CN111825348B - Porous electrochromic glass and preparation method thereof - Google Patents
Porous electrochromic glass and preparation method thereof Download PDFInfo
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- CN111825348B CN111825348B CN202010811769.7A CN202010811769A CN111825348B CN 111825348 B CN111825348 B CN 111825348B CN 202010811769 A CN202010811769 A CN 202010811769A CN 111825348 B CN111825348 B CN 111825348B
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- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
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Abstract
The invention discloses a preparation method of porous electrochromic glass, which comprises the following steps: (1) 1, 4, 5, 8-naphthalene tetracarboxylic anhydride and 3, 4-hydroxy-3' -amino-5-carboxyl biphenyl are mixed and dissolved in DMF to react to prepare naphthalene tetracarboxylic anhydride ligand; (2) naphthalene tetracarboxylic anhydride ligand obtained in the step (1) and Mg2+Dissolving salt in a mixed solvent of DMF, ethanol and water to react to obtain MOFs; (3) and (3) taking the FTO thin film electrode obtained in the step (2) as a working electrode, taking the other piece of cleaned FTO glass as a counter electrode, injecting gel electrolyte between the working electrode and the counter electrode, and packaging to obtain the porous electrochromic glass. The preparation process is simple and time-saving, and the material is economical. The invention also provides the porous electrochromic glass prepared by the method, the application time of the porous electrochromic glass can be guaranteed to be within 1.7s, the minimum can reach 1.5s, the adjustable range of the visible light transmittance can reach 75% at most, and the porous electrochromic glass still has 71% after 500 power-on and power-off cycles.
Description
Technical Field
The invention relates to the technical field of electrochromism, in particular to porous electrochromism glass and a preparation method thereof.
Background
Electrochromism refers to reversible changes in color and transparency of a material caused by an applied electric field or current. The electrochromic materials in the prior art can be mainly divided into inorganic materials and organic materials. Among them, the inorganic color-changing materials are most widely used because of their reduced response time and increased cycle life, and WO3、NiO、TiO2However, inorganic color-changing materials are expensive, single in color and small in adjustable range of visible light transmittance; the organic color-changing material comprises viologen, PANI, PEDOT, PPy and the like, can effectively increase the adjustable range of visible light transmittance, has various changeable colors, can reduce the use cost, and has short response time. Among organic color-changing materials, metal organic framework compounds (MOFs) become a new type of electrochromic material, and its excellent electrochromic properties are gradually discovered, and its high porosity makes low response time possible, such as Ni-MOFs device prepared by CN201711392753.1, the response time can be reduced to 2s, but it is a current difficulty to ensure that other properties are excellent at the same time of reducing the response time, so that it is an urgent need to prepare an electrochromic material with high porosity and high visible light modulation range.
Disclosure of Invention
The invention aims to provide a supported tin dioxide photocatalyst for sewage treatment and a preparation method thereof, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the porous electrochromic glass comprises the following steps:
(1) mixing 1, 4, 5, 8-naphthalene tetracarboxylic anhydride and 3, 4-hydroxy-3' -amino-5-carboxyl biphenyl, dissolving the mixture in DMF, reacting at the temperature of 120 ℃ and 140 ℃ for 22-26h in protective atmosphere, and filtering, drying and washing the mixture after the reaction is finished to obtain a naphthalene tetracarboxylic anhydride group ligand; the concentration of the 1, 4, 5, 8-naphthalene tetracarboxylic anhydride is 0.01-0.15mmol/L, and the concentration of the 3, 4-hydroxy-3' -amino-5-carboxyl biphenyl is 0.005-0.02 mmol/L;
1, 4, 5, 8-naphthalene tetracarboxylic anhydride is a redox active molecule, and can achieve the effect of macroscopic color change along with the mutual conversion of the oxidation state and the reduction state of the molecule; due to the delocalized pi-bonds of the benzene rings, the biphenyl compounds enable the two benzene rings to form a molecular orbit with lower energy in a coplanar manner, namely the two benzene rings are coplanar. A plane organic matter with carboxyl and hydroxyl as end groups can be obtained by mixing a biphenyl compound (3, 4-hydroxy-3' -amino-5-carboxybiphenyl) and 1, 4, 5, 8-naphthalene tetracarboxylic anhydride for a glycidyl reaction, and a specific reaction mechanism is shown in figure 1, so that a basis is provided for establishing ordered and porous MOFs in the step (2).
(2) Naphthalene tetracarboxylic anhydride ligand obtained in the step (1) and Mg2+Dissolving salt in a mixed solvent of DMF, ethanol and water to obtain a mixed solution; immersing one surface of the washed FTO glass in the mixed solution for hydrothermal reaction, and washing and drying after the reaction is finished to obtain an FTO film electrode with one surface attached with metal organic framework compounds (MOFs); the concentration of the naphthalene tetracarboxylic anhydride ligand in the mixed solution is 0.005-2mol/L, and Mg2+The concentration of the salt is 0.01-4 mol/L;
by adding metal ions Mg2+Reacting with naphthalene tetracarboxylic anhydride ligand, the terminal group of the naphthalene tetracarboxylic anhydride ligand will react with Mg automatically2+Coordination structures are formed, i.e. self-assembly into MOFs. Benefiting from naphthalene tetracarboxylic anhydride-based ligandsWith a longer chain length of biphenyl relative to phenyl, in combination with Mg2+After the MOFs are formed, the pores of the metal organic framework are effectively increased, so that electrolyte ions are easier to transport in the framework, and the response time is reduced.
(3) And (3) taking the FTO thin film electrode obtained in the step (2) as a working electrode, taking another piece of cleaned FTO glass as a counter electrode, injecting a gel electrolyte between the working electrode and the counter electrode, wherein the distance between the working electrode and the counter electrode is 0.2-3mm, one surface of the FTO thin film electrode, which is attached to the MOFs, faces inwards and is in contact with the gel electrolyte, and packaging the working electrode and the counter electrode by using two transparent substrates after injection is completed to obtain the porous electrochromic glass.
Further, the protective atmosphere is one or more of nitrogen or inert gas.
Further, the washing is carried out by washing with 0.5-5 wt% acid solution, wherein the acid solution can be one of hydrochloric acid, sulfuric acid and nitric acid.
Further, the temperature of the hydrothermal reaction is 115-125 ℃, and the time is 20-24 h.
Further, said Mg2+The salt may be one of magnesium nitrate, magnesium chloride and magnesium sulfate.
Further, the volume ratio of DMF, ethanol and water in the mixed solvent is (6-9): (0.5-2): 1.
the organic solvents DMF, ethanol and water are mixed according to the optimal value range, so that inorganic salt and organic ligands can be effectively dispersed, and the hydrothermal reaction is promoted.
Further, the gel electrolyte comprises, by mass, 3-10% of potassium chloride, 10-20% of polyvinylidene fluoride, 40-50% of polyacrylonitrile, and the balance of polymethyl methacrylate.
When the porous electrochromic glass is electrified, as potassium ions have moderate ionic radius and monovalent positive charges, the transmission efficiency is not easy to be reduced by the naphthalene tetracarboxylic anhydride ligand through electrostatic adsorption during the transmission in MOFs, so that the response time can be effectively reduced by doping a small amount of potassium chloride, and the adjustable range of the visible light transmittance is improved.
Further, the transparent substrate is one of PET, PU, glass, PI and PDMS.
Further, the drying is carried out at the temperature of 60-80 ℃ for 30-40min in a vacuum environment.
The invention also provides the porous electrochromic glass prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
(1) different from phenyl compounds in the prior art, the invention can obtain a planar organic matter naphthalene tetracarboxylic anhydride group ligand with carboxyl and hydroxyl as end groups by mixing a biphenyl compound (3, 4-hydroxy-3' -amino-5-carboxyl biphenyl) and 1, 4, 5, 8-naphthalene tetracarboxylic anhydride for a glycidyl reaction, and provides a foundation for establishing ordered porous MOFs.
(2) The invention relates to naphthalene tetracarboxylic anhydride ligand and Mg2+After the formation of MOFs, due to the longer chain length of biphenyl, the pores of the metal-organic framework are effectively increased, so that electrolyte ions are easier to transport in the framework, and the response time is reduced.
(3) Because potassium ions have moderate ionic radius and monovalent positive charges, the transmission efficiency in MOFs is higher, the invention can effectively reduce the response time and improve the adjustable range of the visible light transmittance by doping a small amount of potassium chloride.
(4) 1, 4, 5, 8-naphthalene tetracarboxylic anhydride and Mg used in the invention2+The materials such as salt, potassium chloride and the like have wide sources and low prices, and the preparation process is simple and time-saving and has wide application prospect.
Drawings
FIG. 1 is a schematic diagram of the synthesis of a naphthalenetetracarboxylic anhydride-based ligand of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of porous electrochromic glass, which comprises the following steps:
(1) mixing 1, 4, 5, 8-naphthalene tetracarboxylic anhydride and 3, 4-hydroxy-3' -amino-5-carboxyl biphenyl, dissolving the mixture in DMF (dimethyl formamide) for reaction at 120 ℃ for 22 hours, carrying out the reaction in a protective atmosphere, and filtering, drying and washing the reaction product to obtain a naphthalene tetracarboxylic anhydride ligand; the concentration of the 1, 4, 5, 8-naphthalene tetracarboxylic anhydride is 0.01mmol/L, and the concentration of the 3, 4-hydroxy-3' -amino-5-carboxybiphenyl is 0.005 mmol/L;
(2) naphthalene tetracarboxylic anhydride ligand obtained in the step (1) and Mg2+Dissolving salt in a mixed solvent of DMF, ethanol and water to obtain a mixed solution; immersing one surface of the washed FTO glass in the mixed solution for hydrothermal reaction, and washing and drying after the reaction is finished to obtain an FTO film electrode with one surface attached with metal organic framework compounds (MOFs); the concentration of the naphthalene tetracarboxylic anhydride ligand in the mixed solution is 0.005mol/L, and Mg2+The concentration of the salt is 0.01 mol/L;
(3) and (3) taking the FTO thin film electrode obtained in the step (2) as a working electrode, taking another piece of cleaned FTO glass as a counter electrode, injecting a gel electrolyte between the working electrode and the counter electrode, wherein the distance between the working electrode and the counter electrode is 0.2mm, one surface of the FTO thin film electrode, which is attached to the MOFs, faces inwards and is in contact with the gel electrolyte, and packaging the working electrode and the counter electrode by using two transparent substrates after injection is completed to obtain the porous electrochromic glass.
Wherein the protective atmosphere is nitrogen; the washing is carried out by washing with 0.5 wt% of acid solution, and the acid solution is hydrochloric acid; the temperature of the hydrothermal reaction is 115 ℃ and the time is 20 hours; the Mg2+The salt is magnesium sulfate; the volume ratio of DMF, ethanol and water in the mixed solvent is 6: 0.5: 1; the gel electrolyte comprises, by mass, 3% of potassium chloride, 10% of polyvinylidene fluoride, 40% of polyacrylonitrile and the balance of polymethyl methacrylateMethyl methacrylate; the transparent substrate is PET; the drying is carried out at 60 deg.C for 30min in vacuum environment.
The invention also provides the porous electrochromic glass prepared by the method.
Example two
The invention provides a preparation method of porous electrochromic glass, which comprises the following steps:
(1) mixing 1, 4, 5, 8-naphthalene tetracarboxylic anhydride and 3, 4-hydroxy-3' -amino-5-carboxyl biphenyl, dissolving the mixture in DMF (dimethyl formamide) for reaction at 140 ℃ for 26 hours, carrying out the reaction in a protective atmosphere, and filtering, drying and washing the reaction product to obtain a naphthalene tetracarboxylic anhydride ligand; the concentration of the 1, 4, 5, 8-naphthalene tetracarboxylic anhydride is 0.15mmol/L, and the concentration of the 3, 4-hydroxy-3' -amino-5-carboxyl biphenyl is 0.02 mmol/L;
(2) naphthalene tetracarboxylic anhydride ligand obtained in the step (1) and Mg2+Dissolving salt in a mixed solvent of DMF, ethanol and water to obtain a mixed solution; immersing one surface of the washed FTO glass in the mixed solution for hydrothermal reaction, and washing and drying after the reaction is finished to obtain an FTO film electrode with one surface attached with metal organic framework compounds (MOFs); the concentration of the naphthalene tetracarboxylic anhydride ligand in the mixed solution is 2mol/L, and Mg2+The concentration of the salt is 4 mol/L;
(3) and (3) taking the FTO thin film electrode obtained in the step (2) as a working electrode, taking another piece of cleaned FTO glass as a counter electrode, injecting gel electrolyte between the working electrode and the counter electrode, wherein the distance between the working electrode and the counter electrode is 3mm, one surface of the FTO thin film electrode, which is attached to MOFs, faces inwards and is in contact with the gel electrolyte, and packaging the working electrode and the counter electrode by using two transparent substrates after injection is completed to obtain the porous electrochromic glass.
Wherein the protective atmosphere is nitrogen; the washing is carried out by washing with 5 wt% acid solution, and the acid solution is hydrochloric acid; the temperature of the hydrothermal reaction is 125 ℃, and the time is 24 hours; the Mg2+The salt is magnesium sulfate; the volume ratio of DMF, ethanol and water in the mixed solvent is 9: 2: 1;the gel electrolyte comprises, by mass, 10% of potassium chloride, 20% of polyvinylidene fluoride, 50% of polyacrylonitrile and the balance polymethyl methacrylate; the transparent substrate is PET; the drying is carried out at 80 ℃ for 40min in a vacuum environment.
The invention also provides the porous electrochromic glass prepared by the method.
EXAMPLE III
The invention provides a preparation method of porous electrochromic glass, which comprises the following steps:
(1) mixing 1, 4, 5, 8-naphthalene tetracarboxylic anhydride and 3, 4-hydroxy-3' -amino-5-carboxyl biphenyl, dissolving the mixture in DMF (dimethyl formamide) for reacting for 24 hours at 130 ℃, reacting in protective atmosphere, and filtering, drying and washing the mixture after the reaction is finished to obtain a naphthalene tetracarboxylic anhydride ligand; the concentration of the 1, 4, 5, 8-naphthalene tetracarboxylic anhydride is 0.06mmol/L, and the concentration of the 3, 4-hydroxy-3' -amino-5-carboxyl biphenyl is 0.015 mmol/L;
(2) naphthalene tetracarboxylic anhydride ligand obtained in the step (1) and Mg2+Dissolving salt in a mixed solvent of DMF, ethanol and water to obtain a mixed solution; immersing one surface of the washed FTO glass in the mixed solution for hydrothermal reaction, and washing and drying after the reaction is finished to obtain an FTO film electrode with one surface attached with metal organic framework compounds (MOFs); the concentration of the naphthalene tetracarboxylic anhydride ligand in the mixed solution is 0.5mol/L, and Mg2+The concentration of the salt is 0.2 mol/L;
(3) and (3) taking the FTO thin film electrode obtained in the step (2) as a working electrode, taking another piece of cleaned FTO glass as a counter electrode, injecting gel electrolyte between the working electrode and the counter electrode, wherein the distance between the working electrode and the counter electrode is 1mm, one surface of the FTO thin film electrode, which is attached to MOFs, faces inwards and is in contact with the gel electrolyte, and packaging the working electrode and the counter electrode by using two transparent substrates after injection is completed to obtain the porous electrochromic glass.
Wherein the protective atmosphere is nitrogen; the washing is carried out by washing with 3 wt% acid solution, and the acid solution is hydrochloric acid; the temperature of the hydrothermal reaction is 120 ℃,the time is 22 h; the Mg2+The salt is magnesium sulfate; the volume ratio of DMF, ethanol and water in the mixed solvent is 8: 1: 1; the gel electrolyte comprises, by mass, 5% of potassium chloride, 18% of polyvinylidene fluoride, 42% of polyacrylonitrile and the balance polymethyl methacrylate; the transparent substrate is PET; the drying is carried out at 70 deg.C for 35min in vacuum environment.
The invention also provides the porous electrochromic glass prepared by the method.
In order to detect the performance of each porous electrochromic glass, the response time, the adjustable range and the cycle stability of the visible light transmittance and the specific surface area of the MOFs of each glass are respectively tested. The response time is obtained by timing by using a stopwatch, respectively recording the initial time of electrifying and the time when the visible light transmittance of the glass reaches the minimum value, and calculating the difference between the two times. The visible light transmittance is measured by ultraviolet-visible spectrophotometry. The cycle stability performance is that the visible light transmittance of the glass is recorded and compared with the initial value after 500 times of power-on-power-off operations. The specific surface area is obtained by testing an isothermal nitrogen adsorption and desorption curve of the MOFs by using a BET method and calculating.
Through comparative experiments on the three groups of examples, the porous electrochromic glass with excellent performance can be prepared by each group of examples, and specific data are shown in table 1. It can be seen that the porous electrochromic glass prepared by the invention can ensure that the response time is within 1.7s and can reach 1.5s at the lowest, the adjustable range of the visible light transmittance can reach 75% at the highest, and the porous electrochromic glass still has 71% after 500 power-on and power-off cycles, wherein the performance of the third embodiment is the best.
TABLE 1
Comparative example 1: the difference from example three is that the biphenyl compound is replaced with 5-amino-2-hydroxybenzoic acid (phenyl compound). It can be seen that the response time of the porous electrochromic glass prepared after the substitution is increased, and the adjustable range of the visible light transmittance is reduced, because the formed MOFs has reduced pore size and reduced porosity, ions are more difficult to transmit in the MOFs, so that the response time of the electrochromic glass is reduced, and the specific surface area and the visible light transmittance are reduced due to the densification of the material.
Comparative example 2: the difference from example three is that the biphenyl compound is replaced with a linear alkane of seven carbon atoms with unchanged terminal groups. Although the chain length of the linear alkane is increased, the spatial disorder of the linear alkane reduces the orderliness of the synthesized metal organic compound, the pore diameter is not uniform, the specific surface area is greatly reduced, and all properties of the prepared color-changing glass are reduced.
Comparative example 3: the difference from example three is that potassium chloride is replaced by aluminum chloride.
Comparative example 4: the difference from example three is that potassium chloride is added instead of sodium chloride.
It can be seen that the replacement of potassium ions with trivalent aluminum ions leads to enhanced electrostatic adsorption between electrolyte ions and organic ligands of MOFs, making ion transport difficult; and the replacement of potassium ions with sodium ions leads to the adsorption of a large amount of sodium ions with too small ionic radius by the organic ligands, which also hinders the ion transmission efficiency, so that the response time of the photochromic glasses prepared in comparative examples 3 and 4 is reduced.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A preparation method of porous electrochromic glass is characterized by comprising the following steps:
(1) mixing 1, 4, 5, 8-naphthalene tetracarboxylic anhydride and 3, 4-hydroxy-3' -amino-5-carboxyl biphenyl, dissolving the mixture in DMF, reacting at the temperature of 120 ℃ and 140 ℃ for 22-26h in protective atmosphere, and filtering, drying and washing the mixture after the reaction is finished to obtain a naphthalene tetracarboxylic anhydride group ligand; the concentration of the 1, 4, 5, 8-naphthalene tetracarboxylic anhydride is 0.01-0.15mmol/L, and the concentration of the 3, 4-hydroxy-3' -amino-5-carboxyl biphenyl is 0.005-0.02 mmol/L;
(2) naphthalene tetracarboxylic anhydride ligand obtained in the step (1) and Mg2+Dissolving salt in a mixed solvent of DMF, ethanol and water to obtain a mixed solution; immersing one surface of the washed FTO glass in the mixed solution for hydrothermal reaction, and washing and drying after the reaction is finished to obtain an FTO film electrode with one surface attached with metal organic framework compounds (MOFs); the concentration of the naphthalene tetracarboxylic anhydride ligand in the mixed solution is 0.005-2mol/L, and Mg2+The concentration of the salt is 0.01-4 mol/L;
(3) and (3) taking the FTO thin film electrode obtained in the step (2) as a working electrode, taking another piece of cleaned FTO glass as a counter electrode, injecting a gel electrolyte between the working electrode and the counter electrode, wherein the distance between the working electrode and the counter electrode is 0.2-3mm, one surface of the FTO thin film electrode, which is attached to the MOFs, faces inwards and is in contact with the gel electrolyte, and packaging the working electrode and the counter electrode by using two transparent substrates after injection is completed to obtain the porous electrochromic glass.
2. The method for preparing porous electrochromic glass according to claim 1, wherein: the protective atmosphere is one or more of nitrogen or inert gas.
3. The method for preparing porous electrochromic glass according to claim 1, wherein: the washing is carried out by washing with 0.5-5 wt% acid solution, which can be one of hydrochloric acid, sulfuric acid and nitric acid.
4. The method for preparing porous electrochromic glass according to claim 1, wherein: the temperature of the hydrothermal reaction is 115-125 ℃, and the time is 20-24 h.
5. The method for preparing porous electrochromic glass according to claim 1, wherein the method is characterized in thatCharacterized in that: the Mg2+The salt may be one of magnesium nitrate, magnesium chloride and magnesium sulfate.
6. The method for preparing porous electrochromic glass according to claim 1, wherein: the volume ratio of DMF, ethanol and water in the mixed solvent is (6-9): (0.5-2): 1.
7. the method for preparing porous electrochromic glass according to claim 1, wherein: the gel electrolyte comprises, by mass, 3-10% of potassium chloride, 10-20% of polyvinylidene fluoride, 40-50% of polyacrylonitrile, and the balance of polymethyl methacrylate.
8. The method for preparing porous electrochromic glass according to claim 1, wherein: the transparent substrate is one of PET, PU, glass, PI and PDMS.
9. The method for preparing porous electrochromic glass according to claim 1, wherein: the drying is carried out at 60-80 deg.C for 30-40min in vacuum environment.
10. A porous electrochromic glazing obtained by a process as claimed in any one of claims 1 to 9.
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