CN114534717B - Birnessite@hydrated calcium silicate composite material and preparation and application thereof - Google Patents
Birnessite@hydrated calcium silicate composite material and preparation and application thereof Download PDFInfo
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- CN114534717B CN114534717B CN202210182445.0A CN202210182445A CN114534717B CN 114534717 B CN114534717 B CN 114534717B CN 202210182445 A CN202210182445 A CN 202210182445A CN 114534717 B CN114534717 B CN 114534717B
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Abstract
The invention belongs to the technical field of formaldehyde catalysis, and particularly relates to a birnessite@hydrated calcium silicate composite material which comprises a hydrated calcium silicate substrate and birnessite grown on the surface of the substrate. The invention also comprises a preparation method of the material and application of the material in formaldehyde catalytic degradation. The invention discovers that the material has good normal-temperature formaldehyde removal capability.
Description
Technical Field
The invention belongs to the technical field of environmental pollution and harm reduction materials, and particularly relates to a birnessite@hydrated calcium silicate composite material capable of efficiently degrading formaldehyde.
Technical Field
Along with the improvement of human living standard, people pay more attention to interior decoration. However, formaldehyde brought by interior decoration materials also becomes a killer for human health. The adhesive used in artificial boards such as plywood, fiberboard and chipboard used for interior decoration takes formaldehyde as a main component. Wall coverings, wallpaper, chemical fiber carpets, paints, coatings and the like also contain formaldehyde components. These formaldehyde-containing building decorative materials are gradually released to the surrounding indoor environment, and are the main bodies of formaldehyde in indoor polluted air. Since humans can cause death by long-term exposure to low-concentration formaldehyde, which is recognized as a kind of carcinogen by the world health organization, materials for catalytic oxidation of formaldehyde gas at room temperature are in need of development and application.
At present, most of indoor formaldehyde gas treatment depends on adsorption substances, but the adsorption of the substances to formaldehyde is unstable, and formaldehyde is easily released again after the adsorption is saturated. In addition, the photocatalyst is adopted to degrade formaldehyde gas, but external conditions are needed to assist, such as ultraviolet irradiation to activate the formaldehyde gas, so that further application of the formaldehyde gas is limited. Therefore, in practical applications, these substances cannot be guaranteed for the treatment of formaldehyde in the room air.
Birnessite is used as the most widely distributed manganese oxide mineral in soil and is composed of a layer of MnO 6 The octahedron is formed by alternately stacking a layer of water molecule layers containing different cations, and has large specific surface area (up to 50-300 m) 2 Per gram), low charge zero point (1.5-2.5), high cation exchange capacity (0.63-2.40 mol/Kg), strong oxidizing ability, etc. The unique physical and chemical properties of the catalyst can make the catalyst applicable to various fields, in particular to catalytic oxidation. Birnessite has high activity and low toxicity, and the unique d orbitals easily realize the transition of outer electrons between different energy levels to exhibit redox properties. However, the catalytic performance of the birnessite reported in the prior art for formaldehyde is still lower at room temperature, and formaldehyde removal can be realized at a higher temperature. The prior art also lacks materials that still exhibit good formaldehyde removal properties at ambient conditions.
Disclosure of Invention
Aiming at the technical problem that the existing birnessite material has unsatisfactory formaldehyde catalysis performance, particularly room temperature catalysis performance, the first aim of the invention is to provide a birnessite@hydrated calcium silicate composite material, and the invention aims to provide a new material with good catalysis performance, particularly room temperature catalysis performance.
The second aim of the invention is to provide a preparation method of the birnessite@hydrated calcium silicate composite material.
The third purpose of the invention is to provide the application of the birnessite@hydrated calcium silicate composite material in formaldehyde degradation. In particular to a novel indoor building material with long-term effective and self-catalytic formaldehyde degradation function, which is prepared by doping birnessite into hydrated calcium silicate by utilizing the advantage of wide application of the hydrated calcium silicate in building materials.
The conventional birnessite is not ideal in morphology uniformity and is a micron-sized material generally, the performance of the material in formaldehyde catalysis is to be improved, for example, the formaldehyde degradation performance at normal temperature is poor, the material is limited in practical application, in addition, the birnessite is black, the modern variable aesthetic requirements are difficult to fully fit, and the following technical scheme is provided for the technical problem:
a birnessite@hydrated calcium silicate composite material comprises a hydrated calcium silicate substrate and birnessite grown on the surface of the substrate.
According to the invention, the birnessite is innovatively loaded on the hydrated calcium silicate substrate, and the formaldehyde catalysis performance of the material can be effectively improved based on the cooperation of the components and the in-situ growth structure, so that the normal-temperature catalysis performance of the material is improved, and the indoor normal-temperature formaldehyde is realized.
In the invention, the birnessite is formed by in-situ epitaxial growth on the surface of a hydrated calcium silicate substrate. According to the invention, the birnessite grows epitaxially on the surface of the substrate, so that the synergistic advantages of the components and the structure are brought into play, and the formaldehyde removal effect of the material at normal temperature is further improved.
The research of the invention also discovers that the morphology structure of the in-situ grown birnessite is further controlled, which is helpful for unexpectedly further improving the synergies of the composite components and the in-situ loading structure, is helpful for further improving the formaldehyde catalytic performance of the material, and is especially helpful for improving the normal temperature catalytic performance of the material.
The birnessite is a porous secondary structure material formed by staggered assembly of birnessite lamellar primary structures growing on the surface of a substrate.
The composite material is porous spherical birnessite anchored on the surface of hydrated calcium silicate, and the combination is firm;
preferably, the hydrated calcium silicate is at least one of amorphous C-S-H (hydrated calcium silicate) solid gel, tobermorite, calcium zeolite, wollastonite and clinohedral calcium silicate. It is found that the hydrated calcium silicate is a material with a rod-like, sheet-like or whisker-like structure.
Preferably, the mass ratio of the hydrated calcium silicate to the birnessite is 0.5-3: 1.
the invention also provides a preparation method of the birnessite@hydrated calcium silicate composite material, which comprises the following steps:
the method comprises the following steps:
step (1):
mixing (premixing) a divalent manganese source, calcium silicate hydrate and a surfactant liquid phase to obtain a suspension;
step (2):
adding permanganate A into the suspension in the step (1) to perform a first reaction; wherein the molar ratio of the permanganate A to the divalent manganese source is 0.5-2: 1, a step of;
step (3):
adding permanganate B into the reaction system in the step (2), then sealing the mixed solution in a container, heating to perform a second reaction, and separating to obtain a birnessite@hydrated calcium silicate composite material after the reaction is finished;
the molar ratio of the permanganate B to the divalent manganese source is 0.5-5: 1, a step of;
the temperature of the second reaction is 160-250 ℃.
The research of the invention discovers how to grow birnessite on the surface of hydrated calcium silicate and how to regulate the morphology of birnessite, which is a key difficulty in successfully preparing materials and improving the formaldehyde catalytic performance of the materials. Aiming at the preparation difficulty, the inventor finds that the hydrated calcium silicate and the divalent manganese source are premixed under the assistance of the surfactant in advance, then the first reaction is carried out with the permanganate A, then the second reaction is carried out with the permanganate B, based on the two-stage reaction thought, the control of each condition is further matched, the coordination can be realized unexpectedly, the nucleation and the induction of the crystal epitaxial growth can be realized under the induction of the hydrated calcium silicate, the in-situ induction of the growth of the birnessite on the surface of the hydrated calcium silicate is facilitated, the structure of the grown birnessite is regulated and controlled, and the formaldehyde catalytic performance of the prepared material is improved.
In the present invention, the hydrated calcium silicate may be prepared based on existing methods. It is also found that in order to further facilitate in-situ epitaxial growth of birnessite and facilitate formaldehyde catalysis performance of the material, the invention is preferably obtained by hydrothermal reaction of a mixed aqueous solution of a silicon-calcium raw material and alkali at a temperature of 100-250 ℃.
Preferably, the silicon-calcium feedstock comprises a silicon source and a calcium source;
the silicon source is at least one of fly ash, coal gangue, chemical sodium silicate, clay ore, clay, tailings, quartz ore and secondary tailings containing silicon;
the calcium source is at least one of calcium oxide, calcium hydroxide and calcium carbonate;
preferably, the alkali is at least one of sodium hydroxide and potassium hydroxide;
preferably, in the mixed aqueous solution, the molar ratio of silicon to calcium is, for example, 1.2 to 5.5:1, and more preferably 1.5 to 2.5:1;
preferably, the molar ratio of the alkali to the silicon in the silicon-calcium raw material is, for example, 0.5 to 4:1, and more preferably 2 to 3:1;
preferably, the concentration of the alkali in the mixed aqueous solution is 3-20 g/L, preferably 10-15 g/L;
preferably, the temperature of the hydrothermal reaction is 130 to 230 ℃. Researches show that the hydrated calcium silicate with good second reaction structure and morphology is prepared at a preferable temperature, so that the hydrated calcium silicate is beneficial to being cooperated with a subsequent treatment process, the in-situ epitaxial growth of birnessite is induced, and the formaldehyde catalytic performance of the prepared material is beneficial.
Preferably, the hydrothermal reaction time is 0.5 to 4 hours.
The research of the invention discovers that the premixing of hydrated calcium silicate and a divalent manganese source under a surfactant, the stepwise two-stage reaction thought of permanganate and the combined control of synthesis conditions are key to improving the structure and the appearance of the material and the degradation performance of formaldehyde.
In the present invention, calcium silicate hydrate and Mn are pre-mixed 2+ And (3) mixing the source and the surfactant in a liquid phase, and infiltrating Mn on the surface of the hydrated calcium silicate, so that the in-situ induction growth of the birnessite in the two subsequent sections is facilitated.
Preferably, the solvent used for the liquid phase mixing is water or a mixed solvent of water and an organic solvent, and the organic solvent is a water-miscible organic solvent. The organic solvent is, for example, a C1-C4 alcohol, acetone or the like.
In the invention, the divalent manganese source can ionize Mn 2+ Is a water-soluble compound of (2); preferably at least one of manganese sulfate, manganese nitrate, manganese chloride and manganese acetate, or manganese ore extract. The divalent manganese source may be a commercial chemical source or may be derived from a mineral smelting material (e.g., leachate).
Preferably, in suspension, mn 2+ The designed molar concentration of (2) is 0.1-2M; more preferably 0.1 to 0.5M.
Preferably, the surfactant is at least one of a cationic surfactant, an anionic surfactant and a nonionic surfactant; preferably a nonionic surfactant. It has been found that, surprisingly, the use of nonionic surfactants allows a synergistic achievement of a better preparation and a further improvement in the formaldehyde catalysis of the materials produced.
Preferably, the cationic surfactant is at least one of cetyl trimethyl ammonium bromide, benzalkonium chloride and benzalkonium bromide;
preferably, the anionic surfactant is at least one of sodium dodecyl benzene sulfonate, ammonium dodecyl sulfate and sodium dodecyl sulfate;
preferably, the nonionic surfactant is at least one of polyethylene glycol, polyalcohol type and polyether type;
preferably, the mass ratio of the hydrated calcium silicate to the surfactant to the divalent manganese source is 0.5-5:0.1-2:1; more preferably 2 to 5:0.5 to 1.5:1.
Preferably, in the step (1), the liquid phase mixed solvent is water or a mixed solvent of water and an organic solvent, and the organic solvent is a water-miscible organic solvent.
In the invention, the premixing stage can be carried out at room temperature, and the premixing time is not particularly required, and the mixing is uniform, for example, the mixing time can be 0.2-1.5 h.
According to the invention, on the basis of premixing, the subsequent two-stage reaction is further matched, so that the in-situ epitaxial growth of the birnessite on the surface of the water flower calcium silicate can be induced.
The permanganate A can ionize MnO 4 -a water-soluble salt, preferably at least one of potassium permanganate, sodium permanganate, magnesium permanganate.
According to the invention, the permanganate A is added into the suspension, the addition proportion is further controlled, the morphology of the material prepared under the two-stage reaction mechanism can be unexpectedly further improved, and formaldehyde degradation performance is further improved.
Preferably, permanganate A (in MnO 4 -by) a molar ratio relative to the divalent manganese source of 0.5 to 1:1; more preferably 0.5 to 0.6:1.
The first reaction is carried out with stirring, for example, at a stirring speed of 50 to 300r/min during the first reaction.
In the present invention, the first invention may be carried out at room temperature, for example, the temperature of the reaction is, for example, 15 to 45 ℃.
Preferably, in the step (1), the time of the first reaction process is 0.5-3 h; more preferably 1 to 2 hours.
In the invention, permanganate B solid particles are added into a first reaction system, the mixed solution is placed into a pressure-resistant container, the container is closed, and the temperature is raised to carry out a second reaction. It is found that controlling the amount of permanganate B added in the second reaction stage and the reaction temperature helps to further facilitate obtaining a material with better formaldehyde catalytic degradation performance.
In the invention, the molar ratio of the permanganate B to the divalent manganese source is 1-2:1; further preferably 1.5 to 2:1.
Preferably, the temperature of the second reaction is 180 to 240 ℃.
Preferably, the second reaction time is 12-48 h; more preferably 15 to 24 hours.
In the invention, after the second reaction is finished, solid-liquid separation is carried out on the product, and washing and drying are carried out to obtain the product.
The invention also provides the birnessite@hydrated calcium silicate composite material prepared by the preparation method.
The invention also provides application of the birnessite@hydrated calcium silicate composite material in catalytic degradation of formaldehyde.
The invention researches find that the material has good formaldehyde degradation performance, particularly excellent room temperature formaldehyde catalytic degradation performance, and moreover, the material has more acceptable color and can meet the modern aesthetic requirements.
Preferably, the application is added to building materials for catalyzing the degradation of formaldehyde.
Advantageous effects
1. The invention provides a birnessite@hydrated calcium silicate composite material, and the brand new material is found to have good formaldehyde catalytic performance, in particular good normal-temperature catalytic performance;
2. the invention also provides a preparation method of the birnessite@hydrated calcium silicate composite material, which innovatively mixes hydrated calcium silicate and Mn 2+ Premixing is carried out under the condition of surfactant, and the combined control of the two-stage reaction thought of permanganate, the proportion of two-stage materials, the temperature and other conditions is further utilized, so that the synergy can be realized accidentally, the generation of the birnessite can be induced on the surface of hydrated calcium silicate in situ, the morphology structure of the birnessite can be regulated and controlled, and the method is helpful forImproving the electrochemical performance of the prepared material.
3. The preparation method has the advantages of simple process, low cost, no need of adding modifier and environmental friendliness. The birnessite composite material prepared by the method has rich pore canal structure, good stability and higher specific surface area, and can have important application value in various fields such as adsorption, catalysis, oxidative degradation materials, air purification materials and the like.
Drawings
FIG. 1 is a scanning electron microscope image of a birnessite@hydrated calcium silicate composite material prepared in example 1;
FIG. 2 is a scanning electron microscope image of the material prepared in comparative example 1;
FIG. 3 is a scanning electron microscope image of the material prepared in comparative example 2;
FIG. 4 is a scanning electron microscope image of the material prepared in comparative example 3;
FIG. 5 is a scanning electron microscope image of the material prepared in comparative example 4;
FIG. 6 is a scanning electron microscope image of the material prepared in comparative example 5;
FIG. 7 is a scanning electron microscope image of the birnessite@hydrated calcium silicate composite material prepared in example 2;
FIG. 8 is a scanning electron microscope image of the birnessite@hydrated calcium silicate composite material prepared in example 3;
FIG. 9 is a scanning electron microscope image of the birnessite@hydrated calcium silicate composite material prepared in example 4;
FIG. 10 is a scanning electron microscope image of the birnessite@hydrated calcium silicate composite material prepared in example 5;
FIG. 11 is a scanning electron microscope image of the birnessite@hydrated calcium silicate composite material prepared in example 6;
FIG. 12 is a scanning electron microscope image of the birnessite@hydrated calcium silicate composite material prepared in example 7;
FIG. 13 is a scanning electron microscope image of the birnessite@hydrated calcium silicate composite material prepared in example 8;
FIG. 14 is a scanning electron microscope image of the birnessite@hydrated calcium silicate composite material prepared in example 9;
FIG. 15 is a scanning electron microscope image of the birnessite@hydrated calcium silicate composite material prepared in example 10;
the specific embodiment is as follows:
describing a formaldehyde catalytic degradation step and a data measurement method:
catalyst catalytic Activity determination for HCHO (80 ppm): 0.1g of catalyst powder having a particle size of 200 to 250 μm was placed in the middle (inner diameter 6 mm) of the reactor and supported by quartz wool at atmospheric pressure. The total flow rate is 100ml min -1 Corresponding to 60 L.h -1 ·g -1 Gas Hourly Space Velocity (GHSV). Once the given reaction temperature was reached, the catalyst was stable for 1 hour. The reaction products were detected on-line using a gas chromatograph-mass spectrometer equipped with a thermal conductivity detector. Conversion to CO with HCHO 2 The catalytic activity of the catalyst was evaluated by the method of (2). The HCHO conversion of the sample was calculated using the following formula
Wherein [ HCHO]in and [ CO ] 2 ] in Imported HCHO and CO respectively 2 Concentration [ CO ] 2 ] out Representing outlet CO 2 Concentration.
The room temperature according to the invention is, for example, 20 to 35 ℃.
In the following cases, the temperature of the premixing process in the step (2) is not particularly limited, and is, for example, 15 to 45 ℃. The premixing is preferably carried out with stirring, the stirring speed of which is not particularly limited and may be, for example, 100 to 500r/min.
The temperature of the first reaction process of step (3) may be carried out at room temperature, for example 15 to 45 ℃. The stirring speed in the reaction stage is, for example, 200 to 500r/min.
Example 1
(1) Mixing sodium silicate, calcium oxide and sodium hydroxide with water to perform hydrothermal reaction, wherein the molar ratio of silicon to calcium in the raw material solution is 2:1; the molar ratio of sodium hydroxide to silicon is 2:1. the initial concentration of the alkali is 10g/L; the hydrothermal temperature is 150 ℃ and the hydrothermal time is 3 hours, the hydrated calcium silicate is obtained after the reaction and separation, and the hydrated calcium silicate base material is obtained after the drying at 105 ℃;
(2) Uniformly mixing calcium silicate hydrate powder, manganese nitrate and polyethylene glycol according to a mass ratio of 6:2:1, adding 100mL of water, and stirring for 1h (premixing) to obtain a suspension (the concentration of Mn is 1M);
(3) Under stirring, KMnO was added to the suspension at a molar ratio 4 ：Mn 2+ (refer to manganese nitrate in step (2) =0.57:1, potassium permanganate is added to perform a first reaction, and the reaction time is 0.5h;
(4) Continuously adding the amount of potassium permanganate and Mn into the solution under the condition of rapid stirring 2+ (namely manganese nitrate in the step (2) with the molar ratio of 1.71:1 and stirring uniformly, sealing the mixed solution in a container, heating to 200 ℃ (second reaction) and reacting for 20h;
(5) And (3) carrying out suction filtration and washing on the obtained turbid liquid, transferring the powder into an oven, and drying for 10 hours at 80 ℃ to obtain the birnessite composite material, wherein a scanning electron microscope picture is shown in figure 1, and the degradation rate of the birnessite composite material to formaldehyde gas is shown in table 1.
Comparative example 1
The difference from example 1 is that the premixing in step (2) is not performed in advance, but calcium silicate hydrate is added to the system after the first reaction in step (3);
the scanning electron microscope pictures are shown in fig. 2, and the degradation rate of formaldehyde gas is shown in table 1.
Comparative example 2
The difference compared with example 1 is only that no surfactant is added in step (2);
the sodium manganese oxide composite material with high-efficiency formaldehyde degradation prepared in this example has a scanning electron microscope picture shown in fig. 3, and the degradation rate of the sodium manganese oxide composite material on formaldehyde gas is shown in table 1.
Comparative example 3
The difference compared with example 1 is only Mn in the step (3) 2+ The molar ratio of the potassium permanganate to the potassium permanganate is 1:0.01; total (S)The amounts are the same as in example 1, the remainder being added in the second reaction stage;
the scanning electron microscope pictures are shown in fig. 4, and the degradation rate of formaldehyde gas is shown in table 1.
Comparative example 4
The only difference compared to example 1 is that the second reaction temperature in step (4) is 40 ℃;
the sodium manganese oxide composite material with high-efficiency formaldehyde degradation prepared in this example has a scanning electron microscope picture shown in fig. 5, and the degradation rate of the sodium manganese oxide composite material on formaldehyde gas is shown in table 1.
Comparative example 5
The only difference compared to example 1 is that the second reaction temperature in step (4) is 120 ℃;
the sodium manganese oxide composite material with high-efficiency formaldehyde degradation prepared in this example has a scanning electron microscope picture shown in fig. 6, and the degradation rate of the sodium manganese oxide composite material on formaldehyde gas is shown in table 1.
Example 2
The only difference compared to example 1 is that the hydrated calcium silicate substrate in step (1) is prepared at 130 ℃;
the sodium manganese oxide composite material with high-efficiency formaldehyde degradation prepared in this example has a scanning electron microscope picture shown in fig. 7, and the degradation rate of the sodium manganese oxide composite material on formaldehyde gas is shown in table 1.
Example 3
The only difference compared to example 1 is that the calcium silicate hydrate in step (1) is prepared at 230 ℃;
the sodium manganese oxide composite material with high-efficiency formaldehyde degradation prepared in this example has a scanning electron microscope picture shown in fig. 8, and the degradation rate of the sodium manganese oxide composite material on formaldehyde gas is shown in table 1.
Example 4
The only difference compared to example 1 is that the hydrated calcium silicate substrate in step (1) was prepared at 170 ℃;
the sodium manganese oxide composite material with high-efficiency formaldehyde degradation prepared in this example has a scanning electron microscope picture shown in fig. 9, and the degradation rate of the sodium manganese oxide composite material on formaldehyde gas is shown in table 1.
Example 5
The only difference compared with example 1 is that the surfactant added in step (1) is sodium dodecylbenzenesulfonate;
the scanning electron microscope pictures are shown in fig. 10, and the degradation rate of formaldehyde gas is shown in table 1.
Example 6
The difference compared with example 1 is only Mn in the step (3) 2+ The molar ratio of the potassium permanganate to the potassium permanganate is 1:0.6; other parameters and operations were the same as in example 1.
The sodium manganese oxide composite material with high-efficiency formaldehyde degradation prepared in the embodiment has a scanning electron microscope picture shown in figure 11, and the degradation rate of the sodium manganese oxide composite material to formaldehyde gas is shown in table 1.
Example 7
The difference compared with example 1 is only Mn in the step (3) 2+ The molar ratio of the potassium permanganate to the potassium permanganate is 1:0.5; other parameters and operations were the same as in example 1.
The sodium manganese oxide composite material with high-efficiency formaldehyde degradation prepared in this example has a scanning electron microscope picture shown in fig. 12, and the degradation rate of the sodium manganese oxide composite material on formaldehyde gas is shown in table 1.
Example 8
The difference compared with example 1 is only Mn in the step (3) 2+ The molar ratio of the potassium permanganate to the potassium permanganate is 1:2; other parameters and operations were the same as in example 1.
The sodium manganese oxide composite material with high-efficiency formaldehyde degradation prepared in this example has a scanning electron microscope picture shown in fig. 13, and the degradation rate of the sodium manganese oxide composite material on formaldehyde gas is shown in table 1.
Example 9
The only difference compared to example 1 is that the second reaction temperature in step (4) is 240 ℃;
the sodium manganese oxide composite material with high-efficiency formaldehyde degradation prepared in this example has a scanning electron microscope picture shown in fig. 14, and the degradation rate of the sodium manganese oxide composite material on formaldehyde gas is shown in table 1.
Example 10
The only difference compared to example 1 is that the second reaction temperature in step (4) is 180 ℃;
the sodium manganese oxide composite material with high-efficiency formaldehyde degradation prepared in this example has a scanning electron microscope picture shown in fig. 15, and the degradation rate of the sodium manganese oxide composite material on formaldehyde gas is shown in table 1.
The conversion data of formaldehyde at different temperatures for examples 1-10 and comparative examples 1-5 are shown in Table 1
As can be seen from Table 1, the hydrated calcium silicate is added in the first stage reaction process, and further cooperates with the addition amount, addition rate, surfactant type and cooperative control of the second reaction temperature of the second stage reaction, so that the catalytic oxidation performance of the material can be greatly improved, the catalytic oxidation performance at low temperature and high temperature can be improved, and particularly, the catalytic performance at room temperature can be effectively improved, and the method has a larger practical application prospect. In addition, compared with single birnessite, the composite material provided by the invention can obtain quite even better effects under lower birnessite content, and is lighter in color and capable of meeting the aesthetic requirements of modern indoor decoration.
Claims (29)
1. The birnessite@hydrated calcium silicate composite material is characterized by comprising a hydrated calcium silicate substrate and birnessite grown on the surface of the substrate;
the hydrated calcium silicate is amorphous C-S-H solid gel;
the preparation method of the birnessite@hydrated calcium silicate composite material comprises the following steps:
step (1):
mixing a divalent manganese source, calcium silicate hydrate and a surfactant liquid phase to obtain a suspension;
step (2):
adding permanganate A into the suspension in the step (1) to perform a first reaction; wherein the molar ratio of the permanganate A to the divalent manganese source is 0.5-2: 1, a step of;
step (3):
adding permanganate B into the reaction system in the step (2), then sealing the mixed solution in a container, heating to perform a second reaction, and separating to obtain a birnessite@hydrated calcium silicate composite material after the reaction is finished;
the molar ratio of the permanganate B to the divalent manganese source is 0.5-5: 1, a step of;
the temperature of the second reaction is 160-250 ℃.
2. The birnessite@hydrated calcium silicate composite material according to claim 1, wherein the birnessite is a porous secondary structure material formed by interlacing birnessite sheet primary structures grown on the surface of a substrate.
3. The birnessite@hydrated calcium silicate composite material according to claim 1, wherein the mass ratio of hydrated calcium silicate to birnessite is 0.5-3: 1.
4. a method for preparing the birnessite@hydrated calcium silicate composite material according to any one of claims 1 to 3, which is characterized by comprising the following steps:
step (1):
mixing a divalent manganese source, calcium silicate hydrate and a surfactant liquid phase to obtain a suspension;
step (2):
adding permanganate A into the suspension in the step (1) to perform a first reaction; wherein the molar ratio of the permanganate A to the divalent manganese source is 0.5-2: 1, a step of;
step (3):
adding permanganate B into the reaction system in the step (2), then sealing the mixed solution in a container, heating to perform a second reaction, and separating to obtain a birnessite@hydrated calcium silicate composite material after the reaction is finished;
the molar ratio of the permanganate B to the divalent manganese source is 0.5-5: 1, a step of;
the temperature of the second reaction is 160-250 ℃.
5. The method for preparing the birnessite@hydrated calcium silicate composite material according to claim 4, wherein the hydrated calcium silicate is obtained by hydrothermal reaction of a mixed aqueous solution of a silicon-calcium raw material and alkali at a temperature of 100-250 ℃.
6. The method for preparing the birnessite@hydrated calcium silicate composite material according to claim 5, wherein the raw materials of silicon and calcium comprise a silicon source and a calcium source.
7. The method for preparing a birnessite@hydrated calcium silicate composite material according to claim 6, wherein the silicon source is a high silicon material comprising at least one of fly ash, coal gangue, chemical sodium silicate, clay, quartz ore and secondary tailings containing silicon.
8. The method for preparing the birnessite@hydrated calcium silicate composite material according to claim 6, wherein the calcium source is at least one of calcium oxide, calcium hydroxide and calcium carbonate.
9. The method for preparing the birnessite@hydrated calcium silicate composite material according to claim 5, wherein the alkali is at least one of sodium hydroxide and potassium hydroxide.
10. The method for preparing the birnessite@hydrated calcium silicate composite material according to claim 5, wherein the mixed aqueous solution has a silicon/calcium molar ratio of 1.2-5.5: 1.
11. the method for preparing the birnessite@hydrated calcium silicate composite material according to claim 5, wherein the molar ratio of the alkali to silicon in the raw materials of the silicon and the calcium is 0.5-4:1.
12. The method for preparing the birnessite@hydrated calcium silicate composite material according to claim 5, wherein the concentration of alkali in the mixed aqueous solution is 3-20 g/L.
13. The method for preparing the birnessite@hydrated calcium silicate composite material according to claim 5, wherein the hydrothermal reaction time is 0.5-4 h.
14. The method for preparing a birnessite@hydrated calcium silicate composite material according to claim 4, wherein the surfactant is at least one of a cationic surfactant, an anionic surfactant and a nonionic surfactant.
15. The method for preparing a birnessite@hydrated calcium silicate composite material according to claim 14, wherein the cationic surfactant is at least one of cetyl trimethyl ammonium bromide, benzalkonium chloride and benzalkonium bromide.
16. The method for preparing a birnessite@hydrated calcium silicate composite material according to claim 14, wherein the anionic surfactant is at least one of sodium dodecyl benzene sulfonate, ammonium dodecyl sulfate and sodium dodecyl sulfate.
17. The method for preparing a birnessite@hydrated calcium silicate composite material according to claim 14, wherein the nonionic surfactant is at least one of polyethylene glycol, polyol type and polyether type.
18. The method for preparing a birnessite@hydrated calcium silicate composite material according to claim 4, wherein the divalent manganese source is Mn 2+ Is a water-soluble salt of (a).
19. The method for preparing the birnessite@hydrated calcium silicate composite material according to claim 4, wherein the mass ratio of hydrated calcium silicate to a surfactant to a divalent manganese source is 0.5-5:0.1-2:1.
20. The method for preparing the birnessite@hydrated calcium silicate composite material according to claim 19, wherein the mass ratio of hydrated calcium silicate to a surfactant to a divalent manganese source is 2-5:0.5-1.5:1.
21. The method for producing a birnessite@hydrated calcium silicate composite material according to claim 4, wherein in the step (1), the solvent to be mixed in the liquid phase is water or a mixed solvent of water and an organic solvent, and the organic solvent is a water-miscible organic solvent.
22. The method for producing a birnessite@hydrated calcium silicate composite material according to claim 4, wherein in the suspension, mn 2+ The designed molar concentration of (2) is 0.1-2M.
23. The method for preparing the birnessite@hydrated calcium silicate composite material according to claim 4, wherein permanganate A and permanganate B are capable of ionizing MnO 4 - Is a water-soluble salt of (a).
24. The method for preparing a birnessite@hydrated calcium silicate composite material according to claim 23, wherein permanganate a and permanganate B are at least one of potassium permanganate, sodium permanganate and magnesium permanganate.
25. The method for preparing a birnessite@hydrated calcium silicate composite material according to claim 4, wherein the temperature of the first reaction stage is 15-45 ℃.
26. The method for preparing the birnessite@hydrated calcium silicate composite material according to claim 4, wherein the time of the first reaction is 0.5-3 hours.
27. The method for preparing the birnessite@hydrated calcium silicate composite material according to claim 4, wherein the time of the second reaction stage is 8-30 hours.
28. The birnessite@hydrated calcium silicate composite material according to any one of claims 1 to 3 or the application of the birnessite@hydrated calcium silicate composite material prepared by the preparation method according to any one of claims 4 to 27, which is characterized in that the birnessite@hydrated calcium silicate composite material is used as a catalyst for catalytic degradation of formaldehyde gas.
29. Use according to claim 28, in which it is directly prepared as an indoor building material or added to a building material for the catalytic degradation of formaldehyde gas.
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