CN108993468B - Hollow spherical photocatalyst, preparation method and application thereof - Google Patents

Hollow spherical photocatalyst, preparation method and application thereof Download PDF

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CN108993468B
CN108993468B CN201810757299.3A CN201810757299A CN108993468B CN 108993468 B CN108993468 B CN 108993468B CN 201810757299 A CN201810757299 A CN 201810757299A CN 108993468 B CN108993468 B CN 108993468B
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hollow spherical
photocatalyst
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徐晓翔
位顺航
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
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    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

本发明涉及一种中空球形光催化剂及其制备方法及其应用，该光催化剂为呈中空球形的钛酸锌，制备时，通过氨化模板，提高模板的配位能力，成功制备了多孔中空球形钛酸锌，并且可以在壳的内外成功修饰助催化剂，在光催化产氢速率上得到较大提高，促进了该结构光催化剂催化水分解的速率。与现有技术相比，本发明中空结构可以使还原类助催化剂和氧化类助催化剂分别修饰在催化剂材料的内外表面上，有助于光激电子空穴定向流动，降低复合几率，从而提高光催化水分解效率。

Figure 201810757299

The invention relates to a hollow spherical photocatalyst and a preparation method and application thereof. The photocatalyst is a hollow spherical zinc titanate. During preparation, the template is aminated to improve the coordination ability of the template, and the porous hollow spherical photocatalyst is successfully prepared. Zinc titanate, and the cocatalyst can be successfully modified inside and outside the shell, the photocatalytic hydrogen production rate is greatly improved, and the rate of the photocatalyst catalyzed water splitting is promoted. Compared with the prior art, the hollow structure of the present invention can make reduction-type co-catalysts and oxidation-type co-catalysts respectively decorate on the inner and outer surfaces of the catalyst material, which is conducive to the directional flow of photo-excited electron holes, reduces the recombination probability, and thus improves the photoelectric effect. Catalytic water splitting efficiency.

Figure 201810757299

Description

Hollow spherical photocatalyst, preparation method and application thereof
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a hollow spherical photocatalyst, a preparation method and application thereof.
Background
With the development of society, the problem of environmental pollution caused by energy crisis and fossil energy combustion is becoming more serious, and the search for new renewable energy becomes an urgent need. Hydrogen energy has a high combustion value and the combustion product is water, which is an excellent alternative energy source. At present, the hydrogen production mode adopted by the industry is petroleum heat cracking or natural gas hydrogen production, and a large amount of non-renewable fossil energy is still needed and causes the problem of environmental pollution. The photocatalytic water splitting hydrogen production technology becomes an effective way for solving energy and environmental problems due to the characteristics of high efficiency and environmental protection, so the application of the material is directly influenced by the advantages and disadvantages of the performance of the semiconductor catalyst for photocatalytic water splitting.
Recent researches show that the hollow structure can effectively improve the photocatalytic water decomposition rate of the catalyst, and a reduction promoter (platinum, palladium and the like) and an oxidation promoter (rhodium oxide, cobalt oxide and the like) can be respectively modified on the inner surface and the outer surface of the catalyst, so that the directional flow of a light-induced electron hole is facilitated, and the recombination probability is reduced.
For example: a problem group is avoided, a novel and simple template method is adopted to prepare a Ta3N5 photocatalyst with a core-shell structure, a platinum nano cluster is modified inside a shell, and iridium oxide or cobalt oxide is modified outside the shell, so that the water decomposition activity is enhanced, see ANGEW CHEM INT EDIT, 2013, 52, 11252-11256 pages; manganese oxide and cobalt phosphide are respectively modified on the inner surface and the outer surface of a CdS spherical shell by the Zhang Jinlong topic group, so that the hydrogen production performance and the photocatalytic activity for degrading rhodamine B are improved, see ADV FUNCT MATER, 2017, 27, page 1702624. Platinum and manganese oxide are respectively modified on the inner surface and the outer surface of a titanium dioxide shell by the Jingulong project group, so that the photocatalytic oxidation water activity is improved, see CHEM SCI, 2016, 7, 890-895.
However, the hollow spherical catalyst with the co-catalyst modified inside and outside prepared by the template method is only suitable for binary materials, and the main reason is that the template has different adsorption capacities for metal ions in a multi-element compound, so that the metal ions cannot be adsorbed on the template according to molar proportions, and synthesis failure is caused, thereby greatly limiting the selectivity of the photocatalyst types. Therefore, the adsorption capacity of the template is improved, and the structure can be popularized to more multi-element materials.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a hollow spherical photocatalyst with high hydrogen production rate, a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme: the hollow spherical photocatalyst is hollow spherical zinc titanate. The hollow structure can enable the reduction type cocatalyst and the oxidation type cocatalyst to be respectively modified on the inner surface and the outer surface of the catalyst material, so that the directional flow of a light-excited electron hole is facilitated, the recombination probability is reduced, and the photocatalytic water decomposition efficiency is improved.
Preferably, the inside surface or/and the outside surface of the hollow spherical zinc titanate is/are modified with a cocatalyst, wherein the cocatalyst modified on the inside surface is platinum, and the cocatalyst modified on the outside surface is rhodium oxide. Namely, the hollow spherical catalyst of the present invention comprises four forms: pure zinc titanate, zinc titanate with only platinum modified on the inside, zinc titanate with only rhodium oxide modified on the outside, and zinc titanate with platinum modified on the inside and rhodium oxide modified on the outside. Platinum is favorable for collecting electrons as a reduction promoter, rhodium oxide is favorable for collecting holes as an oxidation promoter, and separation modification of the promoters greatly promotes the flow of electron holes to different directions and reduces the recombination rate. The hydrogen production rate also corresponds to that: the hydrogen production performance of the zinc titanate of the internal and external modified cocatalyst is superior to that of single-side modified zinc titanate, and the single-side modified zinc titanate is superior to that of pure zinc titanate.
A preparation method of the hollow spherical photocatalyst comprises the following steps:
(1) placing the carbon spheres in an ammonia atmosphere, and performing high-temperature treatment to obtain ammoniated carbon spheres;
(2) dissolving zinc acetate dihydrate in N, N-dimethylformamide, stirring, then adding tetrabutyl titanate and absolute ethyl alcohol, and stirring until a transparent solution is obtained;
(3) and (3) soaking the aminated carbon sphere obtained in the step (1) in the transparent solution obtained in the step (2), performing ultrasonic treatment, then stirring, centrifuging, cleaning, drying and calcining to obtain the hollow spherical photocatalyst.
Preferably, the temperature of the high-temperature treatment of the carbon spheres in the ammonia atmosphere is not less than 300 ℃, and the time is 2-5 h. After the carbon spheres are subjected to anhua reaction, amino groups are formed on the surfaces of the carbon spheres, the coordination capacity of the amino groups is higher than that of carboxyl groups, and the carboxyl groups on the carbon spheres are substituted by the amino groups through ammoniation, so that the coordination capacity is improved
Preferably, chloroplatinic acid is dropwise added on the surface of the ammoniated carbon sphere, and then the mixture is dried and treated at a high temperature of more than or equal to 300 ℃ for 2-5 hours in an ammonia atmosphere, so that the hollow spherical photocatalyst with the cocatalyst modified on the inner surface is finally obtained.
Meanwhile, if rhodium trichloride is dripped on the outer surface of the hollow spherical photocatalyst of which the inner side surface is modified with the cocatalyst, the hollow spherical photocatalyst of which the inner side surface and the outer side surface are modified with the cocatalyst is obtained by drying and then carrying out high-temperature treatment at the temperature of more than or equal to 250 ℃ for 2-5 hours.
And (3) if rhodium trichloride is dripped on the outer surface of the hollow spherical photocatalyst of pure zinc titanate, drying, and then carrying out high-temperature treatment at the temperature of more than or equal to 250 ℃ for 2-5 h to finally obtain the hollow spherical photocatalyst with the outer surface modified with the cocatalyst.
The molar ratio of the zinc acetate dihydrate to tetrabutyl titanate is 1: 1.
And (3) carrying out ultrasonic treatment for 20-50 min, wherein the calcination sequentially comprises two stages of air atmosphere calcination and ammonia atmosphere calcination, the temperature of the air atmosphere calcination is 450-550 ℃, the calcination time is 3-6 h, the temperature of the ammonia atmosphere calcination is 600-650 ℃, and the calcination time is 2-3 h. The un-ammoniated sample has only ultraviolet light catalytic hydrogen production performance, and after 600-degree ammoniation treatment, the sample has visible light photocatalytic hydrogen production performance.
The application of the hollow spherical photocatalyst is used for preparing hydrogen by water photocatalysis, and sodium sulfite is used as a sacrificial agent. Under the irradiation of light, photoexcited electrons and holes are generated, the holes are consumed by the sacrificial agent, and the electrons reduce water to generate hydrogen.
Compared with the prior art, the invention has the beneficial effects that: the ammoniation of the carbon spheres improves the coordination capacity of the carbon spheres, increases the adsorption capacity to zinc ions, and prepares pure-phase zinc titanate ZnTiO3The hollow structure of the internally and externally modified cocatalyst is favorably expanded to other series of multi-component compounds, the photocatalytic hydrogen production rate is greatly improved, and the application of the photocatalytic material with the structure is promoted.
Drawings
FIG. 1 is an XRD pattern of the product of example 1;
FIG. 2 is an XRD pattern of the product of example 2;
FIG. 3 is an XRD pattern of the product of example 3;
FIG. 4 is a SEM image of a product of example 1;
FIG. 5 is a SEM image of a product of example 2;
FIG. 6 is a TEM image of the product of example 2;
FIG. 7 is a SEM image of a product obtained in example 3;
FIG. 8 is a high resolution TEM image of the product of example 5;
FIG. 9 is a graph of the photocatalytic hydrogen production rate by visible light (λ ≥ 400nm) for the products of examples 2-5;
FIG. 10 is a graph of the photocatalytic hydrogen production rate of the mercury lamp of example 1 and example 7 by means of total spectrum.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
Adding 6g of glucose into 60ml of water, carrying out hydrothermal reaction for 24 hours at 180 ℃, cleaning and drying to obtain the conventional carbon spheres. The obtained conventional carbon spheres were treated at 300 ℃ for 2 hours under an ammonia atmosphere. Zinc acetate dihydrate (0.2217g, AR) was dissolved in N, N-dimethylformamide (50ml, AR), after stirring for several minutes, tetrabutyl titanate (0.3438g, 99%) and absolute ethanol (50ml, AR) were added, the solution became transparent after stirring for several hours, then the above-mentioned aminated carbon spheres (0.35g) were added to the transparent solution, dispersed by ultrasound for about half an hour, after stirring for several hours, centrifuged and washed once with absolute ethanol, and dried at about 80 ℃. Then calcined at 500 ℃ for 5 hours to give a white sample.
The XRD test and the electron microscope scan of the sample were carried out, and the results are shown in fig. 1 and fig. 4, respectively, from which we can see that the sample is pure phase zinc titanate and has a spherical structure.
Example 2
Adding 6g of glucose into 60ml of water, carrying out hydrothermal reaction for 24 hours at 180 ℃, cleaning and drying to obtain the conventional carbon spheres. The obtained conventional carbon spheres were treated at 300 ℃ for 5 hours under an ammonia atmosphere. Zinc acetate dihydrate (0.2217g, AR) was dissolved in N, N-dimethylformamide (50ml, AR), after stirring for several minutes, tetrabutyl titanate (0.3438g, 99%) and absolute ethanol (50ml, AR) were added, the solution became transparent after stirring for several hours, then the above-mentioned aminated carbon spheres (0.35g) were added to the transparent solution, dispersed by ultrasound for about half an hour, after stirring for several hours, centrifuged and washed once with absolute ethanol, and dried at about 80 ℃. Then calcined at 500 ℃ for 5 hours. The obtained sample was calcined at 600 ℃ for 2 hours in an ammonia atmosphere to obtain a yellow sample.
The XRD test, the electron microscope scanning and the transmission electron microscope scanning are carried out on the sample, the obtained results are respectively shown in figure 2, figure 5 and figure 6, and the sample is pure-phase zinc titanate and has a hollow spherical structure.
Example 3
Adding 6g of glucose into 60ml of water, carrying out hydrothermal reaction for 24 hours at 180 ℃, cleaning and drying to obtain the conventional carbon spheres. The obtained conventional carbon spheres were treated at 300 ℃ for 3 hours under an ammonia atmosphere. And adding 0.35g of the aminated carbon ball into 500 mul of chloroplatinic acid solution (1mg/ml) and 4ml of deionized water, drying after ultrasonic dispersion, and calcining for 2 hours at 300 ℃ in an ammonia atmosphere to obtain the aminated carbon ball deposited with the Pt nanocluster. Zinc acetate dihydrate (0.2217g, AR) was dissolved in N, N-dimethylformamide (50ml, AR), after stirring for several minutes, tetrabutyl titanate (0.3438g, 99%) and absolute ethanol (50ml, AR) were added, the solution became transparent after stirring for several hours, then the above-mentioned aminated carbon spheres with deposited Pt nanoclusters were added to the transparent solution, dispersed by ultrasound for about half an hour, after stirring for several hours, centrifuged and washed once with absolute ethanol, and dried at about 80 ℃. Then calcined at 500 ℃ for 5 hours. And calcining the obtained sample at 600 ℃ for 2 hours in an ammonia atmosphere to obtain a yellow sample internally deposited with the cocatalyst.
The XRD test and the electron microscope scan were performed on the sample, and the results are shown in fig. 3 and fig. 7, respectively, from which we can see that the sample has a spherical structure.
Example 4
Adding 6g of glucose into 60ml of water, carrying out hydrothermal reaction for 24 hours at 180 ℃, cleaning and drying to obtain the conventional carbon spheres. The obtained conventional carbon spheres were treated at 300 ℃ for 3 hours under an ammonia atmosphere. Zinc acetate dihydrate (0.2217g, AR) was dissolved in N, N-dimethylformamide (50ml, AR), after stirring for several minutes, tetrabutyl titanate (0.3438g, 99%) and absolute ethanol (50ml, AR) were added, the solution became transparent after stirring for several hours, then the above-mentioned aminated carbon spheres (0.35g) were added to the transparent solution, dispersed by ultrasound for about half an hour, after stirring for several hours, centrifuged and washed once with absolute ethanol, and dried at about 80 ℃. Then calcined at 500 ℃ for 5 hours. The obtained sample was calcined at 600 ℃ for 2 hours in an ammonia atmosphere to obtain a yellow sample. 1ml of rhodium trichloride solution (1mg/ml) was added to the obtained yellow sample, and after ultrasonic dispersion and drying, heating was carried out at 250 ℃ for two hours to obtain a yellow sample with an external deposited cocatalyst.
Example 5
Adding 6g of glucose into 60ml of water, carrying out hydrothermal reaction for 24 hours at 180 ℃, cleaning and drying to obtain the conventional carbon spheres. The obtained conventional carbon spheres were treated at 300 ℃ for 3 hours under an ammonia atmosphere. And adding 0.35g of the aminated carbon ball into 500 mul of chloroplatinic acid solution (1mg/ml) and 4ml of deionized water, drying after ultrasonic dispersion, and calcining for 1 hour at 300 ℃ in an ammonia atmosphere to obtain the aminated carbon ball deposited with the Pt nanocluster. Zinc acetate dihydrate (0.2217g, AR) was dissolved in N, N-dimethylformamide (50ml, AR), after stirring for several minutes, tetrabutyl titanate (0.3438g, 99%) and absolute ethanol (50ml, AR) were added, the solution became transparent after stirring for several hours, then the above-mentioned aminated carbon spheres with deposited Pt nanoclusters were added to the transparent solution, dispersed by ultrasound for about half an hour, after stirring for several hours, centrifuged and washed once with absolute ethanol, and dried at about 80 ℃. Then calcined at 500 ℃ for 5 hours. The obtained sample was calcined at 600 ℃ for 2 hours in an ammonia atmosphere to obtain a yellow sample. 1ml of rhodium trichloride solution (1mg/ml) was added to the obtained yellow sample, and after ultrasonic dispersion and drying, the mixture was heated at 250 ℃ for two hours to obtain yellow samples of the internal and external deposition promoters.
The sample is scanned by a high-resolution transmission electron microscope, the obtained results are respectively shown in fig. 8, and we can see that the inside and the outside of the hollow spherical shell are both beneficial to catalyst modification.
The samples obtained in the embodiments 2 to 5 are applied to photocatalytic water decomposition to prepare hydrogen, and the reaction conditions are as follows: the 10mg sample is added into 100mL water, sodium sulfite is used as a sacrificial agent, and the hydrogen production rate is researched under the illumination of visible light, and the obtained result is shown in figure 9, and it can be seen from the figure that the hydrogen production rate of the inside and outside modified cocatalyst zinc titanate is superior to that of the single-side modified zinc titanate, and the single-side modified zinc titanate is superior to that of the unmodified zinc titanate.
Comparative example 1
Preparation of non-spherical zinc titanate: zinc acetate dihydrate (0.2217g, AR) was dissolved in N, N-dimethylformamide (50ml, AR), stirred for several minutes, then tetrabutyl titanate (0.3438g, 99%) and absolute ethanol (50ml, AR) were added, stirred for several hours, the solution became transparent, stirred and dried, then calcined at 500 ℃ for 5 hours, and washed with dilute hydrochloric acid to give a white sample. The samples obtained in example 1 and example 7 were applied to photocatalytic water splitting for hydrogen production under the following reaction conditions: the result of the study on the hydrogen production rate under the full spectrum irradiation of the mercury lamp by adding 10mg of the sample into 100mL of water and using sodium sulfite as a sacrificial agent is shown in FIG. 10, and it can be seen from the figure that the hydrogen production rate of the spherical zinc titanate is far superior to that of the non-spherical zinc titanate.
Example 6
Adding 6g of glucose into 60ml of water, carrying out hydrothermal reaction for 24 hours at 180 ℃, cleaning and drying to obtain the conventional carbon spheres. The obtained conventional carbon spheres were treated at 300 ℃ for 3 hours under an ammonia atmosphere. And adding 0.35g of the aminated carbon ball into 1ml of chloroplatinic acid solution (1mg/ml) and 4ml of deionized water, drying after ultrasonic dispersion, and calcining for 1 hour at 300 ℃ in an ammonia atmosphere to obtain the aminated carbon ball deposited with the Pt nanocluster. Zinc acetate dihydrate (0.2217g, AR) was dissolved in N, N-dimethylformamide (50ml, AR), after stirring for several minutes, tetrabutyl titanate (0.3438g, 99%) and absolute ethanol (50ml, AR) were added, the solution became transparent after stirring for several hours, then the above-mentioned aminated carbon spheres with deposited Pt nanoclusters were added to the transparent solution, dispersed by ultrasound for about half an hour, after stirring for several hours, centrifuged and washed once with absolute ethanol, and dried at about 80 ℃. Then calcined at 500 ℃ for 5 hours. The obtained sample was calcined at 600 ℃ for 2 hours in an ammonia atmosphere to obtain a yellow sample. 1ml of rhodium trichloride solution (1mg/ml) was added to the obtained yellow sample, and after ultrasonic dispersion and drying, the mixture was heated at 300 ℃ for two hours to obtain yellow samples of the internal and external deposition promoters.

Claims (8)

1.一种中空球形光催化剂的制备方法，其特征在于，包括以下步骤：1. a preparation method of a hollow spherical photocatalyst, is characterized in that, comprises the following steps: （1）将碳球置于氨气氛围内，高温处理，得到氨化碳球；所述碳球在氨气氛围中高温处理的温度为≥300℃，时间为2~5 h；(1) The carbon spheres are placed in an ammonia gas atmosphere and treated at high temperature to obtain ammoniated carbon spheres; the temperature of the high temperature treatment of the carbon spheres in the ammonia gas atmosphere is ≥300°C, and the time is 2-5 h; （2）将乙酸锌二水合物溶解于N, N-二甲基甲酰胺，搅拌，然后加入钛酸四丁酯和无水乙醇，搅拌直至得到透明溶液；所述乙酸锌二水合物与钛酸四丁酯的摩尔比为1:1；(2) Dissolving zinc acetate dihydrate in N, N-dimethylformamide, stirring, then adding tetrabutyl titanate and absolute ethanol, stirring until a transparent solution is obtained; the zinc acetate dihydrate and titanium The molar ratio of tetrabutyl acid is 1:1; （3）将步骤（1）所得氨化碳球浸渍在步骤（2）所得透明溶液中，超声，然后搅拌，离心、清洗、干燥后进行煅烧，即得呈中空球形的钛酸锌。(3) The ammoniated carbon spheres obtained in step (1) are immersed in the transparent solution obtained in step (2), sonicated, then stirred, centrifuged, washed, dried, and then calcined to obtain hollow spherical zinc titanate. 2.根据权利要求1所述的一种中空球形光催化剂的制备方法，其特征在于，在所述氨化碳球表面滴加氯铂酸，滴加后，干燥，再在氨气氛围内经≥300℃的温度高温处理2~5 h，最终得到内侧表面修饰有助催化剂的中空球形光催化剂。2. The preparation method of a hollow spherical photocatalyst according to claim 1, wherein chloroplatinic acid is added dropwise on the surface of the ammoniated carbon sphere, and after the dropwise addition, drying is carried out, and then in an ammonia atmosphere, after ≥ After high temperature treatment at 300 °C for 2 to 5 h, a hollow spherical photocatalyst with a cocatalyst modified on the inner surface was finally obtained. 3.根据权利要求2所述的一种中空球形光催化剂的制备方法，其特征在于，在所述内侧表面修饰有助催化剂的中空球形光催化剂外表面滴加三氯化铑，烘干后，再经≥250℃的温度高温处理2~5 h，最终得到内侧表面和外侧表面均修饰有助催化剂的中空球形光催化剂。3. the preparation method of a kind of hollow spherical photocatalyst according to claim 2, is characterized in that, on the outer surface of the hollow spherical photocatalyst that described inner surface is decorated with promoter, drip rhodium trichloride, after drying, After high temperature treatment at a temperature of ≥250 °C for 2 to 5 h, a hollow spherical photocatalyst with cocatalysts decorated on both the inner and outer surfaces was finally obtained. 4.根据权利要求1所述的一种中空球形光催化剂的制备方法，其特征在于，在所述中空球形光催化剂外表面滴加三氯化铑，烘干后，再经≥250℃的温度高温处理2~5 h，最终得到外侧表面修饰有助催化剂的中空球形光催化剂。4. the preparation method of a kind of hollow spherical photocatalyst according to claim 1, it is characterized in that, drip rhodium trichloride on the outer surface of described hollow spherical photocatalyst, after drying, then through the temperature of ≥ 250 ℃ After high-temperature treatment for 2-5 h, the hollow spherical photocatalyst with the outer surface modified with promoter was finally obtained. 5.根据权利要求1所述的一种中空球形光催化剂的制备方法，其特征在于，步骤（3）中所述超声的时间为20~50min，所述煅烧依次包括空气氛围煅烧和氨气氛围煅烧两个阶段，所述空气氛围煅烧的温度为450~550℃，煅烧时间为3~6h，所述氨气氛围煅烧的温度为600~650℃，煅烧时间为2~3h。5 . The method for preparing a hollow spherical photocatalyst according to claim 1 , wherein the ultrasonic time in step (3) is 20 to 50 min, and the calcination sequentially includes calcination in an air atmosphere and an atmosphere in ammonia gas. 6 . There are two stages of calcination, the temperature of the air atmosphere calcination is 450~550°C, and the calcination time is 3~6h, the temperature of the ammonia gas atmosphere calcination is 600~650°C, and the calcination time is 2~3h. 6.一种如权利要求1-5任一项所述方法制备的中空球形光催化剂。6. A hollow spherical photocatalyst prepared by the method of any one of claims 1-5. 7.根据权利要求6所述的一种中空球形光催化剂，其特征在于，所述中空球形的钛酸锌的内侧表面或/和外侧表面修饰有助催化剂，其中，内侧表面修饰的助催化剂为铂，外侧修饰的助催化剂为氧化铑。7 . The hollow spherical photocatalyst according to claim 6 , wherein the inner surface or/and the outer surface of the hollow spherical zinc titanate is modified with a promoter, wherein the promoter modified on the inner surface is Platinum, the externally modified cocatalyst is rhodium oxide. 8.一种如权利要求6或7所述中空球形光催化剂的应用，其特征在于，该催化剂用于水的光催化制备氢气，使用时，以亚硫酸钠为牺牲剂。8. An application of the hollow spherical photocatalyst according to claim 6 or 7, wherein the catalyst is used for the photocatalysis of water to prepare hydrogen, and when used, sodium sulfite is used as a sacrificial agent.
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