CN112844371A - Catalyst for photolysis of water to produce oxygen and preparation method thereof - Google Patents

Catalyst for photolysis of water to produce oxygen and preparation method thereof Download PDF

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CN112844371A
CN112844371A CN202110148018.6A CN202110148018A CN112844371A CN 112844371 A CN112844371 A CN 112844371A CN 202110148018 A CN202110148018 A CN 202110148018A CN 112844371 A CN112844371 A CN 112844371A
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杨玉蓉
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Heihe University
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Abstract

A catalyst for oxygen production by water photolysis and a preparation method thereof relate to a catalyst for oxygen production by water photolysis and a preparation method thereof. The catalyst aims to solve the technical problems of complex preparation procedure, high cost, expensive reagent and harsh experimental conditions of the existing catalyst for photolysis of water to prepare oxygen. The catalyst for photolyzing water to prepare oxygen is H.23WO3And (4) quantum dots. The preparation method comprises the following steps: firstly, preparing a mixed solution by using tungsten chloride, a phenolic compound and an auxiliary agent; secondly, preparing a hydrated tungsten trioxide block; thirdly, preparing hydrated tungsten trioxide quantum dots; and fourthly, etching to obtain the catalyst for photolyzing water to produce oxygen. The catalyst for preparing oxygen by photolyzing water can generate oxygen by photolyzing water, the oxygen generation amount is up to 68-80 micromoles/gram per hour under the irradiation of simulated sunlight, and the stable oxygen generation is not obviously attenuated within 20 hours. Can be used in the fields of water decomposition, oxygen production and photocatalytic degradation of organic matters.

Description

Catalyst for photolysis of water to produce oxygen and preparation method thereof
Technical Field
The invention belongs to the technical field of preparation processes of inorganic nano photocatalytic materials, and relates to H.23WO3A preparation method of quantum dots.
Background
In the modern times, with the deterioration of the environment and the rapid depletion of natural resources, the global energy crisis requires the development of chemical manufacturing industries toward low energy consumption and the development of low-cost catalysts. In modern chemical industry, sunlight-driven reactions are expected to replace traditional thermochemical reactions, greatly reducing energy consumption. Tungsten oxide has recently received much attention as a very promising catalyst material because of its excellent photocatalytic activity and low cost. However, because the forbidden band width of tungsten oxide is wide (2.7eV), sunlight cannot be sufficiently absorbed, and photo-generated carriers are easy to recombine, which greatly limits the application of tungsten oxide in the preparation of oxygen by photolysis and the photocatalytic degradation of organic pollutants. Therefore, how to modify the tungsten oxide structure to expand sunlight absorption to an infrared region and realize rapid separation of photon-generated carriers, and further improve the photocatalytic activity of tungsten oxide becomes one of the important points of research on photocatalytic materials.
The tungsten oxide rich in oxygen defects has the advantages of good light absorption performance (the maximum absorption wavelength is larger than or equal to 1200nm), long service life of photon-generated carriers, high catalytic efficiency and the like. At present, some experts and scholars try to introduce oxygen vacancies into the tungsten oxide material, and a great deal of research work is carried out on preparing the tungsten oxide material rich in oxygen defects. The specific process mainly comprises the following steps: reduction in hydrogen atmosphere, reduction with strong reducing agents, bombardment with energetic particles (laser, electron or argon ion), photochemical preparation process. However, the above-mentioned methods have various disadvantages, such as: the experimental procedure is complex, the cost is high, the reagent is expensive, the experimental conditions are harsh, and the method can not be applied in large scale in actual production. The low defect content and the poor material stability are also an important problem to be solved urgently in the development of the tungsten oxide nano material rich in oxygen defects.
Disclosure of Invention
The invention provides a catalyst for photolysis water to prepare oxygen and a preparation method thereof, aiming at solving the technical problems of complex preparation procedure, high cost, expensive reagent and harsh experimental conditions of the existing catalyst for photolysis water to prepare oxygen.
The invention is used for photolysisThe catalyst for the preparation of oxygen from water is H.23WO3And (4) quantum dots.
Further, H.23WO3The particle size of the quantum dots is 3-7 nanometers;
the preparation method of the catalyst for oxygen production by photolysis of water comprises the following steps:
firstly, preparing a mixed solution: dissolving tungsten chloride in deionized water to prepare a tungsten chloride solution, dissolving a phenolic compound in ethanol to prepare a phenolic compound solution, adding the tungsten chloride solution into the phenolic compound solution, stirring for 10-30 min, adding an auxiliary agent, and stirring for 15-35 min to obtain a mixed solution;
secondly, preparing a hydrated tungsten trioxide block: transferring the mixed solution into a polytetrafluoroethylene high-pressure autoclave, and putting the polytetrafluoroethylene high-pressure autoclave into an electric heating constant-temperature blast drying oven with the temperature of 120-180 ℃ for 12-15 hours; centrifuging the reacted solution, sequentially washing the solid phase with absolute ethyl alcohol and distilled water, and drying to obtain a hydrated tungsten trioxide block;
thirdly, preparing hydrated tungsten trioxide quantum dots: heating the hydrated tungsten trioxide block in a heating furnace in a nitrogen atmosphere, injecting octylamine when the temperature reaches 160-190 ℃, and reacting for 5-10 min at the temperature to perform nitridation treatment; adding ethanol to generate light blue quantum dots, performing centrifugal separation, collecting the quantum dots on the lower layer, and sequentially washing the collected quantum dots with absolute ethyl alcohol and distilled water to obtain hydrated tungsten trioxide quantum dots;
fourthly, adding the hydrated tungsten trioxide quantum dots obtained in the third step into an etching agent solution with the molar concentration of 0.5-1.0 mol/L, and soaking for 4-8 hours at room temperature; and then centrifugally separating, washing the solid phase with absolute ethyl alcohol and deionized water in sequence, and drying 12 to obtain the catalyst for photolyzing water to prepare oxygen.
Further, in the first step, the molar ratio of the tungsten chloride, the phenolic compound and the auxiliary agent is 1: (1.5-1.8): (1.4-1.7);
further, in the first step, the phenolic compound is phenol, hydroquinone, resorcinol or catechol;
furthermore, in the step one, the auxiliary agent is citric acid, sodium citrate, urea or thiourea;
furthermore, in the third step, the ratio of the mass of the hydrated tungsten trioxide block to the volume of the octylamine is 1g (7.5-60) mL;
furthermore, in the third step, the ratio of the mass of the hydrated tungsten trioxide block to the volume of the ethanol is 1g (100-250) mL.
Furthermore, in the fourth step, the etchant is ammonium bifluoride, acetic acid, acetone or hydrogen peroxide.
According to the invention, oxygen vacancies are introduced into the hydrated tungsten trioxide block, and simultaneously, the hydrogenation of the material is realized, the obtained catalyst for the oxygen production by water photolysis contains hydrogen bonds, a large amount of overlapping of electron orbits in the catalyst containing the hydrogen bonds can promote charge transfer, and the hydrogen bonds in the catalyst can accelerate catalytic reaction and are very stable. The content of oxygen vacancies in the tungsten trioxide quantum dots is effectively controlled through the etching of the ammonium bifluoride solution, the obtained product contains abundant oxygen vacancies, the photocatalytic activity of the material is greatly increased, and the performance of the material for preparing oxygen by photolysis of water can be remarkably improved.
The catalyst for preparing oxygen by photolyzing water can generate oxygen by photolyzing water, the oxygen generation amount is up to 68-80 micromoles/gram per hour under the irradiation of simulated sunlight, and the stable oxygen generation is not obviously attenuated within 20 hours.
The preparation method of the catalyst for oxygen production by photolysis of water has the characteristics of low raw material tungsten chloride equivalent lattice, simple synthesis method operation, simple experimental equipment, mild experimental conditions, low energy consumption, high yield, good experimental repeatability, uniform size of prepared products and the like. The reaction process is easy to regulate and control, the required product can be quickly prepared, and the industrial production is easy to realize.
The catalyst for preparing oxygen by photolyzing water can be used in the fields of preparing oxygen by decomposing water under the irradiation of visible light, degrading organic matters by photocatalysis, and the like, has excellent photocatalytic activity, and has important significance in industrial production.
Drawings
FIG. 1 is a scanning electron micrograph of hydrated tungsten trioxide prepared in step two of example 1;
FIG. 2 is an X-ray diffraction pattern of the catalyst prepared in example 1 for the photolysis of water for oxygen production;
FIG. 3 is a high resolution transmission electron micrograph of the catalyst prepared in example 1 for the photolysis of water for oxygen production;
FIG. 4 is a high resolution transmission electron micrograph of the catalyst prepared in example 1 for the photolysis of water for oxygen production;
FIG. 5 is a graph of a visible light absorption test of the catalyst prepared in example 1 for the photolysis of water to produce oxygen;
FIG. 6 is an electron paramagnetic resonance spectrum of the catalyst for the photolysis of water for oxygen production prepared in example 1;
FIG. 7 is a high resolution transmission electron micrograph of the catalyst prepared in example 2 for the photolysis of water for oxygen production;
FIG. 8 is a high resolution transmission electron micrograph of the catalyst prepared in example 3 for the photolysis of water for oxygen production;
FIG. 9 is a high resolution transmission electron micrograph of the catalyst prepared in example 4 for the photolysis of water for oxygen production;
fig. 10 is a schematic view of the photolytic oxygen production of the catalyst for photolytic oxygen production prepared in examples 1, 2, 3, and 4.
Detailed Description
The following examples are used to demonstrate the beneficial effects of the present invention.
Example 1: the preparation method of the catalyst for oxygen production by photolysis of water in the embodiment comprises the following steps:
firstly, preparing a mixed solution: dissolving 0.36g of tungsten chloride in 15mL of deionized water to obtain a tungsten chloride solution; dissolving 0.17g of hydroquinone in 20mL of ethanol to prepare hydroquinone solution; mixing the tungsten chloride solution and the hydroquinone solution, stirring at room temperature for 10min, then adding 0.29g of citric acid, and stirring for 30min to obtain a mixed solution;
secondly, preparing a hydrated tungsten trioxide block: transferring the mixed solution into a 50 ml polytetrafluoroethylene high-pressure autoclave, and putting the polytetrafluoroethylene high-pressure autoclave into an electric heating constant-temperature air blowing drying oven with the temperature of 120 ℃ for 15 hours; centrifuging the reacted solution, washing the solid phase with absolute ethyl alcohol and distilled water in sequence, and drying at 80 ℃ for 12 hours to obtain a hydrated tungsten trioxide block;
thirdly, preparing hydrated tungsten trioxide quantum dots: placing 0.1g of hydrated tungsten trioxide block in a heating furnace in a nitrogen atmosphere, heating, injecting 3mL of octylamine when the temperature reaches 160 ℃, and reacting for 10min at the temperature to perform nitridation treatment; then adding 20ml of ethanol to obtain light blue quantum dots, performing centrifugal separation, collecting the quantum dots on the lower layer, and sequentially washing the collected quantum dots with absolute ethyl alcohol and distilled water to obtain hydrated tungsten trioxide quantum dots;
fourthly, adding the hydrated tungsten trioxide quantum dots obtained in the third step into an ammonium bifluoride solution with the molar concentration of 1.0 mol/L, soaking for 4 hours at room temperature, then performing centrifugal separation, sequentially washing solid-phase substances with absolute ethyl alcohol and deionized water, and drying at the constant temperature of 60 ℃ for 12 hours to obtain the catalyst for preparing oxygen by photolyzing water.
A scanning electron micrograph of the hydrated tungsten trioxide produced in step two of example 1 is shown in fig. 1, and it can be seen from fig. 1 that the hydrated tungsten trioxide produced in example 1 is a rectangular block having a thickness of about 10 μm.
The X-ray diffraction pattern of the catalyst for the oxygen production by photolysis of water prepared in example 1 is shown in FIG. 2, and it can be seen from FIG. 2 that the catalyst for the oxygen production by photolysis of water prepared in this example is compared with the standard PDF, and found that the catalyst for the oxygen production by photolysis of water and PDF #85-0752 has H.23WO3With good matching, the catalyst for the oxygen production by photolysis of water prepared in the example 1 is H.23WO3。
Fig. 3 shows a high-resolution transmission electron micrograph of the catalyst for oxygen generation by photolysis of water prepared in example 1, and it can be seen from fig. 3 that the catalyst for oxygen generation by photolysis of water prepared in example 1 is a quantum dot with a diameter of 3-7 nm.
The high resolution transmission electron micrograph of the catalyst for the photolysis of water to oxygen prepared in example 1 is shown in FIG. 4. As can be seen from FIG. 4, H prepared in example 1.23WO3The interplanar spacing of the quantum dots is 0.370nm, corresponding to H.23WO3The (110) crystal plane of (a).
After characterization through X-ray diffraction, scanning electron microscope and transmission electron microscope, the catalyst of the final product for photolyzing water to prepare oxygen is H.23WO3And (4) quantum dots.
The graph of the visible light absorption test of the catalyst for the photolysis of water to prepare oxygen prepared in the example 1 is shown in fig. 5, and as can be seen from fig. 5, the prepared H.23WO3The quantum dots have good light absorption in a visible light region (390nm-780nm) and even a near infrared short-wave region (780-1200 nm).
The electron paramagnetic resonance spectrum of the catalyst for the photolysis of water to produce oxygen prepared in example 1 is shown in FIG. 6. from FIG. 6, it can be seen that there is a strong and broad signal peak at g ═ 2.003, which indicates that H is prepared.23WO3A large number of oxygen vacancies are present in quantum dots.
Example 2: the preparation method of the catalyst for oxygen production by photolysis of water in the embodiment comprises the following steps:
firstly, preparing a mixed solution: dissolving 0.36g of tungsten chloride in 15mL of deionized water to obtain a tungsten chloride solution; dissolving 0.14g of phenol in 20mL of ethanol to prepare a phenol solution; mixing the tungsten chloride solution and the phenol solution, stirring at room temperature for 10min, then adding 0.39g of sodium citrate, and stirring for 30min to obtain a mixed solution;
secondly, preparing a hydrated tungsten trioxide block: transferring the mixed solution into a 50 ml polytetrafluoroethylene high-pressure autoclave, and putting the polytetrafluoroethylene high-pressure autoclave into an electric heating constant-temperature air blowing drying oven with the temperature of 140 ℃ for 14 hours; centrifuging the reacted solution, washing the solid phase with absolute ethyl alcohol and distilled water in sequence, and drying at 90 ℃ for 12 hours to obtain a hydrated tungsten trioxide block;
thirdly, preparing hydrated tungsten trioxide quantum dots: placing 0.2g of hydrated tungsten trioxide block in a heating furnace in nitrogen atmosphere, heating, injecting 5mL of octylamine when the temperature reaches 180 ℃, and reacting for 8min at the temperature to perform nitridation treatment; then adding 30 ml of ethanol to obtain light blue quantum dots, performing centrifugal separation, collecting the quantum dots on the lower layer, and sequentially washing the collected quantum dots with absolute ethyl alcohol and distilled water to obtain hydrated tungsten trioxide quantum dots;
fourthly, adding the hydrated tungsten trioxide quantum dots obtained in the third step into an acetic acid solution with the molar concentration of 0.8 mol/L, soaking for 8 hours at room temperature, then performing centrifugal separation, washing the solid phase with absolute ethyl alcohol and deionized water in sequence, and drying at the constant temperature of 70 ℃ for 12 hours to obtain the catalyst for photolysis of water to generate oxygen.
H prepared in example 2.23WO3A high resolution transmission electron micrograph of the quantum dots is shown in fig. 7. As can be seen from FIG. 7, the catalyst for oxygen generation by photolysis of water prepared in the embodiment 2 is a quantum dot with a diameter of 3-7 nm.
Example 3: the preparation method of the catalyst for oxygen production by photolysis of water in the embodiment comprises the following steps:
firstly, preparing a mixed solution: dissolving 0.36g of tungsten chloride in 15mL of deionized water to obtain a tungsten chloride solution; dissolving 0.17g of catechol in 20mL of ethanol to prepare a catechol solution; mixing the tungsten chloride solution and the catechol solution, stirring at room temperature for 10min, adding 0.09g of urea, and stirring for 30min to obtain a mixed solution;
secondly, preparing a hydrated tungsten trioxide block: transferring the mixed solution into a 50 ml polytetrafluoroethylene high-pressure autoclave, and putting the polytetrafluoroethylene high-pressure autoclave into an electric heating constant-temperature air blowing drying oven at the temperature of 160 ℃ for keeping for 13 hours; centrifuging the reacted solution, washing the solid phase with absolute ethyl alcohol and distilled water in sequence, and drying at 90 ℃ for 12 hours to obtain a hydrated tungsten trioxide block;
thirdly, preparing hydrated tungsten trioxide quantum dots: placing 0.3g of hydrated tungsten trioxide block in a heating furnace in a nitrogen atmosphere, heating, injecting 5mL of octylamine when the temperature reaches 200 ℃, and reacting for 8min at the temperature to perform nitridation treatment; then adding 40 ml of ethanol to obtain light blue quantum dots, performing centrifugal separation, collecting the quantum dots on the lower layer, and sequentially washing the collected quantum dots with absolute ethyl alcohol and distilled water to obtain hydrated tungsten trioxide quantum dots;
fourthly, adding the hydrated tungsten trioxide quantum dots obtained in the third step into an acetone solution with the molar concentration of 0.5 mol/L, soaking for 5 hours at room temperature, then performing centrifugal separation, washing the solid phase with absolute ethyl alcohol and deionized water in sequence, and drying at the constant temperature of 70 ℃ for 12 hours to obtain the catalyst for photolysis of water to prepare oxygen.
H prepared in example 3.23WO3A high resolution transmission electron micrograph of the quantum dots is shown in fig. 8. As can be seen from FIG. 8, the catalyst for oxygen generation by photolysis of water prepared in this example 3 is a quantum dot with a diameter of 3-7 nm.
Example 4: the preparation method of the catalyst for oxygen production by photolysis of water in the embodiment comprises the following steps:
firstly, preparing a mixed solution: dissolving 0.36g of tungsten chloride in 15mL of deionized water to obtain a tungsten chloride solution; dissolving 0.17g of resorcinol in 20mL of ethanol to prepare a resorcinol solution; mixing a tungsten chloride solution and a resorcinol solution, stirring at room temperature for 10min, then adding 0.11g of thiourea, and stirring for 30min to obtain a mixed solution;
secondly, preparing a hydrated tungsten trioxide block: transferring the mixed solution into a 50 ml polytetrafluoroethylene high-pressure autoclave, and putting the polytetrafluoroethylene high-pressure autoclave into an electric heating constant-temperature air blowing drying oven with the temperature of 180 ℃ for 12 hours; centrifuging the reacted solution, washing the solid phase with absolute ethyl alcohol and distilled water in sequence, and drying at 90 ℃ for 12 hours to obtain a hydrated tungsten trioxide block;
thirdly, preparing hydrated tungsten trioxide quantum dots: placing 0.4g of hydrated tungsten trioxide block in a heating furnace in a nitrogen atmosphere, heating, injecting 6mL of octylamine when the temperature reaches 220 ℃, and reacting for 5min at the temperature to perform nitridation treatment; then adding 50 ml of ethanol to generate light blue quantum dots, performing centrifugal separation, collecting the quantum dots on the lower layer, and sequentially washing the collected quantum dots with absolute ethyl alcohol and distilled water to obtain hydrated tungsten trioxide quantum dots;
fourthly, adding the hydrated tungsten trioxide quantum dots obtained in the third step into a hydrogen peroxide solution with the molar concentration of 0.6 mol/L, soaking for 6 hours at room temperature, then performing centrifugal separation, washing the solid phase with absolute ethyl alcohol and deionized water in sequence, and drying at the constant temperature of 70 ℃ for 12 hours to obtain the catalyst for preparing oxygen by photolyzing water.
H prepared in example 4.23WO3A high resolution transmission electron micrograph of the quantum dots is shown in fig. 9. As can be seen from FIG. 9, the catalyst for oxygen generation by photolysis of water prepared in the embodiment 4 is quantum dots with diameters of 3-7 nm.
The catalysts prepared in examples 1, 2, 3 and 4 for photolytic water oxygen production were used for photolytic water oxygen production, respectively, and the photolytic water oxygen production test was performed in a top-illuminated quartz flat-bottomed vessel (500mL) connected to a closed gas circulation system. First, 50mg of the catalyst powder for photolysis of water for oxygen production was dispersed in 100mL of a silver nitrate solution having a concentration of 10 mM. Triggering a photocatalytic reaction by taking a 300W xenon arc lamp as a visible light source; oxygen production was measured by an on-line gas chromatograph with model number SP7800 of Ar carrier for 24 hours, and the obtained oxygen production by photolysis of water is shown in fig. 10.
The photolytic water oxygen production of the catalyst for photolytic water oxygen production prepared in example 1 is shown in fig. 10A, and it can be seen from fig. 10A that the catalyst for photolytic water oxygen production prepared in example 1 has an oxygen production amount of up to 79 μmol/g per hour under the irradiation of simulated solar light, and the stable oxygen production does not significantly decrease within 24 hours.
The photolytic water oxygen production of the catalyst for photolytic water oxygen production prepared in example 2 is shown in fig. 10B, and it can be seen from fig. 10B that the catalyst for photolytic water oxygen production prepared in example 2 has an oxygen production amount of up to 68 μm/g per hour under the irradiation of simulated sunlight, and the stable oxygen production does not significantly decrease within 24 hours.
The photolytic water oxygen production of the catalyst for photolytic water oxygen production prepared in example 3 is shown in fig. 10C, and it can be seen from fig. 10C that the catalyst for photolytic water oxygen production prepared in example 3 has an oxygen production amount of up to 75 μm/g per hour under the irradiation of simulated solar light, and the stable oxygen production does not significantly decrease within 24 hours.
The photolytic water oxygen production of the catalyst for photolytic water oxygen production prepared in example 4 is shown in fig. 10D, and it can be seen from fig. 10D that the catalyst for photolytic water oxygen production prepared in example 4 has an oxygen production amount of up to 72 μm/g per hour under the irradiation of simulated solar light, and the stable oxygen production does not significantly decrease within 24 hours.
The catalysts for the oxygen production by photolysis of water prepared in examples 1, 2, 3 and 4 all have good stability.

Claims (9)

1. A catalyst for preparing oxygen by photolyzing water features that said catalyst is H.23WO3And (4) quantum dots.
2. The catalyst of claim 1, wherein H is H.23WO3The particle size of the quantum dots is 3-7 nanometers.
3. The method for preparing the catalyst for the photolysis of water for the production of oxygen according to claim 1, wherein the method comprises the following steps:
firstly, preparing a mixed solution: dissolving tungsten chloride in deionized water to prepare a tungsten chloride solution, dissolving a phenolic compound in ethanol to prepare a phenolic compound solution, adding the tungsten chloride solution into the phenolic compound solution, stirring for 10-30 min, adding an auxiliary agent, and stirring for 15-35 min to obtain a mixed solution;
secondly, preparing a hydrated tungsten trioxide block: transferring the mixed solution into a polytetrafluoroethylene high-pressure autoclave, and putting the polytetrafluoroethylene high-pressure autoclave into an electric heating constant-temperature blast drying oven with the temperature of 120-180 ℃ for 12-15 hours; centrifuging the reacted solution, sequentially washing the solid phase with absolute ethyl alcohol and distilled water, and drying to obtain a hydrated tungsten trioxide block;
thirdly, preparing hydrated tungsten trioxide quantum dots: heating the hydrated tungsten trioxide block in a heating furnace in a nitrogen atmosphere, injecting octylamine when the temperature reaches 160-190 ℃, and reacting for 5-10 min at the temperature to perform nitridation treatment; adding ethanol to generate light blue quantum dots, performing centrifugal separation, collecting the quantum dots on the lower layer, and sequentially washing the collected quantum dots with absolute ethyl alcohol and distilled water to obtain hydrated tungsten trioxide quantum dots;
fourthly, adding the hydrated tungsten trioxide quantum dots obtained in the third step into an etching agent solution with the molar concentration of 0.5-1.0 mol/L, and soaking for 4-8 hours at room temperature; and then centrifugally separating, washing the solid phase with absolute ethyl alcohol and deionized water in sequence, and drying 12 to obtain the catalyst for photolyzing water to prepare oxygen.
4. The method of claim 3, wherein the molar ratio of the tungsten chloride, the phenolic compound and the adjuvant in the first step is 1: (1.5-1.8): (1.4-1.7).
5. The method for preparing the catalyst for the photolysis of water for the production of oxygen according to claim 3 or 4, wherein in the first step, the phenolic compound is phenol, hydroquinone, resorcinol or catechol.
6. The method for preparing the catalyst for oxygen production by photolysis of water according to claim 3 or 4, wherein in the first step, the auxiliary agent is citric acid, sodium citrate, urea or thiourea.
7. The method for preparing the catalyst for oxygen production by photolysis of water according to claim 3 or 4, wherein in the third step, the ratio of the mass of the hydrated tungsten trioxide block to the volume of the octylamine is 1g (7.5-60) mL.
8. The method for preparing the catalyst for the oxygen production by photolysis of water according to claim 3 or 4, wherein the ratio of the mass of the hydrated tungsten trioxide block to the volume of the ethanol in the third step is 1g: (100-250) mL.
9. The method as claimed in claim 3 or 4, wherein the etchant is ammonium bifluoride, acetic acid, acetone or hydrogen peroxide.
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