Rhenium dioxide nanoparticle dispersion and electron beam irradiation preparation method thereof
Patent Information
- Application Number
- CN202611465833.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-09-20
- Publication Date
- 2026-10-27
AI Technical Summary
[0003]本发明的目的是提供一种二氧化铼纳米颗粒分散液的电子束辐照制备方法，解决了现有技术中存在的由高铼酸铵制备二氧化铼时，生成的纳米颗粒容易继续长大和团聚，难以获得粒径和形貌均一的二氧化铼纳米颗粒的问题
（1）本发明在电子束辐照前将聚乙烯吡咯烷酮与高铼酸铵和甲酸钠混合，利用聚乙烯吡咯烷酮调控二氧化铼纳米颗粒的成核和生长，抑制颗粒过度长大和团聚，能够生成粒径和形貌均一的二氧化铼纳米颗粒，同时本发明生成的二氧化铼纳米颗粒不经分离和干燥而保留在水相中，产品形态为二氧化铼纳米颗粒分散液。
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of metal nanomaterial preparation technology, and relates to a rhenium dioxide nanoparticle dispersion. This invention also relates to an electron beam irradiation preparation method of the above-mentioned rhenium dioxide nanoparticle dispersion. Background Technology
[0002] Rhenium is a rare, high-melting-point metal, primarily found as a byproduct of molybdenum ore, and is a crucial component in high-temperature alloys for aero-engines and petroleum reforming catalysts. In molybdenum smelting and rhenium recovery, rhenium is typically obtained as ammonium perperurate after enrichment and crystallization. Rhenium dioxide is an important low-valence oxide of rhenium. When rhenium dioxide is prepared by reduction from ammonium perperurate, the resulting nanoparticles tend to continue growing and agglomerating, making it difficult to obtain rhenium dioxide nanoparticles with uniform particle size and morphology. Ionizing radiation can initiate reduction reactions in a room-temperature liquid phase, providing a new technical route for the preparation of rhenium dioxide from ammonium perperurate. However, existing methods lack effective control over particle nucleation and growth; therefore, a preparation method is needed that can generate rhenium dioxide nanoparticles with uniform particle size and morphology, and ensure that the resulting nanoparticles exist in a dispersion form. Summary of the Invention
[0003] The purpose of this invention is to provide an electron beam irradiation preparation method for rhenium dioxide nanoparticle dispersions, which solves the problem in the prior art that when rhenium dioxide is prepared from ammonium perperurate, the generated nanoparticles tend to continue to grow and agglomerate, making it difficult to obtain rhenium dioxide nanoparticles with uniform particle size and morphology.
[0004] Another object of the present invention is to provide a rhenium dioxide nanoparticle dispersion.
[0005] The technical solution adopted in this invention is an electron beam irradiation preparation method for rhenium dioxide nanoparticle dispersions, which is implemented according to the following steps: Step 1: Prepare the mixture; Step 2: Deoxygenate the mixed aqueous solution with nitrogen; Step 3: Electron beam irradiation to obtain rhenium dioxide nanoparticle dispersion.
[0006] The invention is further characterized by: Step 1 is as follows: using water as the dispersion medium and the water temperature is 10~30℃, add ammonium perrhenate, polyvinylpyrrolidone and sodium formate to water and mix evenly to prepare a mixed aqueous solution.
[0007] The concentration of ammonium perrhenate is 1~20 g / L.
[0008] The concentration of polyvinylpyrrolidone is 1~10 g / L.
[0009] The concentration of sodium formate is 0.1~0.5 mol / L.
[0010] Step 2 specifically involves: introducing nitrogen gas into the mixed aqueous solution for 5-30 minutes to obtain a deoxygenated mixed aqueous solution.
[0011] Step 3 specifically involves irradiating the deoxygenated mixed aqueous solution with an electron accelerator to obtain a rhenium dioxide nanoparticle dispersion.
[0012] The electron beam energy of the electron accelerator is 1.5~20MeV.
[0013] The cumulative absorbed dose from irradiation of the deoxygenated mixed aqueous solution is 30~250 kGy.
[0014] Another technical solution adopted in this invention is a rhenium dioxide nanoparticle dispersion, which is prepared by an electron beam irradiation method for preparing rhenium dioxide nanoparticle dispersion.
[0015] The beneficial effects of this invention are: (1) In this invention, polyvinylpyrrolidone is mixed with ammonium perrhenate and sodium formate before electron beam irradiation. Polyvinylpyrrolidone is used to regulate the nucleation and growth of rhenium dioxide nanoparticles, inhibiting excessive particle growth and aggregation, and generating rhenium dioxide nanoparticles with uniform particle size and morphology. At the same time, the rhenium dioxide nanoparticles generated by this invention are retained in the aqueous phase without separation and drying, and the product form is a rhenium dioxide nanoparticle dispersion.
[0016] (2) The present invention uses an aqueous electron beam irradiation method, which does not require high temperature calcination and high pressure reaction. The reaction conditions are mild and the preparation process is simple. Attached Figure Description
[0017] Figure 1 This is a TEM image with a scale bar of 100 nm of the rhenium dioxide nanoparticle dispersion obtained with a cumulative absorbed dose of 150 kGy in Example 3 of the present invention. Figure 2 This is a TEM image with a scale bar of 50 nm of the rhenium dioxide nanoparticle dispersion obtained with a cumulative absorbed dose of 150 kGy in Example 3 of the present invention. Figure 3 This is a DLS number and particle size distribution diagram of the rhenium dioxide nanoparticle dispersion obtained with a cumulative absorbed dose of 150 kGy in Example 3 of the present invention. Detailed Implementation
[0018] The following detailed description is provided in conjunction with specific implementation methods.
[0019] The electron beam irradiation preparation method for rhenium dioxide nanoparticle dispersions is carried out according to the following steps: Step 1: Prepare the mixture.
[0020] Using water as the dispersion medium and at a water temperature of 10-30℃, ammonium perrhenate, polyvinylpyrrolidone, and sodium formate are added to water and mixed evenly to prepare a mixed aqueous solution with an ammonium perrhenate concentration of 1-20 g / L, a polyvinylpyrrolidone concentration of 1-10 g / L, and a sodium formate concentration of 0.1-0.5 mol / L.
[0021] Polyvinylpyrrolidone was mixed with ammonium perrhenate and sodium formate before electron beam irradiation to regulate the nucleation and growth of rhenium dioxide nanoparticles and inhibit excessive particle growth and aggregation.
[0022] Step 2: Deoxygenate the mixed aqueous solution with nitrogen.
[0023] Nitrogen gas is introduced into the mixed aqueous solution for 5-30 minutes to obtain a deoxygenated mixed aqueous solution.
[0024] Step 3: Electron beam irradiation to obtain rhenium dioxide nanoparticle dispersion.
[0025] An electron accelerator with an electron beam energy of 1.5~20MeV was used to irradiate the deoxygenated mixed aqueous solution with a cumulative absorbed dose of 30~250kGy, resulting in a black rhenium dioxide nanoparticle dispersion with no visible solid precipitate.
[0026] In step 3, perrhenate is reduced by electron beam irradiation with the participation of sodium formate, and rhenium dioxide nanoparticles with uniform particle size and morphology are formed under the regulation of polyvinylpyrrolidone, finally obtaining a rhenium dioxide nanoparticle dispersion.
[0027] Rhenium dioxide nanoparticle dispersion was prepared using an electron beam irradiation method for preparing rhenium dioxide nanoparticle dispersion.
[0028] Example 1 The electron beam irradiation preparation method for rhenium dioxide nanoparticle dispersions is carried out according to the following steps: Step 1: Prepare the mixture.
[0029] Using water as the dispersion medium and at a water temperature of 25°C, ammonium perrhenate, polyvinylpyrrolidone, and sodium formate were added to water and mixed thoroughly to prepare a mixed aqueous solution with an ammonium perrhenate concentration of 20 g / L, a polyvinylpyrrolidone concentration of 5 g / L, and a sodium formate concentration of 0.3 mol / L.
[0030] Polyvinylpyrrolidone was mixed with ammonium perrhenate and sodium formate before electron beam irradiation to regulate the nucleation and growth of rhenium dioxide nanoparticles and inhibit excessive particle growth and aggregation.
[0031] Step 2: Deoxygenate the mixed aqueous solution with nitrogen.
[0032] Nitrogen gas was introduced into the mixed aqueous solution for 15 minutes to obtain a deoxygenated mixed aqueous solution.
[0033] Step 3: Electron beam irradiation to obtain rhenium dioxide nanoparticle dispersion.
[0034] The deoxygenated mixed aqueous solution was irradiated using an electron accelerator with an electron beam energy of 5 MeV, with a cumulative absorbed dose of 50 kGy, to obtain a black rhenium dioxide nanoparticle dispersion with no visible solid precipitate. The macroscopic state of the sample was recorded.
[0035] In step 3, perrhenate is reduced by electron beam irradiation with the participation of sodium formate, and rhenium dioxide nanoparticles with uniform particle size and morphology are formed under the regulation of polyvinylpyrrolidone, finally obtaining a rhenium dioxide nanoparticle dispersion.
[0036] Example 2 The electron beam irradiation preparation method for rhenium dioxide nanoparticle dispersions is carried out according to the following steps: Step 1: Prepare the mixture.
[0037] Using water as the dispersion medium and at a water temperature of 25°C, ammonium perrhenate, polyvinylpyrrolidone, and sodium formate were added to water and mixed thoroughly to prepare a mixed aqueous solution with an ammonium perrhenate concentration of 20 g / L, a polyvinylpyrrolidone concentration of 5 g / L, and a sodium formate concentration of 0.3 mol / L.
[0038] Polyvinylpyrrolidone was mixed with ammonium perrhenate and sodium formate before electron beam irradiation to regulate the nucleation and growth of rhenium dioxide nanoparticles and inhibit excessive particle growth and aggregation.
[0039] Step 2: Deoxygenate the mixed aqueous solution with nitrogen.
[0040] Nitrogen gas was introduced into the mixed aqueous solution for 15 minutes to obtain a deoxygenated mixed aqueous solution.
[0041] Step 3: Electron beam irradiation to obtain rhenium dioxide nanoparticle dispersion.
[0042] The deoxygenated mixed aqueous solution was irradiated using an electron accelerator with an electron beam energy of 5 MeV, with a cumulative absorbed dose of 100 kGy, to obtain a black rhenium dioxide nanoparticle dispersion with no visible solid precipitate. The macroscopic state of the sample was recorded.
[0043] In step 3, perrhenate is reduced by electron beam irradiation with the participation of sodium formate, and rhenium dioxide nanoparticles with uniform particle size and morphology are formed under the regulation of polyvinylpyrrolidone, finally obtaining a rhenium dioxide nanoparticle dispersion.
[0044] Example 3 The electron beam irradiation preparation method for rhenium dioxide nanoparticle dispersions is carried out according to the following steps: Step 1: Prepare the mixture.
[0045] Using water as the dispersion medium and at a water temperature of 25°C, ammonium perrhenate, polyvinylpyrrolidone, and sodium formate were added to water and mixed thoroughly to prepare a mixed aqueous solution with an ammonium perrhenate concentration of 20 g / L, a polyvinylpyrrolidone concentration of 5 g / L, and a sodium formate concentration of 0.3 mol / L.
[0046] Polyvinylpyrrolidone was mixed with ammonium perrhenate and sodium formate before electron beam irradiation to regulate the nucleation and growth of rhenium dioxide nanoparticles and inhibit excessive particle growth and aggregation.
[0047] Step 2: Deoxygenate the mixed aqueous solution with nitrogen.
[0048] Nitrogen gas was introduced into the mixed aqueous solution for 15 minutes to obtain a deoxygenated mixed aqueous solution.
[0049] Step 3: Electron beam irradiation to obtain rhenium dioxide nanoparticle dispersion.
[0050] The deoxygenated mixed aqueous solution was irradiated using an electron accelerator with an electron beam energy of 5 MeV, with a cumulative absorbed dose of 150 kGy, to obtain a black rhenium dioxide nanoparticle dispersion with no visible solid precipitate. The macroscopic state of the sample was recorded.
[0051] In step 3, perrhenate is reduced by electron beam irradiation with the participation of sodium formate, and rhenium dioxide nanoparticles with uniform particle size and morphology are formed under the regulation of polyvinylpyrrolidone, finally obtaining a rhenium dioxide nanoparticle dispersion.
[0052] like Figure 1 As shown, TEM observation of the rhenium dioxide nanoparticle dispersion obtained in Example 3, with a scale bar of 100 nm, reveals a large-scale particle distribution in the field of view. It is evident that the rhenium dioxide nanoparticles do not exhibit large-area severe aggregation on a macroscopic scale, demonstrating good overall dispersion. Figure 2 As shown, TEM observation of the rhenium dioxide nanoparticle dispersion obtained in Example 3 was performed with a scale bar of 50 nm. A large number of nanoscale particles were observed in the field of view. The particles were generally nearly spherical or quasi-spherical, with small differences in particle size. The particle size and morphology were consistent across multiple fields of view, and no morphology dominated by large precipitates was observed. This result indicates that rhenium dioxide nanoparticles with relatively uniform particle size and morphology can be generated in an aqueous phase when polyvinylpyrrolidone is present and the irradiation conditions of this invention are used.
[0053] Using water as the dispersion medium, the rhenium dioxide nanoparticle dispersion obtained in Example 3 was subjected to DLS testing at a water temperature of 25.0℃. The results are as follows: Figure 3 As shown, the DLS number distribution exhibits a single main peak at 4.440 nm, representing 100.0% of the total number of particles, with a peak width of 1.193 nm, indicating a relatively concentrated distribution of nanoparticles in terms of both number and size. The test also yielded a Z-Average of 530.3 nm, a PDI of 0.562, and an intercept of 0.943. Since the Z-Average of DLS is sensitive to a small number of large-sized scatterers, dynamic association between particles, and the PVP hydration layer, it reflects the apparent hydrodynamic scale in the liquid phase and cannot be directly equated to the size of inorganic primary particles observed by TEM. Therefore, in Example 3, TEM was used to evaluate the size and morphology of primary particles, while the DLS number distribution was used to assist in evaluating the particle size distribution. The absence of macroscopic precipitation indicates that the product obtained during the test was a dispersion.
[0054] In summary, this invention utilizes a synergistic formulation of ammonium perrhenate, sodium formate, and polyvinylpyrrolidone, along with nitrogen deoxygenation and fractionated electron beam irradiation, to generate rhenium dioxide nanoparticles with relatively uniform particle size and morphology in an aqueous phase, resulting in a rhenium dioxide nanoparticle dispersion. The experimental phenomena observed in Examples 1-3 and their corresponding parallel samples are consistent, and TEM and DLS characterization results jointly support the aforementioned technical effects.
[0055] Example 4 The electron beam irradiation preparation method for rhenium dioxide nanoparticle dispersions is carried out according to the following steps: Step 1: Prepare the mixture.
[0056] Using water as the dispersion medium and at a water temperature of 10℃, ammonium perrhenate, polyvinylpyrrolidone, and sodium formate were added to water and mixed evenly to prepare a mixed aqueous solution with an ammonium perrhenate concentration of 1 g / L, a polyvinylpyrrolidone concentration of 1 g / L, and a sodium formate concentration of 0.1 mol / L.
[0057] Polyvinylpyrrolidone was mixed with ammonium perrhenate and sodium formate before electron beam irradiation to regulate the nucleation and growth of rhenium dioxide nanoparticles and inhibit excessive particle growth and aggregation.
[0058] Step 2: Deoxygenate the mixed aqueous solution with nitrogen.
[0059] Nitrogen gas was introduced into the mixed aqueous solution for 5 minutes to obtain a deoxygenated mixed aqueous solution.
[0060] Step 3: Electron beam irradiation to obtain rhenium dioxide nanoparticle dispersion.
[0061] The deoxygenated mixed aqueous solution was irradiated with an electron accelerator with an electron beam energy of 1.5 MeV, and the cumulative absorbed dose was 30 kGy, resulting in a black rhenium dioxide nanoparticle dispersion with no visible solid precipitate.
[0062] In step 3, perrhenate is reduced by electron beam irradiation with the participation of sodium formate, and rhenium dioxide nanoparticles with uniform particle size and morphology are formed under the regulation of polyvinylpyrrolidone, finally obtaining a rhenium dioxide nanoparticle dispersion.
[0063] Example 5 The electron beam irradiation preparation method for rhenium dioxide nanoparticle dispersions is carried out according to the following steps: Step 1: Prepare the mixture.
[0064] Using water as the dispersion medium and at a water temperature of 30℃, ammonium perrhenate, polyvinylpyrrolidone, and sodium formate were added to water and mixed evenly to prepare a mixed aqueous solution with an ammonium perrhenate concentration of 20 g / L, a polyvinylpyrrolidone concentration of 10 g / L, and a sodium formate concentration of 0.5 mol / L.
[0065] Polyvinylpyrrolidone was mixed with ammonium perrhenate and sodium formate before electron beam irradiation to regulate the nucleation and growth of rhenium dioxide nanoparticles and inhibit excessive particle growth and aggregation.
[0066] Step 2: Deoxygenate the mixed aqueous solution with nitrogen.
[0067] Nitrogen gas was introduced into the mixed aqueous solution for 30 minutes to obtain a deoxygenated mixed aqueous solution.
[0068] Step 3: Electron beam irradiation to obtain rhenium dioxide nanoparticle dispersion.
[0069] The deoxygenated mixed aqueous solution was irradiated with an electron accelerator with an electron beam energy of 20 MeV, and the cumulative absorbed dose was 250 kGy, resulting in a black rhenium dioxide nanoparticle dispersion with no visible solid precipitate.
[0070] In step 3, perrhenate is reduced by electron beam irradiation with the participation of sodium formate, and rhenium dioxide nanoparticles with uniform particle size and morphology are formed under the regulation of polyvinylpyrrolidone, finally obtaining a rhenium dioxide nanoparticle dispersion.
[0071] Example 6 The electron beam irradiation preparation method for rhenium dioxide nanoparticle dispersions is carried out according to the following steps: Step 1: Prepare the mixture.
[0072] Using water as the dispersion medium and at a water temperature of 20°C, ammonium perrhenate, polyvinylpyrrolidone, and sodium formate were added to water and mixed thoroughly to prepare a mixed aqueous solution with an ammonium perrhenate concentration of 10 g / L, a polyvinylpyrrolidone concentration of 5 g / L, and a sodium formate concentration of 0.25 mol / L.
[0073] Polyvinylpyrrolidone was mixed with ammonium perrhenate and sodium formate before electron beam irradiation to regulate the nucleation and growth of rhenium dioxide nanoparticles and inhibit excessive particle growth and aggregation.
[0074] Step 2: Deoxygenate the mixed aqueous solution with nitrogen.
[0075] Nitrogen gas was introduced into the mixed aqueous solution for 15 minutes to obtain a deoxygenated mixed aqueous solution.
[0076] Step 3: Electron beam irradiation to obtain rhenium dioxide nanoparticle dispersion.
[0077] The deoxygenated mixed aqueous solution was irradiated with an electron accelerator with an electron beam energy of 10 MeV, and the cumulative absorbed dose was 200 kGy, resulting in a black rhenium dioxide nanoparticle dispersion with no visible solid precipitate.
[0078] In step 3, perrhenate is reduced by electron beam irradiation with the participation of sodium formate, and rhenium dioxide nanoparticles with uniform particle size and morphology are formed under the regulation of polyvinylpyrrolidone, finally obtaining a rhenium dioxide nanoparticle dispersion.
[0079] Comparative Example 1 The preparation of rhenium dioxide nanoparticle dispersion is carried out according to the following steps: Step 1: Prepare the mixture.
[0080] Using water as the dispersion medium, ammonium perrhenate, polyvinylpyrrolidone, and sodium formate were added to water and mixed evenly to prepare a mixed aqueous solution with an ammonium perrhenate concentration of 20 g / L, a polyvinylpyrrolidone concentration of 5 g / L, and a sodium formate concentration of 0.3 mol / L.
[0081] Polyvinylpyrrolidone was mixed with ammonium perrhenate and sodium formate before electron beam irradiation to regulate the nucleation and growth of rhenium dioxide nanoparticles and inhibit excessive particle growth and aggregation.
[0082] Step 2: Deoxygenate the mixed aqueous solution with nitrogen.
[0083] Nitrogen gas was bubbled into the mixed aqueous solution for 15 minutes to obtain a deoxygenated mixed aqueous solution. A rhenium dioxide nanoparticle dispersion was obtained, and the macroscopic state of the sample was recorded.
[0084] Comparing the macroscopic states of the samples from Examples 1-3 and Comparative Example 1, it was found that the unirradiated rhenium dioxide nanoparticle dispersion of Comparative Example 1 was clear and transparent with no solid precipitate; the rhenium dioxide nanoparticle dispersion of Example 1 with a cumulative absorbed dose of 50 kGy changed from transparent to black with no solid precipitate; the rhenium dioxide nanoparticle dispersion of Example 2 with a cumulative absorbed dose of 100 kGy showed no significant further change compared to the rhenium dioxide nanoparticle dispersion of Example 1 with a cumulative absorbed dose of 50 kGy, and had no solid precipitate; the rhenium dioxide nanoparticle dispersion of Example 3 with a cumulative absorbed dose of 150 kGy showed no significant further change compared to the rhenium dioxide nanoparticle dispersion of Example 2 with a cumulative absorbed dose of 100 kGy, and had no solid precipitate.
[0085] Repeat Examples 1-3 to obtain parallel samples of Examples 1-3 respectively, and record the macroscopic state of the samples respectively. It was found that the parallel samples had the same phenomena as the samples of Examples 1-3 at each dose node, and there was no visible solid precipitation. This shows that the electron beam irradiation preparation method of rhenium dioxide nanoparticle dispersion of the present invention is reproducible.
Claims
1. A method for preparing rhenium dioxide nanoparticle dispersions by electron beam irradiation, characterized in that, The specific steps are as follows: Step 1: Prepare the mixture; Step 2: Deoxygenate the mixed aqueous solution with nitrogen; Step 3: Electron beam irradiation to obtain rhenium dioxide nanoparticle dispersion.
2. The method for preparing rhenium dioxide nanoparticle dispersion by electron beam irradiation according to claim 1, characterized in that, Step 1 specifically involves: using water as the dispersion medium, with a water temperature of 10~30℃, adding ammonium perrhenate, polyvinylpyrrolidone and sodium formate to water and mixing them evenly to prepare a mixed aqueous solution.
3. The method for preparing rhenium dioxide nanoparticle dispersion by electron beam irradiation according to claim 2, characterized in that, The concentration of ammonium perrhenate is 1~20 g / L.
4. The method for preparing rhenium dioxide nanoparticle dispersion by electron beam irradiation according to claim 2, characterized in that, The concentration of the polyvinylpyrrolidone is 1~10 g / L.
5. The method for preparing rhenium dioxide nanoparticle dispersion by electron beam irradiation according to claim 2, characterized in that, The concentration of sodium formate is 0.1~0.5 mol / L.
6. The method for preparing rhenium dioxide nanoparticle dispersion by electron beam irradiation according to claim 1, characterized in that, Step 2 specifically involves: introducing nitrogen gas into the mixed aqueous solution for 5-30 minutes to obtain a deoxygenated mixed aqueous solution.
7. The method for preparing rhenium dioxide nanoparticle dispersion by electron beam irradiation according to claim 1, characterized in that, Step 3 specifically involves irradiating the deoxygenated mixed aqueous solution with an electron accelerator to obtain a rhenium dioxide nanoparticle dispersion.
8. The method for preparing rhenium dioxide nanoparticle dispersion by electron beam irradiation according to claim 7, characterized in that, The electron beam energy of the electron accelerator is 1.5~20MeV.
9. The method for preparing rhenium dioxide nanoparticle dispersion by electron beam irradiation according to claim 7, characterized in that, The cumulative absorbed dose of the deoxygenated mixed aqueous solution is 30~250 kGy.
10. A rhenium dioxide nanoparticle dispersion, characterized in that, It was prepared using the electron beam irradiation method for preparing rhenium dioxide nanoparticle dispersion as described in any one of claims 1-9.