CN114392734A - Tungsten oxide composite material and preparation method and application thereof - Google Patents

Tungsten oxide composite material and preparation method and application thereof Download PDF

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CN114392734A
CN114392734A CN202111642266.2A CN202111642266A CN114392734A CN 114392734 A CN114392734 A CN 114392734A CN 202111642266 A CN202111642266 A CN 202111642266A CN 114392734 A CN114392734 A CN 114392734A
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composite material
tungsten oxide
oxide composite
solution
preparation
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CN114392734B (en
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席晓丽
赵林艳
刘阳思
沈越岗
聂祚仁
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Beijing University of Technology
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Beijing University of Technology
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    • 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
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
    • B01J35/23—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering
    • G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
    • 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 relates to the technical field of nano materials, in particular to a tungsten oxide composite material and a preparation method and application thereof, wherein the preparation method of the tungsten oxide composite material comprises the following steps: mixing NaCl solution and sodium tungstate solution, adjusting pH, and performing hydrothermal reaction to obtain nanometer WO3A core material; then bismuth nitrate solution and the nano WO are mixed3Mixing the core materials, and carrying out solvothermal reaction. The preparation method of the tungsten oxide composite material provided by the invention is environment-friendly, stable, reliable, simple, convenient and feasible, has high controllability, and the obtained composite material has uniform size, fine appearance and convenience in applicationThe application is as follows. The tungsten oxide composite material prepared by the invention has the double functions of photocatalytic degradation and SERS detection, and has the advantages of excellent double-function application performance and obvious effect.

Description

Tungsten oxide composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of nano materials, in particular to a tungsten oxide composite material and a preparation method and application thereof.
Background
With environmental pollution and ecological destruction, the treatment of pollutants such as water, air, soil, etc. has become a serious problem to be solved, especially since the industrialization, a large amount of waste water of factories and farms is discharged without being treated, and contains a large amount of organic pollutants harmful to human beings and other organisms. The photocatalytic technology is a modern green energy-saving technology, shows great potential in the aspect of wastewater treatment, and gradually becomes a research hotspot in the field of environmental protection. Among the numerous photocatalysts, tungsten trioxide (WO)3) As an n-type semiconductor material, the transition metal oxide is cheap and stable, has unique physicochemical properties, and is widely applied to the fields of environment, energy, life science, information technology and the like.
WO3The narrow band gap structure ensures that the narrow band gap structure has expanded spectral response, can effectively utilize visible light part in natural light, greatly improves the utilization rate of sunlight, but has adverse effects on the other hand, such as fast recombination of photo-generated electron-hole pairs with the narrow band gap structure, low photocatalytic activity and the like; and WO3Lower conduction band positions may also hinder the reductive reaction from proceeding. The general approach to solve this problem is to compound the target semiconductor with other semiconductors or metals having corresponding band structures, construct hetero/homojunctions, and compensate for the structural defects of each other by synergy. In recent years, with the development of nanotechnology, the nano-scale composite tungsten oxide material gradually enters the field of vision of people, and compared with the large-size tungsten oxide material, the nano-scale tungsten oxide has the advantages of adjustable surface energy, obviously increased specific surface area, quantum confinement effect and the like, and is concerned by more and more researchers.
The physical and chemical properties of the material are mainly controlled by the used preparation method and the specific preparation process, and the particle size, the crystal structure, the service performance, the actual application condition and the like of the synthesized material are directly influenced. The existing methods for preparing tungsten oxide can be roughly divided into the following steps according to the properties of raw materials and different reaction processes: a gas phase method (sputtering, thermal evaporation, arc discharge deposition, etc.), a liquid phase method (sol-gel method, electrochemical method, chemical deposition method, hydrothermal/solvothermal method, etc.), and a solid phase method (mechanical pulverization method, solid phase reaction method, etc.). Although the preparation methods are numerous, from the perspective of preparing functional composite materials, it is still a difficult point in the current academia to find a method that can stably prepare composite materials and make the prepared materials have excellent performance in non-single-function applications.
Disclosure of Invention
In order to solve the technical problems, the invention provides a tungsten oxide composite material and a preparation method and application thereof.
In a first aspect, the present invention provides a method for preparing a tungsten oxide composite material, comprising: mixing NaCl solution and sodium tungstate solution, adjusting pH, and performing hydrothermal reaction to obtain nanometer WO3A core material; then bismuth nitrate solution and the nano WO are mixed3Mixing the core materials, and carrying out solvothermal reaction.
The invention discovers that the hydrothermal/solvothermal method can controllably prepare the tungsten oxide composite material with excellent performance by two steps, solves the great problem existing in the field at present, stably prepares the composite material with multiple application functions, simultaneously needs raw materials which are convenient and easy to obtain in the market, has wide sources, multiple varieties and large optional range, has the advantages of environmental protection, stability, reliability, simplicity, convenience, practicability and the like, has uniform size, fine particles and convenient application, has double functions of photocatalytic degradation and SERS detection, has excellent double-function application performance and achieves remarkable effect of spontaneous feedback regulation.
The preparation method of the tungsten oxide composite material provided by the invention comprises the following steps:
1) dropwise adding a NaCl solution into a sodium tungstate solution, stirring, and adding hydrochloric acid to adjust the pH value to obtain a mixed solution;
2) carrying out hydrothermal reaction on the mixed solution obtained in the step 1), cooling, washing, centrifuging and drying to obtain the nano WO3A core material;
3) will be provided withBismuth nitrate solution and the nano WO obtained in step 2)3Mixing the core materials, carrying out solvent thermal reaction, cooling, washing, centrifuging and drying.
Further preferably, in the step 1), the concentration of the NaCl solution is 4.5-5.5 mol/L; and/or the concentration of the sodium tungstate solution is 0.12-0.16 mmol/L; and/or the concentration of the hydrochloric acid is 2.4-2.6 mol/L, and the pH value is 1.8-2.5.
The NaCl solution, the sodium tungstate solution and the hydrochloric acid are all prepared by pure water, the concentration of the NaCl solution, the sodium tungstate solution and the hydrochloric acid is not limited, but when the concentration of the NaCl solution is 4.5-5.5 mol/L, the concentration of the sodium tungstate solution is 0.12-0.16 mmol/L and the concentration of the hydrochloric acid is 2.4-2.6 mol/L and the pH value of the solution is adjusted to be 1.8-2.5, the generation of side reactions can be effectively avoided, and the hydrothermal reaction is improved to obtain the nano WO3The structure and the performance of the core material are beneficial to subsequent reaction, so that the appearance and the application effect of the tungsten oxide composite material are better ensured. The inventor finds out through experiments that the preferable concentration range is as follows: 5mol/L NaCl solution, 0.14mmol/L sodium tungstate solution and 2.5mol/L hydrochloric acid, and the pH value of the solution is adjusted to 2 optimal.
Preferably, in the step 2), the hydrothermal reaction is carried out for 6-24 hours at 160-280 ℃; and/or in the step 3), the solvothermal reaction is performed for 6-24 hours at 160-280 ℃. Further preferably, the optimal reaction conditions of the hydrothermal reaction and the solvothermal reaction are both 180 ℃ for 9 hours.
By adding the optimized reaction conditions, the yield and the purity of the product can be improved, so that the obtained product has a complete structure, uniform appearance and excellent photoelectric property, and is beneficial to subsequent application. Meanwhile, by adding the optimized reaction conditions, the phenomena of incomplete reaction (the required product cannot be obtained) or excessive reaction (the excessive reaction can cause structural damage such as structural collapse, fracture and adhesion) and the like of the product in the reaction process can be further avoided, and the application effect of the prepared composite material is ensured to be more excellent.
Preferably, in the step 3), the concentration of the bismuth nitrate solution is 0.01-0.5 mol/L.
More preferably, the concentration of the bismuth nitrate solution is 0.05 mol/L.
The preferred bismuth nitrate concentration according to the invention is aimed at giving the product good application properties. The proper bismuth nitrate concentration is crucial to obtaining the Bi-containing composite product, and the incomplete morphology structure of the composite product can be caused by the excessively low concentration; excessive concentration can cause by-product formation, increase the processing difficulty of subsequent steps, and affect the application effect of the final product.
Preferably, in step 3), the solvent for the solvothermal reaction may be an organic solvent such as methanol, ethanol, ethylene glycol, butanol, etc., so as to ensure that bismuth nitrate is soluble therein and participates in the reaction.
More preferably, the solvent for the solvothermal reaction is ethylene glycol.
The invention preferably selects the ethylene glycol, aims at ensuring that the bismuth nitrate has considerable solubility in the ethylene glycol and the ethylene glycol has proper viscosity and density, ensures the uniform and stable reaction process, ensures the stable property of the final product and is beneficial to application.
According to the preparation method of the tungsten oxide composite material provided by the invention, the step 3) further comprises the following steps: adding a dispersant to the bismuth nitrate solution.
Further preferably, the dispersant comprises one or more of CTAB, EDTA, SDS.
According to the invention, optionally, a dispersant is added into the bismuth nitrate solution, or no dispersant is added, but the effect of adding the dispersant is better, and the preferable dispersant comprises one or more of CTAB, EDTA and SDS, but the EDTA is most preferably added in consideration of the effect of the final use of the product. Preferably, the concentration range of EDTA in the bismuth nitrate solution is 1.7-10.3 mmol/L. Further preferably, the concentration of EDTA is 6.8 mmol/L.
Preferably, the nano WO3The molar ratio of W in the core material to Bi in the bismuth nitrate solution is 0.72-71.8: 30-1500; more preferably 50.3: 150.
the invention adopts specific raw materials and condition parameters to prepare nano WO by a hydrothermal method3The core material is then prepared by solvothermal method to obtain the tungsten oxide composite materialAnd then the obtained composite material is practically applied to photocatalytic degradation of organic pollutants and SERS detection of organic pollutants. The method disclosed by the invention is environment-friendly, stable, reliable, simple, convenient and feasible, has high controllability, and the obtained composite material has the advantages of uniform size, small appearance and simplicity and convenience in application, can be applied to photocatalytic degradation of organic pollutants and SERS detection of organic pollutants, exerts the dual-functionality of the composite material, and achieves an obvious effect of spontaneous feedback regulation. The method is applied to photocatalytic degradation of organic pollutants and SERS detection of organic pollutants, plays a role in dual functions and achieves the effect of spontaneous feedback regulation. The preparation method provided by the invention is environment-friendly, stable, reliable, simple, convenient and feasible, has high controllability, and the obtained composite material has the advantages of uniform size, small appearance, simplicity and convenience in application and remarkable effect, and can provide theoretical basis and technical support for preparation and application of tungsten oxide and other functional semiconductor materials.
Further preferably, in steps 2) and 3), the washing comprises washing with deionized water and/or ethanol.
According to the preferred embodiment of the invention, the washing conditions are not limited to deionized water and ethanol, and residual organic/inorganic matters possibly existing in the product can be removed, but the washing effect by using the deionized water and the ethanol is optimal; in the invention, the rotating speed of the centrifugal machine is not limited, and the solution and the product can be effectively separated, and the test shows that the separation effect is optimal under 3000 r/min; in the invention, the drying method is not limited, and the modes of blowing by an air blower, drying by a drying oven and the like can be adopted, so that the structure of the product is not damaged in the airing process. Tests show that the optimal drying condition is drying at 60 ℃ for 12 hours. Further preferably, both the hydrothermal reaction and the solvothermal reaction are carried out in an autoclave, the temperature of which is optimally set to 180 ℃. It is to be understood that the invention is directed to specific manufacturing and use conditions that define the best and preferred products, but that the invention is not intended to exclude the proper extrapolation of such defined conditions to produce certain products that are considered to be within the scope of the invention.
In a second aspect, the invention provides a tungsten oxide composite material prepared by the above method.
The composite material prepared by the invention is practically applied to photocatalytic degradation of organic pollutants and SERS detection of organic pollutants, and plays a dual-function role. The practical application effect shows that the composite material prepared by the method has excellent dual-function application performance and obvious effect. The invention also provides theoretical basis and technical support for the preparation and application of tungsten oxide and other semiconductor materials with similar functions.
In a third aspect, the invention provides applications of the tungsten oxide composite material prepared by the method, including one or more of the following applications:
a) the tungsten oxide composite material is applied to photocatalytic degradation of organic pollutants;
b) the tungsten oxide composite material is applied to SERS detection of organic pollutants.
The invention discovers that the tungsten oxide composite material prepared by the invention is practically applied to photocatalytic degradation of organic pollutants and SERS detection of organic pollutants, can well play the dual-function role of the tungsten oxide composite material, and achieves the effect of spontaneous feedback regulation.
Preferably, the specific application method comprises the following steps: 4) the tungsten oxide composite material is uniformly dispersed in an organic pollutant solution with a certain concentration, and the tungsten oxide composite material is placed under a light source to carry out photocatalytic degradation on organic pollutants, so that the final degradation effect of the material is excellent; 5) and uniformly dispersing the tungsten oxide composite material in a pollutant solution with a certain concentration to form a mixed solution, dripping a certain amount of mixed solution on a substrate, and immediately carrying out SERS detection after drying to obtain the material with excellent enhancement effect on the Raman signal peak of the pollutant.
Preferably, the organic pollutants comprise methylene blue, methylene orange, rhodamine B, BPA and the like, and the nondegradable methylene blue is preferred.
In the specific application example of the invention, the quality and the pollutant concentration of the used composite material are not limited, and are proper, so that the photocatalysis requirement can be met; the light source can be sunlight or simulated sunlight, the used simulated sunlight equipment is not limited, and the light source can be a xenon lamp, a mercury-xenon arc lamp, a high-pressure mercury lamp, an ultraviolet/visible lamp and the like, and the illumination required by the catalytic process can be met. If a pollutant solution is required to be prepared in the application process, the solvent type of the pollutant solution can be sufficient to dissolve the pollutants, but ethanol is preferred in view of the subsequent drying requirement; the type of the substrate used for detecting the organic pollutants by SERS is not limited, and the substrate can be a quartz plate, a mica plate, a ceramic plate and the like, and the subsequent SERS detection is not influenced.
The invention has the beneficial effects that: the hydrothermal/solvothermal two-step preparation method provided by the invention can controllably prepare the tungsten oxide composite material with excellent performance, and solves the great problem existing in the field at present, namely stably preparing the composite material with multiple application functions; the raw materials required by the reaction are convenient and easily available in the market, and have wide sources, various types and wide optional range; the method provided by the invention is environment-friendly, stable, reliable, simple, convenient and easy to implement, and high in controllability, the obtained composite material is uniform in size, fine in particles and excellent in performance, the prepared composite material has not only photocatalytic performance, but also excellent SERS (surface enhanced Raman scattering) enhancing effect, and the dual-function application of the composite material is realized.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an SEM photograph of the product obtained in example 1 of the present invention (a is WO, and B and c are B/BO/WO).
FIG. 2 is an XRD picture of the product obtained in example 1 of the present invention.
FIG. 3 is an SEM photograph of the product obtained in comparative example 1 of the present invention.
FIG. 4 is an XRD picture of the product obtained in comparative example 1 of the present invention.
FIG. 5 is a diagram showing the photocatalytic degradation effect of the composite product in example 2 of the present invention.
FIG. 6 is a graph showing the photocatalytic degradation effect of the composite product of comparative example 2 of the present invention.
FIG. 7 shows the detection of the Raman signal of the composite product of example 3 of the present invention with respect to contaminants.
Fig. 8 shows the result (b) of quantitative calculation of the SERS performance enhancement coefficient (EF) of the composite material and the signal peak (a) of pure MB solution in example 3 of the present invention.
FIG. 9 shows the detection of the Raman signal of the composite product of comparative example 3 according to the present invention on contaminants.
Detailed Description
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 with reference to the drawings in the embodiments of the present invention, and the following embodiments are used for illustrating the present invention and are not intended to limit the scope of the present invention. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The reagents or instruments used are not indicated by manufacturers, and are conventional products which can be purchased from regular distributors, and the raw materials and the reagents used are all of commercial analytical purity grades.
Example 1
0.0125mmol of Na was weighed2WO4·2H2Dissolving O in 90ml of pure water, and fully stirring and dissolving to form a solution A; weighing 0.1mol of NaCl, dissolving in 20ml of pure water, and fully stirring and dissolving to form a solution B; under the condition of continuously magnetic stirring, the solution A is dropwise added with the solution B, the pH value of the mixed solution is adjusted to 2 by 2.5M HCl (aq), then the mixed solution is put into an autoclave, hydrothermal reaction is carried out for 9h at 180 ℃, the mixed solution is cooled to room temperature, washing is respectively carried out by deionized water and ethanol, centrifugation is carried out for multiple times (the rotating speed is 3000r/min), and then drying is carried out for 12h at 60 ℃, so as to prepare a hydrothermal sample WO, as shown in figure 1 a.
0.003mol of Bi (NO) was weighed3)3·5H2Dissolving O in 60ml of ethylene glycol, stirring for 30min at room temperature, adding 0.12g of EDTA, stirring for 60min at room temperature, adding 0.7g of WO prepared by the hydrothermal method, stirring uniformly, placing into a high-pressure kettle, reacting for 9h at 180 ℃, cooling to room temperature, washing with deionized water and ethanol, centrifuging (rotating speed of 3000r/min) for multiple times, and drying for 12h at 60 DEG CThis gave a composite sample B/BO/WO, as shown in FIG. 1B.
As can be seen from FIG. 1, the nanoscale 3D composite product with uniform size and good appearance is prepared by the method of the invention, wherein WO3The length of the nano rod is 1-2 μm, and the diameter is 25-60nm (figure 1 a); bi2O3Nanosheet thickness about 10nm, and Bi2O3With WO3Form a 3D flower-like structure (Bi)2O3The nanoplatelets are vertically adhered to WO3Surface growth of nanorods) to form a structure that does not overlap and makes full use of space (fig. 1 b); bi is in the form of small spheres with a diameter of about a few hundred nanometers (fig. 1 c).
FIG. 2 is the XRD patterns of two products obtained in example 1, wherein the WO sample corresponds to h-WO3Phase, B/BO/WO sample corresponds to Bi/Bi2O3/WO3Phase, the product prepared by the invention has good crystallinity and does not contain other impurities.
Comparative example 1
Directly weighing 0.003mol of Bi (NO)3)3·5H2Dissolving O in 60ml ethylene glycol, stirring at room temperature for 30min, adding 0.12g EDTA, stirring at room temperature for 60min, loading into autoclave, reacting at 180 deg.C for 9h, cooling to room temperature, washing with deionized water and ethanol, centrifuging (at 3000r/min), drying at 60 deg.C for 12h to obtain composite sample B/BO with phase shown in FIG. 4, and prepared from Bi and Bi2O3And (4) forming. Meanwhile, as can be seen from FIG. 3, the products prepared by the methods other than the present invention are micron-sized Bi spheres, and Bi is contained in the micron-sized Bi spheres2O3The micron-sized nearly spherical structure formed by the nanosheets is extremely irregular in appearance, large and small spherical structures are very uneven, and no obvious interface connection or 3D structure is formed, so that the actual application effect of the material is not facilitated, and the details are shown in comparative example 2 and comparative example 3.
Example 2
The preparation process of the composite product is the same as that of example 1, and this example is mainly used to illustrate the application effect of photocatalytic degradation of organic dye MB, one of the dual functions of the prepared composite product.
Dispersing 10mg of the composite product into 100ml of 10mg/L MB solution, and stirring for 30min in the dark to achieve adsorption balance; and then placing the sample on a xenon lamp device (a 420nm filter, 20A current), simulating the degradation process of MB under visible light under the condition of continuous stirring, sampling at a fixed time interval, detecting the MB content in the solution after centrifugal separation, and calculating the degradation efficiency corresponding to the product under a certain time. The final degradation effect is shown in fig. 5, and it can be seen that the composite product has a good degradation effect on MB, reaching 95% at 210 min.
Comparative example 2
The preparation process of the product is the same as that of comparative example 1, which is mainly used for illustrating the photocatalytic function of the product prepared by the method other than the method of the present invention, namely the application effect of photocatalytic degradation of organic dye MB.
Dispersing 10mg of the product in 100ml of 10mg/L MB solution, and stirring for 30min in the dark to achieve adsorption balance; and then placing the sample on a xenon lamp device (a 420nm filter, 20A current), simulating the degradation process of MB under visible light under the condition of continuous stirring, sampling at a fixed time interval, detecting the MB content in the solution after centrifugal separation, and calculating the degradation efficiency corresponding to the product under a certain time. The final degradation effect is shown in fig. 6, and it can be seen that the degradation rate of the prepared product is only 52% at 210min, and the degradation effect is general. Compared with the results of example 2, the application effect of the material prepared by the invention is obviously better.
Example 3
The preparation process of the composite product is the same as that of example 1, which is mainly used for illustrating the application effect of SERS (two-function enhanced Raman scattering) detection of the organic dye MB of the prepared composite product.
Respectively taking appropriate amount of composite product, and uniformly dispersing in the concentration range of 10-3M-10-8M in MB to form a mixed solution, and adding 20. mu.L of the mixed solution dropwise to 2 x 2cm2And (3) carrying out SERS detection immediately after drying on the substrate, and obtaining the enhancement condition of the material to the Raman signal peak of the pollutant under the excitation wave of 532 nm. The final signal peak is shown in FIG. 7, and it can be seen that the intensity of the characteristic peak gradually decreases as the solution concentration decreases, until 10-8M, 1622 and 1395cm-1The characteristic peak at (a) is still discernible,the material is shown to have excellent SERS application performance. Comparison of 10-2The signal peak of the M pure MB solution (figure 8a) and the enhancement coefficient (EF) of the SERS performance of the composite material are quantitatively calculated (figure 8b), and the obvious linear relation exists between the dye concentration and the peak intensity, which shows that the material has stable SERS application performance.
Comparative example 3
The preparation process of the product is the same as that of comparative example 1, and the comparative example is mainly used for illustrating the SERS function of the product prepared by the method outside the invention, namely the application effect of SERS for detecting the organic dye MB. Respectively taking appropriate amount of product, and uniformly dispersing in the concentration range of 10-3M and 10-5M in MB to form a mixed solution, and adding 20. mu.L of the mixed solution dropwise to 2 x 2cm2And (3) carrying out SERS detection immediately after drying on the substrate, and obtaining the enhancement condition of the material to the Raman signal peak of the pollutant under the excitation wave of 532 nm. The final signal peak is shown in FIG. 9, and it can be seen that the solution concentration is 10-3At M, the characteristic peak of a portion of MB is still discernible, but when the solution concentration is reduced to 10-5M, the MB characteristic peak is not distinguishable, which is in sharp contrast to the application effect in example 3, and shows that the SERS detection function of the material is obviously inferior to the effect of the material prepared by using the invention.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. A preparation method of a tungsten oxide composite material is characterized by comprising the following steps: mixing NaCl solution and sodium tungstate solution, adjusting pH, and performing hydrothermal reaction to obtain nanometer WO3A core material; then bismuth nitrate solution and the nano WO are mixed3Mixing the core materials, and carrying out solvothermal reaction.
2. The method for preparing a tungsten oxide composite material according to claim 1, comprising the steps of:
1) dropwise adding a NaCl solution into a sodium tungstate solution, stirring, and adding hydrochloric acid to adjust the pH value to obtain a mixed solution;
2) carrying out hydrothermal reaction on the mixed solution obtained in the step 1), cooling, washing, centrifuging and drying to obtain the nano WO3A core material;
3) mixing the bismuth nitrate solution with the nano WO obtained in the step 2)3Mixing the core materials, carrying out solvent thermal reaction, cooling, washing, centrifuging and drying.
3. The preparation method of the tungsten oxide composite material according to claim 2, wherein in the step 1), the concentration of the NaCl solution is 4.5-5.5 mol/L; and/or the concentration of the sodium tungstate solution is 0.12-0.16 mmol/L; and/or the concentration of the hydrochloric acid is 2.4-2.6 mol/L, and the pH value is 1.8-2.5.
4. The preparation method of the tungsten oxide composite material according to claim 2 or 3, wherein in the step 2), the hydrothermal reaction is carried out at 160-280 ℃ for 6-24 h; and/or in the step 3), the solvothermal reaction is performed for 6-24 hours at 160-280 ℃.
5. The method for preparing the tungsten oxide composite material according to any one of claims 2 to 4, wherein in the step 3), the concentration of the bismuth nitrate solution is 0.01 to 0.5 mol/L.
6. The method for preparing a tungsten oxide composite material according to claim 5, further comprising in step 3): adding a dispersant to the bismuth nitrate solution.
7. The method of preparing a tungsten oxide composite material according to claim 6, wherein the dispersant comprises one or more of CTAB, EDTA, and SDS.
8. The method for preparing a tungsten oxide composite material according to any one of claims 2 to 4, wherein the nano WO is3The molar ratio of W in the core material to Bi in the bismuth nitrate solution is 0.72-71.8: 30-1500.
9. A tungsten oxide composite material, characterized in that it is prepared according to the process of any one of claims 1 to 8.
10. Use of the tungsten oxide composite material prepared by the method according to any one of claims 1 to 8, characterized in that it comprises one or more of the following applications:
a) the tungsten oxide composite material is applied to photocatalytic degradation of organic pollutants;
b) the tungsten oxide composite material is applied to SERS detection of organic pollutants.
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