CN113737281B - 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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- CN113737281B CN113737281B CN202111009172.1A CN202111009172A CN113737281B CN 113737281 B CN113737281 B CN 113737281B CN 202111009172 A CN202111009172 A CN 202111009172A CN 113737281 B CN113737281 B CN 113737281B
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- 239000004038 photonic crystal Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000004005 microsphere Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000004408 titanium dioxide Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 229920002545 silicone oil Polymers 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000011324 bead Substances 0.000 claims description 9
- 239000011022 opal Substances 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 7
- 230000007062 hydrolysis Effects 0.000 abstract description 6
- 239000008346 aqueous phase Substances 0.000 abstract description 4
- 239000000839 emulsion Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 abstract description 2
- 230000008020 evaporation Effects 0.000 abstract description 2
- 238000010008 shearing Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 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
- 239000013078 crystal Substances 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 238000006303 photolysis reaction Methods 0.000 description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- -1 polydimethylsiloxane Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002149 hierarchical pore Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
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 oxide spherical photonic crystal with inverse opal structure. According to the preparation method, a continuous aqueous phase emulsion is formed by adopting the injector, spherical liquid drops with a small-size water-in-oil structure are obtained by collecting the shearing force of oil liquid, the follow-up rotation can be used for preventing the liquid drops from being recombined, 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 microsphere is obtained by means of the capillary force of the polymer microsphere in the aqueous 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 manufactured crystals with periodic dielectric structures on the optical scale, which have photonic band gap characteristics that prohibit the propagation of certain specific frequencies of incident light in the photonic crystal structure. If the frequency of the incident light falls within the photonic band gap, the incident light is severely inhibited from propagating in the photonic crystal structure, i.e., the photonic crystal structure may have a reflectivity of up to 100% for incident light within the passband, and may propagate with little loss. Photonic bandgaps show a strong reflection of incident light in a certain band by photonic crystals in the upper part of the spectrum, photons at the edges of the bandgap, i.e. at the edges of the reflection peaks, have extremely low group velocities, so-called slow photons. The reflection of incident light by the photonic crystal structure follows the law of bragg diffraction, and the slow photon effect can be studied by adjusting parameters such as the aperture size, the angle of incident light, the filling rate, the refractive index of the filler and the like 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 pore size, filling rate and refractive index of the filler, and has the advantages of ordered structure height, adjustable size, adjustable pore size, large specific surface area and the like. However, the conventional powder or film products have the problem that slow photon effects only occur at specific angles, namely, angle dependence, due to the change of the incident angle in the catalysis process, so that the development of the slow photon effects is limited. The spherical photonic crystal has a fully symmetrical structure, is not influenced by the angle of incident light, and therefore has more stable performance.
At present, the method for preparing the photonic crystal with the spherical inverse opal structure comprises the following steps: spray drying, electric field driving and microfluidics. However, the use of spray-drying methods that require specialized instrumentation for the microfluidic spray-dryer limits its application; the electric field driving method has the advantages that the obtained size is in millimeter level, the size cannot be regulated and controlled, and the yield is low; the microfluidic method relies heavily on a part of a microfluidic chip, the microfluidic chip made of glass is fragile, and due to the limitation of a glass preparation process, microspheres with smaller sizes cannot be obtained, and the size adjustment of the microfluidic chip is limited, and the chip made of polydimethylsiloxane is firm and durable, but most of organic solvents are soluble in polydimethylsiloxane and swell, and small organic analytes with obvious solubility in water are also soluble in polydimethylsiloxane, so that the use of the microfluidic chip is limited.
In addition, due to the characteristics of the materials, the preparation methods of different materials are different, and no simple method can prepare spherical photonic crystals of various oxides.
Disclosure of Invention
In order to solve the problems, the oxide spherical photonic crystal with the inverse opal structure can be simply prepared by using an emulsion shear polymerization method.
The specific technical scheme is as follows:
The first aspect of the present invention is to provide a simple preparation method of an oxide spherical photonic crystal of inverse opal structure, having such characteristics that it comprises the steps of:
1) Preparing a monodisperse negatively charged template;
2) Preparing an oxide spherical photonic crystal with an inverse opal structure: mixing template solution, precursor and ethanol, sucking the mixture into an injector after ultrasonic mixing, mounting the injector on a driver, connecting a catheter on a needle of the injector, inserting the tail end of the catheter into rotating collecting oil, driving the injector by a propeller, injecting feed liquid in the injector into the collecting oil, continuously stirring, drying water, collecting microspheres, calcining to remove the template, and thus obtaining the oxide spherical photonic crystal with inverse opal structure.
The simple preparation method also has the characteristic that the solid content in the template solution in the step 1) is 5-30%.
The simple preparation method also has the characteristic that the volume ratio of the template solution, the precursor and the ethanol in the step (2) is (1-3.3) (1-3).
The simple preparation method also has the characteristic that the feed liquid advancing speed in the step (2) is 0.1-15mL/h.
The simple preparation method also has the characteristics 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 100-6000r/min.
The simple preparation method also has the characteristics that the drying temperature of the oven in the step (2) is 50-55 ℃, the drying time is 12-48h, and the calcining temperature is 550-700 ℃.
The second aspect of the present invention is to provide an oxide spherical photonic crystal of inverse opal structure prepared according to the above-described simple preparation method.
The third aspect of the invention is to provide an 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 may be a negatively charged polymer microsphere or a silica microsphere; the precursor is a hydrolyzable substance or a feed liquid (solid content is 0.1-3%) containing small-particle oxide, which is prepared from a hydrolyzable salt solution, and for a metal salt with severe hydrolysis conditions, the feed liquid containing small-particle oxide can be prepared as the precursor.
The template with negative electricity and the hydrolysis particles with negative electricity which are generated by partial hydrolysis and alcoholysis are mutually repelled, so that the whole system is in dynamic balance, water and ethanol are gradually evaporated along with the drying process, the charges on the surfaces of the template and the precursor are gradually reduced, at the moment, the energy of the system needs to be kept to be minimum, the template pellets are gradually close to form a sphere under the action of capillary suction pipe force, the precursor is further hydrolyzed on the surfaces of the template pellets to form crystal nuclei in the process, the crystal nuclei are further grown and grown through hydrolysis, and finally the oxide spherical photonic crystal with the inverse opal structure can be obtained after the template pellets are removed by calcination.
The beneficial effect of above-mentioned scheme is:
1) According to the preparation method, a continuous aqueous phase emulsion is formed by adopting an injector, spherical liquid drops with a small-size water-in-oil structure are obtained by collecting the shearing force of oil liquid, the follow-up rotation can be used for preventing the liquid drops from being recombined, 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 microsphere is obtained by means of the capillary force of the polymer microsphere in the aqueous phase;
2) The oxide spherical photonic crystal microsphere with the inverse opal structure prepared by the preparation method has the advantages of complete symmetry, ordered arrangement height, good repeatability, adjustable size and high yield;
3) The spherical photonic crystal prepared by the invention has the inverse opal structure, and the structure not only has the advantages of large specific surface area, more surface active sites and the like, but also solves the problem that the general photonic crystal material has angle dependence, so that the photocatalysis performance is more stable;
4) The oxide spherical photonic crystal prepared by the invention is composed of nano oxide particles, has a plurality of surface active sites and higher photocatalytic performance, and can effectively promote the separation of photogenerated carriers, improve the rate of electron transmission and improve the utilization rate of sunlight;
5) The spherical oxide photonic crystal prepared by the method is applicable to various hydrolyzable oxides and small-particle oxides which can be prepared, so that the universality of the method is greatly improved.
Drawings
FIG. 1is an SEM image of a spherical photonic crystal of titanium dioxide according to example 1 of the present invention;
FIG. 2 is an SEM image of spherical photonic crystals of titanium dioxide according to example 2 of the present invention;
FIG. 3 is an SEM image of spherical photonic crystals of titanium dioxide according to example 3 of the present invention;
FIG. 4 is an SEM image of spherical photonic crystals of zinc oxide according to example 4 of the present invention;
Fig. 5 is a photo-hydrolysis hydrogen production graph of the titanium dioxide spherical photonic crystal provided in the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention is further described below with reference to the drawings and specific examples, which are not intended to be limiting.
Example 1
The preparation method of the titanium dioxide spherical photonic crystal with the inverse opal structure comprises the following steps:
1) Monodisperse negatively charged polystyrene beads were prepared: 0.4g ammonium persulfate, 0.8g ammonium bicarbonate, and 2mL acrylic acid monomer were dissolved in 10mL deionized water and designated as solution A; adding 250mL of deionized water, 10mL of styrene and 1mL of methyl methacrylate monomer into a three-neck flask, mixing and stirring, protecting by N 2, rapidly adding the solution A into the mixed solution in the bottle when the temperature of the mixed solution in the bottle is raised to 70 ℃, and continuously stirring for 12 hours at 70 ℃ to obtain a template solution containing monodisperse sulfonated polystyrene beads with the size of 270 nm;
2) Preparing titanium dioxide spherical photonic crystals with inverse opal structures: mixing 0.8mL of template solution with 15% of solid content, 150 mu L of titanium precursor (TYZOR LA) and 300 mu L of ethanol, sucking the mixture into a syringe after ultrasonic mixing is uniform, connecting a catheter on a syringe needle, inserting the tail end of the catheter 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 propelling speed of 15mL/h, then placing the beaker into an oil bath pot with the temperature of 55 ℃ for 12h, controlling the rotating speed of 6000r/min, washing the silicone oil on the surface of a sample by using normal hexane, and then calcining the sample in a muffle furnace at the temperature of 550 ℃ to obtain the titanium dioxide spherical inverse opal structured photonic crystal microspheres.
Example 2
The preparation method of the titanium dioxide spherical photonic crystal with the opal structure comprises the following steps:
1) Monodisperse negatively charged polystyrene beads were prepared: 0.4g ammonium persulfate, 0.8g ammonium bicarbonate, and 2mL acrylic acid monomer were dissolved in 10mL deionized water and designated as solution A; adding 250mL of deionized water, 12mL of styrene and 1mL of methyl methacrylate monomer into a three-neck flask, mixing and stirring, protecting by N 2, rapidly adding the solution A into the mixed solution in the bottle when the temperature of the mixed solution in the bottle is raised to 70 ℃, and continuously stirring for 12 hours at 70 ℃ to obtain a template solution containing monodisperse sulfonated polystyrene beads with the size of 420 nm;
2) Preparing titanium dioxide spherical photonic crystals with opal structures: mixing 1mL of template solution with 15% of solid content, 100 mu L of titanium precursor and 300 mu L of ethanol, uniformly mixing by ultrasonic, sucking into a syringe, connecting a catheter on a needle of the syringe, inserting the tail end of the catheter into a beaker containing silicone oil with the rotating speed of 100r/min and the viscosity of 30cst, injecting feed liquid into the beaker at the advancing speed of 5mL/h, then placing the beaker into an oil bath pot with the temperature of 60 ℃ for 48h, simultaneously controlling the rotating speed of 100r/min, washing the silicone oil on the surface of a sample by using normal hexane, and then placing the microsphere into a muffle furnace for calcining at the temperature of 600 ℃ to obtain the titanium dioxide spherical inverse opal structured photonic crystal microsphere.
Example 3
The preparation method of the titanium dioxide spherical photonic crystal with the inverse opal structure comprises the following steps:
1) Negatively charged SiO 2 pellets were prepared: 1mL of deionized water, 9mL of ethanol and 14mL of ammonia water are uniformly mixed, 1mL of ethyl orthosilicate is added into the solution, the solution is stirred for 2 hours at room temperature, siO2 pellets are obtained, and 0.2g of SiO 2 pellets are dispersed in a feed liquid containing 60mL of ethanol and 0.5mL of trimethylsiloxane. After the mixture was vigorously stirred at 80℃for 17 hours, it was washed with ethanol. Then, 40mL of H 2O2 was added and stirred at room temperature for 3 hours to obtain a solution containing monodisperse sulfonated silica beads having a size of 310 nm;
2) Preparing titanium dioxide spherical photonic crystals with inverse opal structures: mixing 0.9mL of negatively charged silicon dioxide solution with 15% of solid content, 100 mu L of titanium precursor and 300 mu L of ethanol, sucking the mixture into a syringe after ultrasonic mixing is uniform, connecting a catheter on a syringe needle, inserting the tail end of the catheter into a beaker filled with silicone oil with the rotating speed of 2000r/min and the viscosity of 100cst, injecting feed liquid into the beaker at the advancing speed of 10mL/h, then placing the beaker into an oil bath pot with the temperature of 70 ℃ for 8h, controlling the rotating speed of 5000r/min, washing the silicone oil on the surface of a sample by using normal hexane, calcining the microsphere in a muffle furnace at the temperature of 700 ℃, and removing the silicon dioxide template from the collected microsphere by using hydrofluoric acid to obtain the photonic crystal microsphere with the titanium dioxide spherical inverse opal structure.
Example 4
A zinc oxide spherical photonic crystal with a small-size hierarchical pore structure is prepared by the following steps:
1) Monodisperse negatively charged polystyrene beads were prepared: 0.4g ammonium persulfate, 0.8g ammonium bicarbonate, and 2mL acrylic acid monomer were dissolved in 10mL deionized water and designated as solution A; adding 250mL of deionized water, 11mL of styrene and 1mL of methyl methacrylate monomer into a three-neck flask, mixing and stirring, protecting by N 2, rapidly adding the solution A into the mixed solution in the bottle when the temperature of the mixed solution in the bottle is raised to 70 ℃, and continuously stirring for 12 hours at 70 ℃ to obtain a template solution containing monodisperse sulfonated polystyrene beads with the size of 310 nm;
2) Preparing zinc oxide spherical photonic crystals with hierarchical pore structures: dissolving 0.05mol of zinc acetate in 80mL of ethylene glycol, magnetically stirring at room temperature, transferring to a reaction kettle, reacting for 1h at 160 ℃ and mixing with 3mL of ethanol, uniformly mixing by ultrasound, sucking into a syringe, connecting a catheter on a syringe needle, inserting the tail end of the catheter into a beaker containing silicone oil with the rotating speed of 1000r/min and the viscosity of 50cst, injecting the feed liquid into the beaker at the advancing speed of 0.1mL/h, then placing the beaker into an oil bath pot with the temperature of 70 ℃ for 10h, controlling the rotating speed of 100r/min, washing off the silicone oil on the surface of the sample by normal hexane, and then placing the microsphere into a muffle furnace for calcining at 550 ℃ to obtain the photonic crystal microsphere with the zinc oxide spherical inverse opal structure.
As shown in figures 1-4, the oxide spherical photonic crystal prepared by the simple preparation method provided by the invention has a complete and good integral inverse opal structure and a good spherical structure.
In the invention, 20mg of titanium dioxide spherical photonic crystal microspheres with inverse opal structures prepared in the embodiment 1 and the embodiment 3 are respectively placed in deionized water and methanol solution in a ratio of 1:1, and the photolysis water hydrogen production reaction is started under the irradiation of ultraviolet and visible light in a photolysis water reactor, and the result is shown in fig. 5, and as can be seen from fig. 5, the titanium dioxide spherical photonic crystal microspheres with inverse opal structures prepared in the invention have higher photocatalytic performance, wherein the hydrogen production amount in the embodiment 3 in 5 hours can reach 85.8mmol/g, and the photolysis water hydrogen production effect is better.
The foregoing description is only illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the scope of the invention, and it will be appreciated by those skilled in the art that equivalent substitutions and obvious variations may be made using the description and illustrations of the present invention, and are intended to be included within the scope of the present invention.
Claims (1)
1. The preparation method of the titanium dioxide spherical photonic crystal with the inverse opal structure is characterized by comprising the following steps:
1) Monodisperse negatively charged polystyrene beads were prepared: 0.4g ammonium persulfate, 0.8 g ammonium bicarbonate and 2 mL acrylic acid monomer are dissolved in 10mL deionized water and marked as solution A; adding 250 mL deionized water, 10mL styrene and 1 mL methyl methacrylate monomer into a three-neck flask, mixing and stirring, protecting by N 2, quickly adding the solution A into the mixed solution in the bottle when the temperature of the mixed solution in the bottle is raised to 70 ℃, and continuously stirring at 70 ℃ for 12 h to obtain a template solution containing monodisperse sulfonated polystyrene beads with the size of 270 nm;
2) Preparing titanium dioxide spherical photonic crystals with inverse opal structures: mixing template solution with solid content of 15% of 0.8 mL and 150 mu L of titanium precursor TYZOR LA with 300 mu L of ethanol, sucking the mixture into a syringe after ultrasonic mixing, connecting a catheter on a syringe needle, inserting the tail end of the catheter into a beaker filled with silicone oil with rotation speed of 6000 r/min and viscosity of 10 cst, injecting feed liquid into the beaker at a propulsion speed of 15 mL/h, then placing the beaker into an oil bath pot with the temperature of 55 ℃ for 12 h, controlling the rotation speed of 6000 r/min, washing the silicone oil on the surface of the sample with normal hexane, and then calcining the sample in a muffle furnace at the temperature of 550 ℃ to obtain the titanium dioxide spherical inverse opal structured photonic crystal microspheres.
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