CN113144894B

CN113144894B - Functional material for visually degrading formaldehyde and VOCs at normal temperature and pressure and preparation method thereof

Info

Publication number: CN113144894B
Application number: CN202110613645.2A
Authority: CN
Inventors: 王丹亮; 万远鑫; 韩小兵
Original assignee: Nanjing Fengqingyang Health Technology Co ltd
Current assignee: Nanjing Fengqingyang Health Technology Co ltd
Priority date: 2021-06-02
Filing date: 2021-06-02
Publication date: 2023-01-31
Anticipated expiration: 2041-06-02
Also published as: WO2022253117A1; CN113144894A

Abstract

The invention provides a functional material for visually degrading formaldehyde and VOCs at normal temperature and normal pressure, which comprises a loading agent, an oxidant, a catalyst, a reinforcing agent and a ligand. The reaction efficiency is improved through the synergistic enhancement effect of the negative carrier, the oxidant, the catalyst, the reinforcing agent and the ligand, so that the material has an excellent effect of degrading formaldehyde and VOCs at normal temperature and normal pressure, the structure and the color of the material change before and after the material reacts with the formaldehyde and the VOCs, and the reaction speed and the degree can be directly observed and indicated by naked eyes. The material prepared by the invention can degrade formaldehyde and various VOCs. Due to the synergistic strengthening effect, various components are uniformly distributed and combined firmly, and are water-resistant and moisture-proof, and the material can be prepared into a solid state or a liquid state, so that the problems of performance attenuation, structural damage and the like after the solid catalyst absorbs moisture are solved essentially. The invention is used in the fields of environmental protection and health, and is particularly important for treating polluted gases and industrial VOCs in the space.

Description

Functional material for visually degrading formaldehyde and VOCs at normal temperature and pressure and preparation method thereof

Technical Field

The invention belongs to the field of new materials and gas pollution treatment, and particularly relates to a functional material for visually degrading formaldehyde and VOCs at normal temperature and normal pressure and a preparation method thereof, which are used for the fields of gas purification, environmental protection and health.

Background

With the continuous development of economy, the industries such as real estate, automobiles, chemical engineering, pharmacy, textile and the like are developed at a high speed, and the requirements of people on houses, trips, clothes, medical treatment, living environments and the like are continuously improved. However, the existing production methods of material materials are accompanied by the emission of a large amount of pollutant gases, on one hand, formaldehyde and VOCs (volatile organic compounds) released from various decoration materials such as leather, plates, plastic parts, paint and glue in rooms, cars and spaces; on the other hand, a large number of industrial enterprises discharge several tons of VOCs into the atmosphere. These are serious damages to the health and living environment of people. The above problems have become the most of the concern of people in society.

Formaldehyde is a colorless highly irritating gas and is a highly toxic substance. It is well documented that formaldehyde affects human health primarily in terms of olfactory abnormalities, irritation, allergies, pulmonary, hepatic, and immune dysfunction. The low-concentration formaldehyde solution is formalin for preventing decay of hospital soaked dead body specimens. Formaldehyde and VOC in high concentration indoors may cause various diseases such as leukemia and cancer.

VOC (Volatile Organic Compounds) are often ignored, but may be a more important pollutant in the interior of a vehicle. Taking benzene as an example, benzene in the ambient atmosphere mostly invades the body through the respiratory tract in a vapor form, and animal experimental studies find that long-term exposure to benzene environment can cause the function reduction of hematopoietic stem cells and the occurrence of various diseases, such as aplastic anemia, myelodysplastic syndrome, leukemia and the like; acute poisoning of benzene is due to the fact that the contacter works in an environment of benzene vapor of extremely high concentration for a short time, which is mainly paralyzing the central nervous system; chronic poisoning caused by long-term repeated exposure to low-concentration benzene mainly manifests as damage to the nervous system and the hematopoietic system. Benzene is a human carcinogen confirmed by WHO, is the substance with the greatest harm to human health in eight substances determined by standards, and is a harmful tissue which should be controlled most strictly in pollutants in a vehicle. WHO recommends lower and better benzene in ambient air.

Formaldehyde and VOCs are present in various interior and interior finishing materials including wood panels, artificial boards, paints, coatings, leather, curtains, glues, wallpaper, textiles. The release of formaldehyde and VOCs is long, typically 10-15 years, during which time formaldehyde is released from the items. People spend more than 80-90% of the time indoors or in a vehicle, so the air quality in the rooms and the vehicle directly influences the health of people. The problem of indoor vehicle gas pollution is almost everyone who encounters in a lifetime, and therefore, the development of efficient formaldehyde and VOCs purification technology is very important to the health of individuals and the whole society.

The existing methods for removing formaldehyde in indoor vehicles mainly comprise adsorption, photocatalysis, biological methods, ozone methods, chlorine dioxide methods, plant purification, catalytic oxidation methods and the like. The adsorption method is to utilize the adsorption performance of porous substances, such as activated carbon, molecular sieves, silica gel, zeolite and other materials to adsorb formaldehyde in the air, and the method is only physical adsorption and does not really remove formaldehyde in the space, and formaldehyde is secondarily released after heating or violent shaking and does not have durability. The adsorption method is not targeted adsorption, and can also adsorb other gases such as water vapor, carbon dioxide and the like, so that the adsorption efficiency of formaldehyde is low. Photocatalysis requires ultraviolet light, various decoration materials are aged, the photocatalysis material is not easy to use indoors and in vehicles, and the used nano-scale solid particles can cause secondary pollution. Biological methods are inconvenient and inefficient due to limitations in the conditions of biological activity of bacteria and microorganisms. Both the ozone method and the chlorine dioxide method can generate stronger stimulation, and are not suitable for being used indoors and in vehicles. The plant has little effect on purifying indoor and indoor formaldehyde and VOCs.

In a chemical reaction, some chemical bonds originally existing in a reaction molecule must be dissociated and form new chemical bonds, so that the reaction can occur, and a certain activation energy is required. In the catalytic oxidation reaction, the catalyst performs chemical adsorption on reactant molecules, so that the reactant molecules are activated, the activation energy of the reaction is reduced, and the reaction rate is accelerated. In some systems where chemical reactions are difficult to occur, the addition of a catalyst aids in the rearrangement of the chemical bonds of the reacting molecules, thereby accelerating the chemical reaction. The formaldehyde is removed by the catalytic oxidation method, namely the formaldehyde is converted into carbon dioxide and water by catalytic oxidation, and the method is not limited by ultraviolet rays or biological conditions and has no defect of adsorption saturation by an adsorption method. At present, the catalyst for removing formaldehyde mainly comprises a system for loading noble metals such as Pt, pd, ag, au and the like and a transition metal oxide catalyst. The noble metal catalyst is expensive due to the adoption of noble metal, is easily influenced by temperature and pollution, and cannot be widely applied. Chinese patent CN10380574 discloses a catalyst for catalytic oxidation of formaldehyde at room temperature, which has over-high cost and is not easy to popularize, and the metal loading of the catalyst component is 0.2-30%, preferably 1-10%. The Chinese patent CN1698932A uses Au as a noble metal to catalyze and oxidize formaldehyde, but can exert better catalytic efficiency at higher temperature (80-100 ℃), and limits the wide application of the catalyst. U.S. Pat. No. 5, 5585083 is a catalytic formaldehyde containing 12wt% Pt, which can be completely oxidized at 25 deg.C, but the cost of precious metals is too high, limiting its application. Chinese patent CN1795970a discloses a catalyst for complete catalytic oxidation of low-concentration formaldehyde at room temperature, which uses non-noble metal oxidation as main component, such as ceria, zirconia, titania, alumina, and lanthanum oxide. However, the catalyst still needs to add small amount of noble metal such as gold, silver, platinum and rhodium. Chinese patent CN102941111a shows a metal carrier supported catalyst for room temperature formaldehyde purification, which is composed of a metal carrier, a porous inorganic material and a noble metal element, alkali metal or alkaline earth metal compound, which are supported on the metal carrier. The hopcalite catalyst is a catalyst consisting of a plurality of metal oxides, can be used for the low-temperature and normal-temperature catalytic oxidation of carbon monoxide, has the fatal defect of poor moisture resistance, and is inactivated after moisture absorption. In a word, the catalyst in the existing formaldehyde catalytic oxidation technology contains precious metals, so that the price is high, the use constraint condition is high, and the catalyst is not easy to be widely applied in a large scale. The formaldehyde catalyst which does not need noble metal elements has the defects of low reaction efficiency, high activation temperature, poor moisture resistance, instability and the like.

In addition, the common disadvantage of the above catalysts is the lack of a signal indicator per se which directly indicates the progress and severity of the catalysis or reaction. Ordinary users and professionals can only know the using condition of the catalyst through complicated tests and analysis by professional instruments. The common user can not directly perceive the use effect of the catalyst, can not visually judge the loss condition of the catalyst in real time, can not directly know the pollution degree of formaldehyde and VOC in rooms, vehicles and spaces, and can not change the catalyst at any time. The above catalysts are more problematic from a customer experience point of view. Chinese patent CN1660477A discloses a composite material composed of a porous carrier and potassium permanganate, wherein the material utilizes the oxidizing property of potassium permanganate to treat harmful gases in the air, and a user can judge whether the material fails or not according to the self-fading phenomenon of potassium permanganate. But because potassium permanganate is a strong oxidizing substance, the potassium permanganate can easily damage the surfaces of furniture or clothes contacted with the potassium permanganate by being used alone, and in addition, the material has the color change range from red to brown, and the color change is not sharp. Chinese patent CN 102527228A discloses a visual color-changing formaldehyde scavenger which is respectively composed of three components, namely an adsorption component, a catalytic component and a color-changing component, although the formaldehyde scavenger can generate a color-changing phenomenon after contacting formaldehyde, and the color change of the formaldehyde scavenger depends on the effect of an acid-base indicator, but not the color change caused by the failure of an active functional component in the true sense, and can not directly indicate the information of the change of the purification capacity of a material.

Moreover, most of the prior art only studies the catalytic oxidation effect of the catalyst on formaldehyde, but benzene and homologues thereof are more serious to the health in indoor and in-car spaces. On the other hand, because benzene and homologues thereof are also important components causing indoor and in-car peculiar smells, the catalysts or reactions only capable of catalyzing and oxidizing formaldehyde cannot really reduce the indoor, in-car and in-space peculiar smells.

Disclosure of Invention

Aiming at the defects and shortcomings of the prior art, the invention aims to provide a functional material for efficiently catalyzing and oxidizing formaldehyde and VOCs at normal temperature and normal pressure, which can reduce the cost without using noble metals and is beneficial to popularization and application. The principle is that under the condition that formaldehyde and VOCs are in contact with the surface of the functional material, a special oxidation system is utilized to catalytically oxidize the formaldehyde and the VOCs in the space at normal temperature and normal pressure to oxidize macromolecular organic pollutants into micromolecular organic matters until the macromolecular organic pollutants are oxidized into CO ₂ And water, thereby reducing the concentration of organic gas contaminants in the space.

The functional material provided by the invention does not need to work under the conditions of high physical energy and chemical energy such as light, ozone, strong acid, strong alkali, high temperature and high pressure, and the reaction progress and the reaction intensity for removing formaldehyde and VOCs can be directly and visually indicated through the obvious change of the color of the material before and after the material reacts. In the process of absorbing formaldehyde and VOCs, the material reacts, the internal structure of the material changes before and after the reaction, electron transition is generated, and the absorption spectrum of the material changes, so that color change is generated.

A chemical equation of a reaction between an active ingredient of one material and formaldehyde is used for example to illustrate a catalytic oxidation principle and a discoloration principle of the material for removing the formaldehyde and the VOCs, and the chemical equation is as follows:

wherein ferrate radical and formaldehyde are subjected to catalytic oxidation reaction under acidic condition, and + 6-valent iron (the electron arrangement is 1 s) in the ferrate radical ² 2s ² 2p ⁶ 3s ² 3p ⁶ 3d ² ) And reduced to +3 valent iron (the electron arrangement is 1 s) in the ferric hydroxide ² 2s ² 2p ⁶ 3s ² 3p ⁶ 3d ⁵ ) The final products are ferric hydroxide, carbon dioxide and water. Wherein, the ferrate ions of the reactant are purple black, the ferric hydroxide of the product is reddish brown, and the color changes obviously before and after the reaction. This is because ferrate is of tetrahedral configuration, and after reaction, the structure changes, and thus the color changes. Wherein the reinforcing agent enhances the interfacial reaction and thus enhances the reaction effect.

The functional material can be prepared into a solid state or a liquid state, so that the problems of performance attenuation, structural damage and the like after the solid catalyst absorbs water are essentially solved, and the application field and the use scene are very wide. In addition, the functional material has automatic absorbability, does not need a power device, and has the principle that high-concentration formaldehyde and VOCs in the space are diffused to the material to react by utilizing the gas concentration diffusion principle according to the Fick's first law, so that the automatic absorption effect is obtained. The material has excellent low-temperature activity and removal efficiency on formaldehyde catalytic oxidation, has excellent low-temperature activity, removal efficiency and broad-spectrum effectiveness on various VOCs, and really removes peculiar smells in rooms, vehicles and spaces. Meanwhile, the composite material has high stability and water resistance, and is suitable for gas purification in the fields of indoor, in-car, office buildings, school houses, hospitals, markets, closed or semi-closed spaces, industrial VOC treatment and the like.

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

a functional material for visually degrading formaldehyde and VOCs at normal temperature and normal pressure comprises a loading agent, an oxidant, a catalyst, a reinforcing agent and a ligand;

the loading agent is one or more of inorganic carriers;

the oxidant is a substance with oxidation and standard hydrogen electrode potential greater than zero;

the catalyst is a simple substance, an inorganic compound or an organic compound of non-noble metal transition metal with catalytic activity;

the reinforcing agent is one or more of potassium aluminum sulfate, sodium tartrate, calcium phosphate or sodium pyrophosphate;

the ligand is an atom, molecule or ion that can bond to a metal atom.

The various parts of the functional material synergistically interact to degrade formaldehyde and VOCs at ambient temperature and pressure and to indicate reaction progress and reaction intensity as a color change.

Preferably, the carrier is one or more of activated carbon, white carbon black, calcium carbonate, asbestos, diatomite, kaolin, perlite, barium sulfate, titanium dioxide, talcum powder, gypsum, mica, graphite, zeolite, magnesium sulfate or clay.

Preferably, the carrier has a specific surface area of 1 to 2000m ² Example/g, example/10 m ² /g、100m ² /g、200m ² /g、400m ² /g、600m ² /g、800m ² /g、1000m ² /g、1200m ² /g、1500m ² A ratio of 10 to 100 m/g is preferred ² Per g, more preferably 10 to 50m ² (iv) g. The particle size is 500 to 3000nm, for example 500nm, 1000nm, 1500nm, 2000nm, 2500nm, 3000nm, preferably 650 to 1500nm, more preferably 800 to 1000nm.

Preferably, the load carrier accounts for 20-80% of the functional material by mass. The specific surface area, the particle size and the proportion of the loading agent can ensure that the functional material has excellent catalytic activity, and the stability, the moisture resistance and the manufacturing elasticity of the material are obviously improved.

The oxidant is MnO containing bivalent copper, trivalent iron, trivalent cobalt, tetravalent nickel, tetravalent manganese and permanganate ₄ ^- Dichromate radical Cr ₂ O ₇ ^2- Ferrate FeO ₄ ^2- A compound of positive lead or sulfuric acid H ₂ SO ₄ Nitric acid HNO ₃ Bromine Br ₂ Perchloric acid HClO ₄ Hypochlorous acid HClO, hydrogen peroxide H ₂ O ₂ 。

The mass percentage of the oxidant is 0.1-25% calculated by 100% of the weight of the functional material.

Preferably, the catalyst is one or more of composite oxides of vanadium, cobalt, iron, chromium, manganese, nickel, molybdenum, lanthanum, cadmium, copper or zinc or salts thereof. The catalyst accounts for 0.1-30% of the weight of the functional material by 100%.

The weight percentage of the reinforcing agent is 0.1-10% calculated by 100% of the weight of the functional material.

Preferably, the ligand is selected from one or more of water, chloride ion, sulfate ion, borate ion, phosphate ion or oxalate ion, and the salt or solution thereof. The mass fraction percentage of the ligand is 1-20% based on 100% of the weight of the functional material.

The functional material can be prepared into solid and liquid according to different processes and requirements. The functional material can be used directly without further assembly into modules.

The invention also provides a preparation method of the functional material, which comprises the following steps:

(1) Adding an enhancer and a ligand into a solution containing an oxidant and a catalyst, and regulating the pH value and the temperature to precipitate out in the solution to obtain a negative carrier liquid;

(2) Dispersing a loading agent in the negative carrier liquid, and slowly forming a precipitate by adjusting the pH value to obtain a solid-liquid mixture;

(3) And (3) standing and aging the solid-liquid mixture, and separating out solids to obtain the catalyst.

Further, the preparation method also comprises the following steps:

(4) Dissolving the solid obtained in the step (3) in a solvent to obtain a liquid material; the solvent is one or more of water, ethanol-water solution, hypochlorous acid, sulfuric acid and hydrochloric acid.

Preferably, in the ethanol-water solution in the step (4), the mass ratio of the ethanol to the water is 1:7, the concentration of the hypochlorous acid is 0.01 to 0.5mol/L, the concentration of the sulfuric acid is 0.1 to 1mol/L, and the concentration of the hydrochloric acid is 0.05 to 3mol/L.

For liquid materials, 100% of the above mass fractions are the total mass of the solid material.

Preferably, the loading agent is subjected to a calcination treatment.

Preferably, the temperature of calcination is 700 to 1200 ℃.

Preferably, the solvent of the solution in the step (1) is one or a mixture of more of 10% ethanol hydrochloride solution, 5% ethanol sulfate solution or 25% hydrochloric acid aqueous solution.

Preferably, the method for adjusting the pH in the step (1) is to add one or more of a sodium hydroxide solution, an ammonia solution, a sodium carbonate solution or a sodium bicarbonate solution.

Preferably, the concentration of the sodium hydroxide solution is 0.1-2 mol/L, the concentration of the ammonia water solution is 0.2-2 mol/L, the concentration of the sodium carbonate solution is 0.1-1 mol/L, and the concentration of the sodium bicarbonate solution is 0.05-1.5 mol/L.

Preferably, the method for adjusting the pH in the step (2) is to add one or more of citric acid, hydrochloric acid or acetic acid. Preferably, the concentration of citric acid is 0.1 to 3mol/L, the concentration of hydrochloric acid is 0.1 to 0.5mol/L, and the concentration of acetic acid is 0.1 to 2mol/L.

Preferably, step (3) further comprises the steps of washing, drying, roasting and activating the obtained solid. Preferably, the drying temperature is 40 to 130 ℃. Preferably, the roasting conditions are as follows: roasting at 800-1500 ℃ under the condition of inert atmosphere.

The formaldehyde and VOCs are catalytically oxidized by polarization and protonation of the oxidant and the catalyst, and the pore structure of the loading agent and the electric field distribution of active atoms of the oxidant and the catalyst distributed on the pore structure determine the paths of gas adsorption, activation and reaction. Therefore, in the micro-channel structure with narrow loading agent, the catalytic performance is significantly affected by the fine electric field distribution change and the pH change of the active atoms.

According to the invention, through the addition of the reinforcing agent and the ligand, multi-site catalysis is constructed in a micro-channel structure of the loading agent, namely, reactant molecules such as single formaldehyde, VOCs and the like are adsorbed by a plurality of active sites in a channel of the loading agent. When a single molecule is captured and adsorbed by an active center, the single molecule can be additionally adsorbed by the adjacent active center, so that the adsorption entropy is remarkably changed, the transition state structure of molecule activation is also changed, the reaction path is changed, the actual reaction activation energy of an intermediate cracking product generated by the reaction on the active center is lower, the transition state is more stable, the reaction efficiency is greatly improved, and the material can degrade formaldehyde and VOCs at normal temperature and normal pressure.

Compared with the prior art, the invention has the following beneficial effects:

(1) The functional material does not use noble metal and high-price metal elements, and can realize the advantages of low price, high reaction activity and normal temperature and pressure activation. The formaldehyde is catalytically oxidized at room temperature, and the conversion rate of the formaldehyde can reach 97 percent.

(2) The functional material can be made into various forms including solid and liquid, is water-proof and moisture-proof, has low requirements on the use environment, and has wide use scenes.

(3) The functional material can be directly used without being manufactured into a module or depending on equipment, has extremely simple use conditions and extremely simple operation, and is easy to use by non-professionals.

(4) The functional material can not only catalyze and oxidize formaldehyde, but also catalyze and oxidize a plurality of VOCs. Benzene is catalytically oxidized at room temperature, and the conversion rate of the benzene can reach 54 percent. And the functional material has the advantages of high reactivity and normal temperature and pressure activation, so that the material can have obvious smell removing effect indoors and in a vehicle after being used, the smell can be sensed, and complex instruments and meters are not needed.

(5) Before and after the functional material reacts with formaldehyde and VOCs, the color changes and can be directly observed by naked eyes. The principle is that the material, formaldehyde and VOCs are subjected to catalytic oxidation reaction to generate a new substance, and the reaction speed and degree are indicated by utilizing the difference of the colors of reactants and the product. The visualization is not developed by reaction of a reaction intermediate product and a reaction final product with an added acid-base indicator, does not depend on the effect of the acid-base indicator, is color change caused by failure of active functional components in the true sense, and can directly indicate information of change of the purifying capacity of the material.

Drawings

FIG. 1 is a graph showing the removal efficiency of the functional material prepared in example 1 for formaldehyde catalytic oxidation as a function of time, measured at the building environment detection center of Qinghua university.

Detailed Description

To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:

example 1

Preparation of example material 1: 23.5g of white carbon black, 17.2g of titanium dioxide and 46.5g of active carbon are weighed, mixed and stirred uniformly, and heated in a muffle furnace at 850 ℃ for 12 hours to form the loading agent. Adding 1.5g of aluminum potassium sulfate and 1.1g of sodium sulfate into a hydrochloric acid ethanol solution containing 13.1g of nickel sulfate, 2.1g of nitric acid and 4g of cobalt nitrate, adjusting the pH and the temperature by using 0.2-2 mol/L ammonia water to ensure that a precipitate is just precipitated in the solution, then adding a negative carrier, adjusting the pH by using 0.1-3 mol/L citric acid, placing the solution in a water bath at 95 ℃ for stirring for 24 hours to slowly form the precipitate, standing and aging, and separating a solid. And (3) roasting the solid for 10 hours at 1000 ℃ in a muffle furnace under a nitrogen atmosphere to obtain the functional material for visually degrading formaldehyde and VOCs at normal temperature and normal pressure. The prepared material can be changed from black to yellow brown after reacting with formaldehyde and VOCs at normal temperature and normal pressure, and the formaldehyde removing efficiency reaches 95%.

The reaction rates of the materials are shown in table 1:

TABLE 1 reaction data of example materials within 1 hour

Reaction time (min)	5	10	30	60
					Removal rate of formaldehyde	87.3	89.1	90.7	92.5

Preparation of comparative material 1: comparative material 1 was prepared using the method described above, and comparative material 1 differed from the material prepared in example 1 only in the absence of the reinforcing agent potassium aluminum sulfate, and the test results are shown in table 2:

table 2 comparison of the reaction effects of example material 1 and comparative material 1

	Example Material 1	Comparative Material 1
			Efficiency of removing formaldehyde in 5min	87.3％	1.3％
Benzene removal efficiency for 24h	80.3％	1.2％

From the above data, it is clear that the key to the ability of the present invention to effectively remove VOCs is also the enhancer. The formaldehyde removal rate of 5min can reach 87.3 percent, and the formaldehyde removal rate has great superiority.

Example 2

21.8g of perlite, 19.6g of calcium carbonate and 15.8g of kaolin are weighed, mixed and stirred uniformly, and heated to 900 ℃ in a muffle furnace for 15 hours to form the load carrier. Adding 0.11g of sodium tartrate and 2.5g of sodium borate into a sulfuric acid ethanol solution containing 16.2g of ferric chloride, 15.8g of potassium dichromate and 16.2g of cobalt sulfate, adjusting the pH and the temperature by using a 0.1-2 mol/L sodium hydroxide solution to ensure that just precipitate is separated out from the solution, then adding a negative carrier, adjusting the pH by using 0.1-0.5 mol/L hydrochloric acid, placing the solution in a water bath at 80 ℃ for stirring for 12 hours, standing and aging, and separating solids. And (3) roasting the solid in a muffle furnace for 12 hours at 800 ℃ under a nitrogen atmosphere to obtain the functional material for visually degrading formaldehyde and VOCs at normal temperature and normal pressure. The prepared material can be changed from purple to black after reacting with formaldehyde and VOCs at normal temperature and normal pressure, and the formaldehyde removing efficiency reaches 96 percent.

Example 3

Weighing 5.9g of diatomite, 4.6g of zeolite, 3.1g of gypsum and 35g of barium sulfate, mixing and stirring uniformly, and heating at 1000 ℃ in a muffle furnace for 24 hours to form a load carrier. Adding 5.3g of sodium pyrophosphate and 18g of potassium phosphate into hydrochloric acid aqueous solution containing 15.7g of ferric sulfate, 0.09g of potassium permanganate and 2.3g of zinc nitrate, adjusting the pH and the temperature by using 0.2-2 mol/L sodium bicarbonate solution to ensure that just precipitate is separated out, then adding a negative carrier, adjusting the pH by using 0.1-2 mol/L acetic acid, stirring for 24 hours in a water bath at 95 ℃, standing, aging and separating solid. And (3) roasting the solid for 10 hours at 1000 ℃ in a muffle furnace under a nitrogen atmosphere to obtain the functional material for visually degrading formaldehyde and VOCs at normal temperature and normal pressure. The prepared material can be changed from purple red to khaki after reacting with formaldehyde and VOCs at normal temperature and normal pressure, and the formaldehyde removing efficiency reaches 99 percent. Dissolving the materials in 0.2mol/L hypochlorous acid solution, and magnetically stirring for 24 hours at 80 ℃ to obtain the normal-temperature normal-pressure visual formaldehyde and VOCs degrading functional liquid material. The prepared material reacts with formaldehyde and VOCs at normal temperature and normal pressure, and then gradually becomes solid from liquid, and the formaldehyde removing efficiency reaches 99 percent

Example 4

Weighing 7.2g of clay, 2.5g of mica, 1.1g of magnesium sulfate and 3.2g of talcum powder, mixing and stirring uniformly, and heating at 900 ℃ in a muffle furnace for 18 hours to form the loading agent. Adding 7g of aluminum potassium sulfate and 12.7g of sodium oxalate into a hydrochloric acid ethanol solution containing 15.3g of molybdenum nitrate, 13.1g of lead dioxide and 5.7g of lanthanum nitrate, adjusting the pH and the temperature by using a sodium hydroxide solution to ensure that just precipitate in the solution is separated out, then adding a loading agent, adjusting the pH by using 0.1-2 mol/L of acetic acid, stirring in a water bath at 85 ℃ for 10 hours, standing, aging and separating solids. And (3) roasting the solid for 8 hours at 1000 ℃ in a muffle furnace under a nitrogen atmosphere to obtain the functional material for visually degrading formaldehyde and VOCs at normal temperature and normal pressure. The prepared material can be changed from purple red to khaki after reacting with formaldehyde and VOCs at normal temperature and normal pressure, and the formaldehyde removing efficiency reaches 99 percent.

Example 5

Weighing 11.4g of calcium carbonate, 50g of diatomite, 44g of graphite and 15g of zeolite, mixing and stirring uniformly, heating to 950 ℃ in a muffle furnace for 24 hours to form a loading agent. Adding 2.7g of calcium phosphate and 20.7g of water into a sulfuric acid ethanol solution containing 0.1g of chromium nitrate, 0.1g of copper sulfate, 47g of potassium ferrate and 1g of perchloric acid, adjusting the pH and the temperature by using sodium carbonate to ensure that a precipitate is just precipitated in the solution, then adding a negative carrier, adjusting the pH by using 0.1-2 mol/L of acetic acid, stirring in a water bath at 80 ℃ for 10 hours, standing, aging and separating out a solid. And (3) roasting the solid in a muffle furnace at 1500 ℃ for 12 hours under a nitrogen atmosphere to obtain the functional material for visually degrading formaldehyde and VOCs at normal temperature and normal pressure. The prepared material can be changed from purple red to brown after reacting with formaldehyde and VOCs at normal temperature and normal pressure, and the formaldehyde removing efficiency reaches 99.3 percent. Dissolving the materials in 0.5mol/L sulfuric acid solution, and magnetically stirring at 50 ℃ for 12 hours to obtain the normal-temperature normal-pressure visual formaldehyde and VOCs degrading functional liquid material. The prepared material reacts with formaldehyde and VOCs at normal temperature and normal pressure, and then gradually becomes solid from liquid, and the removal efficiency of benzene can reach 54%.

The applicant states that the detailed composition and preparation method of the material of the present invention are illustrated by the above examples, but the present invention is not limited to the above detailed composition preparation method, i.e. the present invention is not meant to be dependent on the above detailed composition preparation method to be implemented. It will be apparent to those skilled in the art that any modifications, equivalent substitutions of the materials and methods for the products of the invention, and the addition, deletion, selection of specific means, etc., of the materials and methods of manufacture of the invention, are within the scope and disclosure of the invention.

Claims

1. A functional material for visually degrading formaldehyde and VOCs at normal temperature and normal pressure is characterized by comprising a loading agent, an oxidant, a catalyst, a reinforcing agent and a ligand;

the loading agent is one or more of active carbon, white carbon black, calcium carbonate, asbestos, diatomite, kaolin, perlite, barium sulfate, titanium dioxide, talcum powder, gypsum, mica, graphite, zeolite, magnesium sulfate or clay;

the oxidant is a compound containing permanganate acid radicals, dichromate radicals and ferrate radicals or lead dioxide;

the catalyst is one or a combination of more of composite oxides or salts of vanadium, cobalt, iron, chromium, manganese, nickel, molybdenum, lanthanum, cadmium, copper or zinc;

the ligand is selected from one or more of sodium salt or potassium salt formed by sulfate ions, borate ions, phosphate ions and oxalate ions;

the mass percent of the loading agent is 20 to 80 percent, and the mass percent of the oxidant is 0.1 to 25 percent, based on 100 percent of the weight of the functional material; the mass percentage of the catalyst is 0.1 to 30 percent; the mass fraction percentage of the reinforcing agent is 0.1 to 10 percent; the mass percentage of the ligand is 1 to 20 percent.

2. A method for preparing the functional material according to claim 1, comprising the steps of:

(1) Adding an enhancer and a ligand into a solution containing an oxidant and a catalyst, and regulating the pH and the temperature to precipitate in the solution to obtain a negative carrier liquid;

(3) Standing and aging the solid-liquid mixture, separating out a solid, and washing, drying, roasting and activating the solid, wherein the drying temperature is 40-130 ℃; the roasting conditions are as follows: and roasting at 800-1500 ℃ under the inert atmosphere condition to obtain the material.

3. The method of manufacturing according to claim 2, further comprising:

4. The method according to claim 3, wherein the mass ratio of ethanol to water in the ethanol-water solution is 1:7, the concentration of hypochlorous acid is 0.01 to 0.5mol/L, the concentration of sulfuric acid is 0.1 to 1mol/L, and the concentration of hydrochloric acid is 0.05 to 3mol/L.

5. The preparation method according to claim 2, wherein the loading agent is calcined at a temperature of 700 to 1200 ℃.