CN115178230B - Preparation method and application of all-silicon zeolite domain-limited copper nanoparticle adsorbent - Google Patents
Preparation method and application of all-silicon zeolite domain-limited copper nanoparticle adsorbent Download PDFInfo
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01D2257/206—Organic halogen compounds
- B01D2257/2068—Iodine
Abstract
The invention discloses a preparation method and application of a full-silicon zeolite domain-limited copper nanoparticle adsorbent, comprising the following steps: copper nitrate is dissolved in deionized water to obtain copper nitrate solution; sequentially adding tetraethoxysilane and tetrapropylammonium hydroxide into the copper nitrate solution, and stirring for 24 hours at 90 ℃ to obtain a mixture; adding the water solution containing the mineralizer into the obtained mixture, and continuously stirring for 24 hours to obtain a colloid solution; transferring the obtained colloidal solution into a stainless steel autoclave with a Teflon lining, carrying out hydrothermal crystallization at 100-160 ℃, naturally cooling to room temperature, filtering a solid product, washing with deionized water, and carrying out vacuum drying; calcining for 5 hours at 550 ℃ in a reducing atmosphere to obtain the all-silicon zeolite domain-limited copper nanoparticle adsorbent. The all-silicon zeolite domain-limited copper nanoparticle adsorbent prepared by the invention is applied to capture gaseous radioactive iodine, and has excellent iodine capturing capability, low preparation cost, regular shape and high crystallinity of the synthesized adsorbent.
Description
Technical Field
The invention belongs to the technical field of preparation of adsorption materials for treating radioactive waste gas, and particularly relates to a preparation method and application of a full-silicon zeolite domain-limited copper nanoparticle adsorbent.
Background
Under the background of carbon peak and carbon neutralization, nuclear energy is used as clean and safe low-carbon energy, and the active development of nuclear power has become an important content of energy strategy in China. After the Japanese Fudao nuclear accident, the nuclear safety in China is a serious issue in the development of nuclear power industry, and the nuclear waste treatment is an important component of the nuclear safety, so that how to safely treat a large amount of radioactive waste generated in the nuclear fuel circulation process is a problem of great importance and public concern for the government. With the large-scale development of nuclear energy in China, the generation amount of spent fuel in the nuclear power station is increased increasingly. According to the fourteen-five planning, the installed capacity of nuclear power operation in China in 2025 years can reach 7000 kilowatts, and the accumulated quantity of spent fuel in China can reach 1.4 kilotons. The nuclear power development is expected for a long time, the installed capacity of the China nuclear power in 2030 is expected to reach 1.2 hundred million-1.5 hundred million kilowatts, and the accumulated generation amount of the spent fuel of the pressurized water reactor nuclear power station in China is about 2.35 ten thousand tons. How to safely and effectively treat and dispose radioactive wastes, especially the separation and solidification of the key long-life radionuclide, has become a serious problem which must be solved for the sustainable development of nuclear power in China.
In nuclear fuel circulation, iodine isotopes account for approximately 235 0.69% of the U slow neutron fission product. When the spent fuel is dissolved in boiling nitric acid solution, a large amount of radioactive iodine is released 129 I、 131 I) And other gaseous radionuclides 3 H、 14 C、 85 Kr、 133 Xe, etc.). Wherein the radioactive iodine is mainly in the form of highly volatile elemental iodine (I 2 90% -100%) and a small portion of organic iodides (e.g. CH) 3 I and CH 3 CH 2 I, etc., 0% -10%). 129 I is a long-life, high-yield key nuclide with a long half-life (1.6X10) 7 Years), is toxic and highly mobile in most geological environments. 131 I is a volatile short-life isotope with a half-life of only 8.02 days, which is highly enriched in thyroid gland and severely affects human metabolic processes due to its high specific activity, and still needs to be captured immediately after release. Therefore, the radioactive iodine is one of pollutants which are important to be focused on nuclear fuel circulation, spent fuel post-treatment and radioactive waste treatment, effectively captures, treats and fixes the radioactive iodine so as to carry out safe treatment in a geological time range, and has great significance for spent fuel post-treatment and environmental pollution prevention.
From the complications in post-treatment exhaust gas, where the iodine concentration is low, and where there is a large excess of water vapor and acid gases at high temperatures, how to maintain good stability under severe conditions is a challenge. The high volatility and mobility of gaseous iodine in the environment, how to quickly capture and effectively immobilize radioactive iodine remains one of the challenges of radioactive waste disposal. However, the adsorption separation technology for radioactive iodine in complex exhaust gas still needs to be improved, and an effective method for separating and solidifying radioactive iodine needs to be developed so as to eliminate risks to human health and environment. Therefore, it is a significant challenge to find an adsorbent that is inexpensive, simple to process, highly stable and has a high capture capacity.
Disclosure of Invention
It is an object of the present invention to address at least the above problems and/or disadvantages and to provide at least the advantages described below.
To achieve these objects and other advantages and in accordance with the purpose of the invention, there is provided a method for preparing an all-silicon zeolite domain-limited copper nanoparticle adsorbent, comprising the steps of:
step one, copper nitrate is dissolved in deionized water to obtain a copper nitrate solution;
sequentially adding tetraethoxysilane and tetrapropylammonium hydroxide into the copper nitrate solution in the first step, and stirring for 24 hours at 90 ℃ to obtain a mixture;
step three, adding the water solution containing the mineralizer into the mixture obtained in the step two, and continuously stirring for 24 hours to obtain a colloid solution;
transferring the colloid solution obtained in the step three into a stainless steel autoclave with a Teflon lining, performing hydrothermal crystallization at 100-160 ℃, naturally cooling to room temperature, filtering a solid product, washing with deionized water, and performing vacuum drying;
and fifthly, calcining the solid product obtained after the vacuum drying in the step four for 5 hours at 550 ℃ in a reducing atmosphere to obtain the all-silicon zeolite domain-limited copper nanoparticle adsorbent.
Preferably, the molar ratio of the copper nitrate, the tetraethoxysilane, the tetrapropylammonium hydroxide, the mineralizer and the water is 0.02-0.03:1:0.15:1.2:100-120.
Preferably, in the third step, the mineralizer is any one of ammonium fluoride, sodium fluoride and potassium fluoride.
Preferably, in the fourth step, the hydrothermal crystallization time is 72 to 96 hours.
Preferably, in the fourth step, the vacuum drying temperature is 60-80 ℃ and the vacuum drying time is 12-48 h.
Preferably, in the fifth step, the reducing atmosphere is 4%H 2 /Ar。
Preferably, in the fifth step, the temperature rising rate of the calcination is 5 ℃/min.
Preferably, the all-silicon zeolite limited-area copper nanoparticle adsorbent has a sheet structure, and the crystal thickness of the adsorbent is 100-300 nm.
Preferably, wherein, after the step five is performed with calcination of the solid product, ag is used 2 O is subjected to surface modification, and the surface modification method comprises the following steps: respectively preparing 3.5-5 g/L of ethylenediamine tetraacetic acid sodium solution, 1.75-2.5 g/L of sodium hydroxide solution and 0.5-0.8 g/L of AgNO 3 A solution; mixing ethylenediamine tetraacetic acid sodium solution with sodium hydroxide solution in equal volume to obtain solution A, and dropwise adding AgNO into the solution A 3 Solution until the last drop of AgNO 3 Stopping dripping until precipitation occurs after dripping, centrifugally separating, adding polyethyleneimine and solid products into the separated solution, reacting for 4-12 h, and modifying the surface of the solid products to form Ag 2 O film layer, solid-liquid separation, washing, and vacuum drying the separated solid to obtain the full-silicon zeolite limited copper nanoparticle adsorbent; wherein the mass ratio of the polyethyleneimine to the solid product is 0.5-1:5.
Preferably, the prepared all-silicon zeolite limited-area copper nanoparticle adsorbent is applied to trapping gaseous radioactive iodine.
The invention at least comprises the following beneficial effects: according to the invention, the silica colloid generated by hydrolysis of tetraethoxysilane is used as a silicon source, tetrapropylammonium hydroxide is used as a structure directing agent, the all-silicon zeolite is prepared, and the copper metal nano particles are encapsulated in the all-silicon zeolite through an in-situ synthesis strategy to enhance the capture of radioactive iodine. Firstly, fluoride ions are selected as mineralizer to control the growth of zeolite crystals, and the thickness of the zeolite crystals is reduced to nano-scale so as to improve the diffusion rate of guest iodine molecules. Second, the highly hydrophobic, acid-resistant and thermal stability of the zeolite framework imparts the desired good hydrothermal and irradiation stability of the adsorbent under the extreme conditions of post-treatment. Due to the synergistic effect of physical adsorption of all-silicon zeolite and chemical adsorption of limited-area copper nano particles, the excellent iodine capturing capability is proved, and the adsorption capacity can reach 625mg/g. The preparation method provided by the invention is simple, low in cost, regular in shape and high in crystallinity of the synthesized adsorbent.
The method uses sodium ethylenediamine tetraacetate and polyethyleneimine as complexing agents, and prepares Ag on the surface of the copper nanoparticle adsorbent with the limit of all-silicon zeolite by an ion exchange method 2 The O film layer improves the adsorption efficiency of the all-silicon zeolite limited copper nanoparticle adsorbent to gaseous radioactive iodine, and further enhances the adsorption and capture capacity of the all-silicon zeolite limited copper nanoparticle adsorbent to iodine.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is an XRD pattern of all-silica zeolite domain-limited copper nanoparticle adsorbents prepared in examples 1-6 of the present invention;
FIG. 2 is an SEM image of a fully silicalite domain limited copper nanoparticle adsorbent prepared according to example 2 of the present invention;
FIG. 3 is a TEM image of an all-silica zeolite domain-limited copper nanoparticle adsorbent prepared in example 2 of the present invention;
FIG. 4 is an XRD pattern of the all-silica zeolite domain-limited copper nanoparticle adsorbent prepared in example 2 of the present invention after soaking in solutions of different pH and after irradiation;
FIG. 5 is a graph showing adsorption kinetics of all-silica zeolite domain-limited copper nanoparticle adsorbent prepared in example 2 of the present invention and all-silica zeolite to gaseous iodine;
FIG. 6 is a graph showing adsorption kinetics of the all-silicon zeolite domain-limited copper nanoparticle adsorbent prepared in example 2 and example 7 of the present invention to gaseous iodine.
Detailed Description
The present invention is described in further detail below with reference to the drawings to enable those skilled in the art to practice the invention by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
the preparation method of the all-silicon zeolite domain-limited copper nanoparticle adsorbent comprises the following steps:
step one, dissolving 87mg of copper nitrate in 18mL of deionized water;
step two, adding 4.05mL of tetraethoxysilane and 1.1mL of tetrapropylammonium hydroxide in sequence, and stirring for 24 hours at 90 ℃;
adding 0.8g of ammonium fluoride aqueous solution (15 mL) into the mixture, and continuing stirring for 24h to obtain a colloid solution;
transferring the obtained colloidal solution into a stainless steel autoclave with a Teflon lining, performing hydrothermal crystallization for 96 hours at 100 ℃, naturally cooling to room temperature, filtering a solid product, washing with deionized water, and performing vacuum drying;
and fifthly, calcining the solid product obtained in the step four in vacuum drying at 550 ℃ in a reducing atmosphere for 5 hours to obtain the all-silicon zeolite domain-limited copper nanoparticle adsorbent.
Example 2:
the preparation method of the all-silicon zeolite domain-limited copper nanoparticle adsorbent comprises the following steps:
step one, dissolving 87mg of copper nitrate in 18mL of deionized water;
step two, adding 4.05mL of tetraethoxysilane and 1.1mL of tetrapropylammonium hydroxide in sequence, and stirring for 24 hours at 90 ℃;
adding 0.8g of ammonium fluoride aqueous solution (15 mL) into the mixture, and continuing stirring for 24h to obtain a colloid solution;
transferring the obtained colloidal solution into a stainless steel autoclave with a Teflon lining, performing hydrothermal crystallization for 96 hours at 120 ℃, naturally cooling to room temperature, filtering a solid product, washing with deionized water, and performing vacuum drying;
and fifthly, calcining the solid product obtained in the step four in vacuum drying at 550 ℃ in a reducing atmosphere for 5 hours to obtain the all-silicon zeolite domain-limited copper nanoparticle adsorbent.
Example 3:
the preparation method of the all-silicon zeolite domain-limited copper nanoparticle adsorbent comprises the following steps:
step one, dissolving 87mg of copper nitrate in 18mL of deionized water;
step two, adding 4.05mL of tetraethoxysilane and 1.1mL of tetrapropylammonium hydroxide in sequence, and stirring for 24 hours at 90 ℃;
adding 0.8g of ammonium fluoride aqueous solution (15 mL) into the mixture, and continuing stirring for 24h to obtain a colloid solution;
transferring the obtained colloidal solution into a stainless steel autoclave with a Teflon lining, performing hydrothermal crystallization for 96 hours at 140 ℃, naturally cooling to room temperature, filtering a solid product, washing with deionized water, and performing vacuum drying;
and fifthly, calcining the solid product obtained in the step four in vacuum drying at 550 ℃ in a reducing atmosphere for 5 hours to obtain the all-silicon zeolite domain-limited copper nanoparticle adsorbent.
Example 4:
the preparation method of the all-silicon zeolite domain-limited copper nanoparticle adsorbent comprises the following steps:
step one, dissolving 87mg of copper nitrate in 18mL of deionized water;
step two, adding 4.05mL of tetraethoxysilane and 1.1mL of tetrapropylammonium hydroxide in sequence, and stirring for 24 hours at 90 ℃;
adding 0.8g of ammonium fluoride aqueous solution (15 mL) into the mixture, and continuing stirring for 24h to obtain a colloid solution;
transferring the obtained colloidal solution into a stainless steel autoclave with a Teflon lining, performing hydrothermal crystallization for 96 hours at 160 ℃, naturally cooling to room temperature, filtering a solid product, washing with deionized water, and performing vacuum drying;
and fifthly, calcining the solid product obtained in the step four in vacuum drying at 550 ℃ in a reducing atmosphere for 5 hours to obtain the all-silicon zeolite domain-limited copper nanoparticle adsorbent.
Example 5:
the preparation method of the all-silicon zeolite domain-limited copper nanoparticle adsorbent comprises the following steps:
step one, dissolving 87mg of copper nitrate in 18mL of deionized water;
step two, adding 4.05mL of tetraethoxysilane and 1.1mL of tetrapropylammonium hydroxide in sequence, and stirring for 24 hours at 90 ℃;
adding 0.8g of aqueous solution (15 mL) containing sodium fluoride into the mixture, and continuously stirring for 24h to obtain a colloid solution;
transferring the obtained colloidal solution into a stainless steel autoclave with a Teflon lining, performing hydrothermal crystallization for 96 hours at 120 ℃, naturally cooling to room temperature, filtering a solid product, washing with deionized water, and performing vacuum drying;
and fifthly, calcining the solid product obtained in the step four in vacuum drying at 550 ℃ in a reducing atmosphere for 5 hours to obtain the all-silicon zeolite domain-limited copper nanoparticle adsorbent.
Example 6:
the preparation method of the all-silicon zeolite domain-limited copper nanoparticle adsorbent comprises the following steps:
step one, dissolving 87mg of copper nitrate in 18mL of deionized water;
step two, adding 4.05mL of tetraethoxysilane and 1.1mL of tetrapropylammonium hydroxide in sequence, and stirring for 24 hours at 90 ℃;
step three, adding 0.8g of aqueous solution (15 mL) containing potassium fluoride into the mixture, and continuing stirring for 24h to obtain a colloid solution;
transferring the obtained colloidal solution into a stainless steel autoclave with a Teflon lining, performing hydrothermal crystallization for 96 hours at 120 ℃, naturally cooling to room temperature, filtering a solid product, washing with deionized water, and performing vacuum drying;
and fifthly, calcining the solid product obtained in the step four in vacuum drying at 550 ℃ in a reducing atmosphere for 5 hours to obtain the all-silicon zeolite domain-limited copper nanoparticle adsorbent.
Example 7:
the preparation method of the all-silicon zeolite domain-limited copper nanoparticle adsorbent comprises the following steps:
step one, dissolving 87mg of copper nitrate in 18mL of deionized water;
step two, adding 4.05mL of tetraethoxysilane and 1.1mL of tetrapropylammonium hydroxide in sequence, and stirring for 24 hours at 90 ℃;
adding 0.8g of ammonium fluoride aqueous solution (15 mL) into the mixture, and continuing stirring for 24h to obtain a colloid solution;
transferring the obtained colloidal solution into a stainless steel autoclave with a Teflon lining, performing hydrothermal crystallization for 96 hours at 120 ℃, naturally cooling to room temperature, filtering a solid product, washing with deionized water, and performing vacuum drying;
calcining the solid product dried in vacuum in the fourth step for 5 hours at 550 ℃ in a reducing atmosphere, wherein Ag is used 2 O carries out surface modification on the calcined solid product, wherein the surface modification method comprises the following steps: respectively preparing 3.5g/L of ethylenediamine tetraacetic acid sodium solution, 1.75g/L of sodium hydroxide solution and 0.5g/L of AgNO 3 A solution; 50mL of ethylenediamine tetraacetic acid sodium solution is mixed with 50mL of sodium hydroxide solution to obtain solution A, and AgNO is added dropwise to the solution A 3 Solution until the last drop of AgNO 3 Stopping dripping until precipitation occurs after dripping, centrifuging, adding polyethylenimine and solid product into the separated solution, reacting for 8 hr, and modifying the surface of the solid product to form Ag 2 O film layer, solid-liquid separation, washing, and vacuum drying the separated solid to obtain the full-silicon zeolite limited copper nanoparticle adsorbent; wherein the mass ratio of the polyethyleneimine to the solid product is 0.5:5.
FIG. 1 is an XRD pattern of all-silica zeolite domain-limited copper nanoparticle adsorbents prepared in examples 1 to 6, as well as a standard XRD pattern of copper. As can be seen from fig. 1, under crystallization conditions at 100 ℃, no all-silica zeolite phase is obtained, the main component being silica; all-silica zeolite was synthesized under crystallization conditions of 120 to 160 ℃, and diffraction peaks of examples 1 to 6 at 2θ=43.3 °, 50.5 °, and 74.1 ° were attributed to (111), (200), and (220) planes (JCPDS 85-1326) of metallic copper. The results show that the preparation methods of examples 2-6 all successfully synthesize the full-silicon zeolite domain-limited copper nanoparticle adsorbent, the crystallinity is high, and the action effects of ammonium fluoride, sodium fluoride and potassium fluoride are consistent.
As shown in FIG. 2, the all-silicon zeolite domain-limited copper nanoparticle adsorbent has a regular sheet structure, a length of about 3-4 μm and a width of about 1.5-1.7 μm, and a crystal thickness of about 100-300 nm. FIG. 3 is a Transmission Electron Microscope (TEM) image of a full-silica zeolite confinement copper nanoparticle adsorbent, from which it is seen that the particle size of copper nanoparticles confined within the full-silica zeolite is about 20-120 nm.
Figure 4 is an XRD pattern of the all-silicon zeolite domain-limited copper nanoparticle adsorbent prepared in example 2 after soaking in solutions of different pH and after irradiation. Soaking a proper amount of adsorbent in 10mL of aqueous solution with pH values of 1, 7 and 13 respectively, standing for 3 days, filtering and collecting solids, obtaining diffraction peak patterns of samples under different pH values by using an X-ray diffractometer, comparing with XRD patterns of raw materials, and researching acid-base stability of the materials; and (3) receiving beta-ray irradiation with the dosage of 200kGy from the material, and comparing XRD data of the material before and after irradiation to obtain irradiation-resistant stability information of the material. Through experimental data analysis, the all-silicon zeolite domain-limited copper nanoparticle adsorbent maintains the phase structure under the conditions of different pH solutions and after irradiation, and has good acid-base stability and irradiation stability.
The iodine capturing experiment is carried out by using the full-silicon zeolite limited-area copper nanoparticle adsorbent prepared in the embodiment 2 and common full-silicon zeolite, and the specific method of the experiment is as follows: 50mg of the all-silicon zeolite domain-limited copper nanoparticle adsorbent material was placed in a 10mL glass vial and sealed in a 250mL glass vial containing 2g of iodine, and the apparatus was heated to 75℃at ambient pressure to evaporate the iodine. After different time nodes (10, 20, 30, 45, 60, 90, 120, 180, 240, 300, 360 min), the quality difference before and after material adsorption is evaluatedIodine capture and under the same conditions, an equivalent amount of all-silicalite was used as a control experiment. FIG. 5 is a graph showing adsorption time (min) on the abscissa and iodine adsorption amount (mg/g) on the ordinate of adsorption kinetics of all-silica zeolite domain-limited copper nanoparticle adsorbent and all-silica zeolite prepared in example 2 to gaseous iodine. As can be seen from FIG. 5, the all-silicon zeolite domain-limited copper nanoparticle adsorbent pair I prepared in example 2 2 The adsorption of (2) increases gradually with increasing contact time. The adsorbent can reach equilibrium within 45min, and the maximum adsorption quantity is 625mg/g; the full-silica zeolite reaches equilibrium in 90min, and the adsorption quantity is 500mg/g. The adsorption capacity of the all-silicon zeolite domain-limited copper nanoparticle adsorbent prepared in example 2 is far higher than that of all-silicon zeolite, and the adsorption kinetics of the all-silicon zeolite domain-limited copper nanoparticle adsorbent is improved.
FIG. 6 is a graph showing adsorption kinetics of the all-silicon zeolite domain-limited copper nanoparticle adsorbent prepared in example 2 and example 7 of the present invention to gaseous iodine. As can be seen from FIG. 6, the all-silicon zeolite domain-limited copper nanoparticle adsorbent pair I prepared in example 2 2 The adsorption of (2) increases gradually with increasing contact time. The adsorbent can reach equilibrium within 45min, and the maximum adsorption quantity is 625mg/g; the full-silicon zeolite domain-limited copper nanoparticle adsorbent prepared in the example 7 can reach equilibrium in 35min, and the adsorption quantity is 675mg/g. The adsorption capacity of the all-silicon zeolite domain-limited copper nanoparticle adsorbent prepared in the example 7 is higher than that of the all-silicon zeolite domain-limited copper nanoparticle adsorbent prepared in the example 2, and the adsorption kinetics and adsorption efficiency of the all-silicon zeolite domain-limited copper nanoparticle adsorbent are improved by adopting the method in the example 7.
The preparation method of the all-silicon zeolite domain-limited copper nanoparticle adsorbent and the application thereof in trapping gaseous radioactive iodine, and the prepared all-silicon zeolite domain-limited copper nanoparticle adsorbent has high crystallinity and regular shape through an in-situ hydrothermal method and thermal reduction treatment. The adsorbent not only has better acid-base stability and irradiation stability, but also can obviously promote the adsorption of the copper nanoparticles with all-silicon zeolite limited domains on gaseous radioactive iodine. Meanwhile, the preparation process is simple and the cost is low.
The number of equipment and the scale of processing described herein are intended to simplify the description of the present invention. Applications, modifications and variations of the present invention will be readily apparent to those skilled in the art.
Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown and described, it is well suited to various fields of use for which the invention would be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the specific details and illustrations shown and described herein, without departing from the general concepts defined in the claims and their equivalents.
Claims (8)
1. The preparation method of the all-silicon zeolite domain-limited copper nanoparticle adsorbent is characterized by comprising the following steps of:
step one, copper nitrate is dissolved in deionized water to obtain a copper nitrate solution;
sequentially adding tetraethoxysilane and tetrapropylammonium hydroxide into the copper nitrate solution in the first step, and stirring for 24 hours at 90 ℃ to obtain a mixture;
step three, adding the water solution containing the mineralizer into the mixture obtained in the step two, and continuously stirring for 24 hours to obtain a colloid solution;
transferring the colloid solution obtained in the step three into a stainless steel autoclave with a Teflon lining, performing hydrothermal crystallization at 100-160 ℃, naturally cooling to room temperature, filtering a solid product, washing with deionized water, and performing vacuum drying;
calcining the solid product obtained in the fourth step in vacuum drying at 550 ℃ in a reducing atmosphere for 5 hours to obtain the all-silicon zeolite domain-limited copper nanoparticle adsorbent;
the molar ratio of the copper nitrate to the tetraethoxysilane to the tetrapropylammonium hydroxide to the mineralizer to the water is 0.02-0.03:1:0.15:1.2:100-120;
in the third step, the mineralizer is any one of ammonium fluoride, sodium fluoride and potassium fluoride.
2. The method for preparing the all-silicon zeolite domain-limited copper nanoparticle adsorbent according to claim 1, wherein in the fourth step, the hydrothermal crystallization time is 72-96 h.
3. The method for preparing the all-silicon zeolite domain-limited copper nanoparticle adsorbent according to claim 1, wherein in the fourth step, the vacuum drying temperature is 60-80 ℃ and the vacuum drying time is 12-48 h.
4. The method for preparing a copper nanoparticle adsorbent with a limited domain of all-silicon zeolite according to claim 1, wherein in the fifth step, the reducing atmosphere is 4% H 2 /Ar。
5. The method for preparing a copper nanoparticle adsorbent in a confined area of all-silicon zeolite according to claim 1, wherein in the fifth step, the temperature rising rate of calcination is 5 ℃/min.
6. The method for preparing the all-silicon zeolite domain-limited copper nanoparticle adsorbent according to claim 1, wherein the all-silicon zeolite domain-limited copper nanoparticle adsorbent has a sheet structure and a crystal thickness of 100-300 nm.
7. The method for preparing a copper nanoparticle adsorbent with limited area of all-silicon zeolite according to claim 1, wherein after calcining the solid product in the fifth step, ag is used 2 O is subjected to surface modification, and the surface modification method comprises the following steps: respectively preparing 3.5-5 g/L of ethylenediamine tetraacetic acid sodium solution, 1.75-2.5 g/L of sodium hydroxide solution and 0.5-0.8 g/L of AgNO 3 A solution; mixing ethylenediamine tetraacetic acid sodium solution with sodium hydroxide solution in equal volume to obtain solution A, and dropwise adding AgNO into the solution A 3 Solution until the last drop of AgNO 3 Stopping dripping until precipitation occurs after dripping, centrifugally separating, adding polyethyleneimine and solid products into the separated solution, reacting for 4-12 hours, and modifying the surface of the solid products to form Ag 2 O film layer, solid-liquid separation, washing, and vacuum drying the separated solid to obtain the full-silicon zeolite limited copper nanoparticle adsorbent; wherein, the liquid crystal display device comprises a liquid crystal display device,the mass ratio of the polyethyleneimine to the solid product is 0.5-1:5.
8. The method for preparing the all-silicon zeolite domain-limited copper nanoparticle adsorbent according to any one of claims 1 to 7, wherein the prepared all-silicon zeolite domain-limited copper nanoparticle adsorbent is applied to trapping gaseous radioactive iodine.
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