CN116273110A - Carbon nitride material loaded with monoatomic iron and preparation method and application thereof - Google Patents
Carbon nitride material loaded with monoatomic iron and preparation method and application thereof Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 194
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 96
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000000463 material Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 17
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims abstract description 9
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 8
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 8
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZJYYHGLJYGJLLN-UHFFFAOYSA-N guanidinium thiocyanate Chemical compound SC#N.NC(N)=N ZJYYHGLJYGJLLN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 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 abstract description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052786 argon Inorganic materials 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 99
- 239000007800 oxidant agent Substances 0.000 claims description 18
- 239000002957 persistent organic pollutant Substances 0.000 claims description 16
- 230000001590 oxidative effect Effects 0.000 claims description 13
- 239000000356 contaminant Substances 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 6
- 238000005202 decontamination Methods 0.000 claims description 6
- 239000003344 environmental pollutant Substances 0.000 claims description 6
- 231100000719 pollutant Toxicity 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 6
- 239000003242 anti bacterial agent Substances 0.000 claims description 5
- 229940088710 antibiotic agent Drugs 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
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- 150000002989 phenols Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000011941 photocatalyst Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000004753 textile Substances 0.000 abstract 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 35
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
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- 239000000843 powder Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 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 4
- 238000011068 loading method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910001428 transition metal ion Inorganic materials 0.000 description 3
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- 230000003197 catalytic effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 2
- 229960003405 ciprofloxacin Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
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- 230000004298 light response Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 229940090668 parachlorophenol Drugs 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010893 electron trap Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- ZVVIJKOMVIKZGH-UHFFFAOYSA-N ethaneperoxoic acid iron Chemical compound C(C)(=O)OO.[Fe] ZVVIJKOMVIKZGH-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
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- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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
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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
- C02F1/30—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
- 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
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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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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Abstract
The invention discloses a carbon nitride material loaded with monoatomic iron, and a preparation method and application thereof; a preparation method of a carbon nitride material loaded with monoatomic iron is characterized by comprising the following steps: the method comprises the following steps: a) Dissolving a certain amount of dicyandiamide, melamine, urea, dicyandiamide, thiourea, cyanamide, guanidine chloride or guanidine thiocyanate in water, then adding ferric chloride hexahydrate or ferric nitrate nonahydrate for carrying out a mixing reaction, evaporating and collecting a compound, and placing the compound into a tube furnace for high-temperature calcination to obtain a precursor; b) Calcining the prepared precursor at high temperature under the condition of continuously introducing nitrogen or argon, and cooling to room temperature to obtain a carbon nitride material loaded with monoatomic iron; the invention can be widely used in the fields of environmental protection, chemical industry, textile and the like.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a carbon nitride material loaded with monoatomic iron, and a preparation method and application thereof.
Background
With the rapid development of industry, the problem of water pollution caused by the rapid development of industry is also increasingly aggravated. Given the high concentration of organic contaminants that are difficult to achieve in depth removal in traditional biological treatment processes, improper disposal can be detrimental to public health and the ecological environment. The increasingly advanced oxidation technology can realize efficient, rapid and non-toxic oxidative degradation of organic pollutants. However, the existing advanced oxidation technology is still limited in practical applications, for example: the O-O bond energy of the oxidant facing the hydrogen peroxide as the oxidant is high and difficult to activate, and the Fenton system is easy to be limited by pH and mainly focuses on acidity; advanced persulfate-based oxidation systems pose potential environmental risks with high efficiency but with the end product being sulfate ions. Therefore, development of a novel oxidizing agent and efficient activation thereof for innocuous treatment of organic pollutants is urgent.
In contrast, the rising advanced oxidation systems based on peroxyacetic acid are based on the fact that the end product is CO 2 The method has the advantages of no secondary pollution risk, remarkably lower O-O bond energy than the traditional oxidant, easy activation to generate high-performance oxidized species and the like, and has outstanding advantages in the aspect of purifying organic sewage. The current methods applied to peroxyacetic acid activation mainly resort to homogeneous transition metal ions such as Fe 2+ 、Co 2+ Etc., or by means of high energy input, e.g. UV, high temperature assistance, although having particular advantages in enhancing oxidant activation and catalytic oxidation properties, it is possible that these systems still exist secondarilyPollution, high energy consumption, etc., and is therefore hindered in practical application. Therefore, there is an urgent need to develop an environment-friendly and low-energy-consumption peroxyacetic acid activation method. Considering the characteristics of low cost and easy availability of iron and wide application in the traditional Fenton-like system, the difficult problem can be effectively solved if the iron can be used for constructing a visible light response system. How to fix iron to form a heterogeneous photoactivator is key to the practice of this idea. It is contemplated that carbon nitride materials may be used to firmly anchor iron metal because of their rich nitrogen sites. Meanwhile, the material has the advantages of easy preparation, good visible light response, stable chemical property, easy mass production and the like, so that the realization of the idea is possible. In addition, the single carbon nitride photocatalysis has the problems of low charge carrier separation, easy recombination of electron-hole pairs, limited light utilization capacity and the like, and the introduction of iron can effectively relieve the problems. However, by means of only ordinary iron doping, the utilization of iron is still low and its catalytic activity is likewise limited. If the single-atom type load is realized, the maximum exposure and utilization of the iron site can be achieved, and the activity of the single-atom type load is also obviously amplified; meanwhile, by means of carbon nitride, nitrogen vacancies are easy to form in the high-temperature synthesis process to serve as electron traps, and the continuous input of electrons to iron sites can be realized by adjusting and controlling the distance between the nitrogen vacancies and the iron sites. Thus, the high-efficiency visible light activation of the peroxyacetic acid can be realized, so that high-performance oxidized species are generated to accelerate the decontamination process.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a carbon nitride material loaded with monoatomic iron, and a preparation method and application thereof.
The technical scheme of the invention is that the preparation method of the carbon nitride material loaded with single-atom iron is characterized by comprising the following steps: the method comprises the following steps:
a) Dissolving a certain amount of dicyandiamide, melamine, urea, dicyandiamide, thiourea, cyanamide, guanidine chloride or guanidine thiocyanate in water, then adding ferric chloride hexahydrate or ferric nitrate nonahydrate for carrying out a mixing reaction, evaporating and collecting a compound, and placing the compound into a tube furnace for high-temperature calcination to obtain a precursor;
b) And placing the prepared precursor in an uncapped crucible, continuously introducing nitrogen or argon, continuously calcining the precursor at a high temperature of 550-620 ℃ for 3-5 hours, and cooling to room temperature to obtain the carbon nitride material loaded with the monatomic iron.
Wherein dicyandiamide, melamine, urea, dicyandiamide, thiourea, cyanamide, guanidine chloride or guanidine thiocyanate is used as a precursor of a carbon nitride framework, and ferric chloride hexahydrate or ferric nitrate nonahydrate is used as a precursor for acting on a single atom site of iron.
According to the preferred scheme of the preparation method of the carbon nitride material loaded with the monatomic iron, in an aqueous solution, the mass concentration of dicyandiamide, melamine, urea, dicyandiamide, thiourea, cyanamide, guanidine chloride or guanidine thiocyanate is 0-400 g/L, and the mass concentration of ferric chloride hexahydrate or ferric nitrate nonahydrate is 2-8 g/L.
According to the second technical scheme, the monoatomic iron-loaded carbon nitride material is obtained by the preparation method of the monoatomic iron-loaded carbon nitride material.
According to a third technical scheme, the carbon nitride material loaded with single-atom iron is used for removing organic pollutants in water, and is characterized in that: adding a carbon nitride material loaded with monoatomic iron into wastewater containing organic pollutants as a photocatalyst, adding peracetic acid as an oxidant, and activating the peracetic acid with the carbon nitride material loaded with monoatomic iron under the assistance of visible light to form a strong oxidative active species which acts on a decontamination process to remove the organic pollutants in the water.
Further, the addition amount of the carbon nitride material loaded with the monatomic iron is 0.2 g/L.
Further, the organic contaminants include phenols, antibiotics, and dyes.
Further, the amount of peracetic acid to be added is 0.01 to 2 mmol/l.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the carbon nitride material loaded with the monoatomic iron is used as a photocatalyst, the peroxyacetic acid is activated by the carbon nitride material loaded with the monoatomic iron under the assistance of visible light, a novel advanced oxidation system is constructed, organic pollutants in water are removed, various refractory pollutants in wastewater can be efficiently removed, and the method has the advantages of high pollutant decontamination rate, excellent anti-interference performance, no toxic by-product generation, wide pH application range, good tolerance and the like, and secondary pollution caused by transition metal ion precipitation of a homogeneous system is avoided; can efficiently remove various nondegradable pollutants such as dyes, phenols, antibiotics and the like; the carbon nitride activator of single-atom iron can be recycled in a sustainable way, and can be widely applied to the fields of environmental protection, chemical industry, spinning and the like.
Drawings
Fig. 1 is a phase characterization result of a monoatomic iron-supported carbon nitride material synthesized by the method described in this example.
Fig. 2 is a scanning electron micrograph of a monoatomic iron-loaded carbon nitride material synthesized by the method described in this example, showing that the monoatomic iron-loaded carbon nitride material is a layered structure.
Fig. 3 is a transmission electron micrograph of a monoatomic iron-loaded carbon nitride material synthesized by the method described in this example showing the nanoplatelet structure of the monoatomic iron-loaded carbon nitride material.
Fig. 4 is a high angle annular dark field image-scanning transmission electron image of a monatomic iron material synthesized by the method described in this example, showing that a monatomic iron loaded carbon nitride material successfully loaded with iron monatoms.
Fig. 5 shows that the removal rate of bisphenol a by the peroxyacetic acid activated by the monoatomic iron material with different iron loadings synthesized by the method described in this example, the monoatomic iron material with the loading of 0.24 g has excellent performance on bisphenol a removal.
Fig. 6 shows that the carbon nitride material loaded with monoatomic iron shows good stability in 15 cycles by activating the removal rate of peroxyacetic acid to bisphenol a within 30 minutes of each cycle use.
FIG. 7 shows bisphenol A removal rate of the monoatomic iron-supported carbon nitride material-peracetic acid system obtained in accordance with the present example in the absence of light or an oxidizing agent or a catalyst.
Fig. 8a and 8b show the reaction rate constant and bisphenol a removal rate in the visible light activated system of peracetic acid, which is a carbon nitride material loaded with monoatomic iron and added with different amounts of peracetic acid, obtained in this example.
FIGS. 9a, 9b show the reaction rate constant and bisphenol A removal rate at different initial pH conditions as measured in this example.
FIG. 10 shows the removal rate of substances such as parachlorophenol, ciprofloxacin, tetracycline hydrochloride and the like for the degradation of the monoatomic iron-loaded carbon nitride material-peracetic acid visible light activated system obtained according to the example.
FIGS. 11a and 11b are, respectively, the reaction rate constant and bisphenol A removal rate in the visible light activated system of peracetic acid, which is a monoatomic material rich in nitrogen vacancies, to which different kinds of oxidizing agents are added, obtained in this example.
Detailed Description
A method for preparing a carbon nitride material loaded with monoatomic iron, comprising the following steps:
a) Dissolving a certain amount of dicyandiamide, melamine, urea, dicyandiamide, thiourea, cyanamide, guanidine chloride or guanidine thiocyanate in water, then adding ferric chloride hexahydrate or ferric nitrate nonahydrate for carrying out a mixing reaction, evaporating and collecting a compound, and placing the compound into a tube furnace for high-temperature calcination to obtain a precursor;
b) And placing the prepared precursor in an uncapped crucible, calcining at high temperature under the condition of continuously introducing nitrogen or argon, and cooling to room temperature to obtain the carbon nitride material loaded with the monatomic iron.
In a specific embodiment, the mass concentration of dicyandiamide, melamine, urea, dicyandiamide, thiourea, cyanamide, guanidinium chloride or guanidinium thiocyanate in the aqueous solution is 200 g/l, and the mass concentration of ferric chloride hexahydrate or ferric nitrate nonahydrate is 2-8 g/l.
The monoatomic iron-loaded carbon nitride material obtained by the method for producing monoatomic iron-loaded carbon nitride material described in example 1.
The carbon nitride material loaded with the monoatomic iron is used for removing organic pollutants in water, and specifically comprises the following steps: adding a carbon nitride material loaded with monoatomic iron into wastewater containing organic pollutants as a photocatalyst, adding peracetic acid as an oxidant, and activating the peracetic acid with the carbon nitride material loaded with monoatomic iron under the assistance of visible light to form a strong oxidative active species which acts on a decontamination process to remove the organic pollutants in the water.
The adding amount of the carbon nitride material loaded with the monatomic iron is 0-0.6 g/L. The adding amount of the peroxyacetic acid is 0.01-2 millimoles per liter. The organic contaminants include phenols, antibiotics, and dyes.
The invention is described in further detail below with reference to the drawings and the detailed description.
Example 1: preparation of carbon nitride material loaded with monoatomic iron
A clean 100 ml round bottom flask was charged with 60 ml deionized water and placed in a water bath, warmed to 80 degrees, 12 g dicyandiamide was added, stirred until completely dissolved, then 0.24 g ferric chloride hexahydrate was added and reacted for 10 minutes. The temperature of the water bath kettle is raised to 100 ℃ and the reaction is continuously stirred until the water bath kettle is evaporated to dryness, and then a sample is collected. The reaction product was placed in a capped crucible, placed in a tube furnace, heated to 550 degrees at a heating rate of 2 degrees/min under nitrogen atmosphere, reacted at this temperature for 4 hours, cooled to room temperature and then collected for use.
3 parts of 1 gram of the prepared product are respectively placed in three uncapped crucibles in a spreading way, the temperature is raised to 620 ℃ at the temperature rising rate of 2 ℃ per minute under the condition of 20 milliliters per minute of nitrogen flow, the mixture is operated for 4 hours at the temperature, and the mixture is cooled to room temperature to obtain the carbon nitride material loaded with the monatomic iron.
Fig. 1 is a phase characterization result of a monoatomic iron-supported carbon nitride material synthesized by the method described in this example. Fig. 2 is a scanning electron micrograph of a monoatomic iron-loaded carbon nitride material synthesized by the method described in this example, showing that the monoatomic iron-loaded carbon nitride material is a layered structure. Fig. 3 is a transmission electron micrograph of a monoatomic iron-loaded carbon nitride material synthesized by the method described in this example showing the lamellar nanoplatelet structure of the nitrogen-rich vacancy monoatomic iron material. Fig. 4 is a high angle annular dark field image-scanning transmission electron image of a monatomic iron material synthesized by the method described in this example, and it can be seen that the monatomic iron loaded carbon nitride material successfully loaded with iron monatoms.
Example 2: application of monoatomic iron-loaded carbon nitride material-peracetic acid visible light activation system in removal of bisphenol A in water
The monoatomic iron-supported carbon nitride material powder obtained in example 1 was added to an aqueous solution containing bisphenol a. In a bisphenol A solution having a volume of 50 ml and a mass concentration of 5 mg/liter, the amount of the material added was 0.2 g/liter, and the solution was homogenized by magnetic stirring. Under the irradiation of visible light, 1 millimole per liter of peracetic acid is added to start the reaction. FIG. 5 is a graph showing the kinetics of degradation in a monoatomic iron-loaded carbon nitride material-peroxyacetic acid system tested for different iron content, with 0.24 gram of monoatomic iron-loaded carbon nitride material capable of completely removing 5 milligrams per liter of bisphenol A within 30 minutes of degradation. The result shows that the iron loading quantity influences the degradation performance of the material, and the carbon nitride material loaded with the monoatomic iron has the best performance on bisphenol A in water. In fig. 5, this interval of-10 to 0 on the abscissa is the no-illumination condition.
Example 3: continuous recycling of monoatomic iron-loaded carbon nitride materials
The carbon nitride material of the single-atom iron, which was treated with 5 mg/l bisphenol a solution in example 2, was repeatedly used in the reactor a plurality of times, the bisphenol a concentration in the reactor was restored to 5 mg/l by continuing to add the high-concentration bisphenol a solution, and 1 mmol/l peracetic acid was added under magnetic stirring, and a xenon lamp was turned on to perform the reaction. After 30 minutes of reaction, the bisphenol A removal rate was monitored. The reactor was repeatedly charged with high concentrations of bisphenol a and the oxidant peracetic acid according to the above protocol, and bisphenol a removal was monitored after 30 minutes, thereby performing 15 cycles. Fig. 6 shows the removal rate of bisphenol a by activated peroxyacetic acid in 30 minutes per cycle of carbon nitride material loaded with monoatomic iron, although the removal rate is reduced, the removal rate is not significant, and the stability and practical application potential of the system are confirmed.
Example 4: application of monoatomic iron-loaded carbon nitride material-peracetic acid visible light activated system in bisphenol A removal under contrast condition
The carbon nitride material powder supporting single-atom iron obtained in example 1 was added to a solution to be treated with 5 mg/liter of bisphenol a in an amount of 0.2 g/liter. 1 mmol per liter of peracetic acid was added under magnetic stirring, and the mixture was subjected to light irradiation for 30 minutes to prepare a control experiment. FIG. 7 shows the degradation curves of bisphenol A in the visible light activated system of peracetic acid, which is a carbon nitride material loaded with single-atom iron, obtained according to the present example, under the conditions of darkness, no peracetic acid and no catalyst. The invention constructs a carbon nitride material-peracetic acid visible light activated system loaded with single-atom iron, which has multiple synergistic effects on the degradation of bisphenol A.
Example 5: application of different addition amounts of peroxyacetic acid serving as oxidizing agent in removal of bisphenol A in water
The carbon nitride material powder supporting single-atom iron obtained in example 1 was added to a solution to be treated with 5 mg/l bisphenol a in an amount of 0.2 g/l. Adding different amounts of peracetic acid under the irradiation of visible light and magnetic stirring. Fig. 8a and 8b show the reaction rate constant and bisphenol a removal rate in the visible light activated system of peracetic acid, which is a carbon nitride material loaded with monoatomic iron and added with different amounts of peracetic acid, obtained in this example. FIGS. 8a and 8b show that the amount of peroxyacetic acid added has an effect on both the reaction rate and degradation efficiency within 30 minutes. In a certain range, the reaction rate and the removal rate are positively correlated with the addition amount of the peroxyacetic acid. When the addition amount of the peroxyacetic acid is small, the degradation efficiency of bisphenol A is low; bisphenol A can be rapidly and completely degraded when the amount of the peroxyacetic acid is 1 millimole per liter; bisphenol a removal was not significantly enhanced when the amount of peracetic acid was increased to 2 mmoles per liter, with an amount of 1 mmoles per liter of peracetic acid selected from an economic standpoint. The amount of the oxidizing agent is critical, so that it should be considered as a main core factor in practical use.
Example 6: application of carbon nitride material loaded with monoatomic iron-peracetic acid visible light activated system in removal of bisphenol A in water under different pH conditions
The carbon nitride material powder supporting single-atom iron obtained in example 1 was added to a solution to be treated with 5 mg/l bisphenol a in an amount of 0.2 g/l. The pH value of the initial aqueous solution is adjusted by using perchloric acid and sodium hydroxide, and then 1 millimole per liter of peracetic acid is added under the irradiation of visible light and magnetic stirring. FIGS. 9a, 9b show the reaction rate constant and bisphenol A removal rate at different initial pH conditions as measured in this example. As can be seen from fig. 9a and 9b, the visible light activated system of peracetic acid, which is a carbon nitride material loaded with monoatomic iron at an initial pH of 3-9, can rapidly remove bisphenol a within 30 minutes. Therefore, the carbon nitride material-peracetic acid visible light activated system loaded with the monoatomic iron, constructed by the invention, has a wider pH application range.
Example 7: application of monoatomic iron-loaded carbon nitride material-peracetic acid visible light activated system in removal of various refractory organic pollutants
The monoatomic iron-supported carbon nitride material powder obtained in example 1 was added to a solution to be treated with different contaminants in an amount of 0.2 g/l. 1 mmol per liter of peracetic acid was added under irradiation with visible light and magnetic stirring. Fig. 10 is a graph showing degradation curves of the monoatomic iron-loaded carbon nitride material-peracetic acid visible light activation system obtained according to the present example for removing parachlorophenol, ciprofloxacin, tetracycline hydrochloride, etc., and the monoatomic iron-loaded carbon nitride material-peracetic acid visible light activation system constructed according to the present invention has a better capability for removing various organic pollutants as described above, thereby confirming the broad spectrum of the system.
Example 8: application of carbon nitride material loaded with monoatomic iron-multiple oxidants visible light activation system in removal of bisphenol A in actual water source
The carbon nitride material powder supporting single-atom iron obtained in example 1 was added to a solution to be treated with 5 mg/l bisphenol a in an amount of 0.2 g/l. 1 mmol per liter of peracetic acid was added under irradiation with visible light and magnetic stirring. FIGS. 11a and 11b are, respectively, the reaction rate constant and bisphenol A removal rate in the visible light activated system of peracetic acid, which is a monoatomic material rich in nitrogen vacancies, to which different kinds of oxidizing agents are added, obtained in this example. From the graph, the degradation performance of the carbon nitride material-peroxyacetic acid system with the visible light assisted loading of the monatomic iron constructed by the invention is better than that of a part of the oxidant, and the activator has universality for different oxidants.
The invention utilizes the carbon nitride material loaded with single-atom iron to realize a novel process for activating the novel environment-friendly oxidant peracetic acid under the assistance of visible light, and applies the novel process to efficiently remove the refractory organic pollutants in water. Adding the carbon nitride material loaded with the monoatomic iron into the wastewater containing the organic pollutants, and activating the active species with high performance by adding peracetic acid under the assistance of visible light to act on the decontamination process of the pollutants. The novel advanced oxidation system activated by the visible light of the monoatomic iron-loaded carbon nitride material-peracetic acid can be used for rapidly removing various persistent organic pollutants such as phenols, antibiotics, dyes and the like in water. The monoatomic nano material in the system can be continuously and circularly used for at least 15 times, and the problems of transition metal ion leaching and the like are avoided in the reaction process; in addition, the process is a synchronous degradation and mineralization process, and the toxicity of pollutants is gradually reduced. The invention provides a new idea for the fine design and construction of the monoatomic nanomaterial for the peroxyacetic acid activated Fenton-like reaction to be used for purifying organic wastewater.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that variations, modifications, substitutions and alterations herein will occur to those skilled in the art without departing from the principles of the present invention and are to be considered as being within the scope of the invention.
Claims (7)
1. A preparation method of a carbon nitride material loaded with monoatomic iron is characterized by comprising the following steps: the method comprises the following steps:
a) Dissolving a certain amount of dicyandiamide, melamine, urea, dicyandiamide, thiourea, cyanamide, guanidine chloride or guanidine thiocyanate in water, then adding ferric chloride hexahydrate or ferric nitrate nonahydrate for carrying out a mixing reaction, evaporating and collecting a compound, and placing the compound into a tube furnace for high-temperature calcination to obtain a precursor;
b) And calcining the prepared precursor at high temperature under the condition of continuously introducing nitrogen or argon, and cooling to room temperature to obtain the carbon nitride material loaded with the monoatomic iron.
2. The method for producing a monoatomic iron-supported carbon nitride material according to claim 1, wherein the mass concentration of dicyandiamide, melamine, urea, dicyandiamide, thiourea, cyanamide, guanidine chloride or guanidine thiocyanate in the aqueous solution is 0 to 400 g/l, and the mass concentration of ferric chloride hexahydrate or ferric nitrate nonahydrate is 2 to 8 g/l.
3. The monatomic iron-loaded carbon nitride material obtained by the method for producing a monatomic iron-loaded carbon nitride material according to claim 1 or 2.
4. A mono-atomic iron supported carbon nitride material according to claim 3 for removing organic contaminants from water, characterized in that: adding a carbon nitride material loaded with monoatomic iron into wastewater containing organic pollutants as a photocatalyst, adding peracetic acid as an oxidant, and activating the peracetic acid with the carbon nitride material loaded with monoatomic iron under the assistance of visible light to form a strong oxidative active species which acts on a decontamination process to remove the organic pollutants in the water.
5. The monatomic iron-loaded carbon nitride material for use in removing organic contaminants from water of claim 4, wherein the monatomic iron-loaded carbon nitride material is added in an amount of 0-0.6 grams per liter.
6. The mono-atomic iron supported carbon nitride material according to claim 4 for removing organic contaminants from water, wherein the organic contaminants include phenols, antibiotics and dyes.
7. The carbon nitride material loaded with single-atom iron according to claim 4 for removing organic matters in water
The pollutant is characterized in that the adding amount of the peroxyacetic acid is 0.01-2 millimoles per liter.
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