CN112403526B - Ce-MOF/Bi2MoO6Heterojunction photocatalyst and preparation method and application thereof - Google Patents

Ce-MOF/Bi2MoO6Heterojunction photocatalyst and preparation method and application thereof Download PDF

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CN112403526B
CN112403526B CN202011432816.3A CN202011432816A CN112403526B CN 112403526 B CN112403526 B CN 112403526B CN 202011432816 A CN202011432816 A CN 202011432816A CN 112403526 B CN112403526 B CN 112403526B
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蔡炜
于雪
李小海
王虎
江晓明
陈敏东
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Datang Nanjing Environmental Protection Technology Co Ltd
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Abstract

The invention provides Ce-MOF/Bi2MoO6A heterojunction photocatalyst, a preparation method and application thereof. The preparation method comprises the following steps: A) dissolving a cerium source substance and an organic connector in an organic solvent, uniformly stirring and mixing, adjusting the pH value, performing hydrothermal reaction, and then washing and drying to obtain a Ce-MOF photocatalyst; B) dissolving a bismuth source substance and a molybdenum source substance in deionized water, uniformly stirring, adjusting the pH value, carrying out hydrothermal reaction, washing and drying to obtain Bi2MoO6A photocatalyst; C) a Ce-MOF photocatalyst and Bi2MoO6Dispersing the photocatalyst in an organic solvent, stirring, washing and drying to obtain Ce-MOF/Bi2MoO6A heterojunction photocatalyst. The photocatalyst has the advantages of large specific surface area, high transfer rate of photogenerated carriers, long carrier survival life, strong catalytic activity and the like.

Description

Ce-MOF/Bi2MoO6Heterojunction photocatalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of photocatalysts, in particular to Ce-MOF/Bi2MoO6A heterojunction photocatalyst, a preparation method and application thereof.
Background
Currently, energy shortage and environmental deterioration are serious problems facing human beings. Due to the over-development and use of fossil fuels such as coal, petroleum, natural gas and the like, the concentration of carbon dioxide in the atmosphere is continuously increased, and a series of negative results such as acid rain, greenhouse effect and the like are generated. Therefore, it is of great interest to develop clean energy to replace traditional non-renewable energy sources.
The development and utilization of solar energy is an important research subject in the 21 st century, and the photocatalytic technology is expected to become an effective technical means for solving the problems of environmental pollution and energy shortage. CO 22As a C1 resource, the carbon dioxide can be recycled by photocatalysis to use CO2Conversion to CO, CH3OH、 CH4And HCOOH and other energy molecules have important significance on resource recycling and environmental protection.
The photocatalytic technology has the advantages of low cost, mild reaction conditions, environmental friendliness, low energy consumption and the like, and the photocatalytic conversion technology is used for reducing CO2One of the ideal approaches of (1). However, the existing photocatalytic materials generally have the disadvantages of low conversion efficiency, slow reaction rate, poor practical application and the like. Therefore, the development of a novel photocatalytic material with efficient visible light response is a core issue for realizing a photocatalytic carbon fixation technology.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide Ce-MOF/Bi2MoO6The heterojunction photocatalyst has the advantages of large specific surface area, high transfer rate of photogenerated carriers, long carrier survival life, strong catalytic activity and the like.
The invention provides a Ce-MOF/Bi2MoO6The preparation method of the heterojunction photocatalyst comprises the following steps:
A) dissolving a cerium source substance and an organic connector in an organic solvent, uniformly stirring and mixing, adjusting the pH value, performing hydrothermal reaction, and then washing and drying to obtain a Ce-MOF photocatalyst;
B) dissolving a bismuth source substance and a molybdenum source substance in deionized water, uniformly stirring, adjusting the pH value, carrying out hydrothermal reaction, washing and drying to obtain Bi2MoO6A photocatalyst;
C) a Ce-MOF photocatalyst and Bi2MoO6Dispersing the photocatalyst in an organic solvent, stirring, washing and drying to obtain Ce-MOF/Bi2MoO6A heterojunction photocatalyst.
The invention does not strictly limit the cerium source substance, the bismuth source substance, the molybdenum source substance and the organic connector; for example: the cerium source material can be cerium nitrate hexahydrate; the organic linker may be trimesic acid; the bismuth source can be bismuth nitrate pentahydrate; the molybdenum source may be ammonium molybdate tetrahydrate.
In the present invention, step a) may comprise:
A1) respectively dissolving a cerium source substance and an organic connector in an organic solvent, and uniformly stirring to obtain a cerium-containing solution and an organic connector solution;
A2) and stirring and uniformly mixing the cerium-containing solution and the organic connecting body solution, adjusting the pH value, carrying out hydrothermal reaction, and then washing and drying to obtain the Ce-MOF photocatalyst.
Specifically, in the step A), the ratio of the amount of the cerium source substance to the organic linker substance may be 1 (1-3); the organic solvent may be DMF; adjusting the pH value to 3-5, for example, adjusting the pH value to 3-5 by adding ammonia water; the temperature of the hydrothermal reaction can be 120-180 ℃, and the time of the hydrothermal reaction can be 15-20 h; the temperature of drying may be 140-180 ℃.
In the step B), the ratio of the amount of the bismuth source substance to the amount of the molybdenum source substance may be (10-20): 1; adjusting the pH value to 5-9, for example, adjusting the pH value to 5-9 by dropwise adding sodium hydroxide solution; the temperature of the hydrothermal reaction can be 160-220 ℃, and the time of the hydrothermal reaction can be 20-24 h; the drying temperature may be 50-60 ℃. In addition, the hydrothermal reaction is carried out in the reaction kettle, and the volume of the deionized water can be 60-80% of the volume of the reaction kettle.
In the present invention, step C) may comprise:
C1) respectively adding Ce-MOF photocatalyst and Bi2MoO6Dispersing the photocatalyst in an organic solvent, and stirring under the water bath condition to obtain a Ce-MOF dispersion liquid and Bi2MoO6A dispersion liquid;
C2) mixing a Ce-MOF dispersion with Bi2MoO6Stirring the dispersion liquid under the condition of water bath, and then washing and drying to obtain Ce-MOF/Bi2MoO6A heterojunction photocatalyst.
Specifically, in the step C1), the water bath temperature can be 40-80 ℃, and the stirring time can be 0.5-1 h; in the step C2), the water bath temperature can be 40-80 ℃, and the stirring time can be 2-4 h.
In addition, in step C), the organic solvent may be absolute ethanol; Ce-MOF photocatalyst and Bi2MoO6The mass ratio of the photocatalyst can be 0.15 (0.02-0.3); the drying temperature may be 50-60 ℃.
The invention also provides Ce-MOF/Bi2MoO6A heterojunction photocatalyst prepared according to the preparation method.
The invention also provides the Ce-MOF/Bi2MoO6The application of the heterojunction photocatalyst in the carbon dioxide photocatalytic reduction is provided.
The implementation of the invention has at least the following advantages:
1. the preparation method of the invention can obtain the photocatalytic material with narrower band gap while keeping larger specific surface area; in the photocatalyst, Ce-MOF and Bi2MoO6The materials are uniformly dispersed with each other, and a heterostructure is formed on the surfaces of the two materials, so that the band gap of the materials is further reduced, and the recombination of photon-generated carriers is reduced;
2. the photocatalyst effectively overcomes the defects of poor stability, low activity, low quantum efficiency, poor selectivity and the like of the traditional photocatalytic reduction carbon dioxide material, has rich pore structure and larger specific surface area, and has the advantages of high transfer rate of photogenerated carriers, long carrier survival life, strong catalytic activity and the like;
3. the preparation method disclosed by the invention is simple and feasible to operate, mild in reaction conditions, considerable in yield of synthetic materials, free of precious metals, environment-friendly and economical, beneficial to application of the synthetic materials in the reaction process of photocatalytic reduction of carbon dioxide, and wide in application prospect in the aspects of development of alternative energy of fossil fuels, efficient utilization of solar energy and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an SEM photograph of the Ce-MOF photocatalyst prepared in example 1;
FIG. 2 shows Bi prepared in example 12MoO6SEM photograph of the photocatalyst;
FIG. 3 is the Ce-MOF/Bi prepared in example 12MoO6SEM photograph of the heterojunction photocatalyst;
FIG. 4 is a Ce-MOF/Bi mixture prepared in examples 1-52MoO6Photo-reduction of CO by heterojunction photocatalyst2A performance map;
FIG. 5 is a Ce-MOF/Bi mixture prepared in examples 1-52MoO6A photocurrent intensity test chart of the heterojunction photocatalyst;
FIG. 6 shows the photo-reduction of CO by the photocatalyst prepared in example 1 and comparative examples 1 and 22Performance is compared to the graph.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present application. As used herein, the singular forms "a", "an", and "the" include plural forms as well, unless the context clearly indicates otherwise, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, devices, components, and/or combinations thereof.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
This example prepares a catalyst for photocatalytic reduction of CO2Ce-MOF/Bi of2MoO6A heterojunction photocatalyst of Ce-MOF and Bi2MoO6Is 0.15: 0.216; the method comprises the following specific steps:
1. preparation of Ce-MOF
0.216g of cerous nitrate hexahydrate and 0.21g of trimesic acid are respectively dissolved in 4mL and 8mL of DMF, and the solution is uniformly stirred to obtain a cerous nitrate solution and a trimesic acid solution.
Mixing the cerium nitrate solution and the trimesic acid solution, and then adding a certain amount of ammonia water to adjust the pH value of the mixed solution to 4.1; and (3) filling the mixed solution with the adjusted pH value into a reaction kettle, and carrying out hydrothermal reaction for 17 hours at 160 ℃. After the reaction is finished, washing the reaction product, and drying the precipitate in the suspension at 160 ℃ to obtain a white powdery Ce-MOF photocatalyst, wherein the SEM scanning electron microscope result is shown in figure 1.
2、Bi2MoO6Preparation of
Dissolving 1.68g of pentahydrate bismuth nitrate and 0.306g of ammonium molybdate tetrahydrate in deionized water, stirring for 1 hour to mix uniformly, then adding a certain amount of 1mol/L sodium hydroxide solution to adjust the pH value of the mixed solution to 7, transferring the mixed solution to a high-pressure reaction kettle, wherein the volume of the mixed solution accounts for 80% of the volume of the reaction kettle, and carrying out hydrothermal reaction for 24 hours at 180 ℃; after the reaction is finished, washing the reaction product, and then drying the precipitate in the suspension at 60 ℃ to obtain yellow powdery Bi2MoO6The result of SEM scanning electron microscope of the photocatalyst is shown in FIG. 2.
3、Ce-MOF/Bi2MoO6Preparation of heterojunction photocatalyst
0.15g of Ce-MOF photocatalyst was mixed with 0.216g of Bi2MoO6Adding the photocatalyst into absolute ethyl alcohol respectively, and stirring for 1h under the water bath condition of 60 ℃ to obtain Ce-MOF dispersion liquid and Bi2MoO6And (3) dispersing the mixture.
Mixing the above Ce-MOF dispersion with Bi2MoO6Mixing the dispersion, stirring for 4h under the condition of water bath at 60 ℃, then centrifugally washing, and drying and precipitating at 60 ℃ to obtain Ce-MOF/Bi2MoO6The results of SEM scanning electron microscopy of the heterojunction photocatalyst are shown in FIG. 3.
4. Photocatalytic reduction of CO2
The above Ce-MOF/Bi2MoO6Application of heterojunction photocatalyst simulation to photocatalytic reduction of CO2。
Carrying out photocatalytic reduction of CO2The reaction conditions of (a) are as follows:
Ce-MOF/Bi2MoO650mg of heterojunction photocatalyst, 15mL of deionized water, the reaction temperature of 80 ℃, the stirring rate of 400r/min, and filling of CO by irradiation of a 300W xenon lamp26 h. The reaction products were analyzed qualitatively and quantitatively by gas chromatography, and the results are shown in FIG. 4.
Furthermore, the above Ce-MOF/Bi2MoO6The result of the photocurrent intensity test of the heterojunction photocatalyst is shown in figure 5, which proves that the catalyst has stronger carrier separation capability and survival life.
Example 2
This example prepares a catalyst for photocatalytic reduction of CO2Ce-MOF/Bi of2MoO6A heterojunction photocatalyst in which Ce-MOF is in combination with Bi2MoO6Is 0.15: 0.108; the method comprises the following specific steps:
1. preparation of Ce-MOF
0.216g of cerous nitrate hexahydrate and 0.21g of trimesic acid are respectively dissolved in 4mL and 8mL of DMF, and the solution is uniformly stirred to obtain a cerous nitrate solution and a trimesic acid solution.
Mixing the cerium nitrate solution and the trimesic acid solution, and then adding a certain amount of ammonia water to adjust the pH value of the mixed solution to 3; and (3) putting the mixed solution with the adjusted pH value into a reaction kettle, and carrying out hydrothermal reaction for 15h at the temperature of 120 ℃. And after the reaction is finished, washing a reaction product, and drying the precipitate in the suspension at 140 ℃ to obtain a white powdery Ce-MOF photocatalyst.
2、Bi2MoO6Preparation of
Dissolving 1.68g of pentahydrate bismuth nitrate and 0.306g of ammonium molybdate tetrahydrate in deionized water, stirring for 1 hour to mix uniformly, then adding a certain amount of 1mol/L sodium hydroxide solution to adjust the pH value to 5, transferring the mixed solution to a high-pressure reaction kettle, wherein the volume of the mixed solution accounts for 60 percent of the volume of the reaction kettle, and carrying out hydrothermal reaction for 20 hours at 160 ℃; after the reaction is finished, washing the reaction product, and drying the precipitate in the suspension at 60 ℃ to obtain yellow powdery Bi2MoO6A photocatalyst.
3、Ce-MOF/Bi2MoO6Preparation of heterojunction photocatalyst
0.15g of Ce-MOF photocatalyst was mixed with 0.216g of Bi2MoO6Adding the photocatalyst into absolute ethyl alcohol respectively, and stirring for 0.5h under the water bath condition of 40 ℃ to obtain Ce-MOF dispersion liquid and Bi2MoO6And (3) dispersing the mixture.
Mixing the above Ce-MOF dispersion with Bi2MoO6Mixing the dispersion, stirring for 2h under the condition of 40 ℃ water bath, then centrifugally washing, and drying and precipitating at 60 ℃ to obtain Ce-MOF/Bi2MoO6A heterojunction photocatalyst.
4. Photocatalytic reduction of CO2
The above Ce-MOF/Bi2MoO6Application of heterojunction photocatalyst simulation to photocatalytic reduction of CO2。
Carrying out photocatalytic reduction of CO2The reaction conditions of (a) are as follows:
Ce-MOF/Bi2MoO650mg of heterojunction photocatalyst, 15mL of deionized water, reaction temperature of 80 ℃, stirring speed of 400r/min, and filling CO by irradiation of 300W xenon lamp26 h. The reaction product is qualitatively and quantitatively analyzed by gas chromatography, and the result isSee fig. 4.
Furthermore, the above-mentioned Ce-MOF/Bi2MoO6The photocurrent intensity test of the heterojunction photocatalyst is shown in figure 5, which proves that the catalyst has stronger carrier separation capability and survival life.
Example 3
This example prepares a catalyst for photocatalytic reduction of CO2Ce-MOF/Bi of2MoO6A heterojunction photocatalyst in which Ce-MOF is in combination with Bi2MoO6Is 0.15: 0.054; the method comprises the following specific steps:
1. preparation of Ce-MOF:
0.216g of cerous nitrate hexahydrate and 0.21g of trimesic acid are dissolved in 4mL and 8mL of DMF respectively, and the solution is stirred uniformly to obtain a cerous nitrate solution and a trimesic acid solution.
Mixing the cerium nitrate solution and the trimesic acid solution, and then adding a certain amount of ammonia water to adjust the pH value of the mixed solution to 5; and (3) putting the mixed solution with the adjusted pH value into a reaction kettle, and carrying out hydrothermal reaction for 20h at 180 ℃. And after the reaction is finished, washing a reaction product, and drying the precipitate in the suspension at 180 ℃ to obtain a white powdery Ce-MOF photocatalyst.
2、Bi2MoO6Preparation of
Dissolving 1.68g of pentahydrate bismuth nitrate and 0.306g of ammonium molybdate tetrahydrate in deionized water, stirring for 1 hour for uniform mixing, then adding a certain amount of 1mol/L sodium hydroxide solution to adjust the pH to 9, transferring the mixed solution to a high-pressure reaction kettle, wherein the volume of the mixed solution accounts for 70% of the volume of the reaction kettle, and carrying out hydrothermal reaction for 22 hours at 220 ℃; after the reaction is finished, washing the reaction product, and drying the precipitate in the suspension at 60 ℃ to obtain yellow powdery Bi2MoO6A photocatalyst.
3、Ce-MOF/Bi2MoO6Preparation of heterojunction photocatalysts
0.15g of Ce-MOF was mixed with 0.216g of Bi2MoO6Respectively adding the mixture into absolute ethyl alcohol, stirring for 1h under the water bath condition of 80 ℃ to obtain Ce-MOF dispersion liquid and Bi2MoO6And (3) dispersing the mixture.
Mixing the above Ce-MOF dispersion with Bi2MoO6Mixing the dispersion, stirring for 3h under the condition of 80 ℃ water bath, then centrifugally washing, and drying and precipitating at 60 ℃ to obtain Ce-MOF/Bi2MoO6A heterojunction photocatalyst.
4. Photocatalytic reduction of CO2
The above Ce-MOF/Bi2MoO6Application of heterojunction photocatalyst simulation to photocatalytic reduction of CO2。
Carrying out photocatalytic reduction of CO2The reaction conditions of (a) are as follows:
Ce-MOF/Bi2MoO650mg of heterojunction photocatalyst, 15mL of deionized water, reaction temperature of 80 ℃, stirring speed of 400r/min, and filling CO by irradiation of 300W xenon lamp26 h. The reaction products were analyzed qualitatively and quantitatively by gas chromatography, and the results are shown in FIG. 4.
Furthermore, the above-mentioned Ce-MOF/Bi2MoO6The photocurrent intensity test of the heterojunction photocatalyst is shown in figure 5, which proves that the catalyst has stronger carrier separation capability and survival life.
Example 4
This example prepares a catalyst for photocatalytic reduction of CO2Ce-MOF/Bi of2MoO6A heterojunction photocatalyst in which Ce-MOF is in combination with Bi2MoO6Is 0.15: 0.027; the method comprises the following specific steps:
1. preparation of Ce-MOF:
0.216g of cerous nitrate hexahydrate and 0.21g of trimesic acid are dissolved in 4mL and 8mL of DMF respectively, and the solution is stirred uniformly to obtain a cerous nitrate solution and a trimesic acid solution.
Mixing the cerium nitrate solution and the trimesic acid solution, and then adding a certain amount of ammonia water to adjust the pH value of the mixed solution to 5; and (3) filling the mixed solution with the adjusted pH value into a reaction kettle, and carrying out hydrothermal reaction for 18h at the temperature of 140 ℃. After the reaction is finished, washing the reaction product, and drying the precipitate in the suspension at 170 ℃ to obtain the white powdery Ce-MOF photocatalyst.
2、Bi2MoO6Preparation of
Dissolving 1.68g of pentahydrate bismuth nitrate and 0.306g of ammonium molybdate tetrahydrate in deionized water, stirring for 1 hour for uniform mixing, then adding a certain amount of 1mol/L sodium hydroxide solution to adjust the pH to 8, transferring the mixed solution to a high-pressure reaction kettle, wherein the volume of the mixed solution accounts for 80% of the volume of the reaction kettle, and carrying out hydrothermal reaction for 24 hours at 200 ℃; after the reaction is finished, washing the reaction product, and drying the precipitate in the suspension at 60 ℃ to obtain yellow powdery Bi2MoO6A photocatalyst.
3、Ce-MOF/Bi2MoO6Preparation of heterojunction photocatalysts
0.15g of Ce-MOF was mixed with 0.216g of Bi2MoO6Respectively adding the mixture into absolute ethyl alcohol, stirring for 1h under the water bath condition of 50 ℃ to obtain Ce-MOF dispersion liquid and Bi2MoO6And (3) dispersing the mixture.
Mixing the above Ce-MOF dispersion and Bi2MoO6Mixing the dispersion, stirring for 4h at 50 ℃ in a water bath, then centrifugally washing, and drying and precipitating at 60 ℃ to obtain Ce-MOF/Bi2MoO6A heterojunction photocatalyst.
4. Photocatalytic reduction of CO2
The above Ce-MOF/Bi2MoO6Application of heterojunction photocatalyst simulation to photocatalytic reduction of CO2。
Carrying out photocatalytic reduction of CO2The reaction conditions of (a) are as follows:
Ce-MOF/Bi2MoO650mg of heterojunction photocatalyst, 15mL of deionized water, reaction temperature of 80 ℃, stirring speed of 400r/min, and filling CO by irradiation of 300W xenon lamp26 h. The reaction products were analyzed qualitatively and quantitatively by gas chromatography, and the results are shown in FIG. 4.
Furthermore, the above-mentioned Ce-MOF/Bi2MoO6The photocurrent intensity test of the heterojunction photocatalyst is shown in figure 5, which proves that the catalyst has stronger carrier separation capability and survival life.
Example 5
This example prepares a catalyst for photocatalytic reduction of CO2Ce-MOF/Bi of2MoO6A heterojunction photocatalyst of Ce-MOF and Bi2MoO6Is 0.15: 0.027; the method comprises the following specific steps:
1. preparation of Ce-MOF:
0.216g of cerous nitrate hexahydrate and 0.21g of trimesic acid are dissolved in 4mL and 8mL of DMF respectively, and the solution is stirred uniformly to obtain a cerous nitrate solution and a trimesic acid solution.
Mixing the cerium nitrate solution and the trimesic acid solution, and then adding a certain amount of ammonia water to adjust the pH value of the mixed solution to 3; and (3) putting the mixed solution with the adjusted pH value into a reaction kettle, and carrying out hydrothermal reaction for 20h at 180 ℃. And after the reaction is finished, washing a reaction product, and drying the precipitate in the suspension at 180 ℃ to obtain a white powdery Ce-MOF photocatalyst.
2、Bi2MoO6Preparation of
Dissolving 1.68g of pentahydrate bismuth nitrate and 0.306g of ammonium molybdate tetrahydrate in deionized water, stirring for 1 hour for uniform mixing, then adding a certain amount of 1mol/L sodium hydroxide solution to adjust the pH to 7, transferring the mixed solution to a high-pressure reaction kettle, wherein the volume of the mixed solution accounts for 70% of the volume of the reaction kettle, and carrying out hydrothermal reaction for 22 hours at 170 ℃; after the reaction is finished, washing the reaction product, and then drying the precipitate in the suspension at 60 ℃ to obtain yellow powdery Bi2MoO6A photocatalyst.
3、Ce-MOF/Bi2MoO6Preparation of heterojunction photocatalysts
0.15g Ce-MOF and 0.216g Bi2MoO6Respectively adding into absolute ethyl alcohol, stirring for 1h under the condition of 70 ℃ water bath to obtain Ce-MOF dispersion liquid and Bi2MoO6And (3) dispersing the mixture.
Mixing the above Ce-MOF dispersion with Bi2MoO6Mixing the dispersion, stirring for 3h under the condition of 70 ℃ water bath, then centrifugally washing, and drying and precipitating at 60 ℃ to obtain Ce-MOF/Bi2MoO6A heterojunction photocatalyst.
4. Photocatalytic reduction of CO2
Mixing the aboveCe-MOF/Bi2MoO6Application of heterojunction photocatalyst simulation to photocatalytic reduction of CO2。
Carrying out photocatalytic reduction of CO2The reaction conditions of (a) are as follows:
Ce-MOF/Bi2MoO650mg of heterojunction photocatalyst, 15mL of deionized water, reaction temperature of 80 ℃, stirring speed of 400r/min, and filling CO by irradiation of 300W xenon lamp26 h. The reaction products were analyzed qualitatively and quantitatively by gas chromatography, and the results are shown in FIG. 4.
Furthermore, the above-mentioned Ce-MOF/Bi2MoO6The photocurrent intensity test of the heterojunction photocatalyst is shown in figure 5, which proves that the catalyst has stronger carrier separation capability and survival life.
Comparative example 1
1、CeO2Preparation of
0.216g of cerous nitrate hexahydrate is dissolved in 4mL of DMF and is uniformly stirred to obtain a cerous nitrate solution, and then the solution is filled into a reaction kettle and is subjected to hydrothermal reaction for 20 hours at 180 ℃. After the reaction is finished, washing the reaction product, and then drying the precipitate in the suspension at 180 ℃ to obtain yellow powdery CeO2A photocatalyst.
2、Bi2MoO6Preparation of
The preparation method is the same as in example 1.
3、CeO2/Bi2MoO6Preparation of heterojunction photocatalyst
0.15g of CeO2With 0.216g Bi2MoO6The subsequent steps were the same as in example 1.
4. Photocatalytic reduction of CO2
The above-mentioned CeO2/Bi2MoO6Application of heterojunction photocatalyst simulation to photocatalytic reduction of CO2. The test conditions were the same as in example 1; the results are shown in FIG. 6.
From the results of FIG. 6, it can be seen that when Ce-MOF, one of the components of the composite heterojunction photocatalyst, is replaced by CeO2Then, the catalytic activity is obviously reduced, and no methanol is generated.
Comparative example 2
1. Preparation of Ce-MOF
0.216g of cerous nitrate hexahydrate and 0.21g of terephthalic acid are dissolved in 4mL and 8mL of DMF respectively and are stirred uniformly to obtain a cerous nitrate solution and a terephthalic acid solution.
The above cerium nitrate solution and terephthalic acid solution were mixed, and the subsequent procedure was the same as in example 1.
2、Bi2MoO6Preparation of
The preparation method is the same as in example 1.
3、Ce-MOF/Bi2MoO6Preparation of heterojunction photocatalyst
The preparation method is the same as in example 1.
4. Photocatalytic reduction of CO2
The above Ce-MOF/Bi2MoO6Application of heterojunction photocatalyst simulation to photocatalytic reduction of CO2. The test conditions were the same as in example 1; the results are shown in FIG. 6.
From the results of FIG. 6, it is clear that when the ligand (i.e., organic linker) in the Ce-MOF synthesis process is changed from trimesic acid to terephthalic acid, the catalytic activity is also significantly reduced and no methanol is produced. It is thus clear that the use of terephthalic acid and the synthesis of MOF structures are such that the heterojunction photocatalyst has a high CO content2The requirement of reducing performance.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (8)

1. Ce-MOF/Bi2MoO6Preparation method of heterojunction photocatalystThe method is characterized by comprising the following steps:
A) dissolving a cerium source substance and an organic connector in an organic solvent, wherein the mass ratio of the cerium source substance to the organic connector is 1 (1-3), uniformly stirring and adjusting the pH value to 3-5, then carrying out hydrothermal reaction at the temperature of 120-180 ℃ for 15-20h, and then washing and drying to obtain the Ce-MOF photocatalyst;
B) dissolving a bismuth source substance and a molybdenum source substance in deionized water, wherein the mass ratio of the bismuth source substance to the molybdenum source substance is (10-20):1, uniformly stirring and adjusting the pH value to 5-9, then carrying out hydrothermal reaction at the temperature of 160-220 ℃ for 20-24h, and then washing and drying to obtain Bi2MoO6A photocatalyst;
C) a Ce-MOF photocatalyst and Bi2MoO6The photocatalyst is dispersed in an organic solvent, the Ce-MOF photocatalyst and Bi2MoO6The mass ratio of the photocatalyst is 0.15 to 0.02 to 0.3, stirring, washing and drying are carried out to obtain Ce-MOF/Bi2MoO6A heterojunction photocatalyst;
wherein the cerium source substance is cerium nitrate hexahydrate; the organic connector is trimesic acid; the bismuth source substance is bismuth nitrate pentahydrate; the molybdenum source material is ammonium molybdate tetrahydrate.
2. The method of claim 1, wherein step a) comprises:
A1) respectively dissolving a cerium source substance and an organic connector in an organic solvent, and uniformly stirring to obtain a cerium-containing solution and an organic connector solution;
A2) and stirring and uniformly mixing the cerium-containing solution and the organic connecting body solution, adjusting the pH value, carrying out hydrothermal reaction, and then washing and drying to obtain the Ce-MOF photocatalyst.
3. The process according to claim 1 or 2, wherein in step a), aqueous ammonia is added to adjust the pH to 3 to 5; the organic solvent is DMF; the drying temperature is 140-180 ℃.
4. The preparation method according to claim 1, wherein in the step B), a sodium hydroxide solution is added dropwise to adjust the pH value to 5 to 9; carrying out hydrothermal reaction in a reaction kettle, wherein the volume of the deionized water is 60-80% of the volume of the reaction kettle; the drying temperature is 50-60 ℃.
5. The method of claim 1, wherein step C) comprises:
C1) respectively adding Ce-MOF photocatalyst and Bi2MoO6Dispersing the photocatalyst in an organic solvent, and stirring under the water bath condition to obtain a Ce-MOF dispersion liquid and Bi2MoO6A dispersion liquid;
C2) mixing a Ce-MOF dispersion with Bi2MoO6Stirring the dispersion liquid under the condition of water bath, and then washing and drying to obtain Ce-MOF/Bi2MoO6A heterojunction photocatalyst;
wherein, in the step C1), the water bath temperature is 40-80 ℃, and the stirring time is 0.5-1 h; in the step C2), the water bath temperature is 40-80 ℃, and the stirring time is 2-4 h.
6. The process according to claim 1 or 5, wherein in step C),
the organic solvent is absolute ethyl alcohol; the drying temperature is 50-60 ℃.
7. Ce-MOF/Bi2MoO6A heterojunction photocatalyst produced by the production method according to any one of claims 1 to 6.
8. The Ce-MOF/Bi of claim 72MoO6The application of the heterojunction photocatalyst in the carbon dioxide photocatalytic reduction is provided.
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