CN113019415A - Preparation method of iron-based supermolecule graphite phase carbon nitride photocatalyst - Google Patents
Preparation method of iron-based supermolecule graphite phase carbon nitride photocatalyst Download PDFInfo
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- CN113019415A CN113019415A CN202110279141.1A CN202110279141A CN113019415A CN 113019415 A CN113019415 A CN 113019415A CN 202110279141 A CN202110279141 A CN 202110279141A CN 113019415 A CN113019415 A CN 113019415A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 50
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 12
- 239000010439 graphite Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 9
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 24
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 24
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052573 porcelain Inorganic materials 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 2
- 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 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 239000003054 catalyst Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 238000001338 self-assembly Methods 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000000919 ceramic Substances 0.000 description 18
- 239000002351 wastewater Substances 0.000 description 16
- 238000001179 sorption measurement Methods 0.000 description 12
- 239000012528 membrane Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000000227 grinding Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 6
- 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 description 6
- 229940012189 methyl orange Drugs 0.000 description 6
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [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 description 6
- 229940043267 rhodamine b Drugs 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 238000004811 liquid chromatography Methods 0.000 description 5
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910002558 Fe-Nx Inorganic materials 0.000 description 1
- 229910002559 Fe−Nx Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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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
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Abstract
The invention belongs to the technical field of material preparation and photocatalysis, and relates to a preparation method of various iron-based supramolecular graphite phase carbon nitride photocatalysts. The catalyst is prepared by pyrolyzing a precursor generated by the supermolecule self-assembly reaction of melamine, cyanuric acid and ferric salt. On one hand, the supermolecular graphite phase carbon nitride obtained by the self-assembly method has larger specific surface area and more catalytic active sites. On the other hand, due to the action of hydrogen bonds, the iron-based supramolecular graphite-phase carbon nitride is more stable in the preparation process, can anchor and disperse iron elements more efficiently, and improves the separation degree of photo-generated electron holes. The iron-based supermolecule graphite phase carbon nitride has excellent photocatalytic activity, is simple to prepare, has low cost and has huge environmental and economic benefits.
Description
Technical Field
The invention belongs to the technical field of material preparation and photocatalysis, and relates to a preparation method of an iron-based supramolecular graphite phase carbon nitride photocatalyst.
Background
China has a large dye yield, and the pollution of dye wastewater is particularly serious. Without treatment, the environment is seriously threatened. However, the dye wastewater has high toxicity and large chroma, and is a wastewater which is difficult to treat in industrial wastewater. At present, the traditional treatment method of dye wastewater is difficult to completely degrade the dye wastewater, for example, an adsorption method simply adsorbs and transfers the dye in water instead of substantially degrading or mineralizing, and in addition, the problems of recycling of an adsorbent and treatment of the resolved high-concentration dye wastewater exist. Compared with the traditional treatment method, the advanced oxidation technology treatment method has the advantages of simple operation, quick reaction, little or no secondary pollution, wide application range, capability of efficiently treating refractory organic pollutants and the like. The photocatalytic technology is an environment-friendly technology with important application prospect in the field of energy and environmental purification, and is widely concerned, wherein the research and preparation of high-efficiency photocatalytic materials are the primary conditions for developing the photocatalytic technology.
The principle of photocatalysis is that a semiconductor material is excited by light to generate photoproduction electrons and holes, the electrons react with oxygen to generate superoxide radicals, and the holes and water generate hydroxyl radicals to further degrade pollutants. The nature is also an adsorption degradation process between solid-liquid two-phase interfaces, and electrons and holes are often compounded in the process of transferring to the surface of the catalyst, so that the catalytic performance is reduced. The most common modification method is metal element doping, and the metal elements (Fe, Cu and the like) can effectively capture electrons so as to inhibit the recombination of photo-generated electron-hole pairs. However, the development of this method is greatly limited by the agglomeration of metal components during doping and by leaching problems during use. Recently, Hu et al (Hu J, Zhang P, An W, et al, in-situ Fe-sequenced g-C3N4 heterologous catalysis via photocatalytic reaction-Fenton reaction with engineered photocatalytic reaction for removal of complex water [ J]Applied Catalysis B, Environmental 2019,245(130-42.), dissolving melamine and ferric trichloride, evaporating to dryness, and then pyrolyzing and calcining to prepare Fe-doped graphite-phase carbon nitride (g-C)3N4) It was found that g-C3N4The high-density N content can anchor and disperse Fe element, and Fe-N is formed between Fe element and N elementxThe Fe species existing in a bond form not only greatly improves the separation efficiency of the photoproduction electron-hole pairs, but also can effectively inhibit the leaching problem of Fe. However, the pyrolysis of melamine to form g-C3N4At a temperature above 350 ℃ and the melting point of melamine is around 250 ℃, so that the melamine is converted to g-C3N4In a molten state, not only so that g-C is produced3N4Most of the materials are compact block materials, the specific surface area is very low, active sites are reduced, the iron substance dispersion degree is insufficient, and the separation efficiency of photoproduction electrons is influenced. For this reason, improving the stability of the precursor during pyrolysis is a key to solving this problem.
Disclosure of Invention
The invention aims to provide a preparation method of an iron-based supramolecular graphite phase carbon nitride catalyst aiming at the defects of the iron-based graphite phase carbon nitride photocatalyst.
The technical scheme of the invention is as follows: by optimizing the thermal stability of the precursor, melamine, cyanuric acid and ferric salt are used as raw materials, and iron-based supermolecule g-C is generated by pyrolysis3N4(ii) a On one hand, g-C is generated by pyrolysis of melamine-cyanuric acid precursor3N4The process is more stable, more stable 'attachment points' can be provided for Fe, and the dispersion degree is improved; supramolecules g-C on the other hand3N4Has larger specific surface area, increases reactive sites with pollutants and further improves the catalytic effect.
The specific technical scheme of the invention is as follows: a preparation method of an iron-based supramolecular graphite phase carbon nitride photocatalyst comprises the following specific steps:
step A: dissolving equal molar amount of melamine and cyanuric acid in deionized water, and mechanically stirring;
and B: adding a certain amount of ferric salt into the solution obtained in the step A, stirring in a water bath for a period of time, and then continuing stirring in the water bath until the water is completely evaporated to dryness to obtain a precursor;
and C: and D, putting the precursor obtained in the step B into a porcelain boat, wrapping the porcelain boat with tinfoil, putting the porcelain boat into a tubular furnace, and calcining the porcelain boat in the atmosphere of nitrogen to obtain the iron-based supramolecular graphite-phase carbon nitride photocatalyst.
Preferably, the molar concentration of the melamine and the cyanuric acid in the step A) is 0.25-0.4 mol/L.
Preferably, the mechanical stirring speed in the step A) is 200-300 rpm/s, and the time is 0.5-1 h.
Preferably, the ferric salt in the step B) is ferric trichloride hexahydrate or ferric nitrate nonahydrate.
Preferably, the adding amount of the ferric salt in the step B) is 10-20% of the total mass of the melamine and the cyanuric acid.
Preferably, the iron salt in the step B) is added into the solution in the step A, the water bath stirring temperature is 70-80 degrees, and the water bath stirring time is 0.5-1 h.
Preferably, the calcination parameters in step C) are: the heating rate is 2-5 DEG/min; the calcining temperature is 500-600 degrees; the calcination time is 4-6 h.
Preferably, the flow rate of the nitrogen in the step C) is 0.10-0.20L/min.
The invention utilizes a self-assembly method to synthesize the iron-based supramolecular graphite-phase carbon nitride and is used for photocatalytic degradation of dye wastewater.
Detecting the removal rate of the dye in the solution measured by the method provided by the invention:
before the reaction, a dark reaction adsorption experiment is carried out, after adsorption is balanced, a xenon lamp source (the wavelength is more than 420nm) is turned on to start the reaction, and samples are taken every 10 min. And (3) filtering the wastewater after reaction by a water system filter membrane with the aperture of 0.45 mu m, and measuring the residual concentration of the dye in the liquid. Wherein, the concentration of the residual dye is determined by adopting a liquid chromatography, and the result shows that the removal rate of the dye can reach 92.1 to 98.7 percent.
Has the advantages that:
the iron-based supramolecular carbon nitride used for visible light photocatalytic degradation of dye wastewater has the following advantages:
(1) compared with the traditional bulk graphite phase carbon nitride, the supermolecular graphite phase carbon nitride has larger specific surface area and more active sites.
(2) Due to the action of hydrogen bonds, the iron-based supramolecular carbon nitride is more stable in the preparation process, the Fe element can be efficiently anchored and dispersed, the problem of Fe element agglomeration is effectively solved, the separation degree of electron hole pairs is improved, and the catalytic effect is improved.
(3) The Fe species exists in the form of Fe-Nx combined bonds, highly anchored at g-C3N4And in the framework, the leaching of Fe ions is reduced, and the service life of the catalyst is prolonged.
Detailed Description
Example 1:
the catalysts used in the following examples were prepared by the following method:
respectively dissolving equimolar amounts of melamine and cyanuric acid in deionized water, wherein the molar concentrations of the melamine and the cyanuric acid are 0.25mol/L, and mechanically stirring for 30min after mixing, wherein the rotating speed is 200 rpm/s. Weighing a certain mass of FeCl3·6H2O is added into the solution and stirred for 0.5h in a 70 ℃ constant temperature water bath, wherein FeCl is added3·6H2The mass of O is 10% of the total mass of melamine and cyanuric acid. And then, stirring the mixed solution in a water bath until the water content is completely evaporated, fully grinding the obtained solid, putting the ground solid into a ceramic ark, wrapping the ceramic ark with tinfoil, putting the ceramic ark into a tubular furnace, and heating the ceramic ark to 500 ℃ at a speed of 3 ℃/min under a nitrogen atmosphere to calcine the ceramic ark for 5 hours. Introducing N before calcination2For 30min to evacuate the air present in the tube furnace. The gas velocity was controlled at 0.15L/min using a mass flow meter. Naturally cooling to room temperature, taking out the materials, grinding into powder, and sealing for later use.
0.05g of catalyst is added into rhodamine B wastewater, wherein the concentration of the rhodamine B wastewater is 20mg/L, and the volume of the reaction solution is 100 mL. Before the reaction starts, a dark reaction adsorption experiment is carried out for 30min, a filter membrane with the diameter of 0.45 mu m is sampled, the concentration of rhodamine B in water is measured by adopting a liquid chromatography, and the condition that the rhodamine B is adsorbed by 15.3 percent is measured. After adsorption equilibrium, starting a xenon lamp light source (the wavelength is more than 420nm), sampling once every 10min, and measuring the residual concentration of the rhodamine B by using a filter membrane. And calculating to obtain that the removal rate of the rhodamine B is 96.7 percent within 60min of illumination time. After the catalyst is recycled for 5 times, the treatment effect can still reach more than 92.1 percent.
Example 2:
respectively dissolving equimolar amounts of melamine and cyanuric acid into deionized water, wherein the molar concentrations of the melamine and the cyanuric acid are 0.4mol/L, and mechanically stirring for 1h at the rotating speed of 300 rpm/s. Weighing a certain mass of FeCl3·6H2O is added to the above solution and stirred for 1h in a thermostatic water bath at 80 ℃. Wherein FeCl3·6H2The mass of O is 20% of the total mass of melamine and cyanuric acid. And then, stirring the mixed solution in a water bath until the water content is completely evaporated, fully grinding the obtained solid, putting the ground solid into a ceramic ark, wrapping the ceramic ark with tinfoil, putting the ceramic ark into a tubular furnace, and heating the ceramic ark to 550 ℃ at a speed of 4 ℃/min under a nitrogen atmosphere to calcine the ceramic ark for 6 hours. Introducing N before calcination2For 30min to evacuate the air present in the tube furnace. The gas velocity was controlled at 0.2L/min using a mass flow meter. Naturally cooling to room temperature, taking out the materials, grinding into powder, and sealing for later use.
0.04g of catalyst is added into methyl orange wastewater, wherein the concentration of the methyl orange wastewater is 20mg/L, and the volume of the reaction liquid is 100 mL. Before the reaction, a dark reaction adsorption experiment is carried out for 40min, a filter membrane with the diameter of 0.45 mu m is sampled, the concentration of methyl orange in water is measured by adopting a liquid chromatography, and the methyl orange is detected to be adsorbed by 13.2 percent. After the adsorption is balanced, a xenon lamp light source (the wavelength is more than 420nm) is started, samples are taken every 10min, and the residual concentration of the methyl orange is measured by a filter membrane. The removal rate of methyl orange in 50min of illumination time is calculated to be 98.5%. After the catalyst is recycled for 5 times, the treatment effect can still reach more than 94.2 percent.
Example 3:
respectively dissolving equimolar amounts of melamine and cyanuric acid in deionized water, wherein the molar concentrations of the melamine and the cyanuric acid are 0.35mol/L, and mechanically stirring for 45min at the rotation speed of 250 rpm/s. Weighing a certain mass of Fe (NO)3)3·9H2O is added to the above solution and stirred for 45min in a constant temperature water bath of 75 ℃. Wherein, Fe (NO)3)3·9H2The adding amount of O is 15 percent of the total mass of the melamine and the cyanuric acid. Then, the mixed solution is stirred in water bath at 120 ℃ until the water is completely evaporated, and the obtained solid is fully groundThen placing the mixture into a ceramic square boat, wrapping the ceramic square boat by tinfoil, placing the ceramic square boat into a tube furnace, and heating the tube furnace to 600 ℃ at the speed of 5 ℃/min under the nitrogen atmosphere for calcining for 4 hours. Introducing N before calcination2For 30min to evacuate the air present in the tube furnace. The gas velocity was controlled at 0.10L/min using a mass flow meter. Naturally cooling to room temperature, taking out the materials, grinding into powder, and sealing for later use.
0.06g of catalyst was added to Congo red wastewater, wherein the concentration of Congo red wastewater was 10mg/L and the volume of the reaction solution was 100 mL. Before the reaction starts, a dark reaction adsorption experiment is carried out for 30min, a sample is filtered by a 0.45-micron filter membrane, and the Congo red concentration in water is measured by adopting a liquid chromatography, so that the Congo red is adsorbed by 16.8 percent. After the adsorption is balanced, a xenon lamp light source (the wavelength is more than 420nm) is started, samples are taken every 10min, and the filter membrane measures the residual concentration of the Congo red. The calculation result shows that the removal rate of Congo red is 95.7% within 60min of illumination time. After the catalyst is recycled for 5 times, the treatment effect can still reach more than 92.3 percent.
Example 4:
respectively dissolving equimolar amounts of melamine and cyanuric acid in deionized water, wherein the molar concentrations of the melamine and the cyanuric acid are 0.3 mol/L. The mixture was mechanically stirred for 30min at a speed of 200 rpm/s. Weighing a certain mass of Fe (NO)3)3·9H2O is added into the solution and stirred for 45min in a constant temperature water bath of 80 ℃. Wherein, Fe (NO)3)3·9H2The adding amount of O is 10 percent of the total mass of the melamine and the cyanuric acid. And then, stirring the mixed solution in a water bath until the water content is completely evaporated, fully grinding the obtained solid, putting the ground solid into a ceramic ark, wrapping the ceramic ark with tinfoil, putting the ceramic ark into a tubular furnace, and heating the ceramic ark to 500 ℃ at a speed of 2 ℃/min under a nitrogen atmosphere to calcine the ceramic ark for 5 hours. Introducing N before calcination2For 30min to evacuate the air present in the tube furnace. The gas velocity was controlled at 0.15L/min using a mass flow meter. Naturally cooling to room temperature, taking out the materials, grinding into powder, and sealing for later use.
0.05g of the catalyst was added to methylene blue waste water having a concentration of 20mg/L and a reaction liquid volume of 100 mL. Before the reaction, a dark reaction adsorption experiment is carried out for 40min, a filter membrane with the diameter of 0.45 mu m is sampled, the concentration of methylene blue in water is measured by adopting a liquid chromatography, and the condition that the methylene blue is adsorbed by 15.1 percent is measured. After the adsorption is balanced, a xenon lamp light source (the wavelength is more than 420nm) is started, samples are taken every 10min, and the residual concentration of the methylene blue is measured by a filter membrane. The removal rate of methylene blue is calculated to be 98.7% in 70min of illumination time. After the catalyst is recycled for 5 times, the treatment effect can still reach more than 94.1 percent.
Claims (8)
1. A preparation method of an iron-based supramolecular graphite phase carbon nitride photocatalyst comprises the following specific steps:
step A: dissolving equal molar amount of melamine and cyanuric acid in deionized water, and mechanically stirring;
and B: adding a certain amount of ferric salt into the solution obtained in the step A, stirring in a water bath for a period of time, and then continuing stirring in the water bath until the water is evaporated to dryness to obtain a precursor;
and C: and D, putting the precursor obtained in the step B into a porcelain boat, wrapping the porcelain boat with tinfoil, putting the porcelain boat into a tubular furnace, and calcining the porcelain boat in the atmosphere of nitrogen to obtain the iron-based supramolecular graphite-phase carbon nitride photocatalyst.
2. The method of claim 1, wherein: the molar concentration of the melamine and the cyanuric acid in the step A) is 0.25-0.4 mol/L.
3. The method of claim 1, wherein: the mechanical stirring speed in the step A) is 200-300 rpm/s, and the time is 0.5-1 h.
4. The method of claim 1, wherein: the ferric salt in the step B) is ferric trichloride hexahydrate or ferric nitrate nonahydrate.
5. The method of claim 1, wherein: the adding amount of the ferric salt in the step B) is 10-20% of the total mass of the melamine and the cyanuric acid.
6. The method of claim 1, wherein: adding the iron salt in the step B) into the solution in the step A, and stirring in a water bath at the temperature of 70-80 ℃ for 0.5-1 h.
7. The method of claim 1, wherein: the calcination parameters in the step C) are as follows: the heating rate is 2-5 DEG/min; the calcining temperature is 500-600 degrees; the calcination time is 4-6 h.
8. The method of claim 1, wherein: the flow rate of the nitrogen in the step C) is 0.10-0.20L/min.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114177927A (en) * | 2021-12-16 | 2022-03-15 | 南京大学 | Two-dimensional carbon nitride supported iron monatomic catalyst and preparation method and application thereof |
| CN114657593A (en) * | 2022-03-24 | 2022-06-24 | 同济大学 | Preparation method and application of single-atom iron photoelectrode with carbon-based substrate |
| CN114797938A (en) * | 2022-04-28 | 2022-07-29 | 广州大学 | Self-assembled iron monatomic Fenton heterogeneous catalyst, preparation method and application |
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| CN115770601A (en) * | 2021-09-08 | 2023-03-10 | 南京工业大学 | Cobalt-doped porous carbon nitride catalyst and preparation method and application thereof |
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| CN117065783A (en) * | 2023-09-26 | 2023-11-17 | 山东理工大学 | Preparation method and application of precursor-regulated specific surface area-adjustable corn-shaped graphite-phase carbon nitride |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110116016A (en) * | 2019-05-14 | 2019-08-13 | 广州大学 | A kind of in-situ doping type iron series class fenton catalyst and its synthetic method and application |
| CN111939961A (en) * | 2020-08-24 | 2020-11-17 | 南昌航空大学 | Controllable synthesis method of low-cost and high-load monatomic catalyst |
| CN112354555A (en) * | 2020-11-09 | 2021-02-12 | 中国科学院地球环境研究所 | Metal monatomic supported carbon-nitrogen polymer catalyst and preparation method thereof |
-
2021
- 2021-03-16 CN CN202110279141.1A patent/CN113019415B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110116016A (en) * | 2019-05-14 | 2019-08-13 | 广州大学 | A kind of in-situ doping type iron series class fenton catalyst and its synthetic method and application |
| CN111939961A (en) * | 2020-08-24 | 2020-11-17 | 南昌航空大学 | Controllable synthesis method of low-cost and high-load monatomic catalyst |
| CN112354555A (en) * | 2020-11-09 | 2021-02-12 | 中国科学院地球环境研究所 | Metal monatomic supported carbon-nitrogen polymer catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JIU WANG, ET AL: "A Single Cu-Center Containing Enzyme-Mimic Enabling Full Photosynthesis under CO2 Reduction", 《ACS NANO》, 1 July 2020 (2020-07-01), pages 1 - 33 * |
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|---|---|---|---|---|
| CN115770601A (en) * | 2021-09-08 | 2023-03-10 | 南京工业大学 | Cobalt-doped porous carbon nitride catalyst and preparation method and application thereof |
| CN114177927A (en) * | 2021-12-16 | 2022-03-15 | 南京大学 | Two-dimensional carbon nitride supported iron monatomic catalyst and preparation method and application thereof |
| CN114657593A (en) * | 2022-03-24 | 2022-06-24 | 同济大学 | Preparation method and application of single-atom iron photoelectrode with carbon-based substrate |
| CN114797938A (en) * | 2022-04-28 | 2022-07-29 | 广州大学 | Self-assembled iron monatomic Fenton heterogeneous catalyst, preparation method and application |
| CN114797938B (en) * | 2022-04-28 | 2024-02-02 | 广州大学 | Self-assembled iron single-atom Fenton heterogeneous catalyst, preparation method and application |
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| CN117065783A (en) * | 2023-09-26 | 2023-11-17 | 山东理工大学 | Preparation method and application of precursor-regulated specific surface area-adjustable corn-shaped graphite-phase carbon nitride |
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