CN111453804A - Preparation method of iron-doped graphite-like phase carbon nitride/graphene multifunctional nano composite material - Google Patents
Preparation method of iron-doped graphite-like phase carbon nitride/graphene multifunctional nano composite material Download PDFInfo
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- 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 7
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- 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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01J27/24—Nitrogen compounds
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Abstract
A preparation method of an iron-doped graphite-like phase carbon nitride/graphene multifunctional nano composite material belongs to the field of water treatment. Dissolving urea and ferric chloride hexahydrate in absolute ethyl alcohol, stirring and evaporating to obtain a primary compound; carrying out primary calcination in a muffle furnace, cooling, grinding and cleaning; then placing the mixture in a tubular furnace, and carrying out secondary calcination and thermal stripping to obtain an iron-doped graphite-phase carbon nitride nano composite; and carrying out hydrothermal reaction on the obtained iron-doped graphite-like carbon nitride nano composite and the graphene ethanol solution subjected to ultrasonic dispersion, and then drying and grinding to obtain the iron-doped graphite-like carbon nitride/graphene multifunctional nano composite material. The invention also discloses the composite material prepared by the preparation method and a related application method thereof. The iron-doped graphite-like phase carbon nitride/graphene multifunctional nano composite material prepared by the invention reduces the photoproduction electron-hole recombination rate, improves the photoresponse capability and has a remarkable synergistic degradation effect of Fenton-like oxidation/visible light photocatalytic oxidation.
Description
Technical Field
The invention belongs to the field of water treatment, and relates to a preparation method of an iron-doped graphite-phase carbon nitride/graphene multifunctional nano composite material.
Background
The graphite-like carbon nitride is a non-metal semiconductor high polymer material with a graphite structure and can be prepared by thermal polymerization of various raw materials such as urea, dicyandiamide, melamine and the like. The forbidden band width of the graphite-like carbon nitride is about 2.7eV, the graphite-like carbon nitride can respond to visible light, and the graphite-like carbon nitride is widely applied to the research fields of photolysis water to produce hydrogen, degradation of pollutants and the like. The graphite-like carbon nitride has the problems of high electron hole recombination rate, small spectral response range, poor visible light absorption, low photocatalytic efficiency and the like, and the methods for improving the photocatalytic performance of the graphite-like carbon nitride mainly comprise methods of structure regulation, element doping, semiconductor compounding and the like. The transition metals of Ag, Pb, Fe, Zn, Ni and the like are doped into the graphite-like carbon nitride structure, so that the photocatalytic performance of the graphite-like carbon nitride structure can be improved. Research shows that Fe2O3、FeCl3Etc. with g-C3N4The composite photocatalyst is formed by doping, and has dual catalytic degradation functions of photocatalytic oxidation and Fenton-like oxidation, so that the photoresponse of graphite-like carbon nitride can be improved, the photocatalytic efficiency can be improved, and the pH value application range of the traditional Fenton reaction can be widened.
Graphene is a polymer with a pi-pi conjugated structure, has excellent conductivity, and is widely applied to the field of photocatalytic semiconductor materials. The graphene can modify a semiconductor photocatalyst, accelerate the transfer of photo-generated electrons, reduce the recombination of electron-hole pairs, increase the specific surface area of a material, increase the contact sites of pollutants and improve the photocatalytic degradation efficiency. Research shows that after the graphite-like carbon nitride is modified by graphene, strong electronic coupling can be formed at the interface of the graphene/the graphite-like carbon nitride. Therefore, the electronic conductivity and optical absorption of the graphite-like carbon nitride are enhanced, which is advantageous for improving the photocatalytic activity of the graphite-like carbon nitride.
According to the characteristics of the graphite-like carbon nitride and the graphene, the iron-doped graphite-like carbon nitride/graphene multifunctional nano composite material with the visible light response catalysis function is prepared by adopting a material doping and compounding mode and constructing the preparation process and conditions, has stronger photocatalysis activity, larger specific surface area and higher electron transfer efficiency, and can promote electron decomposition H2O2The OH process is formed, and the efficiency of degrading pollutants by Fenton-like photocatalysis is improved.
Disclosure of Invention
The invention relates to a preparation method of an iron-doped graphite-like phase carbon nitride/graphene multifunctional nano composite material, which comprises the steps of firstly synchronously calcining ferric chloride hexahydrate and urea by adopting a two-stage calcination thermal stripping method to form the iron-doped graphite-like phase carbon nitride/composite material; and then compounding the iron-doped graphite-phase carbon nitride with graphene through a hydrothermal reaction to obtain the iron-doped graphite-phase carbon nitride/graphene multifunctional nano composite material. The material has strong adsorbability, and realizes the synergetic degradation effect of Fenton-like oxidation and photocatalytic oxidation.
The technical scheme adopted by the invention is as follows:
(1) dissolving urea and ferric chloride hexahydrate in absolute ethyl alcohol, fully stirring, and evaporating in a water bath to obtain a primary compound; calcining the primary compound in a muffle furnace at a certain temperature, naturally cooling to room temperature, grinding to be uniform powder, cleaning with ethanol for 1-3 times, cleaning with water for 1-3 times, and cleaning to obtain an iron-doped graphite-like carbon nitride compound; and (3) placing the iron-doped graphite-phase carbon nitride compound in a tubular furnace, carrying out secondary calcination thermal stripping treatment at a certain temperature under the argon atmosphere, and naturally cooling and grinding to obtain the iron-doped graphite-phase carbon nitride nano compound.
(2) Adding a proper amount of graphene and absolute ethyl alcohol into a beaker, and dispersing for 1-3h by using ultrasonic waves with the power of 400W to prepare an ethanol suspension of the graphene; adding the iron-doped graphite-phase carbon nitride nano composite into the graphene ethanol turbid liquid, carrying out hydrothermal reaction at a certain temperature in a reaction kettle, then carrying out centrifugal separation and washing, and drying at 80-100 ℃ to obtain the iron-doped graphite-phase carbon nitride/graphene multifunctional nano composite.
The primary calcination temperature in the step (1) of the invention is 550 +/-50 ℃, the heating rate is 2-10 ℃/min, and the temperature holding time is 2-6 h; the secondary calcination heat stripping temperature is 500 +/-20 ℃, the heating rate is 5-15 ℃/min, and the temperature holding time is 1-4 h; the mass percentage of iron in the obtained iron-doped graphite-like phase carbon nitride nano composite is preferably 5-15%, and the dosage relation of urea and ferric chloride hexahydrate can be adjusted according to the content of iron.
The hydrothermal reaction in the step (2) of the invention has the time of 4-8h and the temperature of 100 +/-50 ℃. The mass ratio of the graphene to the iron-doped graphite-like carbon nitride nanocomposite is preferably 1: 8.5-1.2.
The obtained iron-doped graphite-phase carbon nitride/graphene multifunctional nano composite material is used as a catalyst for treating organic wastewater. Adding the composite material catalyst into a solution containing organic pollutants, performing dark adsorption to achieve adsorption balance, turning on a xenon lamp with a light source of 300W, filtering out ultraviolet light by using a 420nm optical filter, and adding H2O2The water undergoes degradation reactions.
THE ADVANTAGES OF THE PRESENT INVENTION
The invention has the following advantages:
(1) the iron-doped graphite-phase carbon nitride/graphene multifunctional nano composite material is prepared by adopting a preparation process combining a primary calcination preparation method based on temperature, heating rate and heat preservation time regulation, an argon atmosphere secondary calcination heat stripping method and a hydrothermal method.
(2) The iron-doped graphite-phase carbon nitride/graphene multifunctional nano composite material has the characteristics of large specific surface area, good photoresponse performance and good recycling performance.
(3) The iron-doped graphite-like phase carbon nitride/graphene multifunctional nano composite material has obvious synergistic effects of adsorption, Fenton-like oxidation and visible light photocatalytic oxidation, has a good synergistic pollution removal function, has a remarkable removal effect when adsorbing and degrading typical dyes, and has a wide application prospect.
Drawings
Fig. 1 is a projection electron microscope image of the iron-doped graphite-like carbon nitride/graphene multifunctional nanocomposite material in example 1.
Fig. 2 is an X-ray diffraction pattern of the iron-doped graphite-like phase carbon nitride/graphene multifunctional nanocomposite material of example 1.
Fig. 3 is an X-ray photoelectron spectrometer of the iron-doped graphite-like phase carbon nitride/graphene multifunctional nanocomposite in example 1.
Fig. 4 is a photoluminescence spectrum of the iron-doped graphite-like carbon nitride/graphene multifunctional nanocomposite material in example 1.
Fig. 5 is a graph showing the decontamination efficiency of the iron-doped graphite-like phase carbon nitride/graphene multifunctional nanocomposite material in example 2. FIG. 5(a) is a rhodamine B degradation efficiency graph under different conditions, and FIG. 5(B) is a rhodamine B degradation efficiency graph of different composite materials under Fenton-like/photocatalytic conditions.
Detailed Description
The present invention is illustrated in detail by the following examples, but the present invention is not limited to the following examples.
Example 1: 10g of urea and 3.5g of ferric chloride hexahydrate (containing 0.725g of iron) are dissolved in absolute ethyl alcohol, fully stirred and evaporated in a water bath to obtain a compound. The compound obtained is subjected to a primary calcination in a muffle furnace: heating to 550 ℃, keeping the temperature for 4h, naturally cooling to room temperature, and grinding to be evenly divided into powder. And cleaning the iron-doped graphite-like phase carbon nitride composite material with ethanol and water. And placing the obtained compound in a tubular furnace, keeping the temperature for 2h at 520 ℃ under the argon atmosphere, carrying out secondary calcination thermal stripping treatment at the heating rate of 10 ℃/min under the condition of keeping the temperature for 2h, and cooling and grinding to obtain the iron-doped graphite-phase carbon nitride nano compound. Weighing 1.05g of graphene, dissolving in ethanol, performing ultrasonic treatment at 400W for 2h, adding 9g of iron-doped graphite-phase carbon nitride nanocomposite into the graphene ethanol suspension, transferring the graphene ethanol suspension into a reaction kettle, performing hydrothermal reaction at 130 ℃ for 4h, and after the reaction is finished, performing centrifugal separation, washing and drying to obtain the iron-doped graphite-phase carbon nitride/graphene multifunctional nanocomposite.
The composite material prepared in this example was subjected to transmission electron microscopy analysis, X-ray diffraction analysis, X-ray photoelectron spectroscopy analysis, and photoluminescence spectroscopy analysis, respectively, and the results are shown in fig. 1 to 4. As can be seen from fig. 1, the C, N, Fe element is uniformly distributed throughout the entire area of the composite material, indicating that iron has been successfully doped into the graphite-like carbon nitride molecular skeleton. As shown in table 1, after the iron-doped graphite-phase carbon nitride is compounded with graphene by a hydrothermal method, the specific surface area of the composite material is significantly increased. As can be seen from fig. 2, all the composites exhibited diffraction peaks at 13.1 ° and 27.4 °, which are (100) and (002) crystal plane diffraction peaks, respectively. After the iron element is doped, the 002 peak intensity of the composite material is weakened, and the characteristic peak of the Fe element does not appear, which indicates that the Fe element is successfully doped into g-C3N4In the structure. As can be seen from FIG. 3, the main peak is 706.7eV, and the peaks are specifically 3 peaks of 706.7, 709.3 and 724.0eV, which correspond to Fe-N, FeO and Fe2O3Bonding energy of (B) indicates Fe-g-C3N4Fe in the material exists mainly in a Fe-N coordination bond form, which is beneficial to photo-charge in Fe3+And g-C3N4To perform rapid transfer and migration. As can be seen from fig. 4, the iron-doped graphite-like carbon nitride/graphene is smaller than the iron-doped graphite-like carbon nitride, which indicates that the graphene and the graphite-like carbon nitride form a pi-pi conjugated structure, thereby further reducing the rate of photon-generated electron-hole recombination and further improving the efficiency of visible light degradation of pollutants.
Table 1 comparison of specific surface area of composite material in example 1
| Name of Material | Specific surface area (m)2/g) |
| Graphite-like phase carbon nitride | 78.535 |
| Iron-doped graphite-like carbon nitride | 63.524 |
| Iron-doped graphite-like phase carbon nitride/graphene | 264.701 |
Example 2 the iron-doped graphite-phase carbon nitride/graphene multifunctional nanocomposite material prepared in example 1 was used as a catalyst, and the test experiments were carried out under different conditions, wherein the main steps include that 20mg of the catalyst was added to 100m L rhodamine B solution with a concentration of 100 mg/L or 10 mg/L, dark adsorption was carried out for 40min to achieve adsorption equilibrium, then a 300W xenon lamp light source was turned on, ultraviolet light was filtered out by a 420nm filter, and 30% H was added2O2(1 mmol/L) and sampling every 5min, filtering with 0.45 μm filter membrane, and measuring the absorbance of rhodamine B at 555nm wavelength with ultraviolet spectrophotometer.
In FIG. 5, (a) the iron-doped graphite-like carbon nitride/graphene multifunctional nanocomposite has a degradation effect on low-concentration rhodamine B (with a concentration of 10 mg/L) under three reaction conditions of visible light catalytic oxidation, Fenton-like oxidation and Fenton-like/photocatalytic oxidation, and it can be seen that, within the reaction time range of 45min, the removal rates of rhodamine B in the photocatalytic oxidation, the Fenton-like oxidation and the Fenton-like/photocatalytic oxidation are respectively 39%, 76% and 96.1%FIG. 5(B) shows a comparison of the degradation efficiencies of graphite-like carbon nitride, iron-doped graphite-like carbon nitride and iron-doped graphite-like carbon nitride/graphene under high concentration (100 mg/L) rhodamine B, and after 45min reaction, the removal rates of rhodamine B are 24.8%, 38.9% and 53.8%, respectively3N4The best effect of/rGO degradation.
Claims (8)
1. A preparation method of an iron-doped graphite-like phase carbon nitride/graphene multifunctional nano composite material is characterized by comprising the following steps:
(1) dissolving urea and ferric chloride hexahydrate in absolute ethyl alcohol, fully stirring, and evaporating in a water bath to obtain a primary compound; calcining the primary compound in a muffle furnace at a certain temperature, naturally cooling to room temperature, grinding to be uniform powder, cleaning with ethanol for 1-3 times, cleaning with water for 1-3 times, and cleaning to obtain an iron-doped graphite-like carbon nitride compound; and (3) placing the iron-doped graphite-phase carbon nitride compound in a tubular furnace, carrying out secondary calcination thermal stripping treatment at a certain temperature under the argon atmosphere, and naturally cooling and grinding to obtain the iron-doped graphite-phase carbon nitride nano compound.
(2) Adding a proper amount of graphene and absolute ethyl alcohol into a beaker, and dispersing for 1-3h by using ultrasonic waves with the power of 400W to prepare an ethanol suspension of the graphene; adding the iron-doped graphite-phase carbon nitride nano composite into the graphene ethanol turbid liquid, carrying out hydrothermal reaction at a certain temperature in a reaction kettle, then carrying out centrifugal separation and washing, and drying at 80-100 ℃ to obtain the iron-doped graphite-phase carbon nitride/graphene multifunctional nano composite.
2. The preparation method of the iron-doped graphite-phase carbon nitride/graphene multifunctional nanocomposite material according to claim 1, wherein the primary calcination temperature in the step (1) is 550 ℃ ± 50 ℃, the heating rate is 2-10 ℃/min, and the holding time is 2-6 h; the secondary calcination heat stripping temperature is 500 +/-20 ℃, the heating rate is 5-15 ℃/min, and the temperature holding time is 1-4 h.
3. The preparation method of the iron-doped graphite-like phase carbon nitride/graphene multifunctional nanocomposite material according to claim 1, wherein the mass percentage of iron in the iron-doped graphite-like phase carbon nitride nanocomposite obtained in the step (1) is 1-15%, and the dosage relationship between urea and ferric chloride hexahydrate is adjusted according to the content of iron.
4. The method for preparing the iron-doped graphite-phase carbon nitride/graphene multifunctional nanocomposite material according to claim 1, wherein the hydrothermal reaction time in the step (2) is 4-8 hours and the temperature is 100 ℃ +/-50 ℃.
5. The method for preparing the iron-doped graphite-like phase carbon nitride/graphene multifunctional nanocomposite material according to claim 1, wherein the mass ratio of the graphene to the iron-doped graphite-like phase carbon nitride nanocomposite is preferably 1: 8.5-12.
6. An iron-doped graphite-like phase carbon nitride/graphene multifunctional nanocomposite material prepared by the method according to any one of claims 1 to 5.
7. Use of an iron-doped graphite-like phase carbon nitride/graphene multifunctional nanocomposite material prepared according to any one of claims 1 to 5 as a catalyst for the treatment of organic wastewater.
8. The method according to claim 7, which comprises adding the composite catalyst into a solution containing organic pollutants, dark adsorbing to reach adsorption equilibrium, turning on a 300W xenon lamp, filtering out ultraviolet light with a 420nm filter, and adding H2O2The water undergoes degradation reactions.
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| CN113101959A (en) * | 2021-03-31 | 2021-07-13 | 中煤嘉沣(湖南)环保科技有限责任公司 | Graphite-like phase carbon nitride composite material for soil remediation and preparation method and application thereof |
| CN113600164A (en) * | 2021-07-30 | 2021-11-05 | 江苏理工学院 | Preparation method and application of iron-doped carbon quantum dot/graphite phase carbon nitride composite photocatalyst |
| CN113751046A (en) * | 2021-10-09 | 2021-12-07 | 东华大学 | Iron-doped resin modified graphite-phase carbon nitride photo-Fenton catalyst and preparation method thereof |
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| CN118059684A (en) * | 2024-04-24 | 2024-05-24 | 杭州水处理技术研究开发中心有限公司 | Flat membrane component with anti-pollution function, membrane filtering device and water purifying system |
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