CN114939410A - Cobalt nanoparticle embedded nitrogen-doped carbon porous catalyst and preparation method and application thereof - Google Patents

Cobalt nanoparticle embedded nitrogen-doped carbon porous catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN114939410A
CN114939410A CN202210799730.7A CN202210799730A CN114939410A CN 114939410 A CN114939410 A CN 114939410A CN 202210799730 A CN202210799730 A CN 202210799730A CN 114939410 A CN114939410 A CN 114939410A
Authority
CN
China
Prior art keywords
cof
cobalt
catalyst
doped carbon
smz
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210799730.7A
Other languages
Chinese (zh)
Other versions
CN114939410B (en
Inventor
赵汝松
谢萌
张世永
苑金鹏
姚明亚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong Analysis and Test Center
Original Assignee
Shandong Analysis and Test Center
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shandong Analysis and Test Center filed Critical Shandong Analysis and Test Center
Priority to CN202210799730.7A priority Critical patent/CN114939410B/en
Publication of CN114939410A publication Critical patent/CN114939410A/en
Application granted granted Critical
Publication of CN114939410B publication Critical patent/CN114939410B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/40—Organic compounds containing sulfur
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Catalysts (AREA)

Abstract

The invention belongs to the technical field of advanced materials and environmental protection, and relates to a cobalt nanoparticle embedded nitrogen-doped carbon porous catalyst, and a preparation method and application thereof. Under the initiation of glacial acetic acid, performing Schiff base reaction on 1,3, 5-tri (4-aminophenyl) benzene (TPB) and 2, 5-divinyl terephthalaldehyde (DVA) in an organic solvent to obtain a COF precursor, mixing the COF precursor and cobalt salt in water, heating and stirring until water is completely evaporated to obtain a solid product, and heating the solid product to 600-800 ℃ under the inert atmosphere condition for pyrolysis to obtain the COF. The catalyst provided by the invention has excellent catalytic performance in the degradation aspect of PMS activation on sulfonamide antibiotics such as SMZ and the like.

Description

Cobalt nanoparticle embedded nitrogen-doped carbon porous catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of advanced materials and environmental protection, and relates to a cobalt nanoparticle embedded nitrogen-doped carbon porous catalyst, and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Sulfonamide Antibiotics (SAs) have high chemical stability and solubility in water, and are difficult to degrade under natural conditions, resulting in a large amount of residues in aquatic environments. SAs can cause poisoning, bacterial resistance and potential carcinogenicity in crustaceans. A novel advanced antibiotic wastewater treatment technology is urgently needed to realize high-efficiency and reasonable treatment.
Peroxymonosulfate (PMS) is an environmentally friendly, stable, non-toxic, easily transportable oxidant in sulfate-based advanced oxidation processes (SR-AOPs). However, the inventor researches and discovers that the degradation efficiency of sulfa antibiotics such as sulfa pyrimidine (SMZ) is low by using only Peroxymonosulfate (PMS), so that a catalyst of peroxymonosulfate capable of degrading sulfa antibiotics is needed.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a cobalt nanoparticle embedded nitrogen-doped carbon porous catalyst, and a preparation method and application thereof.
In order to realize the purpose, the technical scheme of the invention is as follows:
on one hand, under the initiation of glacial acetic acid, 1,3, 5-tri (4-aminophenyl) benzene (TPB) and 2, 5-divinyl terephthalaldehyde (DVA) are subjected to Schiff base reaction in an organic solvent to obtain a COF precursor, the COF precursor and cobalt salt are mixed in water, the mixture is heated and stirred until the water is completely evaporated to obtain a solid product, and the solid product is heated to 600-800 ℃ under the inert atmosphere condition for pyrolysis to obtain the catalyst.
The invention adopts TPB and DVA to form a hexagonal framework structure, has higher specific surface area and N atoms, and can provide more active sites for cobalt nanoparticles. In addition, the formed pore structure can limit the growth of cobalt nanoparticles in a COF framework, avoid excessive aggregation of transition cobalt nanoparticles, improve the dispersion degree and enable the cobalt nanoparticle composite COFs nano material to have higher catalytic performance.
The invention adopts TPB and DVA to form a COF precursor through Schiff base reaction, contains imine, and is formed by periodically stacking nano sheets, and the arrangement has a highly conjugated pi electron system, so that the electron mass transfer efficiency in the oxidation process is improved.
Therefore, the material obtained by compounding the COF precursor formed by reacting the cobalt nanoparticles with the TPB and the DVA through Schiff base has the advantages of good stability, multiple active sites, high dispersibility and the like, and has Co after further pyrolysis at 600-800 DEG C 0 And pyridine N, graphite N and the like, thereby showing excellent catalytic performance in the degradation aspect of sulfonamide antibiotics such as sulfamethazine SMZ and the like by PMS activation.
On the other hand, the nitrogen-doped carbon porous catalyst embedded with the cobalt nanoparticles is obtained by the preparation method.
In a third aspect, the cobalt nanoparticle embedded nitrogen-doped carbon porous catalyst is applied to activation of peroxymonosulfate to degrade sulfonamide antibiotics.
In a fourth aspect, a kit for degrading sulfonamide antibiotics comprises the cobalt nanoparticles embedded nitrogen-doped carbon porous catalyst and peroxymonosulfate.
In a fifth aspect, a method for treating wastewater containing sulfonamide antibiotics is provided, wherein cobalt-coated nano-particles are embedded with a nitrogen-doped carbon porous catalyst and peroxymonosulfate are added into wastewater containing sulfonamide antibiotics to be treated for treatment.
The invention has the beneficial effects that:
according to the invention, TPB and DVA are used to form a COFs material with high crystallinity and large specific surface area, the COFs material is used as a carrier of cobalt nanoparticles, a cobalt nanoparticle embedded nitrogen-doped carbon porous catalyst (Co @ COF) is prepared by high-temperature pyrolysis of the COFs material, and the formed catalyst has a plurality of active sites (Co @ COF) 0 Pyridine N and graphite N) exhibit excellent catalytic performance in terms of SMZ degradation upon PMS activation.
Experiments show that the SMZ degradation efficiency reaches 92.4% in 10min, and the TOC removal rate reaches 70.3% in 30 min. Toxicity evaluation shows that SMZ is effectively removed and biological toxicity is reduced, and Co @ COF/PMS is an effective and promising SMZ-polluted wastewater treatment technology.
The Co @ COF provided by the invention can effectively activate PMS to degrade various SAs, and has good applicability.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a schematic diagram of a catalyst synthesis process in an example of the present invention;
FIG. 2 is SEM pictures, X-ray diffraction pictures (d), N-ray diffraction pictures (d) of COF (a), COF-1(b) and COF-2(c) in the examples of the present invention 2 Adsorption-desorption isotherm (e), Co @ COF 0 、Co@COF 1 、Co@COF 2 (ii) pore size distribution plot (f), Co @ COF 0 (g)、Co@COF 1 (h) And Co @ COF 2 (i) SEM image of (a);
FIG. 3 is Co @ COF in an embodiment of the invention 2 TEM and XPS spectrograms of (a) TEM, (b) TEM, (C) HRTEM, (d) elemental mapping, (e) C1 s, (f) O1 s, (g) N1 s, (h) Co 2 p;
FIG. 4 is a graph showing the characterization of catalytic activity in examples of the present invention, (a) the degradation curves of three COF precursors to SMZ, (b) the degradation curves of three catalysts to SMZ, (c) Co @ COF 2 TOC removal rate of PMS on SMZ degradation, (d) Co @ COF 2 PMS degradation curve for other SAs, reaction parameterNumber: SAs 20mg/L, PMS 0.4mM, Co @ COF 2 ＝0.04g/L；
FIG. 5 is a Co @ COF of an embodiment of the present invention 2 Characterization plots for the identification of the/PMS system reactive species, (a) quenching curves for different scavengers, (b) consumption curves for PMS at different scavengers, EPR spectra for the spin traps with dmpo (c) and temp (d), reaction parameters: (a) SMZ 20mg/L, Co @ COF 2 ＝0.04g/L，PMS＝0.4mM；
FIG. 6 is a graph of reaction conditions vs. Co @ COF in examples of the invention 2 Influence graph of PMS degradation SMZ, (a) PMS dosage, (b) catalyst loading, (c) initial pH, (d) Cl - ，(e)HCO 3 - (f) HA, reaction parameters: (a) SMZ 20mg/L, Co @ COF 2 ＝0.04g/L，PMS＝0.2mM-0.6mM；(b)SMZ＝20mg/L，Co@COF 2 ＝0.01g/L-0.06g/L，PMS＝0.4mM；(c-f)SMZ＝20mg/L，Co@COF 2 ＝0.04g/L，PMS＝0.4mM；
FIG. 7 is a Co @ COF of an embodiment of the present invention 2 Mechanism representation diagram of SMZ degradation by PMS system, (a) stability, (b) Co @ COF 2 XPS spectra before and after reaction, (c) Co @ COF 2 XPS spectra before and after reaction, (d) Co @ COF 2 XPS spectra before and after the reaction, (e) electrochemical impedance spectroscopy, (f) Linear Sweep Voltammetry (LSV) curves; reaction parameters are as follows: (a) SMZ 20mg/L, Co @ COF 2 ＝0.04g/L，PMS＝0.4mM；
FIG. 8 is a Co @ COF in an embodiment of the present invention 2 A schematic diagram of a mechanism for degrading SMZ by a PMS system;
FIG. 9 is Co @ COF in an embodiment of the invention 2 A pathway diagram of SMZ degradation by PMS system.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As introduced in the background art, a catalyst of peroxymonosulfate capable of being degraded by sulfonamide antibiotics is needed, and the invention provides a cobalt nanoparticle embedded nitrogen-doped carbon porous catalyst, and a preparation method and application thereof.
The invention provides a preparation method of a nitrogen-doped carbon porous catalyst embedded with cobalt nanoparticles, which comprises the steps of carrying out Schiff base reaction on TPB and DVA in an organic solvent under the initiation of glacial acetic acid to obtain a COF precursor, mixing the COF precursor and cobalt salt in water, heating and stirring until water is completely evaporated to obtain a solid product, and heating the solid product to 600-800 ℃ under the condition of inert atmosphere for pyrolysis to obtain the catalyst.
The material obtained by compounding the COF precursor formed by reacting the cobalt nanoparticles with the TPB and the DVA through Schiff base has the advantages of good stability, multiple active sites, high dispersibility and the like, and has Co after further pyrolysis at 600-800 DEG C 0 And pyridine N, graphite N and the like, thereby showing excellent catalytic performance in the degradation aspect of sulfa antibiotics such as sulfamethazine SMZ and the like by PMS activation.
The cobalt salt in the present invention refers to a compound having a divalent cobalt ion as a cation, for example, cobalt nitrate, cobalt chloride, cobalt acetate, and the like.
In some embodiments, a cobalt salt is added to the schiff base reaction. Research shows that the catalyst prepared from the COF precursor obtained by Schiff base reaction of TPB and DVA and cobalt salt has better catalytic performance.
In one or more embodiments, the mole ratio of TPB to cobalt salt in the schiff base reaction is 1:0.5 to 2.0. When the molar ratio of TPB to cobalt salt is 1: 1.20-1.40, the obtained catalyst has more excellent catalytic performance.
In some embodiments, the mole ratio of TPB to DVA in the schiff base reaction is 1:1.5 to 3.0.
In some embodiments, the organic solvent is acetonitrile in the schiff base reaction.
In some embodiments, the Schiff base is allowed to stand at room temperature for 48-96 hours. The room temperature refers to the temperature of an indoor environment, and is generally 15-30 ℃.
In some embodiments, the purification process of the COF precursor is: centrifugally separating, washing and drying. Wherein, the washing is carried out for a plurality of times by respectively adopting tetrahydrofuran and ethanol.
In some embodiments, the mass ratio of the COF precursor to the cobalt salt is 10:0.50 to 2.00.
In some embodiments, the temperature increase rate of the pyrolysis is 1-10 ℃/min. Preferably 3 to 7 ℃/min, and more preferably 4 to 6 ℃/min.
In another embodiment of the invention, a nitrogen-doped carbon porous catalyst embedded by cobalt nanoparticles is provided, and is obtained by the preparation method.
The third embodiment of the invention provides an application of the cobalt nanoparticle embedded nitrogen-doped carbon porous catalyst in activating peroxymonosulfate to degrade sulfonamide antibiotics.
In a fourth embodiment of the invention, a kit for degrading sulfonamide antibiotics is provided, which comprises the cobalt nanoparticle embedded nitrogen-doped carbon porous catalyst and peroxymonosulfate.
In some embodiments, a quencher is included. For testing the degradation efficiency of SMZ. The quenching agent is preferably ethanol.
In a fifth embodiment of the invention, a method for treating wastewater containing sulfonamide antibiotics is provided, wherein the cobalt nanoparticle embedded nitrogen-doped carbon porous catalyst and peroxymonosulfate are added into wastewater containing sulfonamide antibiotics to be treated for treatment.
In some embodiments, the catalyst and peroxymonosulfate are added in a ratio of 90 to 110:1, g: and (mol).
The concentration of the peroxymonosulfate is 0.2 to 0.6mM, and studies show that the higher the concentration of the peroxymonosulfate, the higher the degradation rate, and in some embodiments, the concentration of the peroxymonosulfate is 0.4 to 0.6 mM. The degradation rate under this condition is higher.
The addition amount of the catalyst is 0.01-0.06 g/L, and research shows that the higher the addition amount of the catalyst is, the higher the degradation rate is, and in some embodiments, the addition amount of the catalyst is 0.04-0.06 g/L. The degradation rate under this condition is higher.
In some embodiments, the pH is 5 to 10. The pH value is preferably 5.40-9.05, and the degradation rate is higher under the condition.
In some embodiments, the treatment system comprises chloride ions at a concentration of 10 to 15 mM. The degradation rate is higher under the condition.
In some embodiments, the treatment system comprises HCO 3 - ，HCO 3 - The concentration is 5 to 10 mM. The degradation rate is higher under the condition.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Examples
Raw materials:
1,3, 5-tris (4-aminophenyl) benzene (TPB), 2, 5-Divinylterephthalaldehyde (DVA) were purchased from Michelin Chemicals, Inc. (Shanghai, China). Sulfamethazine (SMZ), sulfisoxazole, sulfamethoxazole, sulfapyridine, sulfathiazole, cobalt nitrate hexahydrate, peroxymonosulfate (PMS, KHSO) 5 ·0.5KHSO 4 ·0.5K 2 SO 4 ≧ 47%) and furfuryl alcohol (FFA) were purchased from Aladdin reagents, Inc. (Shanghai, China). Tert-butanol (TBA), ethanol (EtOH), p-benzoquinone (p-BQ) and methanol (MeOH) were purchased from the national pharmaceutical group Chemicals, Inc. (Shanghai, China). Acetonitrile (ACN) was purchased from Fisher chemicals, ltd (shanghai, china). Ultrapure water from a Milli-Q system (Millipore) having a resistivity of 18.25 M.OMEGA.cm was used throughout the examples.
Synthesis of COF, COF-1 and COF-2:
TBP (0.0564g) and DVA (0.0448g) were added to 20mL of 92% ACN solvent, followed by 3.9mL of glacial acetic acid to initiate the reaction. After the ultrasonic dispersion, the above mixed solution was allowed to stand at room temperature for 72 hours. The resulting yellow precipitate was centrifuged at 1000rpm for 5min and washed 3 times with tetrahydrofuran and ethanol, respectively. After drying at 60 ℃ under high vacuum for 6 hours, COF precursors were obtained.
TBP (0.0564g), DVA (0.0448g) and 0.031gCo (NO) 3 ) 2 .6H 2 O was added to 20mL of 92% ACN solvent followed by 3.9mL of glacial acetic acid to initiate the reaction. After the ultrasonic dispersion, the above mixed solution was allowed to stand at room temperature for 72 hours. The resulting yellow precipitate was centrifuged at 1000rpm for 5min and washed 3 times with tetrahydrofuran and ethanol, respectively. After drying at 60 ℃ under high vacuum for 6 hours, a COF-1 precursor is obtained.
TBP (0.0564g), DVA (0.0448g) and 0.062gCo (NO) 3 ) 2 .6H 2 O was added to 20mL of 92% ACN solvent, followed by 3.9mL of glacial acetic acid to initiate the reaction. After the ultrasonic dispersion, the above mixed solution was allowed to stand at room temperature for 72 hours. The resulting yellow precipitate was centrifuged at 1000rpm for 5min and washed 3 times with tetrahydrofuran and ethanol, respectively. After drying at 60 ℃ under high vacuum for 6 hours, a COF-2 precursor was obtained.
Co@COF 0 、Co@COF 1 、Co@COF 2 The synthesis of (2):
80mg of the different COF precursors (COF, COF-1, COF-2) and 10mg of Co (NO) 3 ) 2 .6H 2 O was mixed with 50mL of deionized water. The solution was then heated at 80 ℃ and stirred continuously in an oil bath until all the water had evaporated. The solid product obtained is then brought to 5 ℃ min -1 Was heated to 700 c and maintained under an argon atmosphere for 2 hours. The obtained corresponding catalysts are respectively named as Co @ COF 0 、Co@COF 1 And Co @ COF 2 。
Co@COF 0 、Co@COF 1 And Co @ COF 2 The synthesis of (2) is shown in FIG. 1.
And (3) degradation process:
the degradation experiments of SMZ were performed in 20mL of SMZ solution at 25. + -. 1 ℃. Typically, 0.8mg of catalyst was dispersed in SMZ solution (20mg/L) and 0.16mL PMS (50mM) was added to initiate the reaction. At each time interval, 1.0mL of the reaction solution was sampled and mixed with 0.3mL of ethanol to quench the reaction. The sample solution was filtered through a 0.22 μm Polytetrafluoroethylene (PTFE) membrane and analyzed for SMZ concentration by high performance liquid chromatography (HPLC, UltiMate 3000).
Results and discussion:
structure and morphology:
the COF, COF-1 and COF-2 precursors all show strong XRD diffraction peaks around 2.7 degrees, and among them, all show strong XRD diffraction peaks around 2.7 degrees. The surface areas (SBET) of COF, COF-1 and COF-2 are 2143.54, 2465.43 and 2509.58m, respectively 2 (ii) in terms of/g. They have abundant mesoporous structure, and the aperture is mainly distributed at about 2.3 nm. And observing the morphologies of the COF, the COF-1 and the COF-2 by a scanning electron microscope. As shown in FIGS. 2a-2c, COF-1 and COF-2 have different morphologies. The morphology of COF in fig. 2a is a microspherical structure with nanoparticles with an average diameter size close to 430 nm. Whereas the nanorod cluster structures of COF-1 and COF-2 are more prominent (FIG. 2 b-c). And the average diameter size of the nanoparticles increased to 760nm for COF-1 and 900nm for COF-2. This means that the addition of cobalt significantly changes the morphology of the COF precursor.
Co@COF 0 、Co@COF 1 And Co @ COF 2 From the corresponding COF precursor and cobalt salt, carbonized at high temperature, as shown in fig. 1. Co @ COF 0 、Co@COF 1 And Co @ COF 2 The XRD pattern of fig. 2 d. Diffraction peaks at 23.1 ° and 43.9 ° correspond to the (002) and (100) planes of carbon, respectively, indicating at Co @ COF 0 、Co@COF 1 And Co @ COF 2 Forming a graphite framework. And no other diffraction peaks of the cobalt species appear. Co @ COF 0 、Co@COF 1 And Co @ COF 2 S of BET 573.11, 504.32 and 707.69m respectively 2 In terms of/g (FIG. 2e, Table S1). They are lower than the corresponding COF precursors, which means that part of the mesostructure disappears during carbonization. Co @ COF 0 、Co@COF 1 And Co @ COF 2 Mainly around 4.0nm (fig. 2 f). Co @ COF observed by scanning Electron microscope 0 、Co@COF 1 And Co @ COF 2 The morphology of (2). FIGS. 2g-2i show Co @ COF 0 、Co@COF 1 And Co @ COF 2 Is similar to its corresponding COF precursor. In FIG. 3aCo@COF 2 TEM image of (C) shows Co @ COF 2 Are formed from a combination of nanoflakes. For Co @ COF 2 Uniformly dispersed small nanoparticles with a size close to 20nm are observed in fig. 3 b. The lattice fringe spacing of these nanoparticles in fig. 3c was 0.202nm and 0.191nm, respectively, pointing to the (002) and (101) planes of cobalt, confirming that these nanoparticles are Co. The EDS element mapping in FIG. 3d visually shows C, N and the O element at Co @ COF 2 Uniform distribution on the structure, while the Co element is mainly distributed on the small Co nanoparticles supported by the COF structure.
XPS was used to further verify the surface state and chemical composition of Co @ COF. FIG. S2 shows Co @ COF 2 The XPS measurement spectrum of (a) demonstrates the presence of element C, N, O and Co. As shown in fig. 3e, the C1 s spectrum can be divided into four peaks at 284.75eV, 285.60eV,287.38eV, and 289.10eV corresponding to different chemical states of the C atom: C-C/C ═ C, C-O/C ═ N, C ═ O/C-N, and pi-pi ═ satellite peaks. XPS spectra (fig. 3f) of O1S can be deconvoluted into three types of oxygen: -C ═ O (530.90eV), C-O-C (532.38eV), C-OH (533.80 eV). Co @ COF as shown in FIG. 3g 2 The XPS spectrum of N1 s can be deconvoluted into four peaks of different chemical states of the N atom: pyridine N (398.3eV), pyrrole N (400.5eV), graphite N (401.1eV), and oxidized N (402.34 eV). The XPS spectrum of Co 2p in FIG. 3h has two peaks at 780.48eV and 782.87eV, corresponding to Co 0 And Co 2+ 。
Evaluation of Co @ COF/PMS on degradation of SMZ:
the catalytic activity of Co @ COF catalysts in PMS activation was assessed by SMZ degradation. Figure 4a shows that SMZ degraded 21.6% in PMS system within 10 minutes. When three COF precursors are used as catalysts to activate PMS, the degradation efficiency of SMZ in 10min is not higher than 34.5%, which shows that the catalytic performance of the three COF precursors is poor. FIG. 4b shows the results at Co @ COF 0 /PMS、Co@COF 1 PMS and Co @ COF 2 In a PMS system, the degradation efficiency of SMZ within 10min is 63.6 percent, 70.4 percent and 92.4 percent respectively, and the corresponding k is obs 0.081 min, 0.097 min and 0.236min respectively -1 . The catalyst can effectively activate PMS, especially Co @ COF 2 The combination with PMS works best. Therefore, the temperature of the molten metal is controlled,selection of Co @ COF 2 As a representative of the subsequent experiments. Further, Co @ COF 0 、Co@COF 1 And Co @ COF 2 The adsorption efficiency on SMZ was only 10.9% at most in 10 minutes, indicating that SMZ removal is mainly from catalytic degradation and the adsorption effect is negligible. As shown in FIG. 4c, at Co @ COF 2 In the PMS system, the TOC removal rate in 30 minutes was 70.3%. During the degradation process, a small amount of cobalt ions (2.7mg/L) were released and the contribution of leached cobalt ions to SMZ degradation was 43.1%, well below 92.4%, indicating a change from Co @ COF 2 The leached cobalt ions have negligible effect on the degradation of SMZ. Further, Co @ COF 2 the/PMS can also effectively degrade other sulfanilamide antibiotics with similar structure to SMZ. FIG. 4d shows the degradation efficiencies of sulfisoxazole, sulfamethoxazole, sulfapyridine and sulfathiazole within 10 minutes were 98%, 88%, 87% and 98%, respectively. This indicates Co @ COF 2 Can effectively activate PMS to degrade various SAs, and has good applicability.
Co@COF 2 Identification of reaction species of PMS system:
co @ COF was identified by free radical quenching experiments and EPR analysis 2 Active species generated in PMS system. Methanol can quench SO simultaneously 4 And OH, TBA can effectively quench OH. As shown in FIG. 5a, the degradation efficiency of SMZ was only 57.7% when 1.2M TBA was added to the reaction system. After addition of methanol (1.2M), the degradation efficiency dropped to 42.2%. Indicating the presence of SO in the system 4 -and-OH, which are the main free radical active species. 5, 5-dimethyl-1-pyrroline-N-oxide (DMPO) was used as OH and SO in EPR technology 4 (iv) a trapping agent. OH and SO 4 Can form spin adducts with DMPO, DMPO-OH and DMPO-SO, respectively 4 To be. As shown in FIG. 5c, at Co @ COF 2 A typical seven-peak signal for the DMPOX spin adduct (5, 5-dimethylpyrroline- (2) -oxyl- (1)) occurs in the/PMS system, which is likely to result from secondary oxidation. The signal intensity gradually decreases with time during the reduction process between DMPO and strong oxidant.
In addition, p-benzoquinone (p-BQ) was used to examine the presence of superoxide anion O in the system 2 ·-. As shown in FIG. 5a, only 38.5% of the SMZ was degraded when p-BQ (5.0mM) was present. However, p-BQ can also rapidly deplete PMS, approximately 61.6% of PMS being consumed in 10 minutes (FIG. 5 b). Furthermore, DMPO did not capture O 2 Characteristic signal peak of-. this means Co @ COF 2 O may not be present in a/PMS system 2 To prepare. FFA can be used as 1 O 2 An effective quencher of (1). After the addition of FFA, only 28.8% of the SMZ was degraded. However, FFAs can directly consume PMS. To discern the role of FFA in the quenching process, consumption experiments for FFA/PMS were performed (FIG. 5 b). Only 13.9% of PMS was consumed in 10min, indicating that the inhibition of the degradation process by FFA is a quenching 1 O 2 Rather than consuming the PMS. This indicates that 1 O 2 Are the major non-radical active species. In the EPR technique, 4-amino-2, 2,6, 6-Tetramethylpiperidine (TEMP) is used 1 O 2 The collector of (3). As shown in FIG. 5d, a three-line spectrum with equal intensity was observed, assigned to TEMP- 1 O 2 An adduct, which confirms 1 O 2 Is present. And the signal strength gradually increases with time. In summary, Co @ COF 2 OH and SO are all generated in the/PMS system 4 And non-radical activity 1 O 2 During the degradation of SMZ 1 O 2 Mainly comprises the following steps.
Reaction conditions on Co @ COF 2 Impact of PMS degradation of SMZ:
co @ COF for different reaction solution conditions 2 PMS further activity detection was performed. The effect of PMS concentration and catalyst usage on SMZ degradation was investigated. The effect of PMS concentration on SMZ removal is shown in fig. 6 a. The SMZ degradation efficiency increased from 66.1% to 96.6% with increasing PMS concentration (0.2mM-0.6mM), corresponding to k obs Respectively increased from 0.095 to 0.308min -1 (FIG. S7 a). The results show that high concentrations of PMS can produce more active species to attack SMZ to promote the degradation process. Likewise, the amount of catalyst used also significantly affects the degradation efficiency. The degradation efficiency also increased with increasing catalyst loading (figure 6 b). The SMZ degradation efficiency increased from 58.3% to 0.06g/L when the catalyst loading increased from 0.01 to95.5%, corresponding to k obs Respectively increased from 0.079 to 0.288min -1 (FIG. S7 b). The results show that high concentrations of catalyst loading can provide more active sites to catalyze the oxidation of PMS.
In addition, the pH value of the reaction system is also an important parameter influencing the degradation effect of the SMZ. Therefore, different initial pH values (pH) were investigated 0 ) (3.09-11.07) para Co @ COF 2 Impact of PMS degradation of SMZ system (FIG. 6 c). When the pH is higher 0 Within the range of 5.40-9.05, the degradation rate is not obviously changed, the pH value of the solution after the reaction is about 3.6, and the result shows that Co @ COF 2 the/PMS system is over a wide pH range. However, when the pH is adjusted 0 When the average molecular weight is 3.09 or 11.07, the degradation rate is remarkably decreased. This is probably due to the fact that under strongly acidic conditions, Co @ COF 2 Presence of H in PMS System 2 SO 5 As HSO 5 - The conjugate acid of (2) has obvious advantages, and blocks HSO 5 - Decomposition to SO 4 To prepare. In a strongly alkaline environment, SO 4 OH-is eliminated, OH with weak oxidizing power becomes a main active free radical, and the SMZ removal rate is low.
In general, a variety of inorganic anions (Cl) are present in actual water samples - 、HCO 3 - ) And Humic Acid (HA), all of which affect Co @ COF 2 The degradation process and efficiency of the/PMS system to SMZ. As shown in FIG. 6d, low concentration of Cl - (5mM) inhibited degradation of SMZ due to Cl - With SO 4 Reaction of the-and-OH groups to form Cl and Cl with weak redox 2 Ability of. However, high concentrations of Cl - (10mM, 15mM) improved degradation efficiency due to Cl - And HSO 5 - The direct interaction produces HOCl with longer lifetime and stronger oxidizing power. In addition, low concentration of HCO 3 - (5mM, 10mM) promoted the degradation of SMZ. And high concentration of HCO 3 - (15mM) inhibited the progress of the reaction system (FIG. 6e), in which only 76.2% of the SMZ was degraded. High concentration of HCO 3 - Causing the degradation system to be in an alkaline environment, HCO 3 - Can also be used as free radical scavenger and SO 4 And OH transShould be used. As shown in FIG. 6f, degradation of SMZ was significantly inhibited by HA. HA, as a substance containing carboxyl and phenolic hydroxyl groups widely present in water, generally inhibits the degradation of SMZ by quenching free radicals in solution and competes with PMS for adsorption of active sites.
Co@COF 2 The stability and degradation mechanism of (a):
figure 7a shows that the degradation efficiency drops from 92.4% for the first time to 55.1% after three cycles. The catalyst deactivation may be due to blocking of the active sites on the catalyst surface by intermediates adsorbed on the active sites and PMS, reducing Co @ COF 2 On the other hand, due to the loss of active species. After the third cycle, Co @ COF was placed under Ar atmosphere 2 Heating to 500 deg.C to partially restore the activity of the catalyst.
To study Co @ COF more clearly 2 SMZ degradation mechanism by PMS, fresh and used Co @ COF 2 XPS analysis was performed. With fresh Co @ COF 2 In contrast, used Co @ COF 2 Contains the S element, which is caused by the adsorption of SMZ and intermediates by the catalyst (fig. 7 b). Figure 7c shows the change in the relative content of cobalt in the fresh and recycled material. After repeated use, the atomic percent of Co is reduced from 0.46% to 0.25%, which shows that Co is taken as an active site to participate in the reaction and ion loss occurs. As shown in fig. 7d, pyrrole N increased from 20.81% to 52.9% while pyridine N and graphite N decreased from 23.80%, 45.23% to 13.10%, 29.10%, respectively. This indicates that the graphitic nitrogen and pyridine nitrogen act as active sites during PMS activation. Electrochemical impedance spectroscopy in electrochemical measurements (FIG. 7e) indicated that Co @ COF 2 Has an electronic resistance less than Co @ COF 0 And Co @ COF 1 Indicating Co @ COF 2 Has lower charge transfer resistance and larger electron transfer capability, which is beneficial to PMS activation. The Linear Sweep Voltammogram (LSV) curve in FIG. 7f shows when Co @ COF 2 Co @ COF as catalyst electrode 2 The highest current density.
In this respect, the present invention proposes Co @ COF 2 PMS degrades SMZ. First, Co 0 As an active site can interact with PMSFormation of SO 4 And OH (equations (1) - (2)). Further, Co in the carbon layer 0 The charge transfer resistance of Co @ COF is obviously changed, and the electron transfer capability of PMS activation is enhanced. Graphitic nitrogen and pyridine nitrogen also have a positive effect on the structure and electronic properties of the carbon backbone, which can facilitate electron transfer between carbon atoms, which will help activate PMS to produce active species. Non-radical oxide substance 1 O 2 Can be prepared from O 2 Can also be produced by direct cleavage of PMS (equations (3) - (8)). Active Species (SO) continuously generated by Co and N 4 -,. OH and 1 O 2 ) Exerts excellent synergistic effect, degrades SMZ into intermediate products, and finally mineralizes the intermediate products into CO 2 And H 2 O (formula (9)). This mechanism is illustrated in fig. 8.
Co 0 @COF 2 +2HSO 5 - →Co 2+ @COF 2 +2SO 4 ·- +2OH - (1)
Co 0 @COF 2 +2HSO 5 - →Co 2+ @COF 2 +2 · OH+2SO 4 2- (2)
HSO 5 - +H 2 O→H 2 O 2 +HSO 4 - (3)
H 2 O 2 →2 · OH (4)
· OH+H 2 O 2 →HO 2 · +H 2 O (5)
HO 2 · →H + +O 2 ·- (6)
2O 2 ·- +2H + → 1 O 2 +H 2 O 2 (7)
HSO 5 - +SO 5 2- →HSO 4 - +SO 4 2- + 1 O 2 (8)
ROS+SMZ→intermediates→CO 2 +H 2 O (9)
Degradation pathway and toxicity analysis:
degradation products of SMZ were identified by HPLC-TOFMS. Seven intermediates were identified (m/ z 295, 231, 110, 202, 216, 281 and 313). The route of degradation of SMZ was proposed based on defined intermediates (figure 9). First, terminal-NH-of SMZ 2 Oxidized by the active oxidant to form-NO 2 Thereby forming an intermediate product P1, [ M + H ]] + The peak was at m/z 295 (P1). The S-N bond in P1 is attacked and then broken to generate P2. In addition, P1 can be devulcanized to generate P3, which is [ M + H ]] + The peak is located at m/z 231. The occurrence of N-C bond cleavage and ring opening of the SMZ pyrimidine ring results in the production of P4 and P5. Secondly, the SMZ molecule can be attacked by the activating substance, and the benzene ring is hydroxylated to generate P6 and P7([ M + H ]] + Peaks at m/z 281,313). These degradation products are further oxidized to form small molecule species, which are ultimately mineralized to CO 2 And H 2 O。
Toxicity of SMZ and its degradation intermediates was predicted using the ECOSAR program (version 1.11) using available data based on Quantitative Structure Activity Relationships (QSAR). According to the estimated ecotoxicity values in Table S3, the chronic toxicity of SMZ to daphnia (< 1mg/L) and to fish and green algae (1-10mg/L) was highly detrimental. P1 and P6 are highly toxic to fish in chronic toxicity, but fortunately, P1 and P6 are degraded to P2, a product that is non-toxic or bottom-toxic to fish. P5 and P7 were only harmful to daphnia in chronic toxicity (< 1 mg/L). In summary, SMZ can be represented by Co @ COF 2 the/PMS system is degraded into low-harm or harmless products, and further proves that Co @ COF 2 Practical application potential in water treatment.
And (4) conclusion:
in this embodiment, a novel COFs material with high crystallinity and large specific surface area is used as a cobalt-loaded carrier, and cobalt nanoparticle-embedded nitrogen-doped carbon porous catalyst (Co @ COF) cobalt salt is prepared by high-temperature pyrolysis of the COFs material. Co @ COF has multiple active sites (Co) 0 Pyridine N and graphite N) in the presence of PMS activation to degrade SMZThe catalyst has excellent catalytic performance. The SMZ degradation efficiency reaches 92.4% in 10min, and the TOC removal rate reaches 70.3% in 30 min. The SO in the system is determined by combining a free radical quenching experiment and an EPR analysis 4 -,. OH and 1 O 2 to is that 1 O 2 At Co @ COF 2 Plays a major role in the degradation of SMZ in the/PMS system. In addition, toxicity evaluation shows that SMZ is effectively removed and biological toxicity is reduced, and Co @ COF/PMS is an effective and promising SMZ-polluted wastewater treatment technology.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of a nitrogen-doped carbon porous catalyst embedded with cobalt nanoparticles is characterized by comprising the steps of carrying out Schiff base reaction on TPB and DVA in an organic solvent under the initiation of glacial acetic acid to obtain a COF precursor, mixing the COF precursor and cobalt salt in water, heating and stirring until water is completely evaporated to obtain a solid product, and heating the solid product to 600-800 ℃ under the condition of inert atmosphere for pyrolysis to obtain the catalyst.
2. The method for preparing a cobalt nanoparticle embedded nitrogen doped carbon porous catalyst as claimed in claim 1, wherein a cobalt salt is added in the Schiff base reaction;
preferably, in the Schiff base reaction, the molar ratio of TPB to cobalt salt is 1: 0.5-2.0; the mol ratio of TPB to cobalt salt is preferably 1: 1.20-1.40.
3. The preparation method of the cobalt nanoparticle embedded nitrogen-doped carbon porous catalyst as claimed in claim 1, wherein in the Schiff base reaction, the molar ratio of TPB to DVA is 1: 1.5-3.0;
or in the Schiff base reaction, the organic solvent is acetonitrile;
or standing for 48-96 h at room temperature in the Schiff base reaction.
4. The method of claim 1, wherein the COF precursor is purified by the following steps: centrifugal separation, washing and drying;
or the mass ratio of the COF precursor to the cobalt salt is 10: 0.50-2.00;
or the heating rate of pyrolysis is 1-10 ℃/min; preferably 3 to 7 ℃/min, and more preferably 4 to 6 ℃/min.
5. A cobalt nanoparticle embedded nitrogen-doped carbon porous catalyst, which is characterized by being obtained by the preparation method of any one of claims 1 to 4.
6. Use of the cobalt nanoparticle embedded nitrogen doped carbon porous catalyst of claim 5 in activating peroxymonosulfate to degrade sulfonamide antibiotics.
7. A kit for degrading sulfonamide antibiotics, which comprises the cobalt nanoparticles embedded nitrogen-doped carbon porous catalyst and peroxymonosulfate as claimed in claim 5.
8. The kit for degrading a sulfonamide antibiotic of claim 7, which includes a quencher; the quencher is preferably ethanol.
9. A method for treating wastewater containing sulfonamide antibiotics, which is characterized in that the wastewater containing sulfonamide antibiotics to be treated is treated by adding the cobalt nanoparticle embedded nitrogen-doped carbon porous catalyst and peroxymonosulfate according to claim 5.
10. The method for treating wastewater containing sulfonamide antibiotics according to claim 9, wherein the ratio of the catalyst to the peroxymonosulfate is 90-110: 1, g: mol;
or, the concentration of the peroxymonosulfate is 0.4 to 0.6 mM;
or the addition amount of the catalyst is 0.04-0.06 g/L;
or, the pH is 5-10, and the preferable pH is 5.40-9.05;
or, the treatment system contains chloride ions, the concentration of the chloride ions is 10-15 mM;
in some embodiments, the treatment system comprises HCO 3 - ，HCO 3 - The concentration is 5 to 10 mM.
CN202210799730.7A 2022-07-08 2022-07-08 Cobalt nanoparticle embedded nitrogen-doped carbon porous catalyst and preparation method and application thereof Active CN114939410B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210799730.7A CN114939410B (en) 2022-07-08 2022-07-08 Cobalt nanoparticle embedded nitrogen-doped carbon porous catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210799730.7A CN114939410B (en) 2022-07-08 2022-07-08 Cobalt nanoparticle embedded nitrogen-doped carbon porous catalyst and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114939410A true CN114939410A (en) 2022-08-26
CN114939410B CN114939410B (en) 2023-07-21

Family

ID=82911241

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210799730.7A Active CN114939410B (en) 2022-07-08 2022-07-08 Cobalt nanoparticle embedded nitrogen-doped carbon porous catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114939410B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2020101584A4 (en) * 2019-07-31 2020-09-10 Hefei University Of Technology Preparation method of metal monatomic composite loaded with covalent organic framework (COF)-derived carbon skeleton
WO2021051896A1 (en) * 2019-09-20 2021-03-25 中国科学院宁波材料技术与工程研究所 Monolithic catalyst with cobalt oxide nanowire wrapped by nitrogen-doped carbon, and preparation method therefor
CN112958094A (en) * 2021-02-05 2021-06-15 山东省分析测试中心 Catalyst for efficiently catalyzing and degrading sulfonamide antibiotics and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2020101584A4 (en) * 2019-07-31 2020-09-10 Hefei University Of Technology Preparation method of metal monatomic composite loaded with covalent organic framework (COF)-derived carbon skeleton
WO2021051896A1 (en) * 2019-09-20 2021-03-25 中国科学院宁波材料技术与工程研究所 Monolithic catalyst with cobalt oxide nanowire wrapped by nitrogen-doped carbon, and preparation method therefor
CN112958094A (en) * 2021-02-05 2021-06-15 山东省分析测试中心 Catalyst for efficiently catalyzing and degrading sulfonamide antibiotics and preparation method and application thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
HA TRANG NGUYEN ET AL.: "Metal-complexed covalent organic frameworks derived N-doped carbon nanobubble–embedded cobalt nanoparticle as a magnetic and efficient catalyst for oxone activation", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》, vol. 591, pages 2 *
KAIXIANG CHEN ET AL.: "A novel hollow Co3O4@N-doped carbon nanobubble film composite for high-performance anode of lithium-ion batteries", 《COMPOSITES PART B》, vol. 224, pages 2 *
WENDE MA ET AL.: "Room-temperature controllable synthesis of hierarchically flower-like hollow covalent organic frameworks for brain natriuretic peptide enrichment", 《CHEM. COMMUN.》, vol. 57, pages 7363 *
张春燕等: "共价有机骨架聚合物(COFs)的应用研究进展", 《高分子通报》, no. 2, pages 2 *

Also Published As

Publication number Publication date
CN114939410B (en) 2023-07-21

Similar Documents

Publication Publication Date Title
Zeng et al. Fe/Fe 3 C@ N-doped porous carbon hybrids derived from nano-scale MOFs: robust and enhanced heterogeneous catalyst for peroxymonosulfate activation
Xu et al. Catalytic degradation of sulfamethoxazole through peroxymonosulfate activated with expanded graphite loaded CoFe2O4 particles
Wang et al. Enhanced heterogeneous activation of peroxymonosulfate by Co and N codoped porous carbon for degradation of organic pollutants: the synergism between Co and N
Liu et al. Oxygen vacancies-enriched Cu/Co bimetallic oxides catalysts for high-efficiency peroxymonosulfate activation to degrade TC: Insight into the increase of Cu+ triggered by Co doping
Wang et al. Facile construction of novel organic–inorganic tetra (4-carboxyphenyl) porphyrin/Bi2MoO6 heterojunction for tetracycline degradation: Performance, degradation pathways, intermediate toxicity analysis and mechanism insight
Zhu et al. In-situ formed N-doped bamboo-like carbon nanotubes encapsulated with Fe nanoparticles supported by biochar as highly efficient catalyst for activation of persulfate (PS) toward degradation of organic pollutants
Zhang et al. Carbon nitride nanotubes anchored with high-density CuNx sites for efficient degradation of antibiotic contaminants under photo-Fenton process: Performance and mechanism
Liang et al. An insight into metal organic framework derived N-doped graphene for the oxidative degradation of persistent contaminants: formation mechanism and generation of singlet oxygen from peroxymonosulfate
Wang et al. Adsorption and Fenton-like removal of chelated nickel from Zn-Ni alloy electroplating wastewater using activated biochar composite derived from Taihu blue algae
Xie et al. Sulfur anchored on N-doped porous carbon as metal-free peroxymonosulfate activator for tetracycline hydrochloride degradation: Nonradical pathway mechanism, performance and biotoxicity
Xie et al. Degradation of tetracycline hydrochloride through efficient peroxymonosulfate activation by B, N co-doped porous carbon materials derived from metal-organic frameworks: Nonradical pathway mechanism
Du et al. Construction and application of BiOCl/Cu-doped Bi2S3 composites for highly efficient photocatalytic degradation of ciprofloxacin
Zhao et al. MOFs-derived MnOx@ C nanosheets for peroxymonosulfate activation: Synergistic effect and mechanism
CN114425340B (en) Preparation of biochar modified cobalt-iron bimetallic composite catalyst and application of biochar modified cobalt-iron bimetallic composite catalyst in catalytic degradation of tetracycline
Li et al. Insights into performance and mechanism of ZnO/CuCo2O4 composite as heterogeneous photoactivator of peroxymonosulfate for enrofloxacin degradation
Xiao et al. C-nanocoated ZnO by TEMPO-oxidized cellulose templating for improved photocatalytic performance
Jalil et al. Photodecolorization of methylene blue over EGZrO2/EGZnO/EGFe2O3/HY photocatalyst: Effect of radical scavenger
Huang et al. Enteromorpha prolifera-derived Fe3C/C composite as advanced catalyst for hydroxyl radical generation and efficient removal for organic dye and antibiotic
Lu et al. Three-dimensional electro-Fenton degradation of ciprofloxacin catalyzed by CuO doped red mud particle electrodes: Electrodes preparation, kinetics and mechanism
Yu et al. Ternary metal oxide embedded carbon derived from metal organic frameworks for adsorption of methylene blue and acid red 73
Zhao et al. Investigation of the degradation and dehalogenation properties of florfenicol by heterogeneous Fenton reaction activated with MIL-53 (Al)-supported nano zero-valent iron
Saputra et al. High performance magnetic carbonaceous materials as a photo Fenton-like catalyst for organic pollutant removal
Qin et al. Synergistic activation of peroxymonosulfate by nickel-cobalt hexacyanoferrate derived hybrid metal oxides for efficient sulfamethoxazole degradation
Zhang et al. Catalytic degradation of tetracycline hydrochloride using surface nitrogen-rich activated carbon based on polyaniline
Liu et al. Enhanced degradation of tetracycline by TiO2@ MXene with peroxydisulfate under visible light irradiation

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant