Metal-carbon framework nano / microparticles and methods of making the same

Abstract

The application provides a metal-carbon skeleton nano-microparticle and a preparation method thereof, and belongs to the field of nanometer material preparation, wherein the metal-carbon skeleton nano-microparticle is prepared from raw materials through a solvothermal reaction; the raw materials comprise, in percentage by mass, 3-15% of polymerizable monomers, 0.05-1.5% of initiators, 0.01-1.5% of metal salts and the balance of solvents; the active functional groups of the polymerizable monomers comprise nitrogen and / or oxygen; and the metal salts comprise at least one of aluminum salts, zirconium salts, chromium salts and zinc salts. The application uses metal ions and organic precursors containing active groups as raw materials, realizes controllable adjustment of the particle size of the nano-microparticles in the range of 1-5000 nanometers through metal crosslinking, induced nucleation and in-situ carbonization processes. The preparation process of the application is simple and controllable, the obtained nano-microparticles are uniform in size, stable in structure, high in temperature resistance and salt resistance, and can be widely applied in the fields of catalysis, sensing or oil displacement.

Description

Technical Field

[0001] This invention relates to the field of nanomaterial preparation technology, specifically to a metal-carbon framework structure of nano / micro particles and its preparation method. Background Technology

[0002] Carbonized polymer dots (CPDs) are a class of novel fluorescent or functional carbon nanomaterials formed by the thermal carbonization of cross-linked polymer networks. Due to their advantages such as strong structural designability, abundant surface functional groups, good biocompatibility, and ease of large-scale preparation, they show broad application prospects in fields such as bioimaging, photocatalysis, electrocatalysis, sensing, and energy storage.

[0003] Currently, the synthesis methods for carbon nanoparticles are mainly divided into two major strategies: top-down and bottom-up. Top-down methods often involve cutting large carbon sources, which suffers from problems such as uneven product size and difficulty in precisely controlling the structure. Bottom-up methods, especially hydrothermal / solvothermal methods, have become the mainstream technology for preparing carbon nanoparticles due to their simplicity, mild reaction conditions, and ease of large-scale production. In bottom-up synthesis, precursors typically undergo polymerization, cross-linking, dehydration, and carbonization to form carbon nanoparticles. Some products, retaining the hybrid characteristics of polymer structure and carbon core, exhibit advantages combining the photoelectric properties of quantum dots and polymer properties, further expanding their application scenarios.

[0004] In existing technologies, CPDs are generally small in size, with most reported product particle sizes concentrated in the range of 2–20 nanometers. This small size characteristic endows CPDs with a large specific surface area, good water solubility, and excellent permeability, giving them significant advantages in fields such as bioimaging, photocatalysis, and sensing. However, in oilfield profile control and displacement operations, the functional particles must have sufficient size to effectively block high-permeability channels. CPDs that are too small are prone to rapid penetration of the porous medium with injected water, making it difficult to remain at the target formation, resulting in low blocking efficiency, small swept volume, and inability to exert an effective profile control effect. Therefore, how to overcome the size limit of CPDs while maintaining good dispersibility has become a pressing technical challenge in this field. Summary of the Invention

[0005] In view of the technical problems existing in the background art, the present invention provides a metal-carbon framework structure of nano-micro particles and its preparation method, aiming to solve the technical problems of the difficulty in breaking through the size of existing CPDs, the easy degradation of traditional polymer microspheres in high temperature and high salt environment, and insufficient strength.

[0006] In a first aspect, the present invention provides nano-micro particles with a metal-carbon framework structure, which are prepared from raw materials by a solvothermal reaction. The raw materials for preparation include the following components by mass percentage: 3%~15% polymerizable monomer, 0.05%~1.5% initiator, 0.01%~1.5% metal salt, and the balance solvent; The active functional groups of polymerizable monomers include nitrogen and / or oxygen; Metal salts include at least one of aluminum salts, zirconium salts, chromium salts, and zinc salts.

[0007] Preferably, the particle size of the metal-carbon framework nanoparticles is 1 to 5000 nanometers.

[0008] Preferably, the polymerizable monomers include at least one of acrylamide (AM), N,N-dimethylacrylamide (DMAA), 2-acrylamido-2-methylpropanesulfonic acid (AMPS), sodium p-styrenesulfonate, and acrylic acid.

[0009] Preferably, the initiator includes at least one of azobisisobutyronitrile (AIBN), ammonium persulfate (APS), azobisisobutyramazolinium hydrochloride (VA-044), and azobisisobutyramidine hydrochloride (V-50).

[0010] Preferably, the aluminum salt includes at least one of aluminum nitrate, aluminum chloride, and aluminum sulfate; the zirconium salt includes at least one of zirconium nitrate, zirconium oxychloride, and zirconium tetrachloride; the chromium salt includes at least one of potassium dichromate, potassium chromate, and chromium chloride; and the zinc salt includes at least one of zinc chloride, zinc oxide, and zinc sulfate.

[0011] Preferably, the solvent includes deionized water.

[0012] Preferably, the temperature of the solvothermal reaction is 120~250℃; the time of the solvothermal reaction is 8~16h.

[0013] Secondly, embodiments of the present invention provide a method for preparing nano- and micro-sized particles with a metal-carbon framework structure, comprising the following steps: S1. Mix the polymerizable monomer, initiator, metal salt and solvent evenly to obtain a precursor solution; S2. Place the precursor solution in a closed reactor and carry out a solvothermal reaction at 120~250℃; S3. After the reaction is complete, the reaction solution is cooled to room temperature, and after dialysis and drying, nano- and micron-sized particles with a metal-carbon framework structure are obtained.

[0014] Preferably, the dialysis treatment specifically involves dialyzing the reaction solution through a 3500~8000Da dialysis bag for 24~48 hours.

[0015] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) By introducing specific types and concentrations of metal salts into the precursor system, this invention not only avoids system instability but also synergistically regulates the entire process of crosslinking-nucleation-carbonization, successfully preparing nano-micro particles with controllable particle size in the range of 1-5000 nanometers, good monodispersity, and high metal dispersion. (2) The metal-organic coordination bonds in the nano-micro particles prepared by the present invention enhance the internal structural stability of the particles, making them resistant to temperature and salt, and expanding their application in the field of oilfield flooding. (3) The preparation process of this invention is based on the improvement of the traditional hydrothermal method, which does not require complex equipment, has controllable cost, and is easy to scale up industrially. Attached Figure Description

[0016] Figure 1 Metallographic micrograph of the metal-carbon framework nanoparticles obtained in Example 2 of this invention; Figure 2 The particle size distribution diagrams are shown for the nano- and micro-sized particles obtained in Examples 1-3 and Comparative Example 1 of this invention. Figure 3 This describes the dispersion phenomenon of nano- and micro-sized particles obtained in Example 1 of the present invention in mineralized water with different mineralization degrees. Figure 4 The nano-micro particles prepared in Example 1 of the present invention are aged for 3 days in mineralized water with different mineralization degrees and at 110°C. Figure 5 The dispersion phenomenon of nano- and micro-particles prepared in Comparative Example 1 in mineralized water with different mineralization degrees is shown. Detailed Implementation

[0017] The embodiments of the technical solution of the present invention will now be described in detail with reference to the accompanying drawings. These embodiments are merely illustrative of the technical solution of the present invention and are therefore intended to limit the scope of protection of the present invention.

[0018] To address the technical challenges of existing CPDs (Chemical Polymer Devices) in terms of size, the susceptibility of traditional polymer microspheres to degradation under high temperature and high salt conditions, and insufficient strength, this invention provides a metal-carbon framework structure of nano-micro particles and its preparation method. The particle size can be controllably adjusted within the range of 1-5000 nanometers by introducing metal salts, and precursor nucleation and carbonization are induced by metal ion crosslinking. This allows for the controllable synthesis of nano-micro particles with specific sizes, structures, and a dual metal-carbon framework, expanding their application scenarios.

[0019] In a first aspect, embodiments of the present invention provide nano-micro particles with a metal-carbon framework structure, which are prepared from raw materials through a solvothermal reaction; The raw materials for preparation include the following components by mass percentage: 3%~15% polymerizable monomer, 0.05%~1.5% initiator, 0.01%~1.5% metal salt, and the balance solvent; The active functional groups of polymerizable monomers include nitrogen and / or oxygen; Metal salts include at least one of aluminum salts, zirconium salts, chromium salts, and zinc salts.

[0020] In the technical solution of this invention, nano- and micro-sized particles with a metal-carbon framework structure are formed through a cross-linking induced nucleation and carbonization (CINC) mechanism. Metal ions act as key cross-linking agents, phase separation promoters, and structural stabilizers, coordinating with polymer chains to form a three-dimensional network. This network enhances the thermodynamic stability and kinetic rigidity of the hydrophobic microregions in the system, driving the formation of submicron to micron-sized primary aggregates, which are then transformed into structurally stable final products during subsequent carbonization. The multivalent metal ions, including aluminum, zirconium, chromium, and zinc salts, not only achieve efficient cross-linking through strong coordination capabilities but also synergistically regulate the reaction during carbonization, enhancing the product's temperature and salt resistance stability. This approach balances cost and process adaptability, matching the mechanism and performance requirements of this invention.

[0021] Furthermore, in some embodiments, the particle size of the metal-carbon framework nanoparticles is 1 to 5000 nanometers.

[0022] Furthermore, in some embodiments, the polymerizable monomers include at least one selected from acrylamide (AM), N,N-dimethylacrylamide (DMAA), 2-acrylamido-2-methylpropanesulfonic acid (AMPS), sodium p-styrenesulfonate, and acrylic acid.

[0023] Furthermore, in some embodiments, the initiator includes at least one of azobisisobutyronitrile (AIBN), ammonium persulfate (APS), azobisisobutyramazolinium hydrochloride (VA-044), and azobisisobutyramidine hydrochloride (V-50).

[0024] Furthermore, in some embodiments, the aluminum salt includes at least one of aluminum nitrate, aluminum chloride, and aluminum sulfate; the zirconium salt includes at least one of zirconium nitrate, zirconium oxychloride, and zirconium tetrachloride; the chromium salt includes at least one of potassium dichromate, potassium chromate, and chromium chloride; and the zinc salt includes at least one of zinc chloride, zinc oxide, and zinc sulfate.

[0025] Furthermore, in some embodiments, the solvent includes deionized water.

[0026] Furthermore, in some embodiments, the temperature of the solvothermal reaction is 120~250°C; the time of the solvothermal reaction is 8~16h.

[0027] Secondly, embodiments of the present invention provide a method for preparing nano- and micro-sized particles with a metal-carbon framework structure, comprising the following steps: S1. Mix the polymerizable monomer, initiator, metal salt and solvent evenly to obtain a precursor solution; S2. Place the precursor solution in a closed reactor and carry out a solvothermal reaction at 120~250℃; S3. After the reaction is complete, the reaction solution is cooled to room temperature, and after dialysis and drying, nano- and micron-sized particles with a metal-carbon framework structure are obtained.

[0028] Furthermore, in some embodiments, the dialysis treatment specifically involves dialyzing the reaction solution through a 3500~8000Da dialysis bag for 24~48 hours.

[0029] The key mechanism of this invention lies in the fact that the introduced metal ions coordinate with the nitrogen- and oxygen-containing functional groups on the polymer chain in the early stage of polymerization, forming a "metal-organic hybrid crosslinking network". This network not only increases the local crosslinking density, but more importantly, the strong hydration of the metal ions significantly reduces the effective polarity of the surrounding area, thereby amplifying the hydrophobic interactions and promoting the expansion of the microphase separation scale from the nanometer scale to the submicrometer or even the micrometer scale.

[0030] The following are some specific embodiments. It should be noted that the embodiments described below are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention. Where specific techniques or conditions are not specified in the embodiments, they shall be performed in accordance with the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments used, unless otherwise specified, are all conventional products that can be obtained commercially.

[0031] Example 1 A method for preparing nano- and micro-sized particles with a metal-carbon framework structure, the specific steps of which are as follows: (1) Dissolve acrylamide (AM, 270 mg), N,N-dimethylacrylamide (DMAA, 30 mg), aluminum salt (AlCl3, 5 mg) and azobisisobutyronitrile (AIBN, 10 mg) in 10 mL of deionized water and sonicate until completely dissolved; (2) The solution was transferred to a 25 mL polytetrafluoroethylene-lined stainless steel reactor and reacted at 200 °C for 10 h. After the reaction was completed, the reactor was naturally cooled to room temperature. The product was dialyzed through a 3500 Da dialysis bag for 48 h to obtain a clear yellow nano-micro particle dispersion. The dispersion was then pre-frozen in an ultra-low temperature freezer at -80 °C for 4 h and then dried in a freeze dryer for 48 h to finally obtain the bright yellow nano-micro particles.

[0032] Example 2 The difference between this embodiment and Example 1 is that the amount of aluminum salt added is 10 mg, while the remaining steps and parameters are the same as in Example 1; the specific steps are as follows: (1) Dissolve acrylamide (AM, 270 mg), N,N-dimethylacrylamide (DMAA, 30 mg), aluminum salt (AlCl3, 10 mg) and azobisisobutyronitrile (AIBN, 10 mg) in 10 mL of deionized water and sonicate until completely dissolved; (2) The solution was transferred to a 25 mL polytetrafluoroethylene-lined stainless steel reactor and reacted at 200 °C for 10 h. After the reaction was completed, the reactor was naturally cooled to room temperature. The product was dialyzed through a 3500 Da dialysis bag for 48 h to obtain a clear yellow nano-micro particle dispersion. The dispersion was then pre-frozen in an ultra-low temperature freezer at -80 °C for 4 h and then dried in a freeze dryer for 48 h to finally obtain the bright yellow nano-micro particles.

[0033] Example 3 The difference between this embodiment and Example 1 is that the amount of aluminum salt added is 20 mg, while the remaining steps and parameters are the same as in Example 1; the specific steps are as follows: (1) Dissolve acrylamide (AM, 270 mg), N,N-dimethylacrylamide (DMAA, 30 mg), aluminum salt (AlCl3, 20 mg) and azobisisobutyronitrile (AIBN, 10 mg) in 10 mL of deionized water and sonicate until completely dissolved; (2) The solution was transferred to a 25 mL polytetrafluoroethylene-lined stainless steel reactor and reacted at 200 °C for 10 h. After the reaction was completed, the reactor was naturally cooled to room temperature. The product was dialyzed through a 3500 Da dialysis bag for 48 h to obtain a clear yellow nano-micro particle dispersion. The dispersion was then pre-frozen in an ultra-low temperature freezer at -80 °C for 4 h and then dried in a freeze dryer for 48 h to finally obtain the bright yellow nano-micro particles.

[0034] Example 4 The difference between this embodiment and Example 1 is that the amount of aluminum salt added is 40 mg, while the remaining steps and parameters are the same as in Example 1; the specific steps are as follows: (1) Dissolve acrylamide (AM, 270 mg), N,N-dimethylacrylamide (DMAA, 30 mg), aluminum salt (AlCl3, 40 mg) and azobisisobutyronitrile (AIBN, 10 mg) in 10 mL of deionized water and sonicate until completely dissolved; (2) The solution was transferred to a 25 mL polytetrafluoroethylene-lined stainless steel reactor and reacted at 200 °C for 10 h. After the reaction was completed, the reactor was naturally cooled to room temperature. The product was dialyzed through a 3500 Da dialysis bag for 48 h to obtain a clear yellow nano-micro particle dispersion. The dispersion was then pre-frozen in an ultra-low temperature freezer at -80 °C for 4 h and then dried in a freeze dryer for 48 h to finally obtain the bright yellow nano-micro particles.

[0035] Example 5 A method for preparing nano- and micro-sized particles with a metal-carbon framework structure, the specific steps of which are as follows: (1) Dissolve acrylamide (AM, 270 mg), N,N-dimethylacrylamide (DMAA, 30 mg), zirconium salt (zirconium oxychloride, 5 mg) and azobisisobutyronitrile (AIBN, 10 mg) in 10 mL of deionized water and sonicate until completely dissolved; (2) The solution was transferred to a 25 mL polytetrafluoroethylene-lined stainless steel reactor and reacted at 200 °C for 10 h. After the reaction was completed, the reactor was naturally cooled to room temperature. The product was dialyzed through a 3500 Da dialysis bag for 48 h to obtain a clear yellow nano-micro particle dispersion. The dispersion was then pre-frozen in an ultra-low temperature freezer at -80 °C for 4 h and then dried in a freeze dryer for 48 h to finally obtain the bright yellow nano-micro particles.

[0036] Example 6 The difference between this embodiment and Example 5 is that the amount of zirconium salt added is 10 mg, while the remaining steps and parameters are the same as in Example 1; the specific steps are as follows: (1) Dissolve acrylamide (AM, 270 mg), N,N-dimethylacrylamide (DMAA, 30 mg), zirconium salt (zirconium oxychloride, 10 mg) and azobisisobutyronitrile (AIBN, 10 mg) in 10 mL of deionized water and sonicate until completely dissolved; (2) The solution was transferred to a 25 mL polytetrafluoroethylene-lined stainless steel reactor and reacted at 200 °C for 10 h. After the reaction was completed, the reactor was naturally cooled to room temperature. The product was dialyzed through a 3500 Da dialysis bag for 48 h to obtain a clear yellow nano-micro particle dispersion. The dispersion was then pre-frozen in an ultra-low temperature freezer at -80 °C for 4 h and then dried in a freeze dryer for 48 h to finally obtain the bright yellow nano-micro particles.

[0037] Example 7 The difference between this embodiment and Example 1 is that the amount of zirconium salt added is 20 mg, while the remaining steps and parameters are the same as in Example 1; the specific steps are as follows: (1) Dissolve acrylamide (AM, 270 mg), N,N-dimethylacrylamide (DMAA, 30 mg), zirconium salt (zirconium oxychloride, 20 mg) and azobisisobutyronitrile (AIBN, 10 mg) in 10 mL of deionized water and sonicate until completely dissolved; (2) The solution was transferred to a 25 mL polytetrafluoroethylene-lined stainless steel reactor and reacted at 200 °C for 10 h. After the reaction was completed, the reactor was naturally cooled to room temperature. The product was dialyzed through a 3500 Da dialysis bag for 48 h to obtain a clear yellow nano-micro particle dispersion. The dispersion was then pre-frozen in an ultra-low temperature freezer at -80 °C for 4 h and then dried in a freeze dryer for 48 h to finally obtain the bright yellow nano-micro particles.

[0038] Example 8 The difference between this embodiment and Example 1 is that the amount of zirconium salt added is 40 mg, while the remaining steps and parameters are the same as in Example 1; the specific steps are as follows: (1) Dissolve acrylamide (AM, 270 mg), N,N-dimethylacrylamide (DMAA, 30 mg), zirconium salt (zirconium oxychloride, 40 mg) and azobisisobutyronitrile (AIBN, 10 mg) in 10 mL of deionized water and sonicate until completely dissolved; (2) The solution was transferred to a 25 mL polytetrafluoroethylene-lined stainless steel reactor and reacted at 200 °C for 10 h. After the reaction was completed, the reactor was naturally cooled to room temperature. The product was dialyzed through a 3500 Da dialysis bag for 48 h to obtain a clear yellow nano-micro particle dispersion. The dispersion was then pre-frozen in an ultra-low temperature freezer at -80 °C for 4 h and then dried in a freeze dryer for 48 h to finally obtain the bright yellow nano-micro particles.

[0039] Comparative Example 1 The difference between this comparative example and Example 1 is that no metal salt was added.

[0040] A method for preparing nano- and micro-sized particles, the specific steps of which are as follows: (1) Dissolve acrylamide (AM, 270 mg), N,N-dimethylacrylamide (DMAA, 30 mg) and azobisisobutyronitrile (AIBN, 10 mg) in 10 mL of deionized water and sonicate until completely dissolved; (2) The solution was transferred to a 25 mL polytetrafluoroethylene-lined stainless steel reactor and reacted at 200 °C for 10 h. After the reaction was completed, the reactor was naturally cooled to room temperature. The product was dialyzed through a 3500 Da dialysis bag for 48 h to obtain a light yellow nano-micro particle dispersion. The dispersion was then pre-frozen in an ultra-low temperature freezer at -80 °C for 4 h and then dried in a freeze dryer for 48 h to finally obtain light yellow nano-micro particles.

[0041] Performance testing 1. Nano- and micro-sized particles The particle sizes of the nano- and micro-particles obtained in each embodiment and comparative example are shown in Table 1 below.

[0042] Table 1

[0043] Figure 1 Metallographic micrograph of the metal-carbon framework nanoparticles obtained in Example 2 of this invention; Figure 2 The particle size distribution diagrams are shown for the nano- and micro-particles obtained in Examples 1-3 and Comparative Example 1; combined with... Figures 1-2 The results in Table 1 demonstrate that the size control achieved by adding metal salts in this invention is universally applicable to various metals. In Comparative Example 1, the particle size was only a few nanometers without metal salts. In the embodiments of this invention, the addition of metal salts allows for controllable adjustment of the particle size within the range of 1–5000 nanometers. This indicates that metal ions not only act as crosslinking agents but also significantly enhance the hydrophobicity of the system, thereby greatly promoting and amplifying the microphase separation process.

[0044] 2. Dispersibility of nano- and micro-sized particles in mineralized water To evaluate the colloidal stability of the metal-carbon framework-based nanoparticles prepared in this invention in a high ionic strength environment, nanoparticles prepared in each example and comparative example were added to simulated mineralized water at a solid content of 100 mg / L. After mixing evenly, their dispersibility was observed. The simulated mineralized water was set with three strengths: 100,000 mg / L, 150,000 mg / L, and 200,000 mg / L. The dispersibility observation results are shown in Table 2 below.

[0045] Table 2

[0046] Table 2 shows that the metal-carbon framework nanoparticles prepared in the embodiments of the present invention exhibit excellent dispersion stability in simulated mineralized water with high mineralization. Specifically, Example 1 showed a transparent and uniform dispersion in simulated mineralized water with mineralization of 100,000 mg / L and 150,000 mg / L, without any visible precipitation or agglomeration, indicating that it maintains good colloidal stability even under high ionic strength. In contrast, Comparative Example 1, without the addition of metal salt, showed rapid agglomeration and precipitation in simulated mineralized water with the above mineralization levels, resulting in a turbid dispersion. Further observation of Examples 2 to 8 reveals that the particles prepared with zirconium salt exhibit even better stability at an ultra-high mineralization of 200,000 mg / L. This is attributed to the superior stability of the zirconium salt. 4+ It has more than Al 3+ Higher charge density and stronger coordination ability can form a more dense and complex three-dimensional network, thus endowing the particles with stronger resistance to ion interference. Furthermore, in similar metal salt systems, as the amount of metal salt added increases, the salt resistance of the particles generally shows a trend of "first enhanced and then stabilized", indicating that an appropriate amount of metal ions can improve the cross-linking network and eliminate structural defects.

[0047] Figure 3 The dispersion phenomenon of nano- and micro-particles prepared in Example 1 in mineralized water with different mineralization degrees. Figure 3 The results showed that no precipitation or significant aggregation was observed in the nanoparticles in 150,000 mg / L mineralized water, indicating that the rigid hybrid cross-linking network constructed by metal ions in this invention significantly enhances the structural stability and anti-aggregation ability of nanoparticles in high-salt environments, demonstrating excellent salt resistance.

[0048] Figure 4 The nano-micro particles prepared in Example 1 are aged for 3 days in mineralized water with different mineralization degrees and at 110°C. Figure 4 The results showed that after aging in 150,000 mg / L mineralized water at 110°C for 3 days, the nanoparticles maintained a transparent and homogeneous solution without precipitation, stratification, or significant turbidity changes. This demonstrates the excellent temperature and salt resistance of the nanoparticles. The nanoparticles prepared in this invention have a controllable particle size range of 1-5000 nm. Combined with a metal crosslinking-induced nucleation and carbonization mechanism, metal ions act as crosslinking agents, forming a rigid "metal-organic hybrid network," which significantly enhances the structural integrity and anti-aggregation ability of the particles under extreme conditions.

[0049] Figure 5 The dispersion of nano- and micron-sized particles prepared in Comparative Example 1 in mineralized water with different mineralization levels was observed. It was found that the mineralized water with different mineralization levels was turbid, indicating poor salt tolerance.

[0050] It should be noted that the present invention is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments that have the same structure and perform the same effects as the technical concept within the scope of the present invention are included within the scope of the present invention. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of the present invention, are also included within the scope of the present invention.

Claims

1. A metal-carbon framework structured nanoparticle, characterized in that, The metal-carbon framework nano-micro particles are prepared from raw materials via a solvothermal reaction. The raw materials for preparation have the following components by mass percentage: 3%~15% polymerizable monomer, 0.05%~1.5% initiator, 0.01%~1.5% metal salt and balance solvent; The active functional groups of the polymerizable monomer include nitrogen and / or oxygen; The metal salt includes at least one of aluminum salt and zirconium salt; The nano-micro particles with the metal-carbon framework structure have a particle size of 770~5000 nanometers; The metal ions introduced by the metal salt coordinate with the nitrogen- and oxygen-containing functional groups on the polymer chains formed by the polymerization of the polymerizable monomers in the early stage of polymerization, forming a metal-organic hybrid cross-linked network.

2. The metal-carbon framework structured nanoparticles according to claim 1, characterized in that, The polymerizable monomers include at least one of acrylamide, N,N-dimethylacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, sodium p-styrenesulfonate, and acrylic acid.

3. The nano-micro particles with a metal-carbon framework structure according to claim 1, characterized in that, The initiator includes at least one of azobisisobutyronitrile, ammonium persulfate, azobisisobutyramidoline hydrochloride, and azobisisobutyramidine hydrochloride.

4. The metal-carbon framework structured nanoparticles according to claim 1, characterized in that, The aluminum salt includes at least one of aluminum nitrate, aluminum chloride, and aluminum sulfate; And / or, the zirconium salt includes at least one of zirconium nitrate, zirconium oxychloride, and zirconium tetrachloride.

5. The metal-carbon framework structured nanoparticles according to claim 1, characterized in that, The solvent includes deionized water.

6. The metal-carbon framework structured nanoparticles according to claim 1, characterized in that, The temperature of the solvothermal reaction is 120~250℃; the time of the solvothermal reaction is 8~16h.

7. The method for preparing nano- and micro-sized particles with a metal-carbon framework structure as described in any one of claims 1 to 6, characterized in that, Includes the following steps: S1. Mix the polymerizable monomer, initiator, metal salt and solvent evenly to obtain a precursor solution; S2. The precursor solution is placed in a closed reactor and subjected to a solvothermal reaction at 120~250°C. S3. After the reaction is complete, the reaction solution is cooled to room temperature, and then subjected to dialysis and drying to obtain the nano-micro particles with the metal-carbon framework structure.

8. The method for preparing nano- and micro-sized particles with a metal-carbon framework structure according to claim 7, characterized in that, The dialysis treatment specifically involves dialyzing the reaction solution through a 3500-8000 Da dialysis bag for 24-48 hours.

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