CN112169750B - Application of basic potassium salt modified graphite phase carbon nitride in preparation of cationic dye adsorbent - Google Patents
Application of basic potassium salt modified graphite phase carbon nitride in preparation of cationic dye adsorbent Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 143
- -1 potassium salt modified graphite Chemical class 0.000 title claims abstract description 100
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000003463 adsorbent Substances 0.000 title claims abstract description 12
- 238000001179 sorption measurement Methods 0.000 claims abstract description 50
- 238000001354 calcination Methods 0.000 claims abstract description 22
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000008247 solid mixture Substances 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical group C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 26
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 22
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 7
- 229940012189 methyl orange Drugs 0.000 claims description 7
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical group [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 7
- 229940043267 rhodamine b Drugs 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 12
- 230000007613 environmental effect Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000975 dye Substances 0.000 description 29
- 230000000694 effects Effects 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
- 239000011591 potassium Substances 0.000 description 10
- 229910052700 potassium Inorganic materials 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 230000006872 improvement Effects 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- 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
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Abstract
The invention provides an application of basic potassium salt modified graphite phase carbon nitride in preparing a cationic dye adsorbent. The preparation method of the basic potassium salt modified graphite phase carbon nitride comprises the following steps: (1) Mixing a precursor of carbon nitride and basic potassium salt, and grinding to obtain a solid mixture; (2) And (3) placing the solid mixture obtained in the step (1) in a muffle furnace for calcination to obtain the basic potassium salt modified graphite phase carbon nitride. The preparation method can prepare the surface modified graphite phase carbon nitride material in one step, has the advantages of simple preparation process, convenient operation and environmental protection, can prepare in large scale, and has excellent adsorption performance on cationic dye in water.
Description
Technical Field
The invention belongs to the technical field of material preparation and water treatment, and particularly relates to application of basic potassium salt modified graphite phase carbon nitride in preparation of a cationic dye adsorbent.
Background
Dyes are a typical class of organic contaminants, mainly derived from the dye synthesis, printing and paper industry, which have been detected in many rivers and have attracted considerable attention due to their non-biodegradability, carcinogenicity, bioaccumulation, high toxicity and colour depth. The dye wastewater treatment methods include biological treatment, adsorption, chemical oxidation, membrane separation, electrodialysis, ion exchange and the like, and in the methods, the adsorption technology is low in cost, simple to operate, environment-friendly and effective, and the method is an ideal method for removing the dye in the sewage. Among them, activated carbon has become a popular choice for adsorbing dyes in wastewater, but its high cost presents an economic problem.
CN110975917a discloses a defective carbon nitride material, its preparation method and application. The preparation method comprises the following specific steps: uniformly mixing potassium hydroxide solution with a certain mass concentration with urea aqueous solution for reaction, and drying. Calcining in a muffle furnace by adopting a thermal polymerization method to obtain the defective carbon nitride material. The material is easy to obtain, high in removal efficiency, nontoxic and harmless, and can be produced in a large scale. However, the material is used for removing methylene blue in wastewater by a photocatalysis method, but the adsorption of cationic dye by the material is not studied.
CN109012728A discloses a catalyst for synthesizing hydrogen peroxide by catalytic oxygen reduction under visible light and a preparation method thereof. The catalyst is a graphite phase carbon nitride catalyst doped with phosphorus and potassium, the graphite phase carbon nitride material is derived from urea thermal polymerization, and phosphorus and potassium elements are introduced in situ during the urea thermal polymerization and doped in a framework structure of the graphite phase carbon nitride. The invention utilizes the doping component to catalyze the reduction of oxygen to synthesize hydrogen peroxide under the visible light on the graphite-phase carbon nitride, but the adsorption of the potassium-doped graphite-phase carbon nitride on the cationic dye is not researched.
Therefore, it is very important to develop a novel dye adsorbent which is simple, green, efficient and low in cost for treating dye wastewater.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an application of basic potassium salt modified graphite phase carbon nitride in preparing a cationic dye adsorbent. The basic potassium salt modified graphite phase carbon nitride has more negative charges on the surface, and has excellent adsorption effect on cationic dye.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an application of basic potassium salt modified graphite phase carbon nitride in preparing a cationic dye adsorbent.
Graphite phase carbon nitride (g-C) 3 N 4 ) Is a novel two-dimensional layered material, can be synthesized by a simple pyrolysis method, and has the characteristics of excellent chemical stability, thermal stability, no toxicity and environmental protection. At the same time, g-C 3 N 4 The 3-s-triazine or triazine structural unit with high order can be piled up through hydrophobic effect and pi-pi interaction, and adsorb aromatic pollutants through conjugated pi zone, thus becoming a potential effective adsorbent. However, the method is thatAnd g-C 3 N 4 The adsorption ability to aromatic compounds is insufficient, and therefore further improvement of g-C is necessary 3 N 4 Adsorption properties of the material. The graphite-phase carbon nitride is modified by adopting the basic potassium salt, and the modified basic potassium salt modified graphite-phase carbon nitride has more negative charges on the surface and has excellent adsorption effect on cationic dye.
Preferably, the adsorption capacity of the basic potassium salt modified graphite phase carbon nitride to the cationic dye is 5-310mg/g, and can be 5mg/g, 10mg/g, 50mg/g, 60mg/g, 80mg/g, 100mg/g, 120mg/g, 140mg/g, 160mg/g, 180mg/g, 200mg/g, 220mg/g, 240mg/g, 260mg/g, 280mg/g, 310mg/g and the like.
Preferably, the cationic dye is methylene blue, and the adsorption capacity of the basic potassium salt modified graphite phase carbon nitride to the cationic dye is 50-310mg/g, for example, 50mg/g, 80mg/g, 120mg/g, 160mg/g, 200mg/g, 230mg/g, 260mg/g, 290mg/g, 310mg/g and the like.
In the invention, the basic potassium salt modified graphite phase carbon nitride has adsorption effect on various cationic dyes, but the basic potassium salt modified graphite phase carbon nitride has specific adsorption on the cationic dye methylene blue, and the adsorption capacity can reach 50-310mg/g.
Preferably, the cationic dye is rhodamine B and/or methyl orange, and the adsorption capacity of the basic potassium salt modified graphite phase carbon nitride to the cationic dye is 5-10mg/g, for example, 5mg/g, 6mg/g, 7mg/g, 8mg/g, 9mg/g, 10mg/g and the like.
Preferably, the basic potassium salt modified graphitic carbon nitride has a rich and porous structure.
Preferably, the pore volume of the basic potassium salt modified graphite phase carbon nitride is 0.03-0.06cm 3 Per g, for example, may be 0.03cm 3 /g、0.04cm 3 /g、0.05cm 3 /g、0.06cm 3 /g, etc.
Preferably, the pore diameter of the basic potassium salt modified graphite phase carbon nitride is 20-30nm, for example, 20nm, 22nm, 24nm, 26nm, 28nm, 30nm and the like.
Preferably, the specific surface area of the basic potassium salt modified graphite phase carbon nitride is 6.0-50.0m 2 /g, for example, may be 6.0m 2 /g、10.0m 2 /g、20.0m 2 /g、30.0m 2 /g、40.0m 2 /g、50.0m 2 /g, etc.
Preferably, the preparation method of the basic potassium salt modified graphite phase carbon nitride comprises the following steps:
(1) Mixing a precursor of carbon nitride and basic potassium salt, and grinding to obtain a solid mixture;
(2) And (3) placing the solid mixture obtained in the step (1) in a muffle furnace for calcination to obtain the basic potassium salt modified graphite phase carbon nitride.
In the invention, melamine or urea is used as a precursor, potassium oxalate or potassium hydroxide is used as an alkaline potassium salt auxiliary agent, and a one-step blending calcination method is adopted to prepare the modified graphite-phase carbon nitride material. The preparation method can prepare the surface modified graphite phase carbon nitride material in one step, has the advantages of simple preparation process, convenient operation and environmental protection, can prepare in large scale, and has excellent adsorption performance on cationic dye in water.
Preferably, the mass ratio of the precursor of the carbon nitride to the basic potassium salt in the step (1) is (3-10): 0.1-1;
wherein, "3-10" may be 3, 4, 5, 6, 7, 8, 9, 10, etc.;
wherein, "0.1-1" may be 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9, 1, etc.
Preferably, the grinding time in the step (1) is 10-30min, for example, 10min, 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min, 28min, 30min, and the like, preferably 20min.
Preferably, the carbon nitride precursor in step (1) is selected from melamine and/or urea;
preferably, the basic potassium salt in step (1) is selected from potassium oxalate and/or potassium hydroxide;
preferably, the calcining in step (2) is performed by: heating to 500-600deg.C (e.g., 500 deg.C, 520 deg.C, 540 deg.C, 560 deg.C, 580 deg.C, 600 deg.C, etc.) at a heating rate of 2-10deg.C/min (e.g., 2 deg.C/min, 4 deg.C/min, 6 deg.C/min, 8 deg.C/min, 10 deg.C/min, etc.), and calcining at 500-600deg.C (e.g., 500 deg.C, 520 deg.C, 540 deg.C, 560 deg.C, 580 deg.C, 600 deg.C, etc.) for 1-3 hr, e.g., 1 hr, 1.2 hr, 1.4 hr, 1.6 hr, 1.8 hr, 2 hr, 2.2 hr, 2.4 hr, 2.8 hr, 3 hr, etc.
Preferably, the calcining in step (2) is performed by: after heating to 550 ℃ at a heating rate of 5 ℃/min, the mixture is calcined at 550 ℃ for 2 hours.
Preferably, the preparation method of the basic potassium salt modified graphite phase carbon nitride further comprises the following step (3) post-treatment: grinding the basic potassium salt modified graphite phase carbon nitride obtained in the step (2), and then washing and drying the ground carbon nitride sequentially. Preferably, the washing solvent comprises aqueous hydrochloric acid and/or aqueous ethanol.
Preferably, the concentration of the aqueous hydrochloric acid solution is 0.05-0.2M, and may be, for example, 0.05M, 0.06M, 0.08M, 0.1M, 0.12M, 0.14M, 0.16M, 0.18M, 0.2M, or the like.
Preferably, the mass concentration of the ethanol aqueous solution is 40-60wt%, for example, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, etc.
Preferably, the pH of the washed basic potassium salt modified graphite phase carbon nitride is 6.8-7.2, and can be, for example, 6.8, 6.9, 7.0, 7.1, 7.2, etc.
Preferably, the drying temperature is 70-90 ℃, for example, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ and the like, and the drying time is 10-15 hours, for example, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours and the like.
Preferably, the preparation method of the basic potassium salt modified graphite phase carbon nitride comprises the following steps:
(1) Mixing a precursor of carbon nitride with the mass ratio of (3-5) (0.15-1) and basic potassium salt, and grinding for 10-30min to obtain a solid mixture;
(2) Calcining the solid mixture obtained in the step (1) in a muffle furnace, heating to 500-600 ℃ at a heating rate of 2-10 ℃/min, and calcining at 500-600 ℃ for 1-3 hours to obtain basic potassium salt modified graphite phase carbon nitride;
(3) Grinding the basic potassium salt modified graphite phase carbon nitride obtained in the step (2), washing by adopting 0.05-0.2M hydrochloric acid aqueous solution and 50% ethanol aqueous solution in sequence until the pH value of the basic potassium salt modified graphite phase carbon nitride is 6.8-7.2, and drying at 70-90 ℃ for 10-15h.
Compared with the prior art, the invention has the following beneficial effects:
(1) The basic potassium salt modified graphite phase carbon nitride has more negative charges on the surface, and has excellent adsorption effect on cationic dye.
(2) The g-C of the invention 3 N 4 Compared with the porous g-C prepared by a hard template method and a soft template method 3 N 4 The invention can effectively avoid the complicated operation steps and the harm to the environment of the hard template method, can also avoid the decomposition problem of the template agent in the soft template method, has simple operation and does not introduce other environmental pollutants,
Drawings
Fig. 1 shows the microscopic morphology of the basic potassium salt modified graphite phase carbon nitride provided in example 2 in a scanning electron microscope.
Fig. 2 is an X-ray diffraction pattern of the basic potassium salt modified graphite phase carbon nitride provided in example 2.
Fig. 3 is a graph showing the desorption of carbon nitride of the basic potassium salt modified graphite phase provided in example 2.
Fig. 4 is a Zeta potential plot of the basic potassium salt modified graphite phase carbon nitrides provided in comparative example 1, example 2 and example 9.
Fig. 5 shows the microscopic morphology of the basic potassium salt modified graphite phase carbon nitride provided in example 6 in a scanning electron microscope.
Fig. 6 shows the microscopic morphology of the basic potassium salt modified graphite phase carbon nitride provided in example 9 in a scanning electron microscope.
FIG. 7 is a graph showing the effect of the basic potassium salt modified graphite phase carbon nitride provided in examples 1 to 3 on the adsorption of methylene blue solution by the graphite phase carbon nitride provided in comparative example 1.
FIG. 8 is a graph showing the effect of the basic potassium salt modified graphite phase carbon nitride provided in examples 4 to 6 on adsorbing methylene blue solution with the graphite phase carbon nitride provided in comparative example 2.
FIG. 9 is a graph showing the effect of the basic potassium salt modified graphite phase carbon nitride provided in examples 7 to 9 on the adsorption of methylene blue solution by the graphite phase carbon nitride provided in comparative example 3.
Fig. 10 is a graph showing the effect of the basic potassium salt modified graphite phase carbon nitride provided in example 2 and the graphite phase carbon nitride provided in comparative example 1 on adsorbing three cationic dye solutions.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The following examples and test example instruments are: scanning electron microscopy (manufacturer: zeiss Gemini 300, model: germany); x-ray diffractometer (manufacturer: panac, netherlands, model: X' Pert PRO MPD); zeta potentiometers (manufacturer: markov instruments, inc., model: zetasizer rnano); ultraviolet-visible spectrophotometer (manufacturer: U.S. Hash, model: DR 5000).
Example 1
The embodiment provides a basic potassium salt modified graphite phase carbon nitride, which is prepared by the following preparation method:
(1) Mixing 3.0g of melamine and 0.15g of potassium oxalate, and grinding for 20min to obtain a solid mixture;
(2) Calcining the solid mixture obtained in the step (1) in a muffle furnace, heating to 550 ℃ at a heating rate of 5 ℃/min, and calcining at 550 ℃ for 2 hours to obtain basic potassium salt modified graphite-phase carbon nitride;
(3) Grinding the basic potassium salt modified graphite phase carbon nitride obtained in the step (2), washing by adopting a 0.1M hydrochloric acid aqueous solution and a 50% ethanol aqueous solution in sequence until the pH value of the basic potassium salt modified graphite phase carbon nitride is 7.0, and drying at 80 ℃ for 12 hours.
Example 2
This example provides a basic potassium salt modified graphite phase carbon nitride differing from example 1 only in that 0.15g of potassium oxalate was replaced with 0.3g of potassium oxalate, and the other preparation steps were the same as in example 1.
Fig. 1 shows the microscopic morphology of the basic potassium salt modified graphite phase carbon nitride after the post-treatment in the embodiment in a scanning electron microscope, and as shown in fig. 1, the surface of the modified carbon nitride sample is etched, and the lamellar structure is destroyed. The pore volume of the basic potassium salt modified graphite phase carbon nitride is 0.04cm 3 And/g, pore diameter of 27.9nm. FIG. 2 is an XRD pattern of the basic potassium salt modified graphite phase carbon nitride after the post-treatment of this example, as shown in FIG. 2, the basic potassium salt vs. g-C 3 N 4 The crystal form of the carbon nitride sample is greatly influenced, the (100) crystal face of the modified carbon nitride sample disappears, the in-plane stacking structure is destroyed, the (002) crystal face strength is greatly reduced, the crystal growth is inhibited, and the crystallinity is reduced. FIG. 3 is a graph showing the desorption of carbon nitride of the basic potassium salt modified graphite phase after the post-treatment of this example, as shown in FIG. 3, compared with carbon nitride (5.0 m 2 Per g), the specific surface area of the modified sample (6.9 m 2 And/g) was not greatly increased, indicating that the specific surface area was not the dominant factor in the increase in adsorption capacity.
Example 3
This example provides a basic potassium salt modified graphite phase carbon nitride differing from example 1 only in that 0.15g of potassium oxalate was replaced with 0.45g of potassium oxalate, and the other preparation steps were the same as in example 1.
Example 4
The embodiment provides a basic potassium salt modified graphite phase carbon nitride, which is prepared by the following preparation method:
(1) 10.0g of urea, 0.5g of melamine and 0.105g of potassium oxalate were mixed and ground for 20min to obtain a solid mixture;
(2) Calcining the solid mixture obtained in the step (1) in a muffle furnace, heating to 550 ℃ at a heating rate of 5 ℃/min, and calcining at 550 ℃ for 2 hours to obtain basic potassium salt modified graphite-phase carbon nitride;
(3) Grinding the basic potassium salt modified graphite phase carbon nitride obtained in the step (2), washing by adopting a 0.1M hydrochloric acid aqueous solution and a 50% ethanol aqueous solution in sequence until the pH value of the basic potassium salt modified graphite phase carbon nitride is 7.0, and drying at 80 ℃ for 12 hours.
Example 5
This example provides a basic potassium salt modified graphite phase carbon nitride differing from example 4 only in that 0.105g of potassium oxalate was replaced with 0.210g of potassium oxalate, and the other preparation steps were the same as in example 4.
Example 6
This example provides a basic potassium salt modified graphite phase carbon nitride differing from example 4 only in that 0.105g of potassium oxalate was replaced with 0.315g of potassium oxalate, and the other preparation steps were the same as in example 4.
Fig. 5 shows the microscopic morphology of the basic potassium salt modified graphite phase carbon nitride after the post-treatment in this example in a scanning electron microscope, and as shown in fig. 5, the modified carbon nitride has a fluffy cotton shape and a loose structure. The pore volume of the basic potassium salt modified graphite phase carbon nitride is 0.03cm 3 Per g, pore diameter of 21.3nm, specific surface area of 49.3m 2 And/g. Compared with the original carbon nitride (42.7 m) prepared by calcining pure urea 2 And/g), the specific surface area of the modified sample is not greatly increased, which indicates that the specific surface area is not a dominant factor for increasing the adsorption capacity.
Example 7
The embodiment provides a basic potassium salt modified graphite phase carbon nitride, which is prepared by the following preparation method:
(1) Mixing 3.0g of melamine and 0.15g of potassium hydroxide, and grinding for 20min to obtain a solid mixture;
(2) Calcining the solid mixture obtained in the step (1) in a muffle furnace, heating to 550 ℃ at a heating rate of 5 ℃/min, and calcining at 550 ℃ for 2 hours to obtain basic potassium salt modified graphite-phase carbon nitride;
(3) Grinding the basic potassium salt modified graphite phase carbon nitride obtained in the step (2), washing by adopting a 0.1M hydrochloric acid aqueous solution and a 50% ethanol aqueous solution in sequence until the pH value of the basic potassium salt modified graphite phase carbon nitride is 7.0, and drying at 80 ℃ for 12 hours.
Example 8
This example provides a basic potassium salt modified graphite phase carbon nitride differing from example 7 only in that 0.15g of potassium oxalate was replaced with 0.30g of potassium hydroxide, and the other preparation steps were the same as in example 7.
Example 9
This example provides a basic potassium salt modified graphite phase carbon nitride differing from example 7 only in that 0.15g of potassium oxalate was replaced with 0.45g of potassium hydroxide, and the other preparation steps were the same as in example 7.
Fig. 6 shows the microscopic morphology of the basic potassium salt modified graphite phase carbon nitride after the post-treatment in this example in a scanning electron microscope, and as shown in fig. 6, the surface of the modified carbon nitride is no longer smooth, becomes rough and has holes. The pore volume of the basic potassium salt modified graphite phase carbon nitride is 0.06cm 3 Per g, pore diameter of 23.6nm, specific surface area of 8.2m 2 /g。
Comparative example 1
This example provides a carbon nitride which differs from example 1 only in that potassium oxalate is not added and other preparation steps are the same as example 1.
Comparative example 2
This example provides a carbon nitride which differs from example 4 only in that potassium oxalate is not added and other preparation steps are the same as example 4.
Comparative example 3
This example provides a carbon nitride which differs from example 7 only in that no potassium hydroxide is added and other preparation steps are the same as example 7.
Test example 1
Effect test of methylene blue adsorption
Firstly, 100mL of a methylene blue aqueous solution having a concentration of 60mg/L was measured, and then 0.025g of the basic potassium salt modified graphite-phase carbon nitride provided in examples 1 to 9 and the carbon nitride provided in comparative examples 1 to 3 were added, respectively, under stirring at room temperature. After 0-24h of dark adsorption, separating the adsorbent from the solution by a nylon 66 filter membrane, and analyzing the obtained supernatant by using ultraviolet-visible spectrophotometry to determine the concentration of methylene blue solution in the solution before and after adsorption.
The specific test results are shown in table 1:
TABLE 1
| Project | Methylene blue adsorption capacity mg/g | Project | Methylene blue adsorption capacity mg/g |
| Example 1 | 55.2 | Example 7 | 62.4 |
| Example 2 | 223.0 | Example 8 | 208.8 |
| Example 3 | 175.2 | Example 9 | 231.6 |
| Example 4 | 83.2 | Comparative example 1 | 16.8 |
| Example 5 | 275.2 | Example 2 | 54.4 |
| Example 6 | 307.2 | Example 3 | 22.3 |
As shown by the test results in Table 1, the adsorption capacity of the basic potassium salt modified graphite phase carbon nitride of the invention to methylene blue is 50-310mg/g, which is 0.5-13 times higher than that of unmodified carbon nitride, which indicates that the basic potassium salt modified graphite phase carbon nitride of the invention has excellent adsorption effect to methylene blue.
Wherein FIG. 7 is a graph showing the effect of the basic potassium salt-modified graphite phase carbon nitride provided in examples 1-3 and the basic potassium salt-modified graphite phase carbon nitride provided in comparative example 1 on adsorbing methylene blue, it can be seen from FIG. 7 that the basic potassium salt-modified graphite phase carbon nitride provided in example 2 has the highest adsorption capacity for methylene blue up to 223.0mg/g after 24 hours of dark adsorption, compared with the bulk g-C prepared in comparative example 1 without potassium oxalate 3 N 4 The improvement is about 12.3 times, which indicates that the basic potassium salt modified graphite phase carbon nitride has excellent adsorption effect on methylene blue.
Wherein FIG. 8 is a graph showing the effect of the basic potassium salt-modified graphite phase carbon nitride provided in examples 4 to 6 and the basic potassium salt-modified graphite phase carbon nitride adsorption methylene blue solution provided in comparative example 2As can be seen from FIG. 5, after 24 hours of dark adsorption, the adsorption capacity of the basic potassium salt modified graphite phase carbon nitride provided in example 6 to methylene blue is highest, as high as 307.2mg/g, compared with the bulk g-C prepared in comparative example 2 without potassium oxalate 3 N 4 The improvement is about 4.6 times, which shows that the basic potassium salt modified graphite phase carbon nitride has excellent adsorption effect on methylene blue.
Wherein FIG. 9 is a graph showing the effect of the basic potassium salt-modified graphite phase carbon nitride provided in examples 7 to 9 and the basic potassium salt-modified graphite phase carbon nitride provided in comparative example 3 on adsorbing methylene blue, as can be seen from FIG. 6, the adsorption capacity of the basic potassium salt-modified graphite phase carbon nitride provided in example 9 on methylene blue after 24 hours of dark adsorption is highest, up to 231.6mg/g, as compared with the bulk g-C prepared in comparative example 3 without potassium oxalate 3 N 4 The improvement is about 12.8 times, which shows that the basic potassium salt modified graphite phase carbon nitride has excellent adsorption effect on methylene blue.
Fig. 4 is a Zeta potential diagram of the basic potassium salt modified graphite phase carbon nitride provided in comparative example 1, example 2 and example 9, and as shown in fig. 4, the Zeta potential of the modified sample is more negative, which indicates that the surface of the modified sample has more negative charge, and the electrostatic attraction to methylene blue is enhanced.
Test example 2
Effect test of adsorbing rhodamine B and methyl orange
100mL of rhodamine B (RhB) aqueous solution and Methyl Orange (MO) aqueous solution at a concentration of 10mg/L were measured separately, and then 0.025g of the basic potassium salt modified graphite-phase carbon nitride provided in example 2 above and the carbon nitride provided in comparative example 1 were added separately under stirring at room temperature to perform dark adsorption. After dark adsorption for 24h, the adsorbent was separated from the solution by nylon 66 filter, centrifugation and polyethersulfone filter, and the resulting supernatant was analyzed using uv-vis spectrophotometry for determining dye concentration in the solution before and after adsorption.
The adsorption capacity of the basic potassium salt modified graphite phase carbon nitride is 6.12mg/g to rhodamine B, 5.08mg/g to methyl orange and higher than unmodified carbon nitride, which shows that the basic potassium salt modified graphite phase carbon nitride also has a certain adsorption effect to other cationic dye pages, but has a specific adsorption effect to methylene Lan Juyou.
Fig. 10 is a graph comparing the effects of the basic potassium salt modified graphite phase carbon nitride provided in example 2 on adsorbing different cationic dyes, and it can be seen from fig. 10 that the basic potassium salt modified graphite phase carbon nitride of the present invention has a significant improvement in the adsorption capacity for methylene blue after dark adsorption for 24 hours, but no significant improvement in RhB and MO, which indicates that the basic potassium salt modified graphite phase carbon nitride of the present invention has a higher adsorption selectivity for methylene blue.
The applicant states that the invention has application to the preparation of cationic dye adsorbents by the basic potassium salt modified graphite phase carbon nitride described above, but the invention is not limited to, i.e. it is not meant that the invention must rely on, the examples described above to be practiced. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (14)
1. The application of the basic potassium salt modified graphite phase carbon nitride in preparing the cationic dye dark adsorbent is characterized in that the preparation method of the basic potassium salt modified graphite phase carbon nitride comprises the following steps:
(1) Mixing a precursor of carbon nitride and basic potassium salt, and grinding to obtain a solid mixture;
(2) Calcining the solid mixture obtained in the step (1) in a muffle furnace to obtain basic potassium salt modified graphite phase carbon nitride;
(3) Grinding the basic potassium salt modified graphite phase carbon nitride obtained in the step (2), and then washing and drying sequentially;
the washing solvent comprises aqueous hydrochloric acid and/or aqueous ethanol;
the pH value of the washed basic potassium salt modified graphite phase carbon nitride is 6.8-7.2;
the concentration of the hydrochloric acid aqueous solution is 0.05-0.2M;
the mass concentration of the ethanol water solution is 40-60 wt%;
the carbon nitride precursor in step (1) is selected from melamine and urea;
the basic potassium salt in the step (1) is selected from potassium oxalate and/or potassium hydroxide;
the mass ratio of the precursor of the carbon nitride to the basic potassium salt in the step (1) is (3-10) (0.1-1);
the basic potassium salt modified graphite phase carbon nitride has negative charges on the surface.
2. The use according to claim 1, wherein the adsorption capacity of the basic potassium salt modified graphite phase carbon nitride to cationic dye is 5-310 mg/g.
3. The use according to claim 1, wherein the cationic dye is methylene blue and the adsorption capacity of the basic potassium salt modified graphite phase carbon nitride to the cationic dye is 50-310mg/g.
4. The use according to claim 1, wherein the cationic dye is rhodamine B and/or methyl orange, and the adsorption capacity of the basic potassium salt modified graphite phase carbon nitride to the cationic dye is 5-10 mg/g.
5. The use according to claim 1, wherein the basic potassium salt modified graphitic carbon nitride has a rich and porous structure.
6. The use according to claim 1, wherein the pore volume of the basic potassium salt modified graphite phase carbon nitride is 0.03-0.6. 0.6 cm 3 /g。
7. The use according to claim 1, wherein the pore size of the basic potassium salt modified graphite phase carbon nitride is 20-30 nm.
8. The use according to claim 1, wherein the specific surface area of the basic potassium salt modified graphite phase carbon nitride is 6.0-50.0m 2 /g。
9. The use according to claim 1, wherein the milling in step (1) is for a period of 10-30 min.
10. The use according to claim 9, wherein the milling in step (1) is for a period of 20min.
11. The use according to claim 1, wherein the calcination procedure in step (2) is: heating to 500-600 deg.C at a heating rate of 2-10 deg.C/min, and calcining at 500-600 deg.C for 1-3 h.
12. The use according to claim 11, wherein the calcination procedure in step (2) is: after heating to 550℃at a heating rate of 5℃per minute, the mixture was calcined at 550℃for 2h.
13. The use according to claim 1, wherein the drying is carried out at a temperature of 70-90 ℃ and for a time of 10-15h.
14. The use according to claim 1, wherein the preparation method of the basic potassium salt modified graphite phase carbon nitride comprises the following steps:
(1) Mixing a precursor of carbon nitride with the mass ratio of (3-10) (0.1-1) and basic potassium salt, and grinding for 10-30min to obtain a solid mixture;
(2) Calcining the solid mixture obtained in the step (1) in a muffle furnace, heating to 500-600 ℃ at a heating rate of 2-10 ℃/min, and calcining at 500-600 ℃ for 1-3h to obtain basic potassium salt modified graphite phase carbon nitride;
(3) Grinding the basic potassium salt modified graphite phase carbon nitride obtained in the step (2), washing by adopting 0.05-0.2M hydrochloric acid aqueous solution and 50% ethanol aqueous solution in sequence until the pH value of the basic potassium salt modified graphite phase carbon nitride is 6.8-7.2, and drying at 70-90 ℃ for 10-15h.
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