阅读说明：本技术 一种碳布负载磷酸铋/卤氧化铋的花状光催化剂的制备方法 (Preparation method of carbon cloth-loaded bismuth phosphate/bismuth oxyhalide flower-shaped photocatalyst ) 是由 陈凤华 陈庆涛 贾春晓 石向东 杨茂森 姜利英 方少明 张永辉 于 2021-09-10 设计创作，主要内容包括：本发明公开了一种碳布负载磷酸铋/卤氧化铋的花状光催化剂的制备方法,先通过水热法制备碳布负载BiPO-(4)的复合材料CC/BiPO-(4),然后再经过醇热法在CC/BiPO-(4)上生长BiOX,最后水洗得到碳布负载BiPO-(4)/BiOX三维花状光催化剂CC/BiPO-(4)/BiOX,所述X＝Cl、Br、I。本发明将BiPO-(4)/BiOX三维花状光催化剂负载在碳布上一方面扩展了BiPO-(4)催化剂的光吸收范围,抑制光生电子-空穴对的复合,提高材料对有机物的吸附性能,获得比浸取法制备的碳布负载的非花状BiPO-(4)/BiOX复合光催化剂效率高的催化材料,另一方面有效解决了铋化物粉末存在的分离困难和可能的二次污染等问题,利于回收循环利用,达到实际推广应用的目的。(The invention discloses a preparation method of a flower-shaped photocatalyst of carbon cloth loaded with bismuth phosphate/bismuth oxyhalide, which comprises the steps of firstly preparing carbon cloth loaded BiPO by a hydrothermal method 4 Composite material CC/BiPO 4 Then the mixture is subjected to alcohol heating method to be in CC/BiPO 4 Growing BiOX on the surface of the substrate, and finally washing the substrate to obtain carbon cloth loaded BiPO 4 /BiOX three-dimensional flower-like photocatalyst CC/BiPO 4 and/BiOX, wherein X is Cl, Br and I. The invention uses BiPO 4 The BiOX three-dimensional flower-shaped photocatalyst is loaded on carbon cloth, on one hand, BiPO is expanded 4 The light absorption range of the catalyst inhibits the recombination of photo-generated electron-hole pairs, improves the adsorption performance of the material to organic matters, and obtains the carbon cloth-loaded non-flower BiPO prepared by a leaching method 4 the/BiOX composite photocatalyst is a catalytic material with high efficiency, and on the other hand, the catalyst is effective in decompositionThe problems of difficult separation, possible secondary pollution and the like of the bismuth compound powder are solved, the bismuth compound powder is beneficial to recycling, and the aim of practical popularization and application is achieved.)

1. The preparation method of the carbon cloth loaded bismuth phosphate/bismuth oxyhalide flower-shaped photocatalyst is characterized in that the carbon cloth loaded BiPO is prepared by a hydrothermal method₄Composite material CC/BiPO₄Then the mixture is subjected to alcohol heating method to be in CC/BiPO₄Growing BiOX on the surface of the substrate, and finally washing the substrate to obtain carbon cloth loaded BiPO₄/BiOX three-dimensional flower-like photocatalyst CC/BiPO₄(ii)/BiOX, wherein X ═ Cl, Br, I; the method comprises the following specific steps:

(1) activating the carbon cloth: sequentially immersing the carbon cloth into acetone, ethanol and water for ultrasonic treatment, then putting the carbon cloth into a mixed solution of mixed acid and water for activation, taking out the carbon cloth after the ultrasonic treatment is finished, washing the carbon cloth to be neutral, and drying the carbon cloth to obtain activated carbon cloth;

(2)CC/BiPO₄the preparation of (1): adding Bi (NO)₃)₃·5H₂O dissolved in dilute HNO₃Preparing clear Bi (NO) in solution₃)₃Dissolving, and adding activated carbon cloth into Bi (NO)₃)₃Soaking in the solution, and then slowly dripping Bi (NO)₃)₃Equimolar amount of Na₂HPO₄After the solution is dripped, the pH value is adjusted to be neutral, then the solution is transferred into a reaction kettle for hydrothermal reaction, and after the reaction is finished, the prepared CC/BiPO is₄Taking out, washing with water and ethanol in sequence, and oven dryingUsing;

(3)CC/BiPO₄preparation of BiOX: equimolar of Bi (NO)₃)₃·5H₂Adding O and KX into the polyalcohol solution, stirring until the solution is clear, and then adding the CC/BiPO prepared in the step (2)₄Immersing the mixture in a reaction kettle, carrying out alcohol-heat reaction, and after the reaction is finished, preparing the CC/BiPO₄The BiOX is taken out, washed by water and ethanol in sequence, and put into an oven to be dried, and then the final product is obtained.

2. The method for preparing the flower-like photocatalyst of bismuth phosphate/bismuth oxyhalide supported on carbon cloth according to claim 1, wherein the reaction temperature of the hydrothermal reaction and the reaction time of the alcoholic thermal reaction are both 120-220 ℃, the reaction time is 8-24h, and Bi (NO) is added in the step (3)₃)₃·5H₂The amount of O substance is larger than that of Bi (NO) in the step (2)₃)₃·5H₂The amount of species of O.

3. The method for preparing the carbon cloth supported bismuth phosphate/bismuth oxyhalide flower photocatalyst according to claim 1, wherein the mixed acid is concentrated HNO₃And concentrated H₂SO₄The mixed acid is prepared according to the volume ratio of 3:1, the volume ratio of the mixed acid to the water is 1:9-1:3, the activation temperature is 80-120 ℃, and the activation time is 12-24 h.

4. The method for preparing the flower-like photocatalyst of bismuth phosphate/bismuth oxyhalide supported on carbon cloth according to claim 1, wherein in the step (2), the diluted HNO is₃The solution is prepared from 63 vt% concentrated nitric acid and water according to the volume ratio of 1:5-1: 50.

5. The method as claimed in claim 1, wherein in step (3), the polyol is ethylene glycol, diethylene glycol, triethylene glycol or polyethylene glycol with molecular weight of 200-600-.

6. The method for preparing the flower-like photocatalyst of bismuth phosphate/bismuth oxyhalide supported on carbon cloth according to claim 1, wherein in the step (3), the KX is a mixture of one or more of KCl, KBr and KI.

Technical Field

The invention relates to the technical field of photocatalyst preparation, in particular to a preparation method of a carbon cloth loaded bismuth phosphate/bismuth oxyhalide flower-shaped photocatalyst.

Background

The photocatalysis technology can directly utilize sunlight to catalyze and degrade organic and inorganic pollutants in wastewater and air under the conditions of normal temperature and normal pressure, and compared with the traditional purification treatment methods (such as separation, adsorption, chemical oxidation technology and the like), the photocatalysis technology has the advantages of high efficiency, thoroughness, regeneration, no secondary pollution and the like, and has wide application prospect in the field of environmental protection. The core of the photocatalysis technology is the research and development of high-efficiency photocatalysts.

BiPO₄As the bismuth salt photocatalyst has nonmetal oxygen-containing acid radical, the bismuth salt photocatalyst is beneficial to improving the separation efficiency of electron hole pairs and has TiO more than the traditional TiO₂Better photocatalytic performance, however BiPO₄The forbidden band width is large (3.8-4.2 eV), only ultraviolet light in sunlight can be absorbed, the light utilization rate is low, and compared with a photocatalytic material responding to the ultraviolet light, the photocatalyst responding to visible light is developed and has higher practical value. The BiOX (X ═ C1, Br, I) is a new type of semiconductor photocatalyst, and due to its unique layered structure and electronic structure, a three-dimensional lamellar assembly is easily generated under certain conditions, which can improve the adsorption performance of the material and the utilization rate of sunlight, and at the same time, has better carrier separation performance, thus becoming the key direction of research.

Based on this, consider BiPO₄Matching with the band position of BiOX to obtain BiPO₄Photocatalysis for constructing heterojunction by compounding with BiOX to improve single materialThe performance is feasible, the morphology of the composite photocatalyst has certain influence on the photocatalytic efficiency, and the problems of difficult separation, possible secondary pollution and the like of the powder bismuth compound also exist, so that the practical popularization and application are not facilitated.

Thus, how to provide a BiPO capable of being expanded₄The light absorption range of the catalyst, the improvement of the catalytic efficiency of the photocatalyst, and the solution of BiPO which solves the problems of difficult separation of powder bismuth compounds, secondary pollution and the like₄the/BiOX composite catalyst is a problem which needs to be solved urgently by the technical personnel in the field.

Disclosure of Invention

In view of the above, the invention provides a preparation method capable of preparing a carbon cloth-supported bismuth phosphate/bismuth oxyhalide three-dimensional flower-like photocatalyst.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of a carbon cloth loaded bismuth phosphate/bismuth oxyhalide flower photocatalyst comprises the steps of firstly preparing carbon cloth loaded BiPO by a hydrothermal method₄Composite material CC/BiPO₄Then the mixture is subjected to alcohol heating method to be in CC/BiPO₄Growing BiOX on the surface of the substrate, and finally washing the substrate to obtain carbon cloth loaded BiPO₄/BiOX three-dimensional flower-like photocatalyst CC/BiPO₄(ii)/BiOX, wherein X ═ Cl, Br, I; the method comprises the following specific steps:

(2) activating the carbon cloth: sequentially immersing the carbon cloth into acetone, ethanol and water for ultrasonic treatment, then putting the carbon cloth into a mixed solution of mixed acid and water for activation, taking out the carbon cloth after the ultrasonic treatment is finished, washing the carbon cloth to be neutral, and drying the carbon cloth to obtain activated carbon cloth;

(2)CC/BiPO₄the preparation of (1): adding Bi (NO)₃)₃·5H₂O dissolved in dilute HNO₃Preparing clear Bi (NO) in solution₃)₃Dissolving, and adding activated carbon cloth into Bi (NO)₃)₃Soaking in the solution, and then slowly dripping Bi (NO)₃)₃Equimolar amount of Na₂HPO₄After the solution is dripped, the pH value is adjusted to be neutral, then the solution is transferred into a reaction kettle for hydrothermal reaction, and after the reaction is finished, the prepared CC/BiPO is₄Taking out, washing with water and ethanol in sequence, and drying for later use;

(3)CC/BiPO₄preparation of BiOX: equimolar of Bi (NO)₃)₃·5H₂Adding O and KX into the polyalcohol solution, stirring until the solution is clear, and then adding the CC/BiPO prepared in the step (2)₄Immersing the mixture in a reaction kettle, carrying out alcohol-heat reaction, and after the reaction is finished, preparing the CC/BiPO₄The BiOX is taken out, washed by water and ethanol in sequence, and put into an oven to be dried, and then the final product is obtained.

Preferably, the reaction temperature of the hydrothermal reaction and the reaction temperature of the alcoholic thermal reaction are both 120-220 ℃, the reaction time is both 8-24h, and Bi (NO) is obtained in the step (3)₃)₃·5H₂The amount of O substance is larger than that of Bi (NO) in the step (2)₃)₃·5H₂The amount of species of O; more preferably, the reaction temperature of the hydrothermal reaction and the reaction time of the alcoholic thermal reaction are both 160 ℃ and 12 hours.

Adopt above-mentioned technical scheme's beneficial effect: the temperature of the hydrothermal reaction and the alcoholic thermal reaction has certain influence on the crystallinity and the appearance of the bismuthate. Low temperature leads to reduced crystallinity of the bismuthate; the crystallinity of the bismuth compound is improved by over-high temperature, but the composition is changed, and the shape is converted into a sheet or block structure.

Preferably, the mixed acid is prepared from commercially available concentrated HNO₃And concentrated H₂SO₄The mixed acid is prepared according to the volume ratio of 3:1, the volume ratio of the mixed acid to water is 1:9-1:3, the activation temperature is 80-120 ℃, the activation time is 12-24h, and more preferably, the activation temperature is 100 ℃, and the activation time is 24 h.

Preferably, in step (2), the dilute HNO₃The solution is prepared by mixing commercially available concentrated nitric acid and water according to the volume ratio of 1:5-1:50, and preferably, the dilute HNO₃The solution is prepared from concentrated nitric acid and water according to the volume ratio of 1: 8.

Preferably, in step (3), the polyol is ethylene glycol, diethylene glycol, triethylene glycol or polyethylene glycol with molecular weight of 200-600.

Preferably, in the step (3), the KX is a mixture of one or more of KCl, KBr and KI.

Adopt above-mentioned technical scheme's beneficial effect: the invention can select KX with different types or mixing proportions by controlling the reaction temperature and the types of solvents to obtain the carbon cloth-loaded three-dimensional flower-shaped BiPO with good crystallinity₄The BiOX composite photocatalytic material.

As can be seen from the above technical solutions, compared with the prior art, the present disclosure provides a BiPO₄A method for loading a BiOX three-dimensional flower-shaped photocatalyst on carbon cloth. Carbon Cloth (CC), short for Carbon fiber Cloth, also called Carbon fiber Cloth, is insoluble in organic solvent and acid and alkali, has strong corrosion resistance and good stability, has nano-scale pore diameter on the surface, has large specific surface area, is beneficial to adsorption and desorption, and can be desorbed by a certain physical or chemical method when the Carbon Cloth is saturated in adsorption. In addition, the carbon cloth also has the characteristics of easy separation and excellent electrical conductivity and light transmittance, so that the carbon cloth is a better adsorption and photocatalysis supporting material. Meanwhile, carbon atoms on the surface of the carbon fiber cloth are unstable and can generate active groups with pollutants in water, so that the pollutants are promoted to be degraded. The invention uses BiPO₄the/BiOX three-dimensional flower-shaped photocatalyst is loaded on carbon cloth, thereby not only expanding BiPO₄The light absorption range of the catalyst is enlarged, and on one hand, the specific surface area of the sample is enlarged because the pore gaps formed by the crossed nano sheets on the surface of the flower-shaped sample are obviously enlarged compared with the non-flower-shaped scattered flaky shape, so that more active sites can be provided for the photocatalytic reaction process, and the non-flower-shaped BiPO loaded by the carbon cloth prepared by the leaching method is obtained₄The BiOX composite photocatalyst is a catalytic material with high efficiency, and on the other hand, due to the easy separation characteristic of the carbon cloth supporting material, the problems of difficult separation, possible secondary pollution and the like of bismuth compound powder can be effectively solved, the bismuth compound powder is beneficial to recycling, and the purpose of practical popularization and application is achieved.

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, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.

FIG. 1. carbon cloth-loaded BiPO prepared in example 1 of the present invention₄SEM picture and each elemental area scanning picture of/BiOCl three-dimensional flower shape photocatalyst; (a) 4000 times amplified CC/BiPO₄/BiOCl, (b) CC/BiPO amplified 50000 times₄/BiOCl，(c)BiPO₄The element is/BiOCl, (d) the element is C, (e) the element is O, (f) the element is Cl, (g) the element is Bi;

FIG. 2. carbon cloth-loaded BiPO prepared in example 2 of the present invention₄/BiOCl_0.3Br_0.3I_0.4SEM picture of three-dimensional flower-shaped photocatalyst and surface scanning picture of each element; (a) 2500-fold amplified CC/BiPO₄/BiOCl_0.3Br_0.3I_0.4(b) 10000 times amplification of CC/BiPO₄/BiOCl_0.3Br_0.3I_0.4，(c)BiPO₄/BiOCl_0.3Br_0.3I_0.4A C element, (e) an O element, (f) a Cl element, (g) a Br element, (h) an I element, (I) a Bi element;

FIG. 3 BiPO in examples 1 and 2 of the present invention₄、CC/BiPO₄、BiPO₄/BiOCl、CC/BiPO₄/BiOCl、BiPO₄/BiOCl_0.3Br_0.3I_0.4、CC/BiPO₄/BiOCl_0.3Br_0.3I_0.4Ultraviolet-visible spectrum of (1);

FIG. 4 BiPO in example 1 of the present invention₄，BiPO₄/BiOCl and CC/BiPO₄A fluorescence spectrum of/BiOCl;

FIG. 5 BiPO in example 2 of the present invention₄，BiPO₄/BiOCl_0.3Br_0.3I_0.4And CC/BiPO₄/BiOCl_0.3Br_0.3I_0.4A fluorescence spectrum of (a);

FIG. 6. CC/BiPO prepared in example 2 of the present invention₄/BiOCl_0.3Br_0.3I_0.4A graph of the relationship between RhB concentration and time in the process of RhB degradation;

FIG. 7 is a drawing showing an embodiment 2 of the present inventionPrepared CC/BiPO₄/BiOCl_0.3Br_0.3I_0.4And (3) a relation graph of the recycling frequency of degrading RhB and the degradation efficiency.

FIG. 8 extraction of CC/BiPO₄/BiOCl_0.3Br_0.3I_0.4SEM picture of (1);

FIG. 9. CC/BiPO prepared in example 2 of the present invention₄/BiOCl_0.3Br_0.3I_0.4And CC/BiPO prepared by leaching method₄/BiOCl_0.3Br_0.3I_0.4Comparing the effect of the photocatalyst on degrading RhB;

FIG. 10. carbon cloth-loaded CC/BiPO prepared in example 4 of the present invention₄/BiPO₄/BiOCl_0.5Br_0.5SEM image of photocatalyst;

FIG. 11. carbon cloth-loaded BiPO prepared in example 5 of the present invention₄SEM picture of/BiOCl photocatalyst;

FIG. 12. carbon cloth-loaded BiPO prepared in example 6 of the present invention₄SEM image of/BiOCl photocatalyst.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

Several carbon cloths were sequentially immersed in acetone, water and ethanol solvents for 20 minutes, and then CC was put into mixed acid (mixed acid from commercially available concentrated HNO)₃And concentrated H₂SO₄Prepared according to the volume ratio of 3: 1) and water (the volume ratio of mixed acid to water is 1:9), taking out, washing with water until the washing liquid is neutral, and putting into an oven for drying for later use;

3mmol of Bi (NO)₃)₃·5H₂O dissolved in 9mL of diluted HNO₃Preparing clear Bi (NO) in solution (the volume ratio of concentrated nitric acid to water is 1:8)₃)₃The solution, then the treated CC was immersed in the solution for 24h, after which Na was slowly added dropwise₂HPO₄Solution (3mmol of Na)₂HPO₄Dissolve in 15mL H₂O), adjusting the pH value to 7 by using ammonia water after the dropwise addition is finished, transferring the solution into a reaction kettle for hydrothermal reaction at 180 ℃ for 12 hours, and after the reaction is finished, preparing the CC/BiPO₄Taking out, washing with water and ethanol in sequence, and drying in an oven at 60 deg.C;

adding Bi (NO)₃)₃·5H₂O (0.05mmol) and KCl (0.05mmol) were added to 30ml of ethylene glycol solution, stirred until clear, and the prepared CC/BiPO was then added₄Immersing in it, alcohol-heating at 160 deg.C in reactor for 12 hr, and reacting to obtain CC/BiPO₄and/BiOCl is taken out, washed by water and ethanol in sequence and put into an oven to be dried, and the final product is obtained.

Example 2

Several carbon cloths were sequentially immersed in acetone, water and ethanol solvents for 20 minutes, and then CC was put into mixed acid (mixed acid from commercially available concentrated HNO)₃And concentrated H₂SO₄Prepared according to the volume ratio of 3: 1) and water (the volume ratio of mixed acid to water is 1:9), taking out, washing with water until the washing liquid is neutral, and putting into an oven for drying for later use;

3mmol of Bi (NO)₃)₃·5H₂O dissolved in 9mL of diluted HNO₃Preparing clear Bi (NO) in solution (the volume ratio of concentrated nitric acid to water is 1:8)₃)₃The solution, then the treated CC was immersed in the solution for 24h, after which Na was slowly added dropwise₂HPO₄Solution (3mmol of Na)₂HPO₄Dissolve in 15mL H₂O), adjusting the pH value to 7 by using ammonia water after the dropwise addition is finished, transferring the solution into a reaction kettle for hydrothermal reaction at 180 ℃ for 12 hours, and after the reaction is finished, preparing the CC/BiPO₄Taking out, washing with water and ethanol in sequence, and drying in an oven at 60 deg.C;

adding Bi (NO)₃)₃·5H₂O (0.05mmol), KCl (0.015mmol), KBr (0.015mmol) and KI (0.02mmol) were added to 30ml of an ethylene glycol solution, stirred until clear, and then the preparation was madeCC/BiPO of₄Immersing in it, alcohol-heating at 160 deg.C in reactor for 12 hr, and reacting to obtain CC/BiPO₄/BiOCl_0.3Br_0.3I_0.4Taking out, washing with water and ethanol in sequence, and drying in an oven to obtain the final product.

The invention provides a BiPO loaded carbon cloth which can be prepared₄A preparation method of a/BiOX (X ═ Cl, Br and I) three-dimensional flower-like photocatalyst. To achieve the object of the present invention, we will first prepare Carbon Cloth (CC) -supported BiPO by hydrothermal method₄Composite material (CC/BiPO)₄) Then the mixture is subjected to alcohol heating in CC/BiPO₄Further growing BiOX on the substrate, and finally washing the substrate to obtain carbon cloth loaded BiPO₄/BiOX flower-like light composite catalyst (CC/BiPO)₄/BiOX) wherein X can be a single element of Cl, Br, I, or two or three different halogen elements mixed in any proportion, although carbon cloth supported BiPO₄The morphology of the/BiOX photocatalyst is three-dimensional flower-shaped, but the photocatalytic absorption range and the morphology of a sample are different according to the type and the composition of X.

FIGS. 1 and 2 are carbon cloth-supported BiPO prepared in examples 1 and 2, respectively₄BiPO loaded on/BiOCl and carbon cloth₄/BiOCl_0.3Br_0.3I_0.4SEM image of three-dimensional flower-like photocatalyst and surface scanning image of each element. BiPO supported by carbon cloth can be easily seen from FIGS. 1(b), 1(c), 2(b) and 2(c)₄BiOCl and BiPO₄/BiOCl_0.3Br_0.3I_0.4The photocatalyst presents an obvious three-dimensional flower-like structure, and the appearance of the flower is different due to different components of X in BiOX.

As can be seen from FIG. 3, when BiPO is used₄after/BiOX is loaded on carbon cloth, CC/BiPO₄The absorption of the BiOCl composite photocatalytic material in a visible light region is obviously increased; BiPO₄/BiOCl_0.3Br_0.3I_0.4After being loaded on carbon cloth, CC/BiPO₄/BiOCl_0.3Br_0.3I_0.4The absorption of the composite photocatalytic material in a visible light region is also obviously increased; illustrating the presence of carbon cloth expands BiPO₄The light absorption range of the BiOX material.

From the fluorescence spectrum analysis of FIG. 4, it was revealed that when BiPO was used₄CC/BiPO under the excitation of 350nm wavelength after the/BiOCl is loaded on the carbon cloth₄The fluorescence spectrum intensity of/BiOCl is also reduced greatly; from the fluorescence spectrum analysis of FIG. 5, it was revealed that when BiPO was used₄/BiOCl_0.3Br_0.3I_0.4After being loaded on carbon cloth, the carbon cloth is activated by CC/BiPO at the wavelength of 350nm₄/BiOCl_0.3Br_0.3I_0.4The intensity of the fluorescence spectrum of (2) is much reduced. Description will be given of BiPO₄the/BiOX material is loaded on the carbon cloth, which is beneficial to reducing the recombination rate of photo-generated electron-hole pairs and improving BiPO₄The photocatalytic performance of the/BiOX material.

With CC/BiPO prepared as in example 2₄/BiOCl_0.3Br_0.3I_0.4For the catalyst, 10ml of 10mg/L rhodamine B (RhB) solution is used as a simulation solution of the pollutant, a xenon lamp is used as a simulation light source, an organic matter degradation test is carried out, and CC/BiPO is given in figure 6₄/BiOCl_0.3Br_0.3I_0.4As can be seen from FIG. 6, the percentage of discoloration of RhB by 60min of light irradiation can reach 98%, and after the reaction is finished, the RhB can be easily taken out by tweezers for recycling. FIG. 7 shows CC/BiPO₄/BiOCl_0.3Br_0.3I_0.4A relationship graph of the recycling times and the degradation efficiency of the photocatalytic degradation RhB is shown in FIG. 7, and CC/BiPO is obtained after six cyclic degradation experiments₄/BiOCl_0.3Br_0.3I_0.4Degradation efficiency of photocatalyst due to BiPO₄/BiOCl_0.3Br_0.3I_0.4The carbon cloth is dropped from the carbon cloth, but still has better degradation efficiency.

Comparative example 2, step (3) was replaced by the following step: 0.05mmolBi (NO3)₃·5H₂O is dissolved in 15ml of deionized water and marked as A; 0.015mmol KCl,0.015mmol KBr and 0.02mmol KI were dissolved in 15ml deionized water and labeled B. The CC/BiPO prepared in the step (2)₄The sample is first soaked in the solution A for two minutes and then is sprayed with deionized waterTransferring the washed solution to the solution B, soaking for two minutes, transferring the carbon cloth to the solution A after the same washing, and repeating the steps for 20 times to obtain the CC/BiPO prepared by the leaching method₄/BiOCl_0.3Br_0.3I_0.4A composite material.

FIGS. 8 and 9 are respectively CC/BiPO prepared by the leaching method₄/BiOCl_0.3Br_0.3I_0.4SEM figure of (a) and a graph of RhB concentration versus time during degradation of RhB by the catalyst. It can be seen from the figure that CC/BiPO prepared by leaching method₄/BiOCl_0.3Br_0.3I_0.4The photocatalyst presents a non-flower-like scattered flaky appearance, and the efficiency of degrading RhB is lower than that of CC/BiPO prepared in example 2₄/BiOCl_0.3Br_0.3I_0.4Flower-like photocatalyst. This is probably because the pore space formed by the crossing of the nano-sheets on the flower-shaped sample surface is obviously increased compared with the non-flower-shaped scattered sheet-shaped morphology, so that the specific surface area of the sample in example 2 is increased, and more active sites can be provided for the photocatalytic reaction process.

Example 3

Several carbon cloths were sequentially immersed in acetone, water and ethanol solvents for 20 minutes, and then CC was put into mixed acid (mixed acid from commercially available concentrated HNO)₃And concentrated H₂SO₄Prepared according to the volume ratio of 3: 1) and water (the volume ratio of mixed acid to water is 1:9), taking out, washing with water until the washing liquid is neutral, and putting into an oven for drying for later use;

3mmol of Bi (NO)₃)₃·5H₂O dissolved in 9mL of diluted HNO₃Preparing clear Bi (NO) in solution (the volume ratio of concentrated nitric acid to water is 1:8)₃)₃The solution, then the treated CC was immersed in the solution for 24h, after which Na was slowly added dropwise₂HPO₄Solution (3mmol of Na)₂HPO₄Dissolve in 15mL H₂O), adjusting the pH value to 7 by using ammonia water after the dropwise addition is finished, transferring the solution into a reaction kettle for hydrothermal reaction at 180 ℃ for 12 hours, and after the reaction is finished, preparing the CC/BiPO₄Taking out, washing with water and ethanol in sequence, and drying in an oven at 60 deg.C;

adding Bi (NO)₃)₃·5H₂O (0.05mmol), KBr (0.05mmol) were added to 30ml of ethylene glycol solution, stirred until clear, and the prepared CC/BiPO was then added₄Immersing in it, alcohol-heating at 160 deg.C in reactor for 12 hr, and reacting to obtain CC/BiPO₄and/BiOBr is taken out, washed by water and ethanol in sequence and put into an oven to be dried, and the final product is obtained.

Example 4

Several carbon cloths were sequentially immersed in acetone, water and ethanol solvents for 20 minutes, and then CC was put into mixed acid (mixed acid from commercially available concentrated HNO)₃And concentrated H₂SO₄Prepared according to the volume ratio of 3: 1) and water (the volume ratio of mixed acid to water is 1:9), taking out, washing with water until the washing liquid is neutral, and putting into an oven for drying for later use;

3mmol of Bi (NO)₃)₃·5H₂O dissolved in 9mL of diluted HNO₃Preparing clear Bi (NO) in solution (the volume ratio of concentrated nitric acid to water is 1:8)₃)₃The solution, then the treated CC was immersed in the solution for 24h, after which Na was slowly added dropwise₂HPO₄Solution (3mmol of Na)₂HPO₄Dissolve in 15mL H₂O), adjusting the pH value to 7 by using ammonia water after the dropwise addition is finished, transferring the solution into a reaction kettle for hydrothermal reaction at 180 ℃ for 12 hours, and after the reaction is finished, preparing the CC/BiPO₄Taking out, washing with water and ethanol in sequence, and drying in an oven at 60 deg.C;

adding Bi (NO)₃)₃·5H₂O (0.05mmol), KCl (0.025mmol) and KBr (0.025mmol) were added to 30ml of a solution of ethylene glycol, stirred until clear, and the prepared CC/BiPO was then added₄Immersing in it, alcohol-heating at 160 deg.C in reactor for 12 hr, and reacting to obtain CC/BiPO₄/BiOCl_0.5Br_0.5Taking out, washing with water and ethanol in sequence, and drying in an oven to obtain the final product.

FIG. 10 is the carbon cloth-supported BiPO prepared in example 4₄/BiOCl_0.5Br_0.5SEM picture of photocatalyst can be easily seenBiPO loaded by carbon-out cloth₄/BiOCl_0.5Br_0.5The photocatalyst also presents an obvious three-dimensional flower-like structure, and the appearance of the flower is similar to that of BiPO loaded by the carbon cloth in example 1₄the/BiOCl morphology is very similar.

Example 5

Several carbon cloths were sequentially immersed in acetone, water and ethanol solvents for 20 minutes, and then CC was put into mixed acid (mixed acid from commercially available concentrated HNO)₃And concentrated H₂SO₄Prepared according to the volume ratio of 3: 1) and water (the volume ratio of mixed acid to water is 1:9), taking out, washing with water until the washing liquid is neutral, and putting into an oven for drying for later use.

3mmol of Bi (NO)₃)₃·5H₂O dissolved in 9mL of diluted HNO₃Preparing clear Bi (NO) in solution (the volume ratio of concentrated nitric acid to water is 1:8)₃)₃The solution, then the treated CC was immersed in the solution for 24h, after which Na was slowly added dropwise₂HPO₄Solution (3mmol of Na)₂HPO₄Dissolve in 15mL H₂O), adjusting the pH value to 7 by using ammonia water after the dropwise addition is finished, and transferring the solution into a reaction kettle for hydrothermal reaction for 10 hours at 160 ℃. After the reaction is finished, the prepared CC/BiPO₄Taking out, washing with water and ethanol in sequence, and drying in an oven at 60 deg.C for use.

Adding Bi (NO)₃)₃·5H₂O (0.05mmol) and KCl (0.05mmol) were added to 30ml of a solution of diethylene glycol, stirred until clear, and the prepared CC/BiPO was then added₄Immersing in it, alcohol-heating at 180 deg.C in reactor for 10 hr, and reacting to obtain CC/BiPO₄and/BiOCl is taken out, washed by water and ethanol in sequence and put into an oven to be dried, and the final product is obtained.

FIG. 11 is carbon cloth-supported BiPO prepared in example 5₄SEM image of/BiOCl photocatalyst. As can be seen from comparison with the results of fig. 1, BiPO supported on carbon cloth obtained by replacing ethylene glycol used in the solvothermal process in example 1 with diethylene glycol in example 5₄The shape of the/BiOCl photocatalyst is not changed and still in a flower shape.

Example 6

Several carbon cloths were sequentially immersed in acetone, water and ethanol solvents for 20 minutes, and then CC was put into mixed acid (mixed acid from commercially available concentrated HNO)₃And concentrated H₂SO₄Prepared according to the volume ratio of 3: 1) and water (the volume ratio of mixed acid to water is 1:9), taking out, washing with water until the washing liquid is neutral, and putting into an oven for drying for later use.

3mmol of Bi (NO)₃)₃·5H₂O dissolved in 9mL of diluted HNO₃Preparing clear Bi (NO) in solution (the volume ratio of concentrated nitric acid to water is 1:8)₃)₃The solution, then the treated CC was immersed in the solution for 24h, after which Na was slowly added dropwise₂HPO₄Solution (3mmol of Na)₂HPO₄Dissolve in 15mL H₂O), adjusting the pH value to 7 by using ammonia water after the dropwise addition is finished, and transferring the solution into a reaction kettle for hydrothermal reaction for 10 hours at 160 ℃. After the reaction is finished, the prepared CC/BiPO₄Taking out, washing with water and ethanol in sequence, and drying in an oven at 60 deg.C for use.

Adding Bi (NO)₃)₃·5H₂O (0.05mmol) and KCl (0.05mmol) were added to 30ml of the aqueous solution, stirred until clear, and the prepared CC/BiPO was then added₄Immersing in it, alcohol-heating at 180 deg.C in reactor for 10 hr, and reacting to obtain CC/BiPO₄and/BiOCl is taken out, washed by water and ethanol in sequence and put into an oven to be dried, and the final product is obtained.

FIG. 12 is carbon cloth-supported BiPO prepared in example 6₄SEM image of/BiOCl photocatalyst. As can be seen from comparison with the results of fig. 1, BiPO supported on carbon cloth obtained by replacing ethylene glycol used in the solvothermal process in example 1 with water in example 6 was obtained₄The morphology of the/BiOCl photocatalyst is irregular particle shape and rod shape, which indicates that the alcohol solvent has a certain determining function on the flower-shaped morphology of a sample. This is probably because the higher viscosity of ethylene glycol, monoethylene glycol, etc. inhibits the anisotropic growth of the sample.

The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.