CN113737281A - Oxide spherical photonic crystal with inverse opal structure, simple preparation method and application thereof - Google Patents
Oxide spherical photonic crystal with inverse opal structure, simple preparation method and application thereof Download PDFInfo
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
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- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 239000004793 Polystyrene Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 3
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- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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Abstract
The invention relates to an oxide spherical photonic crystal with an inverse opal structure, a simple preparation method and application thereof, wherein the simple preparation method comprises the following steps: 1) preparing a monodisperse negatively charged template solution; 2) preparing the spherical photonic crystal of the oxide with the inverse opal structure. According to the invention, a continuous water phase emulsion is formed by adopting an injector, spherical liquid drops with small-size water-in-oil structures are obtained by collecting the shearing force of oil, the subsequent rotation can prevent the liquid drops from being fused again, the rotation speed is regulated and controlled to control the evaporation speed of water so as to regulate and control the hydrolysis degree of a precursor, and meanwhile, the photonic crystal microspheres are obtained by means of the capillary force of high-molecular globules in the water phase.
Description
Technical Field
The invention relates to the technical field of green energy material manufacturing, in particular to an oxide spherical photonic crystal with an inverse opal structure, a simple preparation method and application thereof.
Background
Photonic crystals are a class of artificially designed and fabricated crystals that have a periodic dielectric structure on an optical scale, and have the property of a photonic band gap that prohibits the propagation of certain specific frequencies of incident light within the photonic crystal structure. If the frequency of the incident light falls within the photonic band gap, the incident light is strictly forbidden to propagate in the photonic crystal structure, i.e. the reflectivity of the photonic crystal structure can be as high as 100%, and the incident light in the pass band can propagate almost without loss. Photonic band gaps have been shown spectrally to show strong reflection of incident light in a certain wavelength band by photonic crystals, with photons at the edges of the band gap, i.e. the edges of the reflection peak, having very low group velocities, so-called slow photons. The reflection of the incident light by the photonic crystal structure follows the Bragg diffraction law, and the slow photon effect can be researched by adjusting parameters such as the aperture size, the incident light angle, the filling rate and the refractive index of the filler of the photonic crystal structure according to the Bragg equation shown below.
The inverse protein structure is a typical photonic crystal, has the characteristics of easy adjustment of the pore size, the filling rate and the refractive index of a filler, and has the advantages of ordered structure height, adjustable size, adjustable pore size, large specific surface area and the like. However, the general powder or film product can only show slow photon effect at a specific angle due to the change of the incident angle in the catalytic process, namely, has angle dependence, thereby limiting the development. The spherical photonic crystal has a full-symmetrical structure and is not influenced by the incident light angle, so that the spherical photonic crystal has more stable performance.
At present, the method for preparing the spherical inverse opal structure photonic crystal comprises the following steps: spray drying, electric field driven methods, and microfluidic methods. But the application of the spray drying method is limited due to the use of a micro-jet spray dryer which requires a special instrument; the size obtained by the electric field driving method is in millimeter level, the size cannot be regulated and controlled, and the yield is low; the microfluidic method is seriously dependent on the microfluidic chip, the microfluidic chip made of glass is fragile, microspheres with smaller sizes cannot be obtained due to the limitation of a glass preparation process, the size of the microfluidic chip is limited, the chip made of polydimethylsiloxane is firm and durable, most of organic solvents can be dissolved in polydimethylsiloxane and swell, and small organic analytes with obvious solubility in water can also be dissolved in the polydimethylsiloxane to limit the use of the microfluidic chip.
In addition, the preparation methods of different materials are different due to the characteristics of the materials, and no simple method can prepare spherical photonic crystals of various oxides.
Disclosure of Invention
Aiming at the problems, the oxide spherical photonic crystal with the inverse opal structure can be simply prepared by an emulsion shear polymerization method.
The specific technical scheme is as follows:
the first aspect of the invention provides a simple preparation method of an oxide spherical photonic crystal with an inverse opal structure, which is characterized by comprising the following steps:
1) preparing a monodisperse negatively charged template;
2) preparing an oxide spherical photonic crystal with an inverse opal structure: mixing the template solution, the precursor and ethanol, ultrasonically mixing uniformly, sucking into an injector, mounting the injector on a driver, connecting a guide pipe on a needle head of the injector, inserting the tail end of the guide pipe into the rotating collecting oil, driving the injector by a propeller, injecting the material liquid in the injector into the collecting oil, drying water under continuous stirring, collecting microspheres, and calcining to remove the template to obtain the spherical oxide photonic crystal with the inverse opal structure.
The above simple preparation method is also characterized in that the solid content in the template solution in the step 1) is 5-30%.
The simple preparation method is also characterized in that the volume ratio of the template solution, the precursor and the ethanol in the step (2) is (1-3.3) to (1-3).
The simple preparation method is also characterized in that the feed liquid in the step (2) is propelled at a speed of 0.1-15 mL/h.
The simple preparation method is also characterized in that the viscosity of the collected oil in the step (2) is more than or equal to 10cst, and the rotating speed of the collected oil is 100-6000 r/min.
The simple preparation method is also characterized in that the drying temperature of the oven in the step (2) is 50-55 ℃, the drying time is 12-48h, and the temperature condition of calcination is 550-700 ℃.
The second aspect of the present invention is to provide an inverse opal structured oxide spherical photonic crystal prepared according to the above simple preparation method.
The third aspect of the invention is to provide the application of the oxide spherical photonic crystal with the inverse opal structure in photocatalytic hydrogen production.
It should be noted that, the template in the invention can be a negatively charged polymer bead or a silica microsphere; the precursor is a hydrolyzable substance or a feed liquid containing small-particle oxide prepared from a hydrolyzable salt solution (the solid content is 0.1-3%, for metal salts with harsh hydrolysis conditions, the feed liquid containing small-particle oxide can be prepared as the precursor in the invention).
The template with negative electricity and the hydrolytic particles with the same negative electricity due to partial hydrolysis and alcoholysis repel each other, so that the whole system is in dynamic balance, moisture and ethanol are gradually evaporated along with the proceeding of the drying process, the charges on the surfaces of the template and the precursor are also gradually reduced, at the moment, the system needs to keep the lowest energy, so that the template spheres gradually approach to form a sphere under the action of a capillary suction pipe force, the precursor is further hydrolyzed on the surface of the template spheres to form crystal nuclei in the process and further grows up through the hydrolysis action, and finally the oxide spherical photonic crystal with an inverse opal structure can be obtained after the template spheres are removed through calcination.
The beneficial effect of above-mentioned scheme is:
1) according to the preparation method, a continuous water phase emulsion is formed by adopting an injector, spherical liquid drops with small-size water-in-oil structures are obtained by collecting the shearing force of oil, the liquid drops can be prevented from being fused again by subsequent rotation, the hydrolysis degree of a precursor is regulated and controlled by regulating and controlling the evaporation speed of water and the capillary force of high-molecular small balls in the water phase is used for obtaining the photonic crystal microspheres, and the preparation method is mild in condition, simple to operate and controllable in size;
2) the oxide spherical photonic crystal microsphere with the inverse opal structure prepared by the preparation method has the advantages of full symmetry, ordered arrangement height, good repeatability, adjustable size and high yield;
3) the spherical photonic crystal prepared by the method is of an inverse opal structure, and the structure has the advantages of large specific surface area, more surface active sites and the like, and simultaneously solves the problem that a common photonic crystal material has angle dependence, so that the photocatalytic performance of the material is more stable;
4) the oxide spherical photonic crystal prepared by the method consists of nano-scale oxide particles, has many surface active sites and high photocatalytic performance, and can effectively promote the separation of photon-generated carriers, improve the speed of electron transmission and improve the utilization rate of sunlight;
5) the oxide spherical photonic crystal prepared by the method is suitable for various oxides capable of being hydrolyzed and small-particle oxides capable of being prepared, so that the universality of the method is greatly improved.
Drawings
FIG. 1 is an SEM image of a titanium dioxide spherical photonic crystal provided in example 1 of the present invention;
FIG. 2 is an SEM image of spherical photonic crystals of titanium dioxide provided in example 2 of the present invention;
FIG. 3 is an SEM image of spherical photonic crystals of titanium dioxide provided in example 3 of the present invention;
FIG. 4 is an SEM image of spherical photonic crystals of zinc oxide provided in example 4 of the present invention;
FIG. 5 is a photo-hydrolysis hydrogen production diagram of the titanium dioxide spherical photonic crystal provided by the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The invention is further described with reference to the following drawings and specific examples, which are not intended to be limiting.
Example 1
A titanium dioxide spherical photonic crystal with an inverse opal structure is prepared by the following steps:
1) preparation of monodisperse negatively charged polystyrene beads: dissolving 0.4g of ammonium persulfate, 0.8g of ammonium bicarbonate and 2mL of acrylic acid monomer in 10mL of deionized water, and marking as a solution A; adding 250mL of deionized water, 10mL of styrene and 1mL of methyl methacrylate monomer into a three-neck flask, mixing and stirring, introducing N2Protecting, namely quickly adding the solution A into the mixed solution in the bottle when the temperature of the mixed solution in the bottle rises to 70 ℃, and continuously stirring for 12 hours at 70 ℃ to obtain a template solution containing monodisperse sulfonated polystyrene spheres with the size of 270 nm;
2) preparing a titanium dioxide spherical photonic crystal with an inverse opal structure: mixing 0.8mL of template solution with the solid content of 15%, 150 μ L of titanium precursor (TYZOR LA) and 300 μ L of ethanol, sucking the mixture into an injector after ultrasonic mixing, connecting a conduit on a needle head of the injector, inserting the tail end of the conduit into a beaker filled with silicone oil with the rotating speed of 6000r/min and the viscosity of 10cst, injecting feed liquid into the beaker at the advancing speed of 15mL/h, then placing the beaker in an oil bath kettle at 55 ℃ for 12h, controlling the rotating speed of 6000r/min, washing off the silicone oil on the surface of a sample by using normal hexane, then placing the sample in a muffle furnace to be calcined at 550 ℃ to obtain the titanium dioxide spherical inverse opal structure photonic crystal microspheres.
Example 2
A titanium dioxide spherical photonic crystal with an opal structure is prepared by the following steps:
1) preparation of monodisperse negatively charged polystyrene beads: dissolving 0.4g of ammonium persulfate, 0.8g of ammonium bicarbonate and 2mL of acrylic acid monomer in 10mL of deionized water, and marking as a solution A; adding 250mL of deionized water, 12mL of styrene and 1mL of methyl methacrylate monomer into a three-neck flask, mixing and stirring, introducing N2Protecting, namely quickly adding the solution A into the mixed solution in the bottle when the temperature of the mixed solution in the bottle rises to 70 ℃, and continuously stirring for 12 hours at 70 ℃ to obtain a template solution containing monodisperse sulfonated polystyrene spheres with the size of 420 nm;
2) preparing a titanium dioxide spherical photonic crystal with an opal structure: 1mL of template solution with the solid content of 15%, 100 MuL of titanium precursor and 300 MuL of ethanol are mixed, the mixture is sucked into an injector after being uniformly mixed by ultrasonic waves, then a guide pipe is connected to the needle head of the injector, the tail end of the guide pipe is inserted into a beaker filled with silicone oil with the rotating speed of 100r/min and the viscosity of 30cst, the feed liquid is injected into the beaker at the advancing speed of 5mL/h, then the beaker is placed in an oil bath kettle at the temperature of 60 ℃ for 48h, meanwhile, the silicone oil on the surface of a sample is washed away by normal hexane at the rotating speed of 100r/min, and then the microspheres are placed in a muffle furnace for calcining at the temperature of 600 ℃ to obtain the titanium dioxide spherical inverse opal structure photonic crystal microspheres.
Example 3
A titanium dioxide spherical photonic crystal with an inverse opal structure is prepared by the following steps:
1) preparation of negatively charged SiO2And (3) small ball: mixing 1ml deionized water, 9ml ethanol, 14ml ammonia water, adding 1ml ethyl orthosilicate into the solution, stirring for 2h at room temperature to obtain SiO2 pellet, adding 0.2g SiO2The pellets were dispersed in a feed solution containing 60mL ethanol and 0.5mL trimethylsiloxane. The mixture was stirred vigorously at 80 ℃ for 17 hours, and then washed with ethanol. Then, 40mL of H was added2O2Stirring at room temperature for 3h to obtain a solution containing monodisperse sulfonated silica spheres with a size of 310 nm;
2) preparing a titanium dioxide spherical photonic crystal with an inverse opal structure: 0.9mL of negatively charged silicon dioxide solution with the solid content of 15%, 100 muL of titanium precursor and 300 muL of ethanol are mixed, the mixture is sucked into an injector after being uniformly mixed by ultrasonic waves, then a guide pipe is connected to the needle of the injector, the tail end of the guide pipe is inserted into a beaker filled with silicone oil with the rotating speed of 2000r/min and the viscosity of 100cst, feed liquid is injected into the beaker at the advancing speed of 10mL/h, then the beaker is placed in an oil bath kettle at 70 ℃ for 8h, the rotating speed is controlled to be 5000r/min, silicone oil on the surface of a sample is washed away by normal hexane, microspheres are placed in a muffle furnace to be calcined at 700 ℃, and a silicon dioxide template is removed from the collected microspheres by hydrofluoric acid to obtain the titanium dioxide spherical inverse opal structure photonic crystal microspheres.
Example 4
A zinc oxide spherical photonic crystal with a small-size hierarchical pore structure is prepared by the following steps:
1) preparation of monodisperse negatively charged polystyrene beads: dissolving 0.4g of ammonium persulfate, 0.8g of ammonium bicarbonate and 2mL of acrylic acid monomer in 10mL of deionized water, and marking as a solution A; adding 250mL of deionized water, 11mL of styrene and 1mL of methyl methacrylate monomer into a three-neck flask, mixing and stirring, introducing N2Protecting, namely quickly adding the solution A into the mixed solution in the bottle when the temperature of the mixed solution in the bottle rises to 70 ℃, and continuously stirring for 12 hours at 70 ℃ to obtain a template solution containing monodisperse sulfonated polystyrene spheres with the size of 310 nm;
2) preparing a zinc oxide spherical photonic crystal with a hierarchical pore structure: 1mL of template solution with solid content of 5 percent and 3mL of zinc oxide aqueous solution (the preparation method comprises the steps of dissolving 0.05mol of zinc acetate in 80mL of ethylene glycol, magnetically stirring at room temperature, transferring to a reaction kettle, and reacting at 160 ℃ for 1h) are mixed with 3mL of ethanol, the mixture is sucked into an injector after ultrasonic mixing is uniform, a guide pipe is connected to the needle of the injector, the tail end of the guide pipe is inserted into a beaker filled with silicon oil with the rotating speed of 1000r/min and the viscosity of 50cst, feed liquid is injected into the beaker at the advancing speed of 0.1mL/h, then the beaker is placed in an oil bath kettle at 70 ℃ for 10h, the rotating speed is controlled at 100r/min, the silicon oil on the surface of a sample is washed by n-hexane, and then the microspheres are placed in a muffle furnace and are calcined at 550 ℃ to obtain the zinc oxide spherical inverse opal structure photonic crystal microspheres.
As shown in FIGS. 1-4, the oxide spherical photonic crystal prepared by the simple preparation method provided by the invention has a good integral inverse opal structure and a good spherical structure.
In the invention, 20mg of the titanium dioxide spherical photonic crystal microspheres with the inverse opal structure prepared in the embodiment 1 and the embodiment 3 are respectively placed in deionized water and methanol solution at a ratio of 1:1, and the photolysis hydrogen production reaction is started in a photolysis water reactor under the irradiation of ultraviolet and visible light, and as a result, as shown in fig. 5, it can be seen from fig. 5 that the titanium dioxide spherical photonic crystal microspheres with the inverse opal structure prepared by the invention have high photocatalytic performance, wherein the hydrogen production amount in 5h in the embodiment 3 can reach 85.8mmol/g, and the hydrogen production effect on the water hydrolysis is good.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.
Claims (8)
1. A simple preparation method of an oxide spherical photonic crystal with an inverse opal structure is characterized by comprising the following steps:
1) preparing a monodisperse negatively charged template solution;
2) preparing an oxide spherical photonic crystal with an inverse opal structure: mixing the template solution, the precursor and ethanol, ultrasonically mixing uniformly, sucking into an injector, mounting the injector on a driver, connecting a guide pipe on a needle head of the injector, inserting the tail end of the guide pipe into the rotating collecting oil, driving the injector by a propeller, injecting the material liquid in the injector into the collecting oil, drying water under continuous stirring, collecting microspheres, and calcining to remove the template to obtain the spherical oxide photonic crystal with the inverse opal structure.
2. The simple preparation method according to claim 1, wherein the solid content in the template solution in the step (1) is 5-30%.
3. The simplified preparation method as claimed in claim 1, wherein the volume ratio of the template, the precursor and the ethanol in step (2) is (1-3.3) to (1-3).
4. The simple preparation method according to claim 1, wherein the feed liquid in the step (2) is advanced at a rate of 0.1-15 mL/h.
5. The simple preparation method as claimed in claim 1, wherein the viscosity of the collected oil in step (2) is greater than or equal to 10cst, and the rotation speed of the collected oil is 100-.
6. The simple preparation method as claimed in claim 1, wherein the oven drying temperature in step (2) is 50-55 ℃, the drying time is 12-48h, and the calcination temperature is 550-700 ℃.
7. An inverse opal structured oxide spherical photonic crystal, characterized by being prepared by the simple preparation method according to any one of claims 1 to 6.
8. Use of the inverse opal structured oxide spherical photonic crystal of claim 7 in photocatalytic hydrogen production.
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