CN114392736A - Catalytic membrane for purifying formaldehyde at normal temperature and preparation method and application thereof - Google Patents
Catalytic membrane for purifying formaldehyde at normal temperature and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a catalytic membrane for purifying formaldehyde at normal temperature, a preparation method and application thereof, wherein the catalytic membrane for purifying formaldehyde at normal temperature comprises the following components: the first film layer is formed on the surface of the substrate, and the components of the first film layer comprise aluminum oxide; and the second film layer is formed on the first film layer and is positioned on one side of the first film layer far away from the base material, and the components of the second film layer comprise manganic oxide and manganese dioxide. The invention can solve the problem that the catalyst in the prior art has poor activity and long-term stability at normal temperature.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalytic membrane for purifying formaldehyde at normal temperature and a preparation method and application thereof.
Background
In 2017, 10 and 27, in a carcinogen list published by the international cancer research institution of the world health organization, formaldehyde is put in a carcinogen list. Formaldehyde is a recognized source of allergy and is also one of the potentially strong mutant carcinogens. Mild excessive formaldehyde may cause chronic poisoning, and has certain damage to respiratory system and nervous system of human body. When formaldehyde in indoor air containsThe amount of the active component reaches 0.1mg/m3In time, people feel uncomfortable; up to 0.3mg/m3Sometimes, breathing discomfort can occur; up to 0.5mg/m3When it is used, nausea and vomiting symptoms are caused; if the concentration is higher, damage may occur to the lungs and central nervous system of the human.
The mainstream formaldehyde purification technology in the home at present is to treat by an adsorbent, however, the methods are not the only treatment, for example, the activated carbon does not have adsorption capacity after being saturated, or pollutants such as formaldehyde and the like are released after the activated carbon is subjected to high temperature. Most formaldehyde scavengers, photocatalysts, metal catalysts and adsorbents have certain effects on removing formaldehyde. However, in 2021 years, with the improvement of indoor air standard quality, the emphasis is now on the formaldehyde removal rate, i.e. how long it takes to stay, whether there are rebound prevention measures, and for children, the elderly, pregnant women and patients, a more strict standard should be reached, i.e. 0.03mg/m3. The existing catalyst product has low durability at normal temperature, such as about 20 ℃, and the active component in the formula of the catalyst product, such as MnO, is not controlled, and the like, except that the existing preparation process generates pollution and can not control impurities2Carbon-containing species are continuously accumulated due to its excessively high catalytic oxidation performance, resulting in failure to be used for a long period of time. Moreover, according to the inference of the Trasatti volcanic diagram, the key of the catalytic reaction is activity and durability, so that the chemical adsorption capacity of the catalyst is required to be close to the volcanic diagram peak, and is not strong or weak. The excessively strong catalytic performance can cause partial incompletely decomposed products to accumulate on the surface of the catalyst, and the excessively weak catalytic performance can cause the efficiency of the catalyst to be not up to the standard.
Disclosure of Invention
Aiming at the technical problems, the invention provides a catalytic membrane for purifying formaldehyde at normal temperature and a preparation method and application thereof, so as to solve the problems of poor activity and long-term stability of the catalyst at normal temperature in the prior art.
In order to achieve the above object, the present invention provides a catalytic membrane for purifying formaldehyde at normal temperature, comprising: the first film layer is formed on the surface of the substrate, and the components of the first film layer comprise aluminum oxide; and the second film layer is formed on the first film layer and is positioned on one side of the first film layer far away from the base material, and the components of the second film layer comprise manganic oxide and manganese dioxide.
Preferably, the composition of the first film layer further includes a first oxide, and the first oxide is at least one of lithium oxide, sodium oxide, potassium oxide, beryllium oxide, magnesium oxide, calcium oxide, silicon oxide, lanthanum oxide, and cerium oxide.
Preferably, in the first film layer, the mass ratio of the aluminum oxide to the first oxide is 1: 0.05-1: 0.15.
preferably, the thickness of the first film layer is greater than 30nm and less than 90 nm.
Preferably, in the second film layer, the mass percentage of the trimanganese tetroxide is greater than 70% and the mass percentage of the manganese dioxide is less than 30% based on 100% of the total mass percentage of the trimanganese tetroxide and the manganese dioxide.
Preferably, the second film further includes a second oxide, and the second oxide is at least one of lithium oxide, sodium oxide, potassium oxide, beryllium oxide, magnesium oxide, calcium oxide, silicon oxide, lanthanum oxide, and cerium oxide.
Preferably, in the second film layer, the total mass percentage of the trimanganese tetroxide and the manganese dioxide is greater than 70% and the mass percentage of the manganese dioxide is less than 30%, and the ratio of the total mass of the trimanganese tetroxide and the manganese dioxide to the mass of the second oxide is: 1: 0.05-1: 0.3.
preferably, the thickness of the second film layer is greater than 2nm and less than 20 nm.
Preferably, the film further comprises a third film layer formed on the second film layer, the second film layer is located between the first film layer and the third film layer, and the third film layer is a nitride or a carbide of a single metal or a bimetallic element, wherein the single metal or the bimetallic element is selected from titanium, vanadium, chromium, manganese, iron, zirconium, niobium, molybdenum, technetium and ruthenium.
Preferably, the thickness of the third film layer is greater than 0.2 angstroms and less than 2 nm.
The invention also provides the application of the catalytic membrane, wherein the catalytic membrane is used for purifying formaldehyde at room temperature.
The invention also provides a preparation method of the catalytic membrane for purifying formaldehyde at normal temperature, which comprises the following steps:
step S1, vacuumizing a vacuum bin;
step S2, starting an ion generator, wherein the ion source current of the ion generator is a first current, introducing argon with a first ventilation quantity, and purging the substrate;
step S3, keeping the ion source current as the first current, and reducing the ventilation of the argon gas as a second ventilation;
step S4, starting an electron beam evaporator, putting the aluminum oxide film material into an electron gun crucible, introducing oxygen of a third air flow, evaporating the aluminum oxide film material, and forming a first film layer on the substrate;
step S5, starting a resistance evaporator, adjusting the current of the ion source to be a second current, introducing oxygen of a fourth air flow, putting a manganese film material into a evaporation-resistant crucible, evaporating the manganese film material, and forming a second film layer on the first film layer, wherein the second film layer is positioned on one side of the first film layer, which is far away from the substrate; the second current is smaller than the first current, and the fourth ventilation is larger than the third ventilation.
Preferably, step S5 is followed by step S6 of turning on an electron beam evaporator, adjusting the current of the ion source to the first current, introducing a fifth amount of nitrogen gas, placing at least one metal film material in a crucible of an electron gun, evaporating the metal film material to form a third film layer on the second film layer, where the second film layer is located between the first film layer and the third film layer, and the metal film material is selected from the group consisting of metal elements of titanium, vanadium, chromium, manganese, iron, zirconium, niobium, molybdenum, technetium, and ruthenium.
Preferably, the step S4 further includes placing a first oxide film material into an electron gun crucible, and co-evaporating the aluminum oxide film material and the first oxide film material to form the first film layer on the substrate; the first oxide is at least one of lithium oxide, sodium oxide, potassium oxide, beryllium oxide, magnesium oxide, calcium oxide, silicon oxide, lanthanum oxide and cerium oxide.
Preferably, in the first film layer, the mass ratio of the aluminum oxide to the first oxide is 1: 0.05-1: 0.15.
preferably, in the second film layer, the mass percentage of the trimanganese tetroxide is greater than 70% and the mass percentage of the manganese dioxide is less than 30% based on 100% of the total mass percentage of the trimanganese tetroxide and the manganese dioxide.
Preferably, the step S5 further includes simultaneously turning on the electron beam evaporator, and placing a second oxide film into the electron gun crucible to co-evaporate the manganese film and the second oxide film, where the second oxide is at least one of lithium oxide, sodium oxide, potassium oxide, beryllium oxide, magnesium oxide, calcium oxide, silicon oxide, lanthanum oxide, and cerium oxide.
Preferably, in the second film layer, the total mass percentage of the trimanganese tetroxide and the manganese dioxide is greater than 70% and the mass percentage of the manganese dioxide is less than 30%, based on 100% of the total mass percentage of the trimanganese tetroxide and the manganese dioxide, and the ratio of the total mass of the trimanganese tetroxide and the manganese dioxide to the mass of the second oxide is: 1: 0.05-1: 0.3.
preferably, the film formation time of the first film layer and the film formation time of the second film layer are both less than or equal to 5 minutes.
Preferably, the thickness of the first film layer is greater than 30nm and less than 90 nm.
Preferably, the thickness of the second film layer is greater than 2nm and less than 20 nm.
Preferably, the thickness of the third film layer is greater than 0.2 angstroms and less than 2 nm.
Compared with the prior art, the invention can well maintain the activity and long-term stability of the catalyst at normal temperature by changing the composition of the main catalytic film layer of the catalytic film, combining the characteristics of the trimanganese tetroxide and the manganese dioxide, and by the proportion of the compositions and the formed multilayer structure. In addition, divalent and trivalent manganese ions in the trimanganese tetroxide are distributed on two different lattice positions, oxygen ions are in cubic close packing, the divalent manganese ions occupy tetrahedral gaps, and the trivalent manganese ions occupy octahedral gaps. Meanwhile, the treatment concentration range and airspeed range of the catalytic membrane for purifying formaldehyde at normal temperature, which is prepared by the preparation method, are greatly 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, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic structural diagram of one embodiment of a catalytic membrane for purifying formaldehyde at normal temperature according to the present invention;
fig. 2 is a schematic flow chart of a method for preparing a catalytic membrane for purifying formaldehyde at normal temperature according to an embodiment of the present invention.
Detailed Description
In order to further understand the objects, structures, features and functions of the present invention, the following embodiments are described in detail.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention.
Referring to fig. 1, fig. 1 is a schematic structural diagram of an embodiment of a catalytic membrane for purifying formaldehyde at normal temperature according to the present invention; the invention provides a catalytic membrane for purifying formaldehyde at normal temperature, which comprises a first membrane layer 2 and a second membrane layer 3, wherein the first membrane layer 1 is formed on the surface of a substrate 1, and the first membrane layer 2 comprises aluminum oxide. A second film layer 3 is formed on the first film layer 2 and is positioned on the side of the first film layer 2 far away from the substrate 1, and the composition of the second film layer 3 comprises mangano-manganic oxide (Mn)3O4) And manganese dioxide (MnO)2). The substrate is a non-metal substrate known to those skilled in the art, and is not particularly limited, and in the present invention, the substrate is preferably a semiconductor substrate, and more preferably a silicon wafer, quartz or silicon oxide wafer; in the second film layer, the total mass percentage of the trimanganese tetroxide and the manganese dioxide is 100%, the mass percentage of the trimanganese tetroxide is more than 70%, and the mass percentage of the manganese dioxide is less than 30%. Wherein, the first film layer 2 is a catalytic film substrate layer, and the second film layer 3 is a main catalytic film layer. The component manganomanganic oxide in the second film layer 3 is spinel structure, compared with MnO2It is more stable and the divalent and trivalent manganese ions in the trimanganese tetroxide are distributed on two different lattice sites. Oxygen ions are in cubic close packing, bivalent manganese ions occupy tetrahedral gaps, trivalent manganese ions occupy octahedral gaps, and in the catalysis process, due to continuous pulling of crystal faces, the valence state change of the manganese ions is more free, and the transformation of lattice oxygen and adsorbed oxygen is also more free.
Moreover, the thickness of the first film layer is preferably more than 30nm and less than 90 nm; the thickness of the second film layer is more than 2nm and less than 20 nm.
In another embodiment, the composition of the first film layer further comprises a first oxide, wherein the first oxide is at least one of lithium oxide, sodium oxide, potassium oxide, beryllium oxide, magnesium oxide, calcium oxide, silicon oxide, lanthanum oxide, and cerium oxide. Specifically, the first oxides are, for example, second, third and fourth periods of alkali metal oxides and alkaline earth metal oxides and SiO2、CeO2、La2O3。
In addition, in the first film, the mass ratio of the aluminum oxide to the first oxide is 1: 0.05-1: 0.15.
in addition, the second film layer further comprises a second oxide, and the second oxide is at least one of lithium oxide, sodium oxide, potassium oxide, beryllium oxide, magnesium oxide, calcium oxide, silicon oxide, lanthanum oxide and cerium oxide. In the second film layer, the total mass percentage of the trimanganese tetroxide and the manganese dioxide is 100%, the mass percentage of the trimanganese tetroxide is more than 70%, the mass percentage of the manganese dioxide is less than 30%, and the ratio of the total mass of the trimanganese tetroxide and the manganese dioxide to the mass of the second oxide is 1: 0.05-1: 0.3.
in addition, the catalytic membrane for purifying formaldehyde at normal temperature further comprises a third membrane layer, wherein the third membrane layer is formed on the second membrane layer and is nitride or carbide of single metal or double metal elements, the single metal or double metal elements are groups 4-8 of 3-5 periods, lanthanide series metal and radioactive metal Tc are excluded, and the single metal or double metal elements are specifically selected from metal elements of titanium, vanadium, chromium, manganese, iron, zirconium, niobium, molybdenum, technetium and ruthenium. The stability of the catalytic membrane can be obviously improved on the premise of ensuring the catalytic activity of the catalytic membrane by selecting the metal elements or the combination. Therefore, the third film layer can be used for improving the durability of the catalytic film at normal temperature and reducing the ignition temperature of formaldehyde so that the formaldehyde starts to decompose at lower temperature, and the catalytic film prepared by the third film layer is permanently effective at normal temperature and normal pressure.
Moreover, the thickness of the third film layer is preferably greater than 0.2 angstroms and less than 2 nm.
In addition, the invention also provides the application of the catalytic membrane, wherein the catalytic membrane is used for purifying formaldehyde at normal temperature, and is used for purifying formaldehyde at room temperature, the catalytic membrane for purifying formaldehyde at normal temperature can purify formaldehyde at normal temperature, the formaldehyde purifying efficiency is more than 99.9%, and the catalytic membrane has long-term stability.
As shown in fig. 2, fig. 2 is a schematic flow chart of a method for preparing a catalytic membrane for purifying formaldehyde at normal temperature according to an embodiment of the present invention; the invention also provides a preparation method of the catalytic membrane, wherein the catalytic membrane is used for purifying formaldehyde at normal temperature, and the preparation method comprises the following steps:
step S1, vacuumizing a vacuum bin;
step S2, starting an ion generator, wherein the ion source current of the ion generator is a first current, introducing argon with a first ventilation quantity, and purging the substrate; wherein the first current is 10A, the first ventilation rate is 15sccm, and the substrate purging time is 60 s;
step S3, keeping the ion source current as the first current, and reducing the ventilation of the argon gas as a second ventilation; the second ventilation amount is 7sccm for example;
step S4, turning on electron beam evaporator to remove aluminum oxide (Al)2O3) Putting the film material into an electronic gun crucible, introducing oxygen with a third air flow, evaporating the aluminum oxide film material, and forming a first film layer on the substrate; wherein the third ventilation amount is, for example, 20 sccm; here, the deposition rate is set according to the vacuum sound velocity of the film material, for example, Al2O3Film (380mA, 5.0 angstroms/second);
step S5, starting a resistance evaporator, adjusting the current of an ion source to be a second current, introducing oxygen of a fourth air flow, putting a manganese film material into a evaporation-resistant crucible, evaporating the manganese film material, and forming a second film layer on the first film layer, wherein the second film layer is positioned on one side of the first film layer, which is far away from the substrate; the second current is smaller than the first current, and the fourth ventilation volume is larger than the third ventilation volume. Wherein, the second current is 5A, the fourth gas flow is 70 sccm-99 sccm, and the evaporation rate of the manganese film material is as follows: mn (50mA, 1.0A/sec).
In another embodiment, the method for preparing the catalytic film further includes step S6, turning on an electron beam evaporator, adjusting an ion source current to the first current, for example, 10A, introducing nitrogen gas with a fifth gas flow rate (for example, 80sccm), placing at least one metal film material in an electron gun crucible, and depositing the metal film material on the second film layer to form a third film layer, where the second film layer is located between the first film layer and the third film layer, and the metal film material is selected from titanium, vanadium, chromium, manganese, iron, zirconium, niobium, molybdenum, technetium, and ruthenium.
In addition, the step S4 further includes placing a first oxide in the electron gun crucible, co-evaporating a plurality of materials, and evaporating the alumina film material and the first oxide on the substrate to form the first film layer; the first oxide is at least one of lithium oxide, sodium oxide, potassium oxide, beryllium oxide, magnesium oxide, calcium oxide, silicon oxide, lanthanum oxide and cerium oxide. Wherein, preferably, the mass ratio of the aluminum oxide to the first oxide is 1: 0.05-1: 0.15.
in the second film layer, the total mass percentage of the trimanganese tetroxide and the manganese dioxide is 100%, the mass percentage of the trimanganese tetroxide is more than 70%, and the mass percentage of the manganese dioxide is less than 30%.
Step S5 further includes simultaneously turning on the electron beam evaporator, and placing a second oxide into the electron gun crucible to co-evaporate a plurality of materials, where the second oxide is at least one of lithium oxide, sodium oxide, potassium oxide, beryllium oxide, magnesium oxide, calcium oxide, silicon oxide, lanthanum oxide, and cerium oxide. In the second film layer, the total mass percentage of the trimanganese tetroxide and the manganese dioxide is 100%, the mass percentage of the trimanganese tetroxide is more than 70%, the mass percentage of the manganese dioxide is less than 30%, and the ratio of the total mass of the trimanganese tetroxide and the manganese dioxide to the mass of the second oxide is as follows: 1: 0.05-1: 0.3.
the film formation time of the first film layer and the film formation time of the second film layer are both 5 minutes or less, and the film formation time of the third film layer is also 5 minutes or less.
Preferably, the thickness of the first film layer is greater than 30nm and less than 90nm, the thickness of the second film layer is greater than 2nm and less than 20nm, and the thickness of the third film layer is greater than 0.2 angstrom and less than 2 nm.
The present invention will be described with reference to specific examples.
Example 1:
(1) vacuumizing the vacuum bin;
(2) starting an ion generator, wherein the ion source current of the ion generator is 10A, the argon gas introduction amount is 15sccm, and purging the substrate for 60 s;
(3) keeping the ion source current 10A unchanged, and reducing the argon ventilation amount to 7 sccm;
(4) starting an electron beam evaporator to evaporate Al2O3，CeO2Placing into an electron gun crucible, introducing oxygen with a ventilation of 20sccm, setting the evaporation rate according to the vacuum sound velocity of each film material as follows, wherein Al is2O3(380mA, 5.0A/s), CeO2(50mA, 0.5 angstrom/second), the two materials are evaporated for 60s, a first film layer (namely a catalytic film layer substrate) is obtained by evaporation plating on the base material, and the time for forming the film at 33nm is about 1 minute;
(5) starting a resistance evaporator and an electron beam evaporator, adjusting the current of an ion source to be 5A, introducing oxygen with the ventilation volume of 90sccm, and setting the evaporation rate according to the vacuum sound velocity of each film material as follows, wherein Mn (50mA, 1.0 angstrom/second) and CeO2(50mA, 0.5 angstrom per second), evaporating a plurality of materials for 100s, evaporating and plating on the first film layer to obtain a second film layer, wherein the time for forming the film with the thickness of 12nm is about 2 minutes;
(6) starting an electron beam evaporator, adjusting the current of an ion source to be 10A, introducing nitrogen with the air flow of 80sccm, setting the evaporation rate according to the vacuum sound velocity of each film material as follows, wherein W (490mA, 0.1 angstrom per second) is adopted for evaporation of 100s for one material, a third film layer is obtained on the second film layer by evaporation, and the time for forming the film with the thickness of 1nm is about 2 minutes, so that the catalytic film with three film layers is obtained. In this embodiment, the first film layer is a thin film layer of aluminum oxide + cerium dioxide, the second film layer is a thin film layer of 70.4% of mangano-manganic oxide + 9.6% of manganese dioxide + 20% of cerium dioxide, and the third film layer is a WNx thin film layer.
Tests show that the catalytic membrane of the embodiment 1 has the formaldehyde purification efficiency of more than 99.9 percent and can be permanently used.
Example 2
The preparation conditions of example 1 were used to prepare a catalytic film (i.e., two catalytic films) having a first film layer of aluminum oxide and a second film layer of 91% of mangano-manganic oxide + 9% of manganese dioxide.
Tests show that the efficiency of the catalytic membrane of the embodiment 2 for purifying formaldehyde is greater than 99.9%, and the service life is about 8000 h.
Example 3
The preparation conditions of example 1 were used to prepare a catalytic membrane (i.e., two catalytic membranes) having a first membrane layer of alumina + ceria and a second membrane layer of 70.4% trimanganese tetroxide + 9.6% manganese dioxide + 20% ceria.
Tests show that the efficiency of the catalytic membrane of the embodiment 3 for purifying formaldehyde is greater than 99.9%, and the service life is about 1,5000 h.
Moreover, the catalytic membrane prepared in each embodiment does not need to use ozone as an oxidant, and only needs to use oxygen in the air, and the temperature window is 0-150 ℃ (higher temperature is also possible, but the catalytic membrane is used in industry); the treatment concentration range is 0.5-5000 ppm; the reaction volume space velocity range is 2000-60,000/hr, and compared with the prior art that ozone is adopted as an oxidant (the temperature window is 100-. Moreover, since the catalytic membrane of the present invention has a sheet-like structure, it can be folded differentlyThe stacking mode can directly stack the catalytic membrane and also can fold the catalytic membrane into a corrugated board form. And the catalytic membrane of the invention (as an example 28cm x 33 cm) can practically measure formaldehyde in a room with 60 square meters in 2 hours from 0.5mg/m3Purifying to 0.01mg/m3。
In conclusion, the invention can well maintain the activity and long-term stability of the catalyst at normal temperature by changing the composition of the main catalytic film layer of the catalytic film, combining the characteristics of the trimanganese tetroxide and the manganese dioxide, and through the proportion of the compositions and the formed multilayer structure. In addition, divalent and trivalent manganese ions in the trimanganese tetroxide are distributed on two different lattice positions, oxygen ions are in cubic close packing, the divalent manganese ions occupy tetrahedral gaps, and the trivalent manganese ions occupy octahedral gaps. Meanwhile, the treatment concentration range and airspeed range of the catalytic membrane for purifying formaldehyde at normal temperature, which is prepared by the preparation method, are greatly improved.
The present invention has been described in relation to the above embodiments, which are only exemplary of the implementation of the present invention. Furthermore, the technical features mentioned in the different embodiments of the present invention described above may be combined with each other as long as they do not conflict with each other. It should be noted that the disclosed embodiments do not limit the scope of the invention. Rather, it is intended that all such modifications and variations be included within the spirit and scope of this invention.
Claims (22)
1. The catalytic membrane for purifying formaldehyde at normal temperature is characterized by comprising the following components in parts by weight:
the first film layer is formed on the surface of the substrate, and the components of the first film layer comprise aluminum oxide; and
and the second film layer is formed on the first film layer and is positioned on one side of the first film layer, which is far away from the substrate, and the components of the second film layer comprise manganic oxide and manganese dioxide.
2. The catalytic membrane for purifying formaldehyde at normal temperature according to claim 1, wherein the composition of the first membrane layer further comprises a first oxide, and the first oxide is at least one of lithium oxide, sodium oxide, potassium oxide, beryllium oxide, magnesium oxide, calcium oxide, silicon oxide, lanthanum oxide, and cerium oxide.
3. The catalytic membrane for purifying formaldehyde at normal temperature according to claim 2, wherein in the first membrane layer, the mass ratio of the aluminum oxide to the first oxide is 1: 0.05-1: 0.15.
4. the catalytic membrane for purifying formaldehyde at normal temperature according to claim 1, wherein the thickness of the first membrane layer is greater than 30nm and less than 90 nm.
5. The catalytic membrane for purifying formaldehyde at normal temperature according to claim 1, wherein in the second membrane layer, the mass percentage of the trimanganese tetroxide is more than 70% and the mass percentage of the manganese dioxide is less than 30% based on 100% of the total mass percentage of the trimanganese tetroxide and the manganese dioxide.
6. The catalytic membrane for purifying formaldehyde at normal temperature according to claim 1, wherein the second membrane layer further comprises a second oxide, and the second oxide is at least one of lithium oxide, sodium oxide, potassium oxide, beryllium oxide, magnesium oxide, calcium oxide, silicon oxide, lanthanum oxide, and cerium oxide.
7. The catalytic membrane for purifying formaldehyde at normal temperature according to claim 6, wherein in the second membrane layer, the mass percentage of the trimanganese tetroxide is more than 70%, the mass percentage of the manganese dioxide is less than 30%, and the ratio of the total mass of the trimanganese tetroxide and the manganese dioxide to the mass of the second oxide is as follows, based on the total mass percentage of the trimanganese tetroxide and the manganese dioxide being 100%: 1: 0.05-1: 0.3.
8. the catalytic membrane for purifying formaldehyde at normal temperature according to claim 1, wherein the thickness of the second membrane layer is greater than 2nm and less than 20 nm.
9. The catalytic membrane for purifying formaldehyde at normal temperature according to claim 1, further comprising a third membrane layer formed on the second membrane layer, wherein the second membrane layer is located between the first membrane layer and the third membrane layer, and the third membrane layer is a nitride or a carbide of a single metal or a bimetallic element, wherein the single metal or the bimetallic element is selected from titanium, vanadium, chromium, manganese, iron, zirconium, niobium, molybdenum, technetium, and ruthenium.
10. The catalytic membrane for purifying formaldehyde at normal temperature according to claim 9, wherein the thickness of the third membrane layer is greater than 0.2 angstroms and less than 2 nm.
11. Use of a catalytic membrane for purifying formaldehyde at room temperature according to any one of claims 1 to 10.
12. A preparation method of a catalytic membrane for purifying formaldehyde at normal temperature is characterized by comprising the following steps:
step S1, vacuumizing a vacuum bin;
step S2, starting an ion generator, wherein the ion source current of the ion generator is a first current, introducing argon with a first ventilation quantity, and purging the substrate;
step S3, keeping the ion source current as the first current, and reducing the ventilation of the argon gas as a second ventilation;
step S4, starting an electron beam evaporator, putting the aluminum oxide film material into an electron gun crucible, introducing oxygen of a third air flow, evaporating the aluminum oxide film material, and forming a first film layer on the substrate;
step S5, starting a resistance evaporator, adjusting the current of the ion source to be a second current, introducing oxygen of a fourth air flow, putting a manganese film material into a evaporation-resistant crucible, evaporating the manganese film material, and forming a second film layer on the first film layer, wherein the second film layer is positioned on one side of the first film layer, which is far away from the substrate; the second current is smaller than the first current, and the fourth ventilation is larger than the third ventilation.
13. The method of claim 12, further comprising a step S6 after the step S5, wherein the method further comprises the steps of turning on an electron beam evaporator, adjusting the ion source current to the first current, introducing a fifth amount of nitrogen gas, placing at least one metal film material in an electron gun crucible, evaporating the metal film material, and forming a third film layer on the second film layer, wherein the second film layer is located between the first film layer and the third film layer, and the metal film material is selected from the group consisting of metal elements consisting of titanium, vanadium, chromium, manganese, iron, zirconium, niobium, molybdenum, technetium, and ruthenium.
14. The method according to claim 12, wherein the step S4 further comprises placing a first oxide film material in an electron gun crucible, co-evaporating the alumina film material and the first oxide film material, and forming the first film layer on the substrate; the first oxide is at least one of lithium oxide, sodium oxide, potassium oxide, beryllium oxide, magnesium oxide, calcium oxide, silicon oxide, lanthanum oxide and cerium oxide.
15. The method for preparing a catalytic membrane for purifying formaldehyde at normal temperature according to claim 14, wherein in the first membrane layer, the mass ratio of the aluminum oxide to the first oxide is 1: 0.05-1: 0.15.
16. the method according to claim 12, wherein the second film layer contains more than 70% by mass of the trimanganese tetroxide and less than 30% by mass of the manganese dioxide, based on 100% by mass of the trimanganese tetroxide and the manganese dioxide.
17. The method of claim 12, wherein step S5 further comprises simultaneously turning on an electron beam evaporator, placing a second oxide film in the electron gun crucible, and co-evaporating the manganese film and the second oxide film, wherein the second oxide is at least one of lithium oxide, sodium oxide, potassium oxide, beryllium oxide, magnesium oxide, calcium oxide, silicon oxide, lanthanum oxide, and cerium oxide.
18. The method according to claim 17, wherein in the second film layer, the total mass percentage of the trimanganese tetroxide and the manganese dioxide is greater than 70%, the mass percentage of the manganese dioxide is less than 30%, and the ratio of the total mass of the trimanganese tetroxide and the manganese dioxide to the mass of the second oxide is as follows: 1: 0.05-1: 0.3.
19. the method of claim 12, wherein the time for forming the first film layer and the time for forming the second film layer are both less than or equal to 5 minutes.
20. The method of claim 12, wherein the first film layer has a thickness of greater than 30nm and less than 90 nm.
21. The method of claim 12, wherein the second film layer has a thickness of greater than 2nm and less than 20 nm.
22. The method of claim 12, wherein the third film layer has a thickness of greater than 0.2 angstroms and less than 2 nm.
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