-TiO2The rare earth element is holmium, the target doping amount of holmium is 1.5%, and the target content of GO is 3%, namely 3% GO/1.5% Ho-TiO2The preparation method is substantially the same as that of example 5.
Example 16
This example provides an RGO/Ho-TiO2The rare earth element is holmium, the target doping amount of holmium is 2.0%, and the target content of GO is 3%, namely 3% GO/2.0% Ho-TiO2The preparation method is substantially the same as that of example 5.
Comparative example 1
This comparative example provides an RGO/TiO2A photocatalyst was prepared in substantially the same manner as in example 1, except that: no gadolinium nitrate solution was added.
Comparative example 2
This comparative example provides a Pr-TiO2A photocatalyst was prepared in substantially the same manner as in example 6, except that: no graphene oxide solution was added.
Comparative example 3
This comparative example provides a Gd-TiO2A photocatalyst was prepared in substantially the same manner as in example 3, except that: no graphene oxide solution was added.
The photocatalysts of the examples and comparative examples were examined by XRD, SEM, FTIR, UV-Vis DRS characterization analysis, and photocatalytic performance testing.
To GO and TiO respectively2RGO/TiO of comparative example 12Pr-TiO of comparative example 22Gd-TiO of comparative example 32RGO/Pr-TiO of example 62And RGO/Gd-TiO of example 32SEM characterization was performed, and the results are shown in FIGS. 1(a) to 1 (j). FIG. 1(a) is a scanning electron micrograph of GO; FIG. 1(b) is TiO2Scanning electron microscope images of; FIG. 1(c) is RGO/TiO2Scanning electron microscope images of; FIG. 1(d) is RGO/TiO2High power scanning electron microscope images of; FIG. 1(e) shows Pr-TiO2Scanning electron microscope images of; FIG. 1(f) is Gd-TiO2Scanning electron microscope images of; FIG. 1(g) shows RGO/Pr-TiO2Scanning electron microscope images of; FIG. 1(h) shows RGO/Pr-TiO2High power scanning electron microscope images of; FIG. 1(i) is RGO/Gd-TiO2Scanning electron microscope images of; FIG. 1(j) is RGO/Gd-TiO2High power scanning electron microscopy.
To GO and TiO respectively2RGO/TiO of comparative example 121% Pr-TiO of comparative example 221.5% Gd-TiO of comparative example 323% RGO/1% Pr-TiO of example 62And 3% RGO/1.5% Gd-TiO of example 32XRD characterization was performed, and the results are shown in FIGS. 2-4. FIG. 2 shows GO and TiO2And RGO/TiO2An XRD pattern of (a); FIG. 3 shows GO and TiO2、1.5％Gd-TiO2And 3% RGO/1.5% Gd-TiO2An XRD pattern of (a); FIG. 4 shows GO and TiO2、1％Pr-TiO2And 3% RGO/1% Pr-TiO2XRD pattern of (a).
As can be seen from fig. 1 and 2: the photocatalyst of this example successfully supported a large amount of TiO on an RGO sheet2Particles of and TiO2Exhibits an anatase form.
II, respectively to GO and TiO2RGO/TiO of comparative example 121% Pr-TiO of comparative example 221.5% Gd-TiO of comparative example 323% RGO/1% Pr-TiO of example 62And 3% RGO/1.5% Gd-TiO of example 32FTIR characterization and UV-Vis DRS characterization were performed, and the results are shown in FIGS. 5-10.
FIG. 5 shows GO and TiO2And RGO/TiO2(ii) an infrared spectrum; FIG. 6 shows GO and TiO2、1.5％Gd-TiO2And 3% RGO/1.5％Gd-TiO2(ii) an infrared spectrum; FIG. 7 shows GO and TiO2、1％Pr-TiO2And 3% RGO/1% Pr-TiO2Infrared spectrum of (1).
FIG. 8 is TiO2And RGO/TiO2(ii) a diffuse reflectance spectrum of; FIG. 9 is TiO2、1.5％Gd-TiO2And 3% RGO/1.5% Gd-TiO2(ii) a diffuse reflectance spectrum of; FIG. 10 is TiO2、1％Pr-TiO2And 3% RGO/1% Pr-TiO2Diffuse reflectance spectrum of (a).
From the IR spectra in FIGS. 5-7, it can be seen that the RGO/TiO molecules are comparable to those of the non-doped rare earth2This example is RGO/TiO doped with gadolinium and/or praseodymium2The red shift of the absorption edge occurs, the response degree to the light source is increased, and the energy band width is reduced to 1.2-3.0 eV.
Analyzing the ultraviolet photocatalytic degradation rates of different catalysts, wherein the percentage of GO, Pr and Gd in each catalyst is the corresponding doping amount/content, the model of an ultraviolet lamp is ZW30S19W, the power is 30W, and the size is as follows: 894.6mm long, 19 +/-0.5D diameter, 96V working voltage, 0.410A working current and 100UW/CM of one-meter radiation intensity2The average service life is 1000h, and the model number of the lamp holder is G13. The initial concentration of the methylene blue solution is 20mg/L, 3ml of the solution is taken out every 15 minutes of illumination, the absorbance of the supernatant is tested after centrifugation, then the degradation rate is calculated according to the absorbance, and the ultraviolet photocatalytic degradation rates of different catalysts are shown in Table 1.
TABLE 1 UV photocatalytic degradation rates of different catalysts
Figure BDA0002372188480000121
Figure BDA0002372188480000131
The visible light photocatalytic degradation rates of the different catalysts were analyzed as follows, the visible light lamp was a philips 500WR7s230V (power 500W) iodine tungsten lamp, the sampling and testing methods were the same as above, and the visible light photocatalytic degradation rates of the different catalysts are shown in table 2.
TABLE 2 visible light photocatalytic degradation rates of different catalysts
Figure BDA0002372188480000141
Figure BDA0002372188480000151
As can be seen from tables 1 and 2, the photocatalyst of the present example has high photocatalytic efficiency, especially good photocatalytic effect under visible light, especially 3% GO/1.5% Gd-TiO2And 3% GO/1% Pr-TiO2、3％GO/1％Eu-TiO2、3％GO/1.5％Ho-TiO2The performance of (2) is relatively best.
In summary, the rare earth doped RGO/titanium dioxide high-efficiency photocatalyst and the preparation method thereof provided by the embodiment of the application have the advantages of mild reaction conditions and high photocatalytic efficiency of the photocatalyst.
The above description is only an example of the present application and is not intended to limit the scope of the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (9)

1. A preparation method of a rare earth doped RGO/titanium dioxide high-efficiency photocatalyst is characterized by comprising the following steps:
mixing and stirring glacial acetic acid, a graphene oxide solution, a rare earth salt solution and absolute ethyl alcohol, wherein the rare earth element is at least one of gadolinium, praseodymium, europium and holmium, and then adjusting the pH value to be less than or equal to 7 to obtain a first solution;
dropwise adding a second solution prepared from butyl titanate and absolute ethyl alcohol into the first solution, stirring and reacting at room temperature for 0.2-1.0h, and then stirring and reacting at 30-60 ℃ for 0.1-1.0h to obtain sol;
drying the sol, and carrying out heat treatment at the temperature of 300-480 ℃ for 1.5-5.0 h.
2. The method for preparing a rare earth-doped RGO/titania high-efficiency photocatalyst according to claim 1, wherein the graphene oxide solution is prepared by the following steps: dissolving graphene oxide in water, and performing ultrasonic treatment at 40-80 ℃ for 0.5-2.0 h.
3. The method of preparing a rare earth-doped RGO/titania high efficiency photocatalyst as claimed in claim 1, wherein the graphene oxide is prepared by the steps of:
uniformly mixing 5-20g of natural graphite powder and 2.5-7.5g of sodium nitrate powder, slowly adding the mixture into 200mL of concentrated sulfuric acid at the temperature of between 115 and 10 ℃, and magnetically stirring for 0-15min to uniformly mix the system;
slowly adding 10-25g of potassium permanganate into the system under the condition of continuous stirring, keeping the reaction temperature lower than 30 ℃, and placing the system in a water bath at 20-55 ℃ for constant-temperature reaction for 20-50min after the addition;
then slowly dripping 150-530mL of distilled water into the system, stopping stirring, and continuously reacting for 10-25min under the oil bath at the temperature of 70-90 ℃;
and after the reaction is finished, adding 435mL of 255-one, 50-70 ℃ distilled water and 20-50mL of 30% hydrogen peroxide, performing suction filtration while the solution is hot, centrifugally washing filter residues to be neutral, drying at 60-100 ℃, and grinding to obtain the graphene oxide.
4. The method of claim 1, wherein the dropping rate is 1-5 ml/min.
5. The method of claim 1, wherein the rare earth salt is a rare earth nitrate, a rare earth sulfate, or a rare earth hydrochloride; optionally, the rare earth salt is a rare earth nitrate, and the mass ratio of the graphene oxide to the rare earth nitrate is 1: 0.5-2.5.
6. The method for preparing a rare earth-doped RGO/titanium dioxide high-efficiency photocatalyst according to claim 1, wherein the mass ratio of the graphene oxide to the butyl titanate is 1: 100-200.
7. The method of claim 1, wherein the drying temperature is 90-130 ℃.
8. A rare earth-doped RGO/titania high efficiency photocatalyst prepared by the method of preparing the rare earth-doped RGO/titania high efficiency photocatalyst of any one of claims 1 to 7.
9. The rare earth-doped RGO/titania high-efficiency photocatalyst of claim 8, wherein the doped amount of the rare earth element in the high-efficiency photocatalyst is 0.5% -5%, and the content of the graphene oxide is 0.5% -10%.
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