CN113289635A - Quaternary high-efficiency photocatalytic nano material with memory effect, preparation method thereof and air purifier - Google Patents
Quaternary high-efficiency photocatalytic nano material with memory effect, preparation method thereof and air purifier Download PDFInfo
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- 229910020462 K2SnO3 Inorganic materials 0.000 claims description 11
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- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
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- 229910006733 SnO2Sn Inorganic materials 0.000 abstract 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8966—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
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- A—HUMAN NECESSITIES
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- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2209/00—Aspects relating to disinfection, sterilisation or deodorisation of air
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a quaternary high-efficiency photocatalytic nano material with a memory effect, a preparation method thereof and an air purifier, and relates to the technical field of catalysts2O‑SnO2-quaternary composite of Ag, SnO2Sn in (A) can be used as a decorative component in a composite photocatalyst system to capture photogenerated electrons injected from a light absorber component and pass through with O2The reaction releases them in the dark, producing active H2O2Therefore, the four components have the synergistic effect of illuminating photocatalysis 'memory' effect, so that the quaternary high-efficiency photocatalytic nano material with the 'memory' effect has catalytic activity in a dark environment and can be maintained for more than 10 hours, the catalytic activity of the photocatalytic material is obviously improved, and the antibacterial performance is improved.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a quaternary high-efficiency photocatalytic nano material with a memory effect, a preparation method thereof and an air purifier.
Background
Semiconductor-based photocatalysts have been widely used in solar energy conversion and environmental applications over the past few decades. It is generally recognized that photocatalysts, under the appropriate light, can generate a variety of Reactive Oxygen Species (ROSs) in situ to disinfect microorganisms and degrade organic contaminants at ambient temperature and pressure.
Most of the existing photocatalysts only work under light because they generate ROS that rely on continuous light to generate electron-hole pairs. However, many potential applications require continuous activity in the dark for extended periods of time, limiting the use of photocatalysts.
Disclosure of Invention
The invention mainly aims to provide a quaternary high-efficiency photocatalytic nano material with a memory effect, a preparation method thereof and an air purifier, and aims to solve the problem that a photocatalyst loses catalytic activity in a dark environment.
To achieve the above objectsThe invention provides a quaternary high-efficiency photocatalytic nano material with a memory effect, which comprises Cu-Cu2O-SnO2-an Ag quaternary composite material.
The invention further provides a preparation method of the quaternary high-efficiency photocatalytic nano material with the memory effect, which comprises the following steps:
s10, adding Cu (NO)3)2·3H2Dissolving O in a mixed solvent of glycerol, ethanol and water, adding urea, and reacting under sealed heating conditions to obtain a mixed solution;
s20, carrying out solid-liquid separation on the mixed solution to obtain a solid, washing the solid, and carrying out vacuum drying to obtain a first intermediate;
s30, dispersing the first intermediate into an ethanol solution to form a dispersion liquid, and adding K into the dispersion liquid2SnO3·3H2Stirring the water solution of O to obtain suspension;
s40, adding ethyl acetate into the suspension, fully stirring, and reacting under a sealed heating condition to obtain a reaction solution;
s50, carrying out solid-liquid separation on the reaction liquid to obtain a solid, washing the solid, and carrying out vacuum drying on the solid to obtain a second intermediate;
and S60, adding the second intermediate into a silver nitrate solution, adding a reducing agent, carrying out solid-liquid separation after reaction to obtain a solid, and washing and vacuum-drying the solid to obtain the quaternary high-efficiency photocatalytic nanomaterial with the memory effect.
Alternatively, in step S10,
the reaction temperature is 160-200 ℃; and/or the presence of a gas in the gas,
in the mixed solvent of glycerol, ethanol and water, the volume ratio of glycerol to ethanol to water is 7: (6-8): (9-11).
Alternatively, in step S10,
the Cu (NO)3)2·3H2The ratio of the amount of substance of O to the amount of substance of urea is1, (1-3); and/or the presence of a gas in the gas,
the reaction time is 7-10 h.
Alternatively, the Cu (NO)3)2·3H2O and said K2SnO3·3H2The mass ratio of O is 5: (0.03-0.09).
Alternatively, in step S40,
the reaction temperature is 150-180 ℃; and/or the presence of a gas in the gas,
the reaction time is 6-10 h.
Alternatively, in step S50, the washing is washing with water and ethanol in sequence.
Alternatively, in step S60,
the reducing agent comprises at least one of hydrazine hydrate and sodium sulfite; and/or the presence of a gas in the gas,
the reaction time is 1-2 h; and/or the presence of a gas in the gas,
the vacuum drying temperature is 45-65 ℃; and/or the presence of a gas in the gas,
and the vacuum drying time is 5-10 h.
Alternatively, the Cu (NO)3)2·3H2The ratio of the amount of O to the amount of silver nitrate is 5: (0.1-0.3).
The invention further provides an air purifier, which comprises the quaternary high-efficiency photocatalytic nano material with the memory effect.
The quaternary high-efficiency photocatalytic nano material with the memory effect comprises Cu-Cu2O-SnO2-Ag quaternary composite material, in the above-mentioned photocatalytic material SnO2The chemical state of Sn in (1) can be changed into Sn by trapping and releasing electrons2+And Sn4+Exchange between them, and its conduction band potential (0.4V to NHE) is compared with O2The two-electron reduction potential of (2) is low. Thus, it can be used as a decorative component in a composite photocatalyst system to capture photogenerated electrons injected from a light absorber component and pass through with O2The reaction releases them in the dark, producing active H2O2So as to have the effect of illuminating photocatalysis 'memory';further, by Cu, Cu2O、SnO2The four components of Ag act synergistically, so that the quaternary high-efficiency photocatalytic nano material with the memory effect has catalytic activity in a dark environment and can be maintained for more than 10 hours, the catalytic activity of the photocatalytic material is obviously improved, and the antibacterial performance is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic flow chart of an embodiment of a method for preparing a quaternary high-efficiency photocatalytic nanomaterial with a memory effect according to the present invention;
FIG. 2 is an SEM image of a quaternary high-efficiency photocatalytic nanomaterial with a memory effect obtained in example 1 of the present invention;
FIG. 3 is a schematic diagram of the preparation process of the quaternary high-efficiency photocatalytic nanomaterial with the memory effect by using light according to the present invention;
FIG. 4 is a graph showing the comparison of the antibacterial ratio against E.coli in examples 1 to 3 of the present invention and comparative examples 1 to 3 under light conditions;
FIG. 5 is a graph showing the comparison of the antibacterial ratio against Staphylococcus aureus in examples 1 to 3 and comparative examples 1 to 3 according to the present invention under light;
FIG. 6 is a graph showing the comparison of the removal rate of formaldehyde in examples 1 to 3 of the present invention and comparative examples 1 to 3 under light irradiation.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
It should be noted that those whose specific conditions are not specified in the examples were performed according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. 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.
Semiconductor-based photocatalysts have been widely used in solar energy conversion and environmental applications over the past few decades. It is generally recognized that photocatalysts, under the appropriate light, can generate a variety of Reactive Oxygen Species (ROSs) in situ to disinfect microorganisms and degrade organic contaminants at ambient temperature and pressure.
Most of the existing photocatalysts only work under light because they generate ROS that rely on continuous light to generate electron-hole pairs. However, many potential applications require continuous activity in the dark for extended periods of time, limiting the use of photocatalysts.
In view of the above, the invention provides a photocatalytic material, namely a quaternary high-efficiency photocatalytic nanomaterial with a memory effect, a preparation method thereof and an air purifier, and aims to solve the problem that a photocatalyst loses catalytic activity in a dark environment. In the attached drawings, fig. 1 is a schematic flow chart of an embodiment of a method for preparing a quaternary high-efficiency photocatalytic nanomaterial with a memory effect, provided by the invention; FIG. 2 is an SEM image of a quaternary high-efficiency photocatalytic nanomaterial with a memory effect obtained in example 1 of the present invention; FIG. 3 is a schematic diagram of the preparation process of the quaternary high-efficiency photocatalytic nanomaterial with the memory effect by using light according to the present invention; FIG. 4 is a graph showing the comparison of the antibacterial ratio against E.coli in examples 1 to 3 of the present invention and comparative examples 1 to 3 under light conditions; FIG. 5 is a graph showing the comparison of the antibacterial ratio against Staphylococcus aureus in examples 1 to 3 and comparative examples 1 to 3 according to the present invention under light; FIG. 6 is a graph showing the comparison of the removal rate of formaldehyde in examples 1 to 3 of the present invention and comparative examples 1 to 3 under light irradiation.
The quaternary high-efficiency photocatalytic nano material with the memory effect comprises Cu-Cu2O-SnO2-an Ag quaternary composite material.
The quaternary high-efficiency photocatalytic nano material with the memory effect comprises Cu-Cu2O-SnO2-Ag quaternary composite material, in the above-mentioned photocatalytic material SnO2The chemical state of Sn in (1) can be changed into Sn by trapping and releasing electrons2+And Sn4+Exchange between them, and its conduction band potential (0.4V to NHE) is compared with O2The two-electron reduction potential of (2) is low. Thus, it can be used as a decorative component in a composite photocatalyst system to capture photogenerated electrons injected from a light absorber component and pass through with O2The reaction releases them in the dark, producing active H2O2So as to have the effect of illuminating photocatalysis 'memory'; further, by Cu, Cu2O、SnO2The four components of Ag act synergistically, so that the quaternary high-efficiency photocatalytic nano material with the memory effect has catalytic activity in a dark environment and is maintained for more than 10 hours, the catalytic activity of the photocatalytic material is obviously improved, and the antibacterial performance is improvedThe antibacterial agent has high activity, excellent antibacterial performance and wider application range.
The invention further provides a preparation method of the quaternary high-efficiency photocatalytic nanomaterial with the memory effect, please refer to fig. 1, and the preparation method of the quaternary high-efficiency photocatalytic nanomaterial with the memory effect, which comprises the following steps:
s10, adding Cu (NO)3)2·3H2Dissolving O in a mixed solvent of glycerol, ethanol and water, adding urea, and reacting under sealed heating condition to obtain a mixed solution.
In the step, Cu-Cu is mainly prepared2Binary material of O, Cu-Cu2Cu and Cu in O binary material2O is fused together to form a substance similar to an alloy, urea is used as a reducing agent to reduce bivalent copper into monovalent copper and elementary copper under the condition of closed heating, and the reaction can be carried out in an autoclave, for example, Cu (NO) is contained3)2·3H2Adding a solution of O, glycerol, ethanol, water and urea into a stainless steel autoclave lined with polytetrafluoroethylene, and then placing the autoclave in an oven for heating reaction.
A mixed solvent of glycerol, ethanol and water as a solvent for dissolving Cu (NO)3)2·3H2O as a solvent for Cu (NO)3)2·3H2Fully reacting O and urea, wherein the proportion of each component in the mixed solvent of glycerol, ethanol and water is not limited in the invention, and preferably, the volume ratio of glycerol, ethanol and water is 7: (6-8): (9-11), more preferably, the volume ratio of the glycerol to the ethanol to the water is 7: 7: 10, more favorable to Cu (NO)3)2·3H2The O and the urea are fully reacted.
In the embodiment of the invention, the addition amount of urea is critical, the amount of elemental copper in the obtained first intermediate is increased along with the increase of the addition amount of urea, and the elemental copper has good conductivity, so that Cu is contained2The photoproduction electrons on the surface of O are quickly transferred, so that the separation of electron-hole is realized; in addition, Cu has excellent plasma excitation like metal such as Au and AgThe absorption of the system to radiation photons can be increased by the meta-resonance effect, and the photoresponse range is widened. However, the Cu (NO) is preferably added in an excessive amount, which causes a sharp increase in the particle size of the first intermediate and affects the photocatalytic effect of the final product3)2·3H2The ratio of the amount of the substance of O to the amount of the substance of urea is 1 (1 to 3), and may be, for example, 1: 1. 1: 2. 1: and 3, the obtained first intermediate has uniform particle size and proper proportion of elemental copper and monovalent copper.
The reaction temperature is not limited in the present invention, preferably, the reaction temperature is 160 to 200 ℃, for example, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, etc., more preferably, the reaction temperature is 180 ℃, so that the reaction is easy to occur, furthermore, the reaction time is preferably 7 to 10 hours, more preferably 10 hours, and the obtained Cu-Cu2The shape of O is better.
And S20, carrying out solid-liquid separation on the mixed solution to obtain a solid, and washing and vacuum-drying the solid to obtain a first intermediate.
The method mainly comprises the following steps of mixing Cu-Cu2Separating O from the mixed solution, performing solid-liquid separation by centrifugation, and washing with ethanol solution for several times to remove Cu-Cu2Solvent on the surface of O to obtain pure Cu-Cu2O。
The drying process is vacuum drying, and can effectively prevent Cu-Cu2And oxidizing O under the heating condition, wherein the preferable drying temperature is 60-70 ℃, more preferably 65 ℃, the preferable drying time is 5-12 h, and can be 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h and the like, and the structure and the arrangement mode of the cuprous oxide are not easily damaged under the conditions.
S30, dispersing the first intermediate into an ethanol solution to form a dispersion liquid, and adding K into the dispersion liquid2SnO3·3H2And stirring the aqueous solution of O to obtain a suspension.
In this step, SnO is supported on the surface of the first intermediate2Preferably, the Cu (NO)3)2·3H2O and said K2SnO3·3H2Of substances of OThe ratio of the amounts is 5: (0.03 to 0.09), for example, 5: 0.03, 5: 0.04, 5: 0.05, 5: 0.06, 5: 0.07, 5: 0.08, 5: 0.09, and the like, in the above proportion, so that SnO2The first intermediate body is uniformly loaded on the surface.
And S40, adding ethyl acetate into the suspension, fully stirring, and reacting under a sealed heating condition to obtain a reaction solution.
In the step, ethyl acetate is added and reacts under a closed heating condition, and the ethyl acetate is used as a stabilizer to promote the generation of SnO2And can be SnO2The molecules are mutually dispersed to form particles which are all stable, and the reaction can be carried out in an autoclave, for example, in a stainless steel autoclave lined with polytetrafluoroethylene to which the suspension of ethyl acetate is added, and then the autoclave is placed in an oven to heat the reaction.
Preferably, the reaction temperature is 150-180 ℃, such as 150 ℃, 160 ℃, 170 ℃, 180 ℃ and the like, the reaction time is 6-10 hours, such as 6 hours, 7 hours, 8 hours, 9 hours, 10 hours and the like, and the reaction is performed sufficiently under the reaction temperature and time.
And S50, carrying out solid-liquid separation on the reaction liquid to obtain a solid, and washing and vacuum-drying the solid to obtain a second intermediate.
The second intermediate is separated in the step, and the second intermediate is Cu-Cu2O-SnO2After separation, in order to ensure the purity, the product needs to be washed, preferably by sequentially washing with water and ethanol, and the specific operation process can be to perform a plurality of rinsing-centrifugal cycles by using deionized water and ethanol respectively, namely adding the second intermediate into water, centrifugally separating out solids, adding into ethanol, centrifugally separating out solids, and repeating the steps for a plurality of times.
And S60, adding the second intermediate into a silver nitrate solution, adding a reducing agent, carrying out solid-liquid separation after reaction to obtain a solid, and washing and vacuum-drying the solid to obtain the quaternary high-efficiency photocatalytic nanomaterial with the memory effect.
In the step, silver is loaded on the surface of the second intermediate, specifically, the second intermediate is placed in a silver nitrate solution, and silver nitrate is reduced, so that silver is loaded on the surface of the second intermediate.
Reducing agent for reducing silver nitrate to silver, not capable of reacting with Cu2O、SnO2Preferably, the reducing agent comprises at least one of hydrazine hydrate and sodium sulfite, and the silver obtained by reduction can be preferably loaded on the second intermediate by using the reducing agent.
Preferably, the Cu (NO)3)2·3H2The ratio of the amount of O to the amount of silver nitrate is 5: (0.1-0.3) so that silver is uniformly loaded on the surface of the second intermediate body, the silver is only required to be a small amount, the catalytic effect is greatly enhanced, and excessive silver can be effectively prevented from being attached to the surface of the second intermediate body to influence gas and Cu2O、SnO2And (4) contacting.
Preferably, the reaction time is 1-2 h, such as 1h and 2h, and the silver nitrate can be fully reduced into simple substance silver.
And (3) the finally obtained solid is dried under the vacuum condition preferably at the vacuum drying temperature of 45-65 ℃ for 5-10 h, and the quaternary high-efficiency photocatalytic nano material with good appearance and memory effect can be obtained under the above conditions.
The quaternary high-efficiency photocatalytic nanomaterial with the memory effect prepared by the preparation method of the quaternary high-efficiency photocatalytic nanomaterial with the memory effect provided by the invention has all the beneficial effects of the quaternary high-efficiency photocatalytic nanomaterial with the memory effect, and the details are not repeated herein.
An example of the preparation method of the photocatalytic material according to the present invention is given below:
(1) adding Cu (NO)3)2·3H2Dissolving O in a mixed solvent of glycerol, ethanol and water (the volume ratio of glycerol to ethanol to water is 7 (6-8) to 9-11), and adding urea and Cu (NO)3)2·3H2The ratio of the amount of O to the amount of urea is 1 (1-3), and Cu (NO) is added3)2·3H2O, glycerol and ethanolAdding a solution of water and urea into a stainless steel autoclave with a polytetrafluoroethylene lining, and then placing the autoclave in a drying oven at 160-200 ℃ for reaction for 7-10 hours to obtain a mixed solution;
(2) carrying out solid-liquid separation on the mixed solution to obtain a solid, washing the solid, and carrying out vacuum drying on the solid to obtain a first intermediate;
(3) dispersing the first intermediate into an ethanol solution to form a dispersion, and adding K into the dispersion2SnO3·3H2Stirring O water solution to obtain suspension, wherein the Cu (NO) is3)2·3H2O and said K2SnO3·3H2The mass ratio of O is 5: (0.03-0.09);
(4) adding ethyl acetate into the suspension, fully stirring, adding the suspension into a stainless steel autoclave with a polytetrafluoroethylene lining, and then placing the autoclave into a drying oven at 150-180 ℃ for reaction for 6-10 hours to obtain a reaction solution;
(5) carrying out solid-liquid separation on the reaction liquid to obtain a solid, washing the solid with water and ethanol in sequence, and carrying out vacuum drying to obtain a second intermediate;
(6) adding the second intermediate to a silver nitrate solution, Cu (NO)3)2·3H2The ratio of the amount of O to the amount of silver nitrate is 5: (0.1-0.3), adding a reducing agent hydrazine hydrate or sodium sulfite, reacting for 1-2 hours, carrying out solid-liquid separation to obtain a solid, washing the solid, and carrying out vacuum drying at 45-65 ℃ for 5-10 hours to obtain the quaternary efficient photocatalytic nanomaterial with the memory effect.
The invention further provides an air purifier, which comprises the quaternary high-efficiency photocatalytic nano material with the memory effect. The air purifier provided by the invention comprises the quaternary high-efficiency photocatalytic nano material with the memory effect, has all the beneficial effects of the quaternary high-efficiency photocatalytic nano material with the memory effect, and is not repeated herein.
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are only illustrative of the present invention and are not intended to limit the present invention.
Example 1
(1) Adding 5mmol of Cu (NO)3)2·3H2Dissolving O in 30mL of mixed solvent of glycerol, ethanol and water (volume ratio of glycerol to ethanol to water, 7: 7: 10), adding 9mmol of urea, and adding Cu (NO)3)2·3H2Adding a solution of O, glycerol, ethanol, water and urea into a stainless steel high-pressure autoclave lined with polytetrafluoroethylene, and then placing the high-pressure autoclave in a drying oven at 180 ℃ for reaction for 10 hours to obtain a mixed solution;
(2) carrying out solid-liquid separation on the mixed solution to obtain a solid, washing the solid, and carrying out vacuum drying for 12h at 65 ℃ to obtain a first intermediate;
(3) putting the first intermediate into an ethanol solution, performing ultrasonic treatment for 5min to form a dispersion liquid, and adding K into the dispersion liquid2SnO3·3H2Aqueous solution of O (wherein K2SnO3·3H2The amount of O substance is 0.03mmol), and stirring is carried out for 10min to obtain a suspension;
(4) adding ethyl acetate into the suspension, stirring for 1h, adding the suspension into a stainless steel high-pressure autoclave with a polytetrafluoroethylene lining, and then placing the high-pressure autoclave in a drying oven at 160 ℃ for reacting for 6h to obtain a reaction solution;
(5) carrying out solid-liquid separation on the reaction liquid to obtain a solid, washing the solid with water and ethanol in sequence, and carrying out vacuum drying at 45 ℃ for 12h to obtain a second intermediate;
(6) adding the second intermediate into a silver nitrate solution (wherein the amount of silver nitrate substances is 0.1mmol), adding a reducing agent hydrazine hydrate, stirring for reaction for 1h, carrying out solid-liquid separation to obtain a solid, washing the solid with water and ethanol in sequence, and carrying out vacuum drying at 50 ℃ for 10h to obtain the quaternary high-efficiency photocatalytic nanomaterial with the memory effect.
The obtained quaternary high-efficiency photocatalytic nano-material with the memory effect is used as a scanning electron microscope to obtain a figure 2.
Example 2
(1) Adding 5mmol of Cu (NO)3)2·3H2Dissolving O in 30mL of mixed solvent of glycerol, ethanol and water (volume ratio of glycerol to ethanol to water, 7: 7: 10), adding 9mmol of urea, and adding Cu (NO)3)2·3H2Adding a solution of O, glycerol, ethanol, water and urea into a stainless steel high-pressure autoclave lined with polytetrafluoroethylene, and then placing the high-pressure autoclave in a drying oven at 180 ℃ for reaction for 10 hours to obtain a mixed solution;
(2) carrying out solid-liquid separation on the mixed solution to obtain a solid, washing the solid, and carrying out vacuum drying for 12h at 65 ℃ to obtain a first intermediate;
(3) putting the first intermediate into an ethanol solution, performing ultrasonic treatment for 5min to form a dispersion liquid, and adding K into the dispersion liquid2SnO3·3H2Aqueous solution of O (wherein K2SnO3·3H2The amount of O substance is 0.06mmol), and stirring is carried out for 10min to obtain a suspension;
(4) adding ethyl acetate into the suspension, stirring for 1h, adding the suspension into a stainless steel high-pressure autoclave with a polytetrafluoroethylene lining, and then placing the high-pressure autoclave in a drying oven at 150 ℃ for reacting for 6h to obtain a reaction solution;
(5) carrying out solid-liquid separation on the reaction liquid to obtain a solid, washing the solid with water and ethanol in sequence, and carrying out vacuum drying at 45 ℃ for 12h to obtain a second intermediate;
(6) adding the second intermediate into a silver nitrate solution (wherein the amount of silver nitrate substances is 0.1mmol), adding a reducing agent hydrazine hydrate, stirring for reaction for 1h, carrying out solid-liquid separation to obtain a solid, washing the solid with water and ethanol in sequence, and carrying out vacuum drying at 50 ℃ for 10h to obtain the quaternary high-efficiency photocatalytic nanomaterial with the memory effect.
Example 3
(1) Adding 5mmol of Cu (NO)3)2·3H2Dissolving O in 30mL of mixed solvent of glycerol, ethanol and water (volume ratio of glycerol to ethanol to water, 7: 7: 10), adding 9mmol of urea, and adding Cu (NO)3)2·3H2O, glycerol, and,Adding a solution of ethanol, water and urea into a stainless steel high-pressure autoclave with a polytetrafluoroethylene lining, and then placing the high-pressure autoclave in a drying oven at 180 ℃ for reaction for 10 hours to obtain a mixed solution;
(2) carrying out solid-liquid separation on the mixed solution to obtain a solid, washing the solid, and carrying out vacuum drying for 12h at 65 ℃ to obtain a first intermediate;
(3) putting the first intermediate into an ethanol solution, performing ultrasonic treatment for 5min to form a dispersion liquid, and adding K into the dispersion liquid2SnO3·3H2Aqueous solution of O (wherein K2SnO3·3H2The amount of O substance is 0.09mmol), and stirring is carried out for 10min to obtain a suspension;
(4) adding ethyl acetate into the suspension, stirring for 1h, adding the suspension into a stainless steel high-pressure autoclave with a polytetrafluoroethylene lining, and then placing the high-pressure autoclave in a drying oven at 150 ℃ for reacting for 6h to obtain a reaction solution;
(5) carrying out solid-liquid separation on the reaction liquid to obtain a solid, washing the solid with water and ethanol in sequence, and carrying out vacuum drying at 45 ℃ for 12h to obtain a second intermediate;
(6) adding the second intermediate into a silver nitrate solution (wherein the amount of silver nitrate substances is 0.1mmol), adding a reducing agent hydrazine hydrate, stirring for reaction for 1h, carrying out solid-liquid separation to obtain a solid, washing the solid with water and ethanol in sequence, and carrying out vacuum drying at 50 ℃ for 10h to obtain the quaternary high-efficiency photocatalytic nanomaterial with the memory effect.
Example 4
(1) Adding 5mmol of Cu (NO)3)2·3H2Dissolving O in 30mL of mixed solvent of glycerol, ethanol and water (volume ratio of glycerol to ethanol to water, 7: 6: 9), adding 5mmol of urea, and adding Cu (NO)3)2·3H2Adding a solution of O, glycerol, ethanol, water and urea into a stainless steel high-pressure autoclave lined with polytetrafluoroethylene, and then placing the high-pressure autoclave in a drying oven at 160 ℃ for reaction for 7 hours to obtain a mixed solution;
(2) carrying out solid-liquid separation on the mixed solution to obtain a solid, washing the solid, and carrying out vacuum drying for 12h at 65 ℃ to obtain a first intermediate;
(3) putting the first intermediate into an ethanol solution, performing ultrasonic treatment for 5min to form a dispersion liquid, and adding K into the dispersion liquid2SnO3·3H2Aqueous solution of O (wherein K2SnO3·3H2The amount of O substance is 0.05mmol), and stirring is carried out for 10min to obtain a suspension;
(4) adding ethyl acetate into the suspension, stirring for 1h, adding the suspension into a stainless steel high-pressure autoclave with a polytetrafluoroethylene lining, and then placing the high-pressure autoclave in an oven at 180 ℃ for reaction for 10h to obtain a reaction solution;
(5) carrying out solid-liquid separation on the reaction liquid to obtain a solid, washing the solid with water and ethanol in sequence, and carrying out vacuum drying at 45 ℃ for 12h to obtain a second intermediate;
(6) adding the second intermediate into a silver nitrate solution (wherein the amount of silver nitrate substances is 0.3mmol), adding a reducing agent hydrazine hydrate, stirring for reaction for 1h, carrying out solid-liquid separation to obtain a solid, washing the solid with water and ethanol in sequence, and carrying out vacuum drying at 45 ℃ for 5h to obtain the quaternary high-efficiency photocatalytic nanomaterial with the memory effect.
Example 5
(1) Adding 5mmol of Cu (NO)3)2·3H2Dissolving O in 30mL of mixed solvent of glycerol, ethanol and water (volume ratio of glycerol to ethanol to water, 7: 8: 11), adding 15mmol of urea, and adding Cu (NO)3)2·3H2Adding a solution of O, glycerol, ethanol, water and urea into a stainless steel high-pressure autoclave lined with polytetrafluoroethylene, and then placing the high-pressure autoclave into a drying oven at 200 ℃ for reaction for 8 hours to obtain a mixed solution;
(2) carrying out solid-liquid separation on the mixed solution to obtain a solid, washing the solid, and carrying out vacuum drying for 12h at 65 ℃ to obtain a first intermediate;
(3) putting the first intermediate into an ethanol solution, performing ultrasonic treatment for 5min to form a dispersion liquid, and adding K into the dispersion liquid2SnO3·3H2Aqueous solution of O (wherein K2SnO3·3H2The amount of substance O was 0.07mmol), and stirring was performedObtaining suspension after 10 min;
(4) adding ethyl acetate into the suspension, stirring for 1h, adding the suspension into a stainless steel high-pressure autoclave with a polytetrafluoroethylene lining, and then placing the high-pressure autoclave in an oven at 170 ℃ for reacting for 8h to obtain a reaction solution;
(5) carrying out solid-liquid separation on the reaction liquid to obtain a solid, washing the solid with water and ethanol in sequence, and carrying out vacuum drying at 45 ℃ for 12h to obtain a second intermediate;
(6) adding the second intermediate into a silver nitrate solution (wherein the amount of silver nitrate substances is 0.2mmol), adding a reducing agent hydrazine hydrate, stirring for reaction for 1h, carrying out solid-liquid separation to obtain a solid, washing the solid with water and ethanol in sequence, and carrying out vacuum drying at 65 ℃ for 8h to obtain the quaternary high-efficiency photocatalytic nanomaterial with the memory effect.
Example 6
(1) Adding 5mmol of Cu (NO)3)2·3H2Dissolving O in 30mL of mixed solvent of glycerol, ethanol and water (volume ratio of glycerol to ethanol to water, 7: 6: 10), adding 10mmol of urea, and adding Cu (NO)3)2·3H2Adding a solution of O, glycerol, ethanol, water and urea into a stainless steel high-pressure autoclave lined with polytetrafluoroethylene, and then placing the high-pressure autoclave in a drying oven at 180 ℃ for reaction for 9 hours to obtain a mixed solution;
(2) carrying out solid-liquid separation on the mixed solution to obtain a solid, washing the solid, and carrying out vacuum drying for 12h at 65 ℃ to obtain a first intermediate;
(3) putting the first intermediate into an ethanol solution, performing ultrasonic treatment for 5min to form a dispersion liquid, and adding K into the dispersion liquid2SnO3·3H2Aqueous solution of O (wherein K2SnO3·3H2The amount of O substance is 0.04mmol), and stirring for 10min to obtain suspension;
(4) adding ethyl acetate into the suspension, stirring for 1h, adding the suspension into a stainless steel high-pressure autoclave with a polytetrafluoroethylene lining, and then placing the high-pressure autoclave in an oven at 170 ℃ for reaction for 9h to obtain a reaction solution;
(5) carrying out solid-liquid separation on the reaction liquid to obtain a solid, washing the solid with water and ethanol in sequence, and carrying out vacuum drying at 45 ℃ for 12h to obtain a second intermediate;
(6) and adding the second intermediate into a silver nitrate solution (wherein the amount of silver nitrate substances is 0.2mmol), adding a reducing agent sodium sulfite, stirring for reaction for 1h, carrying out solid-liquid separation to obtain a solid, washing the solid with water and ethanol in sequence, and carrying out vacuum drying at 55 ℃ for 7h to obtain the quaternary high-efficiency photocatalytic nanomaterial with the memory effect.
Comparative example 1
The conditions were the same as in example 1 except that only the steps (1) and (2) were carried out.
Comparative example 2
Directly adding K to the mixture except that only the steps (3) and (4) are carried out and the first intermediate dispersion is not added in the step (3)2SnO3·3H2The other conditions were the same as in example 1 except that the aqueous solution of O was added to ethanol.
Comparative example 3
The conditions and procedure were the same as in example 1 except that step (6) was not performed.
Referring to FIG. 2, the SEM image of the photocatalytic material obtained in example 1 shows that the photocatalytic material includes large particles with non-uniform small particles on the surface, and the large particles are Cu-Cu2O, heterogeneous small particles are SnO2And silver, the synthesis of which is shown in FIG. 3, due to K2SnO3·3H2The addition amount of O and silver nitrate is small, so that the concentration of the O and the silver nitrate is balanced, correspondingly, the formed particles are small, and the generated SnO2Relatively large Cu-Cu loading2O surface, silver loaded SnO2And Cu-Cu2O surface to finally form Cu-Cu2O-SnO2the-Ag quaternary composite material enables the photocatalytic material to still have catalytic activity in a dark environment, and can maintain the catalytic activity for more than 10 hours in the dark environment, so that the catalytic activity of the photocatalytic material is remarkably improved.
First, performance test under normal conditions
(1) Antibacterial property
Under the same illumination, the photocatalytic materials of examples 1-3 and comparative examples 1-3 are referred to GB/T20944.3-2008, evaluation part 3 of antibacterial performance of textiles: the antibacterial performance test was carried out by the oscillation method, and the antibacterial rates of the above materials against Escherichia coli and Staphylococcus aureus were respectively measured, and fig. 4 and 5 were obtained.
Referring to FIGS. 4 and 5, comparative example 1 includes Cu-Cu only2O, comparative example 2 comprising only SnO2Comparative example 3 includes Cu-Cu2O-SnO2As can be seen from FIGS. 4 and 5, the photocatalytic materials of examples 1-3 have significantly higher antibacterial rates against Escherichia coli and Staphylococcus aureus than those of comparative examples 1-3, which indicates that Cu-Cu obtained by the inventive examples2O-SnO2Quaternary composite of-Ag, Cu2O、SnO2And the four components of Ag have synergistic effect, so that the antibacterial performance is obviously improved, and compared with single unitary, binary and ternary materials, the antibacterial rate of the antibacterial agent to escherichia coli and staphylococcus aureus is obviously improved, and the advantages are obvious.
(2) Photocatalytic performance
The photocatalytic materials of examples 1-3 and comparative examples 1-3 were tested under the same illumination in a self-designed laboratory chamber having dimensions of 50cm x 50 cm. Introducing formaldehyde solution (mass fraction l%, 5mg) into heating device (60 deg.C) to volatilize in cabin (12 + -1) min, wherein the mass concentration of formaldehyde in cabin reaches (0.5 + -0.025) mg/m3The temperature and humidity of the test chamber are controlled at 27 ℃ and 56 percent. The mass concentration of formaldehyde was recorded by a formaldehyde analyzer (LB-HD), and FIG. 6 was obtained.
As can be seen from FIG. 6, compared with comparative examples 1 to 3, the photocatalytic performance of the photocatalytic materials of examples 1 to 3 has very obvious advantages and the formaldehyde removal rate is obviously higher, which shows that the quaternary high-efficiency photocatalytic nanomaterial with the memory effect, Cu and Cu, obtained by the embodiment of the invention2O、SnO2And the Ag is used for remarkably improving the catalytic activity of the photocatalytic material under the synergistic action of the four components, and compared with single unitary, binary and ternary materials, the photocatalytic material has the advantages of good stability and obvious advantages.
Second, testing the performance in the dark
(1) Antibacterial property
The photocatalytic materials of examples 1-6 and comparative examples 1-3 were exposed to the same light for 10 hours, then placed in the dark, and subjected to dark and no-light treatments for different periods of time, and then tested for their antibacterial properties against escherichia coli and staphylococcus aureus, to obtain tables 1 and 2, respectively.
TABLE 1 test of antibacterial Properties in dark conditions (E.coli)
TABLE 2 dark Condition antimicrobial Performance test (Staphylococcus aureus)
As can be seen from tables 1 and 2, the quaternary high-efficiency photocatalytic nanomaterial with memory effect in the embodiments 1-6 has good antibacterial property and good stability to Escherichia coli and Staphylococcus aureus after lasting for 12 hours in the dark, while the comparative examples 1-3 have small antibacterial property in the dark and are obviously lower than those in the embodiments 1-6, which shows that the quaternary high-efficiency photocatalytic nanomaterial with memory effect in the embodiments of the present invention is prepared by Cu and Cu2O、SnO2And the four components of Ag act synergistically, so that the antibacterial performance is remarkably improved, and the antibacterial performance under dark conditions is better and can last for more than 10 hours.
(2) Photocatalytic performance
The photocatalytic materials of examples 1 to 6 and comparative examples 1 to 3 were subjected to light irradiation for 10 hours under the same light irradiation, then placed in a dark condition, and subjected to dark and dark conditions for different periods of time, and then the catalytic decomposition performance of the photocatalytic materials on formaldehyde and methyl orange was tested, and tables 3 and 4 were obtained, respectively.
TABLE 3 photocatalytic Performance test under dark conditions (Formaldehyde)
TABLE 4 photocatalytic Performance test under dark conditions (methyl orange)
As can be seen from tables 3 and 4, the quaternary high-efficiency photocatalytic nano-materials with the memory effect in the examples 1-6 still have good catalytic decomposition performance and good stability for formaldehyde and methyl orange after lasting for 12 hours in the dark, while the comparative examples 1-3 are weaker in catalytic decomposition performance in the dark and obviously lower than the examples 1-6, which shows that the photocatalytic materials in the examples of the invention are prepared by Cu and Cu2O、SnO2And the Ag four components have synergistic effect, so that the catalytic activity of the photocatalytic material is remarkably improved, the catalytic decomposition performance under dark conditions is better, and the photocatalytic material can last for more than 10 hours.
In summary, the quaternary high-efficiency photocatalytic nanomaterial with the memory effect prepared by the embodiment of the invention is prepared by Cu and Cu2O、SnO2The Ag and the Ag have synergistic effect, so that the catalytic activity of the photocatalytic material is remarkably improved, the antibacterial performance is improved, the catalytic activity is still realized in a dark environment, the catalytic activity can be maintained for more than 10 hours in a dark condition, the antibacterial performance is excellent, the degradation of formaldehyde, organic matters and the like can be catalyzed, and the catalytic effect is good.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.
Claims (10)
1. The quaternary high-efficiency photocatalytic nanomaterial with the memory effect is characterized by comprising Cu-Cu2O-SnO2-an Ag quaternary composite material.
2. The preparation method of the quaternary high-efficiency photocatalytic nanomaterial with the memory effect as claimed in claim 1, is characterized by comprising the following steps:
s10, adding Cu (NO)3)2·3H2Dissolving O in a mixed solvent of glycerol, ethanol and water, adding urea, and reacting under sealed heating conditions to obtain a mixed solution;
s20, carrying out solid-liquid separation on the mixed solution to obtain a solid, washing the solid, and carrying out vacuum drying to obtain a first intermediate;
s30, dispersing the first intermediate into an ethanol solution to form a dispersion liquid, and adding K into the dispersion liquid2SnO3·3H2Stirring the water solution of O to obtain suspension;
s40, adding ethyl acetate into the suspension, fully stirring, and reacting under a sealed heating condition to obtain a reaction solution;
s50, carrying out solid-liquid separation on the reaction liquid to obtain a solid, washing the solid, and carrying out vacuum drying on the solid to obtain a second intermediate;
and S60, adding the second intermediate into a silver nitrate solution, adding a reducing agent, carrying out solid-liquid separation after reaction to obtain a solid, and washing and vacuum-drying the solid to obtain the quaternary high-efficiency photocatalytic nanomaterial with the memory effect.
3. The method of claim 2, wherein in step S10,
the reaction temperature is 160-200 ℃; and/or the presence of a gas in the gas,
in the mixed solvent of glycerol, ethanol and water, the volume ratio of glycerol to ethanol to water is 7: (6-8): (9-11).
4. The method of claim 2, wherein in step S10,
the Cu (NO)3)2·3H2The ratio of the amount of the substance of O to the amount of the substance of urea is 1 (1-3); and/or the presence of a gas in the gas,
the reaction time is 7-10 h.
5. The method for preparing the quaternary high-efficiency photocatalytic nanomaterial with the memory effect according to claim 2, wherein the Cu (NO) is3)2·3H2O and said K2SnO3·3H2The mass ratio of O is 5: (0.03-0.09).
6. The method of claim 2, wherein in step S40,
the reaction temperature is 150-180 ℃; and/or the presence of a gas in the gas,
the reaction time is 6-10 h.
7. The method as claimed in claim 2, wherein in step S50, the washing is sequentially water and ethanol.
8. The method of claim 2, wherein in step S60,
the reducing agent comprises at least one of hydrazine hydrate and sodium sulfite; and/or the presence of a gas in the gas,
the reaction time is 1-2 h; and/or the presence of a gas in the gas,
the vacuum drying temperature is 45-65 ℃; and/or the presence of a gas in the gas,
and the vacuum drying time is 5-10 h.
9. The method for preparing the quaternary high-efficiency photocatalytic nanomaterial with the memory effect according to claim 2, wherein the Cu (NO) is3)2·3H2The ratio of the amount of O to the amount of silver nitrate is 5: (0.1-0.3).
10. An air purifier, characterized in that it comprises the quaternary high efficiency photocatalytic nanomaterial with "memory" effect according to claim 1.
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