CN112871209A - 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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CN112871209A
CN112871209A CN202110187353.7A CN202110187353A CN112871209A CN 112871209 A CN112871209 A CN 112871209A CN 202110187353 A CN202110187353 A CN 202110187353A CN 112871209 A CN112871209 A CN 112871209A
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znwo
hydrogen production
solution
cuo
eosin
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CN112871209B (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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    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • 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

Abstract

The invention relates to a high-efficiency photocatalytic hydrogen production catalytic system and preparation, wherein the catalyst comprises eosin Y photosensitizer dye as a photosensitizer and ZnWO loaded with CuO nano particles4Nanosheet, said ZnWO4The nano-sheet is used as a carrier. The preparation method comprises the following steps: (1) preparing solution A from zinc salt, water and hexadecyl trimethyl ammonium bromide, preparing solution B from tungsten salt and water, mixing the two solutions, carrying out hydrothermal reaction, and carrying out post-treatment to obtain ZnWO4Nanosheets; (2) taking ZnWO4Dispersing the nanosheets in a solvent to obtain a dispersion liquid, adding copper salt, heating, adjusting pH to react, and performing aftertreatment to obtain ZnWO loaded with CuO nanoparticles4Nanosheets; (3) taking ZnWO loaded with CuO nano particles4Dispersing the nanosheets in water to form a dispersion system, adding eosin Y photosensitizer dye, stirring in a dark place, and carrying out post-treatment to obtain the catalyst. Compared with the prior art, the catalyst of the invention generates light intensityHas good stability and high hydrogen production activity when changing, and has weak sensitivity to 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 to be an effective way to solve the environmental and energy crisis problem. To date, research into semiconductor photocatalysts has been conducted extensively, and many efficient, environmentally friendly and economical photocatalysts 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 fluctuates greatly and changes rapidly throughout the day or the four seasons. Therefore, in order to apply the photocatalytic hydrogen production technology to a large scale, it is necessary to produce hydrogen efficiently and stably even under variable intensity light irradiation, and it is required that the catalyst used not only has high catalytic activity but also the light energy utilization efficiency cannot be changed according to the change of the incident light intensity. However, most of the currently reported semiconductor-based photocatalytic hydrogen production systems do not satisfy the above requirements. Therefore, it is very important to develop a high-efficiency photocatalytic hydrogen production catalyst with light energy utilization efficiency which does not change with incident light intensity.
Dye sensitization is one of the effective means to increase the photoelectron yield of the photocatalyst. Under the irradiation of light, the photosensitizer absorbs sunlight to generate excited electrons. These photo-generated excited electrons are injected into the conduction band of the semiconductor main catalyst, so that the electron concentration in the semiconductor increases, the fermi level rises, and the interface electron transfer barrier becomes small. Therefore, 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 change with the change of the incident light intensity. In addition, the molar absorption coefficient of a dye sensitizer is generally high, and the dye sensitizer can still exhibit good photoelectron yield even under light irradiation with low light intensity. The method is very beneficial to constructing the photocatalyst which can efficiently and stably prepare the hydrogen by photocatalysis under low light intensity.
Patent CN102600901A discloses a preparation method of a catalyst for preparing hydrogen by photo-reduction of water, which comprises the steps ofPreparing a carbon nano tube-metal salt precursor, loading CuO on the carbon nano tube, and soaking the carbon nano tube-CuO and a sensitizer together to obtain the sensitizer-carbon nano tube-CuO, which is characterized in that: the CuO is loaded on the carbon nano tubes by a mechanical grinding mode. The method uses a grinding method to enable copper salt to react with NaOH, and then carries out activation at low temperature, thereby loading CuO on the carbon nano tube. In this patent, the carbon nanotubes only function as electron transfer channels and do not have a photocatalytic effect, so the operating wavelength of the light in the above patent is only visible light. In the present invention, ZnWO4Plays the role of a main catalyst and has photocatalytic activity in an ultraviolet light 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 is not changed along with the change of the light intensity. The catalyst also exhibits good catalytic performance under irradiation with light of lower intensity, which is not examined in the comparative patent.
Disclosure of Invention
The invention aims to provide a high-efficiency photocatalytic hydrogen production catalytic system and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
a high-efficiency photocatalytic hydrogen production catalytic system comprises an eosin Y photosensitizer dye as a photosensitizer, CuO nano-particles as a cocatalyst and ZnWO as a main catalyst4Nanosheets, the eosin Y photosensitizer dye and CuO nanoparticles both being supported on ZnWO4Nanosheets. Wherein the eosin Y photosensitizer dye enhances the light absorption capability of the whole catalytic system and ensures that the light utilization rate of the catalyst is not influenced by light intensity, ZnWO4As a main catalyst, CuO is used as an auxiliary catalyst, so that the catalytic performance of the whole catalytic system is improved. The high-efficiency photocatalytic hydrogen production catalytic system is recorded as ZnWO4-CuO-Eosin Y, Eosin Y representing an Eosin Y photosensitizer dye.
In the photocatalysis system, the mass percent of eosin Y photosensitizer dye is 50-88.9%, and ZnWO411.03-49.7% by mass of CuO and 0.07-5.55% by mass of CuO.
The preparation method of the high-efficiency photocatalytic hydrogen production catalysis system comprises the following steps:
(1) preparing a solution A from zinc salt, water and hexadecyl trimethyl ammonium bromide, preparing a solution B from tungsten salt and water, dropwise adding the solution B into the solution A, carrying out hydrothermal reaction, and carrying out post-treatment after the reaction is finished to obtain ZnWO4The nano-sheet, cetyl trimethyl ammonium bromide, acts as a morphology modifier, and zinc tungstate nano-sheet can be prepared by using the same;
(2) taking ZnWO obtained in the step (1)4Dispersing the nanosheets in a solvent to obtain a dispersion liquid, adding a copper salt into the dispersion liquid, heating, adjusting the pH value to react, and performing aftertreatment to obtain ZnWO loaded with CuO nanoparticles4Nanosheets;
(3) taking ZnWO loaded with CuO nano particles obtained in the step (2)4Dispersing the nanosheets in water to form a dispersion system, adding eosin Y photosensitizer dye, stirring in a dark place, and performing post-treatment 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 0.1-0.6 mol L-1The concentration of cetyl trimethyl ammonium bromide is 0.01-0.1 mol L-1In the solution B, the concentration of the 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 1.5-2.5 h, preferably 2h, so as to obtain a mixture, then the obtained mixture is transferred into a hydrothermal kettle, the mixture is hermetically heated to 160-200 ℃, preferably 180 ℃, and the temperature is kept for 18-22 h, preferably 20 h. The activity of the catalytic system is firstly increased and then reduced along with the increase of factors such as temperature, time, pH and the like, so the invention limits reaction parameters.
In the step (1), the post-treatment specifically comprises: and (3) 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 h, preferably 24 h.
In the step (2), the copper salt is copper nitrate trihydrate.
In step (2), ZnWO4The mass ratio of the nanosheets to the copper salt is 500: (9.5-190).
In the step (2), the heating temperature is 20-90 ℃, hydrochloric acid or ammonia water is dripped into the dispersion liquid to adjust the pH value to 3-11, the reaction is carried out for 1-10 hours under the condition of heat preservation, and the reaction is carried out while stirring. The pH may affect the dispersibility and particle size of the copper oxide on the surface of the zinc tungstate, and the pH can be adjusted to ensure that the copper oxide is more uniformly dispersed and the particle size is more suitable.
In the step (2), the post-treatment specifically comprises: and cooling the reaction system after the reaction is finished to room temperature, then sequentially centrifuging and filtering, washing the collected precipitate with water, drying at 60-100 ℃ for 4-8 h, preferably 6h, preferably 80 ℃ to obtain solid powder, and finally calcining the obtained solid powder in an air atmosphere at 100-700 ℃ for 0.5-4 h.
In the step (2), ZnWO loaded with CuO nano particles4In the nanosheets, CuO and ZnWO4The mass ratio of (0.6-11.1): (88.9-99.4).
In the step (3), ZnWO loaded with CuO nano particles is used in the dispersion system4The concentration of the nano-sheets is 0.2mg mL-1The concentration of eosin Y photosensitizer dye is 0.2-1.6 mg mL-1。
In the step (3), the post-treatment specifically comprises: and (3) distilling the system subjected to light-shielding treatment under reduced pressure to remove the solvent, and drying the collected solid powder at 30-50 ℃ and preferably at 40 ℃ in vacuum for 3-5 h and preferably 4 h.
In the step (3), ZnWO loaded with CuO nano particles4The nanoplatelet and eosin Y photosensitizer were added in an amount of 10: (10-80).
Eosin and ZnWO are used in the invention4The nano sheets and the CuO nano particles are used as structural units to construct a novel composite photocatalytic 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 (10mW cm)-2) Under the irradiation of light rays, the catalytic system still can 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 photocatalytic hydrogen production catalytic 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 obtained in comparative example 1 under irradiation with light of different intensities4-a diagram of the photocatalytic hydrogen production activity of CuO;
FIG. 2 shows ZnWO prepared in example 6 under different light intensities4-a diagram of the photocatalytic hydrogen production activity of CuO-Eosin Y;
FIG. 3 is the ZnWO obtained in example 64Nanosheets and ZnWO obtained in example 64XRD pattern of/5.9% Cu (where a represents ZnWO)4Nanosheet, b represents ZnWO4/5.9％Cu)；
FIG. 4 shows ZnWO obtained in example 64TEM photograph of the nanosheets;
FIG. 5 is the ZnWO obtained in example 64TEM micrograph of/5.9% Cu.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
A high-efficiency photocatalytic hydrogen production catalytic system comprises an eosin Y photosensitizer dye as a photosensitizer, CuO nano-particles as a cocatalyst and ZnWO as a main catalyst4The nano-sheet, the eosin Y photosensitizer dye and the CuO nano-particle are all loaded on ZnWO4And (4) nano-chips. In the photocatalysis system, the mass percent of the eosin Y photosensitizer dye is 50-88.9%, and ZnWO411.03-49.7% by mass of CuO and 0.07-5.55% by mass of CuO.
The preparation method of the high-efficiency photocatalytic hydrogen production catalysis system comprises the following steps:
(1) preparing solution A from zinc salt, water and hexadecyl trimethyl ammonium bromide, and preparing solution A from tungsten salt and waterDropwise adding the solution B into the solution A, stirring for 1.5-2.5 hours to obtain a mixture, transferring the mixture into a hydrothermal kettle, heating to 160-200 ℃ in a sealed manner, preserving heat for 18-22 hours, and performing post-treatment after the reaction is finished to obtain ZnWO4The nanosheet is subjected to post-treatment specifically as follows: 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 h, wherein the zinc salt is zinc nitrate hexahydrate, and the tungsten salt is sodium tungstate; in the solution A, the concentration of zinc salt is 0.1-0.6 mol L-1The concentration of cetyl trimethyl ammonium bromide is 0.01-0.1 mol L-1In the solution B, the concentration of the tungsten salt is 0.2-1.5 mol L-1；
(2) Taking ZnWO obtained in the step (1)4Dispersing the nanosheets in a solvent to obtain a dispersion liquid, adding copper salt into the dispersion liquid, heating at the temperature of 20-90 ℃, dropwise adding hydrochloric acid or ammonia water into the dispersion liquid to adjust the pH value to 3-11, reacting for 1-10 h while keeping the temperature, stirring, and performing aftertreatment to obtain ZnWO loaded with CuO nanoparticles4The nanosheet is subjected to post-treatment specifically as follows: cooling a reaction system after the reaction is finished to room temperature, then sequentially centrifuging and filtering, washing the collected precipitate with water, then drying at 60-100 ℃ for 4-8 h to obtain solid powder, and finally calcining the obtained solid powder at 100-700 ℃ in an air atmosphere for 0.5-4 h to obtain ZnWO loaded with CuO nanoparticles4In the nanosheets, CuO and ZnWO4The mass ratio of (0.6-11.1): (88.9 to 99.4) in which ZnWO4The mass ratio of the nanosheets to the copper salt is 500: (9.5-190);
(3) taking ZnWO loaded with CuO nano particles obtained in the step (2)4Dispersing the nanosheets in water to form a dispersion system, adding eosin Y photosensitizer dye, stirring in the dark, and loading ZnWO (zinc indium oxide) with CuO nanoparticles in the dispersion system4The concentration of the nano-sheets is 0.2mg mL-1The concentration of eosin Y photosensitizer dye is 0.2-1.6 mg mL-1ZnWO loaded with CuO nanoparticles4The nanoplatelet and eosin Y photosensitizer were added in an amount of 10: (10-80), carrying out post-treatment to obtain a catalytic system, and carrying outThe treatment specifically comprises the following steps: and (3) distilling the system subjected to light-shielding treatment under reduced pressure to remove the solvent, and then drying the collected solid powder for 3-5 hours at the temperature of 30-50 ℃ in vacuum.
The eosin Y photosensitizer dye, zinc nitrate hexahydrate, cetyl trimethyl ammonium bromide, sodium tungstate and other chemical substances adopted in the invention are all commercially available reagents.
Example 1
A high-efficiency photocatalytic hydrogen production catalytic system comprises an eosin Y photosensitizer dye as a photosensitizer, CuO nano-particles as a cocatalyst and ZnWO as a main catalyst4The nano-sheet, the eosin Y photosensitizer dye and the CuO nano-particle are all loaded on ZnWO4And (4) nano-chips. The catalytic system is prepared by the following steps:
(1) 0.59g of zinc nitrate hexahydrate is weighed and transferred into a beaker, then 20mL of deionized water is added, stirred and dissolved to obtain a solution with the concentration of 0.1mol L-1The zinc nitrate solution of (1).
(2) After 0.072g of cetyltrimethylammonium bromide was slowly added to the above zinc nitrate solution, the mixture was stirred well until the cetyltrimethylammonium bromide was completely dissolved, and the solution was designated as solution A (the concentration of zinc nitrate in solution A was 0.1mol L)-1The concentration of cetyltrimethylammonium bromide was 0.01mol L-1)。
(3) 0.66g of sodium tungstate is weighed and transferred to a beaker, 10mL of deionized water is added to obtain a solution with a concentration of 0.2mol L-1The solution is referred to as solution B.
(4) The solution B was slowly added dropwise to the solution A with stirring. After stirring for 2 hours, the resulting mixture was transferred to a hydrothermal kettle, heated to 180 ℃ in a closed state, and kept warm for 20 hours.
(5) After the reaction is finished, the precipitate is collected by centrifugal technology and filtration, namely the product obtained by the reaction is washed clean by deionized water and dried for 24 hours at 80 ℃, and the obtained solid powder is ZnWO4Nanosheets.
(6) 500mg of ZnWO thus prepared was weighed4And (4) the nanosheets are transferred into a beaker, 30mL of deionized water is added, and the mixture is stirred to obtain a uniform dispersion liquid.
(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 for 1 hour with heat preservation.
(8) The reaction solution was cooled to room temperature, and the precipitate was collected by centrifugation. The precipitate obtained is washed clean with deionized water and dried at 80 ℃ for 6 h. Calcining the obtained solid powder for 0.5 hour at 100 ℃ in air atmosphere to obtain a product of ZnWO loaded with CuO nano particles4Nanosheet (in the product, 0.6% by mass of CuO, ZnWO)499.4% by mass).
(9) Taking 10mg of ZnWO loaded with CuO nano particles4The nanoplatelets were uniformly dispersed in 50mL of 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, the mixture was stirred for 1 hour in the dark, and the solvent was distilled off under reduced pressure. The solid powder obtained is dried in vacuum at 40 ℃ for 4 hours to obtain the target catalytic system (in which the mass percentage of eosin is 50%, ZnWO)449.7 percent of CuO and 0.3 percent of CuO by mass), and the contents of the components are detailed in Table 1.
Putting 20mg of the obtained catalytic system and 60mL of triethanolamine solution with volume fraction of 8 vol% (triethanolamine is used as a sacrificial agent) into a photocatalytic hydrogen production evaluation device, and introducing N under stirring in a dark place2For 30min to remove O in triethanolamine solution2. Then, the light source is turned on at room temperature to start hydrogen production. The light source is a 500W mercury lamp with light intensity of 100mW cm-2. After 4 hours of illumination, the yield of hydrogen produced was determined by gas chromatography. Finally, the performance of the photocatalytic hydrogen production of the catalytic system under ultraviolet-visible light is 0.95mmol g-1h-1See table 1 for details.
Example 2
A high-efficiency photocatalytic hydrogen production catalytic system comprises an eosin Y photosensitizer dye as a photosensitizer, CuO nano-particles as a cocatalyst and ZnWO as a main catalyst4Nanoplatelets, eosin Y photosensitizer dyes and CuO nanoparticles are loaded on ZnWO4And (4) nano-chips. The catalytic system is prepared by the following steps:
(1) 3.57g of zinc nitrate hexahydrate is weighed and transferred to a beaker, then 20mL of deionized water is added, stirred and dissolved to obtain 0.6mol L of zinc nitrate hexahydrate-1The zinc nitrate solution of (1).
(2) After 0.728g of cetyltrimethylammonium bromide was slowly added to the above zinc nitrate, the mixture was sufficiently stirred until the cetyltrimethylammonium bromide was completely dissolved, and the solution was designated as solution A (the concentration of zinc nitrate in the solution A was 0.6mol L)-1The concentration of cetyltrimethylammonium bromide was 0.1mol L-1)。
(3) 3.96g of sodium tungstate is weighed and transferred to a beaker, 10mL of deionized water is added to prepare a sodium tungstate solution (1.2mol L)-1) This solution is denoted as solution B.
(4) The solution B was slowly added dropwise to the solution A with stirring. After stirring for 2 hours, the resulting mixture was transferred to a hydrothermal kettle, heated to 180 ℃ in a closed state, and kept warm for 20 hours.
(5) The resulting product was collected using centrifugation techniques. The obtained product is washed clean by deionized water and dried for 24 hours at 80 ℃. The solid powder obtained is ZnWO4Nanosheets.
(6) 500mg of ZnWO thus prepared was weighed4The nanosheets 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 ammonia was added dropwise to adjust the pH of the solution to 11. Then stirring for 10 hours under heat preservation.
(8) The reaction solution was cooled to room temperature, and the precipitate was collected by centrifugation. The precipitate obtained is washed clean with deionized water and dried at 80 ℃ for 6 h. The solid powder obtained was calcined at 700 ℃ for 4 hours in an air atmosphere. The obtained product is ZnWO loaded with CuO nano particles4Nanosheet (mass percent of CuO is 11.1%, ZnWO)488.9% by mass).
(9) Taking 10mg of ZnWO loaded with CuO nano particles4Nano sheet combined throughIt was uniformly dispersed in 50mL of deionized water at room temperature with stirring. To the above dispersion was added 80mg of eosin Y photosensitizer (1.6mg mL)-1) After that, the mixture was stirred for 1 hour in the dark, and the solvent was distilled off under reduced pressure. The solid powder obtained was dried under vacuum at 40 ℃ for 4 hours and the catalytic system aimed at was obtained (mass% of eosin 88.9%, ZnWO)49.9 percent by mass and 1.2 percent by mass of CuO).
Putting 90mg of the obtained catalytic system and 60mL of triethanolamine solution with volume fraction of 8 vol% (triethanolamine is used as a sacrificial agent) into a photocatalytic hydrogen production evaluation device, and introducing N under stirring in a dark place2For 30min to remove O in triethanolamine solution2. Then, the light source is turned on at room temperature to start hydrogen production. The light source is a 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 1.32mmol g-1h-1See table 1 for details.
Example 3
A high-efficiency photocatalytic hydrogen production catalytic system comprises an eosin Y photosensitizer dye as a photosensitizer, CuO nano-particles as a cocatalyst and ZnWO as a main catalyst4The nano-sheet, the eosin Y photosensitizer dye and the CuO nano-particle are all loaded on ZnWO4And (4) nano-chips. The catalytic system is prepared by the following steps:
(1) 2.98g of zinc nitrate hexahydrate is weighed and transferred into a beaker, then 20mL of deionized water is added, stirred and dissolved to obtain 0.5mol L of zinc nitrate hexahydrate-1The zinc nitrate solution of (1).
(2) After 0.36g of cetyltrimethylammonium bromide was slowly added to the above zinc nitrate, it was sufficiently stirred until it was completely dissolved. This solution was designated as solution A (concentration of zinc nitrate was 0.5mol L)-1The concentration of cetyltrimethylammonium bromide was 0.05mol L-1)。
(3) 3.3g of sodium tungstate was weighed and transferred to a beaker, 10mL of deionized water was added to make 1.0mol L-1The solution is referred to as solution B.
(4) The solution B was slowly added dropwise to the solution A with stirring. After stirring for 2 hours, the resulting mixture was transferred to a hydrothermal kettle, heated to 180 ℃ in a closed state, and kept warm for 20 hours.
(5) The resulting product was collected using centrifugation techniques. The obtained product is washed clean by deionized water and dried for 24 hours at 80 ℃. The solid powder obtained is ZnWO4Nanosheets.
(6) 500mg of ZnWO thus prepared was weighed4The nanosheets 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 stirring for 2 hours under heat preservation.
(8) The reaction solution was cooled to room temperature, and the precipitate was collected by centrifugation. The precipitate obtained is washed clean with deionized water and dried at 80 ℃ for 6 h. The solid powder obtained was calcined at 200 ℃ for 1 hour in an air atmosphere. The obtained product is ZnWO loaded with CuO nano particles4Nanosheet (0.6% of CuO and ZnWO by mass)499.4% by mass).
(9) Taking 10mg of ZnWO loaded with CuO nano particles4The nanoplatelets were dispersed uniformly in 50mL of deionized water at room temperature by stirring. To the above dispersion was added 80mg of eosin Y photosensitizer (1.6mg mL)-1) After that, the mixture was stirred for 1 hour in the dark, and the solvent was distilled off under reduced pressure. The solid powder obtained was dried under vacuum at 40 ℃ for 4 hours and the catalytic system aimed at was obtained (mass% of eosin 88.9%, ZnWO)411.03 percent by mass and 0.07 percent by mass of CuO).
Putting 90mg of the obtained catalytic system and 60mL of triethanolamine solution with volume fraction of 8 vol% (triethanolamine is used as a sacrificial agent) into a photocatalytic hydrogen production evaluation device, and introducing N under stirring in a dark place2For 30min to remove O in triethanolamine solution2. Then, the light source is turned on at room temperature to start hydrogen production. The light source is a 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 1.43mmol g-1h-1In detail, inSee table 1.
Example 4
A high-efficiency photocatalytic hydrogen production catalytic system comprises an eosin Y photosensitizer dye as a photosensitizer, CuO nano-particles as a cocatalyst and ZnWO as a main catalyst4The nano-sheet, the eosin Y photosensitizer dye and the CuO nano-particle are all loaded on ZnWO4And (4) nano-chips. The catalytic system is prepared by the following steps:
(1) 2.98g of zinc nitrate hexahydrate is weighed and transferred into a beaker, then 20mL of deionized water is added, stirred and dissolved to obtain 0.5mol L-1The zinc nitrate solution of (1).
(2) After 0.36g of cetyltrimethylammonium bromide was slowly added to the above zinc nitrate, it was sufficiently stirred until it was completely dissolved. This solution was designated as solution A (0.5 mol L of zinc nitrate)-1Cetyl trimethyl ammonium 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 (1.0mol L)-1). This solution was designated as solution B.
(4) The solution B was slowly added dropwise to the solution A with stirring. After stirring for 2 hours, the resulting mixture was transferred to a hydrothermal kettle, heated to 180 ℃ in a closed state, and kept warm for 20 hours.
(5) The resulting product was collected using centrifugation techniques. The obtained product is washed clean by deionized water and dried for 24 hours at 80 ℃. The solid powder obtained is ZnWO4Nanosheets.
(6) 500mg of ZnWO thus prepared was weighed4The nanosheets 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 ammonia was added dropwise to adjust the pH of the solution to 10. Then stirring for 2 hours under heat preservation.
(8) The reaction solution was cooled to room temperature, and the precipitate was collected by centrifugation. The precipitate obtained is washed clean with deionized water and dried at 80 ℃ for 6 h. The solid powder obtained was calcined at 400 ℃ for 2 hours in an air atmosphere. The obtained product is loaded with CuO nano-particlesZnWO4Nanosheet (mass percent of CuO is 11.1%, ZnWO)488.9% by mass).
(9) Taking 10mg of ZnWO loaded with CuO nano particles4The nanoplatelets were dispersed uniformly in 50mL of deionized water at room temperature by stirring. To the above dispersion was added 10mg of eosin Y photosensitizer (0.2mg mL)-1) After that, the mixture was stirred for 1 hour in the dark, and the solvent was distilled off under reduced pressure. The solid powder obtained was dried under vacuum at 40 ℃ for 4 hours and the catalytic system aimed at was obtained (50% by mass of eosin, ZnWO)444.45 percent of CuO and 5.55 percent of CuO by mass).
Putting 20mg of the obtained catalytic system and 60mL of triethanolamine solution with volume fraction of 8 vol% (triethanolamine is used as a sacrificial agent) into a photocatalytic hydrogen production evaluation device, and introducing N under stirring in a dark place2For 30min to remove O in triethanolamine solution2. Then, the light source is turned on at room temperature to start hydrogen production. The light source is a 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 1.83mmol g-1h-1See table 1 for details.
Example 5
A high-efficiency photocatalytic hydrogen production catalytic system comprises an eosin Y photosensitizer dye as a photosensitizer, CuO nano-particles as a cocatalyst and ZnWO as a main catalyst4The nano-sheet, the eosin Y photosensitizer dye and the CuO nano-particle are all loaded on ZnWO4And (4) nano-chips. The catalytic system is prepared by the following steps:
(1) 2.98g of zinc nitrate hexahydrate is weighed and transferred into a beaker, then 20mL of deionized water is added, stirred and dissolved to obtain 0.5mol L-1The zinc nitrate solution of (1).
(2) After 0.36g of cetyltrimethylammonium bromide was slowly added to the above zinc nitrate, it was sufficiently stirred until it was completely dissolved. This solution was designated as solution A (0.5 mol L of zinc nitrate)-1Cetyl trimethyl ammonium Bromide 0.05mol L-1)。
(3) Weighing 3.3g sodium tungstate and transferring into a beaker, adding10mL of deionized water was added to prepare a sodium tungstate solution (1.0mol L)-1). This solution was designated as solution B.
(4) The solution B was slowly added dropwise to the solution A with stirring. After stirring for 2 hours, the resulting mixture was transferred to a hydrothermal kettle, heated to 180 ℃ in a closed state, and kept warm for 20 hours.
(5) The resulting product was collected using centrifugation techniques. The obtained product is washed clean by deionized water and dried for 24 hours at 80 ℃. The solid powder obtained is ZnWO4Nanosheets.
(6) 500mg of ZnWO thus prepared was weighed4The nanosheets 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 ammonia was added dropwise to adjust the pH of the solution to 10. Then stirring for 2 hours under heat preservation.
(8) The reaction solution was cooled to room temperature, and the precipitate was collected by centrifugation. The precipitate obtained is washed clean with deionized water and dried at 80 ℃ for 6 h. The solid powder obtained was calcined at 200 ℃ for 1 hour in an air atmosphere. The obtained product is ZnWO loaded with CuO nano particles4Nanosheet (CuO 5.9 wt%, ZnWO)494.1% by mass).
(9) Taking 10mg of ZnWO loaded with CuO nano particles4The nanoplatelets were dispersed uniformly in 50mL of deionized water at room temperature by stirring. To the above dispersion was added 20mg of eosin Y photosensitizer (0.4mg mL)-1) After that, the mixture was stirred for 1 hour in the dark, and the solvent was distilled off under reduced pressure. The solid powder obtained was dried under vacuum at 40 ℃ for 4 hours and the catalytic system aimed at was obtained (66.66% by mass of eosin, ZnWO)431.37 percent by mass and 1.97 percent by mass of CuO).
Putting 30mg of the obtained catalytic system and 60mL of triethanolamine solution with volume fraction of 8 vol% (triethanolamine is used as a sacrificial agent) into a photocatalytic hydrogen production evaluation device, and introducing N under stirring in a dark place2For 30min to drive off the O in the catalytic system and the triethanolamine solution2. Then, the light source is turned on at room temperature to start hydrogen production. The light usedThe light intensity of a mercury lamp with a source of 500W is 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-1h-1See table 1 for details.
Example 6
A high-efficiency photocatalytic hydrogen production catalytic system comprises an eosin Y photosensitizer dye as a photosensitizer, CuO nano-particles as a cocatalyst and ZnWO as a main catalyst4The nano-sheet, the eosin Y photosensitizer dye and the CuO nano-particle are all loaded on ZnWO4And (4) nano-chips. The catalytic system is prepared by the following steps:
(1) 2.98g of zinc nitrate hexahydrate is weighed and transferred into a beaker, then 20mL of deionized water is added, stirred and dissolved to obtain 0.5mol L-1The zinc nitrate solution of (1).
(2) After 0.36g of cetyltrimethylammonium bromide was slowly added to the above zinc nitrate, it was sufficiently stirred until it was completely dissolved. This solution was designated as solution A (0.5 mol L of zinc nitrate)-1Cetyl trimethyl ammonium 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 (1.0mol L)-1). This solution was designated as solution B.
(4) The solution B was slowly added dropwise to the solution A with stirring. After stirring for 2 hours, the resulting mixture was transferred to a hydrothermal kettle, heated to 180 ℃ in a closed state, and kept warm for 20 hours.
(5) The resulting product was collected using centrifugation techniques. The obtained product is washed clean by deionized water and dried for 24 hours at 80 ℃. The solid powder obtained is ZnWO4The XRD pattern of the nanosheet is shown in figure 3, and all diffraction peaks in the pattern can be seen to be associated with monoclinic phase ZnWO4Standard XRD cards (JCPDSNo.89-0447) are identical. The TEM micrograph is shown in FIG. 4, and it can be seen that rectangular-like nanosheets were formed, having a size of about 40nm × 30 nm.
(6) 500mg of ZnWO thus prepared was weighed4The nanosheets 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 ammonia was added dropwise to adjust the pH of the solution to 10.7. Then stirring for 2 hours under heat preservation.
(8) The reaction solution was cooled to room temperature, and the precipitate was collected by centrifugation. The precipitate obtained is washed clean with deionized water and dried at 80 ℃ for 6 h. The solid powder obtained was calcined at 200 ℃ for 1 hour in an air atmosphere. The obtained product is ZnWO loaded with CuO nano particles4Nanosheet (CuO 5.9 wt%, ZnWO)494.1%) and the XRD pattern is shown in fig. 3, it can be seen that the crystal structure of zinc tungstate is not changed. The TEM photograph is shown in fig. 5, and it can be seen that the morphology of zinc tungstate is not changed, and the surface of the nanosheet is roughened, which can be attributed to the introduction of CuO.
(9) Taking 10mg of ZnWO loaded with CuO nano particles4The nanoplatelets were dispersed uniformly in 50mL of deionized water at room temperature by stirring. To the above dispersion was added 40mg of eosin Y photosensitizer (0.8mg mL)-1) After that, the mixture was stirred for 1 hour in the dark, and the solvent was distilled off under reduced pressure. The solid powder obtained was dried under vacuum at 40 ℃ for 4 hours and the catalytic system aimed at was obtained (80% by mass of eosin, ZnWO)418.82 percent of CuO and 1.18 percent of ZnWO 45% of CuO/Eosin Y, 5% of which is CuO + ZnWO4At 100%, the mass percentage of CuO is 5% with no 6% change (approximate bit is one).
50mg of the obtained catalytic system and 60mL of triethanolamine solution with volume fraction of 8 vol% (triethanolamine is used as a sacrificial agent) are put into a photocatalytic hydrogen production evaluation device, and N is introduced under stirring in a dark place2For 30min to drive off the O in the catalytic system and the triethanolamine solution2. Then, the light source is turned on at room temperature to start hydrogen production. The light source is a 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 5.07mmol g-1h-1See table 1 and fig. 2 for details.
Further, hydrogen production evaluation was continued in this evaluation apparatus by using only lightThe illumination intensity is adjusted to 60mW cm in sequence-2、30mW cm-2And 10mW cm-2The photocatalytic hydrogen production performance is shown in FIG. 2, and is 3.42mmol g-1h-1、1.65mmol g-1h-1And 0.53mmol g-1h-1。
TABLE 1 photocatalytic Hydrogen production Activity of the samples of the examples
Figure BDA0002943460650000131
Comparative example 1
ZnWO loaded with CuO nano-particles4The nano sheet is prepared by the following steps:
1. 2.98g of zinc nitrate hexahydrate is weighed and transferred into a beaker, then 20mL of deionized water is added, stirred and dissolved to obtain 0.5mol L-1The zinc nitrate solution of (1).
2. After 0.36g of cetyltrimethylammonium bromide was slowly added to the above zinc nitrate, it was sufficiently stirred until it was completely dissolved. This solution was designated as solution A (zinc nitrate 0.5mol L-1, cetyltrimethylammonium 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 (1.0mol L-1). This solution was designated as solution B.
4. The solution B was slowly added dropwise to the solution A with stirring. After stirring for 2 hours, the resulting mixture was transferred to a hydrothermal kettle, heated to 180 ℃ in a closed state, and kept warm for 20 hours.
5. The resulting product was collected using centrifugation techniques. The obtained product is washed clean by deionized water and dried for 24 hours at 80 ℃. The solid powder obtained is ZnWO4Nanosheets.
6. 500mg of ZnWO thus prepared was weighed4The nanosheets 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 ammonia was added dropwise to adjust the pH of the solution to 10.7. Then stirring for 2 hours under heat preservation.
8. The reaction solution was cooled to room temperature, and the precipitate was collected by centrifugation. The precipitate obtained is washed clean with deionized water and dried at 80 ℃ for 6 h. The solid powder obtained was calcined at 200 ℃ for 1 hour in an air atmosphere. The obtained product is ZnWO loaded with CuO nano particles4Nanosheet (CuO 5.9 wt%, ZnWO)4Is 94.1 percent by mass, based on ZnWO 45% Cu, 5% of which is CuO + ZnWO4At 100%, the mass percentage of CuO is 5% (approximate bit is one bit), i.e. 5% is changed to 6%).
Taking 10mg of ZnWO loaded with CuO nano particles4The nanosheets and 60mL of triethanolamine solution with the volume fraction of 8 vol% (triethanolamine as a sacrificial agent) are placed in the photocatalytic hydrogen production evaluation device which is the same as that in the embodiment 1-6, and the illumination intensity is adjusted to be 100mW cm and cm respectively-2、60mW cm-2、30mW cm-2And 10mW cm-2The obtained photocatalytic hydrogen production performance is shown in figure 1, and it can be seen that the photocatalytic hydrogen production performance is 0.13mmol g-1h-1、0.069mmol g-1h-1、0.010mmol g-1h-1And 0.0030mmol g-1h-1。
Fig. 1 shows the photocatalytic hydrogen production activity of the comparative example 1 sample under different light intensities, and fig. 2 shows the photocatalytic hydrogen production activity of the example 6 sample. As can be seen from fig. 2, in combination with the results shown in table 1 above, the photocatalytic hydrogen production system according to the present invention has excellent photocatalytic hydrogen production performance. It exhibits satisfactory photocatalytic hydrogen production activity even at low light intensity. Furthermore, it is of more interest to use the light under stronger illumination (100mW cm)-2) The light energy utilization rate (the calculation formula is the hydrogen production divided by the illumination intensity) of the catalytic system is 0.051mmol cm2 g-1h-1mW-1(ii) a Under weak illumination (10mW cm)-2) The light energy utilization rate of the catalytic system is 0.053mmol cm2 g-1h-1mW-1(ii) a At 60mW cm-2Under the illumination intensity of (2), the luminous energy utilization rate of the catalytic system is 0.057mmol cm2 g-1h-1mW-1(ii) a At 30mW cm-2Under the illumination intensity, the light energy utilization rate of the catalytic system is 0.055mmol cm2 g-1h-1mW-1. It can be seen that the light energy utilization of the catalytic system of the present invention is substantially invariant to variations in light intensity. As can be seen in fig. 1, for ZnWO loaded with CuO nanoparticles4For the nano-sheet, the light energy utilization rate is obviously reduced along with the reduction of the illumination intensity, which shows that the nano-sheet has stronger dependence on the illumination intensity. The photocatalytic system can efficiently produce hydrogen under the irradiation of light with lower light intensity, and the light energy utilization rate is basically not changed along with the change of the light intensity, so that the photocatalytic system has great application potential in the field of solar hydrogen production.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, 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 embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. A high-efficiency photocatalytic hydrogen production catalytic system is characterized in that the catalytic system comprises an eosin Y photosensitizer dye as a photosensitizer, CuO nano particles as a cocatalyst and ZnWO as a main catalyst4Nanosheets, the eosin Y photosensitizer dye and CuO nanoparticles both being supported on ZnWO4And (4) nano-chips.
2. The high-efficiency photocatalytic hydrogen production catalysis system according to claim 1, wherein in the photocatalytic system, the mass percentage of eosin Y photosensitizer dye is 50-88.9%, and the mass percentage of the eosin Y photosensitizer dye is ZnWO411.03-49.7% by mass of CuO and 0.07-5.55% by mass of CuO.
3. The preparation method of the high-efficiency photocatalytic hydrogen production catalytic system as recited in claim 1 or 2, characterized by comprising the following steps:
(1) preparing a solution A from zinc salt, water and hexadecyl trimethyl ammonium bromide, preparing a solution B from tungsten salt and water, dropwise adding the solution B into the solution A, carrying out hydrothermal reaction, and carrying out post-treatment after the reaction is finished to obtain ZnWO4Nanosheets;
(2) taking ZnWO obtained in the step (1)4Dispersing the nanosheets in a solvent to obtain a dispersion liquid, adding a copper salt into the dispersion liquid, heating, adjusting the pH value to react, and performing aftertreatment to obtain ZnWO loaded with CuO nanoparticles4Nanosheets;
(3) taking ZnWO loaded with CuO nano particles obtained in the step (2)4Dispersing the nanosheets in water to form a dispersion system, adding eosin Y photosensitizer dye, stirring in a dark place, and performing post-treatment to obtain the catalytic system.
4. The preparation method of the high-efficiency photocatalytic hydrogen production catalysis system according to claim 3, 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 0.1-0.6 mol L-1The concentration of cetyl trimethyl ammonium bromide is 0.01-0.1 mol L-1In the solution B, the concentration of the tungsten salt is 0.2-1.5 mol L-1。
5. The preparation method of the high-efficiency photocatalytic hydrogen production catalysis system according to claim 3, characterized in that in the step (1), the solution B is dropwise added into the solution A and then stirred for 1.5-2.5 h to obtain a mixture, the obtained mixture is transferred into a hydrothermal kettle, the kettle is sealed and heated to 160-200 ℃, and the temperature is kept for 18-22 h.
6. The preparation method of the high-efficiency photocatalytic hydrogen production catalysis system according to claim 3, wherein in the step (1), the post-treatment specifically comprises: and (3) 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 h.
7. The preparation method of the high-efficiency photocatalytic hydrogen production catalysis system according to claim 3, characterized in that in the step (2), the heating temperature is 20-90 ℃, hydrochloric acid or ammonia water is dripped into the dispersion liquid to adjust the pH value to 3-11, the reaction is carried out for 1-10 h under heat preservation, and the reaction is carried out while stirring.
8. The preparation method of the high-efficiency photocatalytic hydrogen production catalysis system according to claim 3, wherein in the step (2), the post-treatment specifically comprises: and cooling the reaction system after the reaction is finished to room temperature, then sequentially centrifuging and filtering, washing the collected precipitate with water, drying at 60-100 ℃ for 4-8 h to obtain solid powder, and finally calcining the obtained solid powder in an air atmosphere at 100-700 ℃ for 0.5-4 h.
9. The method for preparing the high-efficiency photocatalytic hydrogen production catalytic system according to claim 3, wherein in the step (3), ZnWO loaded with CuO nanoparticles is used as the dispersing system4The concentration of the nano-sheets is 0.2mg mL-1The concentration of eosin Y photosensitizer dye is 0.2-1.6 mg mL-1。
10. The preparation method of the high-efficiency photocatalytic hydrogen production catalysis system according to claim 3, wherein in the step (3), the post-treatment specifically comprises: and (3) distilling the system subjected to light-shielding treatment under reduced pressure to remove the solvent, and then drying the collected solid powder for 3-5 hours at the temperature of 30-50 ℃ in vacuum.
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