CN113548690A - Preparation method of light transition metal doped perovskite aerogel material - Google Patents
Preparation method of light transition metal doped perovskite aerogel material Download PDFInfo
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- 239000004964 aerogel Substances 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 28
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 23
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 46
- 239000002184 metal Substances 0.000 claims abstract description 46
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000352 supercritical drying Methods 0.000 claims abstract description 11
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000011240 wet gel Substances 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 12
- 239000000499 gel Substances 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 10
- 229910052788 barium Inorganic materials 0.000 claims description 10
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- 229910052712 strontium Inorganic materials 0.000 claims description 10
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 claims description 6
- QOYRNHQSZSCVOW-UHFFFAOYSA-N cadmium nitrate tetrahydrate Chemical compound O.O.O.O.[Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QOYRNHQSZSCVOW-UHFFFAOYSA-N 0.000 claims description 4
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 claims description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
- 239000007783 nanoporous material Substances 0.000 abstract description 2
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 238000006068 polycondensation reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 42
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 16
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 14
- 229910002113 barium titanate Inorganic materials 0.000 description 14
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 13
- 239000011259 mixed solution Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 7
- MMLSWLZTJDJYJH-UHFFFAOYSA-N calcium;propan-2-olate Chemical compound [Ca+2].CC(C)[O-].CC(C)[O-] MMLSWLZTJDJYJH-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JJRHNFGVNTWRTI-UHFFFAOYSA-N CO.[Sr] Chemical compound CO.[Sr] JJRHNFGVNTWRTI-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- GYIWFHXWLCXGQO-UHFFFAOYSA-N barium(2+);ethanolate Chemical compound [Ba+2].CC[O-].CC[O-] GYIWFHXWLCXGQO-UHFFFAOYSA-N 0.000 description 2
- BQDSDRAVKYTTTH-UHFFFAOYSA-N barium(2+);methanolate Chemical compound [Ba+2].[O-]C.[O-]C BQDSDRAVKYTTTH-UHFFFAOYSA-N 0.000 description 2
- CPUJSIVIXCTVEI-UHFFFAOYSA-N barium(2+);propan-2-olate Chemical compound [Ba+2].CC(C)[O-].CC(C)[O-] CPUJSIVIXCTVEI-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000011278 co-treatment Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 2
- OHULXNKDWPTSBI-UHFFFAOYSA-N strontium;propan-2-olate Chemical compound [Sr+2].CC(C)[O-].CC(C)[O-] OHULXNKDWPTSBI-UHFFFAOYSA-N 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/006—Alkaline earth titanates
-
- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention belongs to the field of preparation processes of nano porous materials, and particularly relates to a preparation method of a light transition metal doped perovskite aerogel. Dissolving a metal simple substance in an alcohol solution, sequentially adding toluene and a titanium source, introducing light transition metal ions for modification before alkoxide hydrolysis and polycondensation, dropwise adding deionized water to form gel, and performing supercritical drying to prepare the light transition metal doped perovskite aerogel material. The aerogel material prepared by the invention has excellent photocatalytic performance, low material consumption, simple process, high efficiency and low cost, and has wide development prospect.
Description
Technical Field
The invention belongs to the field of preparation processes of aerogel materials, and relates to a preparation method for preparing a light transition metal doped perovskite aerogel material by combining a light transition metal doped double metal alkoxide method with a supercritical drying process.
Background
Since the industrial revolution, the rapid advance of industrial, biological and energy technologies, and simultaneously the environmental problems are becoming more and more serious, especially some substances with complex chemical structures and stability exist in the related chemical industrial waste water, which are limited by the recovery capability of the earth's own ecosystem, and these substances can not be effectively degraded, so that human beings face an unprecedented problem of water resource shortage, and water pollution is one of the huge environmental problems of international concern. The photocatalytic reaction is a catalytic reaction in which light is used as a catalyst to accelerate or decelerate the catalysis. Currently, the water treatment mainly adopted by most countries is roughly provided with the following methods: physical-chemical methods, reverse osmosis methods, electrodialysis methods, gas stripping methods, heterogeneous photocatalytic methods, and the like are used as sewage treatment methods. In recent years, a photocatalytic technology for water treatment is developed and is a new water treatment technology, and the action mechanism of the photocatalytic technology for treating water pollution is that light with a band gap larger than that of a semiconductor material is used for irradiating the semiconductor material, valence band electrons of the semiconductor material are transited to a conduction band, and holes left after the valence band electrons are transited and photo-generated electrons form photo-generated electron-hole pairs. The photoproduction electron-hole pair has strong oxidizing capability, and can oxidize organic pollutants in the sewage into pollution-free small molecular substances such as water, carbon dioxide and the like, thereby treating the organic pollutants in the sewage.
The aerogel is a three-dimensional nano porous material with low density, low dielectric constant, high specific surface area and high porosity, and has wide application prospect in the fields of thermal, optical, acoustic, microelectronic, catalytic, aerospace, energy-saving building and the like. The traditional perovskite photocatalyst has the problem that the specific surface area is not large enough, the ultrahigh specific surface area and the abundant pore structure of the aerogel material have incomparable advantages compared with other materials in the aspects of adsorption and photocatalysis, the perovskite aerogel photocatalyst can highly disperse and improve the light absorption and reaction sites of the photocatalyst in a solution system, more active sites are provided along with the doping of light transition metal ions, the absorption edge position of the material is changed, and the photocatalysis performance is further improved.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of a light transition metal doped perovskite titanate aerogel material, the method has the advantages of simple raw materials and process, low energy consumption and controllable structure, and the prepared aerogel material has the characteristics of low density, high porosity, excellent photocatalytic performance and the like, and has positive production significance for realizing the application of the aerogel material in the fields of photocatalysis, dye wastewater treatment and the like, such as environmental protection and the like.
The technical scheme of the invention is as follows: preparation method of light transition metal doped perovskite titanate aerogel material, wherein the density of the prepared light transition metal doped perovskite titanate aerogel powder is 0.16-0.86 g/cm3The specific surface area is 78.31 to 186.7m2The average pore diameter is 17-32 nm, the concentration of 1g/L is used as the input standard of the light transition metal doped perovskite titanate aerogel, the methyl orange solution with the pH value of 3 and the concentration of 10mg/L is subjected to ultraviolet degradation, 87-95% of MO can be degraded in 1 hour, and the reaction rate reaches 0.0314-0.0532 min-1The method comprises the following specific steps:
(1) preparation of Metal alkoxide solution
Weighing an alcohol solvent, putting the alcohol solvent into a container, adding metal, heating and stirring until the metal is completely dissolved to form a solution A;
(2) mixing of raw materials
After the solution A in the step (1) is completely dissolved, adding toluene and a titanium source, and continuously stirring for reaction to obtain a solution B;
(3) preparation of light transition metal doped perovskite wet gel
Adding hydrated nitrate corresponding to the light transition metal into the clear solution B obtained in the step (2), stirring, then dropwise adding deionized water to form gel, and continuously stirring and aging to obtain wet gel;
(4) drying of light transition metal doped perovskite wet gel
And (4) drying the light transition metal doped perovskite titanate wet gel obtained in the step (3), and taking out a sample to obtain the light transition metal doped perovskite titanate aerogel.
Preferably, the alcohol solvent in step (1) is one or more of methanol, ethanol or isopropanol.
Preferably, the metal in the step (1) is one of calcium, barium or strontium; the volume ratio of the mass of the metal to the alcohol solvent is 5-50 g/L.
Preferably, the temperature rise in the step (1) is 30-80 ℃, and the temperature rise stirring time is 30-180 min.
Preferably, the titanium source used in the step (2) is one of isopropyl titanate or tetrabutyl titanate, the metal and the titanium source are mixed according to a molar ratio of 1 (0.95-1.05), and the mass volume ratio of the metal to the toluene is 2-10 g/L.
Preferably, the reaction temperature in the step (2) is 10-40 ℃, and the stirring time is 30-120 min.
Preferably, the hydrated nitrate corresponding to the light transition element in the step (3) is one of chromium nitrate nonahydrate, nickel nitrate hexahydrate, cobalt nitrate hexahydrate, cadmium nitrate tetrahydrate or manganese nitrate tetrahydrate, and the hydrated nitrate corresponding to the light transition element and the metal are mixed according to a molar ratio of 1 (10-50).
Preferably, the reaction temperature in the step (3) is 10-40 ℃, the stirring time is 30-120 min, and the aging time is 24-72 h.
Preferably, the drying method in step (4) is freeze drying, CO2Supercritical drying or ethanol supercritical drying.
Has the advantages that:
the preparation method of the light transition metal doped perovskite aerogel material prepared by the method has the following characteristics:
(1) the process has the advantages of simple raw materials and production method, low energy consumption, low-temperature synthesis and simple process.
(2) The material has the characteristics of excellent catalytic performance, high porosity, low density, uniform particles and the like.
(3) The light transition metal doped perovskite aerogel prepared by the method is a complete block material, and has positive significance for realizing the application of the aerogel material in the fields of photocatalysis, dye wastewater treatment and the like, such as environmental protection and the like.
Drawings
Fig. 1 is a TEM spectrum of a chromium-doped strontium titanate aerogel of example 1.
Detailed Description
Example 1
Weighing 80ml of methanol solution, putting the methanol solution into a container, adding 0.8762g of metal strontium, stirring the solution at 70 ℃ for 50min until the metal strontium is completely dissolved to form a strontium methanol solution, after the strontium methanol solution is cooled to room temperature, sequentially adding 200ml of toluene and 2.7001g of isopropyl titanate (the molar ratio of the metal strontium to the isopropyl titanate is 1:0.95), stirring the solution at 10 ℃ for 120min to obtain a strontium titanate solution, adding 0.4001g of chromium nitrate nonahydrate (the molar ratio of the chromium nitrate nonahydrate to the metal strontium is 1:10) into the strontium titanate solution, continuously stirring the solution for 120min, dropwise adding deionized water into a needle tube to form gel, continuously stirring and aging the gel for 24h to obtain chromium-doped strontium titanate wet gel, finally putting the chromium-doped strontium titanate wet gel into ethanol supercritical equipment for supercritical drying, setting the drying temperature to be 270 ℃, keeping the pressure at 10MPa after the temperature is increased, keeping the temperature and the pressure at constant pressure for 3h, and then keeping the uniform speed, releasing the gas within 30min, and taking out the gas after the temperature of the reaction kettle is reduced to obtain the chromium-doped strontium titanate aerogel prepared by the double metal alkoxide method. The density of the prepared material is 0.16g/cm3Specific surface area 78.31m2The average pore diameter is 24nm, the concentration of 1g/L is used as the input standard of the chromium-doped strontium titanate aerogel, the methyl orange solution with pH of 3 and the concentration of 10mg/L is subjected to ultraviolet light degradation, 92 percent of MO can be degraded within 1 hour, and the reaction rate reaches 0.0443min-1。
Fig. 1 is a TEM spectrum of a chromium-doped strontium titanate aerogel. The chromium-doped strontium titanate aerogel presents a three-dimensional network structure of the aerogel, and the crystal grains of the aerogel are clear and visible. It can be seen from the HRTEM plot of the inset that the lattice spacing of the sample dropped from 0.278nm to 0.267nm, primarily due to the decreased lattice constant after chromium doping, which also indirectly demonstrates that chromium is doped into the lattice of strontium titanate.
Example 2
Weighing 28ml of ethanol solution, placing the ethanol solution into a container, adding 1.373g of metal barium, stirring the mixture for 80min at 50 ℃ until the metal barium is completely dissolved to form a barium ethoxide solution, after the barium ethoxide solution is cooled to room temperature, sequentially adding 138ml of toluene and 2.9843g of isopropyl titanate (the molar ratio of the metal barium to the isopropyl titanate is 1:1.05), stirring the mixture for 100min at 20 ℃ to obtain a barium titanate solution, adding 0.1255g of manganese nitrate tetrahydrate (the molar ratio of the manganese nitrate tetrahydrate to the metal barium is 1:20) into the barium titanate solution, continuously stirring the mixture for 100min, dropwise adding deionized water into the barium titanate solution through a needle tube to form gel, continuously stirring and aging the barium titanate wet gel for 36h to obtain manganese-doped barium titanate wet gel, and finally placing the manganese-doped barium titanate wet gel into a reaction kettle for CO treatment2Supercritical drying, setting the drying temperature at 50 ℃, keeping constant pressure of 10MPa for 12h at a certain gas outlet rate, closing gas inlet, and releasing the pressure in the reaction kettle to obtain the manganese-doped barium titanate aerogel prepared by the double metal alkoxide method. The density of the prepared material is 0.80g/cm3Specific surface area 176.5m2The average pore diameter is 18nm, the concentration of 1g/L is used as the input standard of manganese-doped barium titanate aerogel, 10mg/L methyl orange solution with pH of 3 is subjected to ultraviolet degradation, 94 percent of MO can be degraded within 1 hour, and the reaction rate reaches 0.0325min-1。
Example 3
Weighing 80ml of isopropanol solution, putting the isopropanol solution into a container, adding 0.4g of metal calcium, stirring the isopropanol solution at 35 ℃ for 180min until the metal calcium is completely dissolved to form a calcium isopropoxide solution, after the calcium isopropoxide solution is cooled to room temperature, sequentially adding 110ml of toluene and 3.5733g of tetrabutyl titanate (the molar ratio of the metal calcium to the tetrabutyl titanate is 1:1.05), stirring the mixture at 30 ℃ for 60min to obtain a calcium titanate solution, adding 0.1164g of cobalt nitrate hexahydrate (the molar ratio of the cobalt nitrate hexahydrate to the metal calcium is 1:25) into the calcium titanate solution, continuously stirring the mixture for 60min, dropwise adding deionized water into a needle tube to form gel, continuously stirring and aging the gel for 72h to obtain cobalt-doped calcium titanate wet gel, finally putting the cobalt-doped calcium titanate wet gel into ethanol supercritical equipment for supercritical drying, setting the drying temperature to be 270 ℃, keeping the pressure at 10MPa and keeping the pressure at a constant pressure state for 3h after the temperature is increased, then protectAnd releasing the gas within 30min at a constant speed, and taking out the gas after the temperature of the reaction kettle is reduced to obtain the cobalt-doped calcium titanate aerogel prepared by the bimetallic alkoxide method. The density of the prepared material is 0.73g/cm3Specific surface area 94.23m2The average pore diameter is 32nm, the concentration of 1g/L is used as the input standard of the cobalt-doped calcium titanate aerogel, a 10mg/L methyl orange solution with the pH value of 3 is subjected to ultraviolet light degradation, 92 percent of MO can be degraded within 1 hour, and the reaction rate reaches 0.0349min-1。
Example 4
Weighing 20ml of isopropanol solution, placing the isopropanol solution into a container, adding 0.4g of metal calcium, stirring the isopropanol solution at 45 ℃ for 90min until the metal calcium is completely dissolved to form a calcium isopropoxide solution, after the calcium isopropoxide solution is cooled to room temperature, sequentially adding 80ml of toluene and 2.95g of isopropyl titanate (the molar ratio of the metal calcium to the isopropyl titanate is 1:1.04), stirring the mixture at 35 ℃ for 40min to obtain a calcium titanate solution, adding 0.23g of cadmium nitrate tetrahydrate (the molar ratio of the cadmium nitrate tetrahydrate to the metal calcium is 1:10) into the calcium titanate solution, continuously stirring the mixture for 40min, dropwise adding deionized water into the calcium titanate solution at a speed of 1 drop/second by using a needle tube to form gel, continuously stirring and aging the mixture for 48h to obtain cadmium-doped calcium titanate wet gel, finally placing the cadmium-doped calcium titanate wet gel into ethanol supercritical equipment for supercritical drying, setting the drying temperature to be 200 ℃, and maintaining the pressure to be 10MPa after the temperature rises, maintaining the state for 3 hours at constant temperature and constant pressure, then keeping the constant speed, releasing the gas within 30min, and taking out the gas after the temperature of the reaction kettle is reduced to obtain the cadmium-doped calcium titanate aerogel prepared by the bimetallic alkoxide method. The density of the prepared material is 0.28g/cm3Specific surface area 186.7m2The average pore diameter is 17nm, the concentration of 1g/L is used as the input standard of cadmium-doped calcium titanate aerogel, methyl orange solution with pH of 3 and the concentration of 10mg/L is subjected to ultraviolet light degradation, 95 percent of MO can be degraded within 1 hour, and the reaction rate reaches 0.0532min-1。
Example 5
Weighing 30ml of mixed solution of methanol and 15ml of isopropanol, putting the mixed solution into a container, adding 1.373g of metal barium, stirring the mixed solution at 80 ℃ for 30min until the metal barium is completely dissolved to form mixed solution of barium methoxide and barium isopropoxide until the barium methoxide is completely dissolvedAnd cooling the mixed solution of the barium isopropoxide to room temperature, sequentially adding 160ml of toluene and 3.5g of tetrabutyl titanate (the molar ratio of the metal barium to the tetrabutyl titanate is 1:1.03), stirring for 30min at 40 ℃ to obtain a barium titanate solution, adding 0.0837g of manganese nitrate tetrahydrate (the molar ratio of the manganese nitrate tetrahydrate to the metal barium is 1:30) into the barium titanate solution, continuously stirring for 30min, dropwise adding deionized water by using a needle tube to form gel, continuously stirring and aging for 48h to obtain manganese-doped barium titanate wet gel, finally quenching the manganese-doped barium titanate wet gel by using liquid nitrogen, and drying for 24h in a 50Pa freeze dryer to obtain the manganese-doped barium titanate aerogel prepared by a double metal alkoxide method. The density of the prepared material is 0.18g/cm3Specific surface area 110.19m2The average pore diameter is 20nm, the concentration of 1g/L is used as the input standard of manganese-doped barium titanate aerogel, methyl orange solution with pH of 3 and the concentration of 10mg/L is subjected to ultraviolet light degradation, 87 percent of MO can be degraded in 1 hour, and the reaction rate reaches 0.0314min-1。
Example 6
Weighing 20ml of mixed solution of ethanol and 20ml of isopropanol, putting the mixed solution into a container, adding 0.8762g (0.01mol) of metal strontium, stirring the mixed solution at 60 ℃ for 70min until the metal strontium is completely dissolved to form a mixed solution of strontium acetate and strontium isopropoxide, cooling the mixed solution of the strontium acetate and the strontium isopropoxide to room temperature, sequentially adding 110ml of toluene and 3.57g (0.0105mol) of tetrabutyl titanate (the molar ratio of the metal strontium to the tetrabutyl titanate is 1:1.05), stirring the mixed solution at 30 ℃ for 80min to obtain a strontium titanate solution, adding 0.0582g of nickel nitrate hexahydrate (the molar ratio of the nickel nitrate hexahydrate to the metal strontium is 1:50) into the strontium titanate solution, continuously stirring the solution for 50min, dropwise adding deionized water by using a needle tube to form gel, continuously stirring and aging the gel for 72h to obtain a nickel-doped strontium titanate wet gel, finally putting the nickel-doped strontium titanate wet gel into a reaction kettle for CO treatment2Supercritical drying, setting the drying temperature to be 60 ℃, maintaining the constant pressure of 10MPa for 12h at a certain air outlet rate, closing air inlet and releasing the pressure in the reaction kettle to obtain the nickel-doped strontium titanate aerogel prepared by the double metal alkoxide method. The density of the prepared material is 0.83g/cm3Specific surface area 124.98m2G, average pore diameter of 20nm, with 1The concentration of g/L is used as the input standard of the nickel-doped strontium titanate aerogel, a 10mg/L methyl orange solution with the pH of 3 is subjected to ultraviolet light degradation, 91 percent of MO can be degraded in 1 hour, and the reaction rate reaches 0.0328min-1。
Claims (9)
1. A preparation method of a light transition metal doped perovskite aerogel material comprises the following specific steps:
(1) preparation of Metal alkoxide solution
Weighing an alcohol solvent, putting the alcohol solvent into a container, adding metal, heating and stirring until the metal is completely dissolved to form a solution A;
(2) mixing of raw materials
After the solution A in the step (1) is completely dissolved, adding toluene and a titanium source, and continuously stirring for reaction to obtain a solution B;
(3) preparation of light transition metal doped perovskite wet gel
Adding hydrated nitrate corresponding to the light transition metal into the clear solution B obtained in the step (2), stirring, then dropwise adding deionized water to form gel, and continuously stirring and aging to obtain wet gel;
(4) drying of light transition metal doped perovskite wet gel
And (4) drying the light transition metal doped perovskite titanate wet gel obtained in the step (3), and taking out a sample to obtain the light transition metal doped perovskite titanate aerogel.
2. The preparation method according to claim 1, wherein the alcohol solvent in step (1) is a mixture of one or more of methanol, ethanol or isopropanol.
3. The method according to claim 1, wherein the metal in step (1) is one of calcium, barium or strontium; the volume ratio of the mass of the metal to the alcohol solvent is 5-50 g/L.
4. The method according to claim 1, wherein the temperature in step (1) is increased to 30 to 80 ℃ and the stirring time is increased to 30 to 180 min.
5. The preparation method according to claim 1, wherein the titanium source used in the step (2) is one of isopropyl titanate or tetrabutyl titanate, the metal and the titanium source are mixed according to a molar ratio of 1 (0.95-1.05), and the mass volume ratio of the metal and the toluene is 2-10 g/L.
6. The method according to claim 1, wherein the reaction temperature in the step (2) is 10 to 40 ℃ and the stirring time is 30 to 120 min.
7. The preparation method according to claim 1, wherein the hydrated nitrate corresponding to the light transition element in the step (3) is one of chromium nitrate nonahydrate, nickel nitrate hexahydrate, cobalt nitrate hexahydrate, cadmium nitrate tetrahydrate and manganese nitrate tetrahydrate, and the hydrated nitrate corresponding to the light transition element and the metal are mixed according to a molar ratio of 1 (10-50).
8. The method according to claim 1. The method is characterized in that the reaction temperature in the step (3) is 10-40 ℃, the stirring time is 30-120 min, and the aging time is 24-72 h.
9. The method according to claim 1. Characterized in that the drying method in the step (4) is freeze drying and CO2Supercritical drying or ethanol supercritical drying.
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