CN110586027A - Preparation method of porous microcrystalline glass containing photocatalytic functional crystalline phase and obtained product - Google Patents
Preparation method of porous microcrystalline glass containing photocatalytic functional crystalline phase and obtained product Download PDFInfo
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- CN110586027A CN110586027A CN201910854195.9A CN201910854195A CN110586027A CN 110586027 A CN110586027 A CN 110586027A CN 201910854195 A CN201910854195 A CN 201910854195A CN 110586027 A CN110586027 A CN 110586027A
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000011521 glass Substances 0.000 title abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 184
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 64
- 239000011148 porous material Substances 0.000 claims abstract description 47
- 238000010438 heat treatment Methods 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 14
- AFSWOABZOLEQMR-UHFFFAOYSA-J iron(4+);hydroxide;phosphate Chemical compound [OH-].[Fe+4].[O-]P([O-])([O-])=O AFSWOABZOLEQMR-UHFFFAOYSA-J 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000013078 crystal Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- 238000010791 quenching Methods 0.000 claims description 11
- 230000000171 quenching effect Effects 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims 2
- 239000003463 adsorbent Substances 0.000 claims 1
- 238000011534 incubation Methods 0.000 claims 1
- 239000011941 photocatalyst Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 14
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 238000010306 acid treatment Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 52
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 14
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 13
- 239000000395 magnesium oxide Substances 0.000 description 13
- 239000007858 starting material Substances 0.000 description 10
- 238000004321 preservation Methods 0.000 description 9
- 238000009826 distribution Methods 0.000 description 5
- 239000002135 nanosheet Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000005373 porous glass Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910010254 TiO2—P2O5 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- GJGGBHXLXWFZOQ-UHFFFAOYSA-K [Cu+2].P(=O)([O-])([O-])[O-].[Mg+2] Chemical compound [Cu+2].P(=O)([O-])([O-])[O-].[Mg+2] GJGGBHXLXWFZOQ-UHFFFAOYSA-K 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- XZTWHWHGBBCSMX-UHFFFAOYSA-J dimagnesium;phosphonato phosphate Chemical compound [Mg+2].[Mg+2].[O-]P([O-])(=O)OP([O-])([O-])=O XZTWHWHGBBCSMX-UHFFFAOYSA-J 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- WZCSFLDGNKKODA-UHFFFAOYSA-H magnesium titanium(4+) diphosphate Chemical compound P(=O)([O-])([O-])[O-].[Mg+2].[Ti+4].P(=O)([O-])([O-])[O-] WZCSFLDGNKKODA-UHFFFAOYSA-H 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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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
- B01J20/0211—Compounds of Ti, Zr, Hf
-
- 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
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
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- 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
- B01J20/0259—Compounds of N, P, As, Sb, Bi
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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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
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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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- 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
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- 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
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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- B01J35/39—Photocatalytic properties
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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Abstract
The invention discloses a titanium dioxide (TiO) containing single anatase2) Crystalline phases or their combination with iron phosphate hydroxide (Fe)4(PO4)3(OH)3) The porous material consists of Fe in 4.76 ~ 11.11.11 mol% and has the composition of2O3,22.22~23.81 mol%MgO,26.67~28.57 mol%CuO,13.33~14.29 mol%TiO2,26.67~28.57mol%P2O5The glass is obtained after heat treatment and acid treatment. By adjusting Fe2O3The method is easy for industrial production, and the obtained porous material has a large specific surface area and is expected to be used as an adsorption and photocatalysis material.
Description
Technical Field
The invention relates to a preparation method of porous glass ceramics containing a single anatase titanium dioxide crystalline phase or a composite crystalline phase of the single anatase titanium dioxide crystalline phase and iron phosphate hydroxide and an obtained product, and belongs to the technical field of porous materials.
Background
Anatase type titanium dioxide (TiO)2) Is a well-known and most widely used photocatalytic material and has wide application prospect in the fields of environment, energy and the like. Increasing its surface area is one of the means to increase the catalytic effectiveness of anatase titania and, for this reason, researchers have developed some methods of producing porous anatase titania materials. Such as: anatase titanium dioxide can be loaded in a porous material, for example, a titanium dioxide particle film with the thickness of about 100 nm is loaded on an activated carbon fiber by adopting a molecular adsorption deposition process to prepare an activated carbon fiber-based titanium dioxide photocatalytic material; preparing mesoporous carrier SBA-15 by a solvothermal method, and performing hydrolytic polycondensation on a titanium source to generate titanium dioxide particles to be deposited on the surface of the carrier to prepare the mesoporous material TiO with photocatalytic degradation performance2-SBA-15. Mixing anatase type titanium dioxide (TiO)2) The crystal phase is compounded with other materials with photocatalytic function to improve anatase type titanium dioxide (TiO)2) The crystal phase photocatalysis effect, one of the common methods for expanding the application range. If a dipping ‒ Czochralski method is used for preparing the graphene ‒ titanium dioxide crystal phase nano composite film on the FTO conductive glass, the photoelectrochemical activity of the titanium dioxide is improved by modifying the titanium dioxide with the graphene.
The above techniques all rely primarily on chemical synthesis methods. Earlier studies prove that anatase-containing titanium dioxide (TiO) is hopeful to be obtained by adopting a glass production technology capable of large-scale production2) A crystalline phase of porous glass ceramics (publication No. CN 109046407A). However, the main crystal phase of the obtained material is phosphate phase without photocatalysis function, namely anatase type titanium dioxide (TiO)2) The crystalline phase is impure and low in content. How to obtain pure anatase titanium dioxide (TiO)2) The crystalline phase or the porous microcrystalline glass material compounded with other crystalline phases with the photocatalytic function is a difficult problem.
Disclosure of Invention
The invention aims to solve the technical problems and provides a titanium dioxide containing pure anatase(TiO2) A preparation method of crystalline phase or porous glass ceramics compounded with other crystalline phases with photocatalytic function and an obtained product. The method is to prepare Fe firstly2O3-MgO-CuO-TiO2-P2O5The glass is heat treated to form microcrystal glass, and is selectively acid etched and in-situ crystal grown to form single anatase type Titania (TiO)2) A crystalline phase of porous glass-ceramics. With Fe2O3The content is increased, and anatase type titanium dioxide (TiO) in the porous microcrystalline glass2) The crystal phase is enhanced, and simultaneously, iron phosphate hydroxide (Fe) with visible light catalytic function is generated4(PO4)3(OH)3) A crystalline phase. The obtained material has high specific surface area, pore volume, large pore diameter and open pore structure.
The specific technical scheme of the invention is as follows:
pure anatase type titanium dioxide (TiO) containing2) Crystalline phase or its mixture with iron phosphate hydroxide (Fe) having visible light catalytic function4(PO4)3(OH)3) The preparation method of the crystalline phase composite porous glass ceramics comprises the following steps:
(1) according to 4.76 ~ 11.11 mol% Fe2O3, 22.22~23.81 mol% MgO, 26.67~28.57 mol% CuO, 13.33~14.29 mol% TiO2, 26.67~28.57 mol% P2O5Weighing the raw materials according to the component content;
(2) uniformly mixing the raw materials, heating the uniformly mixed mixture to a melting temperature, preserving heat for a certain time, and carrying out rapid cooling molding or water quenching on the obtained molten liquid on a mold;
(3) cooling the sample formed by quenching, or drying the sample formed by quenching in water for later use;
(4) preserving heat of the sample in the step (3) at 600 ~ 630 and 630 ℃, preserving heat at 660 ~ 690 and 690 ℃, performing two-section heat treatment, and cooling along with a furnace;
(5) immersing the sample obtained in the step (4) in hydrochloric acid for acid corrosion;
(6) collecting the sample, and drying to obtain anatase onlyTitanium dioxide (TiO) type2) Crystalline phases or their combination with iron phosphate hydroxide (Fe)4(PO4)3(OH)3) A porous material with a composite crystalline phase.
Further, in the step (1), Fe is provided2O3、MgO、CuO、TiO2And P2O5The raw materials of the components are oxides, namely iron oxide, magnesium oxide, copper oxide, titanium dioxide and phosphorus pentoxide. In the formula, the total molar weight of all the components is 100%.
Further, in the step (2), the mixture is heated from room temperature to 600 ℃ at the heating rate of 10 ℃/min, then from 600 ℃ to 1100 ℃ at the heating rate of 5 ℃/min, then from 1100 ℃ to 1250 ℃ at the heating rate of 3 ℃/min, and the mixture is kept at the melting temperature of 1250 ℃ for 1 hour, so that the mixture is completely melted.
Further, in the step (4), the temperature of the sample is raised to 600 ~ 630 ℃ and kept for 1 hour, the first stage heat preservation is carried out at the temperature, the temperature is continuously raised after the first stage heat preservation is finished, the temperature is kept at 660 ~ 690 ℃ for 2 hours, and the second stage heat preservation is carried out.
Further, in the step (5), the concentration of hydrochloric acid is 1 ~ 3 mol/L, the temperature of hydrochloric acid corrosion is 100 ℃, and the corrosion time is 24 ~ 72 hours.
The present invention comprises anatase type titanium dioxide (TiO)2) The formation mechanism of the crystalline phase porous material is that firstly, all raw material components fully react in a high-temperature molten state and are solidified into opaque black blocks or particles through quenching forming or water quenching; the block or the particle is subjected to two-stage heat preservation treatment to separate out magnesium titanium phosphate (Mg)0.5Ti2(PO4)3) Magnesium pyrophosphate (Mg)2P2O7) Copper oxide (CuO), copper magnesium phosphate ((Mg)0.54Cu0.46)3(PO4)6) And titanium dioxide (TiO)2) An isocrystalline phase; treating the bulk or water-quenched particles containing these crystalline phases in a hot hydrochloric acid solution to selectively dissolve out part of the components and carry out complicated in-situ chemical reactions under liquid-phase hydrothermal conditions to finally form anatase-only titanium dioxide (TiO)2) Crystal grainPhase or anatase-containing titanium dioxide (TiO)2) With iron phosphate hydroxide (Fe)4(PO4)3(OH)3) A porous microcrystalline glass material with composite crystal phase.
Furthermore, the porous material obtained by the method is blocky or granular, wherein the product formed by rapid cooling is blocky, and the water quenching product is granular. SEM test shows that the sample is composed of nano-sheets or spherical particles; XRD analysis results show that the obtained porous microcrystalline glass has crystalline phase and Fe2O3The contents are related; wherein, Fe2O3At a content of 4.76 ~ 6.98.98 mol%, the resulting porous material contained only weakly crystalline anatase titanium dioxide (TiO)2) Crystalline phase of Fe2O3At contents higher than 6.98mol% up to 11.11 mol%, the porous material contains strong anatase titanium dioxide (TiO)2) A crystalline phase, and also contains iron phosphate hydroxide (Fe)4(PO4)3(OH)3) A crystalline phase; and Fe2O3The higher the content, the stronger the two phases.
Further, the obtained material has macropores among crystal grains, and N is2Adsorption-confirmed material also has a mesoporous structure; when the acid concentration is increased, the surface area and the pore volume of the porous material are increased, the acid treatment time is prolonged, the pore parameters are also increased, and dual-mode mesopores are generated.
The preparation process of the porous material is easy to industrialize, and the obtained material has a high specific surface area, the pore diameter is distributed in the range from mesopores to macropores, and the material has adsorption and photocatalysis functions. Thus, the anatase titanium dioxide (TiO) containing titanium produced by the above method2) Single crystal phase or its mixture with iron phosphate hydroxide (Fe)4(PO4)3(OH)3) Porous materials with complex crystal phases are also within the scope of the present invention.
The porous material only containing the photocatalytic functional crystal phase is prepared through the steps of melting, heat treatment and acid treatment, and the method has the advantages of low raw material price, easy production process control and suitability for industrial preparation of the porous photocatalytic material. The obtained porous material has pure and positive photocatalytic functional crystal phase, high specific surface area and adjustable crystal phase, and is expected to be applied to the fields of adsorption and photocatalysis.
Drawings
FIG. 1 is an XRD diffraction pattern of the samples obtained in examples 1-5.
FIG. 2 is an SEM photograph of a sample obtained in example 1.
Fig. 3 is a BJH pore size distribution curve of the sample obtained in example 1.
FIG. 4 is an SEM photograph of a sample obtained in example 4.
FIG. 5 shows N in the sample obtained in example 42Adsorption isotherm curve.
Fig. 6 is a BJH pore size distribution curve of the sample obtained in example 4.
Detailed Description
The invention is further described with reference to the following drawings and detailed description, which are illustrative only and not limiting in nature.
Sample N was measured using a nitrogen isothermal adsorption apparatus (Autosorb iQ-C)2An isothermal adsorption curve, calculating specific surface area according to a BET model, obtaining a pore size distribution curve according to a BJH model, determining pore size according to curve peak point data, and determining pore volume from N2The adsorption curve is determined relative to the amount of adsorption at the maximum pressure.
Example 1
1. According to 4.76 mol% Fe2O3、23.81 mol% MgO、28.57 mol% CuO、14.29 mol% TiO2And 28.57 mol% P2O5Selecting the molar composition of the starting material, Fe2O3、MgO、CuO、TiO2And P2O5The starting materials of (a) are the respective oxides themselves. And (3) uniformly mixing all the oxide raw materials to obtain a mixture.
2. Putting the mixture obtained in the step 1 into a crucible, heating from room temperature to 600 ℃ at a heating rate of 10 ℃/min, then heating from 600 ℃ to 1100 ℃ at a heating rate of 5 ℃/min, finally heating from 1100 ℃ to 1250 ℃ at a heating rate of 3 ℃/min, preserving heat for 1 h at the temperature to completely melt the mixture, pouring the molten sample into cold water for quenching and water quenching to obtain a granular sample, and then putting the sample into an oven, preserving heat for 12 h and keeping for later use at 100 ℃.
3. The sample is heated to 630 ℃ at the heating rate of 5 ℃/min and is kept warm for 1 h, and then is heated from 630 ℃ to 690 ℃ at the heating rate of 5 ℃/min and is kept warm for 2 h. And after the heat preservation is finished, cooling the sample to room temperature along with the furnace.
4. And (4) soaking the sample obtained in the step (3) in 1 mol/L hydrochloric acid at 100 ℃ for 24 h, taking out the sample and drying the sample.
5. The product obtained after drying is single anatase type titanium dioxide (TiO)2) A crystalline phase of a porous material.
As can be seen from FIG. 1, the resulting crystalline phase of the product is single anatase titanium dioxide (TiO)2) A crystalline phase. SEM analysis of the product, as shown in figure 2, shows that: the product is a flower cluster-shaped aggregate formed by nano sheets, and macropores are arranged among the nano sheets. Warp of N2The BET surface area of the product, determined by isothermal adsorption analysis, was 18 m2Per g, pore volume of 0.08 cm3The pore diameter is 12.25 nm, and the BJH pore diameter distribution curve is shown in figure 3.
Example 2
1. According to 4.76 mol% Fe2O3、23.81 mol% MgO、28.57 mol% CuO、14.29 mol% TiO2And 28.57 mol% P2O5Selecting the molar composition of the starting material, Fe2O3、MgO、CuO、TiO2And P2O5The starting materials of (a) are the respective oxides themselves. And (3) uniformly mixing all the oxide raw materials to obtain a mixture.
2. The same as in example 1.
3. The sample is heated to 630 ℃ at the heating rate of 5 ℃/min and is kept warm for 1 h, and then is heated from 630 ℃ to 690 ℃ at the heating rate of 5 ℃/min and is kept warm for 2 h. And after the heat preservation is finished, cooling the sample to room temperature along with the furnace.
4. And (3) soaking the sample obtained in the step (3) in 3 mol/L hydrochloric acid at 100 ℃ for 24 h, taking out the sample and drying the sample.
5. The product obtained after drying is single anatase type titanium dioxide (TiO)2) A crystalline phase of a porous material.
As can be seen from FIG. 1, the product obtained a single crystalline phaseAnatase type titanium dioxide (TiO)2) A crystalline phase. Warp of N2The BET surface area of the product, determined by isothermal adsorption analysis, was 120 m2Per g, pore volume of 0.47 cm3The sample has a bimodal mesoporous structure, and the main pore diameters are 2.02 nm and 3.66 nm.
Example 3
1. According to 6.98mol% Fe2O3、23.25 mol% MgO、27.91 mol% CuO、13.95 mol% TiO2And 27.91 mol% P2O5Selecting the molar composition of the starting material, Fe2O3、MgO、CuO、TiO2And P2O5The starting materials of (a) are the respective oxides themselves. And (3) uniformly mixing all the oxide raw materials to obtain a mixture.
2. And (2) putting the mixture obtained in the step (1) into a crucible, heating from room temperature to 600 ℃ at a heating rate of 10 ℃/min, then heating from 600 ℃ to 1100 ℃ at a heating rate of 5 ℃/min, finally heating from 1100 ℃ to 1250 ℃ at a heating rate of 3 ℃/min, preserving heat for 1 h at the temperature to completely melt the mixture, carrying out rapid cooling and tabletting on the molten sample to obtain an opaque black block sample, and then putting the sample into an oven, preserving heat for 12 h and drying for later use at 100 ℃.
3. And (3) heating the sample to 605 ℃ at the heating rate of 5 ℃/min, preserving heat for 1 h, then heating to 680 ℃ from 605 ℃ at the heating rate of 5 ℃/min, and preserving heat for 2 h. And after the heat preservation is finished, cooling the sample to room temperature along with the furnace.
4. And (4) soaking the sample obtained in the step (3) in 1 mol/L hydrochloric acid at 100 ℃ for 24 h, taking out the sample and drying the sample.
5. The product obtained after drying is single anatase type titanium dioxide (TiO)2) A crystalline phase of a porous material.
As can be seen from FIG. 1, the resulting crystalline phase of the product is single anatase titanium dioxide (TiO)2) A crystalline phase. Warp of N2The BET surface area of the product, determined by isothermal adsorption analysis, was 59 m2Per g, pore volume of 0.22 cm3The sample has a dual-mode mesoporous structure, and the main pore diameters of the sample are respectively 2.13 nm and 9.92 nm.
Example 4
1. According to 6.98 mol% Fe2O3、23.25 mol% MgO、27.91 mol% CuO、13.95 mol% TiO2And 27.91 mol% P2O5Selecting the molar composition of the starting material, Fe2O3、MgO、CuO、TiO2And P2O5The starting materials of (a) are the respective oxides themselves. And (3) uniformly mixing all the oxide raw materials to obtain a mixture.
2. The same as in example 1.
3. And (3) heating the sample to 600 ℃ at the heating rate of 5 ℃/min, preserving the heat for 1 h, then heating to 680 ℃ from 600 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 2 h. And after the heat preservation is finished, cooling the sample to room temperature along with the furnace.
4. And (4) soaking the sample obtained in the step (3) in 1 mol/L hydrochloric acid at 100 ℃ for 72 h, taking out the sample and drying the sample.
5. The product obtained after drying is the single anatase type titanium dioxide (TiO)2) A crystalline phase of a porous material.
As can be seen from FIG. 1, the resulting crystalline phase of the product is single anatase titanium dioxide (TiO)2) A crystalline phase. SEM analysis of the product, as shown in fig. 4, can be taken from the figure: the product is composed of nano sheets, and macropores exist between the nano sheets. Subjecting the product to N2The isothermal adsorption analysis showed that the adsorption isotherm of N2 and the pore size distribution curve of BJH in the product are shown in FIGS. 5 and 6, and it can be seen that the BET surface area of the product is 128 m2Per g, pore volume of 0.41 cm3The sample has a bimodal mesoporous structure, and the main pore diameters of the sample are 2.51 nm and 12.34 nm respectively.
Example 5
1. According to 11.11 mol% Fe2O3、22.22 mol% MgO、26.67 mol% CuO、13.33 mol% TiO2And 26.67 mol% P2O5Selecting the molar composition of the starting material, Fe2O3、MgO、CuO、TiO2And P2O5The starting materials of (a) are the respective oxides themselves. And (3) uniformly mixing all the oxide raw materials to obtain a mixture.
2. The same as in example 1.
3. And (3) heating the sample to 600 ℃ at the heating rate of 5 ℃/min, preserving the heat for 1 h, then heating to 660 ℃ from 600 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 2 h. And after the heat preservation is finished, cooling the sample to room temperature along with the furnace.
4. And (4) soaking the sample obtained in the step (3) in 1 mol/L hydrochloric acid at 100 ℃ for 24 h, taking out the sample and drying the sample.
5. Drying to obtain the product of anatase-containing titanium dioxide (TiO)2) Crystalline phase with iron phosphate hydroxide (Fe)4(PO4)3(OH)3) A porous material with a composite crystalline phase.
As can be seen from FIG. 1, the main crystal phase obtained by the product is anatase type titanium dioxide (TiO)2) Iron phosphate hydroxide (Fe) in crystalline and also in paracrystalline phases4(PO4)3(OH)3) A crystalline phase. Warp of N2The BET surface area of the product, analyzed by isothermal adsorption, was 16 m2Per g, pore volume of 0.09 cm3(ii)/g, pore diameter 9.6 nm.
Claims (8)
1. A preparation method of a porous material containing a photocatalytic functional crystal phase is characterized by comprising the following steps:
(1) according to 4.76 ~ 11.11 mol% Fe2O3, 22.22~23.81 mol% MgO, 26.67~28.57 mol% CuO, 13.33~14.29 mol% TiO2, 26.67~28.57 mol% P2O5Weighing the raw materials according to the component content;
(2) uniformly mixing the raw materials, heating the uniformly mixed mixture to a melting temperature, preserving heat for a certain time, and carrying out rapid cooling molding or water quenching on the obtained molten liquid on a mold;
(3) cooling the sample formed by quenching, or drying the sample formed by quenching in water for later use;
(4) preserving heat of the sample in the step (3) at 600 ~ 630 and 630 ℃, preserving heat at 660 ~ 690 and 690 ℃, performing two-section heat treatment, and cooling along with a furnace;
(5) immersing the sample obtained in the step (4) in hydrochloric acid for acid corrosion;
(6) collecting the sample, and drying to obtain the product containing only anatase type titanium dioxide (TiO)2) Crystalline phase or its mixture with iron phosphateSalt hydroxide (Fe)4(PO4)3(OH)3) A porous material with a composite crystalline phase.
2. The method of claim 1, wherein: in the step (1), the component Fe2O3、MgO、CuO、TiO2And P2O5Are each introduced by a respective oxide.
3. The method of claim 1, wherein: in the step (2), during temperature rise, the temperature is raised from room temperature to 600 ℃ at the temperature rise rate of 10 ℃/min, then is raised from 600 ℃ to 1100 ℃ at the temperature rise rate of 5 ℃/min, then is raised from 1100 ℃ to 1250 ℃ at the temperature rise rate of 3 ℃/min, and is kept at the melting temperature of 1250 ℃ for 1 hour, so that the mixture is completely melted.
4. The method according to claim 1, wherein in the step (4), the sample is incubated at 600 ~ 630 ℃ for the first period, and the incubation at 660 ~ 690 ℃ for the second period is continued after the first period.
5. The method according to claim 1, wherein in the step (4), the sample is incubated at 600 ~ 630 ℃ for 1 hour and at 660 ~ 690 ℃ for 2 hours.
6. The process according to claim 1, wherein in the step (5), the hydrochloric acid concentration is 1 ~ 3 mol/L, the etching temperature is 100 ℃ and the etching time is 24 ~ 72 hours.
7. A porous material obtained by the production method according to any one of claims 1 to 6, characterized in that: the porous material contains only anatase type titanium dioxide (TiO)2) Crystalline phase or anatase-containing titanium dioxide (TiO)2) With iron phosphate hydroxide (Fe)4(PO4)3(OH)3) A complex crystalline phase.
8. The anatase-containing titanium dioxide (TiO) of claim 72) Crystalline phases or their combination with iron phosphate hydroxide (Fe)4(PO4)3(OH)3) The porous material with composite crystal phase is used as adsorbent or photocatalyst.
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