CN113198486B

CN113198486B - Spinel type copper-manganese catalytic material for sterilization and aldehyde removal as well as preparation method and application thereof

Info

Publication number: CN113198486B
Application number: CN202110431471.8A
Authority: CN
Inventors: 张惠斌; 方倩; 徐凯
Original assignee: Zhejiang University of Technology ZJUT
Current assignee: Zhejiang University of Technology ZJUT
Priority date: 2021-04-21
Filing date: 2021-04-21
Publication date: 2022-07-01
Anticipated expiration: 2041-04-21
Also published as: CN113198486A

Abstract

The invention relates to the field of catalytic materials, in particular to a spinel type copper-manganese catalytic material for sterilization and aldehyde removal, and a preparation method and application thereof. The method comprises the following steps: adding a copper material into a hydrogen chloride water solution to prepare a copper solution; dissolving potassium permanganate in water to prepare manganese solution; mixing the copper solution and the manganese solution, carrying out hydrothermal reaction, adjusting the pH value of the solution to be neutral or alkalescent after the hydrothermal reaction is finished, continuously stirring, standing for aging, and carrying out spray drying after aging to obtain a precursor; and cleaning and drying the precursor, and then calcining at high temperature to obtain the spinel type copper-manganese catalytic material for sterilization and aldehyde removal. The preparation method is simple and efficient, and has low equipment requirement; the catalyst has good catalytic degradation effect on formaldehyde; the formaldehyde can be directly catalyzed and degraded without the need of matching with additional substances; has excellent bacteria killing performance.

Description

Spinel type copper-manganese catalytic material for sterilization and aldehyde removal as well as preparation method and application thereof

Technical Field

The invention relates to the field of catalytic materials, in particular to a preparation method of a spinel type copper-manganese catalytic material for sterilization and aldehyde removal.

Background

Indoor woodware, wood boards, furniture and walls and coatings for surfaces thereof contain substantially formaldehyde, and it has been found that the formaldehyde emission period is usually three to fifteen years, i.e. many appliances release formaldehyde continuously even after a long period of finishing. And publication No. 153 issued by the world health organization in 2004 identifies: formaldehyde is a carcinogenic and teratogenic substance. It is a well-recognized source of allergy and one of the potential strong mutagens and is one of the risk factors for childhood leukemia. According to medical journal and related literature reports, the harm of indoor formaldehyde to human health can be summarized as stimulation, toxicity and carcinogenesis.

However, even if formaldehyde has such a great hazard, due to the limitation of materials and technologies, the use of materials and materials containing formaldehyde in the process of manufacturing indoor furniture and decoration is still not completely prohibited, and thus the formaldehyde pollution in the room cannot be solved from the root. Further, in order to reduce the influence of formaldehyde pollution on people, many technicians research the absorption and decomposition of formaldehyde, and the development of an environment-friendly purification material capable of effectively absorbing and decomposing formaldehyde is expected.

Most of the materials for catalytic degradation of formaldehyde at present are manganese dioxide, titanium dioxide, diatomite and the like, but the formaldehyde catalytic materials all have certain use limitations and defects, and the titanium dioxide in the materials has the problems of high price and the like.

For this reason, those skilled in the art have made various studies on formaldehyde catalytic degradation materials. For example, the application publication number of the invention patent application of the decorative coating capable of absorbing formaldehyde and the preparation method thereof is CN109401508A, the main active substance in the technical scheme is FeOx. MnOy. TiO2 nano-composite, the nano-composite has certain formaldehyde absorption and degradation capability, but the coating form of the nano-composite cannot be regenerated while being limited by certain use, the coating has poor air permeability after curing, and the contact area with formaldehyde is small, so that the absorption efficiency is limited, and the degradation efficiency after absorption is weak.

The spinel type copper-manganese material is researched to show that the spinel type copper-manganese material has unique catalytic performance, for example, the invention patent authorization of the preparation method of the hollow hexahedron copper-manganese-acid spinel and the application method of the technology for catalyzing ozone oxidation decontamination, which is disclosed by the Chinese patent office in 2017, 11 and 14 is the authorization publication number CN 105195168B. The spinel catalytic material prepared by the technical scheme has the capability of catalyzing ozone to generate high oxidability, can be used for water treatment, but has poor effect when being used for formaldehyde catalytic degradation through a large number of tests and detections, and cannot directly and effectively catalyze and degrade formaldehyde by matching with the ozone.

Disclosure of Invention

The invention provides a preparation method of a spinel type copper-manganese sterilization and aldehyde removal catalytic material, which aims to solve the problems that the existing formaldehyde catalytic material has certain use limitation and defect, and part of formaldehyde catalytic degradation materials have high cost, large preparation difficulty and the like.

The invention aims to: firstly, carrying out double adjustment on the components and the structure of the spinel type copper-manganese material to effectively carry out catalytic degradation on formaldehyde; secondly, the efficiency and the effect of catalytic degradation of formaldehyde are improved; thirdly, the spinel type copper-manganese sterilization and aldehyde removal catalytic material with unit weight can degrade more formaldehyde; fourthly, the service life of the material is prolonged, and the material has better heating self-regeneration capability; fifthly, the catalytic office has good capability of killing bacteria.

In order to achieve the purpose, the invention adopts the following technical scheme.

A preparation method of spinel type copper-manganese catalytic material for sterilization and aldehyde removal,

the method comprises the following steps:

1) adding a copper material into a hydrogen chloride water solution to prepare a copper solution;

2) dissolving potassium permanganate in water to prepare manganese solution;

3) mixing the copper liquid and the manganese liquid, carrying out hydrothermal reaction, adjusting the pH value of the solution to be neutral or alkalescent after the hydrothermal reaction is finished, continuously stirring, then standing for aging, and carrying out spray drying after aging to obtain a precursor;

4) and cleaning and drying the precursor, and then calcining at high temperature to obtain the spinel type copper-manganese catalytic material for sterilization and aldehyde removal.

In the method, copper liquid and manganese liquid are prepared respectively, the pH value is adjusted after hydrothermal treatment to precipitate copper-manganese powder, a spherical precursor is obtained through spray drying, compared with other drying modes, the precursor powder which is close to spherical is obtained through spray drying more easily, and then high-temperature calcination is carried out to obtain the spinel type copper-manganese sterilization and aldehyde removal catalytic material which is mainly formed by matching Cu (II) and Mn (III). The whole preparation method is simple and efficient.

In addition, the researchers of the present invention find that manganese dioxide has good performance in killing common pathogenic bacteria. For example staphylococcus aureus, escherichia coli and other common pathogenic bacteria, the conventional electrolytic manganese dioxide can reach the antibacterial rate of more than 99 percent, but the catalytic material further strengthens the bacterium killing capability of the catalytic material by applying copper-manganese composite and forming multi-valence copper-manganese composite.

As a preference, the first and second liquid crystal compositions are,

the copper material in the step 1) comprises soluble cuprous salt and elemental copper

The molar ratio of the soluble cuprous salt to the simple substance copper is 1: (0.75 to 1.5);

the concentration of the hydrogen chloride aqueous solution in the step 1) is 2.0-3.0 mol/L;

the molar concentration of copper element in the copper liquid in the step 1) is 0.15-0.25 mol/L.

The soluble cuprous salt and the elemental copper are adopted, so that the cuprous ions in the copper liquid can be prevented from being oxidized by oxygen in the air to form copper ions in a large amount, the stability of cuprous ions is ensured, more trivalent manganese ions can be formed in the obtained catalytic material through the matching of the cuprous salt and the elemental copper, more monovalent cuprous ions are kept, the trivalent manganese ions can form a more stable crystal structure and are matched with the cupric ions formed through oxidation, and the cuprous ions are matched with a very small amount of tetravalent manganese ions to form a defect oxide. In addition, compared with the method of singly adopting soluble cuprous salt, the cuprous ion retention degree in the finally obtained catalytic material is higher, the formed cuprous oxide defects are more, and compared with the method of singly adopting simple substance copper, the tetravalent manganese oxide defects can be more retained. The retention of tetravalent manganese oxide (namely manganese dioxide) can improve the catalytic degradation effect on formaldehyde, while cuprous defect oxide (cuprous oxide) has better conductivity than copper oxide and certain photoelectric conversion capability, which is beneficial to improving the heating self-regeneration capability of the catalytic material and enables the catalytic material to be regenerated more easily.

Preferably, the soluble cuprous salt is cuprous chloride.

Cuprous chloride is easy to obtain, and can be easily kept stable in high-concentration hydrogen chloride, and acid radical ions of the cuprous chloride have no oxidizing property.

Preferably, the molar concentration of the manganese element in the manganese solution in the step 2) is 0.33-0.70 mol/L.

The molar concentration of manganese element (equal to the molar concentration of permanganate) and the copper solution are the best to produce the matching effect.

As a preference, the first and second liquid crystal compositions are,

step 3), mixing the copper liquid and the manganese liquid in a volume ratio of 1: (0.8-1.15) mixing;

and 3) carrying out hydrothermal reaction at the temperature of 200-240 ℃ for 16-18 h.

The copper liquid and the manganese liquid are mixed according to the proportion, so that the obtained precursor can form a complete crystal structure and a certain defect oxide structure is reserved. The hydrothermal method adopts relatively higher temperature to promote the valence transformation of copper and manganese and the homogenization of defect structure, and in addition, if the diffusion of ferric ions is matched, the hydrothermal temperature is necessarily increased, and the hydrothermal time is prolonged.

As a preference, the first and second liquid crystal compositions are,

the pH value range of the neutral or weak alkaline in the step 3) is 7-8.5;

the continuous stirring time in the step 3) is 80-100 min, and the stirring speed is 300-600 rpm;

and 3) standing and aging at 20-25 ℃ for 8-10 h.

The precursor can be effectively separated out in the pH value range, and can be continuously dispersed without enrichment in the stirring process, and the precursor can be dried after standing and aging.

Preferably, the high-temperature calcination temperature in the step 4) is 750-850 ℃, and the calcination time is 3-4 h.

The spinel-type copper-manganese sterilization and aldehyde removal catalytic material powder is formed by the catalytic material in high-temperature calcination, and part of trivalent manganese oxide on the surface is further oxidized to form tetravalent manganese oxide, so that the content of manganese dioxide is increased, and the catalytic degradation effect on formaldehyde is further improved.

As a preference, the first and second liquid crystal compositions are,

step 1), a copper liquid preparation process, namely adding an iron material;

the iron material is one or more of simple substance iron, soluble ferrous salt and soluble ferric salt.

After the iron material is added, the permanganate acid radical can oxidize simple substance iron and ferrous ions to form ferric ions under the acidic condition, and the soluble ferric salt can directly provide the ferric ions. In the process of forming a precursor or performing subsequent high-temperature calcination heat treatment, as the ionic radiuses of the ferric iron ions and the ferric manganese ions are similar, the ferric iron ions can easily replace the manganese ions to form copper iron oxide or replace and replace the ferric manganese in the copper manganese oxide, and the formed new structure can further enlarge the lattice defects of the catalytic material per se, so that more and more uniform defect oxides are formed inside the catalytic material, the conversion from the ferric manganese to the tetravalent manganese in the high-temperature calcination process is facilitated, and a better catalytic degradation effect on formaldehyde is generated.

As a preference, the first and second liquid crystal compositions are,

the molar ratio of copper element in the copper material to iron element in the iron material is 1: (0.01-0.05).

The addition of iron element should not be too much, which may cause the stability of spinel structure of the catalytic material to decrease, even pulverization, while too little addition may not have good effect of improving catalytic performance.

A spinel type copper-manganese catalytic material for sterilization and aldehyde removal,

the catalytic material mainly comprises Cu (II) and Mn (III) which form a spinel crystal structure, and a partial defect structure exists;

the defect structure is composed of Cu (I) and Mn (IV), or is compositely composed of Cu (II) and Fe (III), Cu (I) and Mn (IV), Cu (II) and Mn (III).

An application of spinel-type Cu-Mn catalytic material for sterilizing and removing aldehyde,

the catalytic material is used for air purification and/or sterilization.

The invention has the beneficial effects that:

1) the preparation method is simple and efficient, and has low equipment requirement;

2) the catalyst has good catalytic degradation effect on formaldehyde;

3) the formaldehyde can be directly catalyzed and degraded without the need of matching with additional substances;

4) the structure is stable, the service life is long, and the regeneration performance is good;

5) the catalyst has excellent bactericidal performance.

Detailed Description

The present invention will be described in further detail with reference to specific examples. Those skilled in the art will be able to implement the invention based on these teachings. Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without making creative efforts shall fall within the protection scope of the present invention.

Unless otherwise specified, the raw materials used in the examples of the present invention are all commercially available or available to those skilled in the art; unless otherwise specified, the methods used in the examples of the present invention are all those known to those skilled in the art.

Example 1

A preparation method of a spinel type copper-manganese catalytic material for sterilization and aldehyde removal comprises the following steps:

1) mixing a mixture of 1: 0.75 of cuprous chloride and elemental copper are added into 2.0mol/L aqueous hydrogen chloride solution to prepare copper liquid, wherein the molar concentration of copper element in the copper liquid is 0.175 mol/L;

2) dissolving potassium permanganate in water to prepare a manganese solution with the concentration of 0.33 mol/L;

3) mixing copper liquid and manganese liquid in a volume ratio of 1: mixing according to the proportion of 0.8, carrying out hydrothermal reaction at 200 ℃ for 18h, adjusting the pH value of the solution to 7 by using a 3mol/L sodium hydroxide aqueous solution after the hydrothermal reaction is finished, continuously stirring for 8min at 300pm, standing and aging for 10h in an environment at 20 ℃, and carrying out spray drying to obtain a precursor;

4) and cleaning and drying the precursor, and then calcining at the high temperature of 750 ℃ for 4h to obtain the spinel type copper-manganese catalytic material for sterilization and aldehyde removal.

Example 2

1) mixing a mixture of 1: 1.5, adding cuprous chloride and elementary copper into a 3.0mol/L aqueous hydrogen chloride solution to prepare a copper solution, wherein the molar concentration of copper element in the copper solution is 0.25 mol/L;

2) dissolving potassium permanganate in water to prepare a manganese solution with the concentration of 0.70 mol/L;

3) mixing copper liquid and manganese liquid in a volume ratio of 1: 1.15, performing hydrothermal reaction at 240 ℃ for 16h, adjusting the pH value of the solution to 8.5 by using a 3mol/L sodium hydroxide aqueous solution after the hydrothermal reaction is finished, continuously stirring at 600rpm for 100min, standing and aging at 20 ℃ for 8h, and performing spray drying to obtain a precursor;

4) and cleaning and drying the precursor, and then calcining at 850 ℃ for 4h to obtain the spinel type copper-manganese catalytic material for sterilization and aldehyde removal.

Example 3

1) mixing a mixture of 1: 1.0 of cuprous chloride and elemental copper are added into 3.0mol/L aqueous hydrogen chloride solution to prepare copper liquid, wherein the molar concentration of copper element in the copper liquid is 0.20 mol/L;

2) dissolving potassium permanganate in water to prepare a manganese solution with the concentration of 0.55 mol/L;

3) mixing copper liquid and manganese liquid according to a volume ratio of 1: 1.05, performing a hydrothermal reaction at 220 ℃ for 18h, adjusting the pH value of the solution to 7.5 by using a 3mol/L sodium hydroxide aqueous solution after the hydrothermal reaction is finished, continuously stirring at 600rpm for 80min, standing and aging at 25 ℃ for 10h, and performing spray drying to obtain a precursor;

4) and cleaning and drying the precursor, and then calcining at 850 ℃ for 3h to obtain the spinel type copper-manganese catalytic material for sterilization and aldehyde removal.

Example 4

1) mixing a mixture of 1: 1.0 of cuprous chloride and elementary copper are added into 3.0mol/L aqueous hydrogen chloride solution, and simultaneously, the mixture of elementary iron and ferric chloride in a molar ratio of 3: 1, the molar ratio of copper element in the copper material to iron element in the iron material is 1: 0.01, preparing copper liquid, wherein the molar concentration of copper element in the copper liquid is 0.20 mol/L;

3) mixing copper liquid and manganese liquid in a volume ratio of 1: 1.05, performing a hydrothermal reaction at 220 ℃ for 18h, adjusting the pH value of the solution to 7.5 by using a 3mol/L sodium hydroxide aqueous solution after the hydrothermal reaction is finished, continuously stirring at 600rpm for 80min, standing and aging at 25 ℃ for 10h, and performing spray drying to obtain a precursor;

Example 5

1) mixing a mixture of 1: 1.0 of cuprous chloride and elementary copper are added into 3.0mol/L aqueous hydrogen chloride solution, and an iron material consisting of ferrous chloride is added at the same time, wherein the molar ratio of copper element in the copper material to iron element in the iron material is 1: 0.05, preparing copper liquid, wherein the molar concentration of copper element in the copper liquid is 0.20 mol/L;

3) mixing copper liquid and manganese liquid in a volume ratio of 1: 1.05, carrying out a hydrothermal reaction at 220 ℃ for 18h, adjusting the pH value of the solution to 7.5 by using a 3mol/L sodium hydroxide aqueous solution after the hydrothermal reaction is finished, continuously stirring for 80min at 600rpm, standing and aging for 10h in an environment at 25 ℃, and carrying out spray drying to obtain a precursor;

Comparative example 1

The specific procedure was the same as in example 3, except that: the copper material is cuprous chloride.

Comparative example 2

The specific procedure was the same as in example 3, except that: the copper material is elemental copper.

Comparative example 3

The specific procedure was the same as in example 4, except that: the mol ratio of copper element in the copper material to iron element in the iron material is 1: 0.1. the obtained catalytic material was visibly pulverized with naked eyes.

Comparative example 4

The specific procedure was the same as in example 3, except that: the high-temperature calcination temperature is 600 ℃.

Single catalyst Performance test

A1.5 m.times.1.5 m.times.1.0 m sealed reaction chamber with inlet and outlet tubes was set up and a copper dish made of 99% pure copper with a bearing radius of 15cm was prepared. Weighing 500g of the catalytic materials prepared in examples 1-5 and comparative examples 1-4, respectively, marked as A1-A5 (respectively corresponding to examples 1-5) and B1-B4 (respectively corresponding to comparative examples 1-4), sequentially placing the catalytic materials in a copper dish, placing the copper dish in a sealed reaction chamber, sealing the reaction chamber, introducing 100mol of formaldehyde gas, detecting the concentration c of the formaldehyde gas in a rectangular test chamber after 6h, calculating the residual molar quantity m of the formaldehyde gas to be cV according to the volume V, finally calculating the removal rate w of the formaldehyde to be (100-cV)/100 x 100%, and cleaning the copper dish by using deionized water and absolute ethyl alcohol and drying the copper dish by cold air when replacing a catalytic material sample each time. By measurement and calculation, the results shown in table 1 below were obtained.

Table 1: single catalyst performance test results.

As is obvious from Table 1, the catalytic material has a good catalytic degradation effect on formaldehyde, under the action of the catalytic material, the removal rate of formaldehyde in a chamber can reach more than 70% within 6h, and after a new iron-copper oxide defect structure is formed in the catalytic material by matching with an iron material, the removal rate of formaldehyde after catalytic degradation on formaldehyde can basically reach about 95%, and the catalytic material has a very excellent formaldehyde removal effect.

As the general powdery catalytic material can also be used in the field of building materials as a wall coating, the catalytic material powder is added into a proper amount of water and stirred to be pasty, and the powdery catalytic material is further used as a coating to detect the spinel-type copper-manganese sterilization and aldehyde-removal catalytic material prepared in the embodiments 1-5 of the invention according to the JC/T1074-2008 purification performance of the coating material with the indoor air purification function, through detection, the purification efficiency of the catalytic material prepared in the embodiments 1-3 basically meets the II-type standard conditions in JC/T1074-2008 purification performance of the coating material with the indoor air purification function, and the purification efficiency of the catalytic material prepared in the embodiments 4 and 5 is far superior to the II-type standard. The durability of the purification effect is respectively carried out under the conditions of no electricity and 0.5mA current passing through a copper vessel (electricity is that a loaded substrate is made of a conductive material and is connected with a power supply to form a closed circuit for electricity passing, and the voltage of the power supply is controlled to regulate and control the current), under the condition of no electricity, the catalytic materials prepared in the examples 1 to 3 basically accord with the II-class standard, the catalytic materials prepared in the examples 4 and 5 are higher than the II-class standard, under the condition of electricity passing, the catalytic materials prepared in the examples 1 to 3 can be slightly higher than the II-class standard of the durability of the purification effect in JC/T1074 + 2008 < indoor air purification function coating material purification performance >, the purification efficiency can reach 76.3 percent, and when the examples 4 and 5 test the durability of the purification effect according to the JC/T1074 + 2008 < indoor air purification function coating material purification performance >, the purification efficiency can reach 86.2 percent, and the class II standard which is more than or equal to 65 percent and is specified in the durability of the far ultra-purification effect has very obvious and excellent effect.

And the antibacterial performance of the catalytic material is further tested according to the standards of HG/T3950-2007 antibacterial paint, and the test result shows that the catalytic material meets the II-level standard.

Further comparing the performances of the examples and the comparative examples, it can be seen that the fine adjustment of the preparation parameters in the examples 1 to 3 within a reasonable range has a weak influence on the performance of the prepared copper-manganese-formaldehyde catalytic material, and repeated tests show that the copper-manganese-formaldehyde catalytic material prepared in the example 3 has the most stable effect and better effect. In contrast, in comparative example 4 and example 5, it can be seen that fine adjustment of the preparation parameters within a reasonable range has a weak influence on the performance of the prepared copper-manganese-formaldehyde catalytic material. Comparing example 3 with example 4, it is obvious that the performance of the copper-manganese catalytic material is remarkably improved after the iron material is added. The main reason is that the addition of the iron material enables more defect structures to be formed inside the catalytic material, and the defect structures are beneficial to improving the catalytic effect of the catalytic material. Namely, the formaldehyde catalytic decomposition performance of the catalytic material can be effectively improved by adding and using the iron material. Compared with the comparative example 1, cuprous chloride is used for replacing the copper/cuprous chloride mixed copper material, and compared with the comparative example 2, pure copper is used for replacing the copper/cuprous chloride mixed copper material, so that the formaldehyde catalytic decomposition performance of the prepared catalytic material is obviously reduced. Compared with the prior art, the catalytic decomposition method has the advantages that under the condition that cuprous chloride is singly adopted and pure copper is not available, a large amount of cuprous ions can be oxidized into copper ions in the reaction process, actual defect structures are reduced, the catalytic performance and the conductivity are obviously weakened, the catalytic performance of the catalyst is obviously improved under the condition that ozone is matched with the catalyst in the comparative example 1, and the oxidation capacity of the catalyst can be improved by matching with catalytic ozone so as to realize catalytic decomposition of formaldehyde. Comparative example 2 using pure copper alone results in a decrease in spinel structure, directly affecting the content of catalytically active component, resulting in a more significant decrease in catalytic performance. However, comparative example 1 performed less than comparative example 2, and both comparative example 1 and comparative example 2 were inferior to example 3 in the regeneration test. Comparative example 3 compared to example 4, more iron material was used. Due to the excessive addition of iron materials, a large amount of pulverization of the catalyst is caused, and mainly in the high-temperature calcination heat treatment process, the structural stability of the original catalyst is damaged by a large amount of replacement of iron elements, so that the grain boundary of the particles is enlarged until pulverization and crushing, a spinel structure cannot be generated, and the active ingredients of the catalyst are obviously influenced. Comparative example 4 compared to example 3, a lower high temperature calcination heat treatment temperature was used, which resulted in less effective conversion of trivalent manganese to tetravalent manganese and reduced defect structure formation.

Through the comparison and a large number of test analyses, the results show that for the invention, the proportion of cuprous in the copper material and copper is a direct factor directly influencing the catalytic performance of the formaldehyde of the catalytic material of the invention, and the reasonable addition and use of the iron material can remarkably strengthen the catalytic decomposition performance of the formaldehyde. Similarly, the subsequent high-temperature calcination heat treatment can also have a significant influence on the formaldehyde catalytic decomposition performance of the catalytic material.

Sterilization Performance Effect test

The test is handed to a third party test structure. The test standard refers to the project of GB/T21510-. Further, commercially available electrolytic manganese dioxide was set as comparative example 5. The test results are shown in the following tables.

Example 3 test results table

Example 4 test results table

Comparative example 1 test results table

Comparative example 2 test results table

Comparative example 5 test results table

Comparisons were made based on the above test results. A comparison of the test results of examples 3 and 4 above shows that there is a slight, but not significant, increase in the sterilization capacity of the monolithic catalytic material after addition of the iron material. However, as is apparent from comparison between example 3 and comparative examples 1 and 2, in the case where pure copper chloride is used in comparative example 1, the defect structure in the catalytic material is reduced, and a certain negative effect is generated on the antibacterial performance of the catalytic material, while in the case where pure copper is used in comparative example 2, the content of the actual spinel-type copper-manganese crystal is reduced, and the antibacterial performance of the catalytic material is significantly reduced. As can be seen from the comparison, the spinel-type copper-manganese crystal is mainly used for killing bacteria, namely the spinel-type copper-manganese crystal is used as the actual antibacterial active ingredient, and the defect structure formed by Cu (I) and Mn (IV) has the effect of improving and strengthening the sterilization performance of the spinel-type copper-manganese crystal.

Further comparing comparative example 5 with example 3, it can be seen that the conventional electrolytic manganese dioxide on the market has a certain sterilization capability, but is significantly weaker, and the number of residual colonies is 1-2 orders higher than that of example 3. The spinel type copper-manganese catalytic material has good formaldehyde catalytic decomposition performance and very strong sterilization capability, and the actual sterilization capability is far better than that of the manganese dioxide sold on the market.

Claims

1. A preparation method of spinel type copper-manganese catalytic material for sterilization and aldehyde removal, which is characterized in that,

the method comprises the following steps:

the copper material comprises soluble cuprous salt and elemental copper;

the concentration of the hydrogen chloride water solution is 2.0-3.0 mol/L;

the molar concentration of copper element in the copper liquid is 0.15-0.25 mol/L

2) Dissolving potassium permanganate in water to prepare manganese solution;

3) mixing the copper solution and the manganese solution, carrying out hydrothermal reaction, adjusting the pH value of the solution to be neutral or alkalescent after the hydrothermal reaction is finished, continuously stirring, standing for aging, and carrying out spray drying after aging to obtain a precursor;

2. The preparation method of the spinel-type Cu-Mn catalytic material for sterilization and aldehyde removal according to claim 1,

and 2) the molar concentration of a manganese element in the manganese solution is 0.33-0.70 mol/L.

3. The preparation method of the spinel-type Cu-Mn catalytic material for sterilization and aldehyde removal according to claim 1,

step 3), mixing the copper liquid and the manganese liquid in a volume ratio of 1: (0.8-1.15);

and 3) the hydrothermal reaction temperature is 200-240 ℃, and the hydrothermal reaction time is 16-18 h.

4. The preparation method of the spinel-type Cu-Mn catalytic material for sterilization and aldehyde removal according to claim 3,

the pH value range of the neutral or weak alkaline in the step 3) is 7-8.5;

and 3) standing and aging at 20-25 ℃ for 8-10 h.

5. The preparation method of the spinel-type Cu-Mn catalytic material for sterilization and aldehyde removal according to claim 1,

and 4) calcining the mixture at the high temperature of 750-850 ℃ for 3-4 h.

6. The preparation method of spinel type Cu-Mn sterilizing and aldehyde-removing catalyst material according to claim 1, 2, 3, 4 or 5,

step 1), a copper liquid preparation process, namely adding an iron material;

7. The preparation method of the spinel-type Cu-Mn catalytic material for sterilization and aldehyde removal according to claim 6,

8. A spinel-type Cu-Mn catalytic material for sterilization and aldehyde removal prepared by the method of any one of claims 1 to 7,

9. Use of a catalytic material according to claim 8,

the catalytic material is used for air purification and/or sterilization.