A Cu-confined polymer microsphere catalytic material for iron tailings, its preparation method, and its application in degrading organic matter.

Abstract

This invention belongs to the field of inorganic catalyst materials and organic pollutant degradation technology, specifically relating to a Cu@ITGs confined microsphere catalytic material based on iron tailings, its preparation method, and its application in degrading organic matter. The method includes the following steps: mixing activated iron tailings powder and meta-high terephthalic acid to obtain a mixed dry powder; obtaining a composite alkali activator; weighing copper nitrate particles, dispersing them in ethanolamine for complexation, and slowly adding them to the composite alkali activator to obtain a mixed solution; adding the mixed dry powder to the mixed solution to synthesize a gel slurry; dripping the obtained gel slurry into polyethylene glycol-800 to form microspheres; and after fully curing and drying the microspheres, gradient calcining under a N2 atmosphere to obtain the confined catalytic material Cu@ITGs. This invention uses bulk industrial solid waste as the main raw material to prepare a multifunctional catalytic material with both high catalytic activity and excellent stability for use in wastewater treatment, realizing "waste-to-waste" treatment and high-value-added resource utilization of solid waste.

Description

Technical Field

[0001] This invention relates to the fields of solid waste resource utilization, inorganic catalyst materials and organic pollutant degradation technology, and in particular to a Cu catalytic material confined in iron tailings aggregate microspheres, its preparation method and its application in degrading organic matter. Background Technology

[0002] Tailings are the main solid waste generated after mining and mineral processing, and their total accumulation is enormous and continues to grow annually. Large amounts of tailings not only cause geological disasters such as land encroachment and slope instability, but also bring complex environmental risks such as heavy metal migration and acidic leachate pollution. Therefore, achieving high-value-added resource utilization of tailings is key to solving this environmental problem and realizing green mining development. From a resource perspective, the main mineral composition of tailings is a potential source of silicon and aluminum materials. As a raw material for aluminosilicates, tailings have great potential for developing geopolymers, and large-scale resource utilization is of great significance for promoting "zero-waste mining" and alleviating environmental pressure. Geopolymers are three-dimensional network inorganic polymers (NASH gels) composed of silicon-aluminosilicate tetrahedra [SiO4] and aluminum-aluminosilicate tetrahedra [AlO4], generated through a series of depolymerization-condensation reactions from silicon-aluminosilicate raw materials. Due to their well-developed pore structure, high specific surface area, and ion exchange capacity, they have become a research hotspot in the fields of heavy metal fixation and pollutant adsorption.

[0003] Although the applications of geopolymers in adsorption have been extensively studied, their potential in catalysis, particularly as heterogeneous catalysts or catalyst supports, has not been fully explored. Chinese patent CN102430419A discloses a Ni... 2+ This patent describes the preparation of doped geopolymer catalysts and their application in organic matter degradation. It employs an ion exchange method to convert Ni... 2+ While Ni, supported on a geopolymer carrier, achieves catalytic degradation, its active components primarily exist in ionic form, lacking strong chemical bonds. In long-term recycling or complex wastewater environments, Ni... 2+ Leaching loss is prone to occur, leading to decreased catalyst stability and activity, and potentially causing secondary metal ion contamination. Chinese patent CN115041186A discloses a fly ash geopolymer / CuMn composite material and its application. This patent combines biochar and geopolymer to form a membrane material, which improves the recovery performance of the powdered catalyst. However, the interaction between the biochar and the geopolymer matrix is ​​mainly physical blending or weak physical interaction, resulting in insufficient interfacial bonding strength. During the catalytic reaction, the active components are prone to agglomeration and detachment, and the uniformity of biochar distribution is difficult to control precisely, affecting the long-term stability and reproducibility of the catalytic efficiency.

[0004] In summary, existing technologies suffer from problems such as easy migration and aggregation of active components, poor stability, and low catalytic efficiency. Furthermore, the antibiotic pollutants that have been adsorbed and enriched do not disappear from the environment but are merely spatially transferred, still posing a risk of secondary environmental pollution. Summary of the Invention

[0005] This invention addresses the problems of traditional supported catalysts, such as easy migration and aggregation of active nanoparticles, poor stability, and low catalytic efficiency, in practical applications. It provides a Cu catalytic material confined in iron tailings aggregate microspheres, its preparation method, and its application in degrading organic matter. This material can efficiently activate persulfate to remove organic pollutants from wastewater, and also has the advantages of good stability, high catalytic efficiency, and easy recovery.

[0006] The Cu@ITGs geopolymer confined catalytic material for iron tailings of this invention is achieved through the following technical solution: The first aspect of this invention proposes a method for preparing Cu catalytic materials confined in iron tailings aggregate microspheres, comprising the following steps: Step 1: Grind and sieve the iron tailings to obtain iron tailings powder, and calcine and activate it. Mix the activated iron tailings powder and meta-high terephthalic acid in a mass ratio of 7:3 to 8:2, and grind to obtain a mixed dry powder. Then, weigh NaOH and Na2SiO3 according to the modulus M=n(SiO2) / n(Na2O)=1.2 to 1.8 and dissolve them in deionized water, where the water-alkali ratio is n(H2O) / n(Na2O)=16 to 20. Heat and stir until the mixture is clear to obtain a composite alkali activator. Step 2: Weigh out copper nitrate particles, disperse them in ethanolamine, and slowly add them to the composite alkali activator from Step 1. The amount of copper nitrate added is 1-5 wt% of the mixed dry powder, and the mixture is stirred continuously to obtain a mixed solution. Then, according to the alkali-aluminum ratio of n(Na2O) / n(Al2O3) = 1.0-1.5, add the mixed dry powder to the above mixed solution to synthesize a gel slurry. Step 3: The gel slurry obtained in Step 2 is dropped into polyethylene glycol-800 and microspheres are formed under stirring. The microspheres are then removed and washed with anhydrous ethanol until the washing solution is neutral. After thorough curing and drying, the microspheres are placed in a tube furnace and calcined under a gradient of N2 atmosphere to obtain the confined catalytic material Cu@ITGs.

[0007] Preferably, in step one, the iron tailings are ground to a particle size of 75–90 μm.

[0008] Preferably, the heating and stirring in step one is performed by heating and stirring in a water bath at 40-60°C.

[0009] Preferably, in step two, the molar ratio of ethanolamine to copper ions is 1:1 to 1:2.

[0010] Preferably, the stirring speed in step two is 300-400 rpm, the temperature is 40-60℃, and the time is 1-1.5 h.

[0011] Preferably, the stirring speed in step three is 900-1000 rpm, the time is 1-2 hours, and the curing conditions are 60-80℃ and sealed curing for 24-72 hours.

[0012] Preferably, the gradient calcination in step three consists of the following stages: the first stage involves slowly increasing the temperature from 25°C to 110°C for 30 minutes; the second stage involves maintaining the temperature at 110°C for 30 minutes; the third stage involves slowly increasing the temperature from 110°C to 150°C for 40 minutes; and the fourth stage involves maintaining the temperature at 150°C for 2 hours.

[0013] The second aspect of this invention provides a catalytic material prepared by the method described above for preparing Cu catalytic material confined in iron tailings aggregate microspheres.

[0014] The third aspect of this invention proposes a method for preparing Cu catalytic materials confined in iron tailings aggregate microspheres, and the application of the prepared catalytic materials in the degradation of organic matter.

[0015] The fourth aspect of this invention proposes a method for preparing Cu catalytic materials confined in iron tailings aggregate microspheres, and the application of the prepared catalytic materials in the degradation of tetracycline.

[0016] Beneficial effects: This invention proposes a method for preparing multifunctional catalytic materials with spatially confined structures through a controlled geopolymerization process and its application in the catalytic degradation of organic pollutants. The core of this invention lies firstly in using bulk solid waste iron tailings as raw material, which not only successfully disposes of solid waste and reduces environmental risks, but more importantly, iron tailings are naturally rich in silicon and aluminum components and the catalytically active component Fe, providing a far more efficient disposal method than traditional approaches. Secondly, copper nitrate is pre-complexed with ethanolamine, and the complex is then introduced in situ into the geopolymer gel system to avoid Cu... 2+ Hydrolysis and precipitation, as well as aggregation, occur in a strong base activator. Finally, by utilizing the self-assembly behavior of PEG and the dual confinement of the Si-O-Al framework in the geopolymer reaction (Cu-O-Si bond) and pore size constraint (geomer nanopores), transition metal Cu nanoparticles are encapsulated in geopolymer pores, making it difficult for active components to leach out and lose, thus constructing a high-performance catalytic material with a spatially constrained structure in situ.

[0017] Compared with existing technologies, this invention can solve the problems of easy agglomeration, deactivation, and leaching of traditional supported catalysts. In the application of Cu@ITGs in the degradation of organic pollutants by activating potassium persulfate (PMS), the abundant hierarchical channels and large specific surface area of ​​the geopolymers have a good adsorption and enrichment effect on pollutant molecules. The synergistic effect of "adsorption and enrichment" and "confined catalysis" can rapidly concentrate pollutants around the catalytic active sites. The valence state cycle of Fe species in iron tailings geopolymers (ITGs) and the interfacial electronic coupling effect of transition metal Cu drive the efficient activation and degradation of pollutants by PMS, which greatly improves the reaction rate and degradation efficiency. Attached Figure Description

[0018] Figure 1 The BET diagrams are for the catalysts prepared in Example 1, where (a) is the BET diagram of ITGs and (b) is the BET diagram of Cu@ITGs. Figure 2 The microstructure and chemical state characterization of the Cu@ITGs catalyst prepared in Example 1 are shown in (a) and (b) are the XRD patterns of IT, ITGs and Cu@ITGs. Figure 3 The images are TEM images of the Cu@ITGs catalyst prepared in Example 1, where (a) and (b) are morphological structures of Cu@ITGs at different magnifications, (c) is an HRTEM image of Cu@ITGs, (d) is an EDS spectrum of Cu@ITGs, and (e) is an SAED spectrum of Cu@ITGs. Figure 4 The images show the tetracycline removal effect of the Cu@ITGs catalyst activated by PMS in Example 1. (a) is a comparison of the tetracycline removal effect under different systems, (b) is a comparison of the tetracycline removal effect of the Cu@ITGs catalyst after 10 cycles, and (c) is a comparison of the tetracycline removal effect of the CuO-ITGs catalyst after 4 cycles. Detailed Implementation

[0019] To make the technology and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only for explaining the invention and are not intended to limit the scope of protection of the invention; the main components of the iron tailings used in the embodiments are: SiO2 74.7%, Fe2O3 8.8%, Al2O3 6.6%, CaO 5.1%, Mg2O 2.7%, and others 2.1%.

[0020] A method for preparing a Cu catalytic material confined in aggregate microspheres at iron tailings, comprising the following steps: Step 1: Grind and screen iron tailings (IT) to obtain mineral powder with a particle size of 75-90 μm. Place the iron tailings powder in a tube furnace for calcination and activation. Place the obtained activated IT and metakaolinite (MK) in a mortar and grind them together to obtain a mixed dry powder. Accurately weigh NaOH and Na2SiO3 and dissolve them in deionized water. Heat and stir the solution until it becomes clear to obtain a mixed liquid called the composite alkali activator. The pH is controlled within the range of 12-14.

[0021] The calcination conditions for IT are 600–800℃ for 1.5–2 hours; the mass ratio of IT to MK is 7:3–8:2; the dry mixing and grinding time is 15–20 minutes; and the solution is heated and stirred in a water bath at 40–60℃ until clear. Basic formula adjustment: the modulus of the composite alkali activator is M = n(SiO2) / n(Na2O) = 1.2–1.8; the alkali-to-aluminum ratio is n(Na2O) / n(Al2O3) = 1.0–1.5; and the water-to-alkali ratio is n(H2O) / n(Na2O) = 16–20.

[0022] Step 2: Weigh out copper nitrate particles, disperse them in ethanolamine, and slowly add the composite alkali activator from Step 1. Stir continuously with a stirrer, and then add the mixed dry powder to the above mixed solution to synthesize a gel slurry. Since the composite alkali activator of the geopolymer is composed of NaOH and Na₂SiO₃, the pH value is usually as high as 12-14. Therefore, to avoid copper precipitation, the amount of copper nitrate added in this embodiment is 1-5 wt% of the mixed dry powder, and the molar ratio of ethanolamine to Cu is 1:1-1:2 to ensure sufficient coordination (clear solution). In this embodiment, a stable copper-ethanolamine complex is first formed to ensure Cu... 2+ After being fully protected, it is mixed with an alkaline activator and then added dropwise to the complex. The gelation is then delayed at 40-60°C and 300-400 rpm to ensure uniform dispersion of the complex, resulting in a mixed solution. Finally, the mixed dry powder is added to the mixed solution to gradually disperse the solid particles in the liquid phase, preventing Cu from being absorbed. 2+ Decomplexed precipitates and maintain for 1–1.5 h to form a homogeneous slurry.

[0023] Step 3: Using a syringe, the gel slurry obtained in Step 2 is drawn up and dripped uniformly into polyethylene glycol-800 (PEG-800) at a water bath temperature of 80°C. The mixture is continuously and rapidly stirred to form microspheres. The microspheres are then removed and washed with anhydrous ethanol until the washing solution is neutral or near-neutral. After thorough curing and drying, the microspheres are placed in a tube furnace and calcined under a gradient N2 atmosphere to obtain Cu@ITGs, i.e., confined catalytic materials.

[0024] In step three, the stirring speed is 900~1000 rpm, the time is 1~2h, the curing conditions are 60~80℃ sealed curing for 24~72h, under N2 atmosphere, the gradient calcination conditions are 25℃~110℃ for 30min, 110℃ for 30min, 110℃~150℃ for 40min, 150℃ for 2h.

[0025] To address the issues of easy migration and aggregation of active components and poor stability in existing supported catalysts, this application proposes to utilize the self-assembly behavior induced by polyethylene glycol (PEG) to regulate the formation of geopolymer microspheres, coupling the chemical anchoring effect and pore size constraint effect of the geopolymer Si-O-Al framework.

[0026] Specifically, low-temperature curing at 60–80℃ avoids the migration and aggregation problems of copper-based active components that may be caused by high-temperature calcination; long-term curing (24–72 h) ensures that Cu… 2+ It fully contacts and coordinates with the silanol and hydroxyl groups on the surface of the Si-O-Al geopolymer framework to form stable Cu-O-Si chemical bonds, enhancing the chemical anchoring effect; at the same time, the closed curing maintains the stability of the complex, effectively inhibits the formation of Cu(OH)2 precipitation, and ensures the dispersibility and reactivity of the active components.

[0027] To avoid damaging the geopolymer's pore structure while achieving precise reduction and robust confinement of the active components, this embodiment employs gradient calcination. The first stage involves a slow temperature increase from 25°C to 110°C over 30 minutes to gently remove physically adsorbed water from the microsphere surface, preventing rapid vaporization that could cause microsphere cracking and maintaining the integrity of the microsphere structure. The second stage involves maintaining a constant temperature of 110°C for 30 minutes to fully remove internal water of crystallization and residual PEG, while simultaneously allowing the ethanolamine ligands to gradually and slowly decompose, preventing Cu species migration and aggregation. The third stage involves a slow temperature increase from 110°C to 150°C over 40 minutes to completely decompose the ethanolamine ligands and release Cu. 2+ It is reduced in situ to Cu under an inert N2 atmosphere. 0 Alternatively, Cu2O; the fourth stage is a constant temperature of 150℃ for 2 hours, during which the geopolymer framework further condenses and densifies, anchoring and solidifying the formed copper active nanoparticles within the pores, preventing them from being squeezed out by the stress generated by the framework condensation, and completing the final shaping of the confined structure.

[0028] In summary, this embodiment achieves stable confined encapsulation of transition metal Cu nanoparticles within geopolymer channels through a synergistic strategy of 'complexation pre-protection - in-situ gel encapsulation - confined calcination curing', thereby significantly enhancing the catalyst's recyclability stability while improving catalytic degradation efficiency.

[0029] The second aspect of this invention proposes to apply the iron tailings geopolymer confined catalytic Cu@ITGs prepared by the above method to the removal of organic pollutants from wastewater, the steps of which are as follows: All pollutant degradation experiments were conducted in 250 mL beakers. 100 mL of an organic pollutant, such as tetracycline hydrochloride solution (30 mg / L), was added to the beaker, followed by the prepared catalyst Cu@ITGs (0.2 g / L). The mixture was stirred for 30 min to establish adsorption-desorption equilibrium. PMS (0.4 g / L) was added to the suspension to initiate the reaction. 2–3 mL of the suspension was taken every 5–10 min to measure the absorbance of the remaining tetracycline. The reaction was carried out at 300–400 rpm for 1.5 h to degrade the tetracycline hydrochloride pollutant in the water.

[0030] Example 1 The preparation method of Cu@ITGs, a polymer-confined microsphere from iron tailings in this example, includes the following steps: (1) The iron tailings were ground and screened to obtain mineral powder with a particle size of 75-90 μm. The chemical composition of the iron tailings is shown in Table 1. Table 1. Main components of iron tailings and their mass percentage (%)

[0031] (2) Place the iron tailings powder in a tube furnace and calcine and activate it at 700℃ for 2 hours to perform thermal activation treatment on the iron tailings; accurately weigh 8.0g of activated iron tailings powder, add 2.0g of high-purity soil, mix and grind for 15 minutes; (3) Set n(Na2O) / n(Al2O3)=1.2, M=1.5, n(H2O) / n(Na2O)=18, weigh 3.92g sodium silicate and 1.34g NaOH and dissolve them in 12.08mL deionized water. Heat and stir at 60℃ until clear to obtain a composite alkali activator solution.

[0032] (4) Weigh 1.9g of copper nitrate trihydrate, disperse it in 236μL of ethanolamine (MEA), and stir continuously for 30min to ensure full coordination to obtain Cu-MEA solution.

[0033] (5) Slowly add the composite alkali activator to Cu-MEA and stir continuously at 400 rpm and 40°C using a stirrer. Under vigorous stirring, add the mixed dry powder to the above mixed slurry and stir for 1 hour.

[0034] (6) The obtained mixed gel was drawn up with a syringe and dripped into PEG-800 at a uniform rate (water bath 80℃). The mixture was stirred continuously and rapidly until microspheres were formed under stirring. The microspheres were taken out, washed three times with anhydrous ethanol, cured at 60℃ for 48h, and dried thoroughly. The microspheres were then placed in a tube furnace and calcined at 150℃ under N2 atmosphere to obtain Cu@ITGs, i.e. confined catalytic material.

[0035] Simultaneously, an ITG catalyst was prepared as a control. 8.0 g of activated iron tailings powder was weighed and mixed with 2.0 g of high-purity terephthalic acid, then ground for 15 min. With n(Na2O) / n(Al2O3) = 1.2, M = 1.5, and n(H2O) / n(Na2O) = 18, 3.92 g of sodium silicate and 1.34 g of NaOH were weighed and dissolved in 12.08 mL of deionized water. The solution was heated and stirred at 60 °C until clear, obtaining a composite alkali activator solution. Under vigorous stirring, the mixed dry powder was added to the composite alkali activator and stirred for 1 h. The resulting mixed gel was drawn up using a syringe and added dropwise into PEG-800 (water bath 80 °C) at a uniform rate, with continuous rapid stirring until microspheres formed. The microspheres were then removed, washed three times with anhydrous ethanol, cured at 60 °C for 48 h, and thoroughly dried. Finally, the microspheres were placed in a tube furnace and calcined at 150 °C under a N2 atmosphere to obtain iron tailings macropolymer ITGs.

[0036] To reveal the confined structure characteristics of Cu@ITGs, a variety of characterization methods were used to systematically analyze its morphology, phase, chemical state and pore structure.

[0037] The N2 adsorption-desorption curves and pore size distribution diagrams of ITGs and Cu@ITG catalysts are shown below. Figure 1 As shown. From Figure 1 As can be seen from (a) in the figure, the specific surface area of ​​the geopolymer is 27.6 m². 2 / g, total pore volume is 0.0341cm³ 3 / g. After introducing Cu, as... Figure 1 In (b), the BET specific surface area of ​​the Cu@ITGs sample decreased to 10.6 m² / g, and the total pore volume was only 0.00550 cm³ / g. The micropore characteristic peaks almost completely disappeared, leaving only a small amount of mesopores. This indicates that Cu species entered and occupied the micropore / small mesopore channels of ITGs, leading to a significant decrease in pore volume and specific surface area, but the most probable pore size (3-4 nm) remained unchanged. This clearly points to a "pore-blocking" mechanism, where copper nanoparticles fill and occupy the mesopore channels of the support, rather than merely adhering to the outer surface.

[0038] like Figure 2 In (a), only a weak Cu appears in the XRD pattern. 0The diffraction peaks indicate that copper exists in nanocrystalline form with low crystallinity, which is consistent with the small size and enhanced dispersibility resulting from pore confinement. Figure 2 In (b), XPS analysis further detected Cu in the shallow surface layer of the material. 0 Cu + With Cu 2+ The coexistence signal indicates that copper in a confined environment exhibits multiple valence states.

[0039] The morphology of the Cu@ITG catalyst is shown in Figure 3 As shown in (a) and (b), Cu@ITG exhibits a porous microsphere structure. Figure 3 As shown in (c) and (e), clear Cu(111) and (200) lattice fringes and diffraction rings were observed in TEM and SAED, directly confirming the formation of nano-copper crystals, and their size matches the pore size of the support. Figure 3 As shown in Figure (d) and Table 2, neither surface enrichment of copper was detected by SEM-EDS surface scanning nor spot scanning, confirming that copper species are mainly located inside the carrier rather than on the surface. These data, progressively building upon each other, constitute a complete chain of evidence for the confined growth of copper nanoparticles within mesopores.

[0040] Table 2 Figure 3 Table of area scan total spectrum data corresponding to figure (d) in the table

[0041] To test its catalytic performance, 0.02 g of Cu@ITGs and ITGs catalyst were added to 100 mL of a 30 mg / L tetracycline hydrochloride solution. Under dark conditions at room temperature, the solution was stirred at 300 rpm for 30 min to reach adsorption-desorption equilibrium. Then, 0.04 g of PMS was added, and the solution was stirred at 300 rpm for 1.5 h under natural conditions. The absorbance of tetracycline hydrochloride was measured every 10 min. After 90 min of degradation, the degradation rate of TC by ITGs was 70%, while the degradation rate of tetracycline by Cu@ITGs was 93.3%. We also investigated the degradation effect of TC under different systems; the results are shown below. Figure 4 In (a), the natural decomposition rate of TC in the blank group after 90 min was approximately 1.1%, while the degradation rate of TC by PMS alone was 28.4%, by ITGs alone 15.5%, by Cu@ITGs alone 50.9%, and by the Cu-supported catalyst CuO-ITGs under PMS irradiation, the degradation rate of TC was 88%. It can be seen that the confined catalyst significantly improved the degradation efficiency of tetracycline hydrochloride. Figure 4(b) shows the degradation efficiency of the Cu@ITGs catalyst after 10 cycles. After 10 cycles, it still achieves a degradation efficiency of over 88% for TC, thanks to the excellent stability and dispersibility confined by the Cu@ITGs structure. Figure 4 Figure (c) shows the degradation efficiency of the supported catalyst CuO-ITGs after 5 cycles. The comparison reveals that the CuO-ITGs catalyst exhibits significant activity degradation after only 5 cycles. This indicates that the geopolymer confinement structure effectively inhibits the aggregation, leaching, and deactivation of active metal species through physical anchoring and spatial constraint, solving the key problem of poor cycle stability in traditional supported catalysts and laying the foundation for their long-term application in antibiotic wastewater treatment.

[0042] Example 2 (1) The iron tailings were ground and screened to obtain iron tailings powder with a particle size of 75-90 μm. The iron tailings powder was placed in a tube furnace and calcined and activated at 600℃ for 2 hours to perform thermal activation treatment on the iron tailings. 8.0 g of activated iron tailings powder was accurately weighed and mixed with 2.0 g of high-purity soil. The mixture was ground for 15 min. (7) Set n(Na2O) / n(Al2O3)=1.0, M=1.5, n(H2O) / n(Na2O)=18, weigh 3.92g sodium silicate and 0.90g NaOH and dissolve them in 13.54mL deionized water. Heat and stir at 60℃ until clear to obtain a composite alkali activator solution.

[0043] (8) Weigh 1.9g of copper nitrate, disperse it in 236μL of MEA, and stir continuously for 30min to ensure sufficient coordination to obtain Cu-MEA solution.

[0044] (9) Add the composite alkali activator to Cu-MEA and stir continuously at 400 rpm and 40°C using a stirrer. Under vigorous stirring, add the mixed dry powder to the above mixed slurry and stir for 1 hour.

[0045] (10) The obtained mixed gel was drawn up with a syringe and dripped into PEG-800 at a constant rate (water bath 80℃). The mixture was stirred continuously and rapidly until microspheres were formed under stirring. The microspheres were taken out, washed three times with anhydrous ethanol, cured at 60℃ for 48h, and dried thoroughly. The microspheres were then placed in a tube furnace and calcined at 150℃ under N2 atmosphere to obtain Cu@ITGs, i.e. confined catalytic material.

[0046] 0.02 g of Cu@ITGs confined catalyst was weighed and added to 100 mL of tetracycline hydrochloride solution with a concentration of 30 mg / L. Under dark conditions at room temperature, the mixture was stirred at 300 rpm for 30 min to reach adsorption-desorption equilibrium. Then, 0.04 g of PMS was added, and the mixture was stirred at 300 rpm for 1.5 h under natural conditions. The absorbance of tetracycline hydrochloride was measured every 10 min. After 90 min of degradation, the degradation rate of tetracycline by Cu@ITGs was 89.4%.

[0047] Example 3 (1) The iron tailings were ground and screened to obtain iron tailings powder with a particle size of 75-90 μm. The iron tailings powder was placed in a tube furnace and calcined and activated at 600℃ for 2 hours to perform thermal activation treatment on the iron tailings. 8.0 g of activated iron tailings powder was accurately weighed and mixed with 2.0 g of high-purity soil. The mixture was ground for 15 min. (2) Set n(Na2O) / n(Al2O3)=1.2, M=1.5, n(H2O) / n(Na2O)=20, weigh 3.92g sodium silicate and 1.34g NaOH and dissolve them in 13.42mL deionized water. Heat and stir at 60℃ until clear to obtain a composite alkali activator solution.

[0048] (3) Weigh 1.9g of copper nitrate, disperse it in 236μL MEA, and stir continuously for 30min to ensure full coordination to obtain Cu-MEA solution.

[0049] (4) Add the composite alkali activator to Cu-MEA and stir continuously at 400 rpm and 40°C using a stirrer. Under vigorous stirring, add the mixed dry powder to the above mixed slurry and stir for 1 hour.

[0050] (5) The obtained mixed gel was drawn up with a syringe and dripped into PEG-800 (water bath 80℃) at a uniform rate. The mixture was stirred continuously and rapidly until microspheres were formed under stirring. The microspheres were taken out, washed three times with anhydrous ethanol, cured at 60℃ for 48h, and dried thoroughly. The microspheres were then placed in a tube furnace and calcined at 150℃ under N2 atmosphere to obtain Cu@ITGs, i.e. confined catalytic material.

[0051] To test its catalytic performance, 0.02 g of Cu@ITGs confined catalyst was added to 100 mL of tetracycline hydrochloride solution with a concentration of 30 mg / L. Under dark conditions at room temperature, the solution was stirred at 300 rpm for 30 min to reach adsorption-desorption equilibrium. Then, 0.04 g of PMS was added, and the solution was stirred at 300 rpm for 1.5 h under natural conditions. The absorbance of tetracycline hydrochloride was measured every 10 min. After 90 min of degradation, the degradation rate of tetracycline by Cu@ITGs was 91.6%.

[0052] Example 4 (1) The iron tailings were ground and screened to obtain iron tailings powder with a particle size of 75-90 μm. The iron tailings powder was placed in a tube furnace and calcined and activated at 800℃ for 2 hours to perform thermal activation treatment on the iron tailings. 8.0 g of activated iron tailings powder was accurately weighed and mixed with 2.0 g of high-purity soil. The mixture was ground for 15 min. (2) Set n(Na2O) / n(Al2O3)=1.5, M=1.8, n(H2O) / n(Na2O)=16, weigh 4.9g sodium silicate and 0.67g NaOH and dissolve them in 13.98mL deionized water. Heat and stir at 60℃ until clear to obtain a composite alkali activator solution.

[0053] (3) Weigh 1.9g of copper nitrate, disperse it in 236μL MEA, and stir continuously for 30min to ensure full coordination to obtain Cu-MEA solution.

[0054] (4) Add the composite alkali activator to Cu-MEA and stir continuously at 400 rpm and 40°C using a stirrer. Under vigorous stirring, add the mixed dry powder to the above mixed slurry and stir for 1 hour.

[0055] (5) The obtained mixed gel was drawn up with a syringe and dripped into PEG-800 (water bath 80℃) at a uniform rate. The mixture was stirred continuously and rapidly until microspheres were formed under stirring. The microspheres were taken out, washed three times with anhydrous ethanol, cured at 60℃ for 48h, and dried thoroughly. The microspheres were then placed in a tube furnace and calcined at 150℃ under N2 atmosphere to obtain Cu@ITGs, i.e. confined catalytic material.

[0056] To test its catalytic performance, 0.02 g of Cu@ITGs confined catalyst was weighed and added to 100 mL of tetracycline hydrochloride solution with a concentration of 30 mg / L. Under dark conditions at room temperature, the solution was stirred at 300 rpm for 30 min to reach adsorption-desorption equilibrium. Then, 0.04 g of PMS was added, and the solution was stirred at 300 rpm for 1.5 h under natural conditions. The absorbance of tetracycline hydrochloride was measured every 10 min. After 90 min of degradation, the degradation rate of tetracycline by Cu@ITGs was 89.6%.

[0057] Example 5 (1) The iron tailings were ground and screened to obtain iron tailings powder with a particle size of 75-90 μm. The iron tailings powder was placed in a tube furnace and calcined and activated at 600℃ for 2 hours to perform thermal activation treatment on the iron tailings. 8.0 g of activated iron tailings powder was accurately weighed and mixed with 2.0 g of high-purity soil. The mixture was ground for 15 min. (2) Set n(Na2O) / n(Al2O3)=1.5, M=1.5, n(H2O) / n(Na2O)=18, weigh 3.92g sodium silicate and 2.01g NaOH and dissolve them in 10.15mL deionized water. Heat and stir at 60℃ until clear to obtain a composite alkali activator solution.

[0058] (3) Weigh 1.9g of copper nitrate, disperse it in 236μL MEA, and stir continuously for 30min to ensure full coordination to obtain Cu-MEA solution.

[0059] (4) Add the composite alkali activator to Cu-MEA and stir continuously at 400 rpm and 40°C using a stirrer. Under vigorous stirring, add the mixed dry powder to the above mixed slurry and stir for 1 hour.

[0060] (5) The obtained mixed gel was drawn up with a syringe and dripped into PEG-800 (water bath 80℃) at a uniform rate. The mixture was stirred continuously and rapidly until microspheres were formed under stirring. The microspheres were taken out, washed three times with anhydrous ethanol, cured at 60℃ for 48h, and dried thoroughly. The microspheres were then placed in a tube furnace and calcined at 150℃ under N2 atmosphere to obtain Cu@ITGs, i.e. confined catalytic material.

[0061] To test its catalytic performance, 0.02 g of Cu@ITGs confined catalyst was weighed and added to 100 mL of tetracycline hydrochloride solution with a concentration of 30 mg / L. Under dark conditions at room temperature, the solution was stirred at 300 rpm for 30 min to reach adsorption-desorption equilibrium. Then, 0.04 g of PMS was added, and the solution was stirred at 300 rpm for 1.5 h under natural conditions. The absorbance of tetracycline hydrochloride was measured every 10 min. After 90 min of degradation, the degradation rate of tetracycline by Cu@ITGs was 89%.

[0062] Example 6 (1) The iron tailings were ground and screened to obtain iron tailings powder with a particle size of 75-90 μm. The iron tailings powder was placed in a tube furnace and calcined and activated at 800℃ for 2 hours to perform thermal activation treatment on the iron tailings. 8.0 g of activated iron tailings powder was accurately weighed and mixed with 2.0 g of high-purity soil. The mixture was ground for 15 min. (2) Set n(Na2O) / n(Al2O3)=1.0, M=1.2, n(H2O) / n(Na2O)=20, weigh 2.94g sodium silicate and 0.90g NaOH and dissolve them in 13.42mL deionized water. Heat and stir at 60℃ until clear to obtain a composite alkali activator solution.

[0063] (3) Weigh 1.9g of copper nitrate, disperse it in 236μL MEA, and stir continuously for 30min to ensure full coordination to obtain Cu-MEA solution.

[0064] (4) Add the composite alkali activator to Cu-MEA and stir continuously at 400 rpm and 40°C using a stirrer. Under vigorous stirring, add the mixed dry powder to the above mixed slurry and stir for 1 hour.

[0065] (5) The obtained mixed gel was drawn up with a syringe and dripped into PEG-800 (water bath 80℃) at a uniform rate. The mixture was stirred continuously and rapidly until microspheres were formed under stirring. The microspheres were taken out, washed three times with anhydrous ethanol, cured at 60℃ for 48h, and dried thoroughly. The microspheres were then placed in a tube furnace and calcined at 150℃ under N2 atmosphere to obtain Cu@ITGs, i.e. confined catalytic material.

[0066] To test its catalytic performance, 0.02 g of Cu@ITGs confined catalyst was weighed and added to 100 mL of tetracycline hydrochloride solution with a concentration of 30 mg / L. Under dark conditions at room temperature, the solution was stirred at 300 rpm for 30 min to reach adsorption-desorption equilibrium. Then, 0.04 g of PMS was added, and the solution was stirred at 300 rpm for 1.5 h under natural conditions. The absorbance of tetracycline hydrochloride was measured every 10 min. After 90 min of degradation, the degradation rate of tetracycline by Cu@ITGs was 90.2%.

[0067] Example 7 (1) The iron tailings were ground and screened to obtain iron tailings powder with a particle size of 75-90 μm. The iron tailings powder was placed in a tube furnace and calcined and activated at 800℃ for 2 hours to perform thermal activation treatment on the iron tailings. 8.0 g of activated iron tailings powder was accurately weighed and mixed with 2.0 g of high-purity soil. The mixture was ground for 15 min. (2) Set n(Na2O) / n(Al2O3)=1.5, M=1.2, n(H2O) / n(Na2O)=16, weigh 2.94g sodium silicate and 2.01g NaOH and dissolve them in 10.74mL deionized water. Heat and stir at 60℃ until clear to obtain a composite alkali activator solution.

[0068] (3) Weigh 1.9g of copper nitrate, disperse it in 236μL MEA, and stir continuously for 30min to ensure full coordination to obtain Cu-MEA solution.

[0069] (4) Add the composite alkali activator to Cu-MEA and stir continuously at 400 rpm and 40°C using a stirrer. Under vigorous stirring, add the mixed dry powder to the above mixed slurry and stir for 1 hour.

[0070] (5) The obtained mixed gel was drawn up with a syringe and dripped into PEG-800 at a constant rate (water bath 80℃). The mixture was stirred continuously and rapidly until microspheres were formed under stirring. The microspheres were taken out, washed three times with anhydrous ethanol, cured at 60℃ for 48h, and dried thoroughly. The microspheres were then placed in a tube furnace and calcined at 150℃ under N2 atmosphere to obtain Cu@ITGs, i.e. confined catalytic material.

[0071] To test its catalytic performance, 0.02 g of Cu@ITGs confined catalyst was weighed and added to 100 mL of tetracycline hydrochloride solution with a concentration of 30 mg / L. Under dark conditions at room temperature, the solution was stirred at 300 rpm for 30 min to reach adsorption-desorption equilibrium. Then, 0.04 g of PMS was added, and the solution was stirred at 300 rpm for 1.5 h under natural conditions. The absorbance of tetracycline hydrochloride was measured every 10 min. After 90 min of degradation, the degradation rate of tetracycline by Cu@ITGs was 89.7%.

[0072] Example 8 (1) The iron tailings were ground and screened to obtain iron tailings powder with a particle size of 75-90 μm. The iron tailings powder was placed in a tube furnace and calcined and activated at 800℃ for 2 hours to perform thermal activation treatment on the iron tailings. 8.0 g of activated iron tailings powder was accurately weighed and mixed with 2.0 g of high-purity soil. The mixture was ground for 15 min. (2) Set n(Na2O) / n(Al2O3)=1.0, M=1.8, n(H2O) / n(Na2O)=20, weigh 4.9g sodium silicate and 0.66g NaOH and dissolve them in 13.42 mL of deionized water. Heat and stir at 60℃ until clear to obtain a composite alkali activator solution.

[0073] (3) Weigh 1.9g of copper nitrate, disperse it in 236μL MEA, and stir continuously for 30min to ensure full coordination to obtain Cu-MEA solution.

[0074] (4) Add the composite alkali activator to Cu-MEA and stir continuously at 400 rpm and 40°C using a stirrer. Under vigorous stirring, add the mixed dry powder to the above mixed slurry and stir for 1 hour.

[0075] (5) The obtained mixed gel was drawn up with a syringe and dripped into PEG-800 (water bath 80℃) at a uniform rate. The mixture was stirred continuously and rapidly until microspheres were formed under stirring. The microspheres were taken out, washed three times with anhydrous ethanol, cured at 60℃ for 48h, and dried thoroughly. The microspheres were then placed in a tube furnace and calcined at 150℃ under N2 atmosphere to obtain Cu@ITGs, i.e. confined catalytic material.

[0076] To test its catalytic performance, 0.02 g of Cu@ITGs confined catalyst was weighed and added to 100 mL of tetracycline hydrochloride solution with a concentration of 30 mg / L. Under dark conditions at room temperature, the solution was stirred at 300 rpm for 30 min to reach adsorption-desorption equilibrium. Then, 0.04 g of PMS was added, and the solution was stirred at 300 rpm for 1.5 h under natural conditions. The absorbance of tetracycline hydrochloride was measured every 10 min. After 90 min of degradation, the degradation rate of tetracycline by Cu@ITGs was 88.5%.

[0077] Example 9 (1) The iron tailings were ground and screened to obtain iron tailings powder with a particle size of 75~90μm. The iron tailings powder was placed in a tube furnace and calcined and activated at 800℃ for 2h to perform thermal activation treatment on the iron tailings. 8.0g of activated iron tailings powder was accurately weighed and mixed with 2.0g of high-purity soil and ground for 15min. (2) Set n(Na2O) / n(Al2O3)=1.2, M=1.8, n(H2O) / n(Na2O)=16, weigh 4.9g sodium silicate and 0.67g NaOH and dissolve them in 10.74mL deionized water. Heat and stir at 60℃ until clear to obtain a composite alkali activator solution.

[0078] (3) Weigh 1.9g of copper nitrate, disperse it in 236μL MEA, and stir continuously for 30min to ensure full coordination to obtain Cu-MEA solution.

[0079] (4) Add the composite alkali activator to Cu-MEA and stir continuously at 400 rpm and 40°C using a stirrer. Under vigorous stirring, add the mixed dry powder to the above mixed slurry and stir for 1 hour.

[0080] (5) The obtained mixed gel was drawn up with a syringe and dripped into PEG-800 at a constant rate (water bath 80℃). The mixture was stirred continuously and rapidly until microspheres were formed under stirring. The microspheres were taken out, washed three times with anhydrous ethanol, cured at 60℃ for 48h, and dried thoroughly. The microspheres were then placed in a tube furnace and calcined at 150℃ under N2 atmosphere to obtain Cu@ITGs, i.e. confined catalytic material.

[0081] To test its catalytic performance, 0.02 g of Cu@ITGs confined catalyst was weighed and added to 100 mL of tetracycline hydrochloride solution with a concentration of 30 mg / L. Under dark conditions at room temperature, the solution was stirred at 300 rpm for 30 min to reach adsorption-desorption equilibrium. Then, 0.04 g of PMS was added, and the solution was stirred at 300 rpm for 1.5 h under natural conditions. The absorbance of tetracycline hydrochloride was measured every 10 min. After 90 min of degradation, the degradation rate of tetracycline by Cu@ITGs was 89.4%.

[0082] Example 10 (1) The iron tailings were ground and screened to obtain iron tailings powder with a particle size of 75-90 μm. The iron tailings powder was placed in a tube furnace and calcined and activated at 800℃ for 2 hours to perform thermal activation treatment on the iron tailings. 8.0 g of activated iron tailings powder was accurately weighed and mixed with 2.0 g of high-purity soil. The mixture was ground for 15 min. (2) Set n(Na2O) / n(Al2O3)=1.2, M=1.8, n(H2O) / n(Na2O)=18, weigh 4.9g sodium silicate and 0.67g NaOH and dissolve them in 12.08mL deionized water. Heat and stir at 60℃ until clear to obtain a composite alkali activator solution.

[0083] (3) Weigh 1.9g of copper nitrate, disperse it in 236μL MEA, and stir continuously for 30min to ensure full coordination to obtain Cu-MEA solution.

[0084] (4) Add the composite alkali activator to Cu-MEA and stir continuously at 400 rpm and 40°C using a stirrer. Under vigorous stirring, add the mixed dry powder to the above mixed slurry and stir for 1 hour.

[0085] (5) The obtained mixed gel was drawn up with a syringe and dripped into PEG-800 at a constant rate (water bath 80℃). The mixture was stirred continuously and rapidly until microspheres were formed under stirring. The microspheres were taken out, washed three times with anhydrous ethanol, cured at 60℃ for 48h, and dried thoroughly. The microspheres were then placed in a tube furnace and calcined at 150℃ under N2 atmosphere to obtain Cu@ITGs, i.e. confined catalytic material.

[0086] To test its catalytic performance, 0.02 g of Cu@ITGs confined catalyst was weighed and added to 100 mL of tetracycline hydrochloride solution with a concentration of 30 mg / L. Under dark conditions at room temperature, the solution was stirred at 300 rpm for 30 min to reach adsorption-desorption equilibrium. Then, 0.04 g of PMS was added, and the solution was stirred at 300 rpm for 1.5 h under natural conditions. The absorbance of tetracycline hydrochloride was measured every 10 min. After 90 min of degradation, the degradation rate of tetracycline by Cu@ITGs was 90.1%.

[0087] Example 11 (1) The iron tailings were ground and screened to obtain iron tailings powder with a particle size of 75-90 μm. The iron tailings powder was placed in a tube furnace and calcined and activated at 800℃ for 2 hours to perform thermal activation treatment on the iron tailings. 7.0 g of activated iron tailings powder was accurately weighed and mixed with 3.0 g of high-purity soil. The mixture was ground for 15 min. (2) Set n(Na2O) / n(Al2O3)=1.2, M=1.8, n(H2O) / n(Na2O)=18, weigh 4.9g sodium silicate and 0.67g NaOH and dissolve them in 12.08mL deionized water. Heat and stir at 60℃ until clear to obtain a composite alkali activator solution.

[0088] (3) Weigh 1.9g of copper nitrate, disperse it in 236μL MEA, and stir continuously for 30min to ensure full coordination to obtain Cu-MEA solution.

[0089] (4) Add the composite alkali activator to Cu-MEA and stir continuously at 400 rpm and 40°C using a stirrer. Under vigorous stirring, add the mixed dry powder to the above mixed slurry and stir for 1 hour.

[0090] (5) The obtained mixed gel was drawn up with a syringe and dripped into PEG-800 (water bath 80℃) at a uniform rate. The mixture was stirred continuously and rapidly until microspheres were formed under stirring. The microspheres were taken out, washed three times with anhydrous ethanol, cured at 60℃ for 48h, and dried thoroughly. The microspheres were then placed in a tube furnace and calcined at 150℃ under N2 atmosphere to obtain Cu@ITGs, i.e. confined catalytic material.

[0091] To test its catalytic performance, 0.02 g of Cu@ITGs confined catalyst was weighed and added to 100 mL of tetracycline hydrochloride solution with a concentration of 30 mg / L. Under dark conditions at room temperature, the solution was stirred at 300 rpm for 30 min to reach adsorption-desorption equilibrium. Then, 0.04 g of PMS was added, and the solution was stirred at 300 rpm for 1.5 h under natural conditions. The absorbance of tetracycline hydrochloride was measured every 10 min. After 90 min of degradation, the degradation rate of tetracycline by Cu@ITGs was 91.7%.

[0092] Comparative Example 1 (1) The iron tailings were ground and screened to obtain iron tailings powder with a particle size of 75-90 μm. The iron tailings powder was placed in a tube furnace and calcined and activated at 800℃ for 2 hours to perform thermal activation treatment on the iron tailings. 8.0 g of activated iron tailings powder was accurately weighed and mixed with 2.0 g of high-purity soil. The mixture was ground for 15 min. (2) Set n(Na2O) / n(Al2O3)=1.2, M=1.5, n(H2O) / n(Na2O)=18, weigh 3.92g sodium silicate and 1.34g NaOH and dissolve them in 12.08mL deionized water. Heat and stir at 60℃ until clear to obtain a composite alkali activator solution.

[0093] (3) Weigh 1.9g of copper nitrate, disperse it in 236μL MEA, and stir continuously for 30min to ensure full coordination to obtain Cu-MEA solution.

[0094] (4) Add the composite alkali activator to Cu-MEA and stir continuously at 400 rpm and 40°C using a stirrer. Under vigorous stirring, add the mixed dry powder to the above mixed slurry and stir for 1 hour.

[0095] (5) The obtained mixed gel was drawn up with a syringe and dripped into PEG-800 at a uniform rate (water bath 80℃). The mixture was stirred continuously and rapidly until microspheres were formed under stirring. The microspheres were taken out, washed three times with anhydrous ethanol, cured at 60℃ for 48h, and dried thoroughly. The microspheres were then placed in a tube furnace under N2 atmosphere with a heating rate of 5℃ / min and calcined at 150℃ for 2h to obtain Cu@ITGs, i.e. confined catalytic material.

[0096] To test its catalytic performance, 0.02 g of Cu@ITGs confined catalyst was added to 100 mL of a 30 mg / L tetracycline hydrochloride solution. Under dark conditions at room temperature, the solution was stirred at 300 rpm for 30 min to reach adsorption-desorption equilibrium. Then, 0.04 g of PMS was added, and the solution was stirred at 300 rpm for 1.5 h under natural conditions. The absorbance of tetracycline hydrochloride was measured every 10 min. After 90 min of degradation, the degradation rate of tetracycline by Cu@ITGs was 89.8%. After two cycles, the degradation efficiency decreased to 70%. This indicates that rapid heating leads to structural collapse, instability of the active component, and poorer cycle stability of the degradation process.

[0097] In summary, this invention, by controlling the pore structure of geopolymers, encapsulates active nanoparticles within the geopolymer channels, physically preventing the migration and detachment of active components, thus solving the problems of leaching and aggregation. It also achieves atomic-level dispersion of active sites, maximizing the exposure of the active surface, thereby obtaining a catalytic material with ultra-high stability, excellent activity, and unique selectivity. The catalytic material prepared by this invention can be used to degrade organic matter, especially tetracycline.

[0098] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of the claims of this invention and their equivalents, this invention also intends to include these modifications and variations.

Claims

1. A method for preparing a Cu catalytic material confined in iron tailings aggregate microspheres, characterized in that: The steps are as follows: Step 1: Grind and sieve the iron tailings to obtain iron tailings powder, and calcine and activate it. Mix the activated iron tailings powder and meta-high terephthalic acid in a mass ratio of 7:3 to 8:2, and grind to obtain a mixed dry powder. Then, weigh NaOH and Na2SiO3 according to the modulus M=n(SiO2) / n(Na2O)=1.2 to 1.8 and dissolve them in deionized water, where the water-alkali ratio is n(H2O) / n(Na2O)=16 to 20. Heat and stir until the mixture is clear to obtain a composite alkali activator. Step 2: Weigh out copper nitrate particles, disperse them in ethanolamine, and slowly add them to the composite alkali activator from Step 1. The amount of copper nitrate added is 1-5 wt% of the mixed dry powder, and the mixture is stirred continuously to obtain a mixed solution. Then, according to the alkali-aluminum ratio of n(Na2O) / n(Al2O3) = 1.0-1.5, add the mixed dry powder to the above mixed solution to synthesize a gel slurry. Step 3: The gel slurry obtained in Step 2 is dropped into polyethylene glycol-800 and microspheres are formed under stirring. The microspheres are then removed and washed with anhydrous ethanol until the washing solution is neutral. After thorough curing and drying, the microspheres are placed in a tube furnace and calcined under a gradient of N2 atmosphere to obtain the confined catalytic material Cu@ITGs.

2. The method for preparing a Cu catalytic material confined in iron tailings aggregate microspheres according to claim 1, characterized in that: In step one, the iron tailings are ground to a particle size of 75-90 μm.

3. The method for preparing a Cu catalytic material confined in iron tailings aggregate microspheres according to claim 1, characterized in that: The heating and stirring described in step one involves heating and stirring in a water bath at 40–60°C.

4. The method for preparing a Cu catalytic material confined in iron tailings aggregate microspheres according to claim 1, characterized in that: In step two, the molar ratio of ethanolamine to copper ions is 1:1 to 1:

2.

5. The method for preparing a Cu catalytic material confined in iron tailings aggregate microspheres according to claim 1, characterized in that: The stirring speed in step two is 300-400 rpm, the temperature is 40-60℃, and the time is 1-1.5 h.

6. The method for preparing a Cu catalytic material confined in iron tailings aggregate microspheres according to claim 1, characterized in that: The stirring speed in step three is 900-1000 rpm, and the time is 1-2 hours; the curing conditions are 60-80℃ and sealed curing for 24-72 hours.

7. The method for preparing a Cu catalytic material confined in iron tailings aggregate microspheres according to claim 1, characterized in that: The gradient calcination described in step three consists of the following stages: the first stage involves slowly increasing the temperature from 25°C to 110°C for 30 minutes; the second stage involves maintaining the temperature at 110°C for 30 minutes; the third stage involves slowly increasing the temperature from 110°C to 150°C for 40 minutes; and the fourth stage involves maintaining the temperature at 150°C for 2 hours.

8. A catalytic material prepared by the method for preparing Cu catalytic material confined in iron tailings geopolymer microspheres as described in any one of claims 1 to 7.

9. The application of a catalytic material prepared by the method for preparing Cu-confined polymer microspheres in iron tailings as described in any one of claims 1 to 7 in the degradation of organic matter.

10. The application of a catalytic material prepared by the method for preparing Cu-confined polymer microspheres in iron tailings as described in any one of claims 1 to 7 in the degradation of tetracycline.

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