CN109772378B - Method for preparing high-activity iron-doped bismuth oxyhalide photo-Fenton catalyst, product and application thereof - Google Patents
Method for preparing high-activity iron-doped bismuth oxyhalide photo-Fenton catalyst, product and application thereof Download PDFInfo
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Abstract
The invention discloses a method for preparing a high-activity iron-doped bismuth oxyhalide photo-Fenton catalyst, and a product and application thereof, wherein the method comprises the following steps of: 1, respectively adding iron salt and bismuth salt into a solvent, then adding excessive halogen acid to completely dissolve the bismuth salt and the iron salt to form a mixed solution, after the mixed solution is clarified, dripping the mixed solution into a sodium hydroxide solution at a constant speed, continuously stirring until the pH value is 4-14, reacting the reaction solution at a temperature lower than 100 ℃ for at least 1h, washing the obtained precipitate after the reaction is finished, and drying to obtain the high-activity iron-doped bismuth oxyhalide photo-fenton catalyst. The method is simple to operate, the catalyst prepared with low energy consumption effectively reduces the recombination rate of photo-generated electrons and holes, improves the conduction of electrons, has larger specific surface area, is more fully contacted with a reaction substrate, and has high catalytic activity of the photo-Fenton catalyst.
Description
Technical Field
The invention relates to the field of photo-Fenton catalytic materials, in particular to a method for synthesizing a high-activity iron-doped bismuth oxyhalide photo-Fenton catalyst by a normal temperature method, and also relates to a product prepared by the method and application of the product.
Background
Bismuth oxyhalide has high photocatalytic activity and visible light utilization capacity due to a proper forbidden band width and a unique electronic structure, and has remarkable catalytic degradation performance on organic pollutants, dyes, pesticides and biochemical medicines under visible light, so that the bismuth oxyhalide attracts extensive attention of researchers. The synthesis method of the bismuth oxyhalide catalyst comprises a hydrothermal method, a solvothermal method, a template method, a high-temperature solid phase method and the like, needs to synthesize under a high-temperature condition by adding more energy, and has the advantages of high equipment requirement, high technical difficulty, poor safety performance, high production input cost, long synthesis period, low yield and difficulty in realizing large-scale industrial production. Therefore, there is a need to improve the synthesis method of bismuth oxyhalide, change the structure and composition thereof, improve the performance of the catalyst, widen the application range thereof, reduce the production cost thereof, and obtain a novel bismuth-based catalyst with high yield and high efficiency.
In recent years, bismuth ferrite as an important magneto-optical material has attracted great attention of scientists in the fields of material science and photocatalysis. Researchers have introduced this into the field of photocatalysis. For the composition and structure change of bismuth oxyhalide, the removal effect of organic pollutants can be enhanced based on a photo-Fenton reaction system (namely, light source assisted Fenton reaction), but the general photo-Fenton catalyst has high synthesis condition requirement and large energy consumption, so that the general photo-Fenton catalyst cannot be widely used.
Based on the high-efficiency catalytic action of photocatalysis and Fenton effect synergistic enhancement, a Fenton system is formed after iron (III) is doped into bismuth oxyhalide, and the Fe (III)/Fe (II) circulation is accelerated by utilizing the synergistic action among multiple metals (compounds), so that the activity of the catalyst is obviously improved.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing a highly active iron-doped bismuth oxyhalide photo-fenton catalyst, and another object of the present invention is to provide a highly active iron-doped bismuth oxyhalide photo-fenton catalyst prepared by the above method; the invention also aims to provide application of the high-activity iron-doped bismuth oxyhalide photo-Fenton catalyst.
In order to achieve the purpose, the invention provides the following technical scheme:
1. the method for preparing the high-activity iron-doped bismuth oxyhalide photo-Fenton catalyst comprises the following steps of: the molar ratio of the components is 0.01-2: 1, respectively adding iron salt and bismuth salt into a solvent, then adding excessive halogen acid to completely dissolve the bismuth salt and the iron salt to form a mixed solution, after the mixed solution is clarified, dripping the mixed solution into a sodium hydroxide solution at a constant speed, continuously stirring until the pH value is 4-14, reacting the reaction solution at a temperature lower than 100 ℃ for at least 1h, washing the obtained precipitate after the reaction is finished, and drying to obtain the high-activity iron-doped bismuth oxyhalide photo-fenton catalyst.
In the invention, the solvent is one of water or ethanol; the ferric salt is at least one of ferric nitrate, ferric chloride, ferric bromide and ferric sulfate; the bismuth salt is at least one of bismuth subcarbonate, bismuth sulfate and bismuth nitrate.
Preferably, the addition amount of the halogen acid is as follows: the molar ratio of the halogen acid is more than 2: 15. more preferably, the hydrohalic acid is any one of hydrochloric acid, hydrobromic acid, hydroiodic acid or hydrofluoric acid; hydrohalic acid is the most effective hydrobromic acid. In the present invention, the halogen acid may be used as it is as a concentrated acid or as a diluted acid.
In the present invention, preferably, the dissolution is ultrasonic dissolution.
Preferably, the concentration of the sodium hydroxide solution is 0.6-3.15 mmol/ml.
Preferably, the washing is carried out by sequentially washing with water and an organic solvent until the pH of the solution is 6-7 and the conductivity is less than 20 us/cm.
In a preferred embodiment of the present invention, the organic solvent is at least one of absolute ethyl alcohol and acetone.
Preferably, the drying is drying until the moisture content of the bismuth oxyhalide is less than 0.5%.
Preferably, the dye is a RhB dye.
As a more preferable scheme of the invention, in the reaction process, the temperature of the reaction solution is better at 20-80 ℃, the effect is better at 20-60 ℃, and the optimal reaction is carried out at 20 ℃; the reaction time is preferably 1-24 h. The molar ratio of the ferric salt to the bismuth salt is 0.05-0.2: 1, the effect is better, and the molar ratio of the iron salt to the bismuth salt is 0.1: 1 the effect is optimal. The addition amount of the solvent is 0.075-0.25 mmol/ml of bismuth salt.
2. The high-activity iron-doped bismuth oxyhalide photo-Fenton catalyst prepared by the method.
3. The high-activity iron-doped bismuth oxyhalide photo-Fenton catalyst is applied to the degradation of organic pollutants, dyes, pesticides or biochemical medicines under the visible light.
The invention has the beneficial effects that: according to the invention, the high-activity iron-doped bismuth oxyhalide photo-Fenton catalyst is obtained by adding excessive halogen acid into iron salt and bismuth salt to dissolve, then reacting under the condition that the pH value is 4-14, washing after reaction, and drying. The method is simpler, the conditions are controllable, the operation is easy, the energy consumption is lower compared with the traditional hydrothermal reaction, and the prepared catalyst has high photo-Fenton catalytic activity.
Drawings
In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:
FIG. 1 is an SEM image of an iron-doped bismuth oxyhalide sample, wherein a represents an SEM image of an iron-doped bismuth oxybromide sample obtained at a synthesis temperature of 25 ℃ (example 4), and b represents an SEM image of an iron-doped bismuth oxybromide sample obtained at a synthesis temperature of 60 ℃ (example 5);
FIG. 2 is an XRD pattern of an iron-doped bismuth oxyhalide sample showing the XRD patterns of iron-doped bismuth oxybromide samples obtained at a synthesis temperature of 25 deg.C (example 4) and a synthesis temperature of 60 deg.C (example 5);
FIG. 3 is a graph of the results of iron-doped bismuth oxyhalide catalytic efficiency;
FIG. 4 is a Fourier infrared spectrum of a sample of iron-doped bismuth oxyhalide showing the Fourier infrared spectra of a sample of iron-doped bismuth oxybromide obtained at a synthesis temperature of 25 deg.C (example 4) and 60 deg.C (example 5);
fig. 5 is a graph comparing the efficiency of photo-fenton degradation of RhB dye under simulated sunlight for iron-doped bismuth oxychloride preparation at different temperatures.
Fig. 6 is a graph comparing the efficiency of photo-fenton degradation of RhB dye in simulated sunlight for bismuth oxyhalide samples of different iron doping ratios.
Fig. 7 is a graph comparing the efficiency of photo-fenton degradation of RhB dye in simulated sunlight for bismuth oxyhalide samples synthesized from different halogen acids.
Detailed Description
The present invention is further described with reference to the following drawings and specific examples so that those skilled in the art can better understand the present invention and can practice the present invention, but the examples are not intended to limit the present invention.
Example 1
The method for preparing the high-activity iron-doped bismuth oxyhalide photo-Fenton catalyst comprises the following steps of: adding 3mmol of ferric nitrate and 1.5mmol of bismuth subcarbonate into 20ml of deionized water, adding 45mmol of hydrochloric acid, and ultrasonically dissolving ferric nitrate and bismuth subcarbonate until the solution is clear, and marking as solution A; adding 63mmol of sodium hydroxide into 20ml of deionized water, and ultrasonically dissolving the sodium hydroxide until the solution is clear, and marking as solution B; and transferring the solution A to an injection syringe, dropping the solution A into the solution B by an injection pump at a dropping speed of 0.8ml/min, continuously stirring, controlling the rotating speed of a stirrer to be 600r/min, finishing dropping when the pH value of the solution is 12, pouring the reacted solution into a 100ml polytetrafluoroethylene reaction kettle, reacting for 10h at 80 ℃, washing precipitates with deionized water, absolute ethyl alcohol and acetone respectively after the reaction is finished, and drying at 60 ℃ to obtain the product. Wherein the washing process needs to be carried out until the pH value of the solution is 6-7 and the conductivity is less than 20 mu s/cm; drying process until the water content of the obtained product is less than 0.5%.
Example 2
The method for preparing the high-activity iron-doped bismuth oxyhalide photo-Fenton catalyst comprises the following steps of: adding 0.54mmol of ferric chloride and 2.7mmol of bismuth subcarbonate into 20ml of deionized water, adding 45mmol of hydrochloric acid, and ultrasonically dissolving the ferric chloride and the bismuth subcarbonate until the solution is clear and marked as solution A; adding 40mmol of sodium hydroxide into 20ml of deionized water, and ultrasonically dissolving the sodium hydroxide until the solution is clear, and marking as solution B; transferring the solution A to an injection syringe, dripping the solution A into the solution B by an injection pump at a dripping speed of 0.8ml/min, continuously stirring, wherein the rotating speed of a stirrer is 200r/min, and finishing dripping when the pH value of the solution is 9; pouring the solution into a 100ml polytetrafluoroethylene reaction kettle, reacting for 1h at 60 ℃, washing the obtained precipitate with deionized water, absolute ethyl alcohol and acetone respectively after the reaction is finished, and drying at 60 ℃ to obtain the product. Wherein the washing process needs to be carried out until the pH value of the solution is 6-7 and the conductivity is less than 20 mu s/cm; drying process until the water content of the obtained product is less than 0.5%.
Example 3
The method for preparing the high-activity iron-doped bismuth oxyhalide photo-Fenton catalyst comprises the following steps of: adding 0.3mmol of ferric nitrate and 0.6mmol of bismuth sulfate into 20ml of deionized water, adding 11mmol of hydrochloric acid, and ultrasonically dissolving the ferric nitrate and the bismuth sulfate until the solution is clear and marked as solution A; adding 12mmol of sodium hydroxide into 20ml of deionized water, and ultrasonically dissolving the sodium hydroxide until the solution is clear, and marking as solution B; transferring the solution A to an injection syringe, dripping the solution A into the solution B by an injection pump at a dripping speed of 0.1ml/min, continuously stirring, wherein the rotating speed of a stirrer is 300r/min, and finishing dripping when the pH value of the solution is 9; pouring the solution into a 100ml polytetrafluoroethylene reaction kettle, reacting for 5h at 20 ℃, washing the obtained precipitate with deionized water, absolute ethyl alcohol and acetone respectively after the reaction is finished, and drying at 60 ℃ to obtain the product. Wherein the washing process needs to be carried out until the pH value of the solution is 6-7 and the conductivity is less than 20 mu s/cm; drying process until the water content of the obtained product is less than 0.5%.
Example 4
The method for preparing the high-activity iron-doped bismuth oxyhalide photo-Fenton catalyst comprises the following steps of: adding 0.54mmol of ferric nitrate and 2.72mmol of bismuth subcarbonate into 20ml of deionized water, adding 45mmol of hydrobromic acid, and ultrasonically dissolving the ferric nitrate and the bismuth subcarbonate until the solution is clear and marked as solution A; adding 63mmol of sodium hydroxide into 20ml of deionized water, and ultrasonically dissolving the sodium hydroxide until the solution is clear, and marking as solution B; transferring the solution A to an injection syringe, dripping the solution A into the solution B by an injection pump at a dripping speed of 0.8ml/min, continuously stirring, wherein the rotating speed of a stirrer is 600r/min, and finishing dripping when the pH value of the solution is 12; pouring the solution into a 100ml polytetrafluoroethylene reaction kettle, reacting for 10h at 20 ℃, washing the obtained precipitate with deionized water, absolute ethyl alcohol and acetone respectively after the reaction is finished, and drying at 60 ℃ to obtain the product. Wherein the washing process needs to be carried out until the pH value of the solution is 6-7, the conductivity is less than 20 mu s/cm, and the drying process is carried out until the water content of the obtained product is less than 0.5%.
Example 5
The method for preparing the high-activity iron-doped bismuth oxyhalide photo-Fenton catalyst comprises the following steps of: adding 0.54mmol of ferric nitrate and 2.72mmol of bismuth subcarbonate into 20ml of deionized water, adding 45mmol of hydrobromic acid, and ultrasonically dissolving the ferric nitrate and the bismuth subcarbonate until the solution is clear and marked as solution A; adding 63mmol of sodium hydroxide into 20ml of deionized water, and ultrasonically dissolving the sodium hydroxide until the solution is clear, and marking as solution B; transferring the solution A to an injection syringe, dripping the solution A into the solution B by an injection pump at a dripping speed of 0.8ml/min, continuously stirring, wherein the rotating speed of a stirrer is 600r/min, and finishing dripping when the pH value of the solution is 12; pouring the solution into a 100ml polytetrafluoroethylene reaction kettle, reacting for 10h at 60 ℃, washing the obtained precipitate with deionized water, absolute ethyl alcohol and acetone respectively after the reaction is finished, and drying at 60 ℃ to obtain the product. The washing process needs to be carried out until the pH value of the solution is 6-7 and the conductivity is less than 20 mu s/cm. And drying in the drying process until the moisture of the obtained product is lower than 0.5 percent.
Example 6
The method for preparing the high-activity iron-doped bismuth oxyhalide photo-Fenton catalyst comprises the following steps of: adding 0.05mmol of ferric nitrate and 5mmol of bismuth nitrate into 20ml of ethanol, adding 45mmol of hydrobromic acid, and ultrasonically dissolving the ferric nitrate and the bismuth nitrate until the solution is clear and is marked as solution A; and adding 40mmol of sodium hydroxide into 20ml of ethanol, and performing ultrasonic treatment to completely dissolve the sodium hydroxide until the solution is clear, and marking as solution B. Transferring the solution A to an injection syringe, dropping the solution A into the solution B by an injection pump at a dropping speed of 0.8ml/min, continuously stirring, wherein the rotating speed of a stirrer is 600r/min, and the solution is completely dropped when the pH value is 9. Pouring the solution into a 100ml polytetrafluoroethylene reaction kettle, reacting for 10h at 25 ℃, washing the obtained precipitate with deionized water, absolute ethyl alcohol and acetone respectively after the reaction is finished, and drying at 60 ℃ to obtain the product. Wherein the washing process needs to be carried out until the pH value of the solution is 6-7 and the conductivity is less than 20 mu s/cm; drying process until the water content of the obtained product is less than 0.5%.
Example 7
The method for preparing the high-activity iron-doped bismuth oxyhalide photo-Fenton catalyst comprises the following steps of: adding 1.2mmol of ferric sulfate and 2.4mmol of bismuth subcarbonate into 20ml of deionized water, adding 45mmol of hydroiodic acid, and ultrasonically dissolving the ferric sulfate and the bismuth subcarbonate until the solution is clear, and marking as solution A; adding 63mmol of sodium hydroxide into 20ml of deionized water, and ultrasonically dissolving the sodium hydroxide until the solution is clear, and marking as solution B; transferring the solution A to an injection syringe, dripping the solution A into the solution B by an injection pump at a dripping speed of 1.6ml/min, continuously stirring, wherein the rotating speed of a stirrer is 500r/min, and finishing dripping when the pH value of the solution is 4; pouring the solution into a 100ml polytetrafluoroethylene reaction kettle, reacting for 10h at 25 ℃, washing the obtained precipitate with deionized water, absolute ethyl alcohol and acetone respectively after the reaction is finished, and drying at 60 ℃ to obtain the product. Wherein the washing process needs to be carried out until the pH value of the solution is 6-7 and the conductivity is less than 20 mu s/cm. And drying in the drying process until the moisture of the obtained product is lower than 0.5 percent.
Example 8
The method for preparing the high-activity iron-doped bismuth oxyhalide photo-Fenton catalyst comprises the following steps of: adding 0.54mmol of ferric bromide and 2.7mmol of bismuth subcarbonate into 20ml of deionized water, adding 45mmol of hydrobromic acid, and ultrasonically dissolving ferric nitrate and bismuth subcarbonate until the solution is clear and marked as solution A; adding 40mmol of sodium hydroxide into 20ml of deionized water, and ultrasonically dissolving the sodium hydroxide until the solution is clear, and marking as solution B; transferring the solution A to an injection syringe, dropping the solution A into the solution B by an injection pump at a dropping speed of 5.0ml/min, continuously stirring, wherein the rotating speed of a stirrer is 600r/min, and the solution is completely dropped when the pH value of the solution is 14. Pouring the solution into a 100ml polytetrafluoroethylene reaction kettle, reacting for 5h at 25 ℃, washing the obtained precipitate with deionized water, absolute ethyl alcohol and acetone respectively after the reaction is finished, and drying at 60 ℃ to obtain the product. Wherein the washing process needs to be carried out until the pH value of the solution is 6-7 and the conductivity is less than 20 mu s/cm; drying process until the water content of the obtained product is less than 0.5%.
Example 9
The method for preparing the high-activity iron-doped bismuth oxyhalide photo-Fenton catalyst comprises the following steps of: adding 0.54mmol of ferric nitrate and 2.7mmol of bismuth subcarbonate into 20ml of deionized water, adding 45mmol of hydrobromic acid, and ultrasonically dissolving the ferric nitrate and the bismuth subcarbonate until the solution is clear and marked as solution A; adding 40mmol of sodium hydroxide into 20ml of deionized water, and ultrasonically dissolving the sodium hydroxide until the solution is clear, and marking as solution B; transferring the solution A to an injection syringe, dripping the solution A into the solution B by an injection pump at a dripping speed of 0.8ml/min, continuously stirring, wherein the rotating speed of a stirrer is 600r/min, and finishing dripping when the pH value of the solution is 6; pouring the solution into a 100ml polytetrafluoroethylene reaction kettle, reacting for 24h at 25 ℃, washing the obtained precipitate with deionized water, absolute ethyl alcohol and acetone respectively after the reaction is finished, and drying at 60 ℃ to obtain the product. Wherein the washing process needs to be carried out until the pH value of the solution is 6-7, the conductivity is less than 20 mu s/cm, and the drying process is carried out until the water content of the obtained product is less than 0.5%.
Example 10
The method for preparing the high-activity iron-doped bismuth oxyhalide photo-Fenton catalyst comprises the following steps of: adding 0.28mmol of ferric sulfate and 2.9mmol of bismuth sulfate into 20ml of deionized water, adding 45mmol of hydrofluoric acid, and ultrasonically dissolving the ferric sulfate and the bismuth sulfate until the solution is clear and marked as solution A; adding 63mmol of sodium hydroxide into 20ml of deionized water, and ultrasonically dissolving the sodium hydroxide until the solution is clear, and marking as solution B; and transferring the solution A to an injection syringe, dropping the solution A into the solution B by an injection pump at a dropping speed of 10.0ml/min, continuously stirring, pouring the solution into a 100ml polytetrafluoroethylene reaction kettle when the rotation speed of a stirrer is 600r/min and the pH of the solution is 12, reacting for 10h at 25 ℃, washing the obtained precipitate with deionized water, absolute ethyl alcohol and acetone respectively, and drying at 60 ℃ to obtain the product. Wherein the washing process needs to be carried out until the pH value of the solution is 6-7, the conductivity is less than 20 mu s/cm, and the drying process is carried out until the water content of the obtained product is less than 0.5%.
Example 11
The method for preparing the high-activity iron-doped bismuth oxyhalide photo-Fenton catalyst comprises the following steps of: 0.54mmol of ferric chloride and 2.7mmol of ferric chloride are taken. Adding bismuth subcarbonate into 20ml of deionized water, adding 45mmol of hydrobromic acid, and ultrasonically dissolving ferric chloride and bismuth subcarbonate until the solution is clear and marked as solution A; adding 63mmol of sodium hydroxide into 20ml of deionized water, and ultrasonically dissolving the sodium hydroxide until the solution is clear, and marking as solution B; transferring the solution A to an injection syringe, dripping the solution A into the solution B by an injection pump at a dripping speed of 0.8ml/min, continuously stirring, wherein the rotating speed of a stirrer is 600r/min, and finishing dripping when the pH value of the solution is 12; pouring the solution into a 100ml polytetrafluoroethylene reaction kettle, reacting for 5h at 80 ℃, washing the obtained precipitate with deionized water, absolute ethyl alcohol and acetone respectively after the reaction is finished, and drying at 80 ℃ to obtain the product. Wherein the washing process needs to be carried out until the pH value of the solution is 6-7, the conductivity is less than 20 mu s/cm, and the drying process is carried out until the water content of the obtained product is less than 0.5%.
Example 12
The method for preparing the high-activity iron-doped bismuth oxyhalide photo-Fenton catalyst comprises the following steps of: adding 3mmol of ferric nitrate and 1.5mmol of bismuth subcarbonate into 20ml of deionized water, adding 45mmol of hydrofluoric acid, and ultrasonically dissolving ferric nitrate and bismuth subcarbonate until the solution is clear, and marking as solution A; adding 63mmol of sodium hydroxide into 20ml of deionized water, and ultrasonically dissolving the sodium hydroxide until the solution is clear, and marking as solution B; transferring the solution A to an injection syringe, dropping the solution A into the solution B by an injection pump at a dropping speed of 0.8ml/min, continuously stirring, wherein the rotating speed of a stirrer is 600r/min, and the solution is completely dropped when the pH value of the solution is 12. Pouring the solution into a 100ml polytetrafluoroethylene reaction kettle, reacting for 10h at 40 ℃, washing the obtained precipitate with deionized water, absolute ethyl alcohol and acetone respectively after the reaction is finished, and drying at 60 ℃ to obtain the product. Wherein the washing process needs to be carried out until the pH value of the solution is 6-7, the conductivity is less than 20 mu s/cm, and the drying process is carried out until the water content of the obtained product is less than 0.5%.
The hydrohalic acid in the embodiment of the invention can be concentrated acid, and can also be used with the mass fraction of 36-38 percent, so that the aim of the invention can be achieved.
FIG. 1 is an SEM image of an iron-doped bismuth oxyhalide sample. Taking the example of iron-doped bismuth oxybromide, a represents the SEM image of the iron-doped bismuth oxybromide sample obtained at the synthesis temperature of 20 ℃ (example 4), and b represents the SEM image of the iron-doped bismuth oxybromide sample obtained at the synthesis temperature of 60 ℃ (example 5). As can be seen from FIG. 1, the Fe-doped bismuth oxybromide obtained at a synthesis temperature of 60 ℃ is formed by stacking a large number of coarse particles and has fewer strips; the iron-doped bismuth oxybromide obtained at the synthesis temperature of 20 ℃ is a large amount of ultrathin smooth strips, and the surfaces of the strips are loaded with a few rough particles. Compared with a sample with the synthesis temperature of 60 ℃, the characteristic can effectively reduce the recombination rate of photoproduction electrons and holes and improve the conduction of electrons, and the specific surface area is larger, so that the photo-Fenton catalytic performance is higher because the photo-Fenton catalytic material is more fully contacted with a reaction substrate. Similar effects are obtained with iron-doped bismuth oxyiodide, iron-doped bismuth oxychloride, and iron-doped bismuth oxyfluoride.
Figure 2 shows the XRD pattern of iron doped bismuth oxyhalide samples. Taking an example of iron-doped bismuth oxybromide as an example, as XRD patterns of iron-doped bismuth oxybromide samples obtained at a synthesis temperature of 20 ℃ (example 4) and a synthesis temperature of 60 ℃ (example 5), it can be seen from the XRD patterns that the samples obtained at the synthesis temperature of 20 ℃ and the synthesis temperature of 60 ℃ have strong diffraction peaks near crystal planes (312), (004), (600), (604), (316) and (912) (obtained according to the JCPDS card No.38-0493 of the standard card), but have some deviation, probably due to iron doping, indicating that the obtained samples are iron-doped bismuth oxybromide crystals with higher purity, and the obtained iron-doped bismuth oxybromide samples have better crystallinity from the perspective of the sharpness of the high-strength peaks. Secondly, the XRD diffraction peak of the iron-doped bismuth oxybromide obtained at the synthesis temperature of 20 ℃ has a plurality of diffraction peaks with larger intensity besides the standard peaks, which is probably nitrate ions which are not removed in the preparation process. The few XRD diffraction peaks of the iron-doped bismuth oxybromide obtained at the synthesis temperature of 60 ℃ are caused by that nitrate ions are decomposed due to the high synthesis temperature, so that some diffraction peaks are weakened or even disappear. Similar effects are obtained with iron-doped bismuth oxyiodide, iron-doped bismuth oxychloride, and iron-doped bismuth oxyfluoride.
FIG. 3 shows the results of catalytic efficiency of iron-doped bismuth oxyhalide prepared in example 4 with commercial (P25) TiO2The sample of iron-doped bismuth oxybromide synthesized in example 4 was mixed with commercial (P25) TiO2The RhB dye is subjected to photo-Fenton degradation under simulated sunlight, and the graph shows that under the simulated sunlight, the photocatalysis performance of the iron-doped bismuth oxybromide obtained in the experiment is obviously superior to that of the commercial (P25) TiO2. Under simulated sunlight, the degradation of the iron-doped bismuth oxybromide on the substrate can reach more than 90 percent after 20min, and the commercial product (P25) TiO2Only about 30%.
FIG. 4 is a Fourier infrared spectrum of a sample of iron-doped bismuth oxyhalide, wherein the Fourier infrared spectrum of the sample of iron-doped bismuth oxybromide obtained at a synthesis temperature of 20 deg.C (example 4) and 60 deg.C (example 5) is shown, and it can be seen that 551cm of the infrared spectrum of the sample obtained at a synthesis temperature of 20 deg.C-1Has strong absorption (synthesis temperature is 550cm at 60 deg.C)-1) This is due to the vibration of the Bi — O bond in the iron-doped bismuth oxybromide; at 450--1Is observed in a wavelength range of (1), which band is probably due to FeO6Bending and stretching vibrations of Fe — O bonds in octahedral units; at 1471, 2850 and 2918cm-1(the synthesis temperature is 1473 cm, 2851 cm and 2919cm at 60 DEG C-1) The absorption is stronger and corresponds to the characteristic absorption peak of bismuth oxybromide; and 848cm-1(the synthesis temperature was 850cm at 60 ℃ C.)-1)、1392cm-1Bending vibration and stretching vibration respectively corresponding to N-O in the non-removed nitrate ions; 1627cm-1、3414cm-1Respectively correspondingly adsorb H2Bending vibration and stretching vibration of H-O in O (1628 cm at 60 deg.C-1、3414cm-1). Therefore, the iron-doped bismuth oxybromide crystal is obtained no matter the synthesis temperature is 20 ℃ or 60 ℃. Similar results were obtained with iron-doped bismuth oxyiodide, iron-doped bismuth oxychloride, and iron-doped bismuth oxyfluoride.
A graph comparing the photo-Fenton degradation efficiency of RhB dyes in simulated sunlight, following the procedure of example 1, except that the molar ratio of iron salt to bismuth salt is 1:10, followed by the preparation of iron-doped bismuth oxychloride at temperatures of 20 deg.C, 60 deg.C, 80 deg.C, 100 deg.C and 160 deg.C, respectively. The results are shown in FIG. 5. The result shows that the degradation efficiency of the substrate is good when the temperature is lower than 80 ℃, and the preferable temperature range is 20-60 ℃, and the optimal temperature is 20 ℃. Under simulated sunlight, the iron-doped bismuth oxyhalide synthesized at the temperature of 20 ℃ can degrade the substrate by more than 90% after 20min, and the photo-Fenton catalytic performance is excellent.
The results are shown in fig. 6, which is a graph comparing the efficiency of photo-fenton degradation of RhB dye by bismuth oxyhalide samples with different iron doping ratios in simulated sunlight, according to the method of example 1, except that the synthesis temperature is 80 ℃, the synthesis time is 10 hours, and the pH of the synthesis solution is 12. As can be seen from the figure, the iron doping ratio should be within the range of iron salt: the bismuth salt has a better effect of 0.05-0.2, and the optimal effect is 0.1.
A comparison of the efficiency of photo-Fenton degradation of RhB dye by bismuth oxyhalide samples synthesized with different halogen acids under simulated sunlight with respect to the iron doping ratio of 0.1 at a synthesis temperature of 20 ℃ for 10h and a synthesis solution pH of 12 is shown in FIG. 7 according to the method of example 10. As can be seen from the figure, the efficiency of the iron-doped bismuth oxybromide photo-Fenton catalyst synthesized by using hydrobromic acid for photo-Fenton catalytic degradation of a substrate under simulated sunlight is higher than that of the iron-doped bismuth oxychloride photo-Fenton catalyst synthesized by using hydrochloric acid.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (9)
1. The high-activity iron-doped bismuth oxyhalide photo-Fenton catalyst is characterized in that the preparation method comprises the following steps: the molar ratio of the components is 0.05-0.2: 1, respectively adding ferric salt and bismuth salt into a solvent, then adding excessive halogen acid to completely dissolve the bismuth salt and the ferric salt to form a mixed solution, after the mixed solution is clarified, dripping the mixed solution into a sodium hydroxide solution at a constant speed, continuously stirring the mixed solution until the pH value is = 4-14, reacting the reaction solution at 20 ℃ for at least 1h, washing the obtained precipitate after the reaction is finished, and drying the precipitate to obtain the high-activity iron-doped bismuth oxyhalide photo-Fenton catalyst; the hydrohalic acid is hydrobromic acid.
2. The highly active iron-doped bismuth oxyhalide photo-fenton catalyst according to claim 1, wherein: the solvent is one of water or ethanol; the ferric salt is at least one of ferric nitrate, ferric chloride, ferric bromide and ferric sulfate; the bismuth salt is at least one of bismuth subcarbonate, bismuth sulfate and bismuth nitrate.
3. The highly active iron-doped bismuth oxyhalide photo-fenton catalyst according to claim 1, wherein: the addition amount of the halogen acid is as follows: the molar ratio of the halogen acid is more than 2: 15.
4. the highly active iron-doped bismuth oxyhalide photo-fenton catalyst according to claim 1, wherein: the dissolution is ultrasonic dissolution.
5. The highly active iron-doped bismuth oxyhalide photo-fenton catalyst according to claim 1, wherein: the concentration of the sodium hydroxide solution is 0.6-3.15 mmol/ml.
6. The highly active iron-doped bismuth oxyhalide photo-fenton catalyst according to claim 1, wherein: the washing is that water and organic solvent are sequentially washed until the pH value of the solution is 6-7 and the conductivity is less than 20 us/cm.
7. The highly active iron-doped bismuth oxyhalide photo-fenton catalyst of claim 6, wherein: the organic solvent is at least one of absolute ethyl alcohol and acetone.
8. The highly active iron-doped bismuth oxyhalide photo-fenton catalyst according to claim 1, wherein: and the drying is carried out until the moisture content of the bismuth oxyhalide is lower than 0.5 percent.
9. Use of the highly active iron-doped bismuth oxyhalide photo-fenton catalyst according to any one of claims 1 to 8 for catalyzing degradation of organic pollutants, dyes, pesticides or biochemicals under visible light.
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