Search

CN-121974331-A - Nanometer-micrometer particles with metal-carbon skeleton structure and preparation method thereof

CN121974331ACN 121974331 ACN121974331 ACN 121974331ACN-121974331-A

Abstract

The invention provides nano-micron particles with a metal-carbon skeleton structure and a preparation method thereof, and belongs to the field of nano-material preparation, wherein the nano-micron particles with the metal-carbon skeleton structure are prepared from preparation raw materials through solvothermal reaction, the preparation raw materials comprise, 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, 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. According to the invention, metal ions and an organic precursor containing active groups are used as raw materials, and the controllable adjustment of the particle size of nano-micron particles within the range of 1-5000 nanometers is realized through the processes of metal crosslinking, induced nucleation and in-situ carbonization. The preparation process is simple and controllable, the obtained nano-micron particles have uniform size, stable structure and high temperature and salt resistance, and can be widely applied to the fields of catalysis, sensing or oil displacement and the like.

Inventors

  • WANG TENGFEI
  • CHEN HUAN
  • Lai lu
  • WANG ZONGCHENG
  • Peng Junao
  • HU RENXI
  • GUAN YUZHI
  • WU ZHAODONG
  • ZHANG YING

Assignees

  • 长江大学
  • 荆州市隆华石油化工有限公司

Dates

Publication Date
20260505
Application Date
20260409

Claims (9)

  1. 1. The nano-micron particles with the metal-carbon framework structure are characterized in that the nano-micron particles with the metal-carbon framework structure are prepared from preparation raw materials through solvothermal reaction; The preparation raw materials comprise, 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 reactive functional groups of the polymerizable monomer include nitrogen and/or oxygen; The metal salt comprises at least one of aluminum salt, zirconium salt, chromium salt and zinc salt.
  2. 2. The nano-sized particles of a metal-carbon skeleton structure according to claim 1, wherein the nano-sized particles of the metal-carbon skeleton structure have a particle size of 1 to 5000 nm.
  3. 3. The metal-carbon backbone nano-microparticles of claim 1, wherein said polymerizable monomer comprises at least one of acrylamide, N-dimethylacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, sodium p-styrenesulfonate, and acrylic acid.
  4. 4. The metal-carbon backbone nano-particles of claim 1, wherein the initiator comprises at least one of azobisisobutyronitrile, ammonium persulfate, azobisiso Ding Mi, azobisisobutylamidine hydrochloride.
  5. 5. The nano-micron particles of a metal-carbon framework structure according to claim 1, wherein the aluminum salt comprises at least one of aluminum nitrate, aluminum chloride, aluminum sulfate; and/or the zirconium salt comprises at least one of zirconium nitrate, zirconium oxychloride and zirconium tetrachloride; And/or the chromium salt comprises at least one of potassium dichromate, potassium chromate and chromium chloride; and/or the zinc salt comprises at least one of zinc chloride, zinc oxide and zinc sulfate.
  6. 6. The nano-sized particles of a metal-carbon framework structure of claim 1 wherein the solvent comprises deionized water.
  7. 7. The nano-micron particles with the metal-carbon skeleton structure according to claim 1, wherein the solvothermal reaction temperature is 120-250 ℃, and the solvothermal reaction time is 8-16 h.
  8. 8. The method for preparing nano-micron particles with a metal-carbon skeleton structure according to any one of claims 1 to 7, comprising the following steps: S1, uniformly mixing a polymerizable monomer, an initiator, metal salt and a solvent to obtain a precursor solution; S2, placing the precursor solution in a closed reactor, and performing solvothermal reaction at 120-250 ℃; And S3, after the reaction is finished, cooling the reaction liquid to room temperature, and obtaining the nano-micron particles with the metal-carbon skeleton structure through dialysis treatment and drying.
  9. 9. The method for preparing nano-micron particles with a metal-carbon skeleton structure according to claim 8, wherein the dialysis treatment is specifically that the reaction solution is dialyzed for 24-48 hours by a 3500-8000 Da dialysis bag.

Description

Nanometer-micrometer particles with metal-carbon skeleton structure and preparation method thereof Technical Field The invention relates to the technical field of nano material preparation, in particular to nano-micron particles with a metal-carbon skeleton structure and a preparation method thereof. Background Carbonized Polymer Dots (CPDs) are a new class of fluorescent or functional nanocarbon materials formed by carbonizing a crosslinked polymer network via heat treatment. The method has the advantages of strong structural designability, abundant surface functional groups, good biocompatibility, easiness in large-scale preparation and the like, and has wide application prospect in the fields of biological imaging, photocatalysis, electrocatalysis, sensing, energy storage and the like. At present, the synthesis methods of carbon nano particles are mainly divided into top-down and bottom-up strategies. The top-down method is mainly prepared by cutting large carbon sources, has the problems of uneven product size, difficult precise structure regulation and the like, and the bottom-up method, especially the hydrothermal/solvothermal method, is a main technical path for preparing the carbon nano particles due to simple and convenient operation, mild reaction conditions and easy mass production. In the bottom-up synthesis process, the precursor is usually polymerized, crosslinked, dehydrated, carbonized and the like to form carbon nano particles, and part of the product has the advantages of both the photoelectric performance of the quantum dot and the characteristics of the polymer due to the hybridization characteristics of the polymer structure and the carbon core, so that the application scene of the product is further expanded. In the prior art, the size of CPDs is generally smaller, and most reported product particle sizes are concentrated in the range of 2-20 nanometers. The small-size characteristic endows the CPDs with larger specific surface area, good water solubility and excellent permeability, so that the CPDs have remarkable advantages in the fields of biological imaging, photocatalysis, sensing and the like. However, in oilfield profile control and flooding, the profile control operation requires functional particles of sufficient size to effectively block the hypertonic pathways. Too small CPDs are easy to quickly penetrate through pore media along with injected water, are difficult to stay at a target horizon, have low plugging efficiency and small swept volume, and cannot exert an effective profile control effect. Therefore, it is a technical problem to be solved in the art to break through the upper limit of the size of the CPDs while maintaining good dispersibility. Disclosure of Invention In view of the technical problems in the background art, the invention provides nano-micron particles with a metal-carbon skeleton structure and a preparation method thereof, and aims to solve the technical problems that the conventional CPDs are difficult to break through in size, and the conventional polymer microspheres are easy to degrade and have insufficient strength in a high-temperature and high-salt environment. In a first aspect, the present invention provides nano-micro particles of a metal-carbon framework structure, prepared from a preparation raw material by solvothermal reaction; the preparation raw materials comprise, 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; reactive functional groups of the polymerizable monomer include nitrogen and/or oxygen; The metal salt comprises at least one of aluminum salt, zirconium salt, chromium salt and zinc salt. Preferably, the nano-micron particles of the metal-carbon framework structure have a particle size of 1-5000 nanometers. Preferably, the polymerizable monomer includes at least one of Acrylamide (AM), N-Dimethylacrylamide (DMAA), 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), sodium p-styrenesulfonate, and acrylic acid. Preferably, the initiator comprises at least one of Azobisisobutyronitrile (AIBN), ammonium Persulfate (APS), azobisiso Ding Mi (VA-044), azobisisobutylamidine hydrochloride (V-50). Preferably, the aluminum salt comprises at least one of aluminum nitrate, aluminum chloride and aluminum sulfate, the zirconium salt comprises at least one of zirconium nitrate, zirconium oxychloride and zirconium tetrachloride, the chromium salt comprises at least one of potassium dichromate, potassium chromate and chromium chloride, and the zinc salt comprises at least one of zinc chloride, zinc oxide and zinc sulfate. Preferably, the solvent comprises deionized water. Preferably, the temperature of the solvothermal reaction is 120-250 ℃, and the time of the solvothermal reaction is 8-16 h. In a second aspect, an embodiment of the present invention provides a method for preparing nano-micron particles having a metal-carbon skeleton structure, including the steps of: