CN115739164A - Preparation method and application of spherical coralline carbon nitride loaded iron monoatomic atom - Google Patents
Preparation method and application of spherical coralline carbon nitride loaded iron monoatomic atom Download PDFInfo
- Publication number
- CN115739164A CN115739164A CN202211648215.5A CN202211648215A CN115739164A CN 115739164 A CN115739164 A CN 115739164A CN 202211648215 A CN202211648215 A CN 202211648215A CN 115739164 A CN115739164 A CN 115739164A
- Authority
- CN
- China
- Prior art keywords
- carbon nitride
- iron
- preparation
- spherical
- melamine
- 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.)
- Pending
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 95
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 17
- 229940088710 antibiotic agent Drugs 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 230000000593 degrading effect Effects 0.000 claims abstract description 6
- 235000014653 Carica parviflora Nutrition 0.000 claims abstract description 4
- 241000243321 Cnidaria Species 0.000 claims abstract description 4
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 51
- 229920000877 Melamine resin Polymers 0.000 claims description 38
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 26
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 14
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 6
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000007602 hot air drying Methods 0.000 claims description 2
- 238000007603 infrared drying Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 230000003213 activating effect Effects 0.000 abstract description 5
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 abstract description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 24
- GSDSWSVVBLHKDQ-JTQLQIEISA-N Levofloxacin Chemical compound C([C@@H](N1C2=C(C(C(C(O)=O)=C1)=O)C=C1F)C)OC2=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-JTQLQIEISA-N 0.000 description 13
- 229960003376 levofloxacin Drugs 0.000 description 13
- 230000015556 catabolic process Effects 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 12
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 12
- 235000019341 magnesium sulphate Nutrition 0.000 description 12
- 238000009210 therapy by ultrasound Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Images
Classifications
-
- 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
Abstract
The invention discloses a spherical coralline carbon nitride loaded iron monatomic material, and a preparation method and application thereof. The material has good application in the aspect of activating potassium hydrogen Persulfate (PMS) to degrade antibiotics, a carbon nitride supermolecule precursor is prepared by a supermolecule method during preparation, iron monoatomic atoms are chelated and anchored in the process, dimethyl sulfoxide is used as a solvent, and then the spherical coralliform carbon nitride loaded iron monoatomic material is synthesized by high-temperature calcination. The preparation method successfully loads the iron monatomic on the carbon nitride, and the introduced iron monatomic is used as an active site to effectively activate PMS. The three-dimensional spherical coral shape of the carbon nitride can provide more active sites, and the iron dispersed in the form of single atom has the maximum utilization efficiency, shows higher activity and stability in the aspect of degrading antibiotics, and has wide application prospect.
Description
Technical Field
The invention relates to a preparation method of spherical coralline carbon nitride loaded iron monoatomic atoms and application of the spherical coralline carbon nitride loaded iron monoatomic atoms in activation of PMS (magnesium sulfate) degradation antibiotics, and belongs to the field of functional technical materials.
Background
Antibiotics are widely used in medicine, agriculture, animal husbandry and aquaculture because of their good bactericidal effects. However, due to insufficient early recognition, the antibiotics are abused or randomly discharged, and the like, so that the antibiotics are finally discharged into the water environment in a large quantity, and the ecological environment and the human health are harmed.
The existing methods for removing antibiotics mainly comprise methods such as adsorption, photocatalysis, fenton-like, biodegradation and the like. In these methods, the adsorption method can only concentrate antibiotics in the catalyst but can not degrade the antibiotics, the effect of photocatalytic degradation of antibiotics is not ideal, and complete removal of antibiotics is difficult in biological treatment. The PMS activated oxidation method of the Fenton-like method can effectively remove antibiotics, so that the method has more attention and becomes a main method for removing the antibiotics.
In Fenton-like PMS activation oxidation, the activation effect of transition metals is best, but transition metal ions input in homogeneous reaction cannot be recycled for multiple times, and metal ions dispersed in a water body pollute the water body, so that the Fenton-like method has high cost and has the problems of secondary pollution, and the development and application of the Fenton-like PMS activation oxidation are restricted.
The heterogeneous reaction system can effectively avoid the problem, the catalyst can be recycled, and the problem that metal ions pollute the water body is effectively reduced. Studies have shown that among all heterogeneous metal catalysts, the monatomic catalyst exhibits the most superior PMS-activating performance due to its maximum atom utilization.
The carbon nitride is used as a carrier for loading catalytic active substances, and has the advantages of stability, greenness and easy synthesis. By utilizing the characteristic that melamine and cyanuric acid can spontaneously form a three-dimensional spherical carbon nitride precursor in a dissolved state, the three-dimensional morphology can be continuously maintained after high-temperature calcination, and a basis with great development potential is provided for carbon nitride as an excellent carrier: the carbon nitride is used as a carrier, so that the number of active sites can be effectively increased, and the degradation of pollutants by activating PMS is facilitated.
For example, chinese patent application CN113019415A discloses a preparation method of an iron-based supramolecular graphitic carbon nitride photocatalyst, which is prepared by pyrolyzing a precursor generated by a supramolecular self-assembly reaction of melamine, cyanuric acid and ferric salt. However, the proposal adopts water as a solvent, and does not adopt other substances to fix and disperse the iron, and the whole proposal shows that the iron is poor in fixation and dispersion, low in specific surface area and few in active sites. Also, for example, chinese patent application CN111939961A discloses a controllable synthesis method of a low-cost monatomic catalyst with high loading capacity, the monatomic catalyst of the scheme is prepared by a precursor immobilization-high temperature pyrolysis scheme, and the synthesis method is simple, low in production cost, high in synthesized yield and good in purity, and is suitable for the requirement of expanded production. According to the method, metal ions are fixed through a metal-organic complex formed by coordination of an organic ligand and the metal ions, and the complex is dispersed and fixed by using a precursor formed by hydrogen bond self-assembly of melamine, cyanuric acid and the complex, so that the effect of step fixing of the metal ions is achieved. However, although the citric acid complexation solves the problem of fixing and dispersing metal ions to a certain extent, water is used as a solvent, a carbon nitride carrier with a high specific surface area cannot be obtained, and the number of active sites is relatively small.
Based on the research progress and existing problems, it is an urgent need to provide a carbon nitride carrier with sufficient active sites, stable structure and high-efficiency catalytic active substance loading.
Disclosure of Invention
In order to overcome the problems of low specific surface area and few active sites of active substance-loaded carbon nitride in the prior art, the invention provides a preparation method and application of spherical coral-shaped carbon nitride-loaded iron monoatomic ions, and the material can effectively activate PMS to degrade antibiotics. Dimethyl sulfoxide is used as a solvent to successfully prepare three-dimensional spherical coralline iron-loaded monatomic carbon nitride, the specific surface area of the carbon nitride is large, more active sites are provided by dendritic carbon nitride in the spherical coral morphology, and the three-dimensional structure of the carbon nitride can effectively expose the active sites to promote activation of potassium hydrogen Persulfate (PMS).
The first aspect of the invention provides iron-loaded single-atom spherical coral-shaped carbon nitride, the carbon nitride material is in a three-dimensional spherical coral-shaped appearance, iron single atoms are distributed on the three-dimensional structure of the carbon nitride, the average grain diameter of the carbon nitride is 2.5-4.2 mu m, and the specific surface area of the carbon nitride is 162-184m 2 /g。
The second aspect of the present invention provides a preparation method of the iron-loaded single-atom spherical coral-shaped carbon nitride, specifically comprising the following steps:
s1, respectively preparing a melamine solution, a melamine solution and a mixed solution of citric acid and ferric nitrate;
s2, adding the mixed solution of the citric acid and the ferric nitrate into the melamine solution, then adding the melamine solution, and stirring for reaction;
s3, filtering, drying and grinding the reacted liquid to obtain a supramolecular carbon nitride precursor;
and S4, calcining the carbon nitride precursor at high temperature to obtain the iron-single-atom-loaded three-dimensional spherical coralline carbon nitride.
In S1, ferric nitrate is added and metered in the form of ferric nitrate nonahydrate, and three solutions all use dimethyl sulfoxide as a solvent, do not require the concentration of the dimethyl sulfoxide and are suitable for subsequent mixing reaction. For example, 1g of melamine is dissolved in 40mL of DMSO, 1.02g of melamine is dissolved in 20mL of DMSO, and 0.46g of citric acid and 0.32g of ferric nitrate nonahydrate are added to 20mL of DMSO.
Preferably, the present invention applies sonication during the preparation of all three solutions.
Preferably, the mass ratio of the melamine to the cyanuric acid to the citric acid to the ferric nitrate nonahydrate is (0.5-1): (1-1.2): (0.4-0.6): (0.3-0.5).
Preferably, in S2, the stirring reaction time is 10-14h; more preferably, the reaction time is 12 hours.
Preferably, in S3, the drying is infrared drying or hot air drying at 60-80 ℃, and the drying mode and temperature are controlled, so that the shape inheritance of the precursor can be maintained.
Preferably, in S4, the high-temperature calcination is to heat up to 550-575 ℃ at the speed of 3-10 ℃/min for 3-4h under the inert atmosphere, and then naturally cool to room temperature. Further preferably, the inert atmosphere is a nitrogen atmosphere.
In a third aspect, the invention provides the application of the iron-loaded single-atom spherical coral-shaped carbon nitride, namely the iron-loaded single-atom spherical coral-shaped carbon nitride can be used for degrading antibiotics, especially levofloxacin.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with a mechanical stirring mode, the ultrasonic mixing mode has better dispersion effect, can promote the uniform dispersion of the iron monoatomic atoms on the three-dimensional spherical coral-shaped carbon nitride, and carries out step-by-step ultrasonic dispersion on each raw material, thereby improving the dissolving and dispersing effects of the raw materials and further improving the dispersion of the iron monoatomic atoms on the carbon nitride.
2. The invention adopts dimethyl sulfoxide as solvent, and compared with water as solvent, the product obtained by the method has three-dimensional spherical coral shape, larger specific surface area and active site, and the specific surface area can reach 162m 2 More than g, the surface, the inside and the branches of the carbon nitride are uniformly dispersed with iron monoatomic, and the maximum atom utilization rate is achieved.
3. The carbon nitride with special appearance prepared by the invention is in a three-dimensional spherical coral-shaped structure, provides more active sites and is more uniformUniformly loads iron monatomic, greatly improves the performance of the material for activating PMS, greatly improves the degradation capability of levofloxacin, and ensures that the concentration C/C of the levofloxacin is 60min 0 Below 0.25147, the concentration (C/C) is far lower than that of levofloxacin when water is used as solvent 0 0.42713) owing to the uniform distribution of the iron monoatomic atoms on and in the surface and on the branches, the activity and the degradability are greatly improved.
Drawings
FIG. 1 is an XRD pattern of samples prepared in examples 1-3, comparative example 1;
FIG. 2 is an FTIR spectrum of samples prepared in examples 1-3;
FIG. 3 is a fine map of XPS versus Fe2p orbits for the samples prepared in example 3;
FIG. 4 is SEM and TEM spectra of samples prepared in example 3;
FIG. 5 is a high angle annular dark field spherical aberration TEM image of the sample prepared in example 3;
FIG. 6 is a graph showing the degradation kinetics of levofloxacin in samples prepared in examples 1 to 3 and comparative examples 1 to 2.
Detailed Description
In order to better explain the present invention, the invention is explained and illustrated by the following detailed description.
Example 1
A preparation method of three-dimensional spherical coral-shaped carbon nitride loaded iron monoatomic atoms comprises the following steps:
1g of melamine is dissolved in 40mL of dimethyl sulfoxide and subjected to ultrasonic treatment for 30 minutes, 1.02g of melamine is dissolved in 20mL of dimethyl sulfoxide and subjected to ultrasonic treatment for 30 minutes, 0.32g of ferric nitrate nonahydrate and 0.46g of citric acid are dissolved in 20mL of dimethyl sulfoxide and subjected to ultrasonic treatment for 30 minutes, the dissolved ferric nitrate nonahydrate and citric acid are poured into a melamine solution, and then the melamine solution is poured and stirred for reaction for 12 hours. After suction filtration and drying, 1g of the powder is weighed and put into a porcelain ark to be calcined for 4 hours at 550 ℃ in a tube furnace under nitrogen atmosphere, and the heating rate is 5 ℃ per minute. Naturally cooling to room temperature, taking out the sample to obtain the iron-loaded single-atom three-dimensional spherical coralline carbon nitride, named as Fe-CN-550,it was found to have an average particle diameter of 4.2 μm and a specific surface area of 179m 2 The XRD and FTIR patterns are shown in FIGS. 1-2.
Example 2
A preparation method of three-dimensional spherical coral-shaped carbon nitride loaded iron monoatomic atoms comprises the following steps:
0.5g of melamine is dissolved in 30mL of dimethyl sulfoxide and subjected to ultrasonic treatment for 30 minutes, 1.2g of melamine is dissolved in 30mL of dimethyl sulfoxide and subjected to ultrasonic treatment for 30 minutes, 0.3g of ferric nitrate nonahydrate and 0.6g of citric acid are dissolved in 20mL of dimethyl sulfoxide and subjected to ultrasonic treatment for 30 minutes, the dissolved ferric nitrate nonahydrate and citric acid are poured into a melamine solution, and then the melamine solution is poured into the melamine solution again and stirred for reaction for 10 hours. After suction filtration and drying, 1g of the powder is weighed and put into a porcelain ark to be calcined in a tube furnace at 565 ℃ for 3 hours, and the heating rate is 3 ℃ per minute. Naturally cooling to room temperature, taking out a sample to obtain the iron-loaded single-atom three-dimensional spherical coral-shaped carbon nitride named as Fe-CN-565, and detecting that the average particle size of the iron-loaded single-atom three-dimensional spherical coral-shaped carbon nitride (Fe-CN-565) is 3.2 mu m and the specific surface area is 184m 2 /g。
Example 3
A preparation method of spherical coral-shaped carbon nitride loaded iron monoatomic ions comprises the following steps:
0.8g of melamine is dissolved in 40mL of dimethyl sulfoxide and subjected to ultrasonic treatment for 30 minutes, 1g of melamine is dissolved in 30mL of dimethyl sulfoxide and subjected to ultrasonic treatment for 30 minutes, 0.5g of ferric nitrate nonahydrate and 0.4g of citric acid are dissolved in 30mL of dimethyl sulfoxide and subjected to ultrasonic treatment for 20 minutes, the dissolved ferric nitrate nonahydrate and citric acid are poured into a melamine solution, and then the melamine solution is poured and stirred for reaction for 11 hours. After suction filtration and drying, 1g of the powder is weighed and put into a porcelain ark to be calcined in a tubular furnace at 575 ℃ for 4 hours, and the heating rate is 10 ℃ per minute. Naturally cooling to room temperature, taking out the sample to obtain the iron-loaded single-atom three-dimensional spherical coral-shaped carbon nitride named as Fe-CN-575, wherein the average particle size of the iron-loaded single-atom three-dimensional spherical coral-shaped carbon nitride (Fe-CN-575) is 2.5 mu m, and the specific surface area is 162m 2 /g。
Comparative example 1
A preparation method of three-dimensional spherical coralline carbon nitride comprises the following steps:
1g of melamine was dissolved in 40mL of dimethyl sulfoxide and sonicated for 30 minutes, 1.02g of melamine was dissolved in 20mL of dimethyl sulfoxide and sonicated for 30 minutes, after which the dissolved melamine solution was poured into the melamine solution and reacted for 12 hours. After suction filtration and drying, 1g of the powder is weighed and put into a porcelain ark to be calcined in a tubular furnace at 575 ℃ for 4 hours, and the heating rate is 5 ℃ per minute. Naturally cooling to room temperature, taking out the sample to obtain three-dimensional spherical coral-shaped Carbon Nitride (CN), wherein the average particle diameter of the three-dimensional spherical coral-shaped Carbon Nitride (CN) is 4.8 μm, and the specific surface area of the three-dimensional spherical coral-shaped Carbon Nitride (CN) is 171m 2 /g。
Comparative example 2
A preparation method of layered carbon nitride supported iron monoatomic atoms comprises the following steps:
1g of melamine is dissolved in 40mL of water and is subjected to ultrasonic treatment for 30 minutes, 1.02g of melamine is dissolved in 20mL of water and is subjected to ultrasonic treatment for 30 minutes, 0.32g of ferric nitrate nonahydrate and 0.46g of citric acid are dissolved in 20mL of water and are subjected to ultrasonic treatment for 30 minutes, the dissolved ferric nitrate nonahydrate and citric acid are poured into the melamine solution, and then the melamine solution is poured into the melamine solution and is stirred and reacted for 12 hours. After suction filtration and drying, 1g of the powder is weighed and put into a porcelain ark to be calcined in a tubular furnace at 575 ℃ for 4 hours, and the heating rate is 5 ℃ per minute. Naturally cooling to room temperature, taking out the sample to obtain the iron-loaded monatomic layered carbon nitride named Fe-CN, wherein the specific surface area of the iron-monatomic layered carbon nitride load (Fe-CN) is 102m 2 In terms of/g, no three-dimensional spherical coral-like structure could be obtained.
The method for investigating the degradation performance of the simulated pollutants provided by the invention comprises the following steps:
20mg of the products prepared in examples 1-3 and comparative examples 1-2 were mixed with 50mL of a 10mg/L (C) solution in a beaker 0 ) And the suspension was stirred with a magnetic stirrer, PMS was added after equilibrium of adsorption was reached. To obtain degradation kinetic data, 1mL of solution was removed at the specified time and the LVX concentration (C) was determined by high performance liquid chromatography HPLC.
It can be observed from fig. 1 that the peak appears at 13 degrees for the carbon nitride triazine repeat unit and at 27 degrees for the graphite-like layered stack. The corresponding peaks in Fe-CN-550, fe-CN-565 and Fe-CN-575 are weaker, however, because the presence of the iron monoatomic atom destroys the triazine repeat unit to some extent, increasing the interlayer spacing, but they remain in the carbon nitride configuration as a whole.
From FIG. 2, it can be observed that Fe-CN-550, fe-CN-565 and Fe-CN-575 both show a peak at around 800 for the triazine ring of carbon nitride, which indicates that the structure of carbon nitride is maintained after the carbon nitride supports iron single atom.
From fig. 3, the corresponding peak of Fe can be seen, indicating the successful introduction of iron species into the carbon nitride.
From fig. 4 it can be seen that the synthetic material is a three-dimensional spherical coral-like carbon nitride, which is overall spherical and is composed of a dendritic coral-like structure, which facilitates the exposure of more active sites.
From fig. 5 it can be seen that the iron is dispersed in a monoatomic form, indicating successful synthesis of carbon nitride supported iron monoatomic.
From the figure 6, it can be seen that after the iron monoatomic group is introduced into the material, the rate of degrading antibiotics by activating PMS is greatly improved compared with carbon nitride, and when dimethyl sulfoxide is used as a solvent, the prepared carbon nitride is in a three-dimensional spherical coral-shaped structure and provides more active sites, compared with water as a solvent, the performance of activating PMS by the material is greatly improved, the degradation capability of levofloxacin is improved, the degradation capability of the product prepared in the comparative example 1 for simulating pollutants is slow in degrading Levofloxacin (LVX), and at 60min, C/C is high 0 Still as high as 0.91713; the product prepared in comparative example 2 is faster in degrading Levofloxacin (LVX) than the simulated pollutant degradation performance of comparative example 1, which benefits from the uniform loading of iron, but the specific surface area of the obtained product is small, the active site can not be well provided for the iron single atom, and the C/C is higher at 60min 0 Still up to 0.42713; compared with the products prepared by the comparative examples 1-2, the products prepared by the examples 1-3 have obvious rapid degradation capability of simulating pollutant degradation performance to degrade Levofloxacin (LVX), and C/C in the examples 1-3 is 60min 0 Respectively 0.25147, 0.06946 and 0.01934, which mainly benefit from the adoption of dimethyl sulfoxideThe three-dimensional spherical coral-shaped carbon nitride is obtained as a solvent, is spherical as a whole and is formed by a dendritic coral-shaped structure, the three-dimensional spherical coral-shaped structure is favorable for exposing more active sites, and the iron single atoms are uniformly distributed on the surface, the inside and branches of the tree, so that the activity and the degradation capability are greatly improved.
It will be appreciated by those skilled in the art that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The embodiments disclosed above are therefore to be considered in all respects as illustrative and not restrictive. All changes which come within the scope of or equivalence to the invention are intended to be embraced therein.
Claims (10)
1. The iron-single-atom-loaded spherical coral-shaped carbon nitride is characterized in that the carbon nitride is in a three-dimensional spherical coral shape, iron single atoms are distributed on the three-dimensional structure of the carbon nitride, the average particle size of the carbon nitride is 2.5-4.2 mu m, and the specific surface area of the carbon nitride is 162-184m 2 /g。
2. The preparation method of the iron-loaded single-atom spherical coralline carbon nitride as claimed in claim 1, which is characterized by comprising the following steps:
s1, preparing a melamine solution, a melamine solution and a mixed solution of citric acid and ferric nitrate respectively;
s2, adding the mixed solution of the citric acid and the ferric nitrate into the melamine solution, then adding the melamine solution, and stirring for reaction;
s3, carrying out suction filtration, drying and grinding on the reacted liquid to obtain a supermolecule carbon nitride precursor;
and S4, calcining the carbon nitride precursor at high temperature to obtain the iron-monoatomic-loaded three-dimensional spherical coralline carbon nitride.
3. The preparation method according to claim 2, wherein in S1, the solvent in the melamine solution, and the mixed solution of citric acid and ferric nitrate is dimethyl sulfoxide, and ultrasound is applied during solution preparation.
4. The method according to claim 2, wherein in S1, the ferric nitrate is added and metered in the form of ferric nitrate nonahydrate.
5. The method according to claim 2 or 4, wherein the mass ratio of the melamine, the cyanuric acid, the citric acid and the ferric nitrate nonahydrate in S1 is (0.5-1): (1-1.2): (0.4-0.6): (0.3-0.5).
6. The preparation method according to claim 2, wherein in S2, the stirring reaction time is 10 to 14 hours; preferably, the reaction time is 12h with stirring.
7. The method according to claim 2, wherein the drying in S3 is infrared drying or hot air drying at 60 to 80 ℃.
8. The preparation method of claim 2, wherein in the step S4, the high-temperature calcination is to heat up to 550-575 ℃ at a rate of 3-10 ℃/min for 3-4h in an inert atmosphere, and then naturally cool the mixture to room temperature.
9. The production method according to claim 2 or 8, wherein in S4, the inert atmosphere is a nitrogen atmosphere.
10. Use of the iron-loaded single-atom spherical coral-shaped carbon nitride obtained by the preparation method of any one of claims 2 to 9 for degrading antibiotics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211648215.5A CN115739164A (en) | 2022-12-21 | 2022-12-21 | Preparation method and application of spherical coralline carbon nitride loaded iron monoatomic atom |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211648215.5A CN115739164A (en) | 2022-12-21 | 2022-12-21 | Preparation method and application of spherical coralline carbon nitride loaded iron monoatomic atom |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115739164A true CN115739164A (en) | 2023-03-07 |
Family
ID=85348638
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211648215.5A Pending CN115739164A (en) | 2022-12-21 | 2022-12-21 | Preparation method and application of spherical coralline carbon nitride loaded iron monoatomic atom |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115739164A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110465315A (en) * | 2018-05-09 | 2019-11-19 | 湖南大学 | Supermolecule polymerize carbon nitride photocatalyst and its preparation method and application |
| CN111408413A (en) * | 2020-03-30 | 2020-07-14 | 浙江工商大学 | Modified carbon nitride/Fe-based MOF composite material and preparation method and application thereof |
| CN113058635A (en) * | 2021-04-06 | 2021-07-02 | 南昌航空大学 | Monatomic catalyst for activating persulfate to generate pure singlet oxygen and preparation method and application thereof |
| WO2022012098A1 (en) * | 2021-03-01 | 2022-01-20 | 中国科学院过程工程研究所 | Hydrogenation catalyst, preparation method therefor and use thereof |
| CN114534759A (en) * | 2022-01-19 | 2022-05-27 | 湖南大学 | Monoatomic cobalt-supported tubular carbon nitride catalyst and preparation method and application thereof |
-
2022
- 2022-12-21 CN CN202211648215.5A patent/CN115739164A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110465315A (en) * | 2018-05-09 | 2019-11-19 | 湖南大学 | Supermolecule polymerize carbon nitride photocatalyst and its preparation method and application |
| CN111408413A (en) * | 2020-03-30 | 2020-07-14 | 浙江工商大学 | Modified carbon nitride/Fe-based MOF composite material and preparation method and application thereof |
| WO2022012098A1 (en) * | 2021-03-01 | 2022-01-20 | 中国科学院过程工程研究所 | Hydrogenation catalyst, preparation method therefor and use thereof |
| CN113058635A (en) * | 2021-04-06 | 2021-07-02 | 南昌航空大学 | Monatomic catalyst for activating persulfate to generate pure singlet oxygen and preparation method and application thereof |
| CN114534759A (en) * | 2022-01-19 | 2022-05-27 | 湖南大学 | Monoatomic cobalt-supported tubular carbon nitride catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112452346B (en) | Universal method for preparing metal single-atom carbon-based catalyst and application | |
| CN112973754A (en) | Preparation method of novel transition metal monoatomic catalyst loaded on carbon-based material | |
| CN102249395B (en) | Water ozonization treatment method by taking cerium oxide nanomaterial as catalyst | |
| JP2008259993A (en) | Method for dispersing and fixing gold fine particle to carrier, gold fine particle-deposited carrier obtained thereby, catalyst and colorant | |
| CN112521617B (en) | Polyacid-based metal organic framework material for adsorbing antibiotics and preparation method and application thereof | |
| CN107442180B (en) | MOFs-rGO loaded Pd nano-catalyst and preparation and application thereof | |
| CN112264040B (en) | Carbon sphere-graphene oxide catalyst and preparation method and application thereof | |
| CN112206826B (en) | Preparation method and application of cobalt-iron alloy magnetic chitosan carbonized microsphere | |
| CN107930670B (en) | A kind of heterogeneous catalysis material and its preparation method and application that self-cradling type is homogeneously changed | |
| CN102205242A (en) | Method for preparing dispersed palladium nanoparticle catalyst with controllable appearance by using cucurbit[6]uril (CB[6]) | |
| CN113842887B (en) | Co-MIL-53(Fe)-NH 2 /UIO-66-NH 2 Composite material, preparation and application thereof | |
| Zhang et al. | Novel MnCo2O4. 5@ manganese sand for efficient degradation of tetracycline through activating peroxymonosulfate: Facile synthesis, adaptable performance and long-term effectiveness | |
| US20210394164A1 (en) | MILLIMETER-SCALE PEROXYMONOSULFATE ACTIVATOR ZSM-5-(C@Fe) AND PREPARATION METHOD AND APPLICATION THEREOF | |
| CN102008965A (en) | Method for preparing ozone catalytic oxidation catalyst for treating cyanide waste water | |
| CN113893840A (en) | Composite photocatalyst, preparation method and application in dye wastewater | |
| CN101468320B (en) | Inorganic substance intercalation nano zinc polycarboxylate catalyst and preparation method thereof | |
| CN113731416A (en) | Local acid site modified monatomic catalyst, preparation method and application thereof | |
| CN115739164A (en) | Preparation method and application of spherical coralline carbon nitride loaded iron monoatomic atom | |
| CN116673033A (en) | Preparation method of alumina ball in-situ supported hydrotalcite-like catalyst | |
| CN114984997B (en) | Three-dimensional porous carbon nitride based Zn monatomic photocatalyst, preparation method and application | |
| CN113769748B (en) | Preparation of FeNi @ corncob activated carbon composite material | |
| CN114950526B (en) | Algae-based carbon limited single-atom copper catalytic material, preparation method and application thereof | |
| CN109174199A (en) | A kind of microwave prepares the method and application of class fenton catalyst and synchronizing regeneration active carbon | |
| CN114602446A (en) | Catalyst for UV/persulfate process and preparation method and application thereof | |
| CN111821969B (en) | Modified carbon black loaded nickel-gold bimetallic nano-catalyst and preparation method thereof |
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 |