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CN-121988368-A - Hybrid boron carbon nitrogen catalyst, preparation method thereof and application of catalyst in ozone catalysis

CN121988368ACN 121988368 ACN121988368 ACN 121988368ACN-121988368-A

Abstract

The hybridized boron carbon nitrogen catalyst comprises carbon nitrogen carriers with stacked lamellar structures and boron atoms positioned in carbon nitrogen lattices of the carbon nitrogen carriers, wherein the atomic content of the boron atoms in the hybridized boron carbon nitrogen catalyst is 22-42%, and the proportion of B-N 2 O in coordination configuration of the boron atoms in the carbon nitrogen lattices is not lower than 10%. According to the hybridized boron carbon nitrogen catalyst, the B-N 2 O electronic interaction structure is constructed, so that the active site of the catalyst is increased, the inherent catalytic activity of the catalyst is improved, the adsorption/activation of ozone at the B site is accelerated, active oxygen species such as surface atomic oxygen, singlet oxygen and the like with high oxidation-reduction potential are generated, and therefore heterogeneous ozone catalytic oxidation is realized through a non-free radical path, the rapid degradation of pollutants is realized, and the catalyst has high anti-interference capability and circulation stability.

Inventors

  • MA DINGREN
  • CHEN JINFENG
  • YU HAIYING
  • Yang Chenqiang
  • LU JIE
  • ZHANG LINGZHU
  • ZHAO HENING
  • JIN YIFAN

Assignees

  • 浙江师范大学

Dates

Publication Date
20260508
Application Date
20260409

Claims (10)

  1. 1. The hybridized boron carbon nitrogen catalyst is characterized by comprising carbon nitrogen carriers with stacked lamellar structures and boron atoms positioned in carbon nitrogen lattices of the carbon nitrogen carriers, wherein the atomic content of the boron atoms in the hybridized boron carbon nitrogen catalyst is 22-42%, and the proportion of B-N 2 O in coordination configuration of the boron atoms in the carbon nitrogen lattices is not less than 10%.
  2. 2. The hybrid boron carbon nitrogen catalyst according to claim 1, wherein the hybrid boron carbon nitrogen catalyst has a BC 3 /BN 2 C characteristic peak at 189.8eV + -0.1 eV, a BC 2 O/BN characteristic peak at 190.8eV + -0.1 eV, a B-N 2 O characteristic peak at 191.5eV + -0.1 eV, a BN 3 /BCO 2 characteristic peak at 191.9eV + -0.1 eV, and the peak area of the B-N 2 O characteristic peak is not less than 13%.
  3. 3. The hybrid boron carbon nitrogen catalyst of claim 1, further having a graphitic carbon structure having (002) and (100) crystal planes of graphitic carbon at 2Θ of the X-ray diffraction pattern of 24.4 ° ± 0.5 ° and 44.4 ° ± 0.5 °, respectively.
  4. 4. The hybrid boron carbon nitrogen catalyst of claim 1, wherein the average diameter of the hybrid boron carbon nitrogen catalyst is 2-10 μm.
  5. 5. A method of preparing the hybrid boron carbon nitrogen catalyst of any one of claims 1 to 4, comprising the steps of: s1, dissolving urea, polyethylene glycol and boric acid in water, uniformly stirring, and drying at 60-100 ℃ for 20-30 h to obtain a precursor eutectic mixture; s2, calcining the precursor eutectic mixture at 800-1000 ℃ in an inert atmosphere for 3-5 h, and naturally cooling to obtain the hybridized boron carbon nitrogen catalyst.
  6. 6. The preparation method of the hybridization boron carbon nitrogen catalyst according to claim 5, wherein the mass ratio of urea to polyethylene glycol to boric acid is (7-13): 1 (0.5-2).
  7. 7. The method for preparing a hybrid boron carbon nitrogen catalyst according to claim 5, wherein in step S2, the temperature rising rate of the calcination is 3-7 ℃ per minute.
  8. 8. Use of a hybrid boron carbon nitrogen catalyst of any one of claims 1-4 in heterogeneous ozone catalytic oxidation.
  9. 9. The use of claim 8, wherein the hybrid boron carbon nitrogen catalyst is used for ozone catalyzed oxidation to remove organic contaminants including at least one of enrofloxacin hydrochloride, levofloxacin hydrochloride, tetracycline hydrochloride, and norfloxacin hydrochloride.
  10. 10. The use according to claim 8 or 9, characterized in that the ozone concentration in the heterogeneous ozone catalytic oxidation system is 150-500 ppm.

Description

Hybrid boron carbon nitrogen catalyst, preparation method thereof and application of catalyst in ozone catalysis Technical Field The application relates to the technical field of ozone catalytic materials, in particular to a hybridization boron carbon nitrogen catalyst, a preparation method thereof and application of ozone catalysis. Background With the acceleration of the industrialization process, the discharge of refractory organic pollutants (such as drug residues, endocrine disruptors, industrial dyes and persistent organic pollutants) in water bodies is increasingly serious, and serious threats are formed to the ecological system and human health. Conventional water treatment techniques (e.g., biological treatment, conventional oxidation) tend to be difficult to effectively remove these highly stable, highly toxic trace organics. Therefore, development of efficient and green advanced oxidation technology has become a leading edge of research and urgent need in the field of environmental engineering. Catalytic ozonation technology belongs to advanced oxidation technology (AOPs) based on ozone, can oxidize pollutants which are difficult to oxidize by ozone alone at normal temperature and normal pressure, and can effectively solve the problem of incomplete degradation of the pollutants and be widely applied. The catalytic ozone oxidation technology effectively enhances the mass transfer efficiency and the contact time of ozone in an aqueous phase environment through the catalyst so as to enhance the ozone utilization efficiency and save the ozone addition amount and the oxidation time. According to different forms of the catalyst, the catalyst mainly comprises homogeneous ozone catalytic oxidation and heterogeneous catalytic ozone oxidation, wherein a homogeneous catalytic ozone oxidation system has good mass transfer effect and rapid reaction, but metal ions are easy to remain in water to cause secondary pollution, the subsequent treatment cost is increased, and the heterogeneous ozone catalytic oxidation system has the outstanding advantages of easy separation and recovery, reusability, environmental friendliness and the like because the catalyst exists in a solid state, and becomes the research direction with the current most application potential. The heterogeneous ozone catalytic oxidation technology in the prior art mainly depends on a free radical (. OH) path, for example, patent CN116943627A proposes a composite carrier for heterogeneous catalytic oxidation, a catalyst, a preparation method and application thereof, and fibrous carbon is adoptedThe catalyst has good degradation effect on organic matters containing nitrogen, chlorine, sulfur and fluorine and aldehyde ketone substances, the degradation rate is more than 85%, but the catalyst mainly depends on a hydroxyl radical path to realize ozone catalytic oxidation. The circulation stability and the anti-poisoning capability (such as the inhibition effect of inorganic anions and natural organic matters) of the free radical path under the actual complex water quality condition are greatly influenced, while the non-free radical path has stronger anti-interference capability than the free radical path under the complex water quality, but the heterogeneous ozone catalytic oxidation technology based on the non-free radical path has fewer reports and generally has lower degradation efficiency on pollutants. Therefore, development of a high-performance catalytic ozonation catalyst capable of inducing ozone oxidation reaction in a non-radical path is needed, and the catalyst has the characteristics of strong anti-interference capability and high circulation stability in response to complex water body working conditions. Disclosure of Invention The invention aims to overcome the defects and shortcomings of the prior art, and provides a hybridization boron carbon nitrogen catalyst which can generate singlet oxygen (1O2) with high oxidation-reduction potential, so that heterogeneous ozone catalytic oxidation is realized by a non-free radical path, and the catalyst can rapidly degrade various organic pollutants and has the characteristics of strong anti-interference capability and high circulation stability in complex water bodies. Another object of the invention is to provide a method for preparing the hybrid boron carbon nitrogen catalyst. Another object of the invention is to provide the use of a hybrid boron carbon nitrogen catalyst in heterogeneous ozone catalytic oxidation. The above object of the present invention is achieved by the following technical scheme: The invention provides a hybridization boron carbon nitrogen catalyst, which comprises carbon nitrogen carriers with stacked lamellar structures and boron atoms positioned in carbon nitrogen lattices of the carbon nitrogen carriers, wherein the atomic content of the boron atoms in the hybridization boron carbon nitrogen catalyst is 22-42%, and the proportion of B-N 2 O in coordination configura