CN115025798A - High-load cobalt-containing carbon nitride nanosheet integral catalytic material and preparation method and application thereof - Google Patents
High-load cobalt-containing carbon nitride nanosheet integral catalytic material and preparation method and application thereof Download PDFInfo
- Publication number
- CN115025798A CN115025798A CN202210562262.1A CN202210562262A CN115025798A CN 115025798 A CN115025798 A CN 115025798A CN 202210562262 A CN202210562262 A CN 202210562262A CN 115025798 A CN115025798 A CN 115025798A
- Authority
- CN
- China
- Prior art keywords
- cobalt
- catalytic material
- nitrogen
- nanosheet
- source
- 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
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 79
- 239000000463 material Substances 0.000 title claims abstract description 65
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 40
- 239000010941 cobalt Substances 0.000 title claims abstract description 40
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000002135 nanosheet Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004098 Tetracycline Substances 0.000 claims abstract description 23
- 229960002180 tetracycline Drugs 0.000 claims abstract description 23
- 229930101283 tetracycline Natural products 0.000 claims abstract description 23
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 23
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 229920001410 Microfiber Polymers 0.000 claims abstract description 18
- 239000003658 microfiber Substances 0.000 claims abstract description 18
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 18
- 239000010935 stainless steel Substances 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000011068 loading method Methods 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- WBVDQFAPFUMTFF-UHFFFAOYSA-N [C].[N].[Co] Chemical compound [C].[N].[Co] WBVDQFAPFUMTFF-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000003763 carbonization Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 4
- 239000008098 formaldehyde solution Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003618 dip coating Methods 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 15
- 238000006731 degradation reaction Methods 0.000 abstract description 15
- 239000002184 metal Substances 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 229940088710 antibiotic agent Drugs 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 2
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- GSDSWSVVBLHKDQ-UHFFFAOYSA-N 9-fluoro-3-methyl-10-(4-methylpiperazin-1-yl)-7-oxo-2,3-dihydro-7H-[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic acid Chemical compound FC1=CC(C(C(C(O)=O)=C2)=O)=C3N2C(C)COC3=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960003405 ciprofloxacin Drugs 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229960001699 ofloxacin Drugs 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
-
- 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 relates to a high-load cobalt-containing carbon nitride nanosheet integral catalytic material, and a preparation method and application thereof, and belongs to the field of nano materials. The catalytic material takes stainless steel microfiber as an integral catalytic material framework, takes a cobalt-containing carbon nitrogen nanosheet as a catalytic active component, mixes a carbon source, a nitrogen source, a cobalt source and deionized water to prepare a resin precursor, coats the surface of the integral catalytic material framework, and carbonizes at high temperature to prepare the cobalt-containing carbon nitrogen nanosheet integral catalytic material. Wherein, the mass percentage of the cobalt-containing carbon nitrogen nanosheet is 5-20% based on the mass of the integral catalytic material skeleton. The preparation method of the catalyst has the advantages of easily controlled preparation process, good repeatability, easily controlled metal loading and high preparation efficiency. Meanwhile, the material has high catalytic stability, is repeatedly utilized for five times in a PMS continuous degradation macromolecular compound (tetracycline) system, and still has the degradation efficiency of more than 80 percent.
Description
Technical Field
The invention relates to a high-load cobalt-containing carbon nitride nanosheet integral catalytic material, and a preparation method and application thereof, and belongs to the field of nano materials and catalysis.
Background
Antibiotics such as tetracycline, ciprofloxacin and ofloxacin, which are widely used, can help human bodies to resist diseases, but are difficult to biodegrade due to the molecular chemical stability of the antibiotics, so that the antibiotics become main water pollutants. The treatment problem of the antibiotic production wastewater further becomes the difficult point and the hot point of the domestic and foreign wastewater treatment research, so that the design of a continuous degradation mode which is easy to operate and has concentrated energy mass transfer has practical application value. The monolithic material is widely applied to the fixed bed reactor because the pressure drop can be effectively reduced and the mass transfer can be enhanced. However, the low specific surface area of the monolithic material results in less active sites directly loaded on the surface, so that it is important to grow a composite material with high specific surface area and high catalytic activity on the surface.
Disclosure of Invention
The invention aims to provide a high-load cobalt-containing carbon nitrogen nanosheet integral catalytic material aiming at the current situation and problems of tetracycline wastewater treatment.
The technical scheme of the invention is as follows:
a high-load cobalt-containing carbon nitrogen nanosheet integral catalytic material is prepared by mixing a carbon source, a nitrogen source, a cobalt source and deionized water to prepare a resin precursor by taking stainless steel microfiber as an integral catalytic material framework and cobalt-containing carbon nitrogen nanosheet as a catalytic active component, coating the resin precursor on the surface of the integral catalytic material framework, and carbonizing at high temperature to prepare the cobalt-containing carbon nitrogen nanosheet integral catalytic material; wherein, the mass percentage of the cobalt-containing carbon nitrogen nanosheet is 5-20% based on the mass of the integral catalytic material skeleton.
Among the above catalytic materials: the carbon source is a formaldehyde solution with the mass concentration of 10-30%, the nitrogen source is one of dicyandiamide and melamine, and the cobalt source is cobalt nitrate hexahydrate or cobalt chloride hexahydrate.
Among the above catalytic materials: the mass ratio of the carbon source, the nitrogen source and the cobalt source is 1: (1-3): (0.1-2).
Among the above catalytic materials: the stainless steel microfiber is a rod-shaped fiber (Xianfel Metal Filter Co., Ltd.) having a diameter of 40 to 100 μm.
A preparation method of the catalytic material comprises the following steps:
(1) preparation of precursor of catalytic active component
Uniformly mixing a carbon source, a nitrogen source, a cobalt source and deionized water to obtain an active component precursor solution, and continuously reacting at 80-120 ℃ for 6 hours to obtain cobalt carbon nitrogen resin as a catalytic active component precursor for later use;
(2) preparation of catalytic materials
And (2) dip-coating the cobalt carbon nitrogen resin obtained in the step (1) on the surface of the stainless steel microfiber, and drying and carbonizing at high temperature to obtain the cobalt-containing carbon nitrogen nanosheet integral catalytic material.
The preparation method comprises the following steps: in the step (2), the mass ratio of the cobalt-carbon-nitrogen resin to the stainless steel microfiber is (10-20):
1。
the preparation method comprises the following steps: in the step (2), the drying temperature is 80-100 methods, and the drying time is 6-12 h.
The preparation method comprises the following steps: in the step (2), the high-temperature carbonization temperature is 600-800 ℃, and the carbonization time is 4-6 h.
The preparation method comprises the following steps: and (3) introducing nitrogen as a protective atmosphere in the high-temperature carbonization process in the step (2), wherein the flow rate of the introduced nitrogen is 30-50 mL/min.
The technical scheme of the invention is as follows: the high-loading cobalt-containing carbon nitride nanosheet integral catalytic material is applied to the aspect of degrading organic matters by serving as a catalyst, and is preferably applied to the aspect of degrading tetracycline by serving as a catalyst.
The catalytic reaction conditions and results of the invention: the tetracycline content is measured by an ultraviolet spectrophotometer, the ultraviolet absorbance of the tetracycline at the excitation wavelength of 356nm is measured, and the concentration is calculated through a standard curve. The catalytic material was packed in a fixed bed reactor and activity evaluation was performed. The concentration of each solution was: the initial concentration of tetracycline is 25mg/L, the initial concentration of PMS is 0.075mol/L, and the continuous degradation efficiency of the catalyst at normal temperature and normal pressure for 6 hours is over 90 percent; the catalytic material is reused for 5 times, and the degradation efficiency is still over 80 percent.
The invention has the beneficial effects that:
1. the invention prepares the cobalt-containing carbon nitrogen nanosheet integral catalytic material by a simple one-step method, and solves the problems of large heat and mass transfer resistance, uneven liquid flow distribution and the like of the traditional granular Fenton catalytic catalyst.
2. The nano sheet array in dispersed arrangement solves the problem that the metal loading capacity of the surface coating of the monolithic catalytic material is not high, and the two-dimensional nano sheet structure has a fully exposed contact surface, so that the contact efficiency of the catalyst and pollutants is greatly improved.
3. The invention has wider modulation space, metal sites are uniformly dispersed on the carbon nitrogen nano-chip, the metal content is correspondingly increased and reduced within a certain range (nano-scale grain diameter metal is ensured), and the problems of low metal loading capacity, easy agglomeration of the metal sites and the like in the prior art are solved.
Drawings
FIG. 1: SEM pictures of the material of the embodiment 1, wherein (a) and (b) are SEM pictures of the whole catalytic material, and (c) and (d) are SEM pictures of cobalt-containing carbon nitride nanosheets on the surface of the stainless steel microfiber.
FIG. 2: the effect graphs of the materials of example 1, example 2, comparative example 1 and comparative example 2 on continuous degradation of tetracycline.
FIG. 3: cyclic activity test pattern for the material of example 1.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without inventive efforts based on the embodiments of the present invention, are within the scope of protection of the present invention. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without inventive efforts based on the embodiments of the present invention, are within the scope of protection of the present invention.
Example 1
(1) Preparation of precursor of catalytic active component
Weighing 5.7145g of formaldehyde solution with the mass concentration of 20%, 5.7145g of dicyandiamide and 2.8572g of cobalt nitrate hexahydrate, adding 34.287g of deionized water, stirring at normal temperature to obtain an active component precursor solution, and continuously reacting for 6 hours at 80 ℃ to obtain cobalt-carbon-nitrogen resin serving as a catalytic active component precursor for later use;
(2) preparation of catalytic materials
With the mass of the integral catalytic material skeleton as a reference, the mass percentage content of the cobalt-containing carbon nitrogen nanosheet is 5%, 48.5732g of cobalt carbon nitrogen resin obtained in the step (1) is coated on the surface of 4.8573g of stainless steel microfiber (with the diameter of 40 micrometers, manufactured by Sienfield metallic Filter materials Co., Ltd.) in a dipping method for half an hour, taken out after dipping, dried at 80 ℃ for 12 hours, and carbonized at 600 ℃ for 6 hours under the condition of taking nitrogen with the flow rate of 30mL/min as a protective atmosphere to obtain the cobalt-containing carbon nitrogen nanosheet integral catalytic material, as shown in FIG. 1, the surface of the stainless steel microfiber is loaded with a large number of cobalt-containing carbon nitrogen nanosheets.
(3) Catalytic degradation activity test
As shown in figure 2, the tetracycline content test adopts an ultraviolet spectrophotometer to measure the ultraviolet absorbance of the tetracycline at the excitation wavelength of 356nm, and the concentration is calculated through a standard curve. 1g of the catalytic material was added to a beaker, and the reaction solution was added to conduct activity evaluation. The concentration of each solution was: the initial concentration of tetracycline is 25mg/L, the initial concentration of PMS is 0.075mol/L, and the continuous degradation efficiency of the catalyst at normal temperature and normal pressure for 6 hours is over 90 percent; as shown in FIG. 3, the degradation efficiency of the catalytic material is still over 80% after the catalytic material is reused for 5 times.
(4) Scope of application
The cobalt-containing carbon nitrogen nanosheet integral catalytic material prepared by the method is suitable for treating tetracycline and other water body antibiotic organic pollutants.
Example 2
(1) Preparation of precursor of catalytic active component
Weighing 7.2756g of 30% formaldehyde solution, 21.8268g of melamine and 14.5512g of cobalt chloride hexahydrate, adding 43.6536g of deionized water, stirring at normal temperature to obtain an active component precursor solution, and continuously reacting at 120 ℃ for 6 hours to obtain cobalt carbon nitrogen resin serving as a catalytic active component precursor for later use;
(2) preparation of catalytic material
With the mass of the integral catalytic material skeleton as a reference, the mass percentage content of the cobalt-containing carbon nitrogen nanosheet is 20%, 87.3072g of cobalt-carbon-nitrogen resin obtained in the step (1) is coated on the surface of 4.36536g of stainless steel microfiber (with the diameter of 100 micrometers, manufactured by Siemens and Filler metals filtration materials Co., Ltd.) in a dipping way for half an hour and then taken out, the stainless steel microfiber is dried at 100 ℃ for 6 hours, and then the stainless steel microfiber is carbonized at the high temperature of 800 ℃ for 4 hours under the condition that nitrogen with the flow rate of 50mL/min is used as a protective atmosphere, so that the integral catalytic material of the cobalt-containing carbon nitrogen nanosheet is obtained.
(3) Catalytic degradation activity test
The tetracycline content is measured by an ultraviolet spectrophotometer, the ultraviolet absorbance of the tetracycline at the excitation wavelength of 356nm is measured, and the concentration is calculated through a standard curve. 1g of the catalytic material was added to a beaker, and the reaction solution was added to conduct activity evaluation. The concentration of each solution was: the initial concentration of tetracycline is 25mg/L, the initial concentration of PMS is 0.075mol/L, and the continuous degradation efficiency of the catalyst is over 90% in 6h at normal temperature and normal pressure.
(4) Scope of application
The cobalt-containing carbon nitrogen nanosheet integral catalytic material prepared by the method is suitable for treating tetracycline and other water body antibiotic organic pollutants.
Comparative example 1
(1) Preparation of catalytic material
Except that stainless steel microfiber is replaced by anatase type TiO in catalyst preparation 2 Other conditions were the same as in example 1;
(2) catalytic degradation activity test
The tetracycline content is measured by an ultraviolet spectrophotometer, the ultraviolet absorbance of the tetracycline at the excitation wavelength of 356nm is measured, and the concentration is calculated through a standard curve. 1g of the catalytic material was added to a beaker, and the reaction solution was added to conduct activity evaluation. The concentration of each solution was: the initial concentration of tetracycline is 25mg/L, the initial concentration of PMS is 0.075mol/L, and the continuous degradation rate of the catalyst is 75% after 6 hours under normal temperature and pressure.
(3) Contrast effect
As can be seen by comparison with example 1, stainless steel microfibers were replaced with anatase-type TiO 2 The catalytic efficiency drops significantly.
Comparative example 2
(1) Preparation of catalytic material
The same conditions as in example 2 were used except that the cobalt chloride hexahydrate was replaced by cerium nitrate hexahydrate in the preparation of the catalyst;
(2) catalytic degradation activity test
The tetracycline content is measured by an ultraviolet spectrophotometer, the ultraviolet absorbance of the tetracycline at the excitation wavelength of 356nm is measured, and the concentration is calculated through a standard curve. 1g of the catalytic material was added to a beaker, and the reaction solution was added to conduct activity evaluation. The concentration of each solution was: the initial concentration of tetracycline is 25mg/L, the initial concentration of PMS is 0.075mol/L, and the continuous degradation rate of the catalyst is 63% in 6h under normal temperature and pressure.
(3) Contrast effect
As can be seen by comparison with example 2, replacing cobalt chloride hexahydrate with cerium nitrate hexahydrate significantly reduced catalytic efficiency.
Comparative example 3
(1) Preparation of catalytic materials
The conditions were the same as in example 2 except that no melamine was added during the catalyst preparation;
(2) contrast effect
Compared with example 2, it can be seen that when the catalyst is prepared, melamine is not added, the resin precursor of the active component of the catalyst cannot be formed, and the resin precursor cannot be coated on the surface of the stainless steel microfiber, so that the catalytic material cannot be prepared.
Claims (10)
1. The high-load cobalt-containing carbon nitrogen nanosheet integral catalytic material is characterized in that: the catalytic material takes stainless steel microfiber as an integral catalytic material framework and cobalt-containing carbon nitrogen nanosheet as a catalytic active component, a carbon source, a nitrogen source, a cobalt source and deionized water are mixed to prepare a resin precursor, the resin precursor is coated on the surface of the integral catalytic material framework, and the integral catalytic material containing the cobalt carbon nitrogen nanosheet is prepared through high-temperature carbonization; wherein the mass percent of the cobalt-containing carbon nitrogen nanosheet is 5-20% based on the mass of the integral catalytic material skeleton.
2. The monolithic catalytic material of high-loading cobalt-containing carbon nitrogen nanosheet of claim 1, wherein: the carbon source is a formaldehyde solution with the mass concentration of 10-30%, the nitrogen source is one of dicyandiamide and melamine, and the cobalt source is cobalt nitrate hexahydrate or cobalt chloride hexahydrate.
3. The monolithic catalytic material with high loading cobalt-containing carbon nitride nanosheet of claim 1 or 2, characterized in that: the mass ratio of the carbon source, the nitrogen source and the cobalt source is 1: (1-3): (0.1-2).
4. The monolithic catalytic material with high loading cobalt-containing carbon nitride nanosheet of claim 1, characterized in that: the stainless steel microfiber is a rod-shaped fiber with the diameter of 40-100 micrometers.
5. A method of preparing the catalytic material of claim 1, wherein: the preparation method of the catalytic material comprises the following steps:
(1) preparation of precursor of catalytic active component
Uniformly mixing a carbon source, a nitrogen source, a cobalt source and deionized water to obtain an active component precursor solution, and continuously reacting at 80-120 ℃ for 6 hours to obtain cobalt-carbon-nitrogen resin serving as a catalytic active component precursor for later use;
(2) preparation of catalytic materials
And (2) dip-coating the cobalt carbon nitrogen resin obtained in the step (1) on the surface of stainless steel microfiber, and drying and carbonizing at high temperature to obtain the cobalt-containing carbon nitrogen nanosheet integral catalytic material.
6. The method of claim 5, wherein: in the step (2), the mass ratio of the cobalt-carbon-nitrogen resin to the stainless steel microfiber is (10-20): 1.
7. the method of claim 5, wherein: in the step (2), the drying temperature is 80-100 methods, and the drying time is 6-12 h.
8. The method of claim 5, wherein: in the step (2), the high-temperature carbonization temperature is 600-800 ℃, and the carbonization time is 4-6 h.
9. The production method according to claim 5, characterized in that: and (3) introducing nitrogen as a protective atmosphere in the high-temperature carbonization process in the step (2), wherein the flow rate of the introduced nitrogen is 30-50 mL/min.
10. The use of the high-loading cobalt-containing carbon nitrogen nanosheet monolithic catalytic material of claim 1 as a catalyst for degrading organic matters, preferably tetracycline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210562262.1A CN115025798A (en) | 2022-05-23 | 2022-05-23 | High-load cobalt-containing carbon nitride nanosheet integral catalytic material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210562262.1A CN115025798A (en) | 2022-05-23 | 2022-05-23 | High-load cobalt-containing carbon nitride nanosheet integral catalytic material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115025798A true CN115025798A (en) | 2022-09-09 |
Family
ID=83122058
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210562262.1A Pending CN115025798A (en) | 2022-05-23 | 2022-05-23 | High-load cobalt-containing carbon nitride nanosheet integral catalytic material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115025798A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104289242A (en) * | 2013-07-18 | 2015-01-21 | 中国科学院大连化学物理研究所 | Preparation method of carbon based catalyst with high graphitization degree and used for fuel cell cathode |
| CN104681823A (en) * | 2015-01-23 | 2015-06-03 | 西华师范大学 | Nitrogen-doped graphene and Co3O4 hollow nanosphere composite material as well as preparation method and application of composite material |
| WO2018030655A1 (en) * | 2016-08-09 | 2018-02-15 | 한국화학연구원 | Carbon nitride heterogeneous catalyst containing rhodium and palladium, preparation method therefor, acetic acid preparation method using same, and acetic acid prepared thereby |
| CN107999023A (en) * | 2017-11-23 | 2018-05-08 | 河南师范大学 | Carry the preparation method of cobalt ordered mesoporous carbon material and its application in Oxone rhodamine B degradation waste water is catalyzed |
| CN110482524A (en) * | 2019-09-05 | 2019-11-22 | 中国科学院新疆理化技术研究所 | A kind of preparation method and application of the N doping mesoporous carbon of double activated position modification |
| CN111617731A (en) * | 2020-05-13 | 2020-09-04 | 湖南垚恒环境科技有限公司 | Method for treating antibiotics in water body by coupling magnetic nano material with persulfate |
| CN113764689A (en) * | 2021-08-30 | 2021-12-07 | 江苏大学 | Porous graphene supported cobalt-iron sulfide catalyst, and preparation method and application thereof |
-
2022
- 2022-05-23 CN CN202210562262.1A patent/CN115025798A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104289242A (en) * | 2013-07-18 | 2015-01-21 | 中国科学院大连化学物理研究所 | Preparation method of carbon based catalyst with high graphitization degree and used for fuel cell cathode |
| CN104681823A (en) * | 2015-01-23 | 2015-06-03 | 西华师范大学 | Nitrogen-doped graphene and Co3O4 hollow nanosphere composite material as well as preparation method and application of composite material |
| WO2018030655A1 (en) * | 2016-08-09 | 2018-02-15 | 한국화학연구원 | Carbon nitride heterogeneous catalyst containing rhodium and palladium, preparation method therefor, acetic acid preparation method using same, and acetic acid prepared thereby |
| CN107999023A (en) * | 2017-11-23 | 2018-05-08 | 河南师范大学 | Carry the preparation method of cobalt ordered mesoporous carbon material and its application in Oxone rhodamine B degradation waste water is catalyzed |
| CN110482524A (en) * | 2019-09-05 | 2019-11-22 | 中国科学院新疆理化技术研究所 | A kind of preparation method and application of the N doping mesoporous carbon of double activated position modification |
| CN111617731A (en) * | 2020-05-13 | 2020-09-04 | 湖南垚恒环境科技有限公司 | Method for treating antibiotics in water body by coupling magnetic nano material with persulfate |
| CN113764689A (en) * | 2021-08-30 | 2021-12-07 | 江苏大学 | Porous graphene supported cobalt-iron sulfide catalyst, and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| HEXIANG ZHONG ET AL.: "Nitrogen-Enriched Carbon from Melamine Resins with Superior Oxygen Reduction Reaction Activity" * |
| YAN SHAO ET AL.: "Structured Fe3O4-doped ordered mesoporous carbon catalystsupported on sintered metal fibers for intensifying phenoldegradation" * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108579676B (en) | Preparation method of recyclable biochar composite material | |
| CN109999830A (en) | Load C oCr(Mn/Al) FeNi high-entropy alloy nanoparticle catalyst and its preparation method and application | |
| CN109759117A (en) | A method of nitrogen-doped carbon coating metal nano granule composite material is prepared using carbon fiber | |
| CN108499529B (en) | Active coke supported nano gold catalyst and preparation method and application thereof | |
| CN112675842B (en) | Novel sub-nano restricted-domain Ru metal catalyst for hydrogenation and preparation method and application thereof | |
| CN109894134A (en) | A kind of carbon doped graphite phase carbon nitride film and preparation method thereof | |
| CN112795949A (en) | Preparation method and application of biomass carbon-based transition metal diatom electrocatalyst | |
| CN113198508A (en) | Load type iron-nitrogen-carbon composite material and application thereof in treatment of dye wastewater | |
| CN103506144B (en) | The tungsten carbide of core shell structure/platinum composite and its preparation and application | |
| CN110876953A (en) | P and S co-doped carbon nitride homotype heterojunction composite photocatalyst | |
| CN107999081B (en) | Carbon-coated structure nano iron-based Fischer-Tropsch synthesis catalyst and preparation method and application thereof | |
| CN112604690A (en) | Method for preparing rare earth perovskite/biochar composite material by using agricultural and forestry wastes and application thereof | |
| CN114345324B (en) | Biomass carbon-based metal monoatomic composite catalyst, preparation method and application thereof | |
| Zuo et al. | Modification of sulfur doped carbon nitride and its application in photocatalysis | |
| CN113457695A (en) | Manganese-nickel-copper-based water treatment catalyst and preparation method and application thereof | |
| CN117352760B (en) | Preparation method of multistage pore, nitrogen doped graphitized carbon supported platinum-based catalyst | |
| CN115025798A (en) | High-load cobalt-containing carbon nitride nanosheet integral catalytic material and preparation method and application thereof | |
| CN113198515A (en) | Ternary photocatalyst and preparation method and application thereof | |
| CN111957328A (en) | Catalyst module, preparation method and application | |
| CN111939957A (en) | Preparation method of photocatalytic nitrogen fixation material porous carbon nitride nanofiber/graphene | |
| CN107442098B (en) | Strontium titanate catalyst for preparing hydrogen by photolyzing water by adopting visible light and preparation method | |
| CN112619681B (en) | Nitrogen-doped carbonized bacterial cellulose supported palladium catalyst and preparation method and application thereof | |
| CN113751014A (en) | Monodisperse spindle-shaped monatomic catalyst for denitration and sulfur resistance and preparation method thereof | |
| CN107649184B (en) | Perfusion silica gel/nanogold composite microspheres and preparation method and application thereof | |
| CN114832817B (en) | Ultra-high Pt loading capacity sheet-shaped atomic-scale Pt/CeO 2 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 |