CN113893840B - Composite photocatalyst, preparation method and application in dye wastewater - Google Patents

Composite photocatalyst, preparation method and application in dye wastewater Download PDF

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CN113893840B
CN113893840B CN202111014436.2A CN202111014436A CN113893840B CN 113893840 B CN113893840 B CN 113893840B CN 202111014436 A CN202111014436 A CN 202111014436A CN 113893840 B CN113893840 B CN 113893840B
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composite photocatalyst
reaction
xylenol orange
photocatalyst
preparation
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CN113893840A (en
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钟泰林
来水方
朱金梁
金玉婷
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Zhejiang Shuren University
Zhejiang Longsheng Group Co Ltd
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Zhejiang Shuren University
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    • B01J35/39—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/18—Arsenic, antimony or bismuth
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention discloses a composite photocatalyst, a preparation method and application thereof, and the composite photocatalyst Bi 2 O 3 @ C is made of a composite material Bi 2 WO 6 @ D113 is calcined, D113 is cheap and stable, has a plurality of functional groups and is favorable for reaction, and the hollow carbon microsphere with surface folds is obtained by calcination and is Bi 2 O 3 The supporting material of the semiconductor, the hollow carbon material optimizes band gap, and the hollow structure promotes light absorption and utilization rate. Bi 2 O 3 @ C combines materials with macroscopic and microscopic sizes to form a composite photocatalyst with excellent performance; the preparation process is simple and convenient, and is green; bi 2 O 3 The @ C material is novel in structure and has high research value; the photocatalytic degradation effect of the xylenol orange is good; bi 2 O 3 The @ C material has good stability and can be applied to photocatalytic degradation of dye wastewater xylenol orange.

Description

Composite photocatalyst, preparation method and application in dye wastewater
Technical Field
The invention relates to the technical field of synthesis and environment restoration of composite photocatalytic materials, in particular to a composite photocatalyst Bi 2 O 3 @ C, preparation method and application in dye wastewater.
Background
Xylenol Orange (XO) is an organic substance with molecular formula of C 31 H 32 N 2 O 13 S, molecular weight 672.6564, reddish brown crystalline powder. It is hygroscopic, soluble in water, and insoluble in anhydrous ethanol. Decomposing at 210 ℃. The maximum absorption wavelength is 580nm. The administration of xylenol orange by mistake or absorption through the skin can cause headache, dizziness, nausea, vomiting, abdominal pain, exhaustion, coma and other symptoms, and can cause corrosive burn to the skin.
In recent years, environmental pollution is embodied in various ways, wherein water pollution is one of the main aspects to be solved, and organic dye pollution is the dominant one. Therefore, the realization of green degradation of organic dyes becomes a focus of extensive scientific research personnel. The organic dye wastewater has the characteristics of high suspended matter, high COD, high chroma and difficult biochemical degradation of organic matters, has the problems of intermittent discharge, normal temperature and seasonal variation of temperature, large variation of water quality and water quantity with time and the like, belongs to the difficult degradation industrial wastewater, and the xylenol orange dye is a very representative difficult degradation organic matter.
At present, the organic dye wastewater treatment methods mainly comprise a biochemical method and a physicochemical method, and the treatment methods have the following defects: the normal temperature treatment effect is poor, anaerobic, coagulation air flotation and active carbon adsorption units are required to be arranged, the treatment cost is high, and the like.
Among the numerous novel treatment techniques, photocatalytic degradation is appreciated by the researchers due to its environmentally friendly nature. The photocatalytic technology with semiconductor material as core is a new field, and its essence is photochemical reaction under the action of catalyst. However, the core problem faced by the photocatalytic technology is to find a good photocatalyst, and the photocatalytic material still has the problems of small light absorption rate, too high or too low band edge position, poor system stability and the like, so the research on the modification of the photocatalytic material is very necessary.
Bi in photocatalytic research 2 O 3 Is one of novel bismuth-based photocatalytic materials, is a P-type semiconductor, and has a specific electronic structure to enable electric charges to be more active, so that the strong photocatalytic efficiency becomes a bright point. The carbon material has more applications in photocatalysis composite materials in recent years due to good conductivity, and is characterized by promotingThe transportation of electrons on the surface of the carbon material and the separation of electrons and holes, but the cost of common carbon materials such as carbon nanotubes and graphene is high, so that the carbon materials are difficult to be applied in practice, and the replacement and upgrading of cheap carbon materials are urgently needed.
The invention provides a composite photocatalyst, which comprehensively utilizes Bi 2 O 3 And the excellent characteristics of the carbon material and the synergistic effect of the carbon material and the carbon material improve the photocatalytic performance of the composite material, thereby solving the technical problems.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a composite photocatalyst.
In order to achieve the purpose, the invention provides the following technical scheme:
composite photocatalyst Bi 2 O 3 @ C, the composite photocatalyst is Bi 2 O 3 @ C, is made of a composite material Bi 2 WO 6 @ D113 calcining to obtain Bi 2 WO 6 The sodium tungstate-bismuth nitrate composite material is synthesized by a hydrothermal method, and D113 is cheap and stable, has multiple functional groups and is beneficial to reaction. Calcining to obtain the hollow microsphere Bi with surface wrinkles 2 O 3 @C。
Composite photocatalyst Bi 2 O 3 The preparation method of @ C comprises the following steps of a and Bi 2 WO 6 Preparation of @ D113: bismuth nitrate and sodium tungstate are mixed according to a molar ratio of 4:1-1:4, adding the mixture into 60mL of deionized water, adding magnetons at normal temperature, stirring for 20-40min, and mixing the bismuth nitrate and the D113 according to a mass ratio of 1:8-8:1 adding D113, transferring to a polytetrafluoroethylene reaction kettle, and reacting for 15-25h at 120-200 ℃. After the reaction is finished, repeatedly cleaning the product by deionized water, filtering and drying to obtain Bi 2 WO 6 @D113；b、Bi 2 O 3 Preparation of @ C: weighing 1g of the product obtained in the step a, putting the product into a crucible, and calcining the product for 1 to 3 hours in a muffle furnace at the temperature of between 400 and 600 ℃ to obtain Bi 2 O 3 @C。
Preferably, the molar ratio of bismuth nitrate to sodium tungstate in step a is 2:1, the mass ratio of bismuth nitrate to D113 is 1: and 4, stirring for 30min at normal temperature, wherein the reaction temperature is 160 ℃, and the reaction time is 20h.
Preferably, in the step b, the calcination temperature is 500 ℃ and the calcination time is 2h.
Bi 2 O 3 The application of the @ C composite photocatalyst has good photocatalytic degradation performance on xylenol orange.
Preferably, the composite photocatalyst is applied to photocatalytic degradation of xylenol orange in dye wastewater.
Preferably, the method comprises the following steps of photocatalytic degradation, and 80mg of Bi is taken 2 O 3 @ C to 100mL of a 20ppm xylenol orange solution; stirring for 30min under dark condition to reach adsorption-desorption balance; then, a xenon lamp is turned on for photocatalysis for 1h, and a proper amount of solution is taken at regular time during the photocatalysis for measuring the concentrations of the xylenol orange before and after adsorption by using an ultraviolet spectrophotometry.
Preferably, the composite photocatalyst Bi is used for 1h of photocatalysis 2 O 3 The photocatalytic degradation rate of @ C p-xylenol orange can reach 93.57%.
The invention has the beneficial effects that: the macroscopic materials with the microscopic sizes are combined to form the composite photocatalytic material with excellent performance; the reaction process is simple and convenient, and is green; bi 2 O 3 The @ C material is novel in structure and has high research value; the photocatalytic degradation effect of the xylenol orange is superior to that of the prior art; bi 2 O 3 The @ C material has good stability and can be applied to photocatalytic degradation of printing and dyeing wastewater.
Drawings
FIG. 1 is a schematic material diagram of a raw material D113 according to the present invention;
FIG. 2 shows Bi according to the present invention 2 WO 6 Material schematic of @ D113;
FIG. 3 shows the composite photocatalyst Bi of the present invention 2 O 3 Material schematic of @ C;
FIG. 4 shows the raw materials D113 and Bi according to the present invention 2 WO 6 @ D113 and composite photocatalyst Bi 2 O 3 An XRD pattern of @ C;
FIG. 5 shows the raw material D113 and the composite photocatalyst Bi according to the present invention 2 O 3 @ C infrared lightA spectrogram;
FIG. 6 is a diagram of the UV-VIS absorption spectrum of the xylenol orange in the photocatalytic degradation process according to the present invention;
FIG. 7 shows the composite photocatalyst Bi of the present invention 2 O 3 Graph of the degradation rate of @ C p-xylenol orange along with time;
FIG. 8 shows Bi prepared at different hydrothermal reaction temperatures 2 O 3 Graph of the degradation rate change of @ C when degraded for 1h under the same conditions;
FIG. 9 shows Bi prepared at different hydrothermal reaction times 2 O 3 Graph of the degradation rate change when @ C is degraded for 1h under the same conditions;
FIG. 10 shows Bi prepared at different calcination temperatures 2 O 3 Graph of the degradation rate change of @ C when degraded for 1h under the same conditions;
FIG. 11 shows Bi prepared at different calcination times 2 O 3 Graph of the degradation rate change of @ C under the same conditions for 1h of degradation;
FIG. 12 shows Bi prepared with different molar ratios of sodium tungstate and bismuth nitrate 2 O 3 Graph of the degradation rate change of @ C under the same conditions for 1h of degradation;
FIG. 13 shows Bi prepared with different mass ratios of sodium tungstate to D113 2 O 3 Graph of the degradation rate change of @ C under the same conditions for 1h of degradation;
FIG. 14 shows the composite photocatalyst Bi of the present invention 2 O 3 @ C and its monomer Bi 2 O 3 And C is a comparative graph of the photocatalytic degradation rate of xylenol orange.
Detailed Description
The following detailed description of the present invention is provided in conjunction with the accompanying drawings, but it should be understood that the scope of the present invention is not limited to the specific embodiments. It should be noted that the experimental methods used in the following examples are all conventional methods unless otherwise specified; materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below.
Example 1
D113 is polyacrylic acid type weak acid resin taking itaconic acid allyl ester as a main part and divinylbenzene as a secondary crosslinking agent. The D113 resin with good quality is in a neat spherical shape, uniform milky white, high in strength, not easy to break, free of abnormal particles, impurities and cracking balls basically, and the sphericity rate is 100%, as shown in figure 1. D113 has excellent separation and enrichment performance, low cost, large adsorption capacity and better strength, is usually used for selective adsorption and separation of various heavy metal ions, can keep a spherical structure from collapsing during pyrolysis or low-temperature calcination due to a stable framework structure, and is a potential functional carbon raw material.
Bi 2 O 3 Is one of novel bismuth-based photocatalytic materials, is a P-type semiconductor, has a specific electronic structure with more active charges, and is Bi 2 O 3 The semiconductor is composed of a low energy Valence Band (VB) filled with electrons and an empty high energy Conduction Band (CB), and a band gap between the two is called a forbidden band. When Bi is present 2 O 3 When receiving photon with energy equal to or more than band gap energy Eg (i.e. forbidden band width), the electrons in valence band will be excited to jump to conduction band to form conduction band electrons (e) CB - ) While leaving a hole (h) in the valence band VB + ) Thereby forming electron-hole pairs. After photo-generated electrons and holes migrate to the surface of a semiconductor, a series of reactions are initiated, and the holes can react with hydroxyl (OH) adsorbed on the surface of a photocatalyst - ) Or water (H) 2 O) to generate hydroxyl radical (OH), which has strong oxidizing power and can oxidize multiple substances without selectivity, and electrons can react with oxygen (O) 2 ) Generate superoxide radical (O) by reaction 2 · - )。Bi 2 O 3 The main elementary process of the photocatalytic oxidation reaction in the semiconductor is as follows:
(1) photo-generated carriersTo produce Bi 2 O 3 +hν→e CB - +h VB + (1-1)
(2) Capture of photogenerated carriers h VB + +HO - →·OH+H + (1-2)
h VB + +H 2 O→·OH (1-3)
e CB - +O 2 →O 2 · - (1-4)
(3) Recombination of photogenerated carriers e CB - +h VB →heat (1-5)
In addition, recombination of photogenerated electrons and holes may also occur. To improve the quantum efficiency of photocatalytic reactions, the recombination of electron-hole pairs should be minimized. The photogenerated carrier recombination process depends mainly on two factors: the first is the capture process of the current carrier on the surface of the catalyst, and the second is the migration process of the surface charge, and the combination of the current carrier can be effectively inhibited by increasing the capture of the current carrier or improving the migration rate of the surface charge. The recombination rate of photogenerated electrons and holes is fast, and the capture rate is relatively slow, so that the pre-adsorption of the capture agent on the surface of the catalyst is very important for effectively capturing the electrons or holes. In addition, the surface morphology, grain size, crystal structure, and surface defects of the catalyst also affect the recombination and charge transfer processes of the photogenerated carriers.
However, bi 2 O 3 As a nano-grade material, the material has small volume, so the material is easy to agglomerate and difficult to separate, and Bi is used 2 O 3 If the photocatalyst can be combined on a relatively macroscopic object, the photocatalyst can achieve better photocatalytic effect under the synergistic effect of the two objects and can be easily separated. One possible method is to form Bi by self-assembling bismuth tungstate under the action of rich functional groups on the surface of D113 in the hydrothermal process 2 WO 6 @ D113, and then calcined into a composite material Bi of a hollow carbon structure utilizing the structure stabilized by D113 2 O 3 @ C. The innovation point of the method is as follows: (1) the materials with macroscopic and microscopic sizes are combined to form the composite photocatalytic material with excellent performance; (2) simple and convenient reaction process and greening(ii) a (3) The Bi 2 O 3 The structure of the material is novel, and the hollow carbon structure can effectively realize the reflection and absorption of light, so that the light utilization rate is improved; (4) carbon material and Bi 2 O 3 The recombination of the two is beneficial to the optimization of energy level, so that the yield of photon-generated carriers is improved, the separation and the transmission of the photon-generated carriers are promoted, and the photocatalytic degradation effect of the two on xylenol orange under the synergistic effect is predicted to be superior to that of the prior art. Predicting the Bi 2 O 3 The @ C material has good stability and reusability, and can be applied to degradation and purification of XO in dye wastewater.
This example presents Bi 2 O 3 If the material can be combined on a relatively macroscopic object, a better photocatalysis effect can be achieved under the synergistic effect of the two. Specifically, this example is to mix Bi 2 WO 6 Self-assembly of Bi on the surface of D113 2 WO 6 @ D113, as shown in FIG. 2. Then preparing the composite photocatalyst Bi by a calcination method 2 O 3 @ C, where the stable structural unit of D113 ensures that the sphere structure does not collapse during calcination and hollow microspheres are obtained by mass transfer, the semiconductor Bi 2 O 3 Uniformly distributed on the surface thereof, bi 2 O 3 The @ C appearance is shown in FIG. 3. The material is based on a semiconductor Bi 2 O 3 And the synergistic effect between the hollow graphite carbon can effectively improve the light absorption efficiency, and improve the carrier yield and effective separation and transmission, so that the method can be widely applied to the degradation of xylenol orange.
Thus, this embodiment provides a Bi 2 O 3 The @ C composite photocatalyst is used for degrading the xylenol orange in the dye wastewater, and influences of the xylenol orange on the environment and human health are relieved to a certain extent.
Example 2
The embodiment provides a method for preparing a composite photocatalyst Bi 2 O 3 The method of @ C comprises the following process steps:
a、Bi 2 WO 6 preparation of @ D113: bismuth nitrate and sodium tungstate are mixed according to a molar ratio of 4:1-1:4 to 60mL of deionized water, adding magnetons at normal temperature, stirring for 20-40min, adding sodium sulfateThe mass ratio of bismuth acid to D113 is 1:8-8:1 adding D113, transferring to a polytetrafluoroethylene reaction kettle, and reacting for 15-25h at 120-200 ℃. After the reaction is finished, repeatedly cleaning the product by deionized water, filtering and drying to obtain Bi 2 WO 6 @D113；
b、Bi 2 O 3 Preparation of @ C: weighing 1g of the product obtained in the step a, putting the product into a crucible, and calcining the product for 1 to 3 hours in a muffle furnace at the temperature of between 400 and 600 ℃ to obtain Bi 2 O 3 @C。
The actual specific operation comprises the following process steps:
a、Bi 2 WO 6 preparation of @ D113: bismuth nitrate and sodium tungstate are mixed according to the feed ratio of 0.48g: adding 0.16g of bismuth nitrate into 60mL of deionized water, adding magnetons at normal temperature, stirring for 30min, and adding bismuth nitrate and D113 according to a feeding ratio of 0.48g:1.92g of D113 is added into 1.92g of the mixture and then the mixture is transferred to a polytetrafluoroethylene reaction kettle to react for 20 hours at 160 ℃. After the reaction is finished, repeatedly cleaning the product by deionized water, filtering and drying to obtain Bi 2 WO 6 @D113；
b、Bi 2 O 3 Preparation of @ C: weighing 1g of the product obtained in the step a, putting the product into a crucible, and calcining the product for 2h in a muffle furnace at 500 ℃ to obtain Bi 2 O 3 @C。
The D113 macroporous adsorption resin is a net structure due to the special structure, has good adsorption effect due to the macroporous net structure and larger surface area, is a potential effective adsorption carrier for the XO, and has been applied to various fields. Bi 2 O 3 Since it is one of novel bismuth-based photocatalytic materials and is a P-type semiconductor, its specific electronic structure is adopted with more active charges. Bi 2 WO 6 Surface assembly by self-assembly process, mixing D113 with sodium tungstate and bismuth nitrate to form Bi 2 WO 6 @ D113 compound, then calcining at high temperature to obtain Bi 2 O 3 @C。Bi 2 O 3 @ C composite photocatalyst based on semiconductor Bi 2 O 3 And the synergistic effect between the hollow graphite carbon can effectively improve the light absorption efficiency, improve the carrier yield and the effective separation and transmission, and is a novel high-performance photocatalytic degradation material.
Combining the preparation process and the comparison productBi 2 O 3 The preparation method comprises the following steps: bismuth nitrate and sodium tungstate are mixed according to the feed ratio of 0.48g:0.16g of the mixture is added into 60mL of deionized water, stirred for 30min and then transferred into a reaction kettle to react for 20h at 160 ℃. After the reaction is finished, repeatedly cleaning the product by deionized water, filtering and drying to obtain Bi 2 WO 6 . 1g of the product Bi obtained 2 WO 6 Putting the mixture into a crucible, and calcining the mixture for 2 hours in a muffle furnace at 500 ℃ to obtain Bi 2 O 3 。
Combining the preparation process, the preparation of the hollow carbon of the comparison product comprises the following steps: and putting 1g of D113 resin balls into a crucible, and calcining for 2h in a muffle furnace at 500 ℃ to obtain hollow carbon C.
In order to further prove the reaction mechanism, the XRD test and the infrared spectroscopy test were performed on the materials before and after the reaction, and the results are shown in fig. 5 and 6. In FIG. 5, D113 and Bi 2 WO 6 @ D113 is a peak packet, bi 2 O 3 The @ C has obvious diffraction peaks at 27.949 °, 32.691 ° and 46.218 ° diffraction angles, which correspond to Bi respectively 2 O 3 The (201), (220), and (222) diffraction crystal planes of (1), (220), and (222). In FIG. 6, D113 is at 1717cm -1 Is caused by C = O expansion and contraction vibration, 1536cm -1 、1458cm -1 And 700cm -1 Characteristic absorption peaks for C = C, -COOH and C-H, respectively; bi 2 O 3 @ C at 3430cm -1 Is caused by O-H stretching vibration, 1617cm -1 、1458cm -1 、875cm -1 And 797cm -1 Characteristic absorption peaks of Bi-O, -COOH, C-C and C = C, respectively. The XRD and FTIR demonstrated Bi 2 O 3 The chemical structure of @ C.
Example 3
In the embodiment, the composite photocatalyst of the embodiment is used in a photocatalytic degradation experiment of xylenol orange, and the result shows that the Bi is prepared 2 O 3 The @ C material has excellent degradation performance on xylenol orange, and the degradation rate is high and is 93.57%.
The material can be applied to the photocatalytic degradation of MO in environment or food, and xylenol orange can be degraded by the composite photocatalyst in claim 1 in various types of wastewater containing MO dye. The specific degradation process is as follows:
80mg of Bi are taken 2 O 3 @ C to 100mL of a 20ppm xylenol orange solution; stirring for 30min under dark condition to reach adsorption-desorption balance; and then, turning on a xenon lamp for photocatalysis for 1h, periodically taking a proper amount of solution during the photocatalysis, measuring the concentrations of the xylenol orange before and after adsorption by using an ultraviolet spectrophotometry, and calculating the degradation rate of the xylenol orange.
Wherein the ultraviolet spectrophotometry measuring process of the concentration of xylenol orange comprises the following steps:
preparing 1000ppm standard stock solution from xylenol orange by using deionized water, diluting the xylenol orange into 0-20 ppm concentration gradient standard solution by adopting a stepwise dilution method, performing full spectrum scanning by using an ultraviolet spectrophotometer, selecting the wavelength with the maximum absorbance as a test wavelength, measuring the absorbance, establishing a standard curve y =0.0052x-0.0015, determining the concentration gradient of xylenol orange by using the standard curve y =0.0052x-0.0015 2 ＝0.9995。
The ultraviolet spectrophotometry measuring method of the xylenol orange solution with unknown concentration comprises the following steps:
and (3) measuring the absorbance of the sample by the unknown solution through an ultraviolet spectrophotometer, bringing the absorbance into a standard curve, and calculating the sample concentration.
Example 4
To demonstrate that the above examples propose a composite photocatalyst Bi 2 O 3 The practical effect of @ C, actually demonstrated in this example with the degradation rate of XO. The specific experimental procedures and results are as follows.
Bi 2 O 3 Testing of photocatalytic degradation of the @ C material to XO:
80mg of Bi are taken 2 O 3 @ C was added to 100mL of a 20ppm xylenol orange solution; stirring for 30min under dark condition to reach adsorption-desorption balance; and then, opening a xenon lamp for photocatalysis for 1h, periodically taking a proper amount of solution during the photocatalysis, measuring the absorbance before and after degradation by using an ultraviolet spectrophotometry, substituting the absorbance into a standard curve to calculate a final concentration value, and calculating the degradation rate.
As can be seen from FIG. 7, bi 2 O 3 The @ C has obvious degradation effect on xylenol orange, the degradation balance can be achieved only within 1 hour, and the degradation rate reaches 93.57%. This is because Bi 2 O 3 Bi semiconductor of material @ C 2 O 3 The Bi forms obvious synergy under the synergistic action with the hollow carbon material so that the Bi 2 O 3 The @ C material has a remarkable degradation effect on xylenol orange.
The composite photocatalyst Bi prepared in the example 2 O 3 @ C is applied to a xylenol orange degradation experiment, and the degradation rate of xylenol orange is 93.57% under the conditions of xenon light catalysis and 1h of degradation time.
The experimental result shows that the photolysis effect of the xylenol orange is good and superior to that of the prior art, and the synergistic interaction of the composite material is realized.
Example 5
In this example, the reaction temperatures in example 2 were set to 120 ℃,140 ℃,160 ℃, 180 ℃ and 200 ℃ respectively, and the same as in example 2 except that the reaction temperature was changed. And the degradation rate was measured according to example 4. The obtained effect of different reaction temperatures on the degradation rate of the photocatalyst is shown in fig. 8.
Referring to FIG. 8, it can be seen that the degradation rate of the photocatalyst increases with the temperature increase in the reaction temperature range of 120-160 ℃ because more Bi is present at higher temperature 2 WO 6 Supported on D113, the photocatalytic degradation rate increased. In the temperature range of 160-200 ℃, due to Bi loaded on D113 2 WO 6 Tends to be saturated, so that the trend of the attached amount increasing along with the increase of the temperature is weakened, the increase of the photocatalytic degradation rate is not obvious, and the balance is approached. The 140 ℃ is the preferred temperature of the reaction, considering the material performance and the economic benefit comprehensively.
Example 6
In this example, the reaction times in example 2 were set to 16h, 18h, 20h, 22h, and 24h, respectively, and the other examples were the same as example 2. And the degradation rate was measured according to example 4. The resulting effect of different reaction times on the degradation rate of the photocatalyst is shown in fig. 9.
Referring to FIG. 9, the degradation rate of the photocatalyst increases with time in the reaction time range of 16-20h, because more Bi is present in the reaction solution for a longer time 2 WO 6 Supported on D113, the photocatalytic degradation rate increased. The reaction time range is 20-24hIn the enclosure, bi is generated due to overlong hydrothermal time 2 WO 6 The particle is enlarged, so that the specific surface area of the composite material is reduced, the transmission of photon-generated carriers is not facilitated, and the photocatalytic efficiency is reduced. The material performance and the economic benefit are comprehensively considered, and 20 hours is the preferable time of the reaction.
Example 7
In this example, the calcination temperatures in example 2 were set to 300 ℃, 400 ℃,500 ℃, 600 ℃, and 700 ℃, respectively, and the same as in example 2 except that the above-described calcination temperatures were set. And the degradation rate was measured according to example 4. The resulting effect of different calcination temperatures on the photocatalyst degradation rate is shown in fig. 10.
Referring to FIG. 10, it can be seen that the photocatalyst degradation rate increases and then decreases with increasing temperature in the calcination temperature range of 300-700 deg.C, because Bi increases with increasing temperature 2 WO 6 @ D113 calcination is more complete, and more Bi 2 WO 6 Calcination at @ D113 to form Bi 2 O 3 @ C, so that the photocatalytic degradation rate is increased. However, when the temperature is too high, the hollow carbon microspheres collapse or even break, so that the structure or composition of the product is changed, and the photocatalytic efficiency is reduced. The 500 ℃ is the preferred temperature for calcination, considering the material performance and economic benefits.
Example 8
In this example, the calcination times in example 2 were set to 1 hour, 1.5 hours, 2 hours, 2.5 hours, and 3 hours, respectively, and the same procedure as in example 2 was repeated. And the degradation rate was measured according to example 4. The resulting effect of different calcination times on the photocatalyst degradation rate is shown in fig. 11.
Referring to FIG. 11, it can be seen that the photocatalyst degradation rate increases and then decreases with time in the calcination time range of 1 to 3h, because Bi increases with time 2 WO 6 @ D113 calcination is more complete, and more Bi 2 WO 6 Calcination at @ D113 to form Bi 2 O 3 @ C, so that the photocatalytic degradation rate is increased. However, when the time is too long, the hollow carbon microspheres collapse or even break, so that the structure or composition of the product is changed, and the photocatalytic efficiency is reduced. General considerations ofMaterial performance and economic benefit, 2h is the preferred time for calcination.
Example 9
In this example, the molar ratios of sodium tungstate and bismuth nitrate in example 2 were set to 4: 1. 2: 1. 1: 1. 1: 2. 1:4, the rest is equivalent to the embodiment 2. And the degradation rate was measured according to example 4. The influence of the molar ratio of sodium tungstate to bismuth nitrate on the degradation rate of the photocatalyst is shown in fig. 12.
Referring to fig. 12, when the molar ratio of sodium tungstate to bismuth nitrate is 4:1-2: within the range of 1, the degradation rate of the photocatalyst is gradually increased; in the molar ratio of sodium tungstate to bismuth nitrate of 2:1-1:4, the degradation rate of the photocatalyst gradually decreases. Comprehensively considering material performance and economic benefit, 2:1 is the preferred molar ratio of sodium tungstate to bismuth nitrate.
Example 10
In this example, the mass ratios of sodium tungstate and D113 in example 2 above were set to 1: 8. 1: 4. 1: 1. 4: 1. 8:1, the rest is equivalent to example 2. And the degradation rate was measured according to example 4. The influence of the obtained mass ratios of different sodium tungstate and bismuth nitrate on the degradation rate of the photocatalyst is shown in fig. 13.
Referring to fig. 13, in the mass ratio of sodium tungstate to D113 of 1:8-1: in the range of 4, the photocatalyst degradation rate is very slight, because in this range, bi is present 2 WO 6 In excess, but with limited D113 loading sites, the active sites on D113 are all loaded with Bi 2 WO 6 Excessive Bi 2 WO 6 The photocatalyst can not be loaded on D113 completely, so that the photocatalytic degradation rate is very poor; in the mass ratio of sodium tungstate to D113 of 1:4-8: in the range of 1, the photocatalyst degradation rate gradually decreased because in this range, D113 was excessive and Bi was added 2 WO 6 Reduction of Bi on D113 2 WO 6 The loading amount is reduced, so that the photocatalytic degradation rate is reduced. Comprehensively considering material performance and economic benefit, 1: and 4 is the mass ratio of sodium tungstate to D113.
Example 11
In this example, the photocatalyst in the above example 4 was changed to Bi 2 O 3 C, the rest being equivalent to example 4. The obtained effect of different photocatalysts on the degradation rate of xylenol orange by photocatalysis is shown in fig. 14.
Referring to FIG. 14, the composite photocatalyst Bi 2 O 3 The photocatalytic degradation effect of @ C on xylenol orange is superior to that of Bi 2 O 3 And C photocatalytic degradation alone.
It should be understood that the present invention is described by way of embodiments, and the embodiments are only provided for enabling technical solutions proposed by the claims of the present invention to achieve clear and complete descriptions, that is, explanations of the claims, so that when judging whether the technical solutions described in the present specification are sufficiently disclosed, the core meanings of the solutions defined by the claims should be fully considered, and other technical problems that are irrelevant to the solution of the core technical problems proposed by the embodiments are necessarily present in the description, and the corresponding technical features and technical solutions are not referred to in the present embodiment, but belong to unnecessary technical features, so that reference may be made to implicit disclosures, and those skilled in the art can fully combine the prior art with the common general knowledge to achieve the purposes, and therefore, no detailed description is necessary.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.

Claims (5)

1. Hollow carbon composite photocatalyst Bi with wrinkled surface 2 O 3 @ C, characterized by: the preparation method comprises the following steps:
a、Bi 2 WO 6 preparation of @ D113: bismuth nitrate and sodium tungstate are mixed according to a molar ratio of 4:1-1:4, adding the mixture into 60mL of deionized water, adding magnetons at normal temperature, stirring for 20-40min, and mixing the bismuth nitrate and the D113 according to a mass ratio of 1:8-8:1 adding D113 and transferring the mixture to a polytetrafluoroethylene reaction kettle for reaction at 120-200 ℃ for 15-After the reaction is finished, repeatedly cleaning the product with deionized water, filtering and drying to obtain Bi 2 WO 6 @D113；
b、Bi 2 O 3 Preparation of @ C: weighing 1g of the product obtained in the step a, putting the product into a crucible, and calcining the product for 2h in a muffle furnace at 500 ℃ to obtain the hollow carbon composite photocatalyst Bi with wrinkled surface 2 O 3 @C。
2. The surface-wrinkled hollow carbon composite photocatalyst Bi as claimed in claim 1 2 O 3 @ C, characterized by: preferably, the molar ratio of bismuth nitrate to sodium tungstate in step a is 2:1, the mass ratio of bismuth nitrate to D113 is 1: and 4, stirring for 30min at normal temperature, wherein the reaction temperature is 160 ℃, and the reaction time is 20h.
3. The hollow carbon composite photocatalyst Bi with wrinkled surface as claimed in any one of claims 1-2 2 O 3 Use of @ C, characterized in that: the composite photocatalyst has good photocatalytic degradation performance on xylenol orange.
4. The hollow carbon composite photocatalyst Bi with wrinkled surface as claimed in claim 3 2 O 3 Use of @ C, characterized in that: the composite photocatalyst Bi 2 O 3 The photocatalytic degradation rate of @ C on xylenol orange can reach 93.57%.
5. The hollow carbon composite photocatalyst Bi with wrinkled surface as claimed in claim 3 2 O 3 Use of @ C, characterized in that: the composite photocatalyst is applied to photocatalytic degradation of xylenol orange in dye wastewater.
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