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CN109772355B - Preparation method of amorphous iron oxyhydroxide/bismuth vanadate composite photocatalytic material - Google Patents

Preparation method of amorphous iron oxyhydroxide/bismuth vanadate composite photocatalytic material Download PDF

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CN109772355B
CN109772355B CN201910178751.5A CN201910178751A CN109772355B CN 109772355 B CN109772355 B CN 109772355B CN 201910178751 A CN201910178751 A CN 201910178751A CN 109772355 B CN109772355 B CN 109772355B
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bismuth vanadate
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CN109772355A (en
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杨占旭
张莹
石磊
谭文
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Liaoning Shihua University
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Abstract

The invention belongs to the field of photocatalyst preparation, and particularly relates to a preparation method of an amorphous iron oxyhydroxide/bismuth vanadate composite photocatalytic material, which comprises the following steps: and (2) synthesizing bismuth vanadate by adopting a hydrothermal method, taking the synthesized bismuth vanadate as a substrate, putting the bismuth vanadate into a mixed solution of ferric chloride and ammonium bicarbonate, stirring, centrifuging, and drying to obtain an amorphous FeOOH/bismuth vanadate composite photocatalyst. The invention uses amorphous material as cocatalyst, which lacks ordered atomic arrangement and has narrower forbidden bandwidth due to the special structure of the amorphous material. The characteristics enable the surface of the catalyst to generate more defects, provide more active sites, expand the light absorption range and further improve the photocatalytic performance.

Description

Preparation method of amorphous iron oxyhydroxide/bismuth vanadate composite photocatalytic material
Technical Field
The invention belongs to the field of photocatalyst preparation, and particularly relates to a preparation method of an amorphous iron oxyhydroxide/bismuth vanadate composite photocatalytic material.
Background
Photocatalytic water splitting is one of the important methods of solar energy production. The current promoters used for photolyzing water include noble metals such as Pt, Au, Pt/g-C3N4 and the like and noble metal compounds, although the photocatalytic performance is relatively improved, the huge cost also limits the application space. Thus, one has shifted his attention to non-noble metal promoters. For example: fe, Co, Ni, Cu, Zn and carbon-based materials (CoS, Ni (oh)2, NiS, Cu2O, ZnIn2S4, carbon quantum dots, etc.). However, these promoters are in crystalline form to improve photocatalytic performance, and it is also revealed that these promoters strongly depend on the crystal structure and morphology, particularly crystallinity and particle size. Thus, one has shifted his eye to amorphous promoters.
Amorphous materials are more common than crystalline materials in nature. Amorphous materials are of great interest to an increasing number of people due to their complex internal structure. So far, amorphous catalysts have been applied to various fields including electrochemistry, photoelectrochemistry, biochemistry, and the like. In Applied Catalysis B, Environmental,2018,222, 35-43, Liu et al modified non-noble metals g-C3N4 with amorphous NiO and photolyzed water to produce hydrogen under visible light irradiation. The results show that compared with pure g-C3N4 and crystal NiO modified g-C3N4 photocatalysts, the amorphous NiO modified g-C3N4 photocatalyst has obviously enhanced photocatalytic effect.
Iron oxyhydroxide, a non-noble metal hydroxy compound, has a variety of crystalline phases and is widely studied by researchers in the fields of electrochemistry and photoelectrochemistry. The amorphous structure has a narrower forbidden bandwidth, lacks ordered atomic arrangement and has more defects. These characteristics can make its light absorption range wider, promote electron transfer and provide more active sites, and then strengthen the photocatalytic performance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of an amorphous FeOOH/bismuth vanadate composite photocatalytic material, which can effectively improve the photocatalytic performance, has a narrow forbidden band width, a large light absorption range and a plurality of electron transfer active sites.
In order to solve the technical problem, the invention is realized as follows:
a preparation method of an amorphous FeOOH/bismuth vanadate catalytic material comprises the following specific steps:
preparation of BiVO4 catalyst
(1) Weighing a bismuth source, and dissolving the bismuth source in a mixed solution of HNO3 solution and ethylene glycol to prepare solution A;
(2) weighing NH4VO3 and dissolving in 0.1-0.4 g of template solution to prepare solution B;
(3) dropwise adding the solution A into the solution B, adjusting the pH = 2-9 by using a NaOH solution, and stirring the mixed solution to obtain a BiVO4 catalyst precursor;
(4) and (4) transferring the solution obtained in the step (3) into a high-pressure reaction kettle, sealing, putting into an oven, carrying out hydrothermal reaction, naturally cooling to room temperature, washing and drying for 2-20 h, cooling, and grinding to obtain the BiVO4 catalyst.
Preparation of amorphous iron oxyhydroxide/bismuth vanadate composite photocatalytic material
Adding the BiVO4 catalyst powder obtained in the step one into a mixed solution of an iron source and NH4HCO3, and stirring; and (3) centrifuging the mixed solution, washing and drying to obtain the target product amorphous iron oxyhydroxide/bismuth vanadate composite photocatalytic material.
As a preferable scheme, in the first step of the invention, bismuth source is bismuth nitrate pentahydrate or bismuth oxide.
Furthermore, in the first step of the invention, the template agent is sodium dodecyl benzene sulfonate, cetyl trimethyl ammonium bromide or sodium dodecyl sulfate.
Further, in the second step of the invention, FeCl3.6H2O or FeCl3 is used as the iron source.
Furthermore, in the first step of the invention, the hydrothermal reaction temperature is 110 ︒ -200 ︒ C, and the hydrothermal time is 6-30 h.
Further, in the second step of the invention, the molar ratio of the iron source to the NH4HCO3 is 1-5: 1.
Further, adding the BiVO4 catalyst powder obtained in the step one into a mixed solution of an iron source and NH4HCO3, and stirring for 1-20 hours; and (3) carrying out centrifugal treatment on the mixed solution, washing the mixed solution with distilled water for more than three times, and drying the washed mixed solution at 40-90 ℃ for 2-20 hours to obtain the target product amorphous iron oxyhydroxide/bismuth vanadate composite photocatalytic material.
Furthermore, the mass ratio of the amorphous iron oxyhydroxide to BiVO4 is 0.5-11%.
Furthermore, the concentration of iron ions in the iron source is 0.001-0.022 mol/L.
According to the invention, the bismuth vanadate is used as a substrate, and after the amorphous iron oxyhydroxide film is formed on the outer surface of the bismuth vanadate, the amorphous iron oxyhydroxide/bismuth vanadate can effectively improve the photocatalytic performance. The invention utilizes the synthesized amorphous iron oxyhydroxide/bismuth vanadate cocatalyst to carry out a water photolysis experiment, and the experimental result shows that the oxygen content of photolysis water of the amorphous iron oxyhydroxide/bismuth vanadate is 793.9 mu mol h < -1 > g < -1 >, the oxygen content of pure phase bismuth vanadate is 97.4 mu mol h < -1 > g < -1 >, and the oxygen content of crystalline phase iron oxyhydroxide/bismuth vanadate is 381.9 mu mol h < -1 > g < -1 > after the amorphous iron oxyhydroxide/bismuth vanadate cocatalyst is irradiated by visible light for six hours. It can be seen that the oxygen yield of photocatalytic water decomposition of amorphous iron oxyhydroxide/bismuth vanadate is eight times that of pure phase bismuth vanadate and twice that of crystalline phase iron oxyhydroxide/bismuth vanadate at the same time. The ferric oxyhydroxide/bismuth vanadate can effectively improve the photocatalytic performance, and the amorphous material has the characteristics of narrower forbidden band width, lack of ordered atomic arrangement and more defects, expands the light absorption range, promotes electron transfer, provides more active sites, enhances the photocatalytic performance and improves the oxygen yield. The invention has simple synthesis process, utilizes non-noble metal materials and greatly reduces the required cost.
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The invention is further described with reference to the following figures and detailed description. The scope of the invention is not limited to the following expressions.
FIGS. 1-a and 1-b are TEM images of the composite material obtained in example 1.
FIGS. 2-a and 2-b are TEM images of the composite material obtained in example 3.
FIG. 3 is a graph showing the photolytic water-to-oxygen performance of the composites obtained in examples 2 and 3.
Detailed Description
Comparative example:
3mmol of Bi2O3 (analytically pure) is dissolved in 5mL of a mixed solution of 3 mol.L-1 HNO3 and 20mL of ethylene glycol to prepare solution A, and 3mmol of NH4VO3 (analytically pure) is dissolved in 20mL of hot water added with 0.2 g of Sodium Dodecyl Sulfate (SDS) to prepare solution B. Stirring the solution A for 30min at room temperature, then dropwise adding the solution A into the solution B, adjusting the pH value to 4 by using a NaOH solution with the concentration of 1 mol.L < -1 >, and stirring the mixed solution for 60min to obtain the BiVO4 catalyst precursor. And transferring the obtained solution into a 100mL high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, putting into an oven, carrying out hydrothermal reaction at 160 ℃ for 20h, naturally cooling to room temperature, repeatedly washing with distilled water and absolute ethyl alcohol for more than 3 times, drying at constant temperature of 80 ℃ for 12h, cooling, and then grinding by using a mortar to obtain the BiVO4 catalyst.
400mg of BiVO4 catalyst powder was added to 0.025 mol/L FeCl3.6H2O solution, and after stirring for 30 minutes, the mixed solution was transferred to a 100mL polytetrafluoroethylene-lined high-pressure reactor and continuously stirred at 100 ℃ for 12 hours. And cooling the reactor to room temperature, taking out the lining, carrying out suction filtration on substances in the lining, washing the substances with distilled water for more than three times, and placing a suction-filtered sample in an 80 ℃ oven for 12 hours to obtain the beta-FeOOH/BiVO 4 catalyst.
As shown in FIG. 1, TEM observed that a layer of iron oxyhydroxide was coated on the outer surface of bismuth vanadate. As shown in figure 3, the oxygen production performance of the beta-FeOOH/BiVO 4 composite photocatalyst is improved compared with that of pure phase bismuth vanadate.
Example (b):
a solution A was prepared by dissolving 5 mmol of Bi (NO3) 3.5H 2O (analytically pure) in 5mL of a mixed solution of 3 mol.L-1 HNO3 and 15mL of ethylene glycol, and a solution B was prepared by dissolving 5 mmol of NH4VO3 (analytically pure) in 20mL of hot water to which 0.4g of Sodium Dodecylbenzenesulfonate (SDBS) was added. Stirring the solution A for 30min at room temperature, then dropwise adding the solution A into the solution B, adjusting the pH value to 6 by using a NaOH solution with the concentration of 1 mol.L < -1 >, and stirring the mixed solution for 30min to obtain the BiVO4 catalyst precursor. And transferring the obtained solution into a 100mL high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, putting into an oven, carrying out hydrothermal reaction at 200 ℃ for 22h, naturally cooling to room temperature, repeatedly washing with distilled water and absolute ethyl alcohol for more than 3 times, drying at a constant temperature of 60 ℃ for 6h, cooling, and then grinding by using a mortar to obtain the BiVO4 catalyst.
NH4HCO3 (wherein the molar ratio of FeCl3.6H2O to NH4HCO3 is 3: 1) and 400mg of BiVO4 catalyst powder were added to 0.016mol/L FeCl3.6H2O solution, and stirred for 1 hour. After this, the solution was centrifuged and washed with distilled water. And putting the centrifuged sample in an 80 ℃ oven for 12 hours to obtain the amorphous FeOOH/BiVO4 (amophorus FeOOH/BiVO 4) catalyst.
As shown in fig. 2, TEM observed that the bismuth vanadate outer surface was coated with an amorphous layer, which was iron oxyhydroxide. As shown in figure 3, the oxygen production performance of the amorphous FeOOH/BiVO4 composite photocatalyst is improved compared with that of pure-phase bismuth vanadate and beta-FeOOH/BiVO 4 composite photocatalyst, and the amorphous FeOOH/BiVO4 composite photocatalyst is proved to be capable of effectively improving the photocatalytic performance.
It is understood that various other changes and modifications may be made by those skilled in the art based on the technical idea of the present invention, and all such changes and modifications should fall within the protective scope of the claims of the present invention.

Claims (1)

1. A preparation method of an amorphous FeOOH/bismuth vanadate catalytic material is characterized by comprising the following specific steps:
one, BiVO4Preparation of the catalyst
(1) 5 mmol of analytically pure Bi (NO) are weighed3)3·5H2O dissolved in 5mL of 3 mol. L-1 HNO3Preparing a solution A from the solution and 15mL of glycol mixed solution;
(2) 5 mmol of analytically pure NH are weighed4VO3Dissolving in 20mL of hot water with 0.4g of sodium dodecyl benzene sulfonate to obtain solution B;
(3) stirring at room temperature for 30min, adding solution A into solution B dropwise at a concentration of 1 mol. L-1Adjusting the pH value of the NaOH solution to be 6, and stirring the mixed solution for 30min to obtain BiVO4A catalyst precursor;
(4) transferring the obtained solution into a 100mL high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, putting into an oven, performing hydrothermal reaction at 200 ℃ for 22h, naturally cooling to room temperature, repeatedly washing with distilled water and absolute ethyl alcohol for more than 3 times, drying at constant temperature of 60 ℃ for 6h, cooling, and grinding with a mortar to obtain BiVO4A catalyst;
preparation of amorphous iron oxyhydroxide/bismuth vanadate composite photocatalytic material
At 0.016mol/LFeCl3·6H2Adding NH into O solution respectively4HCO3And 400mg BiVO4Catalyst powder of FeCl3·6H2O and NH4HCO3At a molar ratio of 3:1, stirringStirring for 1 hour; after that, the solution was subjected to a centrifugal treatment and washed with distilled water; placing the centrifuged sample in an oven at 80 ℃ for 12 hours to obtain amorphous FeOOH/BiVO4A catalyst.
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CN111790394A (en) * 2020-07-31 2020-10-20 武汉理工大学 Synthesis method of bismuth vanadate photocatalytic material selectively modified by hydroxyl ferric oxide cocatalyst
CN112156787B (en) * 2020-10-30 2022-12-06 武汉工程大学 Amorphous FeOOH modified BiO 2-x Heterojunction photocatalyst and preparation method and application thereof
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CN113304755A (en) * 2020-11-06 2021-08-27 淮阴工学院 BiVO4/MOOH photoelectric catalyst and preparation method thereof
CN113398944B (en) * 2021-05-24 2022-02-22 苏州科技大学 Composite material of bismuth vanadate surface modified nickel cobaltate spinel and preparation and application thereof
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