CN107281997B - Porous oxide/titanium dioxide microsphere composite catalytic material and preparation method thereof - Google Patents
Porous oxide/titanium dioxide microsphere composite catalytic material and preparation method thereof Download PDFInfo
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- CN107281997B CN107281997B CN201710657068.0A CN201710657068A CN107281997B CN 107281997 B CN107281997 B CN 107281997B CN 201710657068 A CN201710657068 A CN 201710657068A CN 107281997 B CN107281997 B CN 107281997B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000004005 microsphere Substances 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 title claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002135 nanosheet Substances 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 230000001699 photocatalysis Effects 0.000 claims abstract description 14
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 238000004108 freeze drying Methods 0.000 claims abstract description 8
- 238000005507 spraying Methods 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 239000011268 mixed slurry Substances 0.000 claims abstract description 4
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 18
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 238000007146 photocatalysis Methods 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 6
- 229940010552 ammonium molybdate Drugs 0.000 claims description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 14
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 3
- 239000010865 sewage Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0218—Compounds of Cr, Mo, W
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0214—Compounds of V, Nb, Ta
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
A porous oxide/titanium dioxide microsphere composite catalytic material and a preparation method thereof are suitable for sewage treatment. The mole ratio of titanium dioxide to oxide is 1/10-1/5, and the titanium dioxide and the oxide are compounded to form a heterojunction; the diameter of the microsphere is 10-70 μm, and the inside of the microsphere is of a porous structure; the specific surface area of the microspheres is 20-90 m2Between/g. Spraying the metal ammonium salt and TiO2And uniformly spraying the powder mixed slurry into liquid nitrogen, freeze-drying in a low-temperature and low-pressure environment, and finally sintering in an air atmosphere to obtain the porous microspheres. The preparation process is simple and easy to industrialize, and the porous microsphere is composed of metal oxide nanosheets and TiO uniformly distributed on the surfaces of the nanosheets2The catalyst is formed by stacking, has large specific surface area and good photocatalytic performance.
Description
Technical Field
The invention relates to a composite catalytic material and a preparation method thereof, in particular to a porous oxide/titanium dioxide microsphere composite catalytic material and a preparation method thereof.
Background
Since the 21 st century, the economy of China has rapidly developed, and the environmental pollution caused by the economy is increasingly severe. The photocatalysis is regarded as the most potential technology for treating water pollution due to the advantages of high efficiency, energy saving, no pollution and the like, while TiO is2Has the advantages of no toxicity, stable chemical property, strong oxidizability and the like, and is widely researched and used for photocatalytic water pollution treatment. However, due to TiO2The energy gap of the solar cell is large (3.2eV), and only ultraviolet rays with high energy can be absorbed, so that the solar cell cannot be effectively utilized, and the practical application is limited. The transition metal oxide is mostly semiconductor, and most of the semiconductor and TiO2Have similar crystal structures, similar atomic spacings, and matched band structures. Thus, transition metal oxides and TiO can be utilized2Forming a heterojunction by recombination of TiO2The light response of the LED light source extends to a visible light area, and the utilization rate of the LED light source to solar energy is improved.
The freeze-drying process for preparing porous material belongs to the wet forming technology, and is a new preparation technology for obtaining porous material by utilizing physical method to freeze or solidify slurry and reducing pressure and drying to remove solidified phase. The invention introduces spray casting on the basis of freeze drying, and perfectly combines the advantages of the two technologies. In the freezing process, as the fog drops are instantly solidified at extremely low temperature, the agglomeration among powder in the traditional drying process can be effectively reduced, and the dried finished product is in a porous spherical shape, so that the dispersity is very good, the physicochemical properties of the material are well maintained, and the method is a novel catalyst preparation technology. Yang et al are based on titanium nanotubes loaded with SnO2And Pt are used for preparing the composite photocatalyst with the heterojunction and the Schottky junction, and the photocatalytic activity of the composite photocatalyst is researched, so that the experiment shows that the heterojunction composite catalyst realizes visible light absorption and improves the photocatalytic activity; li et al prepared BaTiO by hydrothermal method using titanium dioxide nanotube array as template3/TiO2And the results of the heterojunction show that the catalytic effect after the recombination is higher than that of a single catalyst. However, at present, the research of preparing the composite catalytic material by adopting spray freeze drying is not available.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects of the prior art, the porous oxide/titanium dioxide microsphere composite catalytic material with large specific surface area and strong adsorption and catalysis performances and the preparation method thereof are provided.
The invention content is as follows: in order to achieve the technical purpose, the porous oxide/titanium dioxide microsphere composite catalytic material disclosed by the invention has the advantages that titanium dioxide and various oxides are compounded to form a heterojunction, wherein the molar ratio of the titanium dioxide to the oxides is 1/10-1/5; the heterojunction is of a microsphere structure, the diameter of the microsphere is 10-70 mu m, and the inside of the microsphere is of a porous structure; the specific surface area of the microspheres is 20-90 m2Between/g.
The micron sphere is composed of countless oxide nanosheets, the interior of the micron sphere is of a porous structure, light can conveniently enter the interior of the porous sphere, the nanometer pieces are reflected, and the light utilization rate is improved.
The oxide nanosheet component is MoO3、WO3Or V2O5Of which TiO is uniformly distributed on the surface of the oxide nanosheet2Particles of each TiO2A heterojunction is formed between the particles and the nano sheets, so that the active sites of photocatalysis are increased.
A process for preparing the porous oxide/TiO microparticles composite catalyst from metal ammonium salt and TiO2Adopts a spray freeze-drying method as a raw material to realize the purpose of mixing oxide and TiO2To prepare the porous oxide/titanium dioxide composite material;
the specific process comprises the following steps:
(1) preparing a solution: water, 1-3 wt.% of polyvinyl alcohol (PVA), 0.5-1 wt.% of sodium dodecyl benzene sulfonate, water as a solvent, polyvinyl alcohol (PVA) as a binder, and sodium dodecyl benzene sulfonate as a surfactant;
(2) weighing TiO with the molar ratio of 1/10-1/52And ammonium molybdate (ammonium metatungstate and ammonium metavanadate), respectively adding the ammonium molybdate and the ammonium metavanadate into the solution prepared in the step (1), stirring in a water bath at 50-200 r/min for 2h, performing ultrasonic treatment for 1h, and uniformly mixing to prepare slurry;
(3) pouring the mixed slurry into an atomizer, directly spraying the slurry into liquid nitrogen through the atomizer, and keeping the spray head and the liquid level of the liquid nitrogen between 10 cm and 15 cm;
(4) putting the solidified powder into a freeze dryer, keeping the freeze dryer at the temperature of between 50 ℃ below zero and 10 ℃ below zero and in the environment of 2 to 14Pa for 12 to 24 hours, sublimating water, and drying the powder;
(5) and (3) putting the dried powder into a muffle furnace, heating to 300-600 ℃ at the speed of 2-15 ℃/min, preserving the heat for 2-4 h, sintering in the air atmosphere, and cooling along with the furnace after sintering to obtain the porous heterojunction microspheres.
Has the advantages that: the invention prepares TiO by simply controlling the process2MoO with uniform load and porous hollow spherical shape3-TiO2、WO3-TiO2And V2O5-TiO2A composite material. The catalyst prepared by the spray freeze-drying method has good optical performance, and fog drops are instantly solidified at an extremely low temperature in the freezing process, so that agglomeration among powder in the traditional drying process is effectively reduced, the dried finished product is in a porous spherical shape, the catalyst is easy to disperse in water, the physical and chemical properties of materials are kept, the microscopic size of the catalyst is 10-70 mu m, the specific surface area of the catalyst is improved due to the porous shape, the catalytic active sites are increased, the adsorption performance of the catalyst is improved, and the practical process of the photocatalysis technology is accelerated. The preparation process is simple and easy to industrialize. The porous oxide/titanium dioxide microspheres have valuable optical properties, and because the microspheres are composed of countless oxide nanosheets, light can conveniently enter the porous spheres and can be reflected among the nanosheets, so that the light utilization rate is improved. In addition, TiO2The particles are uniformly distributed on the surface of the nano sheet, and each TiO2A heterojunction is formed between the particles and the nano sheets, so that the active sites of photocatalysis are increased. Its advantages are:
the preparation process is simple, the process is controllable, the industrialization is easy, the shape of the catalyst is controllable, the catalyst is in a uniform porous spherical shapeThe specific surface area of the catalyst is larger, and the adsorption and catalysis performances are stronger. The porous micron sphere is composed of metal oxide nanosheets and TiO uniformly distributed on the surfaces of the nanosheets2The balls are regular in shape, the diameter is 10-70 mu m, pores on the surfaces are fine and uniformly distributed, the pore diameter is 5-20 nm, the specific surface area is large, the adsorption performance and the photocatalytic performance are good, and the balls have wide application prospects in the fields of photocatalysis, supercapacitors and gas sensors.
Description of the drawings:
FIG. 1 is a phase composition XRD (X-ray diffraction) diagram of a porous oxide/titanium dioxide microsphere composite catalytic material;
FIG. 2 shows MoO of the porous oxide/titanium dioxide microsphere composite catalytic material3-TiO2Nitrogen adsorption figure and pore size distribution plot;
FIG. 3 is an SEM image of porous oxide/titanium dioxide microspheres of the present invention; wherein, the diagram a is MoO3-TiO2SEM picture of the material, figure b is a partial enlarged view of 3 a; FIG. c is V2O5-TiO2SEM image of the material, and d is a partial enlarged view of the image c; drawing e is WO3-TiO2SEM image of the material, fig. f is a partial magnified view of fig. e;
FIG. 4 shows MoO measured with methylene blue (30mg/L) as contaminant3-TiO2、WO3-TiO2、V2O5-TiO2And TiO2Graph of photocatalysis of.
Detailed Description
Embodiments of the invention are further described below with reference to the accompanying drawings:
as shown in figures 1 and 2, in the porous oxide/titanium dioxide microsphere composite catalytic material, titanium dioxide and a plurality of oxides are compounded to form a heterojunction, wherein the molar ratio of titanium dioxide to oxides is 1/10-1/5; the heterojunction is of a microsphere structure, the diameter of the microsphere is 10-70 mu m, and the inside of the microsphere is of a porous structure; the specific surface area of the microspheres is 20-90 m2Between/g, the microspheres are composed of countless oxide nano-sheets, and the interior of the microspheres is of a porous structureLight is incident into the porous ball and is reflected among the nano sheets, so that the light utilization rate is improved. The oxide nanosheet component is MoO3、WO3Or V2O5Of which TiO is uniformly distributed on the surface of the oxide nanosheet2Particles of each TiO2A heterojunction is formed between the particles and the nano sheets, so that the active sites of photocatalysis are increased.
A process for preparing the porous oxide/TiO microparticles as the composite catalyst material from ammonium metal salt and TiO2Adopts a spray freeze-drying method as a raw material to realize the purpose of mixing oxide and TiO2To prepare the porous oxide/titanium dioxide composite material;
the specific process comprises the following steps:
(1) preparing a solution: water, 1-3 wt.% of polyvinyl alcohol (PVA), 0.5-1 wt.% of sodium dodecyl benzene sulfonate, water as a solvent, polyvinyl alcohol (PVA) as a binder, and sodium dodecyl benzene sulfonate as a surfactant;
(2) weighing TiO with the molar ratio of 1/10-1/52And ammonium molybdate (ammonium metatungstate and ammonium metavanadate), respectively adding the ammonium molybdate and the ammonium metavanadate into the solution prepared in the step (1), stirring in a water bath at 50-200 r/min for 2h, performing ultrasonic treatment for 1h, and uniformly mixing to prepare slurry;
(3) pouring the mixed slurry into an atomizer, directly spraying the slurry into liquid nitrogen through the atomizer, and keeping the spray head and the liquid level of the liquid nitrogen between 10 cm and 15 cm;
(4) putting the solidified powder into a freeze dryer, keeping the freeze dryer at the temperature of between 50 ℃ below zero and 10 ℃ below zero and in the environment of 2 to 14Pa for 12 to 24 hours, sublimating water, and drying the powder;
(5) and (3) putting the dried powder into a muffle furnace, heating to 300-600 ℃ at the speed of 2-15 ℃/min, preserving the heat for 2-4 h, sintering in the air atmosphere, and cooling along with the furnace after sintering to obtain the porous heterojunction microspheres.
As shown in all the drawings of FIG. 3, the porous microspheres are made of metal oxide nanosheets and TiO uniformly distributed on the surfaces of the nanosheets2And stacking the materials. FIG. 3 is a MoO3-TiO2SEM image of material, and image b is that of image aA partial enlarged view; FIG. c is V2O5-TiO2SEM image of the material, and d is a partial enlarged view of the image c; drawing e is WO3-TiO2SEM image of the material, and f is a partial enlarged view of the image e.
As shown in FIG. 4, TiO2The photocatalytic performance of the composite material is higher than that of single TiO after the composite material is compounded with oxide2The catalytic performance of (2).
Example 1: mixing ammonium molybdate with TiO2Mixing and stirring the mixture with a prepared solution (water +1 wt.% of polyvinyl alcohol (PVA) +1 wt.% of sodium dodecyl benzene sulfonate) in a ratio of 10:1 to obtain uniform slurry, pouring the slurry into an atomizer, uniformly spraying the slurry into liquid nitrogen (-196 ℃), instantly solidifying the atomized slurry in the liquid nitrogen, transferring the solidified powder into a freeze dryer, drying the solidified powder at-50 ℃ and 14Pa for 12 hours to sublimate solid ice to obtain porous powder, putting the dried powder into a muffle furnace, raising the temperature to 600 ℃ at a heating rate of 15 ℃/min, preserving the heat for 4 hours, performing the whole sintering process in an air atmosphere, and taking out a sample along with furnace cooling after the sintering is finished to obtain MoO3-TiO2A microsphere composite material.
Example 2: mixing ammonium metatungstate and TiO2Mixing and stirring the mixture with a prepared solution (water, 2 wt.% of polyvinyl alcohol (PVA) and 0.5 wt.% of sodium dodecyl benzene sulfonate) in a ratio of 8:1 to obtain uniform slurry, pouring the slurry into an atomizer, uniformly spraying the slurry into liquid nitrogen (-196 ℃), instantly solidifying the atomized slurry in the liquid nitrogen, transferring the solidified powder into a freeze dryer, drying the powder at-30 ℃ and 8Pa for 18 hours to sublimate solid ice to obtain porous powder, putting the dried powder into a muffle furnace, raising the temperature to 450 ℃ at a heating rate of 10 ℃/min, preserving the heat for 3 hours, performing the whole sintering process in an air atmosphere, and taking out a sample along with furnace cooling after the sintering is finished to obtain WO3-TiO2A microsphere composite material.
Example 3: mixing ammonium metavanadate and TiO2Mixing with a pre-prepared solution (water +3 wt.% polyvinyl alcohol (PVA) +0.7 wt.% sodium dodecylbenzenesulfonate) at a ratio of 5:1, and stirring to obtainPouring the uniform slurry into an atomizer, uniformly spraying the slurry into liquid nitrogen (-196 ℃), instantly solidifying the atomized slurry in the liquid nitrogen, transferring the solidified powder into a freeze dryer, drying for 24 hours at-10 ℃ and 2Pa to sublimate solid ice to obtain porous powder, putting the dried powder into a muffle furnace, raising the temperature to 300 ℃ at the rate of 2 ℃/min, preserving the heat for 2 hours, performing the whole sintering process in an air atmosphere, and taking out a sample along with furnace cooling after sintering is finished to obtain V2O5-TiO2A microsphere composite material.
Claims (3)
1. A preparation method of a porous oxide/titanium dioxide microsphere composite catalytic material is characterized by comprising the following steps: with metal ammonium salts and TiO2Adopts a spray freeze-drying method as a raw material to realize the purpose of mixing oxide and TiO2To prepare the porous oxide/titanium dioxide composite material; the specific process comprises the following steps: (1) solution preparation: water, 1-3 wt.% of polyvinyl alcohol (PVA), 0.5-1 wt.% of sodium dodecyl benzene sulfonate, water as a solvent, polyvinyl alcohol (PVA) as a binder, and sodium dodecyl benzene sulfonate as a surfactant; (2) weighing TiO with the molar ratio of 1/10-1/52And ammonium molybdate, ammonium metatungstate or ammonium metavanadate are respectively added into the solution prepared in the step (1), stirred in a water bath at 50-200 r/min for 2 hours and subjected to ultrasonic treatment for 1 hour, and the mixture is uniformly mixed to prepare slurry; (3) pouring the mixed slurry into an atomizer, directly spraying the slurry into liquid nitrogen through the atomizer, and keeping the spray head and the liquid level of the liquid nitrogen between 10 cm and 15 cm; (4) putting the solidified powder into a freeze dryer, keeping the freeze dryer at the temperature of between 50 ℃ below zero and 10 ℃ below zero and in the environment of 2 to 14Pa for 12 to 24 hours, sublimating water, and drying the powder; and (5) putting the dried powder into a muffle furnace, heating to 300-600 ℃ at the speed of 2-15 ℃/min, preserving heat for 2-4 h, sintering in an air atmosphere, and cooling along with the furnace after sintering to obtain the porous heterojunction microspheres.
2. The porous oxide/titanium dioxide microsphere composite catalytic material prepared by the preparation method of claim 1, which is characterized in that: oxidation of hydrogen dioxideTitanium and oxide are compounded to form a heterojunction, wherein the molar ratio of titanium dioxide to oxide is 1/10-1/5; the heterojunction is of a microsphere structure, the diameter of the microsphere is 10-70 mu m, and the inside of the microsphere is of a porous structure; the specific surface area of the microspheres is 20-90 m2Between/g; the oxide nanosheet component is MoO3、WO3Or V2O5TiO is uniformly distributed on the surface of the oxide nanosheet2Particles of each TiO2A heterojunction is formed between the particles and the nano sheets, so that the active sites of photocatalysis are increased.
3. The porous oxide/titanium dioxide microsphere composite catalytic material of claim 2, wherein: the micron sphere is composed of countless oxide nanosheets, the interior of the micron sphere is of a porous structure, light can conveniently enter the interior of the porous sphere, the nanometer pieces are reflected, and the light utilization rate is improved.
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