CN111589382B - Ptn-MxWO3/SiO2Composite aerogel and preparation method thereof - Google Patents

Ptn-MxWO3/SiO2Composite aerogel and preparation method thereof Download PDF

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CN111589382B
CN111589382B CN202010406887.XA CN202010406887A CN111589382B CN 111589382 B CN111589382 B CN 111589382B CN 202010406887 A CN202010406887 A CN 202010406887A CN 111589382 B CN111589382 B CN 111589382B
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sio
composite aerogel
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CN111589382A (en
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史非
刘敬肖
杨静媛
宋晓颖
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Dalian Polytechnic University
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Abstract

The invention relates to a Ptn‑MxWO3/SiO2A composite aerogel and a preparation method thereof belong to the technical field of new materials, energy conservation and environmental protection. Ptn‑MxWO3/SiO2Composite aerogel of said Ptn‑MxWO3/SiO2The whole composite aerogel has a porous network structure, and the specific surface area of the composite aerogel is 100-300 m2A pore volume of 0.4 to 2.0 cm/g3(iv) per gram, pore diameter is 5-25 nm; pt is embedded in composite aerogel porous network structuren‑MxWO3Nanorod crystal grains of said Ptn‑MxWO3The nanorod grains have hexagonal tungsten bronze MyWO3A crystal structure wherein MyWO3Where M is Li, Na, K, Rb, Cs, NH4Y is 0.2 to 0.7, and n is 0.001 to 0.1. The invention provides Ptn‑MxWO3/SiO2The composite aerogel has visible light transmission, near infrared shielding performance, heat insulation and pollutant adsorption/photocatalytic degradation performance.

Description

Ptn-MxWO3/SiO2Composite aerogel and preparation method thereof
Technical Field
The invention relates to a Ptn-MxWO3/SiO2A composite aerogel and a preparation method thereof belong to the technical field of new materials, energy conservation and environmental protection.
Background
With the development of society and the improvement of productivity, energy crisis and environmental pollution become more serious, and energy conservation, consumption reduction and environmental purification are increasingly concerned by the whole society. Reducing the energy consumption of buildings is one of the main ways of energy conservation and emission reduction at present, and windows are also important media for indoor and outdoor energy exchange. The transparent heat insulation film prepared on the surface of the glass can ensure that the glass achieves ideal heat insulation performance under the condition of ensuring certain visible light transmittance, and the photocatalysis technology for degrading pollutants through photocatalysis is widely applied to the field of environmental purification. Therefore, the development of a new material with the functions of transparent heat insulation and pollutant adsorption-photocatalytic degradation has great practical significance.
MxWO3The material is a semiconductor material with excellent near infrared shielding performance, MxWO3High carrier concentration caused by the special structure of the Pt doped M has strong absorption and shielding functions on near infrared light and full spectrum photocatalytic degradation function on organic pollutants, and Pt is doped with MxWO3(Pt-MxWO3) The functions of near infrared shielding and photocatalytic pollutant degradation can be further improved. SiO 22The aerogel nano-porous material has good adsorption capacity and heat insulation performance due to high specific surface area, high porosity and low heat conductivity. Mixing SiO2AerogelWith Pt-MxWO3Nanoparticle combination for preparing Pt-MxWO3-SiO2The obtained product of the composite aerogel material not only has excellent adsorption-photocatalysis synergistic effect, but also has near-infrared shielding and heat-insulating properties, and has wide application prospect in the fields of heat insulation, energy conservation and environmental purification.
Mixing SiO2The functional composite aerogel materials prepared by compounding the aerogel and the functional nanoparticles have been reported more. Patent CN 104689784A combines photocatalyst with SiO2Compounding, preparing SiO loaded with photocatalyst by solvothermal and atmospheric drying method2Composite aerogel (CN 104689784A, a photocatalyst-supporting SiO2Composite aerogel materials and methods of making the same). Patent CN 107694490A reports a preparation method of silica-iron oxide aerogel and silica-iron aerogel, iron oxide or iron is compounded in different ways, and magnetic SiO is synthesized2Aerogel (CN 107694490 a, a method for preparing silicon-iron composite aerogel). In addition, studies have been reported by combining Cs0.33WO3Dispersing the nano particles in silicic acid solution to prepare Cs0.33WO3-SiO2Composite aerogel material, using SiO2High adsorption efficiency and Cs conferred by the special pore structure of the aerogelxWO3The particles have excellent ultraviolet light catalytic performance, and more excellent adsorption/photocatalysis Materials (Materials) can be obtained&Design,2016(110), 624-. However, at present, the in-situ synthesis process is adopted to prepare the Pt-M with the functions of adsorption/photocatalysis and near infrared shielding/heat insulationxWO3/SiO2The research of the composite aerogel has not been reported.
Disclosure of Invention
The invention aims to provide Pt-MxWO3/SiO2Composite aerogel and a preparation method thereof, wherein M ═ Li, Na, K, Rb, Cs and NH4X is 0.2-1, n is 0.001-0.1, the composite aerogel has a porous network structure, and Pt is embedded in the porous networkn-MxWO3The crystal phase structure of the nanorod cluster is hexagonal tungsten bronze MyWO3The specific surface area of the composite aerogel with a crystal structure is 100-300 m2A pore volume of 0.4 to 2.0 cm/g3(g) the pore diameter is 5-25 nm.
Ptn-MxWO3/SiO2Composite aerogel of said Ptn-MxWO3/SiO2The whole composite aerogel has a porous network structure, and the specific surface area of the composite aerogel is 100-300 m2A pore volume of 0.4 to 2.0 cm/g3Per gram, the diameter of the hole is 5-25 nm; pt is embedded in composite aerogel porous network structuren-MxWO3Nanorod crystal grains of said Ptn-MxWO3The nanorod grains have hexagonal tungsten bronze MyWO3Crystal structure, wherein M ═ Li, Na, K, Rb, Cs, NH4，y＝0.2～0.7，n＝0.001～0.1，x＝0.2～1。
Pt as described in the present inventionn-MxWO3/SiO2The composite aerogel has the high-efficiency adsorption/heat-insulation performance of porous aerogel and Ptn-MxWO3The particles are excellent in near-infrared shielding/photocatalytic properties, and therefore, the Ptn-MxWO3/SiO2The composite aerogel not only has a good heat insulation function, but also has a good pollutant adsorption/photocatalytic degradation function, and has a wide application prospect in the fields of heat insulation, energy conservation and environmental protection.
It is still another object of the present invention to provide the above Ptn-MxWO3/SiO2A preparation method of the composite aerogel.
Ptn-MxWO3/SiO2A process for preparing composite aerogel from industrial water glass as silicon source, sodium tungstate as tungsten source and chloroplatinic acid as Pt source includes such steps as preparing silicic acid and tungstic acid solution by cation exchange method, preparing composite gel block by sol-gel method, and in-situ synthesizing Pt by solvothermal reaction, surface modification and normal-pressure dryingn-MxWO3/SiO2Compounding aerogel materials.
Pt as described in the present inventionn-MxWO3-SiO2The preparation method of the composite aerogel is an in-situ synthesis/normal pressure drying process method, wherein the in-situ synthesis preparation method comprises the steps of preparing silicic acid and tungstic acid solution by using a cation exchange method, preparing mixed sol and gel, and then carrying out aging, solvothermal reaction deposition, modification and drying in a solvent to obtain Ptn-MxWO3-SiO2Compounding aerogel materials. The main process is as follows: the method comprises the steps of taking industrial water glass as a silicon source, sodium tungstate as a tungsten source and chloroplatinic acid as a Pt source, preparing silicic acid and tungstic acid solution by a cation exchange method, preparing composite gel by a sol-gel method, and synthesizing Pt by a solvothermal reaction, surface modification and normal-pressure drying processn-MxWO3-SiO2Compounding aerogel materials.
Pt of the inventionn-MxWO3/SiO2In the preparation method of the composite aerogel, the sol-gel method is preferably as follows: mixing a silicic acid solution and a tungstic acid solution under the condition of stirring, adding M salt, chloroplatinic acid and an inducer, stirring and uniformly mixing to prepare a mixed sol; aging the mixed sol at the temperature of 20-90 ℃ until the mixed sol is converted into gel, wherein,
the ratio of the silicic acid solution to the tungstic acid solution is that the Si/W molar ratio is 0.5-15: 1; the M salt contains Li, Na, K, Rb, Cs and NH4The salt (2) has an M/W atomic molar ratio of 0.2-1: 1; the adding amount of the chloroplatinic acid is that the molar ratio of the chloroplatinic acid to the tungstic acid is 0.001-0.1: 1; the inducer is oxalic acid, formic acid, tartaric acid, acetic acid, lactic acid, citric acid, ascorbic acid, sorbitol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, sorbic acid, polypropylene glycol, potassium borohydride, sodium borohydride, aniline, acetylacetone, N2H4·H2O、N2H4·HCl、N2H4·H2SO4The molar ratio of the inducer to the W atom is 0.05-15: 1.
Further, the sol-gel further comprises an aging treatment step: and (3) placing the composite gel block in an ethanol/water solution, and aging for 0.5-48 h at 20-60 ℃ to obtain the composite gel block.
Further, a pore-expanding agent can be added in the preparation process of the composite sol, and the concentration of the pore-expanding agent in the composite sol is 1-100 g/L; the pore-expanding agent is one or more of bacterial cellulose, cellulose acetate, nano-cellulose, methyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, polymethyl methacrylate (PMMA) microspheres, PMMA fibers, polyvinylpyrrolidone (PVP), PVP fibers, hexamethylenetetramine, dimethylformamide, dimethylacetamide, polystyrene fibers, P123 and F127.
Pt of the inventionn-MxWO3/SiO2In the preparation method of the composite aerogel, the solvothermal reaction is preferably performed in a reaction kettle, and the method specifically comprises the following steps: placing the aged composite gel block into a reaction solution, reacting the composite gel block for 5 to 96 hours at the temperature of between 120 and 400 ℃, washing the reacted composite gel block for 1 to 3 times by using a washing solvent to obtain the gel block,
wherein the volume ratio of the reaction liquid to the gel block is 0.5-3: 1, the reaction solution is one or a mixture of the following solvents: one or a mixture of water, methanol, ethanol, propanol, butanol, isopropanol, diethyl ether, acetone, benzene, toluene, xylene, pentane, hexane, octane, cyclohexane, cyclohexanone, chlorobenzene, dichlorobenzene, dichloromethane, propylene oxide, methyl acetate, ethyl acetate, propyl acetate, acetylacetone, methyl butanone, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine and phenol; the reaction solution is a mixture consisting of the solvent and an inducer, and the inducer is oxalic acid, formic acid, tartaric acid, acetic acid, lactic acid, citric acid, ascorbic acid, sorbitol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, sorbic acid, polypropylene glycol, potassium borohydride, sodium borohydride, aniline, acetylacetone, N-acetyl-N-O-N-L-N-O-L-N-O-N-O-N-O-N-O-N-O-N-O-N-O2H4·H2O、N2H4·HCl、N2H4·H2SO4The concentration of the inducer in the reaction solution is 0.5-2.5 mol/L; the washing solvent is one or more of deionized water, ethanol, isopropanol, acetone, n-hexane, cyclohexane or heptane.
Pt of the inventionn-MxWO3/SiO2In the preparation method of the composite aerogel, the surface modification is preferably as follows: placing the composite gel obtained through solvothermal reaction in a modification liquid, and supplementing and adding new TMCS every 2-24 hours, wherein the volume ratio of the addition amount to the alkane solvent is 0.025-0.5: 1, finishing modification until the composite gel block floats on the liquid level of the modification liquid,
the modification solution is composed of alkane solvents and Trimethylchlorosilane (TMCS), the alkane solvents are selected from one or more of n-hexane, cyclohexane, heptane or pentane and other solvents, and the volume ratio of the addition amount of the initial alkane solvents to the composite gel block is 0.5-3: 1, the volume ratio of TMCS addition to the alkane solvent is 0.025-0.5: 1.
pt of the inventionn-MxWO3/SiO2In the preparation method of the composite aerogel, the normal pressure drying process is preferably as follows: drying the modified wet gel at normal pressure, wherein the heating rate is 0.3-10 ℃/min, and the wet gel is respectively kept at 60 ℃, 80 ℃, 100 ℃, 120 ℃ and 150 ℃ for 2 h; or drying at 70 deg.C, 90 deg.C, 110 deg.C, and 130 deg.C for 2 hr; or slowly heating to 120-150 ℃ from room temperature, and keeping the temperature for 2h, wherein the heating rate is 0.5-5 ℃/min, so as to obtain Pt-MxWO3-SiO2And (3) compounding the aerogel.
Pt of the inventionn-MxWO3/SiO2In the preparation method of the composite aerogel, the method preferably further comprises the following heat treatment steps: drying the obtained Pt under normal pressuren-MxWO3/SiO2The composite aerogel is subjected to a heat treatment process, which specifically comprises the following steps: at H2、N2Or N2/H2(1-5%) heat treatment in mixed gas, raising temperatureThe speed is 1-10 ℃/min, the heat treatment temperature is 200-800 ℃, and the optimal temperature is 300-600 ℃.
The invention has the beneficial effects that: the invention is creative in that the prepared Ptn-MxWO3-SiO2The composite aerogel not only has the advantages of higher specific surface area, high pore volume and the like, but also has Pt embedded in a porous network structuren-MxWO3A nanorod cluster, which can be prepared with high pore volume and high Pt contentn-MxWO3Pt of (2)n-MxWO3-SiO2Composite aerogel material, and Ptn-MxWO3Nano-rod cluster in SiO2The dispersion in the aerogel network is more uniform, and the prior M synthesized by the aerogel networkxWO3Preparation of M by dispersing nano particles in silicic acid sol by mechanical methodxWO3-SiO2Compared with the method for compounding the aerogel, the method avoids MxWO3M in the process of solvent exchange-surface modification treatment of dispersive unevenness and composite wet gel blockxWO3The problem of easy loss is solved by adopting the inlaid Pt prepared by the in-situ synthesis/normal pressure drying process methodn-MxWO3The nanorod cluster composite aerogel porous network structure is more beneficial to achieving high-efficiency pollutant adsorption/photocatalytic degradation capability and has more excellent visible light transmission/near infrared shielding performance.
Pt prepared by the inventionn-MxWO3/SiO2The composite aerogel has a mesoporous network structure, a high specific surface area and a high pore volume, has excellent adsorption performance and heat insulation performance, and simultaneously has excellent visible light transmission-near infrared shielding and photocatalytic performance.
The creativity of the invention is that the Pt prepared by the processes of in-situ sol-gel, solvothermal, surface modification and normal pressure dryingn-MxWO3-SiO2The composite aerogel not only maintains the porous network structure of the aerogel, but also can ensure that the composite aerogel loads Pt with higher content in the hexagonal tungsten bronze crystal structuren-MxWO3Particles, and a porous aerogel network structure embedded with Ptn-MxWO3The nano-rod particles enable the composite aerogel to have high pore volume, high specific surface area and higher Pt simultaneouslyn-MxWO3Characteristic of crystal phase content, embedded with Ptn-MxWO3Pt of nanorod particlesn-MxWO3-SiO2The porous network structure of the composite aerogel is beneficial to excellent adsorption/photocatalysis and heat insulation performance. Under the irradiation of light, the composite aerogel has higher near-infrared absorption/shielding performance under the condition of keeping higher transmittance to visible light; and the composite material can simultaneously have excellent adsorption performance and good photocatalysis performance, and the adsorption-photocatalysis and near infrared absorption synergistic effect and mutual promotion can effectively remove harmful pollutants in water, air and the surrounding environment. Thus, the invention provides Ptn-MxWO3-SiO2The composite aerogel has wide application prospect and market prospect in the aspects of energy-saving glass and environmental purification.
In addition, the invention prepares Pt by a normal pressure drying processn-MxWO3-SiO2The preparation method of the composite aerogel has the advantages of low raw material and process cost, short production period and low requirement on production equipment, can improve the production efficiency of the aerogel, and is convenient for realizing large-scale industrial production.
In conclusion, the beneficial effects of the invention are as follows: (1) the low-cost sodium silicate and sodium tungstate dihydrate are used as a silicon source and a tungsten source, and the normal-pressure drying process has low requirements on equipment and low production cost, and is beneficial to industrial production; (2) preparation of Pt by in situ Synthesisn-MxWO3-SiO2Composite aerogels, Ptn-MxWO3The nano particles are uniformly distributed in the porous aerogel network; (3) pt prepared by the inventionn-MxWO3-SiO2The composite aerogel has excellent performance, not only has the advantages of high specific area, high porosity, low thermal conductivity and the like, but also has visible light transmission, near infrared light shielding/heat insulation performance and adsorption/photocatalysis performance, and gasAdsorptivity, low thermal conductivity and Pt of geln-MxWO3The photocatalysis and near-infrared shielding synergistic effect of the composite aerogel can further improve the adsorption/photocatalysis and heat insulation energy-saving effects of the composite aerogel. Therefore, the invention provides Ptn-MxWO3-SiO2The composite aerogel is expected to be widely applied to the energy-saving and environment-friendly fields of heat insulation, energy conservation, adsorption/photocatalysis and the like.
Drawings
FIG. 1 shows Pt obtained in example 3n-MxWO3/SiO2TEM photograph of the composite aerogel.
FIG. 2 shows Pt obtained in example 4n-MxWO3/SiO2TEM photograph of the composite aerogel. As can be seen from FIGS. 1 and 2, the prepared composite aerogel porous network is embedded with Ptn-CsxWO3Or Ptn-KxWO3And (4) a cluster formed by the nano rods.
FIG. 3 shows Pt obtained in examples 5 to 7n-MxWO3/SiO2XRD spectrogram of the composite aerogel shows that the synthesized Ptn-CsxWO3-SiO2The crystalline phase in the composite aerogel is mainly hexagonal tungsten bronze Cs0.20WO3。
FIG. 4 shows Pt obtained in examples 6 and 7n-MxWO3/SiO2The adsorption/photocatalytic degradation curve of the composite aerogel product to formaldehyde can be seen, the prepared composite aerogel sample has excellent adsorption/photocatalytic degradation effect on formaldehyde, and the adsorption/degradation rate can reach 97.3%.
Fig. 5 is a graph showing spectral transmittance of glass surfaces coated with sample thin films prepared in comparative examples 1, 2 and 7, and it can be seen that example 7 exhibits better near infrared shielding properties than comparative examples 1 and 2.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
In the following examples, the prepared Pt was treatedn-MxWO3-SiO2The properties of the composite aerogel were determined as follows:
(1) characterization of Pt Using an X-ray diffractometer from Shimadzu Japan, model XRD-7000Sn-MxWO3-SiO2The composite aerogel adopts Cu Kalpha rays, lambda is 0.15406nm, the scanning speed is 5 degrees/min, the scanning step is 0.01 degree, and the scanning range 2 theta is 10 degrees to 70 degrees.
(2) The prepared mesoporous Pt is subjected to transmission electron microscope (JEM-2100(UHR), Japan electron)n-MxWO3-SiO2And (5) carrying out surface morphology analysis on the composite aerogel material.
(3) By using N2Model SSA-4200 BET pore size and specific surface area Analyzer for Pt as Carrier gasn-MxWO3-SiO2Specific surface area, pore size distribution, pore volume, and most probable pore size of the composite aerogel.
(4) Coating 0.1g of aerogel powder on a glass sheet of 10cm multiplied by 7cm, placing the glass sheet in a sealed container, and testing the formaldehyde adsorption/photocatalytic degradation effect of the composite aerogel under the irradiation of a fluorescent lamp.
(5) And testing the spectral transmittance of the composite aerogel particle dispersion liquid at a wave band of 250-2500 nm after the composite aerogel particle dispersion liquid is coated on the surface of glass by using a UV-Vis-NIR spectrometer (Lambda 950, Perkin Elmer), so as to evaluate the visible light transmittance and the near-infrared shielding performance of the composite aerogel.
One of the specific implementation modes is as follows:
ptn-MxWO3/SiO2The preparation method of the composite aerogel specifically comprises the following steps:
firstly, dissolving tungstate into water to obtain a tungstate solution with the concentration of 0.01-5 mol/L;
dissolving silicate into water to obtain a silicate solution with the concentration of 0.01-5 mol/L;
thirdly, respectively converting the prepared tungstate solution and silicate solution into a tungstic acid solution and a silicic acid solution by a cation exchange method, wherein the pH value of the tungstic acid solution is 1-5, and the pH value of the silicic acid solution is 1-6;
respectively measuring a certain volume of silicic acid solution and a certain volume of tungstic acid solution, mixing under the condition of stirring, adding a certain amount of M salt, chloroplatinic acid and an inducer, stirring and mixing uniformly, and preparing mixed sol;
placing the mixed sol at the temperature of 20-90 ℃ for aging treatment until the mixed sol is converted into gel;
sixthly, placing the composite gel block in an ethanol/water solution, and aging at 20-60 ℃ for 0.5-48 h (or not performing the step);
selecting a proper solvent, and preparing a reaction solution, wherein the volume ratio of the reaction solution to the gel block is (0.5-3): 1; placing the composite gel block aged in the step (sixthly) in the prepared reaction solution, and reacting the composite gel block at the temperature of 120-400 ℃ for 5-96 hours;
eighthly, washing the reacted composite gel block for 1-3 times by using a solvent;
ninthly, carrying out modification treatment on the composite gel block, wherein a modification liquid is composed of an alkane solvent and Trimethylchlorosilane (TMCS), the alkane solvent is selected from one or more of n-hexane, cyclohexane, heptane or pentane, and the volume ratio of the addition amount of the alkane solvent to the composite gel block is 0.5-3: 1, the volume ratio of TMCS addition to the alkane solvent is 0.025-0.5: 1, supplementing and adding new TMCS every 2-24 hours, wherein the volume ratio of the addition amount to the alkane solvent is 0.025-0.5: 1 until the modification is complete, no water is separated from the gel mass and the gel mass can float on the water surface.
Optionally, drying the modified wet gel at normal pressure at a heating rate of 0.3-10 deg.C/min at 60 deg.C, 80 deg.C, 100 deg.C, 120 deg.C, 150 deg.C for 2h to obtain Pt-MxWO3-SiO2Compounding aerogel;
in the above technical scheme, the tungstate in the step (i) is one or a mixture of sodium tungstate, potassium tungstate, ammonium metatungstate, ammonium ortho-tungstate, ammonium paratungstate and alkali tungstate; the M salt is cesium salt and potassium salt; further, the cesium salt is preferably cesium sulfate, cesium carbonate, cesium chloride, cesium nitrate or cesium acetate, and the potassium salt is preferably potassium sulfate, potassium carbonate, potassium chloride, potassium nitrate or potassium acetate.
In the above technical scheme, the silicate in the step (II) is one or a mixture of sodium silicate and potassium silicate;
in the technical scheme, the tungstate solution in the third step is preferably prepared into a sodium tungstate dihydrate solution, and then the sodium tungstate dihydrate solution is subjected to ion exchange by using styrene cation exchange resin to obtain a tungstic acid solution with the concentration of 0.1-2.8 mol/L, pH-1-4; the silicate solution is preferably industrial water glass with the modulus of 3.0-4.0 according to VWater glass：VWater (W)Diluting the solution with deionized water in a ratio of 1:2 to 1:12, and then performing ion exchange through styrene cation exchange resin to obtain silicic acid with the pH value of 2 to 4;
in the technical scheme, the adding amount of the silicic acid solution and the tungstic acid solution in the step IV is determined according to the Si/W molar ratio of 0.05-15: 1, the M salt contains Li, Na, K, Rb, Cs and NH4The molar ratio of M/W atoms of the salt (2) to (1: 1); the inducer is oxalic acid, formic acid, tartaric acid, acetic acid, lactic acid, citric acid, ascorbic acid, sorbitol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, sorbic acid, polypropylene glycol, potassium borohydride, sodium borohydride, aniline, acetylacetone, N2H4·H2O、N2H4·HCl、N2H4·H2SO4One or a mixture thereof, wherein the molar ratio of the inducer to the W atom is 0.05-15: 1;
further, the Si/W molar ratio is preferably 0.1 to 10: 1.
Further, a pore-expanding agent can be added in the preparation process of the composite sol in the step (iv), wherein the pore-expanding agent is one or more of bacterial cellulose, cellulose acetate, nano-cellulose, methyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, polymethyl methacrylate (PMMA) microspheres, PMMA fibers, polyvinylpyrrolidone (PVP), PVP fibers, hexamethylenetetramine, dimethylformamide, dimethylacetamide, polystyrene fibers, P123 and F127.
In the above technical scheme, the mixed sol in the fifth step is preferably aged at 30-80 ℃ to convert the mixed sol into gel.
In the technical scheme, the volume ratio of ethanol to water in the ethanol/water solution in the step (sixthly) is 0.1-10: 1.
in the technical scheme, the composite gel in the step (sixty) can be aged for 0.5 to 48 hours in air or pure deionized water at the temperature of 20 to 60 ℃.
In the above technical solution, the solvent in step (c) is one or a mixture of water, methanol, ethanol, propanol, butanol, isopropanol, diethyl ether, acetone, benzene, toluene, xylene, pentane, hexane, octane, cyclohexane, cyclohexanone, chlorobenzene, dichlorobenzene, dichloromethane, propylene oxide, methyl acetate, ethyl acetate, propyl acetate, acetylacetone, methyl butanone, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine, and phenol; the reaction solution can also be added with an inducer, wherein the inducer is oxalic acid, formic acid, tartaric acid, acetic acid, lactic acid, citric acid, ascorbic acid, sorbitol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, sorbic acid, polypropylene glycol, potassium borohydride, sodium borohydride, aniline, acetylacetone, N2H4·H2O、N2H4·HCl、 N2H4·H2SO4One or a mixture of the above, wherein the concentration of the inducer in the reaction solution is 0.5-2.5 mol/L;
in the above technical scheme, the reaction condition of the step (c) is preferably at 150-300 ℃ for 10-80 hours.
In the above technical scheme, the solvent in the step (viii) is one or more of deionized water, ethanol, isopropanol, acetone, n-hexane, cyclohexane or heptane.
In the technical scheme, the modified wet gel in the step (c) is dried under normal pressure, the heating rate is 0.3-10 ℃/min, and the heat is preserved for 2 hours at 60 ℃, 80 ℃, 100 ℃, 120 ℃ and 150 ℃ respectively; or drying at 70 deg.C, 90 deg.C, 110 deg.C, and 130 deg.C for 2 hr; or slowly heating from room temperature to 120-150 ℃, and keeping the temperature for 2h, wherein the heating speed is 0.5-5 ℃/min.
The invention provides Ptn-MxWO3/SiO2The composite aerogel has visible light transmission, near infrared shielding performance, heat insulation and pollutant adsorption/photocatalytic degradation performance.
EXAMPLE 1 preparation of Pt0.01-Cs0.5WO3-5SiO2Composite aerogel
Firstly, preparing silicic acid and tungstic acid solution by ion exchange method
Preparation of silicic acid: measuring 60mL of industrial water glass with modulus of 3.0 according to VWater glass：VWater (W)Diluting with deionized water at a ratio of 1:4, and then performing ion exchange through styrene cation exchange resin to obtain silicic acid with a pH of 2-3;
preparing tungstic acid: firstly, 19.791g of sodium tungstate dihydrate is weighed and dissolved in 80mL of deionized water to prepare Na2WO4And then carrying out ion exchange on the solution by using a styrene cation exchange resin to obtain a tungstic acid solution with the concentration of 0.75mol/L, pH-1.5-3.
② preparing mixed sol and gel
Under the condition of stirring, weighing 30mL of silicic acid solution, 9.36mL of tungstic acid solution, 0.6351g of cesium sulfate, 0.915mL of 0.0772M chloroplatinic acid solution and 9.25g of citric acid monohydrate, and sequentially mixing to prepare mixed sol; the mixed sol was placed in a water bath at 60 ℃ to gel.
③ aging of the composite gel and thermal reaction of the solvent
The volume ratio of the composite gel at 25 ℃ is 1:1, aging in ethanol water solution for 8 hours; measuring 60mL of ethanol, adding 6.5g of citric acid monohydrate to prepare a reaction solution, placing the composite gel block in the reaction solution, and reacting at 190 ℃ for 72 hours to complete the solvothermal reaction.
Modification and normal pressure drying of composite gel
Transferring the composite gel block after the solvent thermal reaction into a beaker, soaking and washing the gel block by using normal hexane, and then adding a mixed solution of the normal hexane and TMCS, wherein the adding proportion of the TMCS is VTMCS：VRubber blockAnd (3) when the addition amount of the normal hexane is 0.05:1, the lowest limit is that the gel block can be completely immersed into the solution, after soaking for 24 hours, the water yield and the suspension condition of the gel block are observed to judge whether the modification solution needs to be added again, the steps are repeated until no water is separated out, and the gel block is suspended on the water surface.
Drying the modified rubber block under normal pressure, and keeping the temperature at 60 deg.C, 80 deg.C, 100 deg.C, 120 deg.C, 150 deg.C for 2h to obtain Pt0.01-Cs0.5WO3-5SiO2Compounding aerogel;
heat treatment of composite aerogel
Keeping the temperature of the composite aerogel prepared in the step (iv) at 400 ℃ for 30min under the hydrogen atmosphere condition, and increasing the temperature at a rate of 4 ℃/min to obtain the heat-treated Pt0.01-Cs0.5WO3-5SiO2And (3) compounding the aerogel.
Determined, Pt prepared by the method0.01-Cs0.5WO3-5SiO2The main crystal phase in the composite aerogel is Cs0.20WO3Having a specific surface area of 195m2G, pore volume 1.13cm3The mode pore diameter is 17.48 nm.
Example 2 preparation of Pt0.01-Cs0.5WO3-3SiO2Composite aerogel
Preparation of silicic acid and tungstic acid solutions by ion exchange was performed in the same manner as in example 1.
② preparing mixed sol and gel
Under the condition of stirring, weighing 20mL of silicic acid solution, 10.4mL of tungstic acid solution, 0.71g of cesium sulfate, 1.01mL of 0.0772M chloroplatinic acid solution and 7.03g of citric acid monohydrate, and sequentially mixing to prepare mixed sol; the mixed sol was placed in a water bath at 60 ℃ to gel.
③ aging of the composite gel and thermal reaction of the solvent
The volume ratio of the obtained composite gel at 25 ℃ is 1:1, aging in ethanol water solution for 24 hours; measuring 60mL of ethanol, adding 3.24g of oxalic acid to prepare a reaction solution, placing the composite gel block in the reaction solution, and reacting at 190 ℃ for 72 hours to complete the solvothermal reaction.
Modification and normal pressure drying of composite gel
Transferring the composite gel block after the solvothermal reaction to a beaker, soaking and washing the gel block by using heptane, and then adding a mixed solution of heptane and TMCS, wherein the adding proportion of the TMCS is VTMCS：VRubber blockAnd (3) when the ratio of heptane to the gel block is 0.05:1, the adding amount of heptane is the lowest limit that the gel block can be completely immersed into the solution, after soaking for 24 hours, observing the water yield and the suspension condition of the gel block to judge whether the modification solution needs to be added again, and repeating the steps until no water is separated out, and the gel block is suspended on the water surface.
Drying the modified rubber block under normal pressure, and keeping the temperature at 60 deg.C, 80 deg.C, 100 deg.C, 120 deg.C, 150 deg.C for 2h to obtain Pt0.01-Cs0.5WO3-5SiO2Compounding aerogel;
and fifthly, carrying out heat treatment on the composite aerogel, which is the same as the step fifthly in the embodiment 1.
Determined, Pt prepared by the method0.01-Cs0.5WO3-3SiO2The main crystal phase in the composite aerogel is Cs0.32WO3Having a specific surface area of 151m2Per g, pore volume of 0.75cm3The mode pore diameter is 14.53 nm.
Example 3 preparation of Pt0.01-Cs0.5WO3-2SiO2Composite aerogel
Preparation of silicic acid and tungstic acid solutions by ion exchange was performed in the same manner as in example 1.
② preparing mixed sol and gel
Weighing 20mL of silicic acid solution, 15.6mL of tungstic acid solution, 1.0585g of cesium sulfate, 1.52mL of 0.0772M chloroplatinic acid solution and 8.23g of citric acid monohydrate, and mixing sequentially under the condition of stirring to prepare mixed sol; the mixed sol was placed in a water bath at 60 ℃ to gel.
③ aging the composite gel and carrying out a solvothermal reaction, and the same procedure as in example 1.
Modification and atmospheric drying of the composite gel, which is the same as the step (iv) in example 1.
And fifthly, carrying out heat treatment on the composite aerogel, which is the same as the step fifthly in the embodiment 1.
Determined, Pt prepared by the method0.01-Cs0.5WO3-2SiO2The main crystal phase in the composite aerogel is Cs0.32WO3Having a specific surface area of 145m2Per g, pore volume of 0.43cm3The mode of pore diameter is 9.06 nm.
Example 4 preparation of Pt0.01-K0.5WO3-5SiO2Composite aerogel
Preparation of silicic acid and tungstic acid solutions by ion exchange was performed in the same manner as in example 1.
② preparing mixed sol and gel
Under the condition of stirring, weighing 30mL of silicic acid solution, 9.36mL of tungstic acid solution, 0.3058g of potassium sulfate, 0.915mL of 0.0772M chloroplatinic acid solution and 9.25g of citric acid monohydrate, and sequentially mixing to prepare mixed sol; the mixed sol was placed in a water bath at 60 ℃ to gel.
③ aging the composite gel and carrying out a solvothermal reaction, and the same procedure as in example 1.
Modification and atmospheric drying of the composite gel, which is the same as the step (iv) in example 1.
And fifthly, carrying out heat treatment on the composite aerogel, which is the same as the step fifthly in the embodiment 1.
Determined, Pt prepared by the method0.01-K0.5WO3-5SiO2The main crystal phase in the composite aerogel is K0.20WO3Having a specific surface area of 208m2Per g, pore volume 1.82cm3The mode pore diameter is 23.4 nm.
Example 5 preparation of Pt0.01-Cs0.5WO3-2SiO2Composite aerogel
Preparation of silicic acid and tungstic acid solutions by ion exchange was performed in the same manner as in example 1.
② preparing mixed sol and gel
Weighing 20mL of silicic acid solution, 15.6mL of tungstic acid solution, 1.05g of cesium sulfate, 1.52mL of 0.0772M chloroplatinic acid solution and 2.99g of citric acid monohydrate, and sequentially mixing under the stirring condition to prepare mixed sol; the mixed sol was placed in a water bath at 60 ℃ to gel.
③ aging of the composite gel and thermal reaction of the solvent
60mL of isopropanol is measured, 6.73g of sorbic acid is added to prepare a reaction solution, and the composite gel block is placed in the reaction solution to react for 72 hours at 190 ℃ to complete the solvothermal reaction.
Modification and atmospheric drying of the composite gel, which is the same as the step (iv) in example 1.
Determined, Pt prepared by the method0.01-Cs0.5WO3-2SiO2The main crystal phase in the composite aerogel is Cs0.20WO3Having a specific surface area of 110m2Per g, pore volume of 0.52cm3(ii)/g, most probable pore diameter is 16.16 nm; the visible light transmittance of the prepared film is 76.06%, and the near infrared shielding rate is 29.75%.
Example 6 preparation of Pt0.01-Cs0.5WO3-2SiO2Composite aerogel
Preparation of silicic acid and tungstic acid solutions by ion exchange was performed in the same manner as in example 1.
② preparing mixed sol and gel, and the same procedure as in the second step of the example 5.
③ aging the composite gel and carrying out a solvothermal reaction, and the same procedure as in EXAMPLE 5.
And fourthly, modification and normal pressure drying of the composite gel are carried out in the same way as the step IV in the example 5.
Heat treatment of composite aerogel
Keeping the temperature of the composite aerogel prepared in the step (iv) at 400 ℃ for 30min under the hydrogen atmosphere condition, and increasing the temperature at a rate of 10 ℃/min to obtain the heat-treated Pt0.01-Cs0.5WO3-2SiO2And (3) compounding the aerogel.
The Pt-Cs prepared by the method is determined0.5WO3-2SiO2The main crystal phase in the composite aerogel is Cs0.20WO3Having a specific surface area of 135m2Per g, pore volume of 0.70cm3(ii)/g, most probable pore diameter is 16.37 nm; the visible light transmittance of the prepared film is 78.36%, and the near infrared shielding rate is 41.09%.
EXAMPLE 7 preparation P t0.01-Cs0.5WO3-2SiO2Composite aerogel
Preparation of silicic acid and tungstic acid solutions by ion exchange was performed in the same manner as in example 1.
② preparing mixed sol and gel, and the same procedure as in the second step of the example 5.
③ aging the composite gel and carrying out a solvothermal reaction, and the same procedure as in example 1.
Modification and atmospheric drying of the composite gel, which is the same as the step (iv) in example 1.
Heat treatment of composite aerogel
Keeping the temperature of the composite aerogel prepared in the step (IV) at 450 ℃ for 30min under the condition of hydrogen atmosphere, and raising the temperature at 10 DEG C
Min to obtain heat treated Pt0.01-Cs0.5WO3-2SiO2And (3) compounding the aerogel.
Determined, Pt prepared by the method0.01-Cs0.5WO3-2SiO2The main crystal phase in the composite aerogel is Cs0.20WO3And a specific surface area of 121m2Per g, pore volume 0.62cm3(ii)/g, most probable pore diameter is 7.53 nm; the visible light transmittance of the prepared film is 63.12%, and the near infrared shielding rate is 75.32%.
Example 8 preparation of Pt0.02-Cs0.5WO3-2SiO2Composite aerogel
First, a silicic acid and tungstic acid solution was prepared by an ion exchange method, in the same manner as in example 1.
Preparing a bacterial cellulose solution:
weighing 50g of coconut, adding 75mL of deionized water, uniformly mixing, and juicing to obtain a bacterial cellulose solution.
Preparing mixed sol and gel
Under the condition of stirring, weighing 40mL of silicic acid solution, 4mL of bacterial cellulose solution, 31.2mL of tungstic acid solution, 2.1g of cesium sulfate, 6.08mL of 0.0772M chloroplatinic acid solution and 6.03g of tartaric acid, and sequentially mixing to prepare mixed sol; the mixed sol was placed in a water bath at 60 ℃ to gel.
Fourthly, thermal reaction of composite gel solvent
Weighing 4.95g of tartaric acid, dissolving in 30mL of isopropanol, preparing a gel block reaction solution, placing the composite gel block in the reaction solution, and reacting at 190 ℃ for 72 hours to complete the solvothermal reaction.
Fifthly, modifying the composite gel and drying under normal pressure, and the same as the step (iv) in the example 1.
Heat treatment of composite aerogel
Keeping the temperature of the sample obtained in the fifth step at 450 ℃ for 30min under the condition of hydrogen atmosphere, and increasing the temperature at a rate of 10 ℃/min to obtain the heat-treated Pt0.02-Cs0.5WO3-2SiO2And (3) compounding the aerogel.
Determined, Pt prepared by the method0.02-Cs0.5WO3-2SiO2The main crystal phase in the composite aerogel is Cs0.20WO3Having a specific surface area of 128m2Per g, pore volume 0.84cm3Per g, the most probable pore diameter was 19.36 nm.
Example 9 preparation of Pt0.02-Cs0.5WO3-2SiO2Composite aerogel
First, a silicic acid and tungstic acid solution was prepared by an ion exchange method, in the same manner as in example 1.
② preparing mixed sol and gel
Weighing 40mL of silicic acid solution, 0.5g of polyvinylpyrrolidone, 31.2mL of tungstic acid solution, 2.1g of cesium sulfate, 6.08mL of 0.0772M chloroplatinic acid solution and 2.56g of oxalic acid, and sequentially mixing under the stirring condition to prepare mixed sol; the mixed sol was placed in a water bath at 60 ℃ to gel.
③ the thermal reaction of the composite gel solvent, and the same procedure as the step (iv) of the example 8.
Weighing 2.97g of oxalic acid, dissolving in 30mL of ethanol, preparing a gel block reaction solution, placing the composite gel block in the reaction solution, and reacting at 190 ℃ for 72 hours to complete the solvothermal reaction.
Modification and atmospheric drying of the composite gel, which is the same as the step (iv) in example 1.
Fifthly, heat treatment of the composite aerogel, which is the same as the step (sixthly) in the embodiment 8.
Determined, Pt prepared by the method0.02-Cs0.5WO3-2SiO2The main crystal phase in the composite aerogel is Cs0.20WO3Having a specific surface area of 127m2Per g, pore volume 0.71cm3The mode pore diameter is 18.23 nm.
Comparative example 1 preparation of pure SiO2Aerogel
Preparation of a silicic acid solution by an ion exchange method
Measuring 40mL of industrial water glass with the modulus of 3.0, uniformly mixing the industrial water glass with 160mL of deionized water, and performing ion exchange by using styrene cation exchange resin to obtain a silicic acid solution with the pH value of 2-3;
② taking 50mL of silicic acid solution, aging at 60 ℃ to obtain SiO2Gelling;
③ heat treatment of gel solvent: the gel mass was transferred to a 200ml polytetrafluoro reactor, 60ml absolute ethanol and 6.5g citric acid monohydrate were added and the temperature was maintained at 190 ℃ for 72h.
Gel modification and drying under normal pressure in the same way as in the step (iv) of the example 1.
And transferring the composite gel block after the solvent thermal reaction to a beaker, soaking and washing the gel block by using n-hexane, adding n-hexane to submerge the gel block, dropwise adding 2ml of TMCS, and supplementing and adding 2ml of TMCS every 24 hours until the modification is complete, no water is separated out from the gel block, and the gel block can float on the water surface. After modification, the gel block is cleaned by n-hexane for three times, placed in the air for 1h, and then subjected to normal-pressure drying treatment, and the gel block after modification is subjected to heat preservation for 2h at 60 ℃, 80 ℃, 100 ℃, 120 ℃ and 150 ℃.
Heat treatment, same as example 8 step (v).
The experimental result shows that the SiO prepared by the process2The film prepared by dispersing the aerogel has higher transmittance to the whole spectrum and has no shielding performance to near infrared light.
Comparative example 2 preparation of Pt0.01-Cs0.5WO3Particles
Preparation of tungstic acid solution
Weighing 37.315gNa2WO4·2H2Dissolving O in 150mL of deionized water, and performing ion exchange by using styrene cation exchange resin to obtain a tungstic acid solution.
Preparation of chloroplatinic acid solution
Weighing 1g of chloroplatinic acid, adding 25mL of deionized water, and uniformly stirring and mixing to obtain a chloroplatinic acid solution;
preparing reaction precursor liquid and solvent thermal reaction
Weighing 30mL of absolute ethanol, adding 61.4mL of tungstic acid, 6.08mL of chloroplatinic acid, 4.2g of cesium sulfate and 10.56g of citric acid monohydrate, uniformly mixing to obtain a reaction precursor solution, and reacting at 190 ℃ for 72h.
Fourthly, washing and drying
After the kettle is opened, the sediment in the kettle is washed by water and alcohol for three times respectively, and then dried in an oven at 60 ℃ for 12 hours.
Heat treatment, same as example 8 step (v).
Experimental results show that the Pt is prepared by the process0.01-Cs0.5WO3The film prepared after the particles are dispersed has certain near infrared shielding performance on near infrared light, but Pt0.01-Cs0.5WO3The particles do not have the light porous characteristics of aerogel, have no adsorption capacity and have no low thermal conductivity.
Comparative example 3 preparation of Pt by mechanical mixing method0.01-Cs0.5WO3-SiO2Composite aerogel
Firstly, measuring 9mL of industrial water glass, uniformly mixing the industrial water glass with 36mL of deionized water, and carrying out ion exchange by using strong-acid styrene cation exchange resin to obtain H2SiO3A solution; 20mL of H was measured2SiO3Solution, 1.373g of Pt synthesized in comparative example 2 was added0.01-Cs0.5WO3Particles in H2SiO3In the solution, mechanical ball milling is carried out for 0.5h to ensure that Pt-Cs0.5WO3Particles are uniformly mixed in H2SiO3In solution; then, using NH3·H2Adjusting the pH value of the ball milling liquid to about 7 to enable the ball milling liquid to be gelled to obtain composite gel; placing the gel block in a container filled with 25mL of n-hexane, dropwise adding 2mL of TMCS every 24h, and performing modification treatment until the composite gel in the container completely floats to finish modification; drying the modified composite gel in a drying oven at each temperature segment of 70, 90, 110 and 130 ℃ for 2h at the heating rate of 5 ℃/min to finally obtain Pt0.01-Cs0.5WO3-SiO2And (3) compounding the aerogel.
As a result, it was found that Pt was produced by the above-mentioned method0.01-Cs0.5WO3-SiO2Pt in composite aerogel0.01-Cs0.5WO3The particle distribution uniformity is very poor, and Pt exists in the composite aerogel0.01-Cs0.5WO3The particles are seriously agglomerated, so that most of the aerogel structure has no Pt0.01-Cs0.5WO3The test results of the particle, the pore distribution, the structural performance and the like of the composite aerogel have no regularity.

Claims (5)

1. Ptn-MxWO3/SiO2Composite aerogel, its characterized in that: the Ptn-MxWO3/SiO2The whole composite aerogel has a porous network structure, and the specific surface area of the composite aerogel is 100-300 m2A pore volume of 0.4 to 2.0 cm/g3(iv) per gram, pore diameter is 5-25 nm; pt is embedded in composite aerogel porous network structuren-MxWO3Nanorod crystal grains of said Ptn-MxWO3The nanorod grains have hexagonal tungsten bronze MyWO3Crystal structure, wherein M ═ Li, Na, K, Rb, Cs, NH4，y＝0.2～0.7，n＝0.001～0.1，x＝0.2～1，
Ptn-MxWO3/SiO2The preparation method of the composite aerogel comprises the following steps: the method comprises the steps of taking industrial water glass as a silicon source, sodium tungstate as a tungsten source and chloroplatinic acid as a Pt source, preparing silicic acid and tungstic acid solution by a cation exchange method, preparing a composite gel block by a sol-gel method, and then synthesizing Pt in situ by a solvothermal reaction, surface modification and normal-pressure drying processn-MxWO3/SiO2The composite aerogel material is prepared by compounding the aerogel material,
the sol-gel method is as follows: mixing a silicic acid solution and a tungstic acid solution under the condition of stirring, adding M salt, chloroplatinic acid and an inducer, stirring and uniformly mixing to prepare a mixed sol; aging the mixed sol at the temperature of 20-90 ℃ until the mixed sol is converted into gel, wherein,
the ratio of the silicic acid solution to the tungstic acid solution is that the Si/W molar ratio is 0.05-15: 1; the M salt contains Li, Na, K, Rb, Cs and NH4The molar ratio of M/W atoms of the salt (2) to (1: 1); the adding amount of the chloroplatinic acid is that the molar ratio of the chloroplatinic acid to the tungstic acid is 0.001-0.1; the inducer is oxalic acid, formic acid, tartaric acid, acetic acid, lactic acid, citric acid, ascorbic acid, sorbitol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, sorbic acid, polypropylene glycol, potassium borohydride, sodium borohydride, aniline, acetylacetone, N2H4·H2O、N2H4·HCl、N2H4·H2SO4One or a mixture thereof, the molar ratio of the inducer to the W atom is 0.05-15: 1,
the sol-gel further comprises the step of aging: placing the composite gel block in an ethanol/water solution, aging for 0.5-48 h at 20-60 ℃ to obtain a composite gel block,
the method further comprises a heat treatment step: drying the obtained Pt under normal pressuren-MxWO3/SiO2The composite aerogel is subjected to a heat treatment process, which specifically comprises the following steps: at H2、N2Or H21 to 5% of N2/H2Heat treatment in mixed gas with the temperature rising speed of 1-10 ℃/minThe treatment temperature is 200-800 ℃.
2. Pt according to claim 1n-MxWO3/SiO2Composite aerogel, its characterized in that: a pore-expanding agent can be added in the preparation process of the mixed sol, and the concentration of the pore-expanding agent in the mixed sol is 1-100 g/L; the pore-expanding agent is one or more of bacterial cellulose, cellulose acetate, methyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl hydroxyethyl cellulose, carboxymethyl cellulose, polymethyl methacrylate microspheres, PMMA fibers, polyvinylpyrrolidone, hexamethylenetetramine, dimethylformamide, dimethylacetamide, polystyrene, P123 and F127.
3. Pt according to claim 1n-MxWO3/SiO2Composite aerogel, its characterized in that: the solvothermal reaction is carried out in a reaction kettle, and specifically comprises the following steps: placing the aged composite gel block into a reaction solution, reacting the composite gel block for 5-96 hours at 120-400 ℃, washing the reacted composite gel block for 1-3 times by using a washing solvent to obtain the gel,
wherein the volume ratio of the reaction liquid to the gel block is 0.5-3: 1, the reaction solution is one or a mixture of the following solvents: water, methanol, ethanol, propanol, butanol, isopropanol, diethyl ether, acetone, benzene, toluene, xylene, pentane, hexane, octane, cyclohexane, cyclohexanone, chlorobenzene, dichlorobenzene, dichloromethane, propylene oxide, methyl acetate, ethyl acetate, propyl acetate, acetylacetone, methyl butanone, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine, phenol; or the reaction solution is a mixture consisting of the solvent and an inducer, and the inducer is oxalic acid, formic acid, tartaric acid, acetic acid, lactic acid, citric acid, ascorbic acid, sorbitol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, sorbic acid, polypropylene glycol, potassium borohydride, sodium borohydride, aniline, acetylacetone, N-acetyl-N-O-N-O-N-O-N-O-N-O-N-O-N-O-N-O2H4·H2O、N2H4·HCl、N2H4·H2SO4The concentration of the inducer in the reaction solution is 0.5-2.5 mol/L; the washing solvent is one or more of deionized water, ethanol, isopropanol, acetone, n-hexane, cyclohexane or heptane.
4. Pt according to claim 1n-MxWO3/SiO2Composite aerogel, its characterized in that: the surface modification is specifically as follows: placing the composite gel obtained through solvothermal reaction in a modification liquid, and supplementing and adding new TMCS every 2-24 hours, wherein the volume ratio of the addition amount to the alkane solvent is 0.025-0.5: 1, finishing modification until the composite gel block floats on the liquid level of the modification liquid,
the modification solution is composed of an alkane solvent and trimethylchlorosilane, the alkane solvent is selected from one or more of n-hexane, cyclohexane, heptane or pentane, and the volume ratio of the addition amount of the initial alkane solvent to the composite gel block is 0.5-3: 1, the volume ratio of TMCS addition to the alkane solvent is 0.025-0.5: 1.
5. pt according to claim 1n-MxWO3/SiO2Composite aerogel, its characterized in that: the normal pressure drying process comprises the following steps: drying the modified wet gel at normal pressure, wherein the heating rate is 0.3-10 ℃/min, and the wet gel is respectively kept at 60 ℃, 80 ℃, 100 ℃, 120 ℃ and 150 ℃ for 2 h; or drying at 70 deg.C, 90 deg.C, 110 deg.C, and 130 deg.C for 2 hr; or slowly heating to 120-150 ℃ from room temperature, and keeping the temperature for 2 hours, wherein the heating speed is 0.5-5 ℃/min, so as to obtain Ptn-MxWO3/SiO2And (3) compounding the aerogel.
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