CN112871209B - High-efficiency photocatalytic hydrogen production catalytic system and preparation method thereof - Google Patents

High-efficiency photocatalytic hydrogen production catalytic system and preparation method thereof Download PDF

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CN112871209B
CN112871209B CN202110187353.7A CN202110187353A CN112871209B CN 112871209 B CN112871209 B CN 112871209B CN 202110187353 A CN202110187353 A CN 202110187353A CN 112871209 B CN112871209 B CN 112871209B
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znwo
solution
cuo
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hydrogen production
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CN112871209A (en
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康诗钊
鲍晓洛
郑德温
李向清
秦利霞
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Shanghai Institute 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
    • B01J31/0214—Aryloxylates, e.g. phenolates
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042—Decomposition of water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1094—Promotors or activators
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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Abstract

The invention relates to a high-efficiency photocatalytic hydrogen production catalytic system and a preparation method thereof, wherein the catalyst comprises eosin Y photosensitizer dye serving as a photosensitizing agent and CuO nano particles loaded on the dyeZnWO of (C) 4 Nanoplatelets, said ZnWO 4 The nano-sheet is used as a carrier. The preparation method comprises the following steps: (1) Preparing zinc salt, water and hexadecyl trimethyl ammonium bromide into solution A, preparing tungsten salt and water into solution B, mixing the solution A and the solution B, performing hydrothermal reaction, and performing aftertreatment to obtain ZnWO 4 A nanosheet; (2) ZnWO is taken 4 Dispersing the nano-sheets in a solvent to obtain a dispersion liquid, adding copper salt, heating, adjusting pH for reaction, and performing post-treatment to obtain ZnWO loaded with CuO nano-particles 4 A nanosheet; (3) ZnWO loaded with CuO nano-particles is taken 4 Dispersing the nano-sheets in water to form a dispersion system, adding the eosin Y photosensitizer dye, stirring in a dark place, and performing aftertreatment to obtain the catalyst. Compared with the prior art, the catalyst has good stability and high hydrogen production activity when the light intensity is changed, and has weak sensitivity to the light intensity.

Description

High-efficiency photocatalytic hydrogen production catalytic system and preparation method thereof
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a high-efficiency photocatalytic hydrogen production catalytic system and a preparation method thereof.
Background
Solar catalytic hydrogen production is considered as an effective way to solve environmental and energy crisis problems. So far, research on semiconductor photocatalysts has been intensive, and many photocatalysts which are efficient, environment-friendly and economical have been obtained. It is known that the intensity of sunlight is very unstable due to factors such as time and weather, and the intensity of sunlight varies greatly and changes rapidly throughout the day or the four seasons. Therefore, in order to apply the photocatalytic hydrogen production technology on a large scale, it is required that the hydrogen production be efficiently and stably performed under the condition of light irradiation of variable intensity, and it is required that the catalyst used not only has high catalytic activity, but also the light energy utilization efficiency cannot be changed with the change of the incident light intensity. However, most of the currently reported semiconductor-based photocatalytic hydrogen production systems do not meet the above requirements. Therefore, it is very important to develop a high-efficiency photocatalytic hydrogen production catalyst whose light energy utilization efficiency does not vary with the intensity of incident light.
Dye sensitization is one of the effective means to increase the optoelectronic yield of the photocatalyst. Under the irradiation of light, the photosensitizing agent absorbs sunlight to generate excited electrons. These photo-generated excited electrons are injected into the conduction band of the semiconductor host catalyst, causing an increase in the concentration of electrons within the semiconductor, an increase in the fermi level, and thus a decrease in the interfacial electron transfer barrier. Thus, there is a possibility that a significant electron tunneling effect exists in the dye-sensitized system. If the above assumption holds, the photocatalytic reaction will be a quasi-first order reaction for the incident photons. Meanwhile, the light energy utilization efficiency of the photocatalyst will not vary with the variation of the intensity of incident light. In addition, the molar absorptivity of dye sensitizers is generally relatively high, and dye sensitizers can still exhibit good photoelectron yields even under light irradiation with low light intensities. This is very advantageous for constructing a photocatalyst capable of efficiently stabilizing photocatalytic hydrogen production activity at low light intensity.
Patent CN102600901a discloses a preparation method of a catalyst for hydrogen production by photo-reduction of water, which comprises the steps of preparing a carbon nanotube-metal salt precursor, loading CuO on the carbon nanotube, and soaking the carbon nanotube-CuO and a sensitizer together to obtain the sensitizer-carbon nanotube-CuO, and is characterized in that: the CuO is carried on the carbon nano tube by a mechanical grinding mode. The present invention uses a grinding method to react copper salt with NaOH and then activate at low temperature, thereby loading CuO on carbon nanotubes. In this patent, the carbon nanotubes only act as electron transfer channels and have no light catalytic effect, so that the operating wavelength of the above-mentioned patent light is only visible light. In the present invention, znWO 4 Acting as a primary catalyst, which itself has photocatalytic activity in the ultraviolet region. Thus, the operating wavelength range of the light of the present invention is the ultraviolet-visible region. The most important point is that the light utilization rate of the invention does not change with the change of the light intensity. The light with lower intensity can also show good catalytic performance under the irradiation of light, and the performance is not examined in the comparison patent.
Disclosure of Invention
The invention aims to provide a high-efficiency photocatalytic hydrogen production catalytic system and a preparation method thereof.
The aim of the invention is achieved by the following technical scheme:
a high-efficiency photocatalytic hydrogen production catalytic system comprises eosin Y photosensitizer dye as a photosensitizing agent, cuO nano particles as a cocatalyst and ZnWO as a main catalyst 4 Nanosheets, the eosin Y photosensitizer dye and CuO nanoparticles are both supported in ZnWO 4 A nano-sheet. Wherein, the eosin Y photosensitizer dye enhances the light absorption capacity of the whole catalytic system, and ensures that the light utilization rate of the catalyst is not affected by light intensity, znWO 4 As a main catalyst, cuO is used as a cocatalyst, so that the catalytic performance of the whole catalytic system is improved. The high-efficiency photocatalytic hydrogen production catalytic system is named as ZnWO 4 -CuO-Eosin Y, eosin Y representing an Eosin Y photosensitizer dye.
In the photocatalysis system, the mass percentage of the eosin Y photosensitizer dye is 50 to 88.9 percent, and ZnWO 4 11.03-49.7% by mass and 0.07-5.55% by mass of CuO.
The preparation method of the high-efficiency photocatalytic hydrogen production catalytic system specifically comprises the following steps:
(1) Preparing zinc salt, water and hexadecyl trimethyl ammonium bromide into solution A, preparing tungsten salt and water into solution B, dripping the solution B into the solution A, performing hydrothermal reaction, and performing aftertreatment after the reaction is finished to obtain ZnWO 4 The nano-sheet, cetyl trimethyl ammonium bromide plays a role of a morphology modifier, and zinc tungstate nano-sheets can be prepared by using the nano-sheet;
(2) Taking ZnWO obtained in the step (1) 4 Dispersing the nano-sheets in a solvent to obtain a dispersion liquid, adding copper salt into the dispersion liquid, heating, adjusting pH to react, and performing post-treatment to obtain ZnWO loaded with CuO nano-particles 4 A nanosheet;
(3) Taking the ZnWO loaded with the CuO nano particles obtained in the step (2) 4 Dispersing the nano-sheets in water to form a dispersion system, adding the eosin Y photosensitizer dye, stirring in a dark place, and performing aftertreatment to obtain the catalytic system.
In the step (1), the zinc salt is zinc nitrate hexahydrate, and the tungsten salt is sodium tungstate;
in the solution A, the concentration of zinc salt is 0.1 to 0.6mol L -1 The concentration of the hexadecyl trimethyl ammonium bromide is 0.01 to 0.1mol L -1 In the solution B, the concentration of tungsten salt is 0.2-1.5 mol L -1 。
In the step (1), the solution B is dropwise added to the solution A and then stirred for 1.5 to 2.5 hours, preferably 2 hours, so as to obtain a mixture, and the obtained mixture is transferred into a hydrothermal kettle, is heated to 160 to 200 ℃ in a sealing manner, preferably 180 ℃, and is kept for 18 to 22 hours, preferably 20 hours. The activity of the catalytic system increases with the increase of factors such as temperature, time, pH and the like, and then decreases, so the invention limits the reaction parameters.
In the step (1), the post-treatment specifically includes: and (3) sequentially centrifuging and filtering the reaction system after the hydrothermal reaction is finished, washing the collected precipitate with water, and drying at 60-100 ℃, preferably 80 ℃ for 22-26 hours, preferably 24 hours.
In step (2), the copper salt is copper nitrate trihydrate.
In step (2), znWO 4 The mass ratio of the nano-sheet to the copper salt is 500: (9.5 to 190).
In the step (2), the heating temperature is 20-90 ℃, hydrochloric acid or ammonia water is added dropwise into the dispersion liquid to adjust the pH to 3-11, the reaction is carried out for 1-10 h while maintaining the temperature, and the reaction is carried out while stirring. The pH can influence the dispersibility and the particle size of the copper oxide on the surface of the zinc tungstate, and the adjustment of the pH can lead the copper oxide to be dispersed more uniformly and the particle size to be more suitable.
In the step (2), the post-treatment specifically includes: cooling the reaction system after the reaction is finished to room temperature, centrifuging and filtering in sequence, washing the collected precipitate with water, drying at 60-100 ℃, preferably 80 ℃ for 4-8 hours, preferably 6 hours to obtain solid powder, and calcining the obtained solid powder at 100-700 ℃ for 0.5-4 hours in an air atmosphere.
In step (2), znWO loaded with CuO nanoparticles 4 CuO and ZnWO in nanoplatelets 4 The mass ratio of (1) is (0.6-11.1): (88.9-99.4).
In the step (3), znWO loaded with CuO nano-particles in the dispersion system 4 The concentration of the nano-sheet is 0.2mg mL -1 The concentration of the dye of the eosin Y photosensitizer is 0.2-1.6 mg mL -1 。
In the step (3), the post-treatment specifically includes: the solvent is removed by distillation under reduced pressure from the system after the light-shielding treatment, and the collected solid powder is dried under vacuum for 3 to 5 hours, preferably 4 hours, at 30 to 50 ℃, preferably 40 ℃.
In step (3), znWO loaded with CuO nanoparticles 4 The addition amount of the nanoplatelets and the eosin Y photosensitizer is 10: (10-80).
The invention uses eosin and ZnWO 4 The nano-sheet and CuO nano-particle are used as structural units to construct a novel composite photocatalysis system. The photocatalytic system has good stability and high hydrogen production activity when the light intensity changes, and has weak sensitivity to the light intensity, namely the light energy utilization efficiency does not change along with the change of the incident light intensity, and the light intensity is low (about 10mW cm) -2 ) Under the irradiation of light rays, the catalytic system can still show good photocatalytic performance, still has good hydrogen production performance, has great application potential in the aspect of solar hydrogen production, and provides a solution for efficiently and stably producing hydrogen by photocatalysis under the conditions of sunlight change and unstable light intensity. In addition, the photocatalysis hydrogen production catalysis system has the advantages of economy, no toxicity, easy preparation and the like, and is simple and convenient to prepare.
Drawings
FIG. 1 shows ZnWO prepared in comparative example 1 under irradiation with light of different intensities 4 -a graph of photocatalytic hydrogen production activity of CuO;
FIG. 2 shows ZnWO prepared in example 6 under irradiation with light of different intensities 4 -a graph of the photocatalytic hydrogen production activity of CuO-Eosin Y;
FIG. 3 shows ZnWO prepared in example 6 4 Nanoplatelets and ZnWO prepared in example 6 4 XRD pattern of 5.9% Cu (wherein a represents ZnWO) 4 Nanoplatelets, b represents ZnWO 4 /5.9％Cu)；
FIG. 4 shows ZnWO prepared in example 6 4 TEM photographs of the nanoplatelets;
FIG. 5 shows ZnWO prepared in example 6 4 TEM photograph of 5.9% Cu.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
A high-efficiency photocatalytic hydrogen production catalytic system comprises eosin Y photosensitizer dye as a photosensitizing agent, cuO nano particles as a cocatalyst and ZnWO as a main catalyst 4 The nanosheets, the eosin Y photosensitizer dye and the CuO nanoparticles are loaded on ZnWO 4 On the nanoplatelets. In the photocatalysis system, the mass percentage of the dye of the eosin Y photosensitizer is 50 to 88.9 percent, and ZnWO 4 11.03-49.7% by mass and 0.07-5.55% by mass of CuO.
The preparation method of the high-efficiency photocatalytic hydrogen production catalytic system specifically comprises the following steps:
(1) Preparing zinc salt, water and cetyl trimethyl ammonium bromide into solution A, preparing tungsten salt and water into solution B, dripping the solution B into the solution A, stirring for 1.5-2.5 h to obtain a mixture, transferring the obtained mixture into a hydrothermal kettle, sealing and heating to 160-200 ℃, preserving heat for 18-22 h, and performing post treatment after the reaction is finished to obtain ZnWO 4 The nano sheet is subjected to aftertreatment specifically as follows: sequentially centrifuging and filtering a reaction system after the hydrothermal reaction is finished, washing the collected precipitate with water, and drying at 60-100 ℃ for 22-26 hours, wherein zinc salt is zinc nitrate hexahydrate and tungsten salt is sodium tungstate; in the solution A, the concentration of zinc salt is 0.1 to 0.6mol L -1 The concentration of the hexadecyl trimethyl ammonium bromide is 0.01 to 0.1mol L -1 In the solution B, the concentration of tungsten salt is 0.2-1.5 mol L -1 ；
(2) Taking ZnWO obtained in the step (1) 4 Dispersing the nano-sheets in a solvent to obtain a dispersion liquid, adding copper salt into the dispersion liquid, heating the dispersion liquid at a temperature of between 20 and 90 ℃, dropwise adding hydrochloric acid or ammonia water into the dispersion liquid to adjust the pH to between 3 and 11, carrying out heat preservation reaction for 1 to 10 hours, stirring the reaction product while carrying out reaction, and carrying out post-treatment to obtain ZnWO loaded with CuO nano-particles 4 Nanosheets, post treatment detailsThe method comprises the following steps: cooling the reaction system after the reaction is finished to room temperature, sequentially centrifuging and filtering, washing the collected precipitate with water, drying at 60-100 ℃ for 4-8 hours to obtain solid powder, and finally calcining the obtained solid powder at 100-700 ℃ for 0.5-4 hours in an air atmosphere to obtain ZnWO loaded with CuO nano particles 4 CuO and ZnWO in nanoplatelets 4 The mass ratio of (1) is (0.6-11.1): (88.9-99.4), wherein ZnWO 4 The mass ratio of the nano-sheet to the copper salt is 500: (9.5 to 190);
(3) Taking the ZnWO loaded with the CuO nano particles obtained in the step (2) 4 Dispersing the nano-sheets in water to form a dispersion system, adding the eosin Y photosensitizer dye, and stirring in a dark place, wherein in the dispersion system, znWO loaded with CuO nano-particles 4 The concentration of the nano-sheet is 0.2mg mL -1 The concentration of the dye of the eosin Y photosensitizer is 0.2-1.6 mg mL -1 ZnWO loaded with CuO nanoparticles 4 The addition amount of the nanoplatelets and the eosin Y photosensitizer is 10: (10-80), and then carrying out post-treatment to obtain a catalytic system, wherein the post-treatment specifically comprises: and (3) distilling the system subjected to light shielding under reduced pressure to remove the solvent, and then vacuum drying the collected solid powder for 3-5 h at 30-50 ℃.
The chemical substances such as eosin Y photosensitizer dye, zinc nitrate hexahydrate, cetyltrimethylammonium bromide, sodium tungstate and the like adopted in the invention are all commercial reagents.
Example 1
A high-efficiency photocatalytic hydrogen production catalytic system comprises eosin Y photosensitizer dye as a photosensitizing agent, cuO nano particles as a cocatalyst and ZnWO as a main catalyst 4 The nanosheets, the eosin Y photosensitizer dye and the CuO nanoparticles are loaded on ZnWO 4 On the nanoplatelets. The catalyst system is prepared by the following steps:
(1) 0.59g of zinc nitrate hexahydrate was weighed and transferred to a beaker, then 20mL of deionized water was added thereto, and the mixture was stirred and dissolved to prepare a solution having a concentration of 0.1mol L -1 Zinc nitrate solution of (a).
(2) Slowly adding 0.072g hexadecyl trimethyl ammonium bromide into the zinc nitrate solution, and stirring thoroughly until ten timesThe hexaalkyltrimethylammonium bromide was completely dissolved, and the solution was designated as solution A (in solution A, the concentration of zinc nitrate was 0.1mol L -1 The concentration of hexadecyl trimethyl ammonium bromide is 0.01mol L -1 )。
(3) 0.66g of sodium tungstate was weighed and transferred to a beaker, and 10mL of deionized water was added to make a concentration of 0.2mol L -1 The sodium tungstate solution is denoted as solution B.
(4) Solution B was slowly added dropwise to solution a with stirring. After stirring for 2 hours, the resulting mixture was transferred to a hydrothermal kettle, heated to 180 ℃ with sealing, and incubated for 20 hours.
(5) After the reaction is finished, collecting the precipitate by utilizing a centrifugal technology and filtering, namely a product obtained by the reaction, washing the product obtained by the reaction with deionized water, and drying at 80 ℃ for 24 hours to obtain solid powder which is ZnWO 4 A nano-sheet.
(6) Weighing 500mg of prepared ZnWO 4 The nanoplates were transferred to a beaker, 30mL of deionized water was added and stirred to make a uniform dispersion.
(7) To the above dispersion was added 9.5mg of copper nitrate trihydrate and heated to 20℃and then hydrochloric acid was added dropwise to adjust the pH of the solution to 3, followed by stirring at a constant temperature for 1 hour.
(8) After the reaction solution was cooled to room temperature, the precipitate was collected by centrifugation. The resulting precipitate was washed clean with deionized water and dried at 80℃for 6h. Calcining the obtained solid powder in air at 100deg.C for 0.5 hr to obtain ZnWO loaded with CuO nanoparticles 4 Nanoplatelets (in the product, the mass percentage of CuO is 0.6%, znWO) 4 99.4% by mass).
(9) 10mg of ZnWO loaded with CuO nano particles is taken 4 The nanoplatelets were uniformly dispersed in 50mL deionized water at room temperature by stirring, and 10mg of eosin Y photosensitizer was added to the above dispersion (the concentration of eosin Y photosensitizer in the dispersion was 0.2mg mL -1 ) After that, stirring was carried out for 1 hour under a dark condition, and the solvent was distilled off under reduced pressure. The solid powder obtained was dried in vacuo at 40℃for 4 hours to give the target catalytic system (the quality of eosin in the catalytic systemThe percentage is 50 percent, znWO 4 The mass percent is 49.7 percent, the mass percent of CuO is 0.3 percent, and the content of each component is shown in the table 1.
Putting 20mg of the obtained catalytic system and 60mL of triethanolamine solution with volume fraction of 8vol% (triethanolamine is taken as a sacrificial agent) into a photocatalytic hydrogen production evaluation device, and introducing N under stirring in dark place 2 For 30min to drive off O in the triethanolamine solution 2 . Then, the light source is turned on at room temperature to start hydrogen production. The light source is 500W mercury lamp with light intensity of 100mW cm -2 . After 4 hours of illumination, the hydrogen production produced was checked using gas chromatography. Finally, the photocatalytic hydrogen production performance of the catalyst system under ultraviolet-visible light is 0.95mmol g -1 h -1 Details are shown in Table 1.
Example 2
A high-efficiency photocatalytic hydrogen production catalytic system comprises eosin Y photosensitizer dye as a photosensitizing agent, cuO nano particles as a cocatalyst and ZnWO as a main catalyst 4 The nanosheets, the eosin Y photosensitizer dye and the CuO nanoparticles are loaded on ZnWO 4 On the nanoplatelets. The catalyst system is prepared by the following steps:
(1) 3.57g of zinc nitrate hexahydrate was weighed and transferred to a beaker, then 20mL of deionized water was added thereto, and the mixture was dissolved with stirring to give a concentration of 0.6mol L -1 Zinc nitrate solution of (a).
(2) After slowly adding 0.728g of cetyltrimethylammonium bromide to the above zinc nitrate, stirring was carried out sufficiently until cetyltrimethylammonium bromide was completely dissolved, and the solution was designated as solution A (in solution A, the concentration of zinc nitrate was 0.6mol L -1 The concentration of cetyltrimethylammonium bromide was 0.1mol L -1 )。
(3) 3.96g of sodium tungstate was weighed and transferred to a beaker, and 10mL of deionized water was added to prepare a sodium tungstate solution (1.2 mol L) -1 ) This solution was designated as solution B.
(4) Solution B was slowly added dropwise to solution a with stirring. After stirring for 2 hours, the resulting mixture was transferred to a hydrothermal kettle, heated to 180 ℃ with sealing, and incubated for 20 hours.
(5) By centrifugationThe resulting product was collected by techniques. The resulting product was washed clean with deionized water and dried at 80℃for 24h. The obtained solid powder is ZnWO 4 A nano-sheet.
(6) Weighing 500mg of prepared ZnWO 4 The nanoplates were transferred to a beaker. 30mL of deionized water was added and stirred to obtain a uniform dispersion.
(7) To the above dispersion was added 190mg of copper nitrate trihydrate and heated to 90 ℃, and then aqueous ammonia was added dropwise to adjust the pH of the solution to 11. Then the mixture was stirred for 10 hours with heat preservation.
(8) After the reaction solution was cooled to room temperature, the precipitate was collected by centrifugation. The resulting precipitate was washed clean with deionized water and dried at 80℃for 6h. The solid powder obtained was calcined at 700 ℃ for 4 hours in an air atmosphere. The obtained product is ZnWO loaded with CuO nano-particles 4 Nanosheets (mass percent of CuO is 11.1%, znWO) 4 88.9% by mass).
(9) 10mg of ZnWO loaded with CuO nano particles is taken 4 The nanoplatelets were uniformly dispersed in 50mL deionized water at room temperature by stirring. 80mg of eosin Y photosensitizer (1.6 mg mL) was added to the dispersion -1 ) After that, stirring was carried out for 1 hour under a dark condition, and the solvent was distilled off under reduced pressure. The solid powder obtained was dried in vacuo at 40℃for 4 hours to give the target catalytic system (eosin 88.9% by mass, znWO) 4 9.9 mass percent and 1.2 mass percent of CuO).
Putting 90mg of the obtained catalytic system and 60mL of triethanolamine solution with volume fraction of 8vol% (triethanolamine is taken as a sacrificial agent) into a photocatalytic hydrogen production evaluation device, and introducing N under stirring in dark place 2 For 30min to drive off O in the triethanolamine solution 2 . Then, the light source is turned on at room temperature to start hydrogen production. The light source is 500W mercury lamp with illumination intensity of 100mW cm -2 . After 4 hours of irradiation, the photocatalytic hydrogen production performance of the catalyst system under ultraviolet-visible light is finally obtained to be 1.32mmol g -1 h -1 Details are shown in Table 1.
Example 3
A high-efficiency photocatalytic hydrogen production catalytic system comprises eosin as a photosensitizing agentY photosensitizer dye, cuO nanoparticles as cocatalyst and ZnWO as procatalyst 4 The nanosheets, the eosin Y photosensitizer dye and the CuO nanoparticles are loaded on ZnWO 4 On the nanoplatelets. The catalyst system is prepared by the following steps:
(1) 2.98g of zinc nitrate hexahydrate was weighed and transferred to a beaker, then 20mL of deionized water was added thereto, and the mixture was dissolved with stirring to give a concentration of 0.5mol L -1 Zinc nitrate solution of (a).
(2) After slowly adding 0.36g of cetyltrimethylammonium bromide to the zinc nitrate, the mixture was stirred well until it was completely dissolved. The solution was designated as A solution (zinc nitrate concentration 0.5mol L) -1 The concentration of hexadecyl trimethyl ammonium bromide is 0.05mol L -1 )。
(3) 3.3g of sodium tungstate was weighed and transferred to a beaker, and 10mL of deionized water was added to make a concentration of 1.0mol L -1 The sodium tungstate solution is denoted as solution B.
(4) Solution B was slowly added dropwise to solution a with stirring. After stirring for 2 hours, the resulting mixture was transferred to a hydrothermal kettle, heated to 180 ℃ with sealing, and incubated for 20 hours.
(5) The resulting product was collected using centrifugation techniques. The resulting product was washed clean with deionized water and dried at 80℃for 24h. The obtained solid powder is ZnWO 4 A nano-sheet.
(6) Weighing 500mg of prepared ZnWO 4 The nanoplates were transferred to a beaker. 30mL of deionized water was added and stirred to obtain a uniform dispersion.
(7) To the above dispersion was added 9.5mg of copper nitrate trihydrate and heated to 75 ℃, and then hydrochloric acid was added dropwise to adjust the pH of the solution to 5. Then the mixture was stirred for 2 hours with heat preservation.
(8) After the reaction solution was cooled to room temperature, the precipitate was collected by centrifugation. The resulting precipitate was washed clean with deionized water and dried at 80℃for 6h. The solid powder obtained was calcined at 200℃for 1 hour in an air atmosphere. The obtained product is ZnWO loaded with CuO nano-particles 4 Nanosheets (CuO 0.6% by mass, znWO) 4 99.4% by mass).
(9) 10mg of ZnWO loaded with CuO nano particles is taken 4 The nanoplatelets were uniformly dispersed in 50mL deionized water at room temperature by stirring. 80mg of eosin Y photosensitizer (1.6 mg mL) was added to the dispersion -1 ) After that, stirring was carried out for 1 hour under a dark condition, and the solvent was distilled off under reduced pressure. The solid powder obtained was dried in vacuo at 40℃for 4 hours to give the target catalytic system (eosin 88.9% by mass, znWO) 4 11.03 mass percent and 0.07 mass percent of CuO).
Putting 90mg of the obtained catalytic system and 60mL of triethanolamine solution with volume fraction of 8vol% (triethanolamine is taken as a sacrificial agent) into a photocatalytic hydrogen production evaluation device, and introducing N under stirring in dark place 2 For 30min to drive off O in the triethanolamine solution 2 . Then, the light source is turned on at room temperature to start hydrogen production. The light source is 500W mercury lamp with illumination intensity of 100mW cm -2 . After 4 hours of irradiation, the photocatalytic hydrogen production performance of the catalyst system under ultraviolet-visible light is finally obtained to be 1.43mmol g -1 h -1 Details are shown in Table 1.
Example 4
A high-efficiency photocatalytic hydrogen production catalytic system comprises eosin Y photosensitizer dye as a photosensitizing agent, cuO nano particles as a cocatalyst and ZnWO as a main catalyst 4 The nanosheets, the eosin Y photosensitizer dye and the CuO nanoparticles are loaded on ZnWO 4 On the nanoplatelets. The catalyst system is prepared by the following steps:
(1) 2.98g of zinc nitrate hexahydrate was weighed and transferred to a beaker, then 20mL of deionized water was added thereto, and 0.5mol L was prepared by stirring and dissolving -1 Zinc nitrate solution of (a).
(2) After slowly adding 0.36g of cetyltrimethylammonium bromide to the zinc nitrate, the mixture was stirred well until it was completely dissolved. The solution was designated as A solution (zinc nitrate 0.5mol L) -1 Cetyl trimethylammonium bromide 0.05mol L -1 )。
(3) 3.3g of sodium tungstate was weighed and transferred to a beaker, and 10mL of deionized water was added to prepare a sodium tungstate solution (1.0 mol L) -1 ). This solution was designated as solution B.
(4) Solution B was slowly added dropwise to solution a with stirring. After stirring for 2 hours, the resulting mixture was transferred to a hydrothermal kettle, heated to 180 ℃ with sealing, and incubated for 20 hours.
(5) The resulting product was collected using centrifugation techniques. The resulting product was washed clean with deionized water and dried at 80℃for 24h. The obtained solid powder is ZnWO 4 A nano-sheet.
(6) Weighing 500mg of prepared ZnWO 4 The nanoplates were transferred to a beaker. 30mL of deionized water was added and stirred to obtain a uniform dispersion.
(7) To the above dispersion was added 190mg of copper nitrate trihydrate and heated to 75 ℃, and then aqueous ammonia was added dropwise to adjust the pH of the solution to 10. Then the mixture was stirred for 2 hours with heat preservation.
(8) After the reaction solution was cooled to room temperature, the precipitate was collected by centrifugation. The resulting precipitate was washed clean with deionized water and dried at 80℃for 6h. The solid powder obtained was calcined at 400℃for 2 hours in an air atmosphere. The obtained product is ZnWO loaded with CuO nano-particles 4 Nanosheets (mass percent of CuO is 11.1%, znWO) 4 88.9% by mass).
(9) 10mg of ZnWO loaded with CuO nano particles is taken 4 The nanoplatelets were uniformly dispersed in 50mL deionized water at room temperature by stirring. 10mg of eosin Y photosensitizer (0.2 mg mL) was added to the dispersion -1 ) After that, stirring was carried out for 1 hour under a dark condition, and the solvent was distilled off under reduced pressure. The obtained solid powder was dried under vacuum at 40℃for 4 hours to obtain the target catalytic system (eosin 50% by mass, znWO) 4 44.45 mass percent and 5.55 mass percent of CuO).
Putting 20mg of the obtained catalytic system and 60mL of triethanolamine solution with volume fraction of 8vol% (triethanolamine is taken as a sacrificial agent) into a photocatalytic hydrogen production evaluation device, and introducing N under stirring in dark place 2 For 30min to drive off O in the triethanolamine solution 2 . Then, the light source is turned on at room temperature to start hydrogen production. The light source is 500W mercury lamp with illumination intensity of 100mW cm -2 . After irradiation for 4 hours, finally obtaining the photocatalysis of the catalytic system under ultraviolet-visible lightHydrogen production performance of 1.83mmol g -1 h -1 Details are shown in Table 1.
Example 5
A high-efficiency photocatalytic hydrogen production catalytic system comprises eosin Y photosensitizer dye as a photosensitizing agent, cuO nano particles as a cocatalyst and ZnWO as a main catalyst 4 The nanosheets, the eosin Y photosensitizer dye and the CuO nanoparticles are loaded on ZnWO 4 On the nanoplatelets. The catalyst system is prepared by the following steps:
(1) 2.98g of zinc nitrate hexahydrate was weighed and transferred to a beaker, then 20mL of deionized water was added thereto, and 0.5mol L was prepared by stirring and dissolving -1 Zinc nitrate solution of (a).
(2) After slowly adding 0.36g of cetyltrimethylammonium bromide to the zinc nitrate, the mixture was stirred well until it was completely dissolved. The solution was designated as A solution (zinc nitrate 0.5mol L) -1 Cetyl trimethylammonium bromide 0.05mol L -1 )。
(3) 3.3g of sodium tungstate was weighed and transferred to a beaker, and 10mL of deionized water was added to prepare a sodium tungstate solution (1.0 mol L) -1 ). This solution was designated as solution B.
(4) Solution B was slowly added dropwise to solution a with stirring. After stirring for 2 hours, the resulting mixture was transferred to a hydrothermal kettle, heated to 180 ℃ with sealing, and incubated for 20 hours.
(5) The resulting product was collected using centrifugation techniques. The resulting product was washed clean with deionized water and dried at 80℃for 24h. The obtained solid powder is ZnWO 4 A nano-sheet.
(6) Weighing 500mg of prepared ZnWO 4 The nanoplates were transferred to a beaker. 30mL of deionized water was added and stirred to obtain a uniform dispersion.
(7) To the above dispersion was added 95mg of copper nitrate trihydrate and heated to 75 ℃, and then aqueous ammonia was added dropwise to adjust the pH of the solution to 10. Then the mixture was stirred for 2 hours with heat preservation.
(8) After the reaction solution was cooled to room temperature, the precipitate was collected by centrifugation. The resulting precipitate was washed clean with deionized water and dried at 80℃for 6h. Calcining the obtained solid powder at 200deg.C in air atmosphereFiring for 1 hour. The obtained product is ZnWO loaded with CuO nano-particles 4 Nanosheets (5.9% by mass of CuO, znWO) 4 94.1% by mass).
(9) 10mg of ZnWO loaded with CuO nano particles is taken 4 The nanoplatelets were uniformly dispersed in 50mL deionized water at room temperature by stirring. To the dispersion was added 20mg of eosin Y photosensitizer (0.4 mg mL) -1 ) After that, stirring was carried out for 1 hour under a dark condition, and the solvent was distilled off under reduced pressure. The obtained solid powder was dried under vacuum at 40℃for 4 hours to obtain the target catalytic system (66.66% by mass of eosin, znWO) 4 31.37 mass percent and 1.97 mass percent of CuO).
Putting 30mg of the obtained catalytic system and 60mL of triethanolamine solution with volume fraction of 8vol% (triethanolamine is taken as a sacrificial agent) into a photocatalytic hydrogen production evaluation device, and introducing N under stirring in dark place 2 For 30min to drive off O in the catalytic system and the triethanolamine solution 2 . Then, the light source is turned on at room temperature to start hydrogen production. The light source is 500W mercury lamp with illumination intensity of 100mW cm -2 . After 4 hours of irradiation, the photocatalytic hydrogen production performance of the catalytic system under ultraviolet-visible light is finally obtained to be 2.07mmol g -1 h -1 Details are shown in Table 1.
Example 6
A high-efficiency photocatalytic hydrogen production catalytic system comprises eosin Y photosensitizer dye as a photosensitizing agent, cuO nano particles as a cocatalyst and ZnWO as a main catalyst 4 The nanosheets, the eosin Y photosensitizer dye and the CuO nanoparticles are loaded on ZnWO 4 On the nanoplatelets. The catalyst system is prepared by the following steps:
(1) 2.98g of zinc nitrate hexahydrate was weighed and transferred to a beaker, then 20mL of deionized water was added thereto, and 0.5mol L was prepared by stirring and dissolving -1 Zinc nitrate solution of (a).
(2) After slowly adding 0.36g of cetyltrimethylammonium bromide to the zinc nitrate, the mixture was stirred well until it was completely dissolved. The solution was designated as A solution (zinc nitrate 0.5mol L) -1 Cetyl trimethylammonium bromide 0.05mol L -1 )。
(3) 3.3g of sodium tungstate was weighed and transferred to a beaker, and 10mL of deionized water was added to prepare a sodium tungstate solution (1.0 mol L) -1 ). This solution was designated as solution B.
(4) Solution B was slowly added dropwise to solution a with stirring. After stirring for 2 hours, the resulting mixture was transferred to a hydrothermal kettle, heated to 180 ℃ with sealing, and incubated for 20 hours.
(5) The resulting product was collected using centrifugation techniques. The resulting product was washed clean with deionized water and dried at 80℃for 24h. The obtained solid powder is ZnWO 4 The XRD pattern of the nanoplatelets is shown in FIG. 3, and all diffraction peaks in the pattern can be seen to be compared with that of monoclinic ZnWO 4 Standard XRD card (jcpdsno. 89-0447) was identical. TEM pictures are shown in FIG. 4, and it can be seen that rectangular-like nanoplatelets are formed, which are about 40nm by 30nm in size.
(6) Weighing 500mg of prepared ZnWO 4 The nanoplates were transferred to a beaker. 30mL of deionized water was added and stirred to obtain a uniform dispersion.
(7) To the above dispersion was added 95mg of copper nitrate trihydrate and heated to 75 ℃, and then aqueous ammonia was added dropwise to adjust the pH of the solution to 10.7. Then the mixture was stirred for 2 hours with heat preservation.
(8) After the reaction solution was cooled to room temperature, the precipitate was collected by centrifugation. The resulting precipitate was washed clean with deionized water and dried at 80℃for 6h. The solid powder obtained was calcined at 200℃for 1 hour in an air atmosphere. The obtained product is ZnWO loaded with CuO nano-particles 4 Nanosheets (5.9% by mass of CuO, znWO) 4 94.1% by mass) and the XRD pattern is shown in fig. 3, it can be seen that the crystal structure of zinc tungstate is not changed. TEM pictures are shown in FIG. 5, and it can be seen that the morphology of zinc tungstate is not changed, and the surfaces of the nano-sheets become rough, which can be attributed to the introduction of CuO.
(9) 10mg of ZnWO loaded with CuO nano particles is taken 4 The nanoplatelets were uniformly dispersed in 50mL deionized water at room temperature by stirring. To the dispersion was added 40mg of eosin Y photosensitizer (0.8 mg mL) -1 ) After that, stirring was carried out for 1 hour under a dark condition, and the solvent was distilled off under reduced pressure. Obtained byThe solid powder was dried in vacuo at 40℃for 4 hours to give the target catalytic system (80% by mass of eosin, znWO) 4 18.82 percent by mass and 1.18 percent by mass of CuO, and ZnWO is adopted 4 5% CuO/Eosin Y, wherein 5% is expressed as CuO+ZnWO 4 At 100%, the mass percentage of CuO is 5% instead of 6% (approximate bit is taken).
Putting 50mg of the obtained catalytic system and 60mL of triethanolamine solution with volume fraction of 8vol% (triethanolamine is taken as a sacrificial agent) into a photocatalytic hydrogen production evaluation device, and introducing N under stirring in dark place 2 For 30min to drive off O in the catalytic system and the triethanolamine solution 2 . Then, the light source is turned on at room temperature to start hydrogen production. The light source is 500W mercury lamp with illumination intensity of 100mW cm -2 . After 4 hours of irradiation, finally the photocatalytic hydrogen production performance of the catalytic system under ultraviolet-visible light is 5.07mmol g -1 h -1 See table 1 and fig. 2 for details.
Further, the hydrogen production evaluation was continued in this evaluation apparatus, and only the illumination intensity was sequentially adjusted to 60mW cm -2 、30mW cm -2 And 10mW cm -2 The photocatalytic hydrogen production performance is shown in figure 2, and is 3.42mmol g respectively -1 h -1 、1.65mmol g -1 h -1 And 0.53mmol g -1 h -1 。
Table 1 photocatalytic hydrogen production Activity of samples of examples
Comparative example 1
ZnWO loaded with CuO nano particles 4 The nano-sheet is prepared by the following steps:
1. 2.98g of zinc nitrate hexahydrate was weighed and transferred to a beaker, then 20mL of deionized water was added thereto, and 0.5mol L was prepared by stirring and dissolving -1 Zinc nitrate solution of (a).
2. After slowly adding 0.36g of cetyltrimethylammonium bromide to the zinc nitrate, the mixture was stirred well until it was completely dissolved. This solution was designated as solution A (zinc nitrate 0.5mol L-1, cetyl trimethylammonium bromide 0.05mol L-1).
3. 3.3g of sodium tungstate was weighed and transferred to a beaker, and 10mL of deionized water was added to prepare a sodium tungstate solution (1.0 mol L-1). This solution was designated as solution B.
4. Solution B was slowly added dropwise to solution a with stirring. After stirring for 2 hours, the resulting mixture was transferred to a hydrothermal kettle, heated to 180 ℃ with sealing, and incubated for 20 hours.
5. The resulting product was collected using centrifugation techniques. The resulting product was washed clean with deionized water and dried at 80℃for 24h. The obtained solid powder is ZnWO 4 A nano-sheet.
6. Weighing 500mg of prepared ZnWO 4 The nanoplates were transferred to a beaker. 30mL of deionized water was added and stirred to obtain a uniform dispersion.
7. To the above dispersion was added 95mg of copper nitrate trihydrate and heated to 75 ℃, and then aqueous ammonia was added dropwise to adjust the pH of the solution to 10.7. Then the mixture was stirred for 2 hours with heat preservation.
8. After the reaction solution was cooled to room temperature, the precipitate was collected by centrifugation. The resulting precipitate was washed clean with deionized water and dried at 80℃for 6h. The solid powder obtained was calcined at 200℃for 1 hour in an air atmosphere. The obtained product is ZnWO loaded with CuO nano-particles 4 Nanosheets (5.9% by mass of CuO, znWO) 4 94.1% by mass of ZnWO 4 5% Cu, 5% of which is expressed as CuO+ZnWO 4 At 100%, the mass percentage of CuO is 5% (approximate bit is taken) and 5% is changed to 6%.
10mg of ZnWO loaded with CuO nano-particles was taken 4 Putting the nanosheets and 60mL of triethanolamine solution with volume fraction of 8vol% (triethanolamine is used as a sacrificial agent) into the same photocatalytic hydrogen production evaluation device as in examples 1-6, and adjusting the illumination intensity to be 100mW cm respectively -2 、60mW cm -2 、30mW cm -2 And 10mW cm -2 As shown in FIG. 1, the obtained photocatalytic hydrogen production performance was 0.13mmol g each -1 h -1 、0.069mmol g -1 h -1 、0.010mmol g -1 h -1 And 0.0030mmol g -1 h -1 。
Fig. 1 shows the photocatalytic hydrogen production activity of the sample of comparative example 1 under different illumination intensities, and fig. 2 shows the photocatalytic hydrogen production activity of the sample of example 6. As can be seen from fig. 2, the photocatalytic hydrogen production system according to the present invention has excellent photocatalytic hydrogen production performance in combination with the results shown in table 1 above. It can exhibit satisfactory photocatalytic hydrogen production activity even at low light intensities. Furthermore, it is of greater interest that under stronger illumination (100 mW cm -2 ) The light energy utilization rate (the calculation formula is hydrogen production amount divided by illumination intensity) of the catalytic system is 0.051mmol cm 2 g -1 h -1 mW -1 The method comprises the steps of carrying out a first treatment on the surface of the Under weaker light (10 mW cm) -2 ) The light energy utilization rate of the catalyst system is 0.053mmol cm 2 g -1 h -1 mW -1 The method comprises the steps of carrying out a first treatment on the surface of the At 60mW cm -2 The light energy utilization rate of the catalyst system is 0.057mmol cm under the illumination intensity 2 g -1 h -1 mW -1 The method comprises the steps of carrying out a first treatment on the surface of the At 30mW cm -2 The light energy utilization rate of the catalyst system is 0.055mmol cm under the illumination intensity 2 g -1 h -1 mW -1 . It can be seen that the light energy utilization of the catalytic system of the present invention does not substantially vary with the variation of the light intensity. As can be seen in FIG. 1, for ZnWO loaded with CuO nanoparticles 4 The light energy utilization rate of the nano-sheet is obviously reduced along with the weakening of the illumination intensity, which shows that the nano-sheet has stronger dependence on the illumination intensity. The photocatalysis system can produce hydrogen efficiently under the light irradiation of lower light intensity, and the light energy utilization rate is basically unchanged with the change of the light intensity, thus the photocatalysis system has great application potential in the field of solar hydrogen production.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.

Claims (1)

1. A high-efficiency photocatalytic hydrogen production catalytic system, which is used for catalyzing hydrogen production and has light energy utilization efficiency not influenced by light intensity, is characterized by comprising eosin Y photosensitizer dye as a photosensitizing agent, cuO nano particles as a cocatalyst and ZnWO as a main catalyst 4 Nanosheets, the eosin Y photosensitizer dye and CuO nanoparticles are both supported in ZnWO 4 On the nanosheets;
in the photocatalysis system, the mass percentage of the eosin Y photosensitizer dye is 50 to 88.9 percent, and ZnWO 4 11.03-49.7 percent by mass and 0.07-5.55 percent by mass of CuO;
wherein ZnWO 4 As a main catalyst, cuO is used as a cocatalyst, the light energy utilization efficiency of the high-efficiency photocatalytic hydrogen production catalytic system is not affected by light intensity, the photocatalytic system has good stability and high hydrogen production activity when the light intensity is changed, and the sensitivity to the light intensity is weaker, namely the light energy utilization efficiency is not changed along with the change of the incident light intensity;
the preparation method of the high-efficiency photocatalytic hydrogen production catalytic system comprises the following steps:
(1) Preparing zinc salt, water and hexadecyl trimethyl ammonium bromide into solution A, preparing tungsten salt and water into solution B, dripping the solution B into the solution A, performing hydrothermal reaction, and performing aftertreatment after the reaction is finished to obtain ZnWO 4 A nanosheet;
(2) Taking ZnWO obtained in the step (1) 4 Dispersing the nano-sheets in a solvent to obtain a dispersion liquid, adding copper salt into the dispersion liquid, heating, adjusting pH to react, and performing post-treatment to obtain ZnWO loaded with CuO nano-particles 4 A nanosheet;
(3) Taking the ZnWO loaded with the CuO nano particles obtained in the step (2) 4 Dispersing the nano-sheets in water to form a dispersion system, adding the eosin Y photosensitizer dye, stirring in a dark place,then post-treating to obtain the catalytic system;
wherein in the step (1), the zinc salt is zinc nitrate hexahydrate, and the tungsten salt is sodium tungstate;
in the solution A, the concentration of zinc salt is 0.1 to 0.6mol L -1 The concentration of the hexadecyl trimethyl ammonium bromide is 0.01 to 0.1mol L -1 In the solution B, the concentration of tungsten salt is 0.2-1.5 mol L -1 ；
In the step (1), the solution B is dropwise added into the solution A and then stirred for 1.5 to 2.5 hours to obtain a mixture, the obtained mixture is transferred into a hydrothermal kettle, and the mixture is heated to 160 to 200 ℃ in a sealing manner and is kept for 18 to 22 hours;
in the step (1), the post-treatment specifically includes: sequentially centrifuging and filtering the reaction system after the hydrothermal reaction is finished, washing the collected precipitate with water, and drying at 60-100 ℃ for 22-26 hours;
in the step (2), heating to 20-90 ℃, dropwise adding hydrochloric acid or ammonia water into the dispersion liquid to adjust the pH to 3-11, carrying out heat preservation reaction for 1-10 h, and stirring while reacting;
in the step (2), the post-treatment specifically includes: cooling the reaction system after the reaction is finished to room temperature, sequentially centrifuging and filtering, washing the collected precipitate with water, drying at 60-100 ℃ for 4-8 hours to obtain solid powder, and calcining the obtained solid powder at 100-700 ℃ for 0.5-4 hours in an air atmosphere;
in step (3), znWO loaded with CuO nanoparticles in the dispersion 4 The concentration of the nano-sheet is 0.2mg mL -1 The concentration of the dye of the eosin Y photosensitizer is 0.2-1.6 mg mL -1 ；
In the step (3), the post-treatment specifically includes: and (3) distilling the system subjected to light shielding under reduced pressure to remove the solvent, and then vacuum drying the collected solid powder for 3-5 h at 30-50 ℃.
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