Salt-based building material with photocatalytic effect and preparation method thereof

Abstract

The application discloses a salt-based building material with a photocatalytic effect and a preparation method thereof, and the salt-based building material with the photocatalytic effect is prepared by using 1-3 generation aryl ether dendritic phthalocyanine complexes loaded with SiO2 as a photocatalyst. The salt-based building material with the photocatalytic effect comprises the following components in a mass ratio of 80-120 parts of sea salt, 0.5-2.0 parts of polyvinyl alcohol, 5-15 parts of inorganic fillers, and 5-20 parts of 1-3 generation aryl ether dendritic phthalocyanine complexes loaded with SiO2. The salt-based building material with the photocatalytic effect has good visible light photocatalytic performance, and the preparation method is simple and efficient, and can be applied to photocatalytic degradation treatment of organic pollutants in indoor environments and salt therapy spaces.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of building materials, and particularly relates to a salt-based building material with photocatalytic effect and a preparation method thereof. BACKGROUND

[0002] A preparation method of a 1-3 generation aryl ether dendritic phthalocyanine complex loaded SiO2 visible light photocatalyst and application thereof are disclosed in Chinese patent ZL201410800524.9, which is invented by the inventor. The dendritic phthalocyanine loaded SiO2 has the advantages of high active oxygen yield, good hydrophilicity, not easy to agglomerate, and high electron transfer rate, and can be applied to the degradation of organic pollutants, industrial wastewater treatment, and degradation of dye wastewater.

[0003] Indoor environmental pollution has become a major problem affecting people's health and safety in modern society. Indoor pollution is mainly caused by various volatile organic compounds in indoor air, which pollute the indoor environment. The more harmful ones are radon, formaldehyde, ammonia, ester, trichloroethylene, etc. In particular, indoor environmental formaldehyde pollution caused by indoor decoration and furniture materials is extremely harmful.

[0004] Salt-based building materials based on sea salt can be made into handicrafts, and can also be applied to the construction of salt therapy space to simulate the environment of salt mine cave. The salt aerosol therapy, a non-drug therapy, can enhance the healing ability of the human body by atomizing natural salt and releasing it into the indoor environment through specific technology, so that patients can inhale salt particles to treat respiratory diseases and improve immunity. It is a valuable auxiliary treatment for traditional medicine of respiratory diseases. However, during the medical process in the salt therapy space, odor, peculiar smell, etc. will inevitably be produced, and the degradation and treatment of other indoor environmental organic pollutants need to be solved urgently.

[0005] The present application blends natural sea salt, biological material polyvinyl alcohol, inexpensive inorganic fillers, and dendritic phthalocyanine loaded SiO2 with photocatalytic properties to make salt-based building materials, realizing the application of dendritic phthalocyanine loaded SiO2 in the photocatalytic degradation and treatment of indoor environmental organic pollutants and organic pollutants produced during the medical process in the salt therapy space. SUMMARY

[0006] In view of the above background and problems, the purpose of the present application is to solve the degradation and treatment of indoor environmental organic pollutants and odor, peculiar smell, etc. produced during the medical process in the salt therapy space. The present application provides a salt-based building material with photocatalytic effect and a preparation method thereof. The salt-based building material with photocatalytic effect provided by the present application has good visible light photocatalytic properties, the preparation method is simple and efficient, the raw materials used are inexpensive and easy to obtain, and can be applied to the photocatalytic degradation and treatment of indoor environmental organic pollutants and organic pollutants in the salt therapy space.

[0007] To achieve the above object, the technical scheme adopted by the present application is to provide a salt-based building material with photocatalytic effect, raw materials of the salt-based building material are sea salt and polyvinyl alcohol, and raw materials for photocatalyst are 1-3 generation aryl ether dendritic phthalocyanine complex loaded with SiO2.

[0008] The present application is a salt-based building material with photocatalytic effect, wherein the preparation method of 1-3 generation aryl ether dendritic phthalocyanine complex loaded with SiO2 comprises the following steps:

[0009] (1) 50-80 mL of mother liquor containing 70%-95% isopropyl alcohol aqueous solution or 70%-95% ethanol aqueous solution by volume fraction is configured;

[0010] (2) Concentrated ammonia is added to the solution of step (1) to adjust the pH value to 7-12, and the mixed solution is stirred and mixed uniformly under the condition of water bath at 30-70°C;

[0011] (3) 0.2-1.5 mL of 1-3 generation aryl ether dendritic phthalocyanine complex N,N-dimethylformamide stock solution with a concentration of 0.001-0.02 mol / L is added to the solution of step (2), and it is stirred and mixed uniformly after stirring;

[0012] (4) Tetraethyl orthosilicate is added to the solution of step (3), and it is continuously stirred for 4-12 h to make it fully hydrolyzed, and finally the solution is filtered, washed, and dried at 60-110°C to obtain the required catalyst;

[0013] The central atom in the above-mentioned 1-3 generation aryl ether dendritic phthalocyanine complex is zinc, copper, cobalt or iron.

[0014] The present application is a salt-based building material with photocatalytic effect, wherein the preparation of sea salt comprises the following steps:

[0015] 80-120 parts of sea salt are weighed, and the sea salt is crushed through a 60-100 mesh sieve.

[0016] The present application is a salt-based building material with photocatalytic effect, and the preparation method comprises the following steps:

[0017] First, 10-20 parts of crushed sea salt are weighed, 0.50-2.0 parts of polyvinyl alcohol are added, and stirring and mixing are performed for 15-20 minutes, then 5-15 parts of inorganic filler and 5-20 parts of 1-3 generation aryl ether dendritic phthalocyanine complex loaded with SiO2 are added, and stirring and mixing are performed for 20-30 minutes, finally, the remaining 70-100 parts of crushed sea salt are added, and further stirring and mixing are performed for 20-30 minutes, and it is loaded into a sealed plastic packaging bag.

[0018] The salt-based building material with photocatalytic effect has the characteristics that the dendritic phthalocyanine loaded with SiO2 is applied to indoor environment and salt therapy space, and realizes photocatalytic degradation treatment of organic pollutants such as odor and peculiar smell generated in the medical process in the indoor environment and the salt therapy space.

[0019] The salt-based building material with photocatalytic effect has the characteristics that the dendritic phthalocyanine loaded with SiO2 is applied to indoor environment and salt therapy space, and realizes photocatalytic degradation treatment of organic pollutants such as odor and peculiar smell generated in the medical process in the indoor environment and the salt therapy space. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 The thermogravimetric analysis diagram of the sample prepared in embodiment 4 of the application.

[0021] Figure 2 The activity diagram of the sample product prepared in embodiment 4 of the application in the condition of visible light catalytic degradation of organic pollutants (formaldehyde) for multiple times. DETAILED DESCRIPTION

[0022] Note: The 1-3 generation aryl ether dendritic phthalocyanine complex loaded with SiO2 used in the above embodiments 1-5 is prepared by using the product prepared by the preparation method of the 1-3 generation aryl ether dendritic phthalocyanine complex loaded with SiO2 visible light photocatalyst and its application (ZL201410800524.9) of the inventor's previous granted invention patent, and the specific product is prepared by using any one of the preparation methods disclosed in the specification with the patent number 201410800524.9, i.e. the specific examples 1-3 below, and the specific steps are as follows:

[0023] The preparation method of the 1-3 generation aryl ether dendritic phthalocyanine complex loaded with SiO2 visible light photocatalyst comprises the following steps:

[0024] (1) 50-80 mL of a mother liquor containing isopropyl alcohol aqueous solution with a volume fraction of 70%-95% or ethanol aqueous solution with a volume fraction of 70%-95% is configured;

[0025] (2) Concentrated ammonia water is added to the solution of step (1) to adjust the pH value to 7-12, and the mixed solution is stirred and mixed uniformly under the condition of water bath at 30-70 DEG C;

[0026] (3) 0.2-1.5 milliliters of 1-3 generation aryl ether dendritic phthalocyanine complex N, N-dimethylformamide stock solution with a concentration of 0.001-0.02 mol / L is added to the solution of step (2), and it is stirred and mixed uniformly;

[0027] (4) To the solution of step (3), tetraethyl orthosilicate was added, and stirring was continued for 4-12 h to allow complete hydrolysis. Finally, the solution was filtered, washed, and dried at 60-110°C to obtain the desired catalyst.

[0028] The central atom in the 1-3 generation aryl ether dendritic phthalocyanine complex described above is zinc, copper, cobalt, or iron.

[0029] The sum of the components in the example formulations of the present application is 100%.

[0030] The 1-3 generation aryl ether dendritic phthalocyanine complex used in the product of the present patent application is the product disclosed in the inventor's previously granted invention patent ZL2014108005249. Specific examples are as follows:

[0031] Specific Example 1

[0032] (1) 8 mL of distilled water was added to 50 mL of isopropyl alcohol, and stirring was performed under the condition of a 65°C water bath until uniform;

[0033] (2) 1 mL of concentrated ammonia and 1 mL of 1-3 generation aryl ether dendritic phthalocyanine complex (central atom: zinc) stock solution (0.02 mol / L) were added to the mixed solution, and stirring was continued for 5 min;

[0034] (3) 8 mL of tetraethyl orthosilicate was added to the solution, and stirring was continued for 12 h to allow complete hydrolysis. Finally, the solution was filtered, washed (isopropyl alcohol was used for washing 3 times, 10 mL each time, and distilled water was used for washing 5 times, 10 mL each time), and a solid was obtained. The solid was dried at 70°C to obtain the desired 1-3 generation aryl ether dendritic phthalocyanine complex (central atom: zinc) supported SiO2 catalyst.

[0035] Specific Example 2

[0036] (1) 10 mL of distilled water was added to 50 mL of anhydrous ethanol, and stirring was performed under the condition of a 65°C water bath until uniform;

[0037] (2) 1 mL of concentrated ammonia and 0.5 mL of 1-3 generation aryl ether dendritic phthalocyanine complex (central atom: zinc) stock solution (0.01 mol / L) were added to the mixed solution, and stirring was continued for 5 min;

[0038] (3) 8 mL of tetraethyl orthosilicate was added to the solution, and stirring was continued for 8 h to allow complete hydrolysis. Finally, the solution was filtered, washed (isopropyl alcohol was used for washing 3 times, 10 mL each time, and distilled water was used for washing 5 times, 10 mL each time), and a solid was obtained. The solid was dried at 70°C to obtain the desired 1-3 generation aryl ether dendritic phthalocyanine complex (central atom: zinc) supported SiO2 catalyst.

[0039] Specific Example 3

[0040] (1) 8 mL of distilled water was added to 50 mL of isopropyl alcohol, and stirred uniformly under the condition of 65 °C water bath;

[0041] (2) 0.46 mL of concentrated ammonia and 1 mL of 1-3 generation aryl ether dendritic phthalocyanine complex (central atom is zinc) stock solution (0.02 mol / L) were added to the mixed solution, and continued to stir for 5 min;

[0042] (3) 8 mL of tetraethyl orthosilicate was added to the solution, and continued to stir for 12 h to make it fully hydrolyzed, and finally the solution was filtered, washed (isopropyl alcohol washing 3 times each 10 mL, distilled water washing 5 times each 10 mL) to obtain a solid, and the solid was dried at 70 °C to obtain the desired catalyst.

[0043] Specific Example 4

[0044] The salt-based building material with photocatalytic effect of the present application in the embodiment can be grams or kilograms, wherein the preparation of sea salt includes the following steps: 120 g of sea salt purchased from Wantai Co., Ltd. was weighed, and the sea salt was crushed through a 60-100 mesh sieve. The preparation of the salt-based building material with photocatalytic effect of the present application includes the following steps: 20 g of crushed sea salt was weighed and added to 1.50 g of polyvinyl alcohol, and stirred and mixed for 15 min, then 10 g of light calcium carbonate and 10 g of 1-3 generation aryl ether dendritic phthalocyanine complex loaded with SiO2 prepared in any one of specific examples 1-3 were added, and stirred and mixed uniformly for 25 min, and finally the remaining 80 g of sea salt was added and further stirred and mixed for 30 min, and then packed in a sealed plastic bag.

[0045] The salt-based building material with photocatalytic effect prepared in the above embodiment was subjected to a test of catalytic degradation of formaldehyde under visible light conditions for multiple times, and the results were as follows Figure 2 As shown in the table, in the 5-hour degradation test, the effective degradation rate reached more than 60%, indicating that the salt-based building material has good degradation performance.

[0046] Specific Example 5

[0047] A salt-based building material having a photocatalytic effect according to the present invention, wherein the preparation of sea salt includes the following steps: weighing 120 Kg of sea salt purchased from Yonsei Corporation, and pulverizing the sea salt through a 60-100 mesh screen. A salt-based building material having a photocatalytic effect according to the present invention, wherein the preparation includes the following steps: first, weighing 18 Kg of pulverized sea salt, adding 1.80 Kg of polyvinyl alcohol, and stirring and mixing for 15 minutes, then adding 12 Kg of light calcium carbonate and 12 Kg of the 1-3 generation arylether dendritic phthalocyanine complex supported on SiO2 prepared in any one of Embodiments 1-3, and stirring and mixing uniformly for 25 minutes, and finally, adding the remaining 82 Kg of sea salt, and further stirring and mixing for 30 minutes, and packing in a closed plastic bag weighing 25 Kg.

Claims

1. A salt-based building material having a photocatalytic effect, characterized by, The preparation method comprises the following steps: (1) preparing a mother liquor containing 70-95% isopropyl alcohol or 70-95% ethanol by volume; (2) adding concentrated ammonia to the solution of step (1) to adjust the pH value to 7-12, and stirring the mixed solution in a water bath at 30-70 DEG C until the solution is uniformly mixed; (3) adding 0.2-1.5 mL of 1-3 generation aryl ether dendritic phthalocyanine complex N,N-dimethylformamide stock solution with a concentration of 0.001-0.020 mol / L to the solution of step (2), and stirring until the solution is uniformly mixed; and (4) adding tetraethyl orthosilicate to the solution of step (3), continuing to stir for 4-12 h until the solution is fully hydrolyzed, filtering the solution, washing, and drying at 60-110 DEG C to obtain the required catalyst. The central atom in the 1-3 generation aryl ether dendritic phthalocyanine complex is zinc, copper, cobalt or iron. The polyvinyl alcohol has a polymerization degree of 100-3000 and an alcoholysis degree of 78-99%. The inorganic filler is industrial light calcium carbonate or talcum powder with a mesh size of 400-800. The sea salt is crushed to pass through a 60-100 mesh sieve.

5. A preparation method of a salt-based building material with a photocatalytic effect, comprising the following steps:

2. The salt-based building material having a photocatalytic effect according to claim 1, characterized by, The sea salt is crushed to pass through a 60-100 mesh sieve, 10-20 parts by weight of the crushed sea salt is first stirred with 0.50-2.0 parts by weight of polyvinyl alcohol for 15-20 min, then 5-15 parts by weight of inorganic filler and 5-20 parts by weight of 1-3 generation aryl ether dendritic phthalocyanine complex loaded SiO2 are added and stirred for 20-30 min, and finally the remaining 70-100 parts by weight of the crushed sea salt is added and further stirred for 15-20 min, and then the mixture is packed in a sealed plastic bag.

3. The salt-based building material with photocatalytic effect according to claim 1, characterized in that, The preparation method of the 1-3 generation aryl ether dendritic phthalocyanine complex loaded SiO2 comprises the following steps:

4. The salt-based building material having a photocatalytic effect according to claim 1, characterized by, (1) preparing a mother liquor containing 70-95% isopropyl alcohol or 70-95% ethanol by volume; (2) adding concentrated ammonia to the solution of step (1) to adjust the pH value to 7-12, and stirring the mixed solution in a water bath at 30-70 DEG C until the solution is uniformly mixed; (3) adding 0.2-1.5 mL of 1-3 generation aryl ether dendritic phthalocyanine complex N,N-dimethylformamide stock solution with a concentration of 0.001-0.020 mol / L to the solution of step (2), and stirring until the solution is uniformly mixed; and (4) adding tetraethyl orthosilicate to the solution of step (3), continuing to stir for 4-12 h until the solution is fully hydrolyzed, filtering the solution, washing, and drying at 60-110 DEG C to obtain the required catalyst. ​ ​ ​ ​ ​ ​ (4) adding tetraethyl orthosilicate to the solution of step (3), continuing to stir for 4-12 hours to make it fully hydrolyzed, and finally filtering, washing and drying at 60-110 DEG C to obtain the required catalyst; The central atom in the 1-3 generation aryl ether dendritic phthalocyanine complex is zinc, copper, cobalt or iron.

6. Use of the salt-based construction material having a photocatalytic effect according to any one of claims 1 to 4 or the salt-based construction material having a photocatalytic effect produced by the production method according to claim 5, characterized in that The salt-based building material with the photocatalytic effect is applied to indoor environments and salt therapy spaces, and realizes photocatalytic degradation and treatment of organic pollutants of odor and peculiar smell generated in the medical process in the indoor environments and the salt therapy spaces.

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