Silicon dioxide-loaded cerium dioxide core-shell material, preparation method thereof and application of silicon dioxide-loaded cerium dioxide core-shell material in Ge / Ga separation

Abstract

The invention relates to the technical field of isotope separation, in particular to a silicon dioxide-loaded cerium dioxide core-shell material, a preparation method thereof and application of the silicon dioxide-loaded cerium dioxide core-shell material in Ge / Ga separation. CeO is modified on the surface of mesoporous SiO to form a SiO2-CeO2 core-shell structure, a SiO core provides a rigid framework and irradiation stability, and a CeO shell realizes efficient adsorption of < 68 > Ge and effective elution of < 68 > Ga; the SiO2-coated CeO2 core-shell material is used as a stationary phase, hydrochloric acid is used as a mobile phase, and Ge / Ga is efficiently separated based on solid-phase extraction, so that the SiO2-coated CeO2 core-shell material can be used as a column filler of a 68Ge-68Ga generator.

Description

Technical Field

[0001] This invention relates to the field of isotope separation technology, and in particular to a core-shell material of silica-supported cerium dioxide, its preparation method, and its application in Ge / Ga separation. Background Technology

[0002] In recent years, 68 Ga, due to its superior nuclear properties—such as high positron emission tomography (89%, maximum energy 1899 keV, average energy 890 keV), suitable half-life (68 minutes), and easy labeling—has become a widely used medical isotope in positron emission tomography (PET). Various 68 Ga-labeled radiopharmaceuticals (such as Ga-labeled radiopharmaceuticals) 68 Ga-DOTA-TATE, 68 Ga-DOTA-TOC 68 Ga-PSMA-11, 68 Ga-FAPI-04 has shown significant value in early clinical imaging of various cancers. Furthermore, 68 Ga-labeled diagnostic drugs can be used with 177 Lu or 225 Ac-labeled therapeutic drugs used in combination (e.g.) 68 Ga-DOTATATE and 177 Lu-DOTATATE, 68 Ga-PSMA-617 and 225 Ac-PSMA-617 enables integrated diagnosis and treatment, allowing for simultaneous diagnosis and treatment in cancer management.

[0003] With the expansion of nuclear medicine applications, global attention has increased. 68 The demand for Ga is growing rapidly. Currently 68 Ga is mainly produced through cyclotrons. 68 Zn(p,n) 68 Ga is produced by reaction, or by 68 Ge- 68 Ga is obtained through a Ga generator. The column packing material of the generator has a crucial impact on its performance. Reported adsorbents include inorganic oxides such as Al2O3, SnO2, TiO2, ZrO2, CeO2, and Ta2O5, organic resins, nano-oxides, and inorganic-organic composite materials. Commercially available generator materials mainly include SnO2 from iThemba LABS, pyrogallol-modified SiO2 from ITG, and TiO2 from EZAG.

[0004] SiO2 has a porous structure, which is beneficial for exposing active sites. It also exhibits high chemical stability under strong acid and radiation conditions, with no metal ion dissolution, thus avoiding interference. 68Ga labeling. Its high specific surface area (500~1000 m² / g) and tunable pore size (2~50 nm) contribute to optimization. 68 Ge / 68 The adsorption and elution kinetics of Ga, along with its high mechanical strength, ensured the stability of the column bed. However, SiO2 itself... 68 Ge / 68 Ga lacks selectivity. Summary of the Invention

[0005] The purpose of this invention is to provide a core-shell material of silicon dioxide supported on cerium dioxide, its preparation method, and its application in Ge / Ga separation. CeO2 is modified onto the surface of mesoporous SiO2 to form a SiO2@CeO2 core-shell structure. The SiO2 core provides a rigid framework and radiation stability, while the CeO2 shell achieves… 68 Ge's efficient adsorption and 68 Effective elution of Ga.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: A method for preparing a silica-supported cerium dioxide core-shell material includes the following steps: Step 1: Prepare mesoporous SiO2; Dissolve 5-10 parts by weight of PEG-10000 in 50-100 parts by volume of 1 mol / L acetic acid solution, then add 20-50 parts by volume of tetramethyl orthosilicate (TMOS) and stir for 15-45 min to form a sol. In a sealed environment, the sol is gelled at a temperature of 30-50℃ for 36-48 hours to obtain a wet gel; the wet gel is then subjected to solvent exchange with ammonia for 6-12 hours, dried, and calcined at a temperature of 500-800℃ for 3-6 hours to obtain mesoporous SiO2. Step 2: Prepare SiO2@CeO2 core-shell material; The mesoporous SiO2 prepared in step 1 is dissolved in deionized water to form a mesoporous SiO2 dispersion aqueous solution; cerium nitrate hexahydrate is dissolved in deionized water to form a cerium nitrate hexahydrate aqueous solution; Under stirring, a mesoporous SiO2 dispersion aqueous solution was added to a cerium nitrate hexahydrate aqueous solution, followed by ammonia. The mixture was then precipitated by co-precipitation at a temperature of 80-100℃. After centrifugation, washing, and drying, SiO2@CeO2 core-shell material was obtained, wherein the mass ratio of SiO2 to CeO2 was 1:1-1.5.

[0007] This invention prepares a core-shell material possessing the excellent properties of both SiO2 and CeO2 using raw materials such as PEG-10000, tetramethyl orthosilicate, acetic acid, cerium nitrate hexahydrate, and ammonia. The SiO2 core provides a rigid framework and radiation stability, while the CeO2 shell achieves...68 Ge's efficient adsorption and 68 Effective elution of Ga.

[0008] This invention also provides a method for separating Ge / Ga, using SiO2@CeO2 core-shell material as the stationary phase and inorganic acid as the mobile phase, based on solid-phase extraction. 68 Ge / 68 Ga, thus proving that the SiO2@CeO2 core-shell material... 68 Ge- 68 Column packing for Ga generator. Attached Figure Description

[0009] Figure 1 This is a scanning electron microscope image of the silicon dioxide prepared in Example 1 of the present invention.

[0010] Figure 2 This is a scanning electron microscope image of the SiO2@CeO2 core-shell material prepared in Example 1 of the present invention.

[0011] Figure 3 This is a rinsing effect diagram of the SiO2@CeO2 core-shell material of the present invention.

[0012] Figure 4 This is a diagram showing the effect of SiO2 rinsing in this invention. Detailed Implementation

[0013] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments.

[0014] Example 1:

[0015] This embodiment provides a SiO2@CeO2 core-shell material, the preparation method of which includes the following steps: Step 1: Dissolve 8.86g of PEG-10000 in 75mL of 1mol / L acetic acid solution, and add 50mL of tetramethyl orthosilicate TMOS (Si(OCH3)4), and stir at high speed for 30min to form a sol; The sol was transferred to a polyethylene tube, sealed, and gelled at 30–50°C for 48 hours to form a wet gel. The wet gel was then subjected to solvent exchange with 0.05 mol / L ammonia (the concentration of ammonia affects the pore size of SiO2) for 10 hours. It was then dried at 30–50°C and calcined at 600°C for 5 hours at a heating rate of 8°C / min to obtain mesoporous SiO2. The scanning electron microscope image of the mesoporous SiO2 is shown below. Figure 1 As shown.

[0016] Step 2: Add 1.0 g of mesoporous SiO2 to 50 mL of deionized water to form a mesoporous SiO2 dispersion aqueous solution; dissolve 8 g of cerium nitrate hexahydrate in 50 mL of deionized water to form a cerium nitrate hexahydrate aqueous solution. Under high-speed stirring, the mesoporous SiO2 dispersion aqueous solution was added to a cerium nitrate hexahydrate aqueous solution, followed by 100-200 mL of ammonia solution with a concentration of 0.01-0.5 mol / L. The mixture was then co-precipitated at 80-100°C with high-speed stirring for 5-10 hours. After centrifugation and washing, the mixture was dried at 80-100°C for 12-24 hours, ground, and sieved to obtain the SiO2@CeO2 core-shell material. The scanning electron microscope image of SiO2@CeO2 is shown below. Figure 2 As shown, the mass ratio of SiO2 to CeO2 is 1:1~1.5.

[0017] Example 2:

[0018] This embodiment provides a method for separating Ge / Ga based on solid-phase extraction.

[0019] (1) The SiO2 prepared in step 1 of Example 1 and the SiO2@CeO2 core-shell material prepared in step 2 were respectively packed into an SPE column with a hydrophilic sieve plate by dry packing. A layer of glass fiber was laid on top, and the fine powder in the column was washed away by hydrochloric acid with a concentration of 0.01~0.10 mol / L.

[0020] (2) Prepare a stock solution with a pH=1 and a Ge / Ga concentration of 50ppm using a 1000ppm Ge / Ga standard solution.

[0021] (3) Take 0.5 mL of the stock solution with a concentration of 50 ppm and load it onto an SPE column packed with SiO2 and SiO2@CeO2 core-shell materials, respectively. Then, elute with 4.5 mL of 0.1 mol / L hydrochloric acid at a flow rate of 1 mL / min. Collect the eluent and determine the content of Ge and Ga ions in the eluent components using inductively coupled plasma atomic emission spectrometry to obtain the elution curves of Ge and Ga, as shown in the figure. Figure 3 and Figure 4 As shown, both the prepared SiO2 and SiO2@CeO2 exhibit excellent elution effects on Ga, and 90%-95% of Ga can be recovered within 1-1.5 mL of eluent. Furthermore, the prepared SiO2@CeO2 selectively adsorbs Ge, achieving the separation of Ge and Ga, while SiO2 shows no selectivity for Ge. Therefore, the SiO2@CeO2 core-shell material can be used as a material for separating Ge and Ga, thus representing a novel approach. 68 Ge- 68 Ga generator column packing.

[0022] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A method for preparing a core-shell material of cerium dioxide supported on silica, characterized in that, Includes the following steps: Step 1: Prepare mesoporous SiO2; Dissolve 5-10 parts by weight of PEG-10000 in 50-100 parts by volume of 1 mol / L acetic acid solution, then add 20-50 parts by volume of tetramethyl orthosilicate (TMOS) and stir for 15-45 min to form a sol. In a sealed environment, the sol is gelled at a temperature of 30-50℃ for 36-48 hours to obtain a wet gel; the wet gel is then subjected to solvent exchange with ammonia for 6-12 hours, dried, and calcined at a temperature of 500-800℃ for 3-6 hours to obtain mesoporous SiO2. Step 2: Prepare SiO2@CeO2 core-shell material; The mesoporous SiO2 prepared in step 1 is dissolved in deionized water to form a mesoporous SiO2 dispersion aqueous solution; cerium nitrate hexahydrate is dissolved in deionized water to form a cerium nitrate hexahydrate aqueous solution; While stirring, the mesoporous SiO2 dispersion aqueous solution was added to the cerium nitrate hexahydrate aqueous solution, and then ammonia was added. The mixture was then precipitated by co-precipitation at a temperature of 80~100℃. Centrifugation, washing, and drying were performed to obtain SiO2@CeO2 core-shell materials, wherein the mass ratio of SiO2 to CeO2 was 1:1~1.

5.

2. The method for preparing a silica-supported cerium dioxide core-shell material according to claim 1, characterized in that, The calcination temperature is increased to 500-800℃ at a rate of 5-10℃ / min.

3. The method for preparing a silica-supported cerium dioxide core-shell material according to claim 1, characterized in that, The concentration of the ammonia water is 0.01~0.5 mol / L.

4. A SiO2@CeO2 core-shell material prepared according to the method of claim 1, 2 or 3.

5. A method for separating Ge / Ga using the SiO2@CeO2 core-shell material as described in claim 4, characterized in that, Using SiO2@CeO2 core-shell material as the stationary phase and inorganic acid as the mobile phase, a solid-phase extraction method was used to separate... 68 Ge / 68 Ga.

6. The method for separating Ge / Ga from SiO2@CeO2 core-shell materials according to claim 5, characterized in that, Add 5-15 parts by weight of SiO2@CeO2 core-shell material into an SPE column with a hydrophilic sieve plate, and then lay a layer of glass fiber; elute with an inorganic acid with a concentration of 0.01-0.10 mol / L; containing 68 Ge / 68 The Ga solution was loaded onto the column and eluted with 0.01~0.10 mol / L inorganic acid.

7. The method for separating Ge / Ga from SiO2@CeO2 core-shell materials according to claim 6, characterized in that, The inorganic acid used is hydrochloric acid.

8. A kind 68 Ge- 68 Ga generator, the 68 Ge- 68 The column packing material of the Ga generator is SiO2@CeO2 core-shell material as described in claim 3.

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